Environmental CWA analysis

Environmental CWA analysis
Paula Vanninen
Finnish Institute for Verification of the Chemical
Weapons Convention, VERIFIN
Department of Chemistry, University of Helsinki
Part-financed by
the European Union
(European Regional
Development Fund)
CHEMSEA partners in WP3
Sediment sampling
 IO PAS, Institute of Oceanology of the Polish Academy of Sciences
 LEPA, Environmental Protection Agency, Lithuania
 FI, Thünen Institute (Germany)
 SYKE, Finnish Environment Institute
Analysis of CWA-related chemicals
 FOI, Swedish Defence Research Agency, Sweden
 MUT, Military University of Technology (Poland)
 VERIFIN, Department of Chemistry, University of Helsinki (Finland)
Analysis of arsenic concentration
 IO PAS, Institute of Oceanology of the Polish Academy of Sciences
 MUT, Military University of Technology (Poland)
 LEPA, Lithuania Environmental Protection Agency
WP3: Summary of the results of the sediment analysis
Part-financed by
the European Union
(European Regional
Development Fund)
Studied dumping areas
Analysis of chemical warfare agent related chemicals…
Part-financed by
the European Union
(European Regional
Development Fund)
Major chemicals
and amounts dumped in Bornholm
Sulphur mustard (H)
7 000 tons
Adamsite (DM)
1 500 tons
Clark I (DA)
~1 000 tons
α-Chloroacetophenone (CN)
500 tons
Studied CWA related chemicals
 Sulphur mustard-related chemical
– Mustard + several of its degradation products
 Arsenic-containing chemicals
– Adamsite + its degradation products
– Clark I + its degradation products
– Arsenic oil (e.g. triphenylarsine)
 Other agents
– α-chloroacetophenone
Analysis of chemical warfare agent related chemicals…
Part-financed by
the European Union
(European Regional
Development Fund)
WP3 Status: accomplished
 Analysis of environmental samples
– Totally 178 individual sediment samples analysed and 9 sediment
cores
– 87 VERIFIN, 73 MUT, 89 FOI
– 10 VERIFIN, 10 MUT, 11 FOI pore water samples
– Sediment core samples (3 cores each lab) 30 VERIFIN, 36 MUT, 18
FOI
– Totally 364 sample analysis at 187 sample stations
– Totally ca. 17 analytes studied, ca. 6000 analysis
– Inorganic As 59 LEPA, 47 MUT, 178 IOPAS
 Merging of analytical data of environmental samples with
hydrographical data
– Data processed by PMA
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Part-financed by
the European Union
(European Regional
Development Fund)
Sampling sites
& results
Analysis of chemical warfare agent related chemicals…
Part-financed by
the European Union
(European Regional
Development Fund)
Sampling sites
& results
Analysis of chemical warfare agent related chemicals…
Part-financed by
the European Union
(European Regional
Development Fund)
Sampling sites
& results
Analysis of chemical warfare agent related chemicals…
Part-financed by
the European Union
(European Regional
Development Fund)
Positive and
negative findings
Number of samples
120
Positive
Negative
100
80
60
40
20
0
Bornholm
Gotland
Gdańsk Deep
Gulf of Gdańsk
Słupsk Furrow
Sampling area
WP3: Summary of the results of the sediment analysis
Part-financed by
the European Union
(European Regional
Development Fund)
Most concentrated
findings
Sulphur mustard -related chemicals in CHEMSEA project
µg/kg
1500
1000
500
0
1
11
21
Arsenic chemicals in CHEMSEA Project
µg/kg
1500
1000
500
0
1
11
Analysis of chemical warfare agent related chemicals…
21
Part-financed by
the European Union
(European Regional
Development Fund)
Total arsenic in
different areas
Differences between
As concentrations
in samples
from different
sampling points
are STATISTICALLY
SIGNIFICANT
ANOVA: p=0.0158
with confidence
interval 95%
Analysis of chemical warfare agent related chemicals…
Part-financed by
the European Union
(European Regional
Development Fund)
Summary
 182 sediment samples have been analysed
– 59 positive samples (32 %)
– Intact sulphur mustard detected (although very low concentration)
– Arsenic levels up to 25 mg/kg (but not higher)
 Bornholm
– arsenic-containing chemicals similar to MERCW
– sulphur mustard-related chemicals verified, but still quite low amounts
 Gotland
– Dumping verified
– Lower levels than in Bornholm (as expected)
 Gdansk
– Proof of dumping (not listed in HELCOM 1994 Report)
Analysis of chemical warfare agent related chemicals…
Part-financed by
the European Union
(European Regional
Development Fund)
Unresolved questions
 Point contamination
– Fractal contamination pattern
– Munitions spread unhomogenously
– Chemicals at molecular level unevenly distributed
 Only one sample contained intact agent- sulphur mustard, not a
problem of sensitivity of the methods applied (LOQ less than 3 ppb ;
3 μg/kg)
 Fate of sulphur mustard; totally polymerized in the Baltic Sea?
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Part-financed by
the European Union
(European Regional
Development Fund)
Unresolved questions
 The sulfur mustard-related findings do not reflect the high
amount dumped in the sea. Several hypotheses for the absence
of mustard-finding can be presented. Reasons for this could be
that mustard is
– in an form not detected in the current analysis (i.e. as some other
degradation product),
– not spreading to the sediment (e.g. due to formation of insoluble
lumps),
– removed from the sediment surrounding the dumped munitions
and containers (e.g. by hydrolysis and subsequent dissolution in
sea water and dilution beyond detection or possibly by bacterial
consumption of thiodiglycol) or
– not actually bound to sediment after removal from munitions or
containers.
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Part-financed by
the European Union
(European Regional
Development Fund)
Outcomes from analysis of
environmental samples
 Sulphur mustard poses a high risk to fishermen
 Arsenic containing chemicals like Adamsite and Clark pose a risk to
environment
– Arsenic containing chemicals found also in pore water samples
 Degradation products of Adamsite and Clark are quite toxic
 Bornholm deep is known dumpsite - confirmation of previous data
 Gdansk deep: search and assesment ->
Target for new study
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Part-financed by
the European Union
(European Regional
Development Fund)