United Nations Environment Programme

Transcription

UNITED
NATIONS
SC
UNEP/POPS/COP.1/INF/9
Distr.: General
23 February 2005
English only
United Nations
Environment
Programme
Conference of the Parties of the Stockholm
Convention on Persistent Organic Pollutants
First meeting
Punta del Este, Uruguay, 2–6 May 2005
Item 6 (b) (ii) of the provisional agenda*
Matters for consideration or action by the Conference
of the Parties: measures to reduce or eliminate release
from unintentional production: identification
and quantification of releases
Compilation of comments received on the standardized tool-kit
for the identification and quantification of dioxin and furan
releases**
Note by the Secretariat
As noted in document UNEP/POPS/COP.1/9, the annex to the present note contains a
compilation of comments received in response to paragraph 2 of decision of INC-7/5 of the
Intergovernmental Negotiating Committee for an International Legally Binding Instrument for
Implementing International Action on Certain Persistent Organic Pollutants, inviting Governments and
others to submit to the Secretariat, by 31 March 2004, their additional comments on the tool-kit, as well
as information and methodologies on other chemicals under article 5 and Annex C of the Convention
(see annex I to the report of the Committee on the work of its seventh session, contained in document
UNEP/POPS/INC.7/28). The comments are being circulated as received by the Secretariat and have not
been formally edited.
*
UNEP/POPS/COP.1/1.
**
Stockholm Convention, Article 5 and Annex C; Report of the Intergovernmental Negotiating Committee
on the work of its sixth session (UNEP/POPS/INC.6/22), annex I, decision INC-6/4; Report of the
Intergovernmental Negotiating Committee on the work of its seventh session (UNEP/POPS/INC.7/28), annex I,
decision INC-7/5.
K0580646 XX0305
For reasons of economy, this document is printed in a limited number. Delegates are kindly requested to bring their copies to
meetings and not to request additional copies.
UNEP/POPS/COP.1/INF/9
Annex
2
Responses to Request letter signed December 4, 2003
Input to Toolkit
Sender
Date
Document No.
Armenia
12/08/2003
1
Ecotox NGO
12/10/2003
2
The Gambia
12/18/2003
3
Estonia
02/11/2004
4
Dominican Republic
02/24/2004
5
Norway
03/09/2004
6
Jordan
03/12/2004
7
Bahrain
02/14/2004
8
Sweden
03/22/2004
9
Republic of Congo Brazzaville
03/23/2004
10
Mauritius
03/23/2004
11
Poland
03/23/2004
12
Ecuador
03/23/2004
13
PR China
03/26/2004
14
Slovakia
03/29/2004
15
Barbados
03/30/2004
16
Japan
03/30/2004
17
WCC
03/30/2004
18
Spain
03/31/2004
19
IPEN
03/31/2004
20
Greenpeace
03/31/2004
21
Samoa
03/31/2004
22
Egypt
04/01/2004
23
Moldova
04/01/2004
24
South Africa
04/01/2004
25
Chile
04/30/2004
09/03/2004
10/22/2004
11/12/2004
26
USA
05/13/2004
27
EC
05/19/2004
28
CEMBUREAU
06/02/2004
29
Thailand
07/05/2004
30
1
Republic of Armenia
Ʉɨɦɦɟɧɬɚɪɢɢ ɤ «Ɇɟɬɨɞɢɱɟɫɤɨɦɭ ɪɭɤɨɜɨɞɫɬɜɭ ɩɨ ɜɵɹɜɥɟɧɢɸ ɢ
ɤɨɥɢɱɟɫɬɜɟɧɧɨɣ ɨɰɟɧɤɟ ɜɵɛɪɨɫɨɜ ɞɢɨɤɫɢɧɨɜ ɢ ɮɭɪɚɧɨɜ”
ɉɪɨɟɤɬ ɹɧɜɚɪɶ 2001 ɝɨɞɚ.
«Ɇɟɬɨɞɢɱɟɫɤɨɟ ɪɭɤɨɜɨɞɫɬɜɨ ɩɨ ɜɵɹɜɥɟɧɢɸ ɢ ɤɨɥɢɱɟɫɬɜɟɧɧɨɣ ɨɰɟɧɤɟ ɜɵɛɪɨɫɨɜ
ɞɢɨɤɫɢɧɨɜ ɢ ɮɭɪɚɧɨɜ” ɢɡɥɨɠɟɧɨ ɹɫɧɨ ɢ ɩɨɧɹɬɧɨ. ɉɪɢ ɪɚɛɨɬɟ ɫ ɧɢɦ ɧɟ ɜɨɡɧɢɤɚɸɬ
ɨɫɨɛɵɟ ɬɪɭɞɧɨɫɬɢ. Ɉɞɧɚɤɨ ɧɟɤɨɬɨɪɵɟ ɧɟɫɭɳɟɫɬɜɟɧɧɵɟ ɧɟɬɨɱɧɨɫɬɢ ɠɟɥɚɬɟɥɶɧɨ
ɢɫɤɥɸɱɢɬɶ ɜ ɫɥɭɱɚɟ ɩɟɪɟɢɡɞɚɧɢɹ “Ɇɟɬɨɞɢɱɟɫɤɨɝɨ ɪɭɤɨɜɨɞɫɬɜɚ», ɩɨɫɤɨɥɶɤɭ ɷɬɢ
ɧɟɬɨɱɧɨɫɬɢ ɨɫɥɨɠɧɹɸɬ ɪɚɛɨɬɭ ɩɨ ɜɵɹɜɥɟɧɢɸ ɢ ɤɨɥɢɱɟɫɬɜɟɧɧɨɣ ɨɰɟɧɤɟ ɜɵɛɪɨɫɨɜ
ɞɢɨɤɫɢɧɨɜ ɢ ɮɭɪɚɧɨɜ.
1. Ɍɚɛɥɢɰɵ 4, 8, 9 ɢ 10 ɩɨɜɬɨɪɹɸɬɫɹ ɜ ɜɢɞɟ ɬɚɛɥɢɰ 32, 49, 58 ɢ 64
ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ. ɉɨɞɨɛɧɨɟ ɢɡɥɨɠɟɧɢɟ ɦɚɬɟɪɢɚɥɚ ɧɟɰɟɥɟɫɨɨɛɪɚɡɧɨ, ɩɨɫɤɨɥɶɤɭ
ɨɧɢ ɩɨɜɬɨɪɹɸɬ ɨɞɧɢ ɢ ɬɟ ɠɟ ɨɫɧɨɜɧɵɟ ɤɚɬɟɝɨɪɢɢ ɢ ɩɨɞɤɚɬɟɝɨɪɢɢ.
2. Ⱦɚɧɧɵɟ, ɩɪɢɜɟɞɟɧɧɵɟ ɜ ɫɜɨɞɧɨɣ ɬɚɛɥɢɰɟ (ɬɚɛɥɢɰɚ 8.1, ɫɬɪ.180), ɧɟ ɜɫɟɝɞɚ
ɫɨɜɩɚɞɚɸɬ ɫ ɞɚɧɧɵɦɢ ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɯ ɨɬɞɟɥɶɧɵɯ ɬɚɛɥɢɰ ɨɫɧɨɜɧɨɝɨ ɬɟɤɫɬɚ.
ɍɞɨɛɧɨ ɪɚɛɨɬɚɬɶ ɫɨ ɫɜɨɞɧɨɣ ɬɚɛɥɢɰɟɣ, ɨɞɧɚɤɨ ɢɡ-ɡɚ ɞɨɩɭɳɟɧɧɵɯ ɧɟɬɨɱɧɨɫɬɟɣ
ɜ ɬɚɛɥ. 8.1 ɨɧɚ ɩɪɚɤɬɢɱɟɫɤɢ ɦɚɥɨ ɩɨɥɟɡɧɚ.
ɇɢɠɟ ɩɪɢɜɨɞɹɬɫɹ ɱɚɫɬɧɵɟ ɧɟɫɨɨɬɜɟɬɫɬɜɢɹ ɦɟɠɞɭ ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɦɢ ɨɬɞɟɥɶɧɵɦɢ
ɬɚɛɥɢɰɚɦɢ ɨɫɧɨɜɧɨɝɨ ɬɟɤɫɬɚ ɢ ɨɛɳɟɣ ɫɜɨɞɧɨɣ ɬɚɛɥɢɰɟɣ 8.1, ɩɟɪɟɱɢɫɥɹɸɬɫɹ
ɜɨɡɧɢɤɲɢɟ ɩɪɢ ɷɬɨɦ ɜɨɩɪɨɫɵ, ɬɪɟɛɭɸɳɢɟ ɜɵɹɫɧɟɧɢɣ.
ʋʋ
ɬɚɛɥɢɰ ɜ
ɨɫɧɨɜɧɨɦ
ɬɟɤɫɬɟ
1
Ɍɟɤɫɬ, ɩɪɢɜɟɞɟɧɧɵɣ ɜ
ɭɩɨɦɹɧɭɬɨɣ ɬɚɛɥɢɰɟ
Ɍɟɤɫɬ ɬɚɛɥɢɰɵ 8.1,
ɩɪɢɥɨɠɧɢɟ 8
2
3
13 - 19
ȿɞɢɧɢɰɵ ɢɡɦɟɪɟɧɢɹ ɜ ɞɚɧɧɵɯ
ɬɚɛɥɢɰɚɯ ɭɤɚɡɚɧɵ ɜ ɜɢɞɟ ɦɤɝ
Ɍɗ/ɬ ɫɨɠɠɟɧɧɨɝɨ ɨɬɯɨɞɚ
ȿɞɢɰɢɰɚ ɢɡɦɟɪɟɧɢɹ ɞɚɧɚ ɜ
ɜɢɞɟ ɦɤɝ Ɍɗ/ɬ, ɧɨ ɧɟ ɭɤɚɡɚɧɨ
ɧɚ ɬɨɧɧɭ ɤɚɤɨɝɨ ɩɪɨɞɭɤɬɚ
20
ȿɞɢɧɢɰɵ ɢɡɦɟɪɟɧɢɹ ɭɤɚɡɚɧɵ ɜ
ɜɢɞɟ ɦɤɝ Ɍɗ/ɬ ɠɢɞɤɨɣ ɫɬɚɥɢ
ȿɞɢɰɢɰɚ ɢɡɦɟɪɟɧɢɹ ɞɚɧɚ ɜ
ɜɢɞɟ ɦɤɝ Ɍɗ/ɬ, ɧɨ ɧɟ ɭɤɚɡɚɧɨ
ɧɚ ɬɨɧɧɭ ɤɚɤɨɝɨ ɜɢɞɚ ɫɬɚɥɢ
50
ȿɞɢɧɢɰɵ ɢɡɦɟɪɟɧɢɹ ɭɤɚɡɚɧɵ ɜ
ȿɞɢɧɢɰɚ ɢɡɦɟɪɟɧɢɹ ɞɚɧɚ
ɜɢɞɟ ɦɤɝ Ɍɗ/ɬ ɫɵɪɶɹ ɞɥɹ ɜɨɡɞɭɯɚ ɬɨɥɶɤɨ ɜ ɜɢɞɟ ɦɤɝ Ɍɗ/ɬ ɛɟɡ
ɭɤɚɡɚɧɢɹ ɜɢɞɚ (ɫɵɪɶɟ ɢɥɢ
ɢ ɦɤɝ Ɍɗ/ɬ ɡɨɥɵ ɞɥɹ ɨɫɬɚɬɤɚ
ɡɨɥɚ)
61
ȿɞɢɧɢɰɚ ɢɡɦɟɪɟɧɢɹ ɞɥɹ ɜɨɡɞɭɯɚ
ɞɚɧɚ ɜ ɦɤɝ/ɬ ɛɟɡ ɭɤɚɡɚɧɢɹ
ɷɤɜɢɜɚɥɟɧɬɚ (Ɍɗ)
ȿɞɢɧɢɰɚ ɢɡɦɟɪɟɧɢɹ ɞɥɹ
ɜɨɡɞɭɯɚ ɞɚɧɚ ɜ ɦɤɝ Ɍɗ/ɬt, ɬ.ɟ.
ɫ ɭɤɚɡɚɧɢɟɦ ɷɤɜɢɜɚɥɟɧɬɚ Ɍɗ,
ɧɨ ɧɟɩɨɧɹɬɧɨ ɨɛɨɡɧɚɱɟɧɢɟ
“ɬt”
1
2
1
62
2
ȿɞɢɧɢɰɚ ɢɡɦɟɪɟɧɢɹ ɞɥɹ ɪɚɡɧɵɯ
ɫɪɟɞ ɞɚɧɚ ɜ ɜɢɞɟ ɦɤɝ Ɍɗ/ɬ
ɨɫɬɚɬɤɚ ɞɢɫɬɢɥɥɹɰɢɢ
63
ɫɪɟɞ ɞɚɧɚ ɜ ɜɢɞɟ ɩɤɝ Ɇ-Ɍɗ ɧɚ
ɫɢɝɚɪɭ.
ɇɟɩɨɧɹɬɧɨ, ɱɬɨ ɨɛɨɡɧɚɱɚɟɬ
“ɩɤɝ”, ɦɨɠɟɬ ɷɬɨ ɩɢɤɨɝɪɚɦɦɵ, ɜ
ɬɚɤɨɦ ɫɥɭɱɚɟ ɞɨɥɠɧɨ ɛɵɬɶ
ɨɛɨɡɧɚɱɟɧɢɟ – ɩɝ. Ɍɚɤɠɟ
ɧɟɩɨɧɹɬɧɨ ɩɨɱɟɦɭ ɤ
ɨɛɳɟɩɪɢɧɹɬɨɣ ɟɞɢɧɢɰɟ Ɍɗ
ɩɪɢɛɚɜɥɹɟɬɫɹ ɛɭɤɜɚ Ɇ.
Republic of Armenia
3
ȿɞɢɰɢɰɚ ɢɡɦɟɪɟɧɢɹ ɞɚɧɚ
ɬɨɥɶɤɨ ɜ ɜɢɞɟ ɦɤɝ Ɍɗ/ɬt,
ɨɞɧɚɤɨ ɧɟ ɭɤɚɡɚɧɨ ɧɚ ɬɨɧɧɭ
ɱɟɝɨ ɧɚɞɨ ɩɟɪɟɫɱɢɬɵɜɚɬɶ
ɜɵɛɪɨɫɵ ɢ ɱɬɨ ɨɡɧɚɱɚɟɬ “ɬt”
ȿɞɢɰɢɰɚ ɢɡɦɟɪɟɧɢɹ ɞɚɧɚ
ɬɨɥɶɤɨ ɜ ɜɢɞɟ ɦɤɝ Ɍɗ/ɬt,
ɧɟɩɨɧɹɬɧɨ ɧɚ ɬɨɧɧɭ ɱɟɝɨ
ɧɚɞɨ ɩɟɪɟɫɱɢɬɵɜɚɬɶ
ɜɵɛɪɨɫɵ ɢ ɱɬɨ ɨɡɧɚɱɚɟɬ “ɬt”.
65
ɫɪɟɞ ɞɚɧɚ ɜ ɜɢɞɟ ɩɤɝ Ɍɗ/ɥ
ɜɵɯɨɞɹɳɟɝɨ ɮɢɥɶɬɪɚɬɚ.
ɇɟɩɨɧɹɬɧɨ ɱɬɨ ɨɛɨɡɧɚɱɚɟɬ
ɟɞɢɧɢɰɚ “ɩɤɝ”.
ɪɚɡɧɵɯ ɫɪɟɞ ɞɚɧɚ ɭɠɟ ɜ ɜɢɞɟ
ɩɤɝ Ɍɗ/ɬ, ɩɨɱɟɦɭ
ɢɡɦɟɧɢɥɚɫɶ ɟɞɢɧɢɰɚ
ɢɡɦɟɪɟɧɢɹ ɫ ɥɢɬɪɚ ɧɚ ɬɨɧɧɭ.
66
ȿɞɢɧɢɰɚ ɢɡɦɟɪɟɧɢɹ ɞɥɹ ɜɨɞɵ
ɞɚɧɚ ɜ ɜɢɞɟ ɩɝ Ɇ-Ɍɗ/ɥ, ɚ ɞɥɹ
ɩɪɨɞɭɤɬ=ɨɫɬɚɬɨɤ ɜ ɜɢɞɟ ɦɤɝ
Ɍɗ/ɬ ɫɭɯɨɝɨ ɜɟɳɟɫɬɜɚ.
ɇɟɩɨɧɹɬɧɨ ɩɨɱɟɦɭ ɤ
ɨɛɳɟɩɪɢɧɹɬɨɣ ɟɞɢɧɢɰɟ Ɍɗ
ɩɪɢɛɚɜɥɹɟɬɫɹ ɛɭɤɜɚ Ɇ.
ɫɪɟɞ ɞɚɧɚ ɜ ɜɢɞɟ ɦɤɝ Ɍɗ/ɬ
ɫɭɯɨɝɨ ɜɟɳɟɫɬɜɚ.
ɪɚɡɧɵɯ ɫɪɟɞ ɞɚɧɚ ɭɠɟ ɬɨɥɶɤɨ
ɜ ɜɢɞɟ ɦɤɝ Ɍɗ/ɬ
67
68
ɫɪɟɞ ɞɚɧɚ ɜ ɜɢɞɟ ɩɝ Ɍɗ/ɥ
ɜ ɜɢɞɟ ɦɤɝ Ɍɗ/ɬ, ɧɟɩɨɧɹɬɧɨ
ɬɨɧɧɵ ɱɟɝɨ.
Ⱦɥɹ ɬɟɯ ɠɟ ɮɚɤɬɨɪɨɜ
ɟɞɢɧɢɰɚ ɢɡɦɟɪɟɧɢɹ ɞɥɹ
ɜ ɜɢɞɟ ɦɤɝ Ɍɗ/ɬ
3. ȼ ɧɟɤɨɬɨɪɵɯ ɫɥɭɱɚɹɯ ɜ ɬɟɤɫɬɟ ɪɭɫɫɤɨɹɡɵɱɧɨɝɨ ɜɚɪɢɚɧɬɚ ɜɨɡɧɢɤɚɸɬ ɫɨɦɧɟɧɢɹ.
ɇɚɩɪɢɦɟɪ, ɫɬɪ.119 ɬɚɛɥ.48 (ɬɨ ɠɟ ɫɚɦɨɟ ɢ ɜ ɬɚɛɥ.8.1) “…ɧɟɤɨɧɬɪɨɥɢɪɭɟɦɨɟ
ɫɝɨɪɚɧɢɟ ɛɵɬɨɜɵɯ ɨɬɯɨɞɨɜ», ɬɨɝɞɚ ɤɚɤ ɩɨ ɫɦɵɫɥɭ ɞɨɥɠɧɨ ɛɵɬɶ ɧɚɩɢɫɚɧɨ
“…ɧɟɤɨɧɬɪɨɥɢɪɭɟɦɨɟ ɫɠɢɝɚɧɢɟ ɛɵɬɨɜɵɯ ɨɬɯɨɞɨɜ”.
Focal Point of Stockholm Convention
A. Aleksandryan
Gambia
COMMENTS ON UNEP STANDARDISED TOOLKIT FOR IDENTIFICATION
AND QUANTIFICATION OF DIOXIN AND FURAN RELEASES
The set up of the toolkit indicates that most data was obtained from developed
and not developing countries’ processes, and therefore more adaptable to
developed country needs. Further, the default emission factors given in the tool
kit are based on research and measurement carried out in the developed
countries and therefore for certain cases there is an absence of appropriate
emission factors in the tool kit.
To finalise the Toolkit it is necessary to carry out some measurements of default
emission factors in developing countries. This will validate the PCDD/PCDF inventory
studies carried out in developing countries by providing more accurate default
emission factors. In the Gambia the priority activities that need to be investigated
include open burning of waste, lime making and fish smoking.
Under the National Implementation Plan for POPs Project, an inventory of
unintentionally produced POPs made the following observations on the use of
the Toolkit:
x
x
x
x
x
That generally the toolkit was handy for initial identification of
PCDD/PCDF major sources of release.
It served as an excellent guiding document in the estimation work
and reconciling of toolkit data requirements and actual available
data in the country.
Selection of the appropriate conversion factors for the reconciliation
exercise was very challenging as well as activity assumption
methods applied, to achieve results with acceptable confidence
levels.
That there are certain relevant emission sources, which are not
adequately addressed in the toolkit. Some of these sources found
in developing country may not fit with any of the default emission
factors given in the toolkit. For example in the Gambia fish smoking
may not be the same as the smoke houses referred to in the toolkit.
Lime making also in the Gambia may not be the same as the lime
making referred to in the toolkit.
The emission factors from Category 5 (Transport), of the Toolkit,
were used for heavy fuel oil and diesel to estimate emissions,
as release factors from power generation.
3
x
The Toolkit does not address releases of HCB and PCBs as a
result of unintentional production.
4
From:
Sent:
To:
Cc:
Subject:
Ott Roots [Ott.Roots@klab.ee]
Wednesday, February 11, 2004 11:12 AM
Heidelore Fiedler
SSC; enn@klab.envir.ee; Kerli Aru; olavi.tammemae@ekm.envir.ee; Allan Gromov;
Andres Kratovits
Stockholm Convention Focal Point-Estonia
article.pdf (37 KB)
Subject: Invitation to submit comments on the Standardized Toolkit for
Identification and Quantification of Dioxin and Furan Releases as well as information
and methodologies on other chemicals under Article 5 and Annex C.
Dear Heidelore!
March 3-8, 2003, dioxin air emissions were measured from one Estonian oil shale
processing plant and four fired boilers at two power plants located near the city of
Narva. The two power plants produced more than 90% of the electricity consumption in
Estonia from burning more than 10 million tons of oil shale per year, which is around
85% of the total consumption of oil shale in the country. DANCEE from Denmark sponsored
the project:" Survey of antrophogenic sources of dioxins in the Baltic Region ", and
dk-TEKNIK ENERGY & ENVIRONMENT was responsible for the measurements, which where
conducted in cooperation with our Centre ( Estonian Environment Research Centre ) in
Tallinn, Estonia. By the preliminary data all the measured dioxin emission
concentrations from the power plants and the oil plant are very low. The same was for
dioxin concentration in the Estonian oil shale and fly ash (article.pdf ).As a part of
the European Dioxin Inventory, Landesumweltamt Nordrhein-Westfalen, Germany, carried
out a study of dioxin in oil shale and fly ash in 1998.For the most congeners, the
concentrations were below the analytical limit of detection. My comment: May be useful
if You or Your colleagues put to " Standardized Toolkit for Identification and
Quantification of Dioxin and Furan releases " ( 1st edition May 2003 ) some new
information about PCDD/Fs concentrations in Estonian oil shale, etc. under §6.3 Main
category 3 - Power Generation and Heating ( 6.3.1- Fossil Fuel Power Plants ) or to
page 209 " PCDD/PCDF release inventory for Estonia, reference year 2000 ". Have a nice
day.
Sincerely Yours
Ott Roots,Ph.D
Monitoring Co-ordinator
Estonian Environmental Research Centre
10 617 Tallinn, Marja Str. 4D, ESTONIA
Phone: +372-611-2964
Fax:
+372-611-2901
E-mail:Ott.Roots@klab.ee
1
5
6
7
Message
Page 1 of 1
Heidelore Fiedler
From:
Fatoumata Ouane
Sent:
Sunday, March 14, 2004 4:24 PM
To:
'Afaf Ali Alshola'; Heidelore Fiedler
Cc:
Dr. Ismail Al Madani; Basel.Alyousfi@unep.org.bh
Subject:
FW: Comments on the Tool-Kit for the determination of Dioxins and Furans
8
Importance: High
Dear Afaf
Ali,
Thank you for the comments to the dioxin tollkit. I am forwarding the file to Heidi Fiedler who is responsible for
this subject matter. She may get back to you if needed.
Best regards
Fatoumata Keita-Ouane
-----Original Message----From: Afaf Ali Alshola [mailto:ashola@bahrain.gov.bh]
Sent: Saturday, March 13, 2004 7:19 AM
To: Irina Kossenko
Cc: Dr. Ismail Al Madani; Basel.Alyousfi@unep.org.bh; fairgriever@who.ch; fatma.gordon@unep.ch;
Fatoumata Ouane; Esther Santana
Subject: Comments on the Tool-Kit for the determination of Dioxins and Furans
Importance: High
Dear sirs,
Good morning,
We had used the tool kit to calculate the Dioxins and Furans being emitted from Bahrain Medical waste incinerator.
Please find attached our comments on the above.
Dr. Afaf Sayed Ali Al Sho'ala
Bahrain POPs Focal Point
8/31/2004
8
Bahrain Comments on the Dioxin and Furan Toolkit
Bahrain waste treatment incinerator classified as class 1-C3 according to the
Standardized Toolkit for Identification and Quantification of Dioxin and
Furan Releases, and the results are summarized in the following tables:
Table (1): PCCD/PCDF emission results according to the Toolkit
Class of the incinerator
Emission factor
Production
(µg TEQ/t)
of waste
Residues
(T/Y)
Air
(Fly ash)
Controlled, batch
combustion, good APC
TOTAL
660
525
920
-
-
Emission
(g TEQ/a)
Residues
Air
(Fly ash)
0.347
0.607
0.954
Calculations:
- Release to air = 660 x 525 = 346,500 µg TEQ/a
- Residues = 660 x 920 = 607,200 µg TEQ/a
- Total PCCD/PCDF = 346,500 + 607,200 = 953,700 µg TEQ/a
| 0.954 g TEQ/a
Table (2): Comparison between the results obtained by use of the Toolkit
and Actual that obtained through technical measurements
Class of the incinerator
Controlled, batch
combustion, good APC
Production
of waste
(T/Y)
Toolkit
Emission
result
(g TEQ/a)
Measured
Emission
result
(g TEQ/m3)
660
0.954
0.1932x10-9
The above table shows that the measured result is not comparable with the
Toolkit result, due to the difference in the units used.
Recommendations:
1- Need to add an appendix for appropriate conversion factors, as well as
activity assumption methods applied to achieve results with acceptable
confidence level.
2- More information and data is needed for the estimation of agricultural
residues burning and illegal open burning.
3- Landfill leachate become one of the important hot spot, so need to know
how leachate from landfill and dumps can be estimated.
4- Need to conduct specific training workshop to learn more about
standardized Toolkits and how to be implemented.
5- The results in the toolkit are based on annual calculation, and our data
calculated once a year based on cubic meter, so there are difficulty to
homogenates these units.
8
Dioxins and Furans Summary
Incinerator chamber 1:
Laboratory Result
International Toxic
Equivalent
(ITEQ) ng
0.8916
Volume Sampled
3
Nm dry
7.2
ITE Concentration
3
ng/Nm
Dry
Dry @11% O2
0.1238
0.1932
Incinerator chamber 2:
Laboratory Result
International Toxic
Equivalent
(ITEQ) ng
0.4706
Volume Sampled
3
Nm dry
7.2
ITE Concentration
3
ng/Nm
Dry
Dry @11% O2
0.0654
0.102
The emission summary is mentioned below:
i.
ii.
iii.
iv.
v.
vi.
Oxygen: 16.8%
Stack Gas Temperature: 122.3 C
Stack Gas moisture: 0.66 %
Stack Gas velocity: 8.94 m/sec
Actual Volumetric flow rate: 9860 m3/hour
Normalized Volumetric Flow Rate: 7033Nm3/hour
9
SWEDISH ENVIRONMENTAL PROTECTION AGENCY
Monday, 22 March 2004
Niklas Johansson
Environmental Assessment Department
Environmental Impacts Section
Phone: +46 8 698 1438
Fax: +46 8 698 1584
niklas.johansson@naturvardsverket.se
Secretariat for the Stockholm Convention on
POPs
11-13 chemin des Anémones
CH-1219 Châtelaine, Geneva
Switzerland
Subject: Invitation to submit comments on the Standardized Toolkit for
Identification and Quantification of Dioxin and Furan Releases as
well as information and methodologies on other chemicals under
Article 5 and Annex C
Dear Colleagues,
The Swedish EPA considers the UNEP Standardized Toolkit for Identification and
Quantification of Dioxin and Furan Releases to be a valuable tool within the task of the
Convention.
The Agency has got a request from the Government on the implementation of the Stockholm
Convention and the LRTAP Convention on POPs. We have been screening today’s knowledge
with respect to current sources of these unintentionally formed substances and identified a
number of data gaps and other weak links. We have therefore contracted a number of scientists
that will perform more in-depth studies within a few selected areas. These are e.g. emission
from household biomass burning, backyard burning and heavy oil fired engines. In certain cases
we also intend to use the emission factors in the toolkit to calculate the emissions as a
comparison. This approach could hopefully generate a better basis for selection and setting of
the emission factors.
We will deliver our report to the Government at the end of this year. Thereafter we will be
happy to submit our results that hopefully could contribute to improvements of individual
settings of emission factors as well as to the general toolkit methodology.
Yours sincerely,
Niklas Johansson
BLEKHOLMSTERRASSEN 36
SE-106 48 STOCKHOLM
PHONE +46-8-698 10 00
FAX +46-8-20 29 25
Antal Sidor 1
C:\Documents and Settings\Alexander\Local Settings\Temporary Internet Files\OLK1B\svar på förfrågan inför ver 2_Sweden1.doc
MINISTERE DE L’ECONOMIE FORESTIERE
ET DE L’ENVIRONNEMENT
-=-=-=-=-=-=-=-=DIRECTION GENERALE DE
L’ENVIRONNEMENT
-=-=-=-=-=-=PROJET POLLUANTS ORGANIQUES
PERSISTANTS
-=-=-=-=-= : 82 -56-32
: 14230
E-Mail : congopops@yahoo.fr
10
REPUBLIQUE DU CONGO
Unité * Travail * Progrès
-=-=-=-
Brazzaville, le
AVIS SUR L’OUTIL STANDARDISE POUR L’IDENTIFICATION DES DIOXINES ET
DES FURANNES
les difficultés suivantes ont pu être relevées dans le Toolkit, lors de l’inventaire des
dioxines et furannes au Congo.
Partie théorique de l’introduction au chapitre 5
La partie théorique qui va de l’introduction au chapitre 4 est tout à fait claire. Les
difficultés d’interprétation du Toolkit commencent au chapitre 5 sur la présentation de
l’inventaire.
L’exemple extrait du rapport d’inventaire provisoire pages 35 à 37 tend à dérouter le
lecteur qui a l’impression que les émissions de dioxines et furannes doivent être
données en temps d’intervalles, ce n’est que la lecture du chapitre 6 sur les facteurs
d’émission par défaut que l’on se rend compte que chaque sous catégorie ou
procédé ne doit avoir qu’un seul facteur d’émission, et donc une valeur précise
d’intérêt de la source ou d’émission de dioxines/furannes par an.
Au titre 5.2 sur le rapport final, le Toolkit dit que les données justificatives détaillées
ne devraient pas être incorporées au rapport, afin qu’il reste court. Nous pensons
qu’il est judicieux d’incorporer ces données pour donner l’occasion à la commission
de validation ( ou le comité de direction du projet) de comprendre comment les taux
d’activités ont été calculés, au lieu de présenter des chiffres sans fondement ou qui
seraient pris au hasard.
Dans le document de l’inventaire du Congo, nous avons prévu tout un chapitre à ce
sujet et nous l’avons intitulé : informations détaillées sur les procédés identifiés au
Congo..
Questionnaires standard 71 à 73
Nous avons bien compris le chapitre 6 sur les facteurs d’émission par défaut et les
détails des procédés y relatifs. Mais la présentation des questionnaires 71 à 77 vient
perturber fortement la compréhension sur la manière de réaliser les enquêtes.
C’est après plusieurs lectures en effet qu’on se rend compte que dans les tableaux
71,72,et 73, les informations sur le type de four ne sont là que pour aider à remplir
les parties supérieures de chaque tableau.
En somme, les questionnaires sont bien pour constituer une base de données sur
les différents procédés ou équipements concernés par les émissions de dioxines et
furannes, mais contiennent trop d’informations à rechercher et qui ne rentre pas
directement dans l’objectif recherché qui est le calcul du taux d’activité de la source
ou du procédé.
Dans notre cas, nous avons essayé d’utiliser les questionnaires au début de
l’enquête, mais les interlocuteurs les ont trouvé trop fastidieux. Nous les avons
abandonnés pour aller droit à la recherche des taux d’activité.
Catégorie principal 4 – produits minéraux – produits de briques
Dans beaucoup de pays africains et notamment au Congo, la production de briques
se fait beaucoup plus dans le milieu informel, la proposition ici est de bâtir un
questionnaire pour estimer le nombre de ménages pouvant disposer d’une maison
en brique cuites, tout en connaissant le nombre de briques moyens dans une maison
type
x Catégorie principal 5- transport – essence pour moteur à 4 temps et
moteurs à 2 temps
Dans beaucoup de pays, la dissémination de l’essence consommée par les
moteurs à 4 temps et les moteurs à 2 temps n’est pas faite au niveau de la
ventilation des combustibles fossiles. Le conseil suivant aiderait à faciliter les
calculs :
- Trouver la quantité d’huile consommée par les moteurs à 2 temps , en
mélange avec l’essence, sur la base du taux d’huile par rapport à
l’essence (dans notre cas 40 ml d’huile /litre d’essence) et trouver la
quantité totale d’essence utilisé par les moteurs à 2 temps
- Enfin la quantité d’essence utilisé par les moteurs à 4 temps est la
différence entre la qualité totale d’essence consommée dans le pays et
la quantité d’essence utilisée par les moteur à 2 temps.
x
Catégorie principale 7 – production et utilisation de produits chimiques
et de biens de consommation
Beaucoup de produits utilisés en Afrique ne sont pas produits localement . la
tentation est dire que ces produits ne sont pas fabriqués dans les pays, sans
tenir compte des importations. C’est le cas par exemple des papiers , des
produits chimiques des textiles et du cuir. Une attention particulière doit être
portée sur les produits importés qui contiennent des dioxines et furannes. Doit –
on les prendre en compte tout en courant le risque de se trouver devant des cas
de double comptage ?
Le Congo est un pays pétrolier qui dispose d’une raffinerie de pétrole. On aurait
souhaité avoir des facteurs d’émission au niveau du raffinage du pétrole pour
compléter notre inventaire . Malheureusement le Toolkit n’en mentionne pas.
Fait à Brazzaville , le 22 mars 2004.
Message
Page 1 of 2
11
Heidelore Fiedler
Scientific Affairs Officer
UNEP Chemicals
International Environment House
11-13, chemin des Anémones
CH-1219 Châtelaine (GE)
Switzerland
Tel.: +41 (22) 917-8187; mobile: +41 (79) 477-0833
Fax: +41 (22) 797 3460
E-mail: hfiedler@unep.ch
-----Original Message----From: Mr L. Bullywon [mailto:lbullywon@mail.gov.mu]
Sent: Tuesday, March 23, 2004 12:50 PM
To: SSC
Cc: Heidelore Fiedler
Subject: Comments on standardized Toolkit
MINISTRY OF ENVIRONMENT & NATIONAL DEVELOPMENT UNIT
REPUBLIC OF MAURITIUS
My Reference: ENV/40/37/V8
Date: 23 March 2004
Mr James B. Willis,
Executive Secretary,
Interim Secretariat For the Stockholm Convention,
UNEP Chemicals,
11-13 Chemin des Anemones,
CH-129 Chatelaine,
Switzerland.
Subject: Invitation to submit comments on the Standardized Toolkit for Identification
and Quantification of Dioxin and Furan Releases as well information and
methodologies on other chemicals under Article 5 and Annex C.
Dear Sir,
With reference to your letter dated 4 December 2003 on the above subject, please find
the following comments from our part:
The toolkit is a well presented document. However the term TEQ needs to be more
explicitly explained and section 6.3.2 on Biomass Power Plant needs to mention
large scale use of bagasse as a renewable source of energy for electricity and steam
production.
7/21/2004
Message
We would appreciate if the above comments could be considered at your level.
Yours faithfully,
L.Bullywon.
For Permanent Secretary.
7/21/2004
Page 2 of 2
M I N I S T R Y O F THE E N V I R O N M E N T
DEPARTMENT FOR INTERNATIONAL CO-OPERATION
ul. Wawelska 52/54, WARSZAWA, POLAND
Ph.:(48+22) 579.22.56.
Fax:(48+22) 579.22.63.
23 March 2004
wz.ww.tzo.rcw/
/04
Mr. James B. Willis
Executive Secretary
Interim Secretariat
For the Stockholm Convention on Persistent Organic Pollutants
UNEP Chemicals
11-13, Chemin des Anemones
CH-1219 Chatelaine, Geneva, Switzerland
Fax: (+4122) 797 34 60
Dear Mr. Willis,,
Comment on the 1st edition of the Standardized
Toolkit for Identification and Quantification of Dioxin and Furan Releases
With reference to your letter of 4 December 2003, with the invitation to countries to
submit their comments on the 1st edition of the Standardized Toolkit for Identification and
Quantification of Dioxin and Furan Releases, we would like to offer, attached to this letter, the
comment by Poland to this document.
Enclosing my best regards, I remain
Yours sincerely,
Czesáaw WiĊckowski
Director
cc.
1. Ms. Heidelore Fiedler
UNEP Chemicals
e-mail: hfiedler@chemicals.unep.ch
2. Mr. Stanisáaw KamiĔski, Deputy Director
Department of Environmental Policy
Ministry of the Environment, Warsaw, Poland
12
23 March 2004
Comment by POLAND
on the 1st edition of
"The Standardized Toolkit for Identification and Quantification of Dioxin
and Furan Releases"
In Poland the methodology described in the document "The Standardized Toolkit for
Identification and Quantification of Dioxin and Furan Releases" (the "Toolkit") is used by the
National Emission Centre (KCIE) located at the Institute for Environmental Protection in the
preparation of an inventory of releases of polychlorinated dibenzodioxins (PCDD) and
polychlorinated dibenzofurans (PCDF) into the ambient air. The draft Toolkit has been used
in emission inventories since 2000.
During the application of the Toolkit in the inventory of PCDD/PCDF releases at the
National Emission Centre, a study was prepared concerning the characteristics of production
processes in Poland. Taking into account the information included in the Toolkit, the study
classified individual processes into appropriate groups of indicators for PCDD/PCDF releases,
depending on the type of processes and environmental equipment used in these processes.
A few years of experience, very briefly described above, with the application of the
principles included in "The Standardized Toolkit for Identification and Quantification of
Dioxin and Furan Releases" lead to the following comments relating to the practical value of
this document:

The document contains a wide catalogue of categories and sub-categories of sources
of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans emissions
from numerous areas of activity and to all components of the environment (including
the most comprehensive analysis of these emissions into the ambient air). Individual
categories and sub-categories are presented in a manner allowing for their easy
application in the emission inventory process.

Technical and technological characteristics of individual categories and sub-categories
of sources of releases constitute a short but sufficient set of information allowing for
the classification of individual types of sources to appropriate categories. It should be
emphasised that due to the presentation format of complex technical aspects as well as
the vast presentation of technical and technological sources of PCDD and PCDF
releases, all the descriptions represent educational value. Yet, despite the generally
positive assessment, the Toolkit lacks the homogeneity / uniformity of individual
descriptions which differ in the level of their accuracy. This, however, does not
significantly decrease the value of this document.

Of particular value is the description of differences among indicators of PCDD and
PDF releases from individual sources, depending on the type of technological
processes in use and environmental equipment installed in individual installations. The
table presentation of these indicators shows, in a very practical manner, different
possibilities to reduce releases for different technologies and protection equipment
used.

Analytical results acquired from different countries for releases from various
technological processes, presented in the document for each individual category, are
very valuable. An analysis of these indicators justifies the adoption of certain emission
indicators, thus increasing their credibility. In the future it seems advisable that the
Toolkit be supplemented with a system for the distribution (exchange) of analytical
determinations obtained by individual countries, of actual PCDD/PCDF releases into
ambient air. This would make the correction of emission (releases) indicators easier
and much cheaper.

The tenth category concerning Hot Spots should be subject to a separate assessment.
Its description helps take an appropriate approach to the identification and analyses of
places where production process might have caused persistent organic pollution
(POP). The description of this category facilitates work on past and current residues of
hazardous substances in the environment.

Moreover, it should be emphasized that special computer software for the processing
of data collected from individual sources of PCDD/PCDF releases have been
developed and used for emission inventories, so has the methodology concerning the
preparation of inventory reports.
Considering the above, it should be concluded that huge work has been done putting the
structure on the whole problem of dioxin / furan releases into the environment and helping
individual countries carry out inventories of PCDD/PCDF emissions. Yet, despite the
generally positive assessment and high technical value of the Toolkit, its use in daily practice
would require e.g. in Poland, due to specific nature of the local conditions, the performance of
additional analyses and studies. A similar situation is also likely to occur in other countries. A
good example are PCDD/PCDF releases from households. In Poland this problem was subject
to a detailed analysis due to the high 37 per cent share of dioxins and furans from household
fuel combustion in the total emission of these substances into ambient air.
The analysis showed numerous concerns relating to estimations of national releases/emissions
of PCDD/PCDF. These concerns included:

In Polish conditions, the high (2000 µg TEQ/TJ) rate of releases to residues (total
dust) for demolition wood incineration is unlikely due to the very limited, in
comparison with West European countries, use of penthachlorophenol (PCP) as a
impregnant.

In the case of volatile ashes from household coal incineration (the Toolkit strongly
emphasizes that this item concerns volatile ash), the concentration of PCDD/PCDF
was set without an accurate definition of what is understood by volatile ashes in the
case of primitive furnaces without environmental equipment in place.

In Polish conditions some concerns are also raised by the high (5000 ng/kg of volatile
ash) rate of releases to volatile dust. Even if, for a vast majority of coal-fired furnaces,
volatile dust is understood as carbon black (in which this concentration is possible due
to its absorption qualities), its amount in relation to the amount of coal burnt may turn
out insignificant. Therefore, it must be decided what the above-quoted contents refer
to: ash collected from the furnace or ash separated in dusting installations, and how to
compare industrial combustion with combustion in small fireplaces or household
furnaces.

In the case of large heat and power plants "The Standardised Toolkit" differentiates
releases from joint incineration of mineral fuels and waste from releases from pure
coal combustion. Such differentiation is not made in the case of joint incineration of
coal and waste and pure coal in households while it is known that in some countries
(including Poland) most organic waste is incinerated by households subject to the
proper construction of the furnace.

In the case of households, for coal-fired furnaces "The Standardised Toolkit" adopted
the indicator 70 µg TEQ/TJ for solid fuels with turf which is used in some regions not
being taken into account.

From Poland’s point of view, a problem which must be solved is the way an inventory
should take into account emissions from brown coal combustion which "The
Standardised Toolkit" fails to address. Due to the fact that household consumption of
brown coal (1.8% of the total consumption of coal) is lower in percentage terms than
deviations in the ash content and deviations in the caloric content of hard coal, the
inclusion of brown coal in the total hard coal consumption and the use of the total for
this two fuels seems reasonable in Poland.
The above-described problems connected with household releases have been quoted here only
to indicate the need for further improvements in the content of the document leading to the
gradual elimination of any doubts. The above comments do not, however, reduce the
importance of the Toolkit for inventories of PCDD/PCDF releases, nor the considerable
progress that this document means for the practical protection of the environment.
Finally, we would like to draw everybody’s attention to the problem which is only indirectly
connected with the document. Apart from PCDD/PCDF, the scope of an inventory of
unintended POP releases also covers polychlorinated biphenyls (PCB) and hexachlorobenzene
(HCB). The current methodology used in inventories of the last two groups of substances
significantly differs from the principles outlined in "The Standardised Toolkit" for
polychlorinated dioxins and furans which allows for significant freedom in its application but
means the low credibility of results. Therefore, the following proposal seems reasonable:

Taking into account the experience gathered during the preparation of "The
Standardized Toolkit for Identification and Quantification of Dioxin and Furan
Releases", another document "The Standardised Toolkit" should be developed for
PCB and HCB. This would significantly simplify inventories of atmospheric
emissions of these substances and enable the more accurate definition of their level.
Attention should be drawn to the fact that in comparison with PCDD/PCDF, releases
of these substances into the environment are relatively high.
Moreover, the following editorial errors have been noticed in the first edition of "The
Standardised Toolkit …":
x
page 97, the text under the table; the household releases indicator should be 70 and not
150;
x
page 145, in the footnote 30, the reference is made to normal conditions i.e. 1013 hP
instead of 103.1.
13
14
15
Ministry of the Environment of the Slovak Republic
Waste management department
Bratislava
Number:
29.3.2004
285/2003-min
2143/2003-6.2
ssc@chemicals.unep.ch
Slovak comments on Decision INC-7/5 on the ”Standardized Toolkit for Identification and
Quanticication of dioxin and Furan Releases”
Slovakia welcomes this revised version of the UNEP Toolkit which provides a valuable
information source and a useful tool to assist countries in preparing requested inventories. The
Toolkit provides also a good overview of available technologies with limited controls,
considered as BAT.
We are involved in discussion by E-mail on the Proposal for a Regulation of the European
Parliament and of the Council on POPs amending Council Directive 79/117.
In Slovakia there are on going following international projects to help us to be prepared to
implement the Stockholm Convention on POPs:
1. “Initial assistance to the SR to meet its obligations under the Stockholm Convention on
POPs”
2. “Demonstration of Viability and Removal of Barriers that Impede Adoption and Effective
Implementation of Available, Non-combustion Technologies”
3. ”Dioxin emissions in Candidate Countries”
4. ”Regional approach for the environmentally sound management of POPs as waste in
selected CEE countries”.
We hope that thanks all these projects Slovakia will be able to implement this Regulation and
also the Stockholm Convention on POPs.
We try to ensure to review and update our national implementation plan by the 1. Conference
of the Parties of the Stockholm Convention on POPs. One of the 9 parts of draft of our
national implementation plan is also special national plan for releases of PCDD/F, HCB and
PCB.
In consequence of abundance of information we will consider the expert assistance in proper
use of the Toolkit may be useful.
Contact persons:
Ing. Marta Fratricova from the Waste Management Department at the Ministry of the
Environment of the Slovak Republic (WMD of the MoE).
Nám. ď. Štura c. 1, 812 35 Bratislava, Slovak Republic
E-mail: fratricova.marta@enviro.gov.sk
Tel. + 421 2 5956 2385
Fax. + 421 2 5956 2031
Ing. Marta Fratricova from the WMD of the MoE
Ing. Peter Gallovic, Head of the WMD at the MoE of the SR
ENVIRONMENTAL ENGINEERING DIVISION
MINISTRY OF HOUSING, LANDS & THE ENVIRONMENT
JEMMOTTS LANE, ST. MICHAEL, BARBADOS, W. I.
TEL: (246) 436-4820, FAX: (246) 228-7103, EMAIL: enveng@caribsurf.com
Ref: UNEP 16/2
July 21, 2004
QUERIES & COMMENTS REGARDING USE OF TOOLKIT DOCUMENT AND EXCEL
SPREADSHEET
The following comments and queries arose during the development of the national inventory of
Barbados. The comments speak to both to the general ease of use and comprehensibility of
the document as well as specifics related to the categories, subcategories and class
assignment.
1
Ease of application
In seeking to be scientifically sound while providing the user with an easily used document the
Toolkit was successful. The description and explanation of the approach used in estimating
source emissions was easily understood and easily applicable. In addition the suggestions
made within the introductory chapters were valuable resources in guiding efforts to supplement
or derive information when the required data was not directly available.
2
Clarity
While being largely understood there are however some areas of uncertainty arising either from
the Toolkit or from the EXCEL spreadsheet. These are presented below.
2.1
Release Media
In describing the release media (route) the Toolkit describes three levels of according to the
importance of that route to the subcategory. First, is the release route expected to be
predominant which is denoted by a large X. The second level describes additional release
routes and the third level addresses release routes that may be of concerned but which are
dependent on the operational characteristics of the source.
In describing the predominant release route the Toolkit identifies it as “the release route
expected to be predominant”. The use of the term predominant coupled with “the” suggests that
there is only one such medium. However in most instances at least two “predominant” release
media are identified. This use of terms introduces confusion especially when reporting to
persons not intimately familiar with the inventories.
This situation is further compounded by the identification of additional release routes. For many
subcategories additional release routes are identified without the identification of a predominant
route. Again this is unclear because the use of the term “additional” suggests that is in addition
to a predominant route. In reviewing the two terms (“predominant” and “additional”) together
there appears to be an implicit quantification so that predominant refers to release media
expected to have more than some threshold value while releases to additional routes fall below
the threshold. If this quantification is implied then it should be made clear. If there is no implicit
quantification then the use of the terms should be made clearer.
-1-
16
2.2
Spreadsheet
In presenting the estimated releases no clear rationale was given for the number of significant
figures/decimal places used. For example, the releases for each category are presented to 3
decimal places (d.p.), but the total national releases only to 1 d.p. This inconsistency was
queried by our National Coordinating Committee when reviewing our inventory. It is unclear to
us whether the number of s.f’s/d.p’s present is at the discretion of the user based on his/her
knowledge of the data sources or whether the user is restricted to the significant figures “stated”
in the EXCEL spreadsheet. It may be beneficial to indicate and explain what the appropriate
number of decimal places/significant figures is for the data presented in the inventory.
3
3.1
Technical Issues
Waste Incineration
The comments made here, while relevant primarily to this category, are also applicable to other
subcategories where afterburners play a role in the source operation.
In categorising sources within this category a variety of operational parameters are highlighted.
These are uncontrolled vs. controlled combustion as well as the quality of the APC system.
What is unclear here is the role that an afterburner has on the control of the process. While it
may be assumed that an afterburner increases the control of the process, this is not stated and
is therefore left up to the user to arrive at this conclusion. If this is indeed true then it should be
clearly stated in the Toolkit. In addition there is no discussion as to what operating parameters
e.g. temperature, residence time etc must be met in order for the afterburner to be considered
as effecting an appropriate level of control.
3.2
Category 3: Power Generation
3.2.1 Subcategory: Household heating and cooking (biomass)
Page 95 of the Toolkit says that “Emission factors for releases with residues are given on the
basis of measured concentrations in the ash (and not related [to] the heating value of the fuel).”
However the emission factors for release to ash are quoted in PgTEQ/TJ. The use of these
units appears to contradict the above statement. This is supported by the use of the units
ngTEQ/kg ash for releases to residue from the use of coal.
3.2.2 Household Heating & Cooking (fossil fuel)
The absence of LPG fuel from the fuels listed was notable. In the Barbadian context LPG
represents approximately 60% of the fuel used for cooking. Even in the absence of emission
factors for this fuel it should be mentioned and perhaps some guidance given as to how an
initial assessment can be made. In the national inventory LPG was assessed under the class
‘natural gas fired stoves’ as it was closer in composition to this fuel than to coal or oil.
3.3
Category 6: Uncontrolled Combustion Processes
3.3.1 Subcategory: Biomass Burning
In the written document (May 2003) the following classes are defined
-2-
Fires/burnings - biomass
1
2
3
Forest fires
Grassland and moor fires
Agricultural residue burning (in field), not
impacted
Air
5
5
Potential Release Route (µg TEQ/t)
Water Land
Products Residues
ND
4
NA
ND
ND
4
NA
ND
0.5
ND
10
NA
ND
However in the EXCEL worksheet the following classes are defined
Fires/burnings - biomass
1
2
3
4
Forest fires
Grassland and moor fires
Agricultural residue burning (in field), not
impacted
Agricultural residue burning (in field),
impacted, poor combustion conditions
Air
5
5
Water Land
Products Residues
ND
4
NA
ND
ND
4
NA
ND
0.5
ND
10
NA
ND
30
ND
10
NA
ND
Which of the two i.e. the EXCEL or the written Toolkit, represent the most recent version? In
addition, the terms “impacted” and “poor combustion conditions” need to be defined in this
context.
3.3.2 Subcategory: Waste Burning and Accidental Fires
Again in the written Toolkit document the following emission factors are defined
Fires, waste burning, landfill fires,
industrial fires, accidental fires
Landfill fires
Accidental fires in houses, factories
Air
1,000
Water
ND
Products
NA
Residues
ND
NA
400
NA
600
ND
Land
NA
See
residues
See
residues
See
residues
400
ND
300
ND
94
NA
18
60
ND
ND
NA
10
Uncontrolled domestic waste burning
Accidental fires in vehicles (per vehicle)
Open burning of wood
(construction/demolition)
However in the EXCEL document the term of ‘per event’ is included in describing the second
class (accidental fires in houses, factories). Are the emission factors for this class calculated on
a per event basis or on a mass of material burnt?
3.4
Category 9: Disposal and Landfilling
The highlighted category in the following table is present in the EXCEL worksheet but not in the
written document. There is therefore no explanation as to what constitutes a modern treatment
plant. This should be clarified in updated versions.
-3-
Sewage/sewage treatment
Industrial, mixed domestic with chlorine
relevance
No sludge removal
With sludge removal
Urban environments
No sludge removal
With sludge removal
Remote and residential or modern
treatment plant
-4-
Air
Water
5
0.5
Land
NA
NA
Products
NA
NA
Residues
1,000
1,000
2
0.5
NA
NA
NA
NA
100
100
0.1
NA
NA
10
Heidelore Fiedler
From:
Sent:
To:
Subject:
Mac Word 3.0 (54
KB)
mayumi.suzuki@mofa.go.jp
Tuesday, March 30, 2004 4:29 PM
Heidelore Fiedler
INC7-5: Information for the Annex C
17
Dear Ms. Fiedler,
Following our phone conversation, I am sending you the information for the Annex C,
which was requested from decision INC7-5.
I will send the same message thought FAX, so please check it.
If you have any questions, please do not hesitate to contact me.
Best regards,
Mayumi Suzuki
೧‫ڏڎڏڎڏڎڏڎڏڎڏڎڏڎڏڎڏڎڏڎڏڎڏڎڏڎڏڎ‬
/C[WOK57<7-+
/U
#FXKUQT
2GTOCPGPV/KUUKQPQH,CRCPKP)GPGXG
6GN
(CZ
1
Per-unit HCB & PCB emissions
1. Hexachlorobenzene(HCB)(µg/t)
Cat.
Air
Subcat.
1
Water
Waste incineration
A
Municipal solid waste incineration
3. Controlled comb., good APC
810
(Small Incinerators)
4. High tech. combustion, sophisticated APCS
(Municipal Waste Incineration Facilities)
B
880
Hazardous waste incineration
(Industrial Waste Incineration Facilities)
E
1000
Sewage sludge incineration
3. State-of-the-art, full APCS
5.3
(Sewage sludge incinerators)
8
Miscellaneous
B
Crematoria
150ҏ/body
3. Optimal control
2. Polychlorinated biphenyls(PCB)㧔µg/t㧕
Cat.
Air
Subcat.
1
Waste incineration
A
Municipal solid waste incineration
3. Controlled comb., good APC
570
(Small Incinerators)
(Domestic Waste Incineration Facilities)
B
170
(Industrial Waste Incineration Facilities)
E
410
3. State-of-the-art, full APCS
1400
(Sewage sludge incinerators)
8
Miscellaneous
B
Crematoria
410ҏ/body
3. Optimal control
Water
Per-unit HCB and PCB emissions are estimated by the results of survey conducted by the
Ministry of the Environment of Japan from FY 2001 to 2002.
The methods used for estimating per-unit emissions from individual sources are as follows:
1. Methods of Estimating the per-unit HCB and PCB emissions from Individual Sources
(1) Incineration Facilities
a) Domestic Waste Incineration Facilities
Emission from each ton of waste incineration was 880µg/t (HCB) and 170µg/t (PCB).
These values are obtained by dividing the annual amount of emissions which was
calculated from 12 sets of data (HCB㧦2.4㨪570 ng/Nm3‫ޔ‬PCB㧦2.0㨪250 ng/Nm3㧕
measured in FY 2001 and 2002 by the annual amount of incineration at the 12 facilities.
b) Industrial Waste Incineration Facilities
Emission from each ton of waste incineration was 1,000µg/t (HCB) and 410 µg/t (PCB).
These values are obtained by dividing the annual amount of emissions - which was
measured in FY 2001 and 2002 by the annual amount of incineration at the 12 facilities.
c) Small Incinerators
Emission from each ton of waste incineration was 810µg/t (HCB) and 570 µg/t (PCB).
These values are obtained by dividing the annual amount of emissions which was
measured in FY 2001 by the annual amount of incineration at the 4 facilities.
d) Sewege Sludges Incinerators
Emission from each ton of waste incineration was 5.3µg/t (HCB) and 1,400 µg/t (PCB).
These values are obtained by dividing the annual amount of emissions - which was
calculated from 3 sets of data (HCB㧦0.67㨪3.9 ng/Nm3‫ޔ‬PCB㧦2.2㨪1,700 ng/Nm3㧕
measured in FY 2002 by the annual amount of incineration at the 3 facilities.
(2) Crematoria
Emission from cremation per one body was 5.3µg/body (HCB) and 1,400 µg/body(PCB).
These values are obtained by dividing the amount of emissions which was calculated from
10 sets of data (HCB㧦3.9㨪96 ng/Nm3 ‫ޔ‬PCB㧦5.5㨪160 ng/Nm3 㧕measured in 10
crematoria in FY 2002 by the acrtual numbers of cremations at the 10 facilities.
㧖PCB values include all the homologues (mono through decachlorinated biphenyls). Therefore
they are probably higher than values by some countries which don't include monochlorinated
biphenyl etc.
㧖The data of other sources are under investigation. We will provide additional information
once we get them.
17
18
26 March 2004
Interim Secretariat of the Stockholm Convention
Attention: Decision 7/5
c/o Heidi Fiedler
UNEP Chemicals
11-13 Chemin des Anemones
CH-1219 Chatelaine, Geneva, Switzerland
Fax: +41-22-797-3460
E-mail: ssc@chemicals.unep.ch
HFiedler@unep.ch
On behalf of the World Chlorine Council and the International Council of
Chemical Associations, we appreciate the opportunity to provide comments on the
revised Standardized Toolkit for the Identification and Quantification of Dioxin and
Furan Releases.
During its seventh session held in July 2003, the Intergovernmental Negotiating
Committee (INC) agreed on Decision 7/5, which invited additional comments on the 1st
edition of the Toolkit.
We offer the attached comments in an effort to improve the overall usefulness of
the Toolkit.
If you have any questions or would like any additional information, please
contact William F. Carroll at +972-404-2845 or via e-mail at william_f._carroll@oxy.com
or Robert Simon at +703-741-5866 or via e-mail at robert_simon@americanchemistry.com.
WCC/ICCA Comments on Revised Dioxin Toolkit
I.
General Comments on the 1st Edition of the Dioxin Toolkit
Overall the Toolkit is a very useful approach for assisting countries in identifying
potential sources of dioxin/furan releases and attempting to estimate potential releases from these
sources. It organizes a diffuse set of sources and attempts to characterize them in a way that is
not available elsewhere. The spreadsheet template available on the website also provides a
useful mechanism for developing an “initial” inventory.
There are a number of “pilot projects” in progress now in countries at various points in the
spectrum of development. It will be important to assess the ease of use of the Toolkit,
particularly for developing economies as they work to develop their National Implementation
Plans, including their National Action Plans for unintentional POPs.
II.
The Toolkit should explicitly recognize the limitations and variability resulting from
the use of emissions factor data, and caution users about too rigorous comparison
of sources.
Emission factor data driving calculation of potential releases are, in many cases, sparse and
at least in incineration cases other than BAT, can be very device-specific. Moreover, sources
commonly found in a country will vary in importance by many orders of magnitude. What’s
more, the “error bars” on the largest sources (especially open combustion) may be larger than the
total magnitude of all other medium and small sources.
Users of the Toolkit will be well served to recognize that it is more important to address
very large sources rather than attempting to exactly quantify less significant sources.
III.
The Toolkit should emphasize that the implementation of BAT is the most effective
means for minimizing releases of dioxins and furans and avoid any effort to
promote restrictions/bans on technologies or products simply because they are
listed as a potential source.
The Toolkit should be taken as an affirmation that the use of BAT is extremely effective in
controlling emissions of unintentional POPs. The reductions in existing national inventories as a
result of application of BAT show remarkable results. For example, the substantial reductions in
releases of dioxins and furans that have been achieved through application of BAT as seen in the
German and US inventories.
The Toolkit should not be used as a means of defining Best Environmental Practices (BEP)
beyond the application of BAT. Calls for restrictions or bans on a particular technology solely
because a source is listed in the Toolkit are misguided. For example, production of copper or
steel should not be disallowed solely on the basis of some association with a thermal process or
their listing as a potential source. Unique properties of these materials have utility to society.
Techniques should be used that allow process management to minimize emissions of PCDD/F,
while still allowing society to continue to benefit from such materials/technologies.
BAT/BEP Guidance on minimizing and preventing the formation and release of
unintentional POPs is being developed and will ultimately be adopted by the Parties, so the
Toolkit should not seek to duplicate or contradict this guidance.
IV.
Information and Methodologies for Estimating Other Unintentional POPs Listed
Under Article 5 and Annex C of the Stockholm POPs Convention
For non-PCDD/F unintentional POPs separate Toolkits could possibly be developed;
however there is very limited data available. Emission factors, if sparse for dioxins and furans,
are virtually nonexistent for other unintentional POPs – HCB and PCBs. We believe that the
time and resources necessary to develop additional Toolkits would be better applied to support
other implementation efforts.
Perhaps more importantly, a practical look at most of the Best Available Techniques
suggests that Techniques that minimize PCDD/F also are useful in minimizing other
unintentional POPs. Application of BAT for PCDD/F may, in itself, mitigate the need for
development of similar Toolkits for other unintentional POPs.
In an effort to ensure governments and UNEP have accurate information on other
unintentional POPs, we are attaching a copy of a published study on hexachlorobenzene1. While
this work is in the process of being updated, to our knowledge it represents the most
comprehensive information available on HCB.
V.
Inclusion of A Dioxin Source Identification Strategy in the Toolkit
Inclusion of a source strategy is beyond the scope of the Toolkit and would be duplicative
of the Convention and various Convention implementation activities. The primary purpose of
the Toolkit is to assist countries in estimating releases of PCDD/F where such information is
available.
The Convention clearly outlines key source categories for unintentional POPs.
Furthermore, the most rigorous obligations of the Convention require Parties to focus on source
categories identified in Part II of Annex C. Many Governments have indicated their preference
for Parties and implementation activities to focus on the sources outlined in Part II of Annex C as
sources with the highest potential for emissions.
Unintentional POPs may result from a variety of natural and man-made sources so trying
to document or list all possible sources will not necessarily assist countries in focusing their
limited resources on priority sources nor in achieving substantial reductions of unintentional
POPs.
1
Bailey, R.E., 2001. Global Emissions of Hexachlorobenzene. Chemosphere. 43, 167-182.
MINISTERIO
DE CIENCIA
Y TECNOLOGÍA
19
Centro de Investigaciones
Energéticas, Medioambientales
y Tecnológicas
To: Mr. James B. Willis
Executive Secretary
Secretary of the Stocholm Convention
On Persistent Organic Pollutants
11-13 chemin des Anémones
CH-1219 Châtelaine
Geneva, Switzerland
SUBJECT: Invitation to submit comments on the Standarized Toolkit for Identification and Quantification of Dioxin and Furan
Releases as well as information and methodologies or other chemicals under Article 5 and Annex C
Dear Colleague:
In connection with information request submitted by UNEP Division about application of TOOLKIT in Dioxin and Furans
Inventories, we let you know the following comments:
-
National Dioxin and Furans Inventory is currently being accomplished in Spain since 1998. Well-defined sampling
program has been developed, covering internationally accepted sources of dioxins. We consider that results obtained from
real sampling program may contribute to improve and enlarge data presented in Toolkit.
-
Summary of data from Hot Dip Galvanizing sector. Code CORINAIR : 040307. Non-Ferrous Metal Industry Processes,
reported in “Evaluación De La Generación De Dioxinas Y Furanos En El Sector De Galvanización En Caliente Durante El
Año 2002 “, AUTORES recently submitted to Dr. Fiedler. In our opinion, following information should be included:
within Toolkit scope:
o
o
o
o
o
A specific subcategory of “Galvanizing Processes” within the Main Source Category number 2. “Ferrous and
Non-Ferrous Metal Production”.
For this sector, Potential Releases Routes would be Air and Residues
Different emission factors would be desired for those facilities with or without air pollution control devices
(APCD) (filter bags).
For those facilities with APCD systems (*), two additional subcategories would be desired according to whether
or not facilities include degrease step in the cleaning process.
Emission factor ranges to air obtained were:
Facilities with no degrease step: 41-61 ng I-TEQ/Tonne of galvanized steel
Facilities with degrease step: 7-27 ng I-TEQ/Tonne of galvanized steel
o
PCDD/F concentration ranges in dust (residues) obtained were:
Facilities with no degrease step: 487-8,075 pg I-TEQ/g
Facilities with degrease step: 127-1,804 pg I-TEQ/g
o
No significant differences were found according to production rate between facilities.
o
For those facilities including no APCD systems, atmospheric releases from dust should be considered.
AVENIDA COMPLUTENSE,
22
CORREO ELECTRÓNICO
begona.fabrellas@ciemat.es
28040 - MADRID
TLF: 91 3466019
FAX: 91 3466269
MINISTERIO
DE CIENCIA
Y TECNOLOGÍA
-
Centro de Investigaciones
Energéticas, Medioambientales
y Tecnológicas
Summary of data from “Cement Production Sector”, 4 a).
o
During 2002-2003 period, 41 of the 59 existing kilns have been assessed. Total number of samples was 89: 58
from facilities using conventional fossil fuels and 31 from those using alternative feedings, all of them operating
in dry or semi-dry process conditions. Currently, these data constitute an internal report of Spanish Ministry of
Environment and CIEMAT (Pending edition). In the next future it will be available and sent to you as soon as
possible.
o
Emission factors have been calculated for facilities employing both conventional and alternative fuels. No
significant differences could be identified between them. Emission factors varied from 0.16-196 ng I-TEQ/Tonne
of cement.
o
Total emission values ranged from 0.0199·10-2-0.0541 ng I-TEQ/Nm3
(*) Only data for facilities with APCD systems were available. Method considerations were made according UNE-EN-1948-1,2,3
With regard to convenience of settling contacts between expertises, we let you know that details of contacting person in charged of
Spanish Dioxin and furans Inventory are:
Dr. Begoña Fabrellas Rodriguez
Project Leader . Study and Characterization of Persistent Organic Pollutants
CIEMAT
Avda. Complutense, 22
Madrid 28040
Spain
Ph. 34-91-3466019
Fax. 34-91-3466269
e-mail:begona.fabrellas@ciemat.es
Please, do not hesitate in contact me for any additional information.
Yours sincerely,
[signed]
Dr. B. Fabrellas
AVENIDA COMPLUTENSE,
22
CORREO ELECTRÓNICO
begona.fabrellas@ciemat.es
28040 - MADRID
TLF: 91 3466019
FAX: 91 3466269
20
Dioxin, PCB and Waste Working Group
c/o Arnika, Chlumova 17, CZ-130 00 Prague 3, Czech Republic
tel. + fax: +420.222 781 471, e-mail: petr.hrdina@arnika.org, http://www.ipen.org
Comments on the Standardized Toolkit for Identification and
Quantification of Dioxin and Furan Releases
The Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases,
“is a methodology to help countries just developing their inventories to estimate releases of
PCDD/PCDF and also leads them through the process of how to enhance and refine these
inventories.” The authors of the Toolkit acknowledge that one of the Toolkit’s key elements
is, “an effective methodology for identifying the relevant industrial and non-industrial
processes releasing PCDD and PCDF to air, water, land and with products and residues”.
However, the Toolkit still lacks a comprehensive strategy to identify PCDD/Fs sources as
stated in previous NGOs comments.1 The Toolkit should include a strategy for sources
identification to support the objectives of the Stockholm Convention. We have included a list
of sources which were not included in the Toolkit (see Table 1 below).
The Toolkit should be extended to include PCBs and HCB releases into the environment.
Article 5 of the Stockholm Convention is not limited only to PCDD/PCDF, but also asks
parties to evaluate, “current and projected releases“ as well as,“to address the releases of the
chemicals listed in Annex C“. The proposed Toolkit fails to address the releases of all the
chemicals listed in Annex C, because it does not include PCBs or HCB sources. A large body
of data documents both measurements and sources of PCBs and HCBs, which could be used
as a basis for a comprehensive list and supply default emission factors, after critical
evaluation of these information resources 2, 3, 4, 5, 6, 7, 8, 9, 10. As clearly shown in some
Regionally Based Assessment of Persistent Toxic Substances Reports, there exist country
inventories of PCBs and HCB emissions as by-products in more cases11 and we believe there
are more data available in scientific reports. This raises the question why the Toolkit authors
did not collect data from these inventories to set up a basic report that would help countries to
prepare their own inventories of all by-products.
We have included some examples of emission factors for PCBs air releases used in the Czech
National Implementation Plan Draft in Table 5 of these comments.12
The Toolkit must be revised to include a more comprehensive list of default emission factors
that includes those that are appropriate not only for processes and activities in industrialized
countries but also for those in developing countries and countries with economies in
transition. Default emission factors in the Toolkit are often lower than those given in the
byproducts inventories (including PCDD/Fs). In addition, the Toolkit often uses emission
factors that are lower than actual measurements in industrialized regions as well as those
reported in the scientific literature. Nonetheless, the Toolkit’s authors advise Parties that they
need no monitoring data for any of the sources in their countries in order to estimate
PCDD/Fs releases with sufficient accuracy to prioritize their sources. A summary of the
default emission factors presented in section 8 (Annex 1) of the Toolkit shows that emission
factors for many existing PCDD/Fs sources are missing.
The Toolkit should offer descriptions of both regulatory and affordable analytical means for
obtaining monitoring data that can be used to estimate releases and/or derive emission factors.
Sources Identification Strategy
Greenpeace International submitted a document at INC7 which is highly relevant to our
comments on the Toolkit. 13 The following elements of their document are relevant to the
current discussion:
Numerous dioxin sources have been identified in national and regional inventories, other
government reports, industry reports, and the scientific literature. While many of these are
addressed in the Toolkit, all of them are not. Meanwhile, new dioxin sources are still being
discovered. In other words, the Toolkit does not have a comprehensive “check list” of all
dioxin sources and such a list is unlikely to be compiled in the near future.
Why is a source identification strategy a matter of economic importance?
Equipped with the Toolkit’s incomplete list but no source identification strategy, some
countries will likely be unable to identify important dioxin sources. Sources that remain
unidentified will not, of course, be included in dioxin inventories or, subsequently in national
or regional action plans. Sources that are not included in action plans will not be eligible for
funding being made available to support the implementation of the Stockholm Convention. In
effect, unidentified dioxin sources represent the potential loss of economic assistance for
countries and their public and industrial sectors. This loss of economic assistance is, at the
same time, exacerbated by the economic losses associated with the impacts of unabated
dioxin releases on public health and the environment.
Why is there no dioxin source identification strategy in UNEP’s Dioxin Toolkit?
Greenpeace first recommended inclusion of a source identification strategy in preliminary
comments on the draft Toolkit that were submitted to UNEP in June 2002, again in comments
on the draft Toolkit that were submitted in January 2003, and yet again in comments on the
revised draft Toolkit that were submitted in May 2003. The only acknowledgement given to
this repeated recommendation was the following footnote, which appeared in the revised draft
Toolkit that was circulated for comment in April 2003: “[HF42] Greenpeace but I do not
want to introduce “Strategy” as an own item within the inventory making.”
What is a dioxin source identification strategy?
A dioxin source identification strategy is neither complex nor lengthy. For example, in
preparing its dioxin inventory, Denmark simply tracked the use of chlorine and chlorinecontaining chemicals in its industrial sector. Industries that used chlorine in some form were
given closer consideration as potential dioxin sources while those with no chlorine use were
screened out.14 Including this simple dioxin source identification strategy in UNEP’s Dioxin
Toolkit should be neither difficult nor costly. In addition, countries can follow this same
strategy to evaluate proposals for industrial development and expansion, waste management
projects, etc. for their potential as dioxin sources.
Primarya dioxin sources share one common feature – the availability of chlorine in elemental,
organic or inorganic form. These sources fall into three general classes:
1) Processes and activities in which chlorine or chlorine-containing materials are essential. In
almost all cases, these are chemical manufacturing processes. In some cases, the primary
route of dioxin release to the environment is in products and materials (e.g., some
organochlorine pesticides, such as pentachlorophenol). Most often, dioxins are concentrated
in production wastes so that the wastes and/or the gaseous, liquid and solid residues from their
treatment are the main routes of dioxin release.
2) Processes and activities in which chlorine or chlorine-containing materials are used for
specific purposes that can be fulfilled by a non-chlorinated material (e.g., the use of elemental
chlorine or chlorine dioxide for bleaching wood pulp); and
3) Processes and activities in which chlorine or chlorine-containing materials have no purpose
but are only incidentally present, e.g., the burning of wastes that contain discarded goods
made of polyvinyl chloride (PVC); metallurgical processes involving the recycling of
discarded metal products that are, for example, PVC-clad; power generation in which
municipal wastes that contain PVC- and other chlorine-containing materials are cocombusted, accidental fires involving vehicles with PVC plastic parts or homes that have
pipes and appliances made of PVC; etc.b
We have included Table 3, part of Greenpeace comments on the Toolkit in January 2003, 15
with an indicative list of major chemical products from the uses of chlorine and/or chlorinecontaining materials to support development of the Sources Identification Strategy.
Information about production and producers of elemental chlorine and some of the important
chlorine-containing chemicals would also be helpful to develop such strategy (see Table 2). 16
There are also two Annexes at the end of our Comments that list both “Commercial Chemicals
Known or Suspected to be Accompanied by Dioxin Formation During Their Manufacture” and
“Pesticides Known or Suspected to be Accompanied by PCDD/F Formation During
Manufacture” (see Annex 1 and Annex 2).
Emission Factors
Emission factors are a commonly used tool to construct inventories of different polluting
substances and to fulfill the mission of pollutant release and transfer registers. This justifies
their use in the Toolkit. An emission factor as defined by the Toolkit is the quantity of
PCDD/Fs released to air, water, land, residues, and/or products when a specified quantity of
material is processed or product is produced. In discussing the Toolkit’s emission factors, the
authors effectively acknowledge that the emission factors in their database are not universally
applicable. In fact, the Toolkit uses information from industrialized countries. For example,
the text of Toolkit indicates that, “The “Toolkit” has been assembled using the accumulated
experience of those who have compiled inventories. ... A review by UNEP Chemicals in 1999
identified only 15 [inventories], nearly all from developed Northern countries. ... Many are
a
Primary dioxin sources are those processes and activities that actually generate dioxins, as opposed to
secondary sources, which serve as points of release for dioxins generated by primary sources.
b
This is an end of Greenpeace International document quotation.
23
26
27
28
Oil and gas exploration – well testing
Hog fuel boilers d
Accidental fires involving stockpiles of tires
Thermal stabilization of sewage sludge
Rubber manufacture, vulcanization process
Elemental chlorine manufacture, titanium electrodes e
Trichloroethylene and perchloroethylene manufacture f
Caprolactam manufacture (intermediate for manufacture of nylon)
Titanium dioxide manufacture
Primary copper production
Drum and barrel reclamation
Iron chloride manufacture
Aluminum chloride manufacture
Copper chloride manufacture
Phthalocyanine dyes and pigments manufacture
Printing inks manufacture and/or formulation
Carbon reactivation furnaces (industrial spent carbon and spent carbon from
municipal water treatment)
Alkylamine tetrachlorophenate manufacture
30, 31
29
25
24
21
While it is acknowledged that this process has been otherwise identified as a dioxin source, it is not included in the Toolkit’s list of sources and no data are given on dioxin
releases.
d
While this process may be assumed to be included in the subcategory, “Biomass Power Plants”, it has been specifically identified in the scientific literature as well as in at
least one national inventory as an important source due to high dioxin releases attributed to the high chlorine content of `hog fuel.’
e
In the text of the Toolkit, manufacture of elemental chlorine using titanium electrodes is acknowledged to be a dioxin source. However, the Toolkit’s list of sources includes
only chlorine production with graphite anodes.
f
Manufacture of these chemicals is acknowledged as a dioxin source in the Toolkit and an emission factor is given in the text. However, these are not included in the Toolkit’s
list of sources.
c
Municipal wastwater treatment
Candle burning
22
Fireworks
Primary aluminum production
20
Thermal stabilization of sewage sludge
19
18
Tetrachlorobisphenol-A manufacture
Tire combustion
Reference
Run-off from roads
Accidental fires involving stockpiles of PVC
17
Petroleum refining catalyst regenerators c
Source
Reference
Source
Table 1: Selection of Identified Dioxin Sources Not Included in the Toolkit’s List of Sources
Table 2: Stanford Research Institute Reports on Production and Producers of Chlorine and Chlorinated Products32
Title
Year
Authors
Cost
Production
Production Locations
Chlorine/Sodium
Oct. 2002
Eric Linak
$4,000
US, Canada, Mexico, Brazil, W. Europe, E.
Hydroxide
Europe, Middle East, Japan, ASEAN, China,
India, Republic of Korea, Taiwan, Australia
Hydrochloric Acid
Nov 2001
Eric Linak with
$2,500
16.6M tonnes
US, Canada, Mexico, W. Europe, Japan
Yashuhiko Sakuma
(US, W. Europe,
Japan)
North America, W. Europe, Japan, Taiwan,
Ethylene Dichloride
Jan 2001
Aida Jebens with
$1,500
32M
Katherine Shariq
tones(consumptio Republic of Korea, Other Asia, Other Regions
n)
Vinyl Chloride
Dec. 2000
Aida Jebens with
$2,000
25M tones
North America, W. Europe, Japan, Republic of
Monomer (VCM)
Akihiro Kishi
Korea, Taiwan, Other Asia, Other Regions
Polyvinyl Chloride
Jan 2001
Aida Jebens with
$2,000
25M tones
North America, Latin America, W. Europe,
Resins
Akihiro Kishi
Japan, Republic of Korea, Other Asia, Other
Regions
Chlorinated Methanes
Dec 2001
Eric Linak and
$4,000
($1B global
US, Canada, Mexico, South America, W.
Goro Toki
value)
Europe, E. Europe, Japan, China, Asia Pacific
Phosgene
July 2000
Jamie Lacson
$1,500
US, Canada, Mexico, South America, W.
Europe, Japan, Other Asia, China, Republic of
Korea,
C2 Chlorinated Solvents Jan 2002
Eric Linak and
$2,500
US, Canada, Mexico, Brazil, W. Europe, E.
Goro Toki
Europe, Japan, China, Southeast Asia and
Oceania
Monochloroacetic acid
Jan 2002
Jamie Lacson with
$1,500
US, W. Europe, E. Europe, Japan
Kazuo Yahi
640T tonnes (US, US, W. Europe, E. Europe, Japan, China,
Epichlorohydrin
Dec 2000
Elvira Greiner with $1,800
Republic of Korea, Taiwan, Thailand
W. Europe and
Thomas Kaelin and
Japan)
Mashiro Yoneyama
Chlorobenzenes
Dec 1999
Jamie Lacson with
$1,500
336T tonnes (US, US, Canada, Mexico, Brazil, W. Europe, E.
Chiara Cornetta
W. Europe and
Europe,
and Masahiro
Japan)
Yoneyama
128T tonnes (US
US, Canada, Mexico, W. Europe, E. Europe,
Benzyl Chloride
July 2001
Elvira Greiner with $2,000
and W. Europe)
Japan, Other Asian Countries
John Bottomley
and Goro Toki
Table 3: Indicative List of Uses of Chlorine and Chlorine-containing Products
Product
Elemental chlorine
Hydrogen chloride
C1 Derivatives
Monochloromethane
Uses
• Industrial processes (e.g., pulp and paper bleaching)
• Water and wastewater treatment
• Production of hydrogen chloride
Many
Manufacture of
• Methyl cellulose
• Silicones
• Tetramethyl lead
Dichloromethane
Trichloromethane
Tetrachloromethane
Phosgene
C2 Derivatives
Monochloroethane
1,2-Dichloroethane (EDC)
Trichloroethylene
1,1,1-Trichloroethane
Monochloroacetic acid
Trichloroacetic acid
C3 Derivatives
Allyl chloride
Manufacture of HCFCs o PTFE
Industrial processes
Manufacture of
• Diisocyanates o Polyurethanes
• Polycarbonates
Manufacture of tetraethyl lead
Manufacture of
• Vinyl chloride o Polyvinyl chloride
• PVDC
• PVDF
• Perchloroethylene o HFC
• Trichloroethylene o HFC
Manufacture of HFC
Manufacture of
• HFC
• HCFC
Manufacture of Carboxymethyl cellulose o Foods,
cosmetics
Manufacture of pharmaceuticals
Manufacture of
• Epichlorohydrin Epoxy resins & Glycerols
• Flocculants
• Propylene oxide
o Propylene glycol o Glycol ethers
o Polyols o Polyurethanes
Epichlorohydrin
C4 & Higher Derivatives
Dichlorobutene
Aromatic Derivatives
Manufacture of Chloroparaffins o Linear alkyl benzene
Manufacture of Chloroprene o Polychloroprene
Manufacture of
• Pesticides, Anti-bacterials, etc.
• Dyes and dyestuffs
• Aramide fibers
Inorganic Derivatives
Aluminum chlorides
Iron chlorides
Silicon tetrachloride
Sulfur chlorides
Manufacture of
• Silicon dioxide
• Silicon
Manufacture of
• Pesticides, etc.
• S-resins
Sodium hypochlorite
Titanium tetrachloride
Phosphorus chlorides
Manufacture of titanium dioxide
Manufacture of pesticides, etc.
incomplete, out of date or lack uniform structure. ...Further, only a few inventories address
releases other than to air.”
Analysis of how the default emission factors for all main source categories and subcategories
have been derived and noting that they been determined mostly in the industrialized countries
shows the limitations of their use because they are not equally applicable in various countries,
especially in developing countries and countries with economies in transition.
Having acknowledged the marked limitations of the Toolkit’s emission factors, particularly
with respect to developing countries and countries with economies in transition, the authors
nevertheless advise that: “No emission testing is necessary to apply the Toolkit and to compile
an inventory.”
In addition, the authors state that one of key elements of the Toolkit is, “A detailed database
of emission factors, which provides suitable default data to be applied which is representative
of the class into which processes are grouped. ...”
In addition the Toolkit authors state that, “This database [of emission factors] can be updated
in the future as new data becomes available.” The Toolkit in effect ignores already available
data from measurements and scientific literature to define emission factors in the range closer
to real releases of PCDD/Fs.
Inventories vary widely from year to year or even within the same year (for example in
Holoubek, I. et al. 200433) because they use emission factors commonly based on a limited
number of measurements from a relatively small number of sources that are assumed to be
representative for all sources of the same type. This “top down” approach probably
underestimates PCDD/F releases since it does not take into account the variability in releases
from individual sources or the variability among individual sources of nominally similar
types. In turn, such underestimations can result in inappropriate ranking of PCDD/F sources
so that national action plans do not target the most important PCDD/F sources.
In addition, default emission factors used in Toolkit are derived almost entirely from sampling
and analysis carried out in a small number of industrialized countries. Such default emission
factors do not yield useful results even when applied to similar facilities in the same
industrialized country. For example, Webster and Connett (1998) estimated PCDD/F releases
to air from US incinerators for which monitoring data were available. They compared these
estimated annual air releases with estimates calculated using default emission factors. They
generally found that estimates of air releases based on default emission factors were
considerably smaller than those based on actual monitoring data. In fact, they found that the
measurement-based estimate of annual air releases from two particular incinerators was as
large or larger than 9 of 11 emission factor-based estimates for all incinerators combined.34 A
similar situation occurred during the preparation of a PCDD/PCDF inventory for releases to
air for a National Implementation Plan. Data calculated for incinerators with using old
emission factors originally underestimated value of waste incineration in whole PCDD/Fs
releases into air.35 A similar development occurred in the case of PCDD/PCDF inventory for
releases to air prepared as a part of National Implementation Plan for the Stockholm
Convention in the Czech Republic. Data calculated for incinerators using old emission factors
originally underestimated value of waste incineration in whole PCDD/Fs releases into air. But
not only the value for waste incineration releases into the air changed in the Czech case.36
The examples presented in Table 4, some of which are discussed below, further illustrate the
severe limitations of default emission factors, particularly those derived from PCDD/Fgenerating processes and activities in industrialized countries. Using such emission factors to
estimate PCDD/F releases from processes and activities can result in large under-estimations
of PCDD/F releases in any country.
Table 4: Comparison of Selected Emission Factors
UNEP Toolkit
Emission FactorAIR, µg I-TEQ/ton
Cement kilns, all
0.15 - 5
Cement kilns, hazardous
waste
Cement kilns, no hazardous
waste
Municipal waste incinerator,
high quality pollution
control
Aluminum Production,
Primary
EDC/VCM/PVC
“Modern plants”
No factor given
Thermal metal reclamation
3.3
No factor given
0.5
None or insignificant
No factor given
0.015 i
Emission FactorWATER, µg I-TEQ/ton
EDC/VCM/PVC “Modern
2b
plants”
Municipal waste incinerators
“minor importance”
no factor given
Hazardous waste
“not… important”
incinerators
no factor given
Emission FactorRESIDUE, µg I-TEQ/ton
Aluminum Production,
None or insignificant
Primary
No factor given
Other
0.15 g
OSPAR Guidance37
20.91 U.S.38
0.27 U.S.39
202231 Russia 40 h
1.5
OSPAR Guidance41
11169 Russia 42
0.1 – 33
Germany 43
17
OSPAR Guidance44
400 Germany45
0.5 OSPAR Guidance46
0.09 – 1.87 _g TEQ/L
OSPAR Guidance47
0.15
OSPAR Guidance48
141.1 Russia 49
Comments to data in Table 4 taken from Greenpeace comments presented in January 2003: 50
• PVC Production: The Toolkit’s emission factors for the production chain for polyvinyl chloride –
ethylene dichloride (EDC)/vinyl chloride monomer (VCM)/polyvinyl chloride (PVC) – are those put
forward by the U.S. industry. However, as shown in Table 4, German emission factors for releases to
water and in residues are, respectively 100 and 200 times greater than those presented in the Toolkit.
PCDD/F concentrations in treated wastewater from a Russian facility also support an emission factor
for releases to water that is some 100 times greater than the Toolkit emission factor. However, the
Toolkit’s emission factor for releases to air is similar to that reported for German facilities. 51
g
“Measurements recommended at some plants incinerating wastes”
Value confirmed by N. Klyuev via personal communication, 11 June 2002.
i
This value is based on data from the U.S. PVC industry, according to the Toolkit’s authors.
h
• Cement Kilns: As shown in Table 4, the Toolkit’s air emission factor for the most well controlled
cement kilns is quite close to the U.S. factor for cement kilns fired with conventional fuels. However,
while the Toolkit presents the same air emission factors for all cement kilns regardless of the materials
used to fuel the kilns, air emission factors for U.S. cement kilns burning hazardous waste are some 77
times greater than those for cement kilns fired with conventional fuels. 52 The air emission factor
reported for a coal-fired cement kiln in Russia is more than 40,000 times greater than the Toolkit’s
highest air emission factor for cement kilns
• Aluminum Production: In their discussion of PCDD/F formation in aluminum production, the
Toolkit’s authors note that, in primary aluminum production, PCDD/F levels “are generally thought
to be low and the main interest is in the thermal processing of secondary materials,” i.e., secondary
aluminum production. With that, primary aluminum production is not listed as a PCDD/F source and
no emission factors are presented for this industry. However, as shown in Table 4, monitoring data at a
primary aluminum production facility in Russia resulted in high emission factors for releases to air and
in residues.
Table 5: Examples of Air Emission factors for PCBs releases used in the
Czech POPs emissions inventory 53
Release source category
PCBs emission factors for
SNAP
air releases [mg.t-1]
Ore sintering plants
30301
1.18280
Steel smelting
40203
0.00000
Steelworks
40207
0
Cast iron production
30303
0.13590
Coke production
40201
0
Cement production
30311
0
Leaded glass production
30317
0
Municipal waste incineration
90201
5.8000
90202
331.3050
Medical waste incineration
90207
15.0250
90205
5.4000
Releases to Land, Residues and Products
EU inventories of PCDD/PCDF releases have been prepared in the form of PRTR databases.
One addresses releases to air 54 and the other addresses releases to water and land. 55 The
decision to research and divide releases into these three sectors of the global environment is
quite clear if we look at the routes of pollution in the environment. The databases are based on
geographical or environmental classification of the sectors belonging to environment –
atmosphere (air), hydrosphere (water) and lithosphere or geosphere (land). Following the
releases this way creates no confusion. Land is counted as surface, soil and “underground”
(including underground mines for example).
The Toolkit’s authors decided that releases of PCDD/F inventories should be configured to
address five,“compartments and/or media: air, water, land, wastes (residues), and
products…” This causes confusion. For the purposes of the inventories, the environmental
compartment “land” consists only of “soils”, as in surface soils according to Toolkit. In other
words, they decided that “landfills” are not a part of this or any other environmental
compartment as well as underground mines. As a consequence, releases to landfills do not
constitute releases to the environment according to the Toolkit. For example, in their
discussion in Section 6.9 Disposal/Landfill, the Toolkit authors describe the fate of PCDD/Fcontaminated residues as “containment in secure landfills, destruction (thermally or chemical
decontamination) or release into the environment.”
By defining surface soils as the sole components of the environmental compartment “land”,
the authors of the Toolkit have created a circumstance for municipal solid waste incinerators,
in which they state that, “No release to land is expected unless untreated residue is directly
placed onto or mixed with soil.” In contrast, ashes from municipal waste incinerators
accounted for approximately 20 percent of total PCDD/F releases to land in the EU based on
the EU inventory. 56
According to the Toolkit, even when disposed of in landfills, PCDD/F-contaminated ashes
from hazardous waste incinerators, medical waste incinerators, shredder waste incinerators,
medical waste incinerators, waste wood and waste biomass incinerators, etc. are not
acknowledged as PCDD/F releases to land or, consequently, to the environment. Presumably,
if the Toolkit were to address deep-well injection of PCDD/F-contaminated wastes, (which it
ignores even though this method of disposal is practiced in some countries) injection of
PCDD/F-contaminated wastes down deep-wells would not be considered to be a release to the
environment.
Legislative tools to collect data and PRTRs
An international consensus on inventories was reached at the Aarhus Convention in May
2003 in Kiev with the “Protocol on Pollutant Release and Transfer Registers” (PRTRs) during
the 5th Ministerial meeting, “Environment for Europe.” This Protocol includes the
requirement to follow releases of all chemicals listed in Stockholm Convention. It would be
helpful even to say in the introduction of the Toolkit, that as soon as the Protocol enters into
force it can help Parties collect data for their own inventories and show examples from
existing PRTR systems in the world. With PRTRs and related mechanisms, Parties can
require point sources of by-product POPs, such as manufacturing facilities, waste disposal
facilities, etc., to monitor and report their releases of by-product POPs as well as intentionally
produced POPs.
In support of this addition to the Toolkit, the Stockholm Convention states that each Party
must give sympathetic consideration to PRTRs. 57 Many countries are already moving
towards the use of data collected through PRTR programs for the compilation of national
inventories. 58
To help with collection of data from industry it is necessary in designing the national PRTR
systems to pay attention to thresholds. To get any data for HCB releases into air would be not
possible by establishing a threshold on the level of 10 kg per annum and one facility for
releases into air for example. 59
The Toolkit should help Parties to explain different possible legislative tools or best practices,
which can help to collect data like including the duty to measure or calculate releases in
different parts of legislation such as state decrees. A specific part dedicated to providing a
collection of examples of legislation or environmental policies which helped to collect data
about byproducts’ releases would be helpful.
See also further specific comments on this topic in our detailed comments which follow.
Detailed comments on Standardized Toolkit for Identification
and Quantification of Dioxin and Furan Releases
Page
number
1
Selected excerpts from the Toolkit with comments and suggestions for
changes
“Therefore, sources of unintentionally generated POPs must be quantified and the
methodology used to address sources must be consistent in order to follow or
monitor dioxin releases over time and between countries.”
Comment: There term “dioxin“ in this sentence is often used for PCDD/PCDF by
the public or journalists. But without explaining it includes both PCDDs and
PCDFs it should be not used, especially when other parts of the Toolkit most use
“PCDD/PCDF.”
3
Suggestion: To use “PCDD/PCDF” instead of “dioxin.”
“The final country inventories will clearly show that all potential sources have
been addressed, even if the activity does not exist or is insignificant in that
country.”
Comment: The Toolkit’s list of sources does not include all PCDD/F sources that
have been identified in various inventories, studies, etc., and new sources are still
being discovered. Given this circumstance, the above statement is not accurate.
However, when the Toolkit is modified to include a strategy for identifying
PCDD/F sources, a somewhat parallel statement can be made.
9
Suggestion: The final country inventories will show that all sources listed in the
Toolkit have been addressed, even if the activity does not exist or is insignificant
in that country.
“2.3 Further Reading
This Toolkit is for the preparation of a release inventory for polychlorinated
dibenzo-pdioxins (PCDD) and polychlorinated dibenzofurans (PCDF) ...
respective Web Pages:”
Comment: For further reading, a certain, but limited number of examples is
provided. This part should be supplemented with some more useful sources of
information
Suggestion: to add further text with references after first paragraph with
references:
“The United Nations Economic Commission for Europe web pages on the
PRTR Protocol include the text of the Protocol (so far in English, Russian and
French). Unofficial translations into other languages are also likely to become
available. http://www.unece.org/env/pp/prtr.htm
UNITAR (United Nations Institute for Training and Research) (2003). National
Pollutant Release and Transfer Register Capacity Building Library: A
Compilation of Resource Documents (2nd Edition, 2003). This is an extensive
collection of documents on PRTRs, and links to other relevant websites are also
provided. It is available on CD or on-line.
http://www.unitar.org/cwm/prtrcd/index.htm
OECD (1996).: Pollutant Release and Transfer Registers: Guidance Manual for
Governments (OCDE/GD(96)32). This is a key document which was produced
in conjunction with a series of international multi-stakeholder meetings,
including representatives of government, industry and NGOs. OECD has also
produced a number of other documents. The guidance manual is available at:
http://www.olis.oecd.org/olis/1996doc.nsf/LinkTo/ocde-gd(96)32 (English)
http://www.oecd.org/dataoecd/18/30/1901146.pdf (Russian)”
10
“Pollutant Release and Transfer Registers (PRTR): They will be established
following recommendations contained in UNCED Agenda 21, Chapter 19.
Governments and relevant international organizations with the cooperation of
industry should [among others] “Improve data bases and information systems on
toxic chemicals, such as emission inventory programmes…”
URL of a clearinghouse: http://www.chem.unep.ch/prtr/Default.htm”
Comment: This paragraph is very general and does not make it clear that the
suggested website contains valuable information on national PRTRs and activities
of International organizations.
Suggestion: to change and enlarge this paragraph as follow:
“Pollutant Release and Transfer Registers (PRTR): They will be established
following recommendations contained in UNCED Agenda 21, Chapter 19.
Governments and relevant international organizations with the cooperation of
industry should [among others] “Improve data bases and information systems
on toxic chemicals, such as emission inventory programmes…”
The following website http://www.chem.unep.ch/prtr/Default.htm contains
valuable information on PRTR activities of national and international
organizations. Below are direct links to some well developed national PRTR:
Australia: National Pollutant Inventory
http://www.npi.ea.gov.au
Canada: National Pollutant Release Inventory
http://www.ec.gc.ca/pdb/npri/npri_home_e.cfm
England and Wales: Pollution Inventory
http://216.31.193.171/asp/1_introduction.asp
Japan:
http://www.prtr.nite.go.jp/english/summary2001.html
The Netherlands: Datawarehouse Emission Inventory
http://dm.milieumonitor.net/en/index.htm
Norway:
http://www.sft.no/bmi/ [which has a link to pages in English]
Scotland:
http://www.sepa.org.uk/data/eper/mainpage.htm
Sweden:
http://www.naturvardsverket.se/prtr/
United States: Toxics Release Inventory
http://www.epa.gov/tri/
North America - Commission for Environmental Cooperation (CEC). Their
"Taking Stock" report is a compilation of comparable PRTR data from Mexico,
the United States and Canada:
http://www.cec.org”
10
“The IPPC Directive - Integrated Pollution Prevention and Control of the
European Union: This directive is about minimizing pollution from various point
sources throughout the European Union. All installations covered by an Annex of
the Directive are required to obtain an authorization (permit) from the authorities
in the EU countries. The permits must be based on the concept of Best Available
Techniques (BAT). It has also been decided that policy-makers as well as the
public at large need better information about the. The Directive provides for the
setting up of a European Pollutant Emission Register (EPER) to inform about the
amount of pollution that different installations are responsible for.
URL for IPPC Directive: http://europa.eu.int/comm/environment/ippc/
URL for BAT documents: http://eippcb.jrc.es/
URL for EPER: http://europa.eu.int/comm/environment/ippc/eper/index.htm”
Comments: This paragraph in the Toolkit has to be updated based on the
information already available. We think it is useful to clearly differentiate
between the term BAT used here and “BAT” used as a term in the Stockholm
Convention by including the URL for EPER:
http://europa.eu.int/comm/environment/ippc/eper/index.htm was substituted by: :
http://www.eper.cec.eu.int
Also it looks like there is a missing word at the end of the 4th sentence in this
paragraph.
As we didn’t find notice about the UN ECE PRTR Protocol to Aarhus Convention
we propose to add the information about this important tool after the text on
EPER.
Suggestion: To update this paragraph by adding the text before the reference to
the websites: “The IPPC Directive - Integrated Pollution Prevention and
Control of the European Union: This directive is about minimizing pollution
from various point sources throughout the European Union. All installations
covered by an Annex of the Directive are required to obtain an authorization
(permit) from the authorities in the EU countries. The permits must be based on
the concept of Best Available Techniques (BAT).j It has also been decided that
policy-makers as well as the public at large need better information about the
j
BAT according to EU legislation has different meaning compared to the Best Available
Technique term used in Stockholm Convention.
facility specific pollution. The Directive provides for the setting up of a
European Pollutant Emission Register (EPER) to inform about the amount of
pollution that different installations are responsible for.
EPER lists 50 chemicals and industries caught by the scope of EPER have to
report their releases to water and/or to air, but not to land. This means that the
EPER inventory is not totally integrated across the media. Transfers are not
included. The register became publicly available in February, 2004. It contains
detailed information on pollution from 10 000 industries and enterprises in the
EU and Norway. In March, 2004, additional information from Hungary will be
incorporated. Next reporting year under EPER is 2006. For purpose of POPs
by-products inventories it is important that EPER includes data on PCDD/F
and hexachlorobenzene.
URL for IPPC Directive: http://europa.eu.int/comm/environment/ippc/
URL for BAT documents: http://eippcb.jrc.es/
URL for EPER: http://www.eper.cec.eu.int/eper
All the chemicals that are listed under EPER are incorporated into the
UN ECE Protocol on Pollutant Release and Transfer Registers to the Aarhus
Convention on Access to Information, Public Participation in Decision-Making
and Access to Justice in Environmental Matters. The new Protocol was adopted
at the 2003 “Environment for Europe” Ministerial Conference in Ukraine. As
of the end of 2003, 36 countries and the European Community have signed the
Protocol, but it will take several years to enter into force. Any country in the
world can become a Party, opening up the possibility for the PRTR Protocol to
set a global standard for pollution reporting and transparency. Given that all
the EU countries and the European Community have signed the Protocol,
EPER should develop into a proper PRTR in line with the Protocol in the
future. The full text of the Protocol (in English, French and Russian) can be
found at the UNECE web site: http://www.unece.org/env/pp/prtr.htm “
9 - 10
Because PRTR data are publicly available and widely used, many types of nongovernmental and public organisations have been interested and involved in the
design, implementation, and use of PRTR systems. The Toolkit does not
incorporate any links or information about the activities of non-governmental
organisations. Thus, we suggest including the following paragraph:
Suggestion: “Because PRTR data are publicly available and widely used, many
types of non-governmental organizations have been interested and involved in
the design, implementation, and use of PRTR systems. The following sites
provide information on PRTR related activities implemented by nongovernmental organizations:
The "Scorecard" web site of the NGO Environmental Defense allows a great
range of queries of US Toxics Release Inventory data and other databases. It
has an extensive database of information on specific chemicals:
http://www.scorecard.org
The Working Group on Community Right-to-Know supports a network of rightto-know advocates with an inspiring record of community activism in the US.
http://crtk.org/index.cfm
Silicon Valley Toxics Coalition and Clary-Meuser Research Network web site
has many links to PRTRs, related data and research projects.
http://www.mapcruzin.com/globalchem.htm
The Regional Environmental Centre for Central and Eastern Europe (RECCEE) have a Public Participation Programme which has made substantial
contributions to the discussion on PRTRs in the CEE region.
http://www.rec.org/REC/Programs/PublicParticipation.html
11
The European coalition of non-governmental organizations ECO-Forum
prepared a Guidance Your right to know about sources of pollution, which is a
brief introduction to the Protocol on Pollutant Release and Transfer Registers.
The Guidance is available at:
http://www.eeb.org and http://www.participate.org”
“PCDD/PCDF are formed as unintentional by-products in certain processes and
activities, Annex C of the Stockholm Convention provides two lists for several of
these. Besides being formed as unintentional by-products of manufacturing or
disposal processes, PCDD/PCDF may also be introduced into processes as
contaminants in raw materials. Consequently, releases or transfers of PCDD/Fs
can occur even where the PCDD/Fs are not formed in the process under
consideration.”
Comment: With regard to the first sentence, it is critical that Parties are given at
least the most important facts of PCDD/Fs formation. But the most important
condition for PCDD/Fs formation is not introduced. It seems that authors are
somehow afraid to say that the presence of chlorine is necessary for PCDD/Fs
formation.
11
Suggestion: PCDD/PCDF are formed as unintentional by-products in certain
processes and activities, all of which share one common feature: the availability
of chlorine and/or chlorine-containing materials. Besides being formed as
unintentional by-products of manufacturing or disposal processes,
PCDD/PCDF may also be introduced into processes as contaminants in raw
materials.
“Four conditions, present either individually or in combination, favor generation
of PCDD/PCDF in thermal processes:
• High temperature processes (during cool-down of combustion gases in a
temperature range of ca. 200-450 °C) and/or incomplete combustion;
• Organic carbon;
• Chlorine;
• PCDD/PCDF containing products”
Comment: It is not accurate that any of these “four conditions either individually
or in combination” may cause PCDD/Fs formation. For example, not one of these
conditions individually will lead to PCDD/F formation. Moreover, high
temperature and organic carbon in combination will not lead to PCDD/F
formation. “PCDD/PCDF containing products” do not “cause generation of
PCDD/PCDF”, although they may cause “release to air.’ Indeed, the first three
“conditions” – high temperature, organic carbon, and chlorine – do not result in
PCDD/Fs formation unless oxygen is present.
Suggestion: Correct this text segment as indicated below:
“PCDD/F formation can take place only when the following four elements are
available and brought into contact under appropriate conditions:
• Chlorine
• Carbon
• Oxygen
• Hydrogen
12
PCDD/F formation is known to take place at temperatures ranging from
ambient to those of high-temperature combustion. For example, PCDD/F
formation has occurred during composting of materials contaminated with
pentachlorophenol 60 and through photolysis at ambient temperature of
pentachlorophenol-contaminated soils 61. PCDD/F formation is also known to
occur as furnace gases from high-temperature incinerators cool through a
temperature range of 900 to 240 °C.” 62
“The Toolkit addresses direct releases of PCDD/PCDF to the following five
release vectors to the following compartments and/or media (Figure 1).
• Air
• Water (fresh, ocean, estuarine; then subsequently into sediments)
• Land
• Residue (including certain liquid wastes, sludge, and solid residues, which are
handled and disposed of as waste or may by recycled)
• Products (such as chemical formulations or consumer goods such as paper,
textiles, etc.).”
Comment: Freshwater is sometimes taken in narrow meaning as only surface
water. The same problem might be with explaining the term “Land” as only
surface. But in many cases there are releases of PCDD/Fs below the surface of the
earth. With regard to the bullet point “Residue”, the meaning and purpose of the
phrase “or may be recycled” is not obvious. If the authors are suggesting that
dioxin-containing wastes are mainly recycled, this is not an accurate reflection of
the fate of such materials. For example, fly ash and bottom ash containing dioxins
may be used as a raw material for road cover or as a part of other materials used in
building industries, making them available for environmental release. Inventories
should note this potentially important route of PCDD/Fs releases into the
environment.
Suggestion: “The Toolkit addresses direct releases of PCDD/PCDF to the
following five release vectors to the following compartments and/or media
(Figure 1).
• Air
• Water [freshwater (surface water and groundwater), ocean, and estuarine]
• Land (both surface and below surface)
• Residues (including certain liquid wastes, sludge and other solid residues, that
are handled and disposed of as wastes)
• Products (such as chemical formulations or consumer goods such as paper,
13
textiles, waste declared as product or raw material like bottom ash for example
etc.).”
“Thermal and combustion processes – including incineration of wastes, the
combustion of solid and liquid fuels and the thermal processing of metals;”
Comment: Thermal and combustion processes in which there is no available
chlorine cannot be PCDD/F sources.
13
Suggestion: “Thermal and combustion processes involving chlorine and/or
chlorine-containing materials – including incineration of wastes, combustion of
solid and liquid fuels and the thermal processing of metals;”
“Biogenic processes, which may form PCDD/PCDF from precursors such as
pentachlorophenol.”
Comment: Pentachlorophenol is not the only precursor of PCDD/Fs formation.
Many chlorinated compounds could serve as precursors.
14
Suggestion: “Biogenic and phototransformation processes, which may form
PCDD/PCDF from chlorinated precursors, such as pentachlorophenol.”
“Actual dioxin formation potential and actual release will depend on process
conditions and air pollution controls applied. Technologies have been developed
to reduce formation of PCDD/PCDF and to control emissions to very low levels
for many processes. ”
Comment: Consistency in terminology will minimize confusion. “PCDD/PCDF”,
rather than “dioxin” is the term most commonly used in the draft Toolkit. Also, to
avoid confusion, the word “air” should be used in conjunction with the word
“emissions”, or preferably, the term used should be “air releases”. Also, if means
for reducing PCDD/F formation are to be addressed in this draft report, this
should be done with greater thoroughness, accuracy and consistency.
14
Suggestion: “Actual PCDD/PCDF formation and subsequent release to air will
depend on process conditions and the type and mode of operation of air
pollution controls. Various techniques and technologies exist whereby
PCDD/PCDF formation can be reduced and/or eliminated. For example,
elimination or reduction of chlorine and chlorine-containing materials from
process inputs is a recognized technique for reducing or eliminating
PCDD/PCDF formation in a variety of processes.” 63, 64
“PCDD/PCDF may be present in a discharge if the PCDD/PCDF formed in the
industrial production process, entered the industrial process with the feed
material, or leached from a repository. Examples are:
• Wastewater discharge from pulp and paper production especially when
elemental chlorine is used;
• Wastewater discharge from chemical production processes, production
especially when elemental chlorine is used;”
Comment: Naming only elemental chlorine could lead to confusion when
assembling national inventories that PCDD/F formation is an issue only when
“elemental chlorine” is used. This is not the case since PCDD/F formation also
takes place during pulp and paper bleaching with chlorine derivatives such as
chlorine dioxide.65 Likewise PCDD/F are also formed and released in the
wastewater discharges from industrial processes that involve not only elemental
chlorine but also other inorganic and organic chlorine derivatives, e.g., scrubber
water from incinerators 66 and aluminum production involving the use of
hexachloroethane. 67
14
Suggestion: „PCDD/PCDF may be present in a discharge if the PCDD/PCDF
formed in the industrial production process, entered the industrial process with
the feed material, or leached from landfill or other repository. Examples are:
• Wastewater discharge from pulp and paper production using elemental
chlorine or chlorine derivatives, such as chlorine dioxide;
• Wastewater discharge from chemical production processes that involve
elemental chlorine or chlorine derivatives;”
“Leaching occurs when rainwater is allowed to migrate through inadequately
stored repositories of PCDD/PCDF-containing products, residues and/or wastes.
Additional mobilization will occur if co-disposal of organic solvents has taken
place. However, it has been shown that phenolic structure in “normal” landfill
leachates are capable of mobilizing PCDD/PCDF from wastes. Examples are:
• PCDD/PCDF-contaminated areas such as production or handling sites of
chlorophenol herbicides;
• Timber industry sites where pentachlorophenol or other chlorinated aromatic
pesticides were used as wood preservatives;
• Waste dumps and junk yards, especially when PCDD/PCDF-contaminated
production residues or waste oils have been disposed.”
Comment: It is important that users know that landfills are potential sources of
PCDD/F-containing leachates and that leaching occurs in landfills, regardless of
their design, construction and operation. 68 Not only rainwater can migrate
through the landfills, but also underground streams. 69 Concerning the additional
mobilization of PCDD/Fs, a more user friendly term would be humic acids with
additional information about its presence in all soils.70
Suggestion: “Leaching of PCDD/PCDF occurs when rain- and/or underground
water is allowed to migrate through landfills and/or inadequately stored
repositories of PCDD/PCDF-containing products, residues and/or wastes.
Leaching of PCDD/PCDFs from landfills is enhanced by the presence of humic
acids, which are present in all soils, and by co-disposal of solvents. Examples
are:
• PCDD/PCDF-contaminated areas such as production or handling sites of
chlorophenol herbicides;
• Timber industry sites where pentachlorophenol or other chlorinated aromatic
pesticides were used as wood preservatives;
14
• Landfills and similar repositories of waste, especially when PCDD/PCDFcontaminated production residues such as incinerator ash or waste oils have
been disposed.”
“Consequently, the criteria used to identify potential releases of PCDD/PCDF to
water include:
1. Wastewater discharge from processes involving chlorine and/or PCDD/PCDF
Contaminated products or combustion, incineration and other thermal processes
where wet scrubbers are used to clean flue gases;
2. Use of PCDD/PCDF contaminated pesticides (especially PCP and 2,4,5-T) and
other chemicals (especially PCB);
3. Leachate from storage and/or disposal sites of PCDD/PCDF contaminated
materials.”
Comment: The items listed above do not constitute “criteria”; rather, they are
examples. Items in this list seem to be repetitive of those in the other two lists in
this section. Also, as discussed earlier, it is important to avoid the impression that
only processes involving (elemental) chlorine are relevant to PCDD/F formation.
Suggestion: Combine all three lists into one, avoiding repetition of individual
items. Otherwise, modify the text of this portion as follows:
“Other examples of sources of potential releases of PCDD/Fs to water include:
1. Wastewater discharge from processes involving chlorine and/or chlorinated
materials and/or PCDD/F-contaminated products or combustion, incineration
and other thermal processes where chlorine or chlorine-containing materials
are involved and where wet scrubbers are used to clean flue gases;
2. Use of PCDD/F-contaminated pesticides (especially PCP and 2,4,5-T) and
other chemicals (especially PCB);
3. Leachate from storage, landfills and/or disposal sites of PCDD/Fcontaminated materials.”
15
“3.2.3 Release to Land
Sources releasing PCDD/PCDF to land can be divided into three classes:
PCDD/PCDF contaminated product “applied” to land directly, residues from a
process left on or applied to land or PCDD/PCDF deposited onto land via
environmental processes. In all cases, land serves as a sink for the PCDD/PCDF
from which they can be released into the food-chain through uptake by plants
and/or animals.
Examples include:
• PCDD/PCDF contaminated product or waste use, e.g. pesticides, wood
preservatives;
• Application of sewage sludge on farm land or compost in gardens;
• Direct disposal of PCDD/PCDF containing wastes on land; an example would
be the ashes that are left from combustion, e.g., open burning on the ground;
Deposition of PCDD/PCDF to land via the atmosphere is not addressed in the
Toolkit.”
Comment: The decision by the Toolkit’s authors to consider the environmental
compartment “land” to consist only of surface soils potentially ignores some of
the largest releases of PCDD/Fs to the environment that occur in landfills/
15
Suggestion: The Toolkit should be revised so that the environmental
compartment “land” consists, as is commonly accepted, of all land so that
PCDD/F-containing materials that are sent to landfills, deep well injection,
mines, quarries, etc. do not escape consideration as environmental releases.
“The highest concentrations of PCDD/PCDF have been found in chlorinated
phenols and their derivatives, e.g., pentachlorophenol (PCP and its sodium salt),
2,4,5-trichlorophenoxyacetic acid (2,4,5-T) or polychlorinated biphenyls (PCB).
Wastes and residues from production of these and other chlorinated chemicals are
also contaminated with PCDD/PCDF (see release vector “Residue”).”
Comment: This part requires both qualification and documentation, since wastes
from production of these and other organochlorines contain far higher
concentrations of PCDD/Fs than the products.
15 - 16
Suggestion: “Among products, some of the highest concentrations of PCDD/Fs
have been found in chlorinated phenols and their derivatives, e.g.,
pentachlorophenol (PCP and its sodium salt), 2,4,5-trichlorophenoxyacetic acid
(2,4,5-T) or polychlorinated biphenyls (PCB). However, far higher levels of
PCDD/PCDF have been found in residues from production. For example,
wastes from the manufacture of vinyl chloride, the monomer of polyvinyl
chloride, have been found to contain some of the highest PCDD/PCDF
concentrations ever reported.” 71, 72
“PCDD/PCDF elimination or reduction comes through
(a) Product substitution through ban of production and use of a product known to
be highly contaminated with PCDD/PCDF, so that the process that generates
PCDD/PCDF is no longer realized in a country;
(b) Modification of the problematic step of the process, changing of the process
conditions or moving to other feed materials so that PCDD/Fs are no longer
generated or at least minimized.
Source controls such as the above mentioned affects the PCDD/PCDF at all
points in the product life-cycle, including consumer waste. Effective control of the
PCDD/PCDF source to the product leads to benefits in several other
environmental compartments and media at the same time.”
Comment: This part should address material substitution as a means of reducing
PCDD/Fs formation. The ultimate goal of the Stockholm Convention is not only
the reduction of by-products (including PCDD/Fs), but their elimination. It means
to prevent formation of even low levels of PCDD/PCDF or prevent all processes
and their steps where PCDD/PCDF formation occurs. The last sentence is not true
in all cases, depending on the meaning given to the word “effective,” since some
commonly used methods of reducing PCDD/Fs in products simply shift the
PCDD/Fs from the products to a waste stream.
Suggestion: “PCDD/PCDF elimination or reduction comes through
(a) Product substitution through a ban on the production and use of a product
known to be contaminated with PCDD/PCDF, so that the process that generates
PCDD/PCDF is no longer realized in a country;
(b) Modification of the problematic step of the process, changing of the process
conditions or moving to other feed materials so that PCDD/PCDF are no longer
generated.
Eliminating or reducing PCDD/PCDF formation so that products contain no
PCDD/PCDF also reduces associated releases to the environment.”
16
“3.2.5 Release in Residues
An almost infinite number of processes can transfer PCDD/PCDF to wastes or
(mostly solid) residues. However, the most likely types of wastes can be classified
according to their origin, since PCDD/PCDF are always a by-product. Examples
include:
• Garbage, trash, and rubbish (municipal, industrial, hazardous, medical, etc.);
• By-product waste from combustion and thermal processes (fly ash from flue gas
cleaning equipment, bottom ash, soot, etc.);
• Production residues and residual products (sludge and residues from chemical
production, sewage sludge from wastewater treatment, waste pesticides, waste
transformer oil, etc.).”
Comment: The first sentence is inaccurate: the processes that transfer PCDD/Fs to
residues are not infinite but are, indeed, limited to those processes that involve
some form of chlorine. The meaning of the second sentence is not clear. The
terms used in the bullet points are repetitious, needlessly confusing and fail to
make the important distinction between primary and secondary sources of
PCDD/Fs. Not only fly ash from flue gas cleaning equipment includes PCDD/Fs,
but also washed fly ash as well as fly ash from boilers that in some countries is
classified simply as fly ash.
Suggestion: “Processes in which PCDD/Fs are formed and incorporated into
process residues are those that involve chlorine and/or chlorine-containing
materials. Residues that contain PCDD/Fs include, for example:
• Residues from incineration and other thermal processes in which materials
containing some form of chlorine are burned, e.g., fly ash, bottom ash or slag,
soot, etc. from incinerators, thermal power generators, etc.
• Residues from the production of chlorine-containing chemicals or chemicals
that are produced through the use of chlorine-containing intermediates, e.g.,
process sludge, heavy bottoms, distillation residues, etc.;
• Discarded products, e.g., off-specification or unused pesticides, banned or
discarded PCB transformer oils
• Untreated wastes from households, municipalities, healthcare facilities, etc.
containing discarded products that are contaminated with PCDD/Fs formed
during their manufacture or transferred during their treatment with other
PCDD/F-contaminated products;
16
• Municipal wastewater treatment sludge which contain PCDD/Fs due to the
use of PCDD/F-contaminated cleaning products (detergents, toilet paper, etc.),
laundering of contaminated clothing and other textiles, washing of
contaminated vegetables, etc.”
“Chemical production involving especially elemental chlorine leads to wastes
containing PCDD/PCDF. Whether it is the production of chlorine containing
pesticides or the chlorine bleaching during paper production, chemical
production processes with or around elemental chlorine produce waste streams.
This waste usually contains PCDD/PCDF to some extent. Chapter 6.7 details
what causes the PCDD/PCDF to be concentrated in the waste stream.”
Comment: The fact that PCDD/Fs formation is not limited to chemical production
involving only elemental chlorine should be more visible in this part. PCDD/Fs
formation takes place in processes involving both organic and inorganic forms of
chlorine.
17
Suggestion: “Chemical production involving chlorine and/or inorganic and
organic forms of chlorine variously leads to wastes containing PCDD/PCDF,
e.g., the production of chlorine-containing industrial chemicals and pesticides,
chemicals for which chlorine or chlorine-containing intermediates are used
during their manufacture, such as titanium dioxide.” 73
“For example whereas contaminated wastes from the chemical industry may be
incinerated and effectively destroy any PCDD/PCDF present, dumping of such
residue may result in the creation of a reservoir source. Further, residues from
one process may be used as a raw material in another process and without
adequate controls, PCDD/PCDF releases to air, water or product can occur.”
Comment: The destruction efficiencies achieved by modern incinerators with
PCDD/Fs and other POPs has not been shown to be high. According to available
data, the actual destruction efficiencies of incinerators are relatively low.74 It is
also worthy of note that not only “dumping”, which is a term commonly used to
refer to uncontained surface disposal, but also landfills can be important reservoir
sources. In addition, the second sentence raises an important issue: PCDD/Fcontaining wastes are necessarily POPs wastes. This means that PCDD/Fcontaining wastes must be managed according to the requirements of the
Stockholm Convention, e.g., POPs waste are “[n]ot permitted to be subjected to
disposal operations that may lead to recovery, recycling, reclamation, direct
reuse or alternative uses of persistent organic pollutants.” This suggests that the
reuse of some PCDD/F-containing residues is contrary to the Treaty.
17
Suggestion: “While contaminated residues from, for example, a chemical
process may be effectively destroyed by an appropriate destruction technology,
dumping or landfilling such residues will result in the creation of a reservoir
source. Moreover, the transfer of contaminated residues for destruction or
further processing can result in PCDD/PCDF releases to air, water, land,
products and residues.”
“3.2.6 Potential Hot Spots
Potential Hot Spots are included as a category for assessment (see Section 4.1).
This category 10 differs from the other nine categories as Hot Spots from former
operations known to be related to PCDD/PCDF. Hot spots have the potential to
become sources in the future.”
Comment: This paragraph does not include hot spots formed in relation to current
activities like mines with untreated fly ash containing PCDD/Fs. 75 In addition, the
word “potential” used with respect to “hot spots” is unnecessary. Either a “hot
spot” is a “hot spot” or it is not and so it is or is not included in the inventory. In
addition, it would seem that “hot spots” are “hot spots” because they do have
immediate or ongoing releases of PCDD/Fs or the strong probability for such
releases. The same reasoning applies to legacy contamination.
17
Suggestion:
“3.2.6 Hot Spots
Hot Spots are included as a category for assessment (see Section 4.1). This
category 10 differs from the other nine categories in that there is or should not
be ongoing, deliberate additions to the amount of PCDD/Fs at the hot spot.
Included in this category are pits, piles, ponds, landfills, etc. in which PCDD/F
wastes from former as well as ongoing operations have accumulated or been
deposited.”
“Although the concentrations of PCDD/PCDF in these Hot Spots can be very
high, present releases may be negligible or small.”
Comment: The issues of insignificance have yet to be resolved by the Parties to
the Stockholm Convention.
19
Suggestion: “While the concentrations of PCDD/Fs in these Hot Spots may be
very high, present releases may be relatively small, depending on the
circumstances of each individual Hot Spot.”
“The Toolkit is designed to assemble the necessary activity data and to provide a
means of classifying processes and activities into classes for which appropriate
average emission factors are provided.”
Comment: The Toolkit is not “designed to assemble the necessary activity data.”
Instead, it offers limited advice on possible means for obtaining such data. Also as
discussed earlier, it is important to define as explicitly as possible the uncertainties
of release estimates. Consequently, it is necessary for the Toolkit to present and
advise users to apply a range of emission factors.
19
Suggestion: “The Toolkit offers advice on assembling the necessary activity
data, provides a list of source categories and sub-categories and, for each
source, presents a range of emission factors for each type of releases vector.”
“First, a coarse screening matrix is used to identify the Main PCDD/PCDF
Source Categories present in a country. The second step details these Main
Source Categories further into Subcategories to identify individual activities,
which potentially release PCDD/PCDF.”
Comment: Please refer to the earlier discussion of the need for a Source
Identification Strategy.
20
Suggestion: Insert in this section, a detailed description of the Source
Identification Strategy that will enable users to identify those sources of
PCDD/F and other by-product POPs that are not addressed in the Toolkit.
“1. Apply Screening Matrix to identify Main Source Categories
2. Check subcategories to identify existing activities and sources in the country
3. Gather detailed information on the processes and classify processes into
similar groups by applying the Standard Questionnaire
4. Quantify identified sources with default/measured emission factors
5. Apply nation-wide to establish full inventory and report results using
guidance given in the standard format
Figure 2: The recommended five-step approach to establish a national
PCDD/PCDF release inventory using the Toolkit”
Comment: Please refer to the earlier discussion of the need for a Source
Identification Strategy.
Suggestion:
“1. Apply Screening Matrix to identify Main Source Categories
2. Follow Source Identification Strategy to identify any sources that are not
addressed in the Main Source Categories.
3. Check subcategories and results of Source Identification Strategy to identify
existing activities and sources in the country
4. Gather detailed information on the processes and classify processes into
similar groups by applying the Standard Questionnaire
5. Quantify identified sources with default/measured emission factors
6. Apply nation-wide to establish full inventory and report results using
guidance given in the standard format
20
Figure 2: The recommended six-step approach to establish a national PCDD/F
release inventory using the Toolkit”
“Table 1: Screening Matrix - Main Source Categories
.......“
Comments: The compartment “land” does not include landfills and similar
environmental repositories, causing confusion in this table. This confusion is
exacerbated by Main Source Category 9, which is actually entitled
“Disposal/Landfill” at Section 6.9 and is described as including landfills and
waste dumps; sewage and sewage treatment; open water dumping; composting;
and waste oil treatment (non-thermal).
Inclusion of the term “subcategories” in the third column is confusing, because
this is a list of main categories.
Further, while the attempt to identify “main release routes for each category” is
admirable, there are far too many missing emission factors in the Toolkit’s
database to support this effort. Even in those relatively few cases where all
necessary emission factors are presented, the resulting prioritization of releases is
potentially appropriate only for certain processes and activities in the
industrialized countries. In some countries, industries are known to dump their
process wastes along roadsides and discharge untreated wastes directly into
surface or underground waters.
21
21
Suggestion: Delete the term “and Subcategories” in column 3. Reconfigure
the main source categories into a more rational format. Delete columns 4
through 8. Change the text following the table accordingly.
A new subsection should be inserted between 4.1 Step 1 and 4.1 Step 2 that
describes the source identification strategy, advises users on following this
strategy and includes sources identified in the appropriate subcategories.
Subsequently, the text in the remaining sections of the report should be
modified to reflect the use and results of the source identification strategy.
“Columns identify the five compartments or media into which significant amounts
of PCDD/PCDF are potentially released. The large “X” denotes the release route
expected to be predominant, and the small “x” shows additional release routes to
be considered.”
Comment: Refer to earlier discussions of compartments/media, the designation of
release routes and the determination of the quantity or quantities of PCDD/F that
are to be regarded as significant.
21
Suggestion: Delete these sentences or modify the text as follows: “Columns
identify the five compartments or media into which PCDD/Fs can be released.
In this regard, the large “X” denotes the release route that is often regarded as
predominant, and the small “x” denotes additional release routes that have also
been identified in the industrialized countries.”
“Incineration in this context means destruction in a technological furnace of some
sort; open burning and domestic burning in barrels and boxes does not belong to
these subcategories; they are addressed in Section 4.2.6 – Uncontrolled
Combustion.”
Comment: The term “destruction” is inappropriate in this context, since all
material input to waste incinerators is not necessarily destroyed.
22
Suggestion: “Incineration in this context means treatment in a combustion
furnace of some sort …”
“Wastes differ in composition and combustion characteristics and the combustion
equipment typically differs for each of the waste incineration subcategories.”
Comment: There are also many variations in combustion equipment within
subcategories (see our comments below).
22
Suggestion: “Wastes differ in content, e.g., presence of chlorine, chlorine
derivatives and metals, and combustion characteristics. Combustion equipment
also typically varies both between and within the waste incineration
subcategories.”
“However, releases to air are of greatest importance as they may undergo longrange transport and subsequently contaminate the food-chain.”
Comment: It seems that the importance of secondary releases from residues
(mainly fly ash) for food-chain contamination was not considered by Toolkit
authors. Particles including PCDD/Fs were considered as important source of
food-chain contamination.76 This would be a serious route of contamination in
waste incinerators which are not equipped with appropriate fly ash collection for
example.
23
Suggestion: “However, releases to air including dust burden from inadequately
handled fly ash (primary and secondary as well) are of greatest importance as
they may undergo long-range transport and subsequently contaminate the foodchain.”
“Table 4: Subcategories of the Inventory Matrix – Main Category 2”
Comment: Several sources can be added to this subcategory.
23
Suggestion: Include the following in this subcategory: titanium 77, magnesium
and nickel. 78
“In large, well-controlled fossil fuel power plants, the formation of PCDD/PCDF
is low since the combustion efficiency is usually fairly high, typically they use fuel
that contain more sulphur than chlorine and thus inhibit the formation of
PCDD/PCDF, and the fuels used are homogeneous. However, significant mass
emissions are still possible as large volumes of flue gases are emitted with small
concentrations of PCDD/F.”
Comment: Since, according to the Toolkit, there are no data describing PCDD/F
levels in fossil fuel power plant residues, there is insufficient information to
support the first statement above. As noted in one PCDD/F inventory, “The
combustion of oil and coal emits dioxin [PCDD/F] because these fuels contain
both chlorine and organic precursors.”79 Moreover, studies of power generating
facilities, such as that by Kopponen et al. (1992), have shown that PCDD/F
releases increased with increasing chlorine content in the fuel.80 Other studies,
such as that by Manninen et al. (1996) have shown that “chlorine content of the
fuel correlated with PCDFs and there was an inverse correlation between the S/Cl
ratio and PCDFs.” 81 Gullette and Raghunathan (1997) concluded that, for coal
combustion processes, low or no PCDD/F formation “may be due to a number of
factors including lack of appropriate catalysts, lack of organic products of
incomplete combustion, insufficient chlorine, and the presence of catalystpoisoning sulfur as SO2.” 82
23
Suggestion: Modify wording as follows: “In large, well-controlled fossil fuel
power plants, the formation of PCDD/PCDF is not well documented since there
are no data describing releases in residues. However, PCDD/PCDF formation is
known to vary with the chlorine content of the fuel and, based on available
information, PCDD/F releases to air can be substantial.”
“Where smaller plants or biomass are used, the fuel may be less homogeneous
and burned at lower temperatures or with decreased combustion efficiency. These
conditions can result in increased formation of PCDD/PCDF.”
Comment: There is insufficient evidence to support the conclusion that large fossil
fuel burning power plants have markedly reduced PCDD/F generation rates in
general. Also, as attested to by the emission factors presented in the Toolkit and
documented in Costner (2001) 83, the highest PCDD/F formation occurs when the
fuel burned is wood contaminated with pentachlorophenol or contains polyvinyl
chloride (PVC) cladding or some other source of chlorine.
23
Suggestion: “Where smaller plants are used, the fuel may contain more chlorine
and metal catalysts and such facilities may operate at lower temperatures and
with poorer combustion efficiency. However, the Toolkit’s emission factors are
not adequate for estimating total PCDD/F releases from such facilities.”
“The same may occur when landfill and/or biogas is used as a fuel due to the
presence of unwanted and undefined additional constituents.”
Comment: Refer to Costner (2001) for a compilation of studies that address the
issue of chlorine content and PCDD/F release. 84
23 - 24
Suggestion: “PCDD/F formation and release may occur when landfill or biogas
is used due to the presence of chlorinated species in the gases burned.”
“In the cases of domestic and/or household heating/cooking the quality of the fuel
used is often poor and the combustion efficiency very low, resulting in increased
formation of PCDD/PCDF. The predominant release vectors are to air (flue gas
emissions) and with residues, fly-ashes and bottom ashes.”
Comment: There are sufficient data presented in the Toolkit to estimate PCDD/F
releases for household heating and cooking with contaminated wood/biomass,
virgin wood/biomass, and coal-fired stoves but not domestic stoves fired with oil
and natural gas. In those cases where sufficient data are available, contaminated
wood/biomass and coal appear to be the fuels with the high potential PCDD/F
formation and releases. The last sentence is not fully supported by the release data
presented in the Toolkit. See earlier discussion of the lack of sufficient data in the
Toolkit. Also the chlorine content of the fuel is an important factor in PCDD/F
formation [see Costner (2001)]85.
24
Suggestion: “In the cases of domestic and/or household heating/cooking, the
highest potential for PCDD/F formation and release occurs during the burning
of contaminated wood/biomass and coal, both of which may contain relatively
high levels of chlorine. Where sufficient data are available, PCDD/F releases in
residues are greatest.”
“These are high-temperature processes for melting (glass, asphalt), baking (brick,
ceramics), or thermally induced chemical transformation (lime, cement). In them,
fuel combustion generates PCCD/PCDF as unwanted byproducts. Additional,
formation of PCDD/PCDF may be linked to the process raw materials used.
Cement and lime kilns are large volume processes which often add wastes as a
low/no cost fuel. Where effective controls are in place, use of waste materials like
tires, waste oil, sludges, etc. is not problematic; low emissions have been found.”
Comment: Concerning these processes data is lacking that describes PCDD/F
releases to land, products or residues in the Toolkit (except for cement kilns and
certain asphalt mixing plants). Without this data, it is not possible to estimate
PCDD/F releases. Also in the Toolkit’s emission factors, there is no distinction
between cement kilns and other facilities that burn waste (e.g., tires, municipal
waste, medical waste, hazardous waste, etc.) and those that do not, although
important differences have been documented. PCDD/Fs formation should differ
according to fuel source for these facilities as well, a point that is not reflected in
the Toolkit.
In the U.S. inventory, the average emission factors for air releases from cement
kilns that burn hazardous waste were as much as 100 times higher than those for
cement kilns burning conventional fuels. In addition, PCDD/F levels in the
cement kiln dust of cement kilns burning hazardous waste were some 1000 times
higher than that from conventionally fired cement kilns.86 97
In the absence of emission factors for releases to land and products, the Toolkit
does not present satisfactory information to support the last sentence above. The
last sentence goes against two principles of the Stockholm Convention in such a
case: precautionary principle and the elimination of byproducts releases as an
ultimate goal.
25
Suggestion: “These are high-temperature processes for melting (glass, asphalt),
baking (brick, ceramics), or thermally induced chemical transformation (lime,
cement). Within these processes, combustion of fuel and/or wastes generates
PCCD/PCDF as unwanted byproducts when the fuel or waste contains chlorine
in some form. Additional, formation of PCDD/PCDF may be linked to the
process raw materials used if they contain chlorine in some form. Cement and
lime kilns are large volume processes, which often use various wastes as a
low/no cost fuel. There is not sufficient information to estimate total
PCDD/PCDF releases from these facilities.”
“Table 8: Subcategories of the Inventory Matrix – Main Category 6
(a) (Clean) Biomass burning
(b) Waste burning and accidental fires ”
Comment: It would be useful to separate accidental fires into one subcategory and
to look at the chlorine and chlorine compounds containing products presence
during such fires.
25
Suggestion:
(a) (Clean) Biomass burning
(b) Waste burning
(c) Accidental fires (buildings, vehicles, landfills, warehouses, trains, etc.)”
“Indicators of high probability to form PCDD/PCDF in chemical manufacturing
processes are’ high temperature’, ‘alkaline media’, ‘the presence of UV-light as
an energy source’, and ‘the presence of radicals in the reaction mixture/chemical
process’ (see Section 3.1).
Comment: Refer to earlier discussions of this issue: chlorine or its derivatives has
to be present to form PCDD/PCDFs.
26
Suggestion: “Indicators of high probability to form PCDD/PCDFs in chemical
manufacturing processes are the presence of chlorine in some form and
conditions such as `high temperature’, ‘alkaline media’, ‘the presence of UVlight as an energy source’, and/or ‘the presence of radicals in the reaction
mixture/chemical process’ (see Section 3.1).”
...“
Comment: This table could include more uses.
26
Suggestion: Add the following in the table:
“(f) Application of certain biocides (crops, textiles, buildings, etc.)
(g) Use of certain personal care products (e.g., toothpastes, etc. that contain
certain bactericides)”
“The use of elemental chlorine for bleaching and the use of certain biocides such
as PCP and certain dyestuffs (chloranil-based) have been contributors to direct
releases of PCDD/PCDF to water. Thus, strong emphasis should be put on the
detailed investigation of these few potential sources of major overall significance
of contribution to the overall PCDD/PCDF problem.
Comment: The second sentence would include both chlorine derivatives as well as
elemental chlorine use in processes (see earlier discussions, e.g., PCDD/F
formation in bleaching occurs when any form of chlorine is used). There is no
reason or given evidence to suggest that chemical production facilities are “few”.
26
Suggestion: “The use of chlorine or chlorine derivatives for bleaching and the
use of certain chlorine-containing biocides and dyestuffs, e.g.,
pentachlorophenol and chloranil-based dyes, have been contributors to direct
releases of PCDD/PCDFs to water. Thus, strong emphasis should be given to
detailed investigation of chemical production facilities that use or manufacture
chlorine and/or chlorine-containing materials, since they are of major
significance to the overall PCDD/PCDF problem.”
“Formation of PCDD/PCDF occurs mostly when contaminated fuels are being
used and due to reaction of the hot gases with the organic matter of the materials
to be dried. In case of biomass drying and smoke-houses, wastes such as
used/treated wood, textiles, leather or other contaminated materials have been
used as fuels.”
Comment: This paragraph should include basic information that the presence of
chlorine in the fuel is needed to for PCDD/Fs formation.
27
28
Suggestion: “Formation of PCDD/Fs occurs due to reactions of the hot gases
with sources of chlorine (mostly when contaminated fuels are being used). In
case of biomass drying and smoke-houses these chlorine sources are mostly
chlorophenols and other chlorinated hydrocarbons in used/treated wood,
textiles etc.”
“Table 12”
See our comment on page 20 above.
“Within one subcategory to produce the same product, the emissions of
PCDD/PCDF can vary considerably depending on technology, performance, etc.
and in many cases only an estimate is possible. Estimation methods chosen will
differ and should reflect local conditions and the available resources. Key
parameters used to distinguish high emitting processes from low emitting
processes are given in Section 6.”
Comment: The term “releases” rather than “emissions” better reflects the
philosophy of the Stockholm Convention.
Suggestion: “Within one subcategory to produce the same product, the releases
33
33
of PCDD/Fs …. Key parameters used to distinguish processes releasing large
amounts of PCDD/Fs from those releasing smaller quantities are given in
Section 6.”
“ For each process within a subcategory, releases are calculated by multiplying
the activity rate for the given class by the emission factor provided in the Toolkit
for all release vectors, namely air, water, land, product, and residue (see Chapter
6).”
Comment: The term “total releases” instead of “releases” would clearly signal that
all releases have to be addressed in PCDD/Fs inventories.
Suggestion: “For each process within a subcategory, total releases are
calculated by multiplying the activity rate for .....”
“Default emission factors provided represent average PCDD/PCDF emissions for
each class.”
Comment: The Toolkit should provide a range of emission factors, rather than an
average, for each source or source category.
33
Suggestion: “The Toolkit provides high, low and average emission factors for
each source or source category where such factors are available or can be
derived.”
“Although these default emission factors are based on best available information
from literature or other sources they will be amended or classification expanded
as new data becomes available.”
Comment: This version of the Toolkit lacks data from the scientific literature. In
addition, many of the default emission factors are based only experiences gained
in developed countries. This leaves a question about who will evaluate which
information is the most appropriate.
35
Suggestion: “Although these default emission factors are based on the largest
possible range of available information from literature or other sources based
on scientific data they will be amended or classification expanded as new data
becomes available.”
“An interim inventory will contain the following information:
• a listing of all subcategories that are carried out in the country; ...”
Comment: The first bullet point should be modified to include both sources
identified via the Toolkit’s list and those identified via the Source Identification
Strategy.
36
Suggestion: “An interim inventory will contain the following information:
• a listing of all sources – those in the Toolkit as well as those identified through
the Source Identification Strategy -- that are known to exist within the country.
• …”
“The final country inventory of releases of PCDD/PCDF from all activities listed
in the Toolkit to all media will result from the application of the full Toolkit
methodology.”
Comment: As written, the statement suggests that the Toolkit’s default emission
factors give users sufficient information to prepare complete estimates of releases
to all environmental media/compartments. This is not the case, since there are
many potential release routes for which no emission factors are given or the
emission factors are unrealistic. The final country inventory should go further than
the current version of the Toolkit by using a comprehensive Sources Identification
Strategy.
36
41
Suggestion: Delete this sentence or change as follows: “The final country
inventory of releases of PCDD/PCDF from all activities listed in the Toolkit and
from sources identified as PCDD/PCDF sources based on use of chlorinecontaining materials presence in the processes together with other conditions
needed to form PCDD/PCDF in all media will result from the application of
both the full Toolkit methodology and Source Identification Strategy.”
“An example of result within subcategories is shown in Section 10.1 and summary
tables of national inventories made with the Toolkit in 10.2.”
Comment: See our comments to both Section 10.1 and Table 75 (pp 201 and 203)
below.
“ High PCDD/PCDF formation is associated with poor combustion conditions
(batch operation, high CO, etc.), problematic input materials and dust collectors
operated at high temperatures.”
Comment: The contribution of chlorine and chlorine-containing materials to
PCDD/F formation should be acknowledged here (see Costner (2001) 87).
41
Suggestion: “High PCDD/PCDF formation is associated with poor combustion
(batch operation, high CO, etc.) dust collectors operated at high temperatures,
and waste composition, such as a high chlorine content and the presence of
metals such as copper.”
“The PCDD/PCDF emissions to land are negligible and there is no product.
Relevant releases to water occur only if wet scrubbers are used for the removal of
particulate matter and the water is not recirculated within the process. Releases
to water will occur when the effluent is not adequately treated, e.g., to filter out
the particles with the PCDD/PCDF adsorbed onto them or water is used to cool
down the ashes and the water is not caught. Thus, the most significant release
routes are to air and residue. Typically, higher concentrations are found in the fly
ash, bottom ash has lower concentrations but the larger volume. If both ashes are
mixed, the combined residues will be more contaminated as the bottom ashes
alone. In countries with waste management plans in force, fly ashes are typically
sent to landfills.”
Comments: The statements in this segment attest to the very important
misconceptions created by defining “land” as only surface soils and excluding
landfills. Also, in some European countries e.g. Germany, the Netherlands, France
and Denmark about 50% of the stockpiled municipal waste incinerator bottom ash
is used as secondary building material, in road construction or as raw material for
the ceramic industry inter alia.88, 89, 90, 91, 92, 93,94 In some countries fly ash and
bottom ash alone and/or in mixture are declared as “product” and are not sent to
landfill even these countries have waste management plans in force. 95 According
to this practice it is not true that, “there is no product”.
With regard to the second sentence, the designation of PCDD/F releases as
“relevant” or not is a decision that rests with the Parties of the Stockholm
Convention, not the authors of the Toolkit. This same comment applies to the use
of the word “negligible” in the first sentence.
Referring to earlier comments on the need for terminology that is consistent
within the Toolkit as well as with the Stockholm Convention, “releases to land” is
preferable to “emissions to land”.
42
Suggestion: Delete last sentence and to change the paragraph wording as follows:
“MSW incinerators release PCDD/PCDF into the air via stack gases. However,
MSW incinerator ashes carry the largest share of the PCDD/PCDFs formed.
The ashes are commonly sent to land (landfills) or, in some countries, used as
secondary building material and declared as product. Releases to water may
occur 1) if wet scrubbers are used for the removal of particulate matter, in
which case the amount of PCDD/PCDFs released to water depends on the
efficiency of scrubber water treatment in which PCDD/PCDFs is captured in
the filter cake of the treatment process; and 2) water is used to cool down or
“quench” the ashes and the water is not caught. Thus, the most significant
release routes are to residue and air. Typically, higher concentrations are found
in the fly ash. Bottom ash has lower concentrations but a larger volume. If both
ashes are mixed, the combined residues will be more contaminated as the
bottom ashes alone.”
“Table 16: Emission factors for municipal solid waste incineration”
Comments: The heading for column 4 should be “Bottom ash or slag”, since many
incinerators are operated in a slagging mode. The EU inventory acknowledges the
following types of incinerator residues: boiler ash, grate ash (bottom ash or slag),
fly ash, sludge from the treatment of scrubber water, water used for quenching
bottom ash, wash water and surface runoff and presents emission factors for
bottom ashes, fly ash, and scrubber water sludge. 96
The Toolkit’s Emission Factors are, in many cases, very different from the
emission factors in other inventories and in the scientific literature. For example,
in the U.S. inventory, the seven types of incinerators, all equipped with various
combinations of air pollution control devices, had emission factors to air ranging
from 0.025 to 1,492 µg I-TEQ/ton,97 as compared to the Toolkit’s range of 0.5 to
350 µg I-TEQ/ton. In the EU inventory, the “typical” emission factor to air for
MSW incinerators equipped with “high quality” air pollution control systems was
1.5 µg I-TEQ/ton, in comparison to the Toolkit’s 0.5 µg TEQ/ton.98 The Toolkit’s
Emission Factors of 1.5 to 15 µg TEQ/ton for bottom ash of incinerators with at
least some air pollution control devices are also far lower than the 12 to 72 µg
TEQ/ton used in the EU inventory or, for old plants with electrostatic
precipitators, 6,600 to 31,100 µg TEQ/ton.99 As another example, a recent
PCDD/F mass balance study of a MSW incinerator “equipped with a best
available technology flue gas treatment line” reported a PCDD/F release factor
for slag of 7.59 µg I-TEQ/ton,100 as compared to the value of 1.5 µg TEQ/ton used
by the Toolkit’s authors for bottom ash.
Since the Toolkit does not include citations for its emission factors, it is not
possible to determine their origins.
42
Suggestion: Any emission factors presented in the Toolkit should be identified
as to their sources. Some rationale should be given for their selection and
some indication should be given of their uncertainty. Also, all of the emission
factors presented in the Toolkit should be reassessed and adjusted so as to be
more compatible with existing data.
“These default emission factors are based on the assumption that the waste
burned leads to about 1–2 % of fly ash and 10–25 % bottom ash.”
Comment: The estimated percentage of fly and bottom ash generated by burning
solid waste are quite different from real figures. Based on the values above, the
Toolkit’s authors have assumed that the incineration of one ton of waste is
accompanied by the generation of 10 to 20 kg of fly ash and 100 to 250 kg of
bottom ash. This is significantly different from rates reported in other sources; for
example, the EU inventory notes that the incineration of one ton of waste is
accompanied by the generation of 30 to 38 kg of fly ash and 300 kg of bottom ash.
101
Another (second) example should be production of ashes in the Czech MSW in
2002. These incinerators generated 40 kg fly ash by burning 1 ton of waste (4%
value).102 A third example is a smaller incinerator burning mixed solid and liquid
waste (municipal, medical and hazardous) in the Czech Republic which produced
19 tons of fly ash per year by burning over 600 tons mixed waste giving a value of
more than 3% fly ash generated. 103 One possible result of these non-conservative
assumptions by the Toolkit’s authors is substantial underestimation of
PCDD/PCDF releases in incinerator residues.
42
Suggestion: Revise the Toolkit values so that they are compatible with those
used elsewhere.
“Emission to air is the vector of most concern for MSW combustion.”
Comment: Releases to residues are the predominant pathways for PCDD/PCDF
releases from MSW incinerators, which means they should be also of a great
concern. Referring to the earlier discussions of the importance of consistency in
terminology “air” is a vector but “emission to air” is not a vector, it is a pathway.
Also refer to previous comments concerning the use of the term “emission” which
should be replaced with the term “release.”
42
Suggestion: “The greatest share of PCDD/PCDFs formed by incinerators is
released in residues, e.g., fly ash and bottom ash or slag, but releases to air are
of great concern as well especially when waste incinerators work with no APC
systems.”
“Class 2 assumes a reduction in the specific flue gas volume to
7,000 Nm³/t MSW due to better combustion controls and lower excess air. The
PCDD/PCDF concentration drops to 50 ng TEQ/Nm³ (@11% O2). Plants of this
type may be equipped with an ESP, multi-cyclone and/or a simple scrubber. In
class 3, the combustion efficiency improves further and the efficiency of the APC
system improves (e.g., ESP and multiple scrubbers, spray-dryer and baghouse or
similar combinations) resulting in a drop of the PCDD/PCDF concentration to
about 5 ng TEQ/Nm³ (@11% O2). Also, the specific flue gas volume is reduced to
6,000 Nm³/t MSW. Class 4 represents the current state-of-the-art in MSW
incineration and APC technology (e.g., activated carbon adsorption units or
SCR/DeDiox). Thus, only 5,000 Nm³/t MSW and a concentration of less than 0.1
ng TEQ/Nm³ (@11% O2) will be the norm (LUA 1997, IFEU 1998).”
Comment: This paragraph is irrelevant to practice even with the further
explanation concerning the Thai municipal solid waste incinerator. While the
results of these extrapolations are interesting, estimated releases are more valid
when based on a range of emission factors that are derived from measurements of
some number of existing systems. It is interesting to note that, although the EU
inventory is cited as one of the two sources of the information presented in the
above segment, the inventory’s emission factors were not used in the Toolkit.
Refer also to earlier discussion on Table 16. Both this and its following
paragraphs show the need to use a range of default emission factors and not just
one figure per subcategory and level of technology plus APC system.
Suggestion: Delete this segment.
43
“Releases to water occur only when scrubbers are employed for the removal of
particulate matter or to cool down ashes. In this case the amount of PCDD/PCDF
released through this vector, can best be estimated using the default emission
factors supplied for residue. Normally, concentrations are in the range of a few
pg I-TEQ/L and the highest PCDD/PCDF concentration reported in a scrubber
effluent before removal of particulate matter was below 200 pg/L. Most of the
PCDD/PCDF is associated with the particulate matter and consequently removed
during wastewater treatment. Additionally, most of the APC equipment installed
at MSW incineration plants operates wastewater free. Presently, such releases
cannot be quantified.”
Comment: As described in the discussion above on Table 16, the European
Inventory also identifies the following potential carriers of PCDD/PCDFs from
incinerators: water used for quenching bottom ash, wash water, and surface
runoff. It would also be helpful if the recommended default emission factors were
specified more clearly than as those “supplied for residues.” If the Toolkit’s
authors have data describing PCDD/PCDF concentrations in scrubber water, it
would be most helpful if they provided the exact data and its source. Also the unit
used after figure given on concentration of PCDD/PCDFs in scrubber effluent
(200) is not clear whether it is in units of TEQ.
43
Suggestion: “Releases to water may occur when wet scrubbers are used, when
water is used for quenching bottom ash, and through wash water and surface
runoff. There are no emission factors for such releases.”
“No release to land is expected unless untreated residue is directly placed onto or
mixed with soil. The concentration released in such cases will be covered under
“Release in Residues”, Chapter 6.1.2.5.”
Comment: Referring to several previous comments concerning the definition of
“land” to include only surface soil, this definition presents an unnecessary and
avoidable obstacle to understanding total PCDD/F releases.
43
Suggestion: See general comments.
“The process has no product, thus there will be no emission factor.”
Comment: This statement is incorrect. See earlier comment to the text on page 41:
In some European countries e.g. Germany, the Netherlands, France and Denmark
about 50% of the stockpiled municipal waste incinerator bottom ash is used as
secondary building material, in road construction or as raw material for the
ceramic industry inter al.104, 105, 106, 107, 108, 109,110 In the Czech Republic both
bottom and fly ashes are used as raw material and declared as “product”. 111
43 - 44
Suggestion: “About 50 percent of stockpiled bottom ash is used as a secondary
building material, in road construction or as raw material for the ceramic
industry in Germany, The Netherlands, France and Denmark. In some
countries both bottom and fly ashes are used as a raw material and declared as
product.”
“PCDD/PCDF concentrations in the fly ash are substantial, even though the total
mass generated per ton of MSW is typically only around 1–2 %. PCDD/PCDF
concentrations in the bottom ash are rather low, however, the amount of bottom
ash generated per ton of MSW is around 10–20 % k. Fly ash and bottom ash also
contain unburned carbon from 1 % (class 4) up to 30 % (class 1). Since unburned
carbon in the ash greatly enhances the adsorption of PCDD/PCDF, the
concentration is greatest in class 1; here, 500 ng TEQ/kg were chosen for bottom
ashl. As these types of incinerators do not have a collection system for fly ash,
there will be no emission factor for fly ash. In class 2 the concentration is
assumed to be 30,000 ng TEQ/kg in fly ash and 100 ng TEQ/kg in bottom ash due
to greatly improved combustion efficiency resulting in a much lower LOI of the
ash. Class 3 cuts these values in half based on further improvements. Class 4
assumes not only high combustion efficiency but also a very high collection
efficiency, especially of the very small fly ash particles. These small particles
supply a large adsorption surface for PCDD/PCDF and therefore the overall
concentration does not decrease further. Thus, the value for the fly ash is set at
1,000 ng I-TEQ/kg and the concentration for the bottom ash drops to 5 ng
TEQ/kg.”
Comments: See earlier comments on the generation of fly ash and bottom ash. In
contrast to the footnote comment under c), the scientists who prepared the EU
inventory regarded this as a valid ash generation rate. 112 Also, in contrast to the
statement that unburned carbon in ash enhances adsorption of PCDD/F, scientists
have been reporting for almost twenty years that unburned carbon in fly ash
enhances PCDD/F formation by serving as a source of complex carbon. 113, 114, 115,
116
The emission factors used in the Toolkit for MSW incinerator fly ash and
bottom ash are based on ash generation rates and PCDD/F concentrations that are
substantially lower than those that have been reported in the scientific literature
and used in various inventories. This may lead to a substantial underestimation of
PCDD/F releases in MSW incinerator bottom ash. For example, calculations using
the data presented in the Toolkit - a PCDD/F concentration in bottom ash of 500
ng TEQ/kg and a bottom ash generation rate of 100-200 kg ash/ton of waste
burned – result in PCDD/F release in bottom ash at a rate of 50-100 µg TEQ/ton.
The average of this range, 75 µg TEQ/ton, is the emission factor for bottom ash
k
Remark from the Toolkit text: “In some Western European countries, 300 kg of bottom ash per ton of
municipal solid waste burned (30%) were generated when the share of in inert and glass was higher in the
1960s and 1970s.”
l
Remark from the Toolkit text: “Extrapolated value: assumed 10-fold above the average measured
concentrations from European plants of the 1980s.
given in the Toolkit for class 1 MSWs. Using this same PCDD/F concentration
given in the Toolkit, 500 ng TEQ/kg, and the bottom ash generation rate given in
the European inventory, 300 kg/ton of waste burned, the emission factor for
bottom ash can be calculated to be 150 µg/ton, which is two times higher than that
given in the Toolkit.
The emission factor for fly ash from new MSW incinerators is given as a range,
810 to 1,800 µg I-TEQ/ton in the European inventory. 117 The Toolkit’s emission
factor for the most advanced incinerators is far lower, 15 µg TEQ/ton. Indeed, the
Toolkit’s emission factor for fly ash from MSW incinerators with the most
primitive air pollution control systems, 500 µg TEQ/ton, is markedly lower than
the lower end of the range given in the European inventory. As mentioned earlier,
the Toolkit uses a fly ash generation rate of 10 to 20 kg/ton of waste burned,
which is substantially lower than the range reported in the European inventory (30
- 38 kg/ton of waste burned). 118 Using the Toolkit’s values, an advanced MSW
incinerator that burned 100,000 tons per year of waste would generate 10 to 20
tons of fly ash with a PCDD/F content of 150 to 300 µg TEQ. Using the values
from the European inventory, this incinerator would generate 30 to 38 tons of fly
ash with a PCDD/F content of 24,300 to 68,400 µg TEQ. In summary, the
estimated PCDD/F releases in fly ash from this incinerator are, when prepared
according to the Toolkit, from 81 to 456 times smaller than the releases estimated
using the values in the European inventory.
For the most advanced MSW incinerator, the Toolkit assumes a PCDD/F
concentration of 1,000 ng I-TEQ/kg in fly ash and 5 ng TEQ/kg in bottom ash. In
contrast, a recent study of a fully modernized MSW incinerator reported 1,580 ng
TEQ/kg in fly ash and 60 ng TEQ/kg in bottom ash or slag. 119 In another study of
a smaller incinerator in France that had recently been equipped to meet the EU air
emission standards, the PCDD/F concentrations in fly ash were 10,700 ng TEQ/kg
and, in slag, 43 ng TEQ/kg. 120
44
Suggestion: All of the emission factors and residue generation rates presented
in the Toolkit should be reassessed and, where appropriate, adjusted so as to
be more compatible with existing data. Also any emission factors and
supporting data, such as residue generation rates, presented in the Toolkit
should be identified as to their sources. In addition, some rationale should be
given for the selection of emission factors and some indication should be
given of their uncertainty.
“Hazardous waste (HW) refers to residues and wastes, which contain hazardous
materials in significant quantities. Generally spoken, all materials including
consumer goods, which require special precautions and restrictions during
handling and use belong to this group. Any consumer goods, which are labeled to
such an extent and have entered the waste stream, must be considered hazardous
waste. These include solvents and other volatile hydrocarbons, paints and dyes,
chemicals including pesticides, herbicides, and other halogenated chemicals,
pharmaceutical products, batteries, fuels, oils and other lubricants, as well as
goods containing heavy metals. Also, all materials contaminated with these
materials such as soaked rags or paper, treated wood, production residues etc.
must be considered hazardous waste.”
Comment: The majority of hazardous waste sent to hazardous waste incinerators
is a waste from industrial processes. The information describing the hazardous
contents of consumer goods is interesting, but it is irrelevant in the context of a
discussion of dedicated hazardous waste incinerators.
44
Suggestion: “Hazardous waste (HW) refers to residues and wastes, which
consist of or contain hazardous materials in significant quantities.” Delete
remaining text in paragraph.
“Also, other technologies such as supercritical water oxidation, electric arc
vitrification, etc., which treat hazardous waste can be included in this group
(although they are not necessarily classified as “incineration”).”
Comment: There is no specific classification of releases from these technologies
in the Toolkit. Why they can not be a special subcategory even under “Waste
incineration” category. To put them under hazardous waste incineration without
specification of their emission factors is not systematic.
45
Suggestion: Delete this sentence and make a new subcategory under “h”.
“Table 17 Emission factors for hazardous waste incineration”
Comment: While Table 17 presents only an emission factor for fly ash, the EU
inventory noted as follows with regard to hazardous waste incinerators: “Solid
wastes include bottom ash from the furnace, fly ash and residues from gas
cleaning operations, and filter cakes and collected dusts from flue gas cleaning.
We assume a solid waste production rate of 20% of throughput. … Releases to
water arise mainly from the use of wet scrubbers, which are common on
hazardous waste incinerators. Data from one UK plant indicate that the discharge
is about 6.2 m³ per tonne of waste. … The range of levels in bottom ash and
composite solid wastes is 0.1 - 34 ng I-TEQ/kg. The range of levels for liquid
discharges is 0.01 - 0.6 ng I-TEQ / l.“121 PCDD/PCDF concentrations in a range
0.0029 – 0.0036 ng I-TEQ/kg122 were measured in the slag of the high technology
Czech waste incinerator (class 4 according to Toolkit classification) burning
mostly liquid hazardous waste including PCBs.
45
Suggestion: Table 17 should include columns for emission factors for bottom
ash/slag, scrubber water and scrubber water treatment sludge.
“These default emission factors are based on the assumption that the waste
burned leads to about 3 % of fly ash and the PCDD/PCDF release associated
with the disposal of bottom ash is negligible in classes 3 and 4. No data exist for
classes 1 and 2 for bottom ash concentrations.”
Comment: As noted above, those who prepared the European inventory assumed
hazardous waste incinerators generated solid residues, including fly ash, bottom
ash, etc. at the rate of 200 kg/ton of waste burned. This suggests that the Toolkit
needs to provide more detailed, documented information describing the rates at
which fly ash and bottom ash are generated by hazardous waste incinerators. Also,
as discussed earlier, the decision as to the negligibility of PCDD/F releases lies
with the Stockholm Convention, not with the authors of the Toolkit. Moreover,
the information presented in the preceding comment indicates that hazardous
waste incinerator residues are potentially significant in quantity and PCDD/F
content.
46
Suggestion: Either substantiate the information in these sentences or delete
them.
“The default emission factor for class 1 was derived from a specific flue gas
volume flow rate of about 17,500 Nm³/t of hazardous waste and a concentration of
about 2,000 ng TEQ/Nm³. Class 2 assumes a reduction in the specific flue gas
volume flow rate to 15,000 Nm³/t of hazardous waste due to better combustion
controls and lower excess air. The PCDD/PCDF concentration drops to 20 ng
TEQ/Nm³ (@11% O2) in this case. In class 3, the combustion efficiency improves
further and the efficiency of the APC system improves resulting in a drop of the
PCDD/PCDF concentration to about 1 ng TEQ/Nm³(@11% O2). Also, the
specific flue gas volume flow rate is reduced to 10,000 Nm³/t HW. Class 4
represents the current state-of-the-art in HW incineration and APC technology.
Thus, only 7,500 Nm³/t HW and a concentration of significantly less than 0.1 ng
TEQ/Nm³ (@11% O2) is realistic (LUA 1997, IFEU 1998, Environment Canada
1999).”
Comment: The information in this paragraph is probably based only on the few
countries’ experience. The EU inventory gives the following emission factors for
air for hazardous waste incinerators: 2 µg TEQ/ton, minimum; 20 µg TEQ/ton,
typical; and 200 µg TEQ/ton, maximum.123 Hazardous Waste Incinerators
belonging almost to the class 3 according to Toolkit explanation in the Czech
Republic generated emissions with PCDD/PCDF concentrations measured in
range between 0.026 - 18.285 ng TEQ/Nm³ (@11% O2).124 In many cases
hazardous waste was burned in these furnaces mixed with medical waste.The
values and data used in the Toolkit undermine its credibility.
46
Suggestion: Delete the segment above and replace it with well-substantiated
information.
“The maximum actual PCDD/PCDF concentration found in wet scrubber effluent
was below 0.15 mg TEQ/t (LUA 1997). Overall, this release vector is not
considered to be important for this source type.”
Comment: The Stockholm Convention’s ultimate goal is to eliminate byproducts
release. From this point of view, all byproduct sources are important and should
be considered in PCDD/PCDF inventories. The last sentence above is not
consistent within this goal of the Stockholm Convention. In addition, the source
given for this information “LUA 1997” is cited in these comments as “Quass, U.,
Fermann, M., 1997. Identification of Relevant Industrial Sources of Dioxins and
Furans in Europe (The European Dioxin Inventory). Final Report No. 43, Essen,
Germany: Landesumweltamt Nordrhein-Westfalen” and is, as the title indicates,
the European Dioxin Inventory. This inventory addresses only PCDD/F releases
to air and, as such, contains no information on PCDD/F concentrations in wet
scrubber effluent of hazardous waste incinerators. The other European inventory,
cited in these comments as “Wenborn, M., King, K., Buckley-Golder, D., Gascon,
J., 1999. Releases of Dioxins and Furans to Land and Water in Europe. Final
Report. Report produced for Landesumwaltamt Nordrhein-Westfalen, Germany
on behalf of European Commission DG Environment. September 1999,” reported
scrubber water from hazardous waste incinerators to have PCDD/F concentrations
of 0.01 - 0.6 ng I-TEQ per liter. 125
46
Suggestions: Delete this segment of text and replace it with the information
given in the EU inventory of PCDD/PCDF releases to land and water.
“No release to land is expected unless untreated residue is directly placed onto or
mixed with soil.”
Comment: See our earlier comments on this topic and discussion concerning the
land releases in general comments.
46 - 47
Suggestion: See earlier suggestions on this topic.
“To generate emission factors only fly ash has been taken into account for the
residue, since no data for bottom ash is available for classes 1 and 2. For classes
3 and 4, in which it must be assumed, that the bottom ash is extracted from the
furnace, no substantial contribution to the overall release of PCDD/PCDF
occurs. Consequently, only PCDD/PCDF concentrations in the fly ash residue are
substantial and will be considered further. The amount of fly ash in hazardous
waste is typically around 3 %. Fly ash also contains unburned carbon of 0.5 %
(class 4) up to 20 % (class 1). Since unburned carbon in the fly ash greatly
enhances the adsorption of PCDD/PCDF, the concentration is greatest in class 1.
In class 1 the PCDD/PCDF was assumed to be around 300,000 ng TEQ/kg
residue. In class 2 the concentration drops to 30,000 ng TEQ/kg residue due to
greatly improved combustion efficiency resulting in a much lower LOI of the fly
ash. Class 3 cuts this value down to 15,000 ng TEQ/kg residue based on further
improvements. Class 4 assumes not only high combustion efficiency but also very
high collection efficiency, especially of the very small fly ash particles. These
small particles supply a large adsorption surface for PCDD/PCDF and therefore
the overall concentration decreases to about 1,000 ng TEQ/kg residue. If
absolutely no fly ash data is available but actual stack emission data exists, it is
fair to assume the PCDD/PCDF emissions through the residue vector to be
similar and roughly in the same order of magnitude when compared to the air.
Thus, the overall emissions can roughly be split equally between the air and the
residue vector. However, this provides a much less accurate estimate of the
overall PCDD/PCDF emissions due to the different nature and composition of
hazardous waste fly ash.”
Comment: Refer to previous comments on similar estimations about the residues
from MSW incineration (p 42, 43-44). Again, defining those levels of PCDD/Fs in
incinerator residues that need not be considered in estimating PCDD/F releases is
a matter to be resolved jointly by the Parties. This decision does not fall within the
purview of the Toolkit’s authors.
In addition to our comments to the text on pages 42, 43-44 we refer to
measurement for the Czech hazardous waste incinerator (at least class 2 or 3) fly
ash where 82,400 ng TEQ/kg of PCDD/PCDF residue were found.126
Again, in contrast to the statement that unburned carbon in ash enhances
adsorption of PCDD/F, scientists have been reporting for almost twenty years that
unburned carbon in fly ash enhances PCDD/F formation by serving as a source of
complex carbon. 127, 128, 129, 130 Also, there is missing word, “incineration”, in the
last sentence after “hazardous waste”.
Suggestion: Delete this text and replace it with well-substantiated data and,
47
where appropriate, acknowledgement of the absence of data.
“To reliably destroy viruses, bacteria, and pathogens his waste is often thermally
treated (by incineration or pyrolysis). Further, due to its origin and its
composition, medical waste can contain toxic chemicals, e.g., heavy metals or
precursors, which may form dioxins and furans. In many countries medical waste
is a waste that requires special surveillance and it was found that incineration of
all wastes generated within a hospital would be the most efficient way to get rid of
these wastes.”
Comment: This segment erroneously implies that incineration is the only method
for reliable destruction of pathogens, such as viruses and bacteria. In fact, it is not
even the “most efficient way to get rid of” medical waste as stated in a report
prepared by World Bank.131 There are many other technologies which destroy
pathogens effectively without generating large amounts of PCDD/PCDF as waste
as incineration does.132, 133, 134
The second sentence erroneously implies that toxic chemicals in medical waste
are the major constituents in medical waste that form PCDD/Fs. As stated many
times, the presence of PVC in medical waste is one of main reasons (along with
poor conditions under which medical waste incinerators operate) that medical
waste incineration belongs to one of the main PCDD/PCDF sources.
48
Suggestion: “Incineration has been frequently relied on for the destruction of
the pathogens, such as viruses and bacteria, in medical waste. However, a
substantial fraction of medical waste commonly consists of chlorinated
materials, such as polyvinyl chloride (PVC) blood bags, tubing, etc., that act as
precursors for PCDD/PCDF formation.”
“The major release vectors of concern are air and residue (here fly ash only due
to the lack of data for bottom ash). Water releases are less important since APC
equipment, if present at all, is almost wastewater free.”
Comment: For medical waste incinerators, the European inventory gives a bottom
ash generation rate of 150 kg/ton of waste burned; a fly ash generation rate of 80
kg/ton; and the generation of wet scrubber treatment residue at the rate of 40
kg/ton.135 In the Czech Republic are wet scrubbers often used for both medical
and hazardous waste incinerators too. Ekotermex Vyškov can be taken as example
of such incinerator with maximum capacity 2.900 tons per annum. There was
generated 1510 tons of wet scrubber soluble residue in 2000136, what is unlikely
per one year generated waste water. Important is fact, that waste water from this
incinerator is sent to city waste water treatment, which shows that water releases
of PCDD/PCDF can be important in some cases and in some countries.
In addition, this use of the word “vector” is incompatible with the definition given
earlier in the Toolkit.
48
Suggestion: “The major releases of concern are air and residues. Water releases
have to be considered as well.”
“Table 18: Emission factors for medical waste incineration”
Comment: The emission factors given in this table do not correlate well with those
used in the European inventory, which are shown below (grate ash is equivalent to
bottom ash or slag; and dry scrubber residue, to fly ash): 137
Concentration ranges for the various solid wastes arising are as follows:
grate ash
15-300 ng I-TEQ/kg
dry scrubber residue
1800-4500 ng I-TEQ/kg
wet scrubber residue
680 ng I-TEQ/kg
Even higher figures are reported for Poland for residues from medical waste
incinerators ranging from 8000 - 45000 ng I-TEQ/kg. 138
48
Suggestion: Modify Table 18 to include bottom ash and scrubber water
residues, and modify the emission factors to be more compatible with those
used in other inventories and reported in the scientific literature
“These default emission factors are based on the assumption that the medical
waste burned leads to about 3 % of fly ash and the PCDD/PCDF release
associated with the disposal of bottom ash is currently unknown, since no
measured data are available presently.”
Comment: As discussed and documented in an earlier comment, the fly ash
generation rate for medical waste incinerators that is used in the European
inventory is 80 kg/ton, or 8 percent. This is 2.7 times higher than the Toolkit’s
value. In addition, the European inventory contains the citations for the sources of
the emission factors for the various outputs of medical waste incinerators.
48 - 49
Suggestion: Modify this statement to comply with the available information.
“Release to air is the predominant vector for medical waste incineration. The
default emission factor for class 1 was derived from a specific flue gas volume
flow rate of about 20,000 Nm³/t medical waste and a concentration of about 2,000
ng TEQ/Nm³ (@11% O2). Class 2 assumes a reduction in the specific flue gas
volume flow rate to 15,000 Nm³/t medical waste due to better combustion controls
and lower excess air. The PCDD/PCDF concentration drops to 200 ng TEQ/Nm³
(@11% O2) in this case. Class 3 is based on European data where a
concentration of 35 ng I-TEQ/Nm³ (@11% O2) with 15,000 Nm³/t has been
determined. Class 4 represents the current state-of-the-art in medical waste
incineration and good APC technology. In these cases, only 10,000 Nm³/t of
medical waste was generated and a concentration of less than 0.1 ng TEQ/Nm³
(@11% O2) was measured (LUA 1997, IFEU 1998, Environment Canada 1999).”
Comment: Sufficient data are not presented to support the first statement. The air
emission factors presented in Table 18 are somewhat larger than those of the
European inventory. 139 However, in the absence of sufficient documentation for
the stack gas flow-rates, it is not possible to verify the air emission factors
presented in the Toolkit. See also our comment on hazardous waste incinerators
measurements in the Czech Republic - comment on page 46 of the Toolkit. Also
the second stage of the European inventory states that “there still exist an
unknown number of health care waste incinerators with flue gas PCDD/F
concentrations above 100 ng I-TEQ/m3 which must be considered as important
local sources;“.140
Suggestion: Delete the first sentence and provide sufficient documentation for
49
the remaining data in this paragraph.
“Releases to water occur when wet scrubbers are employed for the removal of
particulate matter and quench water is used to cool ashes. This is hardly ever the
case except in Western Europe where wet scrubbers are occasionally used for
acid gas absorption. This would only be applicable to class 4. Measured
concentrations of PCDD/PCDF in scrubber water after medical waste
incinerators are not available. Where wet scrubbers are identified the water
treatment should be noted.”
Comment: In the absence of well-documented information describing the extent to
which wet scrubbers are used in the rest of the world, the second and third
sentences cannot be considered as correct.
Suggestion: “Releases to water occur when wet scrubbers are employed for the
removal of particulate matter and quench water is used to cool ashes. Measured
concentrations of PCDD/F in these effluents are not available. Where wet
scrubbers are identified the water treatment should be noted.”
49
“6.1.3.3 Release to Land
No release to land is expected unless untreated residue is directly placed onto or
mixed with soil.”
Comment: Refer to earlier comments, both general as well as detailed on the same
topic under previous subcategories.
49 - 50
Suggestion: Refer to earlier suggestions.
“PCDD/PCDF concentrations in the fly ash are substantial. Due to a lack of data
for PCDD/PCDF concentration in bottom ash, default emission factors provided
in the residue category only relate to PCDD/PCDF releases via fly ash
PCDD/PCDF concentrations in the residues can be high, especially where
combustion is poor (e.g., in a simple batch-type incinerator). Classes 1 and 2
medical waste incinerators will not generate fly ash due to the lack of dust
removal equipment. In these cases, all residues will consist of the residue left in
the combustion chamber. The class 1 emission factor is based on the assumption
that the 200 kg of residue per ton of medical waste burned is left in the
combustion chamber with a concentration of 1,000 ng TEQ/kg. For class 2,
combustion is improved, so the bottom ash residue should contain only 100 ng
TEQ/kg; resulting in an emission factor of 20 mg TEQ/t of waste.
For classes 3 and 4, fly ash is being collected and mixed with grate ash; the
amount of fly ash in medical waste typically is around 3 %. Classes 3 assumes
30,000 ng TEQ/kg in the fly ash and 100 ng TEQ/kg in the grate ash (same as
class 2). Class 4 incinerators have high combustion efficiency, resulting in an
organic carbon content of about 1 % of unburned carbon but also a very high
collection efficiency of the very small fly ash particles. Fly ash is collected (30
kg/t of waste) with a concentration of 5,000 ng TEQ/kg and 10 ng TEQ/kg of grate
ash is chosen. These small particles supply a large adsorption surface for
PCDD/PCDF and therefore the overall concentration does not decrease any
further.”
Comment: As described and presented in earlier comments, data describing
PCDD/F concentrations in both fly ash and bottom ash as well as the generation
rates for these ashes are presented in the European inventory. The Toolkit’s values
for both PCDD/F concentrations in fly ash and bottom ash and the generation
rates for these two kinds of ashes are considerably lower than the values in the
European inventory. 141 Other data suggest that some of the Toolkit’s values for
PCDD/F concentrations in ashes are too low. In the UNEP inventory of PCDD/F
releases in Thailand, PCDD/F concentrations in bottom ash of a hospital waste
incinerator were reported as 1,410 and 2,300 ng I-TEQ/kg and described as
“about the highest ever reported in the literature.”142 This is obviously not the
case given the study of 18 hospital waste incinerators in Poland, eight of which
had stack gas concentrations below 0.1 ng TEQ/m3, and that found bottom ash to
contain PCDD/F concentrations in the range of 8,000 to 45,000 ng TEQ/kg.143
51
Suggestion: Delete these two paragraphs and replace them with more
appropriate, well-documented data.
“Releases to air are the most important release vector for LWSF combustion.
There are not many measured data from this type of activity. The default emission
factor for class 1 was derived based on a emission factor of 1,000 ng TEQ/kg as
determined by the US EPA during a barrel burn study of selected combustible
household waste which closely resembles the composition of fluff. Class 2 uses
various emission data from a series of Western European and North American
RDF facilities including Japanese fluidized bed combustors with minimal APC
equipment. An emission factor of 50 µg TEQ/t was determined. Class 3 represents
the current state-of-the-art in LFSW incineration and APC technology. Thus, only
10,000 Nm³/t light-shredder waste and a concentration of less than 0.1 ng
TEQ/Nm³ (@11% O2) is taken (US EPA 1999, LUA 1997, IFEU 1998,
Environment Canada 1999).”
Comment: In the absence of data describing the PCDD/F content of residues from
the incineration of LWSF, this statement cannot be made. Justification should be
given for the selection of each of the various substitute concentrations and
emission factors presented here.
Suggestion: Delete the first sentence. Craft and present well-documented
justifications for the use of the information in the remainder of the
paragraph.
51
mixed with soil.”
51 - 52
Comment and Suggestion: See previous comments and suggestions on the
definition of “land” and the resulting exclusion of landfills.
“The amount of fly ash in LFSW is typically around 1 %. Fly ash also contains
unburned carbon of 5 % (class 3) up to presumably 30 % (class 1). In class 1, no
APC equipment is used and consequently no fly ash is collected but rather most of
it is emitted to the atmosphere with the flue gas. Even though no specific
collection device for fly ash is installed and the majority of the fly ash is
discharged through the stack, some fly ash is expected to collect in the furnace
and the ductwork leading to the stack as well as in the stack itself. Since unburned
carbon in the fly ash greatly enhances the adsorption of PCDD/PCDF, the
concentration is greatest in class 1. However, no accurate data is available. Class
3 assumes not only a high combustion efficiency but also a very high collection
efficiency, especially for the very small fly ash particles. Thus, a value of 15,000
ng TEQ/kg is chosen. These small particles supply a large adsorption surface for
PCDD/PCDF and therefore the overall concentration does not decrease any
further (US EPA 1999, LUA 1997, IFEU 1998).”
Comment: The sources of these data, e.g., the rate of generation of LFSW
incineration fly ash, etc., should be given. (It is not found in the sources that
appear at the end of the paragraph).
52
Suggestion: Either thoroughly and precisely document the information in this
paragraph or delete it.
“Since PCDD/PCDF are virtually insoluble in water, the bulk of the
PCDD/PCDF adsorbs to the solids present in the wastewater. If the solids are not
removed, the PCDD/PCDF will be discharged with the wastewater.”
Comment: While this statement may be true for pure water, it is not necessarily
true for municipal and industrial wastewater that commonly contains substances
that are or act as surfactants, such as linear alkylbenzene sulphonates, common
ingredients of detergents and cleaning agents;144 humic acids, ubiquitous soil
components;145 etc.
52
Suggestion: “PCDD/F are virtually insoluble in pure water. However, municipal
and industrial wastewater may contain substances that are or act as surfactants,
such as humic acids and linear alkylbenzene sulphonates, and increase
PCDD/F solubility. However, the bulk of PCDD/Fs present will adsorb to solids
present in wastewater, which can be removed by filtration or flocculation so that
the PCDD/Fs are collected in the wastewater treatment sludges.”
“… Another option for the disposal of sewage sludge is co-incineration in boilers,
e.g., fossil fuel power plants (see Main Source Category 3 - Section 6.3.1) or in
cement kilns (see Main Source Category 4 - Section 6.4.1).
Sewage sludge is incinerated in either bubbling or circulating fluidized bed
furnaces where the formation of PCDD/PCDF is limited due to good combustion
conditions. Also, high removal efficiencies of particulate matter, which are
critical for the operation of circulating fluidized bed furnaces, reduce
PCDD/PCDF emissions. Other furnace types commonly used are vertical rotary
stage or open hearth-type furnaces, grate-type furnaces or muffle-type furnaces.
All furnace types lead to reasonably low PCDD/PCDF formation depending,
however, on the composition of the sludge burned. Incineration of sludge with a
high content of halogenated hydrocarbons and/or other organic contaminants as
well as heavy metals such as copper can increase the PCDD/PCDF emissions.”
Comment: The sentence appears to resemble a manual on what to do with sludge.
We suggest reorganizing the text and not hiding chlorine as the root for PCDD/Fs
formation.
Suggestion: “Sewage sludge is incinerated in bubbling or circulating fluidized
bed furnaces, vertical rotary stage or open-hearth-type furnaces, grate-type
furnaces and muffle-type furnaces. Sewage sludge is also co-incinerated in
boilers, e.g., fossil fuel power plants (see Main Source Category 3 - Section
53
6.3.1) or in cement kilns (see Main Source Category 4 - Section 6.4.1). The
extent of PCDD/F formation depends on the composition of the sludge.
Incineration of sludge with a higher content of chlorinated hydrocarbons
and/or other sources of chlorine 146 and carbon as well as metals such as copper
can be expected to have greater PCDD/F formation, while increased sulfur
content in the sludge has been associated with reduced PCDD/F formation.” 147
“Table 20: Emission factors for sewage sludge incineration”
Comment: This table presents emission factors only for releases to air and
residues. According to a recent European Commission report on sewage sludge
disposal, “incineration generates emissions to air, soil and water …”148
53
Suggestion: Include a column for Emission Factor WATER.
“Releases to air represent the most important vector for sewage sludge
combustion. The default emission factor for class 1 was determined based on an
average emission concentration of 4 ng TEQ/Nm³ (@11% O2) and a specific flue
gas volume flow rate of about 12,500 Nm³/t of sewage sludge burned based on a
Belgian study as well as value of 77 ng TEQ/kg reported from the UK for a
multiple hearth furnace with ESP. Class 2 is an emission factor determined in The
Netherlands from fluidized bed plants with scrubbers and ESP. Class 3 is for
fluidized bed plants with optimized air pollution control systems consistently
meeting the emission limits equivalent to 0.1 ng I-TEQ/Nm³ (@11% O2) (from
Canadian, German and Swiss measurements) (LUA 1997, IFEU 1998,
Environment Canada 1999).”
Comment: Again, it is not possible to verify this information due to the absence of
cited sources. The three classes of sludge incinerators and their respective
Emission Factors AIR do not coincide well with those presented by the U.S.
Environmental Protection Agency: “The average TEQ emission factor based on
the data for the 11 AMSA facilities and the two facilities reported in U.S. EPA
(1990f) is 6.94 ng I-TEQ DF /kg of dry sludge combusted (or 7.04 ng TEQ DF WHO98 /kg of dry sludge), assuming nondetected values are zero. Other countries
have reported similar results. Bremmer et al. (1994) reported an emission rate of
5 ng ITEQ/kg for a fluidized-bed sewage sludge incinerator, equipped with a
cyclone and wet scrubber, in The Netherlands. Cains and Dyke (1994) measured
CDD/CDF emissions at two sewage sludge incinerators in the United Kingdom.
The emission rate at an incinerator equipped with an electrostatic precipitator
and wet scrubber ranged from 2.75 ng I-TEQ /kg to 28.0 ng I-TEQ /kg. The
emission rate measured at a facility equipped with only an electrostatic
precipitator was 43.0 ng I-TEQ /kg.” 149
Suggestion: Provide source citations for each value as well as each statement
of fact.
53
mixed with soil.”
Comment: See our previous comments on this topic.
Suggestion: See previous suggestions on this issue.
54
“UK testing (Dyke et al 1997) of multiple hearth furnaces showed PCDD/PCDF
in the grate ash at concentrations of 39 ng TEQ/kg and 470 ng TEQ/kg in fly ash
from the ESP. Rates of ash production were 430 kg per ton of grate ash and 13 kg
per ton of ESP ash for the multiple hearth plant. Levels in ash (all the ash was
collected in the ESP) from fluidized bed combustion were much lower (<1 ng
TEQ/kg). 373 kg of ESP ash was produced per ton of sludge combusted in the
fluidized bed.
Class 1 releases to residues (combined) are therefore 23 µg TEQ/ton of waste.
Class 2 releases are 0.5 µg TEQ/ton of waste. Class 3 releases are estimated the
same as class 2.”
Comment: See earlier comment on the classification of incinerators and the lack
of documentation.
Suggestion: Reevaluate the incinerator classes and provide more appropriate,
well-documented data.
54
“6.1.6 Waste Wood and Waste Biomass Incineration”
[including accompanying introductory text]
Comment: First, the use of the terms “waste wood” and “waste biomass” do not
convey clearly the important distinction that needs to be made between wood or
biomass contaminated with pentachlorophenol, chlorine-containing paints, PVC
cladding or scraps, chlorinated pesticides, etc. and wood and biomass that are
simply excess materials.
Suggestion:
“6.16 Contaminated Wood/Biomass Incineration
This subcategory addresses the combustion of contaminated wood/biomass in
furnaces under conditions ranging from no control to highly controlled.
Combustion of clean wood/biomass for generating energy is addressed in
Section 6.3.2, and open burning of clean wood/biomass is addressed in Section
6.6 – Uncontrolled Combustion Processes.
67 - 68
Contaminated wood/biomass may contain materials that support or contribute
to PCDD/F formation, e.g., paints, coatings, pesticides, preservatives, antifouling agents and many other substances that contain chlorine or chlorinated
chemicals as well as metals. Higher levels in the contaminated wood/biomass of
chlorine-containing materials and metals, such as copper, are commonly
associated with greater PCDD/F formation. While PCDD/F formation may be
enhanced by poor combustion conditions, it can be reduced, but not prevented,
by good combustion in well-controlled furnaces equipped with effective,
properly operated air pollution control systems. Three classes of combustion
systems, together with their emissions factors for PCDD/F releases to air and
residues.”
“Table 26: Emission factors for the steel industry and iron foundries”
&
“For electric arc furnaces, most measured emission data relate to plants using
relatively clean scrap and virgin iron and which are fitted with some afterburners and fabric filters for gas cleaning. Emission factors derived from plants
in Sweden, Germany, and Denmark gave emission factors between 0.07 and 9 Pg
I-TEQ/t LS. For the Toolkit, an emission factor of 3 Pg I-TEQ/t LS is applied
(Bremmer et al. 1994, SCEP 1994, Charles Napier 1998).”
Comment: Netherlands reports a much higher emission factor for electric arc
furnaces of 35 Pg I-TEQ/t LS.150
74
Suggestion: State a larger ranger of emission factors that reflect a larger
range of possible releases into the air.
“Older technology furnaces fitted with fabric filters had emissions of 146 to 233
ug TEQ/t of product. Concentrations and volumes of flue gas vary considerably;
up to 10 ng I-TEQ/m3 were reported (SCEP 1994). ...“
Comment: There were measured higher emissions in the furnace even with some
APC systems up to 13.7 ng TEQ/m3 in Germany.151
119
Suggestion: Give emission factors in the larger range reflecting larger differences.
“Older technology furnaces fitted with fabric filters had emissions of 146 to 233
ug TEQ/t of product. Concentrations and volumes of flue gas vary considerably;
up to 10 ng I-TEQ/m3 (SCEP 1994) or 13.7 ng TEQ/m3 152 were reported..”
“Accidental fires are very variable and the emissions will depend strongly on the
materials burned and on the nature of the fire. ... PCDD/PCDF will be present in
residues that may be disposed of or left on the ground.”
Comment: Even though it is mentioned later in the text, there should be a remark
included about the need for the presence of chlorine and/or chlorinated substances
for a fire to become a source of PCDD/PCDF. In cases where PVC is present,
high concentrations of PCDD/PCDF in residues have been found ranging from
0.13 - 2,060 ng/g, 153 suggesting that leaving its residue on the ground is not
suitable. Residue from accidental fires is hazardous waste according to its
PCDD/PCDF content in many cases and it should be processed to avoid further
soil, water and air (by dust particles) contamination.
Suggestion: “Accidental fires are very variable and the emissions will depend
strongly on the materials burned and on the nature of the fire. Presence of
elemental chlorine and/or chlorinated substances creates PCDD/PCDF in air
emissions, water and residues during fire. ... PCDD/PCDF will be present in
residues that should be handled as hazardous waste for its content of
PCDD/PCDF to avoid further pollution caused by PCDD/PCDF.”
121
“Residues from all types of fires considered in this Section are likely to contain
PCDD/PCDF. The amounts will vary depending on the conditions in the fire and
the nature of the materials. The residues may remain in place or be removed.”
Comment: See our comment to page 119 on measurements of PCDD/PCDF in
residues and handling with residues.
Suggestion: “Residues from all types of fires considered in this Section are likely
121
to contain PCDD/PCDF. The amounts will vary depending on the conditions in
the fire and the nature of the materials such as those containing chlorine
and/or chlorine substances. PCDD/PCDF will be present in residues in cases
where chlorine and its substances are present during the fire so these residues
should be handled as hazardous waste for its content of PCDD/PCDF to avoid
further pollution caused by PCDD/PCDF.”
“A wide range of concentrations has been measured but there is often insufficient
information to estimate an emission factor since the amounts of ash produced are
not known. In Germany, an estimate was made that gave emission factors in
residues (including deposited soot) of 1,000 Pg TEQ/t for industrial fires and 350
Pg TEQ/t for residential fires (LUA 1997). As an approximation and to make an
initial estimate, an emission factor of 400 Pg TEQ/t is used giving equal
PCDD/PCDF in air emission and in residues on average from the fires
considered.”
Comment: PCDD/PCDF concentrations in soot were measured up to 2,060 ng/g
from three fires in the Czech Republic where PVC materials were involved. These
levels are much higher than those measured in Germany. The lowest measured
concentration in residues from these fires was 0.13 ng/g in the plaster. 154
161
Suggestion: To give wider ranges of default emission factors for residues that
better reflect real PCDD/PCDF releases in residues.
“Table 71: Emission factors for sewage sludge”
Comment: As Toolkit’s authors refer there were measured different levels of
PCDD/PCDFs in sewage sludge in a range of 6 - 4.100 ng TEQ/kg. It is not clear
how the authors derived emission default factors from these figures. The reality is
very different from treatment to treatment and the emission factor for “Urban
environments” on level of 100 ug TEQ/t d. m. for residue = product should be
underestimated. Adding to the references on Toolkit page 161 there were four
samples of sewage sludge in the Czech Republic with measured results in a range
from 21.2 – 280.2 ug TEQ/t d.m. (data for year 2001). 155 Sewage sludge can be
indirectly contaminated by PCDD/PCDFs releases from fly ash put on landfills
which use municipalities waste water treatment plants to clean up waste water as
well. 156
Refer to our general and previous comments regarding a preference for a range of
emission factors rather than a single number.
201
Suggestion: Set emission factors using a range rather than a single number.
“The major release vectors are to air with a total of 150 g TEQ per year and with
residues, which account for 552 g TEQ per year. The majority of PCDD/PCDF in
the residues is due to contamination in the fly ashes.” ... “This incinerator emitted
87,5 g TEQ in the reference year whereas the state-of-the-art incinerator that
applies BAT burns twice the mass (500,000 t/a), only releases 0,25 g TEQ in the
reference year.”
Comment: These comments given in the Example Tables for the Inventory in
Toolkit Section 10.1 appear to be a promotion of state-of-the-art incineration and
are simply confusing. The major release vector is clearly into the residues, so it
should be given first place. The last sentence in paragraph shows a narrow focus
on air emissions/releases, but this is inconsistent with the Stockholm Convention.
The incinerator in the chosen country did not emit (release) only 87.5 g TEQ
PCDD/PCDF, but 212.5 g TEQ according to table 75 and the state-of-the-art
incinerator would release more g TEQ PCDD/PCDF as well if residues or
products release were taken into account. The last sentence does not help to
explain the PCDD/PCDF country inventory as it appears to be promoting state-ofthe-art incinerators. Also using different terms such as “emitted” and “only
releases” is not consistent within the Toolkit as well as with the Stockholm
Convention terminology. Another problem is that the last sentence focuses on air
releases and neglects releases to other media as specified by the Stockholm
Convention.
203
Suggestion: Change first phrase and delete last sentence about releases from stateof-the-art incinerator:
“The major release vectors are to residues with a total of 552 g TEQ per year
and with air, which account for 150 g TEQ per year. The majority of
PCDD/PCDF in the residues is due to contamination in the fly ashes.”
“Table 75: Copy of an example .....”
Comment: This example seems to be misleading by showing a releases inventory
from waste incinerators. There are no figures on releases to water and there is no
data on releases into product despite the fact that both of these occur in many
countries. If we take into account previous comments, this example may be
confusing in that it implies that countries have to focus mainly on releases into air,
which is inconsistent with the Stockholm Convention, because all releases have to
be reported.
Suggestion: Improve the example by including release data into water and
other media, or delete the table.
Annexes:
ANNEX 1: Commercial Chemicals Known or Suspected to be
Accompanied by Dioxin Formation During Their Manufacture
Chemical
Reference
Dioxins are Known By-Products During Manufacture
157
Chlorine
Sodium hypochlorite (bleach)
158
Ethylene dichloride (1,2-dichloroethane; vinyl chloride
monomer)
Epichlorohydrin
159
Trichloroethylene
Perchloroethylene (tetrachloroethylene)
Hexachlorobutadiene
Chlorobenzenes
Dichlorobenzene
Trichlorobenzene
1,2,4,5-Tetrachlorobenzene
Pentachlorobenzene
161
160
162
Hexachlorobenzene
Chlorophenols
2,4,5-Trichlorophenol
163
2,4,5-Trichlorophenol, sodium salt
164
2,4,6-Trichlorophenol
165
2,4,6-Trichlorophenol, sodium salt
166
2,3,4,6-Tetrachlorophenol
167
2,3,4,6-Tetrachlorophenol, sodium salt
168
Pentachlorophenol
169
Polychlorinated biphenyls (PCBs)
170
4-Chlorotoluene
171
Chloranil (2,3,5,6-tetrachloro-2,5-cyclohexadiene-1,4dione)
Dioxazine dyes (Direct Blue 106, Direct Blue 108, and
Violet 23)
Ni-phthalocyanine dye
172
Printing inks (unidentified)
175
Metal Chlorides
Aluminum chloride
Ferric chloride
Cuprous chloride
Cupric chloride
173
174
176
High Probability of Dioxin Formation During Manufacture
Chlorophenols
o-Chlorophenol
2,3-Dichlorophenol
2,4-Dichlorophenol
2,5-Dichlorophenol
2,6-Dichlorophenol
3,4-Dichlorophenol
4-Chlororesorcinol
4-Bromo-2,5-dichlorophenol
2-Chloro-4-fluorophenol
2-Chloro-4-phenylphenol
Chlorohydroquinone
2-Chloro-1,4-diethoxy-5-nitrobenzene
177
5-Chloro-2,4-dimethoxyaniline
3,5-Dichlorosalicylic acid
Possible or Likely Dioxin Formation During Manufacture
Chlorobenzenes
o-Dichlorobenzene
1,2,4-Trichlorobenzene
1,2,4,5-Tetrachlorobenzene
Hexachlorobenzene
o-Chlorofluorobenzene
3-Chloro-4-fluoronitrobenzene
Chloropentafluorobenzene
1,2-Dichloro-4-nitrobenzene
Chlorophenols
3-Chloro-4-fluorophenol
4-Chloro-2-nitrophenol
o-Benzyl-p-chlorophenol
2,3,6-Trichlorobenzoic acid
178
179
180
2,3,6-Trichlorophenylacetic acid, and sodium salt
3,4-Dichloroaniline
181
3,4-Dichlorobenzaldehyde
3,4-Dichlorobenzotrichloride
3,4-Dichlorobenzotrifluoride
3,4-Dichlorophenylisocyanate
Pentachlorocyclohexane
Pentachloroaniline
Pentabromochlorocyclohexane
Tetrachlorophthalic anhydride
182
*Phenol (from chlorobenzene)
*1,2-Dihydroxybenzene-3,5-disulfonic acid, disodium salt
*2,5-Dihydroxybenzenesulfonic acid
*2,5-Dihydroxybenzenesulfonic acid, potassium salt
*2,4-Dinitrophenol
*2,4-Dinitrophenoxyethanol
*3,5-Dinitrosalicylic acid
*o-Nitroanisole
*2-Nitro-p-cresol
*o-Nitrophenol
*2,4,6-Trinitroresorcinol
*Fumaric acid
*Maleic acid
*Maleic anhydride
*o-Phenetidine
*Phenyl ether
*Phthalic anhydride
*Picric acid
*Sodium picrate
183
*Non-chlorinated chemicals produced via routes involving chlorinated chemicals.
ANNEX 2: Pesticides Known or Suspected to be Accompanied by
PCDD/F Formation During Manufacture
Sources: 1. U.S. Environmental Protection Agency. 1998. The Inventory of Sources of Dioxin in the United States. EPA/600/P98/002Aa, Washington, D.C., April 1998.
2. Bretthauer, E., Kraus, H., di Domenico, A. 1991. Dioxin Perspectives: A Pilot Study on International Exchange on Dioxins and
Related Compounds. New York: Plenum Press.
Common Name
Bromophos
Pesticide
Dichlorodifluoromethane
O-( 4- Bromo- 2,5- dichlorophenyl) O, O- dimethyl
phosphorothioate
Dimethylamine 2,3,5- triiodobenzoate
Neburon
Crufomate
MCPB, 4- butyric acid [4-( 2- Methyl- 4chlorophenoxy) butyric acid]
MCPB, Na salt [Sodium 4-( 2- methyl- 4chlorophenoxy) butyrate]
4- Chlorophenoxyacetic acid
Chloroxuron
Chemical
Abstract Service
Number
75-71-8 1
2104-96-3
Source
17601-49-9
555-37-3
299-86-5
94-81-5
1
1
1
1
6062- 26- 6
1
122- 88- 3
1982- 47- 4
1
1
1
1
Dichlobenil
Propanil
Dichlofenthion
DDT
Dichlone
Ammonium chloramben
Sodium chloramben
Disul
DCNA
MCPP, DEA Salt
MCPP, IOE
Dicapthon
Monuron trichloroacetate
Diuron
Linuron
Metobromuron
Methyl parathion
Dichlorophene
Dichlorophene, sodium salt
Ethyl parathion
Carbophenothion
Ronnel
Mitin FF
Chlorophene
1194- 65- 6
709- 98- 8
97- 17- 6
1
1
1
50- 29- 3
117- 80- 6
1076- 46- 6
1
1
1
3- amino- 2,5- dichlorobenzoic acid
Sodium 2-( 2,4-dichlorophenoxy) ethyl sulfate
2,6- Dichloro- 4- nitroaniline
Potassium 2-( 2- methyl-4-chlorophenoxy)
propionate
Diethanolamine 2-( 2- methyl- 4- chlorophenoxy)
propionate
Isooctyl 2-( 2- methyl- 4- chlorophenoxy)
propionate
O-( 2- chloro- 4- nitrophenyl) O, O- dimethyl
phosphorothioate
3-( 4- chlorophenyl)- 1,1- dimethylurea
trichloroacetate
3-( 3,4- dichlorophenyl)- 1,1- dimethylurea
3-( 3,4- dichlorophenyl)- 1- methoxy- 1methylurea
3-( p- bromophenyl)- 1- methoxy- 1- methylurea
O, O- Dimethyl O- p- nitrophenyl phosphorothioate
Sodium 2,2'- methylenebis( 4- chlorophenate)
Sodium 2,2'- methylenebis( 4- chlorophenate)
1954- 81- 0
136- 78- 7
99- 30- 9
1929- 86- 8
1
1
1
1
1432- 14- 0
1
28473- 03- 2
1
2463- 84- 5
1
140- 41- 0
1
330- 54- 1
330- 55- 2
1
1
3060- 89- 7
298- 00- 0
97- 23- 4
10254- 48- 5
1
1
1
1
1,2,4,5- Tetrachloro- 3- nitrobenzene
O, O- diethyl O- p- nitrophenyl phosphorothioate
S-((( p- chlorophenyl) thio) methyl) O, O- diethyl
phosphorodithioate
O, O- dimethyl O-( 2,4,5- trichlorophenyl)
phosphorothioate
Sodium 5- chloro- 2-( 4- chloro- 2-( 3-( 3,4dichlorophenyl) ureido) phenoxy) benzenesulfonate
Orthodichlorobenzene
Paradichlorobenzene
2- Benzyl- 4- chlorophenol
Potassium 2- benzyl- 4- chlorophenate
Sodium 2- benzyl- 4- chlorophenate
Chlorophenol
2- Chloro- 4- phenylphenol
Potassium 2- chloro- 4- phenylphenate
4- Chloro- 2- phenylphenol, potassium salt
6- Chloro- 2- phenylphenol, potassium salt
4- Chloro- 2- phenylphenol, sodium salt
4 and 6- Chloro- 2- phenylphenol, diethanolamine
salt
117- 18- 0
56- 38- 2
786- 19- 6
1
1
1
229- 84- 3
1
3567- 25- 7
1
95- 50- 1
106- 46- 7
120- 32- 1
35471- 49- 9
3184- 65- 4
95- 57- 8
92- 04- 6
18128- 16- 0
not available
53404- 21
85- 97- 2
18128- 17- 1
10605- 10- 4
10605- 11- 5
53537- 63- 6
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
3', 4'- Dichloropropionanilide
O-( 2,4- Dichlorophenyl) O, O- diethyl
phosphorothioate)
Dichloro diphenyl trichloroethane
2,3- dichloro- 1,4- naphthoquinone
3- amino- 2,5- dichlorobenzoic acid
Fentichlor
Fentichlor
Chlorophacinone
ADBAC
ADBAC
Niclosamide
Tetradifon
Chloranil
Anilazine
Chlorothalonil
Fenac, Chlorfenac
Chlorfenvinphos
PCMX
Piperalin
4- Chloro- 2- cyclopentylphenol
2,2'- Thiobis( 4- chloro- 6- methylphenol)
2,2'- Thiobis( 4- chlorophenol)] 5
4- Chloro- 2- cyclopentylphenol, potassium salt of
4- Chloro- 2- cyclopentylphenol, sodium salt
Alkyl* dimethyl benzyl ammonium chloride *(
50% C14, 40% C12, 10% C16)
Alkyl* dimethyl 3,4- dichlorobenzyl ammonium
chloride *( 61% C12, 23% C14, 11% C16, 5%
C18)
2- Aminoethanol salt of 2', 5- dichloro- 4'nitrosalicylanilide
5- Chlorosalicylanilide
2- Methyl- 4- isothiazolin- 3- one
4- chlorophenyl 2,4,5- trichlorophenyl sulfone
tetrachloro- p- benzoquinone
6- Chlorothymol
2,4- Dichloro- 6-( o- chloroanilino)- s- triazine
Tetrachloroisophthalonitrile
Sodium 2,3,6- Trichlorophenylacetate
O-( 2- Chloro- 1-( 2,5- dichlorophenyl) vinyl) O, Odiethyl phosphorothioate
4- Chloro- 3,5- xylenol
3-( 2- Methylpiperidino) propyl 3,4dichlorobenzoate
Fenamiphos
p- Chlorophenyl diiodomethyl sulfone
Metribuzin
Bifenox
Methazole
Diflubenzuron
Oxadiazon
Fenvalerate
Fluvalinate
Iprodione
Triadimefon
Diclofop - methyl
Profenofos
Oxyfluorfen
methyl 5-( 2,4- dichlorophenoxy)- 2- nitrobenzoate
2-( 3,4- dichlorophenyl)- 4- methyl- 1,2,4oxadiazolidine- 3,5- dione
N-((( 4- chlorophenyl) amino) carbonyl)- 2,6difluorobenzamide
2-Tert- butyl- 4-( 2,4- dichloro- 5isopropoxyphenyl)- delta 2 -1,3,4- oxadiazoline- 5one]
N- 2- Chloro- 4- trifluoromethyl) phenyl- DLvaline (+-)- cyano( 3- phenoxy- phenyl) methyl
ester
3-( 3,5- Dichlorophenyl)- N-( 1- methylethyl)- 2,4dioxo- 1imidazolidinecarboxamide (9CA)
1-( 4- Chlorophenoxy)-3,3-dimethyl-1-( 1H-1,2,4triazol-1-yl)- 2- butanone
Methyl 2-( 4-( 2,4- dichlorophenoxy) phenoxy)
propanoate
O-( 4- Bromo- 2- chlorophenyl)- O- ethyl S- propyl
phosphorothioate
2- chloro- 1-( 3- ethoxy- 4- nitrophenoxy)- 4-(
trifluoromethyl) benzene
31366- 97- 9
13347- 42- 7
4418- 66- 0
97- 2435471- 38- 6
53404- 20- 9
3691- 35- 8
68424- 85- 1
1
1
1
1
1
1
1
1
not available
1
1420- 04- 8
1
4638- 48- 6
not available
116- 29- 0
118- 75- 2
89- 68- 9
101- 05- 3
1897- 45- 6
2439- 00- 1
470- 90- 6
1757- 18- 2
1
1
1
1
1
1
1
1
1
1
88- 04- 0
3478- 94- 2
1
1
not available
20018- 12- 6
21087- 64- 9
42576- 02- 3
20354- 26- 1
1
1
1
1
1
35367- 38- 5
1
19666- 30- 9
1
51630- 58- 1
69409- 94- 5
1
1
36734- 19- 7
1
43121- 43- 3
1
51338- 27- 3
1
41198- 08- 7
1
42874- 03- 3
1
Imazalil
35554- 44- 0
1
63333- 35- 7
1
50471- 44- 8
1
83588- 43- 6
1
58138- 08- 2
1
1
1
1
Dicamba dimethylamine
[a-( 2- chlorophenyl)- a-( 4- chlorophenyl)- 5pyrimidinemethanol]
[3,6- dichloro- o- anisic acid]
76738- 62- 0
78- 70- 6
60168- 88- 9
2300- 66- 5
1
Diethanolamine dicamba
[3,6- dichloro- 2- anisic acid]
25059- 78- 3
1
2,4-D
2,4- Dichlorophenoxyacetic acid
Lithium 2,4- dichlorophenoxyacetate
Potassium 2,4- dichlorophenoxyacetate
Sodium 2,4- dichlorophenoxyacetate
Ammonium 2,4- dichlorophenoxyacetate
Alkanol* amine 2,4- dichlorophenoxyacetate *(
salts of the ethanol and ispropanol series)
Alkyl* amine 2,4- dichlorophenoxyacetate *( 100%
C12)
Alkyl* amine 2,4- dichlorophenoxyacetate *( 100%
C14)
Alkyl* amine 2,4- dichlorophenoxyacetate *( as in
fatty acids of tall oil)
Diethanolamine 2,4- dichlorophenoxyacetate
Diethylamine 2,4- dichlorophenoxyacetate
Dimethylamine 2,4- dichlorophenoxyacetate
N, N- Dimethyloleylamine 2,4dichlorophenoxyacetate
Ethanolamine 2,4- dichlorophenoxyacetate
Heptylamine 2,4- dichlorophenoxyacetate
Isopropanolamine 2,4- dichlorophenoxyacetate
Isopropylamine 2,4- dichlorophenoxyacetate
Morpholine 2,4- dichlorophenoxyacetate
N- Oleyl- 1,3- propylenediamine 2,4dichlorophenoxyacetate
Octylamine 2,4- dichlorophenoxyacetate
Triethanolamine 2,4- dichlorophenoxyacetate
Triethylamine 2,4- dichlorophenoxyacetate
Triisopropanolamine 2,4- dichlorophenoxyacetate
N, N- Dimethyl oleyl- linoleyl amine 2,4dichlorophenoxyacetate
Butoxyethoxypropyl 2,4- dichlorophenoxyacetate
Butoxyethyl 2,4- dichlorophenoxyacetate
Butoxypropyl 2,4- dichlorophenoxyacetate
94- 75- 7
3766- 27- 6
14214- 89- 2
2702- 72- 9
2307- 55- 3
not available
1
1
1
1
1
1
2212- 54- 6
1
28685- 18- 9
1
not available
1
5742- 19- 8
20940- 37- 8
2008- 39- 1
53535- 36- 7
1
1
1
1
3599- 58- 4
37102- 63- 9
6365- 72- 6
5742- 17- 6
6365- 73- 7
2212- 59- 1
1
1
1
1
1
1
2212- 53- 5
2569- 01- 9
2646- 78- 8
32341- 80- 3
55256- 32- 1
1
1
1
1
1
1928- 57- 0
1929- 73- 3
1928- 45- 6
1
1
1
Bromothalin
Vinclozolin
Fenridazon
Tridiphane
1-( 2-( 2,4- Dichlorophenyl)- 2-( 2- propenyloxy)
ethyl)- 1H- imidazole
N- Methyl- 2,4- dinitro- n-( 2,4,6- tribromophenyl)6(trifuloromethyl) benzenamine
3-( 3,5- Dichlorophenyl)- 5- ethenyl- 5- methyl2,4- oxazolidinedione (9CA)
Potassium 1-( p- chlorophenyl)- 1,4- dihydro- 6methyl- 4- oxo- pyridazine- 3- carboxylate
2-( 3,5- Dichlorophenyl)- 2-( 2,2,2- trichloroethyl)
oxirane
Paclobutrazol
Linalool
MCPP, DMA
Bromoxynil
Hexachlorophene
Hexachlorophene, sodium salt
Hexachlorophene, potassium
salt
Irgasan
Bithionolate sodium
Phenachlor
Phenothiazine
Dacthal- DCPA
Endosulfan
Silvex
Tetrachlorvinphos
Edolan
2,4-DB
2,4,5-T
Butyl 2,4- dichlorophenoxyacetate
Isobutyl 2,4- dichlorophenoxyacetate
Isooctyl( 2- ethylhexyl) 2,4dichlorophenoxyacetate
Isooctyl( 2- ethyl- 4- methylpentyl) 2,4dichlorophenoxyacetate
Isooctyl( 2- octyl) 2,4- dichlorophenoxyacetate
Isopropyl 2,4- dichlorophenoxyacetate
Propylene glycol butyl ether 2,4dichlorophenoxyacetate
4-( 2,4- Dichlorophenoxy) butyric acid
Sodium 4-( 2,4- dichlorophenoxy) butyrate
Dimethylamine 4-( 2,4- dichlorophenoxy) butyrate
Butoxyethanol 4-( 2,4- dichlorophenoxy) butyrate
Butyl 4-( 2,4- dichlorophenoxy) butyrate
Isooctyl 4-( 2,4- dichlorophenoxy) butyrate
2-( 2,4- Dichlorophenoxy) propionic acid
(Dichlorprop, 2,4-DP)
Dimethylamine 2-( 2,4- dichlorophenoxy)
propionate
Butoxyethyl 2-( 2,4- dichlorophenoxy) propionate
Isooctyl 2-( 2,4- dichlorophenoxy) propionate
[2-( 2- Methyl- 4- chlorophenoxy) propionic acid]
Dimethylamine 2-( 2- methyl- 4- chlorophenoxy)
propionate
3,5- Dibromo- 4- hydroxybenzonitrile
2,2'- Methylenebis( 3,4,6- trichlorophenol)
Monosodium 2,2'- methylenebis( 3,4,6trichlorophenate)
Potassium 2,2'- methylenebis( 3,4,6trichlorophenate)
5- Chloro- 2-( 2,4- dichlorophenoxy) phenol
Tetrachlorophenols
Tetrachlorophenols, sodium salt
Tetrachlorophenols, alkyl* amine salt*( as in fatty
acids of coconut oil)
Tetrachlorophenols, potassium salt
Disodium 2,2'- thiobis( 4,6- dichlorophenate)
2,4,6- Trichlorophenol
Potassium 2,4,6- trichlorophenate
2,4,6- Trichlorophenol, sodium salt
Dimethyl tetrachloroterephthalate
Hexachlorohexahydromethano- 2,4,3benzodioxathiepin- 3- oxide
2-( 2,4,5-Trichlorophenoxy) propionic acid
2- Chloro- 1-( 2,4,5- trichlorophenyl) vinyl
dimethyl phosphate
Sodium 1,4', 5'- trichloro- 2'-( 2,4,5trichlorophenoxy)
methanesulfonanilide
4-(2,4-Dichlorophenoxy)butanoic acid and its salts
2,4,5-Trichlorophenoxyacetic acid, its esters and
94- 80- 4
1713- 15- 1
1928- 43- 4
1
1
1
25168- 26- 7
1
1917- 97- 1
94- 11- 1
1320- 18- 9
1
1
1
94- 82- 6
10433- 59- 7
2758- 42- 1
32357- 46- 3
6753- 24- 8
1320- 15- 6
120- 36- 5
1
1
1
1
1
1
1
53404- 32- 3
1
53404- 31- 2
28631- 35- 8
7085- 19- 0
32351- 70- 5
1
1
1
1
1689- 84- 5
70- 30- 4
5736- 15- 2
1
1
1
67923- 62- 0
1
3380- 34- 5
25167- 83- 3
25567- 55- 9
not available
1
1
1
1
53535- 27- 6
6385- 58- 6
88- 06- 2
2591- 21- 1
3784- 03- 0
92- 84- 2
1861- 32- 1
115- 29- 7
1
1
1
1
1
1
1
1
93- 72- 1
961- 11- 5
1
1
69462- 14- 2
1
2
2
MCPA
Chloroneb
Erbone
Daconil
salts
Dimethyl-(2,3,5,6-tetrachloro-1,4benzodicarbonate)
4-Chloro-2-methylphenoxy acetic acid
1,4-Dichloro-2,5-dimethoxybenzene
2(2,4,5-Trichlorophenoxy)-ethyl-2,2,dichloropropionate
1,3-dicyano-2,4,5,6-tetrachlorobenzene
2
2
2
2
2
Costner, P., 2003. Greenpeace Coomments on UNEP Chemical’s “ Standardized Toolkit for
Identification and Quantification of Dioxin and Furan Releases“. Greenpeace, Amsterdam, 10
January 2003.
1
2
Bailey, R., 2001. Global hexachlorobenzene emissions. Chemosphere 43: 167-182.
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Esposito, M., Tiernan, T., Dryden, F. 1980. Dioxins. EPA-600/2-80-197, Washington,
D.C.: U.S. Environmental Protection Agency.
178
179
180
Anonymous. 1985. Pesticides `Possibly Contaminated with Dioxins” List Compiled in
OPP,” Pesticide and Toxic Chemical News, pp. 34-38, February 20, 1985.
181
182
183
21
greenpeace international
Ottho Heldringstraat 5, 1066 AZ, Amsterdam, Netherlands
t +31 514 8150 f +31 20 514 8151
k.v.k. reg. 41200415 stichting greenpeace council
www.greenpeace.org
31 March 2004
To: United Nations Environment Programme
Secretariat, Stockholm Convention
11-13, chemin des Anemones
CH-1219 Chatelaine (GE)
Switzerland
Fm: Pat Costner
Senior Science Advisor
Greenpeace International
Re: Greenpeace Comments on the “Standardized Toolkit for Identification and
Quantification of Dioxin and Furan Releases,” First Edition.
We appreciate the opportunity to offer our comments on the first edition of the
“Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases.”
In reviewing the first edition of the Toolkit, we find that the most important issues raised in
our comments on earlier drafts have not yet been addressed. In particular, the Toolkit
provides no strategy for identifying sources of dioxin and furan releases. Without such a
strategy, Parties are not equipped to identify all of their PCDD/PCDFa sources.
The Toolkit’s list of PCDD/PCDF sources is incomplete and will remain so for the
foreseeable future because 1) it does not include all sources that are currently identified
and 2) new sources are still being identified. A source identification strategy is particularly
important with regard to industrial-chemical processes and activities. For example, the
Toolkit’s list includes the manufacture of only eleven chemical products even though one
hundred or more chemical products have been identified as being accompanied or
potentially accompanied by PCDD/PCDF formation during their manufacture. (See, for
example, Tables 1, 2 and 3 in our comments of 10 January 2003). Given this
circumstance, it is essential that the Toolkit includes a source identification strategy.
A source identification strategy must be based on the science of PCDD/PCDF formation.
In fact, the explanation of PCDD/PCDF formation that is presented in the Toolkit is the
scientific foundation of not only the source identification strategy but the Toolkit itself and,
as such, much of the implementation of the Stockholm Convention with respect to
PCDD/PCDF. As a consequence, our comments are directed first to the Toolkit’s current
explanation of PCDD/PCDF formation and the revisions that are necessary to bring it into
agreement with the existing science. Following this, we offer our suggestions on the source
identification strategy. For our comments on the remaining issues in the first edition of the
a
Following the practice used in the Toolkit, the acronym “PCDD/PCDF” is used in these comments to refer
to the polychlorinated dibenzo-p-dioxins (PCDDs or “dioxins”) and dibenzofurans (PCDFs or “furans”).
1
Toolkit, we include herewith by reference our preliminary comments of 14 June 2002, our
comments of 20 May 2003 on the draft Toolkit of January 2001, and our comments of 10
January 2003 on the revised draft Toolkit of January 2003.
1.0 Comments on the Toolkit’s Section 3.1 Formation of PCDD/PCDF
To provide Parties with the resources required to identify sources and estimate releases of
PCDD/PCDF, the Toolkit must present a concise explanation of PCDD/PCDF formation
that accurately reflects the current state-of-the-science of PCDD/PCDF formation. It must
also be comprehensible, to the greatest extent possible, to non-scientists since many who
use the Toolkit will not be highly trained scientists.
The Toolkit’s authors are to be commended for their efforts to meet these stringent
requirements. For instance, the Toolkit’s current description of PCDD/PCDF formation,
“3.1 Formation of PCDD/PCDF,” is admirably concise. However, revisions are necessary
so that this crucial explanation is more accessible to non-scientists and so that it reflects
more accurately the current science of PCDD/PCDF formation.
Toward these two ends, we present below suggested revised wording for the Toolkit’s
Section 3.1, based on the issue-specific rationales and evidence that are presented in
succeeding sections 1.2-1.8 of these comments:
(Please note that each source of information is deliberately cited with each individual
occurrence in order to expedite identification and retrieval of source citations.)
1.1 Suggested Revision of Section “3.1 Formation of PCDD/PCDF”
3.1 Formation of PCDD/PCDF
PCDD/PCDF have no known technical use and are not intentionally produced. They are
formed as unwanted by-products of processes and activities that are distinguished by the
presence of chlorine in any of its forms (elemental, organicb or inorganic). These
processes and activities can be broadly categorized as 1) thermal processes, such as
waste incineration, and 2) industrial-chemical processes, such as chemical
manufacture.c
3.1.2 Thermal Processes
The prerequisites for PCDD/F formation in thermal processes are the following:
x Chlorine in the form of gaseous, elemental chlorine; as organic chlorine, such as
chlorobenzene, polyvinyl chloride (PVC), etc.; or as inorganic chloride, such as
hydrogen chloride, sodium chloride (table salt), etc.;
x Carbon in the form of macromolecular carbon in fly ash, soot , and/or the
activated carbon that is used to reduce releases in flue gases, or in the form of
b
In chemistry, the term “organic” is commonly used to refer to chemicals that have carbon and possibly
hydrogen as part of their molecular structure, while the term “inorganic’ is used to refer to those that do
not. There are, of course, exceptions to these broad classifications.
c
PCDD/PCDF may also be introduced as contaminants in raw materials and/or wastes so that they may
occur in processes in which PCDD/PCDF formation does not occur.
2
organically-bound carbon in compounds that have escaped combustion or formed
as products of incomplete combustion;
x Oxygen as gaseous, elemental oxygen or as oxygen in organic or inorganic
forms e.g., PCDD/PCDF formation can take place in a nitrogen atmosphere1; and
x Hydrogen in any form..
PCDD/PCDF formation in thermal processes is thought to occur primarily through these
pathways:
1. High-temperature, gas-phase formation in homogeneousd reactions of chlorine,
either in elemental form or as hydrogen chloride, and gaseous precursorse;
2. Relatively low-temperature formation from the reaction of macromolecularf
carbon, which occurs in fly ash, soot and activated carbon, with organic or
inorganic chlorine present in the fly ash, (often referred to as de novo formation);
and
3. Formation in heterogeneous reactions of gas-phase organic precursors with metal
oxides, metal chlorides or other catalytically active constituents on fly ash, other
particulates or solid surfaces.
.
The relative importance of these pathways varies, depending on conditions. However,
the two latter pathways are thought to be most important in modern, well-operated
incinerators.
Conditions that favour PCDD/PCDF formation in thermal processes are as follows:
x Elevated temperatures: Formation of PCDD/PCDF in the combustion zones of
lab- and full-scale combustion systems has been reported to occur in the range of
500-1000 oC . 2, 3, 4 Formation in post-combustion zones, including air pollution
control devices, of full-scale incinerators via de novo synthesis or another
heterogeneous pathway has been found to occur at temperatures as low as 150
o
C. 5 However, the optimum temperature for PCDD/PCDF formation in the postcombustion zone has been reported to range between 650 and 250 °C, with
maximum formation at approximately 300 °C. 6
x Metals (for example, copper and iron, 7 zinc,8 and manganese9) can serve as
catalysts that increase and expedite PCDD/PCDF formation. However, some
studies have shown that metals may not be required.10
3.1.2 Industrial-chemical Processes and Activities
In industrial-chemical processes, PCDD/PCDF formation also requires the presence of
chlorine (elemental, organic or inorganic), carbon in some form, oxygen in a gaseous or
bound state, and hydrogen in any form.
Conditions thought to favour PCDD/PCDF formation in industrial-chemical processes
and activities include the following:
d
In this context, the term “homogeneous’ means that all reactants are in the same physical state (gaseous,
liquid or solid), while in “heterogeneous” reactions, reactants differ in their physical states.
e
A precursor is a substance from which another substance is formed, for example, chlorobenzenes and
chlorophenols are precursors of PCDD/PCDF formation in combustion processes. A precursor is
commonly regarded as being somewhat similar in chemical structure to the substance for which it is a
precursor.
f
Macromolecular carbon is carbon that possesses a structure in which all of the carbons are linked by
chemical bonds.
3
x Elevated temperatures (>150 °C),
x Alkaline conditions,
x Metal catalysts,
x UV radiation or other radical starters.
The relative propensities for PCDD/PCDF formation in chemical manufacture have
been reported as follows:11
Chlorophenols < Chlorobenzenes < Aliphatic chlorinated compounds < Inorganic
chlorinated compounds
1.2 Overview of PCDD/PCDF Formation
The first paragraph of Section 3.1 Formation of PCDD/PCDF in the Toolkit is as follows:
“PCDD/PCDF are formed as unintentional by-products in certain processes and
activities, Annex C of the Stockholm Convention provides two lists for several of these.
Besides being formed as unintentional by-products of manufacturing or disposal
processes, PCDD/PCDF may also be introduced into processes as contaminants in raw
materials. Consequently, PCDD/PCDF can occur even where the PCDD/PCDF are not
formed in the process under consideration. PCDD/PCDF formation routes can be
divided into two broad categories: (a) formation in thermal processes and (b) formation
in wet-chemical processes (for further details, see UNEP 2003a).”
This paragraph requires revision so that it captures more thoroughly the salient points of
PCDD/PCDF formation. Potential models for beginning this paragraph include the
following:
x “Under favorable conditions of time and temperature, it is likely that any
combination of C, H, O and Cl can yield some PCDD/F or similar products,” as
presented in Froese and Hutzinger (1996) 12 and attributed to Altwicker (1991) 13 ;
x
“CDD and CDF have no known technical use and are not intentionally produced.
They are formed as unwanted byproducts of certain chemical processes during the
manufacture of chlorinated intermediates and in the combustion of chlorinated
materials,” as proffered by the U.S. Environmental Protection Agency (1997). 14
Also in the first paragraph, PCDD/PCDF sources are categorized as “manufacturing or
disposal processes.” However, these terms may lead some users to assume that
potentially important processes and activities need not be addressed. For example, waste
incinerators with energy recovery are PCDD/PCDF sources but are classified in some
countries as recycling not disposal. Likewise, burning PVC-coated electrical cables is a
source of PCDD/PCDF. However, it may be regarded as recovery rather than disposal. In
yet another example, electrical cable splicing has been identified as a source of
PCDD/PCDF,15 but this can be regarded as use rather than manufacturing or disposal. The
terms used by Fiedler et al. (2000) to describe these two categories -- “industrial-chemical
processes” and “thermal processes” – would seem to be preferable.16
In addition, in the first paragraph “thermal processes” and wet-chemical processes” are
categorized as “PCDD/PCDF formation routes.” However, “formation routes” are most
commonly understood to be the mechanisms for PCDD/PCDF formation while “thermal
processes” and “wet-chemical processes” are two broad categories of potential
PCDD/PCDF sources. Moreover, the term “wet-chemical processes” suggests that only
4
those processes that involve liquid reactants are potential PCDD/PCDF sources although
some PCDD/PCDF-generating processes are gas-phase and/or heterogeneous reactions. A
more useful model in this regard is the World Chlorine Council’s description of
PCDD/PCDF formation in chemical manufacture: 17
“Dioxins can be formed in chemical processes, where the element chlorine is involved.”
1.3 Mechanisms of PCDD/PCDF Formation in Combustion Processes
Paragraph (a) of section 3.1 presents the following explanation of PCDD/PCDF formation
in combustion processes:
(a) PCDD/PCDF are formed in trace quantities in combustion processes via two
primary mechanisms:
1. The so-called de novo synthesis in which PCDD/PCDF are formed from nonextractable carbon (C) structures that are basically dissimilar to the final product
(PCDD/PCDF); and
2. Precursor formation/reactions via aryl structures derived from either incomplete
aromatic oxidation or cyclization of hydrocarbon fragments.
It is well-known that these two mechanisms are among those proposed as primary
mechanisms of PCDD/PCDF formation in large-scale systems, such as municipal waste
incinerators [see, for example, Ryan and Altwicker (2004)18 ]. However, other
mechanisms, including homogeneous gas-phase formation have also been proposed. As
noted by Lemieux et al. (2001, homogeneous gas-phase formation is thought to make a
small contribution to PCDD/PCDF formation in large-scale thermal processes.19 However,
it is plausible that this mechanism is more important in uncontrolled or poorly controlled
combustion. Consequently, at least these three mechanisms should be presented in the
Toolkit. Further, the mechanisms should be described as much as possible in terms that
are perhaps more comprehensible.
Presented below are various explanations of PCDD/PCDF formation, some of which
present useful concepts and phrasings. They also illustrate the diversity of opinion about
the specifics of PCDD/PCDF formation.
x Stanmore, B., 2004. The formation of dioxins in combustion systems. Combustion &
Flame 136: 398-427. 20
“It is now apparent that trace quantities of PCDD/F can be formed under
appropriate conditions in flames when carbon, hydrogen, and chlorine are present.”
x Tuppurainen, K., Halonen, I., Rukokojarvi, P., Tarhanen, J., Ruuskanen, J., 1998.
Formation of PCDDs and PCDFs in municipal waste incineration and its inhibition
mechanisms: A review. Chemosphere 36: 1493-1511. 21
“Combustion of organic matter in the presence of chlorine and metals is widely
recognized as a major source of PCDD/Fs in the environment …PCDD/Fs will also
form in the presence of hydrogen chloride (HCl), which can be converted to Cl2.
…
Three pathways have been proposed so far to explain the formation of PCDD/Fs
during incineration:
(i) pyrosynthesis, i.e. high temperature gas phase formation,
5
(ii) formation from macromolecular carbon (so called residual carbon) and the
organic or inorganic chlorine present in the fly ash matrix at low temperatures, e.g.,
250-350 oC, often referred as the de novo mechanism, and
(iii) through various organic precursors, such as chlorophenols of polychlorinated
diphenyl ethers, which may be formed in the gas phase during incomplete
combustion and combine heterogeneously and catalytically with the fly ash surface.
… These mechanisms vary in their relative importance according to the combustion
conditions, but the following order is usually considered correct: (i) << (ii) < (iii),
although the relative importance of the precursor and de novo mechanisms is still
highly controversial.”
x Lemieux, P., Lee, C., Ryan, J., Lutes, C., 2001. Bench-scale studies on the
simultaneous formation of PCBs and PCDD/Fs from combustion systems. Waste
Management 21: 419-425. 22
“It is generally accepted that three primary mechanisms lead to formation of
PCDD/Fs in combustors: homogeneous gas-phase reactions involving chlorinated
organic precursors such as chlorobenzenes and chlorophenols; heterogeneous
reactions between chlorinated precursor compounds and flyash-based metallic
catalysts such as copper [11,12]; and de novo synthesis involving flyash-bound
carbon, a chlorine (Cl) source, and metallic catalysts [13].
Experimental and theoretical studies have discounted the likelihood of significant
homogeneous formation of PCDD/Fs in most practical combustion systems [14,15];
therefore, the two heterogeneous formation routes are believed to predominate in
these types of combustion systems. It is believed that de novo synthesis occurs on
particles that are being held for times on the order of minutes to hours in particulate
matter (PM) control devices. It is believed that PCDD/F formation from chlorinated
organic precursors occurs in-flight, with gas-phase residence times on the order of 1
s.”
x Matzing, H., 2001. A simple kinetic model of PCDD/F formation by de novo
synthesis. Chemosphere 44: 1497-1503. 23
“Gas-phase, condensed-phase and heterogeneous reactions have been proposed to
explain the formation of PCDD/F. In the order of increasing complexity, these are:
o homogeneous gas-phase reactions of appropriate precursors;
o heterogeneous oxidation of carbon with PCDD/F being formed as byproducts even in the absence of organic precursors (de novo synthesis);
o heterogeneous reactions of gaseous precursors at (particulate) surfaces;
o heterogeneous and/or condensed-phase reactions of particulate precursors;
o heterogeneous and/or condensed-phase reactions of both gaseous and
particulate precursors.”
x Ryan, S., Altwicker, E., 2004. Understanding the role of iron chlorides in the de novo
synthesis of polychlorinated dibenzo-p-dioxins/dibenzofurans. Environ. Sci. Technol.
38: 1708-1717. 24
“The formation of PCDD/F during MSWI has been proposed to occur predominantly
heterogeneously, catalyzed by fly ash. Two types of reactions have been extensively
studied: (i) the formation from chemically similar precursors such as chlorophenols
(3-8) and chlorobenzenes (9-11) and (ii) the formation from particulate carbon in fly
ash involving the chlorination and subsequent oxidation of the macromolecular
6
carbon matrix to release chlorinated organic compounds, including PCDD/F (12).
The latter has been termed the de novo synthesis …”
x Fiedler, H., Hutzinger, O., Welsch-Pausch, K., Schmiedinger, A., 2000. Evaluation of
the Occurrence of PCDD/PCDF and POPs in Wastes and Their Potential to Enter the
Foodchain. Final Report. Study on behalf of the European Commission, DG
Environment. Bayreuth, Germany: University of Bayreuth. 25
“The process by which PCDD/PCDF are formed during incineration are not
completely understood nor agreed upon. Three possibilities have been proposed to
explain the presence of dioxins and furans in incinerator emissions:
1. PCDD/PCDF are already present in the incoming waste … and are incompletely
destroyed or transformed during combustion. …
2. PCDD/PCDF are produced from related chlorinated precursors (= pre-dioxins)
such as PCB, chlorinated phenols and chlorinated benzenes.
3. PCDD/PCDF are formed via de novo synthesis. This is, they are formed from the
pyrolysis of chemically unrelated compounds such as polyvinyl chloride (PVC) or
other chlorocarbons, and/or the burning of non-chlorinated organic matter such as
polystyrene, cellulose, lignin, coal, and particulate carbon in the presence of
chlorine-donors .
From the knowledge gained from MSWIs it can be concluded that PCDD/PCDF can
be formed in other thermal processes in which chlorine-containing substances are
burnt together with carbon and a suitable catalyst (preferably copper) at
temperatures above 300 °C in the presence of excess air or oxygen. Preferentially
dioxin formation takes place in the zone when combustion gases cool down from
about 450 °C to 250 °C (de novo synthesis). Possible sources of the chlorine input
are PVC residues as well as chloroparaffins in waste oils and inorganic chlorine.”
1.4 Carbon Sources for de novo Formation of PCDD/PCDF
Point 1 of paragraph (a) specifically identifies “non-extractable carbon” as the form of
carbon that serves as a carbon source for de novo synthesis. This is inconsistent with the
majority of studies of this subject. Carbon species that have been demonstrated to serve as
carbon sources for de novo formation of PCDD/PCDF are as follows:
x Fly ash-bound carbon: total carbon as well as some of its individual componentsg
including elemental carbon, soluble organic carbon, and non-extractable carbon;
x Activated carbon that is injected or otherwise introduced to post-combustion gas
streams for the purpose of reducing PCDD/PCDF concentrations in flue gases prior
to their release to ambient air; and
x Soot that is formed in the high-temperature zones of incinerators and other
combustion processes.
1.4.1 Fly ash-bound Carbon
g
Total carbon in ash is defined as consisting of carbonate carbon and total organic carbon. Total organic
carbon consists of elemental carbon, water extractable organic carbon, dichloromethane extractable organic
carbon, and non-extractable organic carbon. (See Ferrari, S., Belevi, H., Baccini, P., 2002. Chemical
speciation of carbon in municipal solid waste incinerator residues. Waste Management 22: 303-314).
Studies have shown that that total carbon, elemental carbon, soluble organic carbon and non-extractable
carbon act as carbon sources for PCDD/PCDF formation. No studies were found that directly examined the
potential role of carbonate carbon in de novo synthesis of PCDD/PCDF.
7
The de novo synthesis of PCDD/PCDF is generally defined as PCDD/PCDF formation in
which the carbon source is particulate carbonaceous material in fly ash [see, for example,
Weber et al. (1999)26]. Carbonaceous material in fly ash falls into two categories,
carbonate carbon and total organic carbon with the later consisting of elemental carbon and
organic carbon [see, for example, Rubli et al. (2003)27]. The latter organic carbon is
further sub-divided into water extractable organic carbon, dichloromethane extractable
organic carbon, and non-extractable organic carbon, according to Ferrari et al. (2002). 28
Elemental carbon is well-known as a carbon source for de novo synthesis. In reviewing
research on this topic, Matzing (2001) noted that “PCDD/F formation by de novo synthesis
just requires elemental carbon, gaseous oxygen and particulate chloride mixed together in
a certain, somewhat narrow temperature range.”29 Results of recent work by Fullana et al.
(2003) suggest that both elemental carbon and soluble carbon are primary carbon sources
for de novo formation of PCDD/PCDF formation..30
The Toolkit specifies that “non-extractable carbon” is the only form of carbon that serves
as a carbon source for de novo synthesis. This same specification appears in a report by
UNEP Chemicals (2003)31, a report for the European Commission by Fiedler et al.
(2000),32 and a study by Gullett et al. (2001). 33 However, none of these reports present
data in support of this hypothesis. Gullett et al. (2001) attributed this hypothesis to a study
by Stieglitz and Vogg (1987), 34 but the latter contains no mention of “non-extractable
carbon” or any form of carbon other than the carbon dioxide used as a carrier gas.
Moreover, Stieglitz recently received an international award for his scientific contributions,
including “his concept of the de novo formation of dioxins from elemental carbon.” 35
1.4.2 Activated Carbon
Activated carbon has been shown to be an excellent carbon source for de novo formation
of PCDD/PCDF in laboratory experiments [see, for example, Stieglitz et al. (1989) 36, Ryan
et al. (2000)37, Weber et al. (1999)38]. This is confirmed by studies of full-scale
incinerators in which the injection of activated carbon for the purpose of reducing
PCDD/PCDF releases in stack gases has been accompanied by as much as a 5-fold
increase in total PCDD/PCDF releases (stack gas + fly ash) [see, for example, Chang et al.
(2001)39, Kurata et al. (2000)40, Lanier (1997) 41, Durkee and Eddington (1992)42]. These
findings contradict the generally held belief that fly ash-bound carbon and organic products
of incomplete combustion in furnace gases are the only carbon sources for postcombustion zone PCDD/PCDF formation (see, for example, Konduri and Altwicker
(1994)43 and Schoonenboom and Olie (1995)44.
1.4.3 Soot
Soot that is formed in the flame zone of incinerators and other combustion processes has
also been identified by Sidhu and Fullana (2003) as a carbon source for PCDD/PCDF
formation. 45 Further, Wikstrom et al. (2003) have shown that soot deposits in the postcombustion zone are the main carbon source for PCDD/PCDF under fuel lean conditions.46
As noted by Sidhu and Fullana (2003), these findings, like those with activated carbon,
contradict the commonly held belief that fly ash-bound carbon and organic compounds in
furnace gases are the only carbon sources for post-combustion zone PCDD/PCDF
formation.
1.4.4 Total Carbon
8
Some scientists do not regard the particular form of carbon as a relevant factor in
PCDD/PCDF formation. For example, Olie et al. (1998) concluded, “All types of carbon
can serve as a carbon source.”47 This is supported by Xhrouet et al. (2001) who reported,
“The nature of the carbon source has no influence on the global amounts of PCDF/Fs
formed …” 48 and by Wikstrom et al. (2003) who found that the quantities of
PCDD/PCDF formed via de novo synthesis “appear to be proportional to the total carbon
content in the ash.”49
1.5 Conditions Required for and/or Conducive to PCDD/PCDF Formation in
Thermal Processes
Presented in the second part of paragraph (a) is a list of four conditions related to the
formation of PCDD/PCDF in combustion processes as follows:
Four conditions, present either individually or in combination, favor generation of
PCDD/PCDF in thermal processes:
• High temperature processes (during cool-down of combustion gases in a temperature
range of ca. 200-450 °C) and/or incomplete combustion;
• Organic carbon;
• Chlorine;
• PCDD/PCDF containing products. [emphasis added]
The above description is not scientifically accurate, as can be seen by comparisons to
summaries by Stanmore (2004) 50, Tupperainen et al. (1998) 51 and Fiedler et al. (2000), 52
all of which appear in Section 2 of these comments. For example, Fiedler et al. (2000)
noted, “… PCDD/PCDF can be formed in other thermal processes in which chlorinecontaining substances are burnt together with carbon and a suitable catalyst (preferably
copper) at temperatures above 300 °C in the presence of excess air or oxygen.” While the
summaries by Stanmore (2004), Tupperainen et al. (1998) and Fiedler et al. (2000) are not
identical, all three specify that carbon (or organic matter) and chlorine must be present for
PCDD/PCDF formation to take place. As currently worded, the above excerpt from the
Toolkit specifies that PCDD/PCDF formation can occur if chlorine is present alone or if
carbon is present in alone or if the two are present in combination. Of these three
scenarios, only the last is correct.
1.5.1
Temperatures of PCDD/PCDF Formation
The Toolkit mentions only one temperature range, “ca. 200-450 oC,” for PCDD/PCDF
formation. However, formation of PCDD/PCDF in the combustion zone of incinerators
has been reported to occur in the range of 500-1000 oC . 53, 54, 55 Formation in postcombustion zones, including air pollution control devices, of full-scale incinerators via de
novo or other heterogeneous pathways has been found to occur at temperatures as low as
150 oC. 56 However, the optimum temperature for PCDD/PCDF formation in the postcombustion zone has been reported to range between 650 and 250 ° C, with a maximum at
approximately 300 ° C. 57
1.5.2 Carbon Sources for PCDD/PCDF Formation
The Toolkit specifies that carbon must be present in the form of “organic carbon” if
PCDD/PCDF is to take place. Besides being internally inconsistent with the immediately
preceding contention that “non-extractable carbon” is the carbon source for PCDD/PCDF
formation, this is contrary to a substantial body of scientific evidence. As documented in
9
Section 1.4 of these comments, carbon species that have been demonstrated to serve as
carbon sources for de novo formation of PCDD/PCDF are as follows:
x Fly ash-bound carbon: total carbon as well as some of its individual componentsh
including elemental carbon, soluble organic carbon, and non-extractable carbon;
x Activated carbon that is injected or otherwise introduced to post-combustion gas
streams for the purpose of reducing PCDD/PCDF concentrations in flue gases
released to ambient air; and
x Soot that is formed in the high-temperature zones of incinerators and other
combustion processes.
1.5.3 Chlorine Sources for PCDD/PCDF Formation
The Toolkit does not specify the form or forms of chlorine that can take part in
PCDD/PCDF formation. Many non-scientists will interpret the unmodified term
“chlorine” as referring to elemental chlorine, the form of chlorine with which they may be
most familiar due to its use for water disinfection. To avoid such confusion it is necessary
to specify that sources of chlorine for PCDD/PCDF formation during combustion can
include both organically bound chlorine, such as that in polyvinyl chloride (PVC) and
inorganically bound chlorine, such as that in sodium chloride (NaCl). A similar
specification is made, for example, by Fiedler et al. (2000) 58, which is shown above, and
by Tupperainen et al. (1998) as follows: 59
“Thus the prerequisites for PCDD/F formation can be summarized as being (i) the
presence of organic or inorganic chlorine, (ii) the presence of oxygen, and (iii) the
presence of transition metal cations as catalysts, in particular Cu, which plays a critical
role in the catalytic action of MWI fly ash.”
1.6 PCDD/PCDF Formation in Chemical Manufacturing Processes
Paragraph (b) of Section 3.1 in the Toolkit addresses the issue of PCDD/PCDF formation
in chemical manufacture. However, it is more inclusive to follow the model of Fiedler et
al. (2000) by using the term “industrial-chemical processes.”60 Paragraph (b) also
provides the following summary of PCDD/PCDF formation in chemical manufacture:
“(b) For chemical manufacturing processes, the generation of PCDD and PCDF is
favored if one or several of the conditions below apply:
• High temperatures (>150 °C)
• Alkaline conditions (especially during purification)
• UV radiation or other radical starters.”
Not included in this paragraph is one of the basic prerequisites for PCDD/PCDF formation
in chemical manufacturing, which is described by the World Chlorine Council as follows:
61
h
Total carbon in ash is defined as consisting of carbonate carbon and total organic carbon. Total organic
carbon consists of elemental carbon, water extractable organic carbon, dichloromethane extractable organic
carbon, and non-extractable organic carbon. (See Ferrari, S., Belevi, H., Baccini, P., 2002. Chemical
speciation of carbon in municipal solid waste incinerator residues. Waste Management 22: 303-314).
Studies have shown that that total carbon, elemental carbon, soluble organic carbon and non-extractable
carbon act as carbon sources for PCDD/PCDF formation. No studies were found that directly examined the
potential role of carbonate carbon in de novo synthesis of PCDD/PCDF.
10
The other basic prerequisites for PCDD/PCDF formation in industrial-chemical processes
are the presence of carbon, oxygen and hydrogen. For example, PCDD/PCDF formation
takes place during the manufacture of elemental chlorine when graphite electrodes are
used, as is commonly the case in China.62
USEPA (1997) described the factors that influence PCDD/PCDF formation in the
manufacture of organic chemicals as follows: 63
“A number of factors influence the amount of dioxins and furans that may be formed in
a given manufacturing process, including temperature, pH, catalyst, and reaction
kinetics. …
Four major mechanisms have been postulated for the formation of halogenated
dioxins and furans in the manufacture of halogenated organic chemicals: (1) direct
halogenation of dioxins or furans …); (2) reaction of an ortho halogen with a
phenate…; (3) loss of the halogen (e.g., chlorine or bromine) from a halogenated
phenate to form halogenated furans … ; and (4) reactions between ortho- and metasubstituted halogens ….”
With regard to PCDD/PCDF formation in the manufacture of organic chemicals, Fiedler et
al. (2000) noted as follows: 64
“In wet-chemical processes the propensity to generate PCDD/PCDF during synthesis
of chemical compounds decreases in the following order:
Chlorophenols < Chlorobenzenes < Aliphatic chlorinated compounds < Inorganic
chlorinated compounds”
1.7 Uncontrolled Combustion
The Toolkit’s explanation of PCDD/PCDF formation also includes the following
paragraph:
“Data by Gullett et al. from waste burning experiments under uncontrolled conditions
have shown that the potential to generate PCDD/PCDF does not depend on a single
parameter. High concentrations of PCDD/PCDF have been detected when “normal”
household waste has been burned. The concentrations increased when either the
chlorine content increased (independently of its origin, organic or inorganic), or the
humidity increased, or the load increased, or catalytic metals were present, or in
general: the combustion conditions were bad.”
The information in this paragraph may well be useful in the appropriate context. However,
it is relevant to only one specific source category, uncontrolled burning of household
waste, while Section “3.1 Formation of PCDD/PCDF” addresses PCDD/PCDF formation
in general. Consequently, this paragraph is more appropriately placed in Section 6.6 Main
Category 6 – Uncontrolled Combustion Processes. In addition, the study should be given a
more complete citation. Further the household waste that was burned in this study was not
“normal” household waste but was a collection of materials that were thought to
approximate the general contents of waste generated by a hypothetical household in New
York City, USA.
11
1.8 Further Contents of Toolkit Section 3.1 Formation of PCDD/PCDF
Beginning with the first paragraph on page 12 of the Toolkit through to the end of section
3.1, the text and diagram are not relevant to PCDD/PCDF formation but to other topics.
As such, they should be placed in new or existing sections or sub-sections of the Toolkit.
2.0 Strategy for Identifying PCDD/PCDF Sources
To identify their sources of PCDD/PCDF, Parties require not only a list of all sources that
have been identified thus far but also a strategy for identifying PCDD/PCDF sources that
are not yet identified. The need for such a strategy in the Toolkit was acknowledged at the
Seventh Session of the Intergovernmental Negotiating Committee as follows:65
"Many representatives believed that the Toolkit should also contain guidance
on other chemicals in Annex C, wherever such information and experience were
available, as well as a strategy for identifying sources of dioxins and
furans.”
Many PCDD/PCDF sources have been identified in national and regional inventories, other
government reports, industry reports, and the scientific literature. While the Toolkit lists
many of these sources, it does not list all of them. As noted earlier, the Toolkit lists a
relatively small number of chemical manufacturing processes as potential PCDD/PCDF
sources even though the processes for manufacturing a hundred or more chemicals have
been so identified. Further examples include the manufacture of rubber,66 caprolactam,67i
titanium dioxide,68 and various metal chlorides,69 all of which are potentially important
PCDD/PCDF sources that have been identified but are not listed in the Toolkit.
Meanwhile, new PCDD/PCDF sources are still being discovered. In other words, the
Toolkit’s list of sources is not a complete “check list” of all PCDD/PCDF sources and such
a list is unlikely to be compiled in the near future.
Sources that remain unidentified will not be included in PCDD/PCDF source inventories or
in national or regional action plans. Financial assistance for implementing the Stockholm
Convention is available for addressing only those sources that are included in action plans.
As a consequence, dioxin sources that remain unidentified represent, in effect, potential
losses of economic assistance for Parties and their public and industrial sectors. This loss
of economic assistance is, at the same time, exacerbated by the economic losses associated
with the impacts of unabated PCDD/PCDF releases on public health and the environment.
A PCDD/PCDF source identification strategy is simple. For example, in preparing their
inventory, Denmark identified candidate sources of PCDD/PCDF in the industrialchemical sector by tracking the use of chlorine and chlorine-containing chemicals.
Industries that used chlorine in some form were given closer consideration as potential
PCDD/PCDF sources while those with no chlorine use were screened out [see Hanson and
Hanson (2003)70]. As acknowledged by the World Chlorine Council (1998), the presence
of chlorine is a distinguishing characteristic of chemical manufacturing processes and
activities that are potential sources of PCDD/PCDF,71
i
Caprolactam is an intermediate in the manufacture of nylon.
12
A slightly more detailed strategy for thermal processes and activities is alluded to in the
European Union’s inventory: “The thermal processes which involves carbon and chlorine
containing materials and oxygen is suspected in general to be capable of producing
dioxins and furans …” 72
In summary, the PCDD/PCDF source identification strategy for primaryj PCDD/PCDF
sources is as follows:
All industrial-chemical processes and activities involving any form of chlorine and
all thermal processes and activities involving any forms of chlorine, carbon and
oxygen are considered as potential PCDD/PCDF sources until proven otherwise.
Processes and activities in which chlorine is not present can be dismissed from
further consideration.
This source identification strategy is neither difficult nor costly. In addition, this same
strategy can be followed in evaluating proposals for industrial development and expansion,
waste management projects, etc. for their potential as PCDD/PCDF sources.
Primary PCDD/PCDF sources fall into three general classes:
1. Processes and activities in which chlorine or chlorine-containing materials are
essential, as is the case in certain industrial-chemical processes. Most often,
PCDD/PCDF are concentrated in production wastes so that the wastes and/or the
gaseous, liquid and solid residues from their treatment are the main routes of
PCDD/PCDF release to the environment. PCDD/PCDF are also released in some
products and materials (e.g., some organochlorine pesticides, such as 2,4-D and
pentachlorophenol).
2. Processes and activities in which chlorine or chlorine-containing materials are used for
specific purposes that can be fulfilled by a non-chlorinated material (e.g., the use of
elemental chlorine or chlorine dioxide for bleaching wood pulp); and
3. Processes and activities in which chlorine or chlorine-containing materials have no
purpose but are only incidentally present, e.g., the burning of wastes that contain
discarded goods made of polyvinyl chloride (PVC); metallurgical processes involving
the recycling of discarded metal products that are, for example, PVC-clad; power
generation in which municipal wastes that contain PVC- and other chlorine-containing
materials are co-combusted; accidental fires involving vehicles with PVC plastic parts
or homes that have pipes and appliances made of PVC; etc.
Secondary PCDD/PCDF sources include sites where primary PCDD/PCDF sources once
operated or are still operating as well as sites where liquid and solid wastes and/or offspecification, discarded or obsolete products from primary sources were discharged,
dumped, stored, landfilled or otherwise deposited or accumulated. Such sites may also be
called reservoirs or “hot spots.”
j
Primary PCDD/PCDF sources are processes and activities that actually generate dioxins, as opposed to
secondary sources, which serve as potential points of release for PCDD/PCDF that were generated by
primary sources.
13
.
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Lemieux, P., Lee, C., Ryan, J., Lutes, C., 2001. Bench-scale studies on the simultaneous formation of
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Rubli, S., Belevi, H., Baccini, P., 2003. Optimizing municipal solid waste combustion through organic and
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Ferrari, S., Belevi, H., Baccini, P., 2002. Chemical speciation of carbon in municipal solid waste
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29
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1497-1503
30
Fullana, A., Nakka, H., Sidhu, S., 2003. Carbon chlorination in de novo formation mechanism.
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31
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38
Weber, R., Buekens, A., Segers, P., Rivet, F., Stieglitz, L., 1999. Dioxins from the sintering process. (IV)
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39
40
Kurata, M., Sato, M., Baba, F., Takasuga, T., Kokado, M., 2000. Relation between behavior of pcdd/F and
physical properties of carbonaceous matter in bag filter. Organohalogen Cpds. 45: 364-367
41
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42
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Chemical, Mixed and Medical Wastes. Albuquerque, New Mexico, 11-14 May 1992.
43
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44
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chloroanthracene in a model fly ash system. Environmental Science and Technology 33: 2005-2009.
45
Sidhu, S., Fullana, A., 2003. Impact of soot concentration on PCDD/F emissions. Organohalogen Cpds.
63: 13-17.
46
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47
Olie, K., Addink, R., Schoonenboom, M., 1998. Metals as catalysts during the formation and
decomposition of chlorinated dioxins and furans in incineration processes. J. Air & Waste Manage. Assoc.
48: 101-105.
48
Xhrouet, C., Dohmen, C., Pirard, C., De Pauw, E., 2001. PCDD/Fs and sintering process: Possible
influence of the coke morphology. Presented at Dioxin 2001 -- 21st International Symposium on
Halogenated Environmental Organic Pollutants & POPs, Kyoung ju, Korea, Sept. 9- 14, 2001.
49
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polychlorinated dibenzo-p-dioxins and dibenzofurans. Environ. Sci. Technol. 37: 1962-1970
50
51
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52
15
53
54
Zimmermann, R., Blumenstock, M., Heger, H., Schramm, K.-W., Kettrup, A., 2001. Emission of
nonchlorinated and chlorinated aromatics in the flue gas of incineration plants during and after transient
disturbances of combustion conditions: Delayed emission effects. Environ. Sci. Technol. 35: 1019-1030.
55
56
57
1493-1511.
58
59
1493-1511.
60
61
62
Xu, Y., Zhang, Q., Wu, W., Li, W., 2000. Patterns and levels of PCDD/F in a Chinese graphite electrode
sludge. Chinese Science Bulletin 45: 1471- 1475.
63
U.S. Environmental Protection Agency, 1997. Locating and Estimating Air Emissions from Sources of
Dioxins and Furans. EPA 454/R-97-003. Research Triangle Park, NC: U.S. Environmental Protection
Agency.
64
65
UNEP, 2003. Report of the Intergovernmental Negotiating Committee for an International legally Binding
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Seventh Session. UNEP/POPS/INC.7/28, paragraph 68. Geneva, 14-18 July 2003.
66
Lexen, K., de Wit, C., Jansson, B., Kjeller, L-O., Kulp, S.E., Ljung, K., Soderstorm, G., Rappe, C., 1993.
Polychlorinated dibenzo-p-dioxin and dibenzofuran levels and patterns in samples from different Swedish
industries analyzed within the Swedish Dioxin Survey. Chemosphere 27: 163-170.
67
Kawamoto, K., 2002. New sources of dioxins in industrial processes and their influences on water quality.
Organohalogen Cpds. 56: 229-232.
68
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the Inorganic Chemical Listing Determination. U.S. Environmental Protection Agency, Washington, D.C.
69
U.S. Environmental Protection Agency, 2000. "Exposure and Human Health Reassessment of 2,3,7,8Tetrachlorodibenzo-p-Dioxin (TCDD) and Related Compounds. Part I: Estimating Exposure to Dioxin-Like
Compounds, Volume 2: Sources of Dioxin- Like Compounds in the United States," and in "Part III:
Integrated Summary and Risk Characterization for 2,3,7,8-Tetrachlorodibenzo-p-Dioxin (TCDD) and
Related Compounds": Final Draft. EPA/600/P- 00/001Bb, September 2000.
70
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203. Miljoprojekt. Copenhagen: Danish Environmental Protection Agency, page 37.
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Wenborn, M., King, K., Buckley-Golder, D., Gascon, J., 1999. Releases of Dioxins and Furans to Land
and Water in Europe. Final Report. Report produced for Landesumwaltamt Nordrhein-Westfalen, Germany
on behalf of European Commission DG Environment. September 1999.
16
22
23
24
25
Ref: 12/12//7/2/1/4 Enquiries: M Manzini
Tel: (012) 310 3448 Fax: (012) 320 0024 E-mail: Mgaseitsiwe@deat.gov.za
Mr James B Willis
Director: UNEP Chemicals
11-13 chemin des Anemones
CH-1219 Chatelaine
GENEVA
SWITZERLAND
Fax: 09 4122 917 3460
Dear Mr Willis
SOUTH AFRICA’S COMMENTS ON THE STANDARDIZED TOOLKIT FOR IDENTIFICATION
AND QUANTIFICATION OF DIOXIN AND FURAN RELEASES - 1ST EDITION (MAY 2003)
The Standardized Toolkit guidance document provides a good starting point for inventory
compilation, but there are a couple of concerns that relate to the application of this toolkit to
developing countries.
This guidance document, although comprehensive and ambitious, does not address all the
major release conditions related to developing countries. It is furthermore not a legal document
that will convince managers to take costly interventions to reduce or eliminate production of
PCDD/PCDFs, especially if terminology, such as "potential", "estimations", "best judgement",
"extrapolation" and "approximation" occurs throughout. In the absence of real measurements,
no authority can be applied to convince managers to conform to regulations or policy.
Dioxin-like PCBs are not included in this toolkit. No approximations are provided, and the
possibility exists that additional effort needs to be taken to complete this part of the POPs
spectrum.
As a major aspect of the Toolkit information gathering needs to be done on processes (Step 3).
Much of the information sources, such as labour and tax statistics, economic activity records
and especially historic data, will, if available at all, be highly fragmented and probably in an
unsuitable format. All sources need to be identified, and characterised, which will place a
significant additional burden on developing countries.
Although the documents states that all major sources can be quantified, major assumptions are
apparent, and it is not clear how this relates to real situations in developing countries. The
document clearly states that estimates of release all reflect processes and emission factors that
were all derived from developed countries, and that little is known about conditions, processes,
locally produced equipment and feedstock composition in developing countries. For this 1st
edition to become more useful for developing countries as an assessment tool, additional work
needs to be done. Some of the shortcomings and suggested additions are presented below:
1.
It would probably be useful that, instead of only providing a mean estimate of release
per class, the low, mean and maximum be provided in the table and spreadsheet. This
will allow ranges or releases (best and worst case scenarios) to be included in the
inventory.
2.
Section 6.1.1.5 reads a bit confusing and could be clarified.
3.
Section 6.1.2 states that no data could be obtained for the older technologies dealing
with hazardous waste incineration. Since these technologies will tend to be
predominant in developing countries, additional information on conversion rates will be
very useful in compiling inventories, as well as in planning, motivating and prioritising
interventions. The info given in Table 17 only refers to rotary kilns. No info is available
for bottom ash of any of the technologies, and this therefore constitutes a major data
gap, that could be important to developing countries, since much of this ash could be
discarded in uncontrolled areas or dumps, where further contamination and exposure
can result.
4.
An index of materials, products, activities, processes, classes and other information
should be provided at the end, as it is sometimes difficult to locate the correct class or
Table. It is inevitable that some of the categories read a bit cryptic, due to the nature of
this effort. Three examples: construction debris combustion is included under 6.1.6
(Waste wood and waste biomass incineration), and rubber tyre burning are considered
under open waste burning under 6.6.1 (Waste burning and accidental fires), while
charcoal production is addressed under 6.2.2.
5.
The emission factors of animal carcass destruction are only provided for furnace types
(6.1.7). Many instances occur however, of burning of heaps of carcasses in open land,
due to the lack of furnace capacity in developing countries, and the seemingly
increase in incidences of animal diseases that need to be controlled. This class should
be included.
6.
The emission factors for charcoal should be determined (6.2.2). Much is being
produced in African countries, and taken together with the high chlorine content of our
vegetation, it could be a significant source.
7.
Since South Africa is a major platinum producer, the emission factors for this metal
should be determined as a matter of priority (6.2.10). The location of the mines (close
to major populated areas and major conservation areas), as well as the volumes
produced, require the need for better estimates, especially if a good SA inventory is
required.
8.
The open burning to reclaim wires might be a significant factor in SA, due to the high
incidence of cable theft (6.2.12). Although the air EF is known, and one estimate is
available for the soil, no data is available for the residues, which might be significant,
as the toolkit suggests. This lack of data should be addressed as a matter of urgency,
given the high level of potential human exposure.
9.
Given the preponderance of coal fired power stations and the scarcity of water in SA,
the EF for water from this source needs to be determined, if wet scrubbers are used
(6.2.1).
10.
South Africa is one of the major producers of sugar from sugarcane. Sugarcane is
usually burnt in situ before harvesting; the extent of dioxin and furan releases has not
been quantified. If some sugarcane mills in South Africa use sugarcane waste to
produce heat and electricity (6.3.2), then the EF for the ash needs to be determined,
since it is likely that SA vegetation has a higher than normal Cl content.
11.
Given that the EF for section 6.3.4 was derived for developing country situations, and
the high dependency of indoor cooking and heat from biomass burning in most parts of
Africa, more appropriate EFs (relevant to biomass that is used here) should be
generated. Millions of people are exposed to the air vector, and the unknown land
vector needs more data, since cooking and heat fires are often on the ground, even
sometimes within dwellings. The disposal of the ash, sometimes close to dwellings
(and therefore a potential source of exposure through contact and breathing the dust,
needs also further investigations. It would be useful to derive an EF per household, so
that estimates, based on census data, can be applied.
12.
Fossil fuels (coal and paraffin) are also used in large quantities in SA by millions of
people, and the EFs for use under our conditions should be determined (6.3.5). The
use conditions are likely to be indoors in many kinds of dwellings, and could expose
children and other sectors of the community to a great extend. Coal ash could have
very high EFs, and the real situation for South Africa should be determined. It would be
useful to derive an EF per household, so that estimates, based on census data, can be
applied.
13.
Brick producing industry in South Africa use both tunnel type kilns (6.4.3) as well as a
popular method known as clamp kilns, where bricks are baked in a coal-fired open
system where control of emissions cannot be effected, all emissions are released into
the air. This system is also energy inefficient as most of the heat is lost to the
environment. The extent of dioxins and furans emissions should be investigated.
14.
Although a 10-fold difference in Cl content in straw did not affect the EFs (6.6.1), the
data from Japan suggests that different vegetation types do affect EFs. The relatively
high Cl content in South Africa’s vegetation needs therefore to be investigated, to
derive a better SA inventory.
15.
Burning of waste (6.6.2) is a serious and largely common practice in South Africa, the
extent of which has never been quantified. Before locally applicable EFs can be
generated, the conditions and compositions should be better understood, before the
present EFs can be assessed. There will in all likelihood however, be a need for new
EFs to be determined, especially if the waste combustion situation in Africa is taken
into account.
16.
Although tyre burning has been referred to (to be treated under 6.1.6), no EFs are
known for the combustion of this product. The large piles of disused tyres, as well as
the large amount of second hand tyres imported into Africa, means that the stacks of
tyres could well be a major source, either through accidental or deliberate burning (to
reclaim the metal), or possibly through leaching from the stacks. EFs therefore need to
be generated for this particular case. (There is an effort currently of using waste tyres
for fuel in cement kilns, which is still under investigation).
17.
Residues from explosives are not covered by this toolkit. If known this should be
included, as explosives are used in huge quantities in underground and opencast
mining in South Africa, and elsewhere.
If you have any questions or would like further information, please contact Ms Thembisile
Kumalo by phone at +2712 310-3567, by fax at +2712 320-0024 or e-mail:
tkumalo@deat.gov.za
We hope that these comments will add value and will assist in putting together a Toolkit that
will benefit its users.
Yours sincerely
Dr. Godfrey Mvuma
DIRECTOR: CHEMICALS & HAZARDOUS WASTE MANAGEMENT
DATE:
26
RESUMEN DESCRIPTIVO DE LAS TECNOLOGÍAS Y OPERACIÓN
DE LAS FUNDICIONES PRIMARIAS DE CONCENTRADOS DE
COBRE DE CHILE
Documento Técnico elaborado por la Comisión Chilena del Cobre
en base a la información entregada por las fundiciones chilenas
ABRIL 2004
LAS FUNDICIONES PRIMARIAS DE CONCENTRADOS DE COBRE
EN CHILE
Conceptualmente, una fundición primaria de concentrados de cobre es
aquella cuya alimentación está constituida exclusivamente por concentrados
de cobre, oro y/o plata provenientes de una planta de beneficio de minerales.
Los materiales circulantes (carga fría, ripios, rechazos) y el scrap de ánodos
y rechazo de cátodos provenientes de las refinerías electrolíticas integradas,
constituyen materiales de recirculación interna del complejo de fundiciónrefinería. La única vía externa de ingreso de cobre al proceso es el contenido
en los concentrados.
En Chile, a la fecha, ninguna de las 7 fundiciones primarias de concentrados
de cobre procesa materiales reciclados.
ETAPA DE FUSION
Fundamentos Pirometalúrgicos
El proceso consiste en la fusión de concentrados a temperaturas del orden de 1.150 1.250 °C para producir dos fases líquidas inmiscibles: escoria (óxido) y eje o mata rica en
cobre (sulfuro). El producto principal del proceso de fusión es un eje o mata de Cu2S-FeS
(50-70% Cu), que pasa al proceso de conversión para la producción de cobre blister. La
escoria de fusión se envía a un etapa de limpieza para recuperar la mayor parte del cobre
que contiene.
Además del concentrado y los fundentes, en los hornos a veces se cargan otros
materiales de recirculación tales como:
- Carga fría, que es una mezcla de materiales provenientes del enfriamiento del
material líquido circulante en la fundición;
- Ripios, material recirculado desde la planta de tratamiento de polvos de la
fundición, el que se mezcla con el concentrado;
- Líquidos internos recirculados, metal de los hornos de limpieza de escorias,
escorias de conversión y de las etapas de refinado.
- Cobre rechazado.
Fisico-química de la fusión
Los principales constituyentes de una carga de fusión son los sulfuros y óxidos de hierro y
cobre. La carga también contiene óxidos, tales como Al2O3, CaO, MgO y principalmente
SiO2, que puede estar presente en el concentrado original, pero que también se agrega
como fundente.
Es el hierro, cobre, azufre, oxígeno y sus óxidos lo que controla mayoritariamente la
química y constitución física del sistema eje-escoria. Otra influencia importante es el
potencial de oxidación/reducción de los gases usados para calentar y fundir la carga.
El primer propósito de la fusión es asegurar la sulfurización de todo el cobre presente en
la carga, para que así entre a la fase eje o mata. Esto se asegura por la presencia de FeS
en el eje, el que tiende a sulfurizar virtualmente todo el cobre no sulfurizado de la carga
por las reacciones del tipo:
FeS(l) +
Cu2O(l, escoria)
l
FeO(l, escoria)
+
Cu2S(l)
Descomposiciones Piríticas
Todas estas reacciones dan como resultado la aparición de sulfuro de cobre (Cu2S),
sulfuro de fierro (FeS), y azufre pirítico (S2). Por lo tanto la carga, independiente de su
composición química y mineralógica, puede considerarse formada por cuatro
componentes principales: Cu2S, FeS, S2 pirítico y ganga que pasa a la escoria.
Fusiones y Disoluciones
A la temperatura de trabajo de los hornos de fusión (1.250 °C) el S2 pirítico generado se
encuentra en estado vapor y, por lo tanto, pasa a la fase gaseosa.
El proceso de formación de las dos fases líquidas (eje o mata y escoria) comienza con la
fusión y disolución del FeS y el Cu2S (digestión) en el baño líquido. El eje o mata que se
encuentra en el interior del horno es una solución homogénea formada por dos
componentes Cu2S y FeS, los cuales por tener el mismo tipo de unión química (enlace
covalente), son mutuamente solubles (no se separan en dos fases líquidas diferentes).
Por lo tanto, el eje, es decir la mezcla Cu2S – FeS, siempre darán origen a una sola fase
líquida, cualquiera sea el contenido o ley de cobre.
En tanto, la escoria comienza a formarse por la reacción entre fundentes y los óxidos
generados por el soplado.
Procesos Químicos Principales
Las principales reacciones de oxidación que ocurren a consecuencia del soplado del baño
fundido son las siguientes:
Oxidación del Azufre:
Oxidación del FeS:
S2 + 2O2
2FeS + 3O2
Æ
Æ
2 SO2
2FeO + 2SO2
El oxígeno inyectado oxida el azufre pirítico y el FeS mientras que el calor generado por
estas oxidaciones funde una nueva carga.
Los hornos de fusión utilizados por las fundiciones chilenas de concentrados de cobre son
los siguientes:
1.- Convertidor Teniente (CT)
La tecnología del Convertidor Teniente ha sido aplicada exitosamente en Chile, donde fue
desarrollada, desde 1977.
El proceso de fusión conversión en el Convertidor Teniente está basado en los fenómenos
físico-químicos de inmiscibilidad en fase líquida.
El objetivo del proceso es producir Metal Blanco con un contenido de cobre entre 74 y
76%. Las reacciones de oxidación en el proceso de fusión-conversión se regulan
mediante la razón másica de la carga alimentada y el flujo de oxígeno inyectado al CT. El
calor generado en el CT se debe a las reacciones de oxidación que ocurren en él y su
velocidad de generación depende del flujo de oxígeno y de la ley del metal blanco. El
balance de calor se ajusta mediante la adición de los circulantes fríos generados en el
proceso de fundición, por el grado de enriquecimiento del aire de soplado y por el uso del
quemador sumergido.
La fusión-conversión en el CT se produce a temperaturas cercanas a los 1.240 ºC
mediante la inyección a presión de aire enriquecido al 35 – 36% en oxígeno. El CT
dispone de toberas de aire – oxígeno repartidas en varios paños y una tobera adicional de
inyección de concentrados, por cada paño.
El soplado continuo del baño fundido a través de las toberas, mediante la mezcla gaseosa
formada por aire comprimido de baja presión y oxígeno industrial, permite la agitación del
baño fundido y la oxidación parcial del sulfuro de hierro y del azufre contenido en la carga.
De acuerdo a las condiciones nominales de operación, el concentrado seco es inyectado
continuamente al baño fundido mediante toberas especiales. A través del garr-gun se
alimenta el fundente o sílice y el material circulante. Eventualmente pudiera ser necesario
alimentar concentrado húmedo a través del garr-gun, para propósitos de control
operacional y ajuste de la temperatura del proceso.
En el Convertidor Teniente se generan tres flujos de materiales:
a)
Metal Blanco líquido, con 74 - 76% de cobre (1.220 ºC);
b)
Escoria líquida, con 8% de cobre (1.240 ºC); y
c)
Gases, con un 25% de SO2 (1.260 ºC).
El metal blanco producido en el CT, que contiene como promedio 75% Cu; 3% Fe y 21%
S, se extrae a una temperatura de 1.220 ºC de manera intermitente mediante tazas, a
través del pasaje de sangría respectivo, refrigerado por agua. Las tazas de Metal Blanco
se transportan mediante puentes grúa a los convertidores Peirce-Smith, donde continúa el
proceso de producción con la etapa de conversión.
La escoria, que está formada por óxidos, fayalita, magnetita, sílice libre y componentes de
la ganga, tiene un contenido promedio de 8% Cu; 37,5% Fe total; 28% SiO2 y 18% Fe3O4.
La escoria se extrae a 1.240 ºC por sangrado intermitente, por un pasaje de sangría,
refrigerado por agua, ubicado en la culata hacia la zona de la boca del CT, la cual fluye
hasta una taza que es trasladada a los Hornos de Limpieza de Escoria (HLE), donde se
procesa para recuperar el cobre atrapado.
La composición química de la escoria fayalítica formada en el proceso de fusiónconversión se controla con la adición de fundente silíceo al baño a través del garr-gun
localizado en el extremo superior de la culata, hacia el sector de sangría de Metal Blanco.
Los gases de proceso del reactor, que contienen principalmente anhídrido sulfuroso (25 %
SO2 en volumen, medidos en la boca), se extraen en forma continua a través de la boca
del CT a una temperatura promedio de 1.260 ºC. Estos gases junto con el polvo
arrastrado, se colectan por medio de una campana refrigerada por agua y se envían al
circuito de enfriamiento y manejo de gases y polvos, para ser tratados finalmente en la
Planta de Acido.
Esquema General del Convertidor Teniente
En este corte del CT se aprecia en el fondo el metal blanco. En la zona de soplado, con
mucha agitación, una mezcla mecánica de las dos fases presentes, en tanto que en la
zona de más calma (a la derecha del reactor) la escoria se estratifica en la parte superior,
lo que permite retirarla por el pasaje de sangría de escoria. La sangría del metal blanco,
ubicada a la izquierda del convertidor, permite extraer este producto más denso de la
parte baja del reactor.
Generación de Gases en el proceso de fusión
En el proceso de fusión-conversión por digestión en el baño la fase gaseosa que emite el
reactor es captada por la campana del CT y conducida a la planta de limpieza de gases,
donde se trata para fijar el azufre contenido como ácido sulfúrico. Estas emisiones están
compuestas por:
x
x
x
x
x
Gases y Vapores: entre los que comúnmente se encuentran los siguientes
Nitrógeno: que proveniente principalmente del aire inyectado por toberas y del
aire infiltrado;
Oxígeno: inyectado por toberas y que no alcanzó a reaccionar en el baño,
además del proveniente del aire infiltrado;
Anhídrido Sulfuroso: proveniente de la oxidación del azufre pirítico y de la
oxidación del FeS;
Vapor de agua: proveniente de la evaporación del agua de la carga y de la
quema de combustibles derivados del petróleo;
CO2 y CO: en aquellos casos en que hay quema de un combustible fósil.
-
Humos y Material Particulado: son líquidos o sólidos finamente divididos que
tienden a aglomerarse. Las partículas más grandes sedimentan y caen
rápidamente en los ductos, mientras que las de tamaño mediano se depositan más
lejos y las más pequeñas permanecen suspendidas y son transportadas por los
gases, comportándose como tales.
-
Material Particulado Propiamente Tal: Corresponde a arrastre de material sólido o
líquido desde el reactor, en especial cuando se carga por garr-gun, o proyecciones
de líquido debido a la agitación del baño. También se forma material particulado a
partir del material sublimado desde el interior del reactor y que por efecto del
descenso de la temperatura se solidifica en los ductos, alcanzando tamaños
superiores a 0,01 micrón.
2.- Horno Flash Outokumpu
Los hornos Flash utilizan el calor generado por la oxidación de parte de la carga de
sulfuros para aportar gran parte o el total de la energía requerida para la fusión. Los
hornos Flash son excelentes desde el punto de vista ambiental porque producen gases
ricos en SO2, desde los cuales el anhídrido sulfuroso puede recuperarse eficientemente
como ácido sulfúrico. El producto principal de la fusión en horno Flash es un eje o mata
rico en cobre (45 – 50% Cu).
La fusión Flash consiste en el soplado de concentrados secos junto con aire enriquecido
con oxígeno en el corazón caliente del horno. Una vez en el horno, las partículas de
sulfuro reaccionan rápidamente con los gases oxidantes, produciéndose una oxidación
parcial controlada de los concentrados y una gran generación de calor. La combustión de
las partículas de sulfuro es extremadamente rápida y el calor producido por las reacciones
de oxidación es suficiente para fundir los minerales parcialmente oxidados. Las gotas
fundidas caen a la capa de escoria, donde se completan las reacciones de formación del
eje y la escoria y donde todo el cobre oxidado se reduce nuevamente a Cu2S.
Cu2O +
FeS
l
Cu2S (Eje)
+ FeO (Escoria)
Las gotas de eje resultantes decantan a través de la escoria para formar la capa de eje o
mata.
El proceso Flash Outokumpu, que usa aire precalentado enriquecido con oxígeno, no es
autógeno, por lo que se utilizan combustibles para cubrir el déficit térmico. Para permitir
un flujo ininterrumpido de partículas a través de los quemadores el proceso trata
concentrados secos. El producto gaseoso de las reacciones de oxidación de los sulfuros
es SO2 y los gases efluentes tienen concentraciones de 10 – 15%.
El reactor Flash Outokumpu consta de tres partes principales: la Torre de Reacción
(Reaction Shaft), el Sedimentador (Settler) y la Torre de Salida de Gases (Uptake Shaft).
El gas oxidante, que es aire enriquecido con oxígeno (65 – 85%), se precalienta a 450 –
1.000 °C. Los quemadores de concentrado están ubicados en la parte superior de la Torre
de Combustión, en uno de los extremos del horno, y los concentrados, fundentes y gases
se soplan simultáneamente hacia abajo de la torre sobre la superficie de la escoria. Los
quemadores de petróleo también están ubicados en la parte superior de la torre de
reacción. Los gases efluentes abandonan el horno a través de la Torre de Salida de
Gases que se encuentra ubicada en el extremo opuesto del horno.
La configuración del quemador en sentido vertical hacia abajo tiene por finalidad provocar
el impacto de las partículas de concentrado sobre la superficie de la escoria. Esto
aumenta la tendencia de las partículas de concentrado a adherirse a la superficie de la
escoria, y minimiza las pérdidas de concentrado (polvo) a través de los gases de proceso.
El eje y la escoria se descargan en forma intermitente del sedimentador a través de
canaletas de sangría. La temperatura del eje es del orden de 1.260 °C y los gases de
salida alcanzan temperaturas de 1.300-1.350 °C.
3.- Reactor Noranda
El proceso de fusión Noranda es un proceso de fusión continua de cobre, diseñado para
tratar en forma muy eficiente concentrado de cobre y materiales de reciclables que
contengan el metal. El proceso involucra la producción de un eje con alto contenido de
cobre en un equipo cilíndrico recubierto de refractarios. Es importante destacar que, a
diferencia de las fundiciones de Noranda en Canadá, hasta la fecha, en Chile el reactor se
opera sólo con concentrados de cobre y los circulantes (carga fría) necesarios para el
equilibrio térmico del proceso.
El reactor continuo Noranda conceptualmente es muy similar al Convertidor Teniente. El
concentrado seco se alimenta en forma lateral a través de las toberas de inyección y los
fundentes, circulantes y concentrado húmedo se introducen por la parte superior del
horno. Al igual que en el caso del convertidor Teniente, el calor necesario para el proceso
lo genera la oxidación del azufre y del fierro, suplementado si el balance calórico así lo
requiere, por quemadores de gas natural o diesel y oxígeno. El aire enriquecido con
oxígeno se sopla en el metal fundido usando toberas sumergidas.
En el reactor continuo se produce la fusión de la carga alimentada generando un baño
líquido a una temperatura comprendida entre 1.200 y 1.280 °C. Durante el proceso se
separan las dos fases líquidas: escoria en la parte superior y metal blanco en la inferior.
La escoria se sangra periódicamente por el extremo opuesto a la carga del horno. El
metal blanco extraído del reactor continuo se vacía a ollas y se traslada a los
convertidores Peirce-Smith. Los gases metalúrgicos salen del reactor a una temperatura
de 1.280 °C.
ETAPA DE CONVERSIÓN
Convertidor Peirce-Smith (CPS)
El Metal Blanco o Eje proveniente de los hornos de fusión contiene como principales
componentes cobre, hierro y azufre, así como más de 3% de oxígeno disuelto. Además,
contiene cantidades menores de impurezas metálicas, tales como arsénico, bismuto,
níquel, plomo, zinc y metales preciosos, provenientes del concentrado fresco y que se
eliminaron durante la etapa de fusión. Este Eje o Metal Blanco se carga fundido (1.100 °C)
a los convertidores para obtener “cobre Blister”.
El propósito de la etapa de conversión es eliminar el hierro, el azufre y las otras
impurezas, produciendo así cobre metálico líquido en la forma de cobre Blister (98,5 –
99,5% Cu). Esto se logra oxidando con aire enriquecido con oxígeno el eje fundido a alta
temperatura (1.150 – 1.250 °C), utilizando sílice como fundente. Esta eliminación se
desarrolla en dos etapas sucesivas, conocidas como “soplado a escoria” y “soplado a
cobre”. Las reacciones que se producen son espontáneas y fuertemente exotérmicas,
suministrando el calor necesario para el desarrollo del proceso, lo cual lo convierte en un
proceso autógeno.
En Chile, y en la mayor parte del mundo, el proceso de conversión se realiza en
convertidores Peirce-Smith. El metal blanco o eje fundido se carga en el convertidor por
una gran abertura o “boca” y el aire enriquecido con oxígeno se sopla en el eje a través de
toberas ubicadas a lo largo del reactor.
El convertidor está provisto de un mecanismo de rotación que permite posicionarlo
correctamente para cargar, soplar y vaciar. Esta capacidad de rotación permite también
levantar las toberas desde los líquidos en el caso que falle el ventilador, o bien sumergir
las toberas en los líquidos a la profundidad deseada. Esto último permite al operador,
durante la etapa de “soplado a cobre” dirigir el aire al metal blanco (Cu2S) más que al
cobre blister. Las toberas normalmente están sumergidas 20 a 30 cms. en el eje.
Los productos de la etapa de conversión son:
- cobre blister (99% Cu), que pasa a la siguiente etapa de refinación;
- escoria de convertidor, que se envía a tratamiento para recuperar el cobre
remanente (3 – 5%); y
- anhídrido sulfuroso gaseoso.
Etapas del Proceso de Conversión
La conversión ocurre en dos etapas sucesivas química y físicamente distintas, aunque
ambas involucran el soplado de aire en la fase fundida:
a)
El “soplado a escoria”, en que el FeS se oxida a FeO, Fe3O4 y SO2 gaseoso.
Los puntos de fusión del FeO y el Fe3O4 son 1.385 °C y 1.597 °C
respectivamente, y en esta etapa se agrega sílice como fundente para que se
combine con el FeO y parte del Fe3O4 formando así la escoria líquida. La etapa
de formación de escoria finaliza cuando se ha oxidado casi completamente el
FeS en el eje o mata, es decir cuando contiene menos de 1% de FeS. La
escoria líquida (2FeO*SiO2), saturada con magnetita, se vacía varias veces
durante esta etapa. El principal producto de esta etapa es “metal blanco”, Cu2S
líquido impuro.
b)
El “soplado a cobre”, en que el azufre remanente se oxida a SO2. El cobre no
es oxidado por el aire hasta que está casi exento de azufre, por lo que el
producto de la conversión que es el cobre blister tiene bajos contenidos tanto
de azufre como de oxígeno (0,02 – 0,1% S; 0,5 – 0,8% O2).
Los principales elementos que se eliminan del eje o mata durante el proceso de
conversión son el hierro y el azufre, aunque también se eliminan muchas otras impurezas
tanto a través de los gases, como de las escorias.
Durante la conversión en los gases se van principalmente el arsénico, bismuto, cadmio,
mercurio, plomo, antimonio y estaño, mientras que el zinc es eliminado junto con el hierro
en las escorias.
La mayor parte de los metales preciosos, el níquel y el cobalto continúan en el cobre
blister, desde donde son recuperados durante la electro-refinación.
ETAPA DE REFINACION Y MOLDEO DE ANODOS
El objetivo principal de la refinación a fuego es remover el azufre (del orden de 500 ppm) y
el oxígeno (del orden de 5.000 ppm) del cobre blister, a fin de evitar la formación de
ampollas durante la solidificación. Tradicionalmente, esto se realiza en dos etapas:
-
Oxidación: del azufre a SO2, mediante la adición de aire, hasta alcanzar valores de
10 – 30 ppm de azufre en el cobre.
-
Reducción: eliminación del oxígeno disuelto en el cobre proveniente de la
conversión y de la anterior etapa de oxidación, hasta alcanzar valores del orden de
500 – 1.000 ppm. Esto se realiza introduciendo un reductor (madera en bruto no
impregnada con algún compuesto químico, hidrocarburo, carbón) para remover el
oxígeno como CO y H2O.
El refino a fuego se realiza principalmente en hornos rotatorios alcanzando éstos una
temperatura de operación del orden de 1.200 °C, lo que aporta el suficiente
sobrecalentamiento para la posterior etapa de moldeo de ánodos.
Las reacciones de la etapa de refinación producen muy poco calor, por lo que para
mantener la temperatura de los hornos es necesario utilizar algún combustible.
Una vez terminados los procesos de refinación se realiza el moldeo del producto final en
grandes ruedas de moldeo del tipo giratorio, donde también las temperaturas fluctúan
alrededor de los 1.200 °C.
TRATAMIENTO DE ESCORIAS
Esta etapa del proceso permite la recuperación del cobre contenido en las escorias de
alta ley (4 – 10% Cu) provenientes de los procesos de fusión y/o conversión. En Chile se
usan tres procesos para el tratamiento de las escorias: hornos tipo Teniente, hornos
eléctricos y planta de flotación de escorias.
El tratamiento de las escorias en hornos tipo Teniente o eléctricos es esencialmente el
mismo proceso, que consiste en la reducción del contenido de magnetita (Fe3O4) en la
escoria por medio de un agente sólido, líquido o gaseoso, de manera de cambiar sus
características físicas y químicas. Una posterior sedimentación de las partículas de mata
atrapadas mecánicamente, permite generar una escoria de descarte y una fase rica en
cobre. Este proceso puede desarrollarse en modalidad discontinua (“batch”) o
semicontinua.
La operación de un horno de tratamiento de escoria comprende básicamente las
siguientes etapas:
- Carga de la escoria al horno;
- Reducción: la reducción de la magnetita se traduce en una disminución de la
viscosidad de la escoria, lo que permite la separación de las fases contenidas.
Para que este proceso se lleve a cabo se necesita que el horno tenga una
temperatura superior a los 1.200 °C. Como las reacciones de reducción son
endotérmicas, para mantener la temperatura del baño se requiere, en el caso del
horno tipo Teniente del calor generado por un quemador, y en el caso del horno
eléctrico del calor entregado a través de los electrodos. El agente reductor está
compuesto de carbono, hidrógeno y algo de azufre;
- Sedimentación: la escoria reducida se deja en reposo para permitir la decantación
de las partículas con contenido metálico. La separación de las fases se produce
debido a la mayor densidad de las gotas de sulfuro metálico respecto de la
escoria. Para mantener la temperatura del horno por sobre los 1.200 °C se debe
seguir suministrando calor. El tiempo de sedimentación de la mata varía entre 30 y
60 minutos, pudiendo en algunos casos ser bastante más largos.
Los productos obtenidos después de la sedimentación son: una escoria descartable con
bajo contenido de cobre (0,7 – 1%) que es enviada a botadero, y una mata con alto
contenido de cobre (50 – 70%), que se recircula al proceso, usualmente a los
convertidores Peirce-Smith.
LIMPIEZA Y TRATAMIENTO DE GASES
Los gases metalúrgicos ricos en anhídrido sulfuroso (SO2) que se producen en las etapas
de fusión y conversión se captan en los respectivos hornos mediante campanas y se
someten a un proceso que consta de 3 pasos principales:
-
-
Enfriamiento y purificación del anhídrido sulfuroso (SO2) gaseoso proveniente de
los hornos de fusión y conversión. Para eliminar las impurezas contenidas en el
gas (N2, O2, material particulado, vapor de agua, arsénico, fluor, etc.) se utilizan
cámaras de enfriamiento y precipitadores electrostáticos y luego torres de lavado y
precipitadores electrostáticos húmedos. En las cámaras de enfriamiento el gas se
somete a un proceso de enfriamiento rápido.
Conversión del anhídrido sulfuroso gaseoso a anhídrido sulfúrico (SO3). En la
planta de ácido el gas es secado y luego se conduce al convertidor catalítico.
Absorción del SO3 en ácido sulfúrico (H2SO4), obteniéndose un producto de 98%
de pureza.
Todos los efluentes líquidos evacuados desde el sistema de limpieza, secado y absorción
se tratan en una planta para neutralizarlos y separar el arsénico contenido en ellos,
obteniéndose un producto estable que, previamente envasado, va a disposición final en
vertederos especiales.
DESCRIPCION DE LAS FUNDICIONES PRIMARIAS CHILENAS
1.-
CHUQUICAMATA – CODELCO-Chile
La fundición de Chuquicamata tiene una capacidad instalada de procesamiento de
concentrados de 1,63 millones de toneladas anuales para producir del orden de 550 mil
toneladas de ánodos de cobre.
La fundición recibe concentrados (propios y externos), fundentes y materiales de
recirculación en tolvas y camas de almacenamiento, donde se preparan para los
requerimientos específicos de las diferentes unidades productivas. Desde el
almacenamiento el concentrado es llevado a las unidades de secado (2 secadores
rotatorios), donde entran con una humedad promedio de 8% y se descargan con 0,2%.
El concentrado seco se entrega, vía transporte neumático, a las unidades de fusión que
son: un horno Flash Outokumpu y un Convertidor Teniente (CT). Las características más
relevantes de los productos de los equipos de fusión son:
x Horno Flash :
Eje (60 a 62% Cu)
Escorias (2 a 2,5% Cu)
Gases (18 a 20% SO2) a planta de ácido
x CT
:
Metal Blanco ( 73 a 75% Cu)
Escorias ( 5 a 6% Cu; 18 a 20% Fe3O4)
Gases (8 a 10% SO2) a planta de ácido
El Eje y el Metal Blanco se alimentan a los convertidores Peirce-Smith (CPS) para su
conversión a Blister. La fundición tiene 4 CPS, tres operativos y uno en stand by.
La escoria del horno Flash se trata en un horno pirometalúrgico para recuperar parte del
cobre y luego va a botadero. La escoria del CT va a un horno eléctrico de limpieza de
escorias, donde se recupera el cobre atrapado, el que es retornado a los CPS.
El cobre Blister producido por los CPS pasa a una etapa de refinación que se realiza en
hornos de refino (6 pero normalmente se opera con 4). El cobre resultante se moldea
como ánodos en las ruedas de moldeo.
La fundición tiene también plantas de oxígeno, que proveen del insumo para el proceso y
plantas de ácido con sus respectivas plantas de tratamiento de efluentes, donde se tratan
los gases generados en los procesos de fusión y conversión.
A continuación se muestra un esquema de la operación actual de la fundición.
CONCENTRADO
1.632 KT/AÑO
(32,5% Cu)
(32.5% S)
HORNO FLASH
924 KT/AÑO
CONVERTIDORES RECIRCULACION
PEIRCE-SMITH
36 KTON/AÑO
EJE
SECADOR 4
(62% Cu)
C. TENIENTE
713 KT/AÑO
HORNO
ELECTRICO
METAL
BLANCO
(72% Cu)
SECADOR 5
Pl. ACIDO
ANODOS
517 KT/AÑO Cu NUEVO
36 KT/AÑO RECIRCULADO
553 KT/AÑO Cu MOLDEADO
REFINO Y MOLDEO
1.1
Concentrados fundidos
La composición de los principales elementos contenidos en los concentrados fundidos en
Chuquicamata es la siguiente:
Cobre : 35%
Azufre : 32,7%
Hierro : 19,7%
Arsénico
: 0,78%
Al2O3 : 1,1%
SiO2 : 5,3%
Zinc : 1,7%
Molibdeno
: 0,131%
Calcio : 0,17%
Plomo : 0,048%
Insoluble: 3,4%
El contenido típico de impurezas expresado en ppm es el siguiente:
Plata : 154,4
Oro
: 0,82
Bismuto
: 95,6
Cobalto : 45,7
Magnesio: 337,9
Níquel
: 16,9
Cloro : 135,5
Antimonio: 396,6
1.2
Composición de Fundentes
Los fundentes que se utilizan en el proceso están constituidos por cuarzo, con un
contenido promedio de SiO2 de 85,8%. La composición típica de estos materiales es:
Al2O3 : 2,6%
CaO
: 0,8%
SiO2
: 85,8%
1.3
Combustibles utilizados
Como se indicó anteriormente, las reacciones producidas en los hornos de fusión son
exotérmicas, de modo que el proceso es autógeno para la fusión de la carga. Se utilizan
algunos combustibles en la partida de los procesos, donde es necesario utilizar
quemadores para iniciar la reacción y en el proceso de reducción.
No existe información respecto de la composición de los combustibles utilizados por la
fundición de Chuquicamata.
2.-
POTRERILLOS – CODELCO-Chile
La fundición Potrerillos de la División Salvador tiene una capacidad de procesamiento de
concentrados de 680.000 toneladas anuales, 32% de los cuales provienen de su complejo
mina-concentradora y el resto son concentrados externos.
Los concentrados se almacenan en tolvas en la Planta de Recepción y Mezcla y desde
allí son enviados mediante una correa transportadora de tipo tubular a una tolva de
almacenamiento intermedio, desde donde se alimentan al secador de lecho fluidizado, el
que utiliza una mezcla de aire y gases de combustión de petróleo combustible N°6 como
medio de transferencia de calor.
En la etapa de fusión en el convertidor Teniente (CT) el concentrado seco (0,2%
humedad) se inyecta al baño fundido en forma sumergida a través de toberas y se insufla
aire enriquecido con oxígeno (35 – 37%). En el reactor los concentrados se funden en
forma autógena. A través del garr-gun se alimenta el fundente (sílice) y el material
circulante.
En el CT se generan tres flujos de material:
Metal Blanco líquido, con 72-75% de Cu, 5% Fe y 21%S
Escoria líquida, con 8% Cu, 38% Fe y 26% SiO2
Gases con alto contenido de SO2
El Metal Blanco líquido (1.220 – 1.250 °C) se extrae del CT en forma intermitente a través
de un pasaje de sangría, y se transporta en ollas a los convertidotes Peirce-Smith (CPS)
para continuar con el proceso de conversión.
La escoria líquida (1.220 – 1.250 °C) se extrae también en forma intermitente y se
transporta gravitacionalmente hasta los Hornos pirometalúrgicos de Limpieza de Escoria
(3). La escoria final, con 0,9% Cu, se transporta a botadero para disposición final.
En el proceso de conversión en los CPS (3) se insufla aire enriquecido con oxígeno (25%)
al baño fundido y se alimenta carga fría para controlar la temperatura. El producto, que es
cobre Blister líquido (98 – 99% Cu), se transporta a los Hornos de Ánodos (2), donde se
somete a una refinación a fuego para eliminar el exceso de oxígeno, y luego se moldea a
la forma de ánodos. La escoria semi-líquida se enfría en pozos para ser chancada y
reciclada al CT como circulante.
La fundición Potrerillos en sus instalaciones cuenta también con una planta de oxígeno y
una planta de ácido, con su respectiva planta de tratamiento de efluentes.
PLANTA
OXIGENO
OXIGENO
CHANCADO DE CIRCULANTE
PLANTA
PLANTA RECEPCION Y MEZCLA
MINERAL DE SILICE
PICS
HORNO LIMPIEZA ESCORIA
CONVERTIDORES CPS
CONVERTIDOR TENIENTE
HORNOS ANODOS
VTI
SISTEMA DE MOLDEO
ESP
ESP
GENERACION DE AIRE
LIMPIEZA
TRAT. EFLUENTES
CONTACTO
PLANTA DE ACIDO
2.1
Concentrados Fundidos
La composición de los principales elementos contenidos en los concentrados es la
siguiente:
Cobre : 30,8 – 38,3%
Azufre : 31,2 – 33,6%
Hierro :19,1 – 27,8%
Arsénico : 0,09 - 0,83%
Al2O3 : 3,1 - 6,1%
SiO2 : 3,7 - 7,7%
Oro : 0,5 – 3,0 ppm
Plata : 73 – 110 ppm
Otros : 0,7 – 10%
3.-
CALETONES – CODELCO-Chile
La fundición de Caletones de la División El Teniente de CODELCO-Chile posee una
capacidad instalada para procesar 1,25 millones de toneladas de concentrados de cobre,
siendo aproximadamente un 90% concentrado propio y un 10% externo, proveniente de la
División Andina de la misma empresa. Su producción de cobre blister es del orden de
365.000 toneladas anuales.
El concentrado se alimenta a la fundición con una humedad promedio de 8 – 9%, y es
sometido a una etapa de secado en 2 secadores de lecho fluidizado, de donde sale con
una humedad inferior al 0,2%.
El proceso de fusión se realiza en 2 convertidores Teniente y se inicia con la inyección de
concentrado seco, en forma neumática, por medio de toberas al baño fundido del reactor.
Aquí se aprovecha el calor generado por la reacción del oxígeno presente en el aire de
soplado con los sulfuros de hierro y cobre contenidos en el concentrado, que genera un
eje de alta ley o Metal Blanco de 74 a 76% de cobre, una escoria con 4 a 8% de cobre y
16 a 18% de Fe3O4, y una corriente de gases con un 23 a 26% de SO2 en la boca del
reactor, concentración que depende principalmente del enriquecimiento en oxígeno del
aire de soplado.
Los gases del convertidor Teniente arrastran una cantidad de polvo que es recuperado en
los precipitadotes electrostáticos y posteriormente enviados a la planta de tratamiento de
polvos, donde se recupera el cobre soluble por métodos hidrometalúrgicos y el material no
soluble es retornado a la fundición mezclado con el concentrado. Este retorno representa
alrededor del 0,1% del concentrado alimentado a la fundición.
Además de concentrado en el convertidor Teniente se alimentan otros materiales internos
de la fundición:
Carga fría, que es una mezcla de materiales proveniente del enfriamiento del
material líquido circulante en la fundición;
Ripios, material recirculante desde la planta de tratamiento de polvos mezclado
con el concentrado;
Líquidos internos recirculantes, metal de hornos de limpieza de escorias, escorias
de conversión y etapas de refinado.
La escoria generada en los convertidotes Teniente se trata en 4 hornos pirometalúrgicos
de limpieza de escorias. Los productos que se obtienen en estos hornos son una escoria
descartable con un contenido bajo en cobre (0,7 a 1,0%) y un metal blanco con
contenidos de 60 a 74% de cobre.
El metal blanco producido en los convertidores Teniente y en los hornos de limpieza de
escorias se transporta a los convertidores Peirce-Smith (4) para realizar el proceso de
conversión. Una vez obtenido el cobre blister con un 99% de pureza, éste pasa a la etapa
de refino y moldeo. La escoria que se produce en la etapa de conversión retorna a los
convertidores Teniente.
El cobre blister líquido puede ser refinado en los 2 hornos anódicos o 3 hornos de refinado
a fuego, dependiendo de las necesidades de producción de ánodos o cobre RAF. Una vez
terminado el proceso de refino se realiza el moldeo del producto final.
El diagrama del proceso en la Fundición El Teniente se muestra a continuación:
Concentrado Húmedo
8 - 10 % H2O
Planta Secado
Plantas Limpieza Gases
Tren Gases 2 CT
Concentrado Seco
0,2% H2O
4.210 tpd
CONVERTIDOR
TENIENTE (2)
Ácido Sulfúrico
Metal Blanco CT
Aire + Oxígeno
36% O2
Escoria CT
Tren Gases CPS
Cuarzo
Escoria Descarte 0,95% Cu
Metal Blanco
Escoria CPS
CPS
(4 / 3
soplando)
HLE (4) caliente)
Aire + Oxígeno
22% O2
Aire + Carbón
(gas natural)
Planta Enfriamiento
Escoria
Cobre Blister
HORNOS
ANODICOS(2)
HORNOS
RAF(3)
Plantas Oxígeno
Escoria a Botadero
SISTEMA DE MOLDEO
RUEDA MOLDEO
Ánodos
99,7% Cu
3.1
RAF
99,9% Cu
Composición química de las entradas
Cu
Fe
S
SiO Al2O Fe3O Au
2
3
4
%
%
%
%
%
%
Concentrad 31,
o
8
Ripios
37,
6
Carga fría 27,
fundida
7
24,
5
5,9
30,
1
14,
2
5,9
6,1
2,4
27,
9
20,
5
3
15,6
pp
m
0,3
5
Ag
Pb
Ni
As
Sb
Bi
pp
m
51
ppm
pp
m
24
ppm
ppm
ppm
1890
182
8
9,51 90 0,66
%
%
670 160 1370
0,5
%
247
0,16
%
1
527
El concentrado de cobre tiene un contenido de cloro de origen inorgánico que fluctúa
entre 150 y 200 ppm.
3.2
Características de los fundentes
Los fundentes que utiliza la fundición son cuarzo (SiO2), ceniza de soda (Na2CO3) y
carbonato de calcio (CaCO3) y sus características químicas se pueden apreciar en la
siguiente tabla:
Fundente
SiO2
CaCO3
Na2CO3
CaCO3
-85,0
--
Na2CO3
--99,0
Componente (% peso)
SiO2
CaO
MgO
95,0
0,5
0,5
5,0
-2,5
1,0
---
FeO
1,5
2,5
--
Al2O3
2,5
5,0
--
3.3
Combustibles utilizados
Los principales combustibles y reductores utilizados en la fundición son petróleo
combustible N° 6, diesel y carbón derivado del petróleo.
4.-
VENTANAS – Empresa Nacional de Minería (ENAMI)
Las fundiciones de ENAMI tienen como misión fundamental prestar servicios de fundición
y refinación de cobre a productores de la pequeña, mediana y gran minería.
La fundición Ventanas tiene una capacidad instalada para procesar alrededor de 420.000
toneladas anuales de concentrados para producir 110.000 toneladas de ánodos de cobre.
El proceso productivo comienza con la recepción y manejo de diversos concentrados y
productos mineros provenientes de una gran variedad de proveedores de diversa escala.
Esto incluye productos adquiridos por ENAMI a través de las agencias de compra, como
también productos en calidad de servicios de maquila para fusión y refinación.
Estas materias primas pasan a un proceso de mezcla formando un concentrado húmedo
cuya ley de cobre es del orden de 30%. El proceso de secado de estos concentrados se
realiza en secadores rotatorios, utilizando como combustible gas natural. El concentrado
seco se descarga a un transportador que permite una alimentación controlada a un
sistema de vasos presurizados, que mediante transporte neumático alimentan una tolva.
La tecnología de fusión utilizada es un convertidor Teniente, cuya operación, como ya se
ha señalado, es autónoma, ya que no requiere de eje semilla para mantener el balance de
calor y sólo un leve soporte térmico que se suministra a través de un quemador
sumergido a gas natural. Durante la fusión se inyecta aire enriquecido con oxígeno (36%)
directamente en la fase metálica a través de toberas sumergidas en el baño.
Los productos son una fase líquida rica en cobre, el Metal Blanco (75% Cu), que se envía
a los convertidores Peirce-Smith (3) para continuar el proceso de conversión a Blister, y
una fase líquida pobre en cobre, la escoria (8% Cu), que se envía a un proceso de
limpieza en un Horno Eléctrico. La fase gaseosa rica en SO2 se lleva a la Planta de Acido
previo enfriamiento y limpieza.
En el proceso de conversión se sopla aire enriquecido en oxígeno (24%) a través de
toberas sumergidas en el baño del reactor. Los productos del proceso son una fase
líquida que es el Blister (98% Cu) que va al proceso de refino a fuego y una escoria que
se reprocesa en la fundición.
En el horno eléctrico de limpieza de escoria, que es del tipo de electrodos sumergidos, se
procesan las escorias provenientes del convertidor Teniente y se funden gran parte de los
circulantes que se producen en la fundición, como derrames de metal blanco, costras y
otros materiales. Los productos líquidos que se obtienen son un eje de alta ley (70% Cu)
que va a los CPS y una escoria de descarte que se lleva a botadero.
El proceso de refino a fuego se realiza en un horno basculante, obteniéndose un cobre
anódico que a temperaturas superiores a los 1.200 °C fluye hacia las ruedas de moldeo.
La fundición Ventanas cuenta con una planta de oxígeno y una planta de ácido de doble
contacto.
El diagrama de flujo de la fundición Ventanas es el siguiente:
Concentrado
Húmedo
SECADOR
ROTATORIO
Precipitador
Electrostático (2)
Gases CT
Ventiladores
(2)
TOLVAS
Cámara Enfriamiento
Horizontal
Circulante
Garr-gun
Sílice
Carbón
CONVERTIDOR
TENIENTE
Aire Enriquecido
Inyección Concentrado
Seco
Quemador Sumergido
Ventiladores
Gases
CPS
Cámara
Enfriamiento
Horizontal
Metal
Blanco
CT
Escoria
CT
Precipitador
Electrostático
Ventiladores
Escoria CPS
CONVERTIDOR
PEIRCE-SMITH
(3)
Blister a
Refino a
Fuego
Metal
Blanco
Precipitador
HORNO Electrostático
ELECTRICO
PLANTA DE ACIDO
Escoria a
Botadero
HORNO
BASCULANTE
Ruedas de
Moldeo
ANODO
99,6% Cu
5.
HERNAN VIDELA LIRA (PAIPOTE) – Empresa Nacional de Minería (ENAMI)
La fundición Paipote tiene una capacidad de procesamiento de concentrados de 300.000
toneladas/año para producir sobre 90.000 toneladas de blister y ánodos de cobre.
El proceso de secado de concentrado, al igual que en Ventanas, se realiza en un secador
rotatorio, pero en este caso se usa como combustible petróleo Diesel.
Todo el proceso en la fundición Paipote es idéntico al de la fundición Ventanas, con la
única diferencia que en lugar de gas natural se usa petróleo Diesel como combustible en
el quemador sumergido del convertidor Teniente en la etapa de fusión y en el horno
basculante en la etapa de refino a fuego.
La fundición Paipote cuenta con una planta de oxígeno y dos plantas de ácido, con sus
respectivas plantas de tratamiento de riles.
Horno
Eléctrico
Tratamiento
Escorias
Recepción y
Almacenamiento
Concentrado
Húmedo
Secado e
Inyección de
concentrado
ESCORIA A
BOTADERO
Metal
Blanco
Escoria
Concentrado
Seco
CP
CPS
CONVERTIDOR
T
TENIENT
CONV.
S
E
TENIENTE
Precámara de
Enfriamiento
Planta Oxígeno
Cámara de
Enfriamiento
Radiativa
Precámara de
Enfriamiento
Radiativa
R
AF
RAF
F
Lavador de
Gases
Precipitadores
Electrostáticos
ANODOS
Planta de Acido N° 2
Planta de Acido N° 1
5.1
Concentrados Fundidos
La composición química de los concentrados procesados por las fundiciones de la
Empresa Nacional de Minería (ENAMI) es en promedio la siguiente:
Cobre: 27,6%
Azufre: 31,8%
MgO: 0,3%
5.2
Fierro Total:
Arsénico:
Antimonio:
28,5%
0,04%
0,02%
Fe3O4: 1,7%
Al2O3 : 1,2%
Plomo: 0,2%
SiO2: 6%
CaO: 1,2%
Cloro: 500 ppm
Características de Combustibles
5.2.1 Coke Industrial
Carbono: 94,84%
Hierro: 0,04%
Aluminio: 0,11%
Calcio: 0,04%
Azufre: 1,03%
Magnesio: 0,04%
Sílice: 0,23%
Volátiles: 1,5%
5.2.2 Coke Residual Petróleo
Carbono: 85%
Azufre: 1,2%
Volátiles: 12%
Cenizas: 6%
5.2.3 Gas Natural
Metano: 91%
Etano: 6,05%
Propano: 2,13%
Pentanos y superiores: 0,3%
Dióxido de Carbono: 2%
AcidoSulfhídrico:6 mg/m3
Azufre (mercaptanos): 23 mg/m3
6.
Butano: 0,93%
Nitrógeno:0,8%
Azufre total: 100 mg/m3
ALTONORTE – Noranda Chile Ltda.
Esta fundición acaba de terminar su proyecto de expansión que le permitió aumentar su
capacidad de procesamiento de concentrados a 820.000 toneladas anuales para producir
del orden de 290.000 toneladas/año de ánodos de cobre.
El proyecto de expansión significó el reemplazo del antiguo horno reverbero por un
convertidor de tecnología desarrollada por Noranda, que corresponde a un reactor de
fusión igual al que usan sus fundiciones ubicadas en Canadá.
El reactor tiene 54 toberas destinadas al soplado de aire enriquecido con oxígeno al
proceso y 12 toberas para la inyección de concentrados secos. En condiciones normales
de operación, el concentrado seco es alimentado al reactor vía toberas de inyección
utilizando un transporte neumático en fase ultradensa. El reactor puede ser alimentado,
además, con concentrado húmedo, a través de un inyector localizado en la culata de
metal blanco, y que también es utilizado para agregar fundente, coke y carga fría al
proceso. El calor necesario para el proceso lo genera la oxidación del azufre y fierro,
suplementado si el balance calórico así lo requiere, por quemadores de gas natural o
diesel y oxígeno.
La planta de secado de concentrados incluye un horno rotatorio de 4 metros de diámetro y
40 metros de largo, con sus instalaciones anexas, destinada al secado de concentrados
de cobre nuevos y aquellos provenientes de la planta de flotación de escorias. La
humedad final de los concentrados es de un 0,2%. El concentrado seco se transporta
neumáticamente a las tolvas de almacenamiento para la alimentación del reactor.
En el reactor continuo se produce la fusión de la carga alimentada, generando un baño
líquido a una temperatura entre 1.200 y 1.280 °C, de dos fases líquidas inmiscibles entre
sí, metal blanco y escoria. La carga fría y circulantes son los materiales que se utilizan
para el control de la temperatura del baño líquido del reactor.
La escoria generada - de una ley de entre 6% y 8 % de cobre - es descargada del reactor
de fusión a través de una placa de sangría instalada en el muro opuesto a la sangría de
metal blanco. Para recuperar el contenido de cobre, la escoria se trata posteriormente
mediante enfriamiento, molienda y concentración por flotación.
El metal blanco producido (con un contenido de entre 72% y 75 % de cobre) se extrae del
reactor a través de dos placas de sangrías, instaladas en la parte baja de la culata de
metal blanco y se transporta en ollas a los hornos convertidores tipo Peirce-Smith (3),
para continuar con el proceso de conversión, que involucra la oxidación del azufre
remanente con aire enriquecido con oxígeno insuflado a través de toberas sumergidas en
el baño líquido, para obtener como producto principal cobre blister.
La escoria producida por los convertidores Peirce-Smith se recircula e inyecta como carga
fría para ser procesada por el reactor de fusión en estado sólido.
El cobre blister se transfiere a los hornos de refino, en los cuales se somete primero a una
oxidación que elimina el azufre remanente, y luego a un proceso de reducción mediante
gas natural para eliminar el exceso de oxígeno, quedando finalmente el cobre refinado de
99,6 – 99,7% de pureza, apto para su moldeo en forma de ánodos.
Los gases generados en el proceso (con una temperatura del orden de 1.240 ºC) son
captados a través de campanas. Posteriormente, los gases se enfrían en una cámara
evaporativa con agua atomizada (350 °C a 400 ºC) y se envían a las plantas de ácido (3)
a través de precipitadores electrostáticos y ventiladores de tiro inducido.
ESTAN QU ES
A L M A C E N A M I EN T O
ACIDO
P LA N T A A CID O
S U L F U R IC O N º 3
P LA N T A
A C ID O N º 1
PLA N TA
A C ID O N º 2
C H IM EN EA
E X T RA CT O RE S
EXTRACTO RES
PR EC IPITA D O R ES
C A M A S E N F R IA M IE N T O
E S C O R IA
SECADO R
R O T A T O R IO
E L E C T R O S T A T IC O S
SO PLAD O RES Y
C O M PRESO RES
S ILO S
S O PL A D O R E S Y
C O M PR E S O R E S
R U ED A S M O LD EO
ANODOS
HORNO
REVERBERO
SILOS
C A N C H A R E C E P C IO N
CO N CEN TRADO S
C O N V E R T ID O R E S
R E A C T O R C O N T IN U O
G R U A -P U E N T E
H .R E T E N C I O N
HORNOS DE
R E F IN A C IO N
P LA N T A
F L O T A C IO N
E S C O R IA S
7.
CHAGRES – Anglo American Chile Ltda.
La fundición Chagres tiene una capacidad instalada para procesar 480.000 toneladas
anuales de concentrados de cobre y producir entre 150.000 y 170.000 toneladas de
ánodos.
En la zona de preparación de la carga se hacen las mezclas adecuadas de concentrado y
sílice para ser procesadas en el horno Flash. El secado de concentrado y fundente se
efectúa en 2 hornos secadores a vapor, reduciéndose la humedad del concentrado desde
8% a 0,2% y la de sílice de 2,5% también a 0,2%. La mezcla seca se transporta
neumáticamente hasta una tolva de almacenamiento y al sistema de dosificación
controlada para la alimentación al horno de fusión.
El reactor donde se realiza la fusión es un horno Flash de tecnología y diseño
Outokumpu, que consta de tres partes principales: la torre de reacción, el sedimentador y
la torre de salida de gases.
Una de las partes más importantes del horno Flash es el quemador de concentrado, que
va instalado en el centro del techo superior de la torre de reacción. Recibe
simultáneamente el flujo de carga seca y aire de proceso enriquecido con oxígeno. La
combustión se complementa con los quemadores de oxígeno petróleo instalados en la
misma torre. Las salidas de eje y escoria del sedimentador descargan en canaletas de
sangría de eje y escoria respectivamente.
Los gases salen del horno Flash a una temperatura de 1.400 °C y se enfrían en una
caldera hasta una temperatura entre 350 y 390 °C, para pasar luego al precipitador
electrostático.
El eje o mata del horno Flash y de los hornos de tratamiento de escorias pasan al proceso
de conversión en hornos Peirce-Smith (3), en que se oxida la mata líquida a altas
temperaturas (1.150 – 1.250 °C) soplando aire a través del eje fundido, utilizando sílice
como fundente, lo que permite remover el azufre, hierro y otras impurezas del eje.
Las materias primas que entran a los convertidores son: el eje o mata; fundente o
escorificante (cuarzo); carga fría; aire y oxígeno. La carga fría la constituyen en general
desechos internos de la fundición, tales como escoria del convertidor, cobre rechazado y
eje frío.
Los productos de la etapa de conversión son:
Cobre Blister (99% Cu)
Escoria de convertidor (50% Fe, 25% SiO2), que además del hierro contiene entre
3 y 5% de Cu, el que se recupera recirculando la escoria a los hornos de
tratamiento.
Dióxido de azufre, cuya concentración en los gases del convertidor es del orden de
5 – 8%.
Para la recuperación del cobre contenido en las escorias se utilizan hornos
pirometalúrgicos de tratamiento (2). La operación de estos hornos es un proceso “batch”
que comprende básicamente 4 etapas: carga de la escoria al horno, reducción de la
magnetita contenida en la escoria alimentada, sedimentación de la mata o separación de
las fases metal y escoria, y extracción de la escoria final y mata de alta ley. Los productos
obtenidos son una escoria descartable con bajo contenido de cobre (0,7 – 1%) que va a
botadero, y una mata con alto contenido de cobre (50 – 70%), que es recirculada al
proceso de fundición en los convertidores Peirce-Smith.
El cobre Blister proveniente de la etapa de conversión presenta contenidos de azufre (500
ppm) y oxígeno (5.000 ppm) que es necesario eliminar para evitar la formación de
ampollas durante la solidificación, lo que se logra a través del proceso de refinación a
fuego en los hornos de refino (2).
Posteriormente, viene la etapa de moldeo que se realiza a temperaturas entre 1.190 y
1.205 °C, y para lo cual la fundición cuenta con una rueda de moldeo de ánodos.
Para el manejo y limpieza de gases se cuenta con una caldera recuperadora de calor, un
precipitador electrostático, una cámara de mezcla, ventiladores y la planta de ácido con su
respectiva planta de tratamiento de efluentes.
Tolva de
Alimentación
Tolva de Mezcla
SECADOR
Caldera
Planta
Oxígeno
Gases CPS
Gases HF
Precipitador
Electrostático
CONVERTIDORES
PEIRCE-SMITH (3)
Eje
7.1 Caracterización de Concentrados
El rango de composición química de los concentrados procesados por la fundición de
Chagres es la siguiente:
Cobre: 27,9 – 41,7%
As: 135 – 819 ppm
SiO2: 3,8 – 14,3%
Al2O3: 1,06 – 3,9%
Mn: 0,01 – 0,1%
Hg: 1 – 2 ppm
Mo: 35 – 2.462 ppm
Bi: 10 – 49 ppm
Sb : 8,7 – 59 ppm
Hierro: 21,7 – 24,5%
Ag: 58 – 63 ppm
MgO: 0,12 – 0,9%
Na2O: 0,41 – 1,3%
F: 132 – 144 ppm
Pb: 52 – 196 ppm
Co: 38 – 140 ppm
Te: 0,4 – 1,8 ppm
Sn : < 20 ppm
Azufre: 25,9 – 34,1%
Au: 0,1 – 1 ppm
CaO: 0,28 – 1,5%
K2O: 0,5 – 0,59%
Zn: 311 – 547 ppm
Ni: 10- 51 ppm
Se: 3 – 57 ppm
Cl : 46 – 85 ppm
7.2 Caracterización de Fundentes
La composición de los cuarzos utilizados como fundentes es la siguiente:
Cuarzo Grueso
SiO2: 95,9 – 96,9%
Al2O3: 0,77 – 0,97% CaO: 0,03 – 0,07%
Fe: 0,41 – 1,02%
Cuarzo Fino
SiO2: 82 – 95,2%
Al2O3: 1,1 – 7,76%
Fe: 0,64 – 0,96%
CaO: 0,07 – 4,23%
ANTECEDENTES RESPECTO DE LAS CONDICIONES DE
OPERACIÓN DE LAS FUNDICIONES CUYAS MEDICIONES
SUSTENTAN EL FACTOR DE EMISION DE DIOXINAS
DETERMINADO PARA LA PRODUCCIÓN PRIMARIA DE COBRE
Documento elaborado por la Comisión Chilena del Cobre
ABRIL 2004
EL FACTOR DE EMISION PARA PRODUCCIÓN PRIMARIA DE COBRE DEL
INSTRUMENTAL NORMALIZADO Y LAS MEDICIONES QUE LO SUSTENTAN
El punto 6.2.4.1 del “Instrumental Normalizado para la Identificación y Cuantificación de
Liberaciones de Dioxinas y Furanos” del PNUMA, justifica el valor del factor de emisión
para la producción primaria de cobre, señalado en la Tabla 27, en mediciones realizadas
en fundiciones de Alemania y Suecia, las que fueron reportadas en el Inventario Europeo
de Dioxinas de 1997 (LUA 1997).
En el caso de las fundiciones alemanas de cobre el Volumen 2 del Inventario Europeo de
Dioxinas reporta lo siguiente:
Germany
03 03 06 Primary Copper Production
“Because in Germany no plants exist which could be considered to produce purely with
primary materials this emission source will be treated below (03 03 09)”
03 03 09 Secondary Copper Production
Plant Data
“In Germany there are 3 copper smelters of which one processes copper concentrate as
well as scrap while the other 2 plants are scrap smelters”
Los párrafos citados del Inventario Europeo de Dioxinas dejan claramente establecido que
la producción de cobre en Alemania es mayoritariamente de carácter secundario, aún
cuando una fundición utiliza como materia prima una mezcla de concentrados y
materiales reciclados (NA en Hamburgo).
Para confirmar lo anteriormente señalado en relación a la producción de cobre en
Alemania se visitó la página web http://www.na-ag.com/NA_en/rohstoffe_frame.html de
Nordduetsche Affinerie, donde se señala lo siguiente:
“NA's copper production is based to 60 % on the copper concentrates supplied by the
mines (primary raw materials). These concentrates are generally composed to one third
each of copper, iron and sulphur. The remaining 40 % of the raw material supply is
covered by copper scrap (secondary raw materials) and process residues.
Accordingly, we process, for instance, scrap, shredder scrap, bronze, casting scrap and
cable granules as well as galvanic slimes, slag, ash and filter dusts.
Whilst only secondary materials are used at Hüttenwerke Kayser AG in Lünen for cathode
production, NA uses a mixture of concentrates and recycling materials in its primary
smelting process in Hamburg. In addition to high-purity cathode copper we also recover
the by-products, iron silicate stone and high-purity sulphuric acid, as well as the important
co-elements: lead, silver, gold and various compounds of these co-elements, such as
selenium and nickel.”
Además, en la misma página la empresa destaca su importancia en el mercado mundial
del reciclaje:
“The NA Group recycles significant quantities of copper scrap and is the largest processor
of secondary materials worldwide. Copper scrap comes in a variety of forms and qualities
and is processed in several plants depending on the composition of the material. In
Hamburg scrap is additionally used as a cooling material during the melting of copper
concentrates. Due to the surplus heat arising during this process it is possible to melt
scrap in an environmentally friendly manner without using additional energy.”
“Due to our modern technical facilities we can offer you processing possibilities for a
variety of recycling materials. Examples of these are: printed circuit boards; non-ferrous
metal-bearing waste; lead scrap; NE-contaminated slimes; NE-contaminated slag; NEcontaminated dust; foundry sand; contaminated soil; silicon bearing residue; blast slag
residue; catalysts as well as a variety of other materials.”
En el caso de la producción de cobre en Suecia, el Volumen 2 del Inventario Europeo de
Dioxinas reporta lo siguiente:
Sweden
03 03 06 Primary Copper Production
Plant Data
“A primary smelter is described producing diverse non ferrous metals with copper being
about 50% of the products. The plant uses ores and secondary materials (electronic scrap
and plastic covered cables as well). It is a large and complex operation consisting of
numerous activities”.
La descripción de la planta, que corresponde a la fundición de Rönnskär de Boliden,
aunque la define como una fundición primaria establece que además de concentrados
procesa materiales secundarios, entre otros, scrap de electrónicos y cables recubiertos
con plásticos, lo que se confirma en la página web de la empresa http://www.boliden.com/
que informa:
“The Rönnskär smelter in northern Sweden extracts base metals and precious metals from
concentrates of copper and lead as well as from recycled materials. It also extracts
considerable amounts of zinc clinker and sulphur products.”
“Rönnskär is located in Skelleftehamn, approximately 20 kilometers east to the town of
Skellefteå in northern Sweden. The first copper ingot was cast in 1930. Today, Rönnskär
is one of the largest copper smelters of its kind in the world. It is also one of the largest
plants for the recovery of base metals and precious metals from recycled materials,
such as electronic and metal scrap, residues and slag.”
“Rönnskär is a world leader in the recycling of base metals. Values are extracted from
scrap and other waste containing metal. Copper ashes from the brass industry, scraped
printed circuit boards, sorted metal fractions from dismantlers and shredders, copper
cables and old silver coins illustrate the multitude of sources of recycled materials. Zinc is
recovered from slags and ashes as well as from steel mill dust.”
“At Rönnskär approximately 140,000 tonnes of secondary raw material are recycled every
year; the biggest items are ashes from brass foundries, zinc-rich dust from steel mills,
electronic scrap, copper/lead cable and pure copper scrap.”
“Every year approximately 25,000 tonnes of electronic scrap are recycled. Electrical
and electronic products that have been used for many years are mixed with production
waste from the manufacturing industry. The value is in metals such as copper, gold and
silver in varying proportions. The highest grade electronic scrap is of most interest, and
these materials can have a gold content that is 10 times that of ore from a gold mine.”
“The Kaldo process uses the plastic in the scrap as fuel and as a reducing agent at
the same time as organic compounds are destroyed. The melt is brought together with
the primary copper flow and is refined into metals of a very high quality and purity.”
Como se puede observar de la información transcrita en los párrafos anteriores, a
diferencia de las fundiciones primarias de concentrados de cobre de Chile, la fundición de
Norddeutsche Affinerie en Hamburgo y la de Rönnskär en Suecia no son fundiciones
primarias puras, ya que ambas procesan en sus instalaciones materiales reciclados de
distintas calidades, además de concentrados de cobre.
En otras partes del mundo, como por ejemplo en Canadá, las fundiciones se operan de
manera similar a las fundiciones europeas, esto es, usando como alimentación una
mezcla de concentrados y materiales reciclados.
Noranda, una de las empresas productoras de metales más importantes de Canadá y a
nivel mundial, informa en su página web (http://www.noranda.com) bajo el título de
Canadian Copper and Recycling lo siguiente:
“In 2001, Noranda created a new business unit with a strong strategic focus on recycling
and processing complex materials. Through its Canadian Copper and Recycling business,
Noranda is one of the largest recyclers of copper and precious metals in the world,
sourcing over 300 types of material from more than 18 countries. Recycled material
provides on average about 15% of the feed for Noranda's smelters in Canada.
Noranda's Canadian Copper & Recycling business unit consists of the Horne smelter in
Rouyn-Noranda, Quebec, a custom copper smelter and sulphuric acid plant. It also
operates the CCR copper and precious metals refinery in Montreal-East, Quebec.
With over 50 years of experience in the recycling industry, Noranda is the world's largest
recycler of electronic components and a major recycler of secondary copper, nickel, gold,
silver, platinum, palladium, and lead. Approximately 15% (150,000 tonnes) of the raw
material feed for our primary Canadian copper & recycling operations is from recyclable
materials. Gross value of recyclable raw materials was $328 million in 2001.
Noranda/Falconbridge Canadian operations process approximately 150,000 metric
tonnes of recyclable raw materials annually
In 2001, Canadian Copper and Recycling represented 29% of Noranda/Falconbridge's
total revenue
Of the total refined metal produced by Noranda, recycled materials account for:
Copper
Gold
Silver
Platinum/Palladium
Lead
Total Metal Produced in
2001
323,000 mt
1.2 mil oz
43 mil oz
120,000 oz
108,000 mt
From Recycled Material
2001
10%
15%
10%
90%
7%
Noranda is the world's largest custom processor of copper and precious metal-based
feeds through its smelting and refining facilities in Canada. The versatility of Noranda's
metallurgical process, and strong working relationships with an expanding network of
suppliers to develop innovative recycling solutions, have been key to Noranda's growth as
a recycler.”
Las estadísticas de producción de cobre, de acuerdo a su procedencia (concentrados o
materiales secundarios reciclados), de las distintas fundiciones que se encuentran en la
actualidad operando en el mundo muestran que las fundiciones de Estados Unidos,
México, Chile, Japón, Australia y las de Huelva en España y Harjavalta en Finlandia
procesan cantidades mínimas de carga recirculada interna, que se usa como carga fría en
los convertidores. En el otro extremo, las fundiciones de Beerse y Hoboken en Bélgica y
Brixlegg en Austria son completamente secundarias.
Finalmente, por todo lo anteriormente expuesto, tanto en relación a la descripción
detallada de las tecnologías y condiciones de operación de las fundiciones primarias de
concentrados de cobre en Chile, como respecto de los antecedentes que acreditan que
las fundiciones que se tomaron como referencia para determinar el factor de emisión de
dioxinas de la producción primaria de cobre tienen condiciones distintas de operación y
calidad de la alimentación, que las asimila a operaciones de carácter secundario, es que
Chile solicita revisar la inclusión de la producción primaria de cobre en el Instrumental
Normalizado para la Identificación y Cuantificación de Liberaciones de Dioxinas y
Furanos” preparado por PNUMA.
Comentarios al Toolkit – Marzo 2004
Marzo, 2004
CORMA Región del Bio Bío
Dpto. Celulosa y Papel - Zona Centro Sur
Comité de Medio Ambiente
COMENTARIOS
FOR IDENTIFICATION AND QUANTIFICATION
OF DIOXIN AND FURAN RELEASES
STANDARDIZED TOOLKIT
CORPORACION CHILENA DE LA MADERA A.G.
Página 1 de 1
REFERENCIAS
4.
CONCLUSIONES
Página 2 de 2
16
15
7
2.4.3. FACTORES DE EMISIÓN Y COMENTARIOS
3.
7
COMENTARIOS
2.4.
5
2.4.2. FUENTES EN LA INDUSTRIA
COMBUSTIÓN
2.3.
4
6
BLANQUEO
2.2.
3
3
PÁGINA
2.4.1. GENERALES
ANTECEDENTES TÉCNICOS DE LA INDUSTRIA Y SUS PROCESOS
COMENTARIOS AL TOOLKIT
2.
2.1.
INTRODUCCIÓN
1.
0. CONTENIDO
Página 3 de 3
En los procesos de producción de pulpa química, se forman principalmente en el proceso de blanqueo y a través de la combustión. En cuanto
a la formación de PCDD/PCDF en el proceso de blanqueo de celulosa, detectada en la década de los 80’, ésta se relacionaba con el uso de
antiespumantes que contenían aceites gastados, que actuaban como precursores y con el nivel de lignina remanente en la pulpa antes de
ingresar al proceso de blanqueo, principalmente.
De hecho, más de la mitad de la producción se obtiene en instalaciones industriales que fueron construidas a fines de los ‘80 y comienzos de
los ’90. Este aspecto, unido a la experiencia que los industriales chilenos han obtenido de los países escandinavos, líderes mundiales en la
aplicación de modernas tecnologías de producción, ha llevado a que realmente la industria de celulosa chilena se encuentre en categoría
mundial.
El desarrollo de la industria de la celulosa en Chile es nuevo. El gran impulso a las plantaciones forestales comenzó en la segunda mitad de la
década de los años 70, de modo que para finales de los años ’80 los bosques habían crecido lo suficiente como para sustentar el crecimiento
de esta actividad.
La industria de la celulosa en Chile produce alrededor de 2,2 millones de toneladas por año, usando como materia prima madera proveniente
de bosque de pino radiata y de eucaliptus, plantado especialmente para esta aplicación. De esta producción, el 70 % es de pino.
2.1.1. La industria de la celulosa en Chile y la formación de PCDD/PCDF
2.1. Antecedentes técnicos de la industria y sus procesos
2. COMENTARIOS AL TOOLKIT
Atendiendo lo solicitado por CONAMA en orden a enviar comentarios al “Standardized Toolkit for Identification and Quantification of Dioxin
and Furan Releases” emitido por PNUMA, Corma a través de su Departamento de Celulosa y Papel Zona Centro Sur y de su Comité de
Medio Ambiente, lo ha revisado minuciosamente, directamente y con la colaboración de una empresa consultora extranjera de gran prestigio y
conocimiento técnico sobre la industria –ÅF-Celpap-, derivándose de ello el presente documento. Además, se ha incluido información acerca
de la tecnología existente en Plantas chilenas.
1. INTRODUCCIÓN
Página 4 de 4
De lo señalado es posible concluir que el ClO2 utilizado en el blanqueo debe estar libre de Cloro molecular o presentar un contenido muy
reducido para evitar la formación de PCDD/PCDF; el contenido de Cl2 depende del método utilizado para producir ClO2; en el caso de las
plantas chilenas se usa el proceso R-8, que emplea clorato y el ClO2 producido puede considerarse libre de Cl2.
Durante los años 80 la Forest Industry Foundation for Water and Air Protección Research (SSVL), en Suecia, llevó a cabo mucha
investigación en torno al tema de la formación de PCDD/PCDF en el blanqueo de pulpa, que permitieron concluir que la mayor parte de estos
compuestos formados en el blanqueo se originan en la cloración de Dibenzodioxinas y Dibenzofuranos (DBDs y DBFs) en la primera etapa de
blanqueo. Los DBDs/DBFs se cree se forman durante la cocción de lignina degradada. En estos estudios también se demostró que el agua
de proceso clorada también podría ser una fuente de PCDD/PCDF, como asimismo que un bajo múltiplo de cloro en la primera etapa de
blanqueo reduce drásticamente la formación de PCDD/PCDF
Los 3 principales métodos de blanqueo para pulpa química son: a) Estándar, en el que se utiliza Cloro molecular (Cl2); b) ECF, en el que se
utiliza solamente dióxido de cloro; y c) TCF, en el que no se utiliza ningún tipo de compuesto clorado.
2.2. Blanqueo
Desde mediados de los años 80 se sabe que el blanqueo de pulpa química con Cloro gas es la fuente principal de formación de PCDD/PCDF
mientras que el uso de Dióxido de Cloro la disminuye o la hace no detectable; la acción de otros químicos usados en el blanqueo, como el
Oxígeno, Peróxido de Hidrógeno, Ozono y Ácido peracético no se ha reportado como generadora de estos compuestos.
El contenido de lignina remanente en la pulpa antes de introducir las nuevas técnicas de cocción y deslignificación era de 5.6 % base pulpa
seca. Posteriormente se redujo a 2.9 % y actualmente hay plantas en Chile que están ingresando a la etapa de blanqueo con pulpas con
1.8% de lignina residual. Es decir, se ha disminuido en cerca de 70% la lignina contenida en la pulpa que inicia el proceso de blanqueo. Este
nivel tan bajo de lignina permite que, aún usando cloro en la primera etapa de blanqueo, no se detecte formación de dioxinas y/o furanos.
La forma de reducir el contenido de lignina residual en la pulpa es actuar en la cocción de la madera con técnicas modernas de
deslignificación extendida y posteriormente en una etapa nueva adicional, llamada deslignificación con oxígeno.
A comienzos de los años ’90 la industria eliminó el uso de antiespumantes con precursores y el diseño de las instalaciones nuevas consideró
trabajar con un contenido de lignina residual en la pulpa, suficientemente bajo como para eliminar la formación de dioxinas, al menos al nivel
de detección de las actuales tecnologías analíticas. Las industrias más antiguas incorporaron también estas nuevas tecnologías.
Página 5 de 5
enfriamiento de gases de combustión en rangos de 200-400 °C en procesos de alta temperatura y/o combustión incompleta.
presencia de carbono orgánico
-
2.3. Combustión
PCDD/PCDF se forman en los procesos de combustión principalmente a través de: a) Novo síntesis (200-400 °C) a partir de carbono
contenido en materia orgánica parcialmente combustionada; y b) precursores generados de oxidación incompleta de compuestos aromáticos
ó formación de anillos cíclicos desde fragmentos de hidrocarburos. Ambos mecanismos se ven favorecidos por las siguientes condiciones:
Finalmente, las técnicas de blanqueo en media consistencia, mezcladores dinámicos para la introducción de los reactivos de blanqueo y
moderna instrumentación ha permitido que las dosificaciones de cada uno de los reactivos usados se haga sólo en las proporciones
estequiométricas requeridas, lo que favorece significativamente a la reducción de formación de PCDD/PCDF.
No hay ninguna planta en Chile que use sólo cloro como agente blanqueante. Las secuencias de blanqueo ECF y STD son: D-Eop-D-E-D y
D30/C70-Eop-D-E-D, respectivamente. Estas siglas corresponden a: D: dióxido de Cloro; Eop: extracción con soda cáustica, oxígeno y
peróxido de hidrógeno; Dx/C100-x: X% Dióxido de cloro.
En Chile, el blanqueo de la pulpa se hace aproximadamente en un 40 % sólo con dióxido de cloro y el restante 60 % con una mezcla de cloro
y dióxido de cloro, en un proceso que tiene varias etapas. Unas de reacción del dióxido de cloro o de la mezcla cloro/dióxido y otras de
extracción de los compuestos generados en la reacción.
Dado que PCDD/PCDF son muy difíciles de degradar, no se ven afectados mayormente en los tratamientos de efluentes; aún cuando no
aparece indicado explícitamente en el TOOLKIT, nuestros asesores entienden que sus autores arriban a una conclusión semejante. Siendo
solubles en aceites, grasas y solventes orgánicos (compuestos lipofílicos), no se disuelven en agua pero se adsorben/adhieren fuertemente a
los compuestos orgánicos del agua y suelo; esto indica que la mayor parte de estos compuestos pasa a enriquecer el lodo y el saldo sale con
el efluente. La cantidad total antes del tratamiento se mantiene, en general, inalterada.
Las dioxinas y furanos clorados que se forman en el blanqueo se encontrarán principalmente en el efluente descargado por la planta o en el
lodo del tratamiento secundario con lodos activados, ya que el primario normalmente no incluye cantidades significativas y el tratamiento con
lagunas facultativas no genera lodos. Algunos de los compuestos formados en el blanqueo permanecerán asimismo en la celulosa.
Página 6 de 6
La obtención de datos de emisión de PCDD/PCDF es difícil y costosa; los datos que se obtengan de mediciones locales pueden ser usados
sólo si son representativos y confiables. La utilización de metodología estándar para el muestreo y análisis, experiencia analítica probada y
buena documentación son prerrequisitos para disponer de datos de alta calidad. Cuando se han generado factores de emisión locales con
buenos datos, estos pueden ser utilizados para las estimaciones. Se pueden extrapolar los resultados solo si son del mismo tipo y operan
bajo las mismas condiciones.
En el caso específico de las fábricas de Celulosa, la emisión de PCDD/PCDF presenta diferencias entre ellas e incluso diariamente, para una
misma planta. Los Factores de Emisión sugeridos en el TOOLKIT representan descargas promedio para cada categoría.
2.4.1. Generales
El Toolkit ayuda a identificar las fuentes potenciales y presenta la metodología para realizar los inventarios. Incluye Factores de Emisión “por
defecto” que pueden ser utilizados cuando no hay mediciones o estas son insuficientes.
2.4. Comentarios al Toolkit
- presencia de cloro (Cl2/Cl-)
- productos con PCDD/PCDF
En una fábrica kraft estas condiciones pueden estar presentes en la Caldera Recuperadora, Calderas de Corteza y Hornos de Cal. No
obstante, algunas investigaciones (2,3) han demostrado que las condiciones de operación en las calderas recuperadoras (combustible
homogéneo; temperaturas del hogar altas y estables: 950 – 1150 °C; altos tiempos de residencia en el hogar: 10-15 segundos o más;
ambiente fuertemente alcalino) inhiben la formación de estos compuestos a diferencia de las calderas de corteza en las que la carga de
combustible es variable, hay altos contenidos de metales que pueden ser catalizadores como asimismo combustión inestable e incompleta.
Es sabido que la combustión de corteza de madera salobre puede incrementar la generación de PCDD/PCDF debido a aumentos en la
concentración de cloruros. En el caso de las calderas recuperadoras, el cloruro en el combustible proviene de la materia prima aunque
también puede originarse en el blanqueo si los respectivos filtrados son recuperados; hay sospechas que las emisiones desde estas calderas
podrían aumentar cuando se procesa en las plantas madera salobre. Sin embargo, algunos estudios (1,2) demuestran que un incremento en
la concentración de cloruros no aumentaría las emisiones al aire ambiente, desde las calderas recuperadoras, cuando éstas son operadas en
condiciones normales. La conclusión general es que el contenido de cloruros en el licor negro es de menor importancia que una combustión
estable.
Página 7 de 7
Para CRs el TOOLKIT menciona concentraciones de 0,004 – 0,008 ng TEQ/m3 (CEPA-FPCA 1999); considerando el flujo indicado,
de 6000 – 9000 m3/Adt se obtiene un Factor de Emisión (FE) de 0,02 – 0,07 Pg TEQ/ADt.
El TOOLKIT también menciona un estudio de USEPA del año 2000 y entrega un FE de 0,007Pg TEQ/ton licor negro. Habiendo
revisado este estudio el FE está en el rango 0,029 – 0,078 Pg TEQ/ton sólido seco; con un flujo de 1,8 tss/ADT se obtiene un FE de
0,05 – 0,14 TEQ/ADt
-
-
Comentario 2
Pensamos que la unidad Pg TEQ/t Feed es erróneamente asociada a las emisiones al aire desde Calderas Recuperadoras, debiendo ser
TEQ/ADt. En efecto, de los mismos antecedentes incluidos en el TOOLKIT esto es demostrable, como se indica a continuación:
Comentario 1
La categoría 1, referida –entendemos- a Calderas Recuperadoras, menciona además “lodos” (pueden ser lodos biológicos) y “madera”; esto
último no nos parece que se asocie con la operación tradicional de estos equipos y consecuentemente no entendemos porqué se incluye en
ella.
Emission factors for pulp and paper industry boilers
Emission Factors
Air, Pg TEQ/t Feed
Residue, Pg TEQ/t Ash
1. Black liquor boilers, sludges and wood
0.07
1 000
2. Bark boilers only
0.4
1 000
2.4.3.1. Calderas de Recuperación y Calderas de Poder
La siguiente es una copia de la Tabla 55 del TOOLKIT:
2.4.3. Factores de Emisión
2.4.2. Fuentes en la industria
Las emisiones pueden ocurrir por distintas vías, teniendo como consecuencia presencia de PCDD/PCDF en aire, agua y producto además de
los residuos, en los que se les puede encontrar también. De acuerdo con el TOOLKIT las mayores emisiones son al agua y en los residuos.
Página 8 de 8
Comentario 7
En la sección 6.7.1.1. el TOOLKIT menciona la incineración de lodos primarios y secundarios, refiriéndose a incineradores dedicados y/o a
coincineración en grandes y bien operadas instalaciones de poder que queman combustibles fósiles. El FE asociado a esta emisión a la
Comentario 6
El TOOLKIT asume un promedio de 1.000 Pg TEQ/t ceniza para el FE asociado con las cenizas provenientes de las operaciones de las
Calderas Recuperadoras y de biomasa. En el caso de las Calderas Recuperadoras, consideramos razonable asumir un FE = 50 Pg TEQ/t
ceniza, entendiendo por tal al exceso de ceniza que es retirado desde el precipitador electrostático.
Comentario 5
Lo señalado en el Comentario 4, en relación con la mezcla de unidades en las bases de cálculo, también es aplicable para el FE establecido
para los residuos.
Comentario 4
Para las Calderas de Poder, en la sección 8, Anexo 1 del TOOLKIT y también en la Hoja de Cálculo que incluye, el FE se presenta con las
unidades TEQ/ton de pulpa y no TEQ/ton combustible lo que consideramos un error necesario de subsanar dado que es altamente incidente
en los resultados de los Inventarios.
Comentario 3
El FE de 0,4 TEQ/t combustible que propone el TOOLKIT para la combustión de corteza es razonable para la industria chilena. Si se
considera un poder calorífico de 8 MJ/kg combustible húmedo, este FE equivale a 50 Pg TEQ/TJ de combustible, que se corresponde con el
propuesto para la combustión de “madera limpia” en la sección 6.3.2 del TOOLKIT. En esta sección, que no es la que corresponde a la
industria de la celulosa y el papel, se presentan 2 categorías de calderas, en función del tipo de combustible. Las Calderas de Corteza de la
industria chilena están incluidas en la categoría 2 ya que las otras queman residuos agrícolas, como paja, cuescos, etc, junto con madera.
Hay indicaciones recientes de la industria sueca (sin publicar) que muestran valores menores aún, del orden de los 20 Pg TEQ/TJ de
combustible lo que se atribuye a mejor control de la combustión y menores emisiones de material particulado.
Utilizando ambos antecedentes se concluye que la unidad debe ser TEQ/Adt y no TEQ/t feed. Esta es, además, la unidad utilizada en el
Resumen de FE del TOOLKIT (Sección 8, Anexo 1, Categoría 7) así como en las hojas de cálculo Excel que incluye.
Página 9 de 9
Por otra parte, analizando las otras calderas de poder incluidas en el TOOLKIT, sección 6.3.4.5, se observa un FE = 10 ng TEQ/kg de ceniza;
en este caso se considera 3% de ceniza, con lo que se obtiene FE = 0,3 ng TEQ/kg de combustible seco; con un PC de 16 GJ/t de
combustible seco se obtiene FE = 20 Pg TEQ/TJ de combustible que es el valor propuesto para madera limpia en la Tabla 40.
No ha sido posible encontrar el estudio alemán mencionado como referencia en el TOOLKIT, página 93; tampoco se han encontrado
investigaciones o estudios acerca de contenido de PCDD/PCDF en cenizas de calderas de corteza/madera.
Comentario 9
Sin perjuicio de lo señalado en el Comentario 8, el valor de FE = 15 Pg TEQ/TJ de combustible no se relaciona con las referencias y los
cálculos que aparecen en el TOOLKIT, como se demuestra a continuación:
- de los estudios de referencia que mencionan FE = 30 – 3000 ng TEQ/kg ceniza de fondo y FE = 30 – 23.300 ng TEQ/kg ceniza
volante, el TOOLKIT selecciona 3000 ng TEQ/kg para ambos tipos de ceniza
- luego, considerando 0,5 % de contenido de ceniza en el combustible el FE = 15 Pg TEQ/t de combustible seco.
- Con un Poder Calorífico (PC) de alrededor de 16 GJ/t de combustible seco se obtiene cerca de ¡¡1000 Pg TEQ/TJ de combustible!!, lo
que es un valor muy alto.
Comentario 8
Se presentan contradicciones entre las diferentes Tablas y Factores de Emisión propuestos en el TOOLKIT para la emisión asociada con los
residuos de la combustión de corteza. En efecto, en la Tabla 55 se menciona un FE = 1000 Pg TEQ/t de ceniza, equivalente a unos 50 Pg
TEQ/TJ de combustible, mientras que en la Tabla 38, Categoría 2, el FE = 15 Pg TEQ/TJ de combustible. Tal como se señaló antes, la
Categoría 2 es la que incluye a las Calderas de Corteza existentes en la industria, por lo que este FE se estima razonable.
atmósfera es 0,06 Pg TEQ/t lodo. Este factor de emisión no hace diferencia entre tecnologías, ej: sistemas de depuración de gases. Se
asume que se refiere a modernas plantas de incineración de lodos. Existen valores de referencia en el rango de 0.0004 – 0.118 Pg TEQ/t lodo
para calderas de poder con precipitadores electrostáticos
4.5
0.06
70
2
4.5
0.2
Pg TEQ/ADt pg TEQ/L Pg TEQ/ADt
100
10
Pg TEQ/t seco
Factor de Emisión
Efluente
Lodo
Página 10 de 10
Comentario 12
Cuando en el TOOLKIT se menciona que los FE consideran que todas las plantas tienen sistemas de tratamiento de efluentes que producen
lodos y descargas con bajos contenidos de sólidos suspendidos, se interpreta como tratamiento primario seguido de tratamiento biológico o
químico o ambos. El TOOLKIT no diferencia entre métodos de tratamiento, que podría influir en la distribución entre las fases líquida y sólida.
Las PCDD/PCDF no se degradan en el tratamiento, lo que significa que la misma cantidad que ingresa sale del sistema presentándose tan
solo una redistribución entre las fases líquida (efluente) y sólida (lodos).
Comentario 11
Los cálculos deben hacerse utilizando los FE expresados como concentración en las fases respectivas; sólo cuando no se cuenta con datos
de flujo de efluente o producción de lodos pueden utilizarse los FE relativos a la producción de celulosa.
1. Kraft, tecnología antigua, blanqueo standar (Cl2 & NaClO)
2. Kraft, tecnología moderna, blanqueo ECF & TCF
Clasificación
2.4.3.3. Efluentes y Lodos
La siguiente es una reproducción de la Tabla 56 del TOOLKIT:
Comentario 10
Teniendo presente que todos los hornos de cal en las plantas chilenas de celulosa tienen instalada moderna tecnología para abatir el polvo,
como asimismo los datos del TOOLKIT y mediciones en la industria sueca, se considera que el FE = 0,07 Pg TEQ/t cal producida
(equivalente a 0,014 – 0,021 Pg TEQ/ADt, para consumos de 200 – 300 kg cal/ADt) representa adecuadamente a la emisión de la industria
nacional. Ello, sin perjuicio de mencionar modernas instalaciones de la industria sueca presentan emisiones de 0,01 Pg TEQ/ADt , debido a
mejor control de combustión y menor emisión de material particulado, condiciones que corresponden a la operación de las unidades que se
instalan con los nuevos proyectos en Chile.
2.4.3.2. Hornos de Cal
Factores emisión para celulosa kraft y productos de papel
Clasificación
FE, Pg TEQ/ADt
referencias
TOOLKIT
1. Kraft, tecnología antigua, blanqueo standar (Cl2 & NaClO)
10
2. Kraft, tecnología moderna, pulpa café y blanqueos ECF & TCF
0.3
Página 11 de 11
Tabla 57 de
TOOLKIT
8
0.5
Comentario 14
Utilizando las referencias del TOOLKIT no nos ha sido posible obtener los Factores de Emisión que se presentan en la Tabla 57. En la
siguiente hemos incluido los factores que obtenemos y los propuestos en el TOOLKIT:
2.4.3.4. Celulosa
Complementariamente a lo señalado, los mejoramientos tecnológicos incorporados a la industria chilena han significado también importantes
reducciones del contenido de lignina contenida en la pulpa que se blanquea. En efecto, el 4,5 % inicial se encuentra hoy en 1,8%, es decir,
¡se ha reducido en un 2,5 veces. Este mejoramiento, junto con significar ajustes en la cantidad de producto químico necesario para blanquear,
reduce significativamente las posibilidades de generación de TCDD/TCDF.
Comentario 13
El proceso de producción de celulosa estándar chilena no está representado en la Tabla anterior dado que el que allí aparece mencionado
como “old technology” utiliza para blanquear la pulpa solamente cloro gaseoso (Cl2) mientras que en nuestro país, así como en la mayor parte
del mundo hoy en día, sólo se utiliza una fracción de compuesto blanqueante bajo esta forma y el saldo se adiciona como Dióxido de Cloro
(ClO2). Junto a ello, se han desarrollado e implementado tecnologías de cocción y de deslignificación que significan reducidos contenidos de
lignina en la pulpa que se blanquea, por lo que la cantidad de compuesto blanqueante requerida es menor. Todo ello implica una generación
de PCDD/PCDF muchísimo menor que la especificada en la Tabla 56 del TOOLKIT, reproducida más arriba (8 Pg TEQ/ADt) hecho que
genera la necesidad de definir una tercera categoría de proceso, “Kraft pulps & papers, improved technology, standard bleaching (Cl2 &
ClO2)”. Usando un criterio conservador, nuestros asesores nos indican que el FE asociado se estima en 1.0 Pg TEQ/ADt, para el efluente, y
1.5 Pg TEQ/ADt para los lodos.
Sin embargo, una total eliminación de PCDD/PCDF en productos ECF y sus efluentes depende del número de Kappa y de la pureza del
ClO2. La probabilidad de formar PCDD/PCDF aumenta con altos números de Kappa y ClO2 contaminado.
x
Página 12 de 12
El N° Kappa tiene un menor efecto en la formación de PCDD/PCDF que el del Múltiplo de Cloro en la primera etapa de blanqueo. La
razón entre el Cl2 cargado y el N° Kappa (contenido de lignina), equivalente al Múltiplo de Cloro, tiene un mayor efecto en la generación
de PCDD/PCDF que el total de Cl2 cargado. El efecto de ésto es que pulpas no-deslignificadas con oxígeno, blanqueadas con bajos
Múltiplos de Cloro en la primera etapa generan menos TEQ/ADt.
x
El blanqueo estándar con un bajo múltiplo de cloro en la primera etapa, d 0.10 % Cl2/Kappa, redude drásticamente las PCDD/PCDF tanto
el la celulosa como también en el efluente de blanqueo y en el efluente sin tratar de la planta.
x
Concordamos con estas conclusiones. Queremos agregar que las investigaciones suecas de mediados a fines de los 80’s demostraron que:
Al reemplazar Cl2 con ClO2 (convertir blanqueo estándar en ECF), la emisión de PCDD/PCDF se reduce a niveles no-detectables.
x
Comentario 16
El Toolkit: concluye:
Comentario 15
En el Informe final de SSVL se indica que la celulosa café también contiene pequeñas cantidades de PCDD/PCDF, < 1 Pg Nordic TEQ/ADt,
que en esa fecha se consideraba una concentración del ambiente. Estamos de acuerdo con la perspectiva del TOOLKIT que pone bajo una
misma categoría las pulpas Café, ECF, TCF.
Entre 1987 and 1989 los principales cambios en los procesos fueron la reducción del múltiplo de cloro en la primera etapa del balnqueo
estándar y el blanqueo ECF. El contenido de se redujo a 0.01-1.2 Pg Nordic TEQ/ADt para celulosa sin deslignificación y ND-0.96 Pg Nordic
TEQ/ADt para celulosa deslignificada, con diferencias no significativas para maderas distintas.
Los valores del TOOLKIT están de acuerdo con dos investigaciones, en 13 y 14 plantas, desarrolladas en Suecia por SSVL (Ref. 3) en 1987 y
1989, respectivamente. En la primera el rango hallado fue 0.6-24 Pg Nordic TEQ/ADt de pulpa para celulosa de conífera sin deslignificación
con oxígeno y 0.3-2.2 para las con deslignificación. El contenido en pulpas de latifoliadas fue menor, 0.5-3.4 y 0.4-0.9 Pg Nordic TEQ/ADt de
celulosa, respectívamente.
Otras medidas, para reducir la presencia de PCDD/PCDF in celulosa, efluente y lodo, son un buen lavado de la pulpa antes del blanqueo
y evitar o eliminar la sobre cloración o la misma cloración del agua cruda y usar adtivos puros.
x
0.06 Pg TEQ/t lodo
0.07 Pg TEQ/t cal
Incineración lodo
Hornos de Cal
ND
ND
Factores de Emisión
Aire
Ceniza
C. Recuperadoras 0.07 Pg TEQ/ADt
50 Pg TEQ/t ceniza
C. de Corteza
50 Pg TEQ/TJ corteza
Equipo
Página 13 de 13
Comentario 20
Los siguientes son los FE que proponemos para las calderas de la industria de la celulosa y el papel (ref. en Tablas 55, 38, 44 del Toolkit):
Comentario 19
Las Hojas de Cálculo presentan errores para la emisión de los lodos del tratamiento de efluentes: el FE se presenta como Pg TEQ/t de lodo,
pero en la Hoja de Cálculo se multiplica por la producción total de celulosa lo que entrega una emisión demasiado alta.
Comentario 18
Las Referencias y expresiones del TOOLKIT no están total y claramente definidas dado que se observan errores en algunos de los Factores
de Emisión. Las bases de cálculo (ADt, toneladas de combustible o MJ) se encuentran mezcladas en algunos casos y los FE se refieren a
distintas bases en varias partes del TOOLKIT. Este es el caso principalmente de la Calderas de Poder y de Recuperación en cuanto a las
emisiones al aire y en los residuos. En el TOOLKIT los factores de emisión están calculados en base a toneladas de combustible o cantidad
de ceniza, pero en las Hojas de Cálculo la misma expresión se multiplica con producción de celulosa. Esto implica resultados con emisiones
incorrectas.
Comentario 17
En general, estamos de acuerdo con las recomendaciones del Toolkit que se refieren a que si una planta no tiene mediciones confiables, la
estimación de las emisiones de PCDD/PCDF deba ser hecha con los Factores de Emisión propuestos en él.
Con relación a minimizar o eliminar la formación de PCDD/PCDF, resulta razonable tener bajos N°s Kappa antes del blanqueo, lo que se
logra con deslignificación con oxígeno, y entonces usar el blanqueo ECF.
x
Celulosa
8
3.0
0.5
Página 14 de 14
Comentario 25
Como comentario de carácter general, que apunta a simplificar los cálculos para los inventarios, a una mejor comprensión de los FE y
que contribuye a evitar errores de cálculo, proponemos que todos los Factores de Emisión de TCDD/TCDF para la industria de la celulosa se
expresen en Pg TEQ/ADt.
Comentario 24
En el TOOLKIT la pulpa café se clasifica junto a las ECF and TCF, con lo que estamos de acuerdo. Sin embargo, nada se menciona acerca
de los respectivos efluentes. Al respecto pensamos que estos deben ser los mismos que se definen para los efluentes ECF and TCF.
Comentario 23
De acuerdo con el TOOLKIT no hay diferencias entre las emisiones de PCDD/PCDF con efluentes de celulosas de fibra corta y de fibra larga
y son independientes del N° Kappa. Concordamos con esta aproximación.
Comentario 22
La emisión con un efluente no tratado es la suma de los FE para el efluente y el FE para el lodo. Si sólo hay tratamiento primario o secundario
con lagunas de aireación, no habrá emisión con el lodo pero el total se descarga con el efluente. En caso de tratamientos secundario de alta
eficiencia, lodos activados, el exceso de lodos contendrá PCDD/PCDF acorde con el respectivo FE.
(a) d 0.1 % Cl2/Kappa en la primera etapa
FE, Pg TEQ/ADt
Efluente Lodos
Kraft, tecnología antigua, blanqueo estandar (Cl2) 4.5
4.5
(a)
Kraft, blanqueo estandar (Cl2), bajo múltiplo Cl2 1.0
1.5
Kraft, tecnología moderna, Pulpas Café, ECF, TCF 0.06
0.2
Clasificación
Comentario 21
Los siguientes son los FE que proponemos para las emisiones al agua, lodos y Productos:
0,07 Pg
TEQ/t cal
Hornos de Cal
0,26 Pg
TEQ/ADt
0,26 Pg
TEQ/ADt
4,5 Pg
TEQ/ADt
0,06 Pg
TEQ/ADt
9 Pg
TEQ/ADt
Agua
4,5 Pg
TEQ/ADt
0,2 Pg
TEQ/ADt
1.000 Pg
TEQ/t ceniza
1.000 Pg
TEQ/t ceniza
0,5 Pg
TEQ/ADt
0,5 Pg
TEQ/ADt
8 Pg
TEQ/ADt
ECF & TCF
Estándar
Celulosa
(*) : Blanqueo con Bajo Múltiplo de Cloro en primera etapa (Cl2/N° Kappa)
Sin Blanqueo
Blanqueo ST-BMCl2
(*)
Blanqueo ECF, TCF
Blanqueo Estándar
Tratamiento Efluentes
0,4 Pg
TEQ/t feed
Caldera de Corteza
Aire
0,07 Pg
TEQ/t feed
Caldera
Recuperadora
Toolkit
Residuo
0,07
Pg TEQ/t cal
0,4 Pg
TEQ/feed
0,07 Pg
TEQ/ADt
Aire
4,5 Pg
TEQ/ADt
0,06 Pg
TEQ/ADt
9 Pg
TEQ/ADt
2,5 Pg
TEQ/ADt
0,26 Pg
TEQ/ADt
0,26 Pg
TEQ/ADt
Agua
8 Pg
TEQ/ADt
3 Pg
TEQ/ADt
0,5 Pg
TEQ/ADt
0,5 Pg
TEQ/ADt
ECF & TCF
Estándar
Celulosa
Página 15 de 15
4,5 Pg
TEQ/ADt
0,2 Pg
TEQ/ADt
50 Pg
TEQ/t ceniza
(15,6 Pg
TEQ/TJcomb)
15 Pg
TEQ/TJ fuel
(48 Pg
TEQ/t ceniza)
Corma
Residuo
La siguiente Tabla resume los valores que para los Factores de Emisión presenta el Toolkit y aquellos que se proponen como más
representativos de la industria chilena de la celulosa y el papel, por parte de Corma.
Descripción
3.1.
3. Conclusiones
SSVL, Final Report February 1991, Environment 90.
El proyecto se desarrolló entre 1985-1990. La referencia a investigaciones SSVL desarrolladas a mediados y fines de los 80s
menciona este Informe Final y los Informes intermedios, que fueron la base para nuestros asesores.
AF-Celpap, “Review of UNEP “Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases” and Estimate of
Emission Levels from the Chilean Pulp Mills” (2003)
3.
4.
Página 16 de 16
Luhte C et al, 80(1997)2, 165-169 TAPPI JOURNAL, “Are Salt Laden Recovery Boilers a Significant Source of Dioxins?”
2.
Ahlenius L, TAPPI Pacific Section Seminar Notes on “Closing Up the Bleach Plant - MoDo Experience”, TAPPI PRESS, Atlanta 1993.
1.
4. Referencias
STANDARIZED TOOLKIT
COMMENTS COMPLEMENTS
Pulp and Paper Dep. – South area
Environment Comitee
CORMA Bio Bío Region
Septiembre, 2004
Complemento a Comentarios (marzo 03) al Toolkit – Septiembre 2003
Página 1 de 2
This document has been generated to specify the comments of Corma about Toolkit
from March 2003, having in mind the questions wich Dra. Heidelore Fiedler ask about
them in the meeting with representatives of Corma that was held in Chile, Arauco Mill,
last July 26th.
This time we have decided just include Tables, the Toolkit original ones and the same,
but with the numbers that are envolved in Corma’s comments. We consider that there
are enough arguments in Corma’s Report of March 03.
Our main comments are related with:
-
There are some units problems and weaknesses in process description.
The EF for ashes from combustión of black liquor and biomass don’t
represent well the chilean industry.
The process technology that uses the chilean industry is not included in
the Toolkit classification.
The following Table summarizes what we have include in Anexes.
Combustion
Emission Factor Toolkit
Air
Residue
1. Black liquor boilers, burning of sludge and wood 0.07 Pg TEQ/t Feed 1.000Pg TEQ/t Ash
0.4 Pg TEQ/t Feed 1000Pg TEQ/t Ash
Emission Factor CORMA
Air
Residue
1. Black liquor boilers
0.07 Pg TEQ/ADt
50 Pg TEQ/t Ash
0.16 - 0.4 Pg TEQ/t
48 Pg TEQ/t Ash
Feed
Effluents, sludges and Product
Kraft process, standard bleaching
Emission Factor CORMA (Toolkit doesn’t consider this
(Cl2), low (a) Cl2 multiple
class)
Water
Residue = Sludge
Product
16 pg
1.5 Pg 33.3Pg 3.0Pg TEQ/ADt
1.0 Pg
TEQ/ADt TEQ/L TEQ/ADt TEQ/t
(a): d 0.1 % Cl2/Kappa in first stage
Complemento a Comentarios (marzo 03) al Toolkit – Septiembre 2003
Página 2 de 2
ANNEX 1
TOOLKIT PAGES WITH EMISSION
FACTORS FOR PULP AND PAPER
PRODUCTION
ANNEX 2
PRODUCTION PROPOSED BY CORMA
Emission Factor
1. Black liquor boilers
Air
0.07 Pg TEQ/ADt
0.16 - 0.4 Pg TEQ/t Feed
Pg TEQ/t Ash
Residue
50
48
Classification
1. Kraft process, old technology (Cl2)
2. Kraft process, standard bleaching
2. Kraft process, modern technology
(ClO2)
3. TMP Pulp
4. Recicling Pulp
Emission Factor
Water
Residue = Sludge
pg
TEQ/L
Pg TEQ/ADt
Pg TEQ/ADt Pg TEQ/t in
Sludge
4,5
70
4,5
100
1.0
16
1.5
33.3
0.06
2
0.2
10
ND
ND
ND
ND
ND
ND
ND
ND
(a): d 0.1 % Cl2/Kappa en la primera etapa
Classification
1. Kraft pulps and papers from primary fibers, free chlorine bleaching
2. Kraft pulps and papers from primary fibers, standard bleaching
3. Sulfite papers, old technology (free chlorine)
4. Kraft papers, new technology (ClO2, TCF), unbleached papers
5. Sulfite papers, new technology (ClO2, TCF)
6. Recicling paper
Emission Factors
Pg TEQ/ADt
8
3.0
1
0.5
0.1
10
Source categories
Cat Subca Class
.
t
7
a
1
2
Air
Production of Chemicals, Consumers
Goods
Pulp and Paper mills Boilers
Black liquor boilers (per ton of pulp)
Bark boilers only (per ton of bark)
Effluents and sludges
1
2
3
4
5
1
2
3
4
5
6
Potencial Release Route (Pg TEQ/t)
Water land Products Residues
0.07
0.16
- 0.4
Water
Pg TEQ/ADt
4.5
Kraft process, old
technology (Cl2)
Kraft process, standard
1.0
bleaching (Cl2), low (a) Cl2
multiple
Kraft process, modern
0.06
technology (ClO2)
TMP Pulp
Recicling Pulp
Pulp and Paper
Kraft pulps/papers from primary
fibers (Cl2)
Sulfite papers old technology (Cl2)
Kraft pulps standard bleaching
Kraft papers new technology
(ClO2, TCF), unbleached papers
Sulfite papers new technology
(ClO2, TCF)
Recicling paper
(per ton of
ash)
50
48
Air
Pg TEQ/L
70
Residue
Pg TEQ/ADt
4.5
Pg TEQ/t
|00
16
1.5
33.3
2
0.2
10
Water
Land
Products Residues
8
1
3.0
0.5
0.1
10
ANNEX 1
PRODUCTION
ANNEX 2
(Recicled Paper)
Classification
1. Kraft process, old technology (Cl2)
2. Kraft process, standard bleaching
2. Kraft process, modern technology
(ClO2)
3. TMP Pulp
4. Recicling Pulp
Emission Factor
Water
Residue = Sludge
pg TEQ/L
Pg TEQ/ADt
Sludge
4,5
70
4,5
100
1.0
16
1.5
33.3
0.06
2
0.2
10
ND
ND
ND
ND
ND
ND
ND
ND
Classification
1. Kraft pulps and papers from primary fibers, free chlorine bleaching
2. Kraft pulps and papers from primary fibers, standard bleaching (Cl2), low (a)
Cl2 multiple
3. Sulfite papers, old technology (free chlorine)
4. Kraft papers, new technology (ClO2, TCF), unbleached papers
5. Sulfite papers, new technology (ClO2, TCF)
6. Recicling paper (pulp from old technology)
7. Recicling paper (pulp from standard bleaching (Cl2), low (a) Cl2 multiple)
Emission Factors
Pg TEQ/ADt
8
3.0
1
0.5
0.1
10
3.0
Source categories
Cat Subca Class
.
t
7
a
1
2
Air
Goods
1
2
3
4
5
1
2
3
4
5
6
7
0.07
0.16
- 0.4
Water
Pg TEQ/ADt
4.5
Kraft process, old
technology (Cl2)
1.0
multiple
0.06
technology (ClO2)
TMP Pulp
Recicling Pulp
Pulp and Paper
fibers (Cl2)
(ClO2, TCF)
Recicling paper (pulp from old
technology)
technology)
(per ton of
ash)
50
48
Air
Pg TEQ/L
70
Residue
Pg TEQ/ADt
4.5
Pg TEQ/t
|00
16
1.5
33.3
2
0.2
10
Water
Land
Products Residues
8
1
3.0
0.5
0.1
10
3.0
STANDARIZED TOOLKIT
COMMENTS COMPLEMENTS
(Recicled Paper)
Pulp and Paper Dep. – South area
Environment Comitee
CORMA Bio Bío Region
October, 2004
Comments (March 03) Complements toToolkit – October 2004
Page 1 of 1
This document has been generated to give aditional information about the Emission
Factor for Recicled Paper in the chilean industry according to the conversation with
Dra. Heidelore Fiedler in the meeting with representatives of Corma that was held in
Chile, Arauco Mill, last July 26th.
As we have done earlier for pulp, our comments are included in Tables: the Toolkit
original ones (Annex 1) and the same, but with the Corma’s numbers (Annex 2). As
we haven’t say nothing about recicled paper in Corma’s Report of March 03, we do it
now.
We consider the Toolkit must have in account that in Chile all the recicled paper
come from used newsprint ones (TMP Pulp; EF = ND) and used white papers (Kraft
pulp, standard bleaching (Cl2), low (a) Cl2 multiple; or ECF pulp). According to the
industrial process for the production of recicled paper, this means that the Emission
Factor cannot be higher than those estimated for the pulp (they will be lower than this
because of the use of high amounts of newsprint paper in the manufacture of recicled
paper), wich are:
-
3,0 Pg TEQ/ADt for Kraft pulp, standard bleaching (Cl2), low (a) Cl2 multiple
0,5 Pg TEQ/ADt for Kraft pulp, ECF o TCF bleaching
Since we don’t have measurements, our proposal is consider an Emission Factor of
3,0 Pg TEQ/ton recicled paper instead of 10 Pg TEQ/t.
______________________________
Comments (March 03) Complements toToolkit – October 2004
Page 2 of 2
ANNEX 1
PRODUCTION
ANNEX 2
(Recicled Paper)
Classification
1.
2.
2.
3.
4.
Kraft process, old technology (Cl2)
Kraft process, standard bleaching
Kraft process, modern technology
(ClO2)
TMP Pulp
Recicling Pulp
Emission Factor
Water
Residue = Sludge
pg TEQ/L
Pg TEQ/ADt
Sludge
4,5
70
4,5
100
1.0
16
1.5
33.3
0.06
2
0.2
10
ND
ND
ND
ND
ND
ND
ND
ND
Classification
1.
2.
3.
4.
5.
6.
7.
Kraft pulps and papers from primary fibers, free chlorine bleaching
Kraft pulps and papers from primary fibers, standard bleaching (Cl2), low (a)
Cl2 multiple
Sulfite papers, old technology (free chlorine)
Kraft papers, new technology (ClO2, TCF), unbleached papers
Sulfite papers, new technology (ClO2, TCF)
Recicling paper (pulp from old technology)
Recicling paper (pulp from standard bleaching (Cl2), low (a) Cl2 multiple)
Emission Factors
Pg TEQ/ADt
8
3.0
1
0.5
0.1
10
3.0
Source categories
Cat Subca Class
.
t
7
a
1
2
Air
Goods
1
2
3
4
5
1
2
3
4
5
6
7
0.07
0.16
- 0.4
Water
Pg TEQ/ADt
4.5
Kraft process, old
technology (Cl2)
1.0
multiple
0.06
technology (ClO2)
TMP Pulp
Recicling Pulp
Pulp and Paper
fibers (Cl2)
(ClO2, TCF)
technology)
technology)
(per ton of
ash)
50
48
Air
Pg TEQ/L
70
Residue
Pg TEQ/ADt
4.5
Pg TEQ/t
|00
16
1.5
33.3
2
0.2
10
Water
Land
Products
8
1
3.0
0.5
0.1
10
3.0
Residues
27
May 13, 2004
James P. Willis
Executive Secretary
Interim Secretariat of the Stockholm Convention
11-13, chemin des Anémones
CH - 1219 Châtelaine
Geneva, Switzerland
Dear Mr. Willis:
The United States is pleased to submit the attached comments to the 1st Edition of the
Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases,
issued by the United Nations Environment Program in May 2003. These comments are
being submitted in response to the request issued in accordance with decision 7/5 of the
seventh session of the Intergovernmental Negotiating Committee of the Stockholm
Convention on Persistent Organic Pollutants (UNEP letter dated 4 December 2003).
We appreciate the opportunity to comment on this key document and look forward to the
release of another revised edition. If you have questions or need additional information
related to these comments, please contact Dale Evarts (U.S. Environmental Protection
Agency, Evarts.Dale@epa.gov) or John Thompson (U.S. Department of State,
ThompsonJE2@state.gov).
Sincerely,
Robert Ford
Deputy Director, Office of Environmental Policy
U.S. Department of State
Enclosure
U.S. Comments on the 1st Edition of the Standardized Toolkit for Identification and
Quantification of Dioxin and Furan Releases (United Nations Environment Program, May 2003)
Introduction:
The United States appreciates the extensive work by the United Nations Environmental Program
(UNEP) to complete the 1st Edition of the Standardized Toolkit for Identification and
Quantification of Dioxin and Furan Releases. This version continues to move forward in
providing a basic methodology and tools for developing countries to identify sources and
characterize releases, as well as the necessary information to develop rudimentary inventories.
In this round of comments, we continue to emphasize the need for transparency and to
qualitatively or quantitatively address uncertainty. In that vein, we have included a validation
exercise that we conducted to assess the accuracy of the Toolkit emission factors.
General Comments:
Transparency of Emission Factors: Despite a significant rewrite, and inclusion of additional
information on the sources of information included in the Toolkit, the issue of transparency
remains a problem. The Toolkit lacks adequate description and documentation on the derivation
of the default emission factors (e.g., sources of information and selection criteria used to filter
existing information). In this regard, it is not possible to understand what each emission factor
for each source category is intended to represent. A user of the Toolkit is faced with the problem
of having to match the simplistic and rather generalized emission factors with a particular source
under study, and this requires careful description of each source in terms of technology,
feedstocks, process flow, product produced, fuels used, and technology used for pollution
control. As a suggested improvement, the Toolkit could further sub-classify source categories
and present default emission factors on the basis of type of technology within each class and type
of pollution control systems used within the class. In addition, it would be helpful if the Toolkit
contained technical appendices that document the derivation and calculation of default emission
factors for each source category reviewed in the report. Explaining all mathematical
manipulations of data in a detailed manner would allow less experienced technical staff to
reproduce the calculation of emission factors. This would assist the user in understanding the
degree to which the emission factors can be applied to their source, and would provide a
transparent resource with regard to the facilities used and the computation of the emission factor.
As an example of this problem area, we have computed estimates of air releases operating in the
U.S. in 1987 and 1995 using the Toolkit emission factors, and then compared these results to our
official inventory of air releases (see below).
Uncertainty: The annual TEQ emission to air, land and water is determined by the multiplication
of an emission factor by the annual activity level for a specific source class. The quality and
quantity of information supporting both the estimate of the emission factor and the activity level
varies greatly. In some cases only a single tested source may have been used to develop an
emission factor for the entire source category, and in other cases hundreds of individual facilities
within a class may have been tested. We continue to recommend that the UNEP Toolkit
indicate, at least qualitatively, the uncertainty implicit in each emission factor.
This variability in the robustness of the data introduces uncertainty with regard to how
representative an emission factor is to a particular source class. Currently the Toolkit is silent
with respect to uncertainty, and treats all emission factors as if they were supported by the same
1
quality of information. As a suggestion, the Toolkit could introduce a ranking factor scheme or
scoring system that qualitatively or quantitatively reflects uncertainty. This indication of
uncertainty could be presented along with the emission factor. In this way, the user would have
some understanding of the robustness of the data underlying the emission factor. (The U.S. uses
a ranking system for its emission factors and will be glad to provide UNEP with additional
information and assistance in developing such as system for the Toolkit.)
Vague Air Pollution Control (APC) Descriptors: The Toolkit uses very broad classes of
pollution control to differentiate levels of dioxin emissions from sources that lack any technical
meaning or context, are too qualitative to be applied effectively. For example, in selecting TEQ
emission factors for specific combustion sources, the Toolkit uses the following descriptors of air
pollution control (APC), each of which has a different TEQ emission factor: no APC; minimal
APC; good APC; sophisticated APC. The Toolkit does not offer technical definitions of these
terms that would enable the user to select the emission factor appropriate for their source.
Toolkit Validation: In an attempt to understand the underlying accuracy of the UNEP Toolkit, we
have applied the Toolkit default emission factors towards estimating dioxin emissions from
selected U.S. sources operating in the years 1987 and 1995. This semi-validation exercise
consisted of comparing and contrasting results using the Toolkit default emission factors to the
official U.S dioxin emission inventory developed from direct test data. It was considered good
agreement if the numbers derived from the Toolkit were within a factor of five of the U.S.
Inventory. Table 1(attached) displays the comparison of estimates derived from the application
of the Toolkit to predicting U.S. emissions to the actual U.S. Dioxin Inventory. As a result of this
exercise, the following observations are noted:
¾ In general, the Toolkit worked reasonably well in predicting dioxin emissions from
municipal waste combustors, i.e., predicted results that were from 5 to 6 fold higher than
the U.S. Inventory.
¾ With respect to backyard trash burning, the Toolkit predicted dioxin emissions that were
four times higher than the U.S. Inventory. Because it is likely the default emission factor
of the Toolkit was based on the same U.S. study that was used to estimate emissions in
the U.S. Inventory, it is assumed that this difference is caused by a conversion error when
UNEP calculated their emission factor. This should be verified.
¾ In general, the Toolkit did poorly in predicting dioxin emissions from hospital/medical
waste combustors, i.e., predicted results were from 22 to 80 times higher than the U.S.
Inventory. This suggests the Toolkit default emission factor for hospital waste
incinerators is not representative of dioxin emissions from U.S. facilities.
¾ In general, the Toolkit did poorly in predicting dioxin emissions from secondary
aluminum smelting and processing sources, i.e., predicted results were about 7 times
higher than the U.S. Inventory. This suggests the Toolkit default emission factor
secondary aluminum smelting is not representative of dioxin emissions from U.S.
secondary aluminum smelting facilities.
¾ In general, the Toolkit did poorly in predicting dioxin emissions from iron ore sintering
facilities, i.e., predicted results were about 10 times higher than the U.S. Inventory. This
suggests the Toolkit default emission factor for iron ore sintering is not representative of
dioxin emissions from U.S. iron ore sintering plants.
2
¾ In general, the Toolkit worked reasonably well in predicting dioxin emissions from
secondary copper smelting facilities, i.e., predicted results were in good agreement to the
U.S. Inventory.
This limited validation exercise suggests that heavy reliance on the Toolkit default emission
factors for constructing national inventories of dioxin releases will likely produce results that are
accurate to within one to two-orders of magnitude of inventories based on testing sources. We
recommend that UNEP consider conducting additional validation exercises, for instance using
the Dioxin Inventory of Thailand, and include results in appendices to the Toolkit.
3
High tech,
Controlled,
batch comb.,
good APC
Uncontrolled
batch
combustion,
no APCS
Controlled,
batch, no or
minimal
APCS
Low technol.
combustion,
no APC
system
Controlled
comb.,
minimal
APC
Controlled
comb., good
APC
High tech.
combustion,
sophisticated
APCS
UNEP
Toolkit
Categories
3000
Continuous
and
intermittent
w/wet
scrubber
Continuous
and
intermittent
w/dry
scrubber
Fabric filter/
1
525
40000
13,757,600
TOTAL
Continuous
and
intermittent
296,000
0.5
New tech
with DS/FF
NA
NA
NA
1,430,000
0
30
Older tech
with DS/FF
1,646,600
11,815,000
Activity
level (t/1987)
350
3500
UNEP
Emission
Factor (µg
TEQ/t)
FF, WS,EGB
UNC,
H-ESP
EPA APC
Assumption
USEPA
g TEQ/
1987
(Air)
7,919.26
0.13
0
296.01
7,623.12
NA
NA
NA
57,200
NA
NA
NA
2,590
Hospital Waste Incinerators
41,928.96
0.15
0
576.31
41,352.50
2
5
NA
NA
NA
22
5.3
1.2
NA
UNEP/
USEPA
Municipal Waste Combustors
UNEP
Toolkit
g TEQ/1987
(Air)
699
146,000
370,000
254,000
27,913,800
19,194,800
620,000
6,608,000
1,491,000
Activity
level (t/1995)
0.001
76.65
1,110
10,160
7,559.5
9.60
18.60
2,312.8
5,218.50
UNEP
Toolkit
g TEQ/1995
(Air)
0.48
0.93
3.7
136
1111.46
9.42
13.94
711.40
376.70
USEPA
g TEQ/1995
(Air)
3
14
4
0.0015
82
300
75
6.8
1.02
1.3
UNEP/
USEPA
TABLE 1: COMPARISON OF ESTIMATED TEQ RELEASES FROM SELECTED SOURCES USING THE UNEP TOOLKIT TO THE
USEPA DIOXIN INVENTORY
U.S. Comments on the 1st Edition of the Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases
(United Nations Environment Program, May 2003)
Sec. Cu Basic
technology
High waste
recycling,
incl. oil
contamin.
Materials
Sec. Cu Basic
technology
High waste
recycling,
incl. oil
contamin.
Materials
Processing
scrap Al,
minimal
treatment of
inputs,
simple dust
removal
Backyard
barrel
burning
Uncontrolled
domestic waste
burning
Processing
scrap Al,
minimal
treatment of
inputs,
simple dust
removal
packed bed
EPA APC
Assumption
continuous,
sophisticated
APCS
UNEP
Toolkit
Categories
20
800
150
300
TOTAL
UNEP
Emission
Factor (µg
TEQ/t)
14,500,000
266,600
727,000
7,700,000
1,430,000
Activity
level (t/1987)
2,590
USEPA
g TEQ/
1987
(Air)
Iron Ore Sintering
29.3
10
0.22
Secondary Copper Smelting
213.28
966
290
7.13
573
Secondary Aluminum Smelting
109.05
15.3
2310
22
4.0
UNEP/
USEPA
Backyard Trash Burning in Barrels
57,200
UNEP
Toolkit
g TEQ/1987
(Air)
12,400,000
243,000
1,300,000
8,000,000
770,699
Activity
level (t/1995)
248
194.4
195
2400
11,346.651
UNEP
Toolkit
g TEQ/1995
(Air)
25.1
266
27.4
595
141.11
USEPA
g TEQ/1995
(Air)
4
80
5
10
0.73
7.12
UNEP/
USEPA
TABLE 1: COMPARISON OF ESTIMATED TEQ RELEASES FROM SELECTED SOURCES USING THE UNEP TOOLKIT TO THE
USEPA DIOXIN INVENTORY
U.S. Comments on the 1st Edition of the Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases
(United Nations Environment Program, May 2003)
Heidelore Fiedler
From:
Sent:
To:
Subject:
Stratford, Jane (CGMP) [Jane.Stratford@defra.gsi.gov.uk]
Wednesday, May 19, 2004 6:12 PM
Heidelore Fiedler
Comments from EU Member states on the Standardized Toolkit.
Toolkit comments - Toolkit comments - Toolkit comments Toolkit comments
Italy.doc (...
Spain.doc (...
2004 - German... PD Consulting...
28
Dear Heide
As you are aware, my colleague Mike Collins has moved to another section of the
Department. For the meantime I am taking over responsibility for POPs issues. Before he
left Mike asked me to send you the EU Member States comments on the dioxins toolkits. I
apologise for my delay, but these are attached below.
Most of the comments provide additional or updated information from dioxin sources. I
hope you find them useful.
In addition, I also attach some comments from Patrick Dyke, who has been at training
workshops and helping countries produce their inventories. Again I hope you find his
comments useful.
Finally, I met with Jim Willis several weeks ago and he asked if UK had any emission
estimates from animal carcass incineration (pyres). I attach a link to a report which
has some information from the UK. I hope you find this useful too.
Again, I apologise for my delay in sending this information. Please let me know if UK
or EU can be any further assistance.
I look forward to meeting with you soon.
Best regards
Jane
CGMP Division
Defra
Standardised Toolkit for Identification and Quantification of Dioxin and
Furan Releases as well as information and
methodologies on other
chemicals under Article 5 Annex C
Please find attached comments from EU member states on the above you requested by 31
March 2004.
<<Toolkit comments - Italy.doc>> <<Toolkit comments - Spain.doc>>
<<Toolkit comments 2004 - Germany.doc>>
Please also find further comments from PD Consulting.
<<Toolkit comments PD Consulting.doc>>
I apologise for the delay in sending you the comments.
2
Data on dioxins from pyres
You also requested information on whether we had data on emissions from pyres. Please
find attached report published by the Department of Health following the foot and mouth
outbreak in the UK in 2000/2001:
Foot and Mouth - An Update on Risks to Health of Emissions from Pyres and Other Methods
of Burning Used for Disposal of Animals
This can be found at: http://www.dh.gov.uk/assetRoot/04/01/94/79/04019479.pdf or at:
http://www.dh.gov.uk/PolicyAndGuidance/HealthAndSocialCareTopics/FootAndMout
h/FootAndMouthGeneralInformation/fs/en
Chemicals and GM Policy
DEFRA
1
3/E6 Ashdown House
123 Victoria Street
London SW1E 6DE
Tel: 020 7082 8090
Fax: 020 7082 8086
Department for Environment, Food and Rural Affairs (Defra)
This email and any attachments is intended for the named recipient only. Its
unauthorised use, disclosure, storage or copying is not permitted. If you have received
it in error, please destroy all copies and inform the sender. Whilst this email and
associated attachments will have been checked for known viruses whilst within Defra
systems we can accept no responsibility once it has left our systems. Communications on
Defra's computer systems may be monitored and/or recorded to secure the effective
operation of the system and for other lawful purposes.
2
Federal Environmental Agency
28
Berlin, 01.03.2004
German comments to the „Standardized Toolkit for Identification and Quantification of
Doixins and Furan Releases”
The toolkit is a valuable instrument for assessing PCDD/F releases for developed and
developing countries on a sophisticated basis to be used in a flexible manner. It summarized the
available information for PCDD/F emissions and releases not only for major but also for minor
sources. Above those valuable information referring the technical background in the context of
the relevant status of the installations could be taken from this compendium. German experience
in creating its own inventory are comparable with those in the toolkit.
An update of the information is appreciated to bring in the most recent developments and
investigations in the context of minimization of PCDD/F releases at the source categories.
Germany has some comments for the update of the content, which consist of some additional
information in the context of the emission figures:
Chapter 6.1. Waste incineration
The following data were published for German waste incinerators and should be included into
the toolkit
Table 1: PCDD/F-emission concentrations at different types of waste incinerators basing of
application of best available techniques1
Types of waste incineration
Municipal
Hazardous
Medical
Sewage sludge
Emission concentrations for full implementation of BAT in 2000
0.005 ng I-TE/m3
0.005 ng I-TE/m3
< 0.1 ng I-TE/m3
0.006 ng I-TE/m3
Germany reported about its situation and has 56 incineration plants for municipal waste, all of
which are operated with the grade furnace system, data from 20 plants altogether were selected
to describe the BAT standard for the incineration of non-hazardous waste. The capacity of the
selected plants is in the range between 85,000 and 650,000 Mg/a.
All waste incineration plants are operated in such a way that with the incineration degree
achieved in slag and grate ash, a content of organically bound total carbon (TOC) of less than
1
Steffi Richter, Bernt Johnke “ Status of PCDD/F-emission control in Germany on the basis of the current
legislation and strategies for further action” in Chemosphere 54 (2004) 1299-1302
1
3% or a loss on ignition of less than 5% of the dry weight of the material combusted can be kept.
The incineration conditions in the furnace chamber to achieve an optimised incineration of the
incineration gases can be provided by all plants, as far as minimum temperature and residence
time are concerned.
Table 2: BAT standard for emissions of PCDD/PCDF and PCB in clean gas of waste incinerators
(operating values)2
Parameter
Measur
e
Half-hour
value
average Daily
value
average Annual average
value
Continuous measurement
¦C
CO
3
<1 – 10
<1 - 2
<1 – 2
3
<2 – 100
<1 - 38
< 2 – 17
mg/m
mg/m
Periodical measurement (Average over sampling time)
PCDD/PCDF,I-TE ng/m3
¦ PCB
0,0011 - 0,029
Pg/m3
<0,005
Of the 56 municipal waste incineration plants of the member state, 4 plants are not
operated with zero waste water discharge. Typical an annual average value for cleaned
waste water from such plants is listed below.
Table 3: BAT standard for emissions into the water (operating values)
Parameter
PCDD/PCDF (ng I-TE/l)
Qualified composite samples as
annual average value for cleaned
waste water [mg/l]
0,07 - < 0,1
Table 4: Typical analytical values of grate ashes from incineration plants for municipal waste.
Parameter
Measure
Measured values
TOC
% by mass
<0,1 - < 2,2
Loss on ignition
% by mass
<3
PCDD/PCDF
ng I-TE/kg
< 3,3 - < 15
Solid contents
2
Bernt Johnke, Federal Environmental Agency, Berlin, VGB Power Tech / VGB Kraftwerkstechnik
12/2002 Seite 98 -102 (Volume 82/2002 ISSN 1435-3199
2
Chapter 6.3.4. Household Heating and Cooking with Biomass and
Chapter 6.3.5 Domestic Heating and Cooking with Fossil Fuels
Please compare and consider the following information and data:
Exemplary Investigation of POPs emissions from residential combustion in Austria3
The Austrian assessment comprises emission measurements from three different types of solid
fuel stoves. The appliances included in this experiments were a new low-budget stove suited for
all types of solid fuel (type 1), an approx. 20 year old cast-iron stove for coke (type 2) and a castiron stove approx. ten years old (type 3). Measurements were conducted using coal and coke as
well as wood whereby all fuel was of regularly retailed quality. The samples taken comprised a
complete heating-cycle i.e. starting with the kindling of the fire until the fire had burnt out. The
fumes were analysed for PCCD/F, PCB and polycyclic aromatic hydrocarbons (PAH); the ashes
and the chimney soot were sampled after completion of each heating cycle and analysed for
PCDD/PCDF and PCB.
The results obtained from this project confirm the high PCDD/PCDF values from a study
conducted by the Austrian Federal Environmental Agency in 1997 on the emissions of an
individual domestic heater fuelled with coals. The measured concentrations of PCB - for which
no comparable figures are available - were noticeably lower than the PCDD/PCDF values. While
heating with coal causes the highest discharge of pollutants and wood is the least polluting fuel
examined, PCB concentrations were generally below 10 % of the corresponding PCDD/PCDF
values.
The differences in construction were particularly obvious when burning coal. The results showed
that the newer low-budget (type 1) stoves emit a higher concentration of the examined
pollutants.
Only a small amount of the PCDD/PCDF and PCB formed during combustion of wood and fossil
fuels is found in the ashes and chimney soot; over 90 % of these pollutants are present in the
gaseous and aerosol by-products. The remainder is mainly accumulated in the soot while the
ashes contain only insignificant amounts.
The evaluation of the obtained measurements for a specific type of fuel as shown in Table B 2.2
are not in agreement with literature values for PCDD/PCDF in the case of coal and coke. The
results of this project show average emissions of 7.74ng I-TEQ/MJ for coal and 1.47 ng ITEQ/MJ of coke. These values are about the tenfold of previously published data. The average
value calculated for wood-fuelling amounting to 0.32ng I-TEQ/MJ is in good agreement with
available literature.
3
Thanner G., Moche W.: Emissions of PCDD/PCDF, PCBs and PAHs from Domestic Heating; Federal
Environmental Agency Austria; Monographs, Vol. 153; Vienna 2001
3
Table 5: Concentrations of PCDD/PCDF, PCB, PAH emitted by small-scale heating appliances
)XHO
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QJ1P³ 2
PJ1P³ 2
:RRG
–
–
–
–
&RDO
–
–
–
–
&RNH
–
–
–
–
Table 6: Fuel-specific evaluation of data on the emission of PCDD/PCDF, PCB and PAH from
the examined heating appliances
)XHO
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,7(4
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:+27(4
3$+
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Q Q Q Q Q 0HGLDQ
$YHUDJH
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Similar results were obtained for the concentrations of emitted PAH although the measured
values have a high variation. Nevertheless the highest PAH emissions result when heating with
coal and amount to 145.4 mg PAH4/GJ which is a significantly higher value than
35.2 mg PAH4/GJ as calculated for wood. Measurements for coke resulted in 13.4 mg PAH4/GJ
(PAH4 Sum of four individual PAH according to UN-ECE protocol) but only two measurements
could be evaluated. The figures are within the range of published data for coal and coke while
the value for PAH emission from burning wood is significantly lower than previously published
data.
No comparable data concerning the emission of PCB from small-scale heating appliances could
be found to date. This study performed by the Austrian Federal Environmental Agency showed
4
that the contribution of dioxin-like PCB (PCB WHO-TEQ) to the overall emission of POPs is of
minor importance in the case of small-scale heating applications.
The evaluation of the presented project indicates that the measured emissions from small-scale
heating appliances are subject to a high degree of variation. This circumstance can be put down
to the fact that the possibilities for regulating these appliances is only very rough. Problems
concerning the sampling technique for the experimental set-up lie mainly in the realisation of isokinetic sampling. The flue gas velocity of the investigated devices ranges from ca. 2 m/s during
ignition and refuelling down to 1m/s during the burn-down phase when using coke it will even
sink to below 0.6m/s. Determination of flue gas velocity is difficult on any terms in this particular
range and is further impeded by the high share of soot and other particulate matter. An
examination of published data reveals that even under controlled conditions predominating in
test stands allowing for constant flue gas velocities measurements may vary by up to 100 % (cf.
BRÖKER G., GEUEKE K-J: 6 HIESTER E., 1992; GESSNER A., HIESTER E., QUASS U. &
BRÖKER G., 2000).
Measurements in the field with real-life appliances running under ‘normal’ (i.e. realistic)
conditions can yield substantially higher variations using the same type of stove and identical
type of fuel. PCDD/PCDF concentrations ranging from 0.09 to 9.0ng I-TEQ/MJ where recorded
in a project surveying 7 individual wood-fuelled heating devices conducted by a private institute
(HÜBNER, C. & BOOS, R., 2000).
Chapter 6.7.1. Pulp and Paper Production
Specific comments to the text of pages 124 to 129 and for figures in the context of pulp and
paper industry as source category are included directly and attached as an annex of this paper.
Chapter 6.4.1. Cement Production
Specific measured data for cement productions firing wastes will be available from the guidelines
on BAT and BEP for this type of industrial installations. This guideline is under preparation from
the UNEP Expert Group on BAT and BEP, but currently not finalized.
5
Annex
Comments to chapter Chapter 6.7.1. “Pulp and Paper Production”
page 124
In mechanical pulping the wood fibers are separated from each other by mechanical energy applied to the
matrix; e.g., where logs are pressed against a rotating grinder stone with simultaneous action of water or
by defiberizing wood chips between disc refiners. If chemicals are added to pre-treat the wood chips, the
process is named chemo-thermo-mechanical pulping (CTMP). For high quality paper grades, the pulp
needs to be delignified and/or bleached by chemical pulping. For this purpose, two processes are
employed:
a) the Sulfite Process
This is an acidic cooking liquor process and is based on aqueous sulfur dioxide (SO2) and a base,
calcium 18, sodium 19, magnesium 18 or ammonium. Its importance has decreased over the years and
today only 10 % of the world’s pulp is produced by this method. The sulfite process requires high
quality fibers, while the products are of lower tensile strength. It is more frequently used for softwood.
b) the Kraft or Sulfate Process
It is an alkaline cooking liquor process and is the dominating pulping process worldwide (80 % of the
world pulp production). It is applicable to all kinds of woods/fibers and produces cellulose of high
tensile strength. The Kraft process uses a sodium-based alkaline pulping solution (liquor) consisting of
sodium sulfide (Na2S) and sodium hydroxide (NaOH) in 10 % solution. Unreacted pulping chemicals
(= black liquor) will be recovered to generate white liquor for the first pulping step.
Bleaching
To remove the color associated with remaining residual lignin, the pulp is bleached in three to five
bleaching stages, alternating between acid and alkaline conditions.
The most commonly used chemicals are chlorine, hypochlorite, chlorine dioxide, oxygen, ozone and
peroxide. Lately, peracetic acid has become commercially available as bleaching chemical. Increasing the
chlorine dioxide substitution decreases the formation of chlorinated aromatic substances and eliminates
the formation of PCDD/PCDF. There are four basic approaches to bleaching:
1. Elemental Chlorine Bleaching
It uses chlorine (Cl2) and hypochlorite to brighten the pulp. When elemental chlorine and hypochlorite
react with the lignin, chlorinated compounds including PCDD/PCDF are formed. Bleaching with
chlorine and hypochlorite accounted in 2000 for some 25% of the world market for bleached pulp.
2. Elemental Chlorine Free Bleaching (ECF)
ECF bleaching is a bleaching sequence, which usually uses chlorine dioxide (ClO2) as the main
bleaching agent. Elemental chlorine (chlorine gas, Cl2, also hypochlorite) is no longer used. ECF
results in reduced levels of PCDD/PCDF. In 2000, 67 % of the world market for bleached pulp was
supplied by ECF pulp.
Deleted: October 1998
Deleted: 54
3. Totally Chlorine Free (TCF)
Uses no chlorinated bleaching agents to bleach the pulp; instead oxygen (O2), peroxide (H2O2) or
peracetic acid are used. The effluents are almost chlorine-free. In 2000
6
Deleted: October
page 125
Deleted: 1998
, the TCF pulp totalled 7 % of the world market for bleached pulp.
Deleted: totaled
4. Bleaching of Mechanical Pulps
Deleted: 6
The bleaching of mechanical pulp is completely different from chemical bleaching as it is based on
lignin-saving methods instead of lignin-removing ones. The effect is not permanent and the paper
yellows with time. The lignin-saving is carried out in 1-2 stages using sodium dithionite (Na2S2O3),
peroxide (H2O2) or a combination of the two.
Paper Making
Primary fiber paper: All paper and board machines are based on the same basic process, where a 99 %
aqueous solution of fibers and chemicals is mechanically dewatered by a press and finally run through a
set of cylinders at a temperature of slightly over 100 °C. At the end, the paper is smoothed with hot roll
pairs (calendars or soft-calendars) and finally, the paper is rolled on a so-called parent reel.
Recycling paper: Secondary fiber pulping is a relatively simple process, which utilizes pulping chemicals
such as NaOH. Recycled fiber (RCF) processes are either processes with exclusively mechanical cleaning,
e.g., without de-inking or processes with mechanical cleaning and de-inking. The recovered paper is
dissolved in hot water in a pulper, separated from non-fiber impurities and progressively cleaned to obtain
pulp. For some uses, e.g., graphical papers, the pulp is de-inked to increase whiteness and purity.
Chemical Recovery Systems
The Kraft chemical recovery process has not changed a lot since 1884. Residual weak black liquor is
concentrated by evaporation to strong black liquor, which is burned in a recovery boiler for energy and the
process chemicals are removed from the mixture in molten form. The recovery boilers can be augmented
with fossil fuel-fired or wood-waste boilers (hogged fuel) to cover the energy demand of the plant. The
emissions from these boilers are subject to releases of PCDD and PCDF.
For the Toolkit we will follow the common approach and report data for pulp based on Air Dried tons
(ADt), which refers to pulp at 90 % dryness or 900 kg of bone dry pulp. For paper, the basis is the finished
paper at the dryness that results, typically 94-96 % dryness.
For the pulp and paper industry emission factors should be chosen as shown in Table 55 and Table 57.
Table 55: Emission factor for the pulp and paper industry: boilers
1. Black liquor boilers, burning of sludges and wood
Emission factor
µg TEQ/t Feed
µg TEQ/t Ash
Air
Residue
0,07
1,000
0,4
1,000
Annual emissions with wastewater effluents and pulp and paper sludges (= residues) will calculated by
multiplying the concentration in the effluent (in pg TEQ/L) or the concentration in the sludge (in µg
TEQ/t dry matter) with the annual discharge or production volume, respectively. To assist in estimating
releases typical values in terms of µg TEQ/ADt are given
page 126
the tables along with typical concentrations in effluent and solids – these can be used if mass flow data are
unavailable. The PCDD/PCDF concentrations for different classes are provided in Table 56. These
emission factors assume all plants have effluent treatment facilities producing sludge and effluent low in
suspended solids.
7
Comment for Table 56: Emission factors for effluents and pulp and paper sludges;
Emission Factor for Water - 2. Kraft process, modern technology - Classification µg TEQ/ADt:
0.06 2 [how derived?, better 1] 0.2 10
Comment for Table 57: Emission factors for pulp and paper products:
Emission Factor [µg TEQ/t of Product], Classification:
1. Kraft pulps and papers from primary fibers, free chlorine bleaching 8 [better:10 see p.128]
3. Kraft papers, new technology (ClO2, TCF), unbleached papers 0.5 [how derived?, better 0.1, for TCF
and unbleached paper virtually no dioxins are produced, for all products values are below detection limit]
5. Recycling paper 10 [how derived?, better 0.1]
6.7.1.1 Release to Air
The major emissions to air from pulp and paper mills originate from energy generation and not from the
manufacturing process itself.
Pulp and paper mills burn lignin (from the pulping process) for generation of energy utilized in the mills.
In addition, residual wood chips bark chips, etc. can be burned in the boilers. For both, sulfite and Kraft
mills, average volumes are 6,000-9,000 m³/t of pulp and concentrations around 0.41 ng I-TEQ/m³ (range:
0.036-1.4 ng I-TEQ/m³) (CEPA-FPAC 1999). The higher emissions are based on measurements from
coastal areas in British Colombia where salt-loaded wood enters the pulp mills.
Kraft liquor boilers are used by the pulp and paper industry to burn the concentrated black liquor. Most are
equipped with some simple flue gas cleaning devices, e.g., cyclones, wet scrubbers or electrostatic
precipitators (ESP). Average concentrations are between 0.004 and 0.008 ng I-TEQ/m³ (CEPA-FPAC
1999). For the Toolkit, the emission factor as determined by NCASI and used in the US-EPA
Reassessment of 0.007 µg TEQ/t of black liquor will be used (US-EPA 2000, Volume 2, 5-26).
US-EPA (1998) reported emissions from pulp mills burning sludge and wood residues in wood boilers
(stoker with ESP) between 0.0004 and 0.118 µg I-TEQ/t of sludge or wood,
page 127
respectively. The default emission factor for pulp mills burning sludge or wood residue is 0.06 µg TEQ/t
of feed (i.e., sludge or wood residue). There will be no differentiation between different technologies, e.g.,
flue gas cleaning devices.
Kraft pulp mills have lime kilns to reburn the calcium carbonate formed during the recausticizing process.
The rotary kiln operate at temperatures from 800 °C at the start of the calcination reaction and 1,000-1,100
°C to complete the reaction. The gas flow in the lime kiln is around 1,000 Nm³/t of pulp. Emission factors
for lime kilns should be used, see Section 6.4.2.
The default emission factor for wood burning at pulp mills will be the same as determined for wood
burning, see Section 6.3.
6.7.1.2 Release to Water
The pulp and paper industry is one of the largest water users. Sulfite mills discharge more water than Kraft
mills. A modern bleach plant discharges between 15 and 20 cubic meters of water per ton of Air-dried
pulp (15-20 m³/t ADt).
8
In 1988, in the USA, a typical pulp and paper mill used 16,000 to 17,000 gallons of water per ton of pulp
produced (60-64 m³ of water/t pulp); in the EU water consumption varied between 15 and 100 m³/t. Water
consumption can be reduced by increasing internal water recirculation. Typical figures for wastewater
discharge are 20-40 m³ per ton of pulp. For the Toolkit, 30 m³ of water per ton of pulp produced will be
used.
Concentrations in effluents ranged from 3 pg TEQ/L to 210 pg TEQ/L with a median of 73 pg TEQ/L
(US-EPA 1998a). The default emission factor for Kraft bleached pulp using old bleaching sequences is 4.5
µg TEQ/t of pulp. Alternatively, the concentration in the effluent can be used and multiplied with the total
mass of water discharged per year to calculate the annual release.
Replacement of Cl2 in the first bleaching stage by ClO2 will dramatically reduce the formation of 2,3,7,8Cl4DD and 2,3,7,8-Cl4DF (below detection limits of 0.3-0.9 pg/L).
Data generated and published by NCASI 20 (1998) in the USA from 20 bleach lines at 14 U.S. Kraft mills
that use complete chlorine dioxide substitution for chlorine gave 119 data pairs for 2,3,7,8-Cl4DD and
2,3,7,8-Cl4DF in pulp mill effluents. The results showed that 2,3,7,8-Cl4DD was not detected in any
sample above the proposed guideline concentration of 10 pg/L. 2,3,7,8-Cl4DF was detected in two
samples from the acid stage at concentrations in the range of 15-18 pg/L and in the alkaline stage at
concentrations in the range 11-18 pg/L.
The default emission factor for releases from modern pulp mills utilizing either chlorine dioxide bleaching
agents will be set to 60 ng TEQ/t of bleached pulp sing a conservative approach. The emission factor will
be applied only if there is direct discharge into the environment. If sludges are generated, the dioxin
freight will be collected in the sludges and the effluents leaving from the effluent treatment plant will have
non-accountable concentrations of PCDD/PCDF.
page 128
A special case of higher concentrations has been detected in effluents from pulp mills located in coastal
areas of British Columbia in Canada. Here, special operating conditions occur where salty hog is burned
and where ashes are disposed in the effluent treatment plant. Any similar occurrence should be notified; at
present no default emission factor for these pulp mills can be given.
Pulping of pentachlorophenol treated wood may increase the concentrations in the effluent although no
data have been published. Any use of PCP or of PCP-treated wood in the pulp and paper industry should
be notified. In mechanical pulp and paper mills (integrated mills, TMP), the water systems are usually
quite closed in order to maintain high process temperatures. Consequently, wastewater volumes are small
– 5-10 m³/ADt.
6.7.1.3 Release in Products
Products from the pulp and paper industry can be contaminated with PCDD and PCDF. The degree of the
contamination depends on the technology used in the bleaching. High concentrations of PCDD/PCDF
have been reported when elemental chlorine bleaching sequences have been applied. Modern technologies
result in lower concentrations in the products. Replacing Cl2 with ClO2 results in a reduction of 2,3,7,8Cl4DD and 2,33,7,8-Cl4DF concentrations to non-detectable levels. However, complete elimination of
PCDD/PCDF in ECF bleached effluents and products is a question of kappa-number and purity of ClO2.
With high kappa numbers and impure ClO2 (i.e. high impurities of Cl2) the probability of forming
PCDD/PCDF increases.
Concentrations in pulp can be in the range from 0.6 ng TEQ/kg pulp to 200 ng TEQ/kg bleached pulp
(US-EPA 1998a, Table 8-1). The median concentrations applying “old technology” has been calculated to
be 9 ng TEQ/kg Kraft bleached pulp. The default emission factor is 10 µg TEQ/t of Kraft bleached pulp.
9
Deleted: or totally chlorine-free
TMP 21 pulp had concentrations of around 1 µg TEQ/t pulp (de Wit 1989). The emission factor for TMP
pulp is 1 µg TEQ/t pulp. [how derived?, better 0.1, i.e. below detection limit]
Unbleached sulfite pulps have low concentrations of PCDD/PCDF (0.1 µg TEQ/t pulp). The emission
factor for sulfite pulp is 0.1 µg TEQ/t pulp.
Recycled pulp has a emission factor of 4 µg TEQ/t [how derived?, better 0.1] recycled pulp.
Replacement of Cl2 in the first bleaching stage by ClO2 will dramatically reduce the formation of 2,3,7,8Cl4DD and 2,3,7,8-Cl4DF and to 0.1-0.3 pg/g bleached pulp corresponding to 0.1-0.3 µg/t of bleached
pulp.
The disposal of the ash should be monitored and potential releases into the environment included
(uncontrolled, land spreading) or excluded (landfill). Concentrations of PCDD/PCDF in Kraft bleached
papers using free chlorine and the respectivedefault emission factors are 5 µg TEQ/t for cosmetic tissues,
shopping bags and other 21 Thermo- mechanical pulp
Deleted: echnical
page 129
consumer papers and 2 µg TEQ/t for filter papers and newspapers from primary fibers. If chlorine dioxide
bleaching is utilized, the emission factor will be 0.5 µg TEQ/t. Sulfite papers using old technologies have
an emission factor of 1 µg TEQ/t paper. Applying new technology will lower the emission factor to 0.1 µg
TEQ/t.
Unbleached papers have an emission factor of 0.5 µg TEQ/t[how derived?, better 0.1].
Recycling paper will have an emission factor of 10 µg TEQ/t[how derived?, better 0.1].
10
Deleted: or total chlorine-free
28
Comment by Italy on the Standardized Toolkit for Identification and Quantification on
Dioxin and Furan Releases.
This paper presents some information on chemicals covered under Article 5 and Annex C of the
Stochkolm Convention, as requested by Decision INC-7/5 adopted at the seventh session of the
Intergovernmental Negotiating Committee, held in Geneva 14-18 July 2003.
The presented data refer to Main Category No 2 (ferrous and non-ferrous metal production) of the
Toolkit. They were collected in the framework of the activities carried out by the Italian National
Agency for New Technologies, Energy and the Environment (ENEA), on behalf of the Italian
Ministry of Environment and in co-operation with the Industrialist Association of Brescia (AIB).
The purposes of the joint project were to characterize the releases of persistent organic pollutants
from the secondary metal industry, to identify the best option for the control of the emission of
POPs and to evaluate the feasibility of the reduction of POPs emissions. The investigated plants
belong to the following subcategories of the main category No 2: iron and steel production,
aluminum production, lead production, brass and bronze production, shredders. The facilities
chosen were:
-
five electric steel plants;
-
three secondary aluminim smelter (refiners and remelters)
-
three secondary brass/bronze smelters;
-
one secondary lead smelter;
-
one car shredder;
-
two plants for thermal de-oiling of aluminium turnings;
-
one plant for thermal de-oiling of brass turnings.
During the sampling and analysis program, PCDDs, PCDFs, PCBs, and HCB were monitored in the
stack emissions and in filter dust of plants considered representative of the Italian industry.
Sampling and analysis were performed by accreditated laboratories and according to the test
methods EN 1948 1-3/99, EPA 1613 B/94 and EPA 1668 A/99. In the whole, 29 samples of filter
dust and 34 samples of stack emissions were collected and analysed. From analytical data, emission
factors in Pg TEQ per ton of product (PCDD, PCDF and DLPCB) or mg per ton of product (total
PCB as Aroclor and HCB) were calculated.
The following tables summarize the calculated emission factors, presented according to the general
layout of the Dioxin Toolkit.
Reference:
ENEA/AIB/MATT (2003). Valutazione delle emissioni di inquinanti organici persistenti da parte
dell’industria metallurgica secondaria. Rapporto finale (in Italian).
arc
furnaces,
scrap
POPs, units
0.81
HCB, mg/t of steel
afterburners, quenching, fabric filters.
0.73
2.7
0.2
PCDD/PCDF/DLPCB, µg WHO-TEQ/t of steel
PCB (as Aroclor), mg/t of steel
HCB, mg/t of steel
0.26
7.0
Electric arc furnaces, clean scrap, PCDD/PCDF, µg I-TEQ/t of steel
5.9
4.8
Air
0.01
0.41
5.0
4.1
0.11
4.0
26
24
Filter dust
Emission factors
with PCDD/PCDF, µg I-TEQ/t of steel
general contamination, fabric filters.
Electric
Process
Emission factors for the steel industry.
POP, units
UBCs,
rotary
aluminium
afterburners, fabric filters with lime
0.08
HCB, mg/t of aluminium
scrap,
wet
salt
fabric filters with NaHCO3 injection.
smelting (NaCl), rotary drum furnaces,
non-homogeneous
9.2
11
107
PCB (as Aroclor), mg/t of aluminium
PCDD/PCDF/DLPCB, µg WHO-TEQ/t of aluminium
89
2.5
6.3
Secondary aluminium (refiner process), PCDD/PCDF, µg I-TEQ/t of aluminium
injection.
4.4
5.2
0.25
0.45
0.31
Air
1.0
18
195
183
0.07
0.19
6.2
5.5
-
-
-
-
Filter dust
Emission factors
(remelter PCDD/PCDF, µg I-TEQ/t of aluminium
furnaces,
process), clean scrap, hearth furnaces,
Secondary
afterburners, fabric filters.
crushed
Thermal de-oiling of turnings and PCDD/PCDF, µg I-TEQ/t of aluminium
Process
Emission factors for aluminium industry.
POPs, units
furnaces,
afterburners,
wet
0.61
HCB, mg/t of brass
5.3
14
PCB (as Aroclor), mg/t of brass
HCB, mg/t of brass
scrap, rotary furnaces, fabric filters.
0.50
0.21
21
PCDD/PCDF/DLPCB, µg WHO-TEQ/t of bronze
PCB (as Aroclor), mg/t of bronze
HCB, mg/t of bronze
0.36
4.1
PCDD/PCDF/DLPCB, µg WHO-TEQ/t of brass
Secondary bronze production, mixed PCDD/PCDF, µg I-TEQ/t of bronze
scrap, induction furnaces, fabric filters.
3.4
0.33
2.7
2.3
Air
0.56
0.73
34
33
0.58
11.3
137
125
-
-
-
-
Filter dust
Emission factors
PCB (as Aroclor), mg/t of brass
PCDD/PCDF/DLPCB, µg WHO-TEQ/t of brass
Secondary brass production, mixed PCDD/PCDF, µg I-TEQ/t of brass
scrubber
rotary
Thermal de-oiling of brass turning, PCDD/PCDF, µg I-TEQ/t of brass
Process
Emission factors for the brass and bronze industries
POPs, units
cyclones and wet scrubber.
are also shredded), hammer mills,
5.2
1.0
HCB, mg/t of steel
0.2
0.03
Air
0.20
5.0
50
50
Filter dust
-
-
-
-
Filter dust
Emission Factors
0.25
HCB, mg/t of lead
POPs, units
7.2
7.5
5.0
Air
Emission factors
PCB (as Aroclor), mg/t of lead
PCDD/PCDF/DLPCB, µg WHO-TEQ/t of lead
Car shredders (some consumer goods PCDD/PCDF, µg I-TEQ/t of steel
Process
Emission factors for shredders.
scrubber (H20 + NaOH), fabric filters.
furnaces, paste desulphurization, wet
(pre-treated vehicle batteries), rotary
Secondary lead production from scrap PCDD/PCDF, µg I-TEQ/t of lead
Process
Emission factors for the lead industry.
Toolkit comments Patrick Dyke, May 2003
These comments are provided on the basis of observations from training workshops and
working with countries to use the Toolkit. A detailed review has not been carried out and
these are initial observations rather than any exhaustive review or crosschecking exercise.
The comments were rapidly assembled and I apologise for the resulting brevity and
untidiness.
General
The Toolkit provides a structure for developing inventories and as such has facilitated the
process enormously.
Guidance on providing inventories of PCB (as by-product) and HCB would be valuable.
It may be possible to extend the current Toolkit to cover this but great care would need to
be taken to ensure that the relevant sources were being adequately addressed.
Since the Toolkit was compiled several things have changed – the Stockholm Convention
has been finalised, additional data has become available for emissions from various
processes and experience has been gained from applying the Toolkit and examining
processes and activities in a wider range of countries. These changes should be
considered and the Toolkit updated to reflect them.
The Stockholm Convention has listed sources of PCDD/F that should be addressed, the
Toolkit covers these but it may help a user if the links are made more explicit. The
Convention also requires that inventories consider present and future releases, a little
more guidance on the future releases could be added.
Additional data has been generated in several areas. The use of this additional data
should be informed by the review of classification (see later comments) and the feedback
from application of the Toolkit in countries which have activities and processes different
to those typically found in developed countries and for which most data were available.
Experience from application in the field should be used to improve clarity, ease of
application and reduce ambiguity. It can also guide the need for additional field work.
Feedback that I have received from people applying the Toolkit has indicated some areas
that require clarification, including:
x
A clearer distinction is needed between those processes that form PCDD/F and those
that transfer pollution. Both issues are important but the handling and assessment
may be different in terms of making an inventory and also in directing control
measures. In particular issues arise with dredging (Category 10, part 9), sludge
generation and waste water management in general (Category 9, part 2) and “Open
water dumping” (Category 9, part 4).
x
The chemical industry (Category 7) is a complex subject and the existing section does
not appear to be well able to address some important aspects.
x
For several processes where fuel is burned we find a variety of wastes being used as a
supplement to, or replacement for, fossil fuel. For example brick making. The
Toolkit is unlikely to reflect the full range of emissions that will be found. It may be
that the use of potentially contaminated materials and wastes as fuels needs to be
brought out to a greater extent and perhaps guidance on tracking and identifying such
uses should be emphasized – it may be that emissions may be best estimated by
tracking the burning of wastes in poorly controlled processes in total rather than by
examining sectors for example.
The disposal of wastes is a major issue. The way the Toolkit addresses waste burning
should be strengthened. Open, or poorly controlled combustion of waste could be
clarified, classification of “incineration” and “open burning” can be improved to reduce
potential confusion and emission factors improved also.
Errors and inconsistencies should be cleared up and reduced as far as possible in the text,
the tables and the accompanying spreadsheet.
Summary tables can be misleading (details of emission factors units and means of
application is lost and a user should be clearly directed to use the text not the summary
tables).
The Toolkit could give more help to direct effort to the most important areas and reduce
effort in those which are less significant. All areas should be considered but the level of
effort should be tailored appropriately. A significant streamlining is possible without
losing much, if any utility.
Additional guidance on data generation and gathering that is most applicable could be
provided (going beyond questionnaires and tailoring to the purpose and needs of the
inventory rather than resource intensive data collection in every sector).
Additional guidance to assist a user make classifications may be useful. UNEP may want
to consider providing diagrams or photographs of typical processes that may be
encountered which will help a user recognise the levels or types of technology and
process that are being described. A CD may be a good means to bring together the
Toolkit and various supporting documents and other resources.
The use of the Toolkit should be linked to the generation or NIPs since several issues
overlap.
In the Russian translation I am told that ND and NA were confused. The distinction may
need to be made clearer.
More specific comments and observations
Section 3 – indicates that run-off etc from reservoir sources will not be considered – this
doesn’t square with “open water dumping” (Category 9, part 4) which appears to address
run-off.
Graphic of interim inventory has not reproduced properly, it does not show range as was
intended.
Waste incineration
Significant confusion can arise with classification for this sector and in the potential
overlap with Category 6 (open/uncontrolled burning).
Examples include the burning of medical waste which may be in a variety of equipment
such as barrels. There is an argument for keeping all barrel (or similar) burning in one
place and at present that is Category 6. If so it should be made clear where such wastes
would fall (a simple guide that waste types and practices are noted and taken perhaps as
uncontrolled combustion of domestic and similar wastes may be valuable for several
categories with some additional work on specific waste streams such as medical).
The emission factors for “low-end” incinerators are very high. These might conceivably
represent a worst case that you could find but do not represent a meaningful average
value - eg chemical waste category must cover both EDC combustion as well as nonchlorinated wastes. The intention was always to provide suitable average factors for a
class as a whole. The classes are such that it is inappropriate and misleading to derive
high-end estimates only and apply those to a category as a whole.
This section requires careful review since it can be highly significant.
Category 2
Coke production – covering table3 (p18) indicates X for releases to land, not consistent
with text or table in section.
Table 3 – p18, missing k in table
Category 3
Units are confusing, justification for emission factors dubious. Emission factors based on
mass throughput would be more consistent with the other information in the Toolkit and
would better reflect the information many users will have to hand or could generate.
Only a fraction of the emissions data is based on energy input (or output) and any
uncertainty introduced by conversion to mass would be small.
TJ is a huge and potentially meaningless unit for most countries.
Table 36 units for residues wrong.
Domestic/household – why separate biomass from fossil fuel. Are categories for biomass
useful?
Open fires used for house heating (in a hearth with a chimney) appear to be missing.
Category 7
This sector is important, it is also complex and hard to get a grip on. At present users
may not be picking up the need to consider products as well as production. Emission
factors and classifications could be improved. Practices found in real-world situations
typical of a wider range of countries should be considered.
Releases are expressed per tonne and also as concentration which could be confusing.
For pulp and paper processes the use of the term “free chlorine” too close to “chlorine
free”, the meanings are quite different!
Would recycled paper have more dioxin than chlorine bleached paper?
Chemicals – usage not being picked up – tabulate concentration data – eg PCP levels.
Tables are more eye catching than the text and details may be missed.
Category 8
Confused units and classification for drying of biomass.
Are we talking about fuels or products?
How were the values derived and linked to product made?
Releases to land from dry cleaning? NA rather than ND in the table (62, p 134). X in
covering table for this section for land releases?
For dry cleaning the emission factor is based on tonnes of residue – this may not be
clearly enough explained (in the specific example I am thinking of confusion arose from
using the summary tables).
Category 9 – disposal.
Landfill leachate concentration data is high. Not linked to landfill practice at all.
Sewage treatment – classification does not make much sense for many country situations
and may not mean much to those making the inventory. A more general approach may
be useful which guides a user to take account of all wastewater generation and treatment
within a country and picks up septic tanks and pits.
Some clarification and review of the factors and how they are generated and used may
help – for example at present with no sludge removal a factor is given for product (where
none is produced). Back-of-the-envelope calculations suggest that in case 1 we are
dealing with an effluent with 4.5x10-4% solids, which is not at all realistic and quite
different to case 2.
Composting data high and dubious
Open water dumping – confusing – and potentially meaningless. Huge values and need
guidance on their application. Summary tables get the units wrong.
Waste oil disposal – non thermal – but the only factor is for thermal! Not good for nonmineral oils.
Category 10
2,3,4 T?
PCB – link to inventory work under NIP
Dumps – “only the organic phase should be analysed” – not always so – likely to be in
solids as much as oils. Analyse it all after proper extraction.
Comments Cement section of the D/F toolkit
Heidelore Fiedler
From:
VAN LOO Willem [w.vanloo@cembureau.be]
Sent:
Tuesday, June 01, 2004 6:56 PM
To:
Heidelore Fiedler
Cc:
'khk@sintef.no'
Page 1 of 1
29
Subject: Comments Cement section of the D/F toolkit
<<Toolkit_cement__.doc>>
Dear Heidi,
Please find attached our comments on the cement section the D/F toolkit. Kare and I have used the SINTEF
report to update some parts of the text in the form of track changes. In a few cases we have made comments
or questions to you in italics. If you need any further clarification do not hesitate to call us.
We do apprciate to have had this opportunity in contributing to the toolkit which we think is an important
means for dealing with the D/F issue in a sound and pragmatic way.
With kind regards,
Willem van Loo
Technical Director
CEMBUREAU
Tel. +32-2-2341055
Fax. +32-2-2350264
e-mail: w.vanloo@cembureau.be
8/31/2004
PCDD/PCDF Toolkit 2004
1.1
1
Main Category 4 – Mineral Products
This section summarizes high-temperature processes in the mineral industry. Raw materials
or fuels that contain chlorides may potentially cause the formation of PCDD/PCDF at various
steps of the processes, e.g., during the cooling phase of the gases or in the heat zone. Due to
the long residence time in kilns and the high temperatures needed to fabricate the product,
emissions of PCDD/PCDF are generally low in these processes. In this Toolkit, the
subcategories as shown in Table 1 will be included into the dioxin and furan inventory.
Deleted: , at preheaters
Deleted: Table 1
Deleted: Table 1
Table 1:
No.
4
a
b
c
d
e
f
Subcategories of Main Category 4 – Production of Mineral Products
Subcategories of Main Category
Production of Mineral Products
Cement production
Lime production
Brick production
Glass production
Ceramics production
Asphalt mixing
Inserted: Table 1
Potential Release Route
Air Water Land Product Residue
X
X
X
x
X
x
X
x
X
x
X
x
X
x
x
Relevance to Article 5, Annex C
With relevance to the provisions of Article 5, sources in this category can be classified as
follows:
Annex C, Part II source categories include:
(b)
1.1.1
Source category
Cement kilns firing hazardous waste
Section in Toolkit
1.1.1
Deleted: 1.1.1
Cement Production
Principal raw materials are clay and limestone. Cement manufacture begins with calcination,
which is the decomposition of calcium carbonate (CaCO3) at about 900 °C to leave calcium
oxide (CaO, lime) and carbon dioxide (CO2). Afterwards, lime reacts at temperatures
typically around 1,400-1,500 °C with silica, alumina, and ferrous oxide to form silicates,
aluminates, and ferrites of calcium (= clinker). The clinker is then ground or milled together
with gypsum (CaSO4) and other additives to produce cement (BREF 2000d).
There are four main process routes for the manufacture of cement: the dry, semi-dry, semiwet and wet processes. In the dry process, the raw materials are ground and dried to raw
meal, which is fed to the pre-heater or pre-calciner kiln (or more rarely into a long dry kiln).
The dry process requires less energy than the wet process. Today the majority of clinker
kilns use the dry process. In the wet process, the raw materials (very often with high
UNEP
2004
Deleted: T
Deleted: the European
2
moisture content) are ground in water to form a pumpable slurry, which is fed directly into
the kiln or first into a slurry dryer. (Heidi, this statement is not correct, please look at Steffi
Richter’s report)
The process: the raw materials are first brought to site, are then mixed, crushed and ground to
produce a raw meal of the correct particle size and chemical properties. The raw meal is
converted into cement clinker by pyroprocessing in rotary kilns (50- ?? (to be completed) m
in length and more than 5 m in diameter). These consist of a refractory lined cylindrical steel
shell slightly inclined to the horizontal and rotating at 1–3 rpm. Raw material is fed in at the
upper end and gradually moves downward towards the lower end where a burner provides
counter-current heating. The rotary kilns in the cement manufacture are different from the
classic firing processes as feed materials and off-gases pass each other counter-currently thus
leading to a thoroughly mixing, high temperatures (>1,400 °C at the hot end where clinker is
formed), and long residence times (5-7 s) of the gases. These conditions will result in the
destruction of any organic contaminants introduced with the fuel at the primary burner.
Deleted: Most of the U.S. cement kilns
use the wet process.
Deleted: 50
Modern cement kilns often use the dry process, in which raw mill material may be pre-heated
in a vertically arrayed multi-cyclone pre-heater, in which the rising hot gases exiting the kiln
contact the downward flowing raw materials. Some dry processes also employ a pre-calciner
stage beneath the pre-heater, just before the raw material enters the kiln. The use of the wet
process, where the ground meal is mixed with water and fed into the kiln as a slurry uses
about 40 % more energy than the dry process.
The last stage involves cooling the clinker. As the hot clinker comes off the end of the lower
end of the kiln it is rapidly cooled by ambient air in a clinker cooler, e.g. a travelling grate
with under-grate fans that blow cool air through the clinker (EMEP 1999).
Finally, the cooled clinker is then mixed with gypsum and, for composite cements, other
materials such as blast furnace slag, and ground to a fine homogeneous powder to produce
the final product, which is then stored in silos prior to bulk transportation or bagging.
Deleted: waste
Typical fuels used are coal, oil, gas or petroleum coke. In many cases a variety of alternative
fuels derived from wastes, are also used to supplement the fossil fuel. The wastes used may
include: waste oils, solvents, animal meal, certain industrial wastes, and in some cases
hazardous wastes. Most of these will be fired at the burner (hot) end of the kiln. Tires are
often used and may be added to the kiln some distance from the hot end as whole tires or
chipped.
In the USA tests, carried out in the early nineties, have indicated that higher emissions were
found for some kilns where hazardous wastes were fired (EPA 1998).However, more detailed
investigation has suggested that, provided combustion is good, the main controlling factor is
the temperature of the dust collection device in the gas cleaning system, The plants equipped
with low temperature electrostatic precipitators appear to have well controlled emissions with
or without waste fuels.
Recently SINTEF (ref…….) completed an extensive study on the Dioxins/Furans emissions
from cement kilns. This study provides the most comprehensive data set available, collected
from public liteature, scientific data bases and individual company measurements.
In most cases primary measures (integrated process optimisation) have shown to be sufficient
to comply with with an emission level of 0.1 ng I-TEQ/Nm3 in existing installations. The
2004
UNEP
Deleted: ).
Deleted: M
Deleted: ,
Deleted: t
3
following primary measures are considered to be most critical:
Formatted: Bullets and Numbering
x
Quick cooling of kiln exhaust gases to lower than 200 C in wet kilns (already inherent in
preheater/precalciner kilns)
x
Limit alternative raw material feed as a part of raw-mix if it includes organics
x
No alternative fuel feed during start-up and shut-down.
x
Monitoring and stabilisation of process parameters:
1. Homogeneous raw mix and fuel feed
2. Regular dosage
3. Excess oxygen
Provided that the recommended primary measures are practiced/followed:
1. most cement kilns can meet an emission limit of 0.1 ng TEQ/Nm3
2. co-processing of alternative fuels and raw materials, fed to the main burner or the
preheater/precalciner does not influence or change the emission of Dioxins/Furans
3. cement kilns in developing countries presented in this study meet an emission
level of 0.1 ng TEQ/Nm3
The latter conclusion may be illustrated by the dioxin sampling and analysis program in
Thailand, where PCDD/PCDF samples were taken and analyzed from two rotary kilns at a
modern and well-operated cement plant. The samples were taken from two kilns under
normal operation (full load and fired with a blend of lignite and petroleum coke as primary
and secondary fuels) and with co-firing of (a) used tires and (b) industrial wastes including
waste oils (UNEP 2001, Fiedler et al. 2002).
Deleted: It is thought that the raw
materials themselves can have a
considerable influence on the emissions
and the presence of high levels of organic
matter in the raw materials has been
associated with elevated emissions of
PCDD/PCDF. It should be noted that the
higher emissions measured in the USA
were from wet kilns whereas the lower
emissions (more than 150 measurements)
from European cement kilns (mainly
Germany and Switzerland) were obtained
from plants using the dry
Deleted: process. Off-gases from
Deleted: dry kilns cannot be quenched
to temperatures and thus enter the flue
gas cleaning system at relatively high
temperatures (>300 °C). From European
plants, no elevated PCDD/PCDF
concentrations have been reported from
cement kilns with ESP.
Formatted: Bullets and Numbering
Deleted: low results found in most of
the modern European plants have been
confirmed
Kilns usually have a device to reduce emissions of particulate matter and to capture particles,
which may be valuable as cement product. The pollution control system may be a simple
dust collector (cyclone), electrostatic precipitators or fabric filters. In some plants other
pollution controls may be fitted such as gas scrubbers.
Many national and international inventories use emission factors published in the earlier
literature; very few inventories have established emission factors from actual measurements.
The emission factors found in many articles and reports are often outdated and the
consequence of using those are often too high estimates of PCCD/F release from the cement
industry. Experiences from inventories where emission factors are established by actual
measurements, like Australia (ref…..) , shows that the cement industry contribution is
insignificant compared to, for example, natural sources and is also lowest among industry
sources.
Deleted: Table 2
The following classes of emission factors were developed (Table 2).
Inserted: Table 2
Deleted: Table 2
UNEP
2004
4
Deleted: 2
Table 2:
Emission factors for clinker production
Classification
1.
2.
ESP temperature >300 °C
ESP/FF temperature 200-300 °C
3. , ESP/FF temperature <200 °C
)
Deleted: cement
Emission Factors – µg TEQ/t of clinker
Air
Water Land Product Residue
1.5
ND
ND
ND
???
0.6 (0.2 ND
NA
ND
???
??)
0.05
ND
NA
ND
???
Inserted: 2
Deleted: 2
Deleted: Cement
Deleted: Wet kilns,
Deleted: 5.0
Deleted: 1.0
Deleted: Wet kilns,
Deleted: 0.1
Heidi, we derive the factor of 1.5 in class 1 from maximum emission levels of 0.4 ng
TEQ/Nm3. The factor for class 2 seemed to be derived by interpolation, that is why we
introduced 0.2 (??). Furthermore, what is the justification for the emission factors for
residue, in particular for class 1 ?
In addition we estimate that exhaust gas temperature is the dominant controlling factor
1.1.1.1. Release to Air
Emissions to air in terms of PCDD/PCDF produced per unit production will be influenced by
the concentration of the PCDD/PCDF in the flue gas and the amount of gas produced per unit
production. A larger volume of flue gas is generated in wet kilns per unit output than in dry
kilns (4,000 m³/t versus 2,500 (??) m³/t, HMIP 1995).(to be consistent with the Cement and
Lime BREF)
The SINTEF study (ref….) is based on more than 1700 PCDD/F measurements from the
early nineties until recently. The data represents emission levels from both wet and dry kilns,
performed under normal and worst case operating conditions, with and without the coprocessing of a wide range of alternative fuel and raw materials and with wastes and
hazardous wastes fed to the main burner, to the rotary kiln inlet and preheater/precalciner.
The emissions from dry preheater/precalciner kilns seem to be frequently below 0.1 ng
TEQ/Nm3, and slightly lower than emissions from wet kilns. In most instances, the reported
data from the dry kilns stems from co-processing of waste and alyernative raw materials,
which today is regarded to be normal practice
German measurements at 16 cement clinker kilns (suspension pre-heater kilns and Lepol
kilns) during the last ten years gave an average concentration of about 0.02 ng TEQ/m³
(Schneider, 1996).
Very low concentrations of PCDD/PCDF were found in the sampling campaign in Thailand
at a cement plant utilizing the dry process. During normal operation (lignite/petroleum coke
and full load), the stack emissions were all below 0.02 ng I-TEQ/Nm³ and as low as
0.0001 ng I-TEQ/Nm³; the means were 0.0105 ng I-TEQ/m³ and 0.0008 ng I-TEQ/m³ for the
normal operation conditions and 0.003 ng I-TEQ/Nm³ and 0.0002 ng I-TEQ/Nm³ for the tests
performed with substitute secondary fuels, respectively. The resulting emission factors were
at a mean 0.02 and 0.001 Pg TEQ/t of clinker for the normal operation and 0.005 and
0.003 Pg TEQ/t of clinker in the case of co-firing alternative fuels/wastes. Thus, all test
results were far below the orientation value of 0.1 ng I-TEQ/Nm³. The results demonstrated
2004
UNEP
Deleted: Wet kilns
Deleted: 0.003
Deleted: Dry kilns with APC (all types
5
that the addition of tires and/or liquid hazardous waste had no effect on the emission results
keeping in mind that the dry cement kiln process employed in the cement plant is state-ofthe-art technology and the plant is well-managed (UNEP 2001, Fiedler et al., 2002).
This conclusion is also drawn by the US EPA, which after many years of research and testing
in 1999 stated: “that hazardous waste burning does not have an impact on PCCD/F
formation; PCDD/F is formed post-combustion”
Concentration of PCDD/PCDF in the flue gases seems to be influenced by the temperature of
the dust collection device. Low temperatures (<200 °C) seem to indicate that typical concentrations will be under 0.1 ng TEQ/Nm³, temperatures over 300 °C increase the likelihood of
finding emissions, as high as 0.4 ng TEQ/Nm³ . In some cases much higher emissions may
be found. These seem to be linked to high dust collector temperatures, high levels of organic
matter in the raw materials and may be linked to inappropriate process conditions.
Deleted: higher
Deleted: typical concentrations would
be
Deleted: 3
An average emission factor of 5(???) µg TEQ/t of product (clinker) is applied to kilns with
dust collectors over 300 °C. An average emission factor of 0.6(???) µg TEQ/t of product is
applied where the dust collector is between 200 and 300 °C. An emission factor of 0.05 µg
TEQ/t of product is applied where dust collector temperature is held below 200 °C. (Heidi,
see our comments under table 2)
Examples of cement kilns, where raw materials have unusually high concentrations of
organic matter and dust collector temperatures are high, should be noted for further
consideration. The use of wastes should be recorded noting the wastes used, the means used
to introduce them to the kiln and any controls on operation (e.g., prevention of feeding during
combustion upsets, etc.). This kind of primary measures have shown to be sufficient to
comply with an emission level level of 0.1 ng TEQ/Nm3 in existing suspension preheater and
precalciner kilns under normal operating conditions.
1.1.1.1
Release to Water
Releases to water are not expected. However, if effluents are identified these should be noted
and the origin in the process described.
1.1.1.2
Release to Land
Some residues may be spread on land, in some cases the use of cement kiln dust to increase
alkalinity and add lime has been reported. Any use of cement kiln dust (CKD) in this manner
should be noted.
1.1.1.3
Release in Products
Releases in the cement product are expected to be small since the product has been exposed
to very high temperatures.
UNEP
2004
Deleted: and
Deleted: above
Deleted: use of certain wastes under
6
1.1.1.4
Release in Residues
It should be mentioned that the dusts collected in air pollution control systems, typically
electrostatic precipitators (ESP) or cyclones, mainly consist of raw materials fed into the kiln
(at the end of the secondary burner). The remainder of the dust consists of emissions from
the kiln that has passed the hot zone. Typically, the dusts from the ESPs/cyclones are reintroduced into the kiln.
The principal residue to be disposed off is cement kiln dust (CKD), which is the dust
collected in pollution abatement systems. A range of concentrations of PCDD/PCDF has
been reported in the CKD and the rate of production will vary depending on plant specific
factors and the degree to which the CKD may be reused in the process.
To provide an initial estimate of release of PCDD/PCDF in CKD an average rate of production was 0.4 million tons CKD from 13.5 million tons of clinker/cement production (Dyke et
al. 1997) – approximately 30 kg of CKD per ton of clinker (3 % of clinker production, this
must be a calculation error, however the total CKD production must be much lower, In most
of the dry kilns the kiln dust is reintroduced in the system.)).
Comment: Cuba
Deleted: 0.0
Concentrations of PCDD/PCDF in the CKD are expected to vary. Insufficient data are available to accurately estimate levels of PCDD/PCDF from all kilns. A wide range of concentrations has been reported 0.001-30 ng TEQ/kg (Dyke et al. 1997) for UK kilns, 1-40 ng
TEQ/kg for German tests (SCEP 1994). US tests (please take into account the US EPA
statement in 1999, quoted earlier) indicated that on average kilns burning hazardous waste
had higher levels (35 ng TEQ/kg) than kilns not burning hazardous waste (0.03 ng TEQ/kg)
(EPA 1998). These results were strongly influenced by very high levels in one sample, the
range is reported as 0.045-195 ng TEQ/kg.
To make an initial estimate of releases in CKD, three classes of emission factors as outlined
in Table 2 are proposed. (see our remark about the justification for these numbers under table
2)
Deleted: Table 2
Inserted: Table 2
Deleted: Table 2
2004
UNEP
30