1. 6th Meeting of the EMEP Task Force on Measurement and Modelling, Zagreb, Croatia, April 4th –7th, 2005
Motivation and plans for the emission review on POPs (Persistent Organic Pollutants) and HMs (Heavy Metals) - some preliminary results for POPs
Knut Breivik1, Vigdis Vestreng2, Olga Rozovskaya3, Jozef M. Pacyna1
1) EMEP CCC, NILU, Norway 2) EMEP MSC-West, met.no, Norway 3) EMEP MSC-East, Russia

2. Why do we need reliable emission data?
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Why do we need reliable emission data?
For scientific reasons:
Source-receptor relationships (modelling)
Interpretation of contaminant patterns and trends (monitoring)
For political reasons:
Emission reductions strategies (internal use by a party)
Documentation between parties (external)
If we want to understand and control POPs and HMs, knowledge about the sources is essential!

3. ? § € Two types of emission data – features and aims
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Two types of emission data – features and aims
Research-driven inventory estimates:
+ Complete spatial coverage
+ Complete temporal coverage
+ Complete compound coverage (speciation) ?
Wania and Mackay, 1996 €
Policy-driven inventory estimates:
+ Complete coverage of sources
+ Complete coverage of parties
If we want to understand and control POPs and HMs, knowledge about the sources is essential!

4. Objectives of emission review
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Objectives of emission review
To identify specific data needs and requirements regarding emission data for HMs and POPs by key users of such information.
To compare and contrast policy-driven (official emission data) and research-driven (so-called expert data) emission estimates.
To carry out an initial assessment of emission data quality and uncertainty for selected HMs and POPs submitted by parties to EMEP under the CLRTAP convention with specific regards to the following quality criteria; transparency, consistency, comparability, completeness and accuracy.
To evaluate if officially submitted data are of sufficient quality for source-receptor relationships to be predicted and understood.
To identify bottlenecks in the emission reporting in order to propose short and long-term solutions that may improve the emission data for HMs and POPs with regards to the quality criteria above.

5. Intentionally produced chemicals
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Simplified source classification of POPs and HMs
Anthropogenic emissions
HMs
Natural emissions
Re-emission from environmental compartments Hg
Pesticides
HCHs, DDT etc
Intentionally produced chemicals
Industrial chemicals
PCBs, (BFRs) etc
POPs
Accidentally formed by-products
PCDD/Fs, PAHs etc
Re-emission from environmental compartments
HCHs, PCBs etc

6. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Spatial and temporal completeness: Number of parties submitting official POP emission data (22 parties as of January 2005)
The numbers in parentheses are the number of parties submitting a numerical value (zero or greater), if different from the former value. Data for indicate the annual maximum reporting during the period.

7. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Spatial and temporal completeness: Number of parties submitting official HM emission data (24 parties as of January 2005)
The numbers in parentheses are the number of parties submitting a numerical value (zero or greater), if different from the former value. Data for indicate the annual maximum reporting during the period.

8. Example 1: PCDD/Fs, 1990 TEQ = Σn1[PCDDi*TEFi] + Σn2[PCDFi*TEFi]
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 1: PCDD/Fs, 1990
PCDDs (”dioxins”) n = 75 Cl O Cl 9 1 O 8 2 3 Cl O Cl 7 O
Clx
Cly 6 4
2,3,7,8-TCDD 9 1 O 8 2
TEF: Order-of-magnitude estimate of Ah receptor mediated toxicity of a given compound, relative to 2,3,7,8-TCDD ( = 1)
Assumes additive effects
Concensus values 7 3
Clx
Cly 6 4
PCDFs (”furans”) n = 135
TEQ = Σn1[PCDDi*TEFi] + Σn2[PCDFi*TEFi]

9. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 1: PCDD/Fs, 1990
Three different comprehensive emissions inventories available for Europe (excluding Canada and USA):
Official submissions by parties to EMEP (base year, POPs protocol)
Pacyna et al Atmospheric Environment 37: S119-S131
Berdowski et al TNO-report.
European emissions of PCDD/Fs according to:
EMEP: 1.03*104 g I-TEQ/year (n = 22 countries)
Pacyna et al: 1.12*104 g I-TEQ/year (n = 38 countries)
Berdowski et al: 1.13*104 g I-TEQ/year (n = 38 countries)

10. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 1: PCDD/Fs, 1990 National totals for countries included by all studies
EMEP: 0
More than half of the countries deviate more than a factor of two between max and min estimates

11. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example1: PCDD/Fs, 1990 Implications for emission reduction strategies, France as an example

12. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs, 1990
SPCB7: Sum of PCBs 28, 52, 101, 118, 138, 153, 180
PCBs n = 209 m o o m 3 2 2’ 3’ p 4 1 1’ 4’ p
Clx 5 6 6’ 5’
Cly m o o m
Three possible ”phenomena” may explain current atmospheric levels:
Primary anthropogenic emissions as a direct result of intentional production of technical mixtures in the past
Incidental or unwanted byproduct formation of PCBs (combustion processes)
Volatilisation of previously released PCBs from environmental reservoirs (re-emissions)

13. Germany 1990: Sum sectors 2.5 tonnes / Offical total: 43.6 tonnes
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs, 1990, EMEP data Total PCB emissions in seven countries when summing sectors: 12.8 tonnes
No ”clear” source pattern for PCBs can easily be identified from the EMEP data
Germany 1990: Sum sectors 2.5 tonnes / Offical total: 43.6 tonnes

14. Example 2: PCBs, 1990 Emissions in seven European countries in tonnes
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs, 1990 Emissions in seven European countries in tonnes
PCB emissions (t) EMEP Berdowski et al
Sum all categories
Electrical equipment NA
The templates derived for evaluating emissions of classical air pollutants seem less appropriate for reporting emissions of industrial chemicals / emissions from ”products”

15. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs
Towards a global historical emission inventory for selected PCBs – a dynamic mass balance or ”cradle-to-emissions” approach
Production
Consumption
Atmospheric emissions
Breivik et al 2002 a,b: Science of the Total Environment 290: and

16. Example 2: PCBs Total production as reported in the literature
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs
Total production as reported in the literature
Recently reported: Poland 1,700 t (Sulkowski et al 2003) Unknown amounts produced in Former East Germany

17. PCBs: Large variety of tehcnical mixtures, 21- 68 % Cl (w/w)
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs Cl 3 2 2 ’ 3 ’ 3 2 2 ’ 3 ’ 4 1 1 ’ 4 ’
catalyst 4 1 1 ’ 4 ’ 5 6 6 ’ 5 ’
Clx 5 6 6 ’ 5 ’
Cly
PCBs: Large variety of tehcnical mixtures, % Cl (w/w)

18. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs

19. Example 2: PCBs PRODUCERS CONSUMERS Producing OECD countries
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs
PRODUCERS
CONSUMERS
Production within OECD-countries
Export to OECD countries
Producing OECD countries
67.8 %
Non-producing OECD countries
5.6 %
84.6 %
Export to non-OECD countries
“Other countries”
11.2 %
Czechoslovakia
Eastern Europe (50%)
0.8 %
1.6 %
Czechoslovakia (50%)
0.8 %
USSR
Russia (60%)
7.9 %
13.1 %
Other, USSR (40%)
5.3 %
China (production = consumption)
0.6 %
0.6 %

20. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs

21. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs
Open usages: plasticisers, carbonless copy paper, lubricating oils, inks, laminating and impregnating agents, paints, adhesives, waxes, additives in cement and plaster, casting agents, dedusting agents, sealing liquids, fire retardants, immersion oils, pesticide extenders and kiss-proff lipsticks
Nominally closed systems: Hydraulic and heat transfer fluids
Small capacitors Used in a wide range of products, such as cars and electrical household appliances Closed systems Transformers and large capacitors

22. Example 2: PCBs – congener dependence
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs – congener dependence
Emission factors for open usage were estimated based on measured volatilisation rates of PCBs from sealants at room temperature by Persson et al
PCB-18
log EF (w/w year-1)
PCB-194
log KOA

23. Example 2: PCBs – temperature dependence
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs – temperature dependence
”Hypothetical” relationship between relative atmospheric emission strength due to evaporation, log E, and vapour pressure, log PL

24. ACCIDENTAL RELEASES (A)
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs
CONSUMPTION (C)
Usage factors ()
ACCIDENTAL RELEASES (A)
USAGE (U)
DISPOSAL (D)
Open (1)
Landfills (l)
Small capacitors (2)
Soils (s)
Accidental (af)
Lifetimes (k)
Disposal (df)
Open burning (o)
Nominally closed (3)
Fires (f)
Waste incin.(w)
Closed (4)
Destruction (d)
Emission factors (ef)
EMISSIONS (E)

25. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 2: PCBs

26. Example 3: Denmark – an example to follow!
Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Example 3: Denmark – an example to follow!
“DRAFT GUIDELINES FOR ESTIMATING AND REPORTING EMISSION DATA” (EB.AIR/GE.1/2002/7)
Article 32. When reporting emissions, the level of uncertainty associated with these data and their underlying assumptions should also be reported to the extent practicable. The methodologies used for estimating uncertainties should be indicated in transparent manner. Parties are encouraged to report quantitative information on uncertainties, where this is available.
Based on the simple tier 1 approach in the EMEP/CorinAir Good Practice Guidance for LRTAP Emission Inventories (Pulles & Aardenne 2002). The uncertainty estimates are based on emission data for 2002 and on uncertainties for activity rates and emission factors for each of the main SNAP sectors

27. Motivation and plans for the emission review of POPs and HMs – TFMM 2005
Discussion
Research-driven emission data currently seems to be of limited use with respect to the development of emission reduction strategies, whilst official emission data reported to EMEP seems to be of limited use for modelling purposes… ??? (dual users)
Increased availability of production and usage statistics on an a.i. basis for intentionally produced chemicals (industrial, pesticides) provide useful information (usually fairly reliable / constitute an upper boundary for potential environmental releases).
Subjective and preliminary assessment of emission data quality: HM > POP by-products > POP pesticides > POP industrial chemicals
Closer co-operation with UNEP on emission reporting guidelines for POPs could create useful synergies.
Further targeted research on emissions seems urgently needed to facilitate further improvement of emission reporting guidelines (i.e. the emission inventory guidebook).