Bioaccumulation of per- and polyfluorinated alkyl substances (PFAS) in selected species from the Barents Sea food web.

The present study reports concentrations and biomagnification potential of per- and polyfluorinated alkyl substances (PFAS) in species from the Barents Sea food web. The examined species included sea ice amphipod (Gammarus wilkitzkii), polar cod (Boreogadus saida), black guillemot (Cepphus grylle) and glaucous gull (Larus hyperboreus). These were analyzed for PFAS, polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethanes (DDTs) and polybrominated diphenyl ethers (PBDEs). Perfluorooctane sulfonate (PFOS) was the predominant of the detected PFAS. Trophic levels and food web transfer of PFAS were determined using stable nitrogen isotopes (delta(15)N). No correlation was found between PFOS concentrations and trophic level within species. However, a non-linear relationship was established when the entire food web was analyzed. Biomagnification factors displayed values >1 for perfluorohexane sulfonate (PFHxS), perfluorononanoic acid (PFNA), PFOS and SigmaPFAS(7). Multivariate analyses showed that the degree of trophic transfer of PFAS is similar to that of PCB, DDT and PBDE, despite their accumulation through different pathways.

Validation of a screening method based on liquid chromatography coupled to high-resolution mass spectrometry for analysis of perfluoroalkylated substances in biota.

A screening method for analysis of perfluoroalkylated substances (PFAS) in biota samples has been developed and validated using liver samples from polar cod (Boreogadus saida) and glaucous gull (Larus hyperboreus). The method was based on extraction of target compounds from homogenised samples into the solvent mixture used as mobile phase in high-performance liquid chromatography (HPLC), i.e. methanol/water (50:50; 2 mM ammonium acetate). The extract was filtered and directly injected into a HPLC/time-of-flight mass spectrometry (TOF-MS) system. Quantification was performed using 7H-perfluoroheptanoic acid as internal standard and a calibration standard solution dissolved in sample extract for each matrix type (matrix-matched calibration standard). The method is very time and cost efficient. Except for long-chain compounds and perfluorooctane sulfonamide (which cannot be covered by this method), recoveries were between 60% and 115% and method detection limits were in the range 0.04-1.3 ng/g wet weight. Blank values could be neglected with the exception of perfluorooctane sulfonate (PFOS), perfluorohexanoic acid (PFHxA) and perfluorooctanoic acid (PFOA). One of the major challenges in PFAS analysis is ionisation disturbance by co-eluting matrix in the ion source of the mass spectrometer. Both matrix and analyte specific signal enhancement and suppression was observed and quantified. Repeated extractions (n = 3) gave relative standard deviations (RSD) <35% for all PFAS. Accuracy was examined by comparing the screening method to the generally applied ion pair extraction (IPE) method. PFAS concentration values of a glaucous gull liver sample deviated by less than 30% for the two methods, provided that matrix-matched calibration standards were employed in both methods.

Bioavailability of hexabromocyclododecane to the polychaete Hediste diversicolor: exposure through sediment and food from a contaminated fjord.

Knowledge of the bioavailability of brominated flame retardants for sediment-dwelling organisms is limited. The present study investigated bioaccumulation of hexabromocyclododecane (HBCD) in the ragworm Hediste diversicolor exposed to field-contaminated sediments and food. Sediments and blue mussels (Mytilus edulis) were sampled from a fjord on the Norwegian west coast known to be highly contaminated with the brominated flame retardant HBCD. During a four-week experiment, ragworms were either exposed to sediment containing moderate or high concentrations of HBCD, or they were fed contaminated soft tissue from mussel. Although mean sediment concentrations were as high as 40 microg/g dry weight in the contaminated sediments, no HBCD were detected in the exposed ragworms (detection limit up to 2.0 ng/g wet wt). In contrast, the exposure to contaminated food (mussel) resulted in elevated body concentrations of 9.1 ng HBCD/g wet weight. The partitioning of HBCD in the test-sediments appeared to be influenced by the quantity and quality of the sediment organic matter (up to 15% total organic carbon). The presence of small plastic beads (<2 mm), which were shown to contain a mean of 50 microg/g dry weight of HBCD, could explain the low bioavailability of the flame retardant in the sediment. Hexabromocyclododecane in food appeared to be readily assimilated in the ragworm, however, and the diastereomer pattern indicated a relative increase of alpha-HBCD from mussel to ragworm. Hence, in the sampled areas of the fjord, trophic transfer appeared to be a more important mechanism for the entry of HBCD into the local benthic food web than sediment-to-biota accumulation.

Diastereomer-specific bioaccumulation of hexabromocyclododecane (HBCD) in a coastal food web, Western Norway.

The present study reports diastereomer-specific accumulation of HBCD from a point source in five marine species representing a typical food web in a Norwegian coastal area. Samples of mussels, polychaetes, crabs and seabird eggs were analyzed for the diastereomers α-, ß- and γ-HBCD, as well as lipid content and stable isotopes of nitrogen ((15)N/(14)N) to estimate trophic level. Accumulated HBCD did not correlate well with lipid content for most of the species, thus wet-weight based concentrations were included in an assessment of biomagnification. In contrast to ß- and γ-HBCD, the α-diastereomer increased significantly with trophic level, resulting in magnification factors >1 in this coastal marine ecosystem. Data for poikilotherms did not show the same positive correlation between the α-diastereomer and trophic position as homeotherms. The apparent biomagnification of the α-HBCD could be due to bioisomerization or diastereomer-specific elimination that differed between poikilotherms and homeotherms.

Relevance of 1,2,5,6,9,10-hexabromocyclododecane diastereomer structure on partitioning properties, column-retention and clean-up procedures.

To optimize clean-up procedures for the analysis of alpha-, beta-, and gamma-hexabromocyclododecanes (HBCD) in environmental and biological extracts, their retention behavior on silica gel and florisil was investigated using diverse mobile-phase solvents and accounting for matrix effects. The beta-diastereomer, relative to the alpha- and gamma-diastereomers, is substantially retained on both florisil and silica gel regardless of the solvent used. The beta-diastereomer is therefore prone to undergo selective loss during clean-up. This sequence is counterintuitive to sequences based on reverse-phase chromatography with a C18-column, in which the alpha- (and not the beta-) isomer is eluted first when using a polar solvent. There has been some discrepancy regarding the structures of these diastereomers in the literature, with structures based on X-ray crystallography only becoming recently available. Based on these X-ray crystal structures, physical-chemical properties (the octanol-water partitioning constant, the Henry's law constant, subcooled liquid vapour pressures and subcooled liquid water solubilities) of the HBCD diastereomers were estimated using the quantum-chemistry based software COSMOtherm, and were found to differ from previously calculated values using different structures (e.g. log K(aw) for alpha-, beta-, and gamma-HBCD are here estimated to be -8.3, -9.3 and -8.2 respectively). Hypothesis relating differences in structure to physical-chemical properties and retention sequences are presented. The extra retention of the beta-diastereomer on silica gel and florisil is likely because it can form both greater specific (i.e. polar) and non-specific (i.e. non-polar) interactions with surfaces than the other diastereomers. Non-specific interactions can also account for the counter-intuitive elution orders with C(18)-reverse-phase chromatography. These results indicate that care should be taken when isolating HBCDs and other molecular diastereomers from environmental and biological samples, and that reported concentrations of beta-HBCD in the literature may be negatively biased.

Spatial diastereomer patterns of hexabromocyclododecane (HBCD) in a Norwegian fjord.

Hexabromocyclododecane (HBCD) is the third most used brominated flame retardant globally, and has been found widely distributed in the environment. The present study reports concentrations and spatial patterns of alpha, beta and gamma-HBCD in a contaminated Norwegian fjord. Intertidal surface sediment and selected species from the marine food web were sampled at five locations in increasing distance from a known point source of HBCD. All sediment and biota samples were analyzed for the three HBCD diastereomers by liquid chromatography and mass spectrometry (LC/MS). The results demonstrated a HBCD gradient with decreasing concentrations at increasing distance from the point source in sediment and sedentary species, but less so in the species with large feeding ranges. Mean concentrations of Sigma HBCD at the closest/most remote locations relative to the point source were 9000/300 ng g(-1) TOC in sediment and 150/90 ng g(-1) lw in the species with largest feeding range (great black-backed gull). The HBCD diastereomer patterns were similar for each of the matrices (sediment, organisms) independent of distance from the source, indicating no difference in environmental partitioning between the diastereomers. However, the concentration ratio of diastereomers in each matrix ranged from 3:1:10 (alpha:beta:gamma) in the sediments to 55:1 (alpha:gamma) in the highest trophic level species, suggesting diastereomer-specific bioaccumulation in the organisms.

Accumulation and disposition of hexabromocyclododecane (HBCD) in juvenile rainbow trout (Oncorhynchus mykiss).

The brominated flame retardant hexabromocyclododecane (HBCD) has been reported in environmental samples worldwide. The three diastereomers, alpha-, beta- and gamma-HBCD, behave differently in aquatic food webs; likely depending on different factors influencing assimilation efficiency and metabolism. In the present study, two oral exposure experiments with rainbow trout were performed to assess the role of selective uptake on diastereomer-specific accumulation and disposition of HBCD to liver, brain and muscle. In both experiments, juvenile rainbow trout (Oncorhynchus mykiss) were administrated a technical HBCD-mixture in commercial feed (10mgkg(-1)), followed by up to 21 days of food deprivation. Already 6h after exposure, the HBCD accumulation was significant, and the concentrations peaked 4-8 days after the exposure. The relative change in HBCD pattern during the accumulation process (0-8 days), suggested that there was a diastereomer-selective uptake of alpha- and beta-HBCD in the rainbow trout. During the initial 48h, considerable amounts of all three diastereomers were distributed to liver, brain and muscle. A 70% reduction in SigmaHBCD levels after 21 days, indicated elimination of HBCD from brain and liver, but no clear elimination from the muscle was observed. Differences in HBCD pattern between organs at the end of the experiment support a proposal of an organ-specific diastereomer accumulation.

Perfluorinated alkyl substances in plasma, liver, brain, and eggs of glaucous gulls (Larus hyperboreus) from the Norwegian arctic.

Recent environmental surveys have ascertained the widespread occurrence of perfluorinated alkyl substances (PFAS) in tissues of wildlife from the Arctic. In the present study, we investigated the distribution of a suite of PFAS in plasma, liver, brain, and egg samples from adult glaucous gulls (Larus hyperboreus), an apex scavenger-predator seabird breeding in the Norwegian Arctic. Perfluorooctane sulfonate (PFOS) was the predominant PFAS in all samples and was present at concentrations that are the highest reported thus far in any arctic seabird species and populations. Among the body compartment/ tissue samples analyzed, PFOS was highest in plasma (48.1-349 ng/g wet weight (ww)), followed by liver approximately equal to egg > brain. Perfluorocarboxylic acids (PFCAs) with 8-15 carbon (C) atoms were found, with the highest concentrations determined in plasma (sum PFCA: 41.8-262 ng/g ww), whereas 5C- and 6C-PFCAs were below the limits of detection. Perfluorobutane sulfonate, perfluorooctane sulfonamide, and four saturated (8:2 FTCA and 10:2 FTCA) and unsaturated (8:2 FTUCA and 10:2 FTUCA) fluorotelomer carboxylic acids were not detected in any samples. Perfluorohexane sulfonate was measured at concentrations up to 2.71 ng/g ww. The accumulation profiles of PFCAs were characterized by high proportions of the long and odd-numbered carbon-chain-length compounds, namely perfluoroundecanoic (11C) and perfluorotridecanoic acid (13C), although their individual contribution differed between the matrixes analyzed. Current PFAS concentrations suggest a bioaccumulation potential in Norwegian arctic glaucous gulls that needs to be assessed as part of a broad organohalogen contaminant cocktail with potential for mediating biological processes in this vulnerable top-predator marine species.