Concentrations,patterns and metabolites of organochlorine pesticides in relation to xenobiotic phase I and II enzyme activities in ringed seals (Phoca hispida) from Svalbard and the Baltic Sea

The present study investigates the concentrations and patterns of organochlorine pesticides (OCPs) and their metabolites in liver and plasma of two ringed seal populations (Phoca hispida): lower contaminated Svalbard population and more contaminated Baltic Sea population. Among OCPs, p,p′-DDE and sum-chlordanes were the highest in concentration. With increasing hepatic contaminant concentrations and activities of xenobiotic-metabolizing enzymes, the concentrations of 3-methylsulfonyl-p,p′-DDE and the concentration ratios of pentachlorophenol/hexachlorobenzene increased, and the toxaphene pattern shifted more towards persistent Parlar-26 and -50 and less towards more biodegradable Parlar-44. Relative concentrations of the chlordane metabolites, oxychlordane and -heptachlorepoxide, to sum-chlordanes were higher in the seals from Svalbard compared to the seals from the Baltic, while the trend was opposite for cis- and trans-nonachlor. The observed differences in the OCP patterns in the seals from the two populations are probably related to the catalytic activity of xenobiotic-metabolizing enzymes, and also to differences in dietary exposure.     

Current levels of DDT,PCB and trace elements in the Baltic ringed seals (Phoca hispida baltica) and grey seals (Halichoerus grypus)

Residue levels of polychlorinated biphenyls (PCBs) and 1,1,1-trichloro-2,2-bis[p-chlorophenyl]ethane (DDT) were determined from liver samples of ringed seals (Phoca lispida) from the Baltic Sea and Svalbard, and of grey seals (Halichoerus grypus) from the Baltic Sea and Sable Island in Canada. Both Baltic seal populations showed clearly higher average sum PCB (SPCB) and sum DDT (SDDT) levels than the reference seal populations. Among the Baltic seals, SPCB levels were twice as high as SDDT levels, and both contaminants were higher in ringed seals than in grey seals. A difference in gender was observed only in the Sable Island grey seal population, in which males showed a higher level of contamination than females. A reduction of the SDDT levels, and to a lower extent of the SPCB levels can be observed in the Baltic seals since the peak contaminant levels during the 1970s. The decrease has been more rapid in the grey seals than in the ringed seals. The SPCB levels in the Baltic ringed seals are still high enough to cause a threat to their well being. Residue levels of the trace elements mercury, cadmium, lead and selenium were determined from liver, kidney and muscle samples of grey seals from the Baltic Sea and Sable Island. Only cadmium showed a geographic difference being higher in the seals from Sable Island than from the Baltic Sea. No clear reduction of the metal burden can be observed in the Baltic grey seal population since the 1970s.     

Organochlorine burdens in blood of ringed and bearded seals from north-western Svalbard.

Ringed seal (Phoca hispida) and bearded seal (Erignathus barbatus) are the main prey of polar bears (Ursus maritimus), and information on organochlorines (OCs) in these pinniped species is important to understand the transport, fate and effects of persistent organic pollutants in the Arctic ecosystem. Thus, OCs were analysed in blood samples of bearded and ringed seals from the coastal ecosystem of the north-western Svalbard archipelago (Kongsfjorden, 78.55degrees N). The relative contribution of OCs could be ranked as follows: Ringed seal females: sigmaPCB > sigma DDT > sigma CHL > sigma HCH > HCB > Mirex. Ringed seal males: sigma PCB > or = sigma DDT > sigma CHL > sigma HCH > or = HCB > Mirex. Bearded seal females: sigma PCB > sigma HCH > or = sigma CHL > sigma DDT > Mirex > HCB. Bearded seal males: sigma PCB > sigma DDT > or = sigma CHL > sigma HCH > Mirex > or = HCB. The concentrations of sigmaPCB and sigma DDT were higher in ringed seals than in bearded seals, whereas sigma HCH was higher in bearded than in ringed seals. In ringed seal females and males sigma PCB was 337 +/- 95 ng/g (n= 6) and 625 +/- 443 ng/g (n=6), whereas sigma DDT was 165 +/- 47 ng/g (n=6) and 621 +/- 559 ng/g (n = 6), respectively. In bearded seal females and males, sigmaPCB was 159 +/- 132 ng/g (n = 6) and 248 +/- 93 ng/g (n = 5), whereas sigmaDDT was 46 +/- 41 ng/g (n = 6) and 161 +/- 71 ng/g (n = 5), respectively. The inter-species differences are caused by a higher trophic position of ringed seals in the Svalbard ecosystem compared to bearded seals. OC levels in ringed seals at Svalbard are similar to those reported from the North-American Arctic and in the lower range compared to previously reported data from Svalbard.     

Geographical variation of persistent organochlorine concentrations in blubber of ringed seal (Phoca hispida) from the Canadian Arctic: univariate and multivariate approaches

Geographical variation of organochlorine (OC) concentrations in ringed seal (Phoca hispida) in the Canadian Arctic was studied using univariate and multivariate statistical techniques. The dataset consisted of 80 individual OC components (58 PCB congeners plus DDT- and chlordane (CHL)-related compounds, toxaphene, hexachlorocyclohexanes (HCH), chlorobenzenes (CBz), and dieldrin) determined in 221 ringed seal blubber samples from 13 locations throughout the Canadian Arctic from the period 1983 to 1989. Mean concentrations of the major OC groups in ringed seal blubber (SigmaPCBs, SigmaDDT, SigmaCHL and toxaphene), adjusted for the age and sex of the seals, showed few significant geographical differences. Principal components analysis was used to examine geographical trends. Significant differences in mean factor scores for three of four principal components were found between sampling locations. Locations in the western and high Arctic could be distinguished from those in Hudson Bay by highest scores along principal component two which was associated principally with CBz. PCB congeners with six or more chlorine substitutions declined with increasing north latitude, whereas more volatile OCs (CBz, HCH, less chlorinated PCBs) increased in the proportion of total OCs with latitude. Proportions of less chlorinated PCBs also decreased with increasing longitude, whereas slopes of regressions for more highly chlorinated PCBs increased significantly. The results were generally consistent with the 'cold condensation' hypothesis of increasing proportions of more volatile OCs with increasing latitude and distance from sources.     

Mercury and selenium in wild and experimental seals

This paper describes the tissue distribution of inorganic mercury, organic mercury and selenium in Dutch and British seals as well as in seals which were dosed with methylmercury under experimental conditions.In the experimental animals, a time-related increase of both mercury and selenium was found in liver and kidney after the administration of methylmercury, while in the other tissues examined, e.g. brain, thyroid, blood, only the concentrations of mercury increased.In the wild seals, it was also demonstrated that the selenium concentrations showed a positive correlation with the concentrations of mercury.Atomic ratios of mercury and selenium were close to one in the wild seals as was also found in previous studies. However, atomic ratios above one were found in seals fed additional methylmercury.In vitro studies with liver homogenates of seals did not provide evidence for the presence of a biochemical demethylation mechanism nor for any effect of selenium on the demethylation process.     

Photo-identification, site fidelity, and movement of female gray seals (Halichoerus grypus) between haul-outs in the Baltic Sea

The growing gray seal population in the Baltic Sea has led to increased conflicts with fisheries. Despite limited data on gray seal ecology, management measures, such as culling, have been implemented recently. We studied movements and site fidelity of Baltic gray seals using mark-recapture analysis based on photographic identification of individuals (photo-id). Seals were photographed at the major summer haul-out sites. Profile photographs of the head and neck were matched using purpose-written software to generate a database of capture histories from 1995-2000. The haul-outs were grouped into seven areas. Darroch's method (20) for a two-sample capture-recapture census was adapted to estimate rates of movement between the areas. The majority of seals were estimated to remain within the same area, suggesting that Baltic gray seals exhibit a high degree of site fidelity during the summer, and that fidelity to a site lasts for more than one season.     

Mercury in Precipitation at an Urbanized Coastal Zone of the Baltic Sea (Poland)

Wet deposition is an important source of metals to the sea. The temporal variability of Hg concentrations in precipitation, and the impact of air masses of different origins over the Polish coastal zone were assessed. Samples of precipitation were collected (August 2008–May 2009) at an urbanized coastal station in Poland. Hg analyses were conducted using CVAFS. These were the first measurements of Hg concentration in precipitation obtained in the Polish coastal zone. Since Poland was identified as the biggest emitter of Hg to the Baltic, these data are very important. In the heating and non-heating season, Hg concentrations in precipitation were similar. Hg wet deposition flux dominated in summer, when the production of biomass in the aquatic system was able to actively adsorb Hg. Input of metal to the sea was attributed to regional and distant sources. Maritime air masses, through transformation of Hg(0), were an essential vector of mercury in precipitation.     

Temporal trends of polyfluoroalkyl compounds (PFCs) in liver tissue of grey seals (Halichoerus grypus) from the Baltic Sea, 1974-2008

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in grey seal (Halichoerus grypus) liver from the Baltic Sea over a period of 35 years (1974-2008). In total, 17 of 43 PFCs were found, including the perfluoroalkyl sulfonates (C₄-C₁₀ PFSAs), perfluorooctanesulfinate (PFOSi), long chain perfluoroalkyl carboxylates (C₇-C₁₄ PFCAs), and perfluoroalkyl sulfonamides (i.e., perfluorooctane sulfonamide (FOSA) and N-ethyl perfluorooctane sulfonamide (EtFOSA)), whereas saturated and unsaturated fluorotelomer carboxylates, shorter chain PFCAs and perfluoroalkyl phosphonic acids were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (9.57-1444 ng g⁻¹ wet weight (ww)), followed by perfluorononanoate (PFNA, 0.47-109 ng g⁻¹ ww). C₆-C₈ PFSAs, PFOSi and C₇-C₁₃ PFCAs showed statistically significant increasing concentrations between 1974 and 1997, with a peak in 1997 and then decreased or levelled off (except for C₁₂ and C₁₃ PFCAs). FOSA had a different temporal trend with a maximum in 1989 followed by significant decreasing concentrations until 2008. Toxicological implications for grey seals are limited, but the maximal PFOS concentration found in this study was about 40 times lower than the predicted lowest observed effect concentrations (LOEC). The statistically significant decreasing concentrations or levelling off for several PFCs in the relative closed marine ecosystem of the Baltic Sea indicate a rapidly responding to reduced emissions to the marine environment. However, the high concentrations of PFOS and continuing increasing concentrations of the longer chain PFCAs (C₁₂-C₁₄) shows that further work on the reduction of environmental emissions of PFCs are necessary.     

Organochlorine and organotin compounds in Caspian seals (Phoca caspica) collected during an unusual mortality event in the Caspian Sea in 2000

Polychlorinated biphenyls (PCBs), organochlorine pesticides and organotin compounds were determined in the blubber and liver of Caspian seals (Phoca caspica) found stranded on the coast of the Caspian Sea during an outbreak of canine distemper virus (CDV) in 2000. Among organochlorines analyzed, DDTs were the most dominant contaminants with concentrations ranging from 6.3 to 470 microg/g on a lipid-weight basis. Caspian seals collected in 2000 during the epizootic had higher concentrations of organochlorines than healthy individuals sampled in 1998. However, the blubber layer was generally thinner in the seals collected in 2000 than those in the previous surveys. Although compositions of organochlorine pesticides in seals suggested that the contamination status in the Caspian Sea is improving, the levels found in Caspian seals in 2000 were comparable to those in other marine mammals that have suffered from epizootics. This implies that the present status of contamination found in Caspian seals poses a risk of immunosuppression. Concentrations of butyltin compounds in livers of seals ranged from 0.49 to 17 ng/g on a wet-weight basis and octyltin compounds were below limit of detection in all the samples analyzed, suggesting less contamination by organotin compounds in the Caspian Sea.     

Reprint of: Temporal trends of polyfluoroalkyl compounds (PFCs) in liver tissue of grey seals (Halichoerus grypus) from the Baltic Sea, 1974-2008

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in grey seal (Halichoerus grypus) liver from the Baltic Sea over a period of 35 years (1974-2008). In total, 17 of 43 PFCs were found, including the perfluoroalkyl sulfonates (C₄-C₁₀ PFSAs), perfluorooctanesulfinate (PFOSi), long chain perfluoroalkyl carboxylates (C₇-C₁₄ PFCAs), and perfluoroalkyl sulfonamides (i.e., perfluorooctane sulfonamide (FOSA) and N-ethyl perfluorooctane sulfonamide (EtFOSA)), whereas saturated and unsaturated fluorotelomer carboxylates, shorter chain PFCAs and perfluoroalkyl phosphonic acids were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (9.57-1444 ng g⁻¹ wet weight (ww)), followed by perfluorononanoate (PFNA, 0.47-109 ng g⁻¹ ww). C₆-C₈ PFSAs, PFOSi and C₇-C₁₃ PFCAs showed statistically significant increasing concentrations between 1974 and 1997, with a peak in 1997 and then decreased or levelled off (except for C₁₂ and C₁₃ PFCAs). FOSA had a different temporal trend with a maximum in 1989 followed by significant decreasing concentrations until 2008. Toxicological implications for grey seals are limited, but the maximal PFOS concentration found in this study was about 40 times lower than the predicted lowest observed effect concentrations (LOEC). The statistically significant decreasing concentrations or levelling off for several PFCs in the relative closed marine ecosystem of the Baltic Sea indicate a rapidly responding to reduced emissions to the marine environment. However, the high concentrations of PFOS and continuing increasing concentrations of the longer chain PFCAs (C₁₂-C₁₄) shows that further work on the reduction of environmental emissions of PFCs are necessary.     

Toxaphene levels in salmon (Salmo salar) from the Baltic Sea

Three toxaphene congeners have been determined in salmon from the Swedish coastal environment using both supercritical fluid (SFE) and the traditional liquid/liquid extractions. The levels obtained using a modifier-free SFE technique, followed by group separation on a silica gel column, were by far much lower than concentrations obtained by SFE with a modifier or liquid/liquid extraction. The mean concentrations on fresh weight basis using a liquid/liquid extraction technique were 5.87, 8.70 and 1.59 microg/kg for CHBs 26, 50 and 62, respectively. There was a plausible relationship between the various fishing sites and the toxaphene levels.     

Mercury, lead and cadmium in human milk in relation to diet, lifestyle habits and sociodemographic variables in Madrid (Spain)

Background

Although breastfeeding is the ideal way of nurturing infants, it can be a source of exposure to toxicants. This study reports the concentration of Hg, Pb and Cd in breast milk from a sample of women drawn from the general population of the Madrid Region, and explores the association between metal levels and socio-demographic factors, lifestyle habits, diet and environmental exposures, including tobacco smoke, exposure at home and occupational exposures.

Methods

Breast milk was obtained from 100 women (20 mL) at around the third week postpartum. Pb, Cd and Hg levels were determined using Atomic Absorption Spectrometry. Metal levels were log-transformed due to non-normal distribution. Their association with the variables collected by questionnaire was assessed using linear regression models. Separate models were fitted for Hg, Pb and Cd, using univariate linear regression in a first step. Secondly, multivariate linear regression models were adjusted introducing potential confounders specific for each metal. Finally, a test for trend was performed in order to evaluate possible dose-response relationships between metal levels and changes in variables categories.

Results

Geometric mean Hg, Pb and Cd content in milk were 0.53 μg L⁻¹, 15.56 μg L⁻¹, and 1.31 μg L⁻¹, respectively. Decreases in Hg levels in older women and in those with a previous history of pregnancies and lactations suggested clearance of this metal over lifetime, though differences were not statistically significant, probably due to limited sample size. Lead concentrations increased with greater exposure to motor vehicle traffic and higher potato consumption. Increased Cd levels were associated with type of lactation and tended to increase with tobacco smoking.

Conclusions

Surveillance for the presence of heavy metals in human milk is needed. Smoking and dietary habits are the main factors linked to heavy metal levels in breast milk. Our results reinforce the need to strengthen national food safety programs and to further promote avoidance of unhealthy behaviors such as smoking during pregnancy.     

Mercury and cadmium in common cormorants (Phalacrocorax carbo)

Mercury (Hg) and cadmium (Cd) in common cormorants (Phalacrocorax carbo) collected in Lake Biwa, Japan and Tokyo, Japan, were investigated to elucidate the biological behaviors of these elements, and to assess exposure to these pollutants of wild, fish-eating birds. Hg and Cd concentrations were highest in the liver and kidneys, respectively. The lowest levels of both elements were observed in chicks. Hg concentrations in all tissues except brain increased significantly with growth from chicks to juveniles (p<0.05, U-test). Cd concentrations in the kidneys and liver also increased significantly during growth from juvenile to adult (p<0.005, U-test). When comparing hepatic Hg and Cd in adult birds between 10 samples from Lake Biwa and nine samples from Tokyo, the Cd concentrations in the Lake Biwa samples (1.4+/-0.37 microg/g dry wt) (mean+/-SD) were significantly higher than those from Tokyo (0.32+/-0.16 microg/g dry wt) (p<0.005, U-test), while no statistically significant difference was found in the Hg concentrations. Possible causes of these differences were discussed in relation to their prey.     

Polychlorinated naphthalenes and coplanar polychlorinated biphenyls in tissues of harbor seals (Phoca vitulina) from the northern Gulf of Alaska

Blubber, liver and kidney samples of harbor seals (Phoca vitulina) from the northern Gulf of Alaska were collected during 2000-2001 for the analysis of polychlorinated naphthalenes (PCNs) and coplanar polychlorinated biphenyls (CoplPCBs). On the lipid weight (lw) base, the total concentrations of PCNs (Sigma PCNs) ranged from 0.3 to 27 ng/g lw, and the total concentrations of CoplPCBs (Sigma CoplPCBs) were 3.6-546 ng/g lw in all the tissue samples. Di-ortho PCBs and mono-ortho PCBs were dominant followed by non-ortho PCBs and PCNs. Sigma Mono-ortho PCBs and Sigma di-ortho PCBs in nursing seals were apparently lower than those in male adult seals, but Sigma PCNs and Sigma non-ortho PCBs in female adults were not significantly different from those in male adults. Differences in PCNs and CoplPCBs congener profiles in female and male adult seals are apparently related to their chemical structure and properties, animal's developmental stages and physiological conditions. A large quantity of mono-ortho and di-ortho PCBs might be transferred to newborns from the nursing seals during lactation, while non-ortho PCBs and PCNs were relatively accumulative in the mother seals. Sigma PCNs and Sigma CoplPCBs in the harbor seals correlated with ages, gender, body weight and blubber thickness, but the blubber Sigma PCNs and Sigma CoplPCBs in Kodiak Island and Southern Alaska Peninsula (KIAP) did not significantly differ from those in Prince William Sound (PWS). In addition to the new PCB data, this first report on PCN contamination in Alaskan harbor seal tissues is useful for the wildlife and ecosystem management and human health protection.     

Mercury, cadmium and lead concentrations in different ecophysiological groups of earthworms in forest soils

Bioaccumulation of Hg, Cd and Pb by eight ecophysiologically distinct earthworm species was studied in 27 polluted and uncontaminated forest soils. Lowest tissue concentrations of Hg and Cd occurred in epigeic Lumbricus rubellus and highest in endogeic Octolasion cyaneum. Soils dominated by Dendrodrilus rubidus possess a high potential of risk of Pb biomagnification for secondary predators. Bioconcentration factors (soil-earthworm) followed the sequence ranked Cd > Hg > Pb. Ordination plots of redundancy analysis were used to compare HM concentrations in earthworm tissues with soil, leaf litter and root concentrations and with soil pH and CEC. Different ecological categories of earthworms are exposed to Hg, Cd and Pb in the topsoil by atmospheric deposition and accumulate them in their bodies. Species differences in HM concentrations largely reflect differences in food selectivity and niche separation.     

Screening of hydrophobic DNA adducts in flounder (Platichthys flesus) from the Baltic Sea

Neoplasia and other histopathological lesions in flounder (Platichthys flesus) liver have been investigated in several European sea areas, including the Baltic Sea. Several studies have been able to link neoplasm epizootics in fish with the exposure to genotoxins such as polycyclic aromatic hydrocarbons (PAHs). The level of hydrophobic DNA adducts in tissue DNA reflects the exposure of the organism to PAHs.Using hydrophobic DNA adduct levels as biomarkers, possible PAH exposure was assessed in flounder from 10 different sites in the Baltic Sea, collected during the years 1995–1997. The results show that the overall levels of hepatic DNA adducts were low and, in general, the chromatograms appeared clean. The highest levels of DNA adducts were found at two sites in the southern Baltic Sea. There were no statistically significant differences in adduct levels between the sites. Our results indicate that flounder from studied off shore sites of the Baltic Sea had not been exposed to a greater extent to large polycyclic hydrophobic hydrocarbons in their environment.     

PCDD/Fs in sprat (Sprattus sprattus balticus) from the Gulf of Finland, the Baltic Sea

The concentrations and congeners pattern of the polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in sprat collected by the commercial catches in the Gulf of Finland, Baltic Sea. Based on the toxic equivalent concentrations 2,3,4,7,8-PeCDF prevailed among the congeners of PCDD/Fs. The significance of age- and season-specific relationship between the concentration of lipids and dioxins was demonstrated. On lipid weight basis the concentration of PCDDs was significantly higher in spring than in autumn. This difference was not statistically significant for PCDFs. On lipid weight basis the concentration of dioxins decreased with rising content of lipids. PCDD/Fs toxic equivalent concentration increased with the age of sprat exceeding the EU maximum limit value at more than 5-year-old fish.     

On the leachability and sources of some elements in sediments from the Bothnian Sea and the Gotland Deep (the Baltic Sea)

The partitioning of some elements in sediments of two Baltic Sea basins (the Bothnian Sea and the Gotland Deep) was established by leaching experiments. Both partial (dithionite-citrate-bicarbonate) and "total" (HCl-KClO3) leach were used. Trace metals of both natural and anthropogenic sources (Co, Cu, Ni, Pb, Zn) were evaluated for affinity to terrestrial material and to authigenic mineral elements (Fe, S). The results indicate that the easily leachable "mobile" fraction is not necessarily a good indicator for pollution. Longer stagnation periods result in intensive pyrite formation in the Gotland Deep which mask pollution trends. The permanent oxic conditions in the Bothnian Sea may affect a dissolution capability for selected elements.     

Arsenic in sediments from the southeastern Baltic Sea

Arsenic occurs as a persistent constituent in many of the chemical weapons dumped into the Baltic Sea; it can be used as an indicator of leakage and dispersal of released munitions to the marine environment. Total arsenic was analysed in sediment samples taken from the Lithuanian economic zone in the Baltic Sea, which included samples from the chemical munitions dumpsite in the Gotland Basin and national monitoring stations in the southeastern Baltic Sea. Arsenic concentrations in sediments ranged from 1.1 to 19.0 mg kg(-1), with an average of 3.4 mg kg(-1). Although there was evidence of slightly elevated arsenic content in sediments near the weapons dumpsite, arsenic concentrations were nevertheless quite low relative to other investigations in the Baltic and North Seas.