EG on Particulate Matter, Berlin, May 2005
Relations between PM and
persistent toxic substances
Alexey Ryaboshapko,
Meteorological Synthesizing Center “East”
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
What pollutants do we consider?
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
What pollutants do we consider?
Heavy Metals (HMs):
The first priority:
Cd, Pb, Hg
The second priority: As, Cu, Cr, Ni, Zn
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
What pollutants do we consider?
Persistent Organic Pollutants (POPs):
Dioxins / Furans
Polychlorinated biphenyls
Polyaromatic hydrocarbons
Pesticides
-
210 compounds
209 compounds
hundreds
hundreds
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
Physical properties of HMs in the
atmosphere
HM
Pb
Cd
Hg
As
Cr
Cu
Ni
Zn
Typical particle
size range, m
0.5 – 2
0.5 – 2
0.5 – 1
0.5 – 2
1–3
1–3
1–3
0.5 - 3
Particulate
share, %
100
100
1–5
95
100
100
100
100
Life-time in the
atmosphere
2 – 3 days
2 – 3 days
1 year
2 – 3 days
1 – 2 days
1 – 2 days
1 – 2 days
1 – 3 days
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
Physical properties of POPs in the
atmosphere
POP
Typical particle
size range, m
Particulate Life-time in the
share, %
atmosphere
Dioxins
0.3 – 1
5 - 95
3 – 5 days
PAHs
0.5 – 2
90 – 100
7 – 15 days
PCBs
0.3 – 1
40 – 60
40 – 60 days
Lindane
0.3 - 1
0–1
2 – 3 months
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
Comparison of main categories of sources
for primary PM and HMs
Cd
PPM10
Pb
PPM10
Power Plants
Industry
Transport
Residential
combustion
Metallurgy
Other
EMEP/MSC-E
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EG on Particulate Matter, Berlin, May 2005
Comparison of main categories of
anthropogenic sources for PM and POPs
PCDD/Fs
PPM10
BaP
PPM10
Power Plants
Industry
Transport
Residential
combustion
Metallurgy
Other
EMEP/MSC-E
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EG on Particulate Matter, Berlin, May 2005
Airborne concentrations of primary PM10,
Cd and mass fraction of Cd in PPM10
PPM10, g/m3
Cd, ng/m3
Cd in PPM10, %
Sources: Primary PM10 concentration distribution: CCC & MSC-West (4 / 2004)
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EMEP/MSC-E
Pollutant concentration distributions: MSC-East report (2 / 2004)
EG on Particulate Matter, Berlin, May 2005
Are airborne HMs and POPs harmful ?
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
Are airborne HMs and POPs harmful ?
Yes !
Threshold concentration levels for
residential areas are set in most European
countries as air quality standards.
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
Thresholds accepted for Heavy Metals
by the 1st Daughter Directive and
the 4th Daughter Directive of EU*, ng/m3:
Arsenic
Cadmium
Lead
Nickel
6
5
500
20
*) For the total content in PM10 averaged over one year
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
Thresholds accepted for the sum of dioxins
and furans, fg TEQ/m3:
Russia
Italy
USA
-
500
40
20
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
Thresholds accepted for particulate matter, μg/m3
Particle
size
Time
period
PM2.5 Annual
PM10
EU
2010
(proposed)
15
Daily
65
Annual
50
40
20
150
70
100
Daily
TSP
USA Nether Sweden Russia WHO EU
1996 -lands
1997
1991 1987 2005
1996
70
40
20
50
50
Annual
Daily
150
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
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
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
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.
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
An example:
Cadmium within particulate matter could
make 10% of an air volume unsuitable for
human
1 cubic
meter
clean air
Cd – 10%
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
An example:
B[a]P within particulate matter could make
15% of an air volume unsuitable for human
1 cubic
meter
clean air
B[a]P – 15%
Cd – 10%
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
An example:
Particulate matter itself could make 20% of
an air volume unsuitable for human
1 cubic
meter
clean air
PM – 20%
B[a]P – 15%
Cd – 10%
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
Integral PM pollution
 (HQi) = Hazard Index for PM (dimensionless)
1 cubic
meter
clean air
PM – 20%
B[a]P – 15%
Cd – 10%
HI = (HQi) = 0.45
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
Integral Pollution by Particulate Matter
(Hazard Index)
HI

m

j 1
n
C i, j  i, j
i 1
Ti , j

COV
j
Cij – mass concentration of the i-the pollutant within the j-th
pollutant class;
φij – share of the concentration in particulate phase…
Tij - permissible threshold concentration…
COVj – coverage coefficient for the j-th pollutant class.
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EG on Particulate Matter, Berlin, May 2005
Spatial distribution of hazard indexes
over Europe (PM, Cd, Ni, Pb, B[a]P)
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
Spatial distribution of hazard indexes
over Europe (PM, Cd, Ni, Pb, B[a]P)
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
Northeastern Germany
Pollutant
Cadmium
Annual
Threshold limit
concentration suggested by EU
Hazard
quotient
0.15 ng/m3
5 ng/m3
0.03
2 ng/m3
20 ng/m3
0.10
Lead
10 ng/m3
500 ng/m3
0.02
Benzo[a]pyrene
0.2 ng/m3
1 ng/m3
0.20
PM10
12 g/m3
40 g/m3
0.30
Nickel
Hazard Index for PM :
0.65
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
“Black Triangle”
Pollutant
Cadmium
Hazard
Annual
Threshold limit
concentration suggested by EU quotient
0.5 ng/m3
5 ng/m3
0.10
6 ng/m3
20 ng/m3
0.30
20 ng/m3
500 ng/m3
0.04
Benzo[a]pyrene
1 ng/m3
1 ng/m3
1.00
PM10
20 g/m3
40 g/m3
0.50
Nickel
Lead
Hazard Index for PM :
1.94
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
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
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EMEP/MSC-E
EG on Particulate Matter, Berlin, May 2005
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.
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EMEP/MSC-E