here - Colloquium Spectroscopicum Internationale XXXIX

Transcription

here - Colloquium Spectroscopicum Internationale XXXIX

http://csi2015.fis.uc.pt
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Welcome
Colloquium Spectroscopicum Internationale XXXIX is a conference series which is held every
two years in a different country. The first one happened in Strasbourg, France, 1950, and the
former one in Tromsø, Norway, 2013.
This symposium endeavors to congregate physicists and chemists from universities and
research institutions with industry analysts in all fields of analytical spectroscopy, centering the
discussion not only on the results of basic research and method development but also on the
outcome from daily practice in the field of optical spectroscopy.The Local Organizing
Committee of the Colloquium Spectroscopicum Internationale XXXIX (CSI 2015) is pleased to
welcome all participants in Figueira da Foz, Portugal.
CSI2015 will be held in "CAE - Centro de Artes e Espectáculos", Figueira da Foz, a modern
Conference Hall with pleasant ample space, including an inner garden with glazed roof.
About 280 delegates from 36 countries will have the opportunity to exchange ideas and
knowledge related to all fields of analytical spectroscopy, centering the discussion not only
on the results of basic research and method development but also on the outcome from
daily practice in the field of optical spectroscopy.
The conference programme will consist of 14 plenary lectures and 11 keynote lectures from
distinguished scientists, 82 oral presentations and 204 poster contributions.
We thank our sponsors and all the people that contributed for this event to take place. We
hope that you enjoy your participation in CSI 2015.
On behalf of the Local Organizing Committee,
Maria Luísa de Carvalho
Joaquim M. F. dos Santos
Conference Web-page: http://csi2015.fis.uc.pt/
Cristina M. B. Monteiro
E-mail: csi2015@fis.uc.pt
Local Organizing Committee
Joaquim Santos, Physics Dept., University of Coimbra - Chair
Maria Luisa de Carvalho, Physics Dept., New University of Lisbon - Chair
Cristina Monteiro, Physics Dept., University of Coimbra - Chair
António Varandas, Chemistry Dept., University of Coimbra
Elisabete Freitas, Physics Dept., University of Coimbra
Fernando Amaro, Physics Dept., University of Coimbra
João Veloso, Physics Dept., University of Aveiro and Portuguese Physics Society
José Paulo Santos, Physics Dept., New University of Lisbon
Mário Diniz, Chemistry Dept., New University of Lisbon
Rui Fausto, Chemistry Dept., University of Coimbra
International Advisory Committee
Margaretha De Loos, Netherlands
Robert McCrindle, South-Africa
Alfredo Sanz Medel, Spain
Harpal Minhas, UK
János Mink, Hungary
Nicolo Omenetto, USA
Lars-Otto Reiersen, Norway
Ralf Sturgeon, Canada
Yngvar Thomassen, Norway
Bernhard Welz, Brazil
Gyula Záray, Hungary
Carlo Barbante, Italy
Ramon Barnes, USA
Ewa Bulska, Poland
M. José Calhorda, Portugal
Jiri Dedina, Czech Republic
Alessandro D'Ulivo, Italy
Rene Van Grieken, Belgium
Alexander A. Kamnev, Russia
Jun Kawai, Japan
Ryszard Lobinski, France
Continuation Committee
Yngvar Thomassen, Norway
Balázs Berlinger, Norway
Maria Luisa de Carvalho, Portugal
Joaquim Santos, Portugal
Alessandro D'Ulivo, Italy
Stefano Legnaioli, Italy
1
Scientific Topics
A
B
C
D
E
F
G
H
I
Atomic spectrometry (ICP OES, ICP-MS, GD, AAS, etc.);
Molecular spectrometry (UV-Vis, NMR, Raman, IR, etc.);
Organic and inorganic mass spectrometry (TIMS, MALDI, LC-MS, GC-MS);
X-ray spectrometry (XRF, XRD, XANES, PIXE, etc.);
Hyphenated techniques;
Laser spectroscopy;
Imaging techniques;
Nuclear techniques (Mössbauer spectroscopy, Gamma spectroscopy, NAA);
Methods of surface analysis and depth profiling;
J
Application of spectroscopy in:
J1
J2
J3
J4
J5
J6
J7
J8
J9
J10
Material sciences (nano/micro, surface and interface analysis);
Environmental and geochemical analysis;
Archaeometry and cultural heritage;
Biological applications;
Food analysis;
Clinical and pharmaceutical analysis;
Speciation analysis/Metallomics;
Mass spectrometry in post-genomics and proteomics;
Miniaturisation and nanotechnology;
Fuels and biofuels; Recent Scientific Developments by XRS Instrumentation
Invited Speakers
Randolf Pohl
Opening Talk, Monday 09:15
Alfredo Sanz Medel
CSI Award, Tuesday 08:45
JJ Gomez Cadenas
Topic H, Monday 10:35
Patrick J. Parsons
Topic C, Monday 14:30
Gary Hieftje
Topic B, Tuesday 09:30
György Tarczay
Luo Liqiang
Topic D, Tuesday 14:30
Koen Janssens
Topic J3, Wednesday 08:45
Jose M. Costa-Fernandez
Patricia Smichowski
Zezzi Arruda
Topic J7, Thursday 08:45
Emilia Bramanti
Topic E, Thursday 09:30
Barbara Wagner
Topic J3, Thursday 10:35
Iryna Doroshenko
Topic B, Thursday 14:00
Max-Planck-Institute of Quantum Optics, Germany
University of Oviedo, Spain
IFIC, CSIC & Universitat de València, Spain
Wadsworth Center and University at Albany, USA
Indiana University, USA
Eötvös University, Hungary
National Research Center of Geoanalysis, China
AXES Research Group, University of Antwerp, Belgium
University of Oviedo, Spain
Comisión Nacional de Energía Atómica, Argentina
GEPAM and University of Campinas, Brazil
C.N.R Institute of Chemistry of Organometallic Compounds, Italy
University of Warsaw, Poland
Taras Shevchenko National University of Kyiv, Ukraine
2
Keynote Speakers
Margaretha De Loos Vollebregt
Topic A, Monday 11:25
René Van Grieken
Topic J3, Monday 11:25
Yngvar Thomassen
Topic J2, Monday 11:25
Jun Kawai
Topic D, Monday 11:25
Ghent University, Belgium
University of Antwerp, Belgium
National Institute of Occupational Health, Norway
Kyoto University, Japan
Alessandro D'Ulivo
Topic A, Tuesday 11:25
Robert McCrindle
Topic J2, Tuesday 11:25
Ryszard Łobiński
Institute of Chemistry of Organometallic Compound, Italy
Tshwane University of Technology, South Africa
National Research Council of France, France
Ewa Bulska
Topic J4, Tuesday 11:25
Jiri Dědina
Topic A, Thursday 11:15
Bernhard Welz
Topic C, Thursday 11:15
University of Warsaw, Poland
Institute of Analytical Chemistry of the ASCR, Czech Republic
Universidade Federal de Santa Catarina, Brazil
Alexander A. Kamnev
Topic H, Thursday 11:15
Russian Academy of Sciences, Russia
Proceedings of the CSI 2015
The Proceedings will be published, following peer review, in the Spectrochimica Acta B and in
the Spectrochimica Acta A Journals.
Sponsors

Shimadzu Europa GmbH
http://www.shimadzu.eu/

Perkin Elmer
http://www.perkinelmer.com/
Exhibitors
 Shimadzu Europa GmbH

Milestone S.r.l.
http://www.shimadzu.eu/
http://www.milestonesrl.com/
 KETEK GmbH
http://www.ketek.net/
 Analytik Jena AG
http://www.analytik-jena.com/
 BRUKER
http://www.bruker.com/
 Sarspec, Lda.
http://sarspec.com/en/
 Specanalitica, Lda.
http://www.specanalitica.pt/
 Oxford Instruments
http://www.oxford-instruments.com/businesses/industrialproducts/industrial-analysis
 American Elements
http://www.americanelements.com/optical-materials.html
3
Social Program
Sunday, August 30
14:30-19:00
Registration
15:00-17:00
Guided Visit to “Museu Santos Rocha”
18:15-19:00
Folk dances by “Rancho das Cantarinhas de Buarcos”
19:00-20:00
Welcome Buffet
Monday, August 31
12:55-14:30
Conference Lunch
18:30-19:30
Traditional Portuguese Songs
Tuesday, September 1
12:55-14:30
Conference Lunch
Wine Degustation
18:20-19:20
Sponsored by
Wednesday, September 2
12:15-13:45
15:00-19:30
Conference Lunch
a) Excursion to Coimbra – Visit to the Old University
b) Excursion to Fatima – Visit to the Sanctuary
Thursday, September 3
12:25-14:00
Conference Lunch
18:00-18:45
Coimbra Fado Session
20:00-23:00
Conference Banquet
Coffee-breaks sponsored by
4
5
19:00 - 20:00
18:30 - 19:00
17:00 - 18:30
16:30 - 17:00
15:10 - 16:30
14:30 - 15:05
12:55 - 14:30
11:55 - 12:55
11:25 - 11:55
R
E
G
I
S
T
R
A
T
I
O
N
15:00 - 17:00
BUFFET
Welcome
Folk Dances
18:15 - 19:00
Santos Rocha
Museu
Guided visit to
OP43
D:OP41-
J10+J1:
OP44OP46
J5:OP50 OP52
B:OP47 OP49
Room 2
Portuguese Popular Music
18:30 - 19:30
19:00 - 20:00
NATIONAL DELEGATES MEETING
Wine degustation
Sponsored by SHIMADZU
18:20 - 19:20
POSTER SESSION 2
OP28
Room SA
POSTER SESSION 1
- OP24
Room 1
16:20-16:50 Coffee Break
(Sponsored by Perkin Elmer)
OP20
Room GA
A word from our sponsor SHIMADZU
PL7 - Luo Liqiang
Coffee Break
OP16
Room 2
J1:OP25 -
Room 1
J7:OP21
Room SA
F:OP17 -
Room GA
A:OP13 -
PL3 - Patrick J. Parsons
Lunch
OP38 OP40
OP35 OP37
OP32 OP34
OP29 OP31
OP10 OP12
OP7 OP9
OP4 OP6
OP1 - OP3
Lunch
J4:KL8
Room 2
B:KL7
Room 1
J2:KL6
Room SA
A:KL5
Room GA
D:KL4
Room 2
J2:KL3
J3:KL2
Room 1
Room SA
A:KL1
A word from our Sponsor Perkin Elmer
Room GA
Juan José Gomez-Cadenas
Room SA
Room 1
- OP55
EXCURSION
CONFERENCE
POSTER SESSION
3
Lunch
OP61
13:45 - 15:00
12:15-13:45
OP58
J3:OP53 B:OP56 - D:OP59 -
Room GA
Room 1
Room SA
- OP73
OP79
OP82
POSTER SESSION 4
Fado Session
CONFERENCE DINNER
20:00 - 23:00
18:00-18:45
CSI 2017 , Italy
17:45 Closing Cerimony
16:15-17:45
15:40-16:15 Coffee Break
OP76
E:OP74 - C:OP77 - J5:OP80 -
Room GA
Lunch
OP70
PL14 - Iryna Doroshenko
12:25 - 14:00
OP68
14:00-14:35
OP66
A:KL9
OP765 G+H:
OP62 OP64
Room SA
J4:OP71
Room 2
H:KL11
OP69 -
Room 1
C:KL10
OP67 -
Room GA
Room 2
PL13 - Barbara Wagner
PL10 - Patricia Smichowski
PL6 - György Tarczay
Plenary Lecture 2
10:35 - 11:10
11:10 - 11:20
Coffee Break
Coffee Break
Coffee Break
Coffee Break
PL12 - Emilia Bramanti
PL9 - J. M. Costa-Fernandez
PL5 - Gary Hieftje
10:05 - 10:35
Zezzi Arruda
Koen Janssens
Alfredo Sanz Medel
9:30-10:05
Plenary Lecture 11
Thursday - 3 Sept
Plenary Lecture 8
Wednesday - 2 Sept
CSI AWARD
Tuesday - 1 Sept
Randof Pohl
Opening Lecture
Opening Ceremony
Monday - 31 Aug
9:30 - 10:05
9:15 - 9:30
8:45 - 9:15
Sunday - 30 Aug
LIST OF PARTICIPANTS
ALBUQUERQUE NOGUEIRA,
Bernardo
bernardoalbuquerquenogueira@gmail.com
Departamento de Química,
Universidade de Coimbra
Portugal
ALEKSA, Valdemaras
valdemaras.aleksa@ff.vu.lt
Vilnius University
Lithuania
ALVAREZ, Cesar
ceallas@gmail.com
University of Oviedo
Spain
ALVES PEIXOTO, Rafaella
Regina
rafaella_peixoto@hotmail.com
University of Campinas
Brazil
ALVES, Matilde
mdj.alves@campus.fct.unl.pt
Faculdade de Ciências e
Tecnologia - UNL
Portugal
AMARO, Fernando
famaro@gian.fis.uc.pt
Coimbra University
Portugal
AMARO, Pedro
pdamaro@fct.unl.pt
LIBPhys
Portugal
ARCêNIO, Patricia Passos
patricia.arcenio@gmail.com
UFSC
Brazil
ARI, Hatice
hatice.ari@bozok.edu.tr
Bozok University, YOZGAT
Turkey
ARPA SAHIN, CIGDEM
carpa@hacettepe.edu.tr
HACETTEPE UNIVERSITY
Turkey
ARRUDA, Marco
zezzi@iqm.unicamp.br
University of Campinas - Unicamp
Brazil
ATILGAN, Semin
seatilgan@sisecam.com
SISECAM
Turkey
AUCELIO, Ricardo
aucelior@puc-rio.br
Pontifícia Univrsidade católica do
rio de Janeiro
Brazil
AZEVEDO, Carlos
cdazevedo@ua.pt
I3N – Physics Department,
University of Aveiro
Portugal
BABAGIL, Aynur
ababagil@hotmail.com
Ataturk University, Faculty of
Engineering, Department of Nano- Turkey
Science and Nano-Engineering
BABUSCA, Daniela
danab672001@yahoo.com
Faculty of Physics, Alexandru Ioan
Cuza University of Iaşi
BAğDA, Esra
esraer@cumhuriyet.edu.tr
Cumhuriyet University, Faculty of
Pharmacy, Department of Analytic Turkey
Chemistry, Sivas
BAKIRCIOGLU KURTULUS,
Yasemin
ybakircioglu@trakya.edu.tr
Department of Chemistry, Faculty
of Science, Trakya University
Turkey
BAKIRCIOGLU, dilek
dbakircioglu@trakya.edu.tr
Department of Chemistry, Faculty
of Science, Trakya University
Turkey
BALL, Markus
mball@hiskp.uni-bonn.de
HISKP
Germany
BALOGH, Zsuzsanna
balogh.zsuzsanna.08@gmail.com
University of Debrecen
Hungary
BARATA, Emanuel
emanuel.brt91@gmail.com
Coimbra University
Portugal
BARCIELA-ALONSO, Mª
Carmen
mcarmen.barciela@usc.es
University of Santiago de
Compostela
Spain
BARNES, Ramon
barnes@chemistry.umass.edu
ICP Information Newsletter
USA
BáRTOVá, Hana
hana.bartova@fjfi.cvut.cz
Czech Technical University in
Prague
Czech
Republic
BAZZANO, Francesca
francesca.bazzano@eni.com
eni S.p.A Research &
Technological Innovation
Department
Italy
BEKTAS, SEMA
fsbektas@hacettepe.edu.tr
HACETTEPE UNIVERSITY
Turkey
6
Romania
BENCHEA, Andreea Celia
bencheacelia@yahoo.com
”Al.I.Cuza” University, Faculty of
Physics, Department of Optics and Romania
Spectroscopy, Iasi
BETTENCOURT, Carmen
c.bettencourt@campus.fct.unl.pt
LIBPhys-UNL
Portugal
BRAMANTI, Emilia
bramanti@pi.iccom.cnr.it
Italian National Research Council,
Institute of Chemistry of Organo
Metallic Compounds
Italy
BRESSON, Carole
carole.bresson@cea.fr
CEA
France
BRUNETTI, Antonio
brunetti@uniss.it
University of Sassari
Italy
BRUNI, Stefania
stefania.bruni@enea.it
ENEA
Italia
BULSKA, Ewa
ebulska@chem.uw.edu.pl
University of Warsaw
Poland
CADORE, Solange
cadore@iqm.unicamp.br
UNICAMP
Brazil
CALZA, Cristiane
criscalza@outlook.com
PEN/COPPE/UFRJ
Brazil
CAMPANELLA, Beatrice
beatrice.campanella@for.unipi.it
University of Pisa
Italy
CAPOBIANCO, Giuseppe
giuseppe.capobianco@uniroma1.it
Sapienza University of Rome DICMA
Italy
CARVALHO, Maria Luisa
luisa.carvalho@fct.unl.pt
New University of Lisbon
Portugal
CARVALHO, Marta
mc.carvalho@campus.fct.unl.pt
LIBPhys-UNL
Portugal
CARVALHO, Xavier
xavierpcarvalho@hotmail.com
Coimbra University
Portugal
CASTRO, Joana
jd.castro@campus.fct.unl.pt
Universidade Nova de Lisboa
Portugal
CELIK, Semra
elhamra.387@gmail.com
Ataturk University, Faculty of
Engineering, Department of Nano- Turkey
Science and Nano-Engineering
CERVENY, Vaclav
cerveny2@natur.cuni.cz
Charles University in Prague,
Faculty of Science, Department of
Analytical Chemistry
Czech
republic
CHARTIER, Frederic
frederic.chartier@cea.fr
CEA Saclay DEN/DPC Bât. 450N
France
CHASQUEIRA, Ana
filipach@gmail.com
School of dentistry, University of
Lisbon
Portugal
CHEUNG, Yan
yancheu@indiana.edu
Indiana University Bloomington
USA
CIDADE, Mirla
mirla.jc@hotmail.com
Universidade Federal de Roraima
Brazil
COELHO, Inês
ines.coelho@insa.min-saude.pt
Instituto Nacional de Saúde Dr
Ricardo Jorge
Portugal
COOPERMAN, Helena
Helena.Cooperman@teva.co.il
Teva Pharmaceuticals Ltd
Israel
CORREIA CARREIRA, José
Filipe
correiacarreira@ua.pt
Department of Physics & i3N,
University of Aveiro
Portugal
COSTA SILVA, Pedro
eresthor13@gmail.com
Physics Department University of
Coimbra
Portugal
COSTA, Adriana
acd.costa@campus.fct.unl.pt
FCT/UNL
Portugal
COSTA, Benilde F.O.
benilde@fis.uc.pt
Coimbra
Portugal
COSTA-FERNANDEZ, Jose M.
jcostafe@uniovi.es
Spain
7
CRUZ, João
jdc@fct.unl.pt
LIBPhys
Portugal
DE LOOS-VOLLEBREGT,
Margaretha
margaretha.deloos@ugent.be
Ghent University
Belgium
DEDINA, Jiri
dedina@biomed.cas.cz
Institute of Analytical Chemistry of Czech
the AS CR, v. v. i.
Republic
DESSUY, Morgana
mbdessuy@ufrgs.br
Universidade Federal do Rio
Grande do Sul
Brazil
DIAS, António
aad@fct.unl.pt
LIBPhys-UNL, Universidade Nova
Lisboa
Portugal
DIKBAS, Neslihan
neslidikbas@atauni.edu.tr
Ataturk University, Department of
Enzyme And Microbial
Biotechnology
Turkey
DO NASCIMENTO DA SILVA,
Emanueli
manu_bing@hotmail.com
UNICAMP
Brazil
DOGAN, Mehmet
dogan@hacettepe.edu.tr
hacettepe university
turkey
DOROSHENKO, Iryna
dori11@ukr.net
Taras Shevchenko National
University of Kyiv
Ukraine
D'ULIVO, Alessandro
dulivo@pi.iccom.cnr.it
CNR, Institue of Chemistry of
Organometallic Compounds
Italy
DUYCK, Christiane
cbduyck@vm.uff.br
Universidade Federal FluminenseRJ
Brazil
DYBAL, Jiri
dybal@imc.cas.cz
Institute of Macromolecular
Chemistry AS CR
Czech
Republic
EID, May
maybaker25@gmail.com
Spectroscopy Dep. National
Research Center
Egypt
ER, Engin
eer@ankara.edu.tr
Department of Analytical
Chemistry, Faculty of Pharmacy,
Ankara University
Turkey
ESTEBAN FERNáNDEZ, Diego
diego.esteban-fernandez@bam.de
BAM Federal Institute for
Materials Research and Testing
Germany
FABRIS, José Domingos
jdfabris@gmail.com
Federal University of the
Jequitinhonha and Mucuri Valleys
Brazil
FAN, Chenzi
czfan2013@163.com
China National Research Centre
for Geoanalysis
China
FAUSTO, Rui
rfausto@ci.uc.pt
University of Coimbra
Portugal
FERNANDES, Luis
pancho@gian.fis.uc.pt
Coimbra University
Portugal
FERNANDEZ, Jorge
jorge.fernandez@unibo.it
Alma Mater Studiorum University
of Bologna
Italy
FERNáNDEZ-MENéNDEZ,
Sonia
soniafdezm@gmail.com
Spain
FERREIA, Carina
civ.ferreira@campus.fct.unl.pt
LIBPhys
Portugal
FERREIRA BATISTA, Erica
erica_quim@yahoo.com.br
UFSCar
Brazil
FERREIRA DA SILVA, Fabio
fabio_silva@agilent.com
Agilent Technologies/UFABC
Brazil
FERREIRA MARQUES, Maria
de Fátima
fatima@isec.pt
CFisUC
Portugal
FIGUEIREDO, Alexandra
alexandra.f@netcabo.pt
Egas Moniz CRL
Portugal
8
FILIPCZAK, Paulina
paulina.filipczak@dokt.p.lodz.pl
Department of Molecular Physics
Lodz University of Technology
Poland
FLESCH, Gregory
gflesch@jpl.nasa.gov
Jet Propulsion Laboratory
USA
FRANçA DE Sá, Susana
susana_de_sa@hotmail.com
Faculdade de Ciências e
Tecnologia, Universidade Nova de
Lisboa
Portugal
FREITAS, Elisabete
elisabete@gian.fis.uc.pt
Coimbra University
PORTUGAL
FUJIWARA, Tatsuyoshi
fujiwara@shimadzu.co.jp
SHIMADZU
Japan
FURUHATA, Tadashi
furuhata@wayo.ac.jp
Wayo Woman's University
Japan
GALAZZI, Rodrigo Moretto
rodrigo_galazzi@hotmail.com
University of Campinas UNICAMP
Brazil
GARCíA, Marta
martagarciacortes88@gmail.com
Spain
GARCíA, Marta
martagarciacortes88@gmail.com
University Of Oviedo
Spain
GASPAR, Andre S.
andresilvagaspar@gmail.com
Coimbra
Portugal
GASPAR, Marcos
marcos.gaspar@psi.ch
PSI
Switzerland
GIL, Milene
milenegil@gmail.com
Laboratório HERCULES
Portugal
GODLEWSKA-ŻYłKIEWICZ,
Beata
bgodlew@uwb.edu.pl
University of Bialystok
Poland
GOMEZ-CADENAS, Juan Jose
gomez@mail.cern.ch
Valencia University, CSIC
Spain
GOMEZ-GOMEZ, M.
MILAGROS
mmgomez@quim.ucm.es
Chemistry, Universidad
Complutense de Madrid
Spain
GONçALVES, Mauro
mauro2bx@gmail.com
Portugal
GORDO, Paulo M.
pgordo@ci.uc.pt
CFisUC
Portugal
GOTO, Masayuki
gotoh@wayo.ac.jp
Japanese
Japan
GOTTA, Detlev
d.gotta@fz-juelich.de
Forschungszentrum Juelich
Germany
GREUNZ, Theresia
theresia.greunz@jku.at
JKU Linz, CDL-MS-MACH,
Altenbergerstr. Linz
Austria
GROMBONI, Caio Fernando
cfgromboni@gmail.com
IFBA
Brazil
GUERRA, Mauro
mguerra@fct.unl.pt
LibPhys - UNL Laboratório de
Instrumentação, Engenharia
Biomédica e Física da Radiação
Portugal
GUIMARAES, Diana
dianafcg@gmail.com
Wadsworth Center and University
at Albany
USA
HAHN, Hendrik
hahn.hendrik@web.de
MEET Battery Research Center,
University Of Münster
Germany
HARANGI, Sándor
harangi.sandor@science.unideb.hu
University of Debrecen
Hungary
HARTINGER, Werner
Werner.Hartinger@ketek.net
KETEK GmbH, Germany
Germany
HASEBE, Nobuyuki
nhasebe@waseda.jp
Waseda University
Japan
HENRIQUES, Carlos
henriques@gian.fis.uc.pt
Portugal
HENRIQUES, Marta
marta.henriques@gmail.com
CFisUC, Department of Physics,
Portugal
9
HIEFTJE, Gary
hieftje@indiana.edu
Indiana University
USA
HRANICEK, Jakub
jakub.hranicek@natur.cuni.cz
Czech
Republic
HSU, Che-Lun
jerlun@fda.gov.tw
Food and Drug Administration
Ministry of Health and Welfare
Taiwan
R.O.C.
HUBER, Charles
chahuber@gmail.com
Grande do Sul
Brazil
IWAI, Takahiro
t-iwai@kwansei.ac.jp
Kwansei Gakuin University
Japan
JABUA, Malkhaz
m.jabua@fz-juelich.de
Forschungszentrum Juelich
Germany
JANASIK, BEATA
beatajan@imp.lodz.pl
Nofer Institute of Occupational
Medicine
Poland
JANSSENS, Koen
koen.janssens@uantwerpen.be
University of Antwerp
Belgium
KALKAN, Ekrem
ekalkan@atauni.edu.tr
Ataturk University
Turkey
KAMNEV, Alexander A.
a.a.kamnev@mail.ru
Institute of Biochemistry and
Physiology of Plants and
Russia
Microorganisms, Russian Academy
of Sciences, Saratov
KATONA-TOBIAS, Erzsebet
e.tobias@richter.hu
Gedeon Richter
Hungary
KAVASI, Norbert
norbert@fml.nirs.go.jp
National Insitute of Radiological
Sciences
Japan
KAWAI, Jun
kawai.jun.3x@kyoto-u.ac.jp
Kyoto University
Japan
KEYMEULEN, Didier
didier.keymeulen@jpl.nasa.gov
Jet Propulsion Laboratory
USA
KHAN, Sar zamin
sarzamin81@gmail.com
Researcher, ontifical Catholic
University - Rio de Janeiro (PUCRio) Chemistry Department
Brazil
KNOOP, Jan
jkn@shimadzu.eu
Germany
KOśCIELNIAK, Anna
pawel.koscielniak@uj.edu.pl
Jagiellonian University
Poland
KOśCIELNIAK, Paweł
koscieln@chemia.uj.edu.pl
Jagiellonian University, Faculty of
Chemistry, Department of
Analytical Chemistry, Krakow
Poland
KOWALEWSKA, Zofia
zofia.kowalewskah@gmail.com
Warsaw University of Technology
Poland
KRATZER, Jan
jkratzer@biomed.cas.cz
the ASCR, v.v.i.
Republic
KUZNETSOVA, Valentyna
tinakouznets@gmail.com
Faculty of Science, University of
South Bohemia
Czech
Republic
LABUTIN, Timur
timurla@laser.chem.msu.ru
Lomonosov Moscow State
University
Russia
LARANJEIRA, Pedro
plaranjeira@dias-de-sousa.pt
Bruker GmbH
Portugal
LECH, Teresa
tlech@ies.krakow.pl
Institute of Forensic Research,
Kraków
Poland
LEDNEV, Vasily
lednev@kapella.gpi.ru
Prokhorov General Physics
Institute
Russia
LEGNAIOLI, Stefano
stefano.legnaioli@cnr.it
ICCOM-CNR
Italy
LEITãO, Roberta
roberta@lin.ufrj.br
UFRJ
Brazil
10
LESNIEWSKA, Barbara
blesniew@uwb.edu.pl
University of Bialystok
Poland
LIM, Ho Soo
hslim70@korea.kr
Ministry of food and drug
safety(MFDS)
Republic of
Korea
LIMA, Enrique
lima@iim.unam.mx
Instituto de Investigaciones en
Materiales,UNAM
Mexico
LINHART, Ondrej
linhartona@seznam.cz
Faculty of Science
Czech
Republic
LOBINSKI, Ryszard
ryszard.lobinski@univ-pau.fr
LCABIE CNRS UMR 5254
France
LOPES, Filipa
filipalopes1@gmail.com
CENIMAT/i3N
Portugal
LóPEZ, Ana J.
ana.xesus.lopez@udc.es
Universidade da Coruña
Spain
LUCZYNSKA, Katarzyna
k.luczynska@ichtj.waw.pl
JOINT INSTITUTE FOR NUCLEAR
RESEARCH
Russia
LUíS, José
josemmluis66@hotmail.com
FCTUC
Portugal
LUO, Liqiang
luoliqiang@cags.ac.cn
National Research Center of
Geoanalysis
China
MACHADO, Alessandra
alessandra_fisica@hotmail.com
Federal University of Rio de
Janeiro
Brazil
MACHADO, Raquel
raquelcm.quim@gmail.com
UFSCar
Brazil
MAGARINI, Riccardo
jbarata@ilc.pt
Perkin Elmer
Italy
MAIA, Sandra Maria
sandramaia@iq.ufrgs.br
Grande do Sul - UFRGS
Brazil
MAJEWSKA, Urszula
Urszula.Majewska@ujk.edu.pl
Institute of Physics, Jan
Kochanowski University in Kielce
Poland
MAKSIMOVA, Alevtina
alia55@bk.ru
Ural Federal University
Russia
MANAKA, Yumi
manaka@wayo.ac.jp
Wayo Women’s University
Japan
MANO, Daniel
danielmano22@hotmail.com
Coimbra University
Portugal
MANSO, Marta
marta974@gmail.com
LIBPhys
Portugal
MARANHãO, Tatiane de A.
tatiane.maranhao@gmail.com
UFSC
Brazil
MARQUEZ, CIRO
ciromar@unam.mx
UNIVERSIDAD NACIONAL
AUTONOMA DE MEXICO
MEXICO
MARSCHNER, Karel
karel.marschner@biomed.cas.cz
the ASCR
Republic
MARTíNEZ-FRíAS, Jesús
j.m.frias@igeo.ucm-csic.es
Instituto de Geociencias, IGEO
(CSIC-UCM)
Spain
MATIAS LOPES, José
fcjam@gian.fis.uc.pt
Coimbra University
Portugal
MCCRINDLE, Cheryl
cheryl.mccrindle@gmail.com
University of Pretoria
South Africa
MCCRINDLE, Robert
mccrindleri@tut.ac.za
Tshwane University of Technology
South Africa
MEDINA GARCIA, JESUS
medina@fmc.uva.es
Dpto. Física De La Materia
Condensada, Cristalografía Y
Mineralogía. Universidad De
Valladolid
Spain
MENéNDEZ MIRANDA, Mario
mariomemi@gmail.com
Spain
MENZEL, Jennifer
jennifer.menzel@uni-muenster.de
MEET Battery Research Centre -
Germany
11
Münster University
MINAMI, Takeshi
minamita@life.kindai.ac.jp
Kinki University
Japan
MöNNIGHOFF, Xaver
x.moennighoff@uni-muenster.de
University of Münster
Germany
MONTEIRO, Cristina
cristina@gian.fis.uc.pt
Portugal
MONTEIRO, Jorge
jmonteiro@sarspec.com
SARSPEC, LDA
Portugal
MORALEJA SAN JOSé, Irene
irenemoraleja@ucm.es
University Complutense of Madrid Spain
MORETTI, Lorenzo
lorenzo.moretti@enea.it
ENEA
Italy
MOTOVILOV, Vladimir
vladimir_motovilov87@mail.ru
ITMO University
Russia
MUNIZ, Luiza
portugalluiza@hotmail.com
INCQS Fundação Oswaldo Cruz
Brazil
MUSHTAQ, Sohail
s.mushtaq@londonmet.ac.uk
LONDON METROPOLITAN
UNIVERSITY
UK
MUSIL, Stanislav
stanomusil@biomed.cas.cz
the ASCR, v. v. i
republic
NADAROGLU, Hayrunnisa
hnisa25@atauni.edu.tr
Ataturk University, Erzurum
Vocational School, Department of
Food Technology
Turkey
NAKAGAWA, T. Sachiko
stnak@dap.ous.ac.jp
Okayama Univ. of Science
Japan
NAKAJIMA, Hiromitsu
h-nakaji@ynu.ac.jp
Yokohama National Universtiy
Japan
NOGUEIRA, Ana Rita
ana.nogueira@embrapa.br
Embrapa Southeast Livestock
Brazil
NOMNGONGO, Philiswa
pnnomngongo@uj.ac.za
University of Johannesburg
South Africa
NOVAKOVA, Eliska
novakoe1@natur.cuni.cz
Faculty of Science
Czech
REpublic
NOWAK, Sascha
sascha.nowak@uni-muenster.de
University of Münster - MEET
Germany
OKAJIMA, Toshihiro
okajima@saga-ls.jp
Kyushu Synchrotron Light
Research Center
Japan
OLEJNICZAK, Magdalena
magdalena.olejniczak@dokt.p.lodz.pl
Lodz University of Technology,
Department of Molecular Physics
Poland
OLEKHNOVICH, Roman
r.o.olekhnovich@mail.ru
ITMO University
Russia
OLIVAL, Sofia
s.olival@campus.fct.unl.pt
FCT UNL
Portugal
Olivares, Maitane
maitane.olivares@ehu.eus
University of the Basque Country
Spain
OLIVEIRA, Davi
davifoliveira82@gmail.com
UFRJ
Brazil
OLIVEIRA, IZABEL KALINE
izabelkaline@gmail.com
UNIVERSIDADE FEDERAL DO RIO
GRANDE DO NORTE
Brazil
OLIVEIRA, Pedro V
pvolivei@iq.usp.br
University of São Paulo
Brazil
OMENETTO, Nicolo
omenetto@chem.ufl.edu
University of Florida
USA
ONODERA, Toshiyuki
t_onodera@tohtech.ac.jp
Tohoku Institute of Technology
Japan
ONOR, Massimo
onor@pi.iccom.cnr.it
CNR-ICCOM-Pisa
Italy
OPPERMANN, Uwe
uo@shimadzu.eu
Shimadzu Europa
Germany
OSAN, Janos
janos.osan@energia.mta.hu
HAS Centre for Energy Research
Hungary
12
OSHTRAKH, Michael
oshtrakh@gmail.com
Ural Federal University
Russia
OSTICIOLI, Iacopo
i.osticioli@ifac.cnr.it
IFAC-CNR
Italy
ÖZPOZAN, Talat
ozpozant@erciyes.edu.tr
Erciyes University, Kayseri
Turkey
OZTURK, Birsen
demirata@itu.edu.tr
Istanbul Technical University
Turkey
OZYURT, Dilek
ozyurtd@itu.edu.tr
Istanbul Technical University
Turkey
PADURARU, Nicoleta
paduraru9nicoleta@yahoo.com
“ Dunarea de Jos” University,
Department of Chemistry, Physics
and Environment
Romania
PAIXãO, José António
jap@fis.uc.pt
CFisUC, Dept. Física, Univ.
Coimbra
Portugal
PALLESCHI, Vincenzo
vincenzo.palleschi@cnr.it
ICCOM/CNR
Italy
PALMIERI, Helena
help@cdtn.br
CDTN/CNEN
Brazil
PANICHEV, Nikolai
PanichevN@tut.ac.za
Tshwane University of Technology
South Africa
PARSONS, Patrick
patrick.parsons@health.ny.gov
Wadsworth Center and University
at Albany
USA
PEñA-VáZQUEZ, Elena
elenamaria.pena@usc.es
University of Santiago de
Compostela
Spain
PERALTA CONDE, Álvaro
aperalta@clpu.es
Centro de Láseres Pulsados (CLPU) Spain
PEREIRA, Marcelo
marcelocefetrj@gmail.com
Federal Center for Technological
Education Celso Suckow da
Fonseca (CEFET-RJ)
Brazil
PEREIRA, Vanda
vandampereira.04@gmail.com
Portugal
PESSANHA, Sofia
sofia.pessanha@fct.unl.pt
LIBPhys
Portugal
PIGA, Giampaolo
giapiga@uniss.it
Department of Political Science,
Communication, Engineering and
Information Technologies.
University of Sassari
Italy
PIROLA, Camillo
C.PIROLA@MILESTONESRL.COM
Milestone S.r.l.
Italy
PLOTNIKOVA, Liudmila
ljusja@mail.ru
Russian Federation
Russia
POHL, Randolf
randolf.pohl@mpq.mpg.de
MPQ
Germany
POPOV, Andrey
popov@laser.chem.msu.ru
Lomonosov Moscow State
University
Russia
PYSCHIK, Marcelina
marcelina.pyschik@uni-muenster.de
University of Münster, MEET
Battery Research Center
Germany
QIAN, Yunxian
yqian_01@uni-muenster.de
MEET Battery Center
Germany
QUERALT, Ignasi
iqueralt@ictja.csic.es
Institute of Earth Sciences,
ICTJA/CSIC
Spain
RAMOS, Inês
in.ramos@campus.fct.unl.pt
Faculdade Ciências e Tecnologia
da Universidade Nova de Lisboa
Portugal
REITBöCK, Cornelia
cornelia.reitboeck@jku.at
Johannes Kepler University, CDLMS-MACH
Austria
RESSLEROVA, Tina
tina.resslerova@natur.cuni.cz
Faculty of Science
Czech
Republic
REZENDE, Hélen Cristine
helencristinerezende@yahoo.com.br
Universidade Federal de Goiás
Brazil
13
RINCóN, Jesús Ma.
jrincon@ietcc.csic.es
Instº E. Torroja de Ciencias de la
Construcción- CSIC
Spain
ROCHA, Rui
Rui.Rocha@bruker.com
Bruker GmbH
Germany
RULL, Fernando
rull@fmc.uva.es
University of Valladolid
Spain
RYBíNOVá, Marcela
rybinova@natur.cuni.cz
Czech
Republic
SAINT'PIERRE, Tatiana
tatispierre@puc-rio.br
PUC-Rio
Brazil
SALIM, Daoudi
salz_dg@yahoo.fr
Department of Materials Science,
Faculty of Sciences and
Algeria
Technology, Mohamed El Bachir El
Ibrahimi University
SANTOS DE ALMEIDA ,
Danielle
danielle_almeida2003@ig.com.br
Universidade Federal do Rio de
Janeiro
Brazil
SANTOS, Catarina
cisantos@qui.uc.pt
DQ-FCTUC
Portugal
SANTOS, Joaquim
jmf@gian.fis.uc.pt
Coimbra University
PORTUGAL
SANTOS, José Paulo
jps@fct.unl.pt
LIBPhys-UNL, Universidade Nova
Lisboa
Portugal
SANTOS, Rui
rgaza.rs@gmail.com
Analytik Jena
Portugal
SANZ MEDEL, Alfredo
asm@uniovi.es
Spain
SCHIAVON, Nick
schiavon@uevora.pt
Hercules Lab-University of Évora
PORTUGAL
SCHULTZ, Carola
carola.schultz@uni-muenster.de
MEET Battery Research Centre,
University of Münster
Germany
SCHULZ, Christian
c.schulz@elsevier.com
Elsevier B.V.
The
Netherlands
SCHWARTZ, Andrew
andschwa@indiana.edu
Indiana University
USA
SCHWIETERS, Timo
t.schwieters@wwu.de
Meet Battery Research Center
Germany
SENDREA, Claudiu
claudiusendrea@yahoo.com
Faculty of Applied Chemistry and
Materials Science, University
Romania
Politehnica of Bucharest, Romania
SEQUEIRA, Sílvia
s.o.sequeira@gmail.com
Departamento de Conservação e
Restauro, FCT-UNL
Portugal
SHEN, Ya Ting
always1204@163.com
National Research Center of
Geoanalysis
China
SHI, Hongjun
shihj@iphy.ac.cn
Institute of Physics Chinese
Academy of sciences
China
SHOIFET, Evgeni
evgeni.shoifet@uni-rostock.de
Rostock University
Germany
SILVA, Ana Luisa
analuisa.silva@ua.pt
I3N - Departamento de Física,
Universidade de Aveiro
Portugal
SILVA, Andrea
andrearsqo@gmail.com
CEFET/RJ
Brazil
SILVA, Jessee S. A.
jesseesevero@yahoo.com.br
UFSC
Brazil
SILVA, Manuela
manuela@pollux.fis.uc.pt
Portugal
SILVA, Maria
gsilva@ua.pt
DEMaC - Aveiro University
Portugal
SILVA, Pedro
psidonio@pollux.fis.uc.pt
Portugal
14
SIPILä, Heikki
hjsipila@gmail.com
HS Foils Oy
Finland
SMICHOWSKI, Patricia
Patricia.Smichowski@gmail.com
ATOMIC ENERGY COMMISSION
Argentina
SOHAIL, MISBAH
msohail1007@hotmail.com
LONDON METROPOLITAN
UNIVERSITY, UK & PAKISTAN
UK &
PAKISTAN
SOUSA E SILVA, Ricardo
rss@sarspec.com
SARSPEC, LDA
Portugal
STABRAWA, Ilona
ilona.stabrawa@interia.pl
Institute of Physics, Jan
Kochanowski University
Poland
STANISłAWSKA, Magdalena
magda@imp.lodz.pl
Nofer Institute of Occupational
Medicine
Poland
STEINBERGER, Roland
roland.steinberger@jku.at
JKU Linz, CDL-MS-MACH,
Altenbergerstr
Austria
STREIBEL, Thorsten
thorsten.streibel@uni-rostock.de
University of Rostock
Germany
SUSANO, Maria
maria.susano@gmail.com
Portugal
SVOBODA, Milan
svoboda750@biomed.cas.cz
the ASCR, v.v.i.
Republic
SZYMANSKI, Krzysztof
k.szymanski@uwb.edu.pl
University of Białystok
Poland
TARCZAY, Gyorgy
tarczay@gmail.com
Institute of Chemistry, Eotvos
University
Hungary
TELES, Atila
ateles@con.ufrj.br
Federal University of Rio de
Janeiro
Brazil
THOMASSEN, Yngvar
yngvar.thomassen@stami.no
National Institute of Occupational
Health
Norway
TöRöK, Szabina
torok.szabina@energia.mta.hu
HAS Eneregy Research C
Hungary
TRELLA, Agata
agata.trella@uniroma1.it
Dicma, Sapienza, University of
Rome
Italy
TRUJILLO, Abigail
abigatos@gmail.com
Universidad Nacional Autónoma
de México
Mexico
TUZEN, Mustafa
m.tuzen@gmail.com
Gaziosmanpasa Universitesi
Turkey
VALE, Maria Goreti
mgrvale@ufrgs.br
Grande do Sul
Brazil
VAN DRIEL, Birgit Anne
b.van.driel@rijksmuseum.nl
Rijksmuseum, RCE, TU Delft
Netherlands
VAN GRIEKEN, Rene
rene.vangrieken@uantwerpen.be
University of Antwerp
Belgium
VAN OYEN, Albert
albert.van.oyen@carat-lab.com
Germany
VASILEVA -VELEVA, Emiliya
e.vasileva-veleva@iaea.org
IAEA Environment Laboratories
Monaco
VIEIRA, Ricardo
vieira.fis@gmail.com
Department of Physics Universidade de Coimbra CEMDRX
Portugal
VíTKOVá, Gabriela
gabriela.vitkova@ceitec.vutbr.cz
Masaryk University
Czech
Republic
WAGATSUMA, Kazuaki
wagatuma@imr.tohoku.ac.jp
IMR. Tohoku University
Japan
WAGNER, Barbara
barbog@chem.uw.edu.pl
University of Warsaw
Poland
WANG, Qiuquan
qqwang@xmu.edu.cn
Xiamen University
China
WELZ, Bernhard
w.bernardo@terra.com.br
Universidade Federal de Santa
Brazil
15
Catarina, Florianópolis, SC
WIEMERS-MEYER, Simon
simon.wm@wwu.de
Universität Münster
Germany
WITTKOPP, Andreas
Andreas.Wittkopp@bruker.com
Bruker GmbH, Germany
Germany
WOLLNY, Laura Johanna
Brigitte
laura.wollny@rub.de
Ruhr-Universität Bochum
Germany
WüNSCHER, Sebastian
sebastian.wuenscher@analytik-jena.de
Analytik Jena AG
Germany
YABAş, Ebru
yabasebru@gmail.com
Cumhuriyet University, Faculty of
Science, Department of
Chemistry, Sivas
Turkey
ZAND, Maryam
m_zand@Physics.iust.ac.ir
Iran University of Science and
Technology
IRAN
ZAPATA, Félix
felix.zapata@uah.es
INQUIFOR
Spain
ŽEMBERYOVA, Mária
zemberyova@fns.uniba.sk
Comenius University in Bratislava,
Faculty of Natural Sciences,
Chemistry
Slovak
Republic
ZVěřINA, Ondřej
ondrej.zverina@gmail.com
Masaryk University
16
Czech
Republic
Abstracts
Oral Sessions
17
18
Opening Lecture
PL1
Laser spectroscopy of muonic hydrogen and helium
R. Pohl1 for the CREMA Collaboration2
1
Max-Planck-Institute of Quantum Optics, 85748 Garching, Germany
2
Charge Radius Experiment with Muonic Atoms:
MPQ (Garching), ETH (Zurich), PSI (Villigen, CH), LKB & UPMC (Paris), U. Coimbra (Portugal), U. Aveiro (Portugal),
IFSW U. Stuttgart (Germany), U. Lisbon (Portugal), Nat. Tsing Hua U. (Taiwan)
E-mail: randolf.pohl@mpq.mpg.de
We have recently established laser spectroscopy of muonic atoms as a tool to
measure properties of the lightest nuclei from the proton to helium-4. In muonic
atoms, the heavy muon orbits a bare nucleus with a 200 times smaller Bohr radius,
compared to its electronic counterpart. This results in a tremendously increased
sensitivity (2003 ≈ 107) of the muonic atom's S-states to the finite charge and
magnetic radius of the nucleus.
Our proton charge radius Rp=0.84087(39) fm [1,2] is ten times more accurate, but 7σ
discrepant from the world average [3], which is based on elastic electron-proton
scattering and precision spectroscopy of regular (electronic) hydrogen. Possible
explanations of this ``proton radius puzzle'' include unexpected behavior of the
proton and to physics beyond the Standard Model [4,5].
Our new data on muonic deuterium and helium [6] may help to understand this
puzzle, and will ultimately determine the radii of the lightest nuclei with 10 times
higher accuracy. Together with improved measurements in regular hydrogen
currently pursued e.g. at MPQ [7], this will lead to tests of bound state QED at a new
level of accuracy.
References
[1] R. Pohl et al. (CREMA Coll.) Nature 466, 213 (2010).
[2] A. Antognini et al. (CREMA Coll.), Science 339, 417 (2013).
[3] P.J. Mohr, B.N. Taylor, D.B. Newell (CODATA), Rev. Mod. Phys. 84, 1527 (2012).
[4] R. Pohl et al., Annu. Rev. Nucl. Part. Sci 63, 175 (2013)
[5] C.E. Carlson, Prog. Part. Nucl. Phys. 82, 59 (2015).
[6] A. Antognini et al. (CREMA Coll.), Can. J. Phys. 89, 47 (2011).
[7] A. Beyer et al., J. Phys. Conf. Ser. 467, 012003 (2013).
19
Plenary Lecture: Nuclear Techniques
PL2
PETALO a PET TOF Apparatus based on Liquid Xenon
Juan José Gomez-Cadenas
Instituto de Física Corpuscular (IFIC), CSIC & Universitat de Valencia
Calle Catedrático José Beltrán, 2, 46980 Paterna, Valencia, Spain
E-mail: jjgomezcadenas@gmail.com
The talk will present the concept of a Positron Electron TOF Apparatus using Liquid
xenON (PETALO). LXe has a reasonable high density and an acceptable attenuation
length, which makes it suitable for PET applications. Its advantage with respect to
conventional solid scintillators such as NaI or LYSO are: a) its very high yield,
which in turn can translate in excellent energy resolution; b) its very fast scintillation
decay time (2 ns), which allows a TOF measurement; c) Its ability to provide a 3D
measurement of the interaction point, minimising parallax errors; d) its capability to
identify Compton events depositing all its energy in the detector as separate-site
interaction, due to the relatively large interaction length in xenon; ; and e) its
relatively low cost (e.g, about 10\% of the cost of LSO per unit detector).
The possibility of building a LXe PET (with TOF capabilities) based on the excellent
properties of LXe as scintillator, was first suggested by Lavoie in 1976 and the study
of this type of PET was carried out by the Waseda group some ten years ago. The
Waseda prototype was based in LXe cells read out by VUV-sensitive PMTs. In those
cells one of the sides was left instrumented. The relatively poor performance of the
system can be attributed in part to the use of PMTs and in part to the partial lack of
instrumentation which affected both the energy and the time resolution. PETALO,
solves the problems found in the Waseda prototypes by using a detection cell,
instrumented with SiPMs. Consequently an excellent energy and time resolution can
be achieved. The low cost of the detector makes it suitable for a large ``full body’’
PET apparatus.
20
Plenary Lecture: Organic and Inorganic mass spectrometry
PL3
Application of ICP-MS/MS in Environmental Health –
analysis of human bones for the Rare Earth Elements
A. Galusha1,2, L. Howard3, P. Kruger1 and P. Parsons1,2
1
Wadsworth Center, New York State Department of Health, PO Box 509, Albany, NY, 12201 USA
2
Department of Environmental Health Sciences, University at Albany, Albany, NY, 12201 USA
3
Albany Medical Center Hospital, Albany, NY 12208, USA
E-mail: patrick.parsons@health.ny.gov
The Rare Earth Elements (REEs) include Sc, Y,and La, along with those that comprise
the Lanthanide series. Little is known about “normal” reference ranges for the REEs in
human bone, as low-level measurements are difficult because of the many polyatomic
interferences. Except for Gd, which is used as a contrast agent in MRI studies, little is
known about the toxicity or adverse health effects on bone, from chronic exposure to
REEs, especially in vulnerable populations. During a related study [1] to measure the
Al content in bones collected post-mortem from 7 patients that had received long-term
parenteral nutrition (PN), the element Y was detected. This led to follow-up
investigation of other REEs in PN bones compared to “control” bones from hip/knee
replacement surgeries. A method for the determination of 16 REEs in acid-digested
bone samples was developed using the Agilent 8800 ICP-MS/MS instrument, which is
equipped with two quadrupole mass analyzers (Q1 and Q2) and an Octopole Reaction
System (ORS). As part of the method optimization studies, 31 different isotopes were
monitored for the 16 REEs, along with three different ORS gases as well as none, to
find the most suitable parameters. The finalized ICP-MS/MS method was validated
using 4 SRM/CRMs, of which some were certified or had informational values for
REEs. Results show that many (but not all) of the REEs are undetectable in control
bones. For those REEs that were detected (La, Ce, Pr and Nd), levels were typically
less than 100 ng/g. By contrast, the PN bones were enriched in REE content by a
factor of 8 to 500 times. The source of REEs in these bones was investigated further,
and preliminary data suggest PN solutions used to supply nutrition to this vulnerable
population may be contaminated with ultra trace amounts of the REEs, such that over
many years of receiving PN, the bone compartment acts as a sink, slowly
accumulating REEs from the blood compartment. In two instances, anomalous Gd
“spikes” were observed in PN bone samples, suggesting an MRI contrast agent must
have been used previously.
The accumulation and enrichment of 16 REEs in human bones obtained from PN
patients was established using ICP-MS/MS instrumentation, which was optimized to
remove multiple polyatomic oxide interferences. The method was fully validated and
provides the first evidence of potential REE contamination of PN solutions.
References
[1] Kruger PC, Parsons PJ, Galusha AL, Morrissette M, Recker RR, and Howard LJ, Journal of
Parenteral and Enteral Nutrition, 38(6) 728-35. (2014)
21
Plenary Lecture: CSI Award
PL4
PLASMA ION SOURCES AND INSTRUMENTAL ANALYSERS
DEVELOPMENT FOR ADVANCING MS-BASED MODERN
SPECIATION AND METALLOMICS
A. Sanz Medel & Analytical Spectrometry Group
Department of Physical and Analytical Chemistry, University of Oviedo
C/ Julian Claveria 8, 33006, Oviedo, Spain
asm@uniovi.es
The old frontiers of optical spectroscopy and analytical tools of Atomic Spectrometry are
blurring: more and more “atomic” spectroscopists are inclined to investigate molecules as well
(e.g. trace element speciation) particularly via the measurement of ions by MS. In parallel
biologists tend to learn and use concepts, tools and strategies traditionally associated to atomic
spectroscopy and speciation (e.g in the field of proteomics). In the search to extract the most
complete information possible from the analysed samples, as needed in the frontiers of modern
bioanalytical research in both scientific communities, the extraordinary potential of Mass
Spectrometry is instrumental in order to achieve complete information on elements, molecules,
nanoparticles and nanostructures.
Depending on the sample state (liquid, gas or solid) and the analytical problem to be tackled (e.g.
needed information on increasing chemical complexity molecules, on NPs and/or
nanostructures), it is possible to select the combination of a plasma-based ionization source and a
proper mass analyser to solve eventually our analytical problem. The use of “hard ion source”MS analyser and its limitations for “integral” speciation of high molecular mass proteins in
liquids, via HPLC-ICP-MS will be discussed in detail. Also, we will illustrate the use of a pulsed
glow discharge (GD), coupled to a fast data acquisition MS (Time of Flight) analyser for
elements, fragments and molecular mass in “integrated” speciation of rather small molecules in
gas mixtures. This latter instrumentation [1] holds a great potential for volatile analytes
particularly if coupled to a gas chromatograph (GC). Of course, for higher mass/polarity
molecules (e.g. proteins in biological fluids) the element speciation is better accomplished using
a liquid chromatograph (HPLC) coupled to a more robust hard ionization source (an ICP). It
should be stressed, however, that HPLC-ICP-MS information should be completed today with
“molecular” MS information (e.g. ESI- or MALDI-MS). This fruitful combination has open new
avenues in bioscience particularly for absolute proteins quantifications [2].
To conclude we will illustrate applications in the nanoworld of plasma-sources-MS couplings for
innovative speciation-based problem solving: direct solid speciation in nanostructured materials
via pulsed rf GD-MS(TOF) and our latest research on the uses of CdS nanoparticles and their
bioconjugation for amplified quantitative proteomics (via immunoassay recognition with ICP-MS
detection) particularly to develop early alarm biomarkers of disease [3].
References
[1] A. Solà-Vázquez, B. Fernández, J.M. Costa-Fernández, R. Pereiro, A. Sanz-Medel. Anal
Bioanal Chem 2014, 406, 7431
[2] A. Sanz-Medel, M. Montes-Bayón, J. Bettmer, M.L. Fernández-Sánchez, J. Ruiz-Enzinar,
Trends in Anal. Chem., 2012, 40, 52.
[3] A.R. Montoro Bustos, M. Garcia-Cortes, H. González-Iglesias, J. Ruiz Encinar, J.M. CostaFernández,
M.
Coca-Prados,
A.
Sanz-Medel.
Anal.
Chim.
Acta,
2015
doi:10.1016/j.aca.2015.03.015.
22
Pleanry Lecture: Molecular Spectrometry
PL5
New methods and instrumentation for simultaneous,
high-speed mass spectrometry
G. Hieftje1, S. Ray1, E. Dennis1, A. Graham1, and C. Enke2
1
Department of Chemistry, Indiana University, Bloomington IN 47405 USA
2
University of New Mexico, Albuquerque, NM 87131 USA
E-mail: Hieftje@indiana.edu
Rapid spectral-repetition rate, high spectral resolution, and simultaneous detection
are highly desirable in mass spectrometry; together, they provide better isotope-ratio
precision, elevated signal-to-noise ratios, improved chromatographic resolution, and
simplified spectral interpretation. In this presentation, new mass-spectrometric
instrument designs will be described that yield all these benefits. These designs are
all similar in configuration to a time-of-flight instrument, but differ in one important
way: they employ constant-momentum acceleration rather than the conventional
constant-energy acceleration.
One such design is embodied in a distance-of-flight mass spectrometer (DOFMS).
DOFMS can be understood most easily by comparing it to a time-of-flight mass
spectrometer (TOFMS). In TOFMS, all ions are given the same kinetic energy
(KE=0.5 mV2), so ions separate in a field-free region according to mass-to-charge
ratios and strike a distant detector in order of those mass-to-charge ratios. As a result,
the time-resolved detector output is the mass spectrum itself. In contrast, in DOFMS,
ions are all given the same momentum (M=mV), so again their velocities are massdependent. However, before the lightest ion of interest exits the field-free region, the
ions are driven sideways onto a spatially selective detector or detector array, so each
position corresponds to a different mass-to-charge ratio. Consequently, detection is
truly simultaneous, masses are spatially separated and can be separately collected,
energy focus is improved, spectral resolution is enhanced, and no high-speed
electronics are needed.
The second kind of new mass spectrometer is based on TOFMS itself, but uses
constant-momentum rather than constant-energy acceleration. As in DOFMS, this
mode of operation yields better mass-spectral resolution, albeit here over a limited
mass range. In essence, the TOFMS can be viewed as being a DOFMS system with a
single detector channel. Moreover, because the enhanced resolution applies to only a
limited mass range, ions outside that range can be discarded, so the repetition rate of
ion-batch introduction can be raised, and sensitivity boosted. For maximal flexibility,
the new spectrometer can be operated alternately in a constant-energy mode for wide
mass-range detection, and “zoomed” to constant-momentum mode for greater
resolution and sensitivity for targeted mass regions.
The power of these new instruments will be illustrated with applications ranging
from elemental analysis to the separation and collection of biomolecules.
23
Plenary Lecture: Molecular Spectrometry
PL6
Spectroscopy of isolated and micosolvated biomolecules
György Tarczay
Institute of Chemistry, Eötvös University, 1117 Pázmány P. S. 1/a, Budapest, Hungary
E-mail: tarczay@chem.elte.hu
Recent years our group has used a number of molecular spectroscopic methods,
including IR, Raman, Vibrational Circular Dichroism and Raman Optical Activity
spectroscopy to explore the conformational landscape of small biomolecules and to
study the structure of biomolecule-water complexes. To achieve conformational
resolution some of these spectroscopic methods were combined with the matrix
isolation technique. In order to facilitate the spectral analysis we applied NIR laser
irradiation to induce conformational or structural conversions, and in the complicated
cases, 2D correlation spectroscopic analysis was also performed. First, I will briefly
introduce the principles of these techniques. This will be followed by examples on
amino acids, small peptides, nucleobases and their water complexes, with which I
will demonstrate the power of these combined methods. The presentation will be
concluded by future directions and possibilities.
24
Plenary Lecture: X-ray Spectrometry
PL7
Location and species of Pb within roots of crops and plants
by μXRF and XANES
L, Luo1 , Y. Ma1, J. Sun1 and J. Yuan1, B. Chu1
1
National Research Center of Geoanalysis, Beijing, China, 100037
E-mail:luoliqiang @cags.ac.cn
Pb contamination originates mainly from various anthropogenic activity. One of
them is from Pb mining, which has brought heavy pollution into vegetable soils and
irrigation system. Pb not only affects plant growth and productivity, but also enters
into the food chains causing health hazards to man and animals. Food consumption
has been identified as the major pathway of human exposure and considered to
account for more than 90% compared with inhalation and dermal contact.
As a new strategy for removal of heavy metals from contaminated sites,
phytoremediation is of growing interests. Initial phytoremediation studies focused on
hyperaccumulating species. However, their general characteristics is slow growth
and limited biomass production. Some researchers thought that the species could not
meet the requirement of 1% Pb in shoots for economically realistic ecotechnology.
Therefore, more recent research on phytoremediation focused on crop species.
To understand phytoremediation capability, the type of actual bonding and location
of storage is crucial information. Binding complexes can generally be simplified to
PO43--, COO--, NO3-, N-- and S-- group. In a study on Pb uptake in plants, however,
no bonding to biologically important groups (-S, -N) or precipitation ( -PO4) was
found[1]. On the other hand, it was confirmed by EXAFS that three thiolate sulfur
ligands coordinate Pb(II) in cysteine-substitution mutants[2]. Till now, thus, metalbinding complexes are still quite controversial in biological systems.
The current study aims to (i) examine distribution of Pb within roots of crops and
plants by μXRF, (ii) determine species of Pb in roots and shoots using XANES, and
(iii) evaluate the capability of crops and plants for uptake, accumulation and tolerant
of Pb. In the works, pollution in the crops and plants near a Pb-Zn mine was
investigated. High concentrations of Pb were detected in the whole biogeochemical
chains. The damage of Pb on plant tissues were evaluated. The location and species
of Pb in crops and plants, such as corn, leek and duckweed, were determined by
μXRF and XANES. Different species of Pb were observed in their roots and shoots.
On the basis of the combination of the field investigation and lab cultivation, the
distribution and speciation of heavy metal in the crops may not only reveal the
potential toxicity and risks of them to plants, but also provide useful information to
improve phytoremediation strategy.
References
[1] G. L. Bovenkamp, A. Prange, W. Schumacher, K. Ham, A. P. Smith and J. Hormes,
Environmental Science & Technology, 47, 4375-4382(2013)
[2] L. S. Busenlehner, T.-C. Weng, J. E. Penner-Hahn and D. P. Giedroc, Journal of Molecular
Biology 319, 685-701(2002)
.
25
Plenary Lecture: Archaeometry and Cultural Heritage
PL8
Analytical (X-ray) Micro Spectroscopy to better understand
past & future of famous paintings, painters
and their paint materials
K. Janssens, G. Van der Snickt, F. Vanmeert, S. Legrand,
E. d’Angelo, G. Nuyts
AXES Research Group, Department of Chemistry, University of Antwerp, Belgium
E-mail: koen.janssens@uantwerpen.be
In Western culture, historical paintings are considered to be important windows on
the (distant) past; thus great effort is expended both to understand their meaning and
specific history and to preserve them for future generations. State-of-the-art
analytical spectroscopy and spectroscopic imaging are methods that allow to uncover
information that is highly relevant for such endeavors.
The (inner) structure of paintings may reveal changes made to the paintings by the
artists themselves or by others following them. Traditionally, this inner structure is
examined by means of X-ray radiography (XRR) and Infrared Reflectography (IRR).
Both methods make use of radiation that can penetrate deeply into the paintings
materials; both give rise to black and white images that to some extent reflect the
composition at or below the surface of the paintings. More modern equivalents of
these two methods are Macroscopic X-ray fluorescence imaging (MA-XRF) and
hyperspectral imaging in the Visual and Near Infra-red (VNIR) region. Both
methods (and variants thereof) allow to collect a richer set of (spectroscopic) image
data, allowing to construct false color images of paintings from which valuable
information about the paint composition (at or below the surface) can be gleaned.
On the other hand, in many historical paintings, unwanted chemical transformations
take place that to a larger or lesser extent may influence the general outlook of the
painting for example by causing the color of specific, light- and humidity exposed
paint layers to change color. In many cases, these chemical transformation start with
a (photo-induced) redox reaction but usually other transformation follow such an
initial step. Lab-based micro- and nanoscopic spectrometric methods such as
Raman/Infra-red microscopy and various forms of Electron Microscopy are useful to
understand these transformations and their order. In this respect also the (combined)
use of synchrotron radiation based methods such as microscopic X-ray fluorescence,
X-ray absorption spectroscopy and X-ray diffraction is highly relevant to reconstruct
the degradation mechanism of painters’ pigments such as chrome yellow or red lead.
By discussing a number of case studies involving 15th, 17th and 19th century paintings
or paint samples from painters such as Jan Van Eyck, Pieter Paul Rubens, Henri
Matisse and Vincent Van Gogh, the usefulness of non-invasive analytical imaging at
the macroscopic scale in combination with microscopic multimodal examination of
minute paint fragments will be discussed and their relevance both for art historians
and art conservators highlighted. .
26
Plenary Lecture: Miniaturisation and nanotechnology
PL9
Enhanced detection of biomarkers using metal
nanoparticles
José M. Costa-Fernández, Marta García Cortés, Mario Menéndez Miranda,
Diego Bouzas Ramos, Jorge Ruiz and Alfredo Sanz-Medel
Department of Physical and Analytical Chemistry, University of Oviedo, Avda. Julian Claveria, 8,
33006 Oviedo, Spain
E-mail: jcostafe@uniovi.es
With the recent development of nanotechnology, different types of nanomaterials
have been used successfully in a wide variety of applications in analytical chemistry;
among these nanomaterials semiconducting metal nanoparticles (known as "quantum
dots", QDs) have been used with great success as labels in the development of
bioanalytical applications. In addition, in the development of bioanalytical
methodologies involving the use of QDs, elemental mass spectrometry (ICP-MS) is
especially attractive due to the extreme sensitivity shown by this technique for the
detection of metals (such as those present in the core of QDs), low effects of matrix
and the ability of simultaneous detection multielemental and isotopic (which offers a
high potential for multiplexed analysis) [1].
It should be considered that the success or failure in the use of the luminescent
nanomaterials in these applications is largely determined by the ability to
bioconjugate such nanoparticles to specific recognition elements, such as aptamers or
antibodies, a mandatory previous step for the successful development of new
bioassay and bioanalytical applications based on biolabeling and bioimaging. Despite
recent progress in the use of QDs and NCs for bioanalytical applications, there is still
an urgent need for effective procedures for the nanomaterials bioconjugates
purification and characterization, in order to further facilitate reliable quantitative
bioassays.
In this context, in this communication a diagnostic tool to control the quality of
water-solubilized metal nanoparticles based on the combination of asymmetric field
flow fractionation nanoparticles separation coupled on-line with elemental
(inductively coupled plasma-mass spectroscopy, ICP-MS) and molecular (UV-VIS
and fluorescence) detection will be also presented.
Moreover, we will also describe our latest efforts of using metal nanoparticles lo
label proteins and so to amplify enormously the corresponding ICP-MS signals of the
bioconjugates NPs-antibodies targeting the protein(s) of interest for targeted
proteomics issues. The proof of concept of such novel approaches and application to
real-life simultaneous ICP-MS determinations of a panel of known proteins, to act as
"early alarm biomarkers" of ocular diseases (e.g. glaucoma), will be discussed [2].
References
[1] Diez Fernández S, Sugishama N, Ruiz Encinar J, Sanz-Medel A Anal Chem., 2012, 84: 58515857.
[2] Montoro Bustos AR, Garcia-Cortes M, González-Iglesias H, Ruiz Encinar J, Costa-Fernández J.M,
Coca-Prados M, Sanz-Medel A Anal. Chim. Acta, 2015 doi: 10.10 16/j.aca.2015.03 .015.
27
Plenary Lecture: Environmental and Geochemical Analysis
PL10
Analytical approaches for the determination of trafficrelated elements in the atmosphere of Buenos Aires,
Argentina
P. Smichowski1,2, F. Fujiwara1,2, A. Londonio1,3, D. Gómez1
1
Comisión Nacional de Energía Atómica. Gerencia Química, Av. Gral. Paz 1499, B1650KNA-San
Martín, Pcia. Buenos Aires, Argentina.
2
Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Av. Rivadavia 1917,
C1033AAJ, Buenos Aires, Argentina
3
Instituto de Investigación e Ingeniería Ambiental (3iA), Universidad de San Martín, Campus
Miguelete, 25 de Mayo y Francia, San Martín, Pcia. Buenos Aires, Argentina.
E-mail: smichows@cnea.gov.ar and Patricia.Smichowski@gmail.com
An overview of the research carried out by our group during more than ten years on
the study and determination of traffic-related elements (TREs) in atmospheric
aerosols and related matrices using atomic spectrometric and plasma-based
techniques is presented.
Studies on the air quality of the megacity of Buenos Aires were scarce and
fragmentary in the 20th century; hence our objective has been to contribute to clarify
key issues related to levels of crustal, toxic and potentially toxic elements in this air
basin. In the last years, our interest was focused on the study of levels of TREs in the
urban atmosphere. We have contributed with the first data for a Latin American city
on the content of Pt and Rh (emitted by vehicles equipped with catalytic converters).
Another element of permanent interest is Sb (arising from brake pads wear) and
several studies were conducted to assess concentrations of this metalloid in
atmospheric particles and road dust. This last environmental matrix has been deeply
studied by our group and results on the levels of Hg in Buenos Aires will be also
presented. In all cases, our findings were compared with average concentrations of
metals and metalloids reported for other cities all around the world.
In all our studies, various multivariate statistical techniques were employed to assess
temporal and spatial variability of concentration levels and to identify potential
contribution sources.
Present research includes not only local but also regional aspects of air pollution
through the use of specific chemical markers such as metals, ions, black carbon and
specific organic compounds.
28
Plenary Lecture: Speciation Analysis/Metallomics
PL11
Unraveling biological systems through chemical speciation
M. A. Z. Arruda1,2
1
Spectrometry, Sample Preparation and Mechanization Group – GEPAM
Institute of Science and Technology for Bioanalytics, Institute of Chemistry, Department of
Analytical Chemistry, University of Campinas - Unicamp, PO Box 6154, 13803-970, Campinas,
Brazil
2
E-mail: zezzi@iqm.unicamp.br
There is a growing interest in issues related to fractionation and chemical speciation,
since the chemical, biological and toxicological properties of specie of interest are
highly dependent on how it occurs in the sample [1]. In the context of speciation
chemistry, not only species with different oxidation states must be considered (eg.
As3+ and As5+) but also organic species, isoforms of proteins or isomers, metalloorganic species, for example, are of utmost importance [2] for better characterizing
the applications in transdisciplinary areas.
Following this tendency, this work presents different applications of fractionation
and chemical speciation involving biological systems focusing on toxicology,
bioaccessibility, and tracer studies, and samples such as nanoparticles, soybeans,
metalloproteins, and vitreous humor as well as some mass spectrometry techniques
are emphasized.
References
[1] M. A. Z. Arruda, R. A. Azevedo, Ann. Appl. Biol., 155, 301, 2009
[2] S. L. Shirran, P. E. Barran, J. Am. Soc. Mass Spectrom., 20, 1159, 2009
Acknowledgements
FAPESP, CAPES, CNPq
29
Plenary Lecture: Hyphenated techniques
PL12
Hyphenated Techniques - protein determination and
characterization
E. Bramanti1, B. Campanella1,2, M. Onor1, A. D’Ulivo1
1
C.N.R Institute of Chemistry of Organometallic Compounds, UOS of Pisa, via Moruzzi 1, 56124
Pisa, Italy
2
University of Pisa, Department of Chemistry and Industrial Chemistry, via Moruzzi 3, 56124 Pisa,
Italy
E-mail: bramanti@pi.iccom.cnr.it
The absolute and relative quantitation and characterization of proteins plays a fundamental role in
modern proteomics, as it is the key to understand still unresolved biological questions in medical and
pharmaceutical applications. Highly sensitive analytical methods are required to quantify proteins in
biological samples and to correlate their concentration levels with several diseases. Mass spectrometry
(MS) with electrospray ionization (ESI) or matrix-assisted laser desorption ionization (MALDI) are
currently the major technique for protein identification. Although MS techniques are crucial in the
identification of peptides and proteins, their application to quantitative analysis presents some
important drawbacks such as the differential response of proteins and peptides depending on size,
hydrophobicity, matrix, or solvents. To overcome these disadvantages and obtain better analytical
results, various types of tags have been developed to label proteins for their detection and quantitation.
Additionally, since standards for most biomolecules of natural origin are unavailable, their tagging
using different derivatization approaches is a valuable alternative for their quantitation. The variety of
chemistry available to modify reactive groups in a typical peptide combined with the numerous
structures possible for a quantitative tag creates a large number of possibilities to chemically
incorporate a labeling agent. More specific approaches are frequently directed towards the
derivatization of specific amino acids [1].
Cysteine (Cys) is very frequently used as a probe target because the specific reactivity of –SH groups
toward a large number of chemical probes represents a useful property allowing a wide choice of
detectors for their determination. Cysteine is present in about 70% of all proteins of proteome and it is
estimated that 50% of cysteines form disulfide bonds. Mercurial probes (organic RHg+ and inorganic
mercury Hg2+) interact with –SH groups with high affinity and specificity, and can be revealed by
sensitive instrumental techniques. Cold vapour generation (CVG) coupled with atomic spectrometric
(AS) techniques represents the most popular method for ultra-trace determination of mercury.
We present here a review of our past 15 years-work developed for the determination and
characterization of thiolic proteins by CVGAS, in particular atomic fluorescence spectrometry (AFS),
following their derivatization with inorganic or organic mercury. While Hg(II) is suitable for flow
injection-AS hyphenated systems, p-hydroxymercurybenzoate (PHMB) is a suitable probe for liquid
chromatography experiments (LC-CVGAFS).
References
[1] B. Campanella, E. Bramanti, Detection of proteins by hyphenated techniques with endogenous
metal tags and metal chemical labelling, Analyst 139 (2014) 4124.
30
Plenary Lecture: Archaeometry and Cultural Heritage
PL13
The beauty of chemical heterogeneity.
Analysis of works of art and cultural heritage objects.
B. Wagner1, O. Syta1, L. Kępa1, Z. Żukowska2 and A. Lewandowska3
1
2
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (PL)
Chemical Faculty, Warsaw University of Technology, Pl. Politechniki 1, 00-661 Warsaw (PL)
3
National Museum in Warsaw, Al. Jerozolimskie 3, 00-495 Warsaw (PL)
E-mail: barbog@chem.uw.edu.pl
Chemical composition of works of art and cultural heritage objects can be regarded
usually as very inhomogeneous and unique mixture of mineral and organic
compounds. Analysis of such complex objects are complicated by the fact of their
recognized historic and material value narrowing the use of various instrumental
methods to the ones which offer the lowest intervention to the physic-chemical
structure of the analyzed item. These are the last decades, that brought increased
interest in chemical investigations of cultural heritage objects with the priority for
non-destructive, eventually micro-destructive methods of analysis.
Among many others, Laser Ablation Inductively Coupled Plasma Mass Spectrometry
(LA-ICP-MS) have been applied for investigations of works of art and historic
objects in respect of their provenance or protection and conservation. Multielemental character of the measurements, possibilities to obtain quantitative
information about trace, minor and major elements as well as observations of their
distribution over the selected area are well recognized advantages of this method.
Thanks to these advantages it is often incorporated along with other methods in
multi-instrumental research scenarios.
The growing potential of LA-ICP-MS against the general requirements established
for analysis of works of art and cultural heritage objects is reflected in many papers
devoted to the use of this method [1]. Laser ablation can be executed either directly
from objects or by analyzing microsamples, gently collected prior to analysis,
depending on an agreement for sampling from the object, its size and transportation
to the laboratory [2,3]. Examples will be given for the use of LA-ICP-MS in the
selected projects devoted to (i) authentification of red stoneware from the XVIIIth
century; (ii) investigations of documents written with iron gall ink; (iii) identification
of materials used in mediaeval Nubian wall-paintings and (iv) determination of
chemical composition of pigments from paintings dated back to the XIXth century.
Various scenarios will be described indicating advantages and the flexibility of
coupling LA-ICP-MS with SEM-EDS or Raman spectroscopy, depending on the
general aim of the research and heterogeneity o the investigated items.
References
[1] Giussani B., Monticelli D., Rampazzi L., Anal. Chim. Acta, 635/1, 6-21 (2009)
[2] Glaus R., Koch J., Gunther D., Anal.Chem., 84/12, 5358-5364 (2012)
[3] Syta O., Rozum K., Zielińska D., Żukowska G.Z., Kijowska A., Wagner B., Spectrochim. Acta
Part B, 101, 140–148 (2014) .
31
Plenary Lecture: Molecular Spectrometry
PL14
Analysis of clustering processes in hydrogen-bonded liquids
by matrix-isolation FTIR spectroscopy
I. Doroshenko1, V. Pogorelov1, G. Pitsevich2, V. Sablinskas3 and V. Balevicius3
1
Taras Shevchenko National University of Kyiv, Acad. Glushkov Ave., 4, 03187, Kyiv, Ukraine
2
Belarusian State University, Independence Ave. 4, 220050, Minsk, Belarus
3
Vilnius University, Sauletekio 9-3, LT-10222, Vilnius, Lithuania
E-mail: dori11@ukr.net
Clusters, by definition, are aggregates of atoms/molecules with more or less regular
and arbitrarily scalable repetition of basic building blocks. Their size is intermediate
between that of atoms/molecules and the bulk. The growing interest to the clustering
phenomena that produce partially ordered atomic or molecular structures is due to
the recent developments and challenges in nanotechnologies, smart materials,
heterogeneous systems, basic biochemical research, etc.
The processes of molecular cluster formation in monohydric alcohols were
investigated using FTIR spectroscopy and a matrix isolation technique [1-3]. The
methods of cluster isolation in low-temperature matrices provide the possibility to
study individual clusters of different sizes. FTIR spectra of monohydric alcohols
(from methanol to decanol) in argon and nitrogen matrices were registered in the
frequency range from 500 cm-1 to 4000 cm-1. The gradual transformation of the
spectral bands assigned to different vibrations was observed with matrix heating
from 10 to 50 K, indicating a transformation of the structure of the isolated clusters.
Main changes with the temperature increasing were observed in the spectral regions
of stretch O-H and C-O vibrations.
The observed temperature dependence of the registered spectra may be considered as
a model of structural transformations in alcohols during the phase transition from gas
to liquid state.
The work was supported by Swedish Research Council (grant no. 348-2013-6720).
References
[1] V. Pogorelov, I. Doroshenko, P. Uvdal, V. Balevicius, V. Sablinskas, Mol. Phys., 108, 2165-2170
(2010).
[2] P. Golub, V. Pogorelov, I. Doroshenko, J. Mol. Liq., 169, 80-86 (2012).
[3] P. Golub, I. Doroshenko, V. Pogorelov, Phys. Lett. A, 378, 1937-1944 (2014).
32
Keynote Lecture: Atomic spectrometry
KL1
A study of carbon, sulfur and phosphorus related matrix
effects in inductively coupled plasma – atomic emission and
mass spectrometry
Margaretha de Loos-Vollebregt1, Guillermo Grindlay2 and Juan Mora2
1
Ghent University, Department of Analytical Chemistry, Krijgslaan 281 – S12, 9000 Ghent, Belgium
2
Department of Analytical Chemistry, Nutrition and Food Sciences, University of Alicante,
PO Box 99, 03080 – Alicante, Spain
E-mail: margaretha.deloos@ugent.be
A systematic study on the influence of carbon, sulfur and phosphorus on signals in
inductively coupled plasma – atomic emission (ICP-AES) and mass spectrometry
(ICP-MS) has been carried out. Matrix effects have been evaluated considering
different plasma parameters, sample introduction systems, concentration and type of
matrix and type of mass spectrometer [1-2]. ICP-MS results show that P, As, Se, Sb,
Te, I, Au and Hg sensitivities are higher for carbon-containing solutions than those
obtained without carbon. The matrix effects are explained by changes in the plasma
characteristics and the corresponding changes in ion distribution in the plasma, but
they are also related to an increase in analyte ion population caused by charge
transfer reactions involving carbon-containing charged species in the plasma [1].
Signal enhancements for P, As, Se and Te and I in the presence of sulfuric acid are
explained in relation to an increased analyte ion population as a result of charge
transfer from S+ species [2]. In the presence of phosphorus, positive matrix effects in
ICP-MS are found for As, Sb, Se and Te. Previously reported carbon-related signal
enhancement for As and Se in ICP-AES [3] and findings in ICP-MS suggest that
atomic emission lines of more elements might be affected by carbon-related chargetransfer reactions and that similar matrix effects due to sulfur- and phosphorus-based
charge transfer could also be expected. Therefore, matrix-related charge-transfer
reactions in ICP-AES have been systematically investigated for carbon, sulfur and
phosphorus containing solutions. To this end, the analytical response of several
atomic and ionic emission lines of a total of 33 elements (Ag, Al, As, Au, B, Ba, Be,
Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, In, Ir, K, Li, Mg, Mn, Na, Ni, P, Pb, Pd, Pt, S, Sb,
Se, Sr, Te and Zn) was registered for glycerol, sulfuric acid and phosphoric acid
solutions and compared with the response obtained for a 1% w w-1 nitric acid
solution. Results will be presented and discussed.
References
[1] G. Grindlay, J. Mora, M.T.C. de Loos-Vollebregt, F. Vanhaecke, Spectrochim. Acta Part B 86
(2013) 42-49.
[2] M.C. García-Poyo, G. Grindlay, L. Gras, M.T.C. de Loos-Vollebregt, J. Mora, Spectrochim. Acta
Part B 105 (2015) 71-76.
[3] G. Grindlay, L. Gras, J. Mora, M.T.C. de Loos-Vollebregt, Spectrochimica Acta Part B 63 (2008)
234-243.
33
Keynote Lecture: Archaeometry and cultural heritage
KL2
XRS for (preventive) conservation of Cultural Heritage
R. Van Grieken
Department of Chemistry, University of Antwerp, 2610 Antwerp, Belgium
E-mail: rene.vangrieken@uantwerpen.be
Conservation refers to approaches extending the lifetime of a work of art. Preventive conservation
implies, amongst many other aspects, the characterization of the atmospheric environment around
monuments or cultural heritage (CH) items, with the intention to improve the conditions and to
contribute to the preservation of CH items. While earlier, much interest was on e.g. sulphur
dioxide (mostly from thermal power plants) and its effect on building stones, the focus has now
shifted to the indoor environment and to atmospheric particles in, e.g., museums.
Analytical chemistry does play a key role in the chemical characterization of the environment and
it appears that X-ray spectrometry (XRS), in its many forms, is one of the most relevant analysis
techniques. XRS is also very important in CH research in general (concerning the methodology
used by the artists, provenancing and the discovering of forgeries, and the preparation for
restorations), mostly because of its non-destructive nature. XRS has been booming in recent year,
mostly because of the popularity of portable instruments in e.g. museum environments, and the
recent developments in micro- and macro-XRS.
We have, over the last two decades, intensively used various forms of XRS, always together with
ion chromatography, micro Raman analysis, on-line soot determinations, gravimetry, etc., to
identify particle types and their sources in indoor environments, including museums, while also
gaseous indoor pollutants were assessed using passive diffusion samplers. In each case, both bulk
aerosols and individual aerosol particles were studied.
We have first studied atmospheric aerosols in and around e.g. the Correr Museum in Venice and in
the caves with prehistoric rock paintings in Altamira, Spain. More recently, measurements were
done in e.g. the Metropolitan Museum of Art in New York and the Wawel Castle in Cracow,
Poland, Italian and Polish mountain churches, a number of important museums all over Europe,
cathedrals with medieval stained glass windows, the Alhambra Castle complex in Granada in
Spain, and various museums in South America.
In the Wawel Castle, outdoor pollution particles, like fine soot from diesel traffic, entering via
leaks around the windows and doors, and also street-deicing salts and coal burning pollution
particles, brought in by visitors, mostly in winter, were found to be most worrisome. Preventive
measures were taken to reduce these problems. In the Plantin-Moretus Museum in Antwerp,
atmospheric ozone penetration from outdoors during the summer months, and the poor
characteristics of some showcases, were most threatening for the early books that are exhibited
there. In the Alhambra complex in Granada, Sahara desert dust and local traffic derived particles
(soot and NaNO3 from the reaction of atmospheric seasalt with NOx) were the most important.
Some urgent questions that are far from having been solved presently pertain to the deposition
processes from the atmosphere to the CH items and the critical surface interactions that take place
on the CH items.
34
Keynote Lecture: Environmental and geochemical analysis
KL3
Innovative and analytical approaches in exposomic for chemical and
morphological characterisation of work-room aerosols metrology
Yngvar Thomassen
National Institute of Occupational Health, P.O. Box 8149 DEP,
N-0033 Oslo, Norway
Exposomics is the study of the exposome and relies on the application of internal and
external exposure assessment methods. External exposure assessment relies on
measuring environmental stressors e.g. airborne particulate matter. Although a
number of major advances in both chemical identification and quantitative analysis
have been achieved, exposure assessment remains the weakest part of the majority of
occupational risk assessments.
Common approaches of exposure assessment strategies in occupational health
include personal and stationary air sampling, application of direct reading
instruments and laboratory-based analysis. The use of biomarkers to determine
exposure, effect of exposure, disease progression, and susceptibility factors adds also
to the complexity of exposomics. A key factor in describing the exposome is the
ability to accurately measure exposures and effects of exposures.
A number of factors are involved in determining toxicological responses to chemical
exposures, thus a major aim of our exposomics studies has been to characterize air
particulate matter with respect to particle types, deposited amounts in the human
respiratory tract, aerosol mass size distributions, chemical and biological solubility,
chemical reactivity, particle surface characteristics, as well as frequency and duration
of air exposure. A number of spectrometric and chromatographic methods have been
applied in the characterization of the exposome; ICP-OES, HPLC-ICP-MS, TEM,
SEM, ESEM, ED-XRF, XRD and thermo-optical chromatography (TOC).
The need of applying a variety of different spectrometric techniques in exposomics
will be highlighted with examples from exposure assessment studies developed for
and performed in e.g. tunnel construction, mining, metal and metal alloy production
and welding.
35
Keynote Lecture: X-ray spectrometry
KL4
Sampling problem in forensic analysis
Jun Kawai
Department of Materials Science and Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501,
Japan
E-mail: kawai.jun.3x@kyoto-u.ac.jp
Supposing a sample is a mixture of two powders and the typical grain size is
100 micro meters (diameter), we must ask how much amount we must sample the
powder for quantitative analysis. This is a complicated function of the detection limit
and how low concentration we need, even the mixture is homogeneous enough.
The single atom detection is possible by STM (scanning tunneling
microscope) and this problem is equivalent to how many atoms should be analyzed
to detect ppm level element on a surface. By a numerical Monte Carlo simulation, it
is found that we must measure 10,000,000 atoms in order to analyze quantitatively
the 50 ppm minor element with a standard deviation of a few ppm. However, if the
minor element is 49 % concentration, sampling of 1,000 atoms is enough to obtain
an accurate concentration (standard deviation of a few %). Sampling an enough
amount is possible for industrial analysis.
For ICP-AES analysis, if we need to analyze various elements ranging from
50 ppm to 50 % concentrations, we usually sample a 250 mg amount for quantitative
analysis 5 iterations, if the sample is a mixture of 100 micro-meter powders.
However a sampling problem in forensic analysis is that the total sample amount is
practically limited.
Several examples will be shown by comparing XRF and ICP-AES in forensic
elemental analysis [1,2] of a murder case in Japan.
References
[1] J. Kawai, X-Ray Spectrom. 43, 2 (2014).
[2] J. Kawai, Adv. X-Ray Anal. 57, 177 (2014).
.
36
KL5
Mechanisms in chemical vapor generation for trace
element determination. Focus on Cadmium
D.Angelini1,2, E.Pitzalis1 and A. D’Ulivo1
1
C.N.R., Institute of Chemistry of Organometallic Compounds, UOS of Pisa, Via Moruzzi,1 Pisa (I)
2
University of Pisa, Department of Chemistry and Industrial Chemistry,
E-mail: dulivo@pi.iccom.cnr.it.
Chemical vapor generation (CVG) of cadmium by aqueous boranes has been
investigated by using continuous flow reaction system coupled with quartz tube
atomizer and atomic absorption spectrometry, with the aim to clarify some of the
mechanisms controlling the generation of volatile species.
Experimental evidence collected in the present study indicates that BH3OH‒ is the
most likely effective species in the generation of volatile Cd species. It can be
synthesized on-line by quenching the acid hydrolysis of BH4‒ by NaOH, according
the following reactions [1]:
BH4‒ + H3O+ → BH3(H2O) + H2
BH3(H2O) + OH‒ → BH3OH‒ + H2O
The use of BH3OH‒ in alkaline conditions increases sensitivity of about a factor 2.2
with respect to BH4‒, indicating an improved generation efficiency.
A further parameter controlling dramatically the sensitivity was the presence of
dissolved oxygen in the reagents. Removal of oxygen from analyte and reductant
solutions, by argon purging, resulted in a sensitivity improvement of about 8 fold and
6 fold by using BH4‒ and BH3OH‒ reductant, respectively. Oxygen gas added
between gas-liquid separator and the atomizer hardly affects the sensitivity,
indicating that the oxygen interferes mainly in the liquid phase, during the generation
step of volatile Cd species. The use of BH3OH‒ under oxygen free conditions
resulted about 13 fold improved LODs (about 10 ng L-1, 3s). The use of additives as
thiourea (up to 1%) in the presence of NiII (10 ng mL-1), which are typically
employed as signal enhancers in CVG of Cd [2], resulted in a marked signal
depression for concentration of thiourea > 0.1 g L-1. Signal enhancement (+10%) was
observed with Ni + 0.05 g L-1 thiourea, the use of which is mandatory to keep under
control interference effects in Cd determination in some natural water samples.
References
[1] A. D’Ulivo, Spectrochimica Acta Part B, 59, 793-795 (2004).
[2] X.A. Yang, M.B. Chi, Q.Q. Wang, W.B. Zhang, Analytica Chimica Acta, 869.11-20 (2015).
.
37
Keynote Lecture: Environmental and geochemical analysis
KL6
Use of field portable XRF for rapid identification of
environmental hazards
R.I. McCrindle1, J-N. Oyourou1, S. Combrinck2, C.J.S. Fourie3, K. Maphakela1
and M.P.K Phala1
1
Department of Chemistry, Tshwane University of Technology, P/B X680, Pretoria, 0001
2
Department of Pharmaceutical Sciences, Tshwane University of Technology, P/B X680, Pretoria,
0001
3
Department of Environmental, Water and Earth Sciences, Tshwane University of Technology, P/B
X680, Pretoria, 0001
E-mail: mccrindleri@tut.ac.za
Early detection of potentially hazardous concentrations of pollutants is an important
step in mitigation of risk. A study involving two different environments was
undertaken in which a rapid appraisal of the pollutant levels was made using a field
portable XRF (FP-XRF), followed by analysis with more traditional laboratory
instrumentation. The Edendale lead mine, adjacent to a township in Pretoria East,
South Africa, was opened in 1880 and closed in 1930. The presence of high levels of
contaminants, particularly lead, remaining in the soil at the mine site may pose a risk
to human health and the environment. The mine site, approximately 800 x 400 m,
was divided into 50 x 50 m grids. A FP- XRF instrument was used to measure the
concentrations of lead in the soil. At each point where a measurement was taken, a
sample of top soil was collected from a depth of 20 cm,. The results, together with
the GPS coordinates, were used to construct a map reflecting the levels of lead.
Representative samples of the mine site were further prepared as pellets and analysed
by wavelength dispersive-XRF (WD-XRF) for comparison with the field
measurement. Soil samples were also microwave digested using a mixture of nitric
and hydrofluoric acids. The concentrations of lead in the samples were determined
using an inductively coupled plasma-optical emission spectrometer (ICP-OES) and
compared to the results from the FP-XRF. Concentrations of lead, ranging from 13
to19700 μg/g were determined in soils from the site using the FP-XRF. These levels
were confirmed using WD-XRF after the samples had been pelletised. Low levels of
lead in the soils corresponded to the geological background concentration of the site,
whereas the high values were considered as contamination. Analysis of the
sequential extracts of soil using the ICP-OES revealed low concentrations of lead in
the exchangeable phase and high levels in the residual phase. These results suggest
that lead is strongly bound to particles in the soil, resulting in a low mobility of the
element and a reduced risk under the current environmental conditions. In the second
environment, levels of copper, an element which has been used as a algae- and
fungicide by fruit growers throughout the world, was measured in mango orchards in
South Africa. Copper in the soils of these orchards has now reached concentrations
that may impact negatively on the environment. The FP-XRF was used to evaluate
the problem and the soil samples were then digested and analysed by ICP-OES.
Concentrations of copper as high as 2000 μg/g were found in the soil, indicating that
remediation should be considered.
38
Keynote Lecture: Molecular spectrometry
KL7
"Hard" vs. "soft" ionization techniques for the MS analysis
of metal and metalloid species in biological matrices
R.Łobiński
Laboratory for Analytical Bioinorganic and Environmental Chemistry, National Research Council
of France (CNRS), Hélioparc, 2, avenue Pr. Angot, F-64053 Pau, FRANCE
E-mail: ryszard.lobinski@univ-pau.fr
During the last two decades ICP MS has taken a prominent place as detection
technique in a number of coupled techniques making element speciation analysis
possible. The use of "hard" ionization conditions in the inductively coupled argon
plasma assured the high sensitivity, large dynamic range and tolerance to the
matrix. As a result, ICP MS became an indispensable tool for scientists seeking
for species-specific information in a number of fields including environmental
chemistry, nutrition and life-sciences.
At the same time, the current progress in electrospray (soft) ionization Fourier
transform mass spectrometry (ESI FT MS) using electrostatic orbital trap
(Orbitrap) and ion cyclotron resonance offers unparalleled resolution, accuracy of
mass measurement, and intrascan dynamic range for the analysis of biomolecules.
The combination of such systems with a linear ion trap allows additional
experiments towards structural analysis and opens more and more new
possibilities for elemental speciation. So far, ESI MS has been considered as a
complementary technique used for the identification of elemental species detected
by ICP MS. Nowadays, the coupling of HPLC – Orbitrap allows the detection of
the heteroatom-isotopic pattern (an equivalent of the element-specific signal) in
mass spectra down to the intrascan abundance of 0.001 with the low- and sub-ppm
mass accuracy regardless of the concentration. The species with intrascan
abundance of at least 0.005 produced a cascade of product ion mass spectra to at
least MS4 with the preservation of the isotopic pattern and the sub-ppm mass
accuracy, which largely facilitates the analyte structure elucidation. Thus, the
"soft" ionisation based MS has been not only complementing ICP MS, but also
slowly replacing it for many speciation-related applications in the analysis of
biological samples.
The lecture evaluates the growing potential of "soft" ionization ESI FT-MS for the
detection and identification of metal/metalloid-containing biomolecules in
comparison with classical ICP MS ("hard" ionization) based methods. A
hypothesis is put forward that, taking into account the rate of progress in the
development of ESI MS, this technique is likely to take the place of ICP MS in
speciation studies.
39
Keynote Lecture: Biological applications
KL8
Biological and chemical investigation towards
complementary information about biological systems
Ewa Bulska, Jakub Karasiński, Eliza Kurek, Magdalena MichalskaKacymirow, Anna Ruszczyńska, Marcin Wojciechowski
Faculty of Chemistry, Biological and Chemical Research Centre, University of Warsaw, Zwirki i
Wigury 101, Warsaw, 02-089, Poland
Increased attention is focus on the investigation of the mechanisms of biotransformation and translocation of various species in plants. This become to be of
fundamental interest on the ecological plant physiology. The main issue is to
understand the mechanism of plant tolerance and adaptations to those species. In this
presentation various scenarios towards obtaining complementary information of the
biological and chemical characterization of the plants cells, organelle and tissues,
will be discussed.
Several analytical procedures, included biological and chemical examination
of plant’s tissues were tested towards investigation of the elements biotransformation via examination of the presence of specific compounds in plants
tissues. Two examples, namely Allium cepa L. and Plantago lanceolate will be
presented.
Examined plants of Allium cepa were cultivated hydroponically in Knop’s solution
enriched with various inorganic salts. Biological and chemical techniques were
applied in order to collect complementary information on the plant’s respond to the
type of salt used in the plants’ enrichment. Allium test was used to evaluate the
grown of roots and its mitotic activity in apical meristem. Also, the biomass was
found to deliver important information. Total content of elements of interest was
determined by inductively coupled plasma mass spectrometry (ICP MS). Highperformance liquid chromatography (HPLC), coupled to ICP MS, was used for the
evaluation of chemical speciation. Moreover, several imaging techniques were used
for the investigation of the special distribution of the element of interest over the
plant’s tissues. The imagines from confocal and light microscopy were compared
with the distribution maps obtained by LA ICPMS.
To conclude, the advantageous of multi-technique approach towards obtain
complementary information about the metabolism in plants will be highlighted and
exemplified by the performed researches..
Acknowledgements
Financial support from National Centre of Science (NCN, Poland), for the project
2012/05/B/ST4/01219 is gratefully acknowledged.
The study was carried out at the Biological and Chemical Research Centre,
University of Warsaw, established within the project co-financed by European Union
from the European Regional Development Fund under the Operational Programme
Innovative Economy, 2007 - 2013.
40
KL9
Volatile species generation and atomization for atomic
absorption and atomic fluorescence: new developments
J. Dědina1, J. Kratzer1, S. Musil1, K. Marschner1, T. Matoušek1, M. Svoboda1,
Z. Mester2, R.E. Sturgeon2, M. Talába3 and P. Dvořák3
1
Institute of Analytical Chemistry of the ASCR, v.v.i., Veveří 97, 602 00 Brno, Czech Republic
2
National Research Council of Canada, Ottawa, Canada
3
Department of Physical Electronics, Faculty of Science, Masaryk University Brno, Czech Republic
E-mail: dedina@biomed.cas.cz
This communication will be focused on our recent developments in the field of
generation of volatile species for atomic absorption (AAS) and atomic fluorescence
(AFS).
To fully utilize the potential of volatile species generation for analytical applications
the atomization step has to be optimized. In this vein, a new method of the
investigation of mechanism of volatile species atomization will be reported. This
method, offering exciting perspectives, is based on a direct observation of free
hydrogen radicals by two-photon absorption laser-induced fluorescence. Further, we
have been exploring dielectric barrier discharges (DBD) for atomization of hydrides
for AAS and AFS. A great emphasis will be put on the mechanism of hydride
atomization and on the subsequent fate of free analyte atoms in DBD atomizers.
Performance of individual designs of DBD atomizers for both atomic spectrometry
detectors will be compared - also with conventional quartz tube atomizers. Most
notably, the promising prospect of in-atomizer preconcentration of volatile species
forming elements in DBD atomizers will be assessed. In addition, advantages and
disadvantages of in-atomizer preconcentration of Ag and Au in sapphire and quartz
traps coupled to AAS will be presented.
There are two possible approaches how to employ generation of volatile arsines for
extending limits of arsenic speciation analysis: post-separation generation and
generation of substituted arsines. Possibilities and limitations of both these
approaches interfaced to both atomic spectrometric detectors will be discussed. A
specific attention will be paid to a new method of post-separation arsine generation
that enables to generate arsines from all typically determined hydride active arsenic
species (arsenite, arsenate, monomethyl arsenate and dimethyl arsenate) with the
same efficiency. Generation of substituted arsines incorporates preconcentration of
generated arsines in a cryogenic trap. Progress and outlooks of the miniaturization of
the cryogenic trap will be outlined.
Acknowledgements. This work was supported by the Academy of Sciences of the
Czech Republic (grant No. M200311202), Czech Science Foundation (P206/1423532S), Institute of Analytical Chemistry of the ASCR, v. v. i. (project no. RVO:
68081715) and by project LO1411 (NPU I) funded by Ministry of Education, Youth
and Sports of Czech Republic..
41
Keynote Lecture: Organic and inorganic mass spectrometry
KL10
Determination of halogens using high-resolution graphite
furnace molecular absorption spectrometry and direct solid
sample analysis
Bernhard Welz1, É. R. Pereira1, A. R. Borges1, M. G. R. Vale2
1
Departamento de Química, Universidade Federal de Santa Catarina, 88040-900 Florianópolis, SC,
Brazil
2
Instituto de Química, Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, Brazil
E-mail: w.bernardo@terra.com.br
Atomic absorption spectrometers are not suitable for the determination of the
halogens, as the atomic absorption lines of these elements are located in the vacuumUV below 190 nm, a spectral range that is not accessible for this kind of equipment.
Nevertheless, several researchers started in the 1970s and 80s to investigate the
possibility to determine non-metals with conventional line-source AA spectrometers
using the absorption spectra of diatomic molecules of non-metals formed in flames
and furnaces [1, 2]. However, due to the low resolution of conventional line-source
AA spectrometers, and due to severe problems with background correction, this
approach was abandoned in the 1990s [3]. However, the introduction of highresolution continuum source atomic absorption spectrometry (HR-CS AAS) [4],
changed the situation and opened new possibilities also for molecular absorption
spectrometry (MAS) and the determination of non-metals. Due to the high resolution
of about 1.5 pm per pixel at 200 nm, the rotational fine-structure of the electronic
transitions of diatomic molecules is completely or almost completely resolved,
resulting in a series of lines with a half-width similar to that of atomic lines. As a
high-intensity continuum radiation source is used, any wavelength is available to
measure the the absorbance at any of the molecular ‘lines’, and also theChem.
background absorption in the ‘valleys’ between the lines. The determination of nonmetals via the absorption of diatomic molecules in flames and furnaces using HR-CS
AAS equipment was pioneered by Huang et al. [5], and Heitmann et al. [6]. The state
of the art and the latest developments of this technique for the determination of the
halogens will be presented in this work.
References :
[1] K. Dittrich, Prog. Analyt. Atom. Spectrosc. 5, 209-275 (1980)
[2] K. Dittrich et al. Talanta 31, 341-358 (1984)
[3] B. Welz, F.G. Lepri, R.G.O. Araujo, S.L.C. Ferreira, M.D. Huang, M. Okruss, H.
Becker-Ross, Anal. Chim. Acta 647, 137-148 (2009)
[4] H. Becker-Ross, S. Florek, U. Heitmann, R. Weisse, Fresenius J. Anal. Chem.
355, 300-303 (1996)
[5] M.D. Huang, H. Becker-Ross, S. Florek, U. Heitmann, M. Okruss, J.Anal. Atom.
Spectrom. 21, 338-345 (2006)
[6] U. Heitmann, H. Becker-Ross, S. Florek, M.D. Huang, M. Okruss, J.Anal. Atom.
Spectrom. 21, 1314-1320 (2006)
42
Keynote Lecture: Nuclear techniques
KL11
Emission (57Co) Mössbauer spectroscopy in bioanalysis
A.A. Kamnev1, Yu.D. Perfiliev2, L.A. Kulikov2, A.V. Tugarova1, K. Kovács3,
Z. Homonnay3 and E. Kuzmann3
1
Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and
Microorganisms, Russian Academy of Sciences, 410049, Saratov, Russia
2
Laboratory of Nuclear Chemistry Techniques, Faculty of Chemistry, M.V. Lomonosov Moscow
State University, 119991, Moscow, Russia
3
Laboratory of Nuclear Chemistry, Institute of Chemistry, Eötvös Loránd University, H-1512,
Budapest, Hungary
E-mail: a.a.kamnev@mail.ru; aakamnev@ibppm.sgu.ru
The extremely sensitive and informative emission variant of Mössbauer spectroscopy
(EMS), with the most widely applicable 57Co radionuclide, has been used largely in
materials science and nuclear chemistry. Nevertheless, its sensitivity can also be of
great advantage in revealing fine structural features and for speciation analysis of
sophisticated biological complexes, whenever the 57Co2+ cation can be used as a
substitute for native cobalt or other metal ions (for a recent review, see [1]).
Since our first studies [2, 3], EMS has proven to be sensitive to fine structural
features of the cation-binding sites (CBS) in enzyme active centres. In this lecture,
examples will be presented for cobalt(II) speciation and distribution within the active
centres (with two or three different CBS in each) of 57Co2+-doped enzymes (e.g.,
bacterial glutamine synthetase; alkaline phosphatase from bovine intestinal mucosa).
Informativity of EMS will also be shown for time-dependent monitoring of 57Co2+
binding and transformations in live microbial cells [4, 5]. Finally, EMS interrelation
with transmission (57Fe) Mössbauer spectroscopy will be depicted in comparing Co
and Fe biocomplexes, e.g. Co2+ binding to Fe-S proteins as a basis of Co toxicity [5].
This work was supported in part by the Russian Foundation for Basic Research
(Project 13-04-01538-a) and under the Agreement on Scientific Cooperation between
the Russian and Hungarian Academies of Sciences (Projects 28 and 29; 2011–2013).
References
[1] A.A. Kamnev, in: V.K. Sharma, G. Klingelhöfer, T. Nishida (Eds.), Mössbauer Spectroscopy:
Applications in Chemistry, Biology, and Nanotechnology. Wiley, N.Y., Chap. 17, 333-347 (2013).
[2] A.A. Kamnev, L.P. Antonyuk, V.E. Smirnova, O.B. Serebrennikova, L.A. Kulikov, Yu.D.
Perfiliev, Anal. Bioanal. Chem., 372, 431-435 (2002).
[3] A.A. Kamnev, L.P. Antonyuk, V.E. Smirnova, L.A. Kulikov, Yu.D. Perfiliev, I.A. Kudelina, E.
Kuzmann, A. Vértes. Biopolymers, 74, 64-68 (2004).
[4] A.A. Kamnev, A.V. Tugarova, L.P. Antonyuk, P.A. Tarantilis, L.A. Kulikov, Yu.D. Perfiliev,
M.G. Polissiou, P.H.E. Gardiner, Anal. Chim. Acta, 573-574, 445-452 (2006).
[5] A.A. Kamnev, A.V. Tugarova, K. Kovács, E. Kuzmann, B. Biró, P.A. Tarantilis, Z. Homonnay,
Anal. Bioanal. Chem., 405, 1921-1927 (2013).
43
Perkin Elmer
A WORD FROM OUR SPONSOR
SP-ICP-MS for Detection, Quantitation, Size and Size
Distribution of Engineered Nanoparticles, Improvements
and Applications
Riccardo MAGARINI
PerkinElmer (Italia) Environmental Health
Viale dell’Innovazione 3, 20126 Milano (IT)
riccardo.magarini@perkinelmer.com, Tel: +39 02 3601.2500
In the big nanoparticles (NP) world, the group of engineered nanoparticles (ENP)
containing one or more inorganic elements, i.e. Ag, Au, Fe, Si, Ti …, is fast
growing. This is because of their increase usage in consumer products and various
industrial applications.
After their life cycles, these metals‐containing NPs may be discharged into the
environment or may enter biological systems, in most cases at the low ppb
concentration range. Concerns are raised that metals‐containing NPs could
potentially be harmful and exceed the predicted no‐effect concentration. It is thus
important to detect and quantify these NPs, in order to understand and follow
environmental and biological exposure.
Several analytical techniques are available for nanometrology studies. Among
them, some may not have the required sensitivity to characterize NPs at
environmentally relevant concentrations. Others may not have the selectivity
needed to detect NPs in matrices that may contain the elements in different forms,
i.e. NPs and dissolved. As a consequence, some techniques only could be
successfully applied for environmental health and safety (EHS) and toxicological
studies.
Within the useful analytical techniques group, Inductively Coupled Plasma Mass
Spectrometry (ICP‐MS), coupled to separation techniques such as FFF, HDC,
HPLC …, is a powerful tool to define composition, concentration, and size
distribution of inorganic ENMs in a variety of matrices. ICP‐MS can also be used
on its own as a Single Particle Counter (SPICP‐MS), to differentiate between
ionic and particulate forms, to define particle sizes and to evaluate agglomeration
and size distribution. The benefits provided by a new generation of ICP‐MS for
high throughput SP‐ICP‐MS applications will be here presented, together with
some application examples.
44
Shimadzu
A WORD FROM OUR SPONSOR
In wine there is truth - “state of the art” solutions for wine
analysis
U. Oppermann1, A. van Oyen2 and J. Knoop1
1
Shimadzu Europa GmbH, Albert- Hahn- Str. 6-10, D-47269 Duisburg, Germany
2
CARAT GmbH, Harderhook 20, D-1432 Bocholt, Germany
E-mail: uo@shimadzu.eu
Wine is one of the oldest cultural products in human history. Wines have been
cultivated for over 8000 years. Wines have been cultivated for over 8000 years. The
oldest known archaeological evidence of winemaking is an 8000-year old wine- and
fruit press found near Damascus.
Winemaking is a rather simple process: freshly harvested grapes are crushed and the
resulting juice (must) is collected. The must contains fermentable sugars and natural
yeasts which, either by themselves or with the help of additional yeast cultures, start
the fermentation process in which mainly ethyl alcohol and carbon dioxide are
formed. The latter is a gas and escapes from the must. The fermentation process
comes to a halt when all of the sugars are fermented or the alcohol concentration
becomes too high and kills off the yeasts. At this point the must has turned into wine.
In order to guarantee a certain level of quality, standards are fixed in the national
wine regulations such as the German “Weinverordnung” [1] from 21st April 2012,
which includes the classification of wines from different locations but also the
production process, alcohol concentrations and the maximum allowable
concentrations of elements.
A meticulous quality control procedure is essential, and during each stage of the
production process analytical methods such as Gas- or Liquid-Chromatography,
AAS-, ICP-, FTIR-, and UV-VIS spectroscopy as well as Mass- Spectrometry are
applied for quality assurance or for product characterisation in order to guarantee the
highest level of food quality as well as food safety.
Wine colour was measured at 520 nm using a UV-VIS spectrophotometer.
Quantitative determination of elements has been done with a Shimadzu ICPE-9820
ICP-OES spectrometer. Ultra fast analysis of resveratrol in red wine was done using
the UHPLC- system with an RF-20Axs high-sensitivity fluorescence detector. The
undesired 2,4,6-Trichloroanisole (TCA) in wine is detected using the headspace-trap
GC/MS QP-2010 Ultra. Experimental data of a variety of methods will be presented.
References
[1] Deutsche Weinverordnung, Bundesgesetzblatt Teil 1 S. 827, (2012)
[2] Compendium of International Wine and Must Analysis, Vol. 2, (2012)
45
Parallel Session 1: Atomic Spectrometry
OP1
Potential use of CaF molecular bands for trace fluorine
quantitative analysis using LIBS
C. Álvarez Llamas1, J. Pisonero1 and N. Bordel1
1
Department of Physics, Faculty of Sciences, University of Oviedo, c/Calvo Sotelo s/n 33007
Oviedo, Spain,
E-mail: ceallas@gmail.com
The availability of analytical techniques for the qualitative and quantitative detection
of fluorine and fluoride compounds is an essential point due to their spread use in
pharmaceuticals, refrigerants and polymers. The most common methodologies for
fluorine determination require the sample to be transformed into a suitable form,
either by digestion or by combustion; however, these processes imply several steps
and, in some cases, also the use of hazard chemical compounds[1].
Direct analytical techniques would be an interesting alternative in order to reduce as
much as possible the pretreatment steps. For instance, Neutron Activation Analysis
(AAN) and X-Ray Florescence (XRF) are included in this category. These
techniques present several advantages like multielemental measurement capabilities
or minimum sample pretreatment; nevertheless, important lacks are showed, such as
the need of nuclear protection facilities in the case of AAN, or the low sensitivity for
lighter elements with XRF.
As an alternative, Laser-Induced Breakdown Spectroscopy (LIBS) can also be
considered. This technique is a fast and versatile analytical tool that can analyze
solid, liquid, gas or aerosol samples. LIBS is based on the use of a short-duration
laser pulse, which is focused on a small area of the sample surface, inducing a high
temperature plasma. The main advantages of LIBS include: reduced analysis time,
minimum or none sample pretreatment, multi-elemental detection, high spatial
resolution and the potential of carry out in-lab or standoff analysis.[2]
This presentation deals with the analysis of halogens, in particular fluorine, using
LIBS. In general, spectroscopic techniques are not very sensitive for F analysis since
the strongest analytical lines lie at wavelengths shorter than 100 nm. Spectral region
between 685-780 nm could be also used although the emission intensity for these
lines is significantly lower. In order to overcome this limitation, He is usually used as
a surrounding gas to improve the analytical signal of F emission lines in this region.
Another approach used in this work is the measurement of CaF molecular emission
as an indicator of the F content in a sample [3]. The availability of the CaF molecular
emission for the quantification of low F concentration has been studied and the
results show significant improvements on the achieved LOD operating in air.
Moreover, a real sample of toothpaste was chosen as proof-of-concept, showing the
validity of the methodology.
References
[1]
P. A Mello, J. S. Barin, F. a Duarte, C. a Bizzi, L. O. Diehl, E. I. Muller, E. M. M. Flores,
Anal. Bioanal. Chem., vol. 405, no. 24, pp. 7615–42,. 2013.
[2]
D. A. Cremers and L. J. Radziemski, Handbook of laser-induced breakdown spectroscopy,
1st ed. John Wiley & Sons, Ltd, 2006.
[3]
C. Alvarez, J. Pisonero, N. Bordel, Spectrochim. Acta Part B At. Spectrosc., vol. 100, pp.
123–128,. 2014.
46
OP2
Use of gradient dilution to detect the presence of matrix
interferences in inductively coupled plasma–time-of-flight
mass spectrometry
Yan Cheung, Steven J. Ray, Andrew J. Schwartz, Gary M. Hieftje
Indiana University, Bloomington, IN 47405 USA
E-mail: yancheu@indiana.edu
Dispersion that occurs during flow injection (FI) was investigated earlier by our
research group to detect and correct for matrix interference in inductively coupled
plasma time-of-flight mass spectrometry. The concept is straightforward: in the
absence of an interference, the dilution that occurs during FI should be the same for
all sample constituents. As a result, the ratio of any two elemental signals should be
constant. However, when an interferent is present, the signals from individual
elements are affected differently, so the signals deviate from a constant value,
especially at the peak of the FI curve where the interferent concentration is greatest.
The drawback of this earlier method was that dispersion, and therefore dilution, was
element-specific, causing the ratios to wander even when no interference existed.
Here, we employ a gradient HPLC pump to overcome this drawback. With longer
gradient runs and smaller gradient steps than flow injection, the variation in
dispersion between elements is negligible and difficulties associated with it are
eliminated. In this study, the space-charge effects on five analyte elements in the
presence of six matrix elements were investigated. Signals of ions with different
masses were used as indicators for flagging the existence of a matrix interference.
47
OP3
Spectroscopy of atoms inside Casimir cavities
C. A. O. Henriques, C.M.B. Monteiro, L. M. P. Fernandes and F. D. Amaro
LIBPhys, Departamento de Física, Universidade de Coimbra, 3004-516 Coimbra, Portugal
E-mail: henriques@gian.fis.uc.pt
Stochastic Electrodynamics (SED) is a modern version of the relativistic classic
electrodynamics with the implementation of a random electromagnetic zero-point
field (ZPF) background [1]. This theory has astoundingly described many atomic
systems until now explained only by the Quantum Electrodynamics; for example, the
atomic orbital stability, whose energy levels would be predetermined by the ZPF [2].
Since a Casimir cavity suppresses some of the ZPF modes, the atoms inside such
cavity can undergo level shifts in their ground and exited states. Through this
principle, the switching of ground or excited atoms between Casimir cavities and the
free space could lead, respectively, to the detection of radiation or energetic gain in
their radiative properties [3].
An experimental validation of this hypothesis would have a profound impact on
fundamental physics as well as on applied science since it would also confirm that
ZPF could be used to deliver energy.
We assembled an experimental system to flow low pressure Xe through Casimir
cavities constituted by nano-porous aluminium coated membranes. Two
monochromators were placed on opposite sides of a stainless steel chamber, one of
them coupled to a Vacuum Ultra-Violet (VUV) Deuterium lamp, and the other one
coupled to a Photo Multiplier Tube (PMT) with sensitivity from VUV to the visible
spectrum. This apparatus allowed us to excite atoms to well-defined wavelengths and
simultaneously perform a spectroscopic analysis of the radiation resulting from their
spontaneous emission, either inside or outside the Casimir cavities.
Having performed a spectroscopic analysis from 150 to 550 nm we didn’t observe
any modification in the transition energy between the ground state and the first
resonant (3P1) state of Xe inside Casimir cavities.
Although less probable [3], there is also a possibility for spontaneous emission from
ground state Xe atoms when entering Casimir cavities. We, therefore, performed a
second set of experiments where Xe atoms flowed through the membrane, without
being excited. At first, a spectroscopic study was performed,as described above and,
afterwards, we placed the PMT few mm away from the membrane, increasing the
sensitivity significantly. However, in both these cases we didn’t detect any radiation
emitted from the Xe atoms. Furthermore, from the results of the latter case we can
conclude for certain that there is no radiation emission from the Xe ground state
reduction in the energy range from 1.9 to 7.8 eV and for pores of 50 nm in diameter.
References
[1] Boyer, Timothy H. "Random electrodynamics: The theory of classical electrodynamics with
classical electromagnetic zero-point radiation." Phys. Rev. D 11.4 (1975): 790.
[2] Puthoff, Harold E. "Ground state of hydrogen as a zero-point-fluctuation-determined state." Phys.
Rev. D 35.10 (1987): 3266.
[3] de Oliveira Henriques, Carlos Alberto. Study of atomic energy shifts induced by Casimir cavities.
MSc Thesis, University of Coimbra, 2014. {http://hdl.handle.net/10316/28082}
48
Parallel Session 2: Archaeometry and Cultural Heritage
OP4
Applications of Optical, Laser and X-Ray Spectroscopic
Methods in Archaeology: Analysis of the Wall Paintings of
the Villa of the Vetti (Florence, IV-VI century A.D.)
E. Grifoni1, S. Legnaioli1,2, G. Lorenzetti1, S. Pagnotta1, M. Lezzerini3,
M. Ramacciotti3, F. Cantini4, V. Palleschi1,2,4
1
Applied and Laser Spectroscopy Laboratory, ICCOM-CNR, Via G. Moruzzi 1 - 56124 Pisa, Italy
2
National Interuniversity Consortium of Materials Science and Technology (INSTM)
3
Department of Earth Sciences, University of Pisa, Via S. Maria 53, 56126 Pisa, Italy
4
Department of Civilizations and Forms of Knowledge, University of Pisa, Pisa, Italy
E-mail: vincenzo.palleschi@cnr.it
The Late Roman Villa of the Vetti (4th – 6th century A.D.) is located in the Florence
countryside (Italy). The aim of this communication is the description of the results of
a multi-technique analysis, based on the techniques of Optical microscopy, VisibleInduced Infrared Luminescence (VIL), micro-Raman spectroscopy, X-ray
diffraction, and scanning electron microscopy with X-ray energy-dispersive
spectrometry, for the identification of the main colours and painting techniques used
for the decoration of the interiors of the Villa. The application of these advanced and
variegated scientific techniques allows to determine that the red and yellow colours
were realized with ochers, the black colour was given by carbon black, the white
colour was made by calcium carbonate and the blue colours were made with
Egyptian blue (CaCuSi4O10). Moreover, the multi-technique approach allowed to
determine that the apsidal hall was decorated with a secco (lime-painting) technique,
while the decorations of the cubiculum were painted with a fresco technique.
Fig. 1. Villa of the Vetti. Left: picture of the excavations of the main rooms of the
pars urbana. Right: detail of the pavement mosaic of the apsidal hall.
49
OP5
Shedding new light on PUR degradation
S. França de Sá 1,2, J. L. Ferreira1,2, R. Macedo1,3, A. M. Ramos1,2 and I. Pombo
Cardoso1,2
1
Department of Conservation and Restoration, Faculdade de Ciências e Tecnologia, Universidade
Nova de Lisboa, 2829-516 Caparica, Portugal.
2
LAQV-REQUIMTE, Department of Chemistry, Faculdade de Ciências e Tecnologia, Universidade
Nova de Lisboa, 2829-516 Caparica, Portugal.
3
Instituto de História da Arte, Faculdade de Ciências Sociais e Humanas, Universidade Nova de
Lisboa, Avenida de Berna, 26-C, 1069-061 Lisboa, Portugal.
E-mail: jlaf@fct.unl.pt
This research aims at bringing a new insight into the degradation of ether-based
polyurethane flexible foams (PUR) by studying selected case studies from the Design
and Fashion Museum (MUDE, Lisbon) based on infrared spectroscopy and optical
microscopy. With a life-expectancy of 20 to 50 years, many polyurethane objects
from MUDE’s collection show severe degradation signs (yellowing, crumbling and
brittleness). These foams, due to their open cell structure are especially prone to
degradation in short-term.
Infrared micro-spectroscopy (transmission mode) and optical microscopy (under Vis
and UV light) were used to follow the molecular degradation as well as the visual
aspects of the polymer network upon ageing. For that purpose, the use of different
modes of reflected light illumination was crucial, in particular, darkfield, polarised
light and UV light. Based on the assessment of historical objects’ condition along
with references of unaged and aged PUR samples (all based on poly(propylene
glycol) and aromatic diisocyanates), the visual course and infrared pathway of PUR
degradation might be drawn (Fig.1). Degradation signs such as yellowing, crumbling
and brittleness may be translated into infrared fingerprints and correlated with
different fluorescence behaviours. In addition, several condition grades were
identified according to spectral regions assigned to N-H, C-H, C=O and C-O-C
molecular bonds, with a special focus into the changes of hydrogen bonding.
Figure 1 Infrared spectra and microscopy images (cross-polarized light) for PUR
foams from MUDE’s collection showing different condition grades (from good to
unacceptable): A – unaged (good); B – naturally aged (fair), C – naturally aged
(poor) and D – naturally aged (unacceptable).
50
OP6
Analysis of polychrome baroque sculptures using
XRF, SEM-EDS, Raman and FTIR
C. Calza1, R.P. Freitas2, I.M. Ribeiro3, A.L. Oliveira2, V.S. Felix1,2, R.T. Lopes1
1
Nuclear Instrumentation Laboratory. PEN/COPPE/UFRJ. Rio de Janeiro, RJ. Brazil
2
Federal Institute of Rio de Janeiro (IFRJ). Paracambi, RJ. Brazil
3
Federal Rural University of Rio de Janeiro (UFRRJ). Seropédica, RJ. Brazil
E-mail: ccalza@lin.ufrj.br
The identification of pigments employed in polychrome wooden sculptures provides
an important aid in questions related to conservation and restoration procedures and
also information about the historical period of the analyzed artworks or possible
forgeries. In this work, X-Ray Fluorescence (XRF), Scanning Electron Microscopy
associated with Energy Dispersive Spectroscopy (SEM-EDS), Raman and Fourier
Transform Infrared (FTIR) Spectroscopy were applied in order to characterize the
pigments used in the polychromy of three sculptures dated from the early XVIII
century (Baroque period), portraying Our Lady of Sorrows, St. John Evangelist and
Jesus Christ. The results of this work were used by restorers for effective and
adequate interventions in order to recovery the original characteristics of the
sculptures.
Some small fragments – extracted from the carnation region and clothing - were
analyzed by means of the cited techniques. Stereo and optical microscopes, Olympus
and Carl-Zeiss, respectively, were used in order to study the stratigraphy and the
microstructure of the samples. EDXRF portable system Bruker Tracer III-SD (with
Rh anode, operating at 40 kV and 35 μA) and EDS system coupled to Scanning
Electron Microscope Hitachi TM 3000 (operating at 15 kV and 60 μA) were
employed to characterize the elemental composition of the samples. FTIR analysis
was performed using Bruker VERTEX 70 system, with ATR method. The spectra
were collected in the middle region (4000-400 cm-1), with a resolution of 1 cm-1 and
32 scans. Raman analysis was performed at Horiba Jobin Yvons Raman system
Labram HR Evolution. The spectra were collected using the laser lines of 632.8 nm
and 488 nm adjusted with 1mW power, focused on the samples through 50X
objective lens.
The use of various analytical techniques allowed a more precise identification of the
pigments, as could be observed in the case of the samples showing green color, for
example. These samples presented the elements Cu and Pb in the XRF and EDS
spectra, which could be related to the use of verdigris (Cu(C2H3O2)2.2Cu(OH)2) or
malachite (CuCO3.Cu(OH)2) and a Pb based pigment (lead white? 2PbCO3.Pb(OH)2). However, additional Raman and FTIR analyses revealed a
mixture of the yellow pigment massicot (PbO) with the blue pigment azurite
(2CuCO3.Cu(OH)2). In the preparation layer was employed gypsum (CaSO4.2H2O).
The use of gold foils for gilding was proved by the presence of Au in the XRF and
EDS spectra.
51
Parallel Session 3: Environmental and Geochemical Analysis
OP7
SEM/EDAX, XRD analysis and smart data sharing
in the study of innovative fertilizers
S. Bruni1, E. Burresi2, A. Dall’Ara2, P. Fabbri2, G. Marghella1, L. Moretti1 and
A. Strafella2
1
ENEA UTSISM - Via Martiri di Monte Sole 4, 40129 Bologna (Italy)
2
ENEA UTTMATF - Via Ravegnana 186, 48018 Faenza (Italy)
E-mail: stefania.bruni@enea.it
The demonstration of the production and use of an innovative fertilizer characterized
by reduced salinity, which allow the substitution of chemical and mineral fertilizers,
is the target of the European Project Life12 ENV/IT/356 “RESAFE: innovative
fertilizer from urban waste, bio-char and farm residues as substitute of chemical
fertilizers”. Thus, different types of Urban Organic Waste (UOW), Bio-Char (BC)
and Farm Organic Residues (FOR) produced in Italy, Spain and Cyprus have been
selected in order to obtain a final High Quality fertilizer with desired features.
Different receipt have been tested and enzymatic biostabilization treatment at
laboratory scale have been carried out over 60 days.
The characterisation analyses have been carried out by Scanning electron microscopy
(SEM), Microanalysis (EDAX) and X-Ray diffractrometry (XRD) [1]. Samples have
been observed at the SEM for the morphological study and a significant number of
microanalyses have been performed on each sample to obtain suitable scientific
results for the chemical characterization. XRD has been employed for recognizing
the crystalline phases inside the complex biological and amorphous matrix: the
crystallographic determination of the phases is based on the microanalysis data. Also
the evolution of the mix during biostabilization at laboratory scale was monitored,
comparing receipt with and without BC.
Within the project, data sharing has played a fundamental role in order to make the
big amount of analysis results quickly and always available among the international
partners, both for comparison and for the definition of project steps. Thus, for Life
RESAFE project a smart method has been developed for the easy sharing via web of
any data (analysis reports, charts, graphs, images, files etc.) in an interactive way.
The obtained data have been then related together, allowing the identification of the
best receipt of High Quality fertilizer by means of the morphological,
crystallographic and chemical features.
As final result, farmers and urban waste managers will have the possibility to reduce
costs and obtain environmental and economic advantages, such as the recovery of
waste material and the revenue generated from the selling of the new fertilizer. The
environmental impact will be also significantly reduced and the greenhouse
emissions from landfills will decrease.
Reference
[1] A. Dall’Ara, A. Bonoli, S. Serranti, E. Burresi, L. Stroea, Control methodology for biomasses
quality: A case study for biotreated poultry manure. Journal of Biotechnology, Volume 150,
Supplement, Page 198 (2010), ISSN 0168-1656
52
OP8
Thermal Mud Characteristics of Geo-Materials (KoprukoyErzurum, NE Turkey)
Ekrem KALKAN1 & Hayrunnisa NADAROGLU2
1
Geological Engineering Department, Oltu Earth Sciences Faculty, Ataturk University,
25400 Oltu-Erzurum, Turkey
23
Ataturk University, Erzurum Vocational Training School, Department of Food
Technology, 25240 Erzurum, TURKEY
Thermal muds are hydrothermal or hydrothermalized pastes produced by primary or
secondary mixing of clayey geo-materials with salty thermo-mineral waters,
accompanied by organic materials produced by the biological-metabolic activity of
microorganisms growing during the so-called “maturation” process. Various factors
are ruling the quality of a peloid: virgin clay, thermo-mineral water and maturation
procedure. Nowadays pelotherapy is being more-and-more focused on specific
pathologies and treatments; such innovative health applications need a “certification”
of the peloids suitability. Worse applications of thermal mud could produce nonbeneficial effects, or cause relapse. In this study, clayey material samples have been
collected from Pliocene geological formation deposited in the lacustrine environment
and located Koprukoy (Erzurum) thermal area. The samples of these materials have
been tested to determine the mineralogical and physicochemical properties. The
results show that smectite clay mineral is abundant and kaolinite, illite, zeolite, mika,
quartz, calsite, plagioclase, and feldspar are other clay and non-clay minerals.
Physicochemical properties, such as specific surface area, cation exchange capacity,
plasticity index were also determined. With respect to their physicochemical
properties, all samples have thermal properties which make them potentially suitable
for therapeutic or aesthetic purposes.
Keywords: Koprukoy-Erzurum, Thermal mud, Clayey geo-material
.
53
OP9
Precise measurement of radiogenic (87Sr/86Sr) and stable
(88Sr/86Sr) strontium isotope ratios in Fukushima soil
samples using thermal ionization mass spectrometer
N. Kavasi, S.K. Sahoo and T. Aono
National Institute of Radiological Sciences, 4-9-1Anagawa, Inage, Chiba 263-8555, Japan
E-mail: norbert@fml.nirs.go.jp
Strontium comprises of four stable isotopes i.e.84Sr, 86Sr, 87Sr and 88Sr while 90Sr
being a radioactive isotope (T1/2=28.8 y) which is originated during nuclear weapon
tests and nuclear accident. The fission yield of stable 88Sr (˜3.5×10-2) isotope in
thermal neutron fission is comparable with the radioactive 90Sr (˜5.8×10-2) isotope
consequently, beside the radioactive contamination, 88Sr emission might have
occurred during Fukushima dai-ichi nuclear power plant (FDNPP) accident.
Therefore, it is important to check if there is any variation of the stable strontium
isotope ratio (88Sr/86Sr) in Fukushima affected environmental samples.
Thermal ionization mass spectrometer (TIMS) is one of the most suitable device for
high precision and accurate measurement of Sr isotope ratios. In our laboratory, a
(Phoenix X62) TIMS has been installed and radiogenic and stable strontium isotope
ratios were analysed in soil samples collected from the vicinity (<30 km) of the
damaged FDNPP. The recovery of strontium concentration also was determined
applying isotope dilution procedure with 84Sr spike solution.
The soil sample digestions were accomplished using a closed microwave system with
mixture of Tamapure acids (HF, HNO3 and HClO4). The strontium separation was
accomplished with Sr extraction chromatography resin (Eichrom) [1]. The separated
strontium samples dissolved in 0.1M HNO3 solution were loaded onto Re ribbon
single filament using Ta2O5 activator. The reproducibility of the mass spectrometer
has been checked for more than 6 months using NIST standard (SRM-987). The
average 87Sr/86Sr ratio of this measurement period (n=45) was 0.710246(12).
Detailed information about the radiogenic and stable strontium isotope ratios of
Fukushima soil samples will be presented and discussed.
References
[1] Vajda, N., and C. K. Kim, Appl Radiat Isot 68(12), 2306-26 (2010)
54
Parallel Session 4: X-ray Spectrometry
OP10
Contribution to XRF intensity from inner shell Compton
ionization
Jorge E. Fernández1, Viviana Scot1 and Eugenio Di Giulio1
1
Laboratory of Montecuccolino-DIN, Alma Mater Studiorum University of Bologna, via dei Colli
16, 40136 Bologna. Italy
E-mail: jorge.fernandez@unibo.it
The Compton effect is a well known ionization mechanism of inner shells in atoms.
The produced vacancies can be filled with the same process of atomic relaxation as it
occurs after photoabsorption. Even if this contribution is a source of XRF emission it
is frequently neglected because of the reduced extent of the Compton cross-section
compared with the photoelectric one.
Recently, Pavlinsky and Portnoy [1] have given an approximated description of this
contribution for K-lines, and have shown that it may become dominant for high
excitation energies and low-Z elements. In this article it is given a detailed
description of the XRF contribution due to Compton ionization for single shells in
the framework of the impulse approximation (IA). The description is extended to the
L and M shells, showing that this contribution becomes relevant also for medium-Z
elements. It is given a simple formula to compute the correction which can be used in
deterministic and Monte Carlo codes.
The extent of the contribution is illustrated with some examples involving low- and
medium-Z elements.
References
[1] G.V. Pavlinski and Yu. Pornoy, X-ray Spectrometry 43 (2014), 118-121.
.
55
OP11
Quantum interferences in laser spectroscopy
of muonic atoms
P. Amaro1, B. Franke2, J. J. Krauth2, M. Diepold2, F. Fratini3,
L. Safari4, J. Machado1,5, A. Antognini6,7, F. Kottmann6,
P. Indelicato5, R. Pohl2, J. P. Santos1
1
LIBPhys-UNL, Departamento de Física, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, Portugal.
2
Max-Planck-Institute of Quantum Optics, 85748 Garching, Germany.
3
Vienna Center for Quantum Science and Technology, Atominstitut,
Vienna University of Technology, 1020 Vienna, Austria.
4
IST Austria, Am Campus 1, A-3400 Klosterneuburg, Austria.
5
Laboratoire Kastler Brossel, École Normale Supérieure, CNRS,
Université P. et M. Curie - Paris 6, Case 74; 4, place Jussieu, 75252 Paris CEDEX 05, France.
6
Institute for Particle Physics, ETH Zurich, 8093 Zurich, Switzerland.
7
Paul Scherrer Institute, 5232 Villigen-PSI, Switzerland.
E-mail: pdamaro@fct.unl.pt
In this presentation, we address a subtle quantum effect that occurs in the process of
light scattering by atoms, i.e., the process of absorption and emission of a photon that
happens in resonant laser spectroscopy. This effect occurs due to the coherent
interference between the main resonant path and other non-resonant paths, which
leads to energy shifts that depend on the relative position of each resonance. This is
an important, yet frequently overlooked systematic effect in precision laser
spectroscopy experiments [1, 2], which measure transition frequencies with
uncertainties below 10-5 [3, 4]. High-precision spectroscopy of atomic systems is
primarily devoted for the determination of fundamental physical constants; thus, a
careful analysis of these quantum interference effects is mandatory. Here, we
introduce the effects of such interference in laser spectroscopy of muonic atoms,
which consists of an exotic muon and nucleus. Previous measurements of energy
transitions by laser spectroscopy in these exotic atoms, conducted by the CREMA
collaboration, lead to the determination of the proton charge radius with high
accuracy [3]. We discuss here the effect of quantum interference in several
resonances of muonic hydrogen, deuterium and helium-3, giving emphases to
geometrical and polarization scenarios that minimize it.
References
[1] D. C. Yost, et al, Phys. Rev. A, 90, 012512 (2014).
[2] R. C. Brown et al, Phys. Rev. A, 87, 032504 (2013).
[3] R. Pohl, et al, Nature, 466, 213 (2010).
[4] C. G. Parthey, et al, Phys. Rev. Lett., 107, 203001 (2011).
56
OP12
Remarks on a Johann spectrometer for exotic-atom
research and more
D. Gotta1 and L. M. Simons2
1
2
Institut für Kernphysik, Forschungszentrum Jülich, D-52425 Jülich, Germany
Laboratory for Particle Physics, Paul Scherrer Institut, CH-5232 Villigen, Switzerland
E-mail: d.gotta@fz-juelich.de
Inherent to exotic-atom research is a low count rate in the presence of demanding
background conditions. Therefore, an apparatus for ultimate resolution spectroscopy
constitutes a compromise between conserving almost the resolution achievable with
plane crystals and sufficiently large efficiency to allow for acceptable measurement
times together with mechanical long-term stability [1].
The approach consists of a Johann-type spectrometer equipped with spherically bent
silicon and quartz crystals. Such a setup allows to record simultaneously a finite
energy interval according to the width of the X-ray source when using a
correspondingly extended X-ray detector. Large bending radii of about 3 m minimize
aberrations and result in a sufficient distance to the X-ray source allowing for an
effective shielding. On the other hand, as a low-rate capable device the spectrometer
is also suited for high statistic studies of fluorescence lines [2].
The general features of the spectrometer are discussed by means of simple
geometrical considerations giving at hand rules of thumb to assess a typical setup.
The validity of the approximations is discussed by means of experimental results and
by Monte Carlos studies.
Examples from exotic-atom spectroscopy are given for light antiprotonic and pionic
atoms as well as an application in the field of Ba Lg X-ray fluorescence [3]. The link
is discussed between electronic- and exotic-atom X-ray standards [4].
References
[1] D. Gotta, Prog. Part. Nucl. Phys., 52, 133 (2004).
[2] M. Jabua, contribution to this conference.
[3] D. Gotta et al., Nucl. Phys. A 660, 283 (1999).
[4] D. F. Anagnostopoulos et al., Phys. Rev. Lett. 91, 240801, (2003).
57
OP13
Latest advances in volatile species generation of transition
metals by the reaction with NaBH4
S. Musil1, J. Šoukal1,2, J. Vyhnanovský1,2, J. Hraníček2, O. Benada3
and J. Dědina1
1
Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno, Czech Republic
Charles University in Prague, Faculty of Science, Albertov 6, 128 43 Prague, Czech Republic
3
Institute of Microbiology of the ASCR, v. v. i., Vídeňská 1083, 142 20 Prague, Czech Republic
2
E-mail: stanomusil@biomed.cas.cz
Volatile species generation (VSG) of transition metals by the reaction with NaBH4
still attracts the attention [1]. The advantage of VSG in comparison to nebulization
techniques lies in analyte separation from a matrix and in (potentially) higher
efficiency of analyte introduction for analytical atomic spectrometry detectors.
However, these efficiencies even with the use of various reaction modifiers are still
far from 100% as typically reached for hydride generation. Very little is known about
the actual reaction mechanism of VSG of transition metals. Some insight into the
nature of volatile species was gained in our laboratory some time ago when
nanoparticles of Ag and Au were identified in the gaseous phase by means of
transmission electron microscopy [2,3].
The latest advances achieved in our laboratory in this field will be presented. A
special attention will be paid to Cu and Pd. The conditions of VSG of both elements
were optimized with the use of a miniature diffusion flame atomizer. Although this
combination lacks sufficient sensitivity for trace analysis, it was found very robust
and suitable for such purpose. The most important parameters were investigated (pH
of the reaction mixture, concentration of NaBH4, presence of reaction modifiers –
surfactants, complexing agents, etc.).
The generators were coupled to the quartz/sapphire tube atomizers [4] in the next
step and parameters of on-line atomization were optimized. The possibility of in situ
collection (directly in the optical tube) will be also demonstrated. The overall
generation efficiencies were estimated by means of determination of the trapped
volatile species from the gaseous phase before reaching the atomizer. The volatile
species were also sampled for transmission electron microscopy investigations to
clarify their identity.
The Academy of Sciences of the Czech Republic (no. M200311202), Czech Science
Foundation (no. P206/14-23532S), Institute of Analytical Chemistry of the ASCR, v.
v. i. (RVO: 68081715) and Institute of Microbiology ASCR v.v.i. (RVO: 61388971)
are highly acknowledged.
References
[1] P. Pohl et al., TrAC Trends Anal. Chem. 59, 144–155 (2014).
[2] S. Musil et al., Spectrochim. Acta Part B 64, 1240–1247 (2009).
[3] Y. Arslan et al., J. Anal. At. Spectrom. 26, 828–837 (2011).
[4] S. Musil et al., Spectrochim. Acta Part B 108, 61–67 (2015)..
58
OP14
A New ICP: The Microwave-Sustained, Inductively
Coupled, Atmospheric-Pressure Plasma (MICAP)
Andrew J. Schwartz,1 Yan Cheung,1 Steven J. Ray,1 Jovan Jevtic,2 Ashok
Menon,2 Velibor Pikelja,2 and Gary M. Hieftje1
1
2
Department of Chemistry, Indiana University, Bloomington, IN 47405, USA
RADOM Corporation, 10521 W. Forest Home Ave., Hales Corners, WI 53130, USA
E-mail: andschwa@indiana.edu
A novel, microwave-sustained, inductively-coupled, atmospheric-pressure plasma
(MICAP) has been developed that could serve as an alternative to traditional
radiofrequency inductively coupled plasmas (ICP) for both optical emission and
mass spectrometry.1 In the MICAP, a dielectric resonator ring (comprised of
advanced technical ceramics) is coupled with a 2.45 GHz microwave field generated
from a magnetron. The field induces a rapidly oscillating dielectric polarization
current within the resonator, which generates a magnetic field in a manner analogous
to that of the electrical current in a traditional load coil. This field is capable of
sustaining an annular plasma in either nitrogen or air which can accept sample
solutions in the form of an aerosol.
The MICAP offers a number of advantages that make it an attractive alternative to
the traditional ICP. First, since the magnetic field is generated from polarization
rather than an electrical current, the ring is minimally heated when powered and
thereby requires no external cooling. Similarly, when powered, the dielectric
resonator exhibits a net electric potential of zero on the macroscopic scale. As a
result, no electrostatic coupling occurs—advantageous for preventing secondary
discharges when the plasma is employed as an ion source for mass spectrometry.
Further, the plasma is stable in either nitrogen or air, obviating the need for
expensive argon. Finally, the polarization is induced through microwaves generated
from a traditional microwave-oven magnetron capable of being powered from a 120
V wall outlet, improving portability of the plasma.
Here, we present a preliminary evaluation of the emission characteristics, robustness
and analytical performance (limits of detection, precision, matrix interferences, and
linear range) of the MICAP as a source for optical emission spectrometry (OES).
Results will be critically compared to those of traditional ICP-OES.
References
[1] Jevtic, J.; Menon, A.; and Pikelja, V., MICROWAVE PLASMA SPECTROMETER USING
DIELECTRIC RESONATOR, WO 2014/159590 A1, March 12, 2014.
59
OP15
Quantitative determination of aging related changes in the
elemental distribution in lithium ion battery electrodes.
T. Schwieters, B. Hoffmann, M. Winter and S. Nowak*
University of Muenster, Institute of Physical Chemistry, D-48149 Muenster, Germany
E-mail: t.schwieters@wwu.de / *sascha.nowak@uni-muenster.de
Due to a lack of reliable methods for µm scale determination of the lithium
distribution in aged lithium ion batteries (LIBs) electrodes we developed a method
using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).
The solid sample is investigated using a 213 nm Laser with spot sizes ranging from
10-200 µm and subsequent analysis in an ICP-MS. Evaporating small parts of the
sample with the laser and analyzing the elemental composition of each spot allows a
three dimensional investigation of the electrode composition.
Even state of the art LIB systems show some degree of performance loss over time.
Various causes for this have been proposed or identified [1]. The distribution of
lithium in the LIB is one of the major factors concerning the performance. Thus
changes in the distribution can have a huge impact on the cycle and calendar life of
cells. The method we developed could be used to quantitatively study the lithium
content in the single digit µm-range.
References
[1] J. Vetter, P. Novák, M.R. Wagner, C. Veit, K.-C. Möller, J.O. Besenhard, M. Winter, M.
Wohlfahrt-Mehrens, C. Vogler and A. Hammouche, Journal of Power Sources, 147, 269–281 (2005)
60
OP16
Characterization of an ICP-MS with a new Inductively
Coupled Plasma and improved Interference Management
Sebastian Wünscher, 1 René Chemnitzer, 1 and Alf Liebmann1
1
Analytik Jena AG, Konrad-Zuse-Straße 1, Jena, 07745, Germany
E-mail: sebastian.wuenscher@analytik-jena.de
The deeper understanding of environmental pollution and its effects to the biota, the
invention of new and improved production processes for consumer goods as well as
the use of new optimized materials in all areas of human life require precise and
sensitive analytical techniques to characterize the products and investigate the
consequences.
ICP-MS as high sensitive analytical technique is widely used to characterize a
variety of sample types. The ability to detect not only the elemental concentration but
also use hyphenated techniques for the analysis of elemental species and the isotope
ratios makes ICP-MS a universal tool in many laboratories. The increasing demands
for improved detection limits and matrix robustness drive the innovations in the
instrument development.
On the basis of applications like the analysis of seawater a new inductively coupled
plasma will be described and characterized. The new generation of the Collision
Reaction Interface (iCRC) is presented and the improvements in interference control
are shown by means of typical interferences on elements like vanadium, chromium,
arsenic or selenium in various matrices..
61
Parallel Session 6: Laser Spectroscopy
OP17
Vega: a unique Pettawat laser for Science and Innovation
Álvaro Peralta Conde
CLPU, SCIENCE PARK - C/ Adaja 8 - 37185 - Villamayor (Salamanca), Spain
E-mail: aperalta@clpu.es
During 2015 a new PW laser named VEGA will be operative in CLPU (Pulsed Laser
Center) in Salamanca, Spain. The singular characteristics of this laser system like
the three different synchronized arms at 20 TW, 200 TW, and 1 PW which allows
pump-probe experiments at unprecedented intensities, together with the high
repetition rate of the PW exit, make of VEGA an extraordinary tool for Science and
Innovation at disposal of the community. Regarding the main field of this
conference, VEGA can help to understand not only those phenomena at high
intensities at the moment difficult to access, but also offer new and unexpected tools
for many different applications like for example X-ray spectrometry.
VEGA Laser
62
OP18
Multi-element Content Analysis of Rare Earth
Fluorocarbonates by Laser Ablation-Inductively Coupled
Plasma-Mass Spectrometry
C.Fan1, X.Zhan1, M.Hu1 and P.Zeng1
1
National Research Centre for Geoanalysis, Beijing 100037, China
E-mail: czfan2013@163.com
It is significant for studying the chemical compositions of rare earth fluorocarbonates
to understand the occurrence of rare earth deposits. In situ laser ablation-inductively
coupled plasma-mass spectrometry (LA-ICP-MS) analysis is introduced here instead
of solution methods due to their large errors of mixing with multi minerals.
Bastnäsite and huanghoite from Bayan Obo which show high interference color and
bright backscattered electron image in the polished thin sections are directly
examined by LA-ICP-MS.
Because carbon and fluorine element with high ionization energy cannot be
inaccurately detected in ICP-MS [1], the major element Ba, Ca and light rare earth
are calculated in forms of (Ba,Ca)CO3 and REECO3F respectively in the matrixnormalization methods according to the lattice coordination mode and the
characteristics of light rare earth-rich in fluorocarbonates. These results of bastnäsite
and huanghoite agree with the data of electron microprobe and internal standard
method analyses. The oval laser spot pits and low siginal sensitivity make large data
errors in 5 micron beam spot condition. However, the composition results of
bastnäsite obtained 10 micron beam spot condition are close to those under larger
spot size conditions, which can be suitable for the analysis of small rare earth
fluorocarbonate grains.
References
[1] Frick D A, Günther, Journal of Analytical Atomic Spectrometry, 27:1294-1303(2012).
63
OP19
Characterization of elemental composition of Polish
documents by laser induced breakdown spectroscopy
M. Król, D. Kowalska and P. Kościelniak
Jagiellonian University in Krakow, Faculty of Chemistry, Department of Analytical Chemistry,
3 Ingardena St., 30-060 Krakow, Poland
E-mail: koscieln@chemia.uj.edu.pl
In this study, a very promising technique, laser induced breakdown spectroscopy
(LIBS) was applied to the examination of Polish personal documents – passports and
identity cards from old and actual emission.
Optimization of LIBS method was performed on metallic emblem on the cover of the
booklet. A Q-switch delay time of 175 μs, integration delay time of 1,27 μs and
integration time of 1,5 ms were used. The optimized method was applied to analyze
of several security features of documents: 1) passport (Alphagram®, series number,
and optically variable ink), 2) identity card (kinegram, the date of birth, OVI effect,
security features visible in directional light and under UV – guilloche lines).
Different elemental compositions were identified after comparing the spectra, which
was recorded from various measurement locations. It was possible to identify a
single or several elements such as Ca, Ti, Mn, Zr, Fe, K, Na, Mg, Cr, Li, Pd, La, Cd,
Co, V and Cu, based on type of document, emission date, and evaluated spot. The
potentially good discriminators with unique elemental composition were identified,
e.g. a contour map of Poland printed with the use of optically variable ink.
This study shows the potential of LIBS and as effective and practical tool for
identification and comparative analysis of Polish personal documents. Some
advantages of this method were revealed giving a chance to consider it as an
alternative to analytical methods routinely used for the examination of such kind of
objects.
64
OS20
In-situ Raman characterization of minerals and
degradation mechanisms in cultural and geological heritage
in Spain: Burgos Cathedral and subterranean
environments
F. Rull1, F. Gázquez2, A. Sanz1, J. Medina1 and J.M. Calaforra3
1
Department of Condensed Matter Physics, Crystallography and Mineralogy, University of
Valladolid, Paseo de Belén, 7, 47011, Valladolid, Spain.
2
Department of Earth Sciences. University of Cambridge. Downing Street, Cambridge,
Cambridgeshire, CB2 3EQ, United Kingdom.
3
Water Resources and Environmental Geology Research Group, University of Almería,
Crta.Sacramento s/n, 04120 La Cañada de San Urbano, Almería, Spain
E-mail: rull@fmc.uva.es
Raman spectroscopy is a very powerful technique for in-situ and non-destructive
analysis of materials without any preparation. Here, we present some case studies in
which in-situ Raman spectroscopy has been utilized to obtain valuable information
about degradation processes affecting building materials, as well as mineralogical
characterization of unique speleothems and rock art pigments in some Spanish caves.
As an example, the degradation mechanism experienced by the 15th-century
limestone sculptures that decorate the retro-choir of Burgos Cathedral (N Spain) has
been studied in detail. A variety of secondary hydrated sulphate and nitrate minerals
has been detected by in-situ Raman spectroscopy on the limestone figures. These
results suggest that mechanical forces produced by mineral precipitation in the rock
pores lead to decay of the limestone sculptures.
Additionally, in-situ and non-destructive analyses were performed on unique
speleothems in El Soplao Cave (Cantabria, N Spain) and Wonders Cave (Aracena,
SW Spain). Unusual cave minerals were detected in El Soplao Cave, such as
hydromagnesite (Mg5(CO3)4(OH)2·4H2O), as well as ferromanganese oxides in the
black biogenic deposits recently discovered in this cave. In Wonders Cave, gypsum
(CaSO4·2H2O) has been identified for the first time, forming part of the oldest cave
material, which provides additional evidence of corrosion mechanisms occurred in
this cavity during its earlier genetic stages. Finally, we present preliminary in-situ
Raman analyses of several art rock paintings in the renowned “Polychrome Hall” of
Altamira Cave (Cantabria, N Spain). Hematite (Fe2O3) is the most abundant mineral,
which provides the characteristics ochre-reddish color to the Altamira’s bisons and
deers.
Portable Raman spectroscopy demonstrates to be an analytical technique compatible
with preservations of our cultural heritage, particularly in this last case, in which the
analysis did not required for physical contact between the Raman head and the
paintings. In summary, Raman spectroscopy arises as an alternative methodology to
the traditional sampling and materials gathering for the study of minerals and
degradation mechanisms affecting our cultural and geological heritage.
65
Parallel Session 7: Speciation Analysis/Metallomics
OP21
Development of a HILIC ESI MS method for lanthanides
speciation study
C. Bresson1, L. Beuvier1,2, A. Nonell1, V. Pichon2,3, F. Chartier4
1
CEA, DEN, DANS, DPC, SEARS, LANIE, Gif-sur-Yvette, FRANCE
2
Sorbonne Universités, UPMC, Paris, FRANCE
3
LSABM, UMR CBI 8231, ESPCI Paristech, PSL Research University, Paris, FRANCE
4
CEA, DEN, DANS, DPC, Gif-sur-Yvette, FRANCE
E-mail: carole.bresson@cea.fr
In the framework of French nuclear waste management researches, several liquidliquid extraction processes have been set up to selectively recover the remaining
long-lived radioelements such as minor actinides (americium, curium and
neptunium) and long-lived fission products (iodine, cesium…), after nuclear spent
fuel reprocessing devoted to uranium and plutonium recycling. Separation of
lanthanides from the other elements is also carried out throughout treatment
processes, since these elements are present in spent fuel solutions.
Speciation analysis of actinides (An) and lanthanides (Ln) at different key steps of
the processes is essential to assess their performances as well as to acquire
fundamental data, for a deeper understanding of separation mechanisms and the
associated phenomenological modelling.
In this context, the aim of this work is to develop a separation method by hydrophilic
interaction liquid chromatography (HILIC) coupled with electrospray ionization
mass spectrometry (ESI-MS), in order to separate, characterize and quantify LnEDTA/DTPA complexes representative of species found in aqueous back extraction
phases encountered in nuclear waste treatment processes. HILIC chromatography
offers outstanding potential to carry out such studies, since this technique is
particularly well-suited for the separation of hydrophilic polar compounds and the
organic rich mobile phases involved in this retention mode are compatible with ESI
MS ionization conditions [1].
In a first step, several polar stationary phases and mobile phase compositions were
investigated in order to achieve the better separation conditions of the lanthanides
complexes. The obtained results allowed providing parts of understanding to
separation mechanisms of the lanthanides complexes. A faster HPLC approach was
then undertaken, which is of prime importance in the nuclear field to reduce analysis
times, solvent consumption, waste production and analysts exposition. A
quantification method of Ln-EDTA and Ln-DTPA complexes by HILIC ESI-MS
was developed under these conditions. The detection and quantification limits or
linear dynamic range of the mass spectrometer response will be presented and
discussed. A perspective of this work is the implementation of this coupling in glove
box, in order to meet the requirements needed for radioactive samples analysis.
References
[1] P. Hemström, K. Irgum, Journal of Separation Science, 29, 1784 – 1821, (2006).
66
OP22
HCD fragmentation revealing elemental information in
metallomics studies
D. Esteban-Fernández1,2, A.H. El-Khatib1, Irene Moraleja3, M.M. GómezGómez3 and M.W. Linscheid2
1
BAM Federal Institute for Materials Research and Testing, Richard-Willstätter Str. 11, 12489,
Berlin, Germany
2
Department of Chemistry, Humboldt-Universitaet zu Berlin, Brook-Taylor Str. 2, 12489, Berlin,
Germany
3
Department of Analytical Chemistry, Universidad Complutense de Madrid, Avda. Complutense s/n,
28040, Madrid, Spain
E-mail: diego.esteban-fernandez@bam.de
During the last decade, the complementary use of molecular and elemental mass
spectrometry (MS) has been successfully applied to metallomics studies [1]. Taking
advantage of the outstanding quantitative properties of ICP-MS and the structural
information extracted using molecular MS techniques, important insights into metalbiomolecule interactions have been discovered. However, the difference in
sensitivity and specificity of both techniques and the need to correlate analyses using
instrumentation usually not simultaneously available in the same laboratory, hamper
the development and wide range application of such strategies.
The increasing advance in molecular MS fragmentation techniques allowed us to
investigate a novel strategy trying to integrate elemental and molecular analysis
through combining fragmentation techniques and collision energies in the same run.
In our work, electrospray ionization (ESI) and matrix-assisted laser
desorption/ionization (MALDI) sources combined with different mass analyzers and
fragmentation techniques have been tested for the detection of fragments revealing
elemental information. Multi-charged ions after ESI combined with higher energy
collisional dissociation (HCD) fragmentation at unusual high energies, has been
proved as the best configuration to obtain the so-called elemental reporter ions.
Different heteroatom-containing biomolecules have been used for the
characterization of this approach. Iodinated peptides, DOTA-lanthanide labeled
peptides and platinum containing biomolecules (from antitumoral Pt-based drugs
treatments), have been tested, among others. The strategy has worked for simple and
complex samples, small and big biomolecules as well as for different metals and
metalloids. The integration of such methodology in high throughput screening of
metal-containing species in biological samples or even its use in imaging
experiments have been proved and are potential applications of this approach.
Therefore, a new and valuable tool for metallomics might be emerging from the idea
of high energy dissociation in molecular MS techniques.
References
[1] C. G. Vogiatzis, G. A. Zachariadis, Analytica Chimica Acta, 819, 1-14 (2014).
67
OP23
Comparative study of various Cr(III)-ion imprinted
polymers for speciation analysis of chromium in
environmental samples by atomic absorption spectrometry
B. Leśniewska, L. Trzonkowska, B. Godlewska-Żyłkiewicz
University of Bialystok, Institute of Chemistry, 15-245 Białystok, Ciołkowskiego 1K, Poland
e-mail:blesniew@uwb.edu.pl.
The wide industrial application of chromium (in metallurgy, metal smelting,
electroplating, tanning, pigment manufacturing) leads to the contamination of soil,
sediments, surface and ground water. The speciation analysis of chromium in
environmental samples is of great importance as the biological activity of Cr(III) and
Cr(VI) species, their chemical behavior and toxic effects are dissimilar. Cr(III) is an
essential component of living organisms, having an important role in the metabolism
of glucose, lipids and proteins, whereas Cr(VI) is a potentially carcinogenic and
mutagenic agent. The key problems of chromium speciation analysis are associated
with low content of species, their transformation and strong interference derived
from a complex sample matrix. Therefore, the analytical methods used in such study
should combine selective isolation/separation of chromium species with
determination of species by sensitive detection technique. Recently, the ion
imprinted polymers (IIP) have been extensively used for separation and
preconcentration of trace metals by solid phase extraction (SPE) technique.
In this work various polymers with imprinted Cr(III) ions have been prepared
and characterized by microscopic and spectroscopic techniques. The studies of the
impact of various factors (imprinted templates and polymeric matrices) on the
polymerization process leading to receive suitable properties of polymers have been
performed. The polymers were synthesized using the following complexes of Cr(III):
Cr(III)-pyrrolidinedithiocarbamate,
Cr(III)-1,5-diphenylcarbazone,
Cr(III)-8hydroxyquinoline, Cr(III)-1,10-phenanthroline as template molecules, acrylamide,
methacrylic acid, and styrene as functional monomers, and ethylene glycol
dimethacrylate and divinylbenzene as cross-linking monomers. The parameters that
affect the retention and elution efficiency of Cr(III) on various polymers such as pH
of sample solution, kind, concentration and volume of eluent, flow rates of sample
and eluent were optimized in dynamic mode and compared. The ability of IIP to
separate Cr(III) from Cr(VI) ions, selectivity to other ions, sorption capacity and
mechanical stability were also compared. The obtained results let to formulate more
general rules on the impact of such parameters on analytical performance of
materials. The polymers were tested as solid sorbents for selective separation of
Cr(III) species from environmental samples before their determination by atomic
absorption spectrometric techniques.
The authors kindly acknowledge the financial support from the Polish National
Science Centre (DEC-2012/07/B/ST4/01581).
68
OP24
Efficient post HPLC column generation of arsanes for
speciation analysis
K. Marschner1,2, S. Musil1, P. Rychlovský2 and J. Dědina1
1
2
E-mail: karel.marschner@biomed.cas.cz
Most methods for arsenic speciation analysis are based on HPLC separation [1]. The
most toxic arsenic species could be converted to the corresponding hydride by the
reaction with tetrahydroborate (THB). Therefore, detection limits of these species
could be improved by inserting a hydride generation (HG) step between a HPLC
column and a detector. The advantage of the HG step lies in the separation of analyte
from the liquid matrix and much higher introduction efficiency (up to 100%) to the
detector in comparison to nebulization techniques. 100% efficiency of HG from all
As species is desirable. However, this is hardly achieved without pre-reduction of
arsenate (AsV), monomethyl arsenate (MMAV) and dimethyl arsenate (DMAV) to
their trivalent forms. The pre-reduction requires additional sample preparation which
can lead to contamination of a sample or, if it is performed on-line, more
complicated generators must be used [2].
The aim of this work was to (i) develop an efficient HG from arsenite (iAs III), iAsV,
MMAV and DMAV in a flow injection mode using only HCl medium and THB, (ii)
connect such a generator to HPLC and (iii) apply the developed methods to real
(human urine) samples. The in-house designed atomic fluorescence spectrometer was
used as a detector with a miniature diffusion flame atomizer [3].
Firstly, the optimal conditions of HG from all investigated As species (concentration
of HCl, THB and reaction time which is proportional to volume of the reaction coil)
were investigated. The HG efficiencies were compared to that from iAsIII that is
easily generated in a broad range of pH. When the 2.5% (m/v) THB and 2 mol l–1
HCl was used and the reaction coil was extended up to 10.4 ml, generation
efficiencies of 98 ± 3%, 100 ± 3% and 98 ± 3% were reached for iAsV, MMAV and
DMAV, respectively. Subsequently, the hydride generator was connected to the
HPLC when the flow injection valve was replaced by the outlet from the column.
This postcolumn HG was tested for the analysis of human urine samples. Firstly, the
ion pair chromatography [4] was tested. However, it was found to work well only for
aqueous standards (Fig. 1a) but not for real sample (human urine, Fig. 1b). The anion
exchange chromatography [5], was found as a better solution for urine samples (Fig.
1c and 1d). Limits of detection were 40, 97, 57 and 55 pg ml–1 for iAsIII, iAsV,
MMAV and DMAV, respectively. The same HG efficiencies enabled possibility of a
single species calibration which means that the calibration graph for quantification of
all arsenic species can be constructed only from DMAV that elutes in a front part of
the chromatogram. As consequence the analysis time can be substantially shortened.
69
Parallel Session 8: Material Sciences
OP25
Mn-doped ZnS QDs as dual-mode labels for biomarkers
detection
M. García-Cortés, J. Ruiz Encinar, J.M. Costa-Fernández, A. Sanz-Medel
Department of Physical and Analytical Chemistry (University of Oviedo), Julián Clavería 8, 33006,
Oviedo (Spain)
E-mail: garciacormarta@uniovi.es
Detection of “early alarm” biomarkers is very important in clinical cancer studies
since prompt diagnosis of cancer, previous apparition of malignant tumors, allows a
much better prognostic. An extremely sensitive detection is required for “early
alarm” biomarkers quantification, moreover localization of these biomarkers in
biological samples is very important.
In order to reach the required very low detection limits, deposition of gold and silver
onto gold nanoparticles and clusters surface has been proposed as amplification
strategy of the analytical signal [1]. Although gold nanoparticles are very attractive
for bioanalytical applications, they are not fluorescent and luminescent signal is
especially suited for optical imaging studies without the need of perform a biopsy for
analytical detection. Metal nanoclusters have luminescent properties but fluorescent
emission is affected by autofluorescence of biological media that produces a lack of
sensitivity and selectivity. In this sense, phosphorescent QDs stands out for having
very advantageous properties such as large separation between absorption and
emission wavelength and long emission lifetime that allows time-gated detection in
order to easily avoid autofluorescence of biological media.
In this context, a Mn-doped ZnS QDs-based immunoassay is presented for the
detection of Prostate Specific Antigen (PSA) as analyte model in biological samples.
Catalytic activity of QDs was studied for first time in order to use them for metal
amplification strategies. Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
has been used as detection technique of the amplified labels due to its extremely
sensitivity for metals, minimum matrix effects and multielemental and isotopic
detection [2]. Detection limit with gold amplification improved several orders of
magnitude the obtained with Mn and Zn detection. In the present study, it has been
demonstrated that Mn-doped ZnS QDs are highly valuable as dual-mode labels since
phosphorescent and highly sensitive elemental detection are carried with the same
immunological strategy.
References
[1] C. S. Thaxton, R. Elghanian, A. D. Thomas, S. I. Stoeva, J.-S. Lee, N. D. Smith, A. J. Schaeffer,
H. Klocker, W. Horninger, G. Bartsch, and C. A Mirkin, Proc. Natl. Acad. Sci. U.S.A., 106, 18437–42
(2009).
[2] A. Sanz-Medel, M. Montes-Bayón, J. Bettmer, M. Luisa Fernández-Sanchez, and J. Ruiz Encinar,
Trends Anal. Chem., 40, 52–63 (2012).
Acknowledgements
M. García-Cortés acknowledges the Ph.D. grant (BP13-110) from Gobierno del Principado de Asturias (Spain).
70
OP26
Raman spectroscopy studies on molecular interactions
in thermo-responsible polymer-water-naproxen systems
M.N. Olejniczak1, M. Kozanecki1,
1
Lodz University of Technology, Faculty of Chemistry, Department of Molecular Physics,
Zeromskiego 116, 90-924 Lodz, Poland
E-mail: magdalena.olejniczak@dokt.p.lodz.pl
High content of water as well as good mechanical properties make hydrogels
good materials to medical and cosmetic applications. Thermo-responsive hydrogels
is a special group of hydrogels, in which even small change of temperature causes
imbalance between hydrophilic and hydrophobic interactions in amphiphilic polymer
– water system. Therefore, phase separation occurs and water is pushed out. This
phenomenon is called Volume Phase Transition and VPT temperature (TVPT)
depends on many factors like presence of additional substances [1,2].
Except water, the hydrogels are able to store biologically active agent (drugs,
growth factors etc.). To use thermo-responsive hydrogels as drug delivery system
knowledge of the molecular interactions between polymer, water and drug is
indispensable.
The main area of presented research includes Raman spectroscopy studies on
two and three-component systems based on poly(2-(2-methoxyethoxy)ethyl
methacrylate) (PMEO2MA) hydrogels containing naproxen sodium salt (one of nonsteroidal anti-inflammatory drugs (NSAIDs).
Results of Raman studies showed that in two-component systems (polymerwater) an amount of water taking part in H-bonds with particular hydrophilic centers
depends on the polymer architecture In three-component systems (polymer-waterdrug), naproxen presence has a strong impact on redistribution of intermolecular
interactions. It appears that water-water interactions and water supramolecular
structure play a key role in understanding VPT phenomenon on molecular level.
Acknowledges
The authors are deeply grateful to prof. K. Matyjaszewski, prof. J. M. Rosiak, dr J. A. Yoon and dr S.
Kadlubowski for delivery of the hydrogel samples. This work was financially supported by the
projects 2013/09/B/ST4/03010 (Polish National Science Centre) and Young Scientists’ Fund at the
Faculty of Chemistry, Lodz University of Technology.
References
[1] H. Inomata, S. Goto, K. Otake, S. Saito, Langmuir 8, 687 (1992)
[2] M.N. Olejniczak, K. Piechocki, M. Kozanecki, K. Koynov, A. Adamus, R. Wach, - will be
submitted soon.
71
OP27
Asymmetric flow field-flow fractionation coupled to
elemental mass spectrometry: a powerful tool for study of
QDs bioconjugation to antibodies.
Mario Menéndez-Miranda, Jorge Ruiz Encinar, José M. Costa-Fernández and
Alfredo Sanz-Medel.
Department of Physical and Analytical Chemistry, University of Oviedo. Avd. Julián Clavería 8,
33006, Oviedo, Spain.
E-mail: mariomemi@gmail.com
Bioanalysis often requires labelling of biochemical compounds for their detection.
Although some mass spectrometry methodologies could offer a label-less method of
detection, however, they are expensive and cannot be easily applied for fast
screening tests or in-live studies. Alternatively, other widely used bioanalytical
techniques, such as those based on detection of isotopes, enzyme-linked
chromophore/fluorophores, chemiluminescence and bioluminescence are among the
methods that could require appropriate analyte labelling.
In this context, functional luminescent quantum dots (QDs), as a new generation of
high-value optical labels, have been also applied for molecular detection [1]. The
great potential of such novel optical labels has paved the way to the development of
new biomolecule assays with unprecedented analytical performance characteristics,
related to sensitivity, multiplexing capability, sample throughput, cost effectiveness
and ease of use.
It should be considered that the success or failure in the use of the QDs in these
applications is largely determined by the ability to bioconjugate such nanoparticles to
specific recognition elements, such as aptamers or antibodies, a mandatory previous
step for the successful development of new bioassay and bioanalytical applications
based on biolabeling and bioimaging. Actually, despite recent progress in the use of
QDs for bioanalytical applications, there is still an urgent need for effective
procedures for QDs bioconjugates purification and characterization, in order to
further facilitate reliable quantitative bioassays [2].
In this communication, a novel concept based on the combination of asymmetric
field flow fractionation coupled on-line to inductively coupled plasma-mass
spectroscopy (ICP-MS) detection is proposed as a diagnostic tool to quantify
bioconjugation efficiency and estimate the stoichiometry of water-solubilized
CdSe/ZnS QDs bioconjugated to antibodies.
Acknowledgements
M. Menéndez Miranda acknowledges the Ph.D. grant (BP12-046) from Principado
de Asturias (Spain).
72
OP28
Cross-linked acrylic hydrogels research using ESDR
A.P. Nechiporenko, M.V. Uspenskaya, K.V. Volkova, V.V. Motovilov, R.O.
Olekhnovich
ITMO University, 49 Kronverksky Pr., St. Petersburg, 197101, Russia
E-mail: r.o.olekhnovich@mail.ru
Polymers and hydrogels of poly[(acrylic asid)-co-acrylamide]/N,N’-methylene-bisacrylamide were prepared. The acid-base and optical characteristics of powdered
cross-linked copolymer surfaces were investigated. Their structure and properties
were studied by Fourier transform infrared and diffuse reflectance spectroscopies, pH
method.
Studies of obtained acrylic copolymers by UV-spectroscopy were caused by removal
of a ban on orbital symmetry for n*- transition and bathochromic shift on 30-40
nanometers of both strips (* и n*) electronic transitions of carbonyl group
as a result of formation of a cross-linked polymer matrix. The increase in
concentration of acrylamide in copolymer raises bathochromic effect. It was also
shown that acidity increases and degree of swelling of samples decreases. The
highest acidity and low degree of swelling had 100% of polyacrylamide.
Addition of the cross-linked agent – N,N’-methylene-bis-acrylamide, in structure of
polyacrylamide not considerably influences on the studied optical and acid-base
characteristics of the received polymer materials. However, in the absence of the
cross-linked agent in structure of sodium polyacrylic acid, results in essential
difference in optical properties from one of the cross-linked polymer – hydrogel.
73
OP29
Dielectric barrier discharge hydride atomizer for AAS:
a toy or a valuable tool?
J. Kratzer1, O. Duben1,2, P. Novák1,2, P. Zurynková1,2, M. Svoboda1,
V. Červený2 and J. Dědina1
1
2
Institute of Analytical Chemistry of the ASCR, v.v.i., Veveří 97, 602 00 Brno, Czech Republic
E-mail: jkratzer@biomed.cas.cz
Plasma devices based on dielectric barrier discharges (DBD) [1] have been proven as
useful tools in analytical spectrometry since they may serve as a source of free
atoms, excited species as well as ions. In the field of trace element analysis with
atomic absorption (AAS) detectors, DBD devices are used almost exclusively to
determine hydride forming elements. The fundamental drawback of all the present
DBD works is, with exception of our study focused on Bi [2], that they include only
optimization of the basic DBD parameters without any comparison of the DBD-AAS
atomizer to any reference atomizer employing the same detector. Moreover, no effort
is made to quantify atomization efficiency and understand processes in the DBD.
Atomization of As, Se, Sb and Bi hydrides in a DBD atomizer was individually
optimized in terms of DBD power, discharge gas nature and its flow rate. Analytical
figures of merit such as detection limits (LODs), resistance to interference of other
hydride forming elements, long-term signal stability and piece-to-piece
reproducibility have been investigated and compared to those reached in an
externally heated quartz tube atomizer (QTA). LODs in QTA were comparable for
all hydrides tested reaching ca 0.1 ng ml-1 level, whereas more pronounced
differences were observed in DBD. The best LOD in DBD was reached for As (0.14
ng ml-1) while the worst one was 8-times higher (1.1 ng ml-1 Bi) indicating
differences in atomization efficiency of individual hydrides. Resistance of DBD to
interferences of other hydride forming elements is comparable or even slightly better
than that of QTA. Applicability of the DBD atomizers in analytical routine will be
shown on determination of selected metals in certified reference materials.
Mechanisms of hydride atomization in the DBD plasma and the fate of free analyte
atoms will be outlined including the key-role of hydrogen in the hydride atomization
process. The advantages and disadvantages of the DBD will be discussed.
This work was supported by the Academy of Sciences of the Czech Republic (project
of international cooperation no. M200311202), Czech Science Foundation (project
no. P206/14-23532S), Institute of Analytical Chemistry of the AS CR, v. v. i.
(Institutional Research Plan RVO: 68081715) and Charles University in Prague
(project UNCE 204025/2012).
References
[1] C.Meyer, S.Müller, E.L.Gurevich, J.Franzke, Analyst, 136, 2427-2440 (2011).
[2] J.Kratzer, J.Boušek, R.E.Sturgeon, Z.Mester, J.Dědina, Anal. Chem., 86, 9620-9625 (2014).
74
OP30
Isotope Dilution Analysis for quantitative LA-ICP-MS
bioimaging. Study of the different nephrotoxic behaviour of
cisplatin, carboplatin and oxaliplatin
I. Moraleja1, D. Esteban-Fernández2, M.L. Mena1, B. Humanes3, B.
Neumann4, A. Lázaro3, A. Tejedor3, N. Jakubowski2, M.M. GómezGómez1
1
Department of Analytical Chemistry, Faculty of Chemistry, Universidad Complutense de Madrid, Avda.
Complutense s/n, 28040 Madrid, Spain, irenemoraleja@ucm.es
2
BAM Federal Institute for Materials Research and Testing, Richard-Villstätter-Str. 11, 12489 Berlin,
Germany
3
Renal Physiopathology Laboratory, Dept. of Nephrology, Hospital General Universitario Gregorio Marañón,
28007 Madrid, Spain
4
Proteome Factory AG, Magnusstrasse 11, 12489 Berlin, Germany
Cisplatin, carboplatin and oxaliplatin are currently used in chemotherapeutic
treatments. However, they differ in their efficacy and side effects, such as
nephrotoxicity. The study of the different distribution of the aforementioned drugs
along the kidney may help to understand their different nephrotoxic behaviour. Laser
ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) bioimaging
has shown high potential to monitor the distribution of trace elements within tissue
sections with high spatial resolution [1]. Unfortunately, results obtained by LA-ICPMS are subjected to several variations concerning the sample matrix and
instrumental drifts. Therefore, an internal standardisation method for comparison of
tissue images is required [2,3]. For quantification purposes, several approaches were
described in the literature such as the use of CRMs or matrix matched standards [4].
The use of Isotope Dilution (ID) for quantification by LA-ICP-MS has been also
described, being mainly useful for bulk analysis but not feasible for spatial
measurements so far.
In this work, an inkjet printing based method for internal standardisation of the LAICP-MS signal has been tested. Iridium containing ink was prepared and printed onto
the surface of fresh kidney tissues for comparison of Pt distributions after treatments
with the three Pt-drugs. Alternatively, quantitative kidney bioimages obtained by IDLA-ICP-MS were produced by homogenous deposition on the sample surface of
isotopically enriched platinum by inkjet printing. The results showed that the
different distribution patterns and accumulation levels observed for the three drugs
may be related with their different nephrotoxicity. The acquired tissue images
revealed that cisplatin and carboplatin treatments led to different Pt distribution
compared to oxaliplatin, the latter having never been described as nephrotoxic drug.
Acknowledgements: MINECO Grant Number CTQ 2011-24585. UCM Research
Group nº 910382 “Trazas y Especiación”. I. Moraleja also acknowledges UCM for a
predoctoral fellowship.
References
[1] E. Moreno-Gordaliza, C. Giesen, A. Lázaro, D. Esteban-Fernández, B. Humanes, B. Cañas, U.
Panne, A. Tejedor, N. Jakubowski, M.M. Gómez-Gómez, Anal. Chem., 83, 7933–7940 (2011).
[2] I. Konz, B. Fernández, M. L. Fernández, R. Pereiro, H. González, L. Álvarez, M. Coca-Prados, A.
Sanz-Medel, Anal. Bioanal. Chem., 405, 3091–3096 (2013).
[3] S. Hoesl, B. Neumann, S. Techritz, M.W. Linscheid, F. Theuring, C. Scheler, N. Jakubowski, L.J.
Mueller, J. Anal. At. Spectrom., 450, 1282–1291 (2014).
[4] D. Hare, C. Austin, P. Doble, Analyst, 137, 1527-1537 (2012).
75
OP31
Asymmetric charge transfer excitation involving molecular
ions (H2+, O2+ or N2+) in analytical glow discharges
S. Mushtaq1, E. B.M. Steers1, V. Hoffmann2, J. C. Pickering3, and Z. Weiss4
1
London Metropolitan University, 166-220 Holloway Road, London, N7 8DB, UK
2
IFW Dresden, Helmholtzstraße 20, 01069 Dresden, Germany
3
Imperial College London, Prince Consort Road, London, SW7 2AZ, UK
4
LECO Instrumente Plzeň, spol. s r. o., Plaská 66, 323 25 Plzeň, Czech Republic
E-mail: s.mushtaq@londonmet.ac.uk
Glow discharge optical emission spectroscopy (GD-OES) and mass spectrometry
(GD-MS) are powerful analytical techniques for trace elemental analysis of bulk
materials (conducting and also insulating) and compositional depth analysis of
layered materials and ultra-thin films. Asymmetric charge transfer (ACT), also
known as the Duffendach reaction [1], is one of the most crucial mechanisms for
producing excited ions of the elements analysed in an analytical GD:
Mo + I+ → M+* + Io + ΔE, where M is the analyte atom and I = He, Ne, Ar or Kr.
There have been comprehensive studies regarding ACT excitation for a variety of
matrix elements in Grimm-type glow discharges, (Fe, Cu, Ti, Al, Bi, Pb, Mn etc.)
with argon as the plasma gas (Ar-ACT) [e.g. 2,3] and also with other plasma gases
(He, Ne, or Kr) [e.g. 4]. The Steers GD research group reported the first examples of
ACT by atoms of small amounts of added gases (hydrogen or oxygen) in argon or
neon GD (H-ACT: 13.60 eV or O-ACT: 13.61 eV); this is a vital selective excitation
process for certain analyte ionic spectral lines [5,6]. O-ACT was more obvious in a
neon plasma than in an argon plasma, and that, in the case of neon, ACT was also
produced by the metastable O+ 2D state at 16.93 eV.
Mo + X+ → M+* + Xo + ΔE
(X = H or O)
+
+
Mo + Om → M * + Oo + ΔE
Nevertheless, so far there is little information on ACT processes involving molecular
ions (X2+) in analytical GD. We report here the latest developments regarding ACT
excitation involving the molecular ions (X2+ = H2+, O2+ or N2+) of added gases in a
Grimm-type GD in neon using a copper sample.
Mo + X2+ → M+* + X2 + ΔE
(X2+ = H2+, O2+, or N2+)
Detailed examples of these processes will be presented.
References
[1] O. S. Duffendach and J. G. Black, Phys. Rev., 34, 35-43 (1929).
[2] E.B.M. Steers & R.J. Fielding, J. Anal. At. Spectrom., 2, 239-244 (1987)
[3] E.B.M. Steers & A.P. Thorne, J. Anal. At. Spectrom., 8, 309-315 (1993)
[4] E.B.M. Steers, J. Anal. At. Spectrom,, 12, 1033-1040 (1997)
[5] E. B.M. Steers, P. Smid, and Z. Weiss, Spectrochim. Acta, Part B, 61, 414-420 (2006).
[6] S. Mushtaq, E. B.M. Steers, J. C. Pickering, and V. Weinstein, J. Anal. At. Spectrom., 27, 12641273 (2012).
76
OP32
SEM-EDX, ICP-MS analysis and δ34S isotopic signature of
jarosite from the Jaroso Mars analog (SE Spain)
J. Martínez-Frías1, A. Delgado2, F. Rull3, M.P. Martín-Redondo4, C. MenorSalván5, and J. Medina3
1
CSIC-UCM, Madrid (Spain),2 CSIC-UGR, Granada (Spain),3 UVA, Valladolid
(Spain), 4 Denga,S.A., Madrid (Spain),5 Georgia Institute of Technology, Atlanta,
(GA, USA)
E-mail: j.m.frias@igeo.ucm-csic.es
Early Mars environments show evidence of a significant diversity of geological
processes and features, mainly involving volcanic settings and water. Jarosite is a
hydrated sulfate of iron and potassium (KFe3 (SO4)2(OH)6), which was identified,
in 2004, at Mars’ Meridiani Planum by the Opportunity rover [1]. Further studies
(including recent analyses made by the NASA MSL (Curiosity) rover), have also
confirmed its occurrence at other Martian areas [2]. Jarosite was firstly identified on
Earth in 1852 in the Jaroso ravine in the Sierra Almagrera (SE Spain), which is the
World Type Locality. The Jaroso Hydrothermal System [3] is an extremely
interesting late-volcanic episode including mineralizing hydrothermal processes.
Previous works had already suggested the significance of this area of SE Spain as a
relevant planetary model [4]. The detection of jarosite on Mars reinforced its
scientific interest as a Mars analog. Since 2004, numerous geological and
multianalytical (Raman, XRD, LIPS, FTIR) campaigns were carried out at the
Jaroso. Most of them were organized in the framework of the future ExoMars
mission (2018) in which we are participating with the development of a Raman Laser
Spectrometer (RLS) [5]. The RLS will be hosted in a rover which will analyze the
Martian minerals, rocks and geological outcrops.
This contribution provides: a) the detection and SEM-EDX analysis of first unusual
(extremely scarce) euhedral jarosite crystals from this Mars analog. Jarosite usually
occurs as efflorescences, earthy masses and films or crusts. The tiny jarosite crystals
(around 200 μm), show a hexagonal outline, resulting from combinations of
rhombohedra; occasionally tabular on {0001}, forming hexagonal thick platelets.
Rarely, the negative rhombohedron {01.2} faces are less developed, giving a
pseudooctahedral habit; b) a detailed geochemical characterization by ICP-MS of the
jarosite efflorescences and crusts, and c) the determination of the d34S isotopic
signature of jarosites, in comparison with other sulfates of the area, and also
considering different geological environments and origin. These results will help to
further understanding of similar Martian processes and paleoenvironments.
References
[1] Klingelhöfer et al. Science 306: 1740–1745 (2004).
[2] Cavanagh et al. 46th LPSC, 2735.pdf (2015).
[3] Martínez-Frías et al. Earth Planets Space, 56, v–viii (2004).
[4] Martínez-Frías et al. 2nd Astrobiology Minisymposium, CAB (CSIC/INTA), associated to NASA
Astrobiology Institute, Madrid, Spain (2000).
[5] Rull & Martínez-Frías Spectroscopy Europe 18-1: 18-21 (2006)..
77
OP33
Heavy metals in plastic, recycling and environmental
aspects
A. van Oyen1, J. A. van Franeker2 , U. Oppermann3, M. Egelkraut-Holtus3
1
Research, Harderhook 20, D-1432 Bocholt, CARAT GmbH, Germany
Research, PO Box 167, 1790 AD Den Burg Texel, IMARES, Netherlands
3
Spectroscopy, Albert- Hahn- Str. 6-10, D-47269 Duisburg, Shimadzu Europa GmbH, Germany
2
E-mail: Albert.van.Oyen@Carat-lab.vom
Plastic has become an integral part of our daily life and it’s use is increasing. In 2013
the worldwide production has reached an all- time high of about 300 million tons
(MT). Single use-packaging account for almost 40%, of the total production. In
Europe the produced volume is about 57 MT (demand 46 MT). In 2012, 25,2 million
tons of post-consumer plastics ended up in the waste upstream. Of this 26% was
recycled while 38% still landed on the landfill [1].
In the past the Life Cycle Assessment (LCA) was linear, after usage it became waste
and ended meanly as landfill. Under consumer and political pressure the EU
presented a green paper in 2013[2] indicating that it has to become a circular
economy. In these economical tough times recycling could create about 160.000 jobs
if the recycling rate goes up to 70% in 2020. But is recycling of this single use
material easy? Modern packaging materials consists of many layers (up to 7 or
more). Each layer has special properties but by physical recycling these properties
are lost. Recyclates are becoming a complex mixture.
Another complex problem is presented in plastics in durable applications, like cars,
electronics, crates and so on. These also have to be recycled but during their
functional life new regulations have been introduced. For instance RoHS (2011/65)
restricts the maximum concentration of toxic heavy metals in electronic applications
(e.g, in end- or consumer products the toxic metal cadmium must not exceed 100
ppm). In the EU several regulations have been developed over the past decades, for
instance REACh. The raw materials of the durable recyclates could be contaminated
with the inheritance of the past, toxic metals are diluted by physical recycling. Is
chemical recycling the future?
Nowadays plastic is found littering the environment in large quantities, especially in
our seas and oceans. The ingestions of plastic by seabirds has been monitored in
stomachs of beached fulmars for more than 30 years. [3]. A reduction of industrial
pellets has been observed but in consumer plastic debris no data exists about the
toxic load of plastic ingested by wildlife. First investigations prove that heavy metals
are present in the plastic fragments.
References
[1] Plastics Europe Web site;
http://issuu.com/plasticseuropeebook/docs/final_plastics_the_facts_2014_19122
78
OP34
Combination of cascade impactor sampling and totalreflection X-ray fluorescence for elemental analysis of
airborne particulate matter
J. Osán1, Á. Farkas1, F. Gergely1, E. Börcsök1, L. Bakos2, S. Török1
1
Hungarian Academy of Sciences Centre for Energy Research, P.O. Box 49, H-1525 Budapest,
Hungary
2
Hungarian Welding Society, Budapest, Hungary
E-mail: janos.osan@energia.mta.hu
In order to have a better chemical characterization of atmospheric particulate matter,
determination of the size distribution of elemental concentrations is necessary which
is characteristic to the aerosol sources. The most difficult task is the sampling from
submicron particles that are the most harmful to human health and an analytical
technique capable of determining trace concentrations from sample amounts of less
than a microgram. Combination of non-destructive elemental analysis by means of
total-reflection X-ray fluorescence (TXRF) and harmonized cascade impactor
sampling was developed covering a diameter range of the impactor below 100 nm.
Aerosols composed of CuSO4 and KMnO4 were generated in order to have
information on the collection efficiency at different stages of the cascade impactor.
The size distribution was checked by an optical aerosol spectrometer (200 nm – 10
µm range) and a scanning mobility particle sizer (SMPS, 10–500 nm range) in
parallel to cascade impactor sampling on Si wafers. In addition to measurements,
Computational Fluid Dynamics (CFD) methods have been applied to characterize the
airflow field within the impactor and to compute the collection efficiencies of the
plates. The aerosol-loaded Si wafers were measured using TXRF, calibrated with two
types of standards imitating deposited microparticles, (i) Cr pads prepared using
photolithography and (ii) series of droplet residues prepared using a nanoliter
injector.
The mass size distribution of test aerosols was obtained from the combined dataset of
optical aerosol spectrometer and SMPS results. It was compared to size distribution
of elemental masses of Cu and S as well as K and Mn obtained by TXRF analysis of
the particles deposited on the impactor stages, yielding a good agreement. The CFD
calculation of the collection efficiency model resulted in values close to the expected
ones. The combination of TXRF and cascade impactor sampling on Si wafers was
applied to study the size distribution of elemental concentrations in ambient aerosol
samples in Budapest close to traffic and combustion related sources. The maximum
concentration of elements related to high-temperature processes (e.g. K – biomass
combustion, Zn – traffic) was observed in the 180–300 nm fraction. Based on the
reliable results for atmospheric particulate matter, the method was applied to study
workplace air quality affected by welding fumes. The size distribution of thorium
concentrations in aerosols collected during tungsten inert gas welding using thoriated
electrodes was found to be in agreement with literature results based on 232Th activity
measurements on samples collected with cascade impactors.
79
Parallel Session 11: Molecular Spectrometry
OP35
Spectral Study of Specific Interactions Between
Zwitterionic Compounds and Protic Solvents
Babusca Daniela, Cezarina Morosanu, Dana Ortansa Dorohoi*
Alexandru Ioan Cuza University, Faculty of Physics, Carol I Bvd., RO- 700506, Iasi, Romania.
*Corresponding author: e-mail: ddorohoi@uaic.ro
The zwitterionic compounds, like ylids, interact by cuasichemical forces with
protic solvents [1,2]. As spectrally active molecules, the zwitterionic compounds
have visible electronic absorption bands very sensitive to the solvent nature. In protic
solvents, when spectrally active molecules are passed from gaseuos phase to
solutions, the spectral shifts relative to gaseous phase are higher compared to those
recorded in aprotic solvents. The suplementary shifts of the visible absorption band
in protic solvents are due to the specific interactions (by hydrogen bonds) between
the –OH groups of protic solvents and the hydrogen bond acceptor (HBA)
substituents of zwitterionic compounds. The total energy corresponding to specific
interactions was estimated by the difference between the wavenumbers measured in
the zwitterionic compound spectra recorded in two solvents (one protic and one
aprotic) having almost the same values of macroscopic parameters n and ε [3].
Using ternary solutions of spectrally active molecules achieved in pairs of solvents
(one protic and one aprotic ) the difference between the binary energy in pairs
achieved between zwitterionic compound and one protic or one aprotic solvent are
determined. This study is important because permites us to determine the energy of
specific interactions between one zwitterionic molecule and one protic solvent
molecule
Keywords: zwitterionic compounds, spectrally active molecule, visible elctronic
absorption spectra, specific interactions, protic and aprotic solvents,
References
[1] G. Gheorghieş, L. V. Gheorghieş, D. O. Dorohoi, J. of Mol. Struct., 887 (2008) 122-127
[2] V. Cloşcă, L. M. Ivan and D. O. Dorohoi, Spectrochimica Acta Part A, Molecular and
Biomolecular Spectroscopy, 22 (2014) 671-675.
[3] D. O. Dorohoi, D. G. Dimitriu, M. Dimitriu and V. Cloşcă, J. of Mol. Struct., 1044 (2013)
78-86.
80
OP36
Interaction of a new sandwich type phthalocyanine with
DNA: A potential anticancer agent
E. Bağda1, E. Yabaş2 and E. Bağda3
1
Cumhuriyet University, Faculty of Pharmacy, Department of Analytic Chemistry, Sivas, Turkey
2
Cumhuriyet University, Faculty of Science, Department of Chemistry, Sivas, Turkey
3
Cumhuriyet University, Faculty of Science, Department of Molecular Biology and Genetic, Sivas,
Turkey
E-mail: esraer@cumhuriyet.edu.tr
DNA is an important target for anticancer chemotherapeutics owing to its significant
role in replication and transcription [1]. In the treatment of cancer developments of
small molecules that interact with DNA via different type of mechanism, eg.
intercalation, minor or major groove binding are important due to their potential
usage as anticancer drugs.
Compounds with bearing heteroatoms are interact with DNA by generally forming
strong hydrogen bonding with nucleic acids [2]. Owing to changeable peripheral
substituents and central metal ions [2], designing a phthalocyanine for targeting
anticancer treatment is possible.
In the present study, a new sandwich type phthalocyanine as potential anticancer
drug, was synthesized. For the characterization of the molecule UV-vis, IR and ESR
spectroscopy, NMR, MALDI-TOF mass analysis were conducted.
In the second part of the study, the interaction of sandwich type phthalocyanine with
DNA was investigated. The binding mechanism was clarified by UV-vis spectral
techniques, fluorometric measurements, gel electrophoresis and viscosity
measurements.
References
[1] C. Uslan, B. Ş. Sesalan, Inorganica Chemica Acta, 394, 353-362 (2013).
[2] Y. Özkay, İ. Işıkdağ, Z. İncesu, G. Akalın, European Journal of Medicinal Chemistry, 45, 33203328 (2010).
81
OP37
Analysis of water structure by Raman spectroscopy
P. Filipczak and M. Kozanecki
1
Department of Molecular Physics, Lodz University of Technology,
Zeromskiego 116 90-924 Lodz, Poland
E-mail: paulina.filipczak@dokt.p.lodz.pl
Water is the most common compound all over the world and a vital part of every
living organism. Despite of being so abundant, water has still remained as a not
entirely known substance [1]. There are many models of water structure in liquid
phase [2], generally grouped into two types: models with a continuum of geometric
and energetic states (assuming tetrahedral coordination of water molecules)
and models of water as a mixture of discrete species (water clusters). It is difficult
to choose between them, because the spatial network of hydrogen bonds has features
of both continuous and discrete models [3]. Beside differences, all models assume
“flexibility” of water structure in liquid phase. Simultaneous breaking and formation
of hydrogen bonds play a crucial role in explanation of many anomalous behaviors
in water.
Raman spectroscopy is the most common technique used to investigate the water
structure and intermolecular interactions in water systems. Raman spectrum of water
contains three main components: broad OH stretching vibration band in range:
3000-3800 cm-1; bending band, corresponding to the vibrations of the H-O-H angle
in liquid water, observed around 1645 cm-1 and acoustic modes in low-frequency part
of spectrum below 300 cm-1 assigned to intermonomer vibrations of water molecules.
Straight interpretation of Raman spectrum of liquid water and its deconvolution has
been still a subject of discussions.
This work is focused on an influence of two factors on water structure
and vibrational dynamics: temperature and presence of heavy water (D 2O). Pure
water, heavy water and their mixtures were measured in temperature range:
5 – 80 °C. The most significant changes in Raman spectrum of these samples
are observed in OH stretching vibration region. The comparison of these changes
and subtle differences in low frequency region will be discussed.
References
[1] Chaplin M.F., Biophysical Chemistry, 83, 211-221 (1999).
[2] Eisenberg D., Kauzmann W., The structure and properties of water. Oxford University Press,
London (1969).
[3] Chumaevskii N.A., Rodzinkova M.N., Journal of Molecular Liquids, 109, 2433-2441 (2011).
82
Parallel Session 12: Biological Applications
OP38
Cobalt(II) complexation with small biomolecules in dilute
aqueous solutions as studied by emission (57Co) Mössbauer
spectroscopy
A.A. Kamnev1, L.A. Kulikov2, A.V. Tugarova1, Yu.D. Perfiliev2
1
Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and
Microorganisms, Russian Academy of Sciences, 410049, Saratov, Russia
2
Laboratory of Nuclear Chemistry Techniques, Faculty of Chemistry, M.V. Lomonosov Moscow
State University, 119991, Moscow, Russia
E-mail: a.a.kamnev@mail.ru; aakamnev@ibppm.sgu.ru
In the emission (57Co) variant of Mössbauer spectroscopy (EMS), the 57Co
radionuclide (with a half-life of 9 months) is used that undergoes a nuclear decay
57
Co→57Fe via electron capture followed by the emission of a γ-quantum, the energy
of which is modified by the chemical state and the close coordination environment of
the parent 57Co atom. The γ-quanta are then resonantly absorbed in a standard 57Fecontaining absorber with the help of the Doppler effect (vibrating it within ca. ±10
mm/s along the axis 57Co source (which is the sample in EMS) – 57Fe-containing
absorber; ±1 mm/s corresponds to ±48.1 neV). This very narrow energy interval is
sufficient to detect any possible instances of γ-resonance, and accumulation of data
gives an emission Mössbauer (nuclear γ-resonance) spectrum (for a review, see [1]).
While EMS has been used largely in materials science and nuclear chemistry, its
high sensitivity can also be of great advantage in revealing fine structural features
and for speciation analysis of biological complexes, whenever the 57Co2+ cation can
be used directly as the coordinating metal or as a substitute for native cobalt or other
metal ions. As such EMS applications are yet rare, in order to reliably interpret
emission spectra of sophisticated 57Co2+-doped biosystems [1–4], model EMS studies
of simple cobalt biocomplexes are necessary. In this work, EMS spectroscopic data
are analysed and discussed for rapidly frozen dilute aqueous solutions of 57Co2+
complexes with a range of small biomolecules of different structures, including a few
amino acids, 4-n-hexylresorcinol and homoserine lactone. (Supported in part by the
Russian Foundation for Basic Research, Project 13-04-01538-a.)
References
[1] A.A. Kamnev, in: V.K. Sharma, G. Klingelhöfer, T. Nishida (Eds.), Mössbauer Spectroscopy:
Applications in Chemistry, Biology, and Nanotechnology. Wiley, N.Y., Chap. 17, 333-347 (2013).
[2] A.A. Kamnev, L.P. Antonyuk, V.E. Smirnova, L.A. Kulikov, Yu.D. Perfiliev, I.A. Kudelina, E.
Kuzmann, A. Vértes. Biopolymers, 74, 64-68 (2004).
[3] A.A. Kamnev, A.V. Tugarova, L.P. Antonyuk, P.A. Tarantilis, L.A. Kulikov, Yu.D. Perfiliev,
M.G. Polissiou, P.H.E. Gardiner, Anal. Chim. Acta, 573-574, 445-452 (2006).
[4] A.A. Kamnev, A.V. Tugarova, K. Kovács, E. Kuzmann, B. Biró, P.A. Tarantilis, Z. Homonnay,
Anal. Bioanal. Chem., 405, 1921-1927 (2013).
83
OP39
Different microenvironments in the nanosized iron cores in
human liver ferritin and its pharmaceutical analogues on
the basis of temperature dependent Mössbauer
spectroscopy
M.I. Oshtrakh1, I.V. Alenkina1, Z. Klencsár2, E. Kuzmann3 and
V.A. Semionkin1
1
Institute of Physics and Technology, Ural Federal University,
Ekaterinburg, 620002, Russian Federation
2
Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences,
Hungarian Academy of Sciences, Budapest, Hungary
3
Institute of Chemistry, Eötvös Loránd University, Budapest, Hungary
E-mail: oshtrakh@gmail.com
An iron storage protein ferritin contains 24 protein subunits shell surrounding a
cavity of about 8 nm with the iron core. This core consists of ferric hydrous oxide in
the form of ferrihydrite (5Fe2O39H2O). The iron core can contain up to 4000 iron
atoms. However, ferritin molecule usually contains about 2000–3000 iron atoms.
Storage iron in ferritin is used for synthesis of vitally important iron containing
proteins. However, it takes to introduce additional iron in case of iron deficiency.
Therefore, some pharmaceutically important ferritin analogues such as Ferrum Lek
and Maltofer® are used to treat the iron deficiency anemia. In contrast to ferritin the
macromolecules of Ferrum Lek and Maltofer® consist of nanosized ferric hydrous
oxide core in the form of akaganéite (-FeOOH) surrounded with polymaltose shell.
Samples of human liver ferritin, Ferrum Lek and Maltofer® were studied using 57Fe
Mössbauer spectroscopy with a high velocity resolution in the temperature range
from 295 to 90 K and with a low velocity resolution at temperatures below 90 K.
Mössbauer spectra of human liver ferritin, Ferrum Lek and Maltofer® at the
temperatures down to 60 K demonstrated two non-Lorentzian peaks shape with line
width increased with temperature decrease in spite of paramagnetic character of the
iron cores. These spectra were fitted within the model of heterogeneous iron cores in
which possible different layers (surface and internal) and/or regions with internal
homogeneous structure can exist. In this case all spectra were fitted well using a
superposition of five quadrupole doublets with equal line width which was a subject
to vary during the fitting procedure. The results obtained demonstrated the possibility
to consider at least five different layers and/or regions in the iron cores in the studied
samples. Temperature dependences of Mössbauer parameters for these samples were
evaluated and compared. The differences of corresponding Mössbauer parameters
were related to the different microenvironments in the iron cores of human liver
ferritin, Ferrum Lek and Maltofer®.
84
OP40
The Aplication of Immobilized Nano-Zn on Luffa sponge for
Remove Trypan Blue Dye from Water
Hayrunnisa NADAROĞLU 1,2, Semra ÇİÇEK2,3, Aynur BABAGİL2
1
2
Ataturk University, Faculty of Engineering, Department of Nano-Science and NanoEngineering, 25240 Erzurum, TURKEY
3
Ataturk University, Faculty of Agriculture, Department of Agricultural
Biotechnology,25240 Erzurum, TURKEY
In this study, nano-Zn activity which showed semiconductor characteristic
features was investigated to remove the Trypan Blue dye from the water. To be
immobilized nanoparticles on a support material and used in remediation work is an
important application. It is an important application which immobilized of
nanoparticles used in the remediation studies as a support material for prevention of
the second contamination in terms of environmental pollution. Therefore, the Luffa
sponge (LS) was used in this study. It is preferred due to native, effective efficiency,
light weight, environmentally friendly material [1, 2].
Purified peroxidase enzyme from Euphorbia amygdaloides was used to the
green synthesis of Zn nanoparticles (Zn-NPs). The immobilization was performed
stirring obtained Zn nanoparticles with LS during 1 hour at 500 rpm in magnetic
stirrer. Then, washed and filtered Zn NPs-immobilized LS samples (native-LS, nanoZn-LS) were dried in an oven for 2 hours. Measurements were made for the
optimum contact time, pH, temperature, concentration of dye with UV-visible
spectrometer (590 nm; for Trypan blue dye). The obtained membrane forms (nativeLS, Zn-NPs-LS) were characterized with SEM, XRD.
It is presented some obtained data from our research in Table 1. It is concluded
that Zn-LS membrane form had very high performance against native-LS membrane
form activity for remediation of Trypan Blue azo dye from waste water.
Table 1. Some of the data obtained from the experiments
Parameters
Values
Optimum contact time
15. min
Optimum pH
7.0
Optimum temperature
20oC
Optimum dye concentration
100 mg/L
Literature:
[1] Kaushik, P.; Malik, A., Fungal dye decolourization: recent advances and future
potential. Environment International, 2009; Vol. 35, pp 127–141.
[2] Oboh, I.O.; Aluyor, E.O.; Audu, T.O.K., Application of Luffa cylindrica in
natural form as biosorbent to removal of divalent metals from aqueous solutionskinetic and equilibrium study, In: Waste Water Treatment and Reutilization,
Einschlag, F.S.G., Eds. InTech, 2011; pp 195–212.
85
OP41
Synchrotron Induced TXRF analysis of aqueous samples
and solid suspensions and comparison with laboratory
measurements
E. Marguí1, M.Hidalgo1, A.Migliori2, J.Leani2, A.G.Karydas2 and I. Queralt3
1
Department of Chemistry, Faculty of Sciences, University of Girona, Campus
Montilivi s/n, 17071-Girona, Spain
2
Nuclear Science and Instrumentation Laboratory, IAEA Laboratories, A-2444,
Seibersdorf, Austria
3
Institute of Earth Sciences Jaume Almera ICTJA-CSIC, Sole Sabarís s/n, 08028
Barcelona, Spain
E-mail: eva.margui@udg.edu
Synchrotron Radiation (SR) techniques become more and more important in
advanced analytical studies due to the growing interest for the development of novel
and complex nano-materials but also in diagnosing and studying the release of toxic
metals in the environment and biological systems. Total Reflection X-ray
Fluorescence Analysis is a powerful analytical methodology best suited to analyze
the elemental content of toxic elements down to the ppb region without the
application of any pre-concentration technique, whereas at SR sources, chemical
speciation is also possible for the analysis of trace contaminants.
The International Atomic Energy Agency (IAEA) in collaboration with Elletra
Sincrotrone Trieste operates an endstation facility at the XRF beamline that was
developed to support, among other applications, precise TXRF and XANES
measurements of different kind of samples. The XRF beamline enstation is equipped
with an ultra-thin window Silicon Drift Detector-SDD (30 mm2, <133 eV at Mn-Kα),
photodiodes and a motorized 7-axis manipulator which allows moving the sample to
be investigated in various directions/orientations with respect to the exciting beam
or/and the SDD [1, 2]. The beamline endstation is based on a prototype instrument
designed by PTB and TUB [3]. The XRF beamline delivers an exciting X-ray beam
in the energy range 4-14 keV by means of double crystal Si(111) monochromator
[4].
The aim of the work is to present a first evaluation of the analytical capabilities of
the aforementioned beamline endstation for multielemental analysis of different
types of aqueous samples and solid suspensions under Total Reflection XRF (TXRF)
conditions. The results obtained for both types of samples in terms of sensitivity,
limits of detection and accuracy have been also compared with those obtained using
a conventional laboratory TXRF benchtop system. The findings of the present work
are discussed in view of further exploitation of the facility in different environmental,
biological and industrial fields
86
OP42
Kα X-ray emission in manganese compounds
D. Gotta1, M. Jabua1, Th. Strauch1, Ch. Weidemann1, B. Fricke2, K. Rashid3
1
Institut für Kernphysik, Forschungszentrum Jülich, D-52425 Jülich, Germany
2
Institut für Physik, Universität Kassel, D-34132 Kassel, Germany
3
Centre of Adv. Math. & Phys., Nat’ Univ. of Science & Technology, Islamabad 44000, Pakistan
E-mail: m.jabua@fz-juelich.de
In contrast to Kβ emission, data on chemical effects in the manganese Kα fluorescence
X-rays are rather scarce [1]. As Kα lines are widely used as energy calibration because
of their clear doublet structure, for ultimate precision in the energy determination the
definition of X-ray energy or wave length must include the nature of the emitting
material.
Tabulated X-ray energies or wave lengths are usually given for the peak value. Ignoring
the chemical environment leads to substantial deviations of up to a few eV for Kα lines
of 3d elements as demonstrated in many cases (see, e.g., [2]).
The measurements were performed with a high resolution Johann-type Bragg
spectrometer primarily developed for high-precision exotic-atom X-ray spectroscopy
[3,4]. The spectrometer is equipped with large spherically bent crystals of 10 cm in
diameter having a bending radius of about 3 m.
Results for various manganese compounds are presented. In this experiment, the second
order reflection was used of a quartz crystal cut along the 10-1 plane. The absolute
energy standard is taken from a measurement of metallic manganese [5]. X-ray energies
were determined to an accuracy of 10-20 meV confirming the known overall behavior of
decreasing line energy with increasing ionization state of the manganese atom. In
addition, the significant changes in the line shape are analyzed in a phenomenological
approach adapted from [5].
References
[1] P. Glatzel and U. Bergmann, Coord. Chem. Rev. 249, 65 (2005).
[2] A. Meisel, G. Leonhardt, and R. Szargan, Chem. Phys. , vol37 (1989).
[3] D. Gotta, Prog. Part. Nucl. Phys., 52, 133 (2004).
[4] D. Gotta, contribution to this conference.
[5] G. Hölzer et al., Phys. Rev. A 56, 4554 (1997).
87
OP43
Pb Species in Arabidopsis and the Effects of DOM on Its
Speciation in the Scope of μ-XRF and XAS
Y. T. Shen, Y. F. Song and G. H. Lu
National Research Center of Geoanalysis, Beijing, China
E-mail: shenyating@cags.ac.cn
always1204@163.com
Pb can pass through biologic chain via plants, threatening human health. Speciation
of Pb plays a key role in Pb toxicity. The change of Pb species is an response of
uptake, storage and detoxification mechanisms of Pb in plants. So far as we know, no
agreements have been achived in coordination of Pb in plants, and no Pb-S has been
found in plants[1]. Dissolved organic matter(DOM) attracts wide attention since it
can change Pb speciation and bio-availability. Some reported that DOM significantly
increased bioavailability by increasing extractable Pb and its mobility, e.g. DOM
enhanced 23% absorption of Pb in maize root[2], while others confirmed that it
reduced Pb bioavailability, e.g. 10% humic acid indeed decreased Pb absorption in
duckweed[3]. Therefore, role of DOM as a mediating factor in plant bioavailability
remained controversial.
The goals of this study are to determine the speciation of Pb in plants by XAS, to
identify different bioavailability of Pb in plant cells by a sequential extraction, to
study the roles of DOM in Pb metabolism in plants, and to evaluate the synergy and
antagonistic effects of Cu, Fe, Mn, Zn, Ca on Pb uptake. In this research,
Arabidopsis thaliana was chosen as a model plant, and fulvic acid, humic acid and
citric acid were used in germination test. μ-XRF was used to get distribution and
competition distribution of Pb in plants. And a cell sequential extraction with four
steps was used to separate plant cells into soluble complex, cell wall combination,
hydrophobic protein and low molecular weight organic acids (LMWOA) groups.
From our research, four evidences were concluded. Firstly, Pb-O, Pb-S and Pb-C
coordination were confirmed in the plant via XAS, which implied that sulphur
proteins may be activated and involved in absorption or detoxification of Pb in
plants. Secondly, by the cell sequential extraction of four steps, we found that
hydrophobic protein-Pb (60% in leaf) and LMWOA-Pb (29.3% in stem) were two
main Pb species in plants, which was also confirmed by our XAFS data. Thirdly, the
distribution and competition characteristics of Pb with other elements were affected
by humic acid and citric acid, and they indeed increased the short-term absorption of
Pb in Arabidopsis, especially in cotyledon sections. Finally, inorganic Pb stimulated
more iron plaques on Arabidopsis root than organic Pb which explained why the
absorption of Pb in plant was decreased by DOM.
References
[1] Bovenkamp, G.L., et al., Environmental Science & Technology, 47, 4375-4382 (2013).
[2] Salati, S., et al., Environmental Pollution, 158, 1899-1906 (2010).
[3] Kruatrachue, M., et al., Bulletin of Environmental Contamination and Toxicology, 69, 0655-0661
(2002).
88
Parallel Session 14: Fuels and Biofuels
OP44
Silicon determination in fuels/biofules as a challenging task for
medium- and high-resolution atomic absorption spectrometry
Z. Kowalewska1,2 and J. Pilarczyk1
1
Faculty of Civil Engineering, Mechanics and Petrochemistry, Warsaw University of Technology,
Łukasiewicza 17, Płock, 09-400, Poland
2
Research and Analysis Department, OBR JSC, Chemików 5, Płock, 09-411, Poland
E-mail: zofia.kowalewskah@gmail.com
Silicon, one of the most abundant elements on the earth, usually occurs at trace level
in petroleum products, fuels and biofuels. Si can appear in fuels as a result of
corrosion of steel or contamination by dust, airborne particulate matter, silica based
catalysts as well as siloxanes /polysiloxanes used as antifoaming agents. A source of
contamination can be also biocomponents, produced from variety of plants or wastes.
Determination of trace amount of Si in organic materials is recognized as one of the
most challenging tasks of atomic spectrometry due to, among others: high and
variable volatility of some Si compounds, difficulties of decomposition of silicates,
complex chemistry of Si compounds, high risk of contamination, specific properties
and intereferences in analytical techniques (ICP-MS, ICP-OES, WD XRF) [1-4].
In the presentation, results of research of Si determination in fuels and second
generation biofuels using atomic absorption spectrometry (AAS) will be shown. A
group of defined organic Si compounds of various composition, structure and boiling
point was investigated as well as Conostan oil standards and group of real samples
(including an oil from wasted tires, an oil from wasted plastics, fuel oils and CRMs –
lubricating oils). The main approach was the analysis in an organic solution using
flame AAS. The analyte form effect has been studied and compared with appropriate
results of ICP-OES approach [3].
In the vicinity of resonance Si line (252.611 nm) a few V and Fe atomic lines as well
as rotational lines of CS molecule are situated. The spectral interferences were
investigated and compared using high-resolution AAS with continuum source and
medium-resolution AAS with hollow cathode Si lamp as a radiation source. The
influence of chemical form of interferent (organic S compound) was another
difficulty. To overcome the effect the unique least squares background correction,
available in HR-CS AAS, was applied. The proposed approach is attractive as
enables Si content control in fuels in a fast and costly effective way.
The results of investigation of stated spectral interferences have a general meaning
and should be always taken into account in Si determination at resonance line. On the
other hand, the information on S, V and Fe in a sample can be simultaneously got.
References
[1] K. Van Dyck et al., JAAS, 15, 735-741 (2000).
[2] F. Chainet et al., JAAS, 26, 30-51 (2011).
[3] R. Sanchez et al., JAAS, 24, 391-401 (2009).
89
Parallel Session 14: Fuels and Biofuels
OP45
Characterization of crude oil by pyrolysis-GC/MS applying
two ionization methods in parallel
T. Streibel1, S. Otto1 and R. Zimmermann1
1
Joint Mass Spectrometry Centre
University of Rostock, Chair of Analytical
Chemistry, Germany and Helmholtz-Zentrum
München, CMA (Comprehensive Molecular
Analytics), Germany
E-mail: thorsten.streibel@uni-rostock.de.
A novel analytical system for the characterization of complex samples has been
developed, that enables the sampling introduction via thermal desorption and
pyrolysis. A gas chromatographic separation follows with subsequent mass
spectrometric detection applying two simultaneous ionization methods. On the one
hand, electron ionization quadrupole mass spectrometry is used for the structural
identification of compounds. Resonance enhanced multi-photon ionization (REMPI)
in combination with a time-of-flight mass spectrometer provides a selective and
sensitive detection of aromatic species. The system has been applied for the analysis
of crude oil samples. With the REMPI technique, detection of less abundant
polycyclic aromatic hydrocarbons as well as their sulfur containing derivatives is
enhanced, since they are separated from the paraffinic matrix [1]. Since REMPI is a
soft ionization method generation only molecular ions, an additional separation
dimension is gained (see Figure 1). On the other hand, electron ionization allows the
identification of isomeric structures. More specific knowledge about the sulfur
containing compounds in crude oil will become more and more important for storage
and refinery in the future.
Figure 1: Sketch of the system (left) and two-dimensional analysis of crude oil
References
[1] Otto, S, Streibel, T, Erdmann, S, Sklorz, M, Schulz-Bull, D, Zimmermann,R, Anal. Chim.
Acta, 855, 60-69 (2015)
90
OP46
Influence of Electrolyte Additives on the Decomposition
Layer Formation in Lithium-Ion Batteries
Yunxian Qian, Philip Niehoff, Falko Schappacher* and Martin Winter
Corrensstrasse 28/30, University of Muenster, Institute of Physical Chemistry, D-48149, Germany
E-mail: yqian_01@uni-muenster.de / *falko.schappacher@uni-muenster.de
The adoption of electrolyte additives has been proven to be an effective method in
improving the lifetime performance of lithium-ion batteries (LIBs)1. Solid electrolyte
interphase layers are formed during the first electrochemical charge/discharge cycles
due to the decomposition of the electrolyte at both the anode and the cathode surface.
In this work, different additives were added to the electrolyte system of LP57 (1.0
mol/L of LiPF6 in 3:7 ethylene carbonate (EC): ethyl methyl carbonate (EMC)) to get
a deeper insight into their influence on the thickness of the decomposition layers at
both cathode (commercial LiNi1/3Mn1/3Co1/3O2; NMC) and anode (commercial
mesocarbon microbeads; MCMB). X-ray photoelectron spectroscopy (XPS) and
scanning electron microscopy (SEM) were applied after aging for different
electrochemical cycling, while the corresponding changes in the electrolyte systems
were investigated by gas chromatography–mass spectrometry (GC-MS). A model
was built to demonstrate the correlation between the electrolyte decomposition layer
growth and the difference in electrolyte decomposition mechanism. By the
combination of different characterization methods, a deeper understanding of the
relationship between battery aging and electrode surface change was achieved.
Acknowledgement
The authors would like to thank the German Research Foundation (DFG) for funding
this work within the joint Priority Program 1473 “Materials with New Design for
Improved Lithium Ion Batteries – WeNDeLIB”.
References
[1] S. S. Zhang, J. Power Sources, 162, 1379-1394 (2006).
91
OP47
The use of HgS, green and blue basic copper carbonates in
16th-17th frescoes paintings: a review on their (un)stability
in alkaline environments
M. Gil1,2, M. L.Carvalho3, S. Pessanha3, M. Manso3, L. Dias1, A. Candeias1,2
1
Laboratório HERCULES, Universidade de Évora, Largo Marquês de Marialva 8, 7000-809 Évora,
Portugal
2
Departamento de Química e Escola da Ciência e Tecnologia, Universidade de Évora, Rua Romão
Ramalho, 7000-671 Évora, Portugal
3
LIBPhys-UNL, Laboratory for Instrumentation, Biomedical Engineering and Radiation Physics
Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Portugal
E-mail:milenegil@gmail.com
The selection of proper pigments for painting in fresco were the major concerns of
almost all painting treatises authors since Classical Antiquity1-4.Only natural
pigments were recommended, specially earth pigments such as ochres, burnt and
raw umbers. In what concerns mercury sulphide (HgS) or the mineral basic carbonate
copper malaquite Cu2 (OH)2CO3 and azurite Cu3(OH)2 (CO3)2 , their use in walls
were mainly advisable with a secco technique due, apparently, to lime
incompatibility and/or UV instability. However, mural painters did not seem to have
always followed these recommendations and the three mural paintings under study
appear to be a clear example of it. A review on the pigments nature and (un)stability
in alkaline environments is presented in this paper through elemental analysis by
portable X-ray fluorescence, complemented by Optical and electronic scanning
microscopy and Raman spectroscopy.
Kew-words: Fresco technique, HgS, Copper basic carbonates, EDXRF, OM, SEMEDS, µ-Raman
Acknowledgments
The authors wish to acknowledge the Fundação para a Ciência e Tecnologia for
financial support (Post-doc grant SFRH/BPD/63552/2009) through program QRENPOPH-typology 4.1., co-participated by the Social European Fund (FSE) and
MCTES National Fund and Project PRIM’ART PTDC/CPC-EAT/4769/2012, funded
by financed by national funds through the FCT/MEC and co-financed by the
European Regional Development Fund (ERDF) through the COMPETE Competitiveness Factors Operational Program (CFOP)
References
[1] PLINIO, Natural History, Book XXXIII. Lvi. 158-LV11. 161
[2] The Book of the Art of Cennino Cennini. London: Gerge Allen&Unwin, 1922.
[3] NUNES, Philippe, Arte da Pintura, Symmetria e Perspectiva. Porto: Editorial Paisagem, 1982.
[4] MERRIFIELD, Mrs., The art of fresco painting. London: Alec Tiranti Ltd,1952.
92
OP48
Magnetic dipole transition of an atom embedded
in a solid para-H2
S. T. Nakagawa, Y. Matsubara, and M. Sakai
Department of applied physics, Okayama University of Science, Okayama 700-0005, Japan
E-mail: stnak@dap.ous.ac.jp
We have examined the magnetic dipole transitions in Xe atom that is embedded in
a solid state para-hydrogen (p-H2)n, making use of the ab-initio molecular orbital
method (QMO). The purpose is to examine the possibility of the radiative emission
of the neutrino pair (RENP) process [1, 2] that may be associated with the E1
(electronic dipole) × M1 (magnetic dipole) transition processes. Namely, M1deexcitation and neutrino emission could be quantitatively discussed.
We have used Gaussian code for a cluster of Xe@(p-H2)12. Because the crystal
structure of the solid (p-H2)n is hexagonal (hcp) at liquid helium temperature and is
known to be a quantum solid that may yield almost free ligand field for each atom
located at a lattice point. This cluster is made of twelve (p-H2) molecules that may
yield D3h ligand field to the central Xe atom. The accuracy of the calculation is
checked by the reproduction of an experiment of the excitation spectra of Xe atom
trapped in para-hydrogen (p-H2)n in the region of ultraviolet–visible light (UV-Vis)
[3]. Three E1-type excitation bands (ε1, ε2, ε3, in the order of increasing energy) in the
UV absorption were reported [4], where the second peak (ε2) is not observed in the
case of free Xe atom.
In the previous calculation of excitation spectra, we examined the transition
probability of M1 process in addition to that of E1 process [4]. The second peak (ε2)
was too close to be clearly/well distinguished as an independent peak observed in the
last experiment. Nevertheless, across the second (ε2) band, two associated bands that
may link to the M1-type transition were found. Therefore, after excitation, the M1type de-excitation process may be probable with the help of intensity borrowing from
the ε2 band, which may support the probability of the RENP process. In the present
article, the improved calculation will be shown.
References
[1] M. Yoshimura and N. Sasao, High Energy Physics-Phenomenology, arXiv: 0901.2769
(2009) http://xqw.hep.okayama-u.ac.jp/kakenhi/:
[2] I. J. R. Aitchison, A. J. G. Hey: Gauge Theories in Particle Physics, (Informa, 2003),
vol. 1 and 2, 3rd Ed.
[3] K. Nakajima, Proc. FPUA 2010, pp. 51–59.
http://xqw.hep.okayama-u.ac.jp/files/FPUA2010/FPUA0808/Nakajima.pdf
[4] S. T. Nakagawa and Y. Senju, J. App. Math. Phys. 2, (2014), DOI: 10.4236/jamp.2014.29097
93
OP49
Quantum chemical study of a novel
derivative of 3-substituted dithiocarbamic flavanone
S. Gosav1, N. Paduraru1, D. Maftei2, M.L. Birsa2, M. Praisler1
1“
Dunarea de Jos” University, Department of Chemistry, Physics and Environment, Domneasca St. 47,
800008 Galati, Romania,
2“
Al.I. Cuza” University, Chemistry Department, 11 Carol I Bldv. RO-700506, Iasi, Romania
E-mail: paduraru9nicoleta@yahoo.com
The flavanones have been greatly investigated for their antimicrobial and
antifungal activities [1]. However, the most recent findings indicate that flavanones
can inhibit the proliferation of various types of cancer cells, e.g. colorectal cancer
HCT116 [2], human breast cancer MCF7 [3], colon cancer HT29 [4] andrenal cancer
A498 cells [5].
Flavanones are a subclass of flavonoids that is characterized by a C6-C3-C6
skeleton, i.e. a phenylbenzopyrone structure consisting of two aromatic rings linked
by three carbons included in an oxygenated central pyran ring. In the case of
flavanones, the C6-C3 of chroman-4-one and C6 of the phenyl ring are connected to
each other through a carbon-carbon single bond. The flexibility ensured by their
chiral structure enhances significantly their bioactivity, as compared to other
subclasses of flavonoids [6].
The aim of this work is to characterize a new 3-dithiocarbamic flavonoid by
vibrational spectroscopy in conjunction with Density Functional Theory (DFT)
calculations. Quantum mechanics calculations of energies, geometries and
vibrational wavenumbers in the ground state were carried out by using hybrid
functional B3LYP with 6-311G(d,p) as basis set. The results indicate a remarkable
agreement between the calculated molecular geometries and vibration frequencies
and the experimental data determined for this compound. Thus, a complete
assignment of all the bands observed in the vibrational spectra was performed. In
order to assess its chemical potential, molecular descriptors characterizing the
interactions between the new 3-dithiocarbamic flavonoid and its biological receptors
have been computed. The molecular electrostatic potential (MEP) map, computed for
the identification of the sites of the molecule that are most probably interacting with
electrophilic and nucleophilic species, is discussed.
References
[1] Z.L. Fowler, K. Shah, J.C. Panepinto, A. Jacobs, M.A.G. Koffas, PLoS ONE 6(10)e25681.
doi:10.1371/journal.pone.0025681 (2011).
[2] Y. Woo, S.Y. Shin, J. Hyun, S.D. Lee, Y.H. Lee, Y. Lim, International J. Mol. Medicine 29, 403408(2012).
[3] M. Safavi, N. Esmati, S.K. Ardestani, S. Emami, S. Ajdari, J. Davoodi, A. Shafiee, A. Foroumadi,
European Journal of Medicinal Chemistry 58, 573–580 (2012).
[4] S. Kuntz, U. Wenzel, H. Daniel, European Journal of Nutrition,38, 133–142 (1999).
[5] Y. Murti, P. Mishra, Indian J. Pharm. Sciences 76(2), 163-166 (2014).
[6] K.R. Vega-Villa, C.M. Remsberg, J.K. Takemoto, Y. Ohgami, J.A. Yáñez, P.K. Andrews, N.M.
Davies, Chirality 23, 339-348 (2011).
94
Parallel Session 16: Food Analysis
OP50
Contaminants in black polymeric food contact articles [1]
F. Puype1, J. Samsonek1, J. Knoop2, M. Egelkraut-Holtus2, M. Ortlieb2
1
Institute for Testing and Certification, Laboratory of analytical chemistry, Zlin, Czech Republic
2
Shimadzu Europa GmbH, Spectroscopy, Duisburg, Germany
E-mail: jkn@shimadzu.eu
Black polymeric food-contact articles (FCA) sold on the European market were
measured for their bromine content followed by the identification of presented
brominated flame retardants (BFRs) by use of X-ray fluorescence spectrometry (XRF)
and thermal desorption gas chromatography coupled with mass spectrometry (thermal
desorption GC-MS).
In order to confirm the possibility that recycled fractions from the Waste Electrical and
Electronic Equipment (WEEE) stream were entering the European market in the form
of black polymeric articles, elemental analysis was performed by use of inductively
coupled plasma optical emission spectroscopy (ICP-OES) for the detection of WEEE
relevant elements. In most of the BFR positive samples typical elements used in
electronic equipment (As, Cd, Cr, Cu, Fe, Hg, Ni, Pb, Sb and Zn) were presented
either at trace level or at elevated concentrations.
This poster discribes also the measurement of rare earth elements (REEs) and confirms
additionally the suggested WEEE root of contamination. REEs like Ce, Dy, La, Nd, Pr
and Y were detected in 4 of the 7 BFR positive samples.
The polymer matrixes were identified by combining attenuated total reflectionFourier transform infrared spectroscopy (ATR-FTIR) with pyrolysis GC-MS enabling
to detect impurities from foreign polymer fractions.
References
[1] Puype F, Samsonek J, Knoop J, Egelkraut-Holtus M, Ortlieb M. 2015. Evidence of waste electrical
and electronic equipment (WEEE) relevant substances in polymeric food-contact articles sold on the
European market, Food Additives and Contaminants: Part A, Volume 32, Issue 3, page 410-426 (2015),
http://www.tandfonline.com/doi/full/10.1080/19440049.2015.1009499 (open access)
95
OP51
Bioavailability of trace elements in chocolate drink powder
using human epithelial cell lines
R. R. A. Peixoto1, V. Devesa2, D. Vélez2 and S. Cadore1
1
Institute of Chemistry, University of Campinas, P.O. Box 6154, 13083-970, Campinas, SP, Brazil.
2
Instituto de Agroquímica y Tecnología de Alimentos (IATA-CSIC), Av. Agustín Escardino 7,
46980 Paterna, Valencia, Spain.
E-mail: rafaella_peixoto@hotmail.com
Most of food analysis is aimed to the determination of the total concentrations of
food components. However, this information is not sufficient for nutritional or risk
assessment studies. A more adequate approach should consider their
bioaccessibilities and bioavailabilities. The bioaccessible fraction refers to the
amount of the ingested compound that is released from the food matrix and is soluble
into the human gastrointestinal tract, whereas bioavailability refers to the amount that
is absorbed by the human intestinal barrier and reaches the systematic circulation [1].
Despite of the great consumption of cocoa derivatives and their relevant amounts of
some essential and non-essential elements [2,3], little or no information is available
about their bioaccessibilities and bioavailabilities. Taking this into account, the aim
of this study is to evaluate the bioavailability of some trace elements (B, Ba, Co, Mn,
Ni and Se) in chocolate drink powder using an in vitro digestion method [4] and
human epithelial cell lines [Caco-2 and HT29-MTX monocultures and co-cultures
Caco-2/HT29-MTX (50/50%)] seeded onto polyester membranes (Transwell®) as a
model of human intestinal epithelium. Once confluence and differentiation have been
reached (10-12 days), cells were exposed, adding to the apical (upper) compartment
the bioaccessible chocolate drink powder fraction obtained in the in vitro digestion
method. After 2 hours of exposure, the apical and basolateral contents were collected
and analyzed. The analytical measurements were made by Inductively Coupled
Plasma Mass Spectrometry (ICP-MS) after acid mineralization assisted by
microwave radiation. The following percentages were obtained for the transport of
the elements through the cell monolayers: 19-21% for B, < 4% for Ba, 4-9% for Co,
4-8% for Mn, 3.2-3.4% for Ni and < 7% for Se, with mass balances in the range of
88-133%. The highest bioavailable fractions were obtained by using the HT29-MTX
model, whereas for the Caco-2 and Caco-2/HT29-MTX co-culture very similar
results were obtained. The results showed that a small fraction of the elements were
transported to the basal compartment, suggesting that these elements from chocolate
drink powder would be moderately absorbed.
References
[1] Moreda-Piñero, J.; Moreda Piñero, A.; Romarís-Hortas, V., et al., Trend Anal. Chem., 30(2), 324345 (2011).
[2] Sager, M., J. Nutr. Food Sci, 2:1, 1-10 (2012).
[3] Villa, J.E.L.; Peixoto, R.R.A.; Cadore, S., J. Agr. Food Chem., 62, 8759-8763 (2014).
[4] Laparra, J.M.; Vélez, D.; Montoro, R.; Barberá, R.; Farré, R., J. Agric. Food Chem., 51, 60806085 (2003).
Acknowledgements: Fapesp (Processes nº2011/21023-3 and 2013/21962-5), CNPq and INCTAA.
96
OP52
Applications and Principles of CERAC ( Ce(IV)-Based
Antioxidant Capacity) Methods
D. OZYURT1, B. OZTURK1and R. APAK2
1
Department of Chemistry, Faculty of Science and Letters, Istanbul Technical University, 34469,
Istanbul, Turkey.
2
Department of Chemistry, Faculty of Engineering, Istanbul University, 34320 Istanbul, Turkey.
ozyurtd@itu.edu.tr
Antioxidants are health-beneficial compounds fighting against reactive oxygen and nitrogen species
(ROS/RNS) and free radicals that may eventually give rise to various diseases. The chemical diversity
of antioxidants makes it difficult to separate and quantify antioxidants from the vegetable, fruit and
food matrix. Therefore it is desirable to establish methods that can measure the total antioxidant
capacity (TAC) level directly from vegetable and fruit extracts. After reaction with antioxidant test
compounds, cerium(IV)-based antioxidant capacity (CERAC) methods either measure produced
Ce(III) ions fluorometrically [1] or unreacted Ce(IV) ions spectrophotometrically [2]. The reaction
conditions for both CERAC methods were first optimized to produce meaningful results for
antioxidants. In this regard, 0.3 M H2SO4 and 0.7 M Na2SO4 in aqueous medium maintained the
required redox potential for Ce(IV) ions to oxidize true antioxidant compounds but not citric acid,
simple sugars and pharmacological ingredients. The developed procedure was successfully applied to
the TAC assay of antioxidant compounds such as trolox, quercetin, rutin, gallic acid, ascorbic acid,
catechin, naringin, naringenin, caffeic acid, ferulic acid, glutathione, and cysteine. Since the TEAC
(trolox-equivalent antioxidant capacity) coefficients found with the proposed method of naringin–
naringenin and rutin–quercetin pairs were close to each other, this Ce(IV)-based assay presumably
caused the simultaneous hydrolysis of flavonoid glycosides to the corresponding aglycones and their
subsequent oxidation such that the hydrolysis products exhibed antioxidant capacities roughly
proportional the number of –OH groups contained in a molecule. After the investigation of
experimental results, it can be concluded that the redox potential of reaction between Ce(IV) and
antioxidant molecules disables the interference effects of simple sugars, citric acid and amino acids
(without thiol groups). This property of the improved method increases its importance when compared
to widely used alternative electron transfer-based methods (Fe(III)- phenanthroline with E0 = 1,06 V,
and Folin-Ciocalteu method with an unknown potential) showing high redox potentials.
Spectrophotometric and spectrofluorometric CERAC methods have advantages over other ET−based
assays, namely simplicity, availability and stability of reagents, reproducibility over a wide
concentration range, completion of the redox reactions for most common flavonoids within reasonable
time. Significant differences between the methods were calculated by analysis of variance (ANOVA)
procedures; p < 0.05 were regarded as significant. Moreover, in order to prove the additivity and
accuracy of the method, linear calibration graphs of trolox in ultra-pure water and 3 different plant tea
samples were drawn with the aid of standard addition method. The slopes of parallel calibration lines
were found to be identical with a value of (1.86 ± 0.02) × 10 6. This result shows that the method does
not chemically deviate from Beer’s law due to interferences from other species found in complex
chemical matrices, and improved spectrofluorometric CERAC assay can measure the total antioxidant
capacities of sample mixtures. Methyl alcohol extracts and traditional hot water infusion of curative
plants such as sage, nettle, green tea, chamomile tea, linden, mint and rose hip were anayzed with
spectrophotometric CERAC, spectrofluorometric CERAC and other electron-transfer based total
antioxidant capacity determination methods.
References
[1] Ozyurt, D., Demirata, B., & Apak, R. (2010). Modified cerium(IV)-based antioxidant capacity
(CERAC) assay with selectivity over citric acid and simple sugars, Journal of Food Composition and
Analysis, 23, 282–288.
[2] Ozyurt, D., Demirata, B., & Apak, R. (2011). Determination of total antioxidant capacity by a new
spectrofluorometric method based on Ce(IV) reduction: Ce(III) fluorescence probe for CERAC assay,
Journal of Fluorescence, 21, 2069–2076.
97
OP53
Using known techniques for novel applications: Monitoring
the aging process of titanium dioxide containing paint films
by morphological and elemental surface analysis
B.A. van Driel1,2,3, T.A. Wezendonk4 , K.J. van den Berg3, and J.Dik2
1
2
Rijksmuseum, Hobbemastraat 22, 1071 ZC, Amsterdam
Materials for Arts and Archeology, 3ME, TU Delft, Mekelweg 3, 2628 CD Delft
3
Rijksdienst voor cultureel erfgoed, Hobbemastraat 22, 1071 ZC, Amsterdam
4
Catalysis Engineering, ChemE, TU Delft, Julianalaan 136, 2628 BL, Delft
Email: b.van.driel@rijksmuseum.nl
Titanium dioxide white was first introduced in the 1920s and rapidly became the
most abundantly used pigment of the 20th century. Many famous artists such as
Pablo Picasso, Jackson Pollock and Piet Mondriaan have used this pigment [1,2].
However, the use of titanium dioxide comes with a severe drawback: the pigment has
the ability to degrade the paint in which it is contained. The two most commonly
found forms of titanium dioxide are rutile and anatase: it is the anatase polymorph
that is most photocatalytically active. The photocatalytic degradation can cause
alteration of surrounding pigments or the complete degradation of the paint binder.
These phenomena cause roughening of the surface and eventually lead to chalking:
the top layer of the paint has degraded and the pigment is now located freely on the
surface [3].
TiO2 + hν + binder Volatile organic components
Limited examples of degraded art works are known due to their relatively short
existence and the long time scale of the degradation process. However, we are
dealing with a ticking time bomb! Degradation will inevitably take place in works of
art containing photocatalytically active titanium white pigments.
In this work, a method is presented to monitor the surface of a paint film during its
aging process by the surface analysis techniques AFM and XPS. The combined
morphological and elemental information gathered by these methods is very valuable
for early detection of paint degradation. Furthermore, relating the visual changes of
the paint film to its morphological and elemental properties is of great interest to the
field of cultural heritage.
References
[1] Laver, M. (1997). Titanium White. In Artists' Pigments: A Handbook of their History and
Characteristics (Vol. 3, pp. 295-355).
[2] Klaas Jan Van den, B., Miliani, C., Aldrovandi, A., Brunetti, B. G., Groot, S. d., Kahrim,
K., . . . van Bommel, M. R. (2012). Chapter 7: The Chemistry of Mondrian's paints in
Victory Boogie Woogie. In M. R. van Bommel, H. Janssen, R. Spronk (Eds.), Inside Out
Victory Boogie Woogie: Amsterdam University Press.
[3] Völz Hans, G., Kaempf, G., Fitzky Hans, G., & Klaeren, A. (1981). The Chemical Nature
of Chalking in the Presence of Titanium Dioxide Pigments. Photodegradation and
Photostabilization of Coatings (Vol. 151, pp. 163-182): AMERICAN CHEMICAL
SOCIETY.
98
OP54
Simultaneous -PIXE and -EBS analysis applied to XVI
century silver and copper coins
J. Cruz1, V. Corregidor2 and L.C. Alves3
1
Laboratório de Instrumentação, Engenharia Biomédica e Física da Radiação (LIBPhys-UNL),
Departamento de Física, FCT-UNL, 2829-516 Monte da Caparica, Portugal
2
IPFN, IST-UL, Campus Tecnológico e Nuclear, E.N. 10, 2695-066 Sacavém, Portugal
3
C2TN, IST-UL, Campus Tecnológico e Nuclear, E.N. 10, 2695-066 Sacavém, Portugal
E-mail: jdc@fct.unl.pt.
The quantification of major, minor and trace elements in coins can give valuable
information about metal and monetary circulation, the smelting processes used, and
eventual counterfeiting. Particle Induced X-ray Emission (PIXE) and Elastic
Backscattering Spectrometry (EBS) are non-destructive techniques that can
determine the coin chemical composition fingerprint down to the ppm range.
However, surface inhomogeneities created by corrosion growth may hinder a proper
quantitative analysis unless a micro beam is used, which allows the selection of small
regions with different degrees of corrosion.
Using 1.0 and 2.0 MeV proton beams from the nuclear microprobe (resolution 34
m2) located at the Laboratory of Accelerators and Radiation Technologies at CTN
(Sacavém - Portugal), -PIXE and -EBS spectra were taken simultaneously, for two
copper and four silver XVI century Portuguese coins. 2D-PIXE maps were acquired
for all coins, followed by point analyses in selected regions.
A self-consistent solution is hard to reach analysing the PIXE and EBS spectra
separately, as for these coins a single PIXE or EBS spectrum is not enough to obtain
a unique solution describing a concentration profile changing with depth. Thus, a
simultaneous analysis of these spectra was performed using NDF code [1]. Grazing
incidence XRD was also performed on these coins in order to identify the
compounds present in the corrosion layer, namely oxides, carbides, etc, and that were
used as input for NDF. The simultaneous fitting procedure allowed the
differentiation of the superficial corrosion layer from the uncorroded volume
underneath (as exemplified in fig.1).
Fig.1 – Elemental depth profile obtained by
simultaneous -PIXE and -EBS spectra fitting
18
with NDF (3010 at/cm2  1 m). Coin: 5
Reais (Ag 91.66 wt% - XVI century).
References
[1] C. Pascual-Izarra, M. Reis, N. Barradas, Nucl. Instr. and Meth. B 249, 780-783 (2006).
99
OP55
Sulphur isotope ratio measurement as method for
provenance determination of vermilion in antiquity
T. Minami1 , E. Tsantini2, M. A. Cau2,3
1
School of Sci. & Engineer., Kinki Univ., 3-4-1 Kowakae, Higashiosaka, Osaka
577-8502 Japan
2
Equip de Recerca Arqueològica i Arqueomètrica, Universitat de Barcelona
(ERAAUB), Department de Prehistòria, Història Antiga i Arqueologia, Montalegre,
6-8, 08001 Barcelona, Spain
3
Institució Catalana de Recerca i Estudis Avançats (ICREA)
e-mail: minamita@life.kindai.ac.jp
Provenance determination is an important aspect in Archaeology. To know the origin of
the archaeological materials is essential, among other issues, to study their distribution
and the trade or exchange networks. However, it is often difficult to establish the
effective method for identification of the specific source. This contribution presents a
method for sourcing vermilion using sulphur isotope ratio. Vermilion, a mercuric
sulphide, is a precious red-colour pigment used for decorating and painting in the
Ancient World. Vermilion was provided powdering natural cinnabar that shows a
brilliant red colour when is crushed finely. If the ratios of sulphur isotope in cinnabar ore
collected from mines are different, the original source of vermilion used in Antiquity can
be determined when analysing this substance. To illustrate the method, Spanish
vermilion from Roman wall-paintings found in the Roman city of Baetulo (Badalona,
Catalonia, Spain) was considered as case study. Spanish cinnabar ore samples were
taken from the collections of the Geological and Geophysical Institute of Hungary and
Museum National d’Histoire Naturelle in Paris, France. The aim was to determine the
provenance of the cinnabar ore used for the preparation of the vermilion used in the
paintings found in Badalona. For the analysis, about 10 mg of vermilion was dissolved in
reverse aqua regia and sulphate ion was made by the addition of bromine. The precipitate
of barium sulphate was produced by the addition of BaCl 2. About 40 μg of barium
sulphate was put into a tin cup and sulphur dioxide gas was obtained using an elemental
analyzer, vario PYRO cube (Elementar Analysensysteme GmbH, Hanau, Germany).
Sulphur dioxide gas was directly induced in the isotope ratio mass spectrometer,
IsoPrime 100 (Isoprime Ltd., Cheadle Hulme, Cheadle, England). The peak height was
set to about 1 nA. The isotope compositions are presented as conventional ratios of
34 32
S/ S (δ34S‰). The δ34S value of the Canyon Diablo meteorite was employed as a
standard. Sulphur compounds with abundant 34S have positive δ34S values relative to the
standard, while compounds with abundant 32S have more negative values. The sulphur
isotope ratio of vermilion for the five samples from Badalona (+11.63 ± 1.78 ‰) was
slightly higher than that of cinnabar ores from Almaden mine (+7.83 ± 1.18 ‰, n=5)
which is a very famous cinnabar mine in Spain. The ratios of cinnabar ores of Leon
region in northern Spain were +18.10 ‰ and +21.84 ‰. Therefore, the results obtained
suggested that the vermilion used in Badalona was collected from the Almaden mine. In
conclusion, the ratio of sulphur isotope of vermilion is a useful method to identity the
original source. Nevertheless, considering the possible intra-source variability, for
statistical reasons it is necessary to measure other ore samples in the same mines and to
extend the data base also collect new samples from other mines. More work is needed
but the results are very promising as a method of provenance determination.
100
OP56
Quantification of Lithium-Ion Battery Electrolyte
Degradation Products Including HF by Nuclear Magnetic
Resonance Spectroscopy Using the Solvent as a
Heteronuclear Standard
S. Wiemers-Meyer, M. Winter, S. Nowak*
University of Muenster, MEET Battery Research Center, Corrensstrasse 46, 48149 Muenster,
Germany
s.wiemers-meyer@uni-muenster.de / *sascha.nowak@uni-muenster.de
Mixtures of organic carbonates containing LiPF6 as conductive salt are commonly
used as lithium-ion battery electrolytes.[1] These electrolytes tend to decompose at
elevated temperatures.[2] There are many publications about the identification of
different degradation products, but there are only few concerning their quantification.
Nuclear magnetic resonance (NMR) spectroscopy provides a non-invasive way to
identify and to quantify analytes in a given sample. Within the scope of this work
electrolyte samples consisting of a mixture of ethylene carbonate (EC) and a linear
carbonate (1:1, wt.) and LiPF6 (1 mol/L) were stored at elevated temperatures in
polytetrafluoroethylene tubes placed in flame sealed NMR glass tubes. Thus, gastightness can be guaranteed and highly reactive HF, which is formed during the
aging process of the electrolyte, does not react with the glass tube. These two aspects
are great advantages of this method. In addition the influence of different cell
components on the aging process is investigated.
19
F spectra appear to be most suitable for quantification of the degradation products
of interest. Addition of different internal standards for quantification has been tested
but lead to either a decaying standard signal over time or an influence of the
degradation rate of the electrolyte. Therefore, a method was developed, which does
not need an addition of internal standard. The degradation products can be quantified
by calculating the ratio of their 19F signal area to the 1H or 13C signal area of EC.
Since this ratio is proportional to the 19F concentration and the initial concentration
of LiPF6 is known, all compounds observed in the 19F spectrum can be quantified. A
serial dilution was prepared to validate the method. The results show a linear
calibration curve and triple determinations of each sample lead to very low relative
standard deviations (< 1 %). This method is not limited to electrolyte stability
measurements. If some basic requirements are fulfilled, it is supposed to be
applicable to quantification and reaction rate investigations in general.
References
[1] K. Xu, Chemical Reviews, 114 11503-11618 (2014).
[2] S.E. Sloop, J.K. Pugh, S. Wang, J.B. Kerr, K. Kinoshita, Electrochemical and Solid-State Letters,
4 A42-A44 (2001).
101
OP57
Single-conformation spectroscopy of two diastereomeric
cyclic peptides
L. J. B. Wollny1, J.R. Gord2, N. Berger1, W. Sander1, T.S. Zwier, C. W. Müller1
1
Ruhr-Universität Bochum, Fakultät für Chemie und Biochemie, Universitätsstr. 150, 44801
Bochum, Germany
2
Purdue University, Department of Chemistry, 560 Oval Drive, West Lafayette, IN, USA
E-mail: laura.wollny@rub.de
Cyclo(Boc-Cys-Pro-L-Trp-Cys-OMe) (1) and cyclo(Boc-Cys-Pro-D-Trp-OMe) (2)
are two cyclic tetrapeptides mimicking the biological important β-turn structure.
β-turn structures often link β-strands to antiparallel β-sheet structures and can occur
in nine forms that differ in their torsional internal angles. Single-conformation
spectroscopy in the molecular beam allows us to investigate mass-selectively the
conformers of the bare molecules and their water clusters present in the molecular
beam.
We present the results of our resonance-enhanced two-photon ionization (R2PI), UVUV hole-burning (UVHB) and resonant ion-dip infrared spectroscopy (RIDIRS)
experiments in the amide A region (3100-3800 cm-1) and in the amide I/II region
(1400-1800 cm-1) of the two model peptides. In combination with DFT calculations
(M05-2X/6-31+G(d)), we were able to elucidate the conformational structures.
In both diastereomers only one conformation was found. We show that while (1)
takes on a βI-turn conformation, (2) takes on a βII-turn conformation. These findings
are in agreement with the results obtained by crystal structure analysis and
experiments in solution, carried out by our collaboration partners for (1) and (2) and
other diastereomeric cyclic peptides.[1, 2] Our contribution will also focus on the
intramolecular interactions that stabilize the conformations and affect the
spectroscopic features.
References
[1] F. Li, K. Bravo-Rodriguez, C. Phillips, R.W. Seidel, F. Wieberneit, R. Stoll, N.L. Doltsinis, E.
Sanchez-Garcia, W. Sander, J. Phys. Chem. B, 117, 3560 (2013)
[2] C. Merten, F. Li, K. Bravo-Rodriguez, E. Sanchez-Garcia, Y. Xu, W. Sander, Phys. Chem. Chem.
Phys., 16, 5627 (2014)
102
OP58
Raman spectroscopy as powerful tool for the identification
of IEDs explosive components in post-blast residues
F. Zapata1, C. García-Ruiz1 and F. Ortega-Ojeda1
1
Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering and University
Institute of Research in Police Sciences (IUICP), University of Alcalá, Ctra. Madrid-Barcelona km
33.600, 28871 Alcalá de Henares (Madrid), Spain
E-mail: carmen.gruiz@uah.es
Terrorist assaults based on the use of Improvised Explosive Devices (IEDs) are being
increased worldwide. This threatening tendency must be stopped by means of the
improvement in two relevant actions. First and foremost, the prevention of the attack through
the detection of the IED before its explosion. Secondly, if the attack hasnbeen carried out,
evidence from the scenario must be collected and minutely examined in order to identify the
author and increase the police intelligence to prevent future terrorist assaults.
Spectroscopic techniques are proving its usefulness for the detection of explosives
contributing to both actions. The specific spectral signature for each chemical compound
allow forensic investigators the reliable identification of explosives. Moreover,
spectroscopic techniques are non-destructive which constitutes an attractive feature in the
forensic field where preservation of the evidence is desirable. Specifically, the increasing
number of studies where Raman spectroscopy is being used for explosives detection under
laboratory conditions encourage its use in real threats.
However, regarding to the analysis and characterization of explosives by Raman
spectroscopy, most reported studies accomplish the detection of minimum amounts of
explosive but from pre-exploded samples. The analysis of post-blast residues by Raman
spectroscopy has been barely researched so far, probably due to the difficulties related to
find real post-blast explosive residues.
In this work, current procedures followed by the Spanish EOD (Explosive Ordnance
Disposal) were used and eight IEDs containing TATP, HMTD, TNT, RDX, PETN, ANFO,
dynamite or black powder as explosive were exploded in order to study their post-blast
residues. Eleven matrices affected by the explosion including cotton fabric, plastic bag,
cardboard, metal, glass, plywood, chipboard, brick, plasterboard, tyre and raw pig were
analysed besides the ground from crater. The methodology accomplished to analyse them
involved a previous visualization to the naked eye of post-blast residues followed by
microscopic visualization and Raman analysis. As result, intact particles of the explosive
were detected for ANFO, dynamite and black powder explosives on some of the matrices,
whereas intact remains from the organic explosives were not detected. A possible
explanation to this fact is that ANFO, dynamite and black powder are explosive mixtures
based on inorganic oxidizers whereas TATP, HMTD, TNT, RDX and PETN are pure high
explosive organic compounds with higher detonation velocities. Fortunately, IEDs more
used by criminals and terrorists are those based on inorganic oxidizers due to the easiness to
obtain them from many general sources such as fireworks and fertilizers. However, due to
Raman spectroscopy is not much sensitive, as future work, Surface Enhanced Raman
Spectroscopy (SERS) will be examined for those post-exploded organic explosive samples.
Acknowledgements
With the financial support of the Prevention of and Fight against Crime Programme European
Commission – Directorate-General Home Affairs. This project has been funded with support from the
European Commission. This publication reflects the views only of the author, and the European
Commission cannot be held responsible for any use which may be made of the information contained
therein Project reference HOME/2011/ISEC/AG/4000002480.
103
OP59
Pyroelectric X-ray generation of active X-ray spectrometer
for planetary missions
Nobuyuki Hasebe1,2, Hiroki Kusano2, Hiroshi Nagaoka1, Masayuki Naito1,
Miho Mizone1, Eido Shibamura2, Haruyoshi Kuno2, Kyeong Ja Kim3,
José A. Matias Lopes4, Jesús Martínez-Frías5
1
Physics Department, Waseda University, Tokyo, Japan
Research Institute for Science and Engineering, Waseda University, Tokyo, Japan
3
Korea Institute of Geoscience and Mineral Resources, Daejeon, South Korea
4
Phys. Dep., University of Coimbra, Coimbra, Portugal
5
CSIC, Complutense University, Madrid, Spain
2
E-mail: nhasebe @waseda.jp
Planetary surface concentration of elements and its distribution provide important
clues to characterize geochemical restrictions and modelling the geological evolution
of the planetary bodies. Landing/roving exploration missions to the Moon, Mars and
asteroids are planned in the near future. The Active X-ray Spectrometer (AXS) is a
powerful and useful method for measuring the planetary surface elemental
composition. The AXS can measure major elements: Mg, Al, Si, Ca, Ti, and Fe; minor elements:
Na, K, P, S, Cl, Cr, and Mn, and the trace element Ni, and other elements depending on their
concentrations. The AXS previously carried on spacecraft such as Chang’E-3 [1], MSL
[2] and etc. used radioisotopes to excite planetary surface materials. Although the use
of radioisotopes has the great advantages of lightweight and no high voltage supply,
it is forbidden for today’s Japanese missions to use radioisotopes. Thus we adopted
the pyroelectric X-ray generator (PXG) as an alternative to the radioisotope sources.
The PXG consists of a pyroelectric crystal, a heating and cooling device with
temperature controller, and a thin metallic target. The AXS consists on a silicon drift
detector with an excellent energy resolution and multiple PXGs. The AXS has
outstanding characteristics such as excellent energy resolution, light weight, low
electric power consumption, and no use of high voltage supply, as well as the
possibility of switching-on/off the generator as desired. Also, during the long-time
development process of space mission payloads, the workers exposure to X-ray
radiation can be drastically minimized by using the PXG. On the other hand, the
known weakness of the PXG is a weak and unstable X-ray intensity, what could be a
show-stopper for AXS precise measurements. In this work, we have investigated the
way to increase both intensity and stability of X-ray flux of the PXG exploring
several experimental conditions: heating time, gas pressure, electrodes geometry and
crystal size. Those experimental results will be reviewed and discussed in this
presentation.
References
[1] Xiao-Hui Fu et al., RAA, 14(2014)1595-1606.
[2] S. M. McLennan, Sci., 343 (2014) 1244734.
104
OP60
Technology development for soft x-ray spectroscopy
H. J. Sipilä1, P. T. Törmä1 and T. Koskinen1
1
HS foils Oy, Tietotie 3, 02150 Espoo, Finland
E-mail: pekka.torma@hsfoils.com
The energy range from 50 eV to 500eV has been challenging for x-ray spectroscopy.
X-ray detectors and X-ray sources have been technologically very demanding.
Recently silicon nitride windows [1-2] have opened new possibilities. Windows
starting from 20 nm are vacuum tight and can be used for sealed detectors like
proportional counters and silicon drift detectors. Transmission e.g. for Li-Ka is about
50%. Because proportional counters have internal gain it is relatively easy to
measure very soft X-rays. Electronic noise does not cause limitations and practically
all photons which transmit the window are detected.
The case of silicon drift detector is more complicated. Detector surface may have
dead layer which will cause additional absorption. This phenomenon has been
studied [3] thoroughly for silicon solar panels. It is found that Al2O3 layer deposited
by atomic layer deposition (ALD) method on the top of silicon will cause negative
charge on the surface and greatly improve charge collection. It is obvious that this is
valid also on the SDD detector surface. In addition this negative charge may improve
the lifetime of the detector under heavy radiation load by enhancing the charge
collection.
In commercial X-ray tubes the thinnest window is typically 50 um beryllium.
Because silicon nitride foil tolerates high temperature and is radiation hard, it is
potential window for X-ray tubes. This will improve significantly soft X-ray
excitation efficiency. As an example is shown how intensity of carbon ,oxygen and
sodium will increase by using otherwise same excitation conditions. Only X-ray tube
window is changed.
In order to have the best soft X-ray performance the system needs to combine X-ray
source with soft X-ray friendly exit window, X-ray detector with soft X-ray friendly
entrance window and high soft X-ray sensitivity. In this work we show that the
performance of the soft X-ray spectroscopy is improved by the approaches
mentioned above.
References
[1] P. T. Törmä et al., IEEE Trans. Nuc. Sci., vol. 60, pp. 1311 - 1314 (2013).
[2] P. T. Törmä et al., IEEE Trans. Nuc. Sci., vol. 61, pp. 695 - 699 (2014).
[3] G. von Gastrow et al., Energy Procedia, vol. 38, pp. 890 - 894 (2013).
105
OP61
Evaluation of new XRF instrumentation for assessing
human exposure to toxic metals in field-based studies
D. Guimarães1, M. Praamsma1, and P. Parsons1,2
1
Wadsworth Center, New York State Department of Health, PO Box 509, Albany, NY, 12201 USA
2
Department of Environmental Health Sciences, University at Albany, Albany, NY, 12201 USA
The primary goal of this study was to assess the performance of a novel prototype
instrument, the HD Mobile, for assessing personal exposure to metals through food,
cosmetics, medicines and personal care products. The HD Mobile is a
monochromatic X-ray Fluorescence (XRF) spectrometer manufactured by X-Ray
Optical Systems (XOS), of East Greenbush NY. The instrument uses a High
Definition XRF (HDXRF) technique that comprises Double Curved Crystal (DCC)
optics to enhance measurement intensities. Moreover, it is housed in a self-contained
case designed for use in field-based studies.
The HD Mobile was designed for the analysis of samples with a light matrix, thus the
“plastic mode” was chosen for this project. Parameters such as accuracy, precision
and detection limits were established in a laboratory setting using a variety of
reference materials and standard solutions including: IAEA-413 Algae, NRC-CNRC
TORT-2 Lobster Hepatopancreas, NIST SRM 1571 Orchard Leaves, IRMM BCR627 Tuna Fish, NIST SRM-2976 Mussel Tissue, NRC DORM-2 Dogfish Muscle and
IRMM ERM-CE464 Tuna Fish. Percent bias for the mean of elements such as As,
Cd, Hg and Pb between days (n = 5) ranged from -9% to 10% for one prototype and 12% to 14% for a production model. Five archived samples from our public health
investigations including herbal medicines, ethnic spices and cosmetic products were
analyzed in the laboratory to assess performance with samples resembling those
analyzed in the field. Agreement between the prototype and production model
proved to be fit-for-purpose for the majority of the samples. The presence of the
elements of interest as detected by HDXRF was confirmed by archived ICP-OES
data based on acid digested materials. These HDXRF units were shown to be suitable
for the rapid screening of personal exposure to metals in the field.
106
Parallel Session 20: Imaging Techniques
OP62
Rock porosity quantification by Dual-Energy X-ray
computed microtomography
A. P. Teles1, I. Lima1 and R. T. Lopes1
1
Nuclear Engineering Program, Federal University of Rio de Janeiro, Rio de Janeiro, Brazil; P.O.
Box:68.509.: Zip Code:21941-972.
E-mail: ateles@con.ufrj.br
Since the popularization of computed tomography technique (CT) in others application fields beyond
medicine, geological samples have been studied extensively with this non-invasive method [1-3].
Currently, thanks to great technological advances that allowed the development of computed
microtomography (micro-CT) systems with potential to identify small and low-contrast structures and
computers with large capacity for processing and storage of information, micro-CT has become a
powerful tool to investigate porous space of rocks and their different phases. On the other hand,
conventional X-ray microtomographic scanners face some limitations that are responsible by image
artifacts (beam hardening, ring artifacts, and scatterings) compromising the investigation capacity of
the samples [4].
Accurate Measurements in micro-CT is based in image quality. Thus, knowledge about the
characteristics of the micro-CT system ensures to set the best parameters during image acquisition.
Noise, spatial and density resolutions are the main aspects that describe the quality of one image. The
noise level can be valued by signal to noise ratio (SNR) that indicates the gradation level of image by
the noise. Spatial resolution is defined as the capacity in differentiate closely structures and is strongly
influenced by focal spot size of X-ray tube, small dimensions provide the minimization of geometric
penumbra that is responsible by the increasing in spatial resolution [5]. Finally, density resolution is
the less distinguishable difference in mass attenuation coefficient detectable by microtomographic
system.
However, in many cases, to operate the micro-CT system at best conditions is not sufficient to reach
satisfactory results. Dual-Energy X-ray computed microtomography (microCT-DE) is a method
developed to detect sensitive variations in attenuation coefficients scanning the object in two distinct
energies. MicroCT-DE takes advantage of different modes how x-ray photons interact with matter, in
operation energy range of conventional micro-CT systems, photoelectric effect and Compton
scattering are two dominant effects [6].
In this work one methodology in dual-energy was developed to generate density images based on two
scans made in different voltage (80 kV and 130 KV). The images produced are quantized in 256 gray
levels, where minor value (zero) corresponds to voids and the maximal value (255) corresponds to
denser region mapped (figure 1).
Using density image, porosity was evaluated using commercial
analysis image software. The same process was repeated to
single energy images, scanned in best experimental setup.
Results pointed that density images presented better results than
single energy image when both are compared with porosity
obtained in Helium injection method.
Figure 1: Reconstructed image based on density distribution of
one calcite sample.
References
[1]Ketcham, R. A., Carlson, W. D., Computers & Geosciences, 27, 381-400 (2001).
[2]Baker, D. R., Mancini, L., Polacci, M., Higgins, M. D., Gualda, G. A. R., Hill, R. J., Rivers, M. L.,
Lithos, 148, 262-276 (2012).
[3]Cnudde, V., Boone, M. N., Earth-Science Reviews, 123, 1-17 (2013).
[4]Ketcham, R. A., Hanna, R. D., Computers & Geoscience, 67, 49-61 (2014).
[5]Feser, M., Gelb, J., Chang, H., Cui, H., Duewer, F., Lau, S. H., Tkachuk, A., Measurement Science
And Technology, 19, 1-8 (2008).
[6] Van Geet, M., Swennen, R., Wevers, M., Sedimentary Geology, 132, 25-36 (2000)
107
Parallel Session 20: Imaging Techniques
OP63
Elemental mapping using a gaseous detector: How? Why?
Which advantages?
A.L.M.Silva1, S.Cirino1, M.L.Carvalho2, S. Pessanha2, M. Manso2, J.P. Santos2,
M. Guerra2, M. Costa2 and J.F.C.A. Veloso1
1
2
I3N – Departamento de Física da Universidade de Aveiro, Portugal
LIBPhys-UNL - Faculdade de Ciências e Tecnologia da Universidade Nova de
Lisboa, Campus Caparica, 2829-516 Monte da Caparica, Portugal
E-mail: analuisa.silva@ua.pt
Elemental mapping through EDXRF imaging (EDXRFI) technique has become a
promising method to obtain positional distribution of specific elements in a
nondestructive manner. EDXRFI can be used in several research fields and industrial
applications.
To obtain the elemental distribution of a sample it is necessary to use instruments
capable of providing a precise positioning together with a good energy resolution.
The use of polycapillary beams followed by detectors based on the silicon drift
chamber principle (SDD) included in several commercial systems of the State of'Art
is very popular in the field, however, very cost effective. New concepts of large
gaseous radiation detectors enabling a 2D detection emerged in the last years, namely
the 2D-THCOBRA based detector, proving to be a good substitute at a very reduced
price.
The aim of this work is to study the performance of the EDXRFI system based on
2D-THCOBRA detector in sample analysis context, evaluating the results and
comparing with those obtained with the M4 TORNADO.
Acknowledgements: A. L. M. Silva is supported by the QREN programme Mais Centro –
Programa Operacional Regional do Centro, FEDER and COMPETE, through the project Biomaterials
for Regenerative Medicine (CENTRO-07-ST24-FEDER- 002030). S. Pessanha, M. Manso and
M.Guerra are supported by FCT post-doc grants SFRH/BPD/94234/2013, SFRH/BPD/70031/2010
and SFRH/BPD/92455/2013, respectively.
108
Parallel Session 20: Nuclear Techniques
OP64
Hydrogen polaron in TiO2 investigated by muSR
R. B. L. Vieira1, R. C. Vilão1, H. V. Alberto1, J. M. Gil1, A. Weidinger1, J. S.
Lord2, P. Mengyan3, B. B. Baker3 and R. L. Lichtic3
1
2
CEMDRX, Department of Physics, University of Coimbra
ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX, U.K.
2
Department of Physics, Texas Tech University, Lubbock, TX 79409-1051, USA
E-mail: vieira.fis@gmail.com
The hydrogen impurity is known for long to play a relevant role in the properties of
rutile titanium dioxide. The increase of conductivity due to hydrogen has been
established in the 1960’s [1,2]. However, only recently a renewed interest has been
devoted to the defect physics of hydrogen in rutile TiO2: the effects of hydrogen on
the conductivity of TiO2 have been thoroughly investigated by macroscopic
techniques [3] and hydrogen diffusion in rutile has been found to be enhanced by 9
orders of magnitude when stimulated by resonant infrared light [4].
Muonium, consisting of a positive muon and an electron, can be considered in solids
as a light isotope of hydrogen [5]. This analogy is often used in the literature to gain
information on the hydrogen behavior in a material, but the direct correspondence of
the two species is seldom proven. We show here explicitly the close relationship of
the muonium and hydrogen center in TiO2 by comparing the hyperfine interactions
[6]. In addition, the collapse of the hyperfine splitting with increasing temperature is
studied in detail and the spin-flip rate of the electron is extracted. Data are discussed
in the context of known electron-spin relaxation rates in similar systems.
.
References
[1] P. F. Chester and D. H. Bradhurst, Nature 199, 1056 (1963);
[2] G. J. Hill, J. Phys. D: Appl. Phys. 1, 1151 (1968);
[3] S. Erdal et al., J. Phys. Chem. C 114, 9139 (2010);
[4] E. J. Spahr et al., Phys. Rev. Lett. 104, 205901 (2010);
[5] S. F. J. Cox et al., Physica Scripta 88, 068503 (2013)
[6] A. T. Brandt et al., J. App. Phys. 110, 053714 (2011)
109
OP65
Enrichment of vanadium by green extraction methods and
its GFAAS determination in water and food samples
Mustafa Tuzena, Naeemullaha,b, Tasneem Gul Kazib
a Gaziosmanpaşa
University, Faculty of Science and Arts, Chemistry Department,
60250 Tokat, Turkey
b
National Centre of Excellence in Analytical Chemistry, University of Sindh,
Jamshoro 76080, Pakistan
E-mail: mustafa.tuzen@gop.edu.tr
A number of preconcentration techniques have been used for the separation and
preconcentration of vanadium but most of them are tedious and created
environmental contamination due to use of organic solvents [1]. Room temperature
ionic liquids (RTILs) have attracted considerable attention in recent years due to
their unique chemical and thermal properties [2]. RTILs are highly viscous and water
immiscible than organic solvent and are considered potential alternatives to
conventional organic solvents. We used a new dispersive liquid–liquid
microextraction, magnetic stirrer induced dispersive ionic–liquid microextraction
(MS-IL-DLLME) for the determination of vanadium in water and food samples [3].
A simple and new liquid–liquid dispersive microextraction termed pressure-assisted
ionic liquid dispersive microextraction (PILDME) was developed for the
concentration of trace levels of vanadium in real water samples [2]. A simple and
effective three phase liquid-liquid microextraction (TPLLME) for simultaneous
speciation of vanadium in water samples was developed [4]. Ashing and atomization
temperatures for graphite furnace atomic absorption spectrometry (GFAAS) were
optimized. Various analytical parameters such as pH, amount of ligand, volume of
ionic liquid, stirring time, pressure, etc. were optimized. Matrix effects of alkali,
alkaline earth, some cation and anions were investigated. The accuracy of the method
was confirmed with certified reference materials. Optimized method was applied to
water and microwave digested food samples for the determination of vanadium. The
advantages of this methods are simple, low cost, sensitive, selective, green chemistry
and environmentally friendly. Low detection limit and high preconcentration factor
were observed when compared to literature values.
References
[1] S.K. Wadhwa, M. Tuzen, T.G. Kazi, M. Soylak, Talanta, 116, 205-209
(2013).
[2] Naeemullah, M. Tuzen, T.G. Kazi, D. Citak, M. Soylak, J. Anal. At.
Spectrom. 28, 1441-1445 (2013).
[3] Naeemullah, T.G. Kazi, M. Tuzen, Food Chemistry, 172 161-165 (2015).
[4] O.Z. Pekiner, Naeemullah, M. Tuzen, Journal of Industrial and Engineering
Chemistry, 20, 1825-1829 (2014).
110
OP66
Contribution of charge-transfer collision to excitations of
iron ion in high-power nitrogen microwave induced plasma
K. Wagatsuma, K. Satoh
Institute for Materials Research, Tohoku University, Sendai 980-8577, JAPAN
E-mail: wagatuma@imr.tohoku.ac.jp
This paper describes an ionization/excitation phenomenon of singly-ionized iron
occurring in a high-power microwave induced plasma (MIP) excited with Okamotocavity, in comparison with an argon radio-frequency inductively-coupled plasma
(ICP) [1]. The plasma diagnostics was based on the Boltzmann distribution among
iron ionic lines (Fe II) having a wide range of the excitation energy from 4.76 to 9.01
eV [2]. It indicated in both the plasmas that plots of Fe II lines having lower
excitation energies (4.76 to 5.88 eV) were fitted on each linear relationship, implying
that their excitations were caused by a dominant thermal process such as collision
with energetic electron. However, Fe II lines having higher excitation energies
(more than 7.55 eV) had a different behavior from each other. In the ICP,
Boltzmann plots of Fe II lines assigned to the higher excited levels also followed the
normal Boltzmann relationship among the low-lying excited levels, even including a
deviation from it in particular excited levels having an excitation energy of ca. 7.8
eV. This deviation can be attributed to a charge-transfer collision with argon ion,
which results in the overpopulation of these excited levels, but the contribution is
small. On the other hand, the distribution of the high-lying excited levels was nonthermal in the Okamoto-cavity MIP, which did not follow the normal Boltzmann
relationship among the low-lying excited levels. A probable reason for the nonthermal characteristics in the MIP is that a charge-transfer collision with nitrogen
molecule ion having many vibrational/rotational levels could work for populating the
3d64p (3d54s4p) excited levels of iron ion broadly over an energy range of 7.6 - 9.0
eV, while collisional excitation by energetic electron would occur insufficiently to
excite these high-energy levels. An enhancement factor, which was a ratio of the
observed intensity to the expected value extrapolated from the normal distribution on
the low energy side, could quantitatively estimate the deviation from a normal
Boltzmann distribution and thus could provide useful information for discussing the
state of the MIP plasma.
References
[1] K. Satoh, K. Wagatsuma, Spectrochim. Acta Part B, 108, 21-27 (2015).
[2] L. Zhang, S. Kashiwakura, K. Wagatsuma, Spectrochim. Acta Part B, 67, 24-31 (2012).
.
111
Parallel Session 22: Organic and Inorganic Mass Spectrometry
OP67
Analytical Performance of Gas-Cylinder-Free Plasma Desorption/Ionization
System for Detection of Non-volatile Chemical Warfare Agents
T. Iwai1, K. Kakegawa2, M. Aida2, H. Nagashima3, T. Nagoya3,
H. Miyahara2, Y. Seto3 and A. Okino2
1
Department of Applied Chemistry for Environment, Kwansei Gakuin University,
2-1 Gakuen, Sanda, Hyogo 669-1337 JAPAN
2
Department of Energy Sciences, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku,
Yokohama, Kanagawa 226-8502 JAPAN
3
National Research Institute of Police Science, 6-3-1, Kashiwanoha, Kashiwa,
Chiba 277-0882 JAPAN
E-mail: t-iwai@kwansei.ac.jp
Chemical warfare agents (CWAs) are highly hazardous substances that have been used to incapacitate or decimate people by
military forces or terrorists. To bolster homeland security in mass events such as Tokyo Olympic 2020, a reliable and rapid onsite detection technique for residual CWAs is required. In recent years, ambient desorption/ionization mass spectrometry (ADIMS) based on low temperature plasma (LTP) is receiving a lot of attention as a mobile analytical method for detection of nonvolatile CWAs. In this technique, solid and liquid samples on surfaces can be directly analyzed under atmospheric pressure
without sample preparation. Hendricks et al applied LTP to an ADI source for a portable mass spectrometer and the detection of
CWA simulants, illicit drugs, and explosives was successfully demonstrated. 1 However, CWAs are desorbed in open air and
this represents an exposure risk for analysts during analysis. Moreover, in most cases, a gas cylinder is needed to be carried with
the analytical device because helium was used as a discharge gas. Thus, there are serious problems in terms of safety,
portability and running cost.
In our group, a gas-cylinder-free plasma desorption/ionization system was developed to realize a mobile on-site analytical
device for detection of chemical warfare agents (CWAs). 2 A schematic of this system is shown in Fig. 1. In this system, the
plasma source was directly connected to the inlet of a mass spectrometer. The plasma can be generated with ambient air, which
is drawn into the discharge region by negative pressure in the mass spectrometer. So plasma gas supply is not needed. Highpower density pulsed plasma of 100 kW could be generated by using a microhollow cathode and a laboratory-built highintensity pulsed power supply (pulse width: 10–20 µs, repetition frequency: 50 Hz). This power supply can work even by drycell battery because the average energy consumption is a few W. Thus this power supply can be miniaturized and is suitable for
mobile device. CWAs were desorbed and protonated in the enclosed space adjacent to the plasma source. Protonated sample
molecules were introduced to the mass spectrometer by airflow through the discharge region. Because protonated sample
molecules were not defused outside the ionization region, safety for analysts could be improved.
In this study, the analytical performance of this device was evaluated by using some plasma gasses. Helium and air plasmas
were directly irradiated to CWAs in the gas-cylinder-free plasma desorption/ionization system and the protonated molecules
were analyzed by using an ion-trap mass spectrometer. A blister agent (nitrogen mustard 3) and nerve gases [cyclohexylsarin
(GF), tabun (GA) and VX] in solution in n-hexane were applied to the Teflon rod and used as test samples, after solvent
evaporation. As a result, protonated molecules of CWAs were successfully observed as the characteristic ion peaks at m/z 204,
181, 163, and 268, respectively. In air plasma, the limits of detection were estimated to be 22, 20, 4.8, and 1.0 pmol,
respectively, which were lower than those obtained with helium plasma. Considering the lowest lethal concentration of VX, the
required LOD in the chemical terrorism countermeasure aspect is estimated to be around 200 nmol. We have shown that our
system can satisfy the sensitivity requirement for practical use in on-site detection. To achieve quantitative analysis, calibration
curves were made by using dipinacolyl methylphosphonate (DPMP) as an internal standard. Mass spectrum of the mixture of
DPMP (1.9 nmol) and VX (4.2 nmol) in the air plasma and calibration plot of the peak area ratio of VX/DPMP to VX
concentration are shown in Fig.2. Straight correlation line (R 2 = 0.9998) were successfully obtained irrespective of no linear
plot of VX peak area to the concentration. Remarkably, GA and GF gave protonated dimer ions and the ratios of the protonated
dimer ions to the protonated monomers increased with the amount of GA and GF applied.
References
[1] P. I. Hendricks, J. K. Dalgleish, J. T. Shelley, M. A.
Kirleis, M. T. McNicholas, T. C. Chen, C.-H. Chen, J. S.
Duncan, F. Boudreau, R. J. Noll, J. P. Denton, T. A. Roach,
Z. Ouyang, R. G. Cooks, Analytical Chemistry, 86,
2900−2909 (2014).
[2] T. Iwai, K. Kakegawa, M. Aida, h. Nagashima, T.
Nagoya, M. Kanamori-Kataoka, H. Miyhahara, Y. Seto and
A. Okino, Analytical Chemistry (2015) (Accepted).
.
Fig. 1. Schematic of a gascylinder-free plasma
desorption/ionization system.
Fig. 2. (a) Mass spectrum
of the mixture of DPMP
(1.9 nmol) and VX (4.2
nmol) in air plasma. (b)
Calibration plot of the peak
area ratio of VX/DPMP
112
OP68
Simultaneous on-line coupling of Chromatography to
organic and inorganic Mass Spectrometry for speciation
and quantification of alkyl phosphates in Lithium Ion
Battery Electrolytes
Jennifer Menzel, Vadim Kraft, Martin Winter, Sascha Nowak*
MEET – Münster Electrochemical Energy Technology, Institute of Physical Chemistry
Corrensstraße 46, 48149 Münster, Germany
*E-Mail: Jennifer.menzel@uni-muenster.de
The Lithium Ion Battery (LIB) is a technology of great interest as it is used in every
day portable electronics like mobile phones, cameras and computers. It is also a
promising candidate for the use in electric vehicles (EVs).[1] But still the limited
battery lifetime is an important challenge.[2] This is due to aging processes which
can usually be ascribed to reactions of conducting salt (LiPF6) with other battery
components or protic impurities.[3] Most decomposition products are already
characterized, whereas the species in this work, the alkyl phosphates, are suspected
to be potentially toxic.[2]
The alkyl phosphates were identified with ion chromatography (IC) coupled to
electrospray ionization-mass spectrometry (ESI-MS).[4] Due to the absence of
standards for these species quantification via IC or IC/ESI-MS is impossible. Instead,
ICP-MS is used as selective method for the detection of the phosphorus atom in the
alkyl phosphates independently from the fluoride which has a similar elution time. A
structurally similar compound is used as external standard for the quantification.
For the separation of the different alkyl phosphate species a 2D-IC is used. After the
first separation of the alkyl phosphates from some fluorophosphate species, the alkyl
phosphates are separated on a second column and then forwarded into the ICP-MS.
At the same time the ESI-MS is used to monitor the measurement and to identify
unknown compounds.
Upon investigations of an aged electrolyte, six alkyl phsophate species have been
successfully separated and identified. The effects of different additives on thermally
aged electrolyte were investigated as well. Different amounts of the additives were
applied in order to investigate their influence on the aging rate. For the measurement
of the kinetics of the electrolyte degradation the alkyl phosphates were used as
markers. It was observed that the different alkyl phosphates are formed with different
rates and increase approximately linearly.
Literature:
[1]
M. Winter, J. O. Besenhard, Chemie in Unserer Zeit, 33, 320-332 (1999).
[2]
C.L. Campion, W.T. Li, B.L. Lucht, Journal of the Electrochemical Society,
152, A2327-A2334 (2005).
[3]
K. Xu, Chemical Reviews, 104, 4303-4417 (2004).
[4]
L. Terborg, S. Weber, F. Blaske, S. Passerini, M. Winter, U. Karst, S. Nowak,
Journal of Power Sources, 242, 832-837 (2013).
113
OP69
Methods on hyperfine fields orientation in nuclear probe
techniques
K. Szymański1, D. Satuła1 W. Olszewski1,2 and B. Kalska-Szostko3
1
University of Białystok, Faculty of Physics, K. Ciołkowskiego Str. 1L, 15-245 Białystok, PL
2 ALBA Synchrotron Light Source, Ctra. BP1413 km. 3,3, Cerdanyola del Vallès, 08290 Barcelona,
ES
3
Institute of Chemistry, University of Bialystok, Hurtowa Str. 1, 15-399 Białystok, PL
E-mail: k.szymanski@uwb.edu.pl.
Nuclear probe techniques offer investigation of the hyperfine fields resulting in
interaction of the nuclear spin and the electronic environment. These interactions cause
splitting of nuclear levels. Electromagnetic transitions between the levels can be measured
by the Mössbauer spectroscopy (MS), time-differential perturbed angular correlation
(TDPAC), nuclear magnetic resonance (NMR) and many others techniques. Hyperfine fields
are tensor quantities and cause anisotropy of the interacting radiation intensity. This in turn
allows determination of orientation of the local electric field tensor and direction of
hyperfine magnetic field. Nuclear techniques will be reviewed showing their applications in
determination of selected crystalline properties, magnetic structures and textures.
Mössbauer spectroscopy is well established technique for characterization of
hyperfine interactions of the atom probe, including iron as one of the most important.
Nuclear recoilless emission allows observation electric field gradient, electronic spin density
and charge density at the position of the nucleus. Orientations of the hyperfine fields can be
investigated by use of polarized radiation. Although first experiments employing polarized
radiation in nuclear resonant scattering, done shortly after discovery of Mössbauer effect,
they were not widely included as tools in characterization of solid state because of advanced
instrumentation or the needs of sophisticated preparation of radioactive sources.
We have found chemically stable compound acting as a resonant filter and allowing
efficient polarization of the gamma beam for the Mössbauer experiments. Circularly
polarized radiation [1] can be used for detection of the sign of the hyperfine magnetic field.
Linearly polarized radiation [2] is particularly suitable for determination of orientation of the
electric field gradient. Both polarizations are now available as laboratory option in standard
Mössbauer spectrometers, including detection of the conversion electrons [3]. Application of
the technique will be illustrated by results of investigation of orientation of iron magnetic
moments in disordered alloys, invar alloys, system with competing exchange interactions,
superconductors and oxide nanoparticles. Application of spectroscopic techniques is
connected usually with poorly resolved spectra. We are going to demonstrate some methods
[4] which could be applied effectively for difficult cases of poorly resolved Mössbauer
spectra in order to extract physically important information about nature of interactions at
atomic level.
References
[1] K. Szymański, L. Dobrzyński, B. Prus and M.J. Cooper, A Single line circularly polarized source
for Mössbauer spectroscopy, Nucl. Instr. Meth. B 119 (1996) 438-41
[2] D. Satuła, K. Szymański, L. Dobrzyński, A single line linearly polarized source for Mössbauer
spectroscopy, Nucl. Instr. Meth. B 269 (2011) 2504–2508
[3] W. Olszewski, K. Szymański, D. Satuła, L. Dobrzyński, L. Bottyan, F. Tancziko, Magnetic texture
determination by Conversion Electron Mössbauer Spectroscopy with circularly polarized beam, Nucl.
Inst. and Meth. B 266 (2008) 3319-3324
[4] D. Satuła, K. Szymański, L. Dobrzyński, V. H. Tran, and R. Troć, Mössbauer data analysis based
on invariants and application to UFe5Sn, Phys. Rev. B 78 (2008) 014411-1
114
OP70
Comparison of iron-bearing minerals in ordinary
chondrites from H, L and LL groups using Mössbauer
spectroscopy with a high velocity resolution
A.A. Maksimova, M.I. Oshtrakh, E.V. Petrova, V.I. Grokhovsky and
V.A. Semionkin
Institute of Physics and Technology, Ural Federal University,
Ekaterinburg, 620002, Russian Federation
E-mail: alia55@bk.ru
Ordinary chondrites, a type of stony meteorites, consist of some iron-bearing
minerals such as olivine (Fe, Mg)2SiO4, pyroxene (Fe, Mg)SiO3, troilite FeS,
chromite FeCr2O4, metallic iron in the form of kamacite -Fe(Ni, Co), martensite 2Fe(Ni, Co), taenite -Fe(Ni, Co) and tetrataenite -FeNi, and some other minor
minerals. Ordinary chondrites are subdivided into three groups: H (High iron), L
(Low iron) and LL (Low iron, Low metal). These minerals were formed in the space
in various extreme conditions. Therefore, investigation of structural features of
extraterrestrial minerals is of interest. Mössbauer spectroscopy is a powerful
technique to study iron-bearing compounds which is widely used for various
meteorites investigation. However, complicated composition of ordinary chondrites
makes evaluation of their Mössbauer spectra very difficult in order to extract detailed
information. In this case Mössbauer spectroscopy with a high velocity resolution, as
a method significantly improved the quality of Mössbauer spectra and permitted us
to reach better fit of the complicated spectra [1], was applied for the study of
ordinary chondrites. Samples of ordinary chondrites from H, L and LL groups such
as Ochansk H4, Richardton H5, Vengerovo H5, Zvonkov H6, Saratov L4,
Farmington L5, Mount Tazerzait L5, Tsarev L5, Mbale L5/6, Kunashak L6 and
different fragments of Chelyabinsk LL5 in the form of powders were measured at
room temperature using Mössbauer spectroscopy with a high velocity resolution.
These spectra were fitted in consistent way with accounting for crystallographically
non-equivalent positions M1 and M2 for Fe2+ and Mg2+ ions in both olivine and
pyroxene, different phase composition of metallic iron with variations in Ni
concentration, the presence of ferric compounds resulting from meteorites
weathering. Comparison of the iron-bearing minerals content and the 57Fe hyperfine
parameters for these minerals showed some variations for the studied meteorites.
These differences may be a result of different ways of minerals and meteorites
formation as well as variations in thermal history of ordinary chondrites.
This work was supported in part by the Ministry of Education and Science of Russian Federation and
the Russian Foundation for Basic Research (grant No 15-35-21164). A.A.M. is supported in part by
the Ural Federal University development program for the young scientists’ financial support.
References
[1] Oshtrakh M.I., Semionkin V.A. Spectrochim. Acta, Part A: Molec. and Biomolec. Spectroscopy,
100, 78–87 (2013).
115
OP71
Immobilized of Lactobacillus plantarium on to Magnetite
Florosil Nanoparticules and Its’ Application in Co-production
of Mannanase and Phytase Enzymes
Neslihan Dikbas1, Cem Celenkli1, Hayrunnisa Nadaroglu2,3
1
2
3
In this study, production of the phytase and mannanase enzymes was carried
out in a natural medium which includes corn (C) and wheat (W) using free
and immobilized Lactobacillus plantarium bacterial strains. For this purpose,
the test bacteria were inoculated in a medium containing different amounts of
C (10, 20g) and W (10, 15 gr) and then they were incubated under the growth
conditions of bacteria at pH 6.0-6.5 and 35 °C. Firstly, florisil support
material was attached to the -NH2 group by APTES. An intermediate arm was
created with glutaraldehyde and schiff base was reduced with sodium
borohydride, in order to make it stable. Activated florisil support material was
made magnetic with nano Fe3O4 compounds and used for the immobilization
of bacteria. It was determined that both bacteria were immobilized on the
prepared magnetic florisil nanoparticles approximately at rate of 50%. The
production of phytase and mannanase enzymes was performed with both free
and matrix-immobilized microorganism. An increase was observed
approximately 50-55% in the immobilized ones compared to free ones of L.
plantarium bacteria used in the production of phytase and mannanase
enzymes that C and W were used as a carbon source.
Immobilized in order to support the use of technology of enzymes, especially
different carbon sourcesd produce, magnetite fiorosil nanoparticles due to
bacterial strains of industrial areas of industrial areas( food,medicine,
agriculture, etc.). It was concluded that ıt is safe and long- lasting use.
According to the findings, it was concluded that the test strains that were
immobilized to magnetic florisil nanoparticles could be safely used in many
industrial fields like food, agriculture and particularly medicine.
References
[1] Onem, H.; Cicek, S.; Nadaroglu, H.; Immobilization of A Thermostable Phytase
From Pinar Melkior (Lactarius piperatus) Onto Magnetic Fe3O4-Chitosan
Nanoparticles CYTA - Journal of Food, 2015, (In press).
[2] Nadaroglu, H.; Onem, H.; Preparation and Properties of Purified Phytase From
Oakbug Milkcap (Lactarius quietus) Immobilised On Coated Chitosan With Iron
Nano Particles And Investigation of Its Usability In Food Industry, Journal of Food
and Nutrition Research, 2014; 2(12), 938-945.
116
OP72
ICP-MS based analytical methodology for counting tumor
cells, viruses and pathogenic bacteria
Q.Q. Wang1,2, Y. Liang1, C.L. Liu1 and L.M. Yang1
1
Department of Chemistry, the MOE Key Lab of Spectrochemical Analysis & Instrumentation,
College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
2
State Key Lab of Marine Environmental Science, Xiamen University, Xiamen 361005, China
E-mail: qqwang@xmu.edu.cn
Tumor cell and pathogenic bacterium and virus are “suprabiomarker” of diseases.
Their accurate determination is very helpful for disease diagnosis. We developed an
inductively coupled plasma mass spectrometry (ICP-MS) based methodology to
count tumor cells, pathogenic bacteria and viruses via the determination of the
lanthanide tagged on them (Scheme 1). I will show some examples of (1) tumor cells
counting through targeting (a) v3-integrin overexpressed on the tumor cell
membrane using a lanthanide-tagged homing peptide RGD [1] and (b) PSMA
overexpressed on prostatic cancer cells with a lanthanide-tagged guiding peptide
DUPA; (2) viruses counting via ICP-MS quantification of the lanthanide-tagged viral
conserved DNA sequence after rolling circle amplification [2]; and (3) pathogenic
bacteria counting via determination of the D-alanine that metabolic crosslinked into
the bacterial peptidoglycan cell wall, in which the alkyne D-alanine were tagged with
a azide-modified lanthanide-complex through a biological orthogonal click
chemistry. Besides, the density of D-alanine in the bacterial cell wall could be
determined for the first time using ICP-MS, reflecting the rigidity of bacterial cell
wall. This information is crucial for bacterial biology study and corresponding drug
design.
Scheme 1. Analytical methodology to count tumor cells, pathogenic bacteria and
viruses using ICP-MS together with element-tagging strategy.
References
[1] Z.B Zhang, Q. Luo, X.W. Yan, Z.X. Li, Y.C. Luo, L.M. Yang, B. Zhang, H.F. Chen and Q.Q.
Wang, Anal. Chem., 84, 8946-8951 (2012)
[2] Y.C. Luo, X.W. Yan, Y.S. Huang, R.B. Wen, Z.X. Li, L.M. Yang, C.Y.J. Yang and Q.Q. Wang,
Anal. Chem., 85, 9428-9432 (2013)
117
OP73
Study of mineral translocation and accumulation in
biofortified durum wheat (Triticum durum) grains
M. Guerra1, I. M. Pataco2,6, F. C. Lidon2, I. Ramos1, K. Oliveira2, M. F. Pessoa2,
M. L. Carvalho1, J. C. Ramalho3, A. E. Leitão3, J. P. Santos1, P. S. Campos4, M.
M. Silva5, I. P. Pais4, F. H. Reboredo2
1
Laboratório de Instrumentação, Engenharia Biomédica, e Física da Radiação (LIBPhys-UNL),
Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829516 Caparica, Portugal.
2
GeoBioTec, Departamento de Ciências da Terra, Faculdade de Ciências e Tecnologia, Universidade
Nova de Lisboa, Campus da Caparica, 2829-516 Caparica, Portugal.
3
Grupo Interações Planta-Ambiente & Biodiversidade (PlantStress & Biodiversity), Centro de
Ambiente, Agricultura e Desenvolvimento (BioTrop), Instituto de Investigação Científica Tropical,
I.P. (IICT), Av. República, Quinta do Marquês, 2784-505 Oeiras, Portugal.
4
Unidade Estratégica de Investigação e Serviços de Biotecnologia e Recursos Genéticos, Instituto
Nacional de Investigação Agrária e Veterinária, I.P. (INIAV), Av. República, Quinta do Marquês
2784-505 Oeiras, Portugal.
5
Bolsista da CAPES – Processo 153113-1 – CAPES Fundação, Ministério da Educação do Brasil,
Brasilia-DF 70040-020, Brasil.
E-mail: mguerra@fct.unl.pt
Even in the XXI century, there are still a large group of the world population that
suffers from micronutrient undernourishment, which constitutes a worldwide public
health problem. These nutrition deficiencies not only are resultant from famine but
also from the low nutritional value of food. Thus emerges the need of staple crops
being biofortified with micronutrients such as iron (Fe) and zinc (Zn) [1].
Biofortification has the purpose of increasing these micronutrients concentration on
staple food without compromising their productivity.
The aim of this study is to quantify the major and trace elements present in the
physiological structures of wheat grains, to which were added, during their
development, iron and zinc supplements.
The use of a µ-XRF technique, allowed us to map and quantify the metals in the
grain, allowing some insight into the metabolic elasticity, mineral translocation and
accumulation on the plant.
Through the element distribution maps obtained, it was possible to verify that the
micronutrients used in the wheat grains biofortification (Fe and Zn) are
predominantly present in the bran albeit in different structures. The Fe accumulation
favours the aleurone (inner layer) while Zn on the other hand accumulates preferably
on the cross and tube cells (outer layer). Also, we found that the biofortification
process drastically changes the concentration of these metals in the embryo.
References
[1] F.C Lidon et al. Crop and Pasture Science 66, CP14270 (2015)
118
Parallel Session 25: Hyphenated Techniques
OP74
In situ Swagelok® differential electrochemical mass
spectrometry (ISDEMS): New on-line analysis enables
insight into Lithium Ion Batteries during operation
H. Hahn, R. Wagner, F. Schappacher, M. Winter, S Nowak,*.
MEET Battery Research Center, Institute of Physical Chemistry, University of Münster, Corrensstr.
46, 48149 Münster, Germany
E-mail: Hendrik.hahn@uni-muenster.de/*sascha.nowak@uni-muenster.de
A new method for the in situ analysis of evolving gases during cyclic aging of
Lithium-Ion Batteries (LIBs) was developed, to better assess safety concerns arising
from the electrochemical degradation of the lithium hexafluorophosphate
LiPF6/organic carbonate based electrolyte [1]. For electrochemical characterization at
lab-scale the 3 valve Swagelok® cell (T-shaped) is commonly used. To maintain
comparability to this system an in situ 4 valve Swagelok® (X-shaped) DEMS system,
which varies only slightly from the original setup, was designed. Therefore, many
disadvantages of existing DEMS methods could be avoided, including an excessive
amount of electrolyte compared to the active electrode materials and massive dilution
of the parasitic reaction products with carrier gas, both leading to poor validity of the
obtained results. The new DEMS cell was connected to a modified GC-MS System
from Shimadzu® and a potentiostat (Solartron analytical) for in situ analysis of the
evolving gases and the voltammetry experiments, respectively. The main challenge
of the new setup was to overcome pressure differences between the DEMS cell and
the applied vacuum in the MS device which could be solved with an innovative
capillary connection to the MS. This work comprises the evaluation of the new
ISDEMS method in potentiostatic aging experiments of the conventional electrolyte
1M LiPF6 in EC:EMC (1:1, by wt.) in LiNi1/3Co1/3Mn1/3O2 (NMC)/Li half cells as a
function of the applied cut-off potential. Mainly CO2 release at onset potentials >4.3
V vs. Li/Li+ could be identified. At the potential of 5.0 V vs. Li/Li+ the evolution of
SiF4 was observed stemming from the HF induced degradation of the glass fiber
separator [2]. Oxygen evolution either coming from the oxidative decomposition of
the electrolyte or degradation of the NMC cathode material was not detected at 20°C.
References
[1] W. Weber, V. Kraft, M. Grützke, R. Wagner, M. Winter, S. Nowak, J Chromatogr A, 1394, 128,
(2015).
[2] M. Grützke, V. Kraft, B. Hoffmann, S. Klamor, J. Diekmann, A. Kwade, M. Winter, S. Nowak, J
Power Sources, 273, 83, (2015).
119
OP75
UV-photochemical Se volatile compound generation from
its species for QT-AAS determination
E. Nováková1, P. Rychlovský1
1
Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Hlavova
2030/8, Prague 2, CZ 128 43
E-mail: novakoe1@natur.cuni.cz
This contribution summarizes the results of TiO2/UV-photochemical vapour
generation of volatile form of Se from various selenium species in flow injection
mode. Vapour generation techniques are applied in elemental determinations to
increase the sensitivity and suppress the spectral interferences of analytical atomic
spectrometric methods. [1] The emerging photochemical vapour generation offers
several advantages compared to the widely accepted chemical vapour generation. In
the case of selenium the major advantage is an on-line pre-reduction of the selenate
ion using the TiO2 catalyst. [2] Another general advantages lie in a significantly
lower performance cost, simple operation and avoidance of environmentally harmful
substances. The photochemical reactor used in this study consisted of PTFE tubing
wrapped around a low pressure mercury UV lamp (20 W, 253.7 nm). The vapour
generation took place under UV irradiation in an organic acid reaction medium.
The on-line generation of volatile Se compound from selenate ion required a
reduction step, which was attained by the addition of TiO2 slurry. Superior limits of
detection in the pg∙mL-1 region were obtained for the inorganic forms of Se. On the
other hand, the sensitivity of organic Se species determination at the given conditions
was notably lower due to incomplete reaction. This was proved by the addition of
K2S2O8, which subsequently led to an increase of generation efficiency and
analytical signals of organic Se compounds.
SEM images of the inner surfaces of the used PTFE capillaries were taken to obtain
some information about the reduction and generation mechanisms, particularly
regarding the reduction of the selenate ion.
References
[1] J. Dědina; D.L. Tsalev, Hydride Generation Atomic Absorption Spectrometry,
Wiley 1995, ISBN: 978-0-471-95364-7
[2] E. Kikuchi, H. Sakamoto, J.Electrochem. Soc., 147, 4589-4593 (2000)
Acknowledgements:
The project was financially supported by the Grant Agency of the Charles University
in Prague (GA UK No. 228214).
.
120
OP76
Thermal stability studies on ionic liquids by capillary
electrophoresis hyphenated to an electrospray ionization
mass spectrometer
M. Pyschik, M. Winter and S. Nowak
University of Münster, MEET Battery Research Center, Institute of Physical Chemistry,
Corrensstraße 46, 48149 Muenster, Germany
E-mail: marcelina.pyschik@uni-muenster.de / sascha.nowak@uni-muenster.de
Nowadays, ionic liquids (ILs) are in the center of attention for different chemical
applications e.g. as effective solvents, as catalysts for chemical reactions or as
electrolyte in lithium-ion batteries. The application fields are widely spread.
Therefore, it is important to know the thermal stability of ILs and furthermore, a
detailed knowledge about degradation products. Only a few papers have been
published about the identification of the degradation products via chromatographic
methods. Hao et al.[1] have developed a method to analyze halide impurities in ILs
using ion chromatography (IC). Villagrán et al. [2] quantified chloride using IC and
showed that chloride ions change the density and viscosity of the ILs. Pyschik et al.
[3] investigated the thermal stability of anions in ILs by IC hyphenated to an
electrospray ionization mass spectrometer (ESI-MS).
In literature, there are only a few studies which exam ILs. Furthermore, no
electrophoresis (CE) based methods were found among these studies. We have
developed and optimized a new CE method hyphenated to an ESI-MS system to
analyze, identify and quantify cation and anion degradation products of different ILs.
The investigated ILs were pyrrolidinium- and imidazolium- based. The degradation
products can be separated from each other and can be quantified to ascertain
degradation processes. In addition, with our method, it was possible to investigate the
influence of halide impurities on the decomposition of ILs.
References
[1] F. Hao, P.R. Haddad and T. Ruther, Chromatographia, 67, 495-498 (2008).
[2] C. Villagrán, M. Deetlefs, W.R. Pitner and C. Hardacre, Analytical Chemistry, 76, 2118-2123
(2004).
[3] M. Pyschik, V. Kraft, S. Passerini, M. Winter and S. Nowak, Electrochimica Acta, 130, 426-430
(2014).
121
OP77
Investigations of Fluorinated Flame Retardants for
Lithium-Ion Battery Electrolytes by Gas Chromatography Mass Spectrometry and Ion Chromatography Electrospray Ionization - Mass Spectrometry
X. Mönnighoff, P. Murmann, W. Weber, M. Winter, S. Nowak*
University of Münster, MEET Battery Research Center, Institute of Physical Chemistry,
Corrensstraße 46, 48149 Münster, Germany
E-mail: x.moennighoff@uni-muenster.de / *sascha.nowak@uni-muenster.de
In recent years, lithium-ion batteries (LIBs) and their safety became more and more
important for automotive applications such as electric vehicles or hybrid electric
vehicles.[1]
Most commercially available electrolytes in LIBs contain lithium hexafluoro-phosphate
(LiPF6) as conducting salt and organic carbonates, e.g. diethyl carbonate (DEC) and
ethylene carbonate (EC) as solvents.[2] These organic carbonates are necessary to provide
sufficient solubility of LiPF6, high ion mobility and a wide working temperature range,
but they are highly flammable. For safety reasons, the addition of flame retardants (FR)
to the electrolyte is a possibility to decrease the flammability to obtain in the best case a
nonflammable formulation.
These three FR were investigated and compared concerning their influence on the
flammability and the electrochemical performance in half-cells. In addition to this work,
post mortem analysis of the cycled electrolyte was carried out using GC-MS, GC-CI-MS
in positive and negative mode as well as IC-ESI-MS to determine electrolyte
decomposition products. Therefore, the electrolyte was extracted by centrifugation of the
separator from the half-cells, investigated and compared to the results of the cycling
procedures.
We were able to identify several volatile compounds with GC resulting from
transesterfication and insertion reactions of TFP and TFHP with DEC while no
degradation of TEP was observed. Furthermore, some ionic compounds were identifed
by IC-ESI-MS and ESI-MS-MS experiments.
References:
[1] G. Nagasubramanian, K. Fenton, Electrochimica Acta, 101, 3-10 (2013).
[2] K. Xu, Chemical Reviews, 114 (23), 11503-11618 (2014).
122
OP78
Investigation of Organophosphates
in Thermal and Electrochemical Aged
Lithium Hexafluorophosphate-Based
Lithium Ion Battery Electrolytes
V. Kraft, W. Weber, M. Winter, S. Nowak
MEET Battery Research Center, University of Münster,
Corrensstrasse 46, 48149 Münster
E-mail: sascha.nowak@uni-muenster.de
The electrolyte is one key component in lithium ion batteries (LIBs). LiPF6 based
electrolytes, using a mixture of linear and cyclic organic carbonate solvents are the
dominant conducting salt in lithium ion batteries. However, the biggest disadvantage
of LIBs is the aging and therefore performance loss over time. Additionally, the
mechanisms of aging are not yet completely understood or verified.
Therefore, several electrochemical experiments were carried out to determine the
aging process during the application of LIBs. Furthermore, aging is a strongly
temperature dependent phenomenon since e.g. the used conducting salt LiPF6 is not
thermally stable and begins to decompose even at about 60 °C reacting with the
electrolyte solvents to various degradation products. So, thermal investigations were
taken into account during this work as well.
Since several of the identified decomposition products contain a P-F bond in their
structure, there is a structural resemblance to certain nerve agents. The toxicity of
Organophosphates is because of their reaction with the enzyme acetylcholinesterase
(AChE). AChE hydrolyses acetylcholine, a neurotransmitter regarding muscles and
organs. Therefore, investigation of LIB electrolyte decomposition products in terms
of qualitative and quantitative information is not only important for the cycle life, but
as well for potentially toxicological aspects.
The investigations for the volatile degradation products were carried out with gas
chromatographic techniques (GC-FID, GC-MS) using chemical or negative chemical
ionization for the identification of new compounds. For the ionic decomposition
products, the analytes were investigated by ion chromatography hyphenated to an
electrospray ionization mass spectrometry (IC-ESI-MS) or coupled to an inductively
coupled plasma mass spectrometer (IC-ICP-MS).
123
OP79
Investigations of Organic Electrolytes and their VC
consumption in Lithium-ion Batteries via HPLC-UV/VIS
and HPLC-APCI-MS
Carola Schultz, Yunxian Qian, Falko Schappacher, Martin Winter and Sascha
Nowak*
MEET Battery Research Center, Institute of Physical Chemistry, Westfälische Wilhelms-Universität
Münste, Corrensstrassse 46, 48149 Münster
Email: carola.schultz@uni-muenster.de / *sascha.nowak@uni-muenster.de
The demand of lithium-ion batteries (LiBs) providing a high capacity increases every
day, especially with respect to the developing market of electric vehicles. A major
challenge for the application of LiBs in the market is the short lifetime due to fast
aging. To investigate and improve the aging phenomena, analytical methods for the
determination of aging products in lithium ion batteries are indispensable.
Commonly, six different organic carbonates are used as solvents for an electrolyte:
ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC),
propylene carbonate (PC) and ethylmethyl carbonate (EMC). Vinylene carbonate
(VC) is a common used additive that is consumed during galvnostatic cycling. [1] The
lithium-ion conducting salt that is usually used in LiBs is lithium
hexafluorophosphate (LiPF6). LiPF6 can decompose to PF5 and LiF which induces
decomposition of the organic carbonates, thus their change in concentration gives
information about the aging process in LiBs.[2]
The development of a High Performance Liquid Chromatography (HPLC) method
for the separation and quantification of organic carbonates is explored. The limit of
detection, the limit of quantification and the linear range are determined. Object of
investigation are pristine electrolytes as well as thermal aged electrolytes and those
extracted from self-assembled aged LiBs. For thermal aging of different electrolyte
samples, these are stored at least one week at different temperatures. Self-assembled
LiBs are cycled to achieve electrochemical aging of the contained electrolyte.
Therefore, electrolytes with a different VC content in a range from 1-10 wt% are
used. Object of investigation are LiBs with nickel manganese cobalt oxide (NMC)
cathodes and mesocarbon microbeads (MCMB). Furthermore, the developed method
is compared to an established gas chromatography (GC) with flame ionization
detector (FID) method. Additionally, HPLC measurements coupled to electrospray
ionization mass spectrometry (ESI-MS) and atmospheric pressure chemical
ionization (APCI) were carried out. With this method, the organic carbonates as well
as generated aging products during galvanostatic cycling could be identified.
References
[1] Xu, K. Chem. Rev. 104, 4303 (2004).
[2] Sloop, S.E., Kerr, J. B., Kinoshita, K., Journal of Power Sources, 119-121,330-337 (2003)
124
OP80
Possibilities and Limitations of Reducing Mercury
Concentration in Fish by Cooking
N.A. Panichev and S. E.Panicheva
Department of Chemistry, Tshwane University of Technology, P.O. Box 56208, Arcadia 0007,
Pretoria, South Africa
E-mail:: panichevn@tut.ac.za
The effect of culinary treatment on reducing mercury (Hg) concentration in fish was
studied. Analytical determination of Hg was carried out using a Model RA-915+
Zeeman Mercury analyzer (Lumex, St. Petersburg, Russia) by direct thermal
evaporation of Hg from wet or dry samples of fish. The method does not require any
chemical pretreatment of samples, which greatly simplifies the analytical procedure
and minimizes potential sources of contamination [1]. The Hg concentration had
been determined before and after cooking using dry fish samples to avoid uncertainty
of different water content in cooked and uncooked fish.
It was found that after cooking of the most common 14 fish species on the South
African market by boiling, poaching, simmering, deep frying and grilling on coal
fire, the Hg concentration in most cooked fishes (70.8%) did not change in
comparison with uncooked samples. These results confirm the generally accepted
statement that Hg amount in fish is not changed by cooking [2].
The cooking procedure which could lower Hg concentration in fish is the formation
of soluble complexes of Hg2+ ions with organic acids. Due to the fact that from 73 to
99% of total Hg in fish is present in the form of methylmercury (MeHg) [3], the
treatment of fish with brines or lemon juice can remove only limited amount of Hg.
This conclusion is illustrated by the decrease of Hg concentration in some species of
fish (Snoek, Slinger, Cape Hake and Soldier fish) in the range of 5.8-26.3% after
their treatment in sauerkraut brine and lemon juice.
The other cooking procedure, which allows lowering the amount of Hg as MeHg is
the thermal treatment of fish by grilling. The removal of Hg from fish by high
temperature treatment can be explained by “steam distillation” process, when MeHg
is removed with vapors of water together with fish oil. The most noticeable decrease
in Hg concentration have been observed for Yellowtail fish samples (23.0, 16.3 and
26.5 %), which were grilled over a coal fire. Such a change of Hg concentration has
been observed for fat fish species only.
From the results of this study follows that moderate reducing of Hg concentration in
fish is possible using selected fish species and cooking procedures.
References
[1] Panichev, N. & Panicheva, S., Food Chemistry, 166, 432-441, 2015.
[2] Burger, J., Dixon, C., Boring, S., & Gochfeld, M. . Journal of Toxicology and Environmental Health, Part A,
66 , 817-828, 2003.
[3] May, K., Stoeppler, M., & Reisinger, K. Toxicological & Environmental Chemistry, 13, 153-159, 1987.
111
OP81
Selenium bioaccessibility and speciation in lettuce after
selenium biofortification
E. do Nascimento da Silva1, F. Aureli2, M. D’Amato2, A. Raggi2, F. Cubadda2,
S. Cadore1
1
2
University of Campinas – Rua Josué de Castro, 141, 13083-970, Campinas.
Istituto Superiore di Sanità-Italian National Health Institute, Viale Regina Elena, 299, 00161, Rome.
E-mail: manu_bing@hotmail.com.
In humans, selenium is an essential element and its deficiency is associated to a
variety of adverse health effects. Although the total amount of the element in food is
important, it is not a good predictor of the amount absorbed and retained by the
human body.. In particular, organic forms of Se such as selenomethionine (SeMet)
are more bioavailable than inorganic Se. Thus, this study aimed to explore Se
biofortification in lettuce and evaluate Se bioaccessibility and speciation after in vitro
simulated human gastrointestinal digestion.
Lettuce seedlings (cv. “veneza roxa”) were transplanted into hydroponic systems
filled with different nutrient solutions containing sodium selenite or selenate at rates
of 0, 10, 25 and 40 μmol L-1 Se. After 28 days, the plants were harvested, dried in an
oven (≈60 ºC per 3 days) and the fresh and dry matter weights were recorded. The
bioaccessible Se species were studied using a standardised static in vitro digestion
method [1]. Total and bioaccessible concentrations were determined by ICP-MS after
oxidative digestion in a MW system, whereas Se bioaccessible species were
determined by HPLC-ICP-MS..
Selenite-enriched plants showed total Se concentrations of ~ 25, 40 and 50 mg kg-1,
while for selenate the Se concentration in leaves were ~ 60, 300 and 600 mg kg-1 for
hydroponic solutions containing10, 25 and 40 μmol L-1 Se, respectively. The
investigated Se concentrations were not found to be toxic for the lettuce plants. The
Se bioaccessibility for all selenite assays and for the 10 μmol L-1 selenate assay were
around 60%, while for the others selenate experiments the bioaccessibility showed an
increase of at least 10%. The major selenocompounds present in the lettuce
gastrointestinal extracts were SeMet, SeMetO and Se(VI) for all the assays.
Additionally, Se(IV) and three other organic species were also found for the selenite
assays. For selenite-biofortified plants SeMet (and SeMetO) were found to be the
most abundant species. In plants amended with selenate, Se(VI) was found to be
around 70% of the sum of the species present in the gastrointestinal extract.
References
[1] M. Minekus et al., Food Funct. 5:1113, 2014.
Acknowledgements: Fapesp grant for E.d.N.d.S. (process 2014/15425-0)
112
OP82
Direct Determination of Propylene Glycol and Ethylene
Glycol in Foods by GC-FID
Ho Soo Lim, Ju Young Hwang, EunA Choi, Gun young Lee and Tae Seok Kang
Food Additives and Packaging Division, Ministry of Food and Drug Safety,
Cheongju-si, chungcheongbuk-do, Korea
E-mail: hslim70@korea.kr
A simple method was developed for the simultaneous determination of propylene
glycol (PG) and ethylene glycol (EG) in foods using gas chromatography with flame
ionization detector (GC-FID). PG (food additive) and EG (used as a material of
plastic bottles made from polyethylene terephthalate) in foods were extracted with
water:acetone (30:70), followed by the treatment of Carrez solutions and
centrifugation. The resulting solution was filtered using 0.45 μm membrane syringe
filter and injected into GC. The separation of PG and EG was carried out on HPINNOWAX capillary column (30 m  0.25 mm, 0.25 m). The calibration curves of
PG and EG were linear in the range of 1.0 to 100 μg/ml, with good correlation
coefficients (r2 >0.999). The recoveries ranged from 90% to 98% for PG, from 90%
to 104% for EG at spiking levels of 10, 50, and 100 mg/kg in three samples
(dumpling, coffee, candy and chocolate). The limit of detections (LOD) and limit of
quantifications (LOQ) for PG and EG were 0.4 μg/ml and 1.3 μg/ml, 0.3 μg/ml and
1.0 μg/ml, respectively. For four food matrix studied, expanded uncertainties (U)
expressed as percent were below 20% for PG and EG. Uncertainty associated with
food matrix contributed mostly to the expanded uncertainty. This study is the first
report for direct simultaneous determination of PG and EG in foods by GC-FID.
References
[1] LaKind, J.S., McKenna, E.A., Hubner, R.P. and Tardiff, R.G. Critical Reviews
in Toxicology, 29(4), 331-365 (1999).
[2] Agency for Toxic Substances and Disease Registry Case Studies in
Environmental Medicine (CSEM), Ethylene Glycol and Propylene Glycol
Toxicity, Available at http://www.atsdr.cdc.gov/csem/ (2007).
[3] Houzé, P., Chaussard, J., Harry, P., Pays, M. Journal of Chromatography A,
619(2), 251-257 (1993).
[4] Hložek, T., Bursová, M., Čabalaa, R., Talanta, 130, 470-474 (2014).
113
114
Abstracts
Poster Sessions
115
116
Poster Session 1: Atomic Spectrometry
PS1.1
Stark widths of resonance Mn I lines in laser-induced
plasmas
A.M. Popov, T.F. Akhmetzhanov, T.A. Labutin, N.B. Zorov
Lomonosov Moscow State University, Department of chemistry (Russia, Moscow)
E-mail: popov@laser.chem.msu.ru
Optical emission spectroscopic methods are often used for plasma diagnostics by
spectral lines broadening due to collisions of electrons and emitting particles and
ions. Electron density calculation with the use of Stark broadening is a remote and
non-contact technique even in non-equilibrium plasma. Not surprisingly, it is widely
used to characterize the glow discharge, discharge in a hollow cathode, high-density
star plasma and other plasma objects.
However, we need the following parameters Stark shift and width for the
determination of the electron density. They are reliably calculated for hydrogen-like
atoms and ions. Parameters for lines of other species are hardly calculated by
numerical methods. Experimental determination of the Stark parameters are seriously
hampering by the following reasons: a heterogeneity of plasma sources, a hyperfine
structure of the resonance lines sometimes comparable with the Doppler broadening,
and self-absorption. There have been made several attempts for experimental
determination of the Stark parameters of manganese resonance lines, but the data are
strongly disagreed [1,2].
In this work we used a "long" spark for producing laser plasma to reduce the
heterogeneity of a plasma and aluminum alloys with low manganese content as a
target to suppress the self-absorption. A long spark had a relatively low temperature
and electron density (T=5000 K, Ne=8,7×1016 cm-3 at delay 1.5 μs). Stark widths of
Mn I resonance lines were estimated as a value about 9-10 pm at Ne=1017 cm-3.
However, we have not observed evident Stark shifts of these lines.
References
[1] Bredice F., Borges F.O., Sobral H., Villagran-Muniz M., Di Rocco H.O., Cristoforetti G.,
Legnaioli S., Palleschi V., Salvetti A., Tognoni E., Spectrochim. Acta. Part B., 62, 1237-1245 (2007).
[2] Srećković A., Nikolić Z., J. Quant. Spectrosc. Radiat. Transfer, 105, 536-541 (2007).
117
PS1.2
Arsenic speciation in baby food by HG-CT-AAS
C. S. Huber1,2,3, M. G. R. Vale2, M. B. Dessuy2, M. Svoboda3, J. Dědina3
1
Instituto Federal Sul-rio-grandense, Câmpus Pelotas, Praça Vinte de Setembro 455,
Centro, 96015-360, Pelotas, RS, Brazil
2
Universidade Federal do Rio Grande do Sul, Instituto de Química, Av. Bento Gonçalves 9500,
Agronomia, 91509-900, Porto Alegre, RS, Brazil
3
E-mail: charleshuber@ifsul.edu.br
The determination of trace and ultratrace element concentrations in commercially
available baby foods is necessary to control the dairy intake of essential and toxic
elements. Among the toxic elements, the arsenic takes a prominent place. Infants,
toddlers and preschooler children, consume relatively more food than an adult, when
comparing the ratio of the mass ingested by weight. Because of that, it is important to
determine the arsenic content in baby food. The identity of arsenic species (inorganic
and organic) controls their toxicity in food in general as well as in baby food. There
are two inorganic arsenic forms, arsenite (iAs(III)) and arsenate (iAs(V)) and more
than fifty organic arsenic compounds, among them the most abundant are
methylarsonate (MAs), dimethylarsinate (DMAs) and trimethylarsine oxide
(TMAsO). While the methods for analysis of iAs(III) and iAs(V) are well-known,
the analysis of methylated species are not usual. An automated system for hydride
generation-cryotrapping-atomic absorption spectrometry with multiatomizer (HGCT-AAS), which was recently developed for arsenic speciation analysis in biological
samples [1], is being applied for baby food slurry samples. In general, the use of
hydride generation-atomic absorption spectrometry require a sample pretreatment. A
total sample dissolution is usually accomplished with the use of acids and microwave
sample digestion in closed vessels. Regarding the arsenic speciation, the use of
strong oxidizing reagents such H2SO4, HNO3, HClO4, HBr and aqua regia, besides
being a time-consuming process, is not recommended to avoid the arsenic species
conversion. In order to maintain the original speciation, the sample preparation using
mild reagents is being evaluated. Up to now, two sample preparation approaches
were tested, the first one using HCl 1 mol L-1 and the second one using
tetramethylammonium hydroxide 0.96 mol L-1 (TMAH), both heated at 85-90 °C for
15 min and after that placed in ultrasound bath for 15 min. The reached optimum
conditions for sample preparation and arsines generation will be demonstrated.
This work was supported by Czech Science Foundation (project no P206/14-23532S),
Institute of Analytical Chemistry of the AS CR, v. v. i. (Institutional Research Plan
RVO: 68081715) and Conselho Nacional de Desenvolvimento Científico e
Tecnológico (CNPq, Brazil), grant no 400575/2013-2 and 202810/2014-3.
References
[1] T. Matoušek, A. Hernández-Zavala, M. Svoboda, L. Langrová, B. M. Adair, Z. Drobná, D. J.
Thomas, M. Stýblo, J. Dědina. Spectrochimica Acta Part B 63 (2008) 396-406.
118
PS1.3
Does asymmetric charge transfer play an important role as
the ionization mode in low power-low pressure GDMS?
S. Mushtaq1, E. B.M. Steers1, G. Churchill2, D. Barnhart2, J. C. Pickering3 and
K. Putyera4
1
Nu Instruments Ltd., Unit 74, Clywedog Road South, Wrexham, LL13 9XS, UK
3
4
Evans Analytical Group, 103 Commerce Blvd, Liverpool, NY 13088, USA
2
E-mail: s.mushtaq@londonmet.ac.uk
It has been suggested that in low power (~ 5W) analytical glow discharges (such as
VG9000 type sources) running in low pressure noble gases ~1 hPa, electron impact
ionization and Penning ionization (PI) are the main ionization pathways for the
sputtered atoms [1], and that although asymmetric charge transfer (ACT) may occur
in such sources, there is only minor contribution from this process [2]. On the other
hand, it has been shown that departures from a regular pattern of relative sensitivity
factors (RSF) most likely can be attributed to ACT [3]. In the current work, the ion
signals of the constituent elements in various standard reference materials have been
compared with various plasma gases (Ar, Kr and Ne), using the Nu Instruments
Astrum high resolution glow discharge mass spectrometer (~1 kV & ~3 mA.)
10
B.S. T-2 Ti in Argon
B.S. T-2 Ti in Krypton
1
I(E,M)(g) / I(G+)(g)
0.1
0.01
1E-3
1E-4
1E-5
1E-6
1E-7
1E-8
1E-9
C
N
O
Al
S
Ti
V
Cr Mn Fe
Ni
Cu Nb Mo Sn
W
Constituent elements (E) present in matrix (M)
The figure shows the ion signals of constituent elements relative to that of the plasma
gas. The order of magnitude higher value of this ratio for oxygen when krypton is
used is due to ACT by Kr. It will be shown that other differences in the ratios similar
to those shown above are linked to the arrangement of the ionic energy levels of the
elements concerned and the resulting relative importance of ACT and PI.
References
[1] R. L. Smith, D. Serxner, and K. R. Hess, Anal. Chem., 61, 1103-1108 (1989).
[2] M. K. Levy, D. Serxner, A. D. Angstadt, R. L. Smith, and K. R. Hess, Spectrochim. Acta Part B,
46, 253-267 (1991).
[3] A. Bogaerts and R. Gijbels, J. Anal. At. Spectrom., 11, 841-847 (1996)
119
PS1.4
The use of transition rate diagrams to identify changes in
discharge processes when O2 or H2 is present in a Cu/Ne
glow discharge
Z. Weiss1, S. Mushtaq2, E.B.M. Steers2, J.C. Pickering3, V. Hoffmann4 and
V. Weinstein2
1
2
LECO Instrumente Plzeň spol. s r.o., Plaská 66, 323 25 Plzeň, Czech Republic
3
4
IFW Dresden, Helmholtzstraße 20, 01069 Dresden, Germany
E-mail: WeissZ@leco.cz.
Transition rate (TR) diagrams, recently introduced by Weiss et al. [1-3] are a
powerful new way to study the excitation processes occurring in low pressure glow
discharges (GD), and the changes that occur if, for example, small amounts of
hydrogen are present in an argon discharge. Fig. 1, reproduced from reference [1],
compares the TR diagram for Mn II in pure argon with that for argon + 0.3 % v/v
hydrogen. The spectral lines excited by argon charge transfer excitation (Ar-ACT)
fall in intensity by a factor of about 10.
Fig. 1. Transition rate diagrams for Mn II in Ar (left) and Ar+0.3 % v/v H2 (right) plasma gases
We will use TR diagrams for the Cu II spectrum to compare and discuss the various
excitation processes taking place in analytical glow discharges in neon, neon/oxygen
[4] and neon/hydrogen plasma gases.
References
[1] Z.Weiss, E.B.M.Steers, J.C.Pickering & S.Mushtaq, Spectrochim. Acta, Part B, 92, 70–83 (2014)
[2] Z.Weiss, E.B.M.Steers, J.C.Pickering & S.Mushtaq, J. Anal. At. Spectrom., 29, 2078-2090 (2014)
[3] Z.Weiss, E.B.M.Steers, J.C.Pickering, V.Hoffmann & S.Mushtaq, J. Anal. At. Spectrom., 29,
2256-2261 (2014)
[4] S.Mushtaq, E.B.M.Steers, J.C.Pickering & V.Weinstein, J. Anal. At. Spectrom., 29, 2027-2041
(2014)
120
PS1.5
Relativistic evaluation of the two-photon decay of the
metastable 1s22s2p3P0 state in berylliumlike ions with
an active-electron model
P. Amaro1, F. Fratini2, L. Safari3, J. Machado1,4, M. Guerra1, P. Indelicato4
J. P. Santos1
1
2
Vienna Center for Quantum Science and Technology, Atominstitut,
Vienna University of Technology, 1020 Vienna, Austria.
3
IST Austria, Am Campus 1, A-3400 Klosterneuburg, Austria.
4
Detailed analysis of two-photon properties have revealed unique information about
electron densities in astrophysical plasmas and thermal x-ray sources, as well as
highly precise values of physical constants [1-2]. The study of two-photon decay in
high-Z ions with one or two electrons also provided a sensitive tool for exploring
subtle relativistic and retardation effects that occurs in such strong atomic fields. As
in the case of low-Z ions, predictions for two-photon decay in these kind of ions are
in good agreement with experimental data [3, 4].
Yet, scarce investigations have been performed so far for ions with more then two
electrons. We address here to Berylliumlike ions with zero nuclear spin. Owing to
the 0-0 selection rule, the first excited state 1s22s2p 3P0 is metastable and its
transition to the ground state 1s22s2 1S0 is strictly forbidden for all single-photon
multipole modes.
In this work, we evaluate decay rates considering a relativistic evaluation of the
second-order summation in a jj-coupling active-electron model. To take into account
the electron correlation, we incorporate the evaluation of the second-order
summation via a finite-basis-set and an effective local potential, with a few key
intermediate states calculated using the MultiConfiguration Dirac-Fock (MCDF)
method.
References
[1] S. Seager, et al, Astrophys. J. 523, L1 (1999).
[2] C. Schwob, et al, Phys. Rev. Lett., 82, 4960 (1999).
[3] S. P. Goldman and G. W. F. Drake, Phys. Rev. A, 24, 183 (1981).
[4] P. Amaro, et al, Phys. Rev. A, 79, 062504 (2009).
[5] R. W. Dunford, et al, Phys. Rev. Lett., 62, 2809 (1989).
.
121
PS1.6
Double KK excited states in highly charged sulphur
P. Amaro1, J. P. Marques2, P. Indelicato3, T. K. Mukherjee4,
J. K. Saha5, L. C. Tribedi6, J. P. Santos1
1
2
BioISI - Biosystems & Integrative Sciences Institute, Faculdade de Ciências da Universidade de
Lisboa, Campo Grande, C8, 1749-016 Lisboa, Portugal
3
4
Narula Institute of Technology, Agarpara, Kolkata-700109, India
5
Indian Association for the Cultivation of Science, Jadavpur, Kolkata-700032, India
6
Department of Nuclear and Atomic Physics, Tata Institute of Fundamental Research, Colaba,
Mumbai 400005, India
Double $KK$ excited states have several important applications in astrophysics as
well as in plasma diagnostics [1, 2]. Besides its applicability, the fundamental
interest of dominance of fluorescence over autoionization decay for some KK excited
states has attracted much attention, both from theoreticians and experimentalists [3,
4]. Recently, it was observed the 2p3d(1P0)-1s3d(1De) transition in helium with
sufficient accuracy to distinguish from the H-like Kα line, showing an enhanced
fluorescence rate compared to the one assuming standard selection rules [5].
In this work, we continue the investigation of KK excited states for sulphur by
performing a systematic identification of experimental lines, which includes both
single K and double KK excited states. The relativistic calculations were made
within the MCDF approach using the general relativistic MCDF code (MDFGME)
[6].
Experimental measurements were performed at the Pelletron accelerator facility in
TIFR Mumbai.
In these preliminary calculations, all transition energies and probabilities were
computed in a monoconfiguration approach. Almost all possible combinations of
excitations for Kα, Kβ and Kγ transitions of He through Be charge states were
considered.
References
[1] A. B. C. Walker and Jr., H. R. Rugge, Astrophys. J. 164, 181 (1971).
[2] T. Fujimoto and T. Kato, Astrophys. J., 264, 994 (1981).
[3] T.W. Gorczyca, at al, Phys.Rev.Lett. 85, 1202 (2000).
[4] J. G. Lambourne, at al, Phys.Rev.Lett., 90, 153004, (2003).
[5] S. Kasthurirangan, at al, Phys.Rev.Lett., 24, 243201, (2013).
[6] P. Indelicato and J. P. Desclaux, Phys.Rev.A, 42, 5139-5149 (1990).
122
PS1.7
Photochemical vapor generation of selenium(IV) and
arsenic(III) with commercial and homemade UV lamps
A. Menciassi1,2, B. Campanella1,2, M. Onor1, A. D’Ulivo1, E. Bramanti1, C.
Ferrari3, I. Longo3
1
C.N.R., Institute of Chemistry of Organometallic Compounds, UOS of Pisa, Via Moruzzi, 1,
56124 Pisa, Italy
2
University of Pisa, Department of Chemistry and Industrial Chemistry, Via Moruzzi 3, 56124
Pisa, Italy
3
C.N.R., Optics National Institute, UOS of Pisa, Via Moruzzi, 1, 56124 Pisa, Italy
E-mail: onor@pi.iccom.cnr.it
Nowadays photochemical vapor generation (photo-CVG) is a good competitor
of conventional chemical vapor generation for the determination of hydride–
forming elements, transition metals and non–metals. Photo-CVG is based on the
absorption of ultraviolet (UV) radiation by a low molecular weight organic acid,
which generates radicals necessary to the vapor generation process [1].
Our study is focused on the photo-CVG with formic and acetic acid of Se(IV)
and As(III) inorganic species. For Se(IV), we used a commercial mercury-UV
germicidal lamp with formic acid at low concentrations and we obtained yields
comparable to those of the classic CVG methods. Photo-CVG of As(III) was
much less efficient and the yield was at least 10 times lower than Se(IV), but
with quite similar trends varying the organic acid concentrations [2].
This work was also aimed to extend the operating range of the photo-CVG from
usual electroded lamps to mercury microwave-electrodeless discharge lamps
(MW-EDL). To the best of our knowledge, this type of UV lamps has been
employed for organic matter pre-digestion process [3], and for the photo-CVG
of Hg for trace analysis [4]. Here we report for first time the generation of
volatile hydrides by using photo-CVG with MW-EDL for trace analysis.
Data collected from mercury-MW/UV photo-CVG analysis have shown
behaviors similar to those obtained for the classical UV discharge lamps for both
inorganic As and Se species. The Photo-CVG yields varied with microwave
generator power. Photo-CVG experiments made with classic mercury lamp
(emission spectral line at 254 nm) were compared to those performed with a
homemade cadmium MW-EDL lamp (emission spectral line at 228 nm). The
preliminary results seemed to confirm the possibility of using, for the
photochemical vapor generation, spectral emission lines different from those
achievable by the use of mercury lamp.
References
[1] Y. Yongguang, L. Jinfu, J. Gibin, Trends in Analytical Chemistry, 30, 1672-1684 (2011)
[2] X. Guo, R.E. Sturgeon, Z. Mester, G.J Gardner, Analytical Chemistry, 75, 2092-2099 (2003)
[3] J.S.F. Pereira, H. Wiltsche, G. Knapp, Microwave-Assisted Sample Preparation for Trace
Element Determination, chapter 7, 205–229 (2014)
[4] D. P.C. de Quadros , B. Campanella , M. Onor , E. Bramanti, D. L.G. Borges , A. D'Ulivo,
Spectrochimica ACTA Part B, 101,312-319, 2014
123
PS1.8
Determination of fluorine in soil samples via the CaF
molecule by HR-CS GF MAS
W. Boschetti1, A. H. Pizzatto1, M. G. R. Vale1,2, M. B. Dessuy1,2
1
2
Instituto de Química, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500,
91501-970 Porto Alegre, RS, Brazil
Instituto Nacional de Ciência e Tecnologia do CNPq–INCT de Energia e Ambiente, Universidade
Federal da Bahia, Salvador, BA, Brazil
E-mail: mbdessuy@ufrgs.com
Fluorine may be present in soil naturally, in the form of minerals (fluorite,
fluorapatite and cryolite) or due to environmental pollution. Plants harvested in soils
with high levels of this element might be contaminated and consequently they may
present toxicological effects, such as necrosis or growth reduction. Hence, the
development of reliable and appropriate methods for the accurate determination of F
has become of great importance. The aim of this study was the development of an
analytical method for F determination in soil samples, monitoring the rotational lines
of the CaF molecule by high-resolution continuum source graphite furnace molecular
absorption spectrometry (HR-CS GF MAS) using direct solid sample analysis to
characterize a vineyard area. All measurements were carried out using the
wavelength at 606.440 nm, evaluating the center pixel only, and a standard solution
of 5 g L-1 Ca was used as the molecule-forming agent. The temperature program and
the amount of Ca were optimized, evaluating the integrated absorbance values (A int),
using a soil sample and an aqueous standard solution of fluoride. The pyrolysis and
atomization temperatures were 900 °C and 2100 °C, respectively, and the Ca mass of
75 µg was adequate to guarantee the formation of the CaF molecule in all
measurements. The sample masses weighted varied between 0.03 and 0.2 mg.
Fluoride aqueous standard solutions were used for calibration, resulting in a linear
working range between 1.5 and 27 ng F. The characteristic mass obtained was 0.1 ng
and the limits of detection and quantification were 0.9 and 3.0 ng mg -1, respectively,
calculated for 0.2 mg of sample. A certified reference material (CRM) of Lake
Sediment (LKSD-4, Ontario, Canada) was used to confirm the trueness of the
developed method. The value found for F (234±14 ng mg -1) was in agreement with
the certified value (260±40 ng mg-1), proving that the developed method provides
accurate results for F determination in soil samples. Finally, the developed method
was employed for the analysis of soil samples from a vineyard area of 10.000 m 2 (1
ha), divided in six soil clusters, the F content varied between 122 and 194 ng mg-1.
Acknowledgments: CAPES and CNPq.
124
PS1.9
Sequential and simultaneous determination of three
elements and one diatomic molecule in soil samples via HR CS GF AAS using direct solid sample analysis
W. Boschetti1, M. Orlando1, L. M. G. Dalagnol1, M. Dullius2, M. B. Dessuy1, 3,
M. G. R. Vale1, 3
1
2
Vinícola Geisse, Linha Jansen s/n, 95700-000 Pinto Bandeira, RS, Brazil
3
E-mail: wiliamcaxias@gmail.com
Soil analysis is an important tool to determine nutrient and contaminant content in soil
samples. It is also essential to realize proper use of soil amendments on a farm,
increasing significantly the quality of harvested products. In this context, high-resolution
continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS)
with direct solid sample analysis may provide adequate information on the soil
composition. This technique offers the advantage to perform multi-element analysis in
sequential [1] and/or simultaneous [2] modes and even the possibility of molecular
determination [3] (diatomic molecules). The aim of this study was the development of an
analytical method for the sequential and simultaneous determination of Cd, Cr, Fe and
Al in soil samples by HR-CS GF AAS, via direct solid sample analysis. The sequential
mode allows the determination of Cd (228.802 nm) first, using 800 °C and 1700 °C as
the pyrolysis and atomization temperature, respectively. After that, Cr (425.433 nm), Fe
(425.076 nm) and AlH (425.315 nm) can be determined simultaneously, using 2600 °C
as atomization (Cr and Fe) and vaporization (AlH) temperature. Due to the high
concentration of Cd present in the soil samples, an argon flow rate of 0.1 L min -1 was
applied in the atomization stage; moreover, secondary lines were used for Cr and Fe. The
Al determination was carried out using the diatomic molecule AlH without the necessity
to use a molecule-forming agent. However, aluminum is known to interfere in the
determination of Cd; in order to minimize this interference 10 μL of 10% v/v H2SO4 was
used in all measurements. Aqueous standard solutions were used for calibration and limit
of detection and limit of quantification were obtained as 18 and 61 pg mg-1 for Cd, 0.33
and 1.1 ng mg-1 for Cr, 0.18 and 0.58 μg mg-1 for Fe and 1.1 and 3.5 μg mg-1 for Al. A
certified reference material (CRM) of Montana Soil I (NIST – 2710a) was used to
confirm the accuracy of the obtained results; the values found for all elements are in
agreement with those reported by the CRM, proving that the developed method can be
used to determine Cd, Cr, Fe and Al in soil samples.
References
[1] A. T. Duarte, M. B. Dessuy, M. G. R. Vale, B. Welz, J. B. de Andrade, Talanta, 115, 55-60 (2013)
[2] W. Boschetti, A. R. Borges, A. T. Duarte, M. B. Dessuy, M. G. R. Vale, J. B. de Andrade, B.
Welz, Analytical Methods, 6, 4247-4256 (2014).
[3] A. R. Borges, L. L. François, B. Welz, E. Carasek, M. G. R. Vale, Journal of Analytical Atomic
Spectrometry, 29, 1564-1569 (2014).
125
PS1.10
Determination of chloride in crude oil by high resolution
continuum source molecular absorption spectrometry
I. K. S. Oliveira1, R. L. S. Medeiros1, D. R. Silva1 and T. A. Maranhão2
1
Universidade Federal do Rio Grande do Norte, Centro de Ciências Exatas e da Terra, Instituto de
Química, 59078-970, Lagoa Nova, Natal, Rio Grande do Norte, Brasil
2
Universidade Federal de Santa Catarina, Centro de Ciências Físicas e Matemáticas, Departamento
de Química, 88040-900, Trindade, Florianópolis, Santa Catarina, Brasil
E-mail: izabelkaline@gmail.com
The determination of chlorine and its salts in crude oil are very important, because
the presence of these elements in this matrix can cause severe problems of corrosion
and fouling in the equipment during the refining process. It is necessary first to
evaluate the physical and chemical properties of crude oil and also the presence of
undesirable substances to determine the viability of each of the various stages of
refining [1]. This work aims to develop a method of crude oil sample preparation for
determination of chlorine by molecular absorption spectrometry (MAS) through the
diatomic molecule MgCl. The sample preparation method was chosen
microemulsion. The composition of the microemulsion has been optimized using the
simplex centroid design, and the optimum condition of stability of the microemulsion
was considering 2.0 mL of solution n-propanol / TX-100 = 5, 0.5 mL of 5% HNO3
v/v and 0.5 mL of xylene. The pyrolysis and vaporization temperatures were
optimized considering the use of Pd modifier, 700 ° C and 2500 ° C were adopted
respectively. Quantification was performed by high-resolution and continuous source
molecular absorption spectrometry, (HR- CS MAS). Graphite tubes without platform
were used and measurements were made in wavelength of 377.0100 nm. Crude oil
samples from Rio Grande do Norte, Brazil were analyzed. Addition and recovery test
was used to assess the accuracy.
References
[1] Gary, J.H.; Handwek, G.E., Petroleum Refining – Technology and economics
4th, Marcel Dekker, New York, 455 p., 2001.
126
PS1.11
Characterization of Hf based thin films on Si wafers by
Grazing Incidence XRF Evaluation of the real metal
concentration in nanoparticles post synthesis for their
applications: A case-study using
silver nanoparticles
R.M. Galazzi1,2, E.B. Santos3, T. Caurin1,2, G.S. Pessôa1,2, I.O. Mazali4 and
M.A.Z. Arruda1,2
1
Spectrometry, Sample Preparation and Mechanization Group, Institute of Chemistry, University of
Campinas – Unicamp, P.O. Box 6154, Campinas, SP 13083-970, Brazil
2
National Institute of Science and Technology for Bioanalytics, Institute of Chemistry, University of
Campinas – Unicamp, P.O. Box 6154, Campinas, SP 13083-970, Brazil
3
Institute of Science and Technology, Federal University of São Paulo, 12231-280 São José dos
Campos-SP, Brazil
4
Functional Materials Laboratory, Institute of Chemistry, University of Campinas – Unicamp, P.O.
Box 6154, Campinas, SP 13083-970, Brazil
E-mail: rodrigo.galazzi@iqm.unicamp.br
In the last years, due to technological advances, the synthesis of nanoparticles (NPs)
were improved, enabling the application of these particles for several purposes [1-2].
Then, for metallic NPs, such as Ag, Au, Fe, Zn, Ti, Si, among others, different
strategies for the synthesis and characterization are present in the literature [2-3].
However, the real concentration of the metal present in NP form after the synthesis is
not receiving the same attention, being this important information sometimes
negligible.
For answering if the effect observed in a study is related to the NP only or to its
synergic effect with the “free” metal ions, the real concentration of silver (104 ± 8
and 100 ± 2 mg L-1) after AgNP synthesis was obtained through ICP-MS and ICP
OES, respectively, after the AgNP synthesis (AgNP-total) as well as in different
fractions after the centrifugation (at 8100 g @ 40 min) of this solution. From the
resuspension of AgNP (AgNP-res) contained in the AgNP-total, concentrations of 49
± 3 and 51 ± 3 mg L-1 are found to the AgNP-res and 50 ± 7 and 47 ± 2 mg L-1 to the
supernatant (Ag-sup) are found using ICP-MS and ICP OES, respectively.
The characterization of AgNP-total, AgNP-res and Ag-sup is carried out by HRTEM
and UV-Vis, corroborating all the results in terms of Ag determination, and
indicating that the half of the total silver concentration is in the silver nanoparticles
form and the other half is in the “free” silver. According to these results and taking
AgNPs as example, in studies wherein the entire solution obtained post synthesis is
employed, synergistic effects from NP and their “free” ions can be observed, once
that only AgNP-res fraction should be currently applied for evaluation of NP effects
in different studies.
References
[1] S.K. Ghosh; T. Pal, Chem. Rev., 107, 4797-4862 (2007).
[2] S.C.C. Arruda; A.L.D. Silva; R.M. Galazzi; R.A. Azevedo; M.A.Z. Arruda, Talanta, 131, 693-705
(2015).
[3] B.M. Geilich; A.L. van de Ven; G.L. Singleton; L. J. Sepúlveda; S. Sridhara; T.J. Webster,
Nanoscale, 7, 3511-3519 (2015).
127
PS1.12
Trace metal profiling for geographical characterization of
cocaine, heroin and hashish seizure
A. Moreda-Piñeiro1, P. Herbello-Hermelo1, M.C. Barciela-Alonso1, E. PeñaVázquez,1 P. Bermejo-Barrera,1 P. Cabarcos,2 M.J. Tabernero,2 A.M. Bermejo2
1
Department of Analytical Chemistry, Nutrition and Bromatology. Faculty of Chemistry. University
of Santiago de Compostela. Avenida das Ciencias, s/n. 15782 – Santiago de Compostela. Spain
2
Department of Pathologic Anatomy and Forensic Sciences. Faculty of Medicine. University of
Santiago de Compostela. Rúa de San Francisco, s/n. 15782 – Santiago de Compostela. Spain
E-mail: mcarmen.barciela@usc.es
Twenty-seven elements (Al, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Mo,
Na, Ni, P, Pb, Rb, Sb, Si, Sn, Sr, Ti, V and Zn) were determined in ninety-nine
cocaine, fourteen heroin, and nineteen hashish samples confiscated by the Spanish
police in Pontevedra (Galicia, northwest Spain). Inductively coupled plasma – mass
spectrometry (ICP-MS) was used for assessing metal concentrations in the samples.
Most of the cocaine samples were directly dissolved in 10%(v/v) nitric acid;
otherwise, cocaine samples (as well as heroin and hashish samples) were subjected to
a microwave assisted acid digestion procedure by using concentrated nitric acid and
oxygen peroxide (ramp rate of 17.5 °C/min for 4 minutes, followed by a ramp rate of
20°C/min for 3 minutes, a ramp rate of 50°C/min for 1 minute, and a hold stage at
200°C for 12 minutes).
Elements such as Ba, Ca, Cd, Cr, Hg, K, Li, Mg, Mn, Ni, P, Rb, Sb, Si, Sn, Ti, and V
were the dominating features when studying cocaine seizures by principal
component analysis (PCA) and cluster analysis (CA). Regarding heroin samples, the
elements which offer the highest information were Al, Ba, Ca, Fe, Mg, Mn, Ni, Rb,
Si, Sr, and V. Similarly, elements such as Al, Ba, Ca, Co, Cr, Cu, Fe, K, Li, Mg, Mn,
Na, P, Rb, Si, Sr, Ti, and V were found to be useful when characterizing hashish
samples. Explained variance accounted by PCA was 68, 99, and 83% for cocaine,
heroin and hashish, respectively. Examination of score plots (PCA) and dendrograms
(CA) showed five natural groupings for cocaine samples; whereas, three grouping
were observed for heroin and hashish samples. Available information regarding some
seizures was finally used for establishing the geographical origin of the studied
samples.
128
PS1.13
Determination of Some Trace Elements in Milk and Yogurt
Samples by Inductively Coupled Plasma Optical Emission
Spectrometry (ICP-OES)
D. Bakircioglu, Y. Bakircioglu Kurtulus, M. Kizildere, N. Topraksever
Department of Chemistry, Faculty of Science, Trakya University, Edirne, Turkey
E-mail: dbakircioglu@trakya.edu.tr
Milk and its products contain protein and trace elements which are essential to
promoting growth and the maintenance of human life. Milk and milk products also
contain non-essential trace elements as well as essential elements [1]. Actually, all
elements, including those that are essential nutrients, may be toxic when intakes
exceed safe levels [2].
The purpose of this study was to determine the concentration levels of some elements
at trace levels in milk and yogurt samples which are widely consumed in
Edirne/Turkey. Concentrations of some trace elements in milk and yogurt products
were quantitatively determined by inductively coupled plasma optical emission
spectrometry (ICP-OES). The performances of digestion procedures, namely, dry
ashing, wet ashing and microwave digestion were compared in this study. The
developed analytical method was validated by using both milk certified reference
materials and recovery experiments over different milk products, obtaining
satisfactory results in all cases.
References
[1] H. Sanal, Z. Guler, Y.W. Park, Food Additives and Contaminants: Part B, 4, 275–281, (2011).
[2] A. Hejtmankova, J. Kucerova, D. Miholova, D. Kolihova, M. Orsak, Czech Journal Animal
Science, 69, 253-260, (2002).
129
PS1.14
Production and characterization of activated carbon from
barley (Hordeum vulgare) pomace waste from beer
industries for lead removal
H. C. Rezende1, I. L. S. Almeida2, N. M. M. Coelho2, D. M. dos Santos3, A. G.
Pereira3, A. L. Bukzem3, D. P. R. Ascheri3, C. S. T. Araújo3
1
2
Instituto de Química, Universidade Federal de Goiás, 75805-190, Jataí, GO, Brazil
Instituto de Química, Universidade Federal de Uberlândia, 38400-902, Uberlândia, MG, Brazil
3
UnUCET, Universidade Estadual de Goiás , 75133-900, Anápolis, GO, Brazil
E-mail: helencristinerezende@yahoo.com.br
Increasing the concentration of toxic metals in aqueous systems released from
various industrial processes has caused serious environmental problems especially by
non-biodegradability and ability accumulation in living tissue [1]. Generally, metal
ions are removed from wastewater using conventional dilute physico-chemical
methods such as chemical reduction, electrochemical treatment, ion exchange,
precipitation, recovering by evaporation or adsorption on activated carbon [2].
However, in many cases, these methods are inefficient and require high cost [3]. Use
of the biomass of agricultural residues, such as the residue from the beer industries,
barley pomace, offers an interesting alternative based on its potential to be converted
to activated carbon. In this study, activated carbon was prepared from the pyrolysis
of barley pomace waste impregnated with ZnCl2. The activated carbon was
characterized by scanning electron microscopy (SEM), Fourier transform infrared
spectroscopy (FTIR), point of zero charge (PCZ), thermo-gravimetric analysis
(TGA) and X-ray diffraction (XRD). Batch adsorption process was followed in order
to evaluate the potentiality of the prepared activated carbon for the removal of Pb(II)
ions from aqueous solution with detection by flame atomic absorption spectrometry
(FAAS). The effects of initial concentration, contact time and pH has been studied.
With the optimized conditions was performed the adsorption kinetics and isotherms
study. Kinetic studies revealed that the adsorption process followed pseudo second
order model and adsorption experimental data were fitted to the Langmuir and
Freundlich isotherm adsorptions, and a very good fit to the Langmuir linear model,
giving a maximum adsorption capacity 68.87 mg g-1.
References
[1] SAADAT, S.; KARIMI-JASHNI, A. Chemical Engineering Journal, 173, 743- 749 (2011).
[2] OLORUNDARE, O. F.; KRAUSE, R. W. M.; OKONKWO, J. O.; MAMBA, B. B. Physics and
Chemistry of the Earth, 50–52, 104–110 (2012).
[3] LIU, H.; GAO, Q.; DAI, P.; ZHANG, J.; ZHANG, C.; BAO, N. Journal of Analytical and
Applied Pyrolysis, 102, 7–15 (2013)..
130
PS1.15
Development of a simple method for the determination of
Cd, Pb and Cr in phosphate fertilizers using a ultrasoundassisted extraction and GFAAS
H. C. Rezende1, N. M. M. Coelho2
1
2
Instituto de Química, Universidade Federal de Goiás, 75805-190, Jataí, GO, Brazil
Instituto de Química, Universidade Federal de Uberlândia, 38400-902, Uberlândia, MG, Brazil
E-mail: helencristinerezende@yahoo.com.br
The raw material for production are the phosphate rocks, which have in their
composition beside phosphorus, various contaminants such as arsenic, mercury, lead,
chromium and cadmium [1]. The concentrations of these contaminants are varied,
depending on the rock from which the fertilizer was obtained. As are used in
agricultural successive fertilization, these metals can accumulate in the soil, making
it available for plant uptake and therefore enter the human food chain [2]. Removal
of these elements in the production process or the final product of the fertilizer is not
economically viable, therefore, it is necessary to perform the control of the
concentration of these elements in fertilizers that have been directly applied to the
soil [3].
A simple method for the determination of Cd, Pb and Cr in phosphate fertilizers
using a ultrasound-assisted extraction and graphite furnace atomic absorption
spectrometry was developed. The curves of pyrolysis and atomization were
constructed for the analytes in order to in order to achieve greater analytical
efficiency. Multivariate optimization through a factorial design and desirability
functions was applied to establish a single extraction procedure of metals.
Quantitative extraction was achieved with 20 mL of mixture of HNO 3 and HCl acids
1 mol L-1 and sonication for 7.5 min. The sensitivity of the methods were determined
using the characteristic mass (mo) and limits of quantification (LOQ ) were 0.54,
8.22 and 2.54 pg and 0.11, 0.90 and 0,63 g L-1 for Cd, Pb and Cr , respectively.
Precision was expressed as RSD (%), and was less than 5 % and the accuracy of the
method was evaluated by analysis of certified material NIST SRM 695, not
significant difference at a level of 95 % with the certified values, were observed. The
method was applied in the analysis of phosphate fertilizers produced in the Brazil
and the levels found were below the maximum values established by brazilian
legislation.
References
[1] AYDIN, I.; AYDIN, F.; SAYDUT, A.; BAKIRDERE, E.G.; HAMAMCI, C. Microchemical
Journal, 96, 247–251 (2010).
[2] WU, L.; TAN, C.; LIU, L.; ZHU, P.; PENG, C.; LUO, Y.; CHRISTIE, P. Geoderma, 173-174,
224–230 (2012).
[3] NACKE, H.; GONÇALVES JR., A. C.; SCHWANTES, D.; NAVA, I. A.; STREY, L.; COELHO,
G. F. Archives of Environmental Contamination and Toxicology, 64, 537–544 (2013).
131
PS1.16
Simultaneous Determination of Nd, La, Sr, Al and Ta in
Crystal Nd:LSAT by ICP-AES
HongJun Shi 1, Li Wang1
1
Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, P.R.China,
E-mail: shihj@iphy.ac.cn
A rapid ICP-AES method for the determination of Nd, La, Sr, Al and Ta in Nd:
(La0.272Sr0.728)(Al0.648Ta0.352)O3 (Nd:LSAT) crystals is described.The sample is fused
with a mixture of lithium metabrorate and the ground fusion product is dissolved in
dilute citric acid[1,2]. Matrix effect from lithium metabrorate and spectral interference
to the spectral lines of the elements determined were investigated and corrected by
matrix matching and backround correction method. The detection limits of Nd
element are 28 ng ml-1 and 35 ng ml-1, the recoveries are 96.9%101.3%, the relative
standard deviations are 1.0% (1.5 g ml-1 Nd) and 3.8% (0.4 g ml-1 Nd) for Nd, and
less than 1.0% for rest elements. This method is simple, rapid and accurate, and has
been applied to the analysis of sample with satisfactory results.
References
[1] K. Govindaraju, Appl. Spectry, 20, 302(1966).
[2] K. Govindaraju, Appl. Spectry, 24, 81(1970).
[3] Z. X. Jin, Y. Zheng, Anal. Lab. (Beijing), 7, 36(1988).
[4] X. K. Cheng, Principle and Apply of Inductively Coupled Plasma Atomic
Emission Spectrum, NanKai Univ. Press, 198(1987).
132
PS1.17
Determination of silicon in plant material using
HR-CS GF AAS and direct solid sample analysis
W. Boschetti1, L. M. G. Dalagnol1, E. M. Becker1, M. Dullius2, M. G. R. Vale1, 3
1
3
2
Vinícola Geisse, Linha Jansen s/n, 95700-000 Pinto Bandeira, RS, Brazil
E-mail: mgrvale@ufrgs.br
Silicon (Si) plays an important role to prevent diseases such as Osteoporosis [1] and
Alzheimer’s disease [2]. The development of reliable and appropriate methods for
the accurate determination of silicon has become of great importance. Since Si is
omnipresent, direct solid sample analysis associated with high-resolution continuum
source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) represents
an important tool to overcome contamination risk, mainly caused by sample
pretreatment. The objective of this study was the development of a method to
determine Si by HR-CS GF AAS in different plant materials using direct solid
sample analysis. In order to avoid the formation of stable silicon carbide and volatile
silicon species [3], iridium (Ir) and rhodium (Rh) were investigated as permanent
modifiers alone and also in the presence of Pd/Mg modifier in solution. Certified
reference materials (CRM), NCS ZC73014 (tea) and NCS ZC73349 (bush branches
and leaves), were evaluated for method development. Aqueous Si standard solutions
were used for calibration. Due to the high concentration of Si in CRMs, the
secondary analytical line at 221.174 nm, and a gas flow of 0.1 L min-1 was used in
the atomization stage. The central pixel (CP) was used for signal evaluation. Among
the investigated modifiers, using Rh in addition with Pd/Mg in solution, the results
showed the best improvement on sensitivity, evaluated by integrated absorbance
(Aint), and in the Si signal profile for standards and CRM. The adequate amount of
Pd/Mg in solution, using 300 μg of Rh, was 20 μg Pd + 12 μg Mg. The optimized
pyrolysis and atomization temperatures were 1200 and 2650 °C, respectively. The
CRM and sample masses varied between 0.05 and 0.70 mg without spectral
interferences on CP. The linear range was between 30 and 600 ng Si. The limit of
detection (LOD) and the limit of quantification (LOQ) were 6 and 15 ng mg -1,
respectively, calculated for 0.50 mg of sample. The Si content investigated in ten
plant materials varied between 0.5 and 20 µg mg-1. The accuracy of the method was
evaluated using NCS ZC73014 and NCS ZC73349 CRMs and results presented no
significant difference between the certified and found values. Therefore, the obtained
results prove that an accurate method has been developed and it could be applied to
analyze plants samples with different compositions.
References
[1] H. M. Macdonald, A. C. Hardcastle, R. Jugdaohsingh, W. D. Fraser, D. M. Reid, and J. J. Powell,
Bone, 50, 681-687 (2012).
[2] J. L. Domingo, M. Gomez, M. Teresa Colomina, Nutrition Reviews, 69, 41-51(2011).
[3] H. J. Heinrich, H. Kipphardt, Spectrochimica Acta Part B, 70, 68-73 (2012).
133
PS1.18
Novel dielectric barrier discharge atomizer designs of
volatile compounds for AAS and AFS
M. Svoboda1, J. Kratzer1, A. Michels2, J. Franzke2 and J. Dědina1
1
Institute of Analytical Chemistry of the AS CR, v. v. i., Veveří 97, 602 00 Brno, Czech Republic
2
ISAS – Institute for Analytical Sciences, Otto-Hahn-Str. 6b, 44 227 Dortmund, Germany
E-mail: svoboda750@biomed.cas.cz
Although both AAS and AFS are nowadays considered as well-established techniques there have been
significant instrument developments in last years. Miniature dielectric barrier discharge (DBD) plasma
atomizers of volatile compounds can replace the commonly used quartz tube atomizers in AAS or
diffusion flames in AFS. A DBD atomizer design with planar configuration of metal electrodes is
used in AAS [1]. The optical axis of the spectrometer is parallel with the electrodes since all the main
system components, i.e. radiation source-atomizer-detector, lie on a straight line in AAS
(180 °geometry). Analyte absorption is thus measured through the whole volume of the DBD plasma.
Atomization of As, Se, Sb, Sn and Bi hydrides in the DBD with AAS detection have been reported in
literature so far. Only basic DBD parameters (plasma power, discharge gas flow rate) and fundamental
analytical characteristics (LOD) are usually reported. The most detailed study on Bi originates from
our laboratory [1]. No effort is usually made to study the atomization mechanisms and processes in
the plasma. Moreover, plasma emission characteristics, being a valuable plasma diagnostic tool, can
be recorded due to the non-transparent metal electrodes of the planar design only in the “end view”
mode. Thus, only non-spatially resolved average emission signal through the whole plasma volume is
accessible for measurement in this design. To overcome this disadvantage of the common planar DBD
design with metal electrodes a modification of the DBD with electrodes made of indium tin oxide
(ITO) was constructed. ITO is an electrical conductive material being optical transparent at the same
time. The ITO transparency below 300 nm is negligible. Since almost all analytical lines of hydride
forming elements lie in this spectral range their determination based on observation through the walls
is impossible. On the other hand, emission lines of various discharge gases (Ar, He, N 2, air) can be
effectively detected being well above 300 nm. As a consequence, also spatially-resolved diagnostic
emission measurements are feasible with ITO electrodes allowing separate monitoring of the central
and peripheral plasma regions. Atomization performance of planar DBD designs of the same
geometry with metal (Cu) and ITO electrodes, respectively, will be compared employing AAS
detection. Plasma characteristics of both central and peripheral discharge regions will be outlined as
well as the discharge mode (homogeneous versus filamentary) will be determined.
Contrary to AAS with its 180 °geometry, a 90 ° geometry is dictated by AFS principle. A cylindrical
(tubular) design of DBD atomizer is typical for AFS detection employing concentric arrangement of
the electrodes [2]. The signal in AFS is usually recorded above the top of the DBD atomizer since
metal non-transparent electrodes are used in common designs. However, this region accessible for
signal detection lies completely outside the plasma area, where analyte atomization takes place. As a
consequence, a decay of free analyte atoms resulting in impaired sensitivity occurs in that region even
when employing a protecting gas flow in a designed shielding unit. This limitation of the DBD-AFS
atomizers might be solved by newly proposed design, in which fluorescence could be detected directly
from the plasma region. The plasma discharge is ignited between two metal electrodes of various size
and structures, no other walls are employed in this configuration to delimit the discharge. The whole
discharge area is protected from the ambient atmosphere by a flow of shielding gas. The atomization
performance of the novel DBD atomizer construction will be firstly compared to that of cylindrical
DBD with solid metal electrodes using AAS detection. Subsequently, its applicability to AFS will be
discussed.
This work was supported by the Academy of Sciences of the Czech Republic (project of international
cooperation no. M200311202), Czech Science Foundation (project no. P206/14-23532S) and Institute
of Analytical Chemistry of the AS CR, v. v. i. (Institutional Research Plan RVO: 68081715).
References
[1] J.Kratzer, J.Boušek, R.E.Sturgeon, Z.Mester and J.Dědina, Analytical Chemistry, 86, 9620-9625
(2014).
[2] Z.Xing, B.Kuermaiti, J.Wang, G.Han, S.Zhang and X.Zhang, Spectrochimica Acta B, 65, 10561060 (2010).
134
.
PS1.19
Quantification of bovine serum albumin and L-cysteine by
HRCSAAS
E. Andrade-Carpente, E. Peña-Vázquez and P. Bermejo-Barrera
University of Santiago de Compostela, Department of Analytical Chemistry, Nutrition and
Bromatology, Faculty of Chemistry, Av. das Ciencias, s/n 15782 Santiago de Compostela, Spain
E-mail: elenamaria.pena@usc.es
High Resolution Continuum Source Atomic Absorption Spectroscopy can be
applied for multielemental sequential determination in the entire spectral range (190900 nm) using the atomic peaks, and also for determining elements such us P or S
using the fine structure of molecular absorption bands.
In this study, the content of sulfur was analyzed by Flame HRCSAAS with
the ContrAA® 300 (Analytik Jena) equipment. Flame conditions were optimized
using standards containing 3.0% sulfuric acid and an acetylene-rich flame to generate
CS. The selected conditions were: gas flow 120 L/h, acetylene/air ratio 0.268,
reading height above the burner 12 mm, time delay 15 s, and reading time 25 s. A
number of 200 pixels per spectrum were registered and only the five central pixels
were used to evaluate the absorbance at 258.056 nm. The pixels number 95-97
(258.0474-258.0502 nm) and 109-111 (258.0675-258.0704 nm) were selected for
background correction.
The digestion of bovine serum albumin (BSA) and L-cysteine was performed
using a domestic MW instrument and an Ethos Plus MW labstation. During the
digestion step sulfur was converted to sulfate and afterwards it was determined by
HRCSAAS. The best results were obtained with the Ethos Plus MW labstation that
provided recoveries of sulphur of 105.9% vs. 81.3% (domestic MW).
Finally, the analytical characteristics of the method to analyze proteins via
sulfur determination were studied. The calibration and addition graphs showed
regression coefficients higher than 0.994. The limits of detection were 65.1 mg
BSA/g and 44.3 mg/g of sample for L-cysteine. The method was reproducible with
relative standard deviations values lower than 10%.
135
PS1.20
Determination of the total content of trace elements in
seawater by ICP-MS after UV irradiation
J.I. Carlino-Montpellier, E. Peña-Vázquez, M.C. Barciela-Alonso
and P. Bermejo-Barrera
University of Santiago de Compostela, Department of Analytical Chemistry, Nutrition and
Bromatology, Faculty of Chemistry, Av. das Ciencias, s/n 15782 Santiago de Compostela, Spain
E-mail: elenamaria.pena@usc.es
A method was developed for the determination of the total concentration of
essential (Fe, Cu, V, Co, Mn and Ni) and toxic (Pb, Cd) trace elements in seawater
using the SeaFAST2 (Perkin Elmer, Norwalk, EEUU) preconcentration system
coupled to ICP-MS. Samples acidified with Hiperpur-Plus nitric acid (final
concentration 2%) and containing sodium persulfate (0.2g/100mL) were previously
UV-irradiated for 15 min (UV PSA model 10.570, 78VA). Afterwards, the samples
were desalinated, and the elements preconcentrated using an iminodiacetate column
that was coupled on-line with the ICP-MS detector.
The slopes of the calibrations graphs using different matrixes (acidified
seawater and acidified river water, acidified seawater and river water treated with
persulfate) were compared. Significant differences were found (test t, 95%
confidence level) among the slopes, and therefore the presence of matrix effect was
confirmed. The introduction of several internal standards (Y, Rh, In) did not improve
the results or the linearity of the calibration graphs. Mn was used as a reference and
analyzed using the direct mode and the preconcentration mode. The preconcentration
factor was 50 (slope ratio between the calibrations obtained in preconcentration and
direct mode).
The limits of detection were: 0.0017 μg/mL (Cd111), 0.0009 μg/mL (Co59),
0.0105 μg/mL (Cu63), 0.1584 μg/mL (Fe56), 0.0375 μg/mL (Mn55; direct mode),
0.0050 μg/mL (Mn55, preconcentration mode), 0.0472 μg/mL (Ni60), 0.0079 μg/mL
(Pb208) and 0.2547 μg/mL (V51). The method showed a good precision with relative
standard deviations lower than 10% (n=10). The accuracy was evaluated using the
certified reference materials NASS-4 (ocean water) and CASS-5 (seawater). The
analytical recovery was also calculated with average levels of approximately 100%
for all the elements studied.
The concentration of the analytes was studied in samples from Galicia
(northwestern Spain) with and without UV-irradiation. The concentrations showed
no significant changes for most of the elements with the exception of Co and Cu that
are partially bound to organic matter.
Acknowledgements
The authors wish to thank the economic support from the research project number
CTQ2012-38091-C02-02 (Ministerio Ciencia e Innovación, Government of Spain).
136
PS1.21
Development of method for chlorine determination in
environmental samples by MgCl using high resolution
continuum source molecular absorption spectrometry
R. L. S. Medeiros1, D. R. Silva1, R. G. O. Araújo2 and T. A. Maranhão3
1
Universidade Federal do Rio Grande do Norte, Centro de Ciências Exatas e da Terra, Instituto
de Química, 59078-970, Lagoa Nova, Natal, Rio Grande do Norte, Brasil
2
Universidade Federal da Bahia, Instituto de Química, Departamento de Química Analítica,
40170115, Ondina, Salvador, Bahia, Brasil
3
Universidade Federal de Santa Catarina, Centro de Ciências Físicas e Matemáticas,
Departamento de Química, 88040-900, Trindade, Florianópolis, Santa Catarina, Brasil
E-mail: rlourena@gmail.com
The aim this work was the determination of chlorine by molecular absorption
spectrometry (MAS) through the diatomic molecule MgCl in environmental samples.
Box Behnken design was used to better understand the generation of diatomic molecule
MgCl. The study considered MgCl2.6H2O salt as a source of chloride. Maximum points
was obtained for the response surfaces and the critical value was 16.6 g L-1 of standard
Mg metallic, 47.3 mg L-1 of chloride and 12.5% v/v HNO3, with this condition in which
the amount Mg added should be approximately 350 times greater than the chloride, thus
the chlorine behave as limiting reagent, and the formation of molecular species MgCl is
complete. The wavelength of 377.01 nm (headband) was used as characteristic band of
the molecular specie [1]. The evaluation of the thermal stability was studied and the
molecule was thermally stabilized after using Pd modifier. The optimum temperatures
pyrolysis and atomization was 500 °C and 2500 °C respectively. The method was
applied for two different certified reference material, coal (BCR 182) and bovine muscle
(NIST 8414), the values obtained by the proposed method showed excellent agreement
with the certified values, 107% and 81% was obtained respectively. The detection limit
was 0.17 mg g-1. The method was applied to real samples of produced water, since the
quantification of Cl in these samples is not a trivial action. For samples of produced
water, the recovery test showed values of 81 to 100%.
References
[1] PEARSE, R. W. B.; GAYDON, A. G., Chapman and Hall, 4 ed., 217-219 (1976).
137
PS1.22
A Python code to optimize the operating conditions of the
semiquantitative mode of an ICP-MS spectrometer
J.A. Paixão, M.C. Silva, P.S.P. Silva
CFisUC, Department of Physics, University of Coimbra, Portugal
E-mail: jap@fis.uc.pt
Semiquantitative analytical procedures are offered by modern ICP-MS instruments
and are useful for a quick and rough survey of the concentration of elements not
present in calibration solutions. These procedures rely on a standard instrument
sensitivity function and on a table of “response” factors of analytes that need to be
determined for each operating conditions, as they depend on the plasma temperature,
the main factor determining the degree of ionization of each analyte, as well as on
other factors, including possible matrix effects. The ionization fraction f of each
element depends namely on the ionization energy of the analyte, the temperature and
constitution of the plasma, and can be approximately modeled using the Saha
equation [1,2]:
To use this equation, the ionization potential V, partition functions of the analyte and
its ion Z, Z+, electron density, ne, and temperature T of the plasma must be known.
The analyte parameters are known but the parameters of the plasma are only known
approximately. We have developed a Python code to determine the best response
factors of analytes following the general procedure outline in [2]. The program will
determine by a non-linear least-squares procedure the plasma temperature, plasma
electron concentration, and a polynomial approximation to the sensitivity of the
instrument that results in a minimum residual between the observed and calculated
response, or sensitivity, of the instrument. Optimization of the semiquantitative
analytical procedure using this code on a Thermo ICAP-Qc instrument will be
presented.
Acknowledgement: Access to the ICP-MS instrument at TAIL-UC facility funded
under QREN-Mais Centro Project ICT_2009_02_012_1890 is gratefully
acknowledged.
References
[1] Saha, M.N. Phil. Mag. Series 6, 40, 472-488 (1920).
[2] de Galan, L., Smith, R., and Winefordner, J. D., Spectrochim. Acta, Part B, 23,
521 (1968).
[3] Bayon, M.M., Alonso G.I.J., Medel A.S., J. of Anal. Atomic Spectroscopy, 13(4),
277-282 (1998).
138
PS1.23
PlasmaQuant® PQ 9000 – Advances in Sensitivity and
Matrix Tolerance of ICP Optical Emission Spectrometry
Sebastian Wünscher,1 Jan Scholz, 1 Margrit Killenberg, 1 Heike Gleisner1
and Alf Liebmann1
1
Analytik Jena AG, Konrad-Zuse-Straße 1, 07745 Jena, Germany
E-mail: sebastian.wuenscher@analytik-jena.de
Since the introduction of ICP optical emission spectrometry (OES), both the spectral
resolution and the analytical stability of the plasma have been main concerns with
respect to accuracy and sensitivity.
The wealth of emission lines from the plasma frequently leads to overlapping
between lines of the analyte and that of accompanying elements. In many sample
matrices such spectral interferences impair the recognition of the analyte signal and
thus restrict the free choice of analytical lines. Hence, less sensitive alternative lines
are frequently used that exhibit poorer detection limits.
Similarly, the detection power of ICP optical emission spectrometry is hugely
affected by the ability of the plasma to tolerate high sample loads. For matrix-rich
samples like brine, crude oil or high-alloyed steel effective detection limits will then
be best when excellent plasma and signal stability are achieved, while sample
dilution is minimal. Otherwise, already small analyte signals of traces and ultratraces
will become undetectable.
Herein, we wish to report on the potential of the PlasmaQuant® PQ 9000 for the
ultra-trace analysis of heavy matrices’ samples including brines, refractory metals
and volatile organics.
139
PS1.24
Determination of REE in phosphate-containing fertilizers
and agricultural gypsum by Synchronous Vertical Dual
View ICP OES
R. C. Machado1, C. D. B. Amaral1, D. Schiavo2, J. A. Nóbrega1 and A. R. A.
Nogueira3
1
Group of Applied Instrumental Analysis, Department of Chemistry,
Federal University of São Carlos, São Carlos, SP, Brazil
2
Agilent Technologies, Barueri, SP, Brazil
3
Embrapa Southeast Livestock, São Carlos, SP, Brazil
E-mail: raquelcm.quim@gmail.com
Agricultural inputs, such as mineral fertilizers and gypsum, are essential for ensure
crop grown and development, and to replenish natural nutrients depleted from soils.
However, these external inputs can also be a source of inorganic contaminants and
rare earth elements (REE´s) from phosphate rocks used in fertilizer production. The
monitoring of these specific elements is important in order to know the basal-level
and anthropogenic effects caused by its addition into the soil [1,2]. This work
describes an analytical method for determination of REEs in phosphate-containing
fertilizers and agricultural gypsum using an inductively coupled plasma optical
emission spectrometer ICP OES (Agilent Technologies, Australia), in radial and new
Synchronous Vertical Dual View (SVDV) viewings. Three emission lines with more
intensities for each analyte were selected for determination, but results are presented
only for the ones below mentioned. Samples were microwave-assisted digested with
diluted HNO3 and H2O2. Limits of detection (LODs) were: 0.14, 0.61, 0.10, 2.60,
0.49, 0.81, 0.46, 0.43, 1.02, 0.02, 0.05, 1.27, 0.71, 1.59, 0.08, 8.48, and 1.59 mg kg-1
in SVDV viewing for Ce (446.021 nm), Dy (340.780 nm), Er (269.265 nm), Eu
(397.197 nm), Gd (335.048 nm), Ho (338.895 nm), La (408.671 nm), Lu (307.760
nm), Nd (401.224 nm), Pr (422.532 nm), Sc (335.372 nm), Sm (360.949 nm), Tb
(350.914 nm), Th (283.730 nm), Tm (346.220 nm), Y (371.029 nm) and Yb (289.138
nm), respectively. Comparing different viewings, LODs were slightly better in
SVDV. Accuracy was evaluated by addition and recovery experiments in two spike
levels (0.1 and 1.0 mg L-1) for all elements and in both viewings. Recoveries in
SVDV viewing ranged from 90 to 111 % for evaluated samples. Best results for
gypsum samples were reached in radial viewing owing to higher concentrations of
REEs. On the other hand, best results for fertilizers were obtained in SVDV view
because these samples contained lower amounts of REEs. It may be concluded that
careful choice of viewing position and dilution factors led to proper accuracy and
sensitivities for REEs determination in both viewing modes and concentrations
ranged from 10 to 477 mg kg-1 and 2.5 to 3392 mg kg-1 for phosphate-containing
fertilizers and agricultural gypsum, respectively. Dy, Ho, Lu and Tm were not found
in any mineral samples. Instrument capability for simultaneous measurements in both
views allows fast data acquisition without increasing argon consumption.
References
[1] Spectrochimica Acta Part B, 96, 1-7 (2014).
[2] Microchemical Journal, 96, 247-251 (2015).
140
PS1.25
Electrochemical Hydride Generation of Tellurium Hydride
with QT AAS and MDF-AFS Detection
T. Resslerová1 and J. Hraníček1
1
Department of Analytical Chemistry, Faculty of Science, Charles University in Prague, Hlavova 8,
Prague 2, CZ-12843, Czech Republic
E-mail: hranicek@natur.cuni.cz
Hydride generation is a method of sample introduction commonly used in atomic
spectrometry for the determination of elements forming volatile hydrides. It
possesses several advantages like a separation of the analyte from the matrix and thus
reduction of the majority of interferences, and increase of determination sensitivity.
Hydride generation is a suitable derivatization technique for some important
environmental pollutants. Some of them are not so easily transferred into the volatile
compound, and tellurium was chosen as a representative.
The investigation was focused on the electrochemical tellurium hydride generation
and its atomization in quartz tube AAS and microflame AFS. A laboratory-made
electrolytic cell was designed and the generation setup was optimized; the optimized
parameters included i.e. the cathode material, the composition of catholyte solution,
the flow rates of the catholyte and carrier gas. Limits of detection were determined
for both studied detection techniques and the interferences of various elements on the
Te determination were compared. The interference study covered other hydride
forming elements (As, Se and Pb), transition metals (Fe, Ni and Zn) and alkaline and
alkali-earth metals (K, Ca, Na and Mg). These groups of interferents were selected
due to different mechanism of interference; i) the hydride forming elements interfere
mainly competitively in both gaseous and aqueous phase, ii) the interference of
transition metals takes place mainly in the aqueous phase and by modifying the
electrode surface, iii) the alkali metals group was included because of the high
abundance of these elements in real samples. The study assesses the effect of
individual types of the interferents and focuses on the comparison of the interferents’
influence on different detection techniques.
Acknowledgements
This work was supported by the Czech Science Foundation grant no. P206/14-23532S.
141
PS1.26
Chemical generation of lead hydride with AAS detection:
Interference study
O. Hillmich, T. Resslerová and J. Hraníček1
1
Charles University in Prague, Faculty of Science, Department of Analytical Chemistry,
Hlavova 2030/8, CZ-128 43 Prague 2, Czech Republic
E-mail: jakub.hranicek@natur.cuni.cz
This experimental work is focused on the interference study of different elements
during lead hydride generation. Atomic absorption spectrometry with externally
heated quartz tube atomizer was used as a detection technique. Volatile hydride of
lead (plumbane) was generated by chemical reaction with sodium borohydride as a
reduction agent in acidic solution (hydrochloric acid). As it was mentioned
previously [1], the sensitivity of lead determination increases significantly in the
presence of hexacyanoferrate as an oxidant agent. All experiments were carried out
in flow injection mode.
At first, an apparatus for chemical hydride generation of volatile compounds was
designed. This experimental setup consists of peristaltic pump, Teflon tubes,
injection valve, laboratory made gas/liquid separator and quartz tube as
atomization/detection system. Before interference study, significant experimental
conditions were optimized. The optimizations include flow rate of carrier gas
(argon), concentrations and flow rates of all reagents (HCl, NaBH 4, K3[Fe(CN)6]),
atomization temperature and volume of sample loop. Under the optimal conditions
the calibration dependence was measured. Consequently basic characteristics of lead
determination were determined (sensitivity 0.0012 l∙μg-1 and limit of detection (3.13
μg∙l-1).
For interference study several groups of compounds were tested. First group
contained representatives of other hydride-forming elements (As, Se, Sb, Sn, Bi, Te).
Then the significant transition metals (Fe, Ni, Cu, Zn), one alkali and one alkaline
earth metal (Na, Ca) were tested in their ions form. Finally, common anions (Cl-,
SO42-, NO3-) including acetate anion (as a representative of organic molecule) were
investigated. The most serious interferences were observed for hydride-forming
elements, mainly for selenium. This element at low concentrations increased
absorption signal. However at high concentrations it strongly suppress signal. The
other important interfering elements were antimony, arsenic, copper, tellurium and
bismuth. Bismuth in all concentrations significantly suppressed measured signal.
Practically no interference effects were observed for nickel, zinc, iron, chlorides,
sulfates and nitrates.
References
[1] Kratzer J., Spectrochimica Acta part B, 71-72, 40-47 (2012).
142
PS1.27
(Im)possibilities of Determination of Arsenic Using
UV-photochemical Generation of Its Volatile Compounds
and QF-AAS
Anna Vlckova1, Jana Smolejova1, Ondrej Linhart1, Vaclav Cerveny1,
Jakub Hranicek1 and Petr Rychlovsky1
1
Charles University in Prague, Faculty of Science, Department of Analytical
Chemistry, Albertov 6, CZ-128 43 Prague 2, Czech Republic
E-mail: cerveny2@natur.cuni.cz
The motivation of the presented work has resulted from the lack of definite literature
data about the determination of arsenic employing UV-photochemical generation of
its volatile compounds. The paper [1] remains the main information source about
volatile compounds formed by UV-irradiation of arsenic in formic and acetic acid
media. The authors reported that the calculated signal-to-background ratio is more
than 1500 at 5 ng/mL concentration level of each element studied (As, Sb, Bi, Se and
Te) [1]. However, limits of detection, sensitivity and other methods characterizations
have been reported only for the other elements (excluding As) in all over the
literature. Just the relative enhancement factors for arsenic in formic, acetic and
propionic acid were listed [2] while necessity of the presence of both UV light and
the acids was proved for volatile species production [3]. The enhancement factor
value reported for arsenic was the lowest one in comparison to the other hydride
forming elements [2]. We have not found any other specific value related to the
determination of arsenic using proposed method of UV-photochemical generation of
volatile compounds. This is unusual especially regarding toxicity of arsenic and
analytical importance of its determination.
Due to the reaction times published [1] as well as volatility of the produced arsenic
compounds [3], formic acid was chosen as the most suitable reaction medium for
experiments carried out. The used UV-photochemical generator was constructed by
wrapping of PTFE tube (2.5 m x 1 mm ID x 2 mm OD) around the low pressure Hg
lamp (20 W, 254 nm). After the optimization of the flow injection arrangement, the
sensitivity of the determination of arsenic by the proposed method of UVphotochemical generation of its volatile compounds was around 16 % of the
sensitivity obtained for the conventional chemical hydride generation with the same
detection by quartz furnace atomic absorption spectrometry.
Subsequently, effects of some added chemicals were explored with the aim to find a
suitable reaction modifier which could cause substantial increasing of the analytical
signal. At this time, the sensitivity has risen more than three times by addition of the
selected reaction modifier. Further investigations will be focused on finding of the
place of acting of this modifier in the apparatus and on explanation of possible
mechanism of the long-term modification observed.
Acknowledgments
Charles University in Prague (Projects UNCE204025/2012, GAUK152214 and SVV260205).
References
[1] Guo, X.; Sturgeon, R. E.; Mester, Z.; Gardner, G. J.,Anal Chem, 76, 2401-2405 (2004).
[2] Sturgeon, R. E.; Willie, S. N.; Mester, Z., J Anal At Spectrom, 21, 263-265 (2006).
[3] Guo, X.; Sturgeon, R. E.; Mester, Z.; Gardner, G. J., J Anal At Spectrom, 20, 702-708 (2005).
143
PS1.28
UV-photochemical vapour generation with in-situ trapping
in a graphite tube atomizer for ultratrace determination of
selenium
Marcela Rybínová, Václav Červený and Petr Rychlovský
Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Hlavova
2030/8, CZ-128 43 Prague, Czech Republic
E-mail: rybinova@natur.cuni.cz
A sensitive method has been developed for the determination of selenium (Se(IV)) in sub-ppb range.
UV-photochemical vapour generation (UV-PVG) in combination with in-situ trapping and
atomization of the generated volatile compounds in the graphite tube atomizer of atomic absorption
spectrometer was utilized for this purpose.
UV-PVG represents an interesting alternative to the user's favorite chemical generation or to
electrochemical generation. In general, vapour generation is widely and successfully used sample
introduction technique for analytical applications in atomic spectrometry. Its popularity results from a
number of advantages for analysis, including high transport efficiency of the analyte into the atomic
spectroscopic detectors or efficient matrix separation often leading to a reduction in interferences and
improvement of the detection limits [1]. During UV-PVG, the conversion of nonvolatile precursors
from the condensed phase to the volatile species occurs under the action of UV irradiation. The
assistance of low molecular weight organic acids is also a crucial requirement for this approach to
generation [2].
In terms of the practical implementation, the apparatus was first assembled. Attention was paid
especially to the construction of the UV-generator; a PTFE tubing (1.4 mm o.d./1.0 mm i.d.) wrapped
around UV low-pressure Hg UV lamp (20 W, 254 nm) was used. Optimum experimental conditions
for generation, collection and atomization of volatile compounds were then found and the analytical
characteristics of the method were determined. Formic acid was chosen as a photochemical agent for
the study. The only other chemical added to the liquid reaction mixture was nitric acid, which
significantly increased the analytical signal. To achieve high trapping efficiency, the inner surface of
the graphite furnace was coated with an iridium permanent modifier.
A very low concentration detection limit (LOD) of 4.1 ng L−1 Se(IV) (corresponding to an absolute
LOD 18 pg) was achieved by the proposed method. The repeatability expressed as RSD was 3.0% at
a concentration level of 0.5 µg L−1 Se(IV). Figures of merit were compared with those obtained by
traditional chemical vapour generation using a borohydride/acid system; mutual comparison yielded
better results for UV-PVG. An overall efficiency of all the processes from generation to collection of
volatile compounds of more than 80% was estimated by comparing the slope of the calibration curve
for Se(IV) standards subjected to the proposed method with the value achieved for direct liquid
sample introduction of Se(IV) into the graphite furnace (it was assumed that the overall efficiency of
liquid sample introduction was 100%).
UV-photochemical vapour generation has proven to be a sensitive, relatively inexpensive and
environmentally friendly method, for which only a simple apparatus and a limited amount of
chemicals are necessary. Its connection with in-situ trapping in a graphite tube atomizer atomic
absorption spectrometry led to an improvement in the detection limits even to the same level as was
recorded for the combination of UV-PVG with MS detection [3,4], a technique which is still not
available for many laboratories.
Acknowledgements
The authors acknowledge financial support from Charles University in Prague: GAUK 228214, project UNCE 204025/2012
and project SVV 260205.
References
[1] R. E. Sturgeon and Z. Mester, Applied Spectroscopy, 56, 202–213 (2002).
[2] X. Guo, R. E. Sturgeon, Z. Mester and G. J. Gardner, Analytical Chemistry, 75, 2092–2099 (2003).
[3] C. Zheng, L. Wu, Q. Ma, Y. Lv and X. Hou, Journal of Analytical Atomic Spectrometry, 23, 514–520 (2008).
[4] K. Chandrasekaran, M. Ranjit, D. Karunasagar and J. Arunachalam, Atomic Spectroscopy, 29, 129–136 (2008).
144
PS1.29
Evaluation of analytical capabilities of solid state
techniques for the determination of palladium, platinum
and rhodium in used automobile catalysts
E. Marguí1, M. Flórez2, M. Resano2 and I.Queralt3
1
Department of Chemistry, Faculty of Sciences, University of Girona, Campus Montilivi s/n, Girona
17071-Girona, Spain
2
Department of Analytical Chemistry, Aragón Institute of Engineering Research, University of
Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain
3
Institute of Earth Sciences Jaume Almera ICTJA-CSIC, Sole Sabarís s/n, 08028 Barcelona, Spain
E-mail: eva.margui@udg.edu
Because of their chemical properties, the use of Platinum Group Metals (PGMs) is a
key issue for several industrial applications. Among other uses, Pd, Pt and Rh are
extensively utilized as catalysts to increase the efficiency of those reactions leading
to the destruction of CO, NOx and unburned hydrocarbons. Considering the high
economic value of these elements, there is a growing need to determine the content
of PGMs in used automobile catalysts. The determination of these analytes in many
samples is usually carried out after a tedious and time-consuming digestion
procedure, frequently followed by a pre-concentration/separation step. Alternatively,
the development of methods enabling the direct determination of PGMs in solid
samples can be an appealing option [1].
This contribution investigates the potential of X-ray fluorescence spectrometry
(XRF) and high-resolution continuum source graphite furnace absorption
spectrometry (HR-CS-GFAAS) for the direct determination of Pd, Pt and Rh in
several used automobile catalyst samples. A certified reference material ERM ®EB504 (Platinum Group Elements in used automobile catalysts) was used for
calibration purposes. Obtained results were compared with those obtained by
reference laboratories focused on the analysis of these types of samples (Inspectorate
PLC and Duessmann & Hensel Recycling GmbH) using a combination of acidic
digestion plus inductively coupled plasma optical emission spectrometry (ICP-OES).
Overall, the methods proposed seem suited for the determination of these analytes in
such type of samples, offering a greener and faster alternative that circumvents the
traditional problems associated with sample digestion, requiring a small amount of
sample and providing sufficient sensitivity.
References
[1] M.Resano, M. Del Rosario Flórez, I.Queralt, E.Marguí. Spectrochimica Acta Part B, 105, 38-46
(2015).
145
PS1.30*
Recovery of zinc and manganese from primary batteries
M. M. Puelles1, N. Hatamleh1, A. Ilgisonis1 and A. Gauna2
1
2
National Institute of Industrial Technology – INTI, Chemical Center, Buenos Aires, Argentina.
National Technological University – UTN, Avellaneda Regional School, Buenos Aires, Argentina.
E-mail: puelles@inti.gob.ar, albergauna@hotmail.com
Disused batteries are one of the main environmental problems still unresolved. The
lack of adequate and sustainable waste management causes the accumulation of
metallic elements. We can divide these elements into two main groups: the micro
components such as mercury and lead, among others, which are highly toxic and the
macro components as zinc and manganese. Manganese is a required element in
different industries such as ferroalloys, steels, batteries, fertilizers and medicines.
Recovering the macro elements from spent batteries would allow reuse a nonrenewable resource reducing at the same time the pollution. In addition, giving added
value to a disposable material, we get energy and economic benefits.
The aim of this work was to develop a method to recover two metals, zinc and
manganese, from spent primary batteries: alkaline and zinc-carbon types.
In a first step, it was designed an equipment that allow to cut and open batteries
automatically and separate the different components. The characterization of each
component was carried out: inner salt material, sheet zinc, steel cover, carbon
electrodes, plastic films and paper. For the analysis, the saline material was extracted
from the inside of the batteries, was dried at 105 °C and was pulverized to facilitate
the homogeneity. Then it was characterized by X-ray Diffraction and Fluorescence
Spectroscopy. Samples were digested in an acid-oxidizing mixture and heated until
complete solubility. Zinc and manganese quantification was carried out by Flame
Atomic Absorption Spectroscopy (FAAS).
In a second step it was developed a method for separating zinc and manganese from
the inner salt material of the batteries. Samples were treated by leaching-extracting
with sulfuric acid, decantation and filtration. The optimum treatment conditions were
evaluated. Two phases were obtained solid and liquid. Zinc and manganese from the
liquid phase was analyzed by FAAS. In a future work both elements will be
measured in the solid phase.
References
[1] ASTM D4691 – 11 Standard Practice for Measuring Elements in Water by Flame Atomic
Absorption Spectrophotometry.
[2] S. Kursunoglu, M.Kaya; Physicochemical Problems of Mineral Processing, 50(1), 41-55, 2014.
Acknowledgements
The authors thank the assistance of Lic. Sandra Amore from Crystallines Species Laboratory,
Chemical Center, INTI.
*
Poster not presented
146
PS1.31
CHEMICAL CHARACTERIZATION OF VERDOLAGA
(Portulaca oleracea L ), USING OPTICAL EMISSION
SPECTROSCOPY (ICPOES) AFTER MICROWAVE
DIGESTION
C. Márquez1, X. Barragan1, A.C. Gómez1, L.M. Vera2, R. Bye2 and B. Lucas3
1
2
Departamento de Ingeniería Metalúrgica, Facultad de Química, UNAM
Instituto de Bilogía, UNAM, Departamento de Alimentos, 3 Facultad de Química UNAM.
E-mail: ciromar@unam.mx
In the present work chemical characterization of “Verdolaga” was performed. This is
a herbaceous eatable plant, who growth like native vegetable, it is very common in
Mexican dietary and there is not information regard their elemental composition and
potential heavy metals toxicity.
Verdolaga growths in different sites of Mexican territory and their ingestion it’s
very common in different regional gastronomy of several regions of México. It's
scientific name is Portulaca oleracea L.
Six samples were obtained of two regions from central México.
A portion of samples was lyophilized and other oven dried, in order to verify
differences between both dried methods.
The humidity was evaluated in order to determinate the dry weight composition.
Both dried samples were milled in Agatha mortar. After that they were microwave
digested using high purity grade Nitric Acid, Hydrogen Peroxide and Hydrofluoric
acid, [1].
All the samples were analyzed using ICP-OES with dual vision.
In order to obtain the lowest detection limits the axial vision was used for trace and
toxic elements and for high concentration elements radial vision was used.
In order to obtain reliable results, all potential interferences were evaluated For
results assessment NIST 1547 Peach leaves SRM was used.
Conclusion
In all samples there is not presence of heavy metals at mg/kg level.
SRM results were near the target values..
Ca, Mg, Na, B, Al and Si were the elements founded in high % concentration level.
Mn, Fe, Cu, Zn, Sr and Li were the elements at mg/kg level.
There are not statistical differences between the two types of dry treatment used.
References
[1] Hansen T.H , de Bang T.C., Laursen KH, Pedas P, Husted S, Schjoerring J.K. Methods Mol
Biol.,953, 121-41, (2013).
.
147
Poster Session 1: X-ray Spectrometry
PS1.32
Assembly of a portable X-Ray fluorescence
spectrometer with tri-axial geometry
Matilde Alves, Mauro Guerra and Sofia Pessanha
LIBPhys, Laboratory for Instrumentation, Biomedical Engineering and Radiation Physics
Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Portugal
The aim of this work is to build a portable XRF spectrometer with tri-axial geometry
in between the X-ray tube, the secondary target and the sample. The extensive range
of applications of portable XRF spectrometers results predominantly from their
portability, multi-element capability, fast analysis times, minimal sample preparation
requirements, and non-destructive nature [1].
The advantages of this tri-axial geometry relates to the decreasing effects of scattered
X-rays that do not contribute to photoelectric effect, by polarization. This allows
nearly only monochromatic excitation energy, leading to lower background, lower
detection limits, hence greater sensitivity. [2]
This portable XRF spectrometer attends to the growing need to investigate forensic
sciences samples and cultural heritage elements with non-destructive in situ
techniques. Miniaturization and removal of spatial constraints are significant
limitations these fields of research, due to the inability of moving the objects or to
the impracticality of destroying the proof in forensic investigations. [3] Hence this
XRF spectrometer, allied with the engineered tri-axial strategy for ideal portability,
all together with a compact design, and high sensitivity makes this instrument a
possible viable alternative to other spectrometers in the market.
References
[1] X. Hou, Y. He, and B. T. Jones. “Recent Advances in Portable XRay Fluorescence
Spectrometry”. In: Applied Spectroscopy Reviews 39.1 (2004), p. 1. ISSN: 0570-4928.
[2] G. Vittiglio, S. Bichlmeier, P. Klinger, J. Heckel, W. Fuzhong, L. Vincze, K. Janssens,
P. Engström, A. Rindby, K. Dietrich, D. Jembrih-Simbürger, M. Schreiner, D. Denis, A. Lakdar, and
A. Lamotte. “A compact mu-XRF spectrometer for (in situ) analyses of cultural heritage and forensic
materials”. In: Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions
with Materials and Atoms 213.0 (2004), p. 693. ISSN: 0168-583X.
[3] M. Guerra, S. Longelin, S. Pessanha, M. Manso, and M. L. Carvalho. “Development of a
combined portable x-ray fluorescence and Raman spectrometer for in situ analysis”. In: The Review
of scientific instruments 85.6 (2014). 1089-7623
148
PS1.33
The Calibration of a Conventional X-ray Fluorescence
Analyzer for Depth Profiling
H. Bártová1, T. Trojek1
1
Czech Technical University in Prague, Department of Dosimetry and Application of Ionizing
Radiation, Břehová 7, 115 19 Prague, Czech Republic
E-mail: hana.bartova@fjfi.cvut.cz
The confocal X-ray fluorescence analysis (XRF) is established as a technique for the
determination of depth distribution of elements. In certain applications, the confocal
modality is unsuitable, the use of the conventional XRF is possible. These
applications are mostly performed in the research of cultural heritage objects in
which portable device is demanded. The Kα/Kβ or Lα/M X-ray lines ratios were
used for construction of the calibration diagrams of different element depth
distributions.
The principle of the proposed Kα/Kβ technique lies in the different absorption
coefficients for the Kα and Kβ lines [1]. If an element is present at some depth, its
characteristic radiation has to penetrate through thick layer of the matrix, and the
characteristic X-ray fluxes are significantly changed. The depth of the layer can be
described by Kα/Kβ ratio of an element; i.e. lower ratio indicates deeper position.
The experimental procedure includes measurements of standards of several elements
from thin to thick layer. The standards were covered by a set of materials with
different atomic number (Z) and known thickness. Also, thin layers of real pigments
were measured. The calibration diagrams were constructed from these
measurements. Respective description of unknown samples is presented. The
measured standards, as well as covering materials, were chosen with the respect to
the application in historical paintings survey. The elements in measured standards are
often found in pigments and the covering materials are of similar composition to
binders (low Z material) or layers of pigment (high Z) above the analyzed layer.
References
[1] T. Trojek, T. Čechák, and L. Musílek. Nuclear Instruments and Methods in Physics Research
Section B, 263, 2007, 76-78
149
PS1.34
Palm-top EPMA and TEM
Jun Kawai, Issei Ohtani, Kengo Ohira, Akira Imanishi, Eisuke Hiro, Shoki
Hifumi, Ken Yokoi, Shunsuke Matsuoka, Takashi Yamamoto, Susumu
Imashuku
Department of Materials Science and Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501,
Japan
E-mail: kawai.jun.3x@kyoto-u.ac.jp
We have succeeded to make a focused electron beam using a pyroelectric
crystal [1-7]. The beam size is about 100-300 micro meters on the sample stage, and
the intensity distribution is a Gaussian. The high voltage up to 40 kV is generated by
changing the temperature of the pyroelectric crystal from the room temperature up to
100 degrees using a Peltier device. Electric battery of 3 V is enough to produce the
temperature difference by the Peltier device. The size of the pyroelectric single
crystal is typically 5 mm x 5 mm x 10 mm. 3 mm x 3 mm cross-section and 5 mm
length are also possible. Lithium tantalate LiTO3 is used in our experiment. The
electron emission is not stable but changing with time; the electron beam continues
for a few minutes. The X-ray intensity excited by the high energy electron beam is
strong enough for elemental analysis within one minute. We can analyze a one
hundred micro-meter diameter area by this palm-top device. Therefore this device is
a kind of electron probe X-ray micro-analyzer (EPMA). The size of the vacuum
vessel (25 mm diameter quick coupling nipple, T, or cross is convenient for the
vessel) is palm-top size without a rotary pump. X-rays are detected by a Si-PIN Xray detector.
If the sample is electron beam transparent, we can observe expanded image of
the sample. This is a kind of transmission electron microscope (TEM).
References
[1] S. Imashuku, A. Imanishi, J. Kawai: Development of Miniaturized Electron Probe X-ray
Microanalyzer, Anal. Chem., 83, 8363-8365 (2011).
[2] S. Imashuku, J. Kawai: Development of target changeable palm-top pyroelectric x-ray tube, Rev.
Sci. Instrum., 83, 016106 (2012).
[3] S. Imashuku, A. Imanishi, J. Kawai: Palmtop EPMA by Electric Battery, Proceedings of the 21st
International Congress on X-Ray Optics and Microanalysis, Campinas, Brazil 5 – 9 September 2011,
Eds. C. A. Pérez and A. M. de Souza, AIP Conference Proceedings 1437, pp. 29-31 (2012).
[4] J. Kawai, Y. Nakaye, S. Imashuku: Palmtop EPMA, in “The Scanning Electron Microscope”,
ISBN 979-953-307-309-4, ed. Viacheslav Kazmiruk (2012). InTech - Open Access Publisher, Rijeka,
CROATIA.pp.89-100.
[5] S. Imashuku, A. Imanishi, J. Kawai: Focused electron beam in pyroelectric electron probe
microanalyzer. Rev. Sci. Instrum., 84, 073111-1-3, (2013).
[6] J. Kawai, I. Ohtani, A. Imanishi, S. Imashuku: Palm-top size X-ray microanalyzer using a
pyroelectric focused electron beam with 100-micrometer diameter, J. Phys.: Conf. Ser. 499, 12011-1-4
(2014).
[7] K. Ohira, S. Imashuku, J. Kawai: Investigation of X-ray emission from pyroelectric crystal, Adv.
X-Ray Anal., 293-297 (2014).
150
PS1.35
Characterization of gold nanofilms with x-ray reflectometry
and grazing incident x-ray diffraction
I. Stabrawa1, D. Banaś1,2, K. Dworecki1, A. Kubala-Kukuś1,2, J. Braziewicz1,2,
U. Majewska1,2, M. Pajek1, J. Wudarczyk- Moćko2 and S. Góźdź2,3
1
Institute of Physics, Jan Kochanowski University, Świętokrzyska 15, 25-406 Kielce, Poland
2
Holycross Cancer Center, Artwińskiego 3, 25-734 Kielce, Poland
3
Institute of Public Health, Jan Kochanowski University, Al. IX w. Kielc 19, 25-317 Kielce, Poland
E-mail: ilona.stabrawa@interia.pl
Interactions of complex biomolecules (DNA, RNA, proteins, antibodies) with solid
surfaces play very important role for many research areas in biology, biotechnology,
chemistry, physics and medicine. Understanding of the interaction process and
achieving the ability for controlling of behavior of such biological objects on
surfaces is the main aim of the studies performed nowadays. However, such studies
are very difficult or even not possible without earlier precise characterization of the
surface and near surface regions of a substrates.
In this work the X-ray reflectometry (XRR) and grazing incident X-ray diffraction
(GIXD) were applied to analysis and characterization of surfaces in the form of gold
nanofilms, which are widely used in biomolecules-surface interaction studies. The
gold nanofilms with thicknesses in the range from 5 to 100 nanometers were
prepared by evaporation of gold on different substrates: glass, quartz and crystalline
silicon.
The X-ray reflectometry (XRR) [1], which uses the effect of total external reflection
of X-rays, is surface sensitive analytical technique used for investigation of the near
surface regions of thin films. This technique allows modeling of thin layers density,
thickness and roughness of the surface and the substrate.
The method of grazing incident X-ray diffraction (GIXD) [2] is a modification of
standard X-ray diffraction technique, which due to low incident angle of the X-ray
beam maximizes signal from the surface and as a result allows for phase analysis on
thin layers and depth profiling of the phase composition of layered samples.
The motivation of the experiment, physical basis of the methods used, experimental
setups, results of optimization of the measurement procedure and results of the
measurements for gold surfaces of different substrates and thicknesses will be
presented.
References
[1] L. G. Parratt, Phys. Rev. 95, 359-369 (1954)
[2] J. Als-Nielsen et al., Phys. Rep. 246, 251-313 (1994)
151
PS1.36
Theoretical prediction of Cr K-edge XANES spectra
from Cr ion in dicalcium silicate
T. Okajima1,2, M. Suzuki3, N. Umesaki3 and T. Tanaka3
1
Kyushu Synchrotron Light Research Center, 8-7 Yayoigaoka, Tosu, Saga 841-0005, Japan.
Research Center for Synchrotron Light Applications, Kyushu Univ., 6-1 Kasugakohen, Kasuga,
Fukuoka 816-8505, Japan.
Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 Japan.
2
3
E-mail: okajima@saga-ls.jp
The combination of XANES spectroscopy using synchrotron light and firstprinciples calculation based on DFT is a very powerful method of analyzing the
chemical states and local structures of materials at the atomic level with the
development of first-principles DFT calculation program codes, such as FEFF[1],
WIEN2k[2], and CASTEP[3]. Excellent agreements between calculated and
experimental spectra have been presented in previous studies and the methods have
been successful in quantitatively reproducing the fine structures and chemical states
of many kinds of materials. It is well
known that dicalcium silicate (C2S)
forms solid solutions with many kinds
Cr O
of atoms under high oxidation
numbers. In this study, we examined
the Cr K-edge XANES spectra of Cr
ion in C2S using the program code of
(a ) E xp .
CASTEP in order to reveal the
oxidation state of Cr ion in C2S.
3
In ten sity / a rb . u n its
2
(b ) C a lc.
Figure shows the comparison between
5990
6000
6010
6020
experimental and calculated XANES
Ph o to n en erg y / eV
spectra of Cr2O3 using as a reference Figure Comparison of (a) experimental and
sample. The experimental spectral fine (b) calculated Cr K-edge XANES spectra of
structure is well reproduced by the Cr2O3. The calculated spectrum is shifted by
calculated one. In the calculation, a E=-22.1eV so as to align the peak energy of
core hole was created on a specific the experimental spectra of Cr2O3 with that of
atom in the 2×2×3 super cell, where the calculated spectrum.
the ultrasoft pseudopotential with a
core hole was generated on the fly. We also calculated the XANES spectra of Cr ions
in C2S with oxidation numbers from Cr4+ to Cr6+. The calculated spectra clearly
showed the chemical shift on the pre-edge peak with the oxidation number. The
calculated chemical shift reveals the chemical state of Cr ion in C2S.
References
[1] J.J. Rehr, and R.C. Albers, Rev. Mod. Phys., 72, 621-654 (2000).
[2] P. Blaha, et. al., WIEN2k, an augmented plane wave +local orbitals program for calculating
crystal properties, Karlheinz, Achwarz, TechnicalUniversitat Wien, Austria, 2001.
[3] S.J. Clark, et. al., Z. Krystallogr, 220, 567-570 (2005)..
152
PS1.37
Study of the Concentration of Potential Toxic Elements in
Plants Retrieved from Mining Sites
S. Olival1, H. Gallardo2, I. Queralt2, M. L. Carvalho1, J. P. Santos1, M. Guerra1
1
Departamento de Física, Faculdade de Ciências e Tecnologia, FCT, Universidade Nova de Lisboa,
2829-516 Caparica, Portugal
2
Laboratory of X-ray Analytical Applications, ICTJA/CSIC, Sole Sabaris St. s/n, 08028 Barcelona,
Spain
mguerra@campus.fct.unl.pt
Mining can provide us with essential elements but involves the disruption and
disturbance of land. Despite the economic benefits of the mining industry, negative
impacts on the environment and humans are a cause for concern[1]. This research aims
to study the concentration of potential toxic elements in plants retrieved from mining
sites, in particular, the Tinoca Mine. Waters, vegetation, soils, rocks and ores were
analysed using Energy Dispersive X-ray Fluorescence and X-ray Diffraction methods. It
was determined that algae found in the mine play an important role in the absorption and
excretion of some of the toxic elements present. The study of plant communities, their
interaction with the surroundings and a better knowledge of plant accumulation
mechanisms are crucial steps of research that may strongly contribute in future
improvements for reclamation of mining areas and therefore reduce the adverse effects
of the mining industry.
References
[1] S. C. Pé-Leve Santos, M. E. Cruz, A. M. E. Barroso, C. P. S. Fonseca, M. Guerra, M. L. Carvalho,
and J. P. Santos, “Elemental characterization of plants and soils in Panasqueira tungsten mining
region,” J. Soils Sediments, vol. 14, no. 4, pp. 778–784, Oct. 2014.
153
PS1.38
Determination of Ca, V, Cr and Zn in lubricating oil
employing the Ring Oven and μXRF techniques
M. Cidade1,2, C. Pasquini1 , S. Cadore1 and J. J. R. Rohwedder1
1
2
Institute of Chemistry, University of Campinas, Campinas, SP, Brazil
Chemistry Department, Federal University of Roraima, Boa Vista, RR, Brazil
E-mail: mirla.cidade@ufrr.br
The metals determination in lubricating oil has been of interest since the 90s and is made
with the objective of assessing the engine performance, wherein the presence of these
elements is due to the wear of engine parts, the addition of additives to the oil and the
refining process of oil [1]. The ASTM (American Society for Testing and Materials)
provides some standard methods of analysis that are used for the metals determination in
oil and oil products, but in general, the analysis employed in these methods require
several sample preparation steps [2,3]. In order to obtain a simplified method for sample
preparation, the ring oven and the micro energy dispersive X-ray fluorescence, μXRF,
techniques were evaluated for the determination of Ca, V, Cr, and Zn in lubricating oil.
The studies were carried out in an automatized ring oven system, and then the method
was optimized showing the following conditions: introduction of 250 μL of the sample
(2% w/w lubricating oil in toluene), 50 μL of toluene and 500 μL of eluent solution
(acetic acid 30% v/v ethanol). All of these solutions were added to a silica disk of Ø 47
mm (Marcherey-Nagel, Alugram ® SIL/G) heated to 90 °C, and the addition was always
done in the center of the disk with 36 μL aliquots of sample and toluene, and 44 μL of
the eluent solution, at 30 second intervals. After forming the rings, they are irradiated in
a μXRF (Shimadzu, μEDX-1400), which had a source of rhodium and a silicon detector.
The conditions for the analysis in μXRF were: voltage applied at the X-ray tube of 50
kV; spectra obtained on sequential mode from 0 to 40 keV with energy of 0.01 keV step
by step; probe with an effective radiation area of 50 μm; and integration time of 200
seconds.
The proposed method showed adequate repeatability and stability of rings for lubricating
oil samples. For Cr and V, the addition and recovery tests were performed at three
concentration levels (7.2, 11.8 and 17.8 mg kg-1), and the recovery values obtained were
between 90-110%. However for Ca and Zn it was used the CRM 1848 certified reference
material (0.359 ± 0.011 % of Ca and 0.873 ± 0.022 % of Zn) and the recovery values
were between 90-120%. The reference method (mineralization and ICP OES analysis)
and the proposed methods (ring oven and μXRF) show similar limits of quantification,
but the use of ring oven/μXRF has the advantage of being a simple method, having a low
cost and also presents a smaller sample manipulation time.
References
[1] Pohl, P.; Vorapalawut, N.; Bouyssiere, B.; Carrierd, H.; Lobinskiae, R. J. Anal. At. Spectrom., 25,
704-709 (2010).
[2] Annual Book of ATSM Standard, ASTM D4951 – 09.
[3] Annual Book of ATSM Standard, ASTM D5185 – 09.
Acknowledgements
National Institute of Advanced Analytical Science and Technology (INCTAA) for their financial
support.
154
PS1.39
Analysis of Elemental Impurities by WDXRF in
Pharmaceuticals and Dietary Supplements
A. Figueiredo1, I. M. Costa1 and J. Brito1
1
Instituto Superior de Ciências da Saúde Egas Moniz, Monte de Caparica, Portugal
E-mail: alexandra.f@netcabo.pt
Actual regulatory requirements for elemental impurities monitoring in
pharmaceuticals imposed by EMA (European Medicines Agency) and USP (United
States Pharmacopeia) emphasize the importance of analytical techniques able to
determine the concentration of these impurities in the ppm range with a quantitative,
fast and accurate analysis.[1] [2]
This study aimed to validate an analytical procedure to detect impurities in final drug
products and dietary supplements, according to ICH guidelines [3], using a 4 kW
WDXRF spectrometer (S4 Pioneer, Bruker AXS). In the calibration the following
elements were analyzed: As, Cu, Cr, Ir, Mo, Mn, Ni, Os, Pb, Pt, Ru, V, using
cellulose loose powder spyked with known amounts of each element. The
concentration ranges were (in ppm) 0-10 for Pb; 0-15 for Ir, Os, Pt and Ru; 0-25 for
As; 0-30 for Cr, Mo, Ni and V; 0-300 for Cu and Mn.
The obtained correlation coefficients were all above 0.9 demonstrating the linear
responses within the concentration range. The detection limits, calculated based on
standard error of y-intercept of the regression line, were in the range of 0.44-4.13
ppm, all below the limits imposed by EMA [2].
After validation, this analytical procedure was used in the monitoring of six active
pharmaceutical ingredients, branded and generic (N= 90), and 25 different dietary
supplements (N=75), all widely prescribed and consumed. Eighteen drug samples
showed values of Ru above the imposed limits. In dietary supplements were detected
concentrations above the limits imposed by USP [4] for As in two samples and for
Pb in one sample.
Results underline that wavelength dispersive X-ray fluorescence (WDXRF)
spectrometry is a very promising technique, which fulfills the international
regulatory requirements. Therefore it may be an alternative to the compendial
recommended analytical procedures, with the advantage of an easier and faster
sample preparation.
References
1.
2.
3.
4.
USP 36 <233> Elemental Impurities - Procedures, p. 232–4 (2012).
EMA. Doc Ref EMEA/CHMP/SWP/4446/2000, p. 1–34 (2008).
ICH Q2(R1) (2005).
USP <2232> Elemental Contaminants in Dietary Supplements, 36 (1) (2010).
155
PS1.40
Calculation of L3 subshell fluorescence yields for
the elements with 70≤Z≤92
S. Daoudi1,2, A. Kahoul1,2, B. Deghfel3,4, F. Khalfallah1,2, V. Aylikci5,
N. Küp Aylikci6 and M. Nekkab3,7
1
Department of Materials Science, Faculty of Sciences and Technology, Mohamed El Bachir El
Ibrahimi University, Bordj-Bou-Arreridj 34030, Algeria.
2
LPMRN laboratory, Department of Materials Science, Faculty of Sciences and Technology,
University of Mohamed El Bachir El Ibrahimi, Bordj-Bou-Arreridj 34030, Algeria.
3
Department of Physics, Faculty of Sciences, University of Mohamed Boudiaf, 28000 M’sila,
Algeria.
4
Laboratory of materials physics and their applications, Physics Department, Faculty of Sciences,
University of Mohamed Boudiaf, 28000 M’sila, Algeria.
5
Department of Metallurgical and Materials Engineering, Faculty of Technology, Mustafa Kemal
University, Hatay 31040, Turkey.
6
Department of Energy Systems Engineering, Faculty of Technology, Mustafa Kemal
University, 31040 Hatay, Turkey.
7
LESIMS laboratory, Physics Department, Faculty of Sciences, Ferhat Abbas
University, Setif,19000, Algeria.
E-mail: salz_dg@yahoo.fr
The analytical methods based on X-ray fluorescence are advantageous for practical
applications in a variety of fields including atomic physics, X-ray fluorescence
surface chemical analysis and medical research and so the accurate fluorescence
yields are required for these applications.
In this contribution we report a new parameters for calculation of L3 subshell
fluorescence yields ( ωL3 ) of elements in the range of 70≤Z≤92. All the experimental
data published in the period 1959 till 2015 are interpolated by using the famous
1/q
analytical function ωL3 / 1  ωL3  (were q=4) vs Z to deduce the empirical L3
subshell fluorescence yields. Calculated empirical L3 subshell fluorescence yields
have been compared with those reported by Krause [1], Puri et al. [2], Campbell [3]
and Aylikci et al. [4]. The results are found to be in good agreement with the other
works.
References:
[1] M.O. Krause, J. Phys. Chem. Ref. Data, 8, 307, 1979.
[2] J.L. Campbell, Atom. Data Nucl. Data Tables, 85, 291, 2003.
[3] S. Puri, D. Mehta, B. Chand, N. Singh, P.N. Trehan, X-ray Spectrometry, 22, 358, 1993.
[4] V. Aylikci, A. Kahoul, N. Kup Aylikci, E. Tiraşoğlu, İ.H. Karahan, A. Abassi, M. Dogan.
Radiation Physics and Chemistry 106, 99, 2015.
156
Poster Session 1: Archaeometry and cultural heritage
PS1.41
Characterization of prehispanic ceramics by
LIBS and ICP-OES
A. Trujillo-Vázquez1, V. Lazic2 and H. Sobral1
1 Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de
México, Apartado Postal 70–186, México DF. 04510, Mexico
2 ENEA (UTAPRAD-DIM), Via. E. Fermi 45, 00044 Frascati (RM), Italy
e-mail: abigatos@gmail.com
Analytical techniques for characterization of materials are widely
recognized as valuable tools in the study of cultural heritage.
Nevertheless, they must be versatile and low destructive methods. The laser induced
breakdown
spectroscopy
(LIBS)
requires
only
optical
access to the sample surface. Briefly, the output of a pulsed laser is
concentrated onto a sample producing a plasma which is spectroscopically
analyzed. So, it can be used as a basically non destructive, fast,
non-contact and in situ technique.
In this work, LIBS has been employed for the analysis of prehispanic
ceramics from the archaeological site of Teotihuacan, México. For this
purpose, a set of fragments belonging to late preclassic and early classic
period (150 b. C. to 350 a.C) have been investigated. As the samples showed
different paste types and surface finish, measurements on surface and bulk
were implemented. Analysis of samples were performed using a pulsed Nd-YAG
laser emitting at 1064 nm, coupled to an Echelle spectrograph covering
the 240-780 nm wavelength range. Afterward, the spectral lines were
normalized with respect to a Nitrogen transition line and the major sample
constituents’ were determined.
Besides, a small fragment of each sample was digested and analyzed by
inductively coupled plasma–optical emission spectrometry (ICP-OES), which
is a robust and reliable method for quantitative analysis of materials.
ICP results were used to calibrate the LIBS signal to analyze other
unknown ceramics samples.
157
PS1.42
Study of the effect of protective on wood photo-degradation
by colour measurements, FT-IR spectroscopy and
hyperspectral imaging
G. Agresti1, G. Bonifazi2, L. Calienno3, G. Capobianco2, A. Lo Monaco3, C.
Pelosi1, R. Picchio3, U. Santamaria1, S. Serranti2
1
Department of Cultural Heritage Sciences, University of Tuscia, Viterbo (Italy)
Department of Chemical Engineering Materials & Environment, Sapienza University of Rome,
Rome (Italy)
3
Department of Science and Technology for Agriculture, Forestes, Nature and Energy, University of
Tuscia, Viterbo (Italy)
2
E-mail: silvia.serranti@uniroma1.it
The aim of this work is to investigate the effect of protective materials on poplar (Populus
spp.) wood modifications as consequence of artificial photo-degradation in controlled
environment. Starting from previous results [1-4], this study tried to understand what
happens to wood surface under the protective layer.
As protective materials, shellac, beeswax and Linfoil® were tested to compare traditional
and novel products generally used for wood. The samples covered by these protective layers
were artificially aged in Solar Box for 1064 hours. As comparison, also uncovered samples
were tested.
At chosen times, the samples were investigated by reflectance spectrophotometry, Fourier
transform infrared spectroscopy and hyperspectral imaging in order to study the colour and
chemical modification occurred to wood both covered and uncovered with the protective
products. The obtained data were statistically elaborated in order to verify their significance.
Colour measurements highlighted that the protective materials reduced the wood colour
changes in respect to un-protected samples. FT-IR spectroscopy demonstrated that photodegradation caused mainly lignin decomposition with the production of new chromophore
groups on wood surface. Also in this case un-covered wood underwent greater modifications
in respect to protected one. Hyperspectral imaging in the SWIR range (1000-2500 nm),
coupled with chemometric methods, clearly showed the variation between the spectral
behavior of poplar wood for ageing time 0 and 1064 hours, with different protective layers.
It is interesting to note that protective materials have a partial effect on wood photodegradation by little reducing the changes.
Such results can contribute to evaluate the effect of protective materials on wood during sun
exposure.
References
[1] G. Genco, A. Lo Monaco, C. Pelosi, R. Picchio, U. Santamaria, A study of colour change due to accelerated
sunlight exposure in consolidated wood samples, Wood Research, 56 (4), 511-524 (2011).
[2] G. Agresti, G. Bonifazi, L. Calienno, G. Capobianco, A. Lo Monaco, C. Pelosi, R. Picchio, S. Serranti,
Surface investigation of photo-degraded wood by colour monitoring, infrared spectroscopy and hyperspectral
imaging. Journal of Spectroscopy, 1(1), Article number 380536, 1-13, (2013).
[3] C. Pelosi, G. Agresti, L. Calienno, A. Lo Monaco, R. Picchio, U. Santamaria, V. Vinciguerra, Application of
spectroscopic techniques for the study of the surface changes in poplar wood and possible implications in
conservation of wooden artefacts. In: Proceedings of SPIE, vol. 8790, pp. 1-14 (2013).
[4] G. Bonifazi, L. Calienno, G. Capobianco, A. Lo Monaco, C. Pelosi, R. Picchio, S. Serranti, Modelling color
and chemical changes on normal and red heart beech wood by reflectance spectrophotometry, Fourier Transform
infrared spectroscopy and hyperspectral imaging, Polymer Degradation and Stability, 113, 10-21 (2015).
158
PS1.43
X-Ray micro-fluorescence and chemometrics
applied to Roman coins certification
G. Bonifazi1, G. Capobianco1, S. Serranti1 , G. Bertolami2 and A. Pancotti2
1
Department of Chemical Engineering, Materials & Environment, Sapienza University of Rome,
Rome (Italy)
2
ACR Auctions - Rome, München, London, Barcelona
E-mail: giuseppe.bonifazi@uniroma1.it
The aim of this work is to investigate the possibility offered by a combined use of X-Ray microfluorescence (XRF) [1-2] and chemometric approach to analyze metal objects of historical and artistic
interest, in order to perform an objective evaluation of their composition and elemental distribution
finalized to identify fakes. The results of this evaluation are in fact related not only to the metal
characteristics [3] but also to the manufacturing approach [4]. A methodological strategy, combining
XRF semi-quantitative analysis and a multivariate approach, was thus specifically developed and
applied with reference to two ancient coins of the same type, a Caesar – Crawford cataloging 452/2,
one certified as original and the other of unknown origin (Figure 1). The achieved results (Figure 2)
allowed to objectively sustain the classical numismatic evaluation, contributing to assess as the
unknown coin was a fake.
Figure 1. Certified (on the left) and unknown (on the right) Roman coins of the same type. The first
image (upper left) is referred to the obverse of coin, the remaining sequence is representative of the
map of the main identified chemical elements. The investigated coins are representative of a denarius
struck in a military mint moving with C. Iulius Caesar during 48-47 BC (Crawford cataloging 452/2).
Figure 2. PCA score plot of the map of the elements obtained by micro X-ray fluorescence,
representative of the certified (on the left) and unknown (on the right) Roman coins.
References
[1] E. T. Hall, X-ray fluorescent analysis applied to archaeology, Archaeometry, Volume 3, Issue 1, pages 29–35,
1960.
[2] M. Mantler, m. Schreiner, X-Ray fluorescence spectrometry in art and archaeology, X-ray spectrometry, 29, 3
– 17, 2000.
[3] K. Janssens, G. Vittiglio,I. Deraedt, A. Aerts,B. Vekemans, L. Vincze, F. Wei, I. Deryck, O. Schalm, F.
Adams, A. Rindby, A. Kn̈ochel, A. Simionovici and A. Snigirev, Use of Microscopic XRF for Non-destructive
Analysis in Art and Archaeometry, X-ray spectrometry, 29, 73 – 91, 2000.
[4] M. Ferretti, C. Polese, C. R. García, X-ray fluorescence investigation of gilded and enamelled silver: The
case study of four medieval processional crosses from central Italy, Spectrochimica Acta Part B: Atomic
Spectroscopy, Volumes 83–84, 21–27, 2013.
159
PS1.44
X-Ray Fluorescence analysis of ancient coins
C. Arias1, E. Grifoni1, S. Legnaioli1,2, G. Lorenzetti1, S. Pagnotta1, M. Lezzerini3,
M. Baldassarri4, F. Catalli5, V. Palleschi1,2,6
1
Applied and Laser Spectroscopy Laboratory, ICCOM-CNR, Via G. Moruzzi 1 - 56124 Pisa, Italy
2
3
Department of Earth Sciences, University of Pisa, Via S. Maria 53, 56126 Pisa, Italy
4
Soprintendenza Speciale per i Beni Archeologici di Roma, Museo nazionale Romano
Palazzo Altemps, Piazza S. Apollinare, 46 00186 Roma
5
Museo Civico di Montopoli in Val d'Arno, Via Guicciardini, 61 56020 Montopoli, Italy
6
Department of Civilizations and Forms of Knowledge, University of Pisa, Pisa, Italy
E-mail: vincenzo.palleschi@cnr.it
X-Ray Fluorescence (XRF) is a powerful spectroscopic technique, which allows a
non-destructive precise quantitative analysis of materials, and in particular of
metallic alloys, in very short time. The technique seems thus particularly suitable for
the study of large numbers of ancient coins, belonging to historical collections or
found in archaeological excavations. However, the intrinsic limitation of XRF should
be taken into consideration; depending on the kind of alloy analysed, the effect of
surface contamination might not be negligible. In this communication, we will report
on the results of the analysis of hundreds of bronze, silver and gold ancient coins,
from different collections and historical periods; we will discuss in particular the
information that can be obtained from the XRF results, and the difficulties related to
a proper quantitative analysis. The importance of studying a statistically significant
number of coins will be stressed, for avoiding errors and misinterpretations.
Fig.1 – One of the gold coins analysed by the authors using the XRF technique
(Grosso of Lucca, XIII century A.D.)
References
[1] F. P. Romano, S. Garraffo, L. Pappalardo, and F. Rizzo, “In situ investigation of the surface
silvering of late Roman coins by combined use of high energy broad-beam and low energy microbeam X-ray fluorescence techniques,” SpectrochimicaActa—Part B Atomic Spectroscopy, vol. 73, pp.
13–19, 2012.
[2] L. Pardini, A. El Hassan, M. Ferretti et al., “X-ray fluorescence and laser-induced breakdown
spectroscopy analysis of Roman silver denarii,” Spectrochimica Acta. Part B Atomic Spectroscopy,
vol. 74-75, pp. 156–161, 2012.
[3] M. Baldassarri, G. H. Cavalcanti, M. Ferretti et al., “X-Ray Fluorescence Analysis of XII–XIV
Century Italian Gold Coins”, Journal of Archaeology, Volume 2014, Article ID 519218, 6 pages.
[4] M. Scuotto, C.Bassi, M. Lezzerini et al., “X-ray fluorescence analysis on a group of coins from the
ancient roman city of Tridentum (Trento, Italy)”, X-Ray Spectrom. 43 (2014) 370–374.
160
PS1.45
Automated characterization of binders degradation using
portable T-controlled Raman spectroscopy
I. Osticioli, D. Ciofini, A. A. Mencaglia, S. Siano
1
Institute of Applied Physics “Nello Carrara” (IFAC-CNR), Florence, Italy
E-mail: I.Osticioli@ifac.cnr.it
In this work, Raman spectroscopy has been employed for identifying natural resins
and for assessing molecular changes, which occur during their ageing under artificial
light exposure (photochemical ageing)[1]. For the first time, a temperature-controlled
portable-Raman device (excitation wavelength 1064 nm) has been developed in
order to automatically and continuously monitor the aging process by preventing
phase changes and other undesired alteration effects. Temperature control was
achieved by means of a pyroelectric sensor and a dedicated software producing a
feedback on the laser power supply and then a suitable modulation of the output
beam. This allowed collecting a sequence of spectra in the same area of analysis by
setting fixed maximum temperature and total radiant exposure. Samples were
prepared by applying various terpenoid resins (colophony, shellac, dammar,
sandarac, mastic) ) on glass slides and subjected to artificial ageing in order to
simulate about 50 years natural light exposure in indoor museum conditions. One
spectrum every 4 hours has been measured during the whole aging period of about
two months. Intensity changes and broadening of the bands in Raman spectra have
indicated oxidation after the aging process along with the detection of oxidation
products, which allowed describing the chemical alteration dynamics of molecular
bonds over time.
[1] A. Nevin, D. Comelli, I. Osticioli, L. Toniolo, G. Valentini, R. Cubeddu, Anal.
Bioanal. Chem., 395, 2139-2149 (2009)
161
PS1.46
Analysis of lead seals: a spectroscopic approach by EDXRF
C. I. A. Santos1, T. F. G. C. Cova1, A. A. C. C. Pais1
and T. M. V. D. Pinho e Melo1
1
Departamento de Química, Faculdade de Ciências e Tecnologia da Universidade de Coimbra
3004-535 Coimbra
cisantos@qui.uc.pt
The Archive of the University of Coimbra holds a vast collection of parchments with
pending lead seals for authentication, ranging from the 12th to the 18th centuries.
However, the corrosion of these lead seals is a major problem that must be
addressed. Relating the indoor environment of Archives with the degree of corrosion
of cultural heritage objects requires the study of their elemental composition.
Energy dispersive X-ray fluorescence (EDXRF) has become a non-destructive
analytical technique of choice in Conservation Science. The possibility of carrying
out qualitative and semi-quantitative analysis (by fundamental parameters) of major
and trace elements, without the need to sample artefacts of cultural heritage, make
that technique an exceptional tool [1]. Analysis of lead seals, in several degrees of
corrosion, from almost perfect condition to nearly total conversion into lead salts, has
been made. The spectrometer used was an Hitachi SEA6000 HS Finder, with a W
target and a multi-cathode Si semiconductor detector.
The lead seals from the Archive's collection were grouped per Pope. Of these, Papal
seals existing in larger numbers were chosen, namely from Popes Paul III (1534-49),
Clemens VIII (1592-1605), Urban VIII (1623-44) and Clemens X (1670-76), in order
to study and group by composition, relating to their degree of corrosion. Statistical
analysis such as principal component analysis (PCA) and hierarchical cluster
analysis (HCA) have been used to characterize samples by elemental composition, as
in provenance studies of archaeological artefacts [2].
Acknowledgments: Fundação para a Ciência e Tecnologia (SFRH/BD/80216/2011), Prof. Francisco
Gil and access to TAIL-UC facility funded under QREN-Mais Centro Project ICT/2009/02/012/1890.
References
[1] S. Akbulut, J. Anal. At. Spectrom., 29, 853-860 (2014).
[2] D. Agha-Aligol, P. Oliaiy, M. Mohsenian, M. Lamehi-Racgti, F. Shokouhi, Journal of Cultural
Heritage, 10, 487-492 (2009).
162
PS1.47
SEM/EDAX analysis of historical building materials
for the reconstruction plan of Arsita
S. Bruni1 and G. Marghella1
1
ENEA UTSISM - Via Martiri di Monte Sole 4, 40129 Bologna (Italy)
E-mail: stefania.bruni@enea.it
The seismic event of the April 6th, 2009, which hit the city of L’Aquila and
surroundings in the Abruzzi Region (Italy) struck also several towns and little
villages located in the vicinity. Among them, the town of Arsita suffered
nonnegligible damage, in particular to its historic centre, and was included in the list
of the most affected municipalities that require the drafting of the reconstruction plan
[1]. The activities, performed during approximately two years of activity, foresaw a
multidisciplinary approach (natural hazards, vulnerability/resilience, risk mitigation,
intervention proposals, energy efficiency, development and sustainability) involving
a wide range of expertise [2].
The masonry quality assessment played an important role in the evaluation of
historical building vulnerability: both on-site investigations through the use of a
specific survey form and laboratory tests by means of Scanning Electron Microscope
and Microanalysis were carried out in order to obtain data about the morphological
and compositional characteristics of masonries. Data were acquired for about half of
the 91 structural units included in the reconstruction plan; for the remaining part of
buildings, the presence of plaster coating has not made possible a direct observation
of the masonry surface. Moreover, some samples of stones, bedding mortar and
timber elements were collected from the most important historical buildings of the
town, like the Bacucco Castle, for the elemental characterisation.
Mortar samples were characterised by an high concentration of elements related to
the minerals present in silicate sands, which may have been used as aggregate in their
formulation. Microanalysis results were processed using the principal component
analysis statistical method that allowed to distinguish between two different sets of
samples, one in a good preservation state and the other showing degradation
phenomena such as deposition or efflorescence of saline substances.
References
[1] M. Indirli, S. Bruni, F. Geremei, G. Marghella, A. Marzo, L. Moretti, A. Formisano, C. Castaldo,
L. Esposito, G. Florio, R. Fonti, E. Spacone, S. Biondi, E. Miccadei, I. Vanzi, A. Tralli, C. Vaccaro,
T. Gambatesa, SAHC2014 – 9th International Conference on Structural Analysis of Historical
Constructions, 2014
[2] S. Bruni, A. Gugliandolo, E. L. Algarra Cruz, G. Maino, G. Marghella, A.Marzo, L. Moretti, M.
A. Segreto, L. Travierso, BUILT HERITAGE 2013 –Monitoring, Conservation, Management, 2013.
163
PS1.48
Elemental characterization of human remains from Ermida
Espírito Santo using EDXRF
M. Carvalho1, S. Pessanha1, M. L. Carvalho1, A. F. Silva1, J. P. Santos1, F. R.
Henriques2, F. Curate3,4, A. A. Dias1
1
2
3
Museums Division and Local History- City Hall Almada, Research Centre for Anthropology and
4
Health - University of Coimbra, Interdisciplinary Center for Archaeology and Evolution of Human
Behavior - University of Algarve
E-mail: sofia.pessanha@fct.unl.pt
The human remains of 15 individuals buried between the mid-18th to early 19th
century, were analyzed by energy dispersive X-ray fluorescence technique (EDXRF),
to study the elemental composition. The aim of this research is to evaluate dietary
behavior, environmental surroundings and exposure to toxic elements of a particular
population. Furthermore, there is a possibility of post-mortem contamination from
the surrounding soil of the burial site.
The samples, bone, hair, teeth and brain matter, were collected from a church in
Almada (Portugal), called Ermida do Espírito Santo, located near the Tagus River.
The results were obtained using two setups: one with triaxial geometry that allows
improved detection limits for lower Z matrices[1], and another setup that allows
micro beam as well as performing analysis under a vacuum system which improves
the detection limits for lighter elements.
The detected elements for both setups were P, K, Ca, Fe, Cu, Zn, Br, Sr and Pb. It
was observed high levels of Zn and Sr for bones which are indicative of dietary
habits rich in proteins and fish [2]. The results show a particular individual that has
high concentrations of Pb, especially in brain matter, pulp and root of the tooth and
in spongy bones, reaching about 600 µg/g in the ribs. Moreover, there is also a
woman over 50 years old, which presented an extremely high concentration of Hg in
the hair, about 60000 µg/g, and a lower, but still representative, concentration in the
skull of 43µg/g.
Good agreement was observed between the results obtained by the two setups.
[1]
M. L. Carvalho and A. F. Marques, “Diagenisis evaluation in Middle Ages human bones
using EDXRF,” X-Ray Spectrom., vol. 37, pp. 32–36, 2008.
[2]
M. L. Carvalho, A. F. Marques, M. J.P., and C. C, “Evaluation of the diffusion of Mn, Fe, Ba
and Pb in Middle Ages human teeth by synchroton microprobe X-ray fluorescence,”
Spectrochim. Acta - Part B At. Spectrosc., vol. 62, pp. 702–706, 2007.
.
164
PS1.49
An EDXRF and Montecarlo Simulation Study of
Iron-Age Nuragic Small Bronzes (“Navicelle”) from
Sardinia, Italy
Nick Schiavon(1), Anna de Palmas(2), Claudio Bulla(2), Giampaolo Piga(3) and
Antonio Brunetti(3,4)*
(1) HERCULES Laboratory, University of Evora, Portugal
(2) Dipartimento di Storia, Scienze dell'Uomo e della Formazione, Università di Sassari, Italy
(3) Dipartimento di Scienze Politiche, Scienze della Comunicazione, Ingegneria dell’Informazione,
Università di
Sassari, Italy
(4) CIRTEBEC, Università di Sassari e Cagliari, Italy
*
Corresponding Author:brunetti@uniss.it
The Nuragic civilization flourished in Sardinia, Italy, throughout the Iron Age. It was
characterized by a significant production of metallic artifacts, one of the most interesting
ones being small-scale bronze replicas of ships, called navicelle; these objects were usually
associated with sacred sites as to testify the close, religious link with the sea, a typical trait of
the Nuragic culture. Despite their significance from an archaeological point of view and
artistic value (fig.1), no material study has been ever carried out on these artifacts to shed
light on raw material sources and production technology. In this study, a combined multianalytical Non Destructive approach has been adopted combining EDXRF with
microanalysis (BSEM + EDS) and Montecarlo simulation of experimental spectra, to
analyze 15 “navicelle”. While the BSEM+EDS analysis provided information on the texture
of the corrosion patina, the combined EDXRF + Montecarlo simulation methodology proved
to be an useful tool when compared with EDXRF alone. This was achieved by treating the
sample as a multilayered object. In fact, the Monte Carlo simulations is able to account both
for the presence of the patina and corrosion layer as well as the presence of a protective layer
applied in past restoration interventions [1-3]. It can also account for the roughness effect
introduced by the surface patina and in this sense the Monte Carlo used here is, to the best of
our knowledge, unique. By adopting this approach, the bronze alloy composition can be
determined together with the thickness of the surface layers without the need to remove the
surface patina. The preliminary results are here presented and discussed.
Fig. 1. Two examples of “navicelle” small bronzes
[1] A. Brunetti, B. Golosio, Spectrochim. Acta Part B 94–95 (2014) 58–62.
[2] N. Schiavon, A. Celauro,M. Manso, A. Brunetti, F. Susanna, Appl. Phys. A 113 (2013) 865–875
[3] C. Bottaini et al. / Spectrochimica Acta Part B 103–104 (2015) 9–13.
165
PS1.50
Investigating copper and bronze axes by micro-XRF and
neutron imaging techniques
E. Figueiredo1, M.A. Stanojev Pereira2, F. Lopes1,3, J.G. Marques3, J.P. Santos3,
M.F. Araújo3, R.J.C. Silva1 and J.C. Senna-Martinez4
1
Centro de Investigação em Materiais (CENIMAT/I3N), Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, Quinta da Torre, 2829-516 Caparica, Portugal
2
Instituto de Pesquisas Energéticas e Nucleares (IPEN), Centro do Reator de Pesquisas, Av. Prof.
Lineu Prestes 2242, Cidade Universitária, 05508-000 São Paulo, Brazil
3
Centro de Ciências e Tecnologias Nucleares (C2TN), Instituto Superior Técnico, Universidade de
Lisboa, Estrada Nacional 10, km 139.7, 2695-066 Bobadela LRS, Portugal
4 Centro de Arqueologia da Universidade de Lisboa (UNIARQ), Faculdade de Letras, Universidade
de Lisboa, Alameda da Universidade, 1600-214 Lisboa, Portugal
E-mail: emf12055@campus.fct.unl.pt
Micro-EDXRF analysis and neutron imaging techniques, namely 2D radiography
and 3D tomography, have been applied for the study of metal composition and for
investigating the internal structure of metal axes from the Early/Middle Bronze Age.
Micro-EDXRF analysis has been performed in small superficial areas free of
corrosion and has shown that the axes were made by copper or bronze. Due to the
specificities of neutron interaction with matter, which in the case of copper-based
metals allows a higher penetration than X-rays, neutron imaging allowed the
visualization of internal macro pores, voids and interdendritic vacuoles, resulting in
the gathering of relevant information for the reconstruction of the ancient
manufacturing techniques in a non-invasive way. Additionally, neutron imaging has
allowed the evaluation of corrosion thickness and existence of micro-fissures, with
implications in the conservation state of the artefacts.
Fig.1. Neutron tomography slice of the upper part of an axe showing the presence of a large void.
Acknowledgments
This work is funded by FEDER funds through the COMPETE 2020 Programme and National Funds
through FCT - Portuguese Foundation for Science and Technology under the projects
UID/CTM/50025/2013 to CENIMAT/I3N and UID/Multi/04349/2013 to C2TN/IST. The grants
SFRH/BPD/97360/2013 and SFRH/BD/85329/2012 by FCT are also acknowledged. The authors wish
to thank the Departamento de Conservação e Restauro, Universidade Nova de Lisboa, for the use of
the ArtTAX Pro spectrometer.
166
PS1.51
The ceramics of the Malpaís of Zacapu during the Early
and Middle Postclassic periods (900-1450 A.D.): microchemical characterization of surface paintings
E. Jadot1,2, N. Schiavon3 and M. Manso4,5
1
Université Paris 1 Panthéon–Sorbonne, Centre Michelet, 3 rue Michelet, 75006 Paris, France.
2
ArchAm - UMR 8096 CNRS, MAE, 21 Allée de l’Université, 92023 Nanterre, France.
3
Hercules Laboratory, University of vora, Palácio do Vimioso,Largo Marquês de Marialva 8, 7000809 Évora, Portugal
4
departamento de Física, Faculdade de Ciências e Tecnologias, Universidade Nova de Lisboa,
2829-516 Monte da Caparica, Portugal.
5
Faculdade de Belas-Artes da Universidade de Lisboa, Largo da Academia Nacional de Belas-Artes,
1249-058 Lisboa, Portugal.
E-mail: marta974@gmail.com
The technology involved in the application of pigments and paintings in
archaeological pottery is one of the most interesting aspects of ceramic
manufacturing processes. If forms and decorations of Tarascan ceramics are wellknown worldwide, the chemical nature of the raw materials remains underestimated.
In this study, several ceramic sherds belonging to two archaeological sites dated from
the Early and Middle Postclassic periods (900-1450 A.C.) and situated on the
Malpaís of Zacapu, in the Mexican state of Michoacán, were examined. The ceramic
material has been excavated within the framework of the Uacúsecha project (directed
by G. Pereira, CNRS/MAE/CEMCA) and belongs to two historical phases: the
Palacio phase (900-1200 A.C.) and the Milpillas phase (1200-1450 A.C.). They
represent a long period of cultural changes which led to the creation of the
centralized Tarascan state, in the middle of the XIVth century. While at the Palacio
period painting decoration on ceramics was rare, the Milpillas pots regularly
exhibited a polychrome white and red painting associated to negative decoration. The
multi-analytical spectroscopic approach of these ceramics allowed to shed light on
the technological production technique, as far as the choice and the use of raw
materials intended for the surface covers (slips and paintings), as well as the master’s
degree during the firing (temperature, atmosphere, smudging) are concerned. Energy
dispersive (XRF and SEM+EDS) and Raman spectroscopic analysis indicate the use
of carbon black, hematite, magnetite and poorly crystalline iron oxides as black, red,
brown and yellowish pigments. The presence of magnetite and carbon black suggests
firing under a reducing atmosphere. Titanium oxides in the form of anatase were also
detected on the ceramic surface from Milpillas phase, indicating the use of a firing
temperature below 900ºC [1]. Back-scattered Electron Microscopy EDS mapping
revealed how the pigments are not evenly distributed within the painted slip but
occur in grains and patches.
References
[1] M. Horn, C. F. Schwerdtfeger, E. P. Meagher, Zeitschrift fur Kristallographie, 300, 273–281
(1972).
167
PS1.52
A glance at chronology with X-rays: contribution to the
understanding of Atlantic Bronze to Iron Age transition
gold finds
I. Tissot1,2, L.C. Alves, M. L. Carvalho, V. Corregidor, M. Manso1, and M. F.
Guerra1
1
LIBPhys – UNL 2829-516 Caparica, Lisbon, Portugal
C2TN, IST/CTN, University of Lisbon, E.N. 10, 2686-953 Sacavém, Portugal
3
IPFN, IST/CTN, University of Lisbon, E.N. 10, 2686-953 Sacavém, Portugal
4
ArchAm - UMR 8096 CNRS, MAE, 21 allée de l’Université, 92023 Nanterre, France
2
E-mail: isabeltissot@gmail.com
Among the gold finds in the Iberian Peninsula, the treasure of Herdade do Álamo in Beja
(South of Portugal) and the treasure of Senhora da Guia in Baiões (North of Portugal) are the
most representative of the productions attributed to the transition between the Late Bronze
Age and the Iron Age. The first find consists in two casted necklaces and one casted bracelet,
and the second in three necklaces and two bracelets obtained by joining hollow parts. The
“atypical” typology [1] and the different manufacture techniques of the gold jewellery [2]
found in regions that are separated by the Tagus River, has been raising questions on their
attribution based on the exchanges between the Atlantic and the Mediterranean regions [3,4].
In spite of their analytical study carried out by A. Hartmann in the 1980s by OES [5], the
objects could not be situated in a general context of the Iberian gold finds: indeed, the
destructive analytical method applied impeded access to information on all the different
parts. To bring new evidence to light, the two finds were recently analysed in a nondestructive way by portable µXRF and by µPIXE, and the composition of both the parts and
the joining regions searched. The portable XRF equipment comprises an Eclipse IV X-ray
source with a Rh anode and a XR-100SDD Amptek X-ray detector at 90º geometry. The 2
MeV proton µPIXE analyses were carried out using an external microbeam focused down to
100x100 µm2 at the setup of the IST/ITN van de Graff accelerator comprising an OM150
quadrupole triplet system and a 30 mm2 Bruker SDD X-ray detector.
The data showed that the two treasures are made from different alloys with different Ag/Au
ratios. The objects from the Baiões find are made with one gold, whilst those from the Beja
find show the use of two golds, but different from the gold used in Baiões. The amount of
copper is the same in all the objects from Baiões (about 1 wt%), but ranging from 1.6 to 3.0
wt% in the alloys from Beja. The presence of gold alloys with different melting points used
as hard-solders could also be confirmed.
The data obtained for the two finds was compared with the composition of gold objects
produced in the North and in the South of Portugal from the Bronze and Iron Ages. Their
similarity in the North and distinction in the South is discussed.
References
[1] A. Perea, Trabajos de Prehistoria 62.2, 91-103 (2005).
[2] V. Hipólito-Ferreira, The early Iron Age transition in the goldwork of the west of the Iberian Peninsula. In
Beyond Stonehenge, C. Burgess, P. Topping, F. Lynch eds., Oxbow Books, 90-96 (2007).
[3] P. Kalb, O Arqueólogo Português, s. IV 8/10, 259-276 (1992).
[4] M. Almagro-Gorbea, Celtic goldwork in the Iberian Peninsula. In Prehistoric Gold in Europe, G. Morteani,
J.P. Northover eds., NATO ASI Series 280, 491-501 (1995).
[5] A. Hartmann, Prähistorische Goldfunde aus Europa II. Spektralanalytische Untersuchungen und deren
Auswertung. Studien zu den Anfängen der Metallurgie 5, Mann, Verlag, Berlin (1982).
168
PS1.53
A X-Ray Fluorescence Spectroscopy and Monte Carlo
characterization of a unique Nuragic object (Sardinia, Italy)
A. Brunetti1, A. De Palmas2, F. di Gennaro3, A. Serges3, N. Schiavon4
1
2
Dipartimento di Storia, Scienze dell’uomo e della Formazione, Università di Sassari, Italia
3
4
Polcoming, Università di Sassari, Italia
Soprintendenza Museo Nazionale Preistorico Etnografico "Luigi Pigorini"-Roma, Italia
Hercules Laboratory for the study and Conservation of Cultural Heritage, University of Evora Portugal
E-mail: brunetti@uniss.it
The Nuragic civilization thrived in island of Sardinia, Italy, from Bronze age up to II
century BC. Its legacy left a large number of precious bronze objects. A unique
piece is represented by the bronze known as “ cesta” (basket). It was discovered
around the XVIII century with the first pictorial representation reported around 1761.
In a second draft (1764) the basket was reported as being carried on the shoulder of
the large bronze warrior [1-3]. The two pictures are different as far as the handles
are concerned. Aim of this work was to study for the first time the chemical
composition of the bronze and its corrosion products by combining XRF with
Moontecarlo simulations. Preliminary results revealed that the handles of the object
are composed by brass while the other parts are composed by bronze. This indicate
that the handles have been successively added. The object is covered by a corrosion
patina. In order to determine the bronze composition of the bulk the object has been
modelized as a two layer bronze and Monte Carlo simulations have been performed.
References
[1] BARTHÉLEMY 1761: BARTHÉLEMY J-J., Mémoire sur les anciens monuments de Rome, in
Mémoires de l'Académie des Inscriptions et Belles-Lettres XXVIII, 1755–1757, pp. 579-610.
[2] LILLIU 1966: LILLIU G., Sculture della Sardegna nuragica, Verona.
[3] PINZA 1901: PINZA G., Monumenti primitivi della Sardegna, in MonAnt XI, coll. 5-280
[4] WINCKELMANN 1776: WINCKELMANN J., Geschichte der Kunst des Alterthums, I.
169
PS1.54
New data on the presence of celestite into fossil bones from
the uppermost Cretaceous Molí del Baró 1 site (Isona i
Conca Dellà– Lleida, Spain) and an alternative hypothesis
on its origin
Giampaolo Piga1*, Fabio M. Dalla Vecchia2, Angel Galobart2, Antonio
Brunetti1, Barbara Lasio3, Luca Malfatti3, Stefano Enzo4
1 Department
of Political Science, Communication, Engineering and Information Technologies,
University of Sassari. Viale Mancini 5, I–07100 Sassari (Italy).
2 Institut Català de Palaeontologia "Miquel Crusafont" (ICP). Carrer Escola Industrial 23, E-08201
Sabadell (Spain).
3 Material Sciences and Nanotechnology Laboratory (LMNT), University of Sassari and Porto Conte
Ricerche, I–07041 Alghero (Italy).
4 Department of Chemistry and Pharmacy, University of Sassari. Via Vienna 2, I–07100 Sassari
(Italy).
* corresponding author: Dr. Giampaolo Piga (giapiga@uniss.it)
We have addressed a study by X–ray diffraction (XRD), X–ray fluorescence (XRF)
and ATR–IR spectroscopy on a collection of twenty dinosaur fossil bones belonging
to the Molí del baró 1 paleontological deposit located at Isona i Conca Dellà (Lleida,
Spain), to investigate the fossilization occurred in this site in terms of physico–
chemical properties. The specimens are referred to an age time range of 75–65 Ma.
During the detailed investigation of the bones belonging to this geological setting, it
emerged an extreme complexity and variability of mineralogical phases and chemical
composition of bone specimens. As a general behaviour the XRD patterns showed
the bioapatite mineral at a varying level of percentage and accordingly, the
correspondent XRF spectra turned out to be mainly dominated by the presence of Ca,
obviously accompanied by phosphorus. Simultaneously, other elements such as Sr,
Fe, Ba, and Zn were found at non–negligible concentration levels and helped to
assign the phase components in the XRD spectra.
In three specimens it was observed by XRD the rather unusual case where the
original bioapatite bone mineral was completely substituted for by other
mineralogical phases. In addition to this, celestite was also found as an important
phase in thirteen specimens out of the twenty examined. The occurrence of celestite
in the bone structure appears a rather unusual observation within the literature of
bones diagenesis. Previous explanations of the presence and sometimes abundance of
celestite in the fossil bones from this site were based on the supposed total absence of
marine water in the original depositionary environment. New geological information
suggesting the possibility of marine influence allows formulating an alternative
hypothesis focused on the very peculiar environment of deposition of Molí del Baró
1 site.
170
PS1.55
Non destructive determination of gold leaf thickness in a
Brazilian and Portuguese 18th century Imperial carriages
Sofia Pessanha1, Marcelino J. Anjos3, Maria Luisa Carvalho1 Joaquim T Assis4
1
3
UERJ/IF/DFAT -Rio de Janeiro, RJ-Brasil CEP: 20550-900 4UERJ/IPRJ - Nova Friburgo, RJBrasil CEP: 28625-570;
Gilding techniques have been used throughout history to decorate paper, parchment
and wooden pieces. The most important is gilding with gold leaf. Prior to gilding the
use of a preparatory layer, deliberately applied, in an attempt to obtain a uniform
smooth coating and to increase the adhesion was requested. The most common
ground layer is white lead, or pure lead in some cases of wooden objects. The
thickness of gold layer is usually evaluated by Scanning Electron Microscopy
imaging of samples collected and mounted as cross-sections. This process requires
sampling and has to be avoided. In the present work, the thickness of the gold leaf is
determined, without sampling, using X-ray fluorescence. This methodology is based
on the different attenuation coefficients of the characteristic lines of the substrate
over which the leaf was applied. In this case, the characteristic lines of Pb (Lα and
Lβ) belonging to the lead white substrate, although attenuated in the Au layer, are
still visible in the X-ray fluorescence spectra [1, 2]. By determining the intensity
ratio Lα/Lβ and comparing it with the ratio for an infinitely thick sample of lead
white, the thickness of the attenuating material can be determined. This methodology
was applied to the gilded areas of two carriages produced in the same factory in
different periods. One belongs to Museu Nacional dos Coches, in Lisboa, and the
other belongs to Museu Imperial in Rio de Janeiro. The obtained results for the
carriage in the Museum in Lisbon rendered a homogeneous thickness with an
average value of 0.8 ±0.2 µm. Regarding the analysis performed in Rio de Janeiro,
significant differences were obtained concerning the thickness and values between
0.20 ±0.05 µm and 0.80 ±0.20 µm were determined.
[1] R. Cesareo, A. Brunetti, S. Ridolfi, X-Ray Spectrom. 37, 2008, 309.
[2] S. Pessanha, M. Guerra, S. Longelin, A. Le Gac, M. Manso, M. L. Carvalho, X-Ray Spectrom. 43,
2014, 79.
Acknowledgements
Authors would like to acknowledge Museu Nacional dos Coches, Lisbon and Museu Imperial Rio de
Janeiro for allowing the study of the carriages. S. Pessanha would like to acknowledge FCT for the
postdoc grant SFRH/BPD/94234/2013.
171
PS1.56
The work of José de Escovar, the Alentejo most famous
16th-17th mural painter, in the Chapel of Souls
M.Gil1, Catarina Pereira1, Margarida Nunes1, Cátia Relvas1, Marta Manso2,
S. Pessanha2, Maria Luísa Carvalho2, Teresa Ferreira1,3
1
Laboratório HERCULES, Universidade de Évora, Largo Marquês de Marialva, 8, 7000-554 Évora,
Portugal
2
LIBPhys-UNL, Laboratory for Instrumentation, Biomedical Engineering and Radiation Physics
Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Portugal
3
Departamento de Química, Escola de Ciência e Tecnologia, Universidade de Évora, Rua Romão
Ramalho, 59, 7000-671 Évora, Portugal
E-mail : milenegil@gmail.com and tasf@uevora.pt
José de Escovar is a well-known artist in Alentejo due to the fresco technique that he
profoundly used to decorate a significant number of churches in this region [1, 2].
Nevertheless, most of his work is not documented and the authorship is based mainly
on stylist aspects. Additionally, very few works using the oil technique are attributed
to Escovar. For this reason, the case of the parish church of Vila Nova da Baronia,
Alvito, is a singular one, since the contract between the master and the costumer
survived and it certifies that Escovar was the responsible for the decoration of the
walls and the altarpiece of the Chapel of Souls. In order to better define and compare
Escovar fresco and oil painting techniques in this chapel and crosscheck with other
works in the region, characterization of the materials used in both supports was
carried out using several in situ techniques and microsampling. X ray fluorescence
spectrometry supplied information about the pigments used by the master, while
micro Raman and micro Fourier transform infrared spectroscopy completed the
knowledge about pigments and binders and varnishes, respectively. Other
characterization techniques that were also fundamental for the characterization of the
technical work and pallet definition were technical photography, spectrophotometry,
micro X ray diffraction and scanning electron microscopy with coupled energydispersive X-ray spectrometry.
Kew-words: Fresco technique, oil, EDXRF, OM, SEM-EDS, µ-Raman, µ-FT-IR
Acknowledgement
The authors acknowledge Fundação para a Ciência e Tecnologia for financial support
(Post-doc grant SFRH/BPD/63552/2009) through program QREN-POPH-typology
4.1., co-participated by the Social European Fund (FSE) and MCTES National Fund
and Project PRIM’ART PTDC/CPC-EAT/4769/2012, financed by national funds
through the FCT/MEC and co-financed by the European Regional Development
Fund (ERDF) through the COMPETE - Competitiveness Factors Operational
Program (CFOP)
References
[1] MONTEIRO, Patrícia, A Pintura Mural no Norte Alentejo (sécs. XVI-XVIII): núcleos temáticos
da Serra de São Mamede. Tese de Doutoramento apresentada á Faculdade de Letras da Universidade
de Lisboa, Maio de 2013.
[2] SERRÃO, Vítor, As Pinturas Murais da Capela de São João Baptista em Monsaraz (1622): estudo
do programa artístico e iconológico e fixação de autoria. Reguengos de Monsaraz, Câmara Municipal,
2010.
172
PS1.57
EDXRF analysis of books from XVIII and XIX centuries
M.O. Pereira1, C. Calza2 , R.P. Freitas3 and R.T. Lopes2
1
Federal Center for Technological Education Celso Suckow da Fonseca (CEFET-RJ)
Nova Iguaçu, RJ
2
Nuclear Instrumentation Laboratory, PEN/COPPE/UFRJ
Rio de Janeiro, RJ. Brazil
3
Federal Institute of Rio de Janeiro (IFRJ)
Paracambi, RJ. Brazil
E-mail: marcelocefetrj@gmail.com , ccalza@lin.ufrj.br
The elemental composition of paper provides information related to its provenance,
production technology and historical period. These data can assist in the authentication,
restoration and conservation of historical documents, manuscripts and books. The
differences in the elemental composition - presence or absence of an specific chemical
element, showing low or high concentrations - allow to differentiate papers of distinct
periods. The ink used in a document and the pigments used in engravings, illustrations and
maps can also provide the same kind of information.
This work reports the analysis of the elemental composition of paper employed in books
from XVIII and XIX centuries and also the characterization of pigments used to decorate its
edges by means of Energy Dispersive X-Ray Fluorescence (EDXRF). The analytical
identification of a pigment by XRF involves its color and composition. Since the chronology
of pigments use is well-known, is possible to determine the provenance, historical period
and, consequently, the authenticity of an artifact. Organic pigments, or pigments composed
only by light elements, cannot be directly detected by this technique. However, their
presence may, in some cases, be implied by the absence of certain characteristic elements
associated with the color under investigation. For blue colors, an absence of copper would
exclude azurite, verditer blue, etc.; an absence of cobalt would exclude cobalt blue, cerulean
blue, smalt, etc.; and an absence of iron would exclude Prussian blue, for example.
The EDXRF measurements were carried out with a portable system developed at the Nuclear
Instrumentation Laboratory (PEN/COPPE/UFRJ), consisting of an Oxford TF3005 X-ray
tube (with W anode) and a Si-PIN XR-100CR detector from Amptek. The angle between the
X-ray tube and the detector window is 60°, the source-sample and the detector-sample
distances are 4 cm. Several spectra were obtained, working at 25 kV and 100 µA, with an
acquisition time of 300 seconds and a beam collimation of 2 mm
.
The results identified the elemental composition of the paper used in the books and the use
of the following pigments to decorate its edges: chromium yellow ( 4), barium yellow (4),
chromium oxide (Cr2O3), vermilion (HgS) and Prussian blue (4[Fe(CN)6]3.14-16H2).
These results revealed the presence of highly toxic elements/compounds - like lead, mercury
and chromates - which were used in the manufacture of ancient pigments. This fact
evidences that restorers, conservators and researchers who work directly with these books
need to take adequate safety measures and use personal protective equipments.
173
PS1.59
The bright effects of white chalk ground layers of the 15th
and 16th centuries paintings assessed by multianalytical
spectroscopic techniques
V. Antunes1*, António Candeias2,3, M. J. Oliveira2, M. L. Carvalho4, A. I.
Seruya4, J. Coroado5, L. Dias3, J. Mirão3, V. Serrão1
1
Instituto História da Arte da Faculdade de Letras da Universidade de Lisboa (IHA-FLUL) , Alameda
da Universidade, 1600-214 Lisboa, Portugal
2
Laboratório José de Figueiredo / Direcção-Geral do Património Cultural (LJF-DGPC), Rua das
Janelas Verdes 37, 1249-018 Lisboa, Portugal
3
Laboratório HERCULES, Escola de Ciências e Tecnologia, Universidade de Évora, Largo Marquês
de Universidade de Évora, Largo Marquês de Marialva 8, 7000-676 Évora, Portugal
4
LIBPhys-UNL, Laboratório de Instrumentação, Engenharia Biomédica e Física da Radiação,
Departamento Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516,
Caparica, Portugal.
5
Instituto Politécnico de Tomar (IPT)/GeoBioTec ID&T unit , 2300-313 Tomar, Portugal
* Corresponding author: vanessahantunes@gmail.com
The phenomenon of reflection of light by chalk material, provided largely by
calcareous (mainly cocoliths and calcispheres) is well known since 15th century. Its
excellent workability comes from its fineness and softness. This is afforded by the
rounded shapes of microfossil limestone, which facilitates the sliding in the
application, thereby increasing the speed of handling. The fast application of the
chalk as a painting ground layer allows its homogenization before drying, thus
facilitates the aggregation of particles and their subsequent flattening. Concerning the
grain size of the material and its coloring power, the thinner material gives the best
color effect. These characteristics have been used to optimize the pictorial technique
[1]. In addition to the fineness and smoothness characteristics, chalk has a special
feature required and explored by the artists who used it - a particular light reflection.
The mixture of chalk and animal glue has refractive index characteristics of surface
light, since the chalk constituent elements remain suspended in adhesive bonds,
causing the light to penetrate in depth and reflecting mainly in the surface. The oil
mixed with chalk provides the phenomenon of deep light, since the slow-drying oil
oxidation polymerization encapsulates the particles. This factor allows light to
penetrate deeply, but being partially absorbed [1].
In this perspective, it is justified the existence of a characteristic painting ground
layer stratigraphy containing a proteic binder in the lower region and in the upper
region an oily binder. X ray fluorescence, SEM-EDS and µXRD are the used
analytical techniques to study these ground layers.
[1] Nicolaus, K., Manual de restauración de cuadros. 1999, Köln: Konemann,p.266.
174
Poster Session 1: Nuclear Techniques
PS1.58
Spectroscopic performance of TlBr crystals purified via
vacuum distillation
T. Onodera1, K. Hitomi2 and T. Shoji1
1
Department of Electronics and Intelligent of Systems, Tohoku Institute of Technology, 35-1
Yagiyama Kasumi-cho, Sendai, Japan
2
Cyclotron and Radioisotope Center, Tohoku University, Sendai, Japan
E-mail: t_onodera@tohtech.ac.jp
Thallium bromide (TlBr) is a wide-band-gap (2.68 eV) compound
semiconductor with a high atomic number (Tl: 81, Br: 35) and high density (7.56
g/cm3). These promising properties make TlBr an attractive detector material for
high-energy gamma-ray detection without any cooling at room temperature [1], [2].
In this study, the vacuum distillation method has been employed to purify the starting
material (99.99 % nominal purity) and improve the mobility-lifetime () products
for carriers. The spectroscopic performance and charge transport characteristics were
evaluated using TlBr detectors made from purified and grown TlBr crystals. Figure 1
and 2 show 137Cs gamma-ray spectra obtained from TlBr detectors fabricated from a
raw material and a purified material. As shown in these figure, the spectroscopic
performance of the TlBr detector was obviously improved by the purification and the
TlBr detector exhibited an energy resolution of approximately 4% at 662 keV of
gamma-rays at room temperature.
Cs energy spectrum obtained
Fig.2. 137Cs energy spectrum obtained
from a TlBr detectors fabricated from a raw
from a TlBr detectors fabricated from a
material.
purified material via vacuum distillation.
Fig.1.
137
References
[1] R. Hofstadter, Nucleonics (1949).
[2] T. Onodera, K. Hitomi and T. Shoji, IEEE Trans. Nucl. Sci, vol.54, no.4, pp.860-863 (2007).
175
Poster Session 2: Molecular Spectrometry
PS2.1
Exchanges with Abscisic Acid under Drought Stresses of Glutathion
Reductase Enzyme Activity and mRNA Level in Soybean Plant
Esen TASGIN1 & Hayrunnisa NADAROĞLU2,3
1
Bayburt University, Bayburt Education Faculty, Department of Primary Education,
69000, Bayburt, TURKEY
1
2
Ataturk University, Faculty of Engineering, Department of Nano-Science and NanoEngineering, 25240 Erzurum, TURKEY
Plants have developed variety adaptation mechanisms to tolerate drought and salt
stress conditions and in order to survive in adverse conditions. Environmental
stresses such as drought lead to enhanced generation of reactive oxygen species
(ROS), which will cause the breakdown of membrane lipids and DNA and eventually
lead to cellular death. In many reactions involving reduced glutathione (GSH), the
Cys thiol group is oxidized to yield oxidized glutathione (GSSG), and the reverse
reaction is catalyzed by glutathione reductase (GR, EC 1.6.4.2) using NADPH. The
GSH pool maintained by GR is necessary for active protein function, and millimolar
concentrations of GSH act as a key redox buffer forming a barrier between protein
Cys groups and ROS [1].
It is well known that the amount of the plant hormone abscisic acid (ABA) increases
as a result of water stress, thus playing important roles as a stress signal, not only
under water limitation but in plant adaptation to numerous stress conditions. During
water stress, ABA has also been shown to cause an increased production of O2
radicals and H2O2, enhancing the activities of antioxidant enzymes such as GR [2].
In this study, the relationship among ABA, ROS and GR enzyme in soybean plants
exposed to water stress were determined. Under normal conditions (20 / 16 oC in day
and night temperature and humidity. Soybean plants were grown under normal
conditions (20 / 16 oC in day and night temperature and humidity conditions). After
germination, drought stress was applied to half of the cultivated of soy bean plants.
During 3 days, group ABA (abscisic acid) was applied to the drought stress treated
plants group and measured the changes of enzyme activity and level of mRNA of
glutathion reductase (GR) enzyme in plants.
Literature:
[1] Yannarelli, G.G.; Ferna´ndez-Alvarez, A.J.; Santa-Cruz, D.M.; Tomaro, M.L.;
Glutathione reductase activity and isoforms in leaves and roots of wheat plants
subjected to cadmium stress, Phytochemistry, 2007, Vol. 68, 505-512.
[2]Contour-Ansel, D.; Torres-Franklın, M.L.; Cruz de Carvalho, M.H.; D’arcyLameta, A.; Zuily-Fodil, Y.; Glutathione reductase in leaves of cowpea: cloning of
two cdnas, expression and enzymatic activity under progressive drought stress,
desiccation and abscisic acid treatment, Annals of Botany, 2006; Vol. 98, pp. 12791287.
176
PS2.2
Molecular Structure, Vibrational Spectroscopic Analysis
(FT-IR; FT-Raman), NBO Analysis of
Anti-cancer Drug Sunitinib Using DFT Method
Özlem Mıhçıokur 1, Talat Özpozan 2
1
2
Erciyes University, Institute of Science, Kayseri, Turkey
Erciyes University, Department of Chemistry, Faculty of Science, Kayseri, Turkey
E-mail: ozpozant@erciyes.edu.tr
Sunitinib, a tyrosine-kinase inhibitor, is approved for the treatment of patients with
gastrointestinal tumor (GIST) and advanced renal carcinoma (RCC) [1-3]. It targets
and inhibits cellular signaling of multiple receptor tyrosine kinases (RTKs),
including platelet-derived growth factor (PDGF-Rs) and vascular endothelial growth
factor receptors (VEGFRs) which play essential role in tumor angiogenesis and
tumor cell proliferation [4].
In the present study, the molecular geometry optimization, vibrational analysis, NBO
and HOMO-LUMO analysis of N-(2-diethylaminoethyl)-5-[(Z)-(5-fluoro-2-oxo-1Hindol-3-ylidene)methyl]-2,4-dimethyl-1H-pyrrole-3-carboxamide (SUNITINIB) has
been carried out with the Gaussian 09W software package [5]. The geometry
optimization has been performed using DFT/B3LYP functional combined with
631G(d,p) and 6311G(d,p) basic sets. The assignment of the calculated wavenumbers
of the title compound has been obtained by means of VEDA4 program [6] and
Potential Energy Distribution (PED) has been achieved. The theoretical spectra have
been compared with experimental IR & Raman spectra. The Natural Bond Orbital
(NBO) Analysis has been done to interpret the intramolecular charge transfer
interactions. The possible electronic transitions and their energies are determined by
HOMO–LUMO orbital shapes.
Figure 1. Structure of SUNITINIB
References
[1] Goodman, V.L, Rock, E.P, Dager, R., Ramchandani, R.P, Abraham, S., Gobburu, JV., et al. Clin
Cancer Res 13(5):1367–73 (2007).
[2] Polyzos, A., J Steroid Biochem Mol Biol 108(3):261–266, (2008).
[3] Rock, E.P, Goodman, V., Jiang, J.X, Mahjoob, K., Verbois, S.L, Morse, D., et al. Oncologist,
12(1):107–13, (2007).
[4] http://en.wikipedia.org/wiki/Sunitinib, 18 March (2015).
[5] Gaussian 09, Revision C.02, M. J. Frisch et al., Gaussian, Inc., Wallingford CT, (2009).
[6] Jamroz,M.H., Vibrational Energy Distributing Analysis: VEDA4 program, Warsaw, (2004).
177
PS2.3
Theoretical and IR - Raman Spectroscopic Study of a
Pyrrol-2-ylidene-acetate Derivative in Monomeric and
Dimeric Forms
T. Özpozan1, H. Arı2 and S. Sinan1
1
Department of Chemistry, Faculty of Sciences, Erciyes University, Kayseri, Turkey
Department of Chemistry, Faculty of Arts and Sciences, Bozok University, Yozgat, Turkey
2
E-mail: ozpozant@erciyes.edu.tr
Pyrrole and its derivatives have shown to possess biological activities such as
antibacterial, antitumor, analgesics, antitubercular, antiinflammatory, and
antiallergic effects [1]. The structural and spectral properties of ethyl-(2RS)-[1-(2aminopyridin-3-yl)-4-(4-methoxybenzoyl)-5-(4-methoxyphenyl)-3-oxo-1,3-dihydro2H-pyrrol-2-ylidene]-acetate (PBPA) and its dimers have been studied by IR,
Raman spectroscopy and DFT calculations to see the most stable structure and intraand intermolecular interactions.
Fig. 1 The optimized structure of PBPA in (a) monomeric (b-e) dimeric forms
The monomeric PBPA calculations were performed using the XRD data [1] as input
parameters. Geometrical parameters and frequencies of PBPA and its dimers were
calculated by using DFT/B3LYP method employing 6-31G(d,p) and 6-311+G(d,p)
basis sets. All calculations were made using the Gaussian 09 program package [2].
The vibrational assignments of the normal modes were proposed on the basis of the
PED which was calculated using the program VEDA4 [3].
This study was supported by Erciyes University Scientific Research Project (Project
no: FYL-2015-5822).
References
[1] Mustafa Saçmacı, Hilal Bölükbaşı and Ertan Şahin, Bull. Korean Chem. Soc., 33 (2012).
[2] M. J. Frisch, et al., Gaussian 09, Revision B.01, Gaussian, Inc., Wallingford CT (2010).
[3] M.H. Jamroz, Vibrational Energy Distribution Analysis:VEDA 4 program, Warsaw, (2010).
178
PS2.4
Antioxidant properties of Mentha Longifolia L., DFT study
of free radical scavenging mechanisms of rosmarinic acid
Lütfiye Aydın, Talat Özpozan
Department of Chemistry, Faculty of Science, Erciyes University, Melikgazi, 38039, Kayseri, Turkey
E-mail:ozpozant@erciyes.edu.tr
Medicinal plants contain chemical constituents which exhibit antioxidant properties.
Antioxidants are viewed as compounds that protect cells against oxidative stress,
which might cause cell damage. Mentha species have significant antioxidant
capacities. The genus Mentha L. (Lamiaceae) comprises more than 25 species[1].
These species are known to have pharmacological, antiinflammatory, antimicrobial
and antioxidant activities [2,3]. Polyphenolic antioxidant activities measured by
various assays are better correlated with the Bond Dissociation Enthalpy (BDE) than
with other reaction enthalpies involved in radical scavenging mechanisms.
TFC method
TPC method
0.8
0.2
y = 0.0016x - 0.0008
y = 0.0153x - 0.0101
R2 = 0.9976
0.6
Absorbans
Absorbans
0.16
R2 = 0.994
0.12
0.08
0.4
0.2
0.04
0
0
0
20
40
60
80
100
0
10
20
30
40
50
mg/L quercetin
mg/L gallic acid
a) Standard Gallic acid
b) Standard Quercetin
Figure 1. Calibration curves of the standards
In this study, the total phenolic contents [4], total flavonoid and radical scavenging
activities of ethanolic extracts of Mentha longifolia L. were determined by UV-VIS
spectral measurements. Rosmarinic acid as one of the major components of Mentha
longifolia L., were calculated in terms of the bond cleavage and radical formation
mechanisms of these phenolic antioxidant species. The calculations for studied
compounds have been carried out by DFT/B3LYP methods using Gaussian 09
programme [5].
This study was supported financially by the Research Centre of Erciyes University (Project
No: FDK-2013-4497).
References
[1] M. Gulluce, et al., Food Chemistry, 103, 1449–1456, (2007)
[2] Manju, V., et al., Cellular & Molecular Biology Letters, 10, 535–551, (2005)
[3] Zhang, T., & Chen, D. Journal of Ethnopharmacology, 117, 351–361, (2008)
[4] Singleton, Vernon L.; Orthofer, Rudolf; Lamuela-Raventós, Rosa M. (1999).
[5] Gaussian 09, Revision B.01, M.J. Frisch et al, Gaussian, Inc., Wallingford CT, (2010)
179
PS2.5
Study of interaction between 3MPA-CdTe QDs and
flavonoids in aqueous media
Andrea R. da Silva1, Juliana M. Carvalho2, Ricardo Q. Aucélio2
1
Centro Federal de Educação Tecnológica Celso Suckow da Fonseca (CEFET/RJ),Valença-RJ, 27600000, Brazil.
2
Chemistry Dept, Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Rio de Janeiro-RJ,
22435-900, Brazil.
andrearsqo@gmail.com
Semiconductor nanoparticles (quantum dots or QDs) with highly intense and stable
photoluminescence have been used as probes for the determination of diverse classes
of non-luminescent analytes [1]. Flavonoids are natural polyphenols found in fruits
and vegetables and presents antioxidant properties [2]. The goal this work was to
investigate the interaction of flavonoids as rutin, quercetin, morin, kaempfeol (among
others) with photoluminescent CdTe QDs modified with acid 3-mercaptopropionic
acid (3MPA-CdTe QDs) dispersed either in aqueous buffered solution or in buffered
aqueous media organized with hexadecyltrimethylammonium bromide (CTAB). The
stock dispersion of 3MPA-CdTe was synthesized following the literature procedure
[3]. The excitation wavelength (ex) was 460 nm and photoluminescence collected at
the emission wavelength (λem) of 527 nm. The optimized experimental parameters
were: (i) phosphate buffer concentration (0,01 mol L-1); (ii) pH 7.4; (iii) 10% v/v of
methanol to improve solubility of flavoniods for the systems not containing CTAB
(non-organized system) and (iv) CTAB concentration of 1,0 mmol L-1 for the
surfactant organized aqueous systems. In order to establish a relationship between
luminescence measured from de QDs probe and the concentration flavonoids (from 5
x 10-6 to 6 x 10-5 mol L-1), a Stern–Volmer model was used. Static
photoluminescence quenching was confirmed and the binding constants (QDsflavonoid) indicated that in non-organized system the order interaction is quercetin >
kaempfeol > rutin > morin. In organized systems a weaker interaction between probe
and flavonoids occurred in the cases when hydroxyl substituents were present in the
flavonoid aromatic rings. Thus, non-polar flavonoids such as flavone, 3hydroxyflavone and 7-hydroxyflavone strongly interact with the probe. There was no
filter-effect contribution in the flavonoid induced probe signal attenuation. The
results demonstrated the potential for the indirect quantification of flavonoids
through the photoluminescente quenching of 3MPA-CdTe probe (Figure 1).
Figure 1: Photoluminescence
quenching of 3MPA-CdTe-quercetin
system. Quercetin concentration: 0 (a),
0.5 (b), 1.0 (c), 2.0 (d), 3.0 (e), 4.0 (f),
5.0 (g) and 6.0 (h) x 10 -5 mol L-1.
References
[1] Lima, J.X., Pérez-Gramatges, A., Aucélio, R.Q., Da Silva, A.R., Microchem. J., 110, 775-782 (2013).
[2] El Gharras, H. Int. J. Food Sci. Technol., 44, 2512–2518 (2009).
[3] Gu, Z., Zou, L., Fang, Z,, Zhu, W., Zhong, X., Nanotechnol., 19, 1-7 (2008).
180
PS2.6
Evaluation of spherical gold nanoparticles and gold
nanorods as probes for gentamicin determination
Jarol M. Andrades1, Andrea R. da Silva2, Aurora P. Gramatges1, Omar
Pandoli1, Ricardo Q. Aucélio1
1
Chemistry Dept, Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Rio de Janeiro-RJ,
22435-900, Brazil.
2
Centro Federal de Educação Tecnológica Celso Suckow da Fonseca (CEFET/RJ),Valença-RJ, 27600000, Brazil.
aucelior@puc-rio.br
Gentamicin (GEN) is an aminoglycoside (AMG) antibiotic used to treat bacterial infections
in humans and animals. In the structure of the AMGs there are no chromophores that enable
their direct spectrometric quantification. Therefore, most of the analytical methods are based
on the use of derivatization reactions with fluorogenic or chromophoric reagents. Literature
reports the interaction between spherical gold nanoparticles (AuNPs-Sph) and the AMG
tobramycin with the decreasing of the AuNPs surface plasmon resonance spectral band
intensity and the gradual appearance of another spectral band due to particle aggregation [1].
In the present work, aqueous dispersions of Au nanoprobes were used to enable the indirect
determination of GEN. AuNPs-Sph were synthesized following the Turkevich´s procedure
[2] while gold nanorods (AuNPs-Rod) were synthesized as indicated by Nikoobakht and ElSayed [3] using a hexadecyltrimethylammonium bromide rich medium. The experimental
conditions were adjusted to enable linear optical responses proportional to the increasing of
the quantity of GEN in probe aqueous dispersion. The interaction between GEN and AuNPsSph is electrostatic in nature and it is stronger in acidic conditions (pH 2.5 to 5.5) where the
amino groups of the AMG are positively charged. On the other hand, the interaction between
GEN and AuNPs-Rod is not affected by the change of the pH between 3.9 and 6.5 and also
occurs in the basic pH range. In both cases the agglomeration of nanoparticles occur, causing
the decreasing of both plasmon resonance spectral bands (transverse with max at 516 nm and
longitudinal with max at 662 nm) of the AuNPs-Rod and also of the transverse plasmon
resonance spectral band (max at 526 nm) of the AuNPs-Sph. In addition for the AuNPs-Sph,
it was observed the appearance of a band with maximum intensity at about 680 nm. All of
these spectral responses (Figure 1) enabled limits of detection for GEN in the nmol L-1 range.
Recovery tests using an injectable pharmaceutical formulation containing GEN resulted in
recoveries close to 100%, showing the potential of these probes for the quantification of
GEN.
Figure 1: Gentamicin interaction
spectra with AuNPs-Sph (A) and
AuNPs-Rod (B). Lines a-g (0, 0.8,
2.8, 4.0, 8.4, 11and 16) x 10 -8 mol L-1
of GENTA.
References
[1] Santos, H.S. et al. Microchem. J. 116, 206-215 (2014).
[2]Turkevich, J. et al., Disc. Faraday Soc. 11, 55-75 (1951).
[3] Nikoobakht, B. and El-Sayed, M.A. Chem. Mater. 15, 1957-1952 (2003).
181
PS2.7
On the Vibrational Dynamics of Selected Molecular
Complexes of -Picoline: a Joint Experimental (IR, RS,
INS, THz) and Theoretical (Solid-State DFT) Study
K. Łuczyńska1,2, K. Drużbicki2,3 and J. Cz. Dobrowolski1,4
1 Institute of Nuclear Chemistry and Technology, 16 Dorodna Street, 03-195, Warsaw, Poland
2 Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, 141980, Dubna, Russia
3 Department of Radiospectroscopy, Faculty of Physics, Adam Mickiewicz University, Umultowska
85, 61-614, Poznan, Poland
4 National Medicines Institute, 30/34 Chełmska Street, 00-725 Warsaw, Poland
E-mail: k.luczynska@ichtj.waw.pl
In recent years, hydrogen-bonded, donor-acceptor co-crystals have attracted much interest
for their use as novel functional materials. While revealing potential semiconducting or
ferroelectric properties, they are also useful in the search of low-polluting electrode materials
for batteries, where the redox-active organic compounds represents a promising alternative
to the conventional metal-based systems [1,2]. In addition to its broad - and barely
uncovered - practical utility, the quoted systems are also cognitively intriguing. Small,
molecular hydrogen-bonded synthons are crucial for supramolecular chemistry and crystal
engineering, especially for designing multicomponent crystals. In such a case, the competing
intermolecular interactions play the crucial role. Thus, the progressive exploration of such
systems in the interactions – structure interplay becomes an important issue, for which
crystallography, nuclear magnetic resonance and vibrational spectroscopy are the methods of
choice [3,4]. The complexes of benzoquinones with organic bases are good examples of the
systems, where one can observe a large amount of possible molecular synthons along with a
great variety of competing intermolecular interactions. Here, we report an extensive study of
selected co-crystals of 2-methylpyridine with bromanilic and chloranilic acids, which were
characterized by means of low-temperature X-Ray diffraction; solid-state NMR (13C CP
MAS NMR) and Intermolecular Interactions Analysis (Hirshfeld/NCI). The well-defined
structural properties were then used as a reference in a comprehensive vibrational analysis,
performed by combining, both, optical (IR, Raman, TDs-THz) and inelastic neutron
scattering (INS) spectroscopy techniques with the state-of-the-art solid-state density
functional theory (DFT) computations. Despite of quasi-harmonic approximation assumed
throughout the study, an excellent agreement between the theoretical and experimental data
was achieved over the entire spectral range, allowing for possibly thorough understanding of
the vibrational response and some spectral peculiarities. Particularly, the calculations
revealed the role of a significant long-range dipole coupling on the infrared response as well
as the influence of the structure on the low-wavenumber vibrations. By combining several
experimental techniques with the theory, we were hence able to examine the performance of
modern solid-state calculations in description of the vibrational spectra of middle-strength
hydrogen-bonded molecular complexes and – what is more – find a ternary structure –
intermolecular interaction – spectrum relationship.
References
[1] S. Horiuchi et al. Nat. Mater., 4, 163−166, 2005.
[2] G. Bonnard et al., RSC Adv., 3, 19081–19096, 2013.
[3] K. Łuczyńska, K. Drużbicki, K. Lyczko, W. Starosta, Vib. Spec. 75, 26–38, 2014.
[4] K. Łuczyńska, K. Drużbicki, K. Lyczko, J. Cz. Dobrowolski, J. Phys. Chem. B.
2015, DOI:10.1021/acs.jpcb.5b03279
182
PS2.8
Induced ethanol vaporization by foamed surface
investigated by Raman spectroscopy
E. Shoifet1, A. Hoppe1, E. Hassel1
1
Institute of Technical Thermodynamics, Faculty of Mechanical Engineering and Ship Building,
Rostock, Albert-Einstein-Str. 2, 18051 Rostock, Germany
E-mail: evgeni.shoifet@uni-rostock.de
For an auxiliary heating system, ethanol is a convenient choice of fuel. It has
preferable properties, such as high combustion speed. Its pollutant emission is lower
than in diesel or gasoline. Also, ethanol is a renewable energy source that can be
produced from biomass. Before combustion, it is necessary to vaporize the ethanol to
get a homogeneous mixture with air. This will ensure ideal conditions regarding
pollutant emissions reduction. Optimization of the auxiliary heating system consists
of two steps: induced ethanol vaporization and homogenized ethanol/air mixture. The
first step can be resolved by introducing foams as vaporization surface.
Investigation of the influence of foams with different porosity to the vaporization
process of ethanol and its mixing with air requires a selective and accurate
measurement of the fuel vapor and air species concentration. To address this issue an
approach of vibrational spectroscopy such as Raman scattering is the method of
choice [1].
Because of the need in spatial resolution a custom Raman system was build that
utilizes 90° between line-shaped volume excitation and collection direction.
Preliminary experimental results of the ethanol vaporization depending on the foam
porosity will be presented.
References
[1] J. Kiefer, T. Seeger, S. Steuer, S. Schorsch, M. C. Weikl, and A. Leipertz, Measurement
Science and Technology, vol. 19, no. 8. p. 2008.
183
PS2.9
Discrete variable representation approach to calculations of
translational vibration frequencies in water molecules
trapped in an Ar matrix
G. Pitsevich1, I. Doroshenko2, V. Pogorelov2, E. Kozlovskaya1,
E. Shalamberidze1, V. Sablinskas3 and V. Balevicius3
1
Belarusian State University, Independence Ave. 4, 220050, Minsk, Belarus
Taras Shevchenko National University of Kyiv, Acad. Glushkov Ave., 4, 03187, Kyiv, Ukraine
3
Vilnius University, Sauletekio 9-3, LT-10222, Vilnius, Lithuania
2
E-mail: pitsevich@bsu.by
Matrix isolation methods have long been successfully used for the analysis of the
structure and spectral characteristics, physical and chemical properties of water
molecules and clusters [1-4]. Being one of the smallest polyatomic molecules, the
water molecule can rotate practically freely in an isolating matrix [1, 2]. The authors
of [3, 4] noted also the possibility of coupling between rotational and translational
motions of the water molecule in an Ar matrix. However, we are unaware of any
attempts to estimate the frequencies of translational vibrations for a matrix-isolated
water molecule.
To solve this problem, we assumed that an Ar matrix has a cubic structure. Having
removed one of Ar atoms, we inserted a water molecule into the formed cavity. Then
the water molecule was simulated by a sphere with a radius r equal to the averaged
value of its three linear sizes in mutually perpendicular directions, taking into
account the covalent and van-der-Waals radii of the O and H atoms. The neighboring
Ar atoms were simulated by spheres with radii R equal to the van-der-Waals radius
of the Ar atom. At the final stage the water molecule was simulated as a point with a
mass M  2M H  M O , and an averaged radius of the “spherical” water ( R  r ) was
added to the van-der-Waals radii of the neighboring Ar atoms. The potential energy
equals to zero inside the obtained cavity and is infinitely large beyond it. Now we
can describe the water molecule motion with the following Schrödinger equation:
2
 2  2  2 
x
y
z
 R  2  2  2   U ( X , Y , Z )  E ; R 
; X  ; Y  ; Z  ; l0  1Å ,
2
Y
Z 
2Ml0
l0
l0
l0
 X
where x, y, z  the Cartesian coordinates of the “point” water molecule in a
coordinate system with the origin in the center of a distinct Ar atom. The 3D PES
was defined in the nodes of a 3D grid with a step of 0.1 Å, as it is required in the
DVR method. The results of the calculations are discussed in the frame of the
assignments, suggested in [3, 4], of some absorption bands in IR spectra of water in
an Ar matrix.
References
[1] J.A. Glasel, J. Chem. Phys., 33, 252-255 (1960).
[2] J.P. Perchard, Chem. Phys., 273, 217-233 (2001).
[3] X. Michaut, A.-M.Vasserot, L.Abouaf-Marguin, Low Temp. Phys., 29, 1118-1124 (2003).
[4] X. Michaut, A.-M.Vasserot, L.Abouaf-Marguin, Vibr. Spectr., 34, 83-89 (2004).
184
PS2.10
Synthesis and spectroscopic properties of new water soluble
monophthalocyanines
E. Yabaş1 , E. Bağda2
1
Cumhuriyet University, Faculty of Science, Department of Chemistry, Sivas, Turkey
2
Cumhuriyet University, Faculty of Pharmacy, Sivas, Turkey
E-mail: eyabas@cumhuriyet.edu.tr
Phthalocyanines have been intensively investigated in different scientific and
technological areas due to their interesting electrical, electrochemical and optic
properties, high chemical and thermal stability. These properties of phthalocyanine
complexes were affected strongly by the metal ion in the cavity and the nature of
substituents. Applications of phthalocyanine complexes such as semiconductors [1],
sensors [2], photodynamic therapy [3,4], non-linear optics [5], liquid crystals [6],
solar cell [7], catalysis [8] have shown increased importance. In addition to, the
synthesis of water-soluble phthalocyanines are important for biomedical applications.
In this study, the new water soluble phthalocyanines have been synthesized. The new
compounds were obtained in sufficient purity after successive washing with different
solvents and were characterized by elemental analysis and 1H-NMR, UV-Vis, IR and
mass spectra. Aggregation behaviors of these compounds have been investigated.
Fluorescence behaviors of these compounds were also studied.
N+
N+
N
N
N
N
N
S
S
N
N
N
N
N
N
N
M
N
N
N
N
S
S
N
N
N
N
N
N
N
N
N
+
+N
M: 2H, Zn
References
[1] Y. Zhang, X. Cai, Y. Bian, J. Jiang, Struct. Bond. 135, 275-322 (2010).
[2] L. Huang, F. Zhu, C. Liu, U. Treske, M. Grobosch, H. Tian, J. Zhang, Y. Geng, M. Knup fer, D.
Yan, Adv. Funct. Mater. 22, 4598-4607 (2012).
[3] T. Nyokong, Coord. Chem. Rev. 251, 1707–1722 (2007).
[4] J. T. F. Lau, P. C. Lo, Y. M. Tsang, W. P. Fong, D. K. P. Ng, Chem. Commun. 47,9657-9659
(2011).
[5] C. C. Leznoff, A. B. P. Lever, Phthalocyanines Properties and Applications, Vol.4, VCH
Publisher, 1993.
[6] T. V. Basova, M. Çamur, A. A. Esenpınar, S. Tuncel, A. Hassan, A. Alexeyev, H. Banimuslem,
M. Durmuş, A. G. Gürek, V. Ahsen, Synt. Met. 162, 735-742 (2012).
[7] X. Li, H. Wang, H. Wu, Struct. Bond. 135, 229-274 (2010).
[8] J. H. Zagal, S. Griveau, J. F. Silva, T. Nyokong, F. Bedioui, Coord. Che. Rev. 254, 2755-279
(2010).
185
PS2.11
UV-induced generation of oxo isomeric forms of phenol and
thiophenol type compounds
R. Fausto,1 I. Reva1, N. Kuş,1,2 S. Sagdinc,1,3 B. M. Giuliano,1
L. Lapinski4 and M. J. Nowak4
1
2
Department of Chemistry, University of Coimbra, Portugal. Department of Physics, Anadolu
University, Eskişehir, Turkey. 3 Department of Physics, Kocaeli University, Turkey. 4 Institute of
Physics, Polish Academy of Sciences, Warsaw, Poland.
E-mail: rfausto@ci.uc.pt
In this communication, we report the results obtained in the recent studies 1-3 on the
photochemistry of monomeric phenols and thiophenols isolated in cryogenic matrices. Upon
UV irradiation at different excitation wavelengths, the hydroxy (or thiol) forms of the
matrix-isolated
compounds
(phenol,
phenol-d5,
thiophenol
and
5-hydroxyquinoline) were transformed into the corresponding oxo (or thione) tautomers.
These novel species were then characterized in detail both structurally and vibrationally.
Subsequent selectively-induced reactions of the photoproduced oxo forms could also be
promoted, allowing the establishment of general insights on the photochemistry of matrixisolated phenol and thiophenol type compounds. It is shown that the primary event following
UV-excitation is the homolytic cleavage of the O–H (or S–H) bond, leading to formation of
the corresponding radical. Recombination with the H atom within the matrix cage can
subsequently occur at various positions: (i) at the heteroatom, restoring the reactant species;
and (ii) at carbon atoms occupying different positions of the aromatic ring. Formation of the
oxo (or thione) isomeric forms, resulting from the recombination reactions at the ortho and
para ring carbon atoms, was a common fact for the studied compounds. The para-product
systematically shows an increased photostability over the ortho-product, which converts
easily to open-ring ketenes upon UV-excitation (Figure 1).
N
ring-opening
N
CO
Allene
Etc...
C
N
-H
+H
O
O
O
N
O
Oxo (ortho)
Ketene
N
H
Hydroxy
Radical
O
Oxo (para)
Figure 1. Observed photochemical reactions of matrix-isolated 5-hydroxyquinoline. Initial irradiation at   288
nm led to observation of quinolin-5(6H)-one (Oxo (ortho), major product) and quinolin-5(8H)-one (Oxo (para),
minor product), via the quinolinyl radical; subsequent irradiation at  ≥ 235 nm resulted in the major production
of Oxo (para), isomeric open-ring ketene forms, and fragmentation products (mainly CO and allene).
References
[1] B. M. Giuliano, I. Reva, L. Lapinski and R. Fausto, J. Chem. Phys., 136, Art. nº024505 (2012).
[2] I. Reva, M. J. Nowak, L. Lapinski and R. Fausto, PCCP, 17, 4888–4898 (2015).
[3] N. Kuş, S. Sagdinc and R. Fausto, J. Phys. Chem. A, submitted.
Acknowledgements: The Coimbra Chemistry Centre is supported by the Fundação para a Ciência e a Tecnologia (FCT),
Portuguese Agency for Scientific Research, through the project PEst-OE/QUI/UI0313/2014. Financial support has been also
provided within the framework of the FCT post-doctoral grant SFRH/BPD/88372/2012.
186
PS2.12
Polymorph screening and characterization of a new
polymorph of 1-methylhydantoin
B. A. Nogueira,1 J. Canotilho,2 M. Ermelinda S. Eusébio,1
M. S. C. Henriques,3 M. Ramos-Silva,3 J. A. Paixão,3 and R. Fausto1
1
Department of Chemistry, University of Coimbra, Portugal, 2 Faculty of Pharmacy, University of
Coimbra, Portugal, 3 CFisUC, Department of Physics, University of Coimbra, Portugal.
E-mail: bernardoalbuquerquenogueira@gmail.com
In this communication, we report the screening of 1-methylhydantoin (1-MH; Figure 1),
recrystallized from different solvents and by the sublimation method, followed by the
structural and vibrational characterization of a novel polymorph. The compound was studied
by attenuated total reflectance infrared (ATR-IR) and Raman spectroscopies, as well as by
single crystal X-ray diffraction. The new polymorph is orthorhombic, belonging to the Pna21
space group, with 4 molecules per unit cell, a = 19.0258(4), b = 3.91210(10) and c =
6.82880(10) Å. In the crystal, each molecule exhibits two H-bonds of NH…O= type
established with two neighbor molecules, forming chains, with the oxygen atom of position 2
acting as the acceptor group. Interestingly, the other oxygen atom is not hydrogen bonded.
The chains are stacked forming alternating parallel sheets oriented along two different
directions.
On heating, the new polymorph shows a low-energy solid-solid transition extending from
about 110 ºC to 135 ºC. The solid-solid transition gives rise to the previous known 1-MH
polymorph.1 The polymorphs show quite diverse vibrational signatures, allowing for their
easier spectroscopic identification. Empirical correlations between NH stretching frequency
shifts observed upon H-bond formation (taken isolated molecule frequency values as
reference) allowed to estimate the average energies of the H-bonds in the two polymorphs,
revealing a slightly weaker H-bond network in the new solid form.
Figure 1. Molecular packing and characteristic Raman signature for the polymorphs of 1-MH (new form: right).
References
[1] M. Puszynska-Tuszkanow, M. Daszkiewicz, G. Maciejewska, Z. Staszak, J. Wietrzyk, B.
Filip, and M. Cieslak-Golonka, Polyhedron, 30, 2016-2025 (2011).
through the project PEst-OE/QUI/UI0313/2014.
187
PS2.13
Synthesis, structural and IR study of two polymorphs of a
novel hydrazone, 2-oxoacenaphthylen-1(2H)-ylidene
nicotinohydrazide
M. S. C. Henriques,1 R. Del Amparo,2 M. C. Rodríguez-Argüelles,2
J. A. Paixão1
1
2
CFisUC, Department of Physics, University of Coimbra, Portugal
Departamento de Química Inorgánica. Universidade de Vigo, Spain
E-mail: marta.henriques@gmail.com
Hydrazones and their metal complexes are an interesting group of compounds with a
large number of applications in very different fields [1], namely in medicine [2].
Following our investigation on new compounds with therapeutic activity, we report
the synthesis of a novel hydrazone, 2-oxoacenaphthylen-1(2H)-ylidene
nicotinohydrazide, and its structural and vibrational characterization. The compound
was obtained by refluxing in an ethanol solution acenaphthenequinone and nicotinic
hydrazide following a general procedure [3]. The obtained powder was recrystallized
from DMSO and other solvents that afforded small crystals used for single-crystal
XRD studies.
The molecule was found to crystallize in two polymorphs, depending on the
crystallization conditions. One of the polymorphs (form I) crystallizes in the
centrosymmetric P21/n monoclinic space group, the other (form II) crystallizes in the
noncentrosymmetric, but achiral, orthorhombic space group P212121. Conformation
of the molecules is similar in both polymorphs, but the network of weak
intermolecular interactions determining the crystal packing is different. In form II an
additional C—H…O bond connects molecules related by the screw-axis running
parallel to the a-axis. Crystals of both polymorphs were also screened by FTIR
microscopy; a detailed analysis of the spectra and comparison with that of the
isolated molecule calculated by state of the art ab-initio calculations will be
presented.
References
[1] X. Su, I. Aprahamian, Chem. Soc. Rev. , 43, 1963-1963 (2014).
[2] L.N. Suvarapu, Y.K. Seo, S.O. Baek, V.R. Ammireddy, E-Journal of Chemistry, 9, 1288-1304
(2012).
[3] M.C. Rodriguez-Arguelles, M. Belicchi Ferrari, G. Gasparri Fava, C. Pelizzi, G. Pelosi, R.
Albertini, A. Bonati, P.P. Dall’Aglio, P. Lunghi, S. Pinelli, J. Inorg. Biochem. , 66, 7–17, (1997).
188
PS2.14
Synthesis, structural and conformational analysis, and IR
spectra of ethyl 4-chloro-7-iodoquinoline-3-carboxylate
M. S. C. Henriques,1 N. Kuş,2,3 P. C. Horta,4 M. L. S. Cristiano,4
J. A. Paixão1 and R. Fausto2
1
CFisUC, Department of Physics, University of Coimbra, Portugal.
2
Department of Chemistry, University of Coimbra, Portugal.
3
Department of Physics, Anadolu University, Eskişehir, Turkey.
4
CCMAR and Department of Chemistry and Biochemistry, University of Algarve, Faro, Portugal.
E-mail: marta.henriques@gmail.com
In this communication, we report the synthesis of a novel quinoline derivative, ethyl
4-chloro-7-iodoquinoline-3-carboxylate (CIQC; Figure 1), and its structural,
conformational and vibrational characterization. The compound was studied in its
neat solid phases (crystalline and low-temperature amorphous phases) and as an
isolated species in a cryogenic argon matrix (at ~15 K). Infrared (IR) spectroscopy
and single crystal X-ray diffraction were the chosen experimental techniques. The
conformational space and the vibrational spectra of the isolated molecules of the
compound were also investigated theoretically by means of contemporary quantum
chemical methods.
The CIQC molecule exists in 4 different conformers, with predicted populations of
41:30:17:12% at room temperature (RT). The RT equilibrium conformational
mixture was successfully trapped in an argon matrix, at 15 K, and the vibrational
signature of the various conformers determined. Upon annealing of the matrix of the
compound at higher temperatures (~40 K), conversion of the higher energy forms
into the most stable conformer was found to take place, in consonance with the low
predicted barriers for conformational isomerization. Sublimation of the host matrix
argon atoms (at ~43 K) led to production of a low-temperature amorphous state of
CIQC, containing the lowest but also the higher energy conformers. At T ~243 K the
amorphous rearranged to the crystalline state, whose molecular unit corresponds to
the most stable CIQC conformer, as shown both by infrared spectroscopy and single
crystal X-ray diffraction (Figure 2).
through the project PEst-OE/QUI/UI0313/2014. Financial support has been also provided within the framework of the FCT
post-doctoral grant SFRH/BPD/88372/2012.
189
PS2.15
Quantum-mechanical study and spectral analysis on some
derivatives of rhodamine in solutions
Andreea-Celia Benchea, Babusca Daniela, Dan Gheorghe Dimitriu, Dana
Ortansa Dorohoi*
Faculty of Physics, Alexandru Ioan Cuza University of Iaşi, 11 Carol I Bdv, RO – 700506, Iasi
ddorohoi@uaic.ro
Abstract:
Rhodamine derivatives (6G and B) are a family of chemical heterocyclic compounds,
related to florone dyes [1]. They are often used as dyes with numerous
biotechnological applications. The quantum-mechanical, electro-optical and spectral
proprieties of the isolated molecule in the ground state, were determined using the
molecular modeling programs. The visible electronic absorption and fluorescence
spectra of Rhrodamin 6G and B compounds were recorded in solvents [2, 3] with
different macroscopic parameters (η si ε). Some properties of rhodamine derivatives
in the excited state were determineted by the solvatochromic study.
Keywords:
Rhodamine derivatives, molecular modeling, visible light absorption and
fluorescence, solvatochromic study.
References
[1] Ni Xiao, Jian Deng, Kaihui Huang, Saiqin Ju, Canhui Hu, Jun Liang,
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014)
312–318.
[2] Casey, Kelly G.; Quitevis, Edward L. (1988). "Effect of solvent polarity on
nonradiative processes in xanthene dyes: Rhodamine B in normal alcohols". The
Journal of Physical Chemistry 92 (23): 6590–6594.
[3] Kubin, R. F. and A. N. Fletcher (1982) Fluorescence quantum yields of some
rhodamine dyes, J. Luminescence 27, 455-462.
190
PS2.16
Spectral and Quantum Mechanical Studies of Dimerization Reaction
of Some Carbanion Monosubstituted Pyridazinium Ylids
Cezarina Morosanu (Călugăru), Daniela Babușcă, Dana Ortansa Dorohoi*
Alexandru Ioan Cuza University, Faculty of Physics, Carol I Bvd., RO- 700506, Iasi, Romania.
*Corresponding author: e-mail: ddorohoi@uaic.ro
The carbanion monosubstituted pyridazinium ylids are dipolar molecules
which react by dimerization in different solvents. The dimerization process can be
studied by kinetical means regarding the variation in time of the intensity of the
visible intramolecular charge transfer (ICT) absorption band of ylid. The
dimerization constant for the dimerization process of carbanion monosubstituted
pyridazinium ylids derivatives in protic and aprotic solvents is studied in this paper.
The half time and the dimerization rate constant [1,2] were estimated for the studied
ylids. The obtained values are dependent on the heterocycle carbanion structure and
the solvent nature.
Keywords: monosubstitued pyridazinium ylids, dimerization process, the half time,
dimerization rate constant
This work is co-funded by the European Social Fund through Sectoral Operational
Programme
Human
Resources
Development
2007-2013,
project
number
POSDRU/187/1.5/S/155397, project title “Towards a New Generation of Elite
Researchers through Doctoral Scholarships”.
References
[1] – I. Zugrăvescu, M. Petrovanu, N-Ylid Chemistry, Acad. Press, London, NY,
Sidney (1976).
[2] – D. O. Dorohoi, M. Cotleț, I. Mangalagiu, Int. J. Chem Kinet., 34 (2002) 613-619.
[3] – V. Melnig, I. Humelnicu, D. O. Dorohoi, Int J. Chem. Kinet., 40 (2008) 230-239.
191
PS2.17
Fourier transform infrared spectroscopy in the study of
the interaction between collagen and naturalized and
commercial dyes
D. Pellegrini1, M. Corsi2, M. Bonanni2, R. Bianchini2, A. D’Ulivo1, E. Bramanti1
1
National Research Council of Italy, C.N.R., Istituto di Chimica dei Composti Organo MetalliciICCOM-UOS Pisa, Area di Ricerca, Via G. Moruzzi 1, 56124 Pisa, Italy
2
Department of Chemistry “Ugo Schiff”, Via della Lastruccia 3-13, 50019 Sesto Fiorentino,
Florence, Italy
We recently synthetized naturalized dyes (NDs) which are a new class of
environmental friendly chemicals. ND can be obtained the covalent union of a
dye species (e.g., azo, anthraquinone, aniline type chromophore) with lactose, a
natural sugar. In the present work NDs and the traditional acid dyes (ADs) were
compared by studying the different behavior during the leather dyeing process.
NDs are able to confer water-soluble properties to the dye molecule as a whole.
The interactions between the dyes and the leather proteins were studied by FTIR spectroscopy and thermogravimetric (TG) analyses. The protein cross-linking
of the dyed leather samples was investigated by studying the 1654/1690 cm -1
peak height ratio and a deconvolution procedure of the amide I peak. The helix
secondary structure was the predominant component of the leather proteins of
the samples dyed with low concentrations of NDs (2%), while the b-sheets
prevailed when leather samples were dyed with the traditional ADs and high
concentrations of NDs (>5%). The data were discussed with respect to TG
results
Acnowledgements - This work has been financially supported by the European
Project Life+ 2012 ENV/IT/352-“BIONAD”.
References
[1] D. Pellegrini, M. Corsi, M. Bonanni, R. Bianchini, A. D’Ulivo, E. Bramanti, Dyes and
Pigments, 116, 65-73 (2015)
192
PS2.18
Analysis of high density samples using LO-RAY-LIGH®
diffraction gratings
U. Oppermann1, T. Fujiwara2 and J. Knoop1
1
2
Shimadzu Europa GmbH, Albert- Hahn- Str. 6-10, D-47269 Duisburg, Germany
Shimadzu Device Corporation, Kanda-Nishikicho 1-Chome, 101-8448 Tokyo, Japan
E-mail: uo@shimadzu.eu
It has been more than half a century since the release of the first Shimadzu UV-VIS
spectro-photometer QB-50 in 1952 and during this time more than 160.000 UV-VIS
spectrometers have been produced and installed in a wide variety of different
applications. A lot of technical innovations have been implemented to improve the
performance and significantly reduce the stray light levels. The latest innovation
during development of sophisticated spectrophotometers is based on a new
holographic exposure method and optimized etching process which has made it
possible to produce both high-efficient and exceptionally low stray light gratings.
These LO-RAY-LIGH® gratings have guaranteed values of stray light at the
intermediate position between zero- order and first-order lights. The values are
measured by Shimadzu's laser stray-light-measuring system. The latest development
in the series of UV-VIS spectrophotometers is the UV-2700 which is a true double
beam double monochromator system in a compact design for high-precision spectral
analysis of a wide range of samples including organic and inorganic compounds, biological
samples, optical materials and photovoltaics. The high performance optical system is
designed with “LO-RAY-LIGH®” diffraction gratings, featuring highest efficiency
and exceptionally low stray light. The spectrophotometer operates in the wavelength
range of 185 to 900 nm and allows highly sophisticated applications such as direct
measurement of high density samples up to 8 absorbance units without dilution.
A typical example for high density measurements are KMnO 4 solutions in different
concentrations which show an excellent linearity of up to 8 absorbance units. A
variety of possible system configurations will be discussed on recent application
examples and advantages of the new spectrophotometer series will be explained.
References
[1] Harrison, G. R. J. Opt. Soc. Am. 1949, 39.
[2] Aoyagi, Y.; Namba, S. Opt. Acta 1976, 23, 701.
193
PS2.19
Nonionic and Zwitterionic Forms of
Glycylprolylglycylglycyltyrosine (GPGGY) as a part of
Spider Silk Protein: Vibrational and Structural Study
H. Arı1 and T. Özpozan2
1
2
E-mail:hatice.ari@bozok.edu.tr
Seven different silk types produced by female orb weaving spider. All types of silk
share four types of amino acid motifs comprising of ‘GPGX aXb’ (XaXb= GA, GS,
GY, or QQ), ‘GGX’ (X: A, L, R, Q and Y), ‘polyalanine/ polyglycylalanine’ and
‘spacer sequences’ to prevent fiber formation within glands, align various structural
regions within the fiber and to
provide additional surfaces for
critical interactions. GPGXaXb
repeat conforms to a β-turn spiral
and the proline residue behaves
as the focal point for retraction
energy after stretching [1].
Conformer analyses have been
made for nonionic and zwitterionic forms of GPGGY (nonGPGGY and zwt-GPGGY) parts
of the spider silk chain. The most
stable conformers of the two
forms have been used for
vibrational
analysis,
NBO
analysis and HOMO-LUMO
analysis. β-turn spiral structure of
Fig. 1 The structure of zwt-GPGGY and non- non-GPGGY and zwt-GPGGY
have been calculated and
GPGGY and Raman & IR Spectra
compared with the conformers
which obtained from the conformer analysis. All the calculations were carried out
with Gaussian 09 [2] by the DFT/B3LYP method with 6-31G(d) basis set. NonGPGGY and zwt-GPGGY were calculated in the gas phase and the aqueous media
(using IEFPCM), respectively. The potential energy distribution (PED) of normal
modes was calculated using the program VEDA4 [3].
References
[1] D. Saravanan, Journal of Textile and Apparel, Technology and Management, 5, 1-20 (2006).
194
PS2.20
Comparative Vibrational Spectroscopic Studies of Nonionic
and Zwitterionic Forms of Glycylprolylglycylglycylserine
(GPGGS) as a part of Spider Silk Protein
H. Arı1 and T. Özpozan2
1
2
Spider silk combines many desirable properties which are currently not met by manmade materials [1]. Spiders secrete seven types of silk each of which has different
functions [2]. The chemical structure of the spider silk proteins shows four types of
aminoacid sequences that composes the major part of the macromolecules: (Ala) n /
(Gly Ala)n, GGX and GPGXX (X: any aminoacid) [3,4]. GPGXX repeat has β-turn
spiral structure and provides silk
with elasticity 5–10%.
GPGGS as a part of GPGXX
motif of spider silk spidroin in
nonionic (non-GPGGS) and
zwitterionic (zwt-GPGGS) forms
have been examined from
vibrational spectroscopic and
theoretical aspects. The most
stable conformational isomers of
non-GPGGS and zwt-GPGGS
were obtained through relaxed
scan using the DFT/B3LYP with
6-31G(d) basis set. Nonionic and
zwitterionic forms of β-turn
spiral structures of GPGGS have
also
been calculated
and
Fig. 1 The IR, Raman Spectra and the structures
compared with the most stable
of zwt-GPGGS and non-GPGGS forms.
conformers obtained as a result
of conformer analysis. Nonionic and zwitterionic forms were calculated in the gas
phase and the aqueous media (using the IEFPCM), respectively. All the
computations were carried out with Gaussian 09 program package [3]. VEDA4 [4]
program has been used to calculate Potential Energy Distribution (PED).
References
[1] P. Papadopoulos, J. Sölter and F. Kremer, Eur. Phys. J. E 24, 193–199 (2007).
[2] M. B. Hinman, J.A. Jones and R.V. Lewis, TIBTECH 18 (2000) 274-379.
195
PS2.21
Evolution of Vibrational Spectrum during Oligomerization
of Pyrrolo[3,4b]pyrrole: A DFT Study
H. Arı1, Ö. Mıhçıokur2 and Z. Büyükmumcu2
1
2
Electrochemical oligomerization takes place in multiple steps, such as ionization,
coupling for the formation of the transition state structure, descending from the
transition state to form an intermediate which is followed by proton releasing steps
[1]. In this study, the variation of vibrational spectrum has been examined for the
reaction path described. The structures formed at each step have been optimized and
their vibrational spectrum have been calculated for the pyrrolo[3,4b]pyrrole
oligomerization employing B3PW91 functional [2, 3] with standard basis set 631G(d,p). All of the calculations have been carried out using Gaussian 09 package
[4].
The
optimized
structures
for
dimerization and
their vibrational
spectrum
are
given in Fig. 1.
As seen from the
figure, C-C bond
formation
between
monomers takes
place
through
these
steps
gradually
and
Fig.1. Computed IR spectra and optimized monomer, transition
vibrational
frequencies
state, intermediate, and dimer structures of pyrrolo[3,4b]pyrrole
associated with
this bond vary depending on the steps of the evolution. There is another bond in the
structure strongly affected by the alteration of the C-C bond; C-H bonds formed by
hydrogen atoms attached to these C atoms, separately. Frequencies associated with
this bond also evaluate depending on the steps stated above. This frequency
disappears in the final spectrum due to disappearance of this bond with proton
releasing.
This study has been supported by The Scientific and Technological Research Council
of Turkey (TUBITAK, Project no: 212T051).
References
[1] M. Yurtsever and E. Yurtsever, Polymer, Volume 45, Issue 26, 9039-9045, (2004).
[2] A. D. Becke, J. Chern. Phys., 98 (2), 1372-1377 (1993).
[3] J. P. Perdew and Y. Wang, Phys. Rev. B 45, 13244– 13249 (1992).
196
PS2.22
Investigation of antioxidant capacity of hackberry
(Celtis australis L.)
S. Babacan, KI Berker, D. Ozyurt and B. Demirata
Istanbul Technical University, Faculty of Science & Letters, Department of Chemistry, 34469
Istanbul, Turkey
E-mail: corresponding. demirata@itu.edu.tr
Antioxidants become oxidized while preventing the oxidation process by
deactivating free radicals. Therefore, our body has a continuous need for antioxidants
during a lifetime. Earlier studies are mostly related to effects of air quality on
hackberry leaves and the use of hackberry peel and leaves as bio monitor on
determination of heavy metal concentration of air. There are a few assays about the
antioxidant capacity of hackberry fruit and as the hackberry species are widespread
in the geography of our country it is influential to actualize this study.
Antioxidant determination methods were applied to green, yellow and black cases of
hackberry fruit during the ripeness stage, moreover it is aimed to determine the
change of the antioxidant capacity of hackberry along the growing process and the
causes of the current changes. The antioxidant capacities of Hackberry fruit extracts
and infusions were determined by CUPRAC [1], CERAC [2], Folin-Ciocalteu [3]
and SDS modified ferricyanide methods [4]. Hackber34678 using CUPRAC method,
in the kernel part of hackberry, much lower antioxidant capacity than the fruit part of
hackberry was observed and further studies were proceeded with the fruit fraction of
hackberry. Appropriate type of solvent were tried to determine for the extraction of
hackberry and for this purpose ethanol, methanol and acetone were selected as
extraction solvents. In solvent optimization studies, hackberry extracts were prepared
using absolute, 80%, 70%, 50%, 40% and 25% (v / v) methanol solutions and
applying CUPRAC method to these extracts it was found that the extracts prepared
with 50% (v/v) with methanol had the highest antioxidant capacity with the value of
0.072 (mmol TR/g). Modified Ferricyanide methods by CUPRAC, CERAC, FolinCiocalteu and SDS are applied to 50% (v / v) methanol extracts and infusions and, as
the results of each method, antioxidant capacity amounts were determined in that:
green > yellow > black. Besides, antioxidant capacity amounts for all 4 methods
were seen that 50% hackberry methanol extract > hackberry infusion as mmol TR/g.
References
[1] R Apak, K Guclu, M Ozyurek, SE Karademir, J. Agric. Food Chem., 52, 7970−7981, (2004).
[2] D Ozyurt, B Demirata, R Apak, R. J of Food Composition and Analysis, 23, 282–288, (2010).
[3] O Folin, & V Ciolcalteu, The Journal of Biological Chemistry,73, 627-649, (1927).
[4] KI Berker, K Güçlü, I Tor, B Demirata, R Apak, Food Analytical Methods, 3, 154 –168, (2010).
197
PS2.23
Ageing studies of Tetraphenyl-Butadiene in noble gas
detectors for Dark Matter and Double-beta Decay searches
N. Yahlali(a), M. Garcia(a), L.M.P. Fernandes(b)
(a) Instituto de Fisica Corpuscular, mixed center CSIC-Universidad de Valencia, Paterna, Spain
(b) LIBPhys, Departamento de Física, Universidade de Coimbra, Portugal
pancho@gian.fis.uc.pt
Noble gases (Xe, Ar, Kr) have outstanding spectroscopic properties that make them
very attractive as detector media in dark matter and double-beta decay experiments.
However, their scintillation light is in the vacuum ultra-violet (VUV) region, which
is difficult to detect by most standard photosensors, more efficient in the visible
region. This requires shifting the VUV light in noble gas detectors with optical
readout using photomultiplier tubes (PMTs) or silicon photomultipliers (SiPMs). The
wavelength shifter usually used in noble gas detectors is the organic compound
Tetraphenyl-Butadiene (TPB), which absorbs the VUV light and emits in the blue
range (~430 nm), where photosensors like SiPMs are most sensitive.
TPB is an organic molecule that may degrade due to exposure to environmental
agents and also ultraviolet light. This degradation results in a reduction of the
fluorescence yield of the molecules and the subsequent reduction of the signal
amplitudes in noble gas detectors.
We present here TPB ageing studies due to exposure to VUV light, aiming at
quantifying the reduction of the absolute fluorescence yield of TPB coatings of
several thicknesses (130 nm, 260 nm, 390 nm, 1500 nm), exposed to various doses of
VUV light at 172 nm (peak of the xenon scintillation). The VUV light is produced
from a vacuum monochromator coupled to a deuterium lamp. The absolute quantum
yield of the TPB-coatings is measured using a spectrometer and an integration
sphere. The variation of the absolute quantum yield of the TPB coatings per exposure
dose of VUV light in high-pressure gaseous xenon TPC is discussed. In particular,
the reduction of the absolute fluorescence yield in the electroluminescent gaseous Xe
TPC of the NEXT-100 experiment for neutrino-less double-beta decay is considered,
assuming an exposure time of several years and an event rate of ~10 Hz in
underground operation conditions.
198
PS2.24
Characterization of organic residues in archaeological
ceramic vessels used in Basque Whalers from 16th to 17th
century by means of LVI-PTV-GC-MS
Laura Blanco-Zubiaguirre(1), Maitane Olivares(1), Javier García
Iñañez(1), Kepa Castro(1), Juan Manuel Madariaga(1)
(1) Department of Analytical Chemistry, University of the Basque Country UPV/EHU , Barrio
Sarriena, 48940 Leioa, Biscay, Spain, +34 946015551, *laura.blanco@ehu.es
(2) Department of Geography, Prehistory adn Archaeology, University of the Basque Country
UPV/EHU , 01006 Vitoria-Gasteiz, Araba, Spain,
The analytical investigation of organic residues found in ancient samples such as
ceramic containers can yield important archaeological information. Organic materials
are more subject to degradation than inorganic ones, so if we can understand their
composition then we can ensure that ancient artifacts will remain part of our Cultural
Heritage. These residues can be preserved on the surface or adsorbed in porous
ceramic vessels. Their analysis can help us understand the encompassing history, the
historical, cultural and technological context in which were manufactured and what
purpose they were used for. In this sense, the identification of one or more
biomarkers can provide not only information about the nature of the residue but also
about the transformations undertaken by the sample during the burial process.
The aim of this work was the identification of the organic residues that have
remained in archaeological ceramic samples, concretely, samples collected from a
deposit in Lekeitio (Basque Country, North of Spain). These vessels are suspected to
be used by the Basque Whalers in the period from 16th to 17th Century to store whale
oil. Hence, prior to their analysis, an analytical approach based on an alkaline
hydrolysis by means of focused ultrasound (FUS) followed by liquid extraction in
combination with large volume injection (LVI) in a programmable temperature
vaporizer (PTV) combined with gas chromatography – mass spectrometry (GC-MS)
was fully optimized (and validated). This main goal has been achieved after the
optimization of the main parameters affecting the hydrolysis step (% MeOH/H2O and
volume and FUS parameters such as ultrasound power, pulse and time), the
extraction procedure (extractant nature and volume), the derivatization step
(%BSTFA and derivatization solvent) and the LVI-PTV parameters (Cryofocussing
temperature, Vent flow and Vent time).
No visible residues were detected among the different pieces of ceramics which
difficulties largely the characterization and identification of potential organic
residues. Nevertheless, black crusts were found in the corresponding internal surface
of the vessels. The preliminary results of the analysis of ceramic vessels, led to the
determination of some interesting organic compounds such as pristane, phytane,
several saturated fatty acids and cholesterol, which could be indicative of having
used the vessels to store whale oil. Some other organic biomarkers related to the
presence of whale oil will be confirmed with different oil standards (i.e., alkanoic
acids, phytanic acid or pristanic acid).
.
199
Poster Session 2: LaserSpectroscopy
PS2.25
The SHREDDERSORT Project: selective recovery of
non-ferrous metal automotive shredder by combined
electromagnetic tensor spectroscopy and laser-induced
plasma spectroscopy
E. Grifoni1, S. Legnaioli1,2, G. Lorenzetti1, S. Pagnotta1 and V. Palleschi1,2
1
Applied and Laser Spectroscopy Laboratory, ICCOM-CNR, Research Area of National
Research Council, Via G. Moruzzi, 1 – 56124 Pisa (ITALY)
2
E-mail: stefano.legnaioli@cnr.it
This paper reports the preliminary results obtained in the SHREDDERSORT
project, a project funded by the European Commission aimed at developing a
new dry sorting technology for non-ferrous automotive shredder.
The non-ferrous fractions contain mainly aluminum, magnesium and copper
alloys, although sometimes also zinc-based alloys are found. These materials
results after the non-ferrous separation (usually by an Eddy-current operation)
and can be further sorted by hand-sorting or even by any kind of mechanical
sorting process.
The analyses have been realized in the Applied and Laser Spectroscopy
Laboratory at CNR in Pisa using the Laser Induced Breakdown Spectroscopy
(LIBS) technique, in the perspective of the development of a dedicated
instrument for on-line sorting operation.
Different types of samples have been analyzed and, in particular, different
parameters have been studied to identify the optimum excitation conditions for
the maximization of LIBS signal under double pulse excitation, for instance
changing the inter-pulse delays between the laser pulses (from 0ns
(coincident pulses) to 75μs) and the laser pulse irradiance.
Finally, the LIBS spectra have been processed using an Artificial Neural
Network approach in order to classify different kind of aluminum alloy, using a
set of certified samples.
.
200
PS2.26
The LACOMORE Project: Laser-Based
Continuous Monitoring and Resolution of Steel
Grades in Sequence Casting Machines
E. Grifoni1, S. Legnaioli1,2, G. Lorenzetti1, S. Pagnotta1, V. Palleschi1,2
1
Applied and Laser Spectroscopy Laboratory, ICCOM-CNR, Via G. Moruzzi 1 - 56124
Pisa, Italy
2
Laser induced breakdown spectroscopy (LIBS) is a well-established
technique for on-line industrial applications where robustness, stability,
reliability, speed of analysis and operational availability are important
topics to be taken into account. Recent investigation in LIBS have
focused on the development and testing of field portable instruments and
remote sensing equipment, which exploit the ability to analyze samples
qualitatively and quantitatively with optical access alone. The general
objective of this project is to develop the necessary advanced
methodology for in situ analysis of transition as-cast products during
continuous casting with the purpose of improving the productivity and
cost-efficiency in the fabrication of stainless steel and special steels.
In this project, LIBS is applied for on-line elemental analysis of
continuous casting steels from a distance, without any interference or
delay in the production line. Elemental segregation across the slab/billet
length as well as intermediate chemical composition between sequential
heats are readily identified. Moreover, a new LIBS system will be
designed and built, based on technology that has been proved suitable for
this application. Intermediate chemical composition in transition
materials resulting from successive heats will be then readily identified.
A number of laboratory tests and industrial trials have been carried out to
validate the LIBS technology. The sensor is aimed at working in plant
environment in absence of human intervention. Finally, a mathematical
model based on LIBS measurements to predict the mixing process was
also developed. The project is coordinated by the University of Malaga;
two of major producers of steel products in Europe are partners
(ACERINOX, GERDAU), together with three research institutes
(KIMAB, CNR/ICCOM and CRMASBL) participate to the project
covering three different European states (Spain, Italy and Sweden). The
duration of the project is 36 months from 1 st July 2013. In this
communication, some results, obtained by the CNR partner on test
samples, are presented.
Acknowledgments
The authors thank the the European Commision for funding the project in the
Research Fund for Coal and Steel.
201
PS2.27
Fast Identification of Cast Iron Using
Laser Induced Breakdown Spectroscopy
S.A.Jahdi1, M. Zand2 and E. Eslami2
1
2
Sharif University of Technology, Tehran, IRAN
Iran University of Science and Technology, Tehran, IRAN
E-mail: m_zand@Physics.iust.ac.ir
Iron and steel are the predominant metals used by the transportation, building and construction, oil
and gas and other related industries. From other side steel grades are the world’s most recycled
materials and cast iron as one of the widespread high alloy steels among 3500 different steel grade has
its own emphasis. So, fast identification and sorting of different cast grades are of great importance.
In this article laser induced breakdown spectroscopy (LIBS) was used as a fast technique for
characterization of different samples of cast iron. Effect of focusing lens to sample distance (FLSD)
was studied as a physical factor on LIBS spectra and different plasma parameters. As it can be seen in
Fig.1 focusing lens to sample distance has diverse impression on signal to noise ratio (SNR) of
different elements.
Fig.1. SNR for different elements of cast iron dependant of FLSD
F…
SNR
4.00
2.00
0.00
Ni Cr Mn
Plasma temperature was calculated by Boltzman equation and corresponding electron density was
estimated using stark broadening method for different cast iron samples 1. Discrepancy between
obtained Ne and Ne extracted from Saha equation was studied2. Validation of local thermal
equilibrium (LTE) condition, necessary criteria for quantitative analysis with LIBS method, was
evaluated using the mentioned plasma parameters. Effect of different elements’ concentrations on
plasma temperature was discussed carefully. Furthermore, extraordinary behavior of Ni is studied
from different physical and chemical viewpoints.
Fig.2. Plasma Temperature versus different element concentartions
2
Concentration
(%)
Cr
%
1.5
1
0.5
0
11000
11500
T (ºK)
12000
References
[1] F. Bredice , F.O. Borges , H. Sobral , M. Villagran-Muniz, H.O. Di Rocco, G. Cristoforetti,S.
Legnaioli e, V. Palleschi e, L. Pardini e, A. Salvetti e, E. Tognoni, Spectrochimica Acta Part B, 61
1294–1303 (2006).
[2] Miziolek AW, Palleschi V, Schechter I, editors, Cambridge: Cambridge University Press; 2006.
202
PS2.28
Evaluation of Manganese (MnCl2, nano-Mn) Accumulation
in Rat Tissue Using Laser Ablation Inductively Coupled
Plasma Mass Spectrometry (J200 Tandem LA-LIBS)
Renata Brodzka1, Beata Janasik1 C. Derrick Quarles Jr.2, Jhanis J. Gonzalez 2,3,
Richard E. Russo 2,3, Slawomir Gralewicz1, Katarzyna Domeradzka1, Piotr
Lutz1, Tomaszewska E4, Grobelny J4, Jan Stetkiewicz1, Maciej Stępnik1,
Wojciech Wąsowicz1
1
Nofer Institute of Occupational Medicine, Department of Toxicology and Carcinogenesis, St. Teresy
8, 91-348 Lodz,
2
Applied Spectra Inc., Fremont, CA, USA
3
Lawrence Berkeley National Laboratory, Berkeley, CA, USA
4
University of Lodz, Faculty of Chemistry, Department of Materials Technology and Chemistry,
Lodz, Poland
e-mail:brodzka@imp.lodz.pl
Manganese (Mn) is an essential element in the human body that cause adverse effects
at insufficient levels, but more importantly, major health concerns are seen with
overexposure to Mn. Accumulation of Mn in the brain regions is associated with
neurotoxicity following high-dose Mn inhalation. An extreme case of manganese
neurotoxicity is known as manganism, consists of behavioral and neurological signs
essentially similar to Parkinson's disease.
Because the biological properties of the substance in nanoparticle form may differ
substantially from biological properties of the same substance in the ionized form ,
we investigate toxicokinetics and distribution of nano-Mn (MnO2) and MnCl2 - in
male albino Wistar rats by repeated (8x) intraperitoneal administration at a dose of
10.0 mg Mn/kg body wt. (b.w.).
In our imaging studies with LA-ICP-MS, we used laser ablation systems (J200
Tandem LA-LIBS, Applied Spectra Inc., USA) equipped with a 266 nm laser and 6
channel broadband CCD detector coupled to ICP-MS (Aurora Elite) from Bruker,
USA. Imaging mass spectrometric measurements by LA-ICP-MS are performed by
line scan ablation of thin tissue sections (line per line) with a focused laser beam.
The diameter of the laser crater during imaging mass spectrometric measurements
was 20 and 200 µm. The measurement time for one tissue sample by imaging LAICP-MS depends on the size of the area analyzed, the laser scan speed applied and
the interline distance. To obtain high-resolution images the spot size and laser energy
as well as laser scan speed were optimized.
203
PS2.29
Analysis of occupational exposure to toxic metals using
Laser Ablation Inductively Coupled Plasma Mass
Spectrometry
M. Stanislawska1, R. Brodzka1, B. Janasik1, C. Derrick Quarles Jr.2, Jhanis J.
Gonzales2,3 , Richard E. Russo2,3 , W. Wasowicz1.
1
Nofer Institute of Occupational Medicine, Department of Toxicology and Carcinogenesis,
St. Teresy 8, 91-348 Lodz
2
Applied Spectra Inc., Fremont, CA, USA
3
Lawrence Berkeley National Laboratory, Berkeley, CA, USA
E-mail: magda@imp.lodz.pl.
Assessment of occupational exposure to toxic metals occurring in the workplace is
based on the determination of metals concentrations in the air in the breathing zone
of the employee. The introduction of the LA-ICP-MS (Laser ablation-inductively
coupled plasma-mass spectrometry) technique for determination of air samples offers
great opportunities for eliminating pretreatment steps, like mineralization process.
Reducing execution time and low cost saving necessary to conduct research of
environmental work would be possible.
Aim of present study was to assess of the applicability of LA-ICP-MS technique for
the determination of metals in air samples in the occupational settings. Quartz filters
samples, 200 µm spot size, were analyzed using a J200 Tandem LA-LIBS system
equipped with a 266 nm laser and 6 channel broadband CCD detector (Applied
Spectra Inc.) combined with a Bruker Aurora Elite ICP-MS. Calibration curves for
As, Cd and Pb was performed using NIST Glass SRMs and obtained good R 2 (only
three points) and good precision. The semi-quant method gave only comparison data
between the 4 quartz filters. If standards were provided then quantitative analysis
could have been performed. The parallel lines method provides the ability to map out
the quartz filters to see how the distribution of particles are spread out on the filters.
Results indicate that, LA-ICP-MS can be used in the future to monitoring of work
environment. Application of this technique can be possible after finished few
technical problems, like: heterogeneity of dust covering the surface of the filter and
lack of appropriate commercial standards and reference materials.
204
PS2.30
Influence of measurement conditions on classification of
materials on the base of LIBS spectra
G. Vítková1,2, P. Pořízka2, K. Novotný1 and J. Kaiser2
1
2
Department of Chemistry, Faculty of Science, Masaryk University, 625 00, Brno, Czech Republic
CEITEC - Central European Institute of Technology, Brno University of Technology, Brno, 616 00,
Czech Republic
E-mail: gabriela.vitkova@ceitec.vutbr.cz
Fast qualitative analysis in terms of identifying the chemical elements present in the
sample is one of the advantages of LIBS. Using advanced statistical methods enables
also classification and identification of materials on the base of their spectra without
the knowledge of absolute amounts of particular elements. However, for good results
it is necessary to optimize the measurement conditions properly.
The intensity ratio of the useful signal - i.e. atomic lines to the continuous spectrum
(SNR) and other plasma processes is the subject of a number of optimization steps.
This is usually about finding the ideal time of start and the duration of signal
recording - thus finding the optimal time ‘windows’.
When performing LIBS measurement there is crucial role of so-called matrix effect.
Matrix effect is the name for a phenomenon where the chemical state of the element
in the material (type of molecules and the structure of their arrangement, types of
bonds, etc.) has a significant effect on the ablation. This effect is most often
perceived negatively, because it represents a major limitation of quantification. On
the other hand, for the purposes like classification it may be beneficial. In this
contribution the matrix effect is studied and most suitable measurement conditions
(pulse energy, time windows) for specific purposes are set using standardized
materials of ores with different matrices.
Acknowledgements:
We would like to acknowledge the project ‘CEITEC—Central European Institute of Technology’
(CZ.1.05/1.1.00/02.0068).
205
PS2.31
Spectroanalytical strategies combining laser-induced
breakdown spectroscopy (LIBS) and laser ablation
inductively coupled plasma optical spectrometry (LA-ICP
OES) for sunscreens investigation
Érica Ferreira Batista1,2, Edenir R. Pereira-Filho1, Jose R. Almirall2
1
Federal University of São Carlos, P.O. Box 676, 13565-905, São Carlos, São Paulo State, Brazil.
2
Florida International University, Miami, FL 33199, USA.
E-mail: almirall@fiu.edu
This study shows the applicability of LIBS and LA-ICP OES in combination with
chemometric tools for exploratory analysis of sunscreen samples. The analyses were
performed with three equipment (two different LIBS systems and LA-ICP OES) and
the results obtained between them were compared. The experimental conditions for
LIBS and LA-ICP OES were selected after performing fractional factorial design 2 41. The four variables studied for J-200 LIBS were laser power, spot size, delay time
and frequency, for the RT100HP LIBS were laser power, delay time, frequency and
speedy and, for the LA-ICP OES were flow rate of gas, laser power, frequency and
spot size. The desirability function was used to processing the data [1]. Twenty
samples were analyzed and 2500 spectra were obtained for each LIBS equipment and
the data of LA-ICP OES were obtained in transient mode, and originated a matrix
with 109 rows and 16 columns. A Principal Component Analysis (PCA) was
performed using a data matrix obtained of each equipment. The data set was
normalized by the individual norm and meancentered. The results are shown in Fig.1.
Figure 1 - Graphical of the Scores (a) J200 LIBS (b) RT-100 HP LIBS (c) LA-ICP OES and
Loadings (d) J200 LIBS (e) RT-100HP LIBS (f) LA-ICP OES in relation to signal intensity of the
elements.
It was possible to verify the overall classification of sunscreens according with
characteristics and associate with the levels of metals (mainly Zn and Ti) present in
the samples, using PCA. Quantitative analyzes and amount reported on the label by
the manufacturer for some samples, confirmed the profile obtained in the exploratory
analysis. The authors are grateful to Fapesp 2012/10680-6, 2014/04251-0 and CNPq
401074/2014-5.
References
[1] G. Derringer and R. Suich, J. Qual. Tech., 12, 214-210 (1980).
206
PS2.32
Adaptive Tunable Laser Spectrometers (ATLAS)
Gregory J. Flesch1, Didier Keymeulen1
1
Jet Propulsion Laboratory and California Institute of Technology
4800 Oak Grove Ave Pasadena, CA 91109 U.S.A.
E-mail: gflesch@jpl.nasa.gov
didier.keymeulen@jpl.nasa.gov
Our Tunable Laser Spectrometer (TLS) is currently operating on Mars as part of the
Sample Analysis on Mars (SAM) instrument suite [1], which in turn is part of the
Mars Science Laboratory (MSL) [2] payload. It has produced several important
science results [3][4][5], but this experience has taught us that highly sensitive
tunable laser spectrometers must be robust and autonomously adaptive in order to
maintain optimal performance in remote, unfamiliar and, in particular, extreme
environments. Spectral drift, optical noise and lower-than-expected signals all call
for an electronics/software platform capable of analyzing its own spectra and then
reconfiguring itself to optimize the data products, especially when highly sensitive
isotopic ratios are part of those measurements.
In the case of MSL, we have been able to modify mission surface operations to
increase the sensitivity of TLS but these workarounds exploited the long term nature
of the MSL mission and would not have been possible for a single event mission
such as Venus probe that must capture and transmit all data on a one-time descent.
We have built and will present such a platform. It has been realized with modern
real-time operating systems (RTOS) and reconfigurable hardware (FPGA) as part of
a NASA funded effort (PIDDP) to improve planetary laser spectrometers for future
missions. We will show architecture and data quality improvements with
comparisons to the Mars TLS instrument.
References
[1] Mahaffy, P. R., Webster, C. R., Cabane, M., Conrad, P. G., Coll, P., Atreya, S. K., ... & Ming, D.
W. The sample analysis at Mars investigation and instrument suite. Space Science Reviews, 170(1-4),
401-478. (2012):
[2] Grotzinger, J. P., Crisp, J., Vasavada, A. R., Anderson, R. C., Baker, C. J., Barry, R., ... & Wiens,
R. C. Mars Science Laboratory mission and science investigation. Space science reviews, 170(1-4), 556. (2012):
[3] Webster, C. R., Mahaffy, P. R., Atreya, S. K., Flesch, G. J., Farley, K. A., Kemppinen, O., ... &
Steele, A. Low upper limit to methane abundance on Mars. Science, 342(6156), 355-357. (2013) [4]
Mahaffy, P. R., Webster, C. R., Stern, J. C., Brunner, A. E., Atreya, S. K., Conrad, P. G., ... & Wray,
J. J. (2015). The imprint of atmospheric evolution in the D/H of Hesperian clay minerals on Mars.
Science, 347(6220), 412-414. (2015):
[5] Webster, C. R., Mahaffy, P. R., Flesch, G. J., Niles, P. B., Jones, J. H., Leshin, L. A., ... & Steele,
A. Isotope ratios of H, C, and O in CO2 and H2O of the martian atmosphere. Science, 341(6143),
260-263. (2013).
207
PS2.58
Combined LIBS and Raman measurements within a single
laser event
V.N. Lednev1, R.N. Yulmetov1, M.Ya. Grishin1, V.V. Bukin1, A.N. Fedorov1,
S.M. Pershin1
1
Prokhorov General Physics Institute of Russian Academy of Sciences, Moscow, Russia
E-mail: lednev@kapella.gpi.ru
A new approach combining Raman spectrometry and Laser induced breakdown
spectrometry (LIBS) was suggested. Nearly the same laser systems and detectors are
used for both techniques (Raman and LIBS) but two measurements needs different
levels of laser power density. The conventional way to combine two methods is to
separately measure Raman and LIBS spectra by adjusting laser pulse energy for
every measurement or to use two different experiment setup (two different lasers
or/and two spectrometers). Consequently, the same location at sample surface can’t
be measured with LIBS and Raman methods in case of moving objects analysis or in
laser remote sensing applications.
A double pulse mode lasing (two laser pulses with microsecond delay) was used to
combine two spectrometry methods within a single laser event. First low-energy
laser pulse (power density far below ablation threshold) was used for Raman
measurements while second powerful laser pulse creates the plasma suitable for
LIBS analysis. The time delay between two pulses was adjusted in 30-60 mks range
that allows measuring LIBS and Raman spectra in different moments but within a
single laser event.
The feasibility of combined Raman and LIBS spectrometry measurements was
demonstrated for solid and liquid samples. A mixture of calcite and aragonite crystals
with different additives was used as a test samples for Raman and LIBS
measurements by the technique suggested. Single wall carbon nanotubes dissolved in
distilled water was used as a sample for qualitative analysis (molecular and
elemental) by combined Raman and LIBS method. The perspectives of combined
Raman and LIBS analysis for laser remote sensing applications are discussed.
208
Poster Session 2: Biological Applications
PS2.33
Optimization and validation of an ET AAS method for the
determination of nickel in postmortem material
D. Dudek-Adamska1, T. Lech2
1
Jagiellonian University, Faculty of Chemistry, Department of Analytical Chemistry,
Ingardena 3, 30-060 Kraków, Poland
2
Institute of Forensic Research, Department of Forensic Toxicology,
Westerplatte 9, 31-033 Kraków, Poland
E-mail: tlech@ies.krakow.pl
Exposure to higher concentrations of nickel (Ni) in the environment may lead to the
occurrence of a number of pathological effects (allergic contact dermatitis is the most
common). Due to this fact and the constant increase in the concentrations of heavy
metals (also Ni) in the environment, it is important to establish the total content of
the given element in biological material (body fluids and tissues) at reference
concentrations that normally occur in non-exposed and non-poisoned people or in
poisonings.
Some methods (ET AAS, ICP OES, ICP-MS) allow to determine Ni at low
concentrations in different biological samples, particularly in urine, blood, serum,
plasma and hair, there are, however, limited data regarding the determination of Ni in
other human tissues.
In this paper, optimization and validation of a procedure for the determination of
total nickel in wet digested samples of human body tissues (internal organs) for
forensic toxicological purposes, are presented. Four experimental setups of the
electrothermal atomic absorption spectrometry (ET AAS) using a Solaar MQZe
(Thermo Electron Co.) were compared, using the following: (i) no modifier, (ii)
magnesium nitrate, (iii) palladium nitrate, (iv) magnesium nitrate and ammonium
dihydrogen phosphate mixture as chemical modifiers. It was ascertained that the
ET AAS without any modifier with 1,300/2,400°C as the pyrolysis and atomization
temperatures, respectively, can be used to determine total nickel at reference levels in
biological materials as well as its levels found in chronic and acute poisonings.
The method developed was validated, obtaining a linear range of calibration from
0.76 to 15.0 µg/L, limit of detection at 0.23 µg/L, limit of quantification at 0.76
µg/L, precision (as relative standard deviation) up to 10%, and accuracy of 97.1% for
the analysis of certified material (SRM 1577c Bovine Liver) and within a range from
99.2 to 109.9% for the recovery of spiked liver samples.
The method can be used to establish the reference levels of Ni in the human body, as
well as the concentrations obtained in chronic poisonings (environmental or
industrial contaminated people) or in acute poisonings with nickel compound.
209
PS2.34
Spectroscopic study of the Ag/CS nanoparticles
biosynthesized from Aspergillus deflectus and Penicillium
pinopholium for biological application
M.E.Osman1, M.M. Eid2, O.H. Khattab1, S. M. El-Hallouty3, S.M. El-Marakby4,
D. A.Mahmoud5
1
Botany and Microbiology Department, Faculty of Science, Helwan University, Cairo, Egypt.
2
3
4
Spectroscopy Department, National Research Centre,12662, Dokki, Giza, Egypt.
Pharmacognosy Department, National Research Centre, 12662, Dokki, Giza, Egypt.
Molecular Biophysics Lab, Radiation Physics Department, National Center for
Radiation, Research
and Technology (NCRRT), Atomic Energy Authority (AEA)
5
Microbiology Department, National Organization for Drug Control and Research, Cairo, Egypt.
E-mail: maybaker25@gmail.com
Twenty seven Egyptian soil samples has been screened for fungal species. Among
all isolates, two species was selected for the bio-synthesis of Silver/Chitosan
nanoparticles (Ag/CS NP). The aim of this paper was to characterize the physical
and morphological properties of Ag/CS NP, after optimizing the pH and salt
concentration of the preparation, additionally, the effect of exposure to gamma
radiation was considered. The surface plasmon resonance (SPR) of Ag/CS NP was
analyzed by UV-visible spectroscopy at wavelengths ranging from 200-800 nm.
Characterization of the active group responsible for the reduction and capping of
AgNP was carried out by Fourier transform infrared (FTIR, 1cm-1 resolution), their
shape and size were determined via the High Resolution Transmission Electron
microscope (HRTEM) and the Dynamic Light Scattering Technique (DLS). The
antimicrobial activity of Ag/CSNPs in combination with commercial antibiotic was
assessed on different bacterial and fungal species.
210
PS2.35
Development of a magnetic nanofluid by incorporating
SPIONs in Amazonian oils
A.S. Gaspar1,6, F.E. Wagner2, V.S. Amaral3, S. Lima4, J.G. Santos5,
B.F.O. Costa1, L. Durães6
1
CFisUC, Physics Department, University of Coimbra, 3004-5126 Coimbra, Portugal
2
Physics Department, Technical University of Munich, 85747 Garching, Germany
3
Physics Department and CICECO, University of Aveiro, 3810-193 Aveiro, Portugal
4
UCIBIO-REQUIMTE, Department of Chemistry, Faculty of Pharmacy, University of Porto, 4050313 Porto, Portugal
5
Federal University of Rondônia-UNIR, Faculty of Medicine, Laboratory of Nanomaterials and
Nanobiomagnetism, CEP 76900-000 Amazonia, Brazil
6
CIEPQPF, Chemical Engineering Department, University of Coimbra, Polo II, 3030-790 Coimbra,
Portugal
E-mail: benilde@fis.uc.pt
Currently, the demand for higher quality magnetic nanoparticles for use as a
magnetic nanoprobe to assist in medical imaging techniques and cancer therapy by
hyperthermia has been high [1]. Moreover, recent results [2] regarding the
phytochemistry benefits that some Amazonian essential oils exhibit have sparkled
great interest in developing methods to use these oils in various medical treatments.
The main objective of this work is to develop a biodegradable magnetic nanofluid
which allies the superparamagnetism versatility of iron oxide nanoparticles (SPIONs)
with the benefits associated with Copaiba and Andiroba’s oils.
In order to improve the capabilities of this biodegradable magnetic nanofluid, a
thermolysis method for SPIONs synthesis [3, 4] was studied and certain paths were
tested in order to improve the magnetic properties of the product. Also, in vitro
cytotoxicity studies were conducted on the SPIONs, and the ability and effects of
incorporating the SPIONs in Amazonian essential oils were assessed.
Particle size of SPIONs was around 6 nm. Mössbauer and XRD analyses indicate
maghemite as their main iron oxide phase. Also, small amount of magnetite was
present in some samples. VSM results showed a magnetization saturation of 57
emu/g, at 7 K, and 42 emu/g, at 300 K. After incorporating SPIONs in Copaiba and
Andiroba essential oils these values dropped, which indicates that a blocking effect
occurs with these Amazonian oils.
All the obtained results from the characterization data performed on the various
samples seem promising towards having a biodegradable magnetic nanoprobe of
SPIONs incorporated in Amazonian essential oils.
References
[1] Lodhia, J., Mandarano, G., Ferris, N.J., Eu, P. and Cowell, S.F., Biomedical imaging and
intervention journal, 6(2): p. e12 (2010)
[2] Pieri, F. A., MUSSI, M., and Moreira, M. A. S., Rev. Bras. Plant. Med, 11, p. 465-472 (2009)
[3] Xu, Z., Shen, C., Hou, Y., Gao, H. and Sun, S., Chemistry of Materials, 21(9), p. 1778-1780
(2009)
[4]Sun, S., Zheng, H., Robinson, D.B., Raoux, S., Rice, P.M., Wang, S.X. & Li, G., Journal of the
American Chemical Society, 126(1), p. 273-279 (2004)
211
PS2.36
The Usage of Nano-Ag Immobilized on Luffa sponge for Remove
Direct Blue 15 Dye from Water
Semra CICEK1,2 & Hayrunnisa NADAROĞLU 1,3
1
Ataturk University, Faculty of Engineering, Department of Nano-Scienceand NanoEngineering, 25240 Erzurum, TURKEY
2
3
This study contains the use of silver (Ag) nanoparticle immobilized on Luffa
sponge (LS) for removal of Direct Blue 15 dye which is harmful to human and
ecosystem from the water. The Luffa sponge (LS) material has some features such as
natural, effective efficiency, light weight, environmental friendly [1,2]. Ag
nanoparticles were obtained catalyzing using purified peroxidase enzymes from
Euphorbia amygdaloides with green synthesis method Pre-processing LS with Ag
NPS was immobilized. The immobilization was carried out by vigorous stirring in
magnetic shaker for 1 hour. Then, filtered nanoparticle immobilized LS samples
(pure-LS, nano-Ag-LS) dried for 2 hour in an oven. Optimum contact time, pH,
temperature, concentration of dye were anylzed using using UV-visible
spectrometry. The resulting membrane forms (native-LS, Ag NPs-LS) were
characterized by SEM and XRD. Native-LS was used as a blank sample in all
analyzes.
It was obtained from obtained results that nanoparticles which were obtained
with green synthesis can be used in remediation of azo dyes
Literature:
[1] Kaushik, P.; Malik, A., Fungal dye decolourization: recent advances and future
potential. Environment International, 2009; Vol. 35, pp 127–141.
[2] Oboh, I.O.; Aluyor, E.O.; Audu, T.O.K., Application of Luffa cylindrica in
natural form as biosorbent to removal of divalent metals from aqueous solutionskinetic and equilibrium study, In: Waste Water Treatment and Reutilization,
Einschlag,F.S.G., Eds. InTech, 2011; pp 195–212.
.
212
PS2.37
Synthesis of Platinum Nanoparticles With Green Synthesis
and Investigation of Its Some Properties
Aynur BABAGIL1, Selvi INCE1, Hayrunnisa NADAROĞLU1,2, Azize ALAYLI
GÜNGOR1,2
1
Ataturk University, Faculty of Engineering, Department of Nano-Science and Nano-Engineering,
25240 Erzurum, TURKEY
2
Ataturk University, Erzurum Vocational Training School, Department of Food Technology, 25240
Erzurum, TURKEY
3
Ataturk University, Erzurum Vocational Training School, Department of Chemical Technology,
25240 Erzurum, TURKEY
Nanotechnology is widely used in all areas nowadays. For this reason, nano synthesis
is also an important in all area of researches. According to results of performed
studies, it is determined that nanoparticle synthesis is performed by methods boht
chemical and physical meyhods. It is well known that this syntheses are done at high
cost, high pressure and temperature in harsh conditions. Therefore, when we search
for syhthesis method that we find green synthesis in more mild conditions [1].
Vitamins, proteins, plant or extracts are used as a reducing agent in green synthesis
reactions. Used another natural product for green synthesis is chicken eggs. Egg yolk
has high protein content and another advantage of its is ability to form a moderate
reaction medium mixing with water [2].
Nowadays it has been reported that platinum nanoparticles are used as catalysts in
various chemical reactions such as redox and hydrogenation reactions. Also, catalytic
activity of platinum nanoparticles has played key roles in the development of fuel
cells. [3]. Another application area of nanoplatinum is in the preparation of organic
dyes. Another important usage of platinum nanoparticles are in biomedical
applications by coating non-metallic surfaces or forming alloy with other metals [4].
In this research, quail egg yolk which has high protein and vitamin content was
selected as green synthesis reaction medium and reaction medium was used for
synthesis of platinum nanoparticles. Reaction conditions were optimized for pH,
temperature and concentration using quail egg yolk. The morphology and properties
of obtained platinum nanoparticules were characterized using SEM, XRD and
spectrophotometric methods.
Literature:
[1] Li, S.; Shen, Y.; Xie, A, Green synthesis of silver nanoparticles using Capsicum annuum L.
extracts. Green Chem. 2007, 9, 852-858.
[2] Gabal, M.A.; Mater Lett., Structural and magnetic properties of nano-sized Cu–Cr ferrites
prepared through a simple method using egg white. 2010, 64, 17, 1887-1890.
[3] Bratlie K. M., Lee H., Komvopoulos, K. Yang P., and Somorjai G. A., Platinum nanoparticle
shape effects on benzene hydrogenation selectivity. Nano Lett., 2007, 7(10), 3097-3101.
[4] Goor-Dar, M.; Travitsky N.; Peled E. Study of hydrogen redox reactions on platinum
nanoparticles in concentrated HBr solutions. J. Power Sources., 2012, 97, 111-115.
213
PS2.38
A transient absorption study of the S1 state vibrational
relaxation of open-chain carotenoids
V. Kuznetsova1, M. Fuciman1 and T. Polívka1
1
Faculty of Science, University of South Bohemia, Branišovská 31, České Budějovice 370 05,
Czech Republic
E-mail: tinakouznets@gmail.com
Carotenoids are widespread natural pigments that can be synthesized by
microorganisms and plants. They play an important role in photosynthetic systems,
carotenoids absorb the light in the blue-green region of the spectrum and then
transfer captured light rapidly and efficiently to chlorophyll [1]. Traditionally, the
excited states of carotenoids are described by a three-level model [2]. The strong
absorption in the visible region is assigned to the optically allowed S0 (1Ag-) - S2
(1Bu+) transition, however, the transition from the ground state S0 (1Ag-) to the S1
(2Ag-) state is forbidden by symmetry in the C 2h point group. Upon the excitation
from the ground state to the S2 state, a fast (~200 fs) internal conversion to the singlet
excited state S1 occurs. The energy transfer from the carotenoid to chlorophyll in the
light-harvesting complexes partially proceeds via ultrafast S 2 state, however, the
major pathway involves single excited S1 state. The vibrational levels of S1 state may
be involved in the energy transfer process with equal efficiency [3], which makes
this subject interesting for study. The exact values of these lifetimes and dynamics of
non-radiative internal conversion depend upon conjugated carbon chain length of the
carotenoid [4]. In this work, we present study of two open-chain carotenoids,
neurosporene and spheroidene, having 9 and 10 conjugated π-electron carbon-carbon
double bonds, respectively. The dependence of the vibrational relaxation of the S 1
state on the excitation wavelength has been studied by femtosecond pump-probe
spectroscopy. The excitation wavelengths have been chosen to excite the vibrational
levels (ν = 0, 1 and 2) of the S2 state.
References
[1] Frank H. A. and Cogdell R. J. Carotenoids in photosynthesis. Photochem. Photobiol. 63, 257-264
(1996).
[2] Polívka T., Sundström V. Ultrafast dynamics of carotenoid excited states. From solution to natural
and artificial systems. Chem. Rev. 104, 2021-207 (2004).
[3] Polli D., Cerullo G., Lanzani G., De Silvestri S., Hashimoto H., and Cogdell R. J. CarotenoidBacteriochlorophyll Energy Transfer in LH2 Complexes Studied with 10-fs Time Resolution.
Biophysical Journal 90 (7), 2486–2497 (2006).
[4] Chatterjee N., Niedzwiezki D. M., Kajikawa T., Hasegawa S., Katsumura S., Frank H. A. Effect of
π-electron conjugation length on the solvent-dependent S1 lifetime of peridinin. Chem. Phys. Letters
463, 219-224 (2008).
214
PS2.39
Effect of Cu stress on the allocation of carbohydrates in the
Cu-hyperaccumulator lichen Stereocaulon japonicum
H. Nakajima, N. Fujimoto, T. Amemiya and K. Itoh
79-7 Tokiwadai, Hodogayaku, 240-8501 Yokohama, Japan,
Graduate School of Environment and Information Sciences, Yokohama National University
E-mail: h-nakaji@ynu.ac.jp
Stereocaulon species are Cu-hyperaccumulator lichens, and can be used to monitor
and assess Cu pollution. In a previous study [1], the concentrations of Cu,
chlorophylls, and secondary metabolites in Stereocaulon japonicum were measured,
and negative effects of Cu were observed on these concentrations and chlorophyllrelated indices. For highly Cu-polluted samples (> 100 ppm dry weight), however,
significant linear correlations between Cu and chlorophyll concentrations were
found. In highly Cu-polluted samples the chlorophyll-related indices and
concentration of total secondary metabolites were almost constant regardless of Cu
concentration. These results suggest that the fungal and the algal partners interact
with each other and, moreover, that the algal partners balance the allocation of
carbohydrates in the lichen to adapt to Cu stress.
In this study, to clarified the effect of Cu stress on the allocation of carbohydrates in
S. japonicum, we measured the concentrations of Cu by ICP-MS spectroscopy,
chlorophylls by UV-vis spectroscopy, secondary metabolites by HPLC with a
photodiode-array detector, and sugar alcohols, produced by the algal partner and
stored by the fungal partner, respectively, by HPLC with an electrochemical detector
in Cu-polluted and control samples of the lichen. Considering the relationships
between these concentrations, we will provide a better understanding of the effect of
Cu stress on the lichen.
References
[1] Nakajima et al., Ecotoxicol. Env. Safety, 113, 477-482 (2015).
215
PS2.40
Study on distribution of the Fe, Cu and Cu/Zn in prostate
cell spheroids supplemented with Zn
R.G. Leitão1, C.A.N. Santos2, A. Palumbo Jr.3, P.V.R. Souza4, C.G.L. Canellas5,
M.J. Anjos1,5, L.E. Nasciutti3, R.T. Lopes1
1
Nuclear Instrumentation Laboratory, Federal University of Rio de Janeiro, 21941-942, Rio de
Janeiro, RJ, Brazil.
2
Biotechnology Laboratory – Bioengineering – DIPRO, National Institute of Metrology,
Standardiza-tion and Technology, Xerém., Duque de Caxias, RJ, Brazil
3
Department of Histology and Embryology, Federal University of Rio de Janeiro, RJ, Brazil
4
Department of Urology, Andarai General Hospital, 20541170, Rio de Janeiro, RJ, Brasil
5
Physics Institute, Stated University of Rio de Janeiro, RJ, Brazil
E-mail: roberta@lin.ufrj.br.
Micro X-Ray Fluorescence (µXRF) is a non-destructive technique very frequently
used in biological investigations to obtain information regarding the elemental
distribution in tissue and cell samples. Diseases of the prostate gland such as Prostate
Cancer (PCa) and Benign Prostate Hyperplasia (BPH) are the most frequent health
problems in men after middle age. In this context, the aim of this work was to
investigate the distribution of Fe and Cu using synchrotron X-ray microfluorescence
(SRXRF) in cell spheroids in benign prostate hyperplasia (BPH) and prostate cancer
(DU145) supplemented with Zinc and to analyze the influence on intensity of Fe, Cu
and Cu/Zn after Zinc supplementation. The SRµXRF measurements were performed
at the XRF beam line at the Synchrotron Light National Laboratory (Campinas,
Brazil). The results showed non-uniform distribution of Fe and Cu in all the
spheroids analyzed. It was possible observed that intensity of Fe, Cu and Cu/Zn were
changed with the Zn supplementation. Therefore, the Zn supplementation changes
the metabolic of prostate cell.
216
PS2.41*
Analysis of Zn distribution in human prostate cancer cell
using synchrotron X-ray microfluorescence mapping
R.G. Leitão1, K.M.J. Rocha1, E.G.Oliveira-Barros2, M.A. Oliveira2, C.G.L.
Canellas3, M.J. Anjos1,3, L.E. Nasciutti2, R.T. Lopes1
1
Nuclear Instrumentation Laboratory, Federal University of Rio de Janeiro, 21941-942, Rio de
Janeiro, RJ, Brazil.
2
Institute of Biomedical Sciences, Federal University of Rio de Janeiro, RJ, Brazil
3
Physics Institute, Stated University of Rio de Janeiro, RJ, Brazil
E-mail: roberta@lin.ufrj.br.
Prostate cancer is the most frequently diagnosed form of noncutaneous cancer in
men. Prostatic epithelial cells have a unique capability of accumulating high levels of
zinc and previous studies indicate that zinc may have a protective effect by inhibiting
prostate tumor cell growth and inducing apoptosis. Recent studies identified ZIP1
(SLC39A1) as responsible for the rapid uptake and accumulation of physiologically
effective zinc in prostate cells. The distribution and local chemical environment of
metals and non-metals in tissues and cells is the most fundamental knowledge of any
kind of organism. Synchrotron-based X-ray microfluorescence (SRµXRF) is a
powerful technique for the mapping of elemental distributions at a subcellular level.
This study investigated Zn distribution in prostate cancer (DU145 and PC3) cell
spheroids and analyzed the different response to Zinc supplementation by 24 h and
48 h using synchrotron X-ray microfluorescence (µSRXRF). We evaluated in this
study the cell growth, cell death and the expression of ZIP1. The SRµXRF
measurements were performed at the XRF beam line at the Synchrotron Light
National Laboratory (Campinas, Brazil). The results by SRµXRF showed nonuniform Zn distribution in all the spheroids analyzed. It was possible observed that
Zn intensity were changed with the Zn supplementation. These results suggest that
Zinc affecting cell growth and cell death. Therefore, the Zn supplementation changes
the metabolic of prostate cancer cell.
* Poster not presented
217
PS2.42
Sy-XRF and RAMAN Spectroscopy for investigating tattoo
inks
A. Guilherme1, M. Manso2, M. L. Carvalho2M. Radtke1, U. Reinholz1, S.
Pessanha2
1
BAM Federal Institute for Materials Research and Testing, Richard-Willstaetter-Str. 11, 12489
Berlin, Germany
2
departamento de Física, Faculdade de Ciências e Tecnologias, Universidade Nova de Lisboa,
2829-516 Monte da Caparica, Portugal.
E-mail: ana.buzanich@bam.de
Tattooing practice is adopted worldwide and represents a socio-cultural phenomenon, but the
injection into the skin of coloring (inorganic) agents, such as metals might pose a serious
health problem. Nowadays, azo pigments are frequently used for tattooing because of their
intensity color and their longevity [1]. The origin of chemical and toxicological
specifications of these coloring agents are hardly known by the producers, the performers, or
even by the professionals involved in these procedures and certainly not by the consumers
[2].
A set of tattoo inks from the brand Kuro Sumi was analyzed by means of Synchrotron-based
X-ray Fluorescence spectrometry (Sy-XRF) at BAMline @ BESSY II and Raman
Spectroscopy using the XploRA confocal Raman microscope (785 nm laser). The color
black has revealed to be carbon black in the Raman spectrum (figure 1a). However, a wide
range of transition and heavy metals, potentially hazardous was revealed by Sy-XRF (figure
1b). A semi-quantitative evaluation has revealed, in some cases, amounts higher than the
allowed according to the resolution adopted by the Council of Europe on the safety of tattoos
and permanent make-up (PMU) [3].
Figure 1 - Color black: a) Raman spectrum identifying carbon black; b) Sy-XRF spectrum identifying
various metals.
References
[1]
[2]
[3]
Engel, E., Tattoo Pigments in Sin: Determination and Quantitative Extraction of Red Tattoo
Pigments, in Fakultät für Chemie und Pharmazie, 2007, Universität Regensburg.
Cuyper, C.d., Materials Used in Body Art, in Dermatologic Complications with Body Art Tattoos, Piercing and Permament Make-Up, M.L.P.-C.S.e. C. de Cuyper, Editor 2010,
Springer-Verlag Berlin Heidelberg.
Europe, C.o., Resolution ResAP(2008)1 on requirements and criteria for the safety of tattoos
and permanent make-up (superseding Resolution ResAP(2003)2 on tattoos and permanent
make-up) C.o.E.C.o.E.o.C. Products, Editor 2008.
.
218
PS2.43
Study of mineral composition of hair related to the use of
aesthetic chemical treatments
Gabrielly Peregrino1,2, Isabelle C. Silva1, Julia N. P. Nogueira1, Raiza Rezende1,
Gabrielle S. Ribeiro3, Maria Eduarda S. Amaral3, Pedro A. Vasconcelos3,
Daniela Soluri1, Adriana H. Nudi1, Tatiana D. Saint’Pierre1
1 Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Rio de Janeiro, RJ, Brazil.
2 Instituto Federal de Educação, Ciência e Tecnol. do Rio de Janeiro (IFRJ), São Gonçalo, RJ, Brazil.
3 Centro Integrado de Educação Pública Ayrton Senna da Silva (CIEP), Rio de Janeiro, RJ, Brazil.
E-mail: tatispierre@puc-rio.br
The hair mineralogram is a multielemental analysis, which provides information on
health issues, diet, medicines and supplements ingested and indicates exposure to
pollutants, as well as allows establishing individual levels of stress and oxidation
rates [1]. Although this is a world widespread test, there is no consensus about the
values considered normal in literature [1-4]. The use of aesthetic treatments for hair,
as dyes or straightening, represents exposure to substances that can be harmful to
health, such as toxic elements, both for users and for the professionals who apply
them, and also, make difficult the interpretation of the mineralogram data.
The objective of this work was to establish correlations between aesthetic treatments
and the mineral composition of the hair, for people of different ages and genders.
Samples were collected from 127 volunteers that answer a questionnaire. For that, an
amount of 1 g of hair was washed with acetone and decomposed with nitric acid,
under heating. The mineral content was determined by inductively coupled plasma
mass spectrometry (ICP-MS) and the results evaluated through the free cost
statistical program “R”. The analyzed elements were classified as toxic or essential,
according to orthomolecular medicine [2], which established limits of concentration.
The concentrations of seven toxic elements (Ag, Al, Bi, Ni, Sn, Th, U) were higher
than the maximum limits considered normal [3]. Ag exceed 0.4 mg g-1 in only 13,6%
of the samples, while Al and Bi exceeded 0.4 and 0.35 mg g-1, respectively, in more
than 38% of samples. These data should be better investigated, since, can be
indicative of health problems. For example, Al, found in deodorants, foil and pans,
may affect bone calcification and neurological functions [4]. On the other hand,
higher Ca concentrations, that mean this element is being excreted by hair, were, in
general, found in older women hair. It was interesting to observe that hair dye
increased only the concentration rates of Fe; while straightening seems to increase S.
References
[1] Ashraf. W, Jaffar M, Anwer K, Ehsan U. Environmental Pollution, 87, 61-64 (1995).
[2] Afridi, H.I.; Kazi, T.G.; Brabazon, D. Naher, S. Sci. Total Environm, 412-413, 93–100 (2011).
[3] Miekeley N., Carneiro, M.T.W., Silveira, C.L., Sci. Total Environm, 218, 9-17 (1998).
[4] Wilson, L. http://www.drlwilson.com/articles/HA%20INTRO.htm. Accessed in May, 2015.
219
Poster Session 2: Food Analysis
PS2.44
Iodine determination in cat food by ICP-MS, after alkaline
extraction.
Ana Carolina M. Ferreira, Roberto V. G. Fiuza, Flávia G. Wandekoken, Rafael
C. C. Rocha, Tatiana D. Saint’Pierre
Pontifical Catholic University of Rio de Janeiro (PUC-Rio)
E-mail: tatispierre@puc-rio.br
Iodine is an essential element in the composition of thyroid hormones and influences
the thyroid growth function by auto-regulatory mechanisms. Iodine’s deficiency can
cause malfunctions, such as, hypothyroidism, goiter, increase of perinatal mortality
and development of anomalies. However, excessive consumption can lead to
increased autoimmune thyroid diseases and hyperthyroidism [1]. The Association of
American Feed Control Officials (AAFCO) recommends a minimum of 1.8 and a
maximum of 9.0 mg I/kg of dry food, for cats [2].
Recently, inductively coupled plasma mass spectrometry (ICP-MS) has proven to be
useful to determine iodine in biological fluids and milk [3]. However, the sample
decomposition in acid medium is not recommended because iodine is reduced to I 2
and HI, volatile compounds. Therefore, an alkaline extraction was used alternatively.
In this study, 15 dry cat food samples of different flavors obtained in local pet shops
were analyzed. The samples were ground in a domestic food processor and 1 g was
submitted to an alkaline extraction (in triplicate). The samples were added with 12
mL of a 500 mmol NH3(aq) solution, kept under heating at 90 °C for 3 h and then,
diluted with water to 20.0 mL, centrifuged and filtered. The determined average
water amount was 9.3%. The limit of quantification (LOQ), calculate as 10 times the
standard deviation of 10 measurements of the concentration in the blank solution,
and considering the sample dilution factor, was 14 µg kg-1.
The absence of interferences was verified by comparing the external calibration with
analyte addition curve for one cat food sample. The ICP-MS results were evaluated
by recovery tests, by adding 1 mg kg-1 of I, before the extraction, to the same cat
food sample and to two certified reference materials (NIST 1549 - whole milk
powder and NIST 1577 - bovine liver). Recoveries were between 90% and 105%.
For most analyzed samples, the measured concentrations were slightly higher than
the values informed by the manufacturer, between approximately 1 and 7 mg I/kg of
food.
References
[1] M. Anke, B. Groppel, M. Müller, E. Scholz, K. Krämer, Fresenius J. Anal. Chem., 352, 97101(1995).
[2] AAFCO methods for substantiating nutritional adequacy of dog and cat foods.
http://www.aafco.org/Portals/0/SiteContent/Regulatory/Committees/Pet-Food/Reports/Pet_Food_
Report_2013_Midyear-Proposed_Revisions_to_AAFCO_Nutrient_Profiles.pdf
[3] Y. Gélinas, G. V. Iyengar, R. M. Barnes, Fresenius J. Anal. Chem., 362, 483-488 (1998).
220
PS2.45
Arsenic in rice: variation of arsenic concentration regarding
rice varieties cultivated in the south of Brazil
Fabiana R. Segura, Fabio F. da Silva 2, Tatiana P.1, Ariano M.M. Junior3, Julio
C. Silva3, Daniel F.Franco3, Alexandre L.Souza4, Fernando B. Júnior5, Ana
C.C.Paulelli5, Airton M. Junio5, Heloisa F.Maltez1, Bruno L.Batista1
1
Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Postal Code: 09210-580,
Santo André, SP, Brazil
2
3
4
Agilent Technologies, Postal Code: 06460-040, Barueri, SP, Brazil
Estação Experimental Terras Baixas, Empresa Brasileira de Pesquisa Agropecuária Clima
Temperado, Postal Code: 96010-971 Pelotas, RS, Brazil
Faculdade de Saúde Pública, Universidade de São Paulo, Postal Code: 01246-904, São Paulo, SP,
Brazil
5Faculdade
de Ciências Farmacêuticas de Ribeirão Preto,
Universidade de São Paulo, Postal Code: 14040-903, Ribeirão Preto, SP, Brasil
E-mail: fabiana.segura@ufabc.edu.br
Rice (Oryza Sativa L.) is the third most cultivated grain worldwide. Brazilians has a
substantial annual consumption around 74 – 76 kg per habitant and the South of Brazil is
responsible for 80% of the country’s rice production. In spite of being an extremely
important component of Brazilian’s diet because of its nutritional benefits, arsenic
uptake is improved due rice’s physiology and cultivation commonly made in flooded
soils. Arsenic concentration in the grain varies depending on the cultivar and
localization, also in rice this element can be found in different species: organic arsenic
(O-As) and inorganic arsenic (I-As), and both are known for being harmful to human
health. The present work aimed to study the variation of total arsenic according to
cultivars of brown rice produced in Rio Grande do Sul State (Brazil). Samples of
different rice cultivars (IRGA 424, Puitá) were obtained from EMBRAPA (Brazilian
Enterprise of Agricultural Research). The determination of totals and species of arsenic
were carried out using ICP-MS and HPLC-ICP-MS. Samples from different rice crops
from Pelotas of the cultivar “IRGA 424” (n=4) have shown the following data: Highest
concentration of total arsenic: 350.7±26.7 ppb; lowest concentration of total arsenic:
210.6±40.8 ppb. It shows that total arsenic levels depend on the soil where rice is
cultivated. However, total-As does not provide complete information for risk
assessment. In some cases high total arsenic concentrations may be associated with high
levels of O-As that are less harmful. Further speciation is essential to determinate I-As,
which may result on risks management on a reasonable way, providing the possibility of
adoption of suitable forms of remediation, e.g., bioremediation or intermittent
cultivation. Speciation of the samples was carried out using HPLC-ICP-MS have shown
following results: O-As 35%; I-As 65% (IRGA 424, Pelotas).
References
[1] B. L. Batista, M. Nigar, A. Mestrot, B. A. Rocha, F. B. Junior, A. H. Price, A. Raab and J.
Feldmann. Journal of Experimental Botany. 65, 1467-1479 (2014).
[2] P . N . Williams, A . H . Price , A . Raab , S . A . Hossain , J . Feldmann, A . A . M eharg. Environ.
Sci. Technol. 39, 5531-5540 (2005).
221
PS2.46
Analyze of Aflatoxins in Animal Feed
Y. Bakircioglu Kurtulus, D. Bakircioglu, M. Kuscu, N. Topraksever
Department of Chemistry, Faculty of Science, Trakya University, Edirne, Turkey
E-mail: ybakircioglu@trakya.edu.tr
Aflatoxins, direct with foods or indirectly can be pass to live site by people
consumed of the pet food product containing aflatoxin. [1]. The effects of aflatoxins
in animals (monkeys, trout, rats etc.) depending on exposure dose, duration, type,
grade, dietary or nutritional status, general health status. It can cause health problems
like damage to the liver, cancer, and decrease in milk production, immune
suppression, and anemia. [2].
In this study, different mixtures of methanol (% 60/40, % 70/30, % 80/20) used for
the quantitative determination of aflatoxins in animal feed. Certified reference
material (ERM-BE 376 animal feed) and spiked samples (different concentrations of
total aflatoxin at animal feed: 1.3-2.6-5.2-10.4-15.6 µg/kg) are used for method
validation. At optimum conditions for HPLC (λex = 360 nm, λem = 430 nm, flow
rate: 1.0 mL/min, column temperature: 25 0C, injection volume: 100 µL, C18
column, mobil phase: water/methanol/acetonitrile (56/26/18) with 120 mg KBr and
350 µL 4M HNO3) samples were analyzed. Recoveries of aflatoxin B1, B2, G1 and
G2 were stable when samples were extracted with %70/30 methanol/water mixture.
Aflatoxin B1 were detected with 10- 20 µg/kg at five sample and 122.51 20 µg/kg at
one sample. At twenty nine of eighty sample aflatoxin B1 not detected. Mean
aflatoxin B1 concentration of samples is 4.78 µg/kg. Only one sample (122.51
µg/kg) exceeded the legal limit of 20 µg/kg aflatoxin B1.
References
[1] Y.H. Leong, N. Ismail, A.A. Latif, R. Ahmad, Food Control, 21, 334–338, (2010).
[2] W.F. Jaynes, R.E. Zartman, W.H. Hudnall, Applied Clay Science, 36, 197–205, (2007).
222
PS2.47
Elements concentration in hop cones and several species of
beer determined by TXRF method
M. Sołtysiak1, U. Majewska1,2, I. Sychowska1, D. Banaś1,2,
A. Kubala-Kukuś1,2, I. Stabrawa1, J. Wudarczyk-Moćko2, J. Braziewicz1,2, M.
Pajek1 and S. Góźdź2,3
1
2
3
Institute of Public Health, Jan Kochanowski University, IX Wieków Kielc 19, 25-317 Kielce, Poland
E-mail: urszula.majewska@ujk.edu.pl
Beer is the one of the oldest and the most popular drink. Its key substances are alcohol,
carbon dioxide, malt and hops. It is obtained by enzymatic hydrolysis of proteins and
starch derived from grains, and the product is subjected to alcoholic fermentation.
It is well known that elements from drinks and food penetrate into the human fluids and
tissues and their content might affect health effects of human organism. Due to this fact
and the large and common consumption of beer the knowledge about concentration of
element contained in beer is relevant. Moreover, element in beer can also influence on
the brewing process and the quality of beer [1].
Therefore, the aim of presented study was to determine the concentration of P, S, Cl, K,
Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr and Pb elements in the hop cones and various
species of beer. To this analysis the total reflection X-ray fluorescence method (TXRF)
was used. This technique, very well suited for liquid samples, allows rapid elemental
analysis in wide range of measured atomic number and element concentration during one
measurement. The main advantage of this method is also a limit of detection being on
The spectrometer S2 Picofox (Bruker Nano GmbH) was employed in this study. The
spectrometer operates with 30 W Mo anode X-ray tube at 50 kV, with an electron
current of 0.6 mA.
In this paper the beer production process is described shortly, the preparation procedure
of analyzed samples and finally, the values of element concentration in hop cones and
beer are presented. The relationship between the concentration of certain elements in
different types of beer and hop cones is also described.
References
[1] M. M. Moll, Food science and technology, in: W. A. Hardwick (Ed.), Handbook of Brewing, vol.
64, Marcel Dekker, New York, 133-156 (1995).
223
PS2.48
Analytical methodology for the determination of the low
concentration of five pyrethroid pesticides in hard clams
M. Goto, T. Kaneko, Y. Manaka, H. Nakajima, M. Abe, R. Takanashi
and T. Furuhata
Department of Health and Nutrition, Wayo Women's University
Konodai 2-3-1, Ichikawa, Chiba 272-8533, Japan
E-mail: gotoh@wayo.ac.jp
Background: Although previous articles have described the polluted clams or oysters
by organic chemicals [1], there have been no reports of the pesticide pollution in
marine biota. This paper discusses methodological possibility for the detection of the low
concentration of five pyrethroid pesticides such as biphenthrin, permethrin,
cypermethrin, fenvalerate and dertamethrin in hard clams to clarify the influence on
fisheries food by the environmental pollution of the pyrethroid pesticides.
Materials and methods: Each pyrethroid pesticides was injected into clams at the
concentration of 0.1, 0.5 and 1.0 ppm, respectively. Fresh hard clams of 10 g wet body
were analyzed using an accelerated solvent extractor (ASE-150, Dionex corp., oven
temp.: 100 ℃, extract pressure: 1500 psi, increase time of cell: 5 min, keep time: 5
min, flash volume: 50 %, extract solvent: 33mL of acetonitrile). A gel permeation
chromatography was performed with a fraction collector (GPC column, Shodex
corp., pump: L-2130 Hitachi, column oven: CTO-6A, SHIMADZU, solvent:
acetone: cyclohexane=1:4, flow speed: 5mL/min, column temp.: 40 ℃, injection
volume: 5 mL, fraction collector: SF-160 ADVANTEC corp., collected fraction
volume: 30-100 mL). PSA mini column connected with GC/NH2 mini column
(SPELCO corp., solvent: acetone: n-hexane=1:1, solvent volume: 20 mL) was used
for clean up treatment. GC-MS was performed with GCMS-QP2010, SHIMADZU
[GC: injection temp.: 250 ℃, using column of J&W corp. DB-5MS (0.25 mm φ × 30
m × 0.25 μm) at column oven temp.: 50 ℃ (1 min) → 25 ℃/min → 125 ℃ →
10 ℃/min → 300 ℃ (10 min). MS: interface temp.: 300 ℃, ion source temp.: 200 ℃,
SCAN (interval: 0.2 sec, scan range: m/z 35-500), SIM (interval: 0.2 sec), flow
control: split-less, carrier gas:He 1.3 mL/min , injection volume: 1.0 μL].
Results: The standard curves of five pyrethroid pesticides were all linear within the
tested range, and the detectable concentration of each pesticide was 0.05 ppm. The
recovery ratios of biphenthrin, permethrin, cypermethrin, fenvalerate and
dertamethrin were 67, 86, 76, 82 and 79 %, respectively. No interfering substance
was found in GC-MS.
Conclusion: The developed method was suitable for the analysis of pyrethroid
pesticides at low concentrations in hard clams.
Reference
[1] M. Goto, T. Hobara, H. Kobayashi and M. Okuda, Bull Environ Contam Toxicol, 60, 74-80
(1998).
224
PS2.49
Investigation of iron fortification of fermented cassava
roots, using an inductively coupled plasma optical emission
spectrometer, to improve food safety and the wellbeing of
vulnerable communities in Mozambique
C.M.E. McCrindle1, E.M. Salvatore1 and R.I. McCrindle2
1
School of Health Systems and Public Health, Faculty of Health Sciences, University of Pretoria,
South Africa
2
Department of Chemistry, Tshwane University of technology, P/B X680, Pretoria, South Africa
E-mail: cheryl.mccrindle@gmail.com
Cassava is the staple food of 70% of the population of Mozambique, but cyanogenic
glycosides compromise food safety. Fermenting powdered, cooked roots (mahewu)
decreases toxicity and increases nutrient density; fortification with iron could address
the chronic anaemia present in 40% of the rural population. This study investigated
the concentration of iron in different types of cassava; then compared the
bioavailability of ferrous sulfate and ferrous fumarate, for fortification of mahewu.
Iron concentrations in soils and cassava were analysed using an inductively coupled
plasma optical emission spectrometer, after microwave digestion. The concentration
of iron in soils varied in different parts of Mozambique, but was not correlated with
that of cassava roots grown in those soils. The concentration of iron in cassava roots
was in all cases below the detection limit of the instrument. After fermentation and
fortification, both salts yielded bioavailable iron, whether they were introduced
before or after fermentation for 24 hours. The sulfate was found to be more
bioavailable in bitter varieties while the fumarate was more bioavailable in sweet
varieties. In Mozambique, bitter varieties predominate, as they are drought and pest
resistant. It is probable, that the exceptionally low levels of iron found in all varieties
of cassava, could be a dietary cause of the anaemia seen in young children and
nursing mothers. Fortification of cassava mahewu with iron sulfate, may therefore
play a significant role in reducing iron deficiency anemia in vulnerable rural
populations. It is recommended that the standardized method developed for mahewu
fermentation is adopted at household, as well as commercial level. Fortification at
commercial level could be through flour. At household level, fortification could
occur after fermentation, when sugar is generally added as well, if a nutritional
supplement containing iron sulfate was made available to preschools and clinics in
rural areas.
225
PS2.50
Multi-Element Analysis of Relevant Elements and
Macromolecular Contaminants in Black Polymeric FoodContact Materials and it’s Origin
F. Puype1, J. Knoop2, J. Samsonek1, M. Egelkraut-Holtus2, M. Ortlieb2
1
Institute for Testing and Certification, Laboratory of analytical chemistry, Zlin, Czech Republic
2
Black polymeric food-contact articles (FCA) sold on the European market were
measured for their bromine content followed by the identification of presented
brominated flame retardants (BFRs) by use of X-ray fluorescence spectrometry
(XRF) and thermal desorption gas chromatography coupled with mass spectrometry
(thermal desorption GC-MS).
In order to confirm the possibility that recycled fractions from the Waste Electrical
and Electronic Equipment (WEEE) stream were entering the European market in the
form of black polymeric articles, elemental analysis was performed by use of
inductively coupled plasma optical emission spectroscopy (ICP-OES) for the
detection of WEEE relevant elements. In most of the BFR positive samples typical
elements used in electronic equipment (As, Cd, Cr, Cu, Fe, Hg, Ni, Pb, Sb and Zn)
were presented either at trace level or at elevated concentrations.
This poster discribes also the measurement of rare earth elements (REEs) and
confirms additionally the suggested WEEE root of contamination. REEs like Ce, Dy,
La, Nd, Pr and Y were detected in 4 of the 7 BFR positive samples.
The polymer matrixes were identified by combining attenuated total reflectionFourier transform infrared spectroscopy (ATR-FTIR) with pyrolysis GC-MS
enabling to detect impurities from foreign polymer fractions.
References
[1] Puype F, Samsonek J, Knoop J, Egelkraut-Holtus M, Ortlieb M. 2015. Evidence of waste electrical
and electronic equipment (WEEE) relevant substances in polymeric food-contact articles sold on the
European market, Food Additives and Contaminants: Part A, Volume 32, Issue 3, page 410-426
(2015), http://www.tandfonline.com/doi/full/10.1080/19440049.2015.1009499 (open access)
226
PS2.51
Antimony in Breakfast Tea
Consequences Going Hand in Hand with Today’s Materials
J. Knoop1, M. Egelkraut-Holtus1 M. Ortlieb1, U. Oppermann1, A. van Oyen2
1
2
CARAT GmbH, Bocholt, Germany
In recent times, design, shape and sensation of tea bags on the shelves of retail stores
has changed. It seems that some of them may be made of plastics.
In the food industry, the polymer PET (polyethylene terephthalate) is used widely for
packaging materials and antimony (Sb) is applied in its production. From harmless to
harmful, the effects of antimony and its compounds on human and environmental
health differ widely. Can Sb contaminate food products?
Non-destructive testing using FTIR (Shimadzu Iraffinity-1S equipped with a Specac
Quest single reflection ATR) and XRF (Shimadzu EDX-8000) gives clues about the
material a tea bag is made of and the amount of Sb present in the tea bag. In addition,
the high sensitive ICP-OES technique (Shimadzu’s ICPE-9820 equipped with
hydrideICP, ESI Elemental Scientific) is applied for elemental analysis of the brewed
tea and tea bags.
It was found that paper may be disrupted and lose its functionality after long
immersion in hot water. The newer generation of tea bags is therefore made of
plastics. Of course, tea bags are also still made of cellulose, but is it only cellulose? It
is analysed which further materials are in use and it is shown that different analysis
techniques can shed light on this matter. Diverse tea bags from different suppliers of
tea were analyzed.
227
PS2.52
CHARACTERIZATION OF VEGETABLE OILS
THROUGH SCATTERED RADIATION AND
MULTIVARIED ANALYSIS
D.S. Almeida1, D.F. Oliveira1,2, A.S. Souza3, M.J. Anjos2 and R.T. Lopes1
1
Laboratório de Instrumentação Nuclear/Nuclear Instrumentation Lab-COPPE, Federal University of
Rio de Janeiro, Rio de Janeiro, Brazil.
2
3
Armando Dias Tavares Physics Institute, State University of Rio de Janeiro, Rio de Janeiro, Brazil.
Laboratory of Neurodegenerative Diseases, Institute of Medical Biochemistry, Federal University
of Rio de Janeiro, Rio de Janeiro, Brazil.
E-mail: dani.almeida84@gmail.com
X-ray scattering techniques are being considered promising for the classification and
characterization of many kinds of samples [1, 2, 3]. This research employed the ratio
between the Raileigh and Compton scattering peaks (R/C). The scattering profile was
split in 11 regions and 4 chemical parameters for characterizing and classifying
vegetable oil samples through multivariate analysis techniques and hierarchical
grouping. 54 oil samples with different properties were analyzed (29 oils and 25
olive oils), all of them procured from commercial establishments in Rio de Janeiro.
The samples were chemically characterized according to their iodine, acidity,
saponification and peroxide. In order to obtain the scattering spectrum, an X-ray tube
with a silver anode operating at 40 kV and 50 μA was used. The oils could thus be
divided in two large groups: one containing all kinds of oils and one consisting only
of olive oils. Through PCA, two components were obtained, and they account for
over 80% of the data variance. One component was associated to the chemical
parameters and the other to the scattering profiles on each sample. Thanks to the
main component analysis, it was possible to ascertain that the usage of the scattering
spectrum associated to density and peroxide index parameters allowed the creation of
a ratio that can be used in order to characterize vegetable oils.
References
[1]DUVAUCHELLE (1999) DUVAUCHELLE, P., PEIX, G., BABOT, D. Nuclear Instuments and
Methods in Physics Research Section B: Beam Interactions with Material and Atoms, v.155, n.3,
pp.221-228, 1999.
[2] PEREIRA, F. M. V., PEREIRA-FILHO, E. R., BUENO, M. I. M. S, et al. Journal Agricultural and
Food Chemistry, v.54, pp. 5723-5730, 2006.
[3] TURSUCU, A., DEMIR, D., ONDER, P. Science and Technology of Nuclear Installations, v.
2013, pp.1-6, 2013.
228
PS2.53
Strontium, Arsenic and Arsenic species in beverages from
the Portuguese Total Diet Study
I. Coelho, S. Gueifão and I. Castanheira
1
Departamento de Alimentação e Nutrição, Instituto Nacional de Saúde Doutor Ricardo Jorge, I.P.,
Lisboa, Portugal
E-mail: ines.coelho@insa.min-saude.pt
The main objective of this study was to study the levels of strontium, total arsenic
and inorganic arsenic present in nectars, fruit juices and waters consumed in
Portugal. A second objective was to evaluate the reliability of pooled versus single
samples to derive consistent estimates of exposure assessment to inorganic
contaminants.
Twenty four samples of juices and nectars representative of the domestic market
were acquired in May 2014 in the Lisbon region. Samples of representative brands
were collected randomly in supermarkets of national implementation in accordance
with consumer preference. Afterwards these were analyzed both as single units and
as two pools, one of nectars and the other of juices, composed by 12 samples each.
Prior to analysis samples were digested by high pressure closed vessel microwave
digestion using only ultrapure reagents. An ICP-MS was used to quantify the levels
of Strontium and Arsenic present in samples. Whenever the concentration obtained
for arsenic was equal or above 5 µg.l-1 samples were signalized for speciation
studies. These were carried out by coupling an HPLC to the ICP-MS, and enabled
the determination of two inorganic arsenic species, As(III) and As(V), as well as two
other organic species, AsB and DMA. Extraction of arsenic from samples was based
on previously published work [1] and consisted on a dilution and a filtration steps
previously to introducing the samples to the HPLC.
Arsenic was found above the LQ (LQ=2 µg.l-1) in almost half the samples under
study which shows that arsenic speciation is crucial to clarify the toxicity of arsenic
present in foodstuffs. The speciation study proved that most of this arsenic, whether
in juices, nectars or waters, is present as As(III) and As(V). However, there is no
European legislation for arsenic in fruit juice. Inconsistent results were obtained for
arsenic between pooled and single samples. Also, the present work provided a clear
example of how, due to a dilution factor, pooling might mask the presence of a
contaminant and therefore underestimate exposure assessments.
References
[1]
S. D. Conklin and P. E. Chen, “Quantification of four arsenic species in fruit juices by ionchromatography–inductively coupled plasma–mass spectrometry,” Food Additives &
Contaminants: Part A, vol. 29. pp. 1272–1279, 2012.
229
PS2.54
Evaluation of Metals in Tomato Sauce Stored in Different
Types of Packaging
L.P. Muniz1, L.M.G. Santos1, K.L.C. Magalhães1, S.C. Jacob1
1
Fundação Oswaldo Cruz, Avenida Brasil 4365 - Manguinhos, Rio de Janeiro
E-mail: portugalluiza@hotmail.com
Over the time the consumption of ready processed food or semi-ready has increased a lot.
Most of them are sold in packaging prepared for safety transport, storage, distribution, sale
and final consumption. The issue of food packaging in a security way can be approached in
two ways: the first is to set a very important role to protection and conservation of the
product; and the second, not let packaging be a source of loss to the quality of the product,
since the materials of packaging are in direct contact with the food, which can lead to
physical, chemical and microbiological contamination [1]. There is also a growing concern
among the population about chronic diseases related to the presence of some metals in food.
Some of them are micronutrients for humans but others are extremely toxics, even though, in
small quantities [2]. In the present study it has been hypothesized that sauce tomato has
contained high amounts of metals and a possible leached from packaging. To verify such
hypothesis, concentration of As, Cd, Pb, Cr, Ni, Sb and Sn were determined and compared.
Different brands and metallic, plastic and cellulose packaging were collected in
supermarkets of Rio de Janeiro city, Brazil. The samples were digested in a microwave
digestor model Speed Wave (Berghof) with the addition of nitric acid (65% ultra-pure 3mL).
The determination of concentration As, Cd, Pb, Cr, Ni, Sb and Sn were made by inductively
coupled plasma mass spectrometry (ICP-MS), model Nexion 300D (Perkin Elmer) equipped
with a concentric nebulizer (MEINHARD®), and a glass cyclone spraychamber was used.
Argon gas with a minimum purity of 99.996% was obtained from White Martins (São Paulo,
Brazil). The instrument conditions used were: autolens mode, peak hopping measurement
mode, dwell time of 15 ms, 50 sweeps by reading, 1 reading by replicate, 3 replicates. Nickel
cone, skimmer and hyper-skimmer and a quartz ball joint injector 2.0 mm i.d. were used.
The concentrations found were around: As 0.1 mg kg-1, Cd 0.007 mg kg-1, Pb 0.05 mg kg-1,
Cr 0.3 mg kg-1, Ni 0.1 mg kg-1 and Sb 0.002 mg kg-1. The concentrations of As, Cd, Pb, Sb
and Ni were below the limits established by law, and the concentration of chromium was
higher than the limit established by Brazilian National Health Surveillance Agency
(ANVISA- RDC 𝑁 𝑜 42 29/08/2013): 0.1 mg kg-1. Regarding to packaging, Sn is the only
metal that showed a difference in its behavior when the product is stored in metallic
packaging. While in the plastic and cellulosic packaging the product showed concentrations
around 0.04 mg kg-1, the product stored in metallic packaging had a tin concentration of
about 1.3 mg kg-1. Despite the difference, both concentrations were below the limit
established by ANVISA: 250 mg kg−1.
References
[1] POÇAS, Maria F.; MOREIRA, Raquel. Segurança Alimentar e Embalagem. CINATE
Segurança Alimentar (Serviços de Tecnologia e Inovação), 2003.
[2] POLETTI, Jucelaine. Quantificação de Elementos Traço em Arroz. Universidade Federal do
Rio Grande do Sul, 2012.
230
PS2.55
Study of the elemental concentration in wheat grains by
micro-EDXRF
I. Ramos1, Inês M. Pataco2, Fernando Reboredo2, Fernando C. Lidon2, Maria
Fernanda Pessoa2, M. L. Carvalho1, J. P. Santos1, M. Guerra1
1
2
Departamento de Física, FCT-UNL, 2829-516 Monte da Caparica, Portugal.
GeoBioTec, Departamento de Ciências da Terra, Faculdade de Ciências e Tecnologia, Universidade
Nova de Lisboa, Campus da Caparica, 2829-516 Monte da Caparica, Portugal.
E-mail : in.ramos@campus.fct.unl.pt
Even in the XXI century, there is still a large group of the world population that
suffers from micronutrient undernourishment, which constitutes a worldwide public
health problem. These nutrition deficiencies not only are resultant from famine but
also from the low nutritional value of food. Thus emerges the need of staple crops
being biofortified with micronutrients such as iron (Fe) and zinc (Zn).
Biofortification has the purpose of increasing these micronutrients concentration on
staple food without compromising their productivity.
This study objective is to quantify the major elements and the trace elements present
in wheat grains, to which were added, during their development, iron and zinc
supplements. To evaluate the efficiency of this nutritional intervention, an analytical
methodology, designated energy dispersive X-ray fluorescence technique (EDXRF),
was used. This technique, based on the emission of characteristic X-ray, was
employed to quantify and map the wheat grains elements such as P, S, K, Ca, Mn, Fe
and Zn.
Through the element distribution maps obtained it was possible to verify that the
micronutrients used in the wheat grains biofortification (Fe and Zn) are
predominantly present on the aleurone outer layer and in the delimiting region of the
embryo. In the endosperm and bran region the amount of these elements is
insignificant, instead, elements as potassium (K) and calcium (Ca) are observed in
the last referred region . In the embryo region is mainly composed by phosphorus
(P).
231
PS2.56
Zn CONTENT AND SPECIATION IN HUMAN MILK
AND COMMERCIAL FORMULA MILK
Sonia Fernández Menéndez 1, María Luisa Fernández Sánchez 1, Belén
Fernández Colomer2, Ricardo E. Santelli3, Aline Soares Freire3, Bernardo
Ferreira Braz 3 and Alfredo Sanz Medel1
1
Department of Physical and Analytical Chemistry, Faculty of Chemistry, University
of Oviedo, Spain
2
Department of Neonatology. “Hospital Central de Asturias”, Oviedo, Spain
3
Department of Physical and Analytical Chemistry, Faculty of Chemistry,
Universidade Federal do Rio de Janeiro, Brasil
Zinc is a metal with great nutritional importance, particularly necessary in
cellular replication and the development of the immune response, playing an
important role for normal fetal growth and development during the first years of life.
It has a recognized action on more than 300 enzymes by participating in their
structure or in their catalytic and regulatory actions. Zinc deficiency is a serious
nutritional problem among children of developed and developing countries (1).
During the first months of baby’s life, milk is the only source of macronutrients
(proteins, lipids, carbohydrates) and micronutrients (vitamins, enzymes and minerals)
completely necessary for the correct development of the newborn. Human milk can
be considered as the optimal food for infants as it contains these macro and
micronutrients at the adequate levels. However, the composition of maternal milk
changes along the postpartum time, from colostrum (days 1-3) to mature milk (days
14-28). When infants are not breast-fed or breast-feeding is discontinued very early,
formula milks have to be used instead of human milk. So, composition of formula
milks for newborns should ideally be as similar as possible to maternal milk at every
lactating stage.
Moreover, Zn bioavailability from human milk is higher than that from
formula milks. This difference can be attributed to the existence of a citrate rich
fraction, the presence of lactoferrin and the lower casein or phosphorous content of
breast milk (2).
Thus, the aim of this study is twofold: (a) to investigate the zinc content and
speciation of human milk from mothers of preterm and full-term infants at different
stages of lactation (colostrum, 4th, 14th and 28th day after delivery), and (b) to assess
differences in zinc content and speciation between human milk from mothers of
preterm infants and from preterm commercial infant formulas. The final goal is to
obtain as much information as possible about adequate zinc speciated content in
infant formulas, as compared to maternal milk, via the use of the coupling of HPLC
(SEC) to ICP-MS in combination with post-column isotope dilution analysis (IDA)
for quantification.
References
(1)
R.E. Black “Zinc deficiency, infectious diseases and mortality in the developing world”. J
Nutr 133 (5 Suppl 1) (2003): 1485S−1489S.
(2) R.R. de la Flor St Remy, M.L. Fernández-Sánchez and A. Sanz-Medel. “Total Analysis and
distribution of trace elements in human , cow and formula milk” (2006) J. Wiley & Sons (Ed. Caroli)
ISBN: 9780470141007
232
PS2.57
ANALYSIS OF VOLATILE COMPONENT AND TOTAL
ANTIOXIDANT CAPACITY OF PROSOPIS FARCTA
I. AYDIN 1 ,D. OZYURT1, B. OZTURK1
1
Department of Chemistry, Faculty of Science and Letters, Istanbul Technical University, 34469,
Istanbul, Turkey
aydinil@itu.edu.tr
Plants have been used for medical purposes since many centuries. Prosopis includes
nearly 50 species which are generally spiny trees or shrubs and well adapted to
warm weather. Prosopis farcta is a small, prickly shrub, 30-80 cm tall species of
prosopis and widespread in Northern Africa and much of southwestern Asia, from
Kazakhstan south to the Indian and west to the Middle East. It has an important
ecelogical role for the protection and improvement of soils since has an high degree
of salt toleration. On the other hand leaves and beans of Prosopis farcta have been
used as a traditional medicine for treatment of some diseases and disorders in
Turkey. For example, after boiling P. Farctas leaves used for epidemic disase order.
Beans of prosopis farcta used for treatment of diarrhea among the people in
Turkey.There have been some academic works searching the effect of Prosopis
farcta on cholesterol and diabets hurts. Besides these effects, it’s antitumour
activity, antiparasitic and antimicrobial have been noted recently. There has not been
academic work for antioxidant capacity of prosopis farcta, therefore to research it’s
total antioxidant capacity the beans of prosopis farcta collected in september.The
beans are kept in proper conditions during experiments. In this study, firstly the
beans of prosopis farctas volatile components are identified with two-dimensional
gas chromatography time of flight mass spectrometry (GC*GC-TOF/MS).
Accordingly GC*GC-TOF/MS chromatography, volatile components of prosopis
farcta listed through high percent to the lowest percent. Glicerin is the second
percent of volatile components which effective on diabets disordes. Secondly, we
investigated total antioxidant capacity of prosopis farcta after applying extraction
methods to beans of prosopis farcta. Spectrophotometric and spectrofluorometric
CERAC [1, 2], CUPRAC [3] and Modified Folin-Ciocalteu [4] methods used for
antioxidant capacity analysis.
References
[1] Ozyurt, D., Demirata, B., & Apak, R., Journal of Food Composition and
Analysis, 23, 282–288, (2010).
[2] Ozyurt, D., Demirata, B., & Apak, R., Journal of Fluorescence, 21, 2069–2076,
(2011).
[3] Apak, R.; Guclu, K.; Ozyurek, M.; Karademir, S. E., Journal of Agricultural
Food Chemistry, 52, 7970−7981, (2004).
[4] Berker, K. I., Ozdemir Olgun, F. A., Ozyurt, D., Demirata, B., Apak, R. Journal
of Agricultural and Food Chemistry, 61, 4783-4791, (2013).
233
PS2.59
Evaluation of Brazilian rice-based infant foods: Source of
arsenic
Tatiana Pedron1, Fabiana Roberta Segura1, Fabio Ferreira da Silva2, Alexandre
Luiz de Souza3, Heloisa França Maltez 1, Bruno Lemos Batista1
1Centro
de Ciências Naturais e Humanas, Universidade Federal do ABC (UFABC), Postal Code:
09210-580, Santo André, SP, Brazil
2Agilent Technologies, Postal Code: 06460-040, Barueri, SP, Brazil
3Faculdade de Saúde Pública, Universidade de São Paulo (USP), Postal Code: 01246-904, São Paulo,
SP, Brazil
E-mail: heloisa.maltez@ufabc.edu.br
Arsenic is a toxic element and can be found in different chemical species: organic and
inorganic arsenic. Exposure to these compounds is associated with serious damage to
health, even at low concentrations. Food is a major source of arsenic exposure,
particularly rice due to its type of cultivation and irrigation, which favor the absorption
of this element. Thus, the rice and their derivatives, such as flour, biscuits and infant
food may contain high concentrations of arsenic. Among the groups of people that
consume these foods are children and celiac. Children because it is one of the first kind
of food they eat due to its easy absorption, and high energy. Regarding the celiac, the
main factor is the gluten, a protein that the body cannot digest and interferes with the
absorption of other nutrients. Focused on these two groups were determined
concentrations and speciation of arsenic in several samples (n = 17) of food collected in
multiple locations in Brazil. The samples were baby food, porridge, flour and pasta, all
based on rice. For the analysis of total arsenic concentrations, the samples were
homogenized, digested in 2 ml high purity nitric acid (Savillex DS-100), heated in a
digester block (Analab Easy Digest) for 4 h at 80 °C, diluted in deionized water, and
then analyzed in a mass spectrometer with inductively coupled plasma (ICP-MS Agilent
7700, Hachioji, Japan). Total arsenic concentrations were: pap (18.0 ± 5.7 ug kg -1);
porridge (128.7 ± 27.3 ug kg-1) flour: (95.7 ± 43.9 ug kg-1); pasta (119.4 ± 62.6 ug kg-1).
The samples were undergone (n = 17) an extraction in HNO3 diluted and heated block
digester at 85 °C for 3 h for arsenic speciation [1]. Subsequently the samples were
diluted 1:1 and an aliquot was withdrawn and filtered and then analyzed by HPLC-ICPMS. The preliminary speciation results indicated that samples evaluated contains
arsenite (As3+), arsenate (As5+), dimethylarsenic (DMA) and monomethylarsenic
(MMA). According to the World Health Organization (WHO-2010) the estimative
exposure for body weight to arsenic is 0.1-3 μg kg-1 per day. The values found show that
there are high concentrations and different species of arsenic in rice-based food which
presents a potential health risk to children and celiac, revealing then, urgency and the
improvement in food security policies worldwide and practices code on agriculture to
reduce the contamination of the grains.
References
[1] B. L. Batista, M. Nigar, A. Mestrot, B. A. Rocha, F. B. Junior, A. H. Price, A. Raab and J.
Feldmann. Journal of Experimental Botany. 65, 1467-1479 (2014).
234
Poster Session 3: Environmental and Geochemical Analysis
PS3.1
Concentration Analysis of 15 Trace Elements
in Spring water samples Using ICP-MS
―Observations Over a Seven Year Period ―
Y. Manaka, M. Goto, H. Nakajima and M. Abe
Department of Health and Nutrition, Wayo Women’s University
Konodai 2-3-1, Ichikawa, Chiba 272-8533, Japan
E-mail: manaka@wayo.ac.jp.
Springs have been widely used as a source of drinking water for local residents. In
Japan, the Ministry of the Environment designated numerous springs as the best
springs in Japan on the basis of the conservation of water quality, water volume, and
other factors. The names and locations can be accessed by internet. However, there
are limited scientific reports on water quality data.
In this study, we analyzed the concentrations of 15 trace elements in the springs at
six locations over seven years using ICP-MS (ICPM-8500 system, SHIMADZU).
The use of ICP-MS, which is a highly sensitive analytical method, in this study made
it possible to analyze even ultra-low concentrations.
The 15 trace elements ( B, Al, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Mo, Cd, Sb, Pb and U)
were detected at low concentrations or ultra-low concentrations. The obtained data
were examined and compared with the WHO guidelines for drinking water quality
[1] and the tap water quality standards and the environmental water quality standards
issued by the government of Japan. The results showed that the concentrations of all
trace elements were thought to be appropriate for use as drinking water except for
Miyakogawa. The concentrations of As (24.3µg/L) and U (2.86µg/L) in 2009 and
Mn in 2008 at Miyakogawa exceeded the standards. We speculate that the
concentrations of As and U temporarily increased, because of the inflow of
wastewater from repair work at the spring and the surrounding area. The
concentration of Mn varied significantly by year at every sampling location. Mn is
present in rocks, soil, natural water, and also in most living organisms. The high
concentration of Mn (52.4µg/L) that was detected in this study at the Miyakogawa
spring in 2008 was thought to be a temporary increase in the significant fluctuation.
On the basis of knowledge, we confirmed that there is a little probability of any acute
or chronic effects caused by drinking the samples obtained from the six springs in
Japan. However, it temporarily increases in elemental concentrations that occur
because of the maintenance in the surrounding environment or at the intake, etc., the
water quality should be monitored.
Reference
[1] WHO, Guidelines for drinking-water quality – 4th ed, (2011).
235
PS3.2
Extraction of selected compounds of mercury from the real
samples for speciation analysis using RP-HPLC-UV-CVGQTAAS
Alzbeta Kolorosova1, Ondrej Linhart1, Vaclav Cerveny1, Jan Kratzer2, Jakub
Hranicek1, and Petr Rychlovsky1
1
Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Albertov 6,
CZ-128 43 Prague 2, Czech Republic
2
Institute of Analytical Chemistry of the ASCR, v.v.i., detached workplace - Department of Trace
Element Analysis, Videnska 1083, CZ-14220 Prague 4, Czech Republic
E-mail: alzbetakolorosova@seznam.cz
The aim of the presented work was to develop an extraction method for ultra-trace determination of selected
mercury species from real samples such as fish tissues. Organic mercury species permeate easily through the
biological membranes because of their lipophilic character [1]. Carrying out the speciation analysis is necessary
due to different toxicity of these species. Mercury chloride [Hg+II], methylmercury chloride [MeHg+I],
ethylmercury chloride [EtHg+I], and phenylmercury chloride [PhHg+I] have been chosen as the model
compounds. Hg+II and MeHg+I are the most abundant forms of mercury in the environment [2].
Mercury species were separated by reversed phase high performance liquid chromatography [RP-HPLC]. UVphotochemical generation of cold mercury vapor [UV-CVG] was used as a derivation step between RP-HPLC
and atomic absorption spectrometry with quartz detection tube [QT-AAS]. The UV-photochemical generator was
made of PTFE tube (1 m x 1 mm ID x 2 mm OD) wrapped around the low pressure Hg lamp (20 W, 254 nm). In
order to generate cold mercury vapor from all the selected mercury species under UV-irradiation, acetic acid and
2-mercaptoethanol were added into the mobile phase [3].
Several extraction agents were tested: the mixture of hydrochloric acid and ethanol [4], 2-mercaptoethanol,
thioglycolic acid, sodium pyrrolidinedithiocarbamate [5], potassium hydroxide in methanol [6], L-cystein [7],
potassium bromide with copper sulfate, and tetramethylammonium hydroxide [8]. The best results were obtained
with the mixture of 6.25 % tetramethylammonium hydroxide and 0.05 mol·l-1 hydrochloride acid as extraction
agent.
Besides, the digestion methods were tested. During microwave-assisted digestion, sorption of mercury species on
the inner surface of Teflon vessels occurred. For this reason, the extraction by high temperature (50-60 °C) in
glass vessels was chosen as the best alternative. The efficiency of extraction of mercury species from the real
samples was compared with the total mercury content determined by direct sample combustion employing a
single purpose atomic absorption spectrometer AMA 254. Proposed extraction method together with RP-HPLCUV-CVG-QTAAS are suitable for speciation analysis of mercury in real samples.
Acknowledgments
This work was financially supported by the Charles University in Prague (Project UNCE204025/2012, GAUK152214, and
project SVV260205) and Institutional Research Plan of the IAC ASCR, v. v. i. (RVO: 68081715).
References
[1] Casarett, L.; Doull, J.; Klaassen, C.: Casarett and Doull’s toxicology : the basic science of poisons. New York: McGrawHill Medical Pub. Division, 6th ed.2001.
[2] Uría Sánchez, J. E.; Sanz-Medel, A.: Inorganic and methylmercury speciation in environmental samples. Talanta 47, 509–
524 (1998).
[3] Linhart, O.: Speciation Analysis of Selected Mercury Compuds Using HPLC, UV-Photochemical Cold Merury Vapor
Generation and its AAS Detection. Diploma thesis, Charles University in Prague: 2013.
[4] Rahman, G.; Kingston, H.: Application of speciated isotope dilution mass spectrometry to evaluate extraction methods for
determining mercury speciation in soils and sediments. Anal Chem 76, 3548–3555 (2004).
[5] Falter, R.; Schöler, H.: Determination of mercury species in natural waters at picogram level with on-line RP C18
preconcentration and HPLC-UV-PCO-CVAAS. Fresenius J Anal Chem 353, 34–38 (1995).
[6] Yin, Y.; Liu, J.; He, B.; et al.: Mercury speciation by a high performance liquid chromatography—atomic fluorescence
spectrometry hyphenated system with photo-induced chemical vapour generation reagent in the mobile phase. Microchim Acta
167, 289–295 (2009).
[7] Hight, S. C.; Cheng, J.: Determination of methylmercury and estimation of total mercury in seafood using high performance
liquid chromatography (HPLC) and inductively coupled plasma-mass spectrometry (ICP-MS): Method development and
validation. Anal Chim Acta 567:2, 160–172 (2006).
[8] Yun, Z.; He, B.; Wang, Z.; et al.: Evaluation of different extraction procedures for determination of organic Mercury species
in petroleum by high performance liquid chromatography coupled with cold vapor atomic fluorescence spectrometry. Talanta
106, 60–5 (2013).
236
PS3.3
REE determination in imitation jewelry from China by
ICP-MS
J. S. A. Silva1, P. P. Arcenio1, T. A. Maranhão1 and V. L. Frescura1
1
Universidade Federal de Santa Catarina, Florianópolis, SC, Brasil
E-mail: jesseesevero@yahoo.com.br
The widespread use of technologies as well as the demand for newer, more efficient
and effective products result in a shortening of the life span of electronics and a
drastic increasing in the production of wastes (e-wastes). The recycling of e-wastes is
of great importance because the high content of metals, which can even include
precious metals, can be employed in the production of the same high-tech products.
Besides it contributes to reduce the environmental impact. Nevertheless there is
evidence that metal from e-waste is being used to produce imitation jewelry because
the high content of heavy metal, such as Cd and Pb, found in this jewelry [1].
Since rare earth elements (REE) are essential in the production of electronics it
would be possible that some of these elements would be present in the composition
of these jewelries, were them really produced from e-waste.
In this work, imitation jewelries collected by Brazilian Federal Revenue, with high
content of Cd, were analyzed and the concentration of REE determined. The samples
were digested in HNO3 and measurements of 16 elements were carried out by
ICPMS.
It was found concentrations values for six REE, Nd, La, Ce, Pr, Sm and Eu in the
range of ppm, from 0.04 μg g-1 for Nd to 2.0 μg g-1 for Sm. Values for LOD were
from 0.4 ng g -1 for La to 14.8 ng g -1 for Ce. Recovery tests were also performed.
The results corroborate the evidence that jewelries from China are being produced
from e-waste.
References
[1] Jeffrey D. Weidenhamer, Michael L. Clement, Chemosphere, 69, 1670-1672 (2007)..
237
PS3.4
Prepare and Characterization of a Soil Reference Material
for Inorganic Nutrients and Contaminants
T. R. Verhalen1,2, G. B. Souza1 and A. R. A. Nogueira1
1
Embrapa Southeast Livestock, P. O. Box 339, 13560-970, São Carlos-SP, Brazil
2
Chemical Department, Federal University of Sao Carlos, P. O. Box 676,
13565-905, São Carlos, SP, Brazil.
E-mail: ana.nogueira@embrapa.br
The certified reference materials make an important role in the establishment of
traceability in analytical chemistry, ensuring reliability and accuracy to the
measurements and are fundamental for the validation of analytical methods. The
demand for new certified reference materials increases in all areas of knowledge,
with emphases in the agriculture. Basis for the production of farming products, the
demand for soil analysis is great and the existence of a reference material of a typical
Brazilian soil is important to ensure the quality of results. In this context, a reference
material for Cr, Pb, Cd, and As soil contaminants and Ca, P, Mg, K, Cu, Fe, Mn, Zn,
and Na macro and micronutrients was prepared and characterized.
The material was produced following the internationally accepted ISO Guides 30-35
norms considering the preparation and packaging, homogeneity, short and long term
stability, material characterization and certification. A Typical Paleudult soil was
previously artificially contaminated with 25 mmol L-1 of As, Cd, Cr, and Pb. After
12 month of contamination, 65 kg of soil was dried at room temperature, ground
(particles size < 390µm), homogenized, packaged and gamma ray irradiated (20 - 25
kGy) aiming to increase the shelf-life. The analyte soil extractions were performed
by assisted microwave oven with the use of 14 mol L-1 HNO3, based on the USEPA
3051. The evaluation of the estimate minimum amount, homogeneity and stability of
the material were carried out by using inductively coupled plasma optical emission
spectroscopy (ICP OES) determination technique. The results were submitted to
analysis of variance of single factor (ANOVA). The homogeneity and stability of the
material presented means within a confidence interval of 95% for As, Cd, Pb, Cr, Ca,
Cu, Fe, Na, K, Mg, Mn, and P. The chemical characterization of the material was
performed through a collaborative test and the uncertainties related to each step of
the material prepare were calculated to obtain the expanded uncertainty for each one
of the analytes and to the final drafting of the control chart containing the results of
the reference material.
Acknowledgments: The authors are grateful to Instituto Nacional de Ciências e Tecnologias
Avançadas (INCTAA), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) and
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) for financial support.
238
PS3.5
Trace elemental determination in rock samples by ICP-MS
F. Bazzano1, E. Previde Massara2, N. Sommariva1, P. Casali2
1
2
eni S.p.A. - Downstream Laboratories - Physical Chemistry Laboratories
eni S.p.A. Upstream & Technical Services - Laboratories of Experimental Geology
via F. Maritano 26, 20097 San Donato Milanese (MI) Italy
E-mail: francesca.bazzano@eni.com.
A well-assessed internal method is routinely used for the quantification of both major
and trace elemental composition in geological materials by XRF.
The procedure is based on an instrumental calibration made by means of a great deal
of reference materials.
However, trace quantification by XRF can be critical at very low levels (a few
mg/kg) and/or for some specific elements. Moreover, at least 10 g of sample should
be available.
On the contrary, instrumental ICP-MS quantification of trace elements can be an
alternative procedure [1], [2] [3], [4] because the sensitivity is very high; moreover,
as low as 1 g sample may be enough.
A preliminary work was done using four samples of different origin and bulk
composition to evaluate the alternative procedure.
Ba, Cr, Mn, Ni, Sr, V and Zn (whose elemental content was more than 50 mg/kg)
were determined by ICP-AES and ICP-MS and the results were compared with XRF
data.
Sc, Co, Ga, Se, Y, Nb, Mo, Cs, rare earth elements (REEs), Tl, U, Pb, Th were
quantified by ICP-MS and compared with XRF results.
The quantification of other trace elements, such as In, Cd, Sn, Sb, Bi, Ag, Ir, Re and
other REEs was attempted by ICP-MS.
The precision of the procedure was evaluated on a sample.
References
[1] M. Gregoire, B. N. Moine, S. E. O’Reilly, Journal of Petrology, 41, 477-509 (2000).
[2] Murilo Ferreira Marques dos Santos, Eric Fujiwara, Egont Alexandre Schenkel, Jacinta Enzweiler,
Carlos Kenichi Suzuki, Journal of South American Earth Sciences, 56, 328-338 (2014).
[3] Jianyun Feng, Wenjiao Xiao, Brian Windley, Chunming Han, Bo Wan, Ji’en Zhang, Songjian Ao,
Zhiyong Zhang, Lina Lin, Journal of Asian Earth Sciences 78 114–142 (2013)
[4] Wilfredo Diegor, H. Logerich, T. Abrajano, I. Horn, Analytica Chimica Acta 431, 195-207 (2001)
239
PS3.6
Solid phase extraction and HR ICP-MS determination of
Rare Earth Elements in seawater samples: two case studies
Emilia Vasileva, Irena Wysocka and Eunmi Han
IAEA- Environment Laboratories, Department of Nuclear Sciences Applications, 4
Quai Antoine 1er MC 98000, Principality of Monaco
e-mail: e.vasileva-veleva@iaea.org
There is a growing interest in determining the global distribution of dissolved rare
earth elements (REEs) in the open ocean and understanding the processes that
control their content in the water masses. REE patterns in seawater are a valuable
tracer for anthropogenic pollution and the distinctions in the normalized REE
patterns can be very useful in the ocean monitoring studies.
Despite important technological progresses over the past years, quantifying of REEs
in sea waters remains a very difficult analytical challenge due to lack of sensitivity in
the conventional methods, very high salt content in the sea water and low levels of
REEs. To achieve accurate and reliable results efficient pre-concentration and matrix
separation step before the instrumental measurement is usually required. Two
analytical methods, based on the application of solid-phase extraction (SPE) for
separation and pre-concentration of REEs are proposed in this study. The first one is
based on the application of nano size TiO2 as solid phase extractant and the second
one on the application of chelating resin integrated in SeaFast sample introduction
system coupled to the HR ICP-MS.
The conditions for reproducible separation, elution and subsequent HR-ICP-MS
determination were investigated. Optimum separation from typical seawater sample
was studied by variation on sample size, loading pH, sample and elution rates. High
resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) was applied
in the measurement step of the developed procedure and all interferences – isobaric
and polyatomic carefully investigated.
The validation of the methodology was effectuated according to the ISO-17025
standard. Thereupon, blanks, selectivity, calibration curve, linearity, working range,
recovery, precision, traceability and limits of detection and quantification were
assessed. The estimation of the total uncertainty associated to each measurement
result was fundamental tool for sorting the main sources of measurement biases.
Preliminary forecast of the uncertainty budgets was used as a strategy to ensure that
the determination of REEs in marine waters could be achieved with demonstrated
traceability to a stated system of reference. All major sources of uncertainty were
identified and propagated together following the ISO/GUM guidelines. The obtained
with proposed analytical procedures results were compared and the obtained
correlation was very good.
The proposed analytical procedures were applied for the analysis of Mediterranean,
Pacific, Antarctic and Irish seawater samples.
240
PS3.7
Lead isotope ratios determination in seawater by SeaFast sample
introduction system and High Resolution ICP-MS
Emilia Vasileva, Anna Maria Orani
IAEA- Environment Laboratories, Department of Nuclear Sciences Applications, 4
Quai Antoine 1er MC 98000, Principality of Monaco
e-mail: e.vasileva-veleva@iaea.org
The concentration of lead in world ocean surface waters increased significantly
owing to industrial activity and gasoline consumption during last decades. To
identify the different pollution sources accurately and to quantify their relative
contributions, lead isotope ratios are widely used. Anthropogenic lead in the oceans,
derived from high-temperature industrial processes, fuel combustion, and
incineration can have an isotopic signature distinct from naturally occurring lead,
supplied by rock weathering.
Measurement of 204Pb by ICP-MS is particularly problematic as it is the least
abundant of the four stable Pb isotopes and is subject to isobaric interference during
analysis from 204Hg. Nevertheless 204Pb isotope is of crucial importance for some
geological interpretations. Some studies have dealt with this problem by
concentrating analytical efforts on the more abundant and interference-free 206Pb,
207
Pb and 208Pb isotopes, but this limits the range of measurable isotopic variability,
as much of the natural variation is recorded on 208Pb/204Pb, 207Pb/204Pb and
206
Pb/204Pb ratios. Lead isotopic ratios measurement represents a powerful tool for
environmental monitoring of coastal areas as well as in the open ocean.
An analytical protocol for the measurements of isotope ratios in seawater using
SeaFast sample introduction system and the Nu Attom single collector High
Resolution ICP-MS was developed. Due to the high salt content (approximately
3.5% of total dissolved solids) and very low lead levels (approximately 20 pg ml -1),
seawater samples require preliminary matrix separation and pre-concentration steps.
The pre-concentration/separation step is of crucial importance for decrease isobaric
and matrix interferences during measurement step and helps to decrease combined
uncertainty on the respective isotope ratios. Several separation procedures were
tested, optimised and the remaining matrix concentration carefully investigated.
In order to differentiate between anthropogenic and natural lead sources, both lead
concentration and isotopic composition were determined by proposed analytical
method. The validation of the method was effectuated according to the ISO-17025
standard. All major sources of uncertainty were identified and propagated together
following the ISO/GUM guidelines. The estimation of the total uncertainty
associated to each measurement result was fundamental tool for sorting the main
sources of measurement biases. The method was applied to the coastal and open
seawater samples, collected in different regions of the word.
241
PS3.8
Characterization of an Iron meteorite using 57-Fe
Mössbauer spectroscopy and elemental analysis
P.C. Silva1, M. Guerra2, R. Marques3, M. I. Prudêncio3, A. Ramalho4, V.A.
Khomchenko1, G. Klingelhoefer5, E.I. Alves6, A.C. Batista1, B.F.O. Costa1
1
Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829516 Caparica, Portugal
3
Centro de Ciências e Tecnologias Nucleares (C2TN), IST, Universidade de Lisboa, Estrada Nacional
10 (km 139.7), 2695-066 Bobadela, Portugal
4
CEMUC, Department of Mechanical Engineering, University of Coimbra, 3000-272 Coimbra,
Portugal
5
Institut für Anorganische und Analytische Chemie, Joh. Gutenberg-Universität Mainz, 55099 Mainz,
Germany
6
Centre for Geophysics and Dept. Of earth Sciences, University of Coimbra, 3000-134 Coimbra,
Portugal
2
Iron meteorites are based in Fe and Ni elements and contain from 5 to 60 wt% Ni.
They also have small amounts (<1 wt%) of Co, P, S and C.
An unknown iron meteorite fragment with a mass of 25.6 g, was studied using
different characterization techniques including 57-Fe Mössbauer spectroscopy, X-ray
fluorescence and Instrumental neutron activation analyses.
Microstructure analysis revealed inclusions in the matrix as schreibersite or rhabdite
(Fe,Ni)3P and Neumann lines. Elemental analysis revealed a matrix composition of
93.4wt% Fe, 5.7wt% Ni and 0.48wt% Co. Inclusions have compositions of 52.5wt%
Fe, 34.6wt% Ni and 12.0wt% P. Neutron activation analysis was done to quantify
trace elements.
Mössbauer spectroscopy and X-ray diffraction shown only kamacite (bcc α-FeNi).
Weathering was found as maghemite, goethite, wüstite and nanophasedoxyde/hydroxides.
The characteristics found in this meteorite points to an Hexahedrite. The studies done
so far indicate that most probably this iron meteorite belongs to the IIAB group.
242
PS3.9
GC-CVAFS speciation of Hg in aqueous effluents from the
oil and gas industry using different alkylation reactions
Sarzamin Khan1, Rodrigo A. Gonçalves1, Maria Luiza B. tristão2, Roberta M.
T. de Mattos2, Ricardo Q. Aucelio 1
1
2
Pontifical Catholic University of Rio de Janeiro, Brazil, 22451-900.
Centro de Pesquisa e Desenvolvimento Leopoldo Américo Miguez de Mello-Petrobras, Brazil.
sarzamin81@gmail.com.
Mercury is hazardous pollutant that may be released to the environment during oil and
gas production and processing [1]. In water samples associated with oil production, it
may occur mainly as elemental mercury (Hg0) and “inorganic mercury” (Hg2+) but
metalorganic forms, most predominantly methylmercury (CH3Hg+) also exist. The water
associated to the oil production may vary in composition in terms of salinity and in
organic content (dissolved organic compounds and dispersed crude oil) that imposes
interferences not only in total mercury determination but also in the speciation analysis
of mercury [2]. Atomic fluorescence spectrometry (AFS) is very sensitive for mercury,
detected in their cold vapor (CV) form. In combination with gas-chromatography (GC),
speciation analysis of mercury is enabled. However, sample pretreatment and analyte
derivatization are required. In this work, speciation analysis of mercury was carried out
using a GCCVAFS analytical system. Methylmercury and inorganic mercury were
converted into volatile species by aqueous phase propylation with sodium
tetrapropylborate (in 1% KOH) using acetate buffer to maintain pH 4.5. For
methylmercury, the derivatization with sodium tetraethyl borate (ethylation) was also
used and results were in close agreement with the ones obtained by propylation. A
volume of 40 mL of derivatized sample was transferred to the bubbling cell from where
the volatile species of mercury were carried by an argon flow (99.999%) to be collected
in a trap system. The desorbed mercury species were passed through a GC column (at
35oC) to be separated and then to be detected by atomic fluorescence spectrometry.
Propylation is affected by salt and oil content, thus distillation of the sample prior
alkylation was required. The linear dynamic range covered the concentration range
between 0.5 to 50 pg (as Hg0) with correlation coefficient of 0.9981. The limit of
detection was 0.1 pg, calculated using the baseline signal plus three times the standard
deviation of the signal. The approach was applied for determination of analyte fortified
samples with 4% salt content and 5 mg L-1 of dispersed crude oil. Recoveries were
between 84 and 90 %. The GC-CVAFS was relatively simple technique to implement
speciation analysis and sensitive determination of mercury species. Derivatization and
distillation was crucial to enable the analysis of water associated with the oil production
(high salinity and dispersed oil content).
References
[1] J.H. Tidwell, G.L. Allan, Embo Reports, 958-963 (2001).
[2] T.I.R. Utvik, Chemosphere 39, 2593–2606, (1999)
243
PS3.10
A study for elements determination for evaluating their
mobility in coal and ashes using experimental design
Sandra Maria Maiaa*, Wolfgang Kalkreuthb, Marco F. Ferrãoa, Mikael Gassena
a
Instituto de Química, UFRGS, Avenida Bento Gonçalves 9500, 91501-970,
Brazil, *sandramaia@iq.ufrgs.br
b
Instituto de Geociências, UFRGS, Avenida Bento Gonçalves 9500, 91540-000,
Brazil
The coal combustion in a power plant produces bottom and fly ashes and
usually these combustion residues are improperly stored at the plant site or on-site
disposal. As a consequence an environmental contamination can be produced. The
determination of leaching inorganic pollutant in solid waste, such as coal and ash is
an important topic for further industrial applications and solid waste management.
Environmental contamination caused by coal ash disposal and also their further
industrial application require the knowledge of their total metal concentration besides
the available metal fraction to other environmental compartments1. In the literature2
is reported the use of EDTA as a leaching agent to predict solid waste metal
availability. The objective of this work was to evaluate the mobility of As, Cd, Co,
Cr, Cu, Mn, Mo, Ni, Pb, V and Zn in coal and ashes produced by coal power plants
from the south of Brazil and to predict probable elements which might contribute to
the environmental contamination. The total elements concentration in coal and ashes
were determined by inductively coupled plasma mass spectrometry (ICP-MS), after
acid decomposition in microwave oven and metal block for coals and ashes,
respectively. Before to determine the available concentration of the elements, after
extraction with EDTA, a study was made to investigate the optimal extraction
conditions, considering the influence of factors such as EDTA concentration, sample
mass and contact time. For the experiments one coal sample from Candiota power
plant was used. For this study an experimental design was applied and the response
surface methodology. By using central composite design (CCD) method, 17
experiments (including 3 repetitions at the central point) were designed. The factors
(variables) were: EDTA concentration (0.008 to 0.092 mol L-1), sample mass (0.16 to
1.84 g) and contact time (26 to 94 min). After the extractions, the suspensions were
centrifuged and the supernatants (after dilution) were analyzed by ICP-MS
technique. The preliminary results showed that for As, Co, Cr, Mo, Ni and Zn, the
conditions (0.05 mol L-1, 1 g and 60 min) were adequate for the simultaneous
determination. Concerning the other elements (Cd, Cu, Mn, Pb and V), the optimal
conditions for simultaneous determination will be defined further.
References
1. Flues, M., Sato, I. M, Scapin, M.A., Cotrim, M. B., Figueiredo Filho, P. M.,
Camargo, I. M. C., Química Nova 2008,31(1), 25.
2. Garrabants, A. C, Kosson, D. S., Waste Manage 2000, 20, 155.
Acknowledgements: PROPESQ (BIC)
244
PS3.11
Coal combustion: evaluation of trace elements
enrichment in fly and/or bottom ashes
Sandra Maria Maiaa, Wolfgang Kalkreuthb, Ana Paula Bitelo (IC)1
a
Instituto de Química, UFRGS, Avenida Bento Gonçalves 9500, 91501-970,
Brazil, *sandramaia@iq.ufrgs.br
b
Instituto de Geociências, UFRGS, Avenida Bento Gonçalves 9500, 91540-000,
Brazil
Among the environmental concerns related to the use of coal it is important to
point out: gaseous and particulate emissions produced in the combustion process,
notably NOx, SO2 and toxic trace elements; emissions of CO2 and the implications of
such emissions for global warming; emissions to air, water and land from operations
associated with the mining of coal and the subsequent disposal of ash and spoil 1.
Davison et al.2 reported that the fine particle fraction of fly ash could be enriched in
trace elements compared with the fraction of trace elements in the parent coal. This is
due to the volatilisation of some elements in the boiler and their subsequent
condensation in the cooler sections of the flue gas stream. The aim of this work was
to investigate the enrichment of some trace elements in fly and bottom ashes from
coal combustion. For this purpose the concentrations of elements such as As, B, Be,
Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Sb, Tl, U, V and Zn were determined in coal and
their ashes by inductively coupled plasma mass spectrometry (ICP-MS). The coals
were decomposed with HNO3 + HF in microwave oven and the bottom and fly ashes
samples with HNO3 + HF + H2O2, both in closed PTFE vessels heated in metal
block. All the samples were decomposed in triplicates. Before the analysis the
samples were further diluted to minimize matrix interferences. The elements were
determined by standard calibration technique. The enrichment of trace elements was
calculated as (average trace element content in ash (g g-1)/average trace element
content in coal (g g-1)). In assessing the enrichment of elements in fly and / or
bottom ash it was observed that Mn is enriched in bottom ashes, while others, As,
Cd, Sb, and Tl, more volatile, enriched in fly ashes. While there are exceptions, most
studies find the same elements enriched in the fine particle fraction. For instance
most studies examined by Helble3 found enrichment for the elements As, Cd, Pb, Sb
and Se while, most found depletion in Mn. In this work, B, Co, Be, V and U are
distributed almost equally on both. The decrease of the concentration in bottom ash
is probably due to its volatilization and subsequent condensation on the fly ash
matrix. The determination of the concentrations of trace elements is of great
importance because it allows the evaluation of enrichment of elements in the bottom
and fly ashes that will contribute to environmental contamination.
References
1. Nelson, P. F. et al., Fuel, 2010, 89, 810.
2. Davison RL et al., Environ Sci Technol, 1974;8,1107.
3. Helble JJ., Fuel Process Technol, 2000;63:125.
Acknowledgements: CNPq, PROPESQ (BIC)
245
PS3.12
Analysis of REE in Basalt, Cement, Shale, Rock and Stream
Sediment CRMs by ICP-QMS
Rui Santos, Sebastian Wünscher, Heike Gleisner, René Chemnitzer
Analytik Jena AG
Analytical Instrumentation
Konrad-Zuse-Strasse 1
07745 Jena / Germany
E-mail: rui.santos@analytik-jena.com
Mobile: +351 916 660 140
Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) and Inductively
Coupled Plasma – Optical Emission Spectrometry (ICP-OES) are designed to
determine the composition of a wide variety of materials with excellent sensitivity.
Each method has its strengths, and it can be hard to choose which one of these is the
right tool for your particular analytical need. They are at the present time the most
used instrumental method for Rare Earth Elements (REE) quantification.
Nevertheless, their applicability in the analysis of geological samples exhibits some
constraints, since the accuracy of the data is largely dependent, both on completely
sample dissolution, selection of adequate wavelengths in ICP-OES to avoid any bias
of potential spectral interferences and adequate correction of polyatomic species in
ICP-MS like oxide and hydroxide formation. The High Resolution ICP-OES
(PlasmaQuant PQ9000) with its High Resolution Optics and the new ICP-MS
(PlasmaQuant MS Elite) with its High Sensitivity advantages and Integrated
Collision Reaction Cell technology (iCRC) offer new possibilities for quantifying of
REE in high matrix samples like Geological Materials. In our method development
six geological Reference Materials (RM), BHVO-1, JB-3, AC-E, NIM-G, JGb-1, JG1a and JA-1, were employed to validate all the options made for sample
decomposition, selection of adequate wavelengths and polyatomic corrections. The
quantification of REE in nine samples of the Geopt proficiency-testing program
revealed the capabilities of all the different instruments tested, including the ICP-MS
XSERIES from Thermo Scientifc, in terms of LOQ, accuracy and precision. The
analytical results obtained in very different matrices clearly showed that these
instruments have the required quality for further applications of the REE like,
electronic, optical, magnetic and catalytic applications but also in the growing field
of green energy technology.
246
PS3.13
Determination of inorganic elements in fountain waters of
the Iron Quadrangle, Minas Gerais, Brazil using ICP-MS
and statistical data analysis
C. A. Ferreira1*, 1H. E. L. Palmieri, 1M. A. B. C. Menezes
1
Centro de Desenvolvimento da Tecnologia Nuclear/Comissão Nacional de Energia Nuclear,
CDTN/CNEN
*Pós-graduação em Ciência e Tecnologia das Radiações, Minerais e Materiais
Av. Presidente Antônio Carlos, 6627 Campus UFMG, CEP 31.270-97, Belo Horizonte, MG, Brazil
E-mail: help@cdtn.br
Inorganic and rare earths elements (REE) were determined in 34 fountain waters collected in
different towns of the Iron Quadrangle (IQ), Minas Gerais, Brazil. The IQ is one of the
largest and most well-known mineral deposits in the world. Not only extensive iron deposits
but also hydrothermal gold deposits are found in this region. Because of the toxicological
properties of these elements, monitoring of ground water which is used for drinking water
may be useful if relatively high concentrations are expected. The inorganic (Al, As, Ba, Cu,
Mn, Ni, Rb, Sr, Zn, U) and REE elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
Yb, Lu) were determined by Inductively Coupled Plasma Mass Spectrometry (ICP-MS),
using an ELAN DRCe, PerkinElmer.
Analyses of these fountain water samples showed a broad range in the composition for most
of these elements. In some fountains, elements such Al, Mn, and As presented concentrations
superior to the guideline levels set by Brazilian legislation (Ministry of Health 518- 03/2004)
[1] and World Health Organization, WHO-2008 [2]. The total REE (∑REE) concentrations
in fountain water range from 3 to 33395 ng/L. It was also verified that the concentrations of
high rare-earth elements (LREE) (La, Ce, Pr, Nd and Sm) are greater than those of heavy
rare earth elements (HREE) (Gd, Tb, Dy, Ho, Er and Yb). The obtained patterns of
concentrations of REEs in these samples demonstrated the ODD-Harkins law, in which the
concentrations of even atomic number (Ce, Nd, Sm, Gd, Dy, Er and Yb) are more abundant
than those of odd atomic number (La, Pr, Eu, Tb and Ho).
Multivariate statistical techniques [3] were used to interpret the trace elements data in the
fountain water samples with the intention of determine natural associations between samples
and/or variables, and investigate the temporal evolution of fountain water composition
between the two surveys conducted. The correlation matrix consisted of 24 trace elements
estimated from 68 fountain water samples showed that the ERR elements presented strong
correlation between them and with Al, Mn, Rb and U, concluding that the trace elements in
these fountain waters had similar hydrochemical characteristics in the study area. Cluster
analysis demonstrated that most water samples collected from the same fountain in the study
area during rainy and dry seasons fall into the same group, which can indicate that the
seasonal variability did not affect the fountain water much.
References
[1] Brazilian Ministry of Health Decree -518- 03/2004. Guideline values for drinking water quality.
[2] World Health Organization (WHO). Guidelines for drinking water quality V.1 Recommendations.
Switzerland: Geneva (2008).
[3] Kouping Chen, Jiu J. Jiao, Jianmin Huang, Runqiu Huang, Environmental Pollution 147, 771-780,
(2007)
247
PS3.14
The utilization of nanometer-sized zirconium oxide
for preconcentration and speciation of trace chromium in
waters by solid phase extraction and determination by
electrothermal atomic absorption spectroscopy
L. Okenicová, M. Žemberyová, S. Procházková and R. Halko
Comenius University in Bratislava, Faculty of Natural Sciences, Department of Analytical Chemistry,
Mlynská dolina, Ilkovičova 6, 842 15 Bratislava 4, Slovak Republic
E-mail: zemberyova@fns.uniba.sk
The environmental studies of chromium is inevitably connected with the problem of
speciation, because in its two main oxidation states, Cr(III) and Cr(VI), are
significantly differences in biological, geochemical and toxicological properties.
Cr(III) is considered as indispensable for the metabolism of glucose, lipids and
proteins in living organisms. Cr(VI) as a strong oxidizer is highly toxic and can
affect lungs, liver and kidneys and is also mutagenic, carcinogenic and teratogenic.
The need for highly reliable methods for the determination of trace and ultra-trace
elements has been recognized in analytical chemistry and environmental science.
In the present work a nanometer-sized zirconium oxide (ZrO2) was used as a solidphase extractant for the preconcentration and speciation of trace amounts of Cr(VI)
and Cr(III) prior to its determination by electrothermal atomic absorption
spectrometry (ET AAS). The main factors having influence on the preconcentration
of analytes such as pH of the sample, amount of ZrO2, extraction time, sample
volume, eluent concentration and volume were studied, and the optimal experimental
conditions were established. The optimal conditions for the proposed solid phase
extraction (SPE) (100 mg ZrO2, 30 minutes of extraction time, pH 4.4 for Cr(VI) and
pH 7.6 for Cr(III), NH4OH and HNO3 as eluents) and ET AAS measurement (1500
°C pyrolysis and 2300 °C atomization temperatures) were obtained.
Two modes of the proposed procedures were compared, (1) batch and elution mode
and (2) batch and slurry mode with the direct ZrO2 phase slurry sampling. The
proposed procedures were successfully applied to the determination and speciation of
Cr(VI) and Cr(III) in real water samples and certified reference materials, and
provided satisfactory results.
References
[1] J. Chwastowska, W. Skwara, E. Sterlińska, L. Pszonicki, Speciation of chromium in mineral
waters and salinas by solid-phase extraction and graphite furnace atomic absorption spectrometry,
Talanta, 66, 1345–1349 (2005).
[2] M. J. Marqués, A. Salvador, A. Morales–Rubio, M. De la Guardia, Chromium speciation in liquid
matrices: a survey of the literature, Fresenius J. Anal. Chem., 367, 601–613 (2000).
Acknowledgements
Financial support from the Scientific Grant Agency of the Ministry of Education of the Slovak
Republic VEGA/1/0332/13; VEGA/1/0852/13 and the Slovak Research and Development Agency
APVV-0583-11 is highly acknowledged.
248
PS3.15
Metals, metalloids and ions determination in sizefractionated soils collected in an industrial city of Argentina
Anabella Morales del Mastro1, Marcelo Pereyra2, Agustín Londonio1,3, Victoria
Pereyra1,3, Raúl Jiménez Rebagliati1, Laura Dawidowski1,3, Darío Gómez1,3 and
Patricia Smichowski1,4
1
Comisión Nacional de Energía Atómica. Gerencia Química, Av. Gral. Paz 1499, B1650KNA-San
Martín, Pcia. Buenos Aires, Argentina.
2
INQUISUR (UNS-CONICET). Av. Alem 1253, B8000CPB-Bahía Blanca, Pcia. Buenos Aires,
Argentina.
3
Universidad de San Martín, Instituto de Investigación e Ingeniería Ambiental
4
Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Av. Rivadavia 1917,
C1033AAJ, Buenos Aires, Argentina.
E-mail: smichows@cnea.gov.ar and PatríciaSmichowski@gmail.com
In the city of Bahía Blanca (Argentina), semiarid soils are affected by industrial and
agricultural activities, traffic and increasing urbanization. In this study 16 soil
samples (superficial and sub-superficial) were collected and then sieved in two
fractions (A<37µm, and 37<B<50 µm) for subsequent elemental analysis. Major,
minor and trace elements namely, Al, As, Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Mo, Ni,
Pb, Sb, Ti, V and Zn were determined by inductively coupled plasma optical
emission spectrometry (ICP OES). In addition, Cl-, F-, SO42-, K+, Na+ and NH4+ were
determined by high performance liquid chromatography (HPLC) after an aqueous
extraction.
The study showed that mean elemental concentration ranged from <0.3 µg g-1 (Sb) to
14.6±0.6% (Ca). Ions concentrations in the soluble fraction measured at mg g-1 levels
were in the order Cl- > Na+  SO42- > K+ > NO3-. Three indicators, namely, (i)
coefficient of variation, (ii) coefficient of divergence and (iii) ratio of elemental
concentration with respect to Ca were used to assess chemical, spatial and interprofile variability. Chloride > Ca > Na + > Mo > SO42-, dominated the variability
indicating that these are key chemical markers for future assessment of airborne
particles in the area.
The chemical profiles of topsoil obtained in this study will be used to study soil
resuspension as a source of airborne particulate matter in a forthcoming receptor
model analysis.
249
PS3.16
Bismuth preconcentration and determination by FI-HGAAS involving an on-line solid phase extraction system and
L-proline immobilized on carbon nanotubes
B. Parodi1,2, A. Londonio2,3, G. Polla4, P. Smichowski3,5
1
Instituto Nacional de Tecnología Industrial, Centro de Investigación y Desarrollo en Mecánica, Av.
General Paz 5445, B1650KNA-San Martín, Buenos Aires, Argentina.
2
Instituto de Investigación e Ingeniería Ambiental (3iA), Universidad de San Martín, Campus
Miguelete, Martín de Irigoyen 3100, 1650-San Martín, Buenos Aires, Argentina.
3
Comisión Nacional de Energía Atómica. Gerencia Química, Av. Gral Paz 1499, B1650KNA-San
Martín, Buenos Aires, Argentina.
4
Comisión Nacional de Energía Atómica. Gerencia Investigación y Aplicaciones, Av. Gral Paz 1499,
B1650KNA-San Martín, Buenos Aires, Argentina.
5
Consejo Nacional de Investigaciones Científicas y Técnicas, Av. Rivadavia 1917, C1033AAJBuenos Aires, Argentina.
E-mail: smichows@cnea.gov.a and Patricia.Smichowski@gmail.com
A study was undertaken to ascertain the analytical capabilities of functionalized
multiwalled carbon nanotubes with L-proline (pro-MWCNTs) for the reliable
preconcentration and determination of Bi(III) in different kind of waters using an online flow injection hydride generation atomic absorption spectrometry (FI-HG-AAS)
system [1].
The preconcentration was carried out on a micro-column filled with functionalized
pro-MWCNTs and a low molecular weight polyethylene to avoid carbon
nanoparticles aggregation. The optimization was performed by using a full factorial
design. The factors related to the optimization process were the concentration of
eluent (HCl) and pH of the sample. The dimensions of the column were carefully
studied. Under optimal conditions, the adsorption capacity of the substrate was found
to be 0.1 mg g-1 reaching a preconcentration factor (PF) of 160. A detection limit
(3σ) of 0.7 ng L-1 was reached using only 3.0 mg of substrate. Interferences affecting
Bi(III) signal were also studied. Precision, expressed as relative standard deviation
(RSD) turned to be 1.5 % at the 0.1 µg L-1 level (n=10). Accuracy test for the entire
analytical procedure was performed by means of the Standard Reference Material
(SRM) NIST 1643e (Trace elements in water) and results were in good agreement
with the certified values.
The developed method was applied to the quantitative determination of Bi(III) in
different kind of waters including tap, sea, well, river, thermal waters as well as mine
effluents and waters from Antarctic.
References
[1] B. Parodi, A. Londonio, G. Polla, P. Smichowski, Microchemical Journal, 122,
70-75 (2015).
250
PS3.17
UHPLC-(+) APCI-MS/MS Determination of oxygenated
and nitrated polycyclic aromatic hydrocarbons in airborne
particulate matter and tree barks collected
in Buenos Aires city
F. Fujiwara1,2, M. Guiñez1, P. Smichowski2,3 and S. Soledad Cerutti1,2
1,2
Universidad Nacional de San Luis, Instituto de Química, CCT San Luis-Argentina
2
Consejo Nacional de Investigaciones Científicas y Técnicas, Argentina
3
Comisión Nacional de Energía Atómica, Gerencia Química, Argentina
E-mail: smichows@cnea.gov.ar and Patricia.Smichowski@gmail,com
The content of two oxygenated and two nitrated polycyclic aromatic hydrocarbons
namely, OPAHs and NPAHs in two relevant environmental matrices such as
airborne particulate matter (PM2.5 and PM10), and tree barks was assessed. Four key
pollutants were measured: (i) 1-nitropyrene (1-NPYR), (ii) 9-nitroanthracene (9NANTH), (iii) 2-fluorenecarboxaldehyde (2-FLUCHO), and (iv) 5,12naphthacenequinone (5,12-NAPTH-ONA) [1].
For PM2.5 and PM10 collection different approaches were followed using different
type of filters and sample collectors. Samples of PM2.5 were collected on glass fiber
filters during one month with a low volume collector. For PM10, both glass fiber and
quartz filters were used and samples were collected simultaneously for one week
using a high volume sampler. In addition, five bark samples of Tipa sp. (a typical
tree from the city of Buenos Aires, Argentina) were collected at the same sites.
The technique selected for PAHs derivatives quantification was Ultra high
performance liquid chromatography–atmospheric pressure chemical ionization
tandem mass spectrometry (UHPLC–APCI-MS/MS). Data acquisition under MS/MS
was achieved by applying multiple reaction monitoring (MRM) to provide a high
degree of sensitivity and specificity. Chromatographic separation was performed on a
rapid resolution column using a gradient mode with a total run time of 5.0 minutes.
The results of the study showed that in tree barks only OPAHs were found at
concentrations varying from 0.18 µg g-1 to 0.72 µg g-1. Meanwhile, in airborne
particles matters, the four derivatives PAHs were detected at concentrations ranging
from 0.01 ng m-3 to 24.76 ng m-3.
References
[1] F. Fujiwarea, M. Guiñez, S. Cerutti, P. Smichowski, Microchemical Journal,
116, 118-124 (2014).
251
PS3.18
Supramolecular assembly microextraction of Sudan blue II
in environmental samples prior to its spectrophotometric
determination
SevtapYiğita, Mustafa Tuzena, Mustafa Soylakb, Mehmet Doganc
a
Gaziosmanpasa University, Faculty of Science and Arts, Chemistry Department,
60250 Tokat, Turkey
b
Erciyes University, Faculty of Sciences, Department of Chemistry,38039 Kayseri,
Turkey
c
Hacettepe University, Faculty of Sciences, Department of Chemistry, Ankara,
Turkey
The carcinogenic effect of Sudan dyes is known by various researchers (1, 2). So,
determination of Sudan blue II in environmental samples is very important for
human health. In this study, liquid phase microextraction method based conformation
of supramolecular assembly was developed for the separation and preconcentration
of trace levels of Sudan blue II dye. Various analytical parameters such as pH,
supramolecular solvent type and volume, sample volume and matrix effect etc. were
optimized. The Sudan blue (II) concentration in the extraction phase were
determined by Uv-visible spectrophotometer. Under the optimized conditions,
detection limit and preconcentration factor was found as 0.69 µg L-1 and 250,
respectively. Relative standard deviation value was found to be lower than 10%. The
developed procedure was successfully applied for the determination of trace levels of
Sudan blue II in candy, cosmetic product, ink, waxes and industrial waste water
samples.
Keywords: Microextraction, spectrophotometry, Sudan blue II, environmental
samples.
References
1. Rebane, R., Leito, I., Yurchenko, S., &Herodes, K. (2010) J. Chromatogr. A
1217, 2747-2757.
2. Stiborova, M., Martinek, V., &Rydlova, H. (2002) Cancer Res. 62, 56785684.
252
PS3.19*
Solid phase extraction of mercury from natural waters on
copper particles
N. Panichev, M.M. Kalumba, K.L. Mandiwana
Department of Chemistry, Tshwane University of Technology, P.O. Box 56208, Arcadia 0007,
Pretoria, South Africa
E–mail: panichevn@tut.ac.za
Solid phase extraction of mercury (Hg) from natural waters, based on the treatment
of samples with elemental copper (Cu) particles has been investigated. Elemental Cu
is capable to collect both elemental Hg0 and ionic Hg2+ forms of mercury from
aqueous solutions by reducing of Hg2+ ions to elemental mercury Hg0, followed by
collection of all Hg0 by amalgamation on the surface of Cu particles. The
determination of Hg was carried out with Zeeman atomic absorption mercury
analyzer RA-915+ (Lumex, Saint Petersburg, Russia) after thermal desorption of Hg
from that concentrate.
The LOD (3s criteria) of Hg determination was found to be 0.4 ng (absolute mass) or
4 ng L1 for 100 mL of sample solution. The accuracy of Hg determination was
confirmed through the analysis of NRCORMS-3 with good agreement between
found (12.5 ± 2.0 pg L–1) and certified (12.6 ± 1.1 pg L–1) values. The double
function of Cu as a reducing agent for Hg2+ ions and adsorbent for Hg0 by
amalgamation is offering a simple and very efficient method of Hg collection from
natural water samples.
* Poster not presented
253
PS3.20
Thallium determination in contaminated water and
biological samples: a population-based case–control study
in Valdicastello Carducci and Pietrasanta (Lucca, Italy).
E. Bramanti1, M. Onor1, B. Campanella1,2, A. D’Ulivo1, S. Biagi1, G. Rossi3, O.
Curzio3, R. Giannecchini4, M. D’Orazio4, R. Petrini4
1
2
C.N.R Institute of Chemistry of Organometallic Compounds, UOS of Pisa, via Moruzzi 1, 56124
Pisa, Italy
University of Pisa, Department of Chemistry and Industrial Chemistry, via Moruzzi 3, 56124 Pisa,
Italy
3
C.N.R Istittuto di Fisiologia Clinica, via Moruzzi 1, 56124 Pisa, Italy
4
University of Pisa, Department of Earth Sciences, via S. Maria, 56127 Pisa, Italy
Water-soluble thallium (Tl) compounds are highly toxic for most living organisms.
Tl toxicity to mammals is higher than that of Hg(II), Cd(II) and Pb(II), because it
chemically behaves as a heavy metal and because, due to its charge and size, it is an
analogous of potassium. Thus, it has been notified as an important EPA priority
pollutant. Thallium maximum contaminant level (MCL) in drinking water defined by
EPA is 2 µg/L and 0.1 μg/L in China (CNS 2006) [1].
A recent study showed the presence of Tl at high concentrations (up to 9000 μg/L) in
groundwater near Valdicastello Carducci (Italy). The contamination is supposedly
due to acid drainage from abandoned mining areas. In September 2014 Tl
contamination was also found in water intended for human consumption distributed
in the same area.
We report here the preliminary results of a non-invasive population-based study that
aimed to quantify the Tl levels in about 100 urine and 330 hair samples from the
population of Valdicastello Carducci and Pietrasanta, Italy. Several saliva samples
were also collected in order to explore this matrix as exposure indicator. All samples
were analyzed by ICP-MS. Quality assurance of the results was guaranteed analyzing
two certified reference material (water and urine from NIST).
Tl values found in urine and hair samples were correlated with Tl concentration
levels found in tap water in the living area of each citizen and with his/her habits (use
of tap water both to drink and to cook or only to cook). The kinetics of decay of Tl
concentration in urine samples was also investigated. About 50% of samples had a
Tl concentration value above 0,5 microgram/L; about 70% of hair samples had a Tl
concentration > 10 ng/g (2 1 ng/g is the value of not exposed people). The high
values of thallium found in hair samples suggest a long-term exposure.
References
[1] Agency, U.S.E.P., TOXICOLOGICAL REVIEW OF THALLIUM AND COMPOUNDS (CAS
No. 7440-28-0). EPA/635/R-08/001F http://www.epa.gov/iris 2009.
254
PS3.21
Spectrophotometric determination of uranium after ionic
liquid based dispersive liquid liquid microextraction
Esra Bağda1, Mustafa Tuzen2
1
2
Faculty of Pharmacy, Cumhuriyet University, 58140 Sivas, Turkey
Faculty of Science and Arts, Chemistry Department, Gaziosmanpasa University, 60250 Tokat,
Turkey
Uranium is known as slightly radioactive and toxic as its natural state, so it gets
special interest [1, 2]. According to World Health Organization, the maximum
uranium in drinking water should not exceed 15 µg L-1 [3]. Because of these stringent
limits, development of simple and easily applicable analytical techniques is
important.
In the present study, a simple extraction and spectrophotometric determination of
trace amount of uranium was described. The method based on complex formation
between uranium and a chromagenic reagent, 4-(2-Thiazolylazo)resorcinol (TAR),
and preconcentration of formed complex into a room temperature ionic liquid
(RTIL), 1-Methyl-3-octylimidazolium hexafluorophosphate ionic liquid. After
optimization studies, the analytical characteristics of the method are investigated.
Under optimum conditions, the method was linear in the range of 7.14-1429 µg L-1,
and 3Sb/m value was calculated as 0.26 µg L-1. The method was applied to different
type of water samples. Satisfactory recovery results were obtained.
References
[1] Biswas S, Pathak PN, Roy SB, Spectrochim Acta A, 91, 222-227 (2012).
[2] Jauberty L, Drogat N, Decossas JL, Delpech V, Gloaguen V, Sol V, Talanta, 115, 751-754 (2013).
[3] Dadfarnia S, Shabani AMH, Shakerian F, Esfahani GS, J Hazard Mater 263:670-676 (2013).
255
PS3.22
Determination of zirconium with 2-(5-Bromo-2-pyridylazo)5-(diethylamino) phenol in water, artificial saliva and
dental materials after ionic liquid based microextraction
Esra Bağda1, Mustafa Tuzen2
1
2
Faculty of Pharmacy, Cumhuriyet University, 58140 Sivas, Turkey
Faculty of Science and Arts, Chemistry Department, Gaziosmanpasa University, 60250 Tokat,
Turkey
Extraction techniques are generally unavoidable steps in sample preparation studies.
Conventional liquid liquid extraction, cloud point extraction, liquid liquid
microextraction, solid phase extractions are some examples of extraction techniques.
Among these technique, ionic based microextraction techniques are relatively newest
and "green" extraction techniques with high enrichment factors.
Zirconium is a widely used element [1-3]. Especially, zirconium oxide is employed
in dental materials due to their bio-inert, non-absorbable, biocompatible
characteristics [4]. There are several sophisticated instruments for the determination
of zirconium, but UV-vis. spectroscopy is may be the simplest one.
In the present study, new spectrophotometric method for determination of zirconium
was described. The method is based on the formation of zirconium-Br PADAP
complex, and extraction of Zr-Br PADAP complex into ionic liquid, 1-Hexyl-3methylimidazolium hexafluorophosphate [C6MIM][PF6]. The experimental
parameters were optimized and analytical figures of merit were obtained. The
method was linear in the range of 1.4-714 µg L-1 with a correlation coefficient of
0.99. The LOD value of 3Sb/m was achieved as 0.012 µg L-1 . The method was
successfully applied to zirconium based dental materials, artificial saliva and water
samples.
References
[1] A.S. Al-Kady , Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 97 (2012)
284–289
[2] A.S. Amin, Journal of Taibah University for Science 9 (2014) 227-236.
[3] J.B. Ghasemi, E. Zolfonoun , Talanta 80 (2010) 1191–1197.
[4] V. Sollazzo, F. Pezzetti, A. Scarano, A. Piattelli, C.A. Bignozzi, L. Massari, G. Brunelli, F.
Carinci, Dental Materials 24, 357–361 (2008).
256
PS3.23
Bechar 002 ordinary chondrite: a textural and
chemicalmineralogical study
R. Campanero1, R. Lunar1,2 and J. Martínez-Frías1,2
1
UCM, Madrid (Spain), 2 CSIC, Madrid (Spain)
E-mail: j.m.frias@igeo.ucm-csic.es
Chondrites represent the most primitive meteoritic matter in the solar system. Their
study provides essential mineralogical and cosmochemical keys to understand: a) the
processes that occurred in the early stages of its formation and b) their role and
significance influencing the composition of the surfaces of other planets and moons.
Bechar 001 and 002 correspond to two large (39 kg and 12 kg, plus a number of
numerous fragments) meteorite “finds” from Algeria (30º 50’ N, 3º 20’ W). They are
classified as L5 and H6 chondrites, respectively [1]. Further information about
institutions and meteorite collections hosting the specimens can be found in the
Meteoritical Bulletin database [2] (e.g. Bechar 002, 150 g, Natural History Museum)
[3].
This works presents a detailed study focused on the textural and
chemicalmineralogical features of the chondrules and matrix of a meteorite sample
(65x43x26 mm) classified as Bechar 002, which belongs to the meteorite collection
of the CSIC research group of meteorites and planetary geosciences [4,5]. This study
comprises the multi-analytical characterization of Bechar 002 by using transmitted
and reflected light microscopy, XRD, XRF, SEM-EDX and electron microprobe.
The results obtained provide: 1) an estimation of the chondrules/matrix (3:1) and
silicates/metal (6:1) ratios; 2) the primary compositional make-up of this ordinary
chondrite (olivine, Fa17.1 - Fa17.9), (Ca-rich, En48.1-48.4 - Fs4.6-4.7 and Ca-poor
pyroxenes, En82.6-84 - Fs14.8-16.5), albite, kamacite, taenite, troilite and native copper; 3)
their textural relationships; 4) the weathering (terrestrial alteration) degree (W2-W3)
of the meteorite [6] and 5) the identification and analysis of the secondary processes
(thermal metamorphism), which occurred after its formation in the asteroidal parent
body.
References
[1] Grossman. Meteoritics & Planetary Science, 34, A169-A186, 1999.
[2] http://www.lpi.usra.edu/meteor/metbull.php?code=4989.
[3] Grady. Catalogue of Meteorites, Natural History Museum, 5 th ed. 2000.
[4] Campanero. Master thesis, Universidad Complutense de Madrid, 2014.
[5] Campanero et al. Geogaceta (in press), 2015.
[6] Wlotzka, F. (1993). Meteoritics 28, 460-460.
257
PS3.24
Cost-effective and rapid digestion method for sediment and
soil sample analysis
S. Harangi1, K. Hubay2, B. Tóthmérész3, E. Simon1, M. Braun2
1
University of Debrecen, Department of Ecology Egyetem tér 1., H-4032 Debrecen, Hungary
Institute of Nuclear Research of the Hungarian Academy of Sciences, Hertelendi Laboratory of
Environmental Studies, 4026 Debrecen, Bem tér 18/C
3
MTA-DE Biodiversity and Ecosystem Services Research Group P.O. Box 71, H-4010 Debrecen
Hungary
2
E-mail: harangi.sandor@science.unideb.hu
Sediments of lakes and ponds indicate the environmental and climatic changes in the
aquatic ecosystem. Chemical analysis provides important information about the
chemical composition of the sediments. The aim of our study was to develop a
simple and cost effective sample pre-treatment method to study the effects of
anthropogenic activity on the ecosystem based sediment samples. We developed the
following method; sediments were ashed at 550°C and the residue samples were used
for the inorganic components of analysis. The complete digestion method was
carried out in disposable polypropylene (PP) tubes. 50 mg fine powdered ash was
digested with 1 cm3 37% (m/m) HCl and 1 cm3 38% (m/m) HF in a dry oven at 105
o
C for 2 hour. After cooling, 8 cm3 boric acid 4% (m/m) were added to the samples.
The following standard reference materials were digested to validate the method:
BCR 141 (chalky clay), BCR 142 (sandy soil), BCR 143 (sewage-sludge), and BCR
176 (waste destructor ash). Elemental analysis was carried out by Microwave Plasma
Atomic Emission Spectrometry (MP-AES 4100, Agilent Technologies) and ICPOES method (Thermo Iris Intrepid II XSP Duo, Thermo). Concentration of Al, Ca,
Fe, K, Mg and Ti were measured using different emission lines, respectively. In the
case of MP-AES analysis significant differences were not found between expected
and measured concentration of all elements, expect Ti. Similar results were found in
the ICP-OES analysis but significant difference was found in the Fe concentration
between expected and measured values. Using Pearson correlation significantly
positive correlation was found between the element concentration between MP-AES
and ICP-OES analysis. Our results demonstrated that the plasma of MP-AES was
resistant to the sample matrix which was contained 0.2% boric acid. Thus, the
complex matrix did not cause interferences during the elemental analysis. In
summary, our study demonstrated that the developed pre-treatment method is a
useful and cost-effective technique for routine analysis of sediment and soil samples.
258
PS3.25
Assessment of contamination level of oxbows based on core
sediments in the Upper Tisza Region, Hungary
Zs. Balogh1, S. Harangi1, B. Tóthmérész2, E. Simon1
1
2
Department of Ecology, University of Debrecen, Debrecen, P. O. Box 71, H-4010 Hungary
MTA-DE Biodiversity and Ecosystem Services Research Group, Debrecen, P. O. Box 71, H4010 Hungary
E-mail: balogh.zsuzsanna.08@gmail.com
Many organic and inorganic contaminants can accumulate in the sediment, so the
sediment is useful to study the contamination level of aquatic environment. The
study of contamination level of oxbows is an important subject from conservation
aspect of wetlands. The aim of our study was to analyses the toxic element
concentrations in sediment cores to assess the contamination level in the Upper Tisza
region, in Hungary. Protected (Foltos-kerti-Holt-Tisza), fishing (Vargaszegi-HoltTisza, Szabolcsi-, Tuzséri-Holt-Tisza) and sewage contaminated oxbow (Tímári
Morotva-tó) were studied. The following elements were measured with MP-AES in
sediment cores: Cu, Cr, Ba, Fe, Mn, Pb, Sr and Zn.
Based on the toxic element concentrations of sediment the studied fishing, sewage
contaminated and protected oxbow were entirely separated from each other using
canonical discriminant analysis (CDA). The sediment enrichment of toxic elements
in core sediments was evaluated using the pollution index (PI). The scores of
pollution index indicate that the core sediments all of the measured oxbows were low
level contamination for Ba and Cr. The contamination level of Sr was low in the
protected oxbow and two fishing oxbows, while in the case of one of fishing oxbows
(Szabolcsi-Holt-Tisza) and sewage contaminated oxbow moderate level of
contamination was found for the Sr. The contamination level of Cu was high in the
protected and fishing oxbows and moderate level of contamination was found in the
sewage contaminated oxbow. In case of Zn the contamination level was high in two
fishing oxbows. Moderate level of contamination was found in protected, fishing
(Vargaszegi oxbow) and sewage contaminated oxbow for Zn. Based on the Mn and
Fe contamination level all oxbows were characterized with moderate level of
contamination. The contamination level of Pb was high in the studied oxbows,
except the protected oxbow which was moderately contaminated.
Our findings demonstrated that the effects of anthropogenic activities are caused
markedly differences in the contamination level of oxbows based on sediment cores.
Our result demonstrated that the sediment is a useful tool to assess the effects of
anthropogenic activities on toxic element concentrations of oxbows.
259
PS3.26
Characterization of an innovative waste-derived fertilizer
by hyperspectral imaging
Serranti S., Trella A., Bonifazi G., Santarelli M., Tirillò J. and Valente M.
Department of Chemical Engineering, Materials & Environment, Sapienza University of Rome,
Rome (Italy)
e-mail: silvia.serranti@uniroma1.it
This work was carried out in the framework of the LIFE RESAFE Project (LIFE12
ENV/IT/000356) “Innovative fertilizer from urban waste, bio-char and farm residues
as substitute of chemical fertilizers”. The main objective of RESAFE project is the
production of a waste-derived fertilizer for agricultural activities in order to reduce
the use of chemical fertilizers ensuring a low environmental impact, improving at the
same time the soil health, this latter effect due to a greater availability of nitrogen for
plants. Furthermore the proposed approach produces economic benefits associated to
the recovery of organic materials.
The main aim of the study was to demonstrate the use of hyperspectral imaging as a
fast and non-destructive technique for the waste-derived fertilizer characterization
during all the steps of the production process.
HSI is a multi-parametric analytical technique, rapidly growing in recent years, that
can be profitably utilized for the characterization and analysis of different materials.
It combines spectroscopy and image analysis. For these characteristics it allows the
characterization of sample spectral (i.e. spectroscopic component) and surface
properties (i.e. imaging component) producing for each pixel of the acquired image a
full spectrum constituted by all the wavelengths belonging to the investigated
spectral range (UV–Visible, NIR or IR) [1].
Innovative Italian and Spanish waste-derived fertilizers samples, composed by
different mixtures of UOW (Urban Organic Waste), FOR (Farm Organic Residues),
BC (Biochar) and VAP (Vegetable Active Principles), were collected and acquired
by hyperspectral imaging (HSI) in the near infrared wavelength range (1000-1700
nm), at different curing times until the end of the production process. Classical
physical-chemical analyses were carried out on the same samples.
Hyperspectral data were analyzed adopting chemometric strategies through the
application of Principal Component Analysis (PCA) for exploratory purposes and
Partial Least Squares Analysis (PLS) to build the models for correlation with the
measured physical-chemical parameters in both the Spanish and Italian samples.
References
[1] A. Del Fiore, M. Reverberi, A. Ricelli, F. Pinzari, S. Serranti, A.A. Fabbri, G. Bonifazi, C. Fanelli,
International Journal of Food Microbiology, 144, 64-71 (2010).
260
PS3.27
Determination of Pb2+ in water samples by ultrasound
assisted dispersive liquid-liquid microextraction based on
solidification of floating organic droplet combined with
flame atomic absorption spectrometry
Ç. Arpa Şahin, I. Arıdaşır and S. Bektaş
Hacettepe University, Chemistry Department, 06800, Beytepe, Ankara, Turkey
E-mail:carpa@hacettepe.edu.tr
In this study a simple and inexpensive ultrasound assisted solidified floating organic
drop microextraction (USA-SFODME) method has been reported for the
preconcentration of lead prior to its flame atomic absorption spectrophotometric
determination. The method is based on the formation of neutral complex between the
Pb(II) and Congo Red followed by its extraction into 1-dodecanol and the
measurement of amount of Pb(II) by flame atomic absorption spectrophotometer [1].
Several factors affecting the microextraction efficiency, such as type of extraction
solvent, pH, complexing agent concentration, ultrasound extraction time, sample
volume and equilibration temperature were investigated and optimized. Under
optimized conditions, the preconcentration factor and the enrichment factor were
obtained. The values for limit of detection (3s), the limit of quantification (10s) and
the relative standard deviation (RSD) for 10 replicate measurements were calculated.
The proposed method was successfully applied to the determination of lead in
certified reference material and different water samples.
References
[1] I. Durukan, M. Soylak, M. Doğan, Atomic Spectroscopy, 34(1), 20-25 (2013)
261
PS3.28
Determination of essential elements and inorganic
contaminants in the water and sediment of Mangue Seco
Bay, Bahia, Brazil
C. F. Gromboni1, A. F. Sousa1 and J. P. D. C. de Matos1
1
Instituto Federal de Ciência, Educação e Tecnologia da Bahia, IFBA - Campus Valença. Valença,
Bahia – Brazil.
E-mail: cfgromboni@gmail.com
Located in the city of Jandaíra, the community of Mangue Seco is one of the 32
protected areas in Bahia, situated in a sandy area that goes to the ocean from the
south margin of Real’s River estuary, extreme north of Bahia, in the border with
Sergipe. Mague Seco’s natural characteristics range from the sandbanks, with its
long strings of dunes (about of 40% of total area); the mangrove, constantly buried
by dunes; remnants of Atlantic Forest; coconut trees and small ponds. Due to this
group of beaches, estuaries, mangroves, sandbanks, forests, dunes and wetlands,
there are many species of fish, shellfish and migratory birds. This research aims to
determine essential elements and inorganic contaminants (Na, K, Mg, Ca, P, Al, V,
B, Fe, Mn, Cu, Zn, Si, Cr, As, Cd e Pb) in water samples and sediments in the region.
We collected water and sediments in 12 different places, eight in the Real River and
four on the coast. The water samples were acidified with 1% HNO3 and sediment's
samples were decomposed with HNO3 and H2O2 (30% v.v-1) using methodology
described by the Environmental Protection Agency [1]. The quantification of
chemical elements were accomplished by using optical emission spectrometry with
inductively coupled plasma (ICP OES) with axial configuration, selecting the
wavelengths that had higher intensity and lower spectral noise values, using robust
conditions. It was also evaluated the use of yttrium as internal standard. The results
were compared to reference values fixed by the National Environmental Council
(CONAMA), resolution No. 357/2005 relating to water and resolution No. 454/2012
relating to the sediments. The results indicated high aluminum concentrations at all
points, especially in sample 8, which is about 13 times higher than the limit
established in the resolution of CONAMA (0.1 mg.L-1). High concentrations of this
metal may reduce ovulation of fish species. The Cd and Pb contents were below the
detection limits of the equipment in all samples analyzed. Cr levels are within the
limits established by law (0.050 mg.L-1). Despite being an essential element, Fe
concentrations are above the values fixed in legislation (minimum content: 0.592
mg.L-1 - maximum content: 11.335 mg.L-1) except in sample 8, which is usually the
place with lower concentration of metals, but with a high concentration of aluminum.
Although the levels found in the sediments were normally higher than in the water,
they are according to the resolution of CONAMA, not exceeding the amounts
allowed in the 12 samples collected.
References
[1] EPA – United States Environmental Protection Agency. Technical Resource Document,
EPA/3050B-1, 12p, (1996).
Acknowledgements: FAPESB and IFBA
262
PS3.29
Trace mercury speciation in specific Antarctic soils
O. Zvěřina1,2, R. Červenka1,3, J. Šimůnek2, P. Coufalík1,4, J. Kuta3, J. Komárek1
1
Department of Chemistry, Faculty of Science, Masaryk University, Kotlářská 2, 61137,
Brno, Czech Republic
2
Department of Public Health, Faculty of Medicine, Masaryk University, Kamenice 5, 625 00
3
Research Centre for Toxic Compounds in the Environment (RECETOX), Faculty of Science,
Masaryk University, Kamenice 753/5, 62500, Brno, Czech Republic
4
Institute of Analytical Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Veveří 97, 602 00
E-mail: 175365@mail.muni.cz
Antarctica is isolated from the input of lower latitude contaminants by natural
barriers. Thanks to this fact, the anthropogenic impact is limited mainly to the
vicinity of scientific stations. Specific conditions provide a unique opportunity to
study mercury cycling in this ecosystem. Due to ultra-trace mercury concentration,
speciation analysis presents a challenge for analytical chemistry. This work follows
the recent research of mercury occurrence in ecosystems of James Ross Island (JRI),
Antarctica. Previously conducted research revealed many specifics of mercury
distribution and speciation in soils, sediments and lichens in JRI area.
Here, particular focus is placed on the unusual but locally-important source of
mercury in the Antarctic soils from decaying carcasses of seals. More than 400 seal
mummies and skeletons are mapped in the northern part of JRI. Decomposing bodies
represent a rare source of organic matter with associated elements to the soil. Owing
to a high trophic position, the seals are known to contain significant mercury levels.
The contents of mercury in underlying soils were found to be several times higher
than the background levels. HPLC-ICP-MS technique with isotopically labeled
standards was used for the determination of methylmercury in the soils. Moreover,
the methylation potential of associated molds was investigated. The isolated fungal
strains from the seals' carcasses were incubated in the atmosphere enriched with
mercury vapour. It was investigated if methylmercury formed during fungal growth.
This work assessed seals' carcasses as source of mercury, methylmercury and a
promotors of further mercury methylation.
Acknowledgement
The authors are grateful to Czech Polar project for providing of the infrastructure
(Johann Gregor Mendel Station) and for financial support from the Grant Agency of
the Czech Republic, project P503/12/0682 and the Masaryk University in Brno
project MUNI/A/1461/2014.
263
PS3.30
Combined X-ray microanalytical study of metal uptake
capability of argillaceous rocks
J. Osán1, A. Kéri1, M. Fábián1, F. Gergely1, R. Dähn2, S. Török1
1
2
Hungary
Laboratory for Waste Management, Paul Scherrer Institute (PSI), 5232 Villigen PSI, Switzerland
E-mail: szabina.torok@energia.mta.hu
Argillaceous rock formations, due to their high clay content and low permeability,
have significant radionuclide retention/retardation capacities, thus they are in the
focus of high level and long lived nuclear waste (HLW) repositories of several
countries. In Hungary, two geological sites (Gorica Block and Boda Block) of the
Boda Claystone Formation (BCF) have been selected for the study of potential host
rocks for HLW. The aim of the measurements was to obtain information on the
uptake mechanism of Ni(II), Nd(III) and U(VI) on the micrometer scale, in order to
complete molecular scale sorption results, to understand the behaviour of
radionuclides dissolving from HLW and to identify the possible differences in uptake
capacity between the two possible sites.
Synchrotron radiation microscopic X-ray fluorescence (SR µ-XRF) has sufficient
sensitivity to study the metal uptake on the microscale. SR µ-XRF measurements
with micrometer spatial resolution were performed on thin sections subjected to
uptake experiments involving Ni(II), Nd(III) and U(VI). The thin sections were
prepared on high-purity silicon wafers from geochemically characterized cores of
BCF. In addition, scanning electron microscopy energy dispersive X-ray analysis
(SEM/EDX) was performed on identical sample areas in order to obtain quantitative
information on the rock-forming light elements (e.g. Na, Mg). Correlation analysis of
µ-XRF and SEM/EDX elemental maps indicated that the U and Nd enrichment was
not only correlated to the argillaceous matrix, but cavity filling minerals also played
an important role in the uptake. Applying positive matrix factorization on the
combined SR µ-XRF and SEM/EDX data set, factors with higher metal ion
concentration could be identified. The uptake capacity of the different mineral phases
(argillaceous matrix, fracture-infilling carbonates) could be quantified with
additional mineralogical information. The results were compared with cluster
analysis when regions dominated by different mineral phases were segmented. The
multivariate approach for the identification of minerals responsible for metal uptake
was finally verified by microscopic X-ray diffraction.
Our results revealed a difference in U(VI) retention in samples originating from the
mineralogically different Gorica Block and Boda Block. Mainly clay minerals were
found to be responsible for U(VI) uptake in both samples, while around 20% of
uranium was bound to the ankerite-rich phase in the sample from Boda Block.
264
PS3.31
Correction of X-ray pleochroism in micro-XANES studies
of Fe oxidation state in amphibole crystals
Á. Szabó1,2, J. Osán1, D. Breitner1, C. Szabó2, M. Borchert3, K. Appel4
1
2
Hungary
Lithosphere Fluid Research Lab, Institute of Geography and Earth Sciences, Eötvös University,
Pázmány Péter stny. 1/c, H-1117 Budapest, Hungary
3
HASYLAB at DESY, Notkestr. 85, D-22607 Hamburg, Germany
4
European XFEL, Hamburg, Germany
E-mail: janos.osan@energia.mta.hu
Studying Fe bearing minerals is the easiest way to gain information on oxidation
state of the Earth’s mantle. Amphiboles are present in the mantle only in special
cases as a product of metasomatism, i.e. interaction of fluid and/or melt and mantle
rock. This interaction can result in varied and inhomogeneous oxidation conditions in
the mantle on a small scale. Microscopic X-ray absorption near-edge structure
(micro-XANES) is a promising method to determine Fe3+/ΣFe ratio in individual
microscopic amphibole grains. However, the Fe K-edge micro-XANES spectra of
amphiboles are orientation dependent because of the X-ray pleochroism.
In order to study this phenomenon, nine differently oriented slices were cut from an
amphibole single crystal with known Fe3+/ΣFe ratio. In total, 18 measurements were
carried out on these slices. Each spectrum was measured with different angle
between the optical axes (X, Y, Z) of the amphibole single crystal and the polarization
vector of the synchrotron beam. That is, the amphibole single crystal was measured
from all possible directions with 18 degrees step size (0, 18, 36, 54, 72, 90 degrees).
The experiments were performed at the micro-fluorescence beamline L (DORIS III,
HASYLAB) using a Si(111) double monochromator and a polycapillary half-lens to
obtain a 15 µm tuneable monochromatic beam. Fe-K XANES spectra were recorded
in fluorescent mode using a silicon drift detector.
XANES spectra clearly show significant differences between variously oriented
slices. The dominant factor determining the shape of the spectra is the angle between
the polarization vector (P) and the X optical axis. Based on this dependence of
energies and intensities of the near-edge structures (pre-edge peak, main edge, white
line), a correction procedure was developed for the determination of the iron
oxidation state in randomly oriented amphibole crystals. The correction of X-ray
pleochroism made the determination of Fe3+/ΣFe ratio within a 10% error.
Micro-XANES method with the correction procedure was applied to study
amphiboles of mantle xenoliths from Persani Mt., Romania. The results clearly
revealed that the mantle wall rock has low ferric iron content indicating its reductive
environment, whereas the amphibole-bearing veins, occurring in the mantle, show at
least twice higher Fe3+ content. This oxidative environment corresponds to source of
the fluid causing metasomatic alteration, namely formation of amphibole, in the
mantle. Such circumstances are characteristic for, among others, subduction related
geodynamic environment.
265
PS3.32
Chemometric study of SrBr molecule formation for
bromine determination in environmental samples by high
resolution continuum source molecular absorption
spectrometry
P. P. Arcênio1, J. S. A. Silva1 and T. A. Maranhão1
1
Departamento de Química, Universidade Federal de Santa Catarina (UFSC), 88040-900,
Florianópolis-SC, Brasil.
E-mail: patricia.arcenio@gmail.com
Bromine is widely used in industry, participating in process such as fabric
manufacturing, furniture, medicine and electronics. This versatility leads to the
production of large amounts of wastes containing bromine, resulting in
contamination and possibly its accumulation in the environment. Determination of
halogens is reported to be performed through different techniques including ion
chromatography (IC), inductively coupled plasma mass spectrometry (ICP-MS),
capillary electrophoresis (CE), besides others. The greatest difficulty of these
techniques for Br determination is a proper preparation of the samples, which
requires careful treatment due to the volatility of the element [1, 2]. This study aims
to evaluate the formation of the molecule SrBr in the wavelength 666.2985 nm using
KBr and Sr(NO3)2 salts and development of the method for bromine determination
by HR-CS GF MAS technique in environmental samples. Preliminary studies to
evaluate the formation of SrBr molecule in the presence of nitric acid were
performed. These studies showed that the molecule formation is not favored in the
presence of the acid due to the high volatility of bromine. Pd (10μg) was used as
chemical modifier ensuring better condition for the formation of SrBr molecule even
in the presence of acid and the use of W (500 μg) as permanent modifier was
important to increase the life time of the graphite furnace. Optimal pyrolysis
temperature of 1000 °C and vaporization temperature of 2300 °C were obtained for
KBr aqueous solution and certified sample (SRM 1648) in the absence and presence
of acid. Chemometrics studies are not commonly used in studies with molecular
absorption spectrometry, this study aims to find the best relationship between Br and
Sr to ensure that all bromine, whose concentration in the sample is not known, acts as
the limiting reagent with excess strontium. Box Behnken design was performed with
three variables, Sr, Br e HNO3. The results showed that the presence of the acid is
not a significant factor when Pd is used as chemical modifiers and the ratio of
bromine and strontium for the full molecule formation is 1:435 in mass, respectively.
Studies are being conducted to determine Br in environmental samples using slurry
as sample preparation, calibration curve is being established as well as limits of
detection and quantification for the method development.
References
[1] S. Gunduz and S. Akman, Microchemical Journal, 116, 1-6 (2014)
[2] M. R. Flórez and M. Resano, Spectrochimica Acta Part B, 88, 32-39 (2013)
266
PS3.33
Determination of rare earths elements in geological samples
by LIBS
T.A. Labutin, A.M. Popov, S.M. Zaytsev, N.B. Zorov
Lomonosov Moscow State University, Department of chemistry (Russia, Moscow)
E-mail: timurla@laser.chem.msu.ru
Geochemical methods of ore deposits exploration are widely used by geological
surveys and mining companies for all stages of the exploration process. Many
companies provides such operations and spends about 15% of their exploration
budgets for this purposes. The constant interest to the geochemical methods is
provided due to relatively low cost and high reliability of the results. More than 300
ore deposits, including copper-nickel ones, were discovered with the use of
geochemical prospecting. For example, the largest copper-porphyry deposit in Chile
"Escondida" with copper reserves up to 28.0 million tons was discovered with its
use. The introduction of new instruments for discrimination the geological samples
in the field will improve the efficiency of prospecting. Compact systems for rapid
determination of the mineral composition, based on Laser-Induced Breakdown
Spectroscopy (LIBS), provides a unique opportunity to implement the requirements
for routine analysis of geochemical samples: sensitivity of a wide range of elements
below the mean abundance in the earth’s crust, rapid, and low cost technique. Rare
earths elements (REE) are widely used in geology for characterization of minerals
and ore bodies. But there are only few works on REE determination by LIBS due to
significant spectral interferences between them and relatively low content. Therefore,
the evaluation of sensitivity of the REE determination in rocks and soils by the LIBS
is highly beneficial.
This purpose requires improving the analytical capabilities of LIBS to analyze traces
of metals in the geological samples. We estimate the limit of detection of several
REE (cerium, lanthanum, etc) in soils with the use of 3s-criterion. We also estimated
the limitation of LIBS determination of REE due to the spectral interferences with
the use of synthetic spectra which are sensitive to Stark broadening of lines in laser
plasma.
267
PS3.34
Application of microanalytical X-ray fluorescence
instrumentation (µ-XRF) to study multielemental
composition of vegetables grown in agricultural soils
irrigated with reclaimed waste waters
H. Gallardo1, I.Queralt1, E.Marguí2, J.Tapias3, M. Guerra4, M.L.Carvalho4
1
Institute of Earth Sciences Jaume Almera ICTJA-CSIC, Sole Sabarís s/n, 08028 Barcelona, Spain
2
Department of Chemistry, Faculty of Sciences, University of Girona, Campus Montilivi s/n,
17071-Girona, Spain
3
Department of Natural Products, Plant Biology and Soil Science, University of Barcelona,
Joan XXIII 27-31, 08028 Barcelona, Spain
4
Faculty of Sciences and Technology. Universidade Nova de Lisboa, 2829-516 Caparica, Portugal.
E-mail: hgallardo@ictja.csic.es
Reclaimed wastewater coming from treatment plants (TWW) has been increasingly
used as an additional water supply on the best management practices of hydric
resources in water-deficient regions. TWW can be used for different applications
being the irrigation in agriculture one of the most commonly used ones. Despite the
fact that the organic matter and nutrients present in the TWW provide fertilizer
value, giving benefits on the soils and on the crops, the presence of
microcontaminants may hinder a more confident and widespread application.
The aim of the present study is to contribute to the assessment of the effects of TWW
irrigation in elemental composition of crops. In this context, Na, Mg, Al, Si, P, S, Cl,
K, Ca, Mn, Fe, Cu, Zn, Br, Rb and Sr were determined in Raphanus sativus (radish)
and Daucus carota (carrot) specimens grown in experimental plots irrigated with
TWW (from secondary and tertiary treatments) and with tap water (control samples).
Multielemental analysis was performed using benchtop micro X-ray fluorescence
spectrometry systems (µ-XRF) that allow the rapid analysis of vegetation material
without complicated previous sample pre-treatments [1]. The lateral resolution of the
µ-XRF (reaching down to 25 µm) was thought to be small enough to study the
distribution of the aforementioned elements within vegetable sections providing
relevant information not available from standard bulk techniques such as plasma
emission spectrometry and atomic absorption spectroscopy. Additionally, in order to
correlate the fluorescence intensity of an element (from two-dimensional mappings)
and its concentration, a set of several vegetation certified reference materials
prepared in the form of pressed pellets were analysed using the same analytical
conditions used in the analysis of the vegetables grown in agricultural soils irrigated
with reclaimed waste waters.
References
[1] E.Marguí, A.Jurado, G.Pardini, M.Gispert, M.Hidalgo, I.Queralt. Applied Spectroscopy, 63, 13961402 (2009).
268
PS3.35
Structural characterization of Moroccan Cedrus wooden
artifacts dating to 21th, 19th and 16th centuries using FTIR
Spectroscopy and X-Ray Diffraction: a methodological
approach
S. Fellak1, A. Boukir1,*, L. Hajji1, M. L. Carvalho2
1
Laboratory of Apllied Chemistry, Faculty of Sciences and Techniques of Fez, Sidi Mohamed Ben
Abdellah University, B.P. 2202 –Imouzzer road –Fez-Morroco,
2
Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa,
Caparica, Portugal
* Corresponding author: aboukir@gmail.com
In this study, we will provide an overview on chemical and structural changes of four
rare samples of Cedrus dating to 21th, 19th and 16th centuries, and the last one is
taken from a dead fraction of tree. The comparison of these historical wood samples
during its long-term use and storage has been made using FTIR spectroscopy, and XRay Diffraction.
FTIR results suggest that the observed decrease of intensity bands assigned to
different vibrations of lignin and carbohydrates, with appearance of typical bands
due to photoxidation reaction such as quinone (photoxidation of lignin) refer to the
destruction phenomenon that can affect the sample compounds during ageing
process.
X-Ray Diffraction technique was used to define the wooden degradation that was
observed for old samples by decreasing crystallinity index with insignificant changes
in the size of crystallites. Exception to this behavior was observed in some aged
wood. This can be explained considering that partially degraded cellulose is capable
of forming new and larger cristals, or caused by reduction of the cristalline fractions
of wood, and, consequently, to the enrichment of the relative crystalline content. So,
the effect of degradation was less evident on microcrystalline structure.
Wooden artifacts from past civilizations are a large part of Moroccan national
heritage. They are valuable and therefore require careful attention, conservation and
study. So, in order to elucidate both the nature of degradation process, and to develop
a new consolidation and conservation techniques for ancient wooden artifacts, it is
primordial to study the different changes of wood components. Finally, scientists, art
historians and conservators sectors must establish more detailed data record to
evaluate the adequate conditions of archaeological wood in order to protect it from
extinction.
269
PS3.39
Degradation process of Argania Spinosa Moroccan wooden
artifacts by FTIR and X-ray Diffraction
S. Fellak1, A. Boukir1,*, L. Hajji1, M. L. Carvalho2
1
Laboratory of Apllied Chemistry, Faculty of Sciences and Techniques of Fez, Sidi Mohamed Ben
Abdellah University, B.P. 2202 –Imouzzer road –Fez-Morroco,
2
Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa,
Caparica, Portugal
* Corresponding author: aboukir@gmail.com
Analysis of cultural heritage collections of wooden materials has a vital role in a
modern approach to conservation. Scientific investigations and recent advances in
spectroscopic techniques have opened up a window for studies on this universal
heritage.
The integration of elemental and molecular information acquired by FTIR
spectroscopy and X-ray diffraction has allowed the characterization of both chemical
composition of the outside and inner surface of three samples of Argania Spinosa
wooden artifacts aged 2, 400 and 900 years.
In addition, the dead sample has been characterized. During outdoor exposure,
samples can undergo severe changes of its physical, chemical and structural
properties due to the combined effect of sunlight, oxygen, moisture, atmospheric
pollutants and micro-organisms and this must be taken into account.
The information obtained by FTIR spectroscopy on different molecular groups
indicate that the discernible decrease in all stretching bands intensities assigned to
the cellulose, hemicellulose and lignin components especially for the old samples,
means that degradation rate increases proportionally to the samples age during
artificial ageing. In addition, the external samples surface appears more degraded
than the inner samples surface. X-ray diffraction technique confirmed this finding by
a decrease of crystallinity index and this was used to define the damage degree of the
artifact fibers. The additional diffraction peaks refer to extraneous components to the
wood composition, due to the secretion substances by living organisms such as
fungus.
The experimental results proved that the proposed methods may be a very useful tool
for a rapid and accurate estimation of the degradation level of wood exposed to
ageing. This methodology can find application in the field of conservation and
restoration of wooden artifacts.
270
Poster Session 3: Fuels and Biofuels
PS3.36
Heterogeneous catalyst Si/Ki-Fe2O3 on the
transesterification reaction of triacylglicerols in the kernel
oil of the macaúba palm (Acrocomia aculeata) into methyl
esters
A.L. Macedo1, J.D. Fabris2,*, R. S. Santos1, M.C. Pereira3, W.L. Oliveira4, R.M
Coelho4, E.L. Macedo4, M.J.M. Pires4, R. Augusti5, J.D. Ardisson6
1
DSc student of Biofuels at the Federal University of the Jequitinhonha and Mucuri Valleys
(UFVJM), 39100-000 Diamantina, MG, Brazil
2
Visiting Professor at the UFVJM, PRPPG Campus JK, 39100-000 Diamantina, MG, Brazil
3
Institute of Science, Engineering and Technology, UFVJM, 39803-371 Teófilo Otoni, MG, Brazil
4
Institute of Science and Technology, UFVJM, 39100-000 Diamantina, MG, Brazil
5
Department of Chemistry ICEx, Federal University of Minas Gerais, Campus Pampulha, 31270-901
Belo Horizonte, MG, Brazil
6
Center for the Development of Nuclear Technology (CDTN/CNEN), 31170-130 Belo Horizonte,
MG, Brazil
*Email address: jdfabris@gmail.com
The search for optimized chemical industrial processes to produce biofuels have been
bringing about, in more recent times, scientific efforts towards the research and
development of new efficient heterogeneous catalysts specifically directed to convert
free fatty acids from triacylglicerols of bio-oils into their corresponding mixture of
methyl (but also ethyl) esters to form biodiesels [1]. This report describes a work that is
being devoted to the synthesis of nanosized magnetic iron oxide and the preparation of
the solid mixture with KI-functionalized silica to form the heterogeneous catalyst
destined to the transesterification of triacylglicerols in the kernel oil of fruits of the
macaúba palm (Acrocomia aculeata) into methyl esters. The individual solid
components and the solid mixture of the catalyst were first characterized for their
chemical composition, by X-ray fluorescence, crystallographic features, by powder Xray diffractometry (XRD) and, focusing on the iron oxide, for the 57Fe hyperfine
structures by transmission Mössbauer spectroscopy at room temperature (~298 K) and
2O3) as the
ferrimagnetic iron oxide in this solid catalyst that was used in this transesterification
reaction of triacylglicerols of the kernel oil of the macaúba palm fruit with pure
methanol, at a volume ratio oil:methanol of 1:5. The chemical effectiveness of this
heterogeneous catalyst, as evaluated by analyzing the produced methyl esters mixture
with gas chromatography coupled with mass spectrometer, was found to be indeed very
promising and deserves further development in order to have it suitably optimized for
chemical processes envisaging the industrial production of biodiesel.
Reference
[1] Michelle Cardoso Coimbra and Neuza Jorge, Journal of Food Science, Vol. 76, Nr. 8, 2011.
Acknowledgements:
Work supported by FAPEMIG and CNPq (Brazil). ALM thanks CAPES (Brazil) for
sponsoring her DS studentship at UFVJM. JDF is also indebted to CAPES for granting
his Visiting Professorship at UFVJM under the PVNS program and to CNPq for the
grant # 305755-2013-7.
271
PS3.37
Direct determination of rare earths elements in petroleum
and derivatives by ICP-MS
W. Sandoval 1, C. Duyck2 and T. Saint'Pierre1.
1
Departamento de Química, Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Rua
Marquês de São Vicente 225, 22451-900 Rio de Janeiro, RJ, Brazil
2
Departamento de Química, Universidade Federal Fluminense (UFF), Outeiro São João Batista s/n,
Centro, 24020-150, Niterói, RJ, Brazil
E-mail: cbduyck@vm.uff.br
The distribution of Rare Earth Elements (REE) is representative of the rocks and
soils that originally contain them and is often used as a geochemical or
environmental parameter for source identification [1]. These elements are also
present in petroleum and its derivatives, in particular in its heavy fraction, the
asphaltenes [2].
In this work, a methodology for the direct determination of REE, scandium and
yttrium in petroleum and derivatives by inductively coupled plasma mass
spectrometry (ICP-MS) was developed. The samples were diluted in a xylene/ethanol
solution (80/20, w/w) and introduced into the ICP by pumping continuously, at 1 mL
min-1, the organic solutions into a nebulization system composed by a concentric
nebulizer coupled to a cyclonic spray chamber, refrigerated at -5 ºC by an Isomist TM
device. Oxygen (0.1 L min-1) was added to the argon flow (0.7 L min-1) used for
nebulization and transport, in order to eliminate the excess of carbon due to the
solvents. Inorganic standards were employed for the establishment of the calibration
curve with concentrations varying from 0.2 to 20 ng mL-1. The obtained detection
limits were ranged between 0.002 ng mL-1 (Tb) to 5.3 ng mL-1 (Sc).
The methodology was applied to samples of bitumen used in Brazilian roads
pavement with the objective of establishing REE profiles for source identification in
soil and atmosphere pollution studies. The same samples were also solubilized using
a high pressure acid decomposition method [2], in order to evaluate the accuracy of
the direct dilution methodology. All the REE could be determined by direct dilution,
but only Ce and Nd were in concentrations quantifiable by the acid decomposition
method, due to the high dilution factor. The concentrations of Ce and Nd obtained by
dilution were respectively 6.6 ± 0.1 ng mL-1 and 2.6 ± 0.1 ng mL-1, which were 17%
higher (Ce) and 24% lower (Nd) than the results obtained by the high pressure acid
decomposition method. These results are adequate for preliminary studies and
considering the heterogeneity of the samples. Possible interferences and the stability
of elements in the organic solutions were also investigated.
References
[1] Duyck, C., Miekeley, N., Fonseca, T., Szatmari, P. and Vaz dos Santos, E., J. Braz. Chem. Soc.,
19, 978-986 (2008).
[2] Akinlua, A.; Torto, N. and Ajayi, T. R., Fuel, 87, 1469-1477 (2008).
272
PS3.38
Method for quantification of vanadyl porphyrins in
fractions of crude oils
Flávia G. Wandekoken1, Christiane B. Duyck1,2 and Tatiana D. Saint’Pierre1
1
Departamento de Química, Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Brazil.
2
Departamento de Química, Universidade Federal Fluminense (UFF), Niterói, RJ, Brazil
cbduyck@vm.uff.br
The analysis of natural biomarkers, such as petroporphyrins of Ni and V, as well as
the determination of metals in crude oils is important in petroleum geochemistry and
refining studies [1]. The objective of this work was to quantify V in fractions of
crude oil samples, in order to compare their distribution in crude oils of different
origin and to correlate with geochemical effects, such as secondary migration.
First, crude oils were submitted to fractionation by preparative liquid
chromatography with online UV detection, selected at the Soret band wavelength
(400 nm), and two porphyrin fractions, acidic and neutral, were obtained. Then, the
two achieved fractions were analyzed by High Performance Liquid Chromatography
(HPLC), with a C18 reversed phase, hyphenated to an Inductively Coupled Plasma
Mass Spectrometry (ICP-MS) equipment. A quantitative study of V as V-porphyrins
was carried out by five readings of each organic standard solution (50, 100, 250 and
500 µg of VOOEP in methanol), injected post-column, by means of an injection
valve, for the construction of the calibration curve [2]. The acidic polar fraction was
separated using methanol, however a 20% toluene in methanol had to be used as the
mobile phase, in order to separate and recover the neutral fraction. The stability of
the 51V signal was investigated using a gradient elution program with methanol and
toluene. The signal was lower for inorganic V standard when toluene was added, but
V as VOOEP was stable throughout the separation. Ti, Sc and Ge were tested as
internal standards and a 20 µg L-1 solution of Ge in methanol was used for
quantification. The mass balance of V was carried out by comparing the quantitative
results of V-porphyrins with the total V content of each fraction, determined by ICPMS after dilution in xylene [3] and applied to a petroleum internal reference sample
and to the certified reference material NIST 8505, a Venezuelan crude oil. The Vporphyrins were predominantly eluted in the acidic fraction, with recoveries close to
100%, while lower recoveries were obtained for the neutral fraction.
References
[1] Asghari I, Mousavi SM, Amiri F, Tavassoli S, J Ind Eng Chem, 19, 1069-1081 (2013)
[2] Duyck CB, Saint’Pierre TD, Miekeley N, da Fonseca TCO, Szatmari P, Spectrochim Acta Part B
At Spectrosc, 66, 362-367 (2011)
[3] Souza, J., Duyck, C., Fonseca, T. and Saint’Pierre , T. J. Anal. At. Spectrom., 27, 1280-1286
(2012)
273
PS3.40
Trace Element Characterization of Dried Baby Shrimp:
Bulk Analysis by Portable High Definition XRF compared
to Elemental Mapping by Synchrotron Radiation μXRF
using a MAIA detector
D. Guimarães1,2, P. J. Parsons 1,2, S. Lin3, H. Rong3 and A. Woll3
1 Laboratory of Inorganic and Nuclear
Chemistry, Wadsworth Center, New York State Department of
Health, P.O. Box 509, Albany, NY 12201-0509, USA
2 Department of Environmental Health Sciences, School of Public Health, The University at Albany,
P.O. Box 509, Albany, NY 12201-0509, USA
3 Cornell High Energy Synchrotron Source, Cornell University, Ithaca, NY 14853, USA
A study of the trace element content of Dried Baby Shrimp was conducted as part of
a broader research investigation into exposure to toxic metals/metalloids among the
ethnic Chinese community in Upstate New York. During field visits, samples were
analyzed by a new portable XRF Analyzer (HD Mobile), which uses doubly curved
crystal optics to provide focused monochromatic X-Rays. A total of 75 Chinese and
25 non-Chinese homes were visited, and more than 1,500 samples were analyzed
including various foods, personal care products and traditional Chinese medicines.
During the home visits, three Chinese families provided Dried Baby Shrimp samples
for analysis. These were obtained from local Chinese markets or home made and are
consumed without separating the tail from the shrimp head. Preliminary results
obtained by the HD-Mobile indicated a arsenic (As) content (5-30 μg/g) that
warranted further investigation from a public health perspective.
Further studies of the As content/elemental distribution in these baby shrimp samples
were conducted at bend magnet station F3 at the Cornell High Energy Synchrotron
Source (CHESS). Monochromatic X-rays of 17.2 keV were selected using a Si(220)
monochromator and focused to a 20-μm diameter beam using a single bounce
monocapillary (PeB605) fabricated at CHESS [1]. XRF data were collected by a
384- pixel Maia detector system [2]. This detector enhances trace elemental
sensitivity affording high definition imaging in much shorter time than was
previously possible.
XRF elemental mapping of the Dried Baby Shrimp provided high resolution images
for As, Ca, Br, (among others), and show localized accumulations of As within the
abdominal body. Quantification was achieved using a reference material pellet
(NRC-CNRC TORT-2 Lobster hepatopancreas). Results were in reasonable
agreement with those obtained in the field using the HD Mobile. Speciation analysis
of the shrimp is currently underway to identify which As compound(s) are present.
References
[1] Rong H. and Bilderback D. H., J. Synchrotron Rad., 13, 74-84 (2006).
[2] Kirkham R. et al., AIP Conf. Proc., 1234, 240-243 (2010).
274
PS4.1
Scintillation Emission from Electron Avalanches
in Ar and Xe
C.M.B. Monteiro1
1
LIBPhys-UC, Physics Department, FCTUC, University of Coimbra, 3004-516 Coimbra, Portugal
E-mail: cristina@gian.fis.uc.pt
The mechanism of secondary scintillation production in noble gases and their
mixtures have been extensively described by various authors [1-3]. Under the intense
electric field of the scintillation region, either in uniform fields with values below the
ionisation threshold, or in the very intense and variable fields typical of electron
avalanches, electrons gain from the field energy to excite the gas atoms by electron
impact. Through inelastic collisions the atoms are brought to the first four excited
atomic states 3P2, 3P1, 3P0, 1P1. The atomic states 3P2 and 3P0 are metastable with a
long half life of about 100 s, while the other two are resonant, decaying radiatively
to the ground state. However, for pressures close to the atmospheric pressure the
resonant states present a long half life, similar to that of the metastable states, due to
high absorption and reemission of the resonant atomic radiation. This is the reason
for the atomic emission of noble gases to be only observed at very low pressures,
below 20 mbar.
For pressures above few tens of mbar, atomic emission is progressively replaced by
molecular emission. Collisions of the excited atoms with atoms in the ground state,
in a three-body collision process, lead to the formation of excited dimer states, 3u
and 1u. These states have very close energies but their lifetimes are a lot different,
namely 4.2 and 3200 ns, respectively, for argon, and 6 and 110 ns, respectively, for
xenon. The de-excitation of these molecular states give rise to two continua. The first
continuum occurs from the de-excitation of 3u and 1u in high vibrational levels,
(3u) and (1u), to the repulsive ground state, 1g+. The second continuum is
observed for the de-excitation of 3u and 1u in the lowest vibrational level, (3u)
and (1u), to the ground state.
At pressures of a few hundred mbar, only the second continuum is visible. This is
due to the relaxation of the excited vibrational states to the lowest vibrational state by
collision with the atoms of the gas, before de-excitation. Therefore, at atmospheric
pressure, the secondary scintillation emission of argon and xenon correspond only to
their second continua, a narrow peak of about 10 nm around 128 nm for argon and of
about 14 nm around 172 nm for xenon. One excited atom creates an excited excimer,
X2∗, which decays emitting one VUV photon, hυ.
Studies of the electron avalanches were performed for gaseous Ar and Xe and the
ratios of the number of photons to the number of electrons produced in the
avalanches were determined for these gas media and the influence of the applied
electric fields on these ratios.
[1] M. Suzuki, S. Kubota, Nucl. Instrum. Meth., 164, pp.197 (1979).
[2] M.S.C.P. Leite, Portugal. Phys. 11, pp.53 (1980).
[3] T. Takahashi, S. Himi, J. Ruan, S. Kubota, Nucl. Instrum. Meth., 205, pp. 591 (1983).
275
PS4.2
Electroluminescence Emission around thin anode wires in
Ar and Xe Proportional Scintillation Counters
C.M.B. Monteiro1, C.A.O. Henriques1
1
LIBPhys-UC, Physics Department, FCTUC, University of Coimbra, 3004-516 Coimbra, Portugal
E-mail: cristina@gian.fis.uc.pt
The mechanisms of electroluminescence production are well known [1-3]. E.g., for
pure xenon, the wavelength of the emission depends on the gas pressure. Below 10
mbar, the emission is mainly of atomic nature, with two peaks centred around 130
nm and 147 nm, approximately. For higher pressures, the formation of excited
dimers Xe2* is favoured through three body collisions, and molecular emission
becomes increasingly more important. These emissions are centred around 147 nm
for the first continuum and 172 nm for the second continuum. The first continuum
corresponds to the VUV radiative decay of the vibrationally excited, (Xe 2*),
excimer state, while the second continuum corresponds to the VUV radiative decay
of the vibrationally relaxed, (Xe2*)=0, excimer state. Above 400 mbar, the second
continuum is dominant and the electroluminescence presents only a narrow peak, of
about 10 nm FWHM, centred around 172 nm [3].
In Proportional Scintillation Counters the radiation interacts in the noble gas medium
and the primary ionisation signal is amplified through the electroluminescence
produced by the primary electrons while transversing a uniform electric field
scintillation region. This results in a scintillation output that is proportional to the
number of the produced primary electrons and, thus, proportional to the energy
deposited in the gas medium, with improved energy resolution when compared to the
one achieved in signal amplification through electron avalanches.
Nevertheless, as electrons in the Proportional Scintillation Counter are collected in
the wire mesh of the anode electrode, additional electroluminescence and electron
avalanches can be produced in the stronger field around the anode wires, degrading
the best energy resolution that can be achieved with this type of radiation detectors. It
is, this way, important to quantify this electroluminescence relative to the
electroluminescence produced in the uniform electric field of the scintillation region.
This allows determining the influence of the above mentioned effect on the energy
resolution achievable in Gas Proportional Scintillation Counters.
[1] M. Suzuki, S. Kubota, Nucl. Instrum. Meth., 164, pp.197 (1979).
[2] M.S.C.P. Leite, Portugal. Phys. 11, pp.53 (1980).
[3] T. Takahashi, S. Himi, J. Ruan, S. Kubota, Nucl. Instrum. Meth., 205, pp. 591 (1983).
276
Poster Session 4: Organic and Inorganic Mass Spectrometry
PS4.3
Determination of carboxylic acids in biological matrices by
GC/MS following single-step aqueous derivatization with
triethyloxonium tetrafluoroborate
D. Ferraro1,2, M. Onor1, B. Campanella1,2, S. Tegli3, E. Bramanti1, S. Giannarelli2,
A. D’Ulivo1 and E. Pagliano4
1
2
C.N.R Institute of Chemistry of Organometallic Compounds, UOS of Pisa, via Moruzzi 1, 56124 Pisa,
Italy.
University of Pisa, Department of Chemistry and Industrial Chemistry, via Moruzzi 3, 56124 Pisa, Italy.
3
University of Florence, Dipartimento di Scienze delle Produzioni Agroalimentari e dell'Ambiente,
Laboratorio di Patologia Vegetale Molecolare, via della Lastruccia 10, 50019 Sesto Fiorentino, Italy.
4
National Research Council of Canada, 1200 Montreal Road, Ottawa, ON K1A 0R6, Canada.
E-mail: onor@pi.iccom.cnr.it
The accurate determination of carboxylic acids in biological matrices is crucial for
understanding metabolic pathways related to plant growth and development [1] and for
the determination of i) biomarkers of bacterial activity in food and environmental
samples (e.g. salicylic, propionic, and butyric acid) [2], ii) drug metabolites such as
salicylic acid for aspirin [3], and iii) environmental pollutants associated with adverse
health effects like the perfluorooctanoic acid [4-5].
In this study, the determination of several organic acids was achieved by GC/MS
following a single-step aqueous derivatization with triethyloxonium tetrafluoroborate.
Conversion of the carboxylic acids into the corresponding ethyl-esters was attained for
indole-3-acetic acid, benzoic acid, salicylic acid, propionic acid, butyric acid and
perfluorooctanoic acid.
Before derivatization and quantitation, these analytes were simultaneously extracted in a
slightly alkaline solution from various matrices such as Nicotiana tabacum and Actinidia
deliciosa leaves, urine, and saliva. Compared to common derivatization approaches for
GC analysis, the proposed method has the advantage to be based on a simple aqueous
chemistry. In this regard, the sample preparation involves only centrifugation, aqueous
derivatization and liquid-liquid extraction of the resulting ethyl-esters with MTBE.
Optimization of some effective parameters for the derivatization step – such as pH of the
reaction medium, amount of reagent, and derivatization/extraction time – was established.
For the utmost precision, quantitation was performed based on isotope dilution formalism
by using deuterated internal standards. Linearity, repeatability, recovery, limit of
detection and quantitation were evaluated for each analyte under investigation, along with
the matrix effects.
References
[1] Y. Bai, D. Fuyou, and L. Huwei, Analytical Methods, 2, 1867-1873 (2010).
[2] N.M. Moreau, R. Delépée, D. Maume, B. Le Bizec, P.G. Nguyen, M.M. Champ, L.J. Martin, and H.J.
Dumon, Analytica chimica acta, 512, 305-310 (2004).
[3] M. T. Jafari, Z. Badihi, and E. Jazan, Talanta, 99, 520-526 (2012).
[4] S.D. Richardson, T.A. Ternes, Analytical Chemistry, 86, 2813-2848 (2014).
[5] J. Koponen, P. Rantakokko, R. Airaksinen, and H. Kiviranta, Journal of Chromatography A, 1309, 4855 (2013).
277
Poster Session 4: Imaging Techniques
PS4.4
Progress of graffiti removal with laser Nd:YVO4 in coarse
grained by means of hyperspectral imaging techniques
J.S. Pozo-Antonio1, M.P. Fiorucci1, A. Ramil1, T. Rivas2, A.J. López1,
D. Barral2.
1.
Laboratorio de Aplicacións Industriais do Láser, Centro de Investigacións Tecnolóxicas (CIT),
Departamento de Enxeñaría Industrial II, Escola Politécnica Superior, Universidade de Coruña
(UDC), Campus Ferrol, 15403 Ferrol, Spain.
2
Departmento de Enxeñaría dos Recursos Naturais e Medioambiente, Escola Superior de Minas,
Universidade de Vigo, 36310 Vigo, Spain.
E-mail: santiago.pozo@udc.es.
Hyperspectal imaging techniques are characterized to be non-invasive, fast and easy
to implement in situ. The aim of this paper is to evaluate the ability these techniques
to follow-up the process of laser cleaning in the case of granite covered with
different spray paints (red and silver graffiti). The laser used was a pulsed
nanosecond Nd:YVO4 source operating in the UV range and the ultimate objective
was to determine number of laser scans required for a complete paint removal
without damaging the granite substrate. The characteristics of the rock surface, with
a great variability of grain size and the different reflectivity characteristics of the
forming minerals have a serious effect on the progress of graffiti removal . The
suitability of the hyperspectral imaging technique was evaluated by analyzing the
granite surface at different stages of the cleaning by means of different techniques
(optical microscopy, scanning electron microscopy, Fourier transformed infrared
spectroscopy, color measurements in CIELAB space and confocal microscopy). It
has been observed that the number of laser scans required to achieve an effective
cleaning depends on the paint color. In order to obtain quantitative assessment of the
cleaning, a Cleaning Level index was defined through the values reflectivity spectra.
The cleaning level index has resulted useful to determine the optimal graffiti
extraction and to detect the damage in the different forming minerals.
278
PS4.5
Visualization method for radiographic films through silver
concentration mapping using x-ray fluorescence
E. A. S. Gonçalves1, D. F. Oliveira2,3, M. J. Anjos3, J. T. Assis4, L. F. Oliveira3
and R. T. Lopes2
1
Federal Institute of Rio de Janeiro, Brazil
Nuclear Instrumentation Laboratory, COPPE, Federal University of Rio de Janeiro, Brazil
3
Physics Institute, State University of Rio de Janeiro, Brazil
4
Department of Mechanical Engineering and Energy, Polytechnic Institute, State University of Rio
de Janeiro, Brazil
2
E-mail: davi@lin.ufrj.br
Radiographic films have a large range of applications. In many of these applications, the behavior of
characteristic curves is very important for assessing the image quality and radiography setup.
Radiographic film digitization and visualization are always performed by light transmission, and the
characteristic curve is known as a behavior of optical density in function of the radiation exposure.
Since optical density is a function of metallic silver generated by chemical development in silver
halides, when an image is visualized by light transmission, a silver amount map is indirectly seen [13].
In a first approach, direct proportion was performed by computer simulation: in an attempt to predict
the characteristic curve, the results did not match what was measured experimentally, suggesting a
limitation in this proportion. Light crossing the film is an indirect measure of metallic silver, but it is
limited by the optical instrument, and a very weak light signal cannot be distinguished from
background light or background noise. In this way, highly exposed films can contain areas with
different silver concentrations, but this is not seen due to the fact that the optical density measurement
is limited [1]. The purpose of this research is to employ the XRF imaging technique for detecting
low optical contrast objects in conventional radiographic films. To evaluate the viability of this
technique, radiographic exposures of several samples, of different materials and thicknesses, have
been made, keeping the optical density levels higher than the saturation level of the light transmission
measurement devices. After the chemical development, the radiographic films were analyzed pointby-point by a XRF system in order to obtain the intensity of the silver characteristic peaks,
resulting in a 2D map of the silver distribution.
Figure 1 shows an example of the technique viability. The test sample is a pen composed of a plastic
cap and a metal point. The film, visualized through light transmission, displays only the metal point,
whereas the silver mapping shows the plastic cover as well.
Figure 1 – a) film digitization and b) -XRF silver mapping of the test sample.
The results of this work have shown that small objects and details in low contrast or over-exposed
radiographic images could be visualized by the silver mapping technique, and the same results could
not be achieved using light transmission methods.
References
[1] A. Moslehi, S Hamidi, G. Raisali, F. Gheshlaghi, Optimization of the energy response of radiographic films
by Monte Carlo method, Radiation Measurements, V. 45, pp. 98-102 (2010).
[2] Richard R. Carlton and Arlene McKenna Adler, Principles of Radiographic Imaging: An Art and A Science,
5th Edition, (2013).
[3] Ramesh Singh, Applied Welding Engineering, pp. 253-274 (2012).
279
PS4.6
EDXRF imaging system based on a gaseous detector:
characteristics and adequacy
A.L.M.Silva1, S.Cirino1, I. Fortes1, C.D. Azevedo1, M.L.Carvalho2 and J.F.C.A.
Veloso1
1
I3N – Departamento de Física da Universidade de Aveiro, Portugal
2
LIBPhys-UNL - Faculdade de Ciências e Tecnologia da Universidade Nova de
Lisboa, Campus Caparica, 2829-516 Monte da Caparica, Portugal
E-mail: analuisa.silva@ua.pt
When large areas of detection with position and energy resolution are needed in the
radiation detection field, micropatterned gaseous detectors (MPGDs) are an
interesting and unique solution in some cases.
In this work, a characterization of a EDXRF system based on a THCOBRA detector
is presented. The system is composed by an external radiation source (X-ray tube), a
pinhole and the gaseous detector, filled with Ne/5%CH4. The THCOBRA [1] is a
MPGD with two charge multiplication stages, which makes it a simple and cost
effective device.
The ‘holy grail’ of EDXRF elemental imaging is acquiring elemental images of areas
larger than the probe beam spot size. The use of a large area elemental imaging
MPGD is an elegant approach for a long standing problem.
The low cost detector based on the THCOBRA device has an active area of 10×10
cm2, making it very promising for this kind of purposes. The 2D-THCOBRA have
already shown good prospects and promising results in the field [2]. Within this
project a characterization of the whole system will be presented as well as it
adequacy for this applications. Position resolution and elemental map discrimination
as a function of pinhole diameter, image magnification and detector parameters, such
as detector energy resolution and energy linearity will be shown.
References
[1] "X-ray imaging detector based on a position sensitive THCOBRA with resistive line" A.L.M.
Silva; C.D.R. Azevedo; L.F.N.D. Carramate; T. Lopes; I.F. Castro; R. de Oliveira; and J.F.C.A.
Veloso A.L.M. Silva et al., JINST, 8 (2013) P05016
[2] A large area full-field EDXRF imaging system based on a THCOBRA gaseous detector” A. L.
M. Silva, M. L. Carvalho, K. Janssens and J. F. C. A. Veloso, JAAS, 30, 343 - 352, 2015 DOI:
10.1039/c4ja00301b (2015)
Acknowledgements: A. L. M. Silva is supported by the QREN programme Mais Centro –
Programa Operacional Regional do Centro, FEDER and COMPETE, through the project Biomaterials
for Regenerative Medicine (CENTRO-07-ST24-FEDER- 002030).
280
PS4.7
A Time Projection Chamber with Gas Electron Multipliers
(GEM) for Hadron Spectroscopy
M. Ball1, R. Beck1, B. Ketzer1, J. Ottnad1, D. Schaab1 and R. Schmitz1
1
Helmholtz-Institut für Strahlen- und Kernphysik (HISKP),
Nussallee 14-16, D-53115 Bonn, Germany
E-mail: mball@hiskp.uni-bonn.de
The CB-ELSA/TAPS experiment focuses on baryon spectroscopy by
photoproduction of neutral mesons off nucleons [1]. In order to include channels
with charged mesons, the current inner detector, providing just a point reconstruction
for charged particles, will be replaced by a Time Projection Chamber (TPC) [2]. This
device offers 3-dimensional track reconstruction capabilities, a robust pattern
recognition and momentum resolution, if operated in a magnetic field. Moreover, one
obtains identification of charged particles by the specific energy loss. The interaction
rate will be O(kHz), so that a continuous readout using Gas Electron Multipliers
(GEM) [3] for amplification of the primary charges is envisaged. GEMs offer a
intrinsic ion back flow suppression which keeps the space charge distortions at a
manageable level. A GEM TPC has been developed for the FOPI [4] experiment
which has similar dimensions as the one planned for the Crystal Barrel calorimeter.
The performance of the CB-ELSA TPC is being optimised with respect to spatial and
energy resolution. This implies studies on the charge transfer processes of GEM
structures as well as the implementation of a spatial calibration system. First results
of these studies will be presented.
References
[1] A. Thiel et al.,Phys. Review Lett. 109, 102001, (2012).
[2] D.R. Nygren and J.N. Marx, Phys. Today 31N10, 46, (1978).
[3] F. Sauli, Nucl. Instrum. Meth. A 386, 531, (1997).
[4] B. Ketzer et. al., Nucl. Instrum. Meth. A 732, 237, (2011).
281
PS4.8
Gamma-ray and neutron spectrometers: An investigation
of elemental composition of near-Earth asteroids onboard
the miniature deep space probe
N. Hasebe1,2, H. Kusano2, H. Nagaoka1, T. Adachi1, K. Yoshida1, M. Naito1,
E. Shibamura2, H. Kuno2, Y. Amano2, J. A. Matias Lopes3, J. Martínez-Frías4
1
2
Physics Department, Waseda University, Tokyo, Japan
Res. Inst. for Science and Engineering, Waseda University, Tokyo, Japan
3
Phys. Dep., University of Coimbra, Coimbra, Portugal
4
CSIC- The Complutense University of Madrid, Madrid, Spain
E-mail: nhasebe @waseda.jp
The exploration of near-Earth asteroids (NEAs) would provide synergistic scientific
return from a planetary surface, substantially different in origin, age, and
composition from those of the Moon or Mars. NEA resources provide massive
storages of valuable resources vital to future economic activity in space, and
utilization techniques for water, volatiles, and valuable metals. In recent years,
miniature satellite programs have become a worldwide space activity, which has
huge potential by complying with the very low cost and short time delivery
requirements. With the use of miniature deep space 50 kg-class microsats, we will be
easily and quickly able to investigate NEAs. A nuclear spectrometer, GNS, on the
microsat for asteroid rendezvous or fly-by missions would be attractive as the next
step for deep space exploration using microsats. The GNS is a high performance
combination of neutron spectrometer, NS, and gamma-ray spectrometer, GS, which
are key instruments to determine and map the elemental composition of asteroid
surfaces. The GS is based on a large n-type high purity Ge crystal. The energy
resolution is more than 20 times better than that of any scintillator. The NS is based
on a “phoswich” detector made of a compact assembly of two scintillitators, which
can separately detect thermal, epithermal and fast neutrons. Thanks to its high
spectral resolution and high efficiency, GNS will detect gamma ray lines of most of
the major elements (O, Si, Fe, Ti, Mg, Al, Na, Ca) and of some minor or trace
elements (H, C, S, U, Th, K) which constitute the surface material of NEAs. The
precise knowledge of abundances of those elements will help to discriminate
between various models of formation and evolution of the planet. The measurement
goals of abundance maps will reveal regional heterogeneities in the elemental
composition of the asteroidal surface. The GNS proposed will be a powerful tool for
the future asteroid mission onboard the 50kg-class-microsat deep space probe with
an ion propulsion.
282
PS4.9
High pressure Xenon GSPC based detector for hard X-ray
and gamma spectroscopy
C. D. R. Azevedo1,, B. F. R. Silva1, F. A. B. Pereira1 and J. F. C. Veloso1
1 I3N – Physics Department, University of Aveiro
E-mail: cdazevedo@ua.pt
In this work we will present the initial characterization of a high pressure Xenon Gas
Scintillation Proportional Counter (GSPC) envisaging gamma spectroscopy,
covering the energy range from tens to few hundreds keV.
The detector comprises a high pressure absorption region where the gamma photons
are converted into electrons followed by a scintillation region where the light is
produced through the electroluminescence process. Finally, the photons are collected
through a PhotoMultiplier Tube (PMT) producing a electrical signal with an
amplitude proportional to the energy of the detected gamma photons.
The detector performance is characterized according to gain and energy resolution as
function of the gas pressure, ranging from 1 to 10 bar, and electric fields in the drift
and scintillation region and for different photons energy ranging from a few tens a
few hundreds keV. High signal to noise ratio was achieved as well as energy
resolutions close to the intrinsic values.
The detector system and detailed results will be presented, as well as the possibility
to replace the PMT by a large area and low cost position sensitive gaseous
photomultiplier[1] that will allows position sensitivity of the gamma interaction in
the GSPC detector volume.
References
[1] T. Lopes, 2013 JINST 8 P09002.
283
PS4.10
Gamma irradiation of collagen based materials. Unilateral
NMR, FTIR and thermal microscopy investigations
Claudiu Şendrea1,2, Elena Badea1,3, Ioana Stanculescu4,5, Lucretia Miu1,
Horia Iovu2
1
Advanced Research for Cultural Heritage (ARCH) Group, National Research and Development Institute for
Textile and Leather (INCDTP), ICPI Division, Ion Minulescu 93, 031215 Bucharest, Romania
2
Faculty of Applied Chemistry and Materials Science, University Politehnica of Bucharest, Romania
3
Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of Craiova, Calea 107 I
Bucuresti, 200512 Craiova, Romania
4
Horia Hulubei National Institute for Physics and Nuclear Engineering (HH-IFIN),
Radiation Processing Center, Magurele, Romania
5
University of Bucharest, Department of Physical Chemistry, 4-12 Regina Elisabeta Bd.,
Bucharest, Romania
E-mail: claudiusendrea@yahoo.com
Cultural heritage artefacts made of natural polymers as collagen-based materials, e.g. parchment,
leather, mummies, biological remains, are exposed to various biological risks due to both their
chemical composition and climate and exposure of the object. Among the methods used for
decontamination of infected artefacts, gamma irradiation may represent an alternative to the
fumigation with gases (e.g. ethylene-oxide, sulphuryl-fluoride), liquid biocides and anoxic treatment,
especially against fungi and their spores. Since the dose for fungi must be in excess of 10–20 kGy [1],
this method can affect many materials’ properties and its application is therefore restricted. Extensive
research is still needed to develop treatment methods based on radiation doses that limit the breaking
of chemical bonds, formation of unsaturated bonds, oxidation and crosslinking. Materials’ response
and dose dependence effects are therefore the main criteria for the approach to gamma irradiation
treatment of collagen-based heritage objects.
Collagen-based materials are prone to microbiological attack. In fact, among the first uses of gamma
radiation was the disinfestations of the Ramses II mummy. Large parchment, leather and skin
collections would take a huge profit from a method ensuring a wide biocide effect while guaranteeing
simplicity, safety and low-cost. This paper concerns with the study of the interaction between
vegetable tanned leather and gamma rays using Diffuse Reflectance Fourier Transform Infrared
(DRIFT) spectroscopy, unilateral nuclear magnetic resonance (unilateral NMR) [2] and thermal
microscopy (image MHT method) [3]. These techniques targeting the molecular, nanoscopic and
microscopic levels of the collagen structural hierarchy can provide a comprehensive picture of the
collagen alterations induced by gamma radiation. New vegetable tanned leathers were prepared at
INCDTP-ICPI Division, Bucharest using a patented technology based on the study of ancient recipes.
Leather samples were exposed to 60Co gamma rays at IFIN-HH, Bucharest, the radiation doses being
10, 25, 50 and 100 kGy, with a dose uniformity ratio (DUR) of 1.14.
Longitudinal and transversal relaxation times T1 and T2, measured using a PM 2 portable NMRMOUSE with 20.05 MHz frequency, showed variations that depend on gamma radiation dose.
Moreover, T1 values well correlate with the shrinkage temperature Ts, measured with an automated
MHT equipment, which significantly decreases with the increase of gamma radiation dose. DRIFT
spectral parameters as amide I and amide II band intensities as well as their relative positions showed
significant changes for the highest irradiation doses only.
Financial support of this work by UEFISCDI, contract TEXLECONS 213/2012 is recognized.
Claudiu Şendrea gratefully acknowledges the Sectoral Operational Programme Human Resources
Development 2007-2013, POSDRU/159/1.5/S/132395.
References
[1] M. Nittérus, Fungi in archives and libraries. A literary survey, Restaurator. 2000;21:25–40.
[2] E. Badea, L. Miu, P. Budrugeac, M. Giurginca, A. Mašić, N. Badea, G. Della Gatta, Study of deterioration of historical
parchments by various thermal analysis techniques, complemented by SEM, FTIR, UV-VIS-NIR and unilateral NMR
investigations, J. Therm. Anal. Calorim. 2008;91: 17-27.
[3] O.A. Miu, E. Badea, C. Carsote, S. Ciobanu, Automatic detection of collagen fibres shrinkage activity using Σ-Δ filtering.
In: Proceedings Book of the 5th International Conference on Advanced Materials and Systems, Certex Publishing House,
Bucharest, 2014, p.539.
284
PS4.11
Highly efficient nanoparticles of functionalized iron oxide
for medical practices through magnetically-induced
hyperthermia in oncology
Roberta V. Ferreira1, Priscila P. Silva2, Elene C. Pereira-Maia3, Rosana Z.
Domingues3, J. D. Fabris3,4, Luis Carlos D. Cavalcante3,5
1
Department of Materials, Federal Center of Technological Education of Minas Gerais, Nova Suiça,
30421-16 Belo Horizonte, Brazil.
2
Department of Chemistry, Federal Center of Technological Education of Minas Gerais, Nova Suiça,
30421-16 Belo Horizonte, Brazil.
3
Department of Chemistry – ICEx, Federal University of Minas Gerais (UFMG), 31270-901 Belo
Horizonte, Minas Gerais, Brazil.
4
Federal University of the Jequitinhonha and Mucuri Valleys (UFVJM), PRPPG, Campus JK, 3910000 Diamantina, Minas Gerais, Brazil.
5
Center of Natural Sciences, Federal University of Piauí (UFPI), 64049-550 Teresina, Piauí, Brazil.
E-mail: jdfabris@ufmg.br
Magnetic iron oxide nanoparticles are potentially suitable to be used in cancer
diagnostic and therapy through the hyperthermia technique, as they efficiently
dissipate heat, if submitted to an alternating magnetic field (AMF). In this work,
well-dispersed nanosized (mean diameter, 10 ± 2 nm; hydrodynamic diameter,
~40 nm) particles of magnetite synthesized through the co-precipitation method were
suspended in an aqueous solution of citric acid. The synthetic iron oxide appears to
be chemically stable with time, as it can be deduced from the hyperfine structure of
the 57Fe measured by Mössbauer spectroscopy. Hyperthermia assays point to a strong
dependence of the temperature increase with the magnitude of the magnetic field but
also with the iron oxide concentration in the suspension. In vitro hyperthermia assays
by using K562 cells line with the functionalized nanoparticles under an AMF show
efficient cytotoxic activity. The IC50 value is time-dependent, reaching to 3.5 x 104
g/L in 10 min. Our results show that these citric acid-functionalized nanoparticles
can safely inhibit the cell growth of tumors at relatively low concentrations and in a
suitable temperature increase.
Acknowledgements
Work supported by FAPEMIG and CNPq (Brazil). JDF is indebted to CAPES for
granting his Visiting Professorship at UFVJM under the PVNS program and to
CNPq for the grant # 305755-2013-7.
285
Poster Session 4: Methods of Surface Analysis and Depth Profiling
PS4.12
Challenges and limitations of X-ray photoelectron
spectroscopy investigations in surface and depth analysis
R. Steinberger1, J. Walter2, T. Greunz1, J. Duchoslav1,
M. Arndt3, T. Steck3, J. Faderl3 and D. Stifter1
1
2
CDL-MS-MACH / ZONA, JKU Linz, Altenberger Straße 69, 4040 Linz, Austria
Inst. für Exp. Physik, TU Bergakademie Freiberg, Leipziger Str. 23, 09599 Freiberg, Germany
3
voestalpine Stahl GmbH, voestalpine-Straße 3, 4031 Linz, Austria
E-mail: roland.steinberger@jku.at
Surface sensitive techniques like X-ray photoelectron spectroscopy (XPS) or Augerelectron spectroscopy (AES) are eminently suitable for analysis of the elemental and
chemical composition of unknown materials. Besides investigations of the surface,
the possibility of characterizing layered systems or observing chemical gradients
over depth is given by the application of sputter erosion techniques (e.g. Ar + ion
sputtering). In principle, XPS is mostly claimed to be of non-destructive nature.
However, due to our experience - gained from various measurements performed on
different material systems from industrial partners - we have learned that in reality
even modern XPS setups using sophisticated equipment may alter and degrade the
sample of interest.
This study is focused on various compounds, which are of interest for corrosion
science and for Zn-based galvanized coatings from the steel industry, and shows that
different components of the XPS system destructively/negatively influence the
chemical nature of the sample and therefore, complicate a reliable data evaluation.
On one hand monochromatic X-ray radiation was identified to induce a rapid
chemical transformation from Zn(OH)2 into ZnO [1]. On the other hand dual flood
guns, which are absolutely essential for the compensation of charges built up on the
surface of very rough, heterogeneous or insulating samples during XPS
measurements, were found to reduce chromium oxides from higher oxidation state to
lower ones [2]. Furthermore, the destructive impact of ion sputtering, exemplified in
detail for various Zn based corrosion products, could be shown [3]. In order to find
counter-measures the potential of using more gentle parameters for ion sputtering
and the new concept of gas cluster sputtering was tested [4]. Last but not least, also
the influence of the composition of the residual gas inside the UHV chamber has to
be taken into account as a potential pitfall, especially when metallic components are
present.
References
[1] J. Duchoslav, R. Steinberger, M. Arndt, D. Stifter, Corros. Sci., 82, 356-361 (2014).
[2] R. Steinberger, J. Duchoslav, T. Greunz, M. Arndt, D. Stifter, Corros. Sci., 90, 562-571 (2015).
[3] R. Steinberger, J. Duchoslav, M. Arndt, D. Stifter, Corros. Sci., 82, 154-164 (2014).
[4] R. Steinberger, J. Walter, T. Greunz, J. Duchoslav, D.C. Meyer, D. Stifter, Corros. Sci. accepted.
286
PS4.13
Methodology for depth analysis of polymers by means of
ultra-low-angle microtomy and X-ray photoelectron
spectroscopy
T. Greunz1, S. E. Schausberger2, H. Duchaczek3, R. Steinberger1, J. Walter4, B.
Strauß3 and D. Stifter1
1
CDL-MS-MACH / ZONA, JKU Linz, Altenberger Straße 69, 4040 Linz, Austria
Department of Soft Matter Physics, JKU Linz, Altenberger Straße 69, 4040 Linz, Austria
3
voestalpine Stahl GmbH, voestalpine-Straße 3, 4031 Linz, Austria
Inst. for Exp. Physics, TU Bergakademie Freiberg, Leipziger Str. 23, 09599 Freiberg, Germany
2
4
E-mail: theresia.greunz@jku.at
In industry organic coatings applied on substrates represent a valuable enhancement
of the final product in several ways. Especially in the automotive industry they are
typically employed to achieve decorative demands and fulfill a corrosion inhibitive
purpose on top of the Zn-coated steel panels. Although these organic systems are
widely used they are by far not fully understood. Segregation and migration effects
of chemical groups inside the coating are responsible for, e.g., the adhesion
performance and consequently the longevity of the final product.
To investigate such systems X-ray photoelectron spectroscopy (XPS) is a powerful
method that stands out due to its high surface sensitivity (< 10nm). Depth profiling in
XPS is challenging, since ion sputtering leads to a prompt degradation of the
chemical matrix [1]. Alternatively, the XPS analysis on conventional cross sections
is not a choice either as the smallest spot size in XPS exceeds the coating thickness.
In our work we suggest a different approach [2, 3]. The sample sectioned with an
ultra-low-angle microtome. The exposed surface allows XPS measurements on top of
the surface and in selected depths of the coating [3].
Fig. 2: Schematic depiction of the of the sample preparation with an ultra-low-angle microtome (ULAM)
(a). XPS C1s data recorded on the wedge shaped taper on top and at two different depths inside of the
organic coating. Chemical functions change with increasing depth towards the Zn-coated steel substrate
(b-d).
References
[1] A. Holländer, Plasma Process. Polym., 4, 773-776 (2007).
[2] S. J. Hinder, J. Mater. Sci., 40, 285-293 (2005).
[3] T. Greunz, Anal. Bioanal. Chem., 405, 7153-7160 (2013).
287
PS4.14
Nondestructive and monolayer sensitive investigations of
semi-conductors and organic surfaces by nonlinear optical
methods
C. Reitböck1, E. Głowacki2, N. S. Sariciftci2 and D. Stifter1
1
Christian Doppler Laboratory for Microscopic and Spectroscopic Material Characterization, Center
for Surface- and Nanoanalytics, Johannes Kepler University, Altenbergerstr. 69, 4040 Linz, Austria
2
Linz Institute for Organic Solar Cells (LIOS), Department of Physical Chemistry, Johannes Kepler
University Linz, Altenbergerstr. 69, 4040 Linz, Austria
E-mail: cornelia.reitboeck@jku.at
Sum frequency generation (SFG) spectroscopy is a nonlinear optical method to study
nondestructively the chemical composition, structure and orientation of monolayers
on surfaces under ambient conditions [1,2].
In this work the SFG investigations were performed with a picosecond laser system
tunable from 680 nm to 10 µm operating at a repetition rate of 50 Hz (see Fig. 1 left).
In SFG two laser beams – one at a fixed wavelength, 1, the other tunable, 2 overlap on a surface or interface. If the frequency of the tunable beam is in resonance
with a vibrational mode of a material lacking a center of inversion a photon at
1+2=SFG is generated. Additional information about the orientation of molecules
adsorbed on the surface can be obtained by choosing different combinations of
polarization of the excitation and signal beams.
The focus of our SFG studies is on the chain length dependence of phosphonic acid
self-assembled monolayers (SAMs) deposited on aluminum oxide since such
structures are relevant for the fabrication of advanced organic field effect transistors
(OFETs) [3,4] (see Fig. 1 right).
Figure 3: Setup for sum frequency generation spectroscopy (left). SFG spectra of a phosphonic acid with
18 carbon atoms in comparison to a phosphonic acid with 4 carbon atoms (right).
References
[1] Y.R. Shen, Nature, 337, 519-525 (1989).
[2] M. Buck, M. Himmelhaus, J. Vac. Sci. Technol. A, 19 (6), 2717-2736 (2001).
[3] E. Głowacki. et al., Adv. Funct. Mater. 25, 776–787 (2015).
[4] M. Novak et al., Org. Electron., 11, 1476-1482 (2010).
288
Poster Session 4: Material Sciences
PS4.15
Spectroscopic and X-ray scattering studies of ordering of
cellulose and Pluronics in ionic liquids – the role of water
J. Dybal, N. Kotov, A. Šturcová, A.Zhigunov and V. Raus
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Sq.
2, 162 06 Prague 6, Czech Republic
E-mail: dybal@imc.cas.cz
Cellulose is practically inexhaustible natural material available for the production of
environmentally friendly products. The full potential of cellulose has not yet been
realized due to its poor solubility and processability. In recent years, certain ionic
liquids have been shown to dissolve cellulose, and blending cellulose with synthetic
polymers in ionic liquids can lead to new materials with promising applications in
various fields. In this work, cellulose (AVICEL® PH-101) and Pluronic® F88
((ethylene oxide)103-block-(propylene oxide)39-block-(ethylene oxide)103) were
dissolved in ionic liquid 1-butyl-3-methylimidazolium chloride (bmimCl).
Attenuated-total-reflection Fourier-transform infrared spectroscopy (ATR FTIR),
Raman spectroscopy, small-angle X-ray scattering (SAXS) and wide-angle X-ray
scattering (WAXS) were used in characterization of neat compounds and of binary
and ternary mixtures.
Significant changes were detected in the ATR FT-IR spectra of the ternary mixture
compared with the spectra of neat compounds. New narrow bands were observed at
about 905, 880, and 820 cm-1 in the spectra of F88/cellulose/bmimCl. The
appearance of these bands in the spectra may be caused either by changes in the
conformation of PEO blocks of Pluronic due to interaction with cellulose or by
partial ordering of ionic liquid molecules around the Pluronic and/or cellulose chains.
Raman spectroscopy showed that the mixtures contained only one of the two
reported conformers of the butyl group in bmimCl, in contrast to molten bmimCl
with both conformers present. X-ray scattering methods revealed the presence of
highly ordered structures depending on the composition and thermal history of the
samples.
As the imidazolium-based ionic liquids are hygroscopic, the ionic liquid-water
interactions must be taken into account. To bring more insight into the water-ionic
liquid interactions at the molecular level bmimCl/water mixtures were studied using
vibrational spectroscopy and WAXS. Three crystalline forms were detected
depending on the water concentration, temperature and time allowed for
equilibration. Moreover, it was found that capillary forces may affect the process of
ordering and/or crystallization.
289
PS4.16
The hybrid pigments, one way to capture the color of
flowers
E. Perez-Ramírez1, E. Lima1 and A. Vargas1
1
2
Instituto de Investigaciones en Materiales, UNAM, Circuito Exterior, 04510, DF, Mexico
Instituto Politecnico Nacional, ESIQIE, Avenida IPN UPALM Edificio 7, 07738 DF, Mexico
E-mail: lima@iim.unam.mx
Betalains are chromophores present in different natural sources like bougainvillea
glabra flowers. These compounds are employed as food dyes. The betalains, as many
natural dyes, have poor stability and their decomposition processes are very fast. A
way to stabilize them is their incorporation onto inorganic hosts [1,2]. In this context,
we propose the extraction of betalain from bougainvillea glabra as a dye, i.e. as an
aqueous purple colored solution, and then fixe the colors in a betalain-alumina
composite system.
Figure 1 shows that color of bougainvillea glabra can be transferred from flowers to
an alumina host. The color of pigments was measured precisely using the CIEL*a*b*
parameter. However, the color depends greatly of the properties of alumina.
Figure 1. Hybrid pigments containing betalain extracted from bougainvillea flowers
and alumina synthesized by sol-gel method using different solvents: ethanol (left), 2propanol (middle) and 2-buthanol (right).
The purple chromophores are not the only ones adsorbed at alumina surface but also
other cromophores present in extract of bougainvillea become stable onto the
alumina and leads to a yellow pigment and several purple-hues pigments.
In order to obtain a hybrid purple pigments is required, on the one hand, that host
alumina matrix have a high amount of five-fold coordinated aluminum (AlV) species
and, on the other, to textural parameters as very high specific surface areas (at least
350 m2/g) and pore diameters sized between 10 and 15 nm [3].
Accelerated ageing of pigments reveals that color could be stable as time goes on but
variations occur in the colorimetric parameters. Chromophore stabilized inside pores
leads to stable purple pigments and those where the organic molecules are mainly at
surface are easily removed or react to produce yellow pigments
References
[1] Lima E., Guzmán A., Vera M., Rivera J., Fraissard J., J. Phys. Chem. C,116, 4556-4563 (2012).
[2] Laguna H., Loera S., Ibarra A., Lima E., Vera M., Micr. Mes. Mater., 98, 234–241 (2007).
[3] Pérez-Ramírez E., Lima E., Guzmán A., Dyes and Pigments, 120, 161-168 (2015).
290
PS4.17
Naproxen release from thermo-responsive hydrogels
monitored by UV-Vis Spectroscopy
M.N. Olejniczak1, K. Piechocki, M. Kozanecki1,
1
Lodz University of Technology, Faculty of Chemistry, Department of Molecular Physics,
Zeromskiego 116, 90-924 Lodz, Poland
E-mail: magdalena.olejniczak@dokt.p.lodz.pl
Hydrogels, according to the IUPAC definition, are non-fluid colloidal or
polymer network that is expanded throughout its whole volume by water. High
content of water makes hydrogels biocompatible what results in variety of potential
biomedical application like contact lenses or dressings. Recently, the special interest
is focused on the thermo-responsive hydrogels exhibiting Volume Phase Transition
(VPT), which can be a trigger to drug release from such gel. Temperature increase
causes imbalance between hydrophilic and hydrophobic polymer-water interactions
and hydrogel releases a water content. Thus, VPT temperature is the critical release
rate-determining parameter. [1]
Hydrogels obtained by radiation-induced free radical polymerization of 2-(2methoxyethoxy)ethyl methacrylate were immersed in aqueous solutions of naproxen,
sodium salt differing on drug concentration. Thermo-optical analysis was used to
determine influence of drug presence on VPT temperature. UV-Vis spectroscopy was
used to monitor dose and rate of drug release at various temperatures.
The thermo-optical results showed that VPT temperature was highly
influenced by presence of the drug - effect was directly proportional to its
concentration. The UV-Vis studies showed that rate of drug release (r) slightly
increases with temperature (T), and VPT is a trigger significantly accelerate this
process result in discontinuity of r(T) dependency
Acknowledges
The authors are deeply grateful to prof. K. Matyjaszewski, prof. J. M. Rosiak, dr J. A. Yoon and dr S.
Kadlubowski for delivery the hydrogel samples. This work was financially supported by the projects
2013/09/B/ST4/03010 (Polish National Science Centre) and Young Scientists’ Fund at the Faculty of
Chemistry, Lodz University of Technology.
References
[1] D. Schmaljohann, Advanced Drug Delivery Reviews 58, 1655 – 1670 (2006)
291
PS4.18
Structure of magnesium aluminosilicate glasses and glassceramics with and without chromium oxide
M.G. Ferreira da Silva
CICECO, DEMaC, University of Aveiro, 3810-193 Aveiro, Portugal
E-mail: gsilva@ua.pt
Magnesium aluminosilicate glasses doped with and without Cr2O3 have been studied
using the 27Al MAS-NMR (Magic Angle Spinning – Nuclear Magnetic Resonance)
and XRD (X-ray Diffraction) techniques. The glass samples were prepared using the
sol-gel method and the evolution gel-glass was also taken in consideration in this
study. In the Cr2O3 samples, heat treated at 900ºC and 1000ºC, the presence of
MgAl2O4 nanocrystals was detected
292
PS4.19
Novel protocol for the solid-state synthesis of magnetite for
medical practices
D.L. Paiva1, A.L. Andrade1, J.D. Fabris2,4, J.D. Ardisson3 and R.Z. Domingues4
1
Department of Chemistry ICEB, Federal University of Ouro Preto,
35400-000 Ouro Preto, Minas Gerais, Brazil.
2
Federal University of the Jequitinhonha and Mucuri Valleys (UFVJM),
39100-000 Diamantina, Minas Gerais, Brazil.
3
Laboratory of Applied Physics, Center for the Development of the Nuclear Technology,
31270-901 Belo Horizonte, Minas Gerais, Brazil.
4
Department of Chemistry ICEx, Federal University of Minas Gerais (UFMG),
31270-901 Belo Horizonte, Minas Gerais, Brazil.
E-mail: jdfabris@ufmg.br
Real benefits of nanotechnology both in industrial processes and in medicine are
being inimitable. Reducing sizes may significantly change some physical and
chemical properties, including electrical conductivity, magnetic response, active
surface area, chemical reactivity, and biological activity, relatively to the
corresponding characteristics of the bulk counterpart material. The way nanoparticles
are synthesized may determine their morphological uniformity, their particle sizes
distribution and, as a critical feature for clinical purposes, their purity. These
conditions become one of the key-issues for researchers in nanoscience and
developers in nanotechnology, particularly to plan the synthesis of maghemite
(Fe2O3) or magnetite (Fe3O4) with controlled form, size in the nanoscale and
magnetically induced hyperthermic behavior, if the material is to be destined to
medical clinical practices. This work was devoted to the synthesis of magnetite
nanoparticles by reducing the chemical oxidation state of iron in a commercial
synthetic maghemite. The direct solid-state chemical conversion procedure that was
first used by Pereira [1] to obtain magnetite by mixing and burning a natural hematite
(Fe2O3) with glucose was found unsuccessful, in the present case. Instead, the
magnetite could only be effectively produced by putting the reacting mixture of the
starting synthetic commercial maghemite (Sigma-Aldrich # 544884-25) mixed with
sucrose in two inversely coupled crucibles in a furnace at 400 C for 20 min. The
after-reaction residual carbon was removed with hydrogen peroxide to render the
suitably pure magnetic oxide.
The samples were characterized by Mössbauer spectroscopy; powder X-ray
diffraction and Fourier transform infrared (FTIR).
Acknowledgements:
Work supported by FAPEMIG and CNPq (Brazil). JDF is indebted to CAPES for
granting his Visiting Professorship at UFVJM under the PVNS program and to
CNPq for the grant # 305755/2013-7.
References
[1] Pereira, MC, Preparação de novos catalisadores tipo Fenton heterogeneous à base de óxidos de
ferro formados em litologia de itabirito. DSc thesis. UFMG, Brazil. In Portuguese (2009).
293
PS4.20
L-histidinium thiocyanurate: Experimental and theoretical
studies of a new nonlinear optical material
M. A. Pereira Gonçalves1, P. S. Pereira Silva1, M. Ramos Silva1and J. A.
Paixão1
1
CFisUC, Department of Physics, University of Coimbra, P-3004-516 Coimbra,Portugal
E-mail: psidonio@pollux.fis.uc.pt
Classical molecular requirements for second-order nonlinear optical (NLO) effects
are strongly elongated and conjugated molecules, asymmetrized by interacting donor
and acceptor groups. Although they often exhibit extremely large
hyperpolarizabilities, some major drawbacks are associated with their dipolar
character, e.g. a high tendency towards unfavorable aggregation and small offdiagonal tensor components. It was recognized that octupolar molecules can
circumvent the aforementioned disadvantages, since these nonpolar molecules
combine excellent (second-order) NLO characteristics with a strict cancellation of all
vectorial properties [1].
A new organic compound with an octupolar chromophore has been synthesized: Lhistidinium thiocyanurate thiocyanuric acid dihydrate (see Figure). Its structure was
determined by X-ray diffraction and it was found that it crystallizes in the
noncentrosymmetric and chiral space group P21, with cell parameters a = 11.3096(2)
Ǻ, b = 6.94250(10) Ǻ, c = 14.2779(3) Ǻ,  = 98.9193(9)º, V = 1107.50(3) Ǻ3.
The second harmonic generation efficiency was measured using the Kurtz and Perry
method [2] at a fundamental wavelength of 1064 nm. The molecular
hyperpolarizabilities were calculated with the PM7 Hamiltonian available in
MOPAC2012 [3] and with Density Functional Theory using the Firefly code [4]. The
IR spectrum was also measured.
References
[1] J. Zyss, J. Chem. Phys., 98, 6583(1993).
[2] S. K. Kurtz and T. T. Perry, J. Appl. Phys. 39, 3798-3813 (1968).
[3] MOPAC2012, James J. P. Stewart, Stewart Computational Chemistry, Version 15.127W web:
http://OpenMOPAC.net.
[4] A. A. Granovsky (2009) PC GAMESS/Firefly
classic.chem.msu.su/gran/gamess/index.html.
294
version
7.1.G,
web:
http://
PS4.21
Positron Annihilation Studies on Nanocrystalline Copper
Thin Films Doped with Nitrogen
P.M. Gordo1, M.F. Ferreira Marques1, M.T. Vieira2
1
CFisUC, Department of Physics, University of Coimbra,
Rua Larga, P-3004-516 Coimbra, Portugal
2
CEMUC®, Department of Mechanical Engineering, University of Coimbra,
R. Luís Reis Santos, P-3030-788 Coimbra, Portugal
Email: pgordo@ci.uc.pt
The addition of solutes with a strong affinity for grain boundary segregation can
inhibit grain growth, particularly during the manufacturing process, but the effects
of impurities and dopants on the mechanical and physical properties of the
nanocrystalline-materials are still not well known.
In this work, nitrogen doped nanocrystalline copper thin films were investigated
by Positron Annihilation Techniques (PAT), Transmission Electron Microscopy
(TEM) and X-ray Diffraction (XRD). The electrical resistivity was also measured.
The films were deposited onto glass substrates by dc magnetron sputtering. The
copper target was sputtered in reactive mode using 0, 1:60, 1:30, and 1:2 pN2:pAr
partial pressure ratios (Pdep = 0,3 Pa). It was possible to decrease significantly the
copper grain size down to 30 nm without formation of nitride phases as observed
by TEM and XRD. A conventional slow positron beam was used to identify the
structure of defects present in the films. The S parameter of the film shows a
strong dependence with the concentration of N in the films. The highest value of S
was observed for the film with the highest N concentration (7 at. % N content)
and it must be related with the presence of nanopores at the intersection of
interfaces (triple-lines). The films with lower N content revealed an S value that
can be associated with vacancy-sized defect at the interfaces between the grains.
The dependency of electrical conductivity of the films on the doping was also
measured. The increase of N content in the films makes the electrical resistivity to
increase, too. Films with smaller N concentration (< 3.5 % N content) show
typically good values for resistivity (< 3x10 -8 .m). On the other hand for the
highest N content this parameter increases one order of magnitude.
295
PS4.22
STRUCTURE OF CYCLOHEXANE RING
CONTAINING COMPOUNDS WITH SILICON AND
GERMANIUM SUBSTITUENTS AS STUDIED BY
MEANS OF VIBRATIONAL SPECTROSCOPY
V. Aleksa1, C. Cotter2, V. Jocys1, M. Pucetaitė1, V. Sablinskas1, G. A. Guirgis2
1
2
Faculty of Physics, Vilnius University, Sauletekio av. 9 block 3, Vilnius, LT-10222, Lithuania
Department of Chemistry and Biochemistry, College of Charleston, Charleston, SC 29424, USA
E-mail: valdemaras.aleksa@ff.vu.lt
Six-membered rings have been of interest to structural physicist and chemist because
they may have any one of the three different stable conformers, i.e., planar, twisted
and envelope forms, or possibly more than one of these forms [1]. Cyclic
hydrocarbons are known to have good surface adsorption properties, which are
mainly related with  electron orbitals. Tailoring of hydrophobic properties of such
coatings is achieved by changing of radicals attached to the ring. Modified ring
compounds with silicon or germanium as substituents have big potential for many
applications related to surface modifications. They are playing an increasing role in
controlling the interaction of water with a surface. Silicon or germanium as carbon
substituent in the ring is considered to enhance adhesion since they act as
hydrolytically sensitive centers, that can react with inorganic substrates such as glass
to form stable covalent bonds. The enhancement effect can be different for various
organosilicon compounds since such substituents can drastically change geometry of
the ring as well as conformational variety of the compounds.
The objective of this work is to elucidate spatial structure of a newly
synthesized derivatives of cyclohexane. We carried out theoretical ab initio and DFT
studies at 6-311G(3df,3pd) level as well Raman and Infrared spectroscopic analysis
of 2,2-Dimethyl-1,2-oxasilinane and Germacyclohexane. Infrared absorption
spectroscopic measurements include gas and liquid phase measurements as well as
matrix isolation technique. For the first time assignment of vibrational spectra of
both newly synthesized compounds was performed in the work. The calculated
spectra were compared with the experimental ones. It was found that both
compounds under study exist as one stable so called chair conformer. The
calculations reveal that both substituents - silicon and germanium are reasoning
flattering of the cyclohexane ring.
References
[1] G. A. Guirgis, C. J. Nielsen, A. Horn, V. Aleksa, and P. Klaeboe, J. Mol. Struct., vol. 1023, pp.
189–196 (2012).
296
PS4.23
Carbonate rocks pore network connectivity anisotropy
A. C. Machado1, R.T. Lopes1 and I. Lima1
1
Nuclear Instrumentation Laboratory, PEN/COPPE, Federal University of Rio de Janeiro, RJ, Brazil
alecastro@lin.ufrj.br
The anisotropy and connectivity of the sedimentary rocks porous space are essential petrophysical
parameters to the fluids flow comprehension through to these rocks. This comprehension is oil and
gas industrial special interest, because from the knowing of these reservoir rocks particularities is
possible to characterize a well and also manage their production in order to obtain the best possible
performance.
Anisotropy is defined as the physical and mechanical properties variability condition of a rock along
different directions. So if there is a preferred direction of the pores or fissures of a rock, this will also
be the preferred direction for the flow of fluid through that rock [1;2].
The reservoir usually has horizontal and vertical variations of porosity. The amount, size, geometry
and degree of pore connectivity directly control the permeability of the rock and reservoir productivity
[3] .
This study evaluated the degree of anisotropy and its eigenvalues, the number of Euler and
connectivity density of the porous space of six samples of heterogeneous carbonate rocks from the
Brazilian pre-salt region through the high resolution X-ray microtomography technique (micro -CT).
Micro-CT is a non-destructive analysis technique that allows the assessment of an internal structure of
materials with resolution in micron order. With a voltage of 130 kV and a current of 61 μA were made
the microtomography of samples studied using the microtomography system SkyScan / Bruker ,
model 1173 [4] . The images obtained were reconstructed by software that uses a filtered
backprojection algorithm that is based on Feldkamp [5] works generating images from serial sections
(slices) to object studied. These slices provides the view of the sample in 2D and in 3D and can be
processed digitally, so qualitative and quantitative information can be obtained from these images
after they are subjected to a series of mathematical operations such as binarization, removing noise,
improved image contrast, etc.
The results showed that the degree of anisotropy of the samples had a small variation, indicating a
default result. There was also a default behavior in eigenvalues found showing that these rocks have a
transversely isotropic symmetry its network of pores. The density connectivity and the Euler number
results indicated more connected pore space for the sample B. Figure 1 shows the 3D model of the
pore space of all samples.
Figure 1: 3D model of the sample A (a), sample B (b), sample C (c), sample D (d),
sample E (e) and sample F (f).
References
[1] Bidgoli, M.N., Jing, L., Engineering Geology, 169, 80–90 (2014).
[2] Zeng, L., Zhao, J., Zhu, S., Xiong, W., He, Y., Chen, J., Progress in Natural Science, 18, 1403–
1408 (2008).
[3] Renard, P., Allard, D., Advances in Water Resources, 51, 168–196 (2013).
[4] Machado, A.C., Oliveira, T.J.L., Cruz, F.B., Lopes, R.T., Lima, I., Applied Radiation and
Isotopes, 96, 129–134 (2015).
[5] Feldkamp, L.A., Davis, L.C., Kress, J.W., J. Opt. Soc. Am., A1, 612–619 (1984).
297
PS4.24
Structural and optical properties of TSAG and TSLAG
crystals grown by Czochralski
J. F. C. Carreira 1, J. Rodrigues 1, P. M. M. Correia 1, M. Peres 2, I. F. C.
Castro1, J. F. C. A. Veloso 1, L. Rino 1, L. C. Alves 2, K. Shimamura 3, E. G.
Villora 3, K. Lorenz 2 and T. Monteiro 1
1
2
Departamento de Física e I3N, Universidade de Aveiro, 3810-193 Aveiro, Portugal
CTN, Instituto Superior Técnico (IST), Campus Tecnológico e Nuclear, Estrada Nacional 10, P2695-066
3
National Institute for Materials Science, 1-1 Namiki, Tsukuba 305-0044, Japan
E-mail: correiacarreira@ua.pt
Terbium scandium aluminum garnet (TSAG) and terbium scandium lutetium aluminum
garnet (TSLAG) are transparent oxide materials with important applications as optical
Faraday devices [1], radiation monitoring and light converters.
In this work, the single crystals of the aluminum garnets grown by the Czochralski
technique [2] were investigated by structural and optical techniques. As-grown and
thermally annealed TSAG and TSLAG samples were studied by Rutherford
Backscattering Spectrometry (RBS), Raman spectroscopy, absorption, steady state
photoluminescence (PL), PL excitation (PLE) and time resolved PL (TRPL).
Additionally, the scintillation properties of the materials under gamma ray irradiation
were evaluated.
Although the TSAG and TSLAG samples crystalline quality was found to increase after
annealing in air at 1200 oC no changes in the absorbance occur upon the performed
thermal treatments. In the 200-850 nm spectral range, the absorption is mainly due to
Tb3+ intra-configurational 4f 8 transitions, namely 7F6 5D4 (~486 nm) and from the
ground state to the higher excited manifolds 5D3, 5G6, 5L10, 5G5, 5L9, 5L8, 5L7 in the 336392 nm region. Additionally, an intense absorption line occurs at 317 nm in the expected
inter-configurational region, followed at shorter wavelengths than 298 nm, by a steeper
increase in the absorption due to the materials band edge. Independently of the used
selective excitation (above band gap, inter or intra-configurational excitation) the room
temperature PL spectra is dominated by the emission arising from the 5D4 multiplet to
the 7F6,5,4,3,2 levels. A bright green luminescence is observed at RT due to the 5D4 7F5
transition. The preferential population mechanisms of the samples were identified and
the recombination models of luminescence are discussed.
References
[1] Encarnación G. Víllora, Pablo Molina, Masaru Nakamura, Kiyoshi Shimamura, Tsubasa
Hatanaka, Akiharu Funaki, and Kunihiro Naoe, Appl. Phys. Lett., 99, 011111 (2011);
[2] Kiyoshi Shimamura, Takayuki Kito, Elias Castel, Anastasiya Latynina, Pablo Molina,
Encarnación G. Víllora, Prakasam Mythili, Philippe Veber, Jean-Pierre Chaminade, Akiharu Funaki,
Tsubasa Hatanaka, and Kunihiro Naoe, Cryst. Growth & Design, 10, 3466 (2010).
298
PS4.25
Spectroscopic analysis of LYSO:Ce crystals
A. F. Martins, J. F. C. Carreira, J. Rodrigues, I. F. C. Castro,
J. F. C. A. Veloso, L. Rino and T. Monteiro
Departamento de Física e I3N, Universidade de Aveiro, 3810-193 Aveiro, Portugal
E-mail: correiacarreira@ua.pt
Rare earth orthosilicates are among the most widely used scintillator materials in the
last decades. Particularly, lutetium-yttrium oxyorthosilicate (LYSO) is known to
exhibit great potentialities in the field of the detectors development for medical
imaging [1]. Despite the interest in such applications the investigation of the material
fundamental properties is still scarce nowadays. Therefore a more detailed analysis is
required in order to improve the material in-depth knowledge.
In this work the spectroscopic properties of commercial cerium doped lutetium
oxyorthosilicate crystals (LYSO:Ce) were investigated by Raman spectroscopy,
steady state photoluminescence (PL), PL excitation (PLE) and time resolved PL
(TRPL).
The crystals with monoclinic crystalline structure (C2/c space group) exhibit at 14 K
two main emitting optical centers with distinct spectral shapes and peak positions
studied host. By using site selective excitation (266 nm; 325 nm) and temperature
dependent PL (14 K to room temperature) the spectral evolution of the LYSO:Ce
luminescence was investigated and models for the recombination processes are
purposed. At RT the ions photoluminescence was found to be fast, of the order of
tens of nanoseconds.
The samples were further submitted to gamma-rays excitation to evaluate their
functionality as scintillator material. An energy resolution of 12.5% at 662 keV and a
quantum yield of 26 photons/keV were obtained.
References
[1] C.M. Pepin, P. Berard, A.L. Perrot, C. Pepin, D. Houde, R. Lecomte, C.L. Melcher, H. Dautet,
“Properties of LYSO and recent LSO scintillators for phoswich PET detectors”, IEEE Transactions on
Nuclear Science, 51, 789, 2004.
299
PS4.26
The role of CdO in the structure of glasses from a section
in the CdO-TeO2-GeO2 system
C. G. Pérez-Hernández1, Ma. E. Zayas2, J. Alvarado-Rivera 3, D. A. RodríguezCarvajal1, Ma. B. Manzanares-Martínez1, M. E. Álvarez1, R. Lozada-Morales4
and J. Ma. Rincón5
1
Departamento de Física, Universidad de Sonora, Blvd. Encinas y Rosales S/N, Col. Centro, C. P.
83000, Hermosillo, Sonora, México.
2
Departamento de Investigación en Física, Universidad de Sonora, Blvd. Encinas y Rosales S/N, Col.
Centro, C. P. 83000, Hermosillo, Sonora, México.
3
Cátedras Conacyt, Departamento de Investigación en Física, Universidad de Sonora, Blvd. Encinas y
Rosales S/N, Col. Centro, C. P. 83000, Hermosillo, Sonora, México.
4
Benemérita Universidad Autónoma de Puebla, Postgrado en Física Aplicada, Facultad de Ciencias
Físico-Matemáticas, Av. San Claudio y Av. 18 Sur, Col. San Manuel, Ciudad Univ., Puebla, C. P.
72570, México.
5
The Glass-Ceramics Lab., Inst. E. Torroja Ciencias Construcción (CSIC). P. O. Box 19002, Madrid,
Spain.
E-Mail: mzayas@cifus.uson.mx
jrincon@ietcc.csic.es
In the Gibbs’ triangle of the CdO-TeO2-GeO2 system, eight different formulations were selected to
study the effect of CdO variation in the glass structure. The investigated compositions have been in
the ranges: CdO (10-80%) and GeO2 (80-10%) content and fixing the TeO2 proportion at 10% wt.
Reagent grade oxides powders of high purity were used for glass fabrication. The glasses were
prepared by melting the oxides powders mixtures in a high alumina crucible at 1350°C. The obtained
samples show a variation in coloration as the CdO proportion increase, from amber, yellow and
orange. X-ray diffraction (XRD) patterns of the glasses showed that most of the samples are
amorphous evidenced by a broad band in the range of 15° to 40° (2θ). Partial crystallization occurred
for the glass M6 (60CdO.10TeO2.30GeO2) presenting the formation of GeO2 (2θ = 26.4°) and
CdTeO3 (2θ = 29.5°). Sample M7 (70CdO.10TeO2.20GeO2) displays very intense diffraction peaks
corresponding to the Cd3 Al2 (GeO4)3 crystalline phase.
The Infrared Spectroscopy exhibits very weak and broad absorption bands related to Te-O-Te
vibrations (800-600 cm-1) in all the glasses. However, it is observed that at low frequencies (550-400
cm-1) predominates intense absorption peaks corresponding to GeO 6 (520-470 cm -1) and Cd-O (440420 cm-1) bonds vibrations.
Moreover, Raman spectra is dominated by two bands at 980-670 cm-1 and 640-370 cm-1. The first
band is assigned to stretching vibrations Te-O of TeO4 units and the second band is related to Ge-OGe bonds in 4- and 3- membered GeO4 rings, As the CdO content increase, changes in the glasses
structure are noticed, the band at 980-670 cm-1 shifts to lower wavenumber values of 800 – 750 cm-1
corresponding to TeO3/TeO3+1 units. In addition, the band associated to Ge-O-Ge bonds gradually
decrease in intensity until it disappear for the glass with the lowest content of GeO 2.
Thus, CdO as a modifier oxide induce a change in the Te ions coordination with the introduction of
non-bonding oxygen to the glass network. This is, even at the lowest concentration of glass network
former oxides a transparent orange glass can be obtained and this sample can be identified as an
inversed glass. Absorption spectra of the glasses was also performed and energy band gap values of
the glasses were estimated. Results showed that the energy band gap decrease as the content of CdO
rises. The obtained glasses are promising materials for Infrared materials applications in non-linear
optics and design of laser devices.
300
PS4.27
Mössbauer, XRD and XRF studies of Roman Haltern 70
amphorae from Roman Provinces of Lusitania and Baetica
F. Wagner1, U. Wagner1, W. Häusler1, A. Francisco2, M. Guerra2, B.F.O.
Costa3 and A.J.M. Silva4
1 Physics Department, Technical University of Munich, 85747 Garching, Germany
2 Laboratório de Instrumentação, Engenharia Biomédica e Física da Radiação
(LIBPhys-UNL), Departamento de Física, Faculdade de Ciências e Tecnologia,
FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
3 CFisUC, Physics Department, University of Coimbra, 3004-512 Coimbra, Portugal
4 Centro de Estudos Arqueológicos das Universidades de Coimbra e do Porto/CAM, Palácio de SubRipas, 3004-395 Coimbra, Portugal (FCT Post-Doc Grant)
Roman Haltern 70 amphora sherds found at Castro do Vieito [1,2], an archeological
site in the north of Portugal, in the former Roman Province of Lusitania, were
studied by 57-Fe Mössbauer spectroscopy, X-ray diffraction and X-ray fluorescence
in order to obtain information on their firing conditions and their site of production.
For comparison, Haltern 70 amphorae sherds found at eight kiln sites in the south of
Portugal and south of Spain, the former provinces of Lusitania and Baetica, were
studied by the same methods.
The sherds from Castro do Vieito as well as the ones from the kiln sites were found
to have been fired at temperatures around 800ºC in atmospheres that changed
between reducing and oxidizing at least once during the firing cycle. Oxidation
during the final stage of firing often lead to sherds with more divalent iron in the core
than on the surface.
The amphorae found at Castro do Vieito appear to have been produced in Baetica
(south of Spain) and used to transport agricultural produce to the north, but a definite
location for their production cannot yet be given.
References
[1] A. J. Marques da Silva, Vivre au-delà du fleuve de l’Oubli. Portrait de la
communauté villageoise du Castro do Vieito au moment de l’intégration du NO de la
péninsule ibérique dans l’orbis Romanum (estuaire du Rio Lima, NO du Portugal),
Archaeopress, BAR International Series 2342, Oxford (2012).
[2] A. J. Marques da Silva, “Ceramics. Food and local ‘sub-cultures’ in northwestern Iberia at the height of the Roman Empire. The Castro do Vieito case study“,
HEROM – Journal on Hellenistic and Roman Material Culture, 4-1, pp. 11-32
(2015). http://dx.doi.org/10.11116/HEROM.4.1.1
301
PS4.28
Structural and nonlinear optical studies of a salt with an
octupolar chromophore: guanidinium
cyclopropanecarboxylate
P. S. Pereira Silva1, M. A. Pereira Gonçalves1, M. Ramos Silva1and J. A.
Paixão1
1
CFisUC, Department of Physics, University of Coimbra, P-3004-516 Coimbra,Portugal
E-mail: psidonio@pollux.fis.uc.pt
The antiparallel alignment of the dipole moments of one-dimensional chromophores
leads the majority of -conjugated organic molecules to crystallize in
centrosymmetric space groups, having therefore null second-order bulk
susceptibility. One of the solutions to achieve dipole minimization without losing the
molecular hyperpolarizability is the use of octupolar systems since their threefold
rotational symmetry ensures cancellation of the molecular dipole moment [1].
Furthermore, a noncentrosymmetric octupolar structure facilitates an optimal transfer
of the molecular hyperpolarizability components to the macroscopic level [2].
During the course of a research program aimed at the structural and optical
characterization of newly synthesized compounds based on guanidine, the crystal
structure of guanidinium cyclopropanecarboxylate (see Fig.) have been determined
by single crystal X-ray diffraction using Mo K radiation. The structure is
noncentrosymmetric with the chiral space group P212121.
The Second Harmonic Generation (SHG) efficiency was measured with the Kurtz
and Perry method [3] using a Nd-YAG laser of 1064 nm. The molecular
hyperpolarizability was calculated with semi-empirical and ab initio methods. The
components of the lowest-order nonlinear optical susceptibility tensor dijk of the
crystal were calculated using the oriented-gas model [4] and the results are compared
with the experimental SHG efficiency. The IR spectrum was also measured for this
material and compared with the spectrum calculated by ab initio methods.
References
[1] J. Zyss, J. Chem. Phys., 98, 6583(1993).
[2] J. Zyss, I. Ledoux-Rak, H. C. Weiss, D. Bl• aser, R. Boese, P. K. Thallapally, V. R. Thalladi G. R.
Desiraju. Chem. Mater., 15, 3063 (2003).
[3] S. K. Kurtz and T. T. Perry, J. Appl. Phys. 39, 3798-3813 (1968).
[4] J. Zyss and J. L. Oudar, Phys. Rev. A 26, 2028 (1982).
302
PS4.29
Searching for Porphyrin-Based Lanthanide Complexes
With Both Visible and NIR Emission
M. Susano1, C. T. Arranja2, L. C. J. Pereira3, M. Ramos Silva1 and A.J.F.N.
Sobral2
1
CFisUC, Department of Physics, FCTUC, University of Coimbra, P-3004-516 Coimbra, Portugal.
2
Department of Chemistry, University of Coimbra, P-3004-516 Coimbra, Portugal
3
Solid State Group, UCQR, IST/CTN, Instituto Superior Técnico, UTL, 2695-066 Bobadela, Portugal
E-mail: manuela@pollux.fis.uc.pt
Lanthanide near infrared luminescence (NIR) is of great interest because of its
potential applications in biological imaging and in telecommunications [1–2]. One of
the most important applications of lanthanide complexes is as luminescent labels in
clinical diagnostics where they provide an alternative to radioactive probes. Due to
the f–f forbidden transitions impeding direct absorption, Ln(III) cations need to be
sensitized by a chromophore acting as an antenna for efficient light absorption. The
porphyrin derivatives are perfect candidates to address the above mentioned
requirement since they are strong chromophores absorbing both in the UV and
visible regions, the backbone may be readily functionalized at meso and -pyrrolic
positions thus offering a large variety of possibilities and variations and, most
importantly, its excited state levels are perfectly adapted for the sensitization of
Ln(III) NIR emitters (mammalian tissues are very transparent to NIR radiation). For
other applications like in cellulo sensing, visible emission is more adequate [3-4] but
to achieve that a second ligand has to be used in combination with the porphyrin
core.
In this context, we have developed and characterized porphyrin-based lanthanide
complexes, searching for both NIR and Visible emission of Ln(III) cations. The
materials preparation was done in 3 major steps: synthesis of meso-tetra-phenyl
porphyrin (TPP) by the Adler-Longo [5] method, purification and complexation with
Ln(acac)3- 3H2O. Crystallization was conducted by slow solvent evaporation at room
temperature. Structural determination was performed using single crystal and powder
X-ray diffraction. Luminescent properties were studied, including emission in the
NIR- and Visible-region. The structural, thermal, optical and magnetic properties of
the new compounds will be presented and discussed.
Acknowledgements: This work was supported by FEDER/QREN/COMPETE - FCT
through projects PTDC/AAC-CLI/118092/2010 and PEst-OE/QUI/UI0313/2014
(Coimbra Chemistry Centre). Maria Susano thanks FCT for providing her a grant
under the doctoral programme ChemMat.
References
[1] K. Binnemans, Chem. Rev., 109, 4283-4374 (2009).
[2] P. Martín-Ramos et al., J. of Materials Chemistry C, 1, 5701-5710 (2013).
[3] J-CG Bunzli. 2013 Interface Focus 3: 20130032 (2013).
[4] S. Pandya, J. Yu, D. Parker, Dalton Trans., 2757-2766 (2006).
[5] A. D. Adler et al., J. Org. Chem., 32, 476 (1967).
303
PS4.30
Magnetic coupling through cyanoacetate bridges:
Syntheses, structure and physical properties of two low
dimensional compounds
M. Ramos Silva1, J. Coutinho2, L.C.J. Pereira2, P. Martín-Ramos1,3 and J.C.
Waerenborgh2
1
2
CFisUC, Department of Physics, University of Coimbra, P-3004-516 Coimbra, Portugal
C2TN, Instituto Superior Técnico, Campus Tecnológico e Nuclear, Estrada Nacional 10 (km
139,7),
2695-066 Bobadela LRS, Portugal
3
Escuela Politécnica Superior de Huesca, Universidad de Zaragoza, 22071 Huesca, Spain
In modern coordination chemistry, much work is devoted to the synthesis and
investigation of compounds with exchange-coupled structural fragments, known as
exchange clusters [1]. Within this family, 3d-metal carboxylates have been more
extensively studied due to their vast applications [2]: catalysis, analytical chemistry,
materials science, and as precursors of magnetic materials; [Mn12O12(OAc)16(H2O)4]
and [Fe8O2(OH)12(tacn)6]Br clusters represent prototypes of manganese and iron
complexes showing SMM behavior [3-4]. Furthermore, iron and manganese clusters
have been widely studied as models for biological systems such as the iron-storage
protein ferritin and for the water-oxidizing complex in photosystem II, respectively
[5-6]. Here we report the synthesis of two new coordination compounds using
cyanoacetic acid: a Fe(III) compound with the metal ions assembled in trinuclear
clusters and a Mn(II) compound with the metal ions congregated in layers. The result
of samples characterization using IR-spectroscopy, X-ray diffraction, magnetometry,
Mossbauer spectroscopy etc will be presented and discussed.
Figure 1. Crystal structure of a new Mn(II)-cyanoacetic acid coordination compound.
References
[1] O. Kahn, Molecular Magnetism, VCH, New York (1993).
[2] R. C. Mehrota and R. Bohra, Metal Carboxylates, Academic Press, London (1983).
[3] R. Sessoli, D. Gatteschi, A. Caneschi, M. A. Novak, Nature, 365, 141 (1993).
[4] A.-L. Barra, et al., Europhys. Lett., 35, 133 (1996).
[5] Wieghardt, K. Angew. Chem., Int. Ed. Engl. 33, 725 (1994).
[6] S. T. Ochsenbein, et al., Inorg. Chem., 41, 5133 (2002).
304
PS4.31
Mössbauer spectroscopy studies on supersaturated FeCoSn
solid solutions and their ordering by annealing
B. Malaman1, G. Le Caër2, B.F.O. Costa3, P.M. Gordo3 and A. Ramalho4
1
Institut Jean Lamour, Département P2M, Equipe 103, CNRS (UMR 7198)- Université de Nancy,
B.P. 70239, 54506 Vandoeuvre-les-Nancy Cedex, France
2
IPR, UMR URI-CNRS 6251, Université de Rennes I, Campus de Beaulieu, Bat 11A, 35042 Rennes
Cedex, France
3
4
CEMUC, Department of Mechanical Engineering, University of Coimbra, 3000-272 Coimbra,
Portugal
Iron-cobalt alloys have exceptional magnetic properties and are mechanically
relatively strong [1]. Near-equiatomic FeCo alloys are bcc (A2) below ~1250K [1]
and they order to a CsCl type structure (B2) at temperatures below ~1000K. A
possible way to study alloys which tend to order is first to prepare them in a
metastable state by high-energy ball-milling from mixtures of elemental powders [2].
The Fe-Co-Sn system is essentially uninvestigated. The equilibrium solubility of Sn
in FeCo (A2 or B2) is ~ 1 at% [3].
Milling of Fe, Co and Sn powders was performed in argon using a planetary Fritsch
Pulverisette P6 mill. As-milled alloys were vacuum annealed at 673K for 15h.
Here we present results on the evolution of the alloying process of (FeCo)100-xSnx and
the annealed alloys characterization by 57Fe and 119Sn Mössbauer spectroscopy (MS)
and scanning electron microscopy (SEM).
Previous studies of ground powders [4, 5, 6] showed the presence of nanocrystalline
disordered bcc phases. The maximum solubility of Sn in near-equiatomic FeCo, in
our milling conditions, is about 20 at% Sn.
MS shows that the average 57Fe hyperfine magnetic field (HMF) decreases when the
Sn content increases in the as-milled state. The decrease is much less for annealed
alloys. The 57Fe HMF’s are not very sensitive to chemical order in these alloys. By
contrast, the 119Sn HMF’s show a strong sensitivity to chemical order when dissolved
in B2 FeCo (~0.3 at.%Sn) [3]. The 119Sn spectra vary strongly when the as-milled
alloys are annealed at 673K. For x=12 the average 119Sn HMF increases from 9.8 T
to 16.3 T between the as-milled and the annealed states. The maximum 119Sn HMF,
24.5 T, is close to the value measured for Sn dissolved in perfectly ordered FeCo [3].
We conclude that the metastable as-milled alloys are bcc and disordered, and order
by annealing at moderate temperatures (here 673K) for Sn content less than 20 at.%.
References
[1] T. Sourmail, Prog. Mater. Sci. 50, 816 (2005).
[2] C. Suryanarayana, Prog. Mater. Sci., 46, 1(2001)
[3] N.N. Delyagin and E.N. Kornienko, Sov. Phys. Solid State 13, 1254 (1971)
[4] J.M. Loureiro, B.F.O. Costa and G. Le Caër, J. Alloys Comp 536S, S31 (2012)
[5] J.M. Loureiro, B.F.O. Costa, G. Le Caër and B. Malaman, Solid State Phenom 194, 187 (2013)
[6] J.M. Loureiro, B.F.O. Costa, B. Malaman, G. Le Caër, S. Das and V.S. Amaral, J. Alloys
Comp 615, S559 (2014)
305
PS4.32
Positron lifetime spectroscopy studies on moisture
absorption and thermal ageing of an epoxy
J.M.M. Luís1, P.M. Gordo1, M.F. Ferreira Marques1,
M. Duarte Naia2, José J.L. Morais3
1
2
CFisUC, Department of Physics, University of Coimbra, 3004-516 Coimbra, Portugal
CEMUC®, Department of Physics, ECT-UTAD, PO Box 1013, 5001-801 Vila Real, Portugal
3
CITAB, Department of Engineering, ECT-UTAD, 5001-801 Vila Real, Portugal
E-mail: pgordo@ci.uc.pt
The epoxy resins are cross-linked polymers with excellent chemical and thermal stability. They are
important engineering materials used in structures subjected to complex mechanical, hygrothermal
and chemical loadings and many other applications. The long-term behavior of these materials is still
challenging issue, but whose knowledge is crucial to ensure the integrity and reliability of structures
based on epoxy resins. Two of the overall problems of durability of polymers are the moisture
absorption and the thermal ageing.
The absorbed moisture plasticize the epoxide, induces differential swelling stresses and generally
degrades the physical properties of the epoxide. Some of the effects are a decrease of the glasstransition temperature, i.e. a decreased thermal stability; a decrease in yield strength, a change of the
yield/deformation mechanisms, or both; the creation of microcracks or crazes; and chain scission
through hydrolysis reactions. Due to these factors it is important to control or inhibit moisture
absorption to prevent these undesirable events to happen and it’s of main importance the
understanding of the transport mechanism in epoxides. It is generally believed that moisture
absorption is closely related to the free volume properties of the epoxide.
Similarly, the evolution of the physical aging characteristics of the polymer, e.g. the endothermic peak
temperature and enthalpy of relaxation (these quantities showed an exponential increase to the
equilibrium with the ageing time), are considered to be strictly related to the free volume.
Positron Annihilation Lifetime Spectroscopy (PALS) is a well-established and very sensitive
technique for probing sub-nanometer-sized local free volumes between molecular chains in polymeric
structures and it was used in the study to characterize the free volume fraction of a commercial epoxy
and its evolution during the processes of moisture absorption and thermal ageing.
The study of the effect of water uptake on the free volume of the samples exposed to atmospheres
with relative humidity ranging from 30.5% to 95.8% was also analyzed by gravimetric measurements.
When exposed to humidity the mean hole volume remains constant and the number of holes not
occupied by water molecules decrease with increasing of both the exposition time and the relative
humidity as indicated by the constancy of 3 (the o-Ps lifetime) and the decrease of its intensity, I3.
The moisture saturation is achieved after approximately 400 h and the increment rate is very high.
The study of the physical ageing was performed at constant temperatures of 30, 40 and 50°C. The
Fourier transform infrared spectroscopy (FTIR) was used to monitor the chemical integrity of the
material composition, and it was found that the material is unchanged during the ageing program. The
specimens, after a well-controlled rejuvenation process, were subjected to mechanical study. Three
points bending tests were performed under monotonous and relaxation loading, to evaluate the effect
of physical aging on elastic and viscoelastic behavior.
To attempt an explanation of the different macroscopic mechanical, physical, and chemical properties
of the epoxy, the specimens were also measured with PALS. However, and contrary to the observed
during the moisture absorption process, the variation of the PALS parameters during the molecular
relaxation process, associated with the thermal ageing, was very slow during the time selected for this
study. This reveals that the time scales for moisture absorption and molecular relaxation processes are
significantly different. The relaxation process is largely slower than the moisture absorption process.
It was still possible to observe that the effects of structural relaxation are more difficult to observe at
temperatures closer to the glass transition temperature of the epoxy.
306
PS4.33
Synthesis, structure and physical properties of luminescent
Pr(III) -diketonate complexes
V. Pereira1, A. Costa2, J. Feldl1,3, T.M.R. Maria2, J.S.S. Melo2, P. MartínRamos1,4, J. Martín-Gil5 and M. Ramos Silva1
1
CFisUC, Department of Physics, University of Coimbra, P-3004-516 Coimbra, Portugal
CQC, Department of Chemistry, University of Coimbra, P-3004-535 Coimbra, Portugal
3
Fakultät für Physik, Ludwig-Maximilians-Universität, Schellingstrasse 4,
80799 München, Germany
4
Escuela Politécnica Superior de Huesca, Universidad de Zaragoza, 22071 Huesca, Spain
Advanced Materials Laboratory, ETSIIAA, Universidad de Valladolid, 34004 Palencia, Spain
2
5
The research on low cost materials emitting in the near-infrared (NIR) has great
interest, given its potential applications in optical communication networks and in
the nanobiophotonics field. Among these materials, lanthanide complexes (including
Pr(III)) are especially promising because they emit well defined bright light, in the
near infrared region. However, lanthanide direct excitation is difficult due to their
low optical cross section arising from the forbidden nature of their 4f → 4f
transitions. One way to overcome this problem is by complexing the lanthanide ions
with organic molecules specifically designed for this purpose. These molecules
absorb the excitation energy efficiently and transfer it to the lanthanide ion, that
further re-emits it: a sequence of processes called antenna effect [1-3]. We have
probed the luminescence properties of similar Pr(III) complexes with the
replacement of one bridging water molecule to an aromatic bulkier molecule. The
results will be compared and discussed.
The full structural description of the three Pr(III) complexes obtained by single
crystal X-Ray diffraction will also be presented along with their characterization
through several other techniques such as infrared spectroscopy, differential scanning
calorimetry, thermomicroscopy, X-ray fluorescence, absorption spectroscopy,
magnetometry, etc.
Figure 1. Molecular structure of Tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate)mono(bathophenanthroline)Praseodymium(III)
References
[1] K. Binnemans, Chem. Rev., 109, 4283-4374 (2009).
307
Poster Session 4: Clinical and Pharmaceutical Analysis
PS4.34
Spectroscopic and Thermal Analysis of serum in multiple
myeloma patients
L. Plotnokova1, T. Nosenko1, M. Uspenskaya1, R. Olekhnovich,
A. Polyanichko2, S. Voloshin3, A. Garifullin3
1
Saint Petersburg National Research University of Information Technologies, Mechanics and Optics,
Kronverksky Pr. St. Petersburg,197101,Russian Federation
2
Department of Molecular Biophysics and Polymer Physics, Saint-Petersburg State University, 1
Ulyanovskaya Str., Petrodvorets, Saint-Petersburg, 198504, Russian Federation.
3
Russian Scientific Research Institute of Hematology and Transfusion, 16, 2-nd Sovetskaya Str.,
Saint-Petersburg, 191024, Russian Federation.
E-mail: ljusja@mail.ru
Multiple myeloma (MM) accounts for about 1% of all types cancers. MM are
characterized by the proliferation of a single clone of plasma cells, which may
produce and secrete a homogeneous monoclonal immunoglobulin. The monoclonal
immunoglobulin is commonly referred to as an M protein. The M protein acts as a
serological “tumor” marker that is useful for diagnosis and disease monitoring. The
monoclonal protein electrophoretic pattern shows a single peak or localized band in
80% of MM patients. In our study we applied a combination of high-resolution
agarose gel protein electrophoresis (PEL), spectroscopic techniques and thermal
analysis to identify the key differences in protein composition, protein structure and
their thermal behavior for the samples obtained from the serum of MM patients and
healthy donors.
Based on the refractometric analysis we have shown that the total amount of the
proteins in the MM serum is considerably higher, that in the serum of the healthy
donors. Using Differential Scanning Calorimetry (DSC) we have shown, that in some
cases the dependences of the Specific Heat Capacity on temperature of the MM
serum can be characterized by a unique profile, qualitatively discriminating samples
obtained from the MM patients and the healthy donors. Using FTIR spectroscopy we
have estimated the major parameters of the secondary structure for the proteins in the
serum. The potential applications of the techniques applied in this study for the
diagnostics of multiple myeloma are discussed.
This work was financially supported by Government of Russian Federation, Grant
074-U01. Part of the research was performed using the equipment of the Centre for
Optical and Laser Materials Research of St Petersburg State University.
.
308
PS4.35
Elements concentration in human urine determined using
TXRF method
U. Majewska1,2, P. Łyżwa3, K. Łyżwa4, D. Banaś1,2, A. Kubala-Kukuś1,2, J.
Wudarczyk-Moćko2, I. Stabrawa1, J. Braziewicz1,2, M. Pajek1, G. Antczak2, B.
Borkowska2 and S. Góźdź2,5
1 Institute of Physics, Jan Kochanowski University, Świętokrzyska 15, 25-406 Kielce, Poland
2 Holycross Cancer Center, Artwińskiego 3, 25-734 Kielce, Poland
3 Władysław Buszkowski Children's Hospital of Kielce, Langiewicza 2, 25-381 Kielce, Poland
4 Provincial Hospital in Kielce, Grunwaldzka 45, 25-736 Kielce, Poland
5 Institute of Public Health, Jan Kochanowski University, IX Wieków Kielc 19, 25-317 Kielce,
Poland
Total reflection X-ray fluorescence (TXRF) analysis is one of the method commonly
used in elemental analysis of different kind of samples. This technique allows to
determine many elements in wide range of concentrations during one measurement. The
level of detection limit, depending on the kind of sample, can reach level even a few
ng/g. One of the possible research area of this method is its implementation in medical
applications. Analysis of human urine is commonly used in biomonitoring studies to
assess exposure to macro (e.g. P, S, K, Ca, Fe) and trace (e.g. Cr, Mn, Cu, Zn, Rb, Pb)
elements. These data could be also used in studies to evaluate potential correlations
between elements exposure and various health effects within a population. Therefore the
aim of this work has been to determine the elements in human urine of randomly
selected people. The concentration values obtained are reference values with which one
will be able compare the content of a given element obtained in urine of a patient.
As results of discussed studies the values of concentration of P, S, K, Ca, Cr, Mn, Fe, Ni,
Cu, Zn, Br, Rb, Sr and Pb elements have been determined in 100 urine samples taken
from 62 women (aged between 13 and 84 years old) and 38 men (aged between 16 and
82 years old). Donors were presumable healthy volunteers.
In the case of ,,nondetects”, i.e. measurements, in which concentration is below detection
limit of method used (Cr, Mn, Ni, Se, Pb), the random-left censoring approach [1] has
been applied in statistical analysis of the results.
The method of selection of the control group, the experimental system, method of
samples preparation and finally the measurement procedure were also described in the
paper.
References
[1] M. Pajek, A. Kubala-Kukuś, J. Braziewicz, Spectrochim. Acta B, 59, 1091-1099 (2004).
309
PS4.36
Determination of element levels in human serum: Total
Reflection X-ray Fluorescence medical applications
U. Majewska1,2, P. Łyżwa3, K. Łyżwa4, D. Banaś1,2, A. Kubala-Kukuś1,2, J.
Wudarczyk-Moćko2, I. Stabrawa1, J. Braziewicz1,2, M. Pajek1, G. Antczak2, B.
Borkowska2 and S. Góźdź2,5
1
2
3
Władysław Buszkowski Children's Hospital of Kielce, Langiewicza 2, 25-381 Kielce, Poland
4
Provincial Hospital in Kielce, Grunwaldzka 45, 25-736 Kielce, Poland
5
Institute of Public Health, Jan Kochanowski University, IX Wieków Kielc 19, 25-317 Kielce, Poland
It is known that elements have a significant role in numerous physiological processes of
human organism and consequently affect the human health and diseases. Deficiency or
excess of elements could disrupt proper functioning of the human body and could lead to
several disorders. Determination of their concentrations (not only Na, K, Ca and Fe but
also trace elements such as, for example, Cr, Cu, Zn, Se, Rb, Pb ) in the different
biological human fluids and tissues should become a routine practice in medical
treatment. Therefore the knowledge about appropriate element concentrations and their
proportions in human organism is required. Results presented in this paper are a
continuation of research conducted in our laboratory and described in [1] (the number of
samples tested was increased; the spectrometer used to analysis has better detection
limit).
The purpose of this study was to determine the concentration of several elements (P, S,
K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Se, Br, Rb, Sr, Pb) in human serum. Samples of serum
were obtained from 105 normal presumable healthy volunteers (66 women aged between
15 and 78 years old; 39 men aged between 15 and 77 years old). Total reflection X-ray
fluorescence (TXRF) method was used to perform the elemental analyzes. This
technique is competitive to chemical methods because it requires a very small amount of
material for analysis and one measurement gives information about many elements in
wide range of measured concentrations. These advantages and level of detection limit
that can reach level even a few ng/g results that TXRF method is very convenient for
quick analysis of the daily work of hospital laboratory.
Spectrometer S2 Picofox (Bruker Nano GmbH) was used to identify and measure
elemental composition of serum samples. Details of experimental set-up as well as
preparation and measurement procedures were described in the paper.
In the case of ,,nondetects”, i.e. measurements, in which concentration is below detection
limit (e.g. Sr), the random-left censoring approach [2] has been applied in statistical
analysis of the results.
References
[1] U. Majewska, D. Banaś, J. Braziewicz, A. Kubala-Kukuś, M. Pajek, I. Sychowska, J. WudarczykMoćko, G. Antczak, B. Borkowska and S. Góźdź, Acta Phys. Pol. A, 125, 864-868 (2014).
[2] M. Pajek, A. Kubala-Kukuś, J. Braziewicz, Spectrochim. Acta B, 59, 1091-1099 (2004).
310
PS4.37
Application of X-ray microtomography in environmental,
biological and pharmaceutical solid dosage forms studies
A. Kubala-Kukuś1,2, D. Banaś1,2, U. Majewska1,2, I. Stabrawa1,
J. Wudarczyk-Moćko2, J. Braziewicz1,2, M. Pajek1 and S. Góźdź2,3
1
2
3
Institute of Public Health, Jan Kochanowski University, IX Wieków Kielc 19, 25-317 Kielce,
Poland
E-mail: aldona.kubala-kukus@ujk.edu.pl
X-ray microtomography is a technique in which the internal structures of the studied
samples are reconstructed as series of 2D cross sections which are next used to create
a virtual three dimensional image of the scanned object. The resolution achieved in
typical X-ray microtomographic measurements is on the level about 5 microns. The
imaging capabilities of X-ray microtomography are available for small objects in a
wide range of applications [1-3].
The main aim of the presented studies is demonstration of the application of SkyScan
1172 microtomograph in environmental, biological and pharmaceutical industry
studies. In this work different examples of microtomographic imaging will be
presented, namely: bone and tooth analysis, food studies, insects and animals
imaging, minerals research. We concentrate our efforts on three-dimensional
structural imaging of pharmaceutical solid dosage forms and samples with soil and
geological matrices. In the case of pharmaceutical samples the studies concentrate on
their properties, function and structural features like a shape and dimension of the
regions that are not readily accessible (the thickness of layers in multilayer tablets,
structure of the interface between these layers). In this imaging the small defects,
damages, impurities and composites can be found. Also distribution of components
in studied materials can be investigated. The microtomography studies of soil and
geological samples concentrate on the sample morphometry, porosity and fractal
analysis. Morphology of each sample can be in this way characterized in
micrometers scale especially in the context of the information about grains size.
In the presented work the aims, the images and the quantitative results of performed
X-ray microtomography studies will be shown and discussed. Additionally, for many
applications it will be demonstrated that X-ray microtomography technique can
provide complementary information to spectroscopic (WDXRF, TXRF) and
diffraction (XRPD) methods.
References
[1] A. Madra, N. El Hajj, M. Benzeggagh, Composites Science and Technology, 95, 50-58 (2014)
[2] N. L. Cordes, S. Seshadri, G. J. Havrilla, X. Yuan, M. Feser, B. M. Patterson, Spectrochim. Acta
B, 103-104, 144-154 (2015)
[3] X. Fu, M. Dutt, A. Craig Bentham, B. C. Hancock, R. E. Cameron, J. A. Elliott, Powder
Technology, 167, 134-140 (2006)
311
PS4.38
A novel approach based on spectrofluorimetry for the
determination of Silodosin in pharmaceutical dosage forms
E. Er and N. Erk
1
Department of Analytical Chemistry, Faculty of Pharmacy, Ankara University, Ankara, Turkey
E-mail: eer@ankara.edu.tr
Herein, we present a fully-validated spectrofluorimetric method for the determination
of Silodosin in pharmaceutical dosage forms. Silodosin (SLD) is a novel therapeutic
agent for the treatment of the signs and symptoms of benign prostatic hyperplasia
[1]. Therefore, it is highly important to detect the SLD in real samples [2]. The
spectrofluorimetric method was used by measuring the native fluorescence feature of
SLD at different pH values and excitation wavelengths in the range from 340.0 to
600.0 nm. The maximum fluorescence intensity was obtained at the wavelength of
460 nm after excitation at 330 nm in pH 6 phosphate buffer. The linear working
range of SLD was found to be 0.2 – 36.4 µM with the low detection limit of 7.7 nM.
The proposed method was validated in terms of accuracy, precision and selectivity. It
was successfully carried out for assay of SLD in pharmaceutical samples. The
accuracy of the proposed method was compared to the validated high performance
liquid chromatography (HPLC) results. The system consisted of Agilent Zorbax CN
Column (150 mm, 4.6 mm, 5 µM), and the UV detection was performed at 270 nm
with diode-array detector. The mobile phase was a mixture of methanol: acetonitrile:
ammonium acetate (pH: 4.0; 0.015 M) (30:50:20, v/v/v) pumped at 25 °C with a flow
rate of 1.3 mL min-1. Considering all these data, a rapid, simple, highly sensitive and
selective spectrofluorimetric method was developed for the determination of SLD in
pharmaceutical samples. The proposed method may be promising alternative for the
quantification of SLD in pharmaceutical or clinical samples.
References
[1] M. Yoshida, Y. Homma, K. Kawabe, Exp. Opin. on Invest. Drugs, 16, 1955-1965 (2007).
[2] E. Er, H. Çelikkan, N. Erk, M. L. Aksu, Electrochim. Acta, 157, 252–257 (2015).
312
PS4.39
Study of the Element Concentration in Cancerous Tissues
C. Bettencourt1, M. L. Carvalho1, J. P. Santos1 and M. Guerra1
1 Laboratório de Instrumentação, Engenharia Biomédica e Física da Radiação (LIBPhys-UNL),
E-mail: mguerra@fct.unl.pt.
The incidence of cancer worldwide has increased from 12.7 million in 2008 to 14.1
million in 2012, and this trend is expected to continue. The predicted number of cancer
cases is near to 25 million over the next two decades.
An understanding of cancer biology is crucial to develop therapies and offer preventive
options. The role of trace elements in cell metabolism has been studied and related to the
carcinogenesis process. In this study the elemental composition of healthy and cancerous
human samples of the colon, lung, breast and kidney tissues were obtained by X-ray
Fluorescence Spectrometry. This quantitative and qualitative technique features a high
resolution and provides a multi elemental analysis. The objective was to determine
which elements differentiate cancerous and normal tissues, correlations between
elements and ratios considered important indicators of cancer development.
313
PS4.40
Analysis of trace elements in the hair of
newborns using XRF Spectrometry
J. Carmo1, I. Salva2, L. Pereira-da-Silva3,
J. G. O'Neill4, M. L. Carvalho1, J. P. Santos1 and M. Guerra1
1 Laboratório de Instrumentação, Engenharia Biomédica e Física da Radiação (LIBPhys-UNL),
2 Área de Pediatria Médica, Hospital de Dona Estefâia, Centro Hospitalar de Lisboa Central E.P.E.,
1169-045 Lisboa, Portugal
3 Unidade de Neonatologia, Hospital de Dona Estefânia, Centro Hospitalar de Lisboa Central E.P.E.,
4 Departamento de Anatomia, Faculdade de Ciências Médicas, FCM, Universidade Nova de Lisboa,
E-mail: j.carmo@campus.fct.unl.pt
The current study aims to compare the trace elements present in the hair[1] of fullterm and pre-term newborns. This analysis allows us to determine how nutrients are
absorbed throughout pregnancy, especially during the twenty-fourth and forty-second
weeks, which ultimately reflects the importance of gestational time on the
development of the fetus. We used the technique of X-rays Fluorescence by making
use of the apparatus Tornado M4, which analyzed spectra obtained from X-rays
fluorescence, followed by its quantification in the WinAxil™ software. Various
points were analyzed in each hair, lying approximately 1.5 mm apart in order to
study the evolution of the concentration of the trace elements over time of
pregnancy. The values obtained were lower than the standard used, which derived
from the state of immature development of the studied hair as well as its
heterogeneity and shape [2]. There was an overall decrease in the concentration of
trace elements with distance from the root. Some results were not as expected,
probably because of some sort of postpartum contamination. Regarding the
comparison of full-term vs pre-term there was a higher concentration of trace
elements in the first case, but the differences are not significant. This is due to the
high number of factors which contribute to the absorption of nutrients by the fetus
beyond the gestation time as its type, maternal habits and conditions, lung maturation
cycle and even the newborn's genetics. It would be interesting to repeat this analysis
in the future using different comparison factors.
References
[1] I. Baranowska, L. Barchański1, M. Bąk, B. Smolec, Z. Mzyk, Polish Journal of Environmental
Studies, Vol. 13, No. 6, 639-646 (2004)
[2] Sz. Torok, P. Van Dyck, R. Van Grieken, X-Ray Spectometry, Vol. 13, No. 1, 27-32 (1984)
314
PS4.41
Raman spectroscopy in dental research: analysis of the
interface between dentin and direct composite restorations
F. Chasqueira1,2, S. Pessanha1,3, M. L. Carvalho1,3, J. Portugal1,2, S. ArantesOliveira1,2
1
2
Faculdade de Medicina Dentária, Universidade de Lisboa, Portugal
3
The restoration of a decayed tooth with a direct filling is one of the most common
procedures in dentistry. Nowadays, the material most often used for this purpose is a resin
composite. Since this material, a polymer, cannot adhere directly to the tooth, an
intermediate adhesive system must be used to infiltrate the tooth structure and copolymerize
with the restorative resin, under the application of a curing light source. The procedure
involved in this kind of restorations is very sensitive, with some limitations and concerns,
mainly due to the instability and durability of the interface, created by the adhesive, between
the composite and the tooth substrate. Over time, degradation of the adhesive interface
occurs, with subsequent nanoleakage of saliva and bacteria, leading to secondary decay and
restoration failure.
In this study, we intend to study two alternative application protocols, beyond the
manufacturer´s recommendation, for one of the adhesives most frequently used in the
clinical practice (Scotchbond 1XT, 3M ESPE). We also made a six-month ageing of the
specimens after the restoration procedure, since it is more relevant for clinical practice than
immediate results and since the consequences of the interface degradation become more
evident over time. A gauge of the quality of the adhesive interface is its degree of conversion
(DC), since it has a direct correlation with the permeability of the interface. DC represents
the amount of monomers that are chain linked and the greater the DC, the better the quality
of the adhesive interface.
Six specimens were made covering slices of dentin with the adhesive system, and a
restorative resin above, both light cured independently. Three experimental groups were
created according to the application protocols in study: 1) manufacturer´s recommendations
2) three adhesive layers, 3) extra hydrophobic adhesive layer. The specimens were immersed
in distilled water with an antibacterial and stored in a greenhouse, at 37ºC, for 6 months.
Raman spectra were acquired with the XploRA confocal Raman spectrometer and a 785 nm
laser was used. Two line scans with steps of ~1 m were performed per specimen. DC was
determined by comparing the band at ~1608 cm -1 in the C=C bond region with the band at
~1638 cm-1 not affected by polymerization.[1]
For all the application protocols, the DC varied throughout the hybrid layer, with lower
values close to dentin and higher close to adhesive. Also, the two alternative protocols in
study, achieved higher DC values than the manufacturer´s. The DC for the two alternative
protocols had always values above 80%, unlike the manufacturer´s protocol that revealed DC
values below 80% for the deepest measurements (near dentin).
[1] Navarra CO et al. Eur J Oral Sci 2009; 117: 463–469
315
PS4.42
Study of the effects of unsupervised OTC whitening
products in dental enamel using μ- XRF and μ- Raman
spectroscopies: 39 days protocol
J. Castro1,2, J. Godinho1,3, A. Mata1,3, M. L. Carvalho1,2, J. M. Silveira 1,3 and S.
Pessanha 1,2
1
2
3
Faculty of Dentistry, University of Lisbon, Lisboa, Portugal
Aesthetic dentistry has received extensive focus in recent years, particularly because
of the importance that people give to the appearance of the smile [1-3]. It is desired a
smile as white as possible and preferably easy to obtain, effective, fast, economic and
less invasive [2] [4]. In order to satisfy this need, a high diversity of Over The
Counter (OTC) products have appeared on the market. OTC products can be easily
bought by anyone and at a low cost, such as through internet sites. Many of these
products have active agent concentrations well above the European Commission
safety levels. Many authors have demonstrated a concern for safety and consequent
effects on the tooth surface due to the possible abuse of these products [1]. The
purpose of this in vitro study is to assess whether the elemental content and trace
elements in tooth enamel are altered when bleaching the teeth with two different
OTC bleaching gels, exceeding the recommendations of the manufacturer. In order to
perform this evaluation, twelve healthy teeth that were extracted for periodontal or
orthodontic reasons were used. Six samples were treated with the bleaching product
(Teeth Whitening Home Kit) and the other six samples were treated with the OTC
product (WHITE! -Bingo-UK) for the period of 39 days and stocked in human saliva
between each application. The elemental content of each sample, before and after
was obtained by micro Energy Dispersive X-ray Spectrometry (μ- EDXRF) and
phosphate (PO43-) profile was evaluated with micro Raman Spectroscopy (μRaman). No significant differences were obtained in the elemental concentrations,
however, the obtained results show that after 14 days the phosphate band decreased.
This could happen due to superficial changes in the surface of the enamel that are not
perceived in the XRF spectra because the analyzed volume is larger than the
superficial approach that we find when using μ- Raman.
References
[1] Demarco, FF; Meireles, SS; Masotti, AS. Over-the-counter whitening agents: a concise review.
São Paulo, Brazil : s.n., 2008. Braz Oral Res 2009;23(Spec Iss 1):64-70.
[2] Silveira, João. Efeitos do Peróxido de Hidrogénio nos Tecidos Dentários. Doutoramento em
Medicina Dentária. Lisboa : Faculdade de Medicina Dentária, Universidade de Lisboa, 2014.
[3] Ferreira, Sofia. Perspectiva dos Médicos Dentistas acerca da metodologia clínica aplicada nos
tratamento de branqueamento dentário.Licenciatura em Medicina Dentária. Porto : Faculdade Ciências
da Saúde, Universidade Fernando Pessoa, 2009.
[4] Mota, Luís. Branqueamento de dentes vitais:Perspectiva quanto à eficiência química, eficácia
clínica e segurança do paciente. Porto : Faculdade das Ciências da Saúde, Universidade Fernando
Pessoa, 2011..
316
PS4.43
Study of the distribution of toxic elements in
teeth treated with amalgam using µ-EDXRF
Carina Ferreira1,2, Filipa Chasqueira1,3, Sofia Pessanha1,2 and Mauro Guerra1,2
1
2
3
Faculty of Dentistry, University of Lisbon, Portugal
Over the years, the mercury present in amalgam fillings has raised some safety
concerns. Amalgam can release small amounts of mercury vapor over time, and
patients can absorb these vapors by inhaling or ingesting them [1]. However, it is not
clear whether amalgam components are absorbed and drifted through teeth material.
Amalgam is one of the most commonly used tooth fillings and contain approximately
50% elemental mercury and 50% other metals, mostly silver with some tin and
copper [2].
In this study, 10 human teeth treated with dental amalgam were analyzed using
energy dispersive X-ray fluorescence (EDXRF) to study the possible diffusion of its
constituents, Ag, Cu, Sn and Hg. The used EDXRF setup, M4 Tornado from Bruker,
makes use of a polycapillary lens to focus radiation up to 25 µm allowing to perform
mappings of the elemental distribution in the samples. Moreover, analysis were
performed under vacuum improving the detection limits for low Z elements.
Quantification was perform using the inbuilt software based on the Fundamental
Parameter method for bulk samples, considering and hydroxyapatite matrix,
The teeth were longitudinally cut and each slice was scanned from the surface
enamel to the inner region (dentin and pulp cavity. Hg concentration profiles show
strongly levels on this element close to the amalgam region, reaching 100 µg/g,
decreasing significantly in the dentin, and increasing up to 1000 µg/g in the cavity
were the pulp existed when the tooth was vital.
The distribution of these elements during the analysis suggest diffusion from the
amalgam to teeth tissues most likely through the tubules [3]. The fact Hg reaches the
pulp region might mean that there is contact with the blood stream while the teeth
was vital.
References
[1] G. M. Richardson, R. Wilson, D. Allard, C. Purtill, S. Douma e J. Gravière, “Mercury exposure
and risks from dental amalgam in the US population, post-2000”, The Science of the total
environment, pp. 4257-4268, 2011.
[2] T. Syversen e P. Kaur, “The toxicology of mercury and its compounds.,” Journal of trace elements
in medicine and biology : organ of the Society for Minerals and Trace Elements (GMS), pp. 215-226,
2012.
[3] A. Silva, R. Figueroa, A. Jaramillo, M. L. Carvalho e J. Veloso, “Performance of a gaseous
detector based energy dispersive X-ray fluorescence imaging system: Analysis of human teeth treated
with dental amalgam,” Spectrochimica Acta Part B: Atomic Spectroscopy, vol. 86, pp. 155-122, 2013.
317
PS4.44
Analysis of geometric factors in the Ca-P ratio measuring in
bones by µ-EDXRF
A.Costa1, M. Fonseca1, C. Santos1, A. F. Silva1, M. L. Carvalho1, J. P. Santos1,
M. Guerra1
1
LIBPhys, Dep. Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-
516 Caparica, Portugal
Contact email: acd.costa@campus.fct.unl.pt
Osteoporosis is the most common metabolic bone disease in the world and is
characterized by reduced bone mass and deterioration of bone microarchitecture, which
leads to a weakening of the bone making them more liable to fracture [1]. The relative
Ca-P content is essential for the maintenance of mineral homeostasis and bone
metabolism and therefore it is considered a suitable biomarker for assessing the health of
bones [2]. To measure this ratio, we used the techniques of Micro X-Ray Fluorescence
Spectroscopy (μ-XRF) using a beam of 25 μm and Proton Induced Gamma-ray Emission
(PIGE) with a beam of 2 mm, that give different ratios of Ca-P. The implication of
geometric factors in the study of trabecular bone, using micro beams, becomes important
because the topology of the bone is very different from a usual pellet sample. Thus, the
attenuation path of X-rays through the sample is quite diverse from the picture found in
the Sherman equation model, resulting in widely variable Ca-P ratios. Therefore, after
measurements, the samples were reduced to powder so as to remove the existing
roughness and were again analysed by μ-XRF and PIGE and compared to the previous
result to assess the influence of the geometrical attenuation factors in trabecular bone.
The results were then compared to control samples, following the same procedure.
[1] A. M. Rodrigues, “Osteoporose e outras doenças ósseas metabólicas,” in
Reumatologia fundamental, 2013, pp. 125–130.
[2] N. Kourkoumelis, I. Balatsoukas, and M. Tzaphlidou, “Ca/P concentration ratio at
different sites of normal and osteoporotic rabbit bones evaluated by Auger and energy
dispersive X-ray spectroscopy,” J. Biol. Phys., vol. 38, no. 2, pp. 279–291, 2012.
318
Poster Session 4: Speciation Analysis/Metallomics
PS4.45
Investigation of metalloprotein expressions of Perna perna
mussels from differentially contaminated areas of Rio de
Janeiro, Brazil by SEC-HPLC-ICP-MS
R. T. Lavradas1, R. C. C. Rocha1, T. D. Saint’Pierre1, R. A. Hauser-Davis1 and
J. M. Godoy1
1
Pontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Chemistry Department, Rua
Marquês de São Vicente, 225, Gávea, CEP: 22453-900, Rio de Janeiro, RJ, Brazil
E-mail: corresponding. rachel.hauser.davis@gmail.com
Currently, ICP-MS is the most powerful elemental detector used to screen for the
presence of elements in large biomolecules [1], able to conduct selective, real-time
monitoring of elements associated with compounds eluted from a chromatographic
column. Its synergic use with a previous high-resolution protein separation offers a
revolutionary analytical tool in the determination of metalloprotein (MP) expressions
in biological specimens [2]. The mussel Perna perna is one of the most
commercially produced bivalves in Brazil [3], and is considered an adequate
bioindicator, being sessile and a filter-feeder. It has not, however, been characterized
with regard to its MP expression in response to environmental contaminants. Thus,
the aim of this study was to investigate MP expressions in mussels from four
differentially metal-contaminated sites in Rio de Janeiro, Brazil. Forty mussels per
site were collected. Muscle tissue and digestive glands were removed and MP were
extracted according to Erk et al. [4] with TCEP as reducing agent [5]. Protein
separation was conducted with a Superdex 75 Column (GE Healthcare ®) on a
Shimadzu HPLC coupled to a NexIon 300X Perkin Elmer ICP-MS and 60Ni, 65Cu,
66
Zn, 75As, 82Se, 114Cd, 202Hg and 208Pb were monitored online. Several metal-bound
proteins were observed in both organs, indicating some degree of metal excretion in
the form of metal-bound proteins. Chromatographic profiles showed some
differences, but all elements eluted between 10 and 30 minutes, in 2-5 metal-bound
protein peaks, except for protein-bound Hg, not observed in any of the samples. Cu,
Zn and Ni were the most evident protein-bound metals. Low-intensity Pb, Se and As
peaks were present in all samples, whereas low-intensity Cd peaks were observed in
some of the samples. The differences between MP among the sampling sites indicate
differences in metal excretion and thus, reflect the different contamination levels
present, further corroborating the adequacy of this organism as a sentinel species.
References
[1] Wanick, R. C., Freire, A. S., Coutinho, C. C., Santelli, R. E, Br. J. Anal Chem. 4, 206-221 (2011).
[2] Sanz-Medel, A.; Montes-Bayon, M.; Sanchez, M.L.F. Anal. Bioanal. Chem. 377, 236-247 (2003).
[3] IBAMA. Coordenação Geral de Autorização de Uso e Gestão da Fauna e Recursos Pesqueiros, pp.
113 (2007).
[4] Erk, M., Ivankovi, D., Raspor, B., Pavicic, J., Talanta 57, 1211–1218 (2002).
[5] Tenório-Daussat, C. L.; Resende, M. C. M.; Ziolli, R. L.; Hauser-Davis, R. A.; Schaumloffel, D;
Saint’Pierre, T. D. Talanta 120, 491-497 (2014).
319
PS4.46
Effect of the use of copper compounds on plants for the
control of bacterial diseases
B. Campanella1,2, M. Onor1, A. D’Ulivo1, S. Tegli3, P. Bogani3, M. Cerboneschi3,
E. Bramanti1
1
C.N.R., Institute of Chemistry of Organometallic Compounds, UOS of Pisa, Via Moruzzi, 1, 56124
Pisa, Italy
2
University of Pisa, Department of Chemistry and Industrial Chemistry, Via Moruzzi 3, 56124 Pisa,
Italy
3
University of Florence, Dipartimento di Scienze delle Produzioni Agroalimentari e dell’Ambiente
(DiSPAA), Laboratorio di Patologia Vegetale Molecolare, Via della Lastruccia 10, 50019 Sesto
Fiorentino, Italy
E-mail: beatrice.campanella@pi.iccom.cnr.it
Copper is an essential plant micronutrient involved in numerous biochemical
functions. However, above optimal concentrations copper can act as a toxin, causing
nutrient loss and oxidative stress. At cellular level, toxicity may result from the
binding to sulfhydryl groups of proteins, thereby inhibiting the enzyme activity or
protein functions or inducing the deficiency of other essential elements.[1]
The determination of the total concentration of heavy metal is the routine method to
monitor the exposure of plants to metal pollution, but there is increasing evidence
that the identification, characterization and determination of the metal species, i.e.
the speciation, represents a more suitable approach to investigate metals
ecotoxicity.[2]
The AFTER-Cu LIFE+ project aims at demonstrating the negative impact on plants
of the use of copper compounds in conventional and organic agriculture. In order to
study the effect of the use of copper compounds, we performed the quantitation and
speciation of copper in Nicotiana tabacum plants (in vitro cultivation, and in
Actinidia deliciosa and Olea europaea leaves (cultivation in field), treated with
copper solutions at various concentrations. For this study a) we determined the total
content of copper and other elements after microwave digestion of the samples
followed by flow injection – inductively coupled plasma mass spectrometry (FI-ICPMS) analysis; b) we developed a hyphenated method for the quantitation and
speciation of copper in plant samples by coupling of size-exclusion chromatography
(SEC) with ICP-MS. In the latter approach it is possible to investigate the complexes
of copper with compounds biosynthesized by the plants exposed to metal stress (e.g.
phytochelatins, metal binding proteins…etc.).
Acnowledgements - This work has been financially supported by the European
Project Life+12 ENV/IT/336-AFTER-CU.
References
[1] De Vos, CH Ric, et al., Plant Physiology 98, 853-858 (1992).
[2] Prasad, Majeti Narasimha Vara, Heavy metal stress in plants: from biomolecules to ecosystems.
Springer Science & Business Media (2004).
320
PS4.47
Method development for selenoaminoacids determination
in selenized yeast by HPLC-ICP OES
Vivian M. O. Carioni1*, Bruno M. Siqueira1,2, Alexandre M. Fioroto1,
Angerson N. Nascimento3 and Pedro V. Oliveira1
1
Chemistry Institute, University of São Paulo, São Paulo, SP, Brazil
Nova Analitica Importação e Exportação LTDA, São Paulo, SP, Brazil
3
Federal University of São Paulo, Diadema Campus, São Paulo, SP,Brazil
*E-mail: vivian.carioni@gmail.com
2
Selenium plays an important role for human and animal health. Its bioavailability,
however, depends of the chemical form in which it is available. In general, Seorganic is better absorbed by the living organism than Se-inorganic [1]. Due to its
low concentration in foods, raw materials with higher Se content, as Se-enriched
yeast, have been produced for human and animal supplementation. During Seenriched yeast production, method for quality control are required to guarantee the
incorporation of Se-inorganic added to the raw material to selenoaminoacids, mainly
Selenomethione (SeMet)[2]. One of the biggest challenges for the chemical
speciation in routine analyses is the lack of low cost methods and of easy
implementation. The coupling between high performance liquid chromatography
(HPLC) and inductively coupled plasma optical emission spectrometry (ICP OES)
can be a good alternative, principally when an ICP OES instrument with a highly
sensible detector (CID – Charge Injection Device), which allows better limits of
detection is used. This work describes a method development for selenoaminoacids
determination using online coupling HPLC-ICP OES. Extraction of
selenoaminoacids were performed by using 500 mg of a yeast sample with high Se
content (2011 ± 11 mg kg-1), 50 mg of Pronase E and 10 ml of Tris/HCl buffer
pH=7.4, at 38°C, and 200 rpm for 24h. The supernatant was separated by
centrifugation and submitted to two different procedures: 1) acid decomposition in
microwave oven and analysis by ICP OES; 2) injection of 100 μl into HPLC-ICP
OES system using an anion exchange column, acetate buffer pH=4.8 as mobile phase
at a flow rate of 1500 µl min-1 and Se(IV) 20 mg l-1 as internal standard. The
remaining solid was also submitted to procedure 1. Results showed 87% of Se was
extracted to the supernatant (1891± 42 mg kg-1) and 17% remained in the solid (351
± 26). The sum of Selenocysteine (SeCys) (281 ± 47 mg kg-1) + SeMet (1404 ± 76
mg kg-1) can account for 89% of Se in the supernatant and 84% of total Se
concentration present in the sample. Limits of detection (LOD) calculated for SeCys
and SeMet were 0.8 and 2.0 mg l-1, and Limits of Quantification (LOQ) were 2.4 and
6.0 mg l-1, respectively. In addition, good resolution was observed during the
chromatographic separation, showing HPLC-ICP OES is suitable for Se speciation
analysis of high selinized content samples. The authors kindly acknowledge
University of São Paulo, Fapesp (2013/25377-0) and Nova Analitica Importação e
Exportação LTDA.
References
[1] M. Grotti, C. Lagomarsino, E. Magi, Ann Chim, 96, 751-764 (2006).
[2] K Pyrzynska, Food Chem, 114, 1183–1191 (2009).
321
PS4.48
Differences in Pt-drugs reactivity towards peptides
containing methionine or histidine
G. Artiaga, A. Iglesias-Jiménez, E. Moreno-Gordaliza, M.L. Mena and
M.M. Gómez-Gómez
Department of Analytical Chemistry, Universidad Complutense de Madrid, Avda. Complutense s/n,
28040, Madrid, Spain
E-mail: mmgomez@quim.ucm.es
The antineoplastic activity of platinum drugs is mainly due to their ability to bind and distort the
nuclear DNA [1]. However, there are competitive interactions with other biomolecules containing
nucleophilic groups (S- and N-donor), such as proteins. Pt-protein bindings are related with the
accumulation of this element in tissues and the induction of side-effects, especially nephrotoxicity [2].
Therefore, it is important to understand the principles that govern the formation and reactivity of these
complexes, in order to design improved treatments with reduced side-effects.
In this work, the reactivity of three Pt-drugs of wide clinical administration -cisplatin, oxaliplatin and
carboplatin- was evaluated towards two synthetic peptides that contain the same peptide sequence,
except for one amino acid residue, being methionine (S-donor) or histidine (N-donor) in each case.
This simple model let us study the kinetics and the extent of reaction of these drugs towards two
different donor groups, and the characterization of the binding sites and the nature of adducts formed.
Incubations of both peptides with the drugs (30:15 M) in a peptide molar excess of 2:1, were carried
out at physiological conditions at different incubation times (90 min-15 days). The wide diversity of
Pt-complexes and their low concentrations (trace level) make advisable the use of mass spectrometry
techniques, both elemental and molecular, coupled to different separation methods. SEC-ICP-MS was
used for the separation and quantification of the different Pt-complexes generated, and nESI-LIT-MS
for their structural characterization. The combination of both techniques provided high sensitivity and
selectivity for the attainment of the objectives.
The results obtained by SEC-ICP-MS showed that the velocity of reaction for cisplatin and oxaliplatin
was very similar for the first two days. However, cisplatin reacted more intensively for longer
incubation times (3-15 days). Although the behavior of both drugs was analogous, different affinity
was found depending on the donor group present in each peptide. Methionine-containing peptide was
6-fold more reactive than histidine-containing peptide, reaching the steady state after 7 days, while it
was achieved after 2 days in the latter. In addition, this fact was more pronounced for carboplatin. In
this case, histidine-containing peptide showed no platination up to 15 days. Furthermore, although
carboplatin showed a slower platination rate in the first stages with methionine-containing peptide, its
reactivity was similar than the other two drugs after 15 days.
nESI-LIT-MS analysis of the samples confirmed that methionine and histidine amino acid residues
were the preferential Pt binding sites for the three drugs studied. Additionally, in most cases, it was
observed that cisplatin was coordinated to these peptides with no preservation of its original ligands.
Oxaliplatin retained DACH group in all cases, however oxalate group was shifted by nucleophile
groups.
Acknowledgments
This work was financially supported by MINECO, Grant number CTQ 2011/24585. G.Artiaga also
acknowledges MECD, for her FPU predoctoral fellowship (13/01693).
References
[1] R. C. Todd and S. J. Lippard. Metallomics, 1, 280-291 (2009).
[2] N. Pabla and Z. Dong. Kidney International, 73, 994-1007 (2008).
322
PS4.49
Arsenic biotransformation by resistant bacteria in highly
contaminated areas in El Tatio Geyser Field of Chile
M. Gómez-Gómez1, I.Pizarro2, G. Artiaga1, D. Román2, M. A. Palacios1
1
Department of Analytical Chemistry, Faculty of Chemistry, Universidad
Complutense de Madrid, Avda. Complutense s/n, 28040, Madrid, Spain.
2
Department of Chemistry, Faculty of Basic Sciences, Universidad de Antofagasta, Avda. Argentina,
2000, Antofagasta, Chile.
E-mail: mmgomez@quim.ucm.es
Arsenic in the Antofagasta Region of Chile is worldwide recognized as highly As contaminated area
[1]. As in this Region has attracted much attention since in 1958 its concentration in drinking water
was 870 µg·L-1, 87-fold higher than the Who guideline value of 10 µg·L -1 causing an enormous
increase in overall mortality [2]. Due to its abundance, mainly as As (V) and As (III), certain
microorganisms such as several types of bacteria have evolved and developed the necessary genetic
components which confer resistance mechanisms, allowing them to survive and grow in environments
that would be toxic to most other organisms [3]. These mechanisms include reactions of reduction,
oxidation and methylation. Therefore, the changes produced in arsenic species by microorganisms,
play a significant role in the occurrence and behavior of this element in the environment.
The aim of this work was to study the most relevant arsenic resistant bacteria that exist in highly
arsenic contaminated sediments in El Tatio geyser field. This field is located in the Atacama Desert of
northern Chile at 4,300 m of altitude. This place is a suitable habitat to study the adaptation of
endemic species subjected to extreme environmental conditions.
32 arsenate-resistant bacterial strains, with different colony morphologies and varying arsenic
transformation abilities, were isolated and identified. The identification of the bacterial genera was
determined by analyzing their 16S rRNA genes, finding Pseudomonas and Aeromonas in most cases.
All bacterial strains isolated were grown with increasing concentration of arsenate, exhibiting high
levels of arsenate resistance ranging from to 5 to 30 mM. Inductively coupled plasma mass
spectrometry (ICP-MS) was employed to determine the concentration of As within intact cells of each
bacterial strain. Results showed a great accumulation of this element in all strains, never being less
than 20 mg/L. The separation of bacterial cells into cytoplasmic, membrane and DNA fractions was
carried out by differential centrifugation in order to know the distribution of arsenic in the different
cellular compartments. Most of arsenic was mainly located in the cytoplasmic fraction, while small
concentrations at level trace (100-500 ng/L) were found in the DNA. Indeed, the optimization of
chromatographic methods coupled to ICP-MS allowed us to separate and quantify the different arsenic
species as a result of bacterial transformations. The results demonstrated that in half of the isolated
strains, between 20-70% of arsenate was reduced to arsenite. Only in one case it was observed the
presence of methylated species of arsenic such as DMA and MMA. Finally it was confirmed that the
arsenic into the cells was not only as free form, but also associated with biomolecules such as
proteins.
Acknowledgments
Authors thank the Community of Madrid (S2013/ABI-3028, AVANSECAL-CM) and the European
founding from FEDER program. G.Artiaga also acknowledges MECD, for her FPU predoctoral
fellowship (13/01693).
References
[1] P. Ravenscroft. Proceedings of Arsenic: the geography of a global problem. London, U.K. Royal
Geographical Society. (2007).
[2] Who, Guideline for drinking Water Quality. 1,2 Geneve: World Health Organization, 41, (1992).
[3] R. Oremland and J. Stolz. Science, 300, 939-944, (2003).
323
PS4.50
Speciation studies of metal-binding proteins in pore water
O.C. Vázquez-Padín, M.C. Barciela-Alonso, A. Moreda-Piñeiro
P. Herbello-Hermelo and P. Bermejo-Barrera
Department of Analytical Chemistry, Nutrition and Bromatology. Faculty of Chemistry. University of
Santiago de Compostela. Avda. das Ciencias s/n 15782. Santiago de Compostela
E-mail: mcarmen.barciela@usc.es
Speciation study of metal-binding proteins in pore water has been performed.
Offgel Electrophoresis combined with Lab-on-a-Chip technology was applied for
protein analysis in pore water after tangential flow ultrafiltration followed by
centrifugal ultrafiltration (preconcentration factor 450). Dissolved proteins isolation
was performed by treating the ultrafiltrated fraction with methanol-chloroform as
precipitating reagents following the procedure described by García Otero et al [1].
Cd, Cu, Fe, Mn, Ni, Pb and Zn were determined in each fraction of the OFFGEL
electrophoresis. Cd, Cu, Mn, Pb and Ni were determined by electrothermal atomic
absorption spectrometry, while Fe and Zn were analyzed by inductively coupled
plasma atomic emission spectrometry.
Cd and Pb were not detected in any of the 24 fractions studied. Iron was found at low
concentrations (0.3-8.7 mg L-1) associated to proteins with isoelectric points between
3.0 and 10. The highest Fe concentrations were found in fractions 12, 14 and 16 (pI
6.3-7.7). Copper was bound to proteins with low molecular weights (7.0 kDa) and
with a concentration of 803 µg L-1. Ni was associated to proteins with molecular
weight ranging from 5.1 to 87 kDa at concentration levels ranging from 78 to 258 µg
L-1. Mn concentrations were between 146-267 µg L-1 and was associated with
proteins with 5-7 and 87.0 kDa. Zn was bound to proteins with molecular weights
ranging from 14.1-53.3 kDa. The highest Zn concentration (14.5 mg L-1) was found
in fraction 9 associated with proteins with MW of 22.8 kDa.
References
[1] Natalia García-Otero, Elena Peña-Vázquez, María Carmen Barciela-Alonso, Pilar BermejoBarrera, Antonio Moreda-Piñeiro. Analytical Chemistry, 85 (12), 5909-5916 (2013).
324
PS4.51
Speciation of inorganic Sb, Se and Te in food and
environmental samples using modified TiO2/MWCNTs
nanocomposite packed micro column coupled with HGICP-OES
P.N. Nomngongo and J.C. Ngila
Department of Applied Chemistry, Faculty Science, University of Johannesburg, Doornfotein
Campus, P.O. Box 17011, Johannesburg, 2028, South Africa
E-mail: pnnomngongo@uj.ac.za
Knowledge of the speciation of trace elements in food and environmental is important
because the physiological and toxicological effects as well as bioavailability of the
elements depend on their chemical form [1]. For this reason, many studies have focused
on the speciation analysis of different elements. It has been reported that efficient
elemental speciation can be carried out by combining a selective separation method with
a sensitive detection technique [2]. In this study, a simple, sensitive and selective method
based on the combination micro solid phase extraction and generation-inductively
coupled plasma optical emission spectrometry for speciation analysis of Sb, Se and Te in
food and environmental samples, has been developed. Titanium dioxide/multiwalled
carbon nanotubes (TiO2/MWCNTs) nanocomposite functionalised with Aliquat 336 was
used as the sorbent material. Optimization of factors affecting the speciation of the target
analytes was achieved using factorial and Box- Behnken designs. Under optimum
conditions, the limit of detection (n=20) of the proposed method ranged from 0.1-0.8 ng
L-1 in the diluted samples. The repeatability and reproducibility (expressed in terms of
standard deviation) raged from 1.3-2.1% and 2.5-4.1%, respectively. The accuracy of the
developed method was tested by the analysis of certified reference materials and spiked
samples and the recovery percentages ranged from 96–100%. The proposed method was
applied for quantification of Sb, Se and Te in real samples. The concentrations of total
trace metals determined using the developed method was compared with those obtained
using ICP-MS after microwave assisted digestion and the results obtained were in close
agreement as statistically confirmed using Student t-test.
References
[1]ALOthman, Z. A., Habila, M., Yilmaz, E. and Soylak, M., Microchimica Acta, 177(3-4), 397403(2012).
[2] Chen, S., Zhu S., and Lu D., Food chemistry, 169 156-161 (2015)
325
Poster Session 4: Miniaturisation and Nanotechnology
PS4.52
Critical comparison between different quantum dot watersolubilization approaches based on asymmetrical flow fieldflow fractionation coupled to inductively coupled plasma
mass spectrometry analysis
D. Bouzas-Ramos, M. Menéndez-Miranda, M. García Cortés, J. M. CostaFernández, J. R. Encinar and A. Sanz-Medel
University of Oviedo, Analytical Spectrometry Research Group, Julián Clavería 8, Oviedo, Spain
E-mail: jcostafe@uniovi.es
The design of surface coatings of Quantum Dots (QDs), seeking for doing them watersoluble and biocompatible, has been subject of comprehensive study in recent years [1].
Core-shell structured QDs (CdSe/ZnS QDs), prepared by the conventional synthesis in
organic media at high temperature, have the drawback of only being soluble in organic,
nonpolar solvents, due to the alkyl chains of the ligands, such as trioctylphosphine
(TOP) and trioctylphosphine oxide (TOPO), that extend from the QD surface. However,
before an eventual use of such QDs in bioanalytical applications, they must be
transferred to aqueous solutions [2].
Appropriate QDs surface modification is required in order to render them soluble and
stable in water media, and to open the possibility to easily attach appropriate functional
groups in their surface which would allow further bioconjugations to biological probes
such as proteins or recognition units. In the present work, two different watersolubilization approaches of the QDs have been compared: one in which the QDs have
been coated with an amphiphilic polymer (based on poly-maleic anhydride functional
groups) via hydrophobic interactions, and a second one in which the QDs have been
transferred to aqueous media by capping them with dihydrolipoic acid (DHLA) via
ligand exchange.
Characterization of the polymer- and DHLA-coated CdSe/ZnS QDs in water media have
been thoroughly assessed by asymmetric flow field-flow fractionation (AF4) coupled online to Triple Quad inductively coupled plasma mass spectrometry (ICPQQQ) detector.
Moreover, other techniques like dynamic light scattering (DLS), fluorescence and high
resolution-transmission electron microscopy (HR-TEM) provided additional information
to assess the stability and quality of the solubilized nanoparticles.
Acknowledgements
Financial support provided by the Spanish Ministry of Education (MINECO-13-CTQ2013-49032-C21-R), Principado de Asturias (Spain, FC-15-GRUPIN14-092) and Agilent Technologies Foundation.
Diego Bouzas-Ramos acknowledges the Ph.D. grant (BP14-137) from Principado de Asturias (Spain).
References
[1] A. M. Coto-García et al., Journal of Nanoparticle Research, 15, 1330-1340 (2013).
[2] A. M. Smith et al., Analyst, 129, 672-677 (2004).
326
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