Chapter 5
PTS levels in biota
and biomagnification
in food chains

---

5.1. Sampling strategy
Chapter 5
These two aims place somewhat different requirements
5.1. Sampling strategy
on sampling, sample treatment, and analysis. For the
Environmental sampling and analysis within the frame-
first objective, in order to estimate PTS intake with
work of Activity 4 `Biomagnification in Arctic food
food, it is necessary to obtain as reliable and represen-
chains' had two objectives:
tative data as possible on PTS levels in those species
·
determination of current PTS levels in main biota
and tissues that are widely used as traditional food. For
species, particularly those which are a utilised as
the second objective, it is necessary to determine the
part of the traditional diet of the indigenous popu-
average levels of contamination in species representing
lations in the pilot areas covered by the project;
a range of trophic levels (and in specific tissues of
·
evaluation of the extent to which biomagnification
organisms at higher trophic levels), and from this
occurs, i.e., the measurement of PTS accumulation
information, evaluate the degree to which PTS are
in terrestrial, freshwater, and marine food chains,
being accumulated and biomagnified in the various
in which humans represent the uppermost trophic
food chains that form the basis for food items in the
level.
traditional diet.
Coordinates of working area
X1=34.303°E
Y1=67.798°N
X2=36.102°E
Y2=68.765°N
Coordinates of field base (settlement Lovozero)
X=35.000°E
Y=68.021°N
Scale 1:2 500 000
Figure 5.1. Location of the environmental sampling area on the Kola peninsula.
82

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Chapter 5
5.1. Sampling strategy
Coordinates of working area
X1=52.906°E
Y1=67.955°N
X2=53.292°E
Y2=68.226°N
Coordinates of field base (X)
X=53.203°E
Y=68.189°N
Scale 1:1 000 000
Figure 5.2. Location of the environmental sampling area
in the lower Pechora basin.
To these ends, environmental sampling was carried
It is also important to note that the optimal season for
out in six areas within the four main project regions,
environmental sampling differed between locations. It
these areas being located around settlements with
depends, not only on availability of the specified
the highest indigenous populations. Bearing in mind
species, but on the hunting seasons, which may vary
that hunting and fishing grounds can be located at
between different regions. In addition, sampling of
some distance from the actual settlements, and that
certain species of biota, particularly those species
migration of reindeer herds depends upon the sea-
which are obtained by hunting or fishing, had to be
son and weather conditions, field sampling was based
arranged in close collaboration with local hunters and
on prior consultations with local indigenous peoples
fishers. This was important, not only to ensure effi-
involved in traditional activities. The environmental
ciency in sampling related to these activities, but also
sampling areas that were defined following these con-
from a legal point of view, since licences for the hunt-
sultations are shown in Figures 5.1­5.4.
ing of some species and for marine mammals in partic-
ular, can only be obtained by indigenous communities.
83

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5.1. Sampling strategy
Chapter 5
Coordinates of working area
X1=100.527°E
Y1=71.957°N
X2=105.788°E
Y2=74.519°N
Coordinates of field base (settlement Khatanga)
X=102.500°E
Y=71.981°N
Coordinates of working area
X1=83.633°E
Y1=69.366°N
X2=89.121°E
Y2=70.696°N
Coordinates of field base (settlement Dudinka)
X=86.182°E
Y=69.406°N
Figure 5.3. Location of the environmental sampling areas
on the Taymir peninsula.
media was designed to ensure that reliable data could be
obtained for average concentrations of selected contami-
For these reasons, in addition to the main field sam-
nants at the sample sites. For example, pooled water sam-
pling expeditions undertaken, additional field work in
ples, which combined a number of replicated samples
Chukotka was arranged in order to sample marine
taken at different depths within the water column (e.g.
species (and particularly marine mammals) over the
sub-surface, middle and bottom), were utilized. A similar
area shown in Figure 5.5.
approach, i.e. using pooled samples, was employed for
the lower trophic levels of food chains, and in particular
The number and type of environmental samples were
for vegetation such as lichens, mosses, and mushrooms.
selected in accordance with the stated objectives of the
activity. i.e., to study biomagnification in food chains and
For biota species at higher trophic levels, specific
to measure PTS levels in traditional food sources of select-
organs and tissues known to be important with respect
ed indigenous communities. Sampling of environmental
to PTS accumulation, were sampled. Tissue and organ
84

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Chapter 5
5.1. Sampling strategy
Coordinates of working area
X1=171.786°W
Y1=65.715°N
X2=170.942°W
Y1=65.115°N
Coordinates of field base (settlement Lavrentiya)
X=171.144°W
Y=65.763°N
Scale 1:3 000 000
Coordinates of working area
X1=176.315°E
Y1=65.048°N
X2=177.380°E
Y2=65.518°N
Coordinates of field base (settlement Kanchalan)
X=176.761°E
Y=65.178°N
Figure 5.4. Location of the environmental sampling areas
on the Chukotka peninsula.
rines, due to the high fat content in their bodies, and
also high levels of methyl mercury. For these animals,
samples from animals of the same sex and similar age
samples were treated and analyzed individually and not
groups were then pooled. An exception to this
pooled. All samples were frozen immediately after
approach was made in the case of marine mammals,
delivery to the field camp, and stored frozen until
which feed at the top of (in some cases, long) marine
shipped to the laboratory. Samples pooling took place
food chains and can accumulate particularly high lev-
in the laboratory as a part of sample treatment prior to
els of lipophilic contaminants, including organochlo-
analysis.
85

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5.2. Analytical methods and quality control
Chapter 5
Figure 5.5. Location of the area in which marine food chain species were collected
around the Chukotka peninsula.
Standardization Committee (Gosstandart), were also
used when appropriate (GOST 17.4.4.02-84, 26929-86,
Table 5.1 contains a list of environmental samples col-
26927-86, 26932-86, 26933-86, 7636-85, PND F
lected during field work, and a list of the pooled and
14.1:2:4.124-97, 14.2:4.74-96, 16.1.7-97, 16.1.4-97
individually analyzed samples of environmental media
14.2:4.70-96, RD 52.10.556-95, 52.18.180-89, 52.18.578-
and biota is presented in Table 5.2.
97, 52.44.590-97, 52.18.191-89, 52.44.592-97).
5.2. Analytical methods and quality control
5.2.1. Quantitative determination of chlorinated and
brominated organic compounds
The analytical methods used for PTS determination in
individual and pooled environmental and biotic sam-
Conventional extraction and clean-up procedures were
ples were based on internationally recognized method-
utilised in the analytical treatment of samples.
ologies (ISO methods 8288:1986, 6468:1996,
Extraction efficiency was checked by introducing inter-
5666:1983, 10382, 11048:1995, 10382, 19258, 14653-2;
nal standards (PCB-198 and dibromo-octafluo-
US EPA methods 200, 245.5, 245.6, 508, 525.1, 550,
rodiphenyl (DBOF)) prior to extraction.
608, 680, 8082, 8275a, 8290a, 8310a, PP-006; ASTM
methods D 3534-85, D 3557-95, D 3559-96, D 5175-91,
Quantitative analysis of organochlorines (OC) was per-
D 5412-93, D-5673-96, D5812-96; JAMP, 1999a and
formed using gas chromatography (GC) with an elec-
1999b; NOAA, 1998; UNEP, 1993) also taking into
tron capture detector (ECD). In addition, gas chro-
account AMAP recommendations. Russian standard
matography with mass spectroscopy (GC-MS) was
methodologies, as certified by the Russian State
employed for samples with an anomalous composition
86

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Chapter 5
5.2. Analytical methods and quality control
Table 5.1.
List of environmental media
and biotic samples obtained
in the project study areas.
or high concentrations of pollutants, to confirm the
Analysis of chlorinated compounds by mass-spectrome-
presence of the substances under consideration.
try was carried out using a Fisons 8060 gas chromato-
Samples in which brominated biphenyls and brominat-
graph and an MD800 mass spectrometer operating in
ed diphenyl ethers were detected in significant con-
the electron shock mode (70 eV). For brominated com-
centrations, were also subjected to additional GS-MS
pounds, the comparable system comprised a Carlo-Erba
examination.
8060 gas chromatograph and MD800 mass spectrome-
ter as above. Operational control of the above systems,
Quantitative determination was made using an
recording of mass-spectra, and their subsequent pro-
absolute calibration method, using target components
cessing was undertaken using the MassLab1.3 software
and the (DBOF) internal standard that was added to
package, and the National Institute of Science and
the sample before its analysis.
Technology (NIST) library of organochlorine com-
pounds.
Routine analyses were performed using a measure-
ment system consisting of a Fisons Mega-2 chromato-
A measurement system consisting of a Carlo Erba
graph with ECD800 detector, and a chromatographic
8035 chromatograph, and an Autospec-Ultima (VG)
data processing system consisting of a Multichrome-1.4
high resolution mass-spectrometer, operating in
and Kristall-2000M chromatograph with electron cap-
electron impact mode (36 eV) and with a resolution
ture detector, an automated sampler, and the chro-
of 10.000, was used for isomer-specific analysis of
matographic data processing software, Chromatec
polychlorinated dibenzo-p-dioxin and dibenzofu-
Analytic 1.21.
rans (PCDD/Fs), brominated compounds and
87

---

5.2. Analytical methods and quality control
Chapter 5
Table 5.2.
List of pooled or individually
analyzed samples of environ
mental media and biota.
toxaphenes. Separation of isomers was carried out
dium layer to ensure mercury retention in the furnace.
in a 60 m non-polar DB-5MS J &W Scientific column.
The detection limit for mercury in the solutions under
consideration was 0.001 µg/L, with a relative error of
All standard solutions of organochlorine pesticides
20% at this level of concentration.
and PCBs used for calibration were produced by Ultra
Scientific (USA) and certified by ISO9001. Standards
Measurements of lead and cadmium were carried
for toxaphenes, brominated diphenyl ethers, and
out using a Kvant-Z-ETA
atomic absorption spec-
brominated biphenyls were produced by St. Petersburg
trophotometer, with electrochemical atomization of
University.
the sample, using Zeeman background correction
and a constant aliquot volume of 5 µL of sample
5.2.2. Quantitative determination of heavy metals
solution. Prior to any measurements, a palladium
Measurements of mercury were carried out using a
modifier (at a concentration of 20 µg/L (Pd)) was
(Russian) Kvant-Z-ETA atomic absorption spectropho-
added to the samples.
tometer (analogous to the Western Varian AA-8000 sys-
tem), operating with a GRG-106 mercury generator in
5.2.3. Quantitative determination
automatic mode, using Zeeman background correc-
of polyaromatic hydrocarbons (PAHs)
tion.
Determination of PAHs in all samples involved liquid
extraction, followed by clean-up of extracts to remove
Mercury in samples was reduced to its metal state using
substances that could cause interference during analy-
tin dichloride, and then transferred in an argon gas
sis. Octafluoronaphthalene (OFN) was introduced as
flow (`Cold Vapor' method) to a graphite furnace, the
an internal standard to check the extraction efficiency
internal surface of which was covered with a fine palla-
of PAHs.
88

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Chapter 5
5.2. Analytical methods and quality control
PAH analytical determination was made using High
was added to the sample before its analysis. Analysis was
Resolution Liquid Chromatography (HRLC), with tar-
performed using a measurement system consisting of
get components registered by diode-matrix and fluo-
an 1090 chromatograph with a standard diode-
rescent detectors connected in series. Quantification
matrix component, a Spectraphysics fluorescent detector
of PAH levels was made by absolute calibration, using
with programmed excitation wavelength, and Hewlett-
standard solutions of target components and a control
Packard hardware/software processing system for
based on the internal standard (OFN) solution, which
chromatographic data.
Table 5.3. Quality control analyses performed as part of the analysis of environmental and biotic samples.
89

---

5.2. Analytical methods and quality control
Chapter 5
Table 5.4.
Comparison of concentra
tions of brominated com
pounds in environmental and
biotic samples obtained by
routine GC, and by high res
olution GC MS methods.
TeBD=tetra brominated
diphenyl, PeBD=pentabromi
nated diphenyl, TeBDE=tetra
brominated diphenyl ether,
PeBDE=pentabrominated
diphenyl ether.
All standard solutions for PAHs used for calibration
analysis using high resolution GC-MS (Carlo Erba
were produced by Ultra Scientific (USA) and certified
8010/Autospec Ultima V6 system, described above)
by ISO9001. The octafluoronaphthalene standard was
(Table 5.4). The control analyses confirmed the validi-
produced by St. Petersburg University.
ty of the data obtained using the routine methods.
5.2.4. Quality control
5.2.5. Processing and presentation of analytical results
Analytical quality control and quality assurance
Results of analyses were grouped according to sam-
involved the execution of a full programme of work
pling site and sample types. Concentrations of individ-
including analyses of blank samples, standard solu-
ual compounds within related groups of substances
tions, replicate samples, samples spiked with target
were summed to provide a total value for the group.
components, and analysis of samples of different
For purposes of calculation, where results were below
matrix compositions containing known levels of the
the detection limit, a value of half the detection limit
determined components (Table 5.3). In addition, labo-
was used if this did not contribute more than 20% of
ratories involved in the work participated in interna-
the summed value; otherwise no sum was calculated.
tional intercalibration exercises within the framework
of the `QUASIMEME' Programme, and the
Sums were calculated for the following groups of sub-
Ring Test on analysis of POPs in human blood samples.
stances:
HCH: the sum of -, - and -isomers of HCH.
Under an arrangement made through the AMAP
DDT: the sum of o,p'- and p,p'-DDT, -DDE, -DDD.
Secretariat, the laboratory responsible for analysis of
CHLOR: the sum of cis- and trans-chlordane and cis-
environmental and biotic samples participated in the
and trans-nonachlor.
first stages of Rounds 22, 24 and 25 of the laboratory
PCB15: the sum of 15 PCB congeners (#28, #31, #52,
performance studies organized by `QUASIMEME'.
#99, #101, #105, #118, #128, #138, #153, #156, #170,
These concerned the analysis of bottom sediments and
#180, #183, and #187).
biota samples for levels of PAHs, OCs and HMs
PCB7: the sum of 7 PCB congeners (#28, #52, #101,
(Rounds 22 and 24), and the analysis of samples of sea
#118, #138, #153, and #180); calculated to allow com-
and estuarine waters for OCs, HM and mercury
parison with data obtained in the Russian North in
(Round 25).
1994/1995.
Toxaphene: the sum of Parlar-26, Parlar-50, and
Calibration standards used were the Russian State
Parlar-62.
Certified Standards and certified standards produced
PCDD/F: the sum of all 2,3,7,8-substituted con-
in other countries (by ULTRA Scientific, Wellington
geners of dibenzo-p-dioxin and dibenzofuran.
Laboratories, etc.). Previously analyzed samples,
spiked with specific components at levels approximate-
Environmental contaminants commonly exhibit a
ly 2-4 times greater than those detected during their
log-normal frequency distribution in their concentra-
original analysis, were employed as matrix samples con-
tion values (WHO, 1983). A log-normal distribution
taining known levels of the determined components.
was therefore assumed to apply for concentrations of
In addition, residual material from test samples dis-
a particular contaminant (and concentration ratios)
tributed as part of the `QUASIMEME' laboratory per-
within any given sample type collected at a particular
formance studies, with known composition and pub-
site. In most cases, therefore, data are reported as the
lished `assigned' concentration values, were also used
geometric mean concentration (or ratio) and the
as control samples.
associated standard deviation. Arithmetic mean con-
centrations and standard deviations were only calcu-
As concentrations of toxaphenes, brominated
lated when concentration variability was low (i.e.
diphenyl ethers and brominated biphenyls in most
where the standard deviation was less than 30% of the
pooled samples were found to be very low (below the
mean for most contaminants). This latter calculation,
levels of reliable determination for these compounds
however, facilitated comparison with results from
using routine methods), 40 samples (6 bottom sedi-
other studies, where PTS concentrations are com-
ment, 6 soil, 6 lichen, 6 berry, 3 reindeer kidney, 4 hare
monly reported in terms of mean values and their
liver, and 3 fish liver samples) were sent for control
standard deviations.
90

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Chapter 5
5.3. Results ­ Terrestrial environment
Table 5.5a.
Concentrations (mean and
standard deviation, or range;
ng/g dw) of OCs in vegeta
tion in the Russian Arctic
in 2001.
a A range is given when the
standard deviation is greater
than 50% of the mean, or the
concentration in one of the
samples is below the detec
tion limit. When lower and
upper limits of the concen
tration interval were estimat
ed for summed concentra
tions, any individual values
that were below the detection
limit were either set to zero
or to the detection limit (see
Section 5.2.5).
n = number of pooled sam
ples analyzed.
5.3. Results ­ Terrestrial environment
The number of individual samples of each vegetation
type collected at a given site and used in the prepara-
5.3.1. PTSs in plants and mushrooms
tion of a pooled sample was usually 10, but ranged
The following species were collected and analysed for
between 4 and 20 (see Table 5.1). Vegetation was
PTSs:
analysed for all PTS listed in Section 1.2.4.
Lichens -- Cetraria cuculata, Cetraria islandica, Cladina
rangiferina, Cladina alpica, Cladina stellaris, Cladina
Levels and trends
mitis;
Bryophytes -- Polytrichum commune, Pleurozium schreberi;
(a) Organochlorines
Mosses -- Dicranum sp., Sphagnum balticum, Hylocomium
Concentrations of organochlorines (OCs) in vegeta-
splendens;
tion that significantly exceeded detection limits are
Berries -- low-bush cranberry (Vaccinium vitis-idaea),
shown in Tables 5.5a and 5.5b. Data for those OCs
cloudberry (Rubus chamaemorus), bilberry (Vaccinium
which occurred at concentrations below the detection
myrtillus), blueberry (Vaccinium uliginosum), crowberry
limit in most samples are not presented. The level of
(Empetrum nigrum);
HCB was above the detection limit in all samples of
Mushrooms -- orange-cap boletus (Leccinum auranti-
plants and mushrooms. PCB15 and PCB7, DDT and
acum), brown-cap boletus (Leccinum scabrum), mossi-
HCH were detectable in all samples of lichens and
ness mushroom (Xerocomus sp.).
mosses and PCB7 and DDT also in most of the berry
Table 5.5b.
Concentrations
(mean and standard
deviation, or range; ng/g dw)
of OCs in vegetation in the
Russian Arctic in 2001.
a A range is given when the
standard deviation is greater
than 50% of the mean, or the
concentration in one of the
samples is below the detec
tion limit. When lower and
upper limits of the concen
tration interval were estimat
ed for summed concentra
tions, any individual values
that were below the detection
limit were either set to zero
or to the detection limit (see
Section 5.2.5).
n = number of pooled sam
ples analyzed.
91

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5.3. Results ­ Terrestrial environment
Chapter 5
and mushroom samples. The PCB7 value, when mul-
Peninsula; and below the detection limit in the
tiplied by two, can be used to provide an estimate of
Pechora basin). The PCB7 concentration in mosses in
the total PCB concentration in mosses and, most likely,
2001 is significantly higher (10.3­013.9 ng/g).
also in other plants (AMAP, 1998). Of the DDT group,
only p,p'-DDT occurs in detectable concentration in all
The PCB congener patterns seen in lichens differ signif-
berry and most mushroom samples. DDT concentra-
icantly from those occurring in most of the common
tion in berries and mushrooms were therefore estimat-
technical mixtures used in Western countries. In
ed using the ratio of p,p'-DDT/DDT found in lichens
Western products, PCB-138 and 153 dominate, while in
and mosses (0.39±0.07). This probably provides a con-
the environment of Russian Arctic, PCB-28 makes the
servative estimate as, at the three sites where DDT in
greatest contribution to the summed value in samples
berries could be calculated directly, this ratio was
from all sites. However, relative levels of the congeners
equivalent to 0.5±0.2.
PCB-28, 52, 118, 138, 153 and 180 found in remote
Arctic areas of North America also differ from those
Concentrations of HCB, HCH, and DDT in mosses are
found in American technical mixtures (Wilcke and
comparable to those in lichens, while PCB levels are 2-
Amelung, 2000) and are close to those found in the
4 times higher in mosses at all sites. Concentrations of
Russian Arctic. Therefore, the PCB composition pat-
these substances in berries and mushrooms are several
terns provided in Figure 5.6 could also be a result of the
times lower than those found in mosses and lichens.
fractionation of congeners during long-range transport.
Levels of HCB, HCH, and DDT follow a similar geo-
Concentrations of CBz (sum of HCB and pen-
graphical trend, with highest levels found at the two
tachlorobenzene (PeCBz), not shown in tables) meas-
locations on the Taymir Peninsula, and in the lower
ured in plants in this study, in 2001, are distinctly high-
Pechora basin. In contrast, no geographical trend in
er than levels previously reported for the Russian
PCB levels was observed. With only one exception
North (see Figure 5.7). In August 1995, on the Taymir
(berries from Dudinka), all differences in PCB con-
Peninsula, concentrations of 0.25 and 0.4 ng/g of
centrations between the sites could be explained by
CBz were found in lichens and mosses, respectively
analytical variability.
(AMAP, 1998). Mean concentrations of CBz in lichens
and mosses obtained during the current study at two
PCB levels in the Arctic have been found to be gener-
sites on the Taymir Peninsula, were 0.64±0.16 and
ally decreasing over time. Over the last few years, how-
1.3±0.3 ng/g, and 0.9±0.1 and 1.4±0.2 ng/g, respec-
ever, the rate of decrease has been small and levels have
tively. Concentration of CBz in 3 samples of lichen
remained relatively constant (AMAP, 2002). In accor-
collected near Khatanga in 1995 (AMAP, 1998) ranged
dance with this tendency, mean PCB7 concentrations
from 0.16 to 0.66 ng/g, while concentrations of 1.2-
measured in 2001 in samples of lichens collected near
1.5 ng/g CBz were found at Khatanga in 2001 (see
Khatanga, in eastern Taymir (2.5 ng/g) and at
Figure 5.7). In the Pechora basin, mean CBz concen-
Chukotka (2.2 and 2.5 ng/g) were slightly lower than
trations in lichens and mosses in 1994/1995 ranged
those determined in these areas in 1995 (3.2 and
from 0 (i.e., below the detection limit) to 0.08 ng/g
3.82 ng/g, respectively) (AMAP, 1998). In contrast, the
(AMAP, 1998), whilst in 2001 values of 0.2­1.0 ng/g
PCB7 concentration for lichens from the Pechora
were found. Thus, a comparison of the data obtained
basin in 1995 was below the detection limit, while
in 1994/1995 and in 2001, indicates that the concen-
2.3 ng/g was found in 2001. An unexpected increase
tration of chlorinated benzenes in lichens and mosses
was also observed in the PCB7 concentration in moss-
(and by inference in air) in the Russian North has
es, which in 1994/1995 in the Russian North ranged
shown a tendency to increase during recent years.
from 0 to 3.6 ng/g (0­02.4 ng/g on the Taymir
Figure 5.7. Mean values and ranges of OC concentrations measured in lichen
Figure 5.6. PCB congener contributions to PCB15 levels in lichen in the Russian
in Eastern Taymir and the Pechora Basin in 1995 and in 2001. Values for Eastern
Arctic in 2001. The congeners shown are the main contributors within
Taymir were derived from the analysis of three samples in 1995, and two samples
each homologue group.
in 2001. CBz = sum of HCB and PeCBz, DDT=DDT.
92

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Chapter 5
5.3. Results ­ Terrestrial environment
Table 5.6a. Concentrations (geometric means and ranges; ng/g dw) of PAHsa in vegetation in the Russian Arctic in 2001.
a NAP = Naphthalene, ACNLE = Acenaphthylene, BIPN = Biphenyl, NAP2M = 2 Methylnaphthalene, FLE = Fluorene, ACNE = Acenaphthene, PA= Phenanthrene.
The mean HCH concentration in 3 samples of lichens
Mirex has not been used in the fSU/Russia.
collected near Khatanga in 1995 (AMAP, 1998) was twice
However, it does occur at detectable concentrations
as high as those measured in the current study in the
in some samples of lichens and mosses, presumably
same area (3.42 and 1.6 ng/g, respectively). In contrast,
as a result of long-range atmospheric transport from
HCH concentrations in lichens and mosses in the
remote sources. The geographical distribution pat-
Pechora basin in 1995 ranged from 0.17 to 0.38 ng/g,
tern of Mirex is similar to that of DDT, HCH and
whilst concentrations of 0.74­1.4 ng/g were found in
HCB. In the most highly contaminated areas (the
this area in 2001. Despite the difference in values, these
Pechora basin and the Taymir peninsula), Mirex
results are unlikely to be indicative of a trend, as there is
concentration in lichens and mosses ranged from
known to be a high degree of spatial variability in levels of
0.2 to 0.5 ng/g. However, in the majority of samples
contamination from HCH across the Russian North. In
collected in less contaminated areas (on the Kola
1994/1995, the concentration of HCH, as a function of
peninsula, and Chukotka), Mirex concentrations
sampling site, varied within two orders of magnitude,
were below the detection limit of 0.1 ng/g. The sim-
even for samples taken in the same area (AMAP, 1998).
ilarity between the spatial distribution observed for
DDT, HCH, and HCB, and that of Mirex indicates
No temporal trend in DDT concentrations in lichens
that trans-boundary transport is at least an impor-
and mosses was evident in the Russian North. The mean
tant source, and most likely the main source of con-
concentration of DDT in 3 samples of lichens collected
tamination in the Russian Arctic for these com-
near Khatanga in 1995 (AMAP, 1998) was almost the same
pounds.
as that found in 2001 (2.96 and 2.9 ng/g, respectively).
The range of DDT concentrations (0.7­3 ng/g) deter-
Samples of plants and mushrooms were also analyzed
mined in lichens and mosses in five other areas in the
for other OCs listed in Section 1.2.4, with the excep-
Russian North in 1994/1995 (AMAP, 1998) is consistent
tion of PCDD/Fs. Of these substances, only hep-
with data obtained from the current study (1.0­3.1 ng/g).
tachlor was detected in some samples of lichen and
Concentrations of DDT, HCH, and CBz found in
mosses, in concentrations ranging
from 0.1 to
lichens in the Russian Arctic in 2001 are all comparable
0.3 ng/g. As all of these samples were collected in the
with those found in the Canadian Arctic in 1993/4. PCB
Pechora basin and the Taymir peninsula, the spatial
concentrations in Canada in 1993/4 were several times
pattern of heptachlor distribution appears, at least
lower, while toxaphene levels were significantly higher,
qualitatively, similar to that of Mirex, DDT, HCH,
than those measured in Russia in 2001 (AMAP, 1998).
and HCB.
Table 5.6b. Concentrations (geometric means and ranges; ng/g dw) of PAHsa in vegetation in the Russian Arctic in 2001.
a ANT= Anthracene, FLU = Fluoranthene, PYR = Pyrene, BAA = Benz[a]anthracene, CHR = Chrysene, BBF = Benzo[b]fluoranthene, BKF = Benzo[k]fluoranthene.
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5.3. Results ­ Terrestrial environment
Chapter 5
(b) PAHs
Geometric means and ranges of concentrations of
PAHs in lichen and mosses are provided in Tables
5.6a and 5.6b. PAH composition is similar at all sites,
with naphthalene, 2-methylnaphthalene and
phenanthrene contributing 70-90% of the value of
PAH in both lichen and mosses. The highest con-
centrations, and especially those of heavier PAHs,
are normally found near Khatanga. Lichens and
mosses were also analyzed for benzo[e]pyrene,
benzo[a]pyrene, perylene, dibenz[ah]anthracene,
indeno[1,2,3-cd] pyrene and benzo[ghi] perylene. In
the most cases, concentrations of these compounds
were below the detection limit of 0.5 ng/g. Perylene,
indeno[1,2,3-cd]pyrene and benzo[ghi] perylene
Figure 5.8. Concentrations of HMs in lichen (L) and mosses
were, however, found in concentrations which
(M) in the Russian Arctic in 2001.
ranged from 1 to 10 ng/g in several samples, prima-
rily from the Kola and Taymir peninsulas. A notable
bromodiphenyl ether. In all samples these substances
exception was the concentration of benzo[ghi]pery-
were below the detection limit of 0.2 ng/g dw.
lene found in mosses from Eastern Taymir, which
was as high as 30 ng/g.
(d) Heavy metals
The heavy metals, mercury (Hg), lead (Pb) and cadmi-
Naphthalene levels determined in berries and mush-
um (Cd) were detected in all samples of lichens, moss-
rooms are normally several times lower than those
es and mushrooms (see Figure 5.8 and Table 5.7). In
found in lichen and mosses. The difference in concen-
the majority of berry samples, Hg and Cd were below
trations occurring between the two groups of plants
the detection limits (0.001 and 0.005 µg/g, respective-
increases with the molecular weight of the substance in
ly), while the Pb level was detectable in all samples. Pb
question, and for the heaviest PAHs can be as much as
concentrations ranged from 2.6 to 4.5 µg/g in mosses,
two orders of magnitude. This may indicate that the
from 0.9 to 4.1 µg/g in lichens, from 0.04 to 0.1 µg/g
greater efficiency of lichens and mosses for intercep-
in mushrooms and from 0.01 to 0.05 µg/g in berries.
tion of gaseous and particulate PAHs from the air is
Concentrations of Hg and Cd in samples of lichens and
partially offset by the ability of plants and mushrooms
mosses ranged from 0.01 to 0.2 µg/g. No pronounced
to take up PAHs with logKow < 4 from the soil and
spatial trend was observed in HM contamination of
translocate them to the aboveground parts of the plant
lichens and mosses (see Figure 5.8). The relatively high
(McLachlan, 1996).
Hg concentration in mosses collected at Chukotka is,
very likely, due to a single anomalous sample, and was
(c) Brominated flame-retardants
not confirmed by data for lichen from the same loca-
Vegetation samples were analyzed for 2,2',4,4'-tetra-
tion. The only notable spatial tendency was a slight
bromodiphenyl; 2,2',4,4',5-pentabromodiphenyl; 2,2',
decreasing gradient in Cd concentrations from the
4,4'-tetrabromodiphenyl ether; and 2,2',4,4',5-penta-
Kola Peninsula towards Chukotka.
Table 5.7.
Concentrations (mean and
standard deviations; µg/g
dw) of HMs in vegetation in
the Russian Arctic in 2001.
a Range is given when the
standard deviation is greater
than 50% of the mean,
or the concentration
in one of samples is below
the detection limit.
b Concentration detected
in both samples.

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Chapter 5
5.3. Results ­ Terrestrial environment
Comparison between data obtained in 1995 (AMAP,
Similarly, differences in OC concentrations between
1998) and 2001, indicates that an increase in the Hg
the two age groups, and between different tissue types
deposition rate in Chukotka may have taken place
were not statistically significant, the ratios for
during this period. Hg levels in lichens and mosses
`old/young' reindeer groups ranging from 0.8 to 1.3
in 1995 (0.02 and 0.03 µg/g, respectively) were sev-
(1.1­1.3 for p,p'-DDT, p,p'-DDE, PCB-118 and PCB-153
eral times lower than those found in 2001 (0.06 and
and 0.8 for HCB).
0.15 µg/g, respectively). A similar temporal trend in
Hg concentration in lichen is observed on the
The geometric mean of the liver/muscle lipid con-
Taymir Peninsula (0.01 µg/g in 1995, and 0.06 µg/g
centration ratios, from the data collected in this
in 2001).
study, was 1.5. Based on this value, somewhat high-
er concentrations of OCs might be expected in
For the other HMs and sample sites, changes over time
liver tissue when compared with muscle. However,
are less significant, with the exception of a decrease by
the geometric means of both the liver/muscle and
an order of magnitude (from 0.9 to 0.06 µg/g) in Cd
kidney/muscle concentration ratios for all of the
concentration in lichen from Chukotka. However, over
OCs investigated were close to unity and independ-
the same period, an increase in Cd levels in mosses was
ent of site.
also observed in this area. Given the similar pathways
for Cd uptake in mosses and lichen, these results sug-
From these results, it was decided to calculate mean
gest that the above-mentioned differences in HM con-
concentrations based on data from both age groups;
centrations occurring between 1995 and 2001 are most
values for OCs in muscle tissue only are presented in
likely a reflection of normal intersample variability.
Tables 5.8a and 5.8b.
Similar to the majority of OCs, HM concentrations
measured in lichen and mosses in Russia in 2001 are
consistent with concentration ranges obtained in the
Canadian Arctic in 1993/4.
5.3.2. PTS in reindeer
Samples of reindeer (Rangifer tarandus) tissues were
collected at all 6 sites in the four regions. The num-
ber of individual tissue/organ samples collected at a
given site and combined in the preparation of
pooled samples was 2-3 in most cases, but ranged
from 1 to 6 (see Table 5.2). Pooled samples were pre-
pared from tissue samples of animals of the same sex
Table 5.8a. Concentrations (geometric mean and range; ng/g ww) of OCs
and with an age difference of less than 2 years. The
in muscle of reindeer in the Russian Arctic in 2001.
ages of animals ranged from 1 to 8 years, and equal
numbers of animals of each sex were sampled at all
sites, except for Western Taymir, where tissue sam-
ples from 3 male and 2 female reindeer were collect-
ed. Samples were grouped according to sex, (female
and male), age group (1-3 years and 4-8 years), and
tissue type (liver, kidney, or muscle). Reindeer mus-
cle, liver and kidney were analysed for all PTS listed
in Section 1.2.4.
PTS concentration relationships with reindeer sex, age,
and tissue type
Table 5.8b. Concentrations (geometric mean and range; ng/g ww) of OCs
(a) Organochlorines
in muscle of reindeer in the Russian Arctic in 2001.
Concentration dependence on animal sex, age, and
tissue type was investigated for OCs that exhibited con-
(b) Heavy metals
centrations above detection limits in most cases (p,p'-
As for OCs, the concentrations of HMs in reindeer tis-
DDT, p,p'-DDE, PCB-118, PCB-153 and HCB).
sues do not show any significant sex dependence.
However, a slight, but consistent increase in concentra-
Ratios of (geometric mean) concentrations of various
tions does occur with increasing age of the animals
OCs between male and female reindeer were in the
sampled. Concentration ratios between the two age
range 1.1 to 1.3, and were found to be independent of
groups (3 years and under, and over 3 years) are similar
site, age group, and tissue type. The difference
for all HMs, sites, and tissue types; the geometric
between these values and unity had very low statistical
means of the age ratios, calculated for almost 30 sam-
significance and therefore mean concentrations were
ples, equal to 1.8, 1.7 and 1.9 for Hg, Pb, and Cd,
calculated using data for both sexes.
respectively. Figure 5.9 shows examples of age depend-
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5.3. Results ­ Terrestrial environment
Chapter 5
ency of HM concentrations in reindeer tissues for the
3 times higher for younger animals. Relative concen-
two locations where samples included the greatest
trations of HMs in the muscle, liver and kidney appear,
range of age groups. Similar relationships between con-
respectively, in the ratios of 1:5:5 for Pb, 1:11:33 for Cd
centrations and age are observed in samples from
and 1:11:42 for Hg in reindeer over 3 years of age, and
other sites. In all reindeer tissues, HM concentrations
1:31:136 for Hg in younger reindeer (figures are based
increase in direct proportion to the age of the animal
on the geometric means of the ratios for pooled sam-
sampled. This implies that the effective rate of HM
ples). The degree of variability between liver/muscle
accumulation in various tissues, expressed in µg/g per
and liver/kidney concentration ratios for HMs within
year, is independent of age, at least in the sampled
a herd is greatest for Hg. The level of variability
mean age interval of 1.5­7.5 years. The only reasonably
between reindeer herds is similar. The liver/muscle
clear deviation from direct proportionality is the rela-
concentration ratios are slightly lower than those cal-
tively low level of muscle contamination, primarily for
culated for Swedish herds, but the difference was not
Hg, seen in the youngest animals of 1.5­2.5 years of
statistically significant (see Figure 5.10). As the distri-
age. This possibly indicates that a steady state liver/kid-
bution of HMs between tissues is herd specific, the age
ney concentration ratio is established quite rapidly,
concentration ratios for HMs are relatively constant,
whilst a steady state distribution of HM between the
and concentration variability within a herd is quite low,
liver and muscle may require several years to develop.
mean concentrations of Hg, Pb and Cd were calculated
separately for all three tissue types and are shown only
The HM distribution between reindeer tissues,
for the oldest age group. The calculation of separate
appears similar for both age groups and sexes. Only for
mean concentrations for each age group does not sig-
Hg are liver/muscle and kidney/muscle ratios about
nificantly improve the representativeness of the results,
because the variability found in concentrations of HMs
Figure 5.9.
within a herd is low.
Relationships between HM
concentration in reindeer
tissues and age, for the Kola
Levels and trends
peninsula (1) and the
Pechora basin (2).
(a) Organochlorines
Concentrations of OCs reliably detected in reindeer
muscle are given in Tables 5.8a and 5.8b. Levels of
PCB, HCB, HCH and DDT vary within fairly narrow
ranges and do not follow any pronounced spatial
trend, although somewhat higher levels of PCB,
HCB, and DDT are found in inland Chukotka (see
Figure 5.11).
Figure 5.10.
Geometric means
and ranges of HM
liver/muscle concentration
ratios in Swedish and
Russian reindeers.
The Swedish data were
for 10 herds (AMAP, 1998)
and the Russian data
for 6 herds.
Figure 5.11. Geometric means and ranges of OC concentrations in reindeer
muscle in the Russian Arctic in 2001. PCB= PCB15, HCH=HCH, DDT=DDT.
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Chapter 5
5.3. Results ­ Terrestrial environment
OCs in reindeer show no correlation with the spatial
Samples of reindeer tissue were also analyzed for the
trends found for OC contamination in lichen. All con-
other OCs listed in Section 1.2.4. In the majority of
centrations are far below the maximum permissible
samples, all of these additional OCs exhibited levels
concentrations (MPC) for OCs in meat, established by
below the detection limit. Only Mirex and some of the
the Russian Ministry of Health; the MPC of 0.1 mg/kg
cyclodienes were found in concentrations close to the
for HCH and DDT, given in Chapter 3, is equivalent
detection limit (about 0.1 ng/g), and then only in a
to 100 ng/g. Concentrations for all OCs measured in
few samples. This is again consistent with results of pre-
reindeer liver in 2001 coincide with the lower end of
vious studies carried out in Canada and in the Russian
corresponding ranges obtained for the Russian North
North in 1995 (AMAP, 1998).
in 1994/1995 (AMAP, 1998) Values are also in reason-
ably good agreement with data on reindeer muscle OC
(b) PCDD/Fs
contamination reported from Canada and Norway
Concentrations of 2,3,7,8-substituted PCDD/Fs were
(AMAP, 1998). For example, the following concentra-
analyzed using pooled samples of reindeer tissue. The
tions of OCs were found in muscle samples from two
results are presented in Table 5.9.
Canadian reindeer herds: 1 ng/g for HCH, 1-2 ng/g
for DDT and 2-10 ng/g for PCB. The ranges of the
PCDD/F levels in reindeer in the Russian Arctic follow
geometric means for OC concentrations determined
a distinct spatial distribution, that is reflected in other
in Russia in 2001 were 0.4-1.2 ng/g for HCH; 0.4 -
terrestrial mammals, birds, and fish (see Figure 5.12).
2.6 ng/g for DDT; and 1.3-2.8 ng/g for PCB. The
The highest PCDD/F levels are found at the Kola
Canadian data for summed PCB concentrations
Peninsula, where they are an order of magnitude
included more PCB congeners than did the Russian
greater than those found at other sites. After correc-
2001 data. The agreement between the Canadian and
tion for tissue lipid content, residual differences still
Russian reindeer data is similar to that seen in the data
remain in PCDD/F concentrations between the vari-
concerning OCs measured in lichen and mosses in
ous tissues types. In contrast to other OCs, PCDD/F
Russia in 2001, and in Canada in 1994.
levels occurring in the liver of reindeer are, on average,
7 times higher than those in the muscle. Maximum
contamination levels were found in liver tissue from
the Kola Peninsula (6.5 pg WHO-TEQ/g) and from
the Pechora basin (2.4 pg WHO-TEQ/g). The liver
concentrations associated with these TEQ values, and
also those in muscle of reindeer from the Kola
Peninsula, exceed the maximum permissible level for
meat, established by the Russian Ministry of Health,
which is 0.9 ng/g. All other concentrations measured
were below this level.
Three congeners (2,3,7,8-TeCDD, 1,2,3,7,8-PeCDD,
and 2,3,4,7,8-PeCDF) contribute more than half (and
up to 85%) of the total WHO-TEQ in the majority of
samples. The average contribution of 2,3,4,7,8-PeCDF,
Table 5.9. Concentrations (expressed as TEQ) of PCDD/Fs in reindeer tissues
and the most toxic of the dioxins to the total TEQs are
the Russian Arctic in 2001.
* ­ ratio of PCDD/F concentration in pg WHO TEQ/g to that in pg/g
similar in waterfowl, terrestrial birds, fish and marine
mammals (4.4% and 4.7%, respectively). In terrestrial
animals, the average contribution of 2,3,4,7,8-PeCDF
is significantly higher, whilst the contribution from the
most toxic dioxins is almost the same (13% and 4.2%,
respectively). For this reason, the ratio of concentra-
tion in pg WHO-TEQ to weight concentration for ter-
restrial animals is also higher.
(c) PAH
Reindeer tissue was analyzed for the same PAH set as
vegetation. The geometric means and ranges of PAH
concentrations determined in reindeer muscle in the
Russian Arctic in 2001 are shown in Tables 5.10a and
5.10b. Results obtained from two sites in Chukotka
were treated as one data set, due to the similarity of
contamination levels and the small number of samples
analyzed. PAH concentrations in liver were, on aver-
Figure 5.12. Levels of PCDD/Fs in muscle of reindeer, hare,
waterfowl (molluscivores), fish (whitefish species), and terrestrial birds (browsers)
age, 3-5 times higher than those in muscle, while con-
in the Russian Arctic in 2001.
centrations found in kidney and muscle are comparable.
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5.3. Results ­ Terrestrial environment
Chapter 5
Table 5.10a. Concentrations (geometric mean and range; ng/g ww) of PAHsa
in reindeer muscle in the Russian Arctic in 2001.
a NAP = Naphthalene, NAP2M = 2 Methylnaphthalene, FLE = Fluorene,
PA = Phenanthrene.
Figure 5.13. Means and ranges of HM concentrations in reindeer liver (wet weight)
in the Russian Arctic in 2001. Red lines indicate the maximum permissible
concentrations allowed by food safety standards.
4,4',5-pentabromodiphenyl ether. In all samples these
occurred at levels below the detection limit of
0.2 ng/g ww.
(e) Heavy metals
Concentrations of HMs in reindeer tissues are shown
in Table 5.11 and Figure 5.13. Levels of Pb are below
the corresponding MPCs in all tissues, although the
difference in the case of liver is quite small. Cadmium
Table 5.10b. Concentrations (geometric mean and range; ng/g ww) of PAHsa
in reindeer muscle in the Russian Arctic in 2001.
and Hg levels in all tissues, and at all sites, except for
a ANT = Anthracene, FLU = Fluoranthene, PYR = Pyrene, CHR = Chrysene
Hg in tissues from Chukotka, are either close to or
exceed corresponding MPCs. The greatest disparity
As for OCs, no trend in spatial distribution was found.
between observed levels of the metals under the scope
The PAH composition pattern in reindeer tissues
and MPCs occurred in kidney tissue from the Pechora
reflects that found in lichen. Naphthalene, 2-methyl-
basin, which exceeded the MPC by two and a half
naphthalene and phenanthrene contribute well over
times.
half of the PAH value. Reindeer tissues were also ana-
lyzed for the other PAH listed in Section 5.3.1.(b). In
The spatial distribution of HM concentrations in rein-
the majority of samples these PAHs were below the cor-
deer liver tissue is shown in Figure. 5.13. HM levels in
responding detection limits (0.5­2 ng/g) or, in a few
other tissues follow a similar pattern. As for OCs, there
samples of liver tissue, were only slightly above detec-
is no pronounced correlation with the spatial distribu-
tion limits.
tion of HMs in lichen. For all HMs, however, the least
contaminated areas are inland Chukotka and the east
(d) Brominated flame-retardants
Taymir (Khatanga) regions. As mentioned above, the
Samples of reindeer tissues were analyzed for 2,2',
HM concentration relationship with reindeer age is
4,4'-tetrabromodiphenyl, 2,2', 4,4',5-pentabromodi-
almost directly proportional, at least for the first few
phenyl, 2,2', 4,4'-tetrabromodiphenyl ether, and 2,2',
years of the animals' life. The coefficients for this rela-
Table 5.11.
Concentrations (mean and
standard deviation; g/g ww)
of HMs in tissues of reindeer
(>3 years of age) in the
Russian Arctic in 2001.

a Hg level in one sample was

close to the detection limit
(0.001 ng/g ww), and below
the detection limit in another.
b Hg level in both samples
was close to the detection
limit.
c Concentration range.
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