Regional and inter annual patterns of heavy metals, organochlorines and stable isotopes in narwhals (Monodon monoceros) from West Greenland.

Samples of 150 narwhals obtained in different years from two West Greenland areas, Avanersuaq and Uummannaq, were compared for concentrations of and regional differences in heavy metals and organochlorines and stable-carbon and nitrogen isotopes. Cadmium, Hg, and Se concentrations increased in the first 3-4 years of the animal's life, after which no dependence on age was observed. Females had significantly higher concentrations of Cd in all tissues and of Hg and Se in liver than males. No consistent difference in metal levels between narwhals from Avanersuaq and Uummannaq was found. Year-to-year variation in metal levels at one location was larger than the geographical variation. Metal levels were within the range of previous published results for narwhals from Arctic Canada. Organochlorine (OC) concentrations in blubber of narwhals were dependent on age and sex. Females showed decreasing OC concentration in the first 8-10 years, while for males increases were detected in the first few years of life, after which the concentrations became stable. Few statistical differences in mean OC concentrations among individuals were observed. However, narwhals from Avanersuaq in 1993 had the lowest levels, indicating a temporal decrease of SigmaPCBs. SigmaPCBs, DDTs, HCHs and toxaphenes seem to be at similar levels in West Greenland and Arctic Canada, which can be explained by the close winter distributions of populations as well as large ranges in concentrations, time span, number of analyses and the size/age composition of the data. PCB and DDT concentrations in West Greenland narwhals were half those found in East Greenland and Svalbard. Stable-carbon isotope ratios in muscle of 150 narwhals showed a decreasing trend in the first year when they gradually reduced their dependency on mother's milk, after which they became relatively stable. delta15 N values were significantly higher in samples from Uummannaq in 1993 compared to samples from Avanersuaq in 1984 and 1985 indicating that the diet of the narwhals in Uummannaq was at a higher trophic level. However, only a few significant correlations were found between stable isotope ratios and metal and OC concentrations.

Organochlorines in Greenland marine fish, mussels and sediments.

Shorthorn sculpin (Myoxocephalus scorpius), polar cod (Boreogadus saida), blue mussels (Mytilus edulis) and sediments were sampled in Greenland 1994-1995 at three locations at the west coast and one at the east coast. Fish liver, mussel soft tissue and sediments were analysed for PCBs (10 congeners), DDTs (pp,'), HCHs (alpha, beta, gamma), HCB and trans-nonachlor. The overall geometric mean concentrations found for PCBs were 17 micrograms kg-1 wet wt. in shorthorn sculpin liver, 33 micrograms kg-1 wet wt. in polar cod liver, and 0.86 microgram kg-1 wet wt. in blue mussels. For the three species, the geometric mean concentrations for DDTs were 11, 36, and 0.39 micrograms kg-1 wet wt., respectively; for HCHs: 8.7, 32 and 0.56 micrograms kg-1 wet wt., respectively; for HCB: 4.2, 11 and 0.06 micrograms kg-1 wet wt., respectively; and for trans-nonachlor: 6.3, 19 and 0.16 microgram kg-1 wet wt., respectively. All organochlorines in the sediment samples were below the detection limit of 0.1 microgram kg-1 dry weight. For sculpins and mussels, most organochlorine compounds were found to increase with increasing lipid content. The weight of mussels did not influence organochlorine concentrations, whereas organochlorine content in general increased with fish length of sculpins. The concentrations were found to be comparable to levels in other Arctic regions, but orders of magnitude lower than levels found in the southern part of the North Sea. Organochlorine concentrations in sculpins showed a decreasing trend following the ocean current flowing from north to south at the east coast and from south towards north at the west coast of Greenland. The proportion of higher chlorinated PCBs (Cl atoms > or = 6) in sculpin liver followed the decreasing trend of PCB concentrations.

Organochlorines in Greenland ringed seals (Phoca hispida).

Twenty-five ringed seals (Phoca hispida) were sampled in 1994 at each of four areas in Greenland, three on the west coast and one on the east coast. Seal blubber samples were analysed for polychlorinated biphenyls (PCBs, IUPAC Nos. 28, 31, 52, 101, 105, 118, 138, 153, 156 and 180), DDTs (p,p'-DDE, p,p'-DDD, p,p'-DDT), hexachlorocyclohexanes (alpha-, beta- and gamma-HCH), hexachlorobenzene (HCB) and trans-nonachlor. A number of the seals (n = 56) were also analysed for toxaphene (total toxaphene and single congeners: CHB Nos. 26, 32, 50 and 62). The overall geometric means (and ranges) found in seals were in microgram kg-1 wet wt. for sigma PCBs: 452 (85-4200), sigma DDTs: 607 (97-6040), sigma HCHs: 123 (51-382), HCB: 13 (3-27), trans-nonachlor: 83 (21-1236) and total toxaphene: 263 (71-950). The geometric means for HCB, trans-nonachlor, toxaphenes and the sums of PCBs and DDTs were higher for the east coast samples than for those from the west coast, and a decreasing trend in concentrations followed the east Greenland current. No geographical trend was apparent for HCHs. Differences in concentrations between females and males were only significant for HCB and HCH within certain age classes and sampling areas. A tendency for concentrations to increase with age was observed, but was not statistically significant. Principal component analyses for PCB congeners revealed that the proportion of higher chlorinated PCBs (Cl atoms > or = 6) decreased with decreasing concentrations of PCBs found for the four sampling areas. No differences between the higher and lower chlorinated PCBs were seen in females and males, but a higher proportion of CB-105 and CB-118 compared to CB-52 and CB-101 was seen in male seals compared to female seals.

Organochlorines in Greenland glaucous gulls (Larus hyperboreus) and Icelandic gulls (Larus glaucoides).

Glaucous gulls (Larus hyperboreus) and Icelandic gulls (Larus glaucoides) were sampled in 1994 from four different areas in Greenland, three on the west coast and one on the east coast. Livers of 93 glaucous gulls and seven Icelandic gulls were analysed for polychlorinated biphenyls (PCBs, IUPAC Nos. 28, 31, 52, 101, 105, 118, 138, 153, 156 and 180), DDTs (p,p'-DDE, p,p'-DDD, p,p'-DDT), hexachlorocyclohexanes (alpha-, beta- and gamma-HCH), hexachlorobenzene (HCB) and trans-nonachlor (TNC). The overall geometric means of the concentrations found in glaucous gull liver were for sigma PCBs 388 (range 20-5557), for sigma DDTs 363 (17-8604), sigma HCHs 7.4 (1-53), HCB 47 (4-594) and trans-nonachlor 19 (3-187) micrograms kg-1 wet wt., respectively. The geometric means of concentrations in Icelandic gull liver were for sigma PCBs 112 (24-435), for sigma DDTs 95 (25-298), sigma HCHs 2.9 (1.4-5.2), HCB 22 (8-58) and trans-nonachlor 5.1 (2.4-8.6) micrograms kg-1 wet wt., respectively. Significantly (P = 0.05) higher concentrations of PCBs, DDTs and HCHs were found in glaucous gulls at Ittoqqortoormiit at the east coast than in gulls from Qeqertarsuaq at the west coast of Greenland. This tendency was also seen for HCB and trans-nonachlor, but the differences were not statistically significant (P = 0.05). A decreasing trend in organochlorine concentrations followed the East Greenland Current, flowing from north to south down the east coast and to the north on the west coast. Gulls taken from the most northerly sampling area of the west coast, however, showed slightly higher concentrations than those from the central west coast. There appeared to be a tendency for higher concentrations to be found in males than females, and in adults compared to young glaucous gulls, but the differences were not statistically significant (P = 0.05). The concentration ranges found in gulls from Greenland were similar to those reported previously for gulls from northern Norway and Russia. A principal component analysis revealed no obvious link between the presence of higher chlorinated PCBs and higher PCB concentrations in glaucous gulls. Significantly higher proportions of higher chlorinated PCBs were found in glaucous gulls than in Icelandic gulls, and in adult glaucous gulls compared to young gulls of 1-2 calendar years. As no such difference was found between female and male gulls it seems that PCBs of all degrees of chlorination may be passed equally well from mother to offspring.

Organochlorines in Greenland lake sediments and landlocked Arctic char (Salvelinus alpinus).

Lake sediments and landlocked Arctic char (Salvelinus alpinus) were sampled in 1994 and 1995 at four different locations in Greenland, three at the west coast and one at the east coast. Sediments, char muscle and char liver were analysed for PCBs (10 congeners), DDTs (pp'), HCHs (alpha, beta, gamma), dieldrin, HCB and chlordanes (5) and char in addition to toxaphene (total and 4 congeners). All organochlorines in the sediment samples were below the detection limit of 0.1 microgram kg-1 dry wt., while the overall geometric means in Arctic char muscle were, in microgram kg-1 wet wt., for PCBs 11 (range 1-140), for DDTs 4.0 (1-35), for HCHs 0.4 (0.06-1.5), for dieldrin 0.7 (< 0.1-4.2), for HCB 0.7 (0.09-3.8), for chlordanes 4.8 (1-57) and for total toxaphene 13 (1-180). The sums of PCBs, DDTs, chlordanes and total toxaphene disclosed higher concentrations in muscle of char from the east coast compared to char from the west coast. Dieldrin and HCB showed the same tendency, but less pronounced, while the sum of HCHs were found in highest concentrations at the west coast. PCB, DDT, chlordane and toxaphene concentrations showed a decreasing trend following the East Greenland Current. Principal component analysis on PCB congeners showed that the proportion of higher chlorinated PCBs (Cl > 5) were higher in Qaqortoq in south Greenland compared to the three other sampling areas in Greenland. However, no correlation was seen either between degree of chlorination and latitude or between degree of chlorination and PCB concentrations.

Analytical methods, quality assurance and quality control used in the Greenland AMAP programme.

The majority of analytical results in the Greenland AMAP (Arctic Monitoring and Assessment Programme) have been produced by laboratories that participate regularly in performance studies. This makes it possible to judge the quality of the results based on objective measurements made by independent assessors. AMAP laboratories participated while analysing the AMAP samples in the QUASIMEME laboratory performance study programme, in the 'Interlaboratory Comparison Program' organised by Le Centre de Toxicologie du Québec, in a toxaphene intercomparison study organised by The Food Research Division of Health Canada, and in an International Atomic Energy Agency Intercomparison exercise. The relative errors of the trace analyses, i.e. the relative deviation of the result obtained by the AMAP laboratory from the assigned value, are in most cases less than the 25% which is regarded as acceptable by QUASIMEME. Usually the errors, especially for trace elements, are less than 12.5%, while errors for trace organics below 1 microgram kg-1 may rise to 50% or more. This study covers the period 1993 to 1998 for trace elements and one or more years from the period 1994-1996 for trace organics.

Comparison of contaminants from different trophic levels and ecosystems.

The present paper provides an overview of the priority contaminants and media from the Greenland part of the Arctic Monitoring and Assessment Program. Levels and accumulation patterns of heavy metals, POPs and a radionuclide (137Cs) are compared from the terrestrial, freshwater and marine ecosystems. Of the nine compounds presented, seven (Cd, Hg, Se, sigma PCB, sigma DDT, sigma HCH, HCB) increased in concentration towards higher trophic levels. For these contaminants the concentrations in soil and aquatic sediment were in the same order of magnitude, whereas the concentrations in marine biota were higher than found in the freshwater and terrestrial ecosystems probably due to the presence of longer food chains. Pb and 137Cs showed the reverse pattern compared with the other compounds. The concentrations in soil and aquatic sediments decreased in the order terrestrial, freshwater and marine ecosystems, which was reflected in the biota as well. Reindeer had similar or lower levels of Pb and 137Cs than lichens. Levels of Pb and 137Cs in marine biota did not show the same clear increase towards higher trophic as found for the other analysed compounds. Greenland Inuit contains considerably less mercury but higher levels of sigma PCB, sigma DDT and HCB than other Arctic marine top consumers.

Evaluation of the Greenland AMAP programme 1994-1995, by use of power analysis (illustrated by selected heavy metals and POPs).

The levels of PCBs, HCB, HCHs, DDTs, Cd, Pb, Hg and Se, and especially the variability in biota obtained during Phase 1 of the Greenland AMAP-programme have been used to illustrate the ability of the programme to detect differences in contaminant levels over time. The statistical power of t-tests of contaminant levels are illustrated according to various scenarios of magnitude of change, significance level and sample size. The statistical power of various time series of contaminant levels to detect linear trends in mean log-concentrations, including a random between-year variation component, is illustrated. We conclude that the ability to detect differences is rather poor for many combinations of contaminants and media, and that long time series are needed before temporal trends are likely to be detected.

Review on persistent organic pollutants in the environment of Greenland and Faroe Islands.

The literature concerning persistent organic pollutants (POPs) in the environment of Greenland and the Faroe Islands covering the period up to 1995 has been revisited. It is difficult to compare data from earlier studies with those from more recent investigations. Thus as the former quantified the content of CBs by comparison to a technical mixture of CBs (e.g. Aroclor 1254), the latter analyses typically are quantified on a single congener level. Single CB congeners have in some cases been determined, but the results were subsequently expressed as total PCB related to an Aroclor standard. For studies based on single CB congener determinations, the highest levels are reported for porpoise blubber from Greenland (700-4500 micrograms/kg wet weight), the conclusion, however being based on two determinations only. In Greenlandic seal blubber and peregrine falcon plasma equal levels of CBs (130-750 micrograms/kg ww) and of DDTs (150-860 micrograms/kg ww) were found. Levels of CBs and DDTs in fish liver were found to be around 40-75 micrograms/kg ww. In sediment samples the CBs were almost all below the detection limit (< 0.02-0.1 microgram/kg dry weight), and thereby being the matrix with the lowest CBs concentration levels. Earlier data based on Aroclor standards showed DDT levels in Greenlandic whale blubber in the range of 2700-4100 micrograms/kg ww and PCB levels of 3700 micrograms/kg-5400 micrograms/kg ww. DDT levels for seal blubber were at the same level (2700-4500 micrograms/kg ww) whereas the PCB level was lower (900-3900 micrograms/kg ww). The PCB level corresponds to the level found in human adipose tissue determined with a similar quantification technique. The lowest levels reported for mammals correspond to walrus blubber, the sum of PCBs and DDTs being in the ranges of 180-360 micrograms/kg ww and 50-90 micrograms/kg ww, respectively. The content of PCBs in scallops was found to be 3 micrograms/kg ww near the Thule Air base.

Gas chromatographic determination of propoxyphene and norpropoxyphene in plasma.

Propoxyphene and its major metabolite norpropoxyphene have been determined simultaneously by using gas chromatography. In order to avoid the on-column decomposition of the propoxyphene, derivatives were formed with the aid of lithium aluminium hydride, which cleaves the propionic acid ester of propoxyphene and reduces the norpropoxyphene amide. Promethazine was used as an internal standard. Propoxyphene and norpropoxyphene levels in plasma were determined in samples from six male volunteers receiving a single oral dose of 150 mg of propoxyphene hydrochloride in a sustained-release form (Abalgin Retard).