1. 1 Relations between PM and persistent toxic substances Alexey Ryaboshapko, Meteorological Synthesizing Center “East” EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E

2. 2 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E What pollutants do we consider?

3. 3 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E What pollutants do we consider? Heavy Metals (HMs): The first priority: Cd, Pb, Hg The second priority: As, Cu, Cr, Ni, Zn

4. 4 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E What pollutants do we consider? Persistent Organic Pollutants (POPs): Dioxins / Furans -210 compounds Polychlorinated biphenyls -209 compounds Polyaromatic hydrocarbons -hundreds Pesticides -hundreds

5. 5 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Physical properties of HMs in the atmosphere HMTypical particle size range, m Particulate share, % Life-time in the atmosphere Pb0.5 – 21002 – 3 days Cd0.5 – 21002 – 3 days Hg0.5 – 11 – 51 year As0.5 – 2952 – 3 days Cr1 – 31001 – 2 days Cu1 – 31001 – 2 days Ni1 – 31001 – 2 days Zn0.5 - 31001 – 3 days

6. 6 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Physical properties of POPs in the atmosphere POPTypical particle size range, m Particulate share, % Life-time in the atmosphere Dioxins0.3 – 15 - 953 – 5 days PAHs0.5 – 290 – 1007 – 15 days PCBs0.3 – 140 – 6040 – 60 days Lindane0.3 - 10 – 12 – 3 months

7. 7 Comparison of main categories of sources for primary PM and HMs EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E PPM10 CdPb Power Plants Residential combustion Industry Metallurgy Transport Other

8. 8 Comparison of main categories of anthropogenic sources for PM and POPs EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Power Plants Residential combustion Industry Metallurgy Transport Other PPM10 PCDD/Fs BaP

9. 9 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Airborne concentrations of primary PM10, Cd and mass fraction of Cd in PPM10 Sources: Primary PM10 concentration distribution: CCC & MSC-West (4 / 2004) Pollutant concentration distributions: MSC-East report (2 / 2004) PPM10, g/m 3 Cd, ng/m 3 Cd in PPM10, %

10. 10 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Are airborne HMs and POPs harmful ?

11. 11 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Yes ! Threshold concentration levels for residential areas are set in most European countries as air quality standards. Are airborne HMs and POPs harmful ?

12. 12 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Thresholds accepted for Heavy Metals by the 1 st Daughter Directive and the 4 th Daughter Directive of EU*, ng/m 3 : Arsenic 6 Cadmium 5 Lead 500 Nickel 20 *) For the total content in PM10 averaged over one year

13. 13 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Thresholds accepted for the sum of dioxins and furans, fg TEQ/m 3 : Russia-500 Italy- 40 USA- 20

14. 14 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Thresholds accepted for particulate matter, μg/m 3 Particle size Time period USA 1996 Nether -lands 1996 Sweden 1997 Russia 1991 WHO 1987 EU 2005 EU 2010 (proposed) PM2.5Annual15 Daily65 PM10Annual5040204020 Daily150701007050 TSPAnnual Daily150

15. 15 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Approach to assessment of integral pollution by PM Individual pollutants have different toxicity… We need to find a quantitative criterion, which has property of additivity… An approach based on idea of “threshold concentration level” is widely used

16. 16 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Quantitative additive criterion: A portion of an air volume, which could become unsuitable for humans because of presence of a given pollutant in air. Let us call this portion “Hazard Quotient” (HQ): HQ = C / T, where  C – airborne concentration of a given pollutant;  T - permissible threshold concentration for a given pollutant.

17. 17 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E An example: Cadmium within particulate matter could make 10% of an air volume unsuitable for human 1 cubic meter Cd – 10% clean air

18. 18 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E An example: B[a]P within particulate matter could make 15% of an air volume unsuitable for human 1 cubic meter B[a]P – 15% clean air Cd – 10%

19. 19 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E An example: Particulate matter itself could make 20% of an air volume unsuitable for human 1 cubic meter PM – 20% clean air B[a]P – 15% Cd – 10%

20. 20 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Integral PM pollution  ( HQ i ) = Hazard Index for PM (dimensionless) HI =  (HQ i ) = 0.45 1 cubic meter PM – 20% clean air B[a]P – 15% Cd – 10%

21. 21 EG on Particulate Matter, Berlin, May 2005 Integral Pollution by Particulate Matter (Hazard Index) C ij – mass concentration of the i-the pollutant within the j-th pollutant class; φ ij – share of the concentration in particulate phase… T ij - permissible threshold concentration… COV j – coverage coefficient for the j-th pollutant class.

22. 22 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Spatial distribution of hazard indexes over Europe (PM, Cd, Ni, Pb, B[a]P)

23. 23 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Spatial distribution of hazard indexes over Europe (PM, Cd, Ni, Pb, B[a]P)

24. 24 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Northeastern Germany PollutantAnnual concentration Threshold limit suggested by EU Hazard quotient Cadmium0.15 ng/m 3 5 ng/m 3 0.03 Nickel2 ng/m 3 20 ng/m 3 0.10 Lead10 ng/m 3 500 ng/m 3 0.02 Benzo[a]pyrene0.2 ng/m 3 1 ng/m 3 0.20 PM10 12 g/m 3 40 g/m 3 0.30 Hazard Index for PM :0.65

25. 25 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E “Black Triangle” PollutantAnnual concentration Threshold limit suggested by EU Hazard quotient Cadmium0.5 ng/m 3 5 ng/m 3 0.10 Nickel6 ng/m 3 20 ng/m 3 0.30 Lead20 ng/m 3 500 ng/m 3 0.04 Benzo[a]pyrene1 ng/m 3 1.00 PM10 20 g/m 3 40 g/m 3 0.50 Hazard Index for PM :1.94

26. 26 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Examples of usage of the approach to assess cumulative risk caused by different pollutants Novikov G.V. and Dudarev A.Ya., 1978. Sanitary protection of the environment of a modern city. Leningrad, Medicina, 215 pp. Berlyand M.E. (editor), 1994. Yearbook on the state of air pollution and emissions of pollutants into the atmospheres of cities and industrial centers of Russian Federation. Sankt-Peterburg, Main Geophysical Observatory, 407 pp. Hampshire Research Institute (www.hampshire.org/risk01.htm) US EPA, 2003 EPA/630/P-02/001F May 2003

27. 27 EG on Particulate Matter, Berlin, May 2005 EMEP/MSC-E Possible output information:  Spatial distribution (50*50 km) of hazard index for PM averaged over one year.  Number of days during a year when the hazard index is higher than unity in all EMEP grid cells.  Product of hazard index for PM and population in all EMEP grid cells for population risk assessment.