Download Chapter 7 Heavy metals

Chapter 7
Heavy metals
Authors:
Ilia Ilyin, Torun Berg, Sergey Dutchak, Jozef Pacyna
7.1 Introduction
Heavy metals are naturally occurring elements, and are present in varying concentrations in all
ecosystems. There is a huge number of heavy metals. They are found in elemental form and in a
variety of other chemical compounds. Those that are volatile and those that become attached to fine
particles can be widely transported on very large scales. Each form or compound has different
properties which also affect what happens to it in food web, and how toxic it is. Human activities have
drastically changed the biochemical cycles and balance of some heavy metals. Between 1850 and
1990, production of copper, lead and zinc increased 10-fold (Nriagu 1995; CACAR 1996). The main
anthropogenic sources of heavy metals are various industrial processes, mining, foundries, smelters,
combustion of fossil fuel and gasoline, and waste incinerators. The major heavy metals of concern to
EMEP are Hg, Cd and Pb, because they are the most toxic and have known serious effects on e.g.
human health. Environmental exposure to high concentrations of heavy metals has been linked with
e.g. various cancers and kidney damage. There are considerably more measurements data on Hg, Cd
and Pb in Europe than for other metals.
7.2 Emissions of heavy metals
The UNECE 1998 Aarhus Protocol on Heavy Metals currently has 36 signatories and 21 ratifications
(May 11, 2004) and entered into force by the end of 2003. Complete and accurate data on heavy metal
emissions are thus increasingly important within the CLRTAP convention. In particular, reliable
emission data are needed to assess further measures to reduce environmental exposure to heavy metals
(HMs) as well as to understand and predict source-receptor relationships of heavy metals on a regional
scale. Three particularly harmful metals are targeted in the protocol, namely cadmium (Cd), lead (Pb)
and mercury (Hg). In accordance with this agreement, parties will have to reduce their emissions for
these three heavy metals below their levels in 1990 (or an alternative year between 1985 and 1995).
The Protocol further aims to cut emissions from various industrial sources, selected combustion
processes as well as waste incineration. It furthermore lays down stringent limit values for emissions
from stationary sources and suggests best available techniques (BAT) for these sources, such as
special filters or scrubbers for combustion sources or mercury-free processes.
The emission data presented herein is based on official submissions to UNECE (e.g. Vestreng
2003) as well as expert estimates (Olendrzynski et al 1996; Berdowski et al 1997; Pacyna and
Pacyna 2002).
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7.2.1 Emissions of lead
Gasoline lead additives have been the key source of lead to the European atmosphere over the last
decades. Lead from road traffic still remains the key source with non-ferrous metal manufacturing,
stationary
fuel combustion
7.2.1
Emissions
of lead as well as iron and steel production as additional significant source
categories.
Figure 1. Atmospheric emissions of lead in Europe in 1980 (left), 1990 (middle) and 2000 (right) in
kg km-2 year-1.
Lead (Pb) provides an interesting and important example of a heavy metal that has experienced
significant changes in anthropogenic atmospheric emissions over the last decades (Pacyna and Pacyna,
2000). The Protocol requires Parties to phase out leaded petrol, and the significant changes in temporal
and spatial patterns from 1980 to 2000 are to a large extent influenced by the substantial reductions in
use of gasoline lead additives. It is evident that these changes in emissions also have had a marked
impact on the transboundary air pollution of lead in Europe during the same period (von Storch et al.
2003).
Denmark
100000
600
400
200
0
1980
1985
1990
1995
2000
Pb emissions, tons year
Pb emissions, tons year
-1
-1
20000
-1
Pb emissions, tons year
Europe
Russia
800
15000
10000
5000
0
1980
1985
1990
1995
2000
80000
60000
40000
20000
0
1980
1985
1990
1995
2000
Figure 2. Temporal trend in emissions of lead in Europe (left), Russia (middle) and Denmark (right)
from 1980 to 2000 in tons year-1.
Still, there are marked differences in the temporal trend in emissions of lead in various countries
across Europe. For example, a continued use of lead in gasoline in Russia over the last decade has
limited further steep reductions during the 1990s (von Storch et al 2003).
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Chapter 7: Heavy metals
7.2.2 Emissions of cadmium
Atmospheric cadmium may originate from multiple sources. Of key significance are various
combustion processes based on fossil fuels (in particular coal and oil), as well as various processes
in the pyrometallurgical non-ferrous metal industries.
Figure 3. Atmospheric emissions of cadmium in Europe in 1980 (left), 1990 (middle) and 2000 (right)
in g km-2 year-1.
Figure 2 displays the spatial pattern of cadmium emissions across Europe in 1980, 1990 and 2000. As
for the other heavy metals discussed, there are significant differences in the spatial pattern. The
situation around 1980 reflects cadmium emission in heavily industrialized zones of Europe as well as
regions utilizing coal as an important source of energy.
Germany
Europe
200
600
400
200
1985
1990
1995
2000
Cd emissions, tons year
800
-1
-1
Cd emissions, tons year
-1
Cd emissions, tons year
1000
0
1980
Poland
200
1200
160
120
80
40
0
1980
1985
1990
1995
2000
160
120
80
40
0
1980
1985
1990
1995
2000
Figure 4. Temporal trend in emissions of cadmium in Europe (left), Germany (middle) and Poland
(right) from 1980 to 2000 in tons year-1.
By the year 2000, there had been a 63% reduction in emissions of cadmium in Europe as compared to
1980 (Figure 4). Certain industrialized countries relying on coal, such as Germany, have seen
substantial reductions in atmospheric emissions (92%).
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EMEP Assessment Report – Part I
7.2.3 Emissions of mercury
Atmospheric levels of mercury are affected by both natural and anthropogenic sources, although
anthropogenic emissions are suggested to be the largest source in Europe. The most important
anthropogenic sources of mercury are the combustion of fuels and in particular coal. Additional
anthropogenic sources of key significance are chlor-alkali production, cement production and waste
incineration.
Figure 5. Atmospheric emissions of mercury in Europe in 1990 (left) and 2000 (right) in g km-2 year-1.
Much effort has been devoted to understand and predict the sources and emissions of mercury
(Hg) in various research projects over the last few years. This has greatly facilitated frequent
updates of European and global scale atmospheric emission inventories for Hg and its
associated forms (Pacyna and Pacyna 2002; Pacyna et al 2001). Figure 5 presents estimated
emissions of mercury in Europe in 1990 and 2000.
Europe
40
400
300
200
100
0
1990
1992
1994
1996
1998
2000
-1
Hg emissions, tons year
-1
Hg emissions, tons year
-1
Hg emissions, tons year
United Kingdom
Sweden
2
500
1.5
1
0.5
0
1990
1992
1994
1996
1998
2000
30
20
10
0
1990
1992
1994
1996
1998
2000
Figure 6. Temporal trend in emissions of mercury in Europe (left), Sweden (middle) and United
Kingdom (right) from 1990 to 2000 in tons year-1.
The data contained in Figure 6 suggest that there has been a 52% reduction in the emissions of Hg in
Europe from 1990 to 2000. The emissions of mercury from various combustion processes have seen a
limited reduction, whereas significant decreases are suggested from industrial sources. Of key
importance has been the reduction of mercury emissions from the production of chlor-alkali plants
employing the Hg cell process (Pacyna et al 2001). It should be mentioned that the Protocol
additionally introduces measures to lower heavy metal emissions from products, such as mercury in
batteries, and proposes the introduction of management measures for other mercury-containing
products.
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Chapter 7: Heavy metals
7.2.4 Discussion
The available information on emissions of heavy metals is generally considered more reliable
and complete as compared to the persistent organic pollutants (see chapter 8.2), although
significant gaps in knowledge remain (e.g. relative importance of natural sources, chemical
speciation of emissions). Table 1 presents official submissions of national HM emission totals
to EMEP during the period from 1996 to 2001 (Vestreng, 2003). For some countries, the
available data at EMEP include historical emissions dating back to 1980 as well as emission
projections up to year 2020.
Table 1. Official submissions of HM emission totals to EMEP MSC-W from 1996 to 2001 among the
49 parties to the convention (Vestreng, 2003).
Lead
Cadmium
Mercury
Chromium
Copper
Nickel
Selenium
Zinc
1996
31
28
29
22
21
21
17
22
1997
29
26
26
20
20
19
15
18
1998
30
27
27
21
21
20
16
22
1999
29
26
26
20
19
18
14
19
2000
28
26
26
20
20
19
14
20
2001
23
22
22
18
19
17
14
18
Still, the data on HM emissions reported to EMEP are generally considered incomplete in terms of
spatial and temporal coverage, as well as sector coverage. Therefore, modellers are often utilising socalled expert estimates of HM emissions to provide more complete input to their models. A number of
studies have been devoted to European emissions of HMs over the last two decades (e.g. Pacyna,
1983; Axenfeld et al 1989; 1991; Berdowski et al 1994;1997; Olendrzynski et al 1996; Pacyna et al
2001) whilst others investigations have had a global approach (e.g. Nriagu and Pacyna, 1988; Pacyna
and Pacyna 2001/2002; Pacyna et al 2003).
7.3. Heavy metal pollution levels
Assessment of environmental pollution can be carried out by means of monitoring and modelling. In
order to realize integrated view of pollution EMEP combines these two approaches. Heavy metals
were included in EMEP’s monitoring program in 1999. However, earlier data have been available and
collected, and the EMEP database thus also includes older data, even back to 1991 for a few sites
[www.nilu.no/projects/ccc]. A number of countries have been reporting heavy metals within the
EMEP area in connection with different national and international programmers such as HELCOM,
AMAP and OSPAR. The number of stations has been increasing, and in 2001 it was 69 measurement
sites altogether. Among them 22 sites measured heavy metals in both in air and in precipitation
[Figure 7a]. Mercury was measured at 15 sites [Figure 7b].
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(a)
(b)
Figure 7. Measurement network of heavy metals, 2001. (a): lead and cadmium; (b) mercury
Measurement network covers only part of EMEP region. In order to provide coverage for the entire
Europe, modelling tools are used. Models can also provide additional information on transboundary
depositions. For the needs of European assessment Eulerian three-dimensional model of atmospheric
transport of heavy metals was used. The model was described in the General Introduction. The model
output includes deposition and concentration fields, tranboundary transport, and long-term trends of
pollution levels. Additionally, following the request of the Working Group on Effects (WGE),
ecosystem –dependent depositions are evaluated.
The following chapter provides an overview of heavy metals (lead, cadmium and mercury) pollution
levels in Europe in the period from 1980 to 2000. The review of mercury levels is made only for the
period from 1990 to 2000 because of lack of emission data prior to 1990.
7.3.1 Pollution levels of lead
In nature lead is a ubiquitous, non-essential element and toxic. Its natural concentrations are not
very high. Lead concentrations are locally and regionally, much higher than they were. Some lead
is taken up by plants and animals and may affect brain and nerve tissue.
Trends in annual means 1980-2000
Emissions and depositions of lead in Europe decreased considerably from 1980 to 2000 (Figure 8).
Lead emissions have dropped down about 8 times, and depositions – more than 6 times. The highest
reduction of emissions and depositions took place between 1985 and 1990. The rate of deposition
decline was less than that of emissions due to the impact of natural emissions, re-emission and the
contribution of sources located outside Europe.
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Chapter 7: Heavy metals
100
Anthropogenic em issions
Deposition
kt / y
80
60
40
20
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
1985
1980
0
Figure 8. Trends of lead emissions and depositions in Europe for 1980-2000.
Lead- Trends in Europe
1980-2001
Norway
Iceland
Finland
Birkenes(NO01)
16000
Irafoss(IS02)
16000
12000
14000
14000
10000
10000
12000
8000
10000
ng/m2
ng/m 2
12000
ng/m2
Virolahti II(FI17)
14000
16000
6000
8000
4000
6000
4000
4000
0
1979
0
1979
1984
1989
1994
1984
1999
1989
1994
16000
14000
14000
12000
12000
ng/m 2
ng/m 2
1984
1989
14000
12000
ng/m2
ng/m 2
1994
14000
4000
2000
0
1979
4000
1984
1989
1994
1999
1999
1984
Netherlands
1989
1994
1989
1994
1999
1999
Germany
Kollumerwaard(NL09)
16000
Deuselbach(DE04)
16000
12000
14000
10000
12000
8000
10000
ng/m 2
14000
ng/m2
1984
2000
0
1979
6000
Czech Republic
8000
6000
4000
4000
2000
Svratouch(CZ01)
2000
0
1979
1984
1989
1994
1999
France
0
1979
16000
14000
1984
1989
1994
1999
12000
ng/m 2
10000
Porspoder(FR90)
8000
6000
16000
4000
14000
2000
12000
0
1979
10000
ng/m2
8000
6000
8000
6000
0
1979
1989
Rucava(LV10)
16000
10000
2000
1984
Latvia
1999
10000
2000
0
1979
1994
12000
ng/m2
ng/m 2
4000
1989
14000
8000
6000
4000
1984
Ulborg(DK31)
10000
8000
8000
0
1979
1999
16000
12000
6000
1994
Denmark
16000
10000
1999
2000
0
1979
East Ruston(GB90)
12000
1994
4000
2000
Turlough Hill(IE02)
1989
6000
4000
16000
1984
10000
8000
6000
14000
0
1979
Bredkälen(SE05)
16000
10000
Ireland
2000
Sweden
1999
Jergul(NO30)
Great Britain
8000
6000
2000
2000
1984
1989
1994
1999
8000
6000
4000
2000
0
1979
1984
1989
1994
1999
Figure 9. Trends for lead deposition between 1980 and 2001 at a number of European EMEP sites
with long data series.
The negative trends simulated by the models are also confirmed at some of the measurement sites with
longest time series, e.g. NO30 (Jergul) which shows the highest decrease in the eighties and a much
more moderate decrease in the nineties (Figure 9). At most of monitoring stations wet depositions of
lead were also decreasing.
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EMEP Assessment Report – Part I
Deposition fluxes of lead over the major part of Europe exceeded 5 kg/km2/y in 1980 (Figure 10). In
some countries (e.g. Germany, Austria, the Netherlands) deposition fluxes were as a rule higher than
10 kg/km2/y. In 2000 deposition fluxes were below 1.5 kg/km2/y in most part of Europe.
a)
b)
c)
Figure 10. Spatial distribution of lead deposition fluxes 1980(a) , 1990 (b) and 2000 (c).
Spatial pattern of air concentrations of lead is similar to that of depositions. Obviously, the highest
concentrations occur in regions with high emissions. In 1980 concentrations varied between 5 and 70
ng/m3. By 2000 typical range was 2 - 12 ng/m3.
25
20
15
10
5
0
Ne
th
L u e rla
xe
n
mb d s
o
Un
ited B el u rg
Ki n giu m
gd
o
Re
Fra m
pu
b lic
De n c e
of
nm
Mo
a
ld r k
G e ova
rm
B e a ny
la
Uk ru s
L it r ain
e
hu
an
i
La a
t
A u via
Mo stri a
na
Cz
e c S lo v co
h R en
ia
e
p
S w ub
l
itz
e rl ic
an
Es d
to n
ia
Ma Ire la
ced n d
Hu o nia
ng
a
S p ry
G e a in
o
S w rg ia
e
B u de n
lg
S lo a ria
va
Fin kia
Ru
la
s si
an
P nd
Fe ol an
de
d
A z ra ti o
er b n
a ija
No n
A rm rwa y
e
Cr ni a
oa
ti a
I
A lb taly
Bo
sn
Ro an ia
ia a
ma
nd
ni a
He
Se
rze Ma l
r bi
go ta
aa
vin
nd
Mo G r a
n te e ec
e
n
Ka egr
za o
khs
I ce t a n
la
Tu n d
P o rke y
r tu
g
Cy a l
p ru
s
Deposition decrease, times
In each country the rate of deposition decline was different during the period from 1980 to 2000
(Figure 11). The highest decrease – almost 24 times – took place in the Netherlands. In most countries
this value ranges between 5 and 15 times. The reduction of the pollution levels results from a decline
of national emissions and transboundary transport.
Figure 11.
countries.
Decrease of lead total depositions between 1980 and 2000 in different European
Emission reduction in European countries caused the decline of heavy metal levels and, in particular,
of transboundary depositions. Since 1980 absolute values of transboundary depositions have decreased
to a great extent. For example, in Cyprus this drop made up about 3 times, in Ireland – almost 40 times
(Figure 12). For most countries transboundary depositions cut down 5 – 15 times.
115
45
36
27
18
9
0
Ire
B e lan d
lg
Mo iu m
na
c
L u Icel o
xe
an
m
Ne b o d
the u rg
rla
nd
s
Ge Italy
r
m
Un
ited No a ny
Ki n rwa
gd y
om
La
t
E s via
t
De o n ia
nm
C
Ru ze c
F ar k
ssi h R ra n
an
e p ce
Fe ub l
i
de
ra t c
i
Re
B e on
pu
l ar
b lic
u
of P ol a s
Mo
n
ld o d
v
L it
hu a
an
A u ia
s
S w tri a
e
S lo de n
A z vak
er b ia
a
S lo ija n
v
Ro en ia
ma
n
Sp i a
Fin a in
la n
Uk d
P o r ain e
r tu
Cr ga l
oa
G r ti a
ee
c
Se
M e
r bi
A lb a lta
aa
an
nd
Mo G eo ia
n te rg i
ne a
g
Hu ro
Bo
S
wit ng a
sn
ia a
ze ry
n d Ma c rla n
He ed d
rze o ni
go a
vin
a
K a Tu rk
za
khs e y
B u ta n
lg
A rm a ria
en
Cy i a
p ru
s
Deposition decrease, times
Chapter 7: Heavy metals
Figure 12. Decrease of lead depositions from transboundary transport between 1980 and 2000 in
different European countries.
Rate of deposition decrease, estimated by the model, is confirmed by EMEP monitoring data.
For example, variations of modelled depositions to Finland and Norway are well correlated
with averaged over country measured wet depositions (Figure 13).
3.0
Observed
2.5
2.0
200
1.5
1.0
100
0.5
2000
1999
1998
1997
1996
1995
1994
1993
1992
a
1991
0.0
1990
0
300
1.2
Observed
2000
1999
1998
1997
0.0
1996
0
1995
0.4
1994
100
1993
0.8
1992
200
1991
b
1.6
Modelled
1990
Modelled depositions, t/y
400
Observed depositions,
2
kg/km /y
Modelled depositions, t/y
300
Modelled
Observed depositions,
2
kg/km /y
3.5
400
Figure 13. Modelled total depositions to a country and averaged over country wet deposition
flux of lead (a) – Norway, (b) - Finland
Nevertheless, the role of transboundary transport in air pollution of countries remains significant.
Transboundary depositions vary essentially among European countries (Figure 14). On the average
this contribution amounted to 40%, ranging from about 75% (Macedonia) to 5% (Iceland) in 2000.
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EMEP Assessment Report – Part I
Contribution, %
80
60
40
20
Bo
sn
ia Ma c
H e ed
r ze o ni
go a
vin
L u Au a
s
xe
Re
mb tri a
pu
o
b li
c o Hu u rg
n
f M ga
o ld ry
ov
A lb a
an
ia
Ma
S
lt
Ne lo ve a
the n ia
rl
L it a nd s
hu
A r an ia
S w me n
itz
e rl i a
a
B e nd
l ar
u
La s
Cz
t
e c S lo v via
h R ak
e p ia
u
De b lic
nm
ar
C
K a r oa k
za
kh ti a
sta
Fra n
S w n ce
e
B u de n
l ga
Uk ria
ra
E s in e
to
Fin n ia
Ge la nd
rm
a
No ny
Se
r bi
Ro rwa y
aa
m
a
nd
Mo G r ni a
n te e ec
e
ne
g
B e ro
l giu
Ge m
o rg
P o ia
l an
Cy d
Mo p ru s
na
Un
co
ite
d K Tu r
i ng ke y
Ru
do
ss
m
ia n
Fe S pa
de
in
A z ra tio
er b n
a
P o ija n
r tu
g
Ire a l
lan
d
It
Ice aly
l an
d
0
Figure 14. Contribution of transboundary pollution to total depositions in the European
countries.
The contribution of transboundary transport is non-uniformly distributed over countries. An
example of this distribution is given for Romania (Figure 15), where the contribution of
transboundary depositions over the whole country amounted to 25% in 2000 (Figure 5).
Regions neighbouring the countries with powerful emission sources (Bulgaria, Serbia and
Montenegro) are most subjected to external anthropogenic sources. The contribution of
transboundary depositions along the state borders is more than 50%. The input of
transboundary transport is the least in central regions and regions with significant national
emissions.
Figure 15. Contribution of transboundary depositions of lead in Romania in 2000
More detailed information about source-receptor relationships for each country one can see in
EMEP/MSC-E reports [Ilyin et al., 2002, 2003] or Internet: www.msceast.org.
7.3.2 Pollution levels of cadmium
Cadmium is not essential for plants, animals and human beings, but has toxic effects. It can be
taken up directly from air and water, and accumulates in living organisms. In addition to
atmospheric long-range transport and the ubiquitous distribution of cadmium, emissions lead to
Trends
in annual means 1980-2000
local and regional pollution of soil and river sediments.
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Chapter 7: Heavy metals
Cadmium emissions in Europe decreased about 4 times, and depositions – almost 3 times for the
period from 1980 to 2000 (Figure 16). The most significant decrease of pollution levels was in the
period from 1985 to 1990.
1200
Anthropogenic em iss ions
Depos ition
t/y
900
600
300
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
1985
1980
0
Figure 16. Trends of cadmium emissions and depositions in Europe for 1980-2000.
Cadmium- Trends in Europe
1980-2002
Norway
Iceland
Finland
B irken e s(N O 01)
600
V ir ola ht i II( FI17)
Irafoss(IS02)
500
400
400
400
300
ng/m 2
ng/m 2
500
200
2
ng/m
600
500
600
300
200
100
200
100
0
1979
1983
1987
1991
1995
1999
Sweden
2003
100
Je rg ul(N O 3 0)
600
0
1979
1983
1987
1991
1995
1999
0
1979
1983
1987
1991
1995
1999
2003
B r ed kä le n (S E05 )
2003
600
500
500
400
400
2
300
ng/m 2
ng/m
300
200
300
200
100
100
0
197 9
1983
1987
1991
1995
1999
2003
0
197 9
198 3
1987
1991
1995
1999
2003
Great Britain
Latvia
Ireland
Rucava(LV10)
Denmark
E as t R us to n (G B 90 )
600
500
600
500
U lb o rg (D K 31)
600
ng/m 2
ng/m 2
500
300
400
500
200
400
100
ng/m 2
Turlough Hill(IE02)
600
ng/m 2
400
400
200
300
100
200
0
197 9
300
198 3
1987
1991
1995
1999
2003
0
1979
100
200
300
0
1979
1983
1987
1991
1995
1999
1983
1987
1991
1995
1999
2003
2003
100
0
1979
1983
1987
1991
1995
1999
Netherlands
2003
Germany
K o llu m e rw a ar d (N L 09 )
600
D eu s elb ach (D E04 )
600
400
500
300
400
ng/m 2
ng/m
2
500
200
100
300
Czech Republic
200
0
19 7 9
198 3
19 87
1991
19 95
1999
20 03
S v ra to uc h (C Z 01 )
100
600
0
197 9
198 3
1987
1991
1995
1999
2003
500
France
ng/m 2
400
P o rsp o d er(F R 9 0)
600
200
500
100
400
ng/m 2
300
0
1979
1983
1987
1991
1995
1999
2003
300
200
100
0
197 9
198 3
1987
1991
1995
1999
2003
Figure 17. Trends for cadmium deposition between 1980 and 2002 at a number of European EMEP
sites with long data series.
As for lead, the negative trends observed by the models are also confirmed at some of the
measurement sites with longest time series, e.g. NO30 (Jergul) which shows the highest decrease in
the eighties and a much more moderate decrease in the nineties (Figure 17). Other sites also
demonstrate decrease of wet depositions of cadmium.
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EMEP Assessment Report – Part I
Over most part of Europe deposition fluxes varied from 30 g/km2/y to 150 g/km2/y in 1980 (Figure18).
In some countries (Poland, Germany, Bulgaria) deposition fluxes were even higher. The fluxes have
reduced substantially nearly in all regions of Europe by 2000 and have reached 20 – 50 g/km2/y.
b
a
Figure 18. Spatial distribution of cadmium deposition fluxes, 1980 (a) and 2000 (b)
Similar to depositions, cadmium concentrations in air declined substantially. Over major part of
Europe the concentrations ranged 0.1 – 0.7 ng/m3 in 1980. In 2000 concentrations typically laid
between 0.07 and 0.25 ng/m3.
Deposition decrease, times
Variation of depositions in each European country for the considered period is demonstrated in
Figure19. In the majority of countries depositions diminished from 1.5 to 5 times. In some countries,
like Macedonia, Luxembourg or Germany, the decrease was more significant. The reduction of
cadmium depositions to countries, compared to lead, was smaller mainly because of smaller decline of
the emissions.
24
22
20
10
8
6
4
2
M
Lu ace
xe do
Re
m nia
pu
bli Ge bou
c o rm rg
fM a
ol ny
B do
Yu ulg va
go ari
s a
Uk lavia
r
Ne Slo aine
th ven
er ia
la
Po nds
Be lan
Cz D lg d
ec en ium
hR m
ep ark
u
Be blic
l
Al arus
ba
C nia
Ro roa
m ti
Li an a
th ia
u
Hu an
n ia
G gary
re
e
La ce
Bo
sn
Au tvia
iaH G st
er eo ria
ze rg
g ia
Sl ovin
o a
Ru
Ar vak
ss
m ia
ian E en
Fe sto ia
d n
Un Az era ia
ite erb tion
dK a
ing ijan
d
Fr om
a
Sw S nce
itz pa
e in
Swrlan
ed d
M en
Fi alta
nl
Ire and
lan
d
I
Ka Tu taly
za rk
kh ey
M s ta
on n
No aco
r
Cy way
p
Ic rus
ela
Po n
rtu d
ga
l
0
Figure 19. Decrease of cadmium total depositions for 1980 – 2000.
119
Chapter 7: Heavy metals
Magnitude of the decrease of cadmium depositions in European countries is comparable with that
derived from results of monitoring. Similar to lead, modelled cadmium total depositions to countries
generally capture observed variation of measured wet depositions. Examples of this comparison are
given for Norway and Finland (Figure 20).
45
4
30
Modelled
2
15
Observed
2000
1999
1998
1997
1996
1995
1994
1993
1992
a
1991
0
1990
0
Modelled depositions, t/y
12
30
Modelled
25
Observed
8
20
15
4
10
5
2000
1999
1998
1997
1996
1995
1994
1993
1992
1991
b
0
1990
0
Observed depositions,
g/km2/y
Modelled depositions, t/y
60
6
Observed depositions,
2
g/km /y
75
8
Figure 20. Modelled total depositions to a country and averaged over country wet deposition flux of
cadmium (a) – Norway, (b) - Finland
A significant portion of cadmium total atmospheric depositions in European countries is caused by
transboundary transport. Transboundary depositions contributed around 30% to total depositions on
the average in 2000. Maximum contribution (55%) was obtained for Lithuania, and the lowest (2%) –
for Iceland.
Depositions caused by transboundary transport of cadmium have declined since 1980 (Figure 21). In
Luxembourg the decrease of depositions from external sources was highest (about 13 times). Over
most countries the decrease ranges from 3 to 6 times.
In spite of the decline, the role of transboundary transport of cadmium remains significant in Europe.
For example, total depositions of cadmium from transboundary sources to Russia amounted to 11 t/y,
to the Ukraine – 7 t/y and to Poland – 5 t/y in 2000 (Figure 22).
ssi
an
Fe
de
ra t
i
Uk on
ra
P o in e
G e l an d
rm
a
B e ny
l ar
Fra u s
S w n ce
e
Ro de n
ma
Hu ni a
ng
Cz
e c L ithu a ry
h R an
e p ia
ub
l
Tu ic
S lo rke y
vak
Fin ia
l
B u a nd
Se
K a l ga
r bi
za ria
aa
k
hs
nd
ta n
Mo
n te I ta
ne ly
gr
Gr o
ee
c
La e
tv
A u ia
st r
i
S w No rw a
itz
Bo
e rl a y
a
sn
ia
Cr nd
an
d H B e oa ti a
l
Un e rze giu m
it e
d K go vin
a
i
Ne ng do
t he m
rla
nd
Re
pu
Sp s
b li
c o E s a in
f M to n
o ld ia
o
De va
nm
G e ar k
o
S lo rg ia
Ma ven
i
ce
do a
P o nia
r tu
A ga l
A z lb an
er b ia
a
A r ija n
me
n
L u Ire i a
l
xe
mb an d
ou
Cy rg
p
Ice ru s
l an
M d
Mo a lta
na
co
Ru
Depositions, t/y
Deposition decrease, times
mb
o
A lb u rg
a
I ce n ia
l an
Ne Ire l d
t he an d
rla
n
Gr d s
Re Cze Ro e ece
m
pu
c
b lic h Re a ni
a
p
of
Mo ub lic
Se
Ma ld ov
r bi
ced a
aa
on
nd
ia
Mo
n te I ta
ne ly
g ro
Au
S lo st ri a
ve
Un
B
ited ul g n ia
Bo
sn
K
i ng a ria
ia a
do
nd
P m
He
rze ol an
d
Ru
go
ssi A z vina
a n er b
Fe a ija
de
ra t n
i
No on
rwa
Sp y
Cr a in
S lo oa ti a
v
B e akia
l giu
m
La
Hu tvia
ng
a
Tu ry
rk
Fra e y
Uk n ce
r
Mo ain e
na
E s co
t
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o
G e rg ia
rm
a
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De l aru s
n
L it m ar
hu
an k
ia
Ma
lt a
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r
za
khs u s
Fin ta n
A rm la nd
S e ni
S w we d a
itze e n
r
P o la nd
r tu
ga
l
Lu
xe
120
EMEP Assessment Report – Part I
14
12
10
8
6
4
2
0
Figure 21. Decrease of cadmium depositions from transboundary transport for 1980 – 2000.
12
10
8
6
4
2
0
Figure 22. Total cadmium depositions from external anthropogenic sources.
7.3.3 Pollution levels of mercury
Mercury is a toxic environmental pollutant that is among the most highly bioconcentrated metals
in the human food chain. Once emitted, mercury may be deposited by dry and wet processes to
environmental surfaces. In aqueaous systems, mercury is methylated, incorporated into
microorganisms, and bioaccumulated through the food chain where human exposure occurs.
Trends in annual means 1980-2000
For the period from 1990 to 2000 mercury anthropogenic emissions in Europe were reduced by half
and depositions decreased 1.5 times. A significant fraction of mercury depositions is caused by
natural, global anthropogenic sources and re-emission. Deposition decline rate is less than that of
anthropogenic emissions (Figure 23).
121
Chapter 7: Heavy metals
500
Anthropogenic em iss ions
Deposition
t/y
400
300
200
100
2000
1999
1998
1997
1996
1995
1994
1993
1992
1991
1990
0
Figure 23. Trends of mercury emissions and depositions in Europe for 1990-2000.
A few stations have measured mercury in wet deposition (Figure 24). The Swedish station SE002 has
the longest time series and confirm the emission and modelled data.
Mercury- Trends in Europe
1989-2001
Sweden
Rörvik(SE02)
25000
20000
Norway
ng/m 2
15000
Lista(NO99)
10000
25000
5000
20000
ng/m 2
0
1988
15000
1990
1992
1994
1996
1998
2000
2002
10000
5000
0
1988
1990
1992
1994
1996
1998
2000
2002
Netherlands
Kollumerwaard(NL09)
25000
Germany
20000
Westerland(DE01)
25000
ng/m 2
15000
20000
10000
15000
ng/m2
5000
10000
0
1988
1990
1992
1994
1996
1998
2000
2002
5000
0
1988
1990
1992
1994
1996
1998
2000
2002
Belgium
Knokke(BE04)
120000
Zingst(DE09)
25000
100000
20000
80000
ng/m
2
ng/m2
15000
60000
10000
40000
5000
20000
0
0
1988
1990
1992
1994
1996
1998
2000
2002
1988
1990
1992
1994
1996
1998
2000
2002
Figure 24. Trends for cadmium deposition between 1980 and 2001 at a number of European EMEP
sites with long data series.
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EMEP Assessment Report – Part I
Changes in mercury pollution levels were overviewed for the period from 1990 to 2000. During this
period spatial pattern of mercury depositions changed significantly (Figure 25). In 1990 deposition
fluxes mainly ranged from 8 to 40 g/km2/y over Europe. Relatively high levels of deposition fluxes
took place in Germany, Poland, the United Kingdom and some Balkan countries. Deposition fluxes
have reduced almost in all regions of Europe by 2000, ranging from 8 to 25 g/km2/y over the most part
of Europe.
a
b
Figure 25. Spatial distribution of mercury deposition fluxes, 1990 (a) and 2000 (b)
In 1990 concentrations of mercury in Europe varied between 1.7 - 3 ng/m3. In 2000 the concentrations
were somewhat reduced compared to 1990. Relatively little reduction of concentrations (about 15 %
on average) is explained mainly by global nature of mercury atmospheric transport.
4
3
2
1
lic
of
Mo
ld
G e ova
N
Un e th r ma n
e
ite
d K rla n y
ds
in
Ma g do
ce m
do
B n
L u ul g ia
a
xe
mb ria
ou
Uk rg
ra
Cz
e c S lo v in e
h R ak
e p ia
u
B b lic
S w el giu
itze m
rla
A u nd
s
E s tri a
t
De o n ia
nm
Hu ar k
ng
Cr a ry
S lo oa ti a
ven
Fra ia
nc
La e
tvia
Bo
sn
It a
ia H
ly
Se
er z P ol a
r bi
eg n d
aa
ov
nd
i
Mo G eo n a
n te rg i
ne a
g ro
M
Ro a lta
ma
ni
Ru
Sp a
s si
a n S w a in
Fe e d
de e n
ra
A r ti on
me
Mo ni a
na
Fin co
la n
Tu d
r
A lb ke y
an
B e ia
la
No ru s
rw
Ire a y
l
G an d
L it re ece
hu
A z an
er b ia
a
P ija n
K a or tu g
za
a
khs l
t
Cy a n
p
Ice ru s
l an
d
0
Re
pu
b
Deposition decrease, times
Due to different rate of emission reduction, rate of deposition decline varies from country to country
(Figure 26). In the majority of countries depositions cut down 1.2 – 2.5 times. The highest deposition
decline is noted in Republic of Moldova and in Germany (3.5 times). Some countries are characterized
by a negligible deposition decrease or even increase. This is connected with a low rate of emission
reduction in these and neighbouring countries and meteorological variability.
Figure 26. Decrease of mercury total depositions for 1990 – 2000.
123
Chapter 7: Heavy metals
Average contribution of mercury depositions from external anthropogenic sources to total depositions
in European countries amounted to 20% in 2000. However, this contribution is different for different
countries. The highest input of external sources (almost 50%) is made to the Netherlands, the lowest
(1%) – to Iceland.
5
4
3
2
1
L u Ire
l
xe
mb an d
ou
ia n
Ice rg
l
Fe
de an d
ra t
Cz
i
ec
P o on
h R l an
e
d
K a p ub
za lic
kh
Hu s t a n
n
Ro g a ry
Ne ma
the ni a
rla
nd
Re
Au s
pu
st r
b li
ia
co
S
fM
p
o ld a in
o
v
Ge a
rm
a
E s ny
to n
Un
N
ited
o ia
Ki n rwa y
gd
S lo o m
A z ven
er b ia
a
G e ija n
o rg
B e ia
la
G r ru s
ee
Cr ce
oa
Fra ti a
De n ce
n
L it m ar
hu
k
an
Uk ia
r ai
n
Bo
e
sn
Ita
ia
H e Fin l ly
r ze a nd
go
v
S lo in a
vak
i
La a
A rm tvia
Se
en
r bi
i
aa
Ma a
nd
Mo S we lta
d
n te
ne e n
g ro
Tu
rk
Cy e y
P o p ru s
r
Ma tu g
ced a l
o
B nia
S w ul ga
itze ria
rl
B e a nd
l gi
u
A lb m
a
Mo n ia
na
co
0
Ru
ss
Deposition decrease, times
Mercury depositions caused by transboundary transport have decreased in all European countries
(Figure 27). The decrease ranges mainly between 1.5 and 3 times. The highest decline took place in
Ireland followed by Luxembourg and Iceland.
Figure 27. Decrease of mercury depositions from transboundary transport for 1990 – 2000.
In contrast to lead and cadmium, mercury is a global pollutant, i.e. it can be transported by
atmospheric flows all around the globe. That is why mercury emission sources located in other
continents have a significant impact on pollution of Europe. Apart from that, natural emission sources
and re-emission contribute significantly to mercury penetration to the atmosphere.
Evaluation of mercury intercontinental transport was made for 1996. Main regions - contributors of
intercontinental mercury depositions in Europe are depicted in Figure 28. About 60% of deposited
mercury to Europe came from its own sources and 40% – from sources located outside Europe.
Total Hg deposition, t/y
150
Natural
61%
120
Anthropogenic
90
60
15%
30
12%
5%
3%
North
America
Africa
4%
0
Europe
Asia
Oceans
South
Hemisp
Figure 28. Contributions of global sources to mercury depositions in Europe in 1996. The last column
of the chart – contribution of mercury transported from the Southern Hemisphere.
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EMEP Assessment Report – Part I
The contribution of non-European sources to mercury deposition fluxes in Europe is spatially nonuniform (Fig 29). Obviously, in the central part of Europe the contribution of external sources is the
least. Over most part of Europe this contribution varied from 25 to 60% in 1996. On the periphery of
the continent – in Scandinavia, west of the Iberian Peninsula, the contribution exceeded 60%, to the
Caucasus – was more than 75%.
Figure 29. Relative contribution of non-European sources to mercury deposition in Europe in 1996.
Europe, in turn, is a source of global mercury pollution. Around 60% of mercury emitted in Europe
was transported outside the region in 1996. Deposition fluxes of mercury from European sources
exceed 2 g/km2/y in such remote regions as South-eastern Asia, the North Pacific and the west of
North America (Figure 30). Considerable levels of mercury deposition over the Northern Hemisphere
were caused by the long - about a year - atmospheric lifetime of mercury.
Figure 30. Depositions of mercury from European sources in 1996. The black line is the border of the
EMEP region in 1996.
125
Chapter 7: Heavy metals
The ability of mercury to travel over thousands of kilometres, results in elevated deposition levels in
remote and vulnerable regions. One of such a region is the Arctic. More than 20% of depositions onto
this region came from sources located in Europe in 1996 (Figure 31). Most of these sources were of
anthropogenic origin. Other major anthropogenic sources of mercury atmospheric pollution in the
Arctic were Asia and North America [Dutchak et al., 2003].
Total Hg deposition, t/y
100
33%
Anthropogenic
80
Natural
24%
22%
60
40
10%
20
7%
4%
0
Europe
Asia
North
America
Africa
Oceans
South
Hemisp
Figure 31. Contribution of different regions to the total annual deposition of mercury to the Arctic in
1996. The last column of the chart – contribution of mercury transported from the Southern
Hemisphere.
7.3.4. Special issues
Ecosystem-dependent depositions
Research groups working with the effects of atmospheric pollution need information on ecosystemdependent deposition fluxes. In order to provide them with this information, estimates of heavy metal
depositions to various types of ecosystems were made. An example of cadmium decrease of
depositions to arable lands in the period 1980-2000 is presented in Figure 32. More detailed
information about ecosystem-dependent depositions of lead, cadmium and mercury one can find in the
report [Ilyin et al., 2003] and in the Internet: http://www.msceast.org.
a
b
Figure 32. Deposition fluxes of cadmium to arable lands, 1980 (a) and 2000 (b).
Pollution of marginal seas
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EMEP Assessment Report – Part I
The seas surrounding Europe are receptors of airborne pollutants like heavy metals. Depositions of
lead to the Baltic Sea amounted to about 150 t, of cadmium – about 10 t, of mercury – 3.5 t in 2000
(Figure 33). Depositions of these metals to other seas (the Black, the North, the Mediterranean) have a
similar order of magnitude.
Cd and Hg deposition, t/y
30
1200
Cadmium
M ercury
Lead
1000
24
800
18
600
12
400
6
200
0
0
Baltic
Black
Pb deposition, t/y
36
North M editerranean
Figure 33. Lead, cadmium and mercury depositions to regional seas in 2000.
For the considered period atmospheric depositions of lead, cadmium and mercury declined due to the
reduction of anthropogenic emissions. The rate of deposition decline was different for each metal and
sea (Table 2). Since the rate of lead emission reduction was higher than that of cadmium, lead
depositions to the regional seas cut down to a greater extent than cadmium depositions. The mercury
depositions to the Black and the Baltic Seas in 1990 – 2000 almost halved. Mercury deposition
reduction to the Mediterranean Sea was negligible.
Table 2. Decrease (times)
1990–2000 (Hg).
Sea
Lead
Baltic
7.7
Black
4.3
North
10.9
Mediterranean
4.2
of heavy metal depositions to regional seas for 1980–2000 (Pb, Cd) and
Cadmium
2.5
2.2
2.0
1.6
Mercury
1.5
1.3
1.7
1.1
7.4. Conclusions
During the period of 1980-2000, levels of European pollution by lead and cadmium demonstrate a
stable declining trend. The same could be indicated for mercury pollution levels during 1990 – 2000.
Lead is characterized by the highest deposition decrease due to effective emission reduction.
Atmospheric depositions of metals in countries of Europe depend on both national emissions and
transboundary transport. The latter factor can contribute tens of percents to total heavy metal
Chapter 7: Heavy metals
127
depositions in countries. Therefore, in spite of significant reduction of pollution levels of heavy
metals, transboundary transport continues to play an important role in atmospheric pollution in
Europe. In case of mercury pollution significant impact is made by intercontinental transport to
Europe.
7.5 References
Axenfeld, F., Münch, J., Pacyna, J.M., Duiser, J.A. and Veldt, C., 1989. Emissionsdatenbasis für die
Spurenelement As, Cd, Hg, Pb, Zn und für Spezielle Organische Verbindungen γ-HCH
(Lindan), HCB, PCB und PAK. Umweltforschungsplan des Bundesministers für Umwelt,
Naturschutz und Reaktorsicherheit. Luftreinhaltung. Forschungsbericht 104 02 588. Dornier,
Juli 1989.
Berdowski. J.J.M., Pacyna, J.M. and Veldt, C., 1994. Chapter 3: Emissions: In: van den Hout, K.D.
(ed.), 1994: The Impact of Atmospheric Deposition of Non-Acidifying Pollutants on the
Quality of European Forest Soils and the North Sea. Main report of the ESQUAD project. Air
and Energy Directorate of the Dutch Ministry of Housing, Spatial Planning and the
Environment.
Berdowski, J.J.M., Baas, J., Bloos, J.P.J., Visschedijk, A.J.H., Zandweld, P.Y.J., 1997. The European
Emission Inventory of Heavy Metals and Persistent Organic Pollutants for 1990.
Forschungsbericht 104 02 672 / 03. Umweltforschungsplan des Bundesministers für Umwelt,
Naturschutz und Reaktorsicherheit. TNO Institute of Environmental Sciences, Energy
Research and Process Innovation.
CACAR, 2003: Canadian Contaminants Assessment Report II, Sources, Occurrence, Trends and
Pathways in the physical environment, Northern Contaminants program, Minister of Indian
Affairs and Northern Development, Minister of Public Works and Government Services
Canada, p,p. 332.
Dutchak S. Fedyunin M., Gusev A., Ilyin I., Malanichev A., Mantseva E., Resnyansky Yu., Shatalov
V., Strukov B., Travnikov O., Varygina M., Vulykh N. and Zelenko A. [2003]. Assessment of
long-range transport of Hg, PCBs and γ-HCH to the Russian North. EMEP/MSC-E Technical
Report for AMAP, 260 pgs.
Ilyin I., Ryaboshapko A., Afinigenova O., Berg T., Hjellbrekke A.G., Lee D.S. [2002]. Lead,
cadmium and mercury transboundary pollution in 2000. MSC-E/CCC Technical Report
5/2002
Ilyin I., Travnikov O., Ass W. and Ugerud H. Th. [2003]. Heavy metals: transboundary pollution of
the environment. EMEP Status Report 2/2003. MSC-E, June, 2003. 40 pgs.
Nriagu, J.O., Pacyna, J.M. 1988. Quantitative assessment of worldwide contamination of air, water
and soils by trace metals. Nature 333 (6169): 134-139.
Olendrzynski K., Anderberg S., Bartnicki J., Pacyna J., and Stigliani W., 1996. Atmospheric emissions
and depositions of cadmium, lead, and zink in Europe during the period 1955-1987. Environ.
Rev., 4, pp. 300-320.
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Pacyna, J.M., 1983. Trace element emission from anthropogenic sources in Europe. Norwegian
Institute for Air Research, NILU Technical Report No. 10/82. Lillestrøm, Norway.
Pacyna, J. M. and E. G. Pacyna, 2000. Atmospheric emissions of anthropogenic lead in Europe:
improvements, updates, historical data and projections. GKSS 2000/31 Geesthacht GmbH,
Geesthacht, Germany. ISSN 0344-9629.
Pacyna, E.G., Pacyna, J.M., 2001. An assessment of global and regional emissions of trace metals to
the atmosphere from anthropogenic sources worldwide. Environmental Reviews 9: 269-298.
Pacyna, E.G., Pacyna, J.M., 2002. Global emission of mercury from anthropogenic sources in 1995.
Water, Air and Soil Pollution 137: 149-165.
Pacyna, E.G., Pacyna, J.M., Pirrone, N., 2001. European emissions of atmospheric mercury from
anthropogenic sources in 1995. Atmospheric Environment 35: 2987-2996.
Pacyna JM, Breivik K., Münch J., Fudala J. 2003. European atmospheric emissions of selected
persistent organic pollutants, 1970-1995. Atmospheric Environment 37: S119-S131.
Pacyna, J.M., Pacyna, E.G., Steenhuisen, F., Wilson, S., 2003. Mapping 1995 global anthropogenic
emissions of mercury. Atmospheric Environment 37: S109-S117.
Vestreng, V., 2003. Review and Revision. Emission data reported to CLRTAP. MSC-W Status Report
2003. EMEP/MSC-W Note 1/2003.
von Storch, H., Costa-Cabral, M., Hagner, C., Feser, F., Pacyna, J.M., Pacyna, E.G., Kolb, S., 2003.
Four decades of gasoline lead emissions and control policies in Europe: a retrospective
assessment. The Science of the Total Environment 311: 151-176.