Chapter 5
5.4. Freshwater environment
Table 5.21a. Concentrations (geometric mean and range; ng/g wet weight) of OCs in fish muscle in the Russian Arctic in 2001.
a More than half of concentrations were below the detection limit in at least 50% of the samples. In such cases, when lower and upper limits of the concentration interval were
estimated, concentrations below the detection limits was set to zero or to the detection limit, respectively.
of all species are comparable. The high lipid concen-
group and show no significant relationship to site.
tration of burbot liver makes it a popular component
Geometric means of the liver/muscle concentration
of the diet of indigenous peoples.
ratios for Hg, Pb and Cd in freshwater species are equal
to 2.0, 2.8 and 4.8, respectively. For salmon species
(b) Heavy metals
these values are somewhat higher (2.4, 8.6 and 7.5,
Concentrations of HMs are similar in male and female
respectively).
fish of each species. Concentrations measured in the
oldest fish groups are, on average, twice as high as in the
Levels and trends
corresponding youngest age group, whereas the mid-
age/young-age group ratio is equal to 1.2. These values
(a) Organochlorines
are consistent with ratios of mean ages in the groups,
OC concentrations in fish muscle are shown in Tables
i.e., even for relatively old fishes, HM contamination
5.21a and 5.21b. Concentrations of all OCs that were
levels are close to being proportional to age. Examples
found at detectable levels are broadly similar for both
of Hg concentration dependence on fish age for those
salmon and freshwater groups, although slightly high-
sites with the maximum number of sample age groups
er concentrations were found in salmon species. No
are given in Figure 5.21. Effective rates of HM accumu-
pronounced geographic trend was found for any OC.
lation in fish species are given in Table 5.20. For Pb they
All concentrations in muscle were below the corre-
are comparable with those found in reindeer tissues,
sponding MPCs established in Russia for freshwater
whilst for Hg and particularly Cd, rates are lower.
fish (0.03 mg/kg for HCH, and 0.3 mg/kg for
DDT) as well as those for sea fish. Most OC levels are
Concentrations of HMs in the liver of all species is
comparable with those detected in reindeer. The only
higher than that in the muscle. The liver/muscle con-
exception to this concerned concentrations of DDT,
centration ratios are similar for all species within a fish
which are several times higher in fish. Mean OC con-
Table 5.21b
Concentrations
(geometric mean and range;
ng/g wet weight) of OCs
in fish muscle in the Russian
Arctic in 2001.
a More than half of concen
trations were below the
detection limit in at least
50% of the samples. In such
cases, when lower and upper
limits of the concentration
interval were estimated, con
centrations below the detec
tion limits was set to zero or
to the detection limit, respec
tively.
109
5.4. Freshwater environment
Chapter 5
centrations in muscle of whitefish species from three
Samples of fish tissues were also analysed for other OCs,
lakes in the Canadian Arctic in 19931999 ranged from
listed in Section 1.2.4. In the majority of samples, all
4.7 to 24.7 ng/g for PCB (102 congeners), from 0.32
other OCs were below detection limits. Only Heptaclor
to 2.66 ng/g for HCH, from 1.7 to 9.0 ng/g for
was found in few samples of burbot and whitefish liver
CHLOR, and from 1.9 to 24.6 ng/g for DDT (all --
and in broad whitefish muscle in concentrations close
in ww) (CACAR, 2003). In comparison with the
to the detection limit of 0.05 ng/g ww.
Canadian data, Figure 5.22, the upper limit of concen-
tration ranges for whitefish species in the Russian
(b) PCDD/Fs
North in 2001 coincides with the lower limit of the con-
Concentrations of 2,3,7,8-substituted PCDD/Fs were
centration ranges calculated for whitefish in Canada.
analyzed in pooled fish muscle samples. Results are
The upper limits of concentration ranges for all OCs
presented in Table 5.22 and Figure 5.12. PCDD/Fs in
from the Canadian studies are several times higher than
fish species follow a similar, but less pronounced, geo-
those seen in the Russian Arctic. In comparison with
graphical distribution to that seen in reindeer. All con-
results from studies in northern Scandinavia, however,
centrations are far below the maximum permissible
contamination levels in Russia are reasonably similar to
levels associated with consumption of meat.
concentrations measured in lake whitefish at three
Norwegian sites in 1994 (0.51.6 ng/g for the sum of 6
Levels of PCDD/Fs found in this study (0.03-0.2 WHO-
PCB
congeners;
0.100.12
ng/g
for
HCH;
TEQ/g) were of an order of magnitude lower than in
0.030.23 ng/g for CHLOR; and 0.15-0.63 ng/g for
fish muscle samples from the Grate Slave Lake in
DDT), and also with concentrations measured in
northern Canada in 1994/5 (0.6-1.1 WHO-TEQ/g;
Arctic char in Finland (AMAP, 1998).
CACAR, 2003). PCDD/Fs concentrations in lake white-
fish sampled in Norwegian lakes (1994) were even
higher (5.3 ng I-TEQ/g). At four other sites in
Scandinavian countries, however, PCDD/F levels in
fish muscle were more comparable with those meas-
ured in the Russian North in 2001 (0.05-0.09 and 0.02-
0.15 ng I-TEQ/g, respectively; AMAP, 1998).
Figure 5.22 Comparison of mean OC concentrations
in whitefish species in the Canadian Arctic (1993 1999), Norway (1994), and Russia
(2001). The lower part of each column corresponds to the minimum mean
concentration, and the total column height, to the maximum mean concentration.
Table 5.22. Concentrations (expressed as TEQ) of PCDD/Fs in fish muscle
PCB=PCB15, HCH=HCH, CHLOR=CHLOR, DDT=DDT
the Russian Arctic in 2001.
* ratio of PCDD/F concentration in pg WHO TEQ/pg to that in pg/g
Table 5.23. Concentrations (geometric mean and range; ng/g ww) of PAHsa in muscle of fish species in the Russian Arctic.
a NAP = Naphthalene, NAP2M = 2 Methylnaphthalene, FLE = Fluorene, PA= Phenanthrene, FLU = Fluoranthene
110
Chapter 5
5.4. Freshwater environment
(c) PAHs
centrations measured on the Kola Peninsula are con-
The geometric means and ranges of PAH concentra-
sistently higher than at other sites. Hg and Cd concen-
tions in the muscle of fish species in the Russian Arctic
trations are generally comparable in all species at all
are given in Table 5.23. PAH levels in fish, in contrast to
sites, apart from relatively low Cd levels occurring in
OCs, are higher than those in waterfowl, including the
Arctic grayling. Pb levels are, as a rule, somewhat high-
piscivores. The distribution of PAH between tissues is
er in freshwater species. All concentrations, with one
also very different from that of OCs. For example, the
exception, are significantly below the relevant MPCs
OC concentration in liver tissue in burbot can be sever-
(of 0.6 mg/kg for Hg, 0.2 mg/kg for Cd, and
al hundred times higher than that in muscle, while PAH
1.0 mg/kg for Pb), established in Russia for predatory
levels in both of these tissues are comparable. No geo-
fish. The exception is Hg in whitefish from the
graphic trend in PAH levels in fish is apparent, although
Khatanga River, the concentration of which exceeds
concentrations in pike from inland Chukotka are sever-
permissible limits by a factor of 1.5.
al times higher than those on the Kola Peninsula.
However, for other fish species there are no noticeable
No significant difference was observed in Cd and Pb
differences between Chukotka and other regions.
levels in caregonids in the Russian North between 1995
and 2001. Levels of Hg in these species in the Yenisey
(d) Brominated flame-retardants
and Khatanga Rivers were higher in 2001 than in 1995,
Samples of fish tissues were analysed for 2,2',4,4'-tetra-
while Hg levels reported for whitefish caught in the
bromodiphenyl, 2,2',4,4',5-pentabromodiphenyl, 2,2',
Pechora River in 1995 (AMAP, 1998) are comparable
4,4'-tetrabromodiphenyl ether and 2,2',4,4',5-penta-
with those measured in 2001. Hg levels in species in
bromodiphenyl ether. In the majority of samples, con-
the Russian North are also consistent with results from
centrations were below the detection limit of 0.2 ng/g
the Canadian Arctic. Mean concentrations of Hg in
ww. Only 2,2',4,4'-tetrabromodiphenyl ether was found at
whitefish species in Canadian lakes in 1996-2000
higher levels in a few samples of fish liver (see Table 5.24).
ranged from 0.03 to 0.35 µg/g (CARCAR, 2003), and
those in Russian lakes and rivers in 2001 from 0.055 to
(e) Heavy metals
0.15 µg/g. These concentrations are also similar to
No pronounced geographic trends are apparent in the
those found in fish in northern Norway in 1995
levels of HMs in fish (see Table 5.25), although Hg con-
(AMAP, 1998).
Figure 5.23. Absolute and relative levels of p,p' DDE and p,p' DDT in aquatic food
chains in the Khatanga area. Geometric means and ranges of DDE and DDT levels in
Table 5.24. Concentrations (ng/g ww) of 2,2',4,4' tetrabromodiphenyl ether in liver
sediments are given on a dry weight basis, while levels in the muscle of birds and fish
of fish in the Russian Arctic in 2001.
are on a wet weight basis. Ratios are shown with 95% confidence limits.
Table 5.25.
Concentrations
(geometric mean and range;
µg/g ww) concentrations
of HMs in the freshwater fish
muscle in the Russian Arctic
in 2001.
111
5.4. Freshwater environment
Chapter 5
KOW values of other OC's were taken from the publica-
5.4.2. PTS transfer in the freshwater food chain
tion by Mackay et al. (1992). For fish species harvested in
Lake Lovozero, and from rivers in the study, most TFWF
(a) Organochlorines
values calculated for p,p'-DDT and p,p'-DDE, as well as
The major link in the contamination of many aquatic
for other OCs with detected levels and with logKOW 6
food chains by OCs, is their transfer from water to fish.
are about 1000 mL/g ww, or somewhat higher.
As an example of p,p'-DDT and p,p'-DDE uptake patterns
in freshwater aquatic food chains, Figure 5.23 shows lev-
The TFWF values predicted for p,p'-DDE, with only one
els of these contaminants in fish muscle and waterfowl
exception, overestimate experimental values, while
from the Khatanga area of eastern Taymir, (the only site
those for p,p'-DDT underestimate values in most cases.
where all fish and bird groups were sampled).
This is unlikely to be the result of poor choice of KOW
values, because according to equation 5.5, when KOW is
The characteristic time for hexachlorobiphenyl (PCB-
sufficiently large, the accuracy of its value is not critical
155) absorption/depuration, as determined by labora-
for freshwater, and the relative concentrations of all
tory experiments on adult rainbow trout, is about highly hydrophobic contaminants in fish and water are
1 month (Gobas et al., 1999). This indicates that steady
expected to be similar. However, the measured
state OC concentrations in fish are established within a
DDE/DDT ratio in fish is several times higher (see
period of months, even for OCs with a logKow value as
Figure 5.23 and Table 5.26a and 5.26b), probably indi-
high as 7. As shown, OC distribution between water
cating a faster rate of p,p'-DDT metabolism in fish tissues
and fish tissues can be quite accurately described by a
than predicted. In any event, the assumption seems rea-
simple adsorption/desorption model, with the water-
sonable for waterfowl, in which the DDE/DDT ratio is 1-
to-fish transfer factor (TFWF, mL/g ww of muscle) cal-
2 orders of magnitudes higher than in water, sediments
culated as follows (Verhaar et al., 1999):
and fish. As the chemical and physical properties of p,p'-
DDE and p,p'-DDT are quite similar, it is unrealistic to
TFWF = (VLMKOWa1 + VWM)/(VLWKOWa2 + VWW)
(5.5)
expect that the dramatic difference in their relative con-
centrations could have a non-metabolic explanation.
Where:
Comparison with whitefish species provides further evi-
VLM and VLW are lipid fractions in the muscle
dence of an enhanced rate of metabolic transformation
of fish and in water, respectively;
of p,p'-DDT into p,p'-DDE in birds and/or in their food.
VWM and VWW are water fractions in the muscle
Levels of p,p'-DDT and p,p'-DDE in whitefish are, respec-
of fish and water, as a physical body respectively;
tively, higher and lower than in birds, whilst levels of the
a1 and a2 are Collander coefficients, which com-
sum of p,p'-DDT and p,p'-DDE are comparable and con-
pare the similarity of the lipid in a given compart-
sistent with the corresponding lipid concentrations.
ment with octanol.
Despite feeding at the highest trophic level, piscivore tis-
sues do not contain the highest levels of p,p'-DDT and
A typical value for dissolved organic matter (DOM) con-
p,p'-DDE, nor do they have the highest DDE/DDT ratio.
centration in surface freshwater is about 10 mg/L
Only DDE concentration is consistently higher in pisci-
whilst the normal lipid concentration in the muscle of
vore bird species than in fish, while other OC levels
fish is several percent. A typical value for the Collander
(such as p,p'-DDT) are comparable or even lower. From
coefficient for the organic matter of soil and sediments
this it can be inferred that the fish-to-birds transfer fac-
(a1) is 0.8 (Schwarzenbach et al., 1993). A significantly
tor is close to unity for OCs which do not undergo sig-
smaller coefficient a2 might be expected, however,
nificant metabolic transformation in bird tissues.
when experimental data are applied to equation 5.5 a
similar value is obtained for both coefficients (Verhaar
et al., 1999). Therefore, for the purposes of this study, a
value of 0.8 was used for both a1 and a2. Using these
input parameters, equation 5.5 predicts almost con-
stant transfer factors (TFWF 1000 mL/g ww) for all
hydrophobic substances with logKOW > 6. This is consis-
tent with previously reported experimental TFWF - KOW
dependences (Verhaar et al., 1999). KOW values selected
by Pantolillo and Eganhouse (2001) were used for p,p'-
DDT (logKOW = 6.6, the geometric mean of two selected
Table 5.26a. DDE/DDT ratios (geometric means and 95% confidence interval)
KOW values), and for p,p'-DDE (logKOW 7.0), while the
in freshwater food chains.
Table 5.26b. DDE/DDT
ratios (geometric means
and 95% confidence interval)
in freshwater food chains.
112
Chapter 5
5.5. Marine environment
Contaminants in water also constitute the basis for the
environmental media or in the food supply, contami-
most important food chain pathways that give rise to
nation levels in fish tissues would be expected to be rel-
contaminants in waterfowl. All other conditions (such
atively constant and in equilibrium with levels found in
as forage composition, DOM concentration etc.) being
the environment.
equal, OC levels in birds are directly proportional to
the level of contamination in water. This being so, it is
An example of HM distribution patterns in an aquatic
possible for water-to-bird transfer factors to be calculat-
food chain are presented in Figure 5.25. Despite occu-
ed. These are comparable for all bird groups at all sites
pying a higher trophic level, HM contamination levels
and equal 5700 and 980 mL/g ww for p,p'-DDE, and
in piscivorous birds are comparable with those of fish.
p,p'-DDT, respectively. Transfer factors for HCB and
Water-to-fish and water-to-bird transfer factors for HMs
PCBs range from 460 mL/g ww (HCB, water- to- pisci-
vary within an order of magnitude. Values of water-to-
vores in eastern Taymir) to 67000 mL/g ww (PCB-153,
fish transfer factors for Hg and Cd are similar for
water-to-molluscivores in western Taymir). The geo-
salmon species and for freshwater fish, while the water-
metric means of transfer factors are in a good agree-
to-fish transfer factor for Pb is several times higher for
ment with those predicted using equation 5.5 and
freshwater species. Geometric means of Hg and Cd
equal 1200 mL/g ww for HCB, 1800 mL/g ww for
TFWFs, calculated using pooled sets of data, are equal
PCB-153 and 4100 mL/g ww for PCB-28. The lower
to 3300 and 570 mL/g ww, respectively. Geometric
value obtained for PCB-153 when compared with that
means of Pb TFWFs are equal to 280 mL/g ww for
of PCB-28 may be due to the kinetic limitation of high-
freshwater species and 60 mL/g ww for salmon species.
ly hydrophobic compound levels in bird tissues.
Default values for Hg and Pb biomagnification in fish
Higher transfer factors for waterfowl when compared
edible parts provided in the IAEA Handbook (IAEA,
to fish are consistent with the bird/fish concentration
1994) are consistent with values obtained in this study.
ratio for PCDD/F of ~ 2.2, and with the approximately
two times greater lipid concentration in the muscle of
As shown in section 5.3.4, HM contamination levels are
birds. All differences between waterfowl /fish concen-
close to being directly proportional to fish age, even
tration ratios for lipids and OCs are within a small (fac-
for relatively old fish. This indicates that HM elimina-
tor of two) variance, and there is close correlation
tion rates are low and that the biological half-lives for
between the ranges for OC ratios and those of lipids
the 3 HMs considered are about 10 years. The elimina-
(see Figure 5.24).
tion rates determined in this study are significantly
slower than those measured in laboratory experiments,
(b) Heavy metals
in which a state of equilibrium was normally reached
Equillibrium levels of Hg, Pb and Cd in fish in labora-
within several weeks or months (WHO 1989a, 1989b,
tory experiments can normally be established in sever-
1991, 1992, 1995). A possible explanation for this dis-
al weeks or months (WHO 1989a, 1989b, 1991, 1992,
crepancy is the relatively short duration of laboratory
1995). This indicates that, in the absence of sudden
experiments. If this is the case, HMs could have accu-
temporal or spatial changes in HM concentrations in
mulated primarily in tissues and organs that are capa-
ble of fast absorption and elimination of HMs. This
Figure 5.24.
hypothesis is supported by observations from laborato-
Concentration ratios (geo
metric mean and 95% confi
ry experiments that the elimination rate decreases with
dence limits) for OCs and
time. The biological half-life of the remaining HM frac-
lipid content in waterfowl/
tion may, therefore, be many years. This is the slowest
fish, for all sample sites.
stage of HM elimination and is, quite possibly, the con-
trolling rate under natural conditions.
5.5. Marine environment
5.5.1. PTSs in marine fish
Among marine fish species, only yellowfin sole floun-
Figure 5.25.
der (Limanda aspera), harvested in the Bering Sea was
The HM distribution pattern
in water fish bird food chains
sampled and analysed for PTSs content. However, for
on the Kola Peninsula in
this analysis, some anadromous fish species such as
2001. HM concentrations
smelt (Osmerus eperlanus), chum salmon (Oncorhynchus
and their ranges in bird and
fish muscle are in µg/g ww,
keta) and sea-run Arctic char (Salvelinus alpinus) were
while those in water are in
included in the group of sea fish, since they inhabit sea
µg/L.
waters for a major part of year, migrating into river
mouths only in the fall season for spawning.
(a) Organochlorines
As it is shown in Tables 5.27a and 5.27b, concentrations
of OCs in muscle tissue of yellowfin sole are within the
range of OC levels for anadromous fish. For concen-
113
5.5. Marine environment
Chapter 5
Table 5.27a.
Concentrations
(geometric mean and range;
ng/g wet weight) of OCs
in muscle tissue of marine
and anadromous fish
in the Russian Arctic
in 2001.
Table 5.27b.
Concentrations
(geometric mean and range;
ng/g wet weight) of OCs
in muscle tissue of marine
and anadromous fish
in the Russian Arctic
in 2001.
trations of OCs found above detection limits, such as
broad circumpolar distribution and prefer annual,
PCB15, HCB, HCH and CHLOR, yellowfin sole
land-fast ice, but are also found near multiyear ice.
muscle is approximately in the middle of the range of
Adults are believed to be relatively sedentary, but sub-
values for anadromous fish, although it had the lowest
adults can disperse over long distances. Ringed seals
levels of DDT and its metabolites.
are a key component of the diet of the Inuit in north-
ern Canada and Greenland, and of the Yupik and
(b) Heavy metals
coastal Chukchi on the Chukotka Peninsula of Arctic
From Table 5.28, it can be seen that levels of Hg and Cd
Russia.
in yellowfin sole were, as for OCs, within the range of
values for Hg and Cd found in anadromous fish, how-
14 samples of ringed seal liver, kidney, muscle and
ever, Pb concentrations in its flesh were higher than
blubber, together with 5 samples of bearded seal, and
those in the anadromous fish group. Concentrations of
22 samples of larga seal were collected from various
all HM tested were well below guidelines concerning
communities located on the shores of Lavrentiya Bay in
permissible levels of Hg, Pb and Cd in marine fish (0.4,
the Bering Sea, during the summer and fall periods of
1.0 and 0.2 µg/g ww, respectively).
2000 and 2002.
5.5.2. PTSs in marine mammals
PTS concentration relationships to seal sex, age,
and tissue type
5.5.2.1. Seal species
As the age range of sampled animals among the seal
The seal family (Phoca sp.) in this study is represented
species was very low (from 0.5 to 3.5 years), it was con-
by the ringed seal (Phoca hispida), the bearded seal
sidered that neither age nor sex difference was likely
(Erignatus barbatus) and the larga, or spotted seal
to be particularly important in explaining variations in
(Phoca largha). Seals are the most abundant and widely
contaminant levels. Consequently, averages were cal-
distributed of the resident Arctic pinnipeds. Their diet
culated based on values obtained from both sexes and
consists of fish and crustaceans. Ringed seals have a
all ages.
Table 5.28.
Concentrations
(geometric mean and range;
g/g wet weight) of HMs
in muscle tissue of marine
and anadromous fish
in the Russian Arctic
in 2001.
Table 5.29.
Concentrations (mean ± S.D.
ng/g ww) of OCs in blubber
of male and female seals
harvested in the Russian
Arctic (Chukotka), compared
with data from northern
Canada (CACAR, 1997).
114
Chapter 5
5.5. Marine environment
Table 5.30a. Concentrations (geometric mean and range; ng/g ww) of OCs in organ and tissues of seal species in the Russian Arctic.
a More than a half of concentrations measured were below the detection limit in at least one of the pooled samples.
In the ringed seal samples, PCBs, HCH, chlordanes,
lated (Tables 5.30a and 5.30b). No statistically signifi-
and DDT were the most prominent contaminants,
cant differences were found between concentrations of
while chlorobenzenes and toxaphene were present at
OCs detectable in muscles, liver and kidney of ringed
lower concentrations. Average concentrations of PCB
seal, but OC concentrations in blubber were about 50
and chlordanes in females were higher than those in
times higher in comparison with other organs and tis-
males, while mean levels of HCH and DDT in males
sues. Concentrations of OCs in muscles, liver, kidney
exceeded those in females (Table 5.29). Mean concen-
and blubber of larga seal occured in the approximate
trations of the sum of chlorobenzenes (CBz) and
ratio 1 : 0.3 : 0.2 : 15.
toxaphene were very similar in both males and females.
The highest level of muscle contamination by OCs was
In larga seals, PCBs, CHLOR, DDT, and HCH were
found in larga seal. Concentrations of all OCs in the mus-
the main contaminants found, and average concentra-
cle of other seal species were several times lower and close
tions of all OCs tested were higher in males than in
to those found in terrestrial mammals, waterfowl and fish.
females.
Concentrations of HCH and DDT and its metabolites in
muscle, liver and kidney of seals were below correspon-
Comparison of OC levels in the blubber of ringed seal
ding guidelines established for consumption of seal meat
harvested in the Canadian and Russian Arctic have
in Russia (0.01 mg/kg for HCH, and 0.03 mg/kg for
shown that for all OCs under consideration, except for
DDT). No significant difference was observed between
HCH, concentrations in the blubber of ringed seal
concentrations of any OCs in other tissues of seals, with
from the Canadian Arctic, exceeded those in ringed
the exception of relatively low HCB and HCH levels in
seal from the Bering Sea. The most probable explana-
the muscle and blubber of bearded seal. Like in fish mus-
tion for this is the difference in age between the two
cle, levels of OCs in the blubber of seals were close to the
groups of seals, since seals hunted in the Bering Sea
lower margin of concentration ranges reported for seals
were no older than 3.5 years of age, whereas ringed seals
from the Canadian Arctic in 1998-2001 (CACAR, 2003).
from the Canadian North were 6 years or more in age.
Results of a comparative assessment of OC contamina-
Levels and trends
tion of ringed seal blubber in the Canadian and the
(a) Organochlorines
Russian Arctic are shown in Figure 5.26. As can be seen
For the pooled data set of seal species, which included
from the Figure, concentrations of major OCs in the
all ages and both sexes, geometric means were calcu-
blubber of ringed seal in the Canadian Arctic meas-
Table 5.30b Concentrations (geometric mean and range; ng/g ww) of OCs in organ and tissues of seal species in the Russian Arctic.
a More than a half of concentrations measured were below the detection limit in at least one of the pooled samples.
115
5.5. Marine environment
Chapter 5
Table 5.31.
Concentrations (ng/g ww)
of of 2, 2', 4, 4' tetrabro
modiphenyl ether in seal
species in the Russian Arctic
in 2000 2002.
ured during the period 1989 to 2001 (CACAR, 1997;
CACAR, 2003) were higher when compared with those
measured in the Russian Arctic during the period
2000-2002.
(b) Brominated flame-retardants
Samples of tissues of marine mammals were analyzed for
2, 2', 4, 4'-tetrabromodiphenyl, 2, 2', 4, 4', 5-pentabromo-
diphenyl, 2, 2', 4, 4'-tetrabromodiphenyl ether and 2, 2',
4, 4', 5-pentabromodiphenyl ether. In most samples,
these substances occurred below the detection limit of
0.2 ng/g. Only 2, 2', 4, 4'-tetrabromodiphenyl ether was
found in few samples at higher levels (see Table 5.31).
(c) Heavy metals
Figure 5.26. Comparison of mean OC concentrations in ringed seal blubber
Concentrations of HMs in seal species are shown in
in the Canadian Arctic (Canada 1: 1989 1994, Canada 2: 1998 2001) and Russia
Table 5.32. The highest levels of contamination by Hg
(2000 2002). The lower part of each column corresponds to the minimum mean
concentration, and the total column height, to the maximum mean concentration.
were found in the tissues of bearded and larga seal, and
PCB=PCB (sum of 15 congeners in Russia; sum of more than 100 congeners
the lowest levels in ringed seal. Lead and Cd concentra-
in Canada), HCH=HCH, CHLOR=CHLOR, DDT=DDT.
tions were similar in all seals. Hg concentrations in the
muscle of seal species were significantly higher when
(0.5, 0.6, and 1.0 mg/kg, respectively). However, all Hg
compared with those in terrestrial mammals, birds, and
and most Cd concentrations in seals significantly
fish. Lead levels in seals were somewhat lower than those
exceeded corresponding guidelines (Table 5.33).
in birds and terrestrial animals, while Cd concentrations
in all mammals, birds, and fish were comparable. All Pb
As seen in Table 5.32, the organ showing the greatest
concentrations in the muscle, liver and kidney of seals
degree of contamination by Hg, in all seal species, was
were below corresponding guidelines established for
liver, followed by muscle tissue, and kidney. With
human consumption of meat, liver, and kidney in Russia
respect to Cd, the most contaminated organ was kid-
Table 5.32.
Concentrations (geometric
mean and range; µg/g ww)
of HMs in tissues and organs
of seals in the Russian Arctic
in 2000 2002.
Table 5.33.
Amount by which
concentrations of Hg and Cd
measured in tissues and
organs of seal species
harvested in the Russian
Arctic exceed guidelines for
consumption of meat, liver,
and kidney products.
116
Chapter 5
5.5. Marine environment
Table 5.34a.
Concentrations
(geometric mean and range;
ng/g ww) of OCs in tissues
and organs of male
and female walrus in the
Russian Arctic in 2002.
Table 5.34b.
Concentrations (geometric
mean and range; ng/g ww)
of OCs in tissues and organs
of male and female walrus in
the Russian Arctic in 2002.
ney, followed by liver. Concentrations of Cd in muscle
the bioaccumulation of contaminants in benthic
tissue in seal species were below guideline levels.
marine food webs. Although they have an important
role in the traditional hunts and diets of indigenous
The ranges of all HM concentrations in muscle, liver
peoples, relatively little is known about contaminant
and kidney of seals were consistent with concentrations
levels in walrus. Some individuals, however, are known
determined in 1998-2001 in ringed seal in the
to feed at higher trophic levels and include ringed seal
Canadian Arctic (CACAR, 2003). However, HM con-
in their diet, and as a result have much higher contam-
centrations in ringed seal from Canada are somewhat
inant concentrations in their tissues (AMAP, 1998;
lower than those determined in ringed seal in the
CACAR, 2003). Walrus tissues and organs, including 22
Russian Arctic, this despite the fact that the were
samples each of liver, kidney, muscle, and blubber,
reported on the dry weight basis. HM concentrations
were collected in the summer and fall of 2002 from
in ringed seal muscle in the Russian Arctic fall almost
coastal communities of the Chukotka Peninsula.
in the middle of concentration ranges determined in
Canada in 1987-1994 (CACAR, 1997; see Figure 5.27).
PTS concentrations relationship to walrus sex,
age and tissue type
5.5.2.2. Walrus
The age distribution of male walrus sampled was as fol-
Walrus (Odobenus rosmarus) are long-lived benthic feed-
lows: 3 individuals aged 1.5 years, 2 individuals aged
ers and, as such, are an important indicator species for
3.5 years, 2 individuals aged 4.5 years, and 4 individu-
als aged 5.5 years. Female walrus sampled showed
Figure 5.27.
greater variability in age distribution and were repre-
Comparison of mean HM
concentrations in ringed seal
sented by 1 walrus aged 0.5 years, 4 individuals aged
muscle in the Canadian
2.5 years, 3 individuals aged 3.5 years, and 1 individual
Arctic (1987 1994) and
each of 4.5, 5.5 and 6.5 years.
Russia (2000 2002). The
lower part of each column
corresponds to the minimum
As the mean age difference between male and female
mean concentration, and the
walrus was relatively small (3.8 years vs 3.4 years, respec-
total column height,
to the maximum mean
tively), average PTS levels in walrus tissues and organs
concentration.
were calculated without distinguishing between age
groups. Tables 5.34a, 5.34b show OC concentrations as
measured in different organs and tissues of male and
female animals.
Table 5.35.
Concentrations
(geometric mean and range;
µg/g wet weight) of HMs in
tissues and organs of male
and female walrus in the
Russian Arctic in 2002.
117
5.5. Marine environment
Chapter 5
Table 5.36a.
Concentrations
(geometric mean and range;
ng/g ww) of OCs in tissues
and organs of walrus in the
Russian Arctic in 2002.
Table 5.36b.
Concentrations
(geometric mean and range;
ng/g ww) of OCs in tissues
and organs of walrus in the
Russian Arctic in 2002.
Table 5.37.
Concentrations (geometric
mean and range; µg/g wet
weight) of HMs in tissues
and organs of walrus in the
Russian Arctic in 2002.
The distribution of HM concentrations in walrus tis-
of Cd were highest in kidney and exceeded those in
sues and organs for each sex is shown in Table 5.35.
muscles by a factor of nearly 700, and those in liver by
Levels of Hg in the muscle, liver, and kidney of male
a factor of approximately 6.
walrus were slightly higher than in females, but con-
centrations of Pb and Cd in females, in contrast to Hg,
Concentrations of Cd in the liver and kidney of walrus
exceeded those in males.
were 8- and 14-times higher, respectively, than the
Levels and trends
human consumption guideline values for Cd in inter-
nal organs, established in the Russian Federation.
(a) Organochlorines
Levels of Hg in muscle, liver, and kidney of walrus
For the pooled data set, geometric means were calcu-
were, respectively, 1.4-, 16.6- and 1.3-times higher than
lated including all ages and both sexes of walrus
the associated human consumption guidelines values.
(Tables 5.36a and 5.36b). No statistically significant dif-
Although high, these levels of exceedance of guideline
ferences were found between concentrations of HCB,
values are less than those noted for seal species.
chlordane-related compounds, or DDT in the mus-
cle, liver and kidney of walrus; however, PCB15 con-
5.5.2.3. Grey whale
centrations in blubber were approximately 68, 47, and
Grey whales (Eschrichtius gibbosus), taken from the
21 times higher when compared to the muscle, kidney
Bering Sea by indigenous hunters of the coastal com-
and liver, respectively. Concentrations of HCH in the
munities of Chukotka were sampled. The sampled
muscle, kidney, liver, and blubber of walrus were found
whales included 2 females, with a mean age of 3 years,
in the ratio of 1 : 1.8 : 3.3 : 109; levels of CHLOR in
3 females with the mean age of 7.3 years, and 2 males
these organs and tissues occurred in the ratio of 1 : 1.2 :
with a mean age of 6.5 years.
1.5 : 32; and DDT levels in muscle, kidney, liver, and
blubber were found in the ratio of 1 : 1.4 : 1.9 : 45.
PTS concentration relationships to whale sex,
age and tissue type
Concentrations of HCH and DDT measured in muscle
tissue and the blubber of walrus were compared with
Most OCs, except for HCH, were found in lower con-
existing Russian guidelines for HCH and DDT com-
centrations in female whales than in males, possibly
pounds, in both the meat of marine mammals (includ-
due to the elimination of these lipophilic compounds
ing walrus), and in animal fat. The levels of HCH and
during lactation. No significant trend in OC concen-
DDT measured in walrus muscle were found to be,
tration levels with age was found in male grey whale,
respectively, 12 and 35 times, lower than the corre-
but a substantial decrease in OC concentration in
sponding guidelines values (of 10 and 30 ng/g ww).
females occurred after six years of age, which corre-
The levels of summed HCH isomers in the blubber of
sponds to the age at which first parturition takes place.
walrus, measured at 93.9 ng/g ww and were approxi-
For example, the average concentration of PCB con-
mately 2.1 times lower than the guideline value of
geners in the blubber of grey whale females of 3 years
200 ng/g ww.
was 135 ng/g ww, whilst in female of 7.3 years, PCBs
averaged 87.5 ng/g ww (Table 5.38). The levels of the
(b) Heavy metals
main OCs in the liver, kidney and blubber of females
Concentrations of heavy metals in walrus organs and
aged 3 years, exceeded those in females aged 7.3 years
tissues are shown in Table 5.37. Levels of Hg were high-
1.4- to 1.8-fold. This is consistent with the influence of
est in the liver, 42-fold greater than those in muscle,
parturition and lactation, which are associated with the
and 6-fold greater than those in kidney. Concentrations
elimination of contaminants from maternal whales. An
118
Chapter 5
5.5. Marine environment
Table 5.38. Concentrations (geometric mean and range; ng/g ww) of OCs in tissues and organs of grey whale in the Russian Arctic, by age and sex.
exception to this is seen in muscle tissue, in which lev-
els of DDT, HCB, and chlordane-related compounds
were higher in females of over 7 years than in females
of 3 years. It is important to note however, that the sta-
tistical significance of most age-related differences in
concentrations of PTS from the limited dataset avail-
able is rather low.
As can be seen from Table 5.39, Hg levels varied
according to age and sex, with higher levels observed
in males, followed by females of 7.3 years, and lowest
levels in females of 3 years of age. Concentrations of Pb
and Cd did not follow the same pattern; for Pb, the
highest levels were found in older females, followed by
males, with lowest levels in females of 3 years of age.
Levels and trends
(a) Organochlorines
For the pooled data set, which included all ages and
both sexes, geometric means were calculated for PTS
concentrations in grey whale. From Table 5.40 it can
be seen that the highest concentrations of all OCs
tested were found in the whale blubber. For the other
organs and tissues, levels of PCB15, toxaphene,
Table 5.39.
Concentrations (geometric mean and range; µg/g ww) of HMs
HCH, DDT, and CHLOR were highest in liver,
in tissues and organs of grey whale in the Russian Arctic, by age and sex.
although higher in kidney than in liver in the case of
a Range given, as one of the sampled whales had concentrations below
HCB.
the detection limit.
Table 5.40.
Concentrations (geometric
mean and range; ng/g ww)
of OCs in tissues and organs
of grey whale in the Russian
Arctic.
119
5.5. Marine environment
Chapter 5
whale were high compared to concentrations of these
metals in other organs and tissues. Hg concentrations
in blubber, muscle, kidney, and liver were measured in
the ratio 1 : 2.9 : 4.3 : 7.5, while levels of Pb in kidney,
blubber, muscle, and liver were found in the ratio of
1 : 1.2 : 1.5 : 2.0.
Concentrations of Hg measured in muscle tissue of
grey whale exceeded the human consumption guide-
line values for Hg in meat by almost 1.5 times. Cd lev-
Table 5.41 Concentrations (geometric mean and range; µg/g ww) of HMs in tis
sues and organs of grey whale in the Russian Arctic.
els in liver were 2.5-fold the guideline value for Cd in
a Range given as more than a half of concentrations were below the detection limit in
internal organs (0.3 µg/g ww), and Cd concentrations
at least one of the samples contributing to the mean.
in kidney exceeded the associated guideline value
(1.0 µg/g ww) by almost 1.9 times.
5.5.3. PCDDs/Fs in marine mammals
Concentrations of 2,3,7,8-substituted PCDDs/Fs were
analyzed in samples of marine mammals collected
from the coastal survey site off the Chukotka
Peninsula. Results are presented in Table 5.42.
PCDDs/Fs levels in the blubber of marine mammals
from the Bering Sea measured in 2001 (0.6-1.0 pg
I-TEQ/g) were an order of magnitude lower than levels
in ringed seals from the Barents Sea in measured in 1987
(6-26 pg I-TEQ/g; AMAP, 1998). This difference is, how-
Table 5.42. Concentrations (expressed as TEQ) of PCDD/Fs in marine mammals
ever, consistent with spatial trends observed for other
harvested in the Russian Arctic in 2000 2002.
* ratio of PCDD/F concentration in pg WHO TEQ/g to that in pg/g
non-mammalian marine species, presented above.
5.5.4. PTS transfer in the marine food chain
(a) Organochlorines
Levels of p,p'-DDT and p,p'-DDE, and the DDE/DDT
ratio in the water-fish-seal food chain are shown in
Figure 5.28. The water-to-fish transfer factors for p,p'-
DDT and p,p'-DDE in the marine food chain are signif-
icantly higher than those calculated for the freshwater
environment in the Russian Arctic (14000 and
2500 mL/g ww of muscle, respectively). These results
may be explained by the lower DOM concentration in
sea water, normally, an order of magnitude lower than
in freshwater. However, TFWF values for other OCs are
similar, around 1000 mL/g ww in both freshwater and
Figure 5.28. Absolute and relative levels of p,p' DDE and p,p' DDT in the marine
marine systems. The high TFWF value for DDE is pos-
food chain in the Lavrentiya Bay. Geometric means and ranges are shown for DDE
and DDT concentrations in muscle tissue, water concentrations are in g/L.
sibly a result of accelerated transformation from DDT
Ratios are shown with 95% confidence limits.
to DDE in marine fish or invertebrates.
The observed concentrations of HCH and DDT in the
Concentrations of OCs found in fish and seals mus-
organs and tissues of grey whale were below the human
cles are comparable, which is consistent with the sim-
consumption guidelines values established in Russia
ilar lipid content in their muscles. Slightly higher con-
for these contaminants. For example, levels of HCH
tamination levels occur in larger seals, and slightly
in muscle and blubber were approximately a factor of
lower contamination in ringed seals, compared with
8.5 and 2, respectively, lower than the corresponding
other species, however, all differences are of fairly low
guideline values (10 ng/g ww for meat, and 200 ng/g
statistical significance. Similar patterns between
ww for animal fat). Observed concentrations of DDT
species and values for the fish-to-seal transfer coeffi-
in muscle were two orders of magnitude lower than
cient are observed for other OCs and marine mam-
the guideline value (200 ng/g ww) for human con-
mals. The geometric mean of the fish-to-seal transfer
sumption of meat of marine mammals.
coefficient, calculated using data on all OCs found at
detectable levels is equal to 0.5 for ringed seals and
(b) Heavy metals
1.4 for larga seals. DDE/DDT ratios in fish and seals
Concentrations of HMs in grey whale are presented in
are also comparable and are several times higher than
Table 5.41. Levels of Hg and Pb in the liver of grey
the ratio in water. Comparison of OC levels with cor-
120
Chapter 5
5.6. Conclusions
responding lipid concentrations, indicates that OC
trations, while the Cd level in birds is close to, or
distribution in the marine environment, as for the
slightly higher than the maximum permissible con-
terrestrial and freshwater environment, is close to
centration.
being in a state of equilibrium. However, the differ-
·
Concentrations of Pb and Cd in waterfowl are nor-
ence is clearly seen while comparing OCs in fish and
mally below permissible levels and only in few sam-
blubber of marine mammals, which is consistent with
ples attain a maximum level that exceeds the permis-
high lipid difference.
sible level by a factor of up to two. Concentrations of
Hg in molluscivorous, omnivorous, and piscivorous
(b) Heavy metals
birds are consistently close to the permissible level,
HM water-to-fish transfer factors (i.e., the ratios of the
and in most samples actually exceed it, by a maxi-
geometric mean of concentrations) for chum salmon
mum of up to 4 times. All concentrations in fish mus-
and Arctic char are similar in value. The geometric
cle are below the corresponding maximum permissi-
means of the TFWFs of both species equal 9400, 340
ble concentrations established in Russia for fish, with
and 2900 mL/g ww for Hg, Pb and Cd, respectively.
only one exception; this being Hg in whitefish from
These are somewhat higher than transfer factors calcu-
the Khatanga River, for which concentrations are 1.5
lated for the freshwater environment, the probable rea-
times the permissible level.
son being that anadromous fish species absorb HMs
·
All Hg and most Cd concentrations in seals are sig-
from both fresh and sea waters, and that HM levels are
nificantly higher than the corresponding maximum
normally lower in seawater than in freshwater. HM con-
permissible concentrations. The greatest difference
centrations in marine fish species (flounder and smelt)
between measured and guideline values is for Hg
are comparable with those in seals and walrus (i.e., TF
concentrations in seal muscle, which exceed per-
values are close to unity). The single exception to this
missible concentrations by as much as 100 times. All
is seen for Hg concentrations in seals, which are 7-18
Pb concentrations measured in muscle, liver, and
times higher than those in fish.
kidney of seals occur at levels below the correspon-
ding maximum permissible concentrations.
5.6. Conclusions
·
The level of contamination in male animals is nor-
mally slightly higher than that measured in females,
Levels
but in most cases the difference is not statistically
·
Concentrations of PCDD/Fs in reindeer muscle
significant. The single exception found was for Pb
from the Kola Peninsula, exceed maximum permis-
in browsers, where concentrations in male browsers
sible levels in meat by approximately 10%.
are consistently twice as high as those in females at
Concentrations of HCH and DDT in all tissues of
all 6 sites.
the mammals, birds and fish sampled in the Russian
·
Concentrations of both OCs and HMs are, as a rule,
Arctic are far below the corresponding maximum
higher in older animals. However, the greatest dif-
permissible concentrations established by the
ferences observed in this study between older and
Russian Ministry of Health. Only in some marine
younger age groups is within a factor of two. This
mammal species are concentrations of OC's found
was particularly the case for fish species, where the
to be close to these permissible levels, in some sam-
range in the age groups was relatively small. The
ples.
most pronounced concentration relationship to age
·
Concentrations of PCDD/Fs in muscle tissue are
was observed for HMs in reindeer. For the first few
highest in reindeer and lowest in terrestrial birds,
years of life, this relationship is close to being direct-
however the range is not large and well within an
ly proportional, with the rate of HM elimination cal-
order of magnitude. Other OCs occur in compara-
culated as being around 10 years for all 3 metals
ble concentrations in marine mammals, salmon
studied.
species, and waterfowl. In terrestrial mammals and
·
Contamination levels in the liver and kidney are nor-
birds, concentrations are, as a rule, several times
mally higher than those in muscle, especially for
lower than in other species and are generally high-
HMs. The liver/muscle concentration ratio for Hg
est in reindeer.
in reindeer, and for OCs in burbot, and also the kid-
·
At all sites, Pb concentration in reindeer tissues are
ney/muscle ratio for Cd in marine mammals can be
at least several times lower than the corresponding
up to between two and three orders of magnitude.
maximum permissible concentrations. Cd and Hg
The highest OC concentrations found in this study
levels for all tissues and sites, with the exception of
occur in the liver of burbot, fished from the Yenisey
Hg in Chukotka, are either close to the correspon-
River (580 ng/g ww of PCB15, 470 ng/g ww of
ding maximum permissible concentrations or
DDT, and 39 ng/g ww of CHLOR).
slightly exceed them. The greatest difference
·
Levels of brominated flame-retardants are below
between measured and guideline levels is seen in
the detection limit of 0.2 ng/g ww in all samples of
the Pechora basin, where Cd concentration in rein-
soil, vegetation, terrestrial mammals, and birds.
deer kidney are 2.5 times higher than the permissi-
However, in a few samples of fish and seal liver, as
ble level. Levels of Pb and Hg in muscle tissue of
well as in seal blubber, 2,2',4,4'-tetrabromodipheny
hares and terrestrial birds are significantly below
ether was found in concentrations ranging from 0.2
the corresponding maximum permissible concen-
to 1.9 ng/g ww.
121
5.6. Conclusions
Chapter 5
Trends
the Canadian Arctic in 1996-2000, and in northern
·
PCDD/F levels in the tissues of reindeer and hare
Norway in 1995.
from the Kola Peninsula are an order of magnitude
·
HM concentrations in the muscle, liver, and kidney
higher than those found at other sites.
of seals in the Russian Arctic in 2001 generally
Concentrations of PCDD/Fs in birds and fish fol-
occur within ranges similar to those found in
low similar, but less pronounced, trends.
ringed seal in the Canadian Arctic in 1998-2001.
·
No significant spatial trend in concentrations of
·
No significant temporal trend in contamination lev-
OCs, other than for PCDD/Fs in terrestrial mam-
els in any of the sampled biological species, for
mals, birds, and fish, was identified in the Russian
either OCs or HMs, is evident when the results of
Arctic in 2001. Only OC concentrations found in
this study are compared with those of previous
molluscivorous birds show a distinct maximum in
studies. However, the consistent level of concentra-
eastern Taymir.
tions, and, at some sites, significantly higher con-
·
OC levels measured in reindeer are in reasonably
centrations of HCH and Hg in mosses and lichen in
good agreement with levels previously reported for
2001, indicates that it is possible that some increase
Russian, Canadian, and Norwegian Arctic areas.
in depositions of these contaminants has taken
This is consistent with the finding that levels of
place in the Russian North during the past few
lichen contamination in Arctic Canada and Russia
years.
are comparable.
·
OC levels in fish in the Russian Arctic, are at the
Biomagnification
lower end of corresponding concentration ranges
·
OC concentration distribution patterns in both ter-
for OCs in fish in the Canadian Arctic, and are sim-
restrial and aquatic food chains in the Russian
ilar to those measured at three locations in Norway
Arctic are similar to those of lipids. This indicates
in 1994.
that OCs in Arctic ecosystems, are close to an equi-
·
As seen for OC concentrations in fish, OC levels in
librium state distribution.
the blubber of seals in the Russian Arctic are found
·
Concentrations of OCs in lichens reflect those in
to be close to the lower end of concentration ranges
mosses, with lichen/mosses concentration ratio for
obtained for seals in the Canadian Arctic in 1998-
OCs close to unity. Concentration of OCs in lichen
2001.
can therefore provide a direct estimate of the con-
·
Fish muscle from the Grate Slave Lake in northern
centration in mosses at a given site, and vice versa.
Canada in 1994/5, contained PCDD/Fs at levels an
·
The OC lichen-to-reindeer transfer factor obtained
order of magnitude higher than those determined
in this study is equal to 0.3 (ww muscle to dw lichen)
in samples from Russia in this study. In contrast,
and is consistent with factors previously determined
PCDD/Fs levels measured in the muscle of freshwa-
in the Canadian Arctic.
ter fish at four Scandinavian Arctic sites are close to
·
The OC water-to-fish transfer factors (TFWFs)
those found in the Russian North in 2001.
obtained in this study are in a reasonably good
·
Concentrations of HMs in terrestrial mammals and
agreement with those predicted using octanol-water
birds are lowest in inland Chukotka and in eastern
partition coefficients.
Taymir. However, differences between these and the
·
Values of Hg and Cd water-to-fish transfer factors
other studied locations in northern Russia are with-
are similar for both freshwater and marine fish
in a factor of 3.
groups, while the transfer factor for Pb is several
·
Levels of HMs in fish and waterfowl do not follow a
times higher for freshwater species. Geometric
pronounced spatial trend.
means of Hg and Cd TFWFs, calculated using
·
Levels of HMs in reindeer tissues determined in
pooled sets of data, are 3300 and 570 mL/g ww,
recent studies in the Canadian Arctic are, as a rule,
respectively. The geometric mean of Pb TFWFs is
somewhat higher than those measured in the
280 mL/g ww for freshwater species, and 60 mL/g
Russian Arctic.
ww for marine species. Transfer factor values for Hg
·
Concentrations of Hg in whitefish species in the
and Pb are in a good agreement with corresponding
Russian Arctic in 2001 are close to those found in
default values previously published by the IAEA.
122