Accumulation of perfluorooctane sulfonate (PFOS) in the food chain of the Western Scheldt estuary: Comparing field measurements with kinetic modeling.

The environmentally persistent perfluorooctane sulfonate (PFOS) is a perfluoroalkylated acid (PFA), which has been found to accumulate and biomagnify through food webs all over the world. In the present investigation, the accumulation kinetics of PFOS was explored using the bioaccumulation model OMEGA. As accumulation behavior of PFOS may show similarities to fatty acids as well as to neutral organic compounds, different modeling approaches were used. Accumulation kinetics of PFOS was modeled similar to (1) moderately and (2) highly hydrophobic compounds, (3) metals and (4) as a combination of hydrophobic compounds and metals. Modeled elimination and uptake rate constants were compared to empirical rate constants from literature. Subsequently, model predictions were compared to field-based biota-suspended solids accumulation ratios (BSAF) in the estuarine food chain of the Western Scheldt, The Netherlands. Results show that uptake of PFOS is comparable to moderately hydrophobic compounds and elimination is best described by elimination kinetics of metals. These observations indicate that the accumulation behavior of PFOS is comparable to that of short and medium chained fatty acids.

PFOS levels in the blood and liver of a small insectivorous songbird near a fluorochemical plant.

Perfluorooctane sulfonate (PFOS) is the stable end product of the degradation of various perfluorinated compounds and is the predominant compound found in the environment and biota. PFOS is a widespread environmental contaminant that is found in a great diversity of wildlife species with more elevated tissue concentrations in animals from populated and industrialized areas. In this study we determined the PFOS accumulation in blood and livers of a small songbird, the great tit (Parus major), in the vicinity of a large fluorochemical plant in Antwerp, Belgium. PFOS concentrations ranged from 553 ng/g to 11359 ng/g in liver and ranged from 24 to 1625 ng/ml in blood, which are among the highest ever reported in free-living animals, and exceeded in almost all birds the hepatic benchmark concentrations for the protection of avian species [Beach SA, Newsted JL, Coady K, Giesy JP. Ecotoxicological evaluation of perfluorooctanesulfonate (PFOS). Rev Environ Contam Toxicol 2006;186:133-174]. Although PFOS concentrations in liver and blood decreased significantly within approximately 5.5 km of the plant, differences were smaller than previously described for wood mice (Apodemus sylvaticus) and nestling great tits. PFOS concentrations in liver and blood were higher in young birds (one-year old). No significant sex differences were found. A highly significant correlation between liver and blood concentrations indicates the usefulness of blood as a non-destructive matrix for biomonitoring purposes.

Perfluorooctane sulfonic acid and organohalogen pollutants in liver of three freshwater fish species in Flanders (Belgium): relationships with biochemical and organismal effects.

A perfluorooctane sulfonic acid (PFOS) assessment was conducted on gibel carp (Carassius auratus gibelio), carp (Cyprinus carpio), and eel (Anguilla anguilla) in Flanders (Belgium). The liver PFOS concentrations in fish from the Ieperlee canal (Boezinge, 250-9031 ng/g wet weight, respectively) and the Blokkersdijk pond (Antwerp, 633-1822 ng/g wet weight) were higher than at the Zuun basin (Sint-Pieters-Leeuw, 11.2-162 ng/g wet weight) and among the highest in feral fish worldwide. Eel from the Oude Maas pond (Dilsen-Stokkem) and Watersportbaan basin (Ghent) had PFOS concentrations ranging between 212 and 857 ng/g wet weight. The hepatic PFOS concentration was significantly and positively related with the serum alanine aminotransferase activity, and negatively with the serum protein content in eel and carp. The hepatic PFOS concentration in carp correlated significantly and negatively with the serum electrolyte concentrations whereas a significant positive relation was found with the hematocrit in eel. Although 13 organochlorine pesticides, 22 polychlorinated biphenyl (PCB) congeners and 7 polybrominated diphenyl ethers (PBDEs) were also measured in the liver tissue, only PCB 28, PCB 74, gamma-hexachlorocyclohexane (gamma-HCH) and hexachlorobenzene (HCB) were suggested to contribute to the observed serological alterations in eel.

Evaluation of biochemical effects related to perfluorooctane sulfonic acid exposure in organohalogen-contaminated great tit (Parus major) and blue tit (Parus caeruleus) nestlings.

A perfluorooctane sulfonic acid (PFOS) biomonitoring survey was conducted on great tit (Parus major) and blue tit (Parus caeruleus) nestlings from Blokkersdijk, a bird reserve in the proximity of a fluorochemical plant in Antwerp (Belgium) and Fort IV, a control area. PFOS, together with 11 organochlorine pesticides, 20 polychlorinated biphenyl congeners and 7 polybrominated diphenyl ethers were measured in liver tissue. The hepatic PFOS concentrations at Blokkersdijk (86-2788 and 317-3322 ng/g wet weight (ww) for great and blue tit, respectively) were among the highest ever measured and were significantly higher than at the control area (17-206 and 69-514 ng/g ww for great and blue tit, respectively). The hepatic PFOS concentration was species- and sex-independent and correlated significantly and positively with the serum alanine aminotransferase activity and negatively with the serum cholesterol and triglyceride levels in both species but did not correlate with condition or serum protein concentration. In the great tit, a significant positive correlation was observed between the liver PFOS concentration and the relative liver weight. In the blue tit, the hepatic PFOS concentration correlated positively and significantly with hematocrite values. None of the investigated organohalogen pollutants except for PFOS were suggested to be involved in the observed biological alterations.

Biochemical effect evaluation of perfluorooctane sulfonic acid-contaminated wood mice (Apodemus sylvaticus).

Wood mice (Apodemus sylvaticus) were captured at Blokkersdijk, a nature reserve in the immediate vicinity of a fluorochemical plant in Antwerp, Belgium, and at Galgenweel, 3 kilometers farther away. The liver perfluorooctane sulfonic acid (PFOS) concentrations in the Blokkersdijk mice were extremely high (0.47-178.55 micro g/g wet weight). Perfluorononanoic, perfluorodecanoic, perfluoroundecanoic, and perfluorododecanoic acids were found sporadically in the liver tissue of the Blokkersdijk mice. The liver PFOS concentrations at Galgenweel were significantly lower than those at Blokkersdijk (0.14-1.11 micro g/g wet weight). Further results suggest sex independence of the liver PFOS levels, increased levels of PFOS bioaccumulation in older mice, and maternal PFOS transfer to the young. Several liver end points were significantly elevated in the Blokkersdijk mice: liver weight, relative liver weight, peroxisomal beta-oxidation activity, microsomal lipid peroxidation level, and mitochondrial fraction protein content. For the mitochondrial fraction catalase activity, no significant difference between locations was found. The liver weight, relative liver weight, and liver microsomal lipid peroxidation level increased significantly with the liver PFOS concentration. No indications for PFOS-mediated effects on the serum triglyceride, cholesterol, or potassium levels were obtained. The liver PFOS concentration was negatively related to the serum alanine aminotransferase activity.

Perfluorooctane sulfonic acid in bib (Trisopterus luscus) and plaice (Pleuronectes platessa) from the Western Scheldt and the Belgian North Sea: distribution and biochemical effects.

A biomonitoring campaign was conducted in the Belgian North Sea and in the Western Scheldt (The Netherlands) with the primary goal to assess perfluorooctane sulfonic acid (PFOS) contamination and distribution in different biota. This study covers the results obtained for bib (Trisopterus luscus) and plaice (Pleuronectes platessa) and includes the assessment of some stress-related biochemical endpoints. Analysis of liver and muscle PFOS concentrations of both species provided evidence for the existence of a PFOS pollution gradient along the Western Scheldt with higher levels at the upstream locations and a lower degree of PFOS pollution at the marine locations. Cellular necrosis was studied by measuring aspartate aminotransferase (AST) and alanine aminotransferase (ALT) levels in the serum. Serum ALT but not serum AST was shown to correlate positively with the PFOS liver concentration in bib (r = 0.44, p < 0.05), indicating that PFOS might contribute to the induction of hepatic damage in bib in the area of study. Analysis of total carbohydrate, lipid, and protein content of bib liver tissue revealed a positive correlation between the protein content and the PFOS liver concentration (r = 0.55, p < 0.01). Whether this is due to induction of compensatory mechanisms, detoxification, or repair processes remains unclear.

Exposure patterns of perfluorooctane sulfonate in aquatic invertebrates from the Western Scheldt estuary and the southern North Sea.

Over the past decades little research has been conducted on the environmental behavior and effects of fluorinated organochemicals (FOCs). Recently it has been reported that perfluorooctane sulfonic acid (PFOS) is occurring worldwide. Little is known about the PFOS levels in organisms originating from the southern North Sea and the Western Scheldt estuary. In this study, we determined, for the first time, the PFOS-exposure levels in Crangon crangon, Carcinus maenas, and Asterias rubens from these ecosystems. Concentrations on a wet-weight basis in soft tissues of shrimp, crab, and starfish ranged from 19 to 520 ng/g, from 24 to 877 ng/g, and from 9 to 176 ng/g, respectively. These results show the existence of a PFOS pollution gradient in organisms along the Western Scheldt estuary, with the highest concentrations near Antwerp. The range of PFOS levels in shrimp and crab are slightly higher in coastal regions compared with sampling sites in open water. This study shows widespread distribution of PFOS in the Belgian and Dutch marine and estuarine environment at rather high concentrations.

Occurrence of perfluorooctane sulfonate and other perfluorinated alkylated substances in harbor porpoises from the Black Sea.

Perfluorooctane sulfonate (PFOS) and other perfluorinated alkylated substances (PFAS) were determined in liver, kidney, muscle, brain, and blubber samples of 31 harbor porpoises (Phocoena phocoena relicta) of different age and sex stranded along the Ukrainian coast of the Black Sea. In all individuals and in all tissues, PFOS was the predominant PFAS, accounting for on average 90% of the measured PFAS load. PFOS concentrations were the highest in liver (327+/-351 ng/g wet wt) and kidney (147 +/-262 ng/g wet wt) tissue, and lower in blubber (18+/-8 ng/g wet wt), muscle (41+/-50 ng/g wet wt), and brain (24 +/-23 ng/g wetwt). No significant differences could be determined between males and females, nor between juvenile and adult animals (p > 0.05). Perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid could be detected in liver tissue of approximately 25% of the individuals. Perfluorobutane sulfonate, perfluorobutanoic acid, and perfluorooctanoic acid were not detected in any of the porpoise livers. Although we investigated a potential intraspecies segregation according to the source of prey, using stable isotopes, no statistically significant correlation between PFOS concentrations and stable isotopes could be determined. It is, however, noteworthy that the contamination by PFOS in the Black Sea harbor porpoises is comparable to levels found in porpoises from the German Baltic Sea and from coastal areas near Denmark and, therefore, might pose a threat to this population.

Tissue distribution of perfluorinated chemicals in harbor seals (Phoca vitulina) from the Dutch Wadden Sea.

Perfluorinated acids (PFAs) are today widely distributed in the environment, even in remote arctic areas. Recently, perfluorooctane sulfonate (PFOS) has been identified in marine mammals all over the world, but information on the compound-specific tissue distribution remains scarce. Furthermore, although longer perfluorinated carboxylic acids (PFCAs) are used in industry and were shown to cause severe toxic effects, still little is known on potential sources or their widespread distribution. In this study, we report for the first time on levels of longer chain PFCAs, together with some short chain PFAs, perfluorobutane sulfonate (PFBS) and perfluorobutanoate (PFBA), in liver, kidney, blubber, muscle, and spleen tissues of harbor seals (Phoca vitulina) from the Dutch Wadden Sea. PFOS was the predominant compound in all seal samples measured (ranging from 89 to 2724 ng/g wet weight); however, large variations between tissues were monitored. Although these are preliminary results, it is, to our knowledge, the first time that PFBS could be found at detectable concentrations (2.3 +/- 0.7 ng/g w wt) in environmental samples. PFBS was only detected in spleen tissue. PFCA levels were much lower than PFOS concentrations. The dominant PFCA in all tissues was PFNA (perfluorononanoic acid), and concentrations generally decreased in tissues for all other PFCA homologues with increasing chain length. No clear relationship between PFOS levels in liver and kidney was observed. Furthermore, hepatic PFDA (perfluorodecanoic acid) levels increased with increasing body length, but in kidney tissue, PFDA levels showed an inverse relationship with increasing body length. These data suggest large differences in tissue distribution and accumulation patterns of perfluorinated compounds in marine organisms.