Polyfluorinated substances in abiotic standard reference materials.

The National Institute of Standards and Technology (NIST) has a wide range of Standard Reference Materials (SRMs) which have values assigned for legacy organic pollutants and toxic elements. Existing SRMs serve as homogenous materials that can be used for method development, method validation, and measurement for contaminants that are now of concern. NIST and multiple groups have been measuring the mass fraction of a group of emerging contaminants, polyfluorinated substances (PFASs), in a variety of SRMs. Here we report levels determined in an interlaboratory comparison of up to 23 PFASs determined in five SRMs: sediment (SRMs 1941b and 1944), house dust (SRM 2585), soil (SRM 2586), and sludge (SRM 2781). Measurements presented show an array of PFASs, with perfluorooctane sulfonate being the most frequently detected. SRMs 1941b, 1944, and 2586 had relatively low concentrations of most PFASs measured while 23 PFASs were at detectable levels in SRM 2585 and most of the PFASs measured were at detectable levels in SRM 2781. The measurements made in this study were used to add values to the Certificates of Analysis for SRMs 2585 and 2781.

Determination of perfluorinated alkyl acid concentrations in biological standard reference materials.

Standard reference materials (SRMs) are homogeneous, well-characterized materials used to validate measurements and improve the quality of analytical data. The National Institute of Standards and Technology (NIST) has a wide range of SRMs that have mass fraction values assigned for legacy pollutants. These SRMs can also serve as test materials for method development, method validation, and measurement for contaminants of emerging concern. Because inter-laboratory comparison studies have revealed substantial variability of measurements of perfluoroalkyl acids (PFAAs), future analytical measurements will benefit from determination of consensus values for PFAAs in SRMs to provide a means to demonstrate method-specific performance. To that end, NIST, in collaboration with other groups, has been measuring concentrations of PFAAs in a variety of SRMs. Here we report levels of PFAAs and perfluorooctane sulfonamide (PFOSA) determined in four biological SRMs: fish tissue (SRM 1946 Lake Superior Fish Tissue, SRM 1947 Lake Michigan Fish Tissue), bovine liver (SRM 1577c), and mussel tissue (SRM 2974a). We also report concentrations for three in-house quality-control materials: beluga whale liver, pygmy sperm whale liver, and white-sided dolphin liver. Measurements in SRMs show an array of PFAAs, with perfluorooctane sulfonate (PFOS) being the most frequently detected. Reference and information values are reported for PFAAs measured in these biological SRMs.

Polluted porpoises: Generational transfer of organic contaminants in harbour porpoises from the southern North Sea.

Persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs) and hexachlorobenzene (HCB), bioaccumulate in marine ecosystems. Top predators contain high levels of POPs in their lipid-rich tissues, which may result in adverse effects on their reproductive, immune and endocrine functions. Harbour porpoises (Phocoena phocoena) are among the smallest of cetaceans and live under high metabolic demand, making them particularly vulnerable to environmental pressures. Using samples from individuals of all maturity classes and sexes stranded along the southern North Sea (n = 121), we show the generational transfer of PCBs, PBDEs and HCB from adults to foetuses. Porpoise placentas contained 1.3-8.2 mg/kg lipid weight (lw) Sum-17PCB, 9 mg/kg lw). This was particularly true for adult males (92.3% >9 mg/kg lw), while adult females had relatively low PCB levels (10.5% >9 mg/kg lw) due to offloading. Nutritional stress led to higher offloading in the milk, causing a greater potential for toxicity in calves of nutritionally stressed females. No correlation between PCB concentration and parasite infestation was detected, although the probability of a porpoise dying due to infectious disease or debilitation increased with increasing PCB concentrations. Despite current regulations to reduce pollution, these results provide further evidence of potential health effects of POPs on harbour porpoises of the southern North Sea, which may consequently increase their susceptibility to other pressures.

The toxic exposure of flamingos to per- and Polyfluoroalkyl substances (PFAS) from firefighting foam applications in Bonaire.

In 2010 an oil terminal next to nature reservation Saliña Goto (Bonaire) caught fire. Firefighting resulted in elevated per- and polyfluoroalkyl substances (PFAS) concentrations in the salt lake. Within months flamingo abundance in Goto dropped to near complete absence. After statistical analysis, rainfall was deemed an unlikely cause for this decline. Toxicological effects on abundance of prey are likely the main cause for the flamingo absence. This reduced PFAS exposure via food and thus risk towards flamingos during the first years after the fires. Although the sediment is still polluted with persistent PFAS, flamingos returned, and started to feed on organisms with PFAS levels that exceed safety thresholds, placing the birds and other wildlife at risk. Monitoring bird populations is advised to assess potential toxic effects on birds and their offspring. This case suggests that applying persistent chemicals to reduce incident impacts may be more harmful than the incident itself.

Preliminary assessment on the bioaccessibility of contaminants of emerging concern in raw and cooked seafood.

A preliminary assessment of the bioaccessibility of contaminants of emerging concern (CeCs), including perfluorinated compounds (PFCs; i.e. PFOS and PFUnA), brominated flame retardants (BFRs; i.e. BDE47, BDE100, α-HBCD) and pharmaceuticals and personal care products (PPCPs; i.e. venlafaxine, methylparaben and UV-filter OC) was performed in seafood species available in the European markets. Additionally, the effect of steaming on CeCs bioaccessibility was also investigated for the first time. Overall, steaming affected differentially contaminants' concentrations, for instance, decreasing PFOS levels in flounder, but increasing both BDE47 and BDE100. CeCs bioaccessibility varied according to seafood species and contaminant group, i.e. in general, lower bioaccessibility values were obtained for PBDEs (<70%, except for mackerel), while PFCs and PPCPs revealed higher bioaccessibility percentages (between 71 and 95%). The lowest bioaccessibility value was obtained for α-HBCD (mussel; 14%), whereas the highest percentage was observed in venlafaxine (mullet; 95%). Our preliminary study reports also, for the first time, the effects of steaming on CeCs bioaccessibility. In most cases, bioaccessibility was not affected by cooking, however, a decrease was observed in PBDEs and venlafaxine bioaccessibility in steamed mussels and mullet, respectively, thus lowering the potential health risks associated with seafood consumption.

Partitioning of perfluorooctanesulfonate and perfluorohexanesulfonate in the aquatic environment after an accidental release of aqueous film forming foam at Schiphol Amsterdam Airport.

In summer 2008, an accidental release of aqueous film forming foam (AFFF) took place at Schiphol Amsterdam Airport (The Netherlands). After the release, water, fish, and sediment samples were collected and analyzed for perfluoroalkyl sulfonates (PFSAs). In situ perfluorooctane sulfonate (PFOS) sediment-water distribution factor (KD ) values, bioaccumulation factor (BAF) values, and biota-sediment accumulation factor (BSAF) values showed a remarkable agreement among reference and impacted sites, 10 wk after the incident as well as after 3 yr.