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The escalating concern of perfluoroalkyl and polyfluoroalkyl substances (PFAS), particularly at contaminated sites, has prompted extensive investigations. In this study, samples of multimedia including air, rhizosphere soil, and tissues of wheat at various growing stages were collected near a mega fluorochemical industrial park in China. Perfluorooctanoic acid (PFOA) was predominant in both air and soil with a strong correlation, highlighting air deposition as an important source in the terrestrial system. PFAS concentrations in wheat decreased in the stem and ear but increased in the leaves as wheat matured. Specifically, perfluorobutanoic acid (PFBA) dominated in the aboveground tissues in the full-life-cycle, except that PFOA surpassed and became predominant in leaves during the filling and maturing stages, hinting at an airborne source. For all PFAS, both bioaccumulation factors and translocation factors (TFs) were inversely correlated with the carbon chain length during the full-life-cycle. The obtained TF values were considerably higher than those obtained from ambient sites reported previously, further suggesting an unneglectable foliar uptake from air, which was estimated to be 25% for PFOA. Moreover, spray irrigation remarkably enhanced the absorption of PFAS in wheat via foliar uptake relative to flood irrigation. The estimated daily intake of PFBA via wheat consumption and air inhalation was 0.50 μg/kg/day for local residents, at least one magnitude higher than the corresponding threshold, suggesting an alarmingly high exposure risk.

Globally, perfluoroalkyl acids (PFAA) are ubiquitous due to their almost unlimited applications in industry and households and are detected in a wide variety of matrices.Aquatic ecosystems are of particular importance due to the spread of PFAA via water fluxes. The majority of published studies describe PFAA concentrations in fish or aquatic mammals, but not the dependence of PFAA concentrations in tissues and organs in fish of different ages. Since this is very important for understanding the accumulation behavior of these substances our study systematically investigates the influence of age on the PFAA concentration in the tissues of 74 perches (Perca fluviatilis), a very popular edible fish. Fish are particularly suitable as indicators of PFAA contamination of water because of their uptake via water (gills and skin) and food (predominantly piscivorous diet). The mean total PFAA concentrations (as the sum of the individual concentrations of 11 compounds) were: 114 μg/kg (kidney), 112 μg/kg (heart), 79.9 μg/kg (liver), 78.4 μg/kg (spleen), 64.6 μg/kg (gills) and 21.7 μg/kg (muscle), with longer-chain compounds accounting for 90% of the substances. Perfluorooctanesulfoic acid (PFOS) accounted for the largest percentage of the total PFAA concentration in all tissues at 43-63%. With the exception of the heart and spleen, a significant increase in total concentrations was observed with increasing age of the perch. The strongest correlation was observed for the kidney, followed by the liver and gills. With regard to their consumption as human nutrition the tolerable weekly PFAA intake of 4.4 ng/kg bodyweight and week for the sum of the 4 EFSA PFAA in adults and children was exceeded many times over (860% and 1600% respectively) with an average fish consumption per week. The maximum PFAA levels set in the E.U. since January 2023 were exceeded five times., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Mangrove estuaries are an important land-sea transitional ecosystem that is currently under various pollution pressures, while there is a lack of research on per- and polyfluoroalkyl substances (PFAS) in the organisms of mangrove estuaries. In this study, we investigated the distribution and seasonal variation of PFAS in the tissues of organisms from a mangrove estuary. The PFAS concentrations in fish tissues varied from 0.45 ng/g ww to 17.67 ng/g ww and followed the order of viscera > head > carcass > muscle, with the highest tissue burden found in the fish carcass (39.59 ng). The log BAF values of PFDoDA, PFUnDA, and PFDA in the whole fish exceeded 3.70, indicating significant bioaccumulation. The trophic transfer of PFAS in the mangrove estuary food web showed a dilution effect, which was mainly influenced by the spatial heterogeneity of PFAS distribution in the estuarine environment, and demonstrated that the gradient dilution of PFAS in the estuary habitat environment can disguise the PFAS bio-magnification in estuarine organisms, and the larger the swimming ranges of organisms, the more pronounced the bio-dilution effect. The PFOA-equivalent HRs of category A and B fish were 3.48-5.17 and 2.59-4.01, respectively, indicating that mangrove estuarine residents had a high PFAS exposure risk through the intake of estuarine fish., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Legacy and emerging per- and polyfluoroalkyl substances (PFASs) were measured in livers of finless porpoises (Neophocaena asiaeorientalis; n = 167) collected in Korean waters from 2002 to 2015 to investigate their occurrence, bioaccumulation feature, temporal trends, and ecotoxicological implications. Perfulorooctane sulfonate (PFOS), perfluoroundecanoate (PFUnDA), and perfluorotridecanoate (PFTrDA) were the predominant PFASs found in the porpoises. The concentration of 6:2 chlorinated polyfluoroalkyl ether sulfonate (F-53B), an alternative to PFOS, was comparable to that of PFTrDA. Perfluorooctane sulfonamide (FOSA), a precursor of PFOS, was also detected in all the porpoises examined. All PFASs, including F-53B, accumulated to higher concentrations in immature porpoises compared with mature specimens, implying substantial maternal transfer and limited metabolizing capacity for PFASs. A significant correlation was observed between PFOS and F-53B concentrations, indicating similar bioaccumulation processes. Based on prenatal exposure and toxicity, F-53B is an emerging contaminant in marine ecosystems. Significantly increasing trends were observed in the concentrations of sulfonates, carboxylates, and F-53B between 2002/2003 and 2010, whereas the FOSA concentration significantly decreased. During 2010-2015, decreasing trends were observed in the concentrations of FOSA and sulfonates, whereas concentrations of carboxylate and F-53B increased without statistical significance, likely due to a gap for the implementation of regulatory actions between sulfonates and carboxylates. Although PFOS and PFOA were found to pose little health risk to porpoises, the combined toxicological effects of other contaminants should be considered to protect populations and to mitigate PFAS contamination in marine ecosystems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative, and toxic synthetic chemicals of concern, which have been detected in nearly all environmental compartments. The present study provides a data analysis on PFAS concentrations in the Dutch inland and coastal national waters and fish sampled from 2008 to 2022 and 2015 to 2022, respectively. Although the fish database is relatively small, the water database is unique because of its temporal dimension. It appears that PFAS are omnipresent in Dutch water and fish, with relatively small spatial differences in absolute and relative concentrations (fingerprints) and few obvious temporal trends. Only perfluorooctanoic acid and perfluorooctanesulfonic acid (PFOS) aqueous concentrations in the rivers Rhine and Scheldt have substantially decreased since 2012. Still, PFOS concentrations exceed the European water quality standards at all and fish standards at many locations. Masses of PFAS entering the country and the North Sea are roughly 3.5 tonnes/year. Generally, the data suggest that most PFAS enter the Dutch aquatic environment predominantly through diffuse sources, yet several major point sources of specific PFAS were identified using fingerprints and monthly concentration profiles as identification tools. Finally, combining concentrations in fish and water, 265 bioaccumulation factors were derived, showing no statistically significant differences between freshwater and marine fish. Overall, the analysis provides new insights into PFAS bioaccumulation and spatiotemporal trends, mass discharges, and sources in The Netherlands. Environ Toxicol Chem 2024;43:965-975. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., (© 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.)

There is an acute deficit of data on per- and polyfluoroalkyl substances (PFASs) and mercury (Hg) in the open waters of Lake Victoria, East Africa, relative to nearshore areas. We analyzed stable isotopes (δ 15 N and δ 13 C), PFASs and Hg in Nile Perch and Nile Tilapia muscle and liver samples from nearshore and open lake locations from the Ugandan part of the lake. The δ 15 N values of Nile Perch muscle indicated a higher trophic level for samples from the open lake than from nearshore locations. Averages of ∑PFAS concentrations in Nile Perch muscle and liver (0.44 and 1.75 ng/g ww, respectively) were significantly higher than in Nile Tilapia (0.24 and 0.50 ng/g ww, respectively). ∑PFAS concentrations in muscle of open lake Nile Perch were significantly higher than for nearshore samples. A similar observation was made for total mercury concentrations in muscle (THg _Muscle ) of Nile Perch. THg was dominated by methyl mercury (MeHg + , 22-124 ng/g ww) and mercuric mercury (Hg 2+ , + and some PFASs (e.g. PFOS: r = 0.704, P = 0.016) suggested similar exposure routes or factors. Estimated human daily intake values of PFOS from fish consumption were below international limits whereas for MeHg +, the US EPA reference dose was exceeded., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Contamination by per- and polyfluoroalkyl substances (PFASs) is of great concern in global environments. Due to strong regulation of legacy PFASs, emerging PFASs including alternatives and precursors have been introduced to the industrial market. In this study, legacy and emerging PFASs were measured in seawater, sediment, and bivalves collected along the Korean coast to investigate the occurrence, distribution, contamination sources, and bioaccumulation potential of PFASs. Wide concentration ranges of legacy PFASs were detected in multiple environmental samples, indicating widespread contamination. C8-based PFASs (e.g., PFOA and PFOS) were still major contaminants in all of the environmental samples. Some precursors, such as 8:2 fluorotelomer sulfonate (8:2 FTS) and N-ethyl-perfluorooctane sulfonamidoacetic acid (N-EtFOSAA), and perfluoro-2-propoxypropanoic potassium 9-chlorohexadecafluoro-3-oxanonane-1-sulfonate (F-53B), an alternative to PFOS, were detected in sediment or bivalve samples, implying a shift in consumption patterns from legacy to emerging PFASs. The highest concentrations of PFASs in environmental samples were found at the locations near industrial complexes, such as those for the semi-conductor, paper mill, automobile, and metal-plating industry. This result indicates that PFAS contamination is associated with intensive industrial activities in the coastal environment. Matrix-dependent contamination and profiles of PFASs were observed. Seawater was dominated by short-chained PFASs as a prompt reflection of regulation, while the sediment and bivalves were dominated by long-chained PFASs. Carbon-chain length was a major factor governing environmental behavior and bioaccumulation of PFASs. This was the first nation-wide survey on legacy and emerging PFASs in the coastal environment of Korea., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Information on the occurrence and trophodynamics of per- and polyfluoroalkyl substances (PFASs) in the Antarctic region is limited. We investigated the occurrence of PFASs in an ecosystem in the Fildes Peninsula at King George Island and Ardley Island, Antarctica. The profiles, spatial distribution, and trophic transfer behavior of PFASs were further studied. ∑PFASs ranged from 0.50 ± 38.0 ng/g dw (dry weight) in algae to 4.97 ± 1.17 ng/g dw in Neogastropoda (Ngas), which was lower than those in the low- and mid-latitude regions and even Arctic regions. Perfluorobutyric acid (PFBA) was predominant with detection frequencies above 50% in all types of samples, and the relative contribution of PFBA ranged from 22% to 57% in the biota samples. The biomagnification factors of PFBA, perfluoroheptanoate (PFHpA), perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS) between Archaeogastropoda (Agas) and Ngas were 0.67 ± 0.54, 0.77 ± 0.38, 1.04 ± 1.56, 3.30 ± 4.07, and 1.61 ± 0.89, respectively. The trophic magnification factors of PFHxS and PFOS were 2.09 and 2.92, respectively, which indicated that they could be biomagnified through the food chain. Considering the increasing production and uncertain toxicological risks of emerging PFASs and the sensitive ecosystems in Antarctic regions, more attention should be paid, especially for the short-chain ones in the Antarctic region., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The present work examined the trophic transfer of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in a typical urban river (Orge River, near Paris, France), and aimed to investigate the potential contribution of precursors to the biomagnification of perfluoroalkyl acids (PFAAs). Sixteen PFAAs, twelve of their precursors (pre-PFAAs targeted ) and two fluorinated alternatives to long-chain PFASs were analyzed in water, sediments and biota (including biofilm, invertebrates and fish). Twenty two compounds were detected in biological samples (2.0-147 ng g -1 wet weight), perfluorooctane sulfonate (PFOS) and C 12 -C 14 perfluoroalkyl carboxylates (PFCAs) being predominant while ∑pre-PFAAs targeted contributed to 1-18% of ∑PFASs. Trophic magnification factors (TMFs) were >1 (i.e. denoting biomagnification) for C 9 -C 14 PFCAs, C 7 -C 10 perfluoroalkyl sulfonates (PFSAs) and several pre-PFAAs (e.g. 8 : 2 and 10 : 2 fluorotelomer sulfonates). The significant decrease in ∑pre-PFCAs/∑PFCAs concentration ratio with trophic level suggested a likely contribution of selected precursors to the biomagnification of PFCAs through biotransformation, while this was less obvious for PFOS. The total oxidizable precursor assay, applied for the first time to sediment and biota, revealed the presence of substantial proportions of extractable unknown pre-PFAAs in all samples (i.e. 15-80% of ∑PFASs upon oxidation). This proportion significantly decreased from sediments to invertebrates and fish, thereby pointing to the biotransformation of unattributed pre-PFAAs in the trophic web, which likely contributes to the biomagnification of some PFAAs (i.e. C 9 -C 12 PFCAs and C 7 -C 10 PFSAs).

Major point sources of per- and polyfluoroalkyl substances (PFASs) cause ubiquitous spread of PFASs in the environment. In this study, surface water and aquatic invertebrates at three Swedish sites impacted by PFAS point sources were characterized, using homologue, isomer and extractable organofluorine (EOF) profiling as well as estimation of bioaccumulation factors (BAFs) and mass discharge. Two sites were impacted by fire training (sites A and R) and the third by industrial runoff (site K). Mean Σ 25 PFASs concentration in water was 1920 ng L -1 at site R (n = 3), which was more than 20- and 10-fold higher than those from sites A and K, respectively. PFOS was the most predominant PFAS in all waters samples, constituting 29-79% of Σ 25 PFAS concentrations. Several branched isomers were detected and they substantially contributed to concentrations in surface water (e.g. 49-78% of ΣPFOS) and aquatic invertebrates (e.g. 15-28% of ΣPFOS). BAFs in the aquatic invertebrates indicated higher bioaccumulation for long chain PFASs and lower bioaccumulation for branched PFOS isomers compared to linear PFOS. EOF mass balance showed that Σ 25 target PFASs in water could explain up to 55% of EOF at site R. However, larger proportions of EOF (>92%) remained unknown in water from sites A and K. Mass discharges were for the first time estimated for EOF and revealed that high amounts of EOF (e.g. 8.2 g F day -1 at site A) could be transported by water to recipient water bodies relative to Σ 25 PFASs (e.g. 0.15 g day -1 at site A). Overall, we showed that composition profiling, BAFs and EOF mass balance can improve the characterization of PFASs around point sources.

The concentrations of 17 perfluoroalkyl substances (PFASs) were investigated in paddy soil, void water, and brown rice collected from 30 paddy fields to examine the uptake of PFASs from soil by rice. The total concentrations of PFASs ranged from 7.76 to 3020 ng/L (average = 166 ng/L) in void water, 0.120 to 13.9 ng/g dry-weight (dw) (1.92 ng/g dw) in paddy soils, and from not-detected to 1.85 ng/g (0.403 ng/g) in brown rice samples. The highest PFAS concentrations were observed in brown rice cultivated in a paddy field where high levels of PFASs were observed in void water and paddy soil. Among target PFAS compounds, perfluorocarboxylic acids were dominant and detected in all matrices, and perfluorooctanoic acid (PFOA) was the most predominant compound in brown rice and void water. Significant positive correlations were examined for some detected PFASs between each matrix. PFOA in brown rice was positively correlated with PFOA in void water as well as perfluorodecanoic acid (PFDA) in paddy soil (p < 0.01). PFOA in void water also had correlated with PFDA in paddy soil. However, there was no correlation of other compounds between each matrix, except for correlations of perfluorononanoic acid (PFNA) and PFDA in paddy soil with those in void water, respectively (p < 0.05). Moreover, PFOA concentration in brown rice (0.093 ng/g) was much higher than one in white rice detected with a non-detectable level., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Eggs of snow buntings (Plectrophenax nivealis) were applied as a bio-indicator to examine differences in exposure to legacy persistent organic pollutants (POPs) and perflouroalkyl subtances (PFAS) from the terrestrial environment surrounding the settlements of Longyearbyen, Barentsburg and Pyramiden on Svalbard, Norway. Significantly higher concentrations of summed polychlorinated biphenyls (sumPCB7) in eggs collected from Barentsburg (2980 ng/g lipid weight (lw)) and Pyramiden (3860 ng/g lw) compared to Longyearbyen (96 ng/g lw) are attributed to local sources of PCBs within these settlements. Similar findings were observed for p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) where higher median concentrations observed in Pyramiden (173 ng/g lw) and Barentsburg (75 ng/g lw) compared to Longyearbyen (48 ng/g lw) may be influenced by guano inputs from breeding seabird populations, although other point sources cannot be ruled out. Concentrations of perfluorooctane sulphonate (PFOS) and several perfluorinated carboxylic acids (PFCAs) in snow bunting eggs were found to be statistically higher in the populated settlements of Longyearbyen and Barentsburg compared to the abandoned Pyramiden. Narrow foraging ranges of snow buntings during breeding season was useful in assessing point sources of exposure for PCBs and PFAS at particular sites with extreme differences observed between nest locations. SumPCB7 concentrations ranged from 2 μg/g ww to below detection limits between nest sites located less than a kilometer from each other in Pyramiden. Similar findings were observed in Longyearbyen, where several PFCAs ranged from 2 to 55 times higher between nest sites with similar spatial distances. These findings indicate that snow buntings can be a useful bio-indicator offering high spatial resolution for contaminant source apportionment in terrestrial environments on Svalbard., (Copyright © 2019 Elsevier B.V. All rights reserved.)

PFAAs have emerged as persistent organic pollutants (POPs) in a variety of environmental matrixes and biota, posing potential hazards for wildlife and humans. Diet has been considered as an important source for human exposure to PFAAs and seafood accounts for a relatively large proportion in human diets, especially for coastal residents. In an effort to clarify the impact of PFAAs in seafood on human health, 17 PFAAs were determined in 42 pooled seafood samples (14 species) from the Yellow Sea areas, China. The concentrations of total PFAAs (sum of 17 PFAAs, ∑PFAAs) were in the range of 1.10-1067 ng/g dry weight (dw), with the highest concentration found in swimming crab (Portunus trituberculatus) and the lowest in silvery pomfret (Pampus argenteus). Concentrations and composition profiles of PFAAs varied significantly among different species, suggesting that bioaccumulation potential of PFAAs differed from species to species. The distinct spatial distribution of PFAAs in four categories of seafood could be mainly attributed to the contamination patterns of PFAAs in three nearby cities. PFBA was presented as the most abundant PFAA in this study, which was different from the findings in many other studies where PFOS was the predominant compound. Furthermore, the human health risk assessment suggested that a comprehensive action plan is needed to protect people from high exposure to PFAAs through seafood consumption., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The bioavailability and bioaccumulation of sedimentary hydrophobic organic compounds (HOCs) is of concern at contaminated sites. Passive samplers have emerged as a promising tool to measure the bioavailability of sedimentary HOCs and possibly to estimate their bioaccumulation. We thus analyzed HOCs including organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) in sediment, porewater, and river water using low-density polyethylene passive samplers and in 11 different finfish species and blue crab from the lower Passaic River. In addition, perfluorinated alkyl acids (PFAAs) were measured in grab water samples, sediment, and fish. Best predictors of bioaccumulation in biota were either porewater concentrations (for PCBs and OCPs) or sediment organic carbon (PBDEs and PFAAs), including black carbon (OCPs, PCBs, and some PCDD/F congeners)-normalized concentrations. Measured lipid-based concentrations of the majority of HOCs exceeded the chemicals' activities in porewater by at least 2-fold, suggesting dietary uptake. Trophic magnification factors were >1 for moderately hydrophobic analytes (log octanol-water partitioning coefficient [K OW ] = 6.5-8.2) with low metabolic transformation rates (<0.01 d -1 ), including longer alkyl chain PFAAs. For analytes with lower (4.5-6.5) and higher (>8.2) K OW s, metabolic transformation was more important in reducing trophic magnification. Environ Toxicol Chem 2019;38:872-882. © 2019 SETAC., (© 2019 SETAC.)

We investigated the profiles and levels of perfluoroalkyl carboxylic acid (PFCA) contamination in Pacific cod (Gadus macrocephalus) from the North Pacific Ocean. The mean concentrations of PFCAs containing 8 to 14 carbon atoms (C8-C14) in edible Pacific cod muscle ranged from 216 to 670 pg g -1 wet weight in the Northeast Pacific Ocean (Seattle, Vancouver, Alaska, and Russia), from 819 to 1710 pg g -1 wet weight in Japanese coastal waters (Hokkaido, Aomori, Iwate, Miyagi, Tottori, and Shimane), and from 288 to 892 pg g -1 wet weight in Korean waters (Sokcho, Busan, and Yeosu). These results indicate there are geographical differences in the distribution of PFCAs. The long-chain PFCAs (C9-C14) contributed 96% of the total PFCA concentration across Japan, whereas they contributed only 33% of the total PFCA concentration in the USA and Canada. Long-chain PFCA concentrations in cod samples collected in Japanese and Korean waters were about three to four times those in samples from the USA, Canada, and Russia. Because seafood is considered an important dietary source of PFCAs, high concentrations of long-chain PFCAs in Pacific cod from Japanese and Korean waters may affect human dietary exposure and blood concentrations of long-chain PFCAs., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

As a result of their ubiquitous presence in the environment perfluoroalkyl acids (PFAAs) have been demonstrated in numerous organisms worldwide, in particular in those of higher trophic levels. The fact that PFAAs have been detected in various human matrices, together with the resultant potential human health risks, knowledge of possible paths of entry and distribution in various ecosystems, is of great importance. In this context pooled samples of terrestrial ecosystems - roe deer liver (n = 141), earthworms (n = 44) as well as leaves from beech and poplar trees (n = 70) - from the year 1989-2015 were obtained from the German Environmental Specimen Bank and examined for the presence of 11 PFAAs for the first time. In addition to determining individual and total PFAA concentrations, temporal trends have been deduced in order to determine the effectiveness of regulatory measures. The highest total mean concentration of PFAAs (sum of the concentrations of the 11 analytes) were 9.9 μg/kg in the roe deer liver samples, followed by earthworm samples with a mean PFAA concentration of 3.5 μg/kg and leaves with a mean total concentration of 2.5 μg/kg. In regard to temporal trends there was a significant reduction of concentrations for perfluorooctane sulfonate, perfluorooctanoic acid, perfluorononanoic acid and perfluorodecanoic acid in roe deer liver from 2003 to 2015, an indication of the effectiveness of regulatory measures. The same is true for the perfluorooctane sulfonate concentrations in earthworms and for perfluorooctanoic acid concentrations in the leaves. In contrast, an increase in perfluorobutanoic acid concentrations was observed from 2003 to 2015 in all three matrices. In summary it must be noted that in spite of the discernible effectiveness of minimization strategies, PFAAs are still detectable in terrestrial matrices and concentrations of other PFAAs as perfluorobutanoic acid appear to be increasing., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Although bird eggs have been used in biomonitoring studies on perfluoroalkyl acids (PFAAs), effects of environmental concentrations on reproduction remain largely unknown in wild birds. In the present study we examined the associations between the concentrations of 4 perfluoroalkyl sulfonic acids (PFSAs) and 11 perfluoroalkyl carboxylic acids (PFCAs) in the eggs of great tits (Parus major), collected along a distance gradient from a pollution source, and multiple reproductive parameters (including the start of egg laying, clutch size, hatching success, fledging success and total breeding success) along with egg shell thickness and body condition of the nestlings. The PFAA concentrations measured at the plant site were among the highest ever reported in wild bird eggs. PFAA concentrations decreased sharply with increasing distance (0-11 km) from the plant, but remained relatively elevated in the adjacent sites. PFAAs were grouped into principal components (PCs) to prevent collinearity. High concentrations of PFOS, PFDS, PFDoDA, PFTrDA and PFTeDA (grouped as PC1) were associated with a reduced hatching success of nests where at least one egg hatched, thinner egg shells and increased survival of the hatched chicks. High concentrations of PFDA (PC2) were associated with a reduced hatching success, especially in nests where no eggs hatched, an earlier start of egg laying and a reduction of total breeding success, mainly caused by the failure in hatching. Although the major manufacturer of PFAAs phased out the production of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and related products in 2002, concentrations appear to have increased since previous measurements. Surprisingly, despite the very high concentrations close to the fluorochemical plant, there was no clear evidence for reproductive impairment as the observed associations between PFAA concentrations and reproductive parameters were rather limited compared to previous studies in songbirds. These findings also suggest potential differences in sensitivity between species. CAPSULE: Despite the very high PFAA concentrations at the perfluorochemical hotspot, correlations with reproductive parameters were limited., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A field study was conducted to elucidate distribution and partitioning of perfluoroalkyl carboxylic acids (PFCAs; C7-12) in a terrestrial ecosystem that was contaminated with industrial sources of release. Surface soil (0-6 cm), plants, and earthworms were collected from a field located within a 1-mile radius of a fluoropolymer industry that had been manufacturing fluorochemicals for over five decades. The mean concentrations of ∑PFCAs were 150, 420, 61, 68, and 430 ng/g dry weight (dw) in surface soil, earthworms, grass roots, grass leaves, and tree leaves, respectively. The measured concentrations were higher than those reported for corresponding matrices in other locations worldwide, suggesting that fluorochemical manufacturing operations have contributed to the contamination of this nearby land. Soil and plant tissues consisted mainly of perfluorooctanoic acid (PFOA; C8) (77.3-97.1% of the total PFCAs), whereas longer-chain PFCAs, such as perfluoroundecanoic acid (PFUnDA; C11: 17.6%) and perfluorododecanoic acid (PFDoDA; C12: 31.9%), accounted for relatively higher proportions in earthworms. Spatial distribution of PFCAs at this site suggested that both atmospheric deposition and groundwater recharge have contributed to the sources of contamination. Both earthworm- and grass-accumulated PFCAs from soil with biota-soil accumulation factors and root concentration factors increased with perfluorocarbon chain length. The translocation factors of PFCAs in grass decreased as the number of carbons in the fluorocarbon moiety increased. This field study is appropriate to improve our understanding of partitioning of PFCAs among soil, plants, and earthworms., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In birds, incubation-related behaviors and brood patch formation are influenced by hormonal regulation such as prolactin secretion. Brood patch provides efficient heat transfer between the incubating parent and the developing embryo in the egg. Importantly, several environmental contaminants are already known to have adverse effects on avian reproduction. However, relatively little is known about the effect of contaminants on incubation temperature (T inc ) in wild birds. By using temperature thermistors placed into artificial eggs, we investigated whether the most contaminated parent birds are less able to provide appropriate egg warming and thus less committed to incubating their clutch. Specifically, we investigated the relationships among 3 groups of contaminants (organochlorines, perfluoroalkyl substances [PFASs], and mercury [Hg]) with T inc and also with prolactin concentrations and brood patch size in incubating Arctic black-legged kittiwakes (Rissa tridactyla). Our results reveal that among the organochlorines considered, only blood levels of oxychlordane, the main metabolite of chlordane, a banned pesticide, were negatively related to the minimum incubation temperature in male kittiwakes. Levels of PFASs and Hg were unrelated to T inc in kittiwakes. Moreover, our study suggests a possible underlying mechanism: since we reported a significant and negative association between blood oxychlordane concentrations and the size of the brood patch in males. Finally, this reduced T inc in the most oxychlordane-contaminated kittiwakes was associated with a lower egg hatching probability. Environ Toxicol Chem 2018;37:2881-2894. © 2018 SETAC., (© 2018 SETAC.)

Non-invasive samples present ethical and practical benefits for investigating human exposure to hazardous contaminants, but analytical challenges and difficulties to interpret the results limit their application in biomonitoring. Here we investigated the potential for using hair, nail and urine samples as a measure of internal exposure to an array of legacy and emerging per- and polyfluoroalkyl substances (PFASs) in two populations with different exposure conditions. Paired urine-serum measurements of PFASs from a group of highly exposed fishery employees displayed strong correlations for PFASs with three to eight perfluorinated carbons (ρ > 0.653; p < 0.01). Consistent statistical correlations and transfer ratios in nails and hair from both populations demonstrated that these non-invasive samples can be used as a measure of internal exposure to perfluorooctane sulfonic acid and C8 chlorinated polyfluoralkyl ether sulfonic acid (C8 Cl-PFESA). Contrastingly, the infrequent detections and/or lack of consistent transfer ratios for perfluorooctanoic acid, perfluorononanoic acid and short-chain PFASs in hair and nail samples indicate passive uptake from the external environment rather than uptake and internal distribution. Collectively, the study supports the use of urine samples as a valid measure of internal exposure for a range of short- and medium-chain PFASs, while the validity of nail and hair samples as a measure of internal exposure may vary for different PFASs and populations. The ubiquitous detection of C8 Cl-PFESA in all sample matrices from both populations indicates widespread exposure to this contaminant of emerging concern in China., (Copyright © 2018 Elsevier B.V. All rights reserved.)

To evaluate the bioaccumulation potential of perfluoroalkyl acids (PFAAs) in an aquatic food web, we measured the concentrations of nine PFAAs in the water and aquatic organisms from an estuary of the Omuta River, Japan. Average log bioaccumulation factors for all PFAAs ranged from 2.0 to 2.8. There was no positive correlation observed between PFAA carbon chain length and there was no evidence of trophic magnification demonstrated among the sample types collected. These results differed from the findings of previous studies in enclosed bodies of water, perhaps because river mouth-estuarine ecotones are more variable spatially and temporally and include some fish that are highly migratory. Further investigations of bioaccumulation factors will be needed to elucidate the tendency of amphiphilic chemicals to bioaccumulate in these river mouth-estuarine ecotones.

The contamination profiles of sixteen perfluoroalkyl substances (PFAS) were examined in coral reef fish samples collected from the South China Sea (SCS) where no information about this topic was available in the literature. The results revealed that six PFAS were found in coral reef fish samples from the SCS. Perfluorooctane sulfonate (PFOS) was the most predominant PFAS contaminant detected in most of the samples, with the highest concentration value of 27.05 ng/g wet weight (ww) observed in Cephalopholis urodelus. Perfluoroundecanoic acid (PFUnDA) and Perfluorotridecanoic acid (PFTrDA) were the second and third dominant PFAS, respectively. Mean PFOS concentrations in muscle of seven coral reef fish varied from 0.29 ng/g ww in Lethrinus olivaceus to 10.78 ng/g ww in Cephalopholis urodelus. No significant linear relationship was observed between PFOS levels and coral reef fish traits (length, weight) collected in this region. Average daily intake of PFOS for the seven coral reef fishes ranged from 0.79 ng/kg/d for Lethrinus olivaceus to 29.53 ng/kg/d for Cephalopholis urodelus. The hazard ratio (HR) values for human consumption of PFOS-contaminated coral reef fishes ranged from 0.04 to 1.48, with Cephalopholis urodelus having the highest HR value of 1.18 (higher than 1) among the species, indicating frequent consumption of Cephalopholis urodelus might pose potential health risk to local population. The present work have provided the first hand data of PFAS in coral reef fishes in the SCS and indirectly demonstrated the existence of low level PFAS pollution in the SCS in China., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Telomeres are non-coding DNA repeats located at the termini of eukaryotic chromosomes, regulated by dynamic processes balancing shortening and maintenance. Despite a mechanism to slow-down telomere shortening, cell division leads to progressive attrition of chromosomes, leading to the onset of cellular senescence or apoptosis. However, telomere restoration based on telomerase activity is the primary mechanism for telomere maintenance. Telomere length is associated to health and survival and can be impacted by a broad panel of environmental factors. However, the effect of contaminants on telomeres is poorly known for living organisms. The aim of this study was to investigate relationships between some poly- and perfluoroalkyl substances (PFASs), body condition and telomere length by using both a cross-sectional and longitudinal approach in adult breeding Black-legged kittiwakes (Rissa tridactyla) from Svalbard. First, we examined the associations between absolute telomere length and PFASs contamination in a given year (cross-sectional approach). Second, we investigated the relationships between telomere dynamics and PFASs contamination within a two years' time frame (longitudinal approach). Our results did not show any significant relationships of PFASs and body condition with absolute telomere length in a given year. Surprisingly, we found a positive and significant relationship between PFASs and telomere dynamics in both sexes with elongated telomere in birds bearing the highest concentrations of PFASs. Our study underlines (i) the need to investigate PFAS effects on telomere dynamics with a longitudinal approach and (ii) a potential positive effect of these contaminants on telomere length, with the most contaminated birds showing the slowest rate of telomere shortening or even displaying elongated ones. Our study is the first to report a relationship between PFASs and telomere length in free-living vertebrates. A possible underlying mechanism and other potential confounding factors are discussed., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Environmental contamination resulting from the production or release of harmful chemicals can lead to negative consequences for wildlife and human health. Perfluorinated alkyl acids (PFAAs) were historically produced as protective coatings for many household items and currently persist in the environment, wildlife, and humans. PFAAs have been linked to immune suppression, endocrine disruption, and developmental toxicity in wildlife and laboratory studies. This study examines the American alligator, Alligator mississippiensis, as an important indicator of ecosystem contamination and a potential pathway for PFAA exposure in humans. Alligator meat harvested in the 2015 South Carolina (SC) public hunt season and prepared for human consumption was collected and analyzed for PFAAs to determine meat concentrations and relationships with animal body size (total length), sex, and location of harvest. Of the 15 PFAAs analyzed, perfluorooctane sulfonate (PFOS) was found in all alligator meat samples and at the highest concentrations (median 6.73ng/g). No relationship was found between PFAA concentrations and total length or sex. Concentrations of one or all compounds varied significantly across sampling locations, with alligators harvested in the Middle Coastal hunt unit having the highest PFOS concentrations (median 16.0ng/g; p=0.0001). Alligators harvested specifically from Berkley County, SC (located in the Middle Coastal hunt unit) had the highest PFOS concentrations and the greatest number of PFAAs detected (p<0.0001). The site-specific nature of PFAA concentrations in alligator meat observed in this study suggests a source of PFAA contamination in Berkley County, SC., (Copyright © 2017. Published by Elsevier B.V.)

This study examined concentrations of 15 perfluoroalkyl acids (PFAAs) in tissues from male Mozambique tilapia (Oreochromis mossambicus) collected at Loskop Dam, Mpumalanga, South Africa in 2014 and 2016. Nine of the 15 PFAAs were detected frequently and were included in statistical analysis and included two of the most commonly known PFAAs, perfluorooctanesulfonic acid (PFOS) (median, 41.6ng/g) and perfluorooctanoic acid (PFOA) (median, 0.0825ng/g). Of the tissues measured, plasma (2016 and 2014 median, 22.2ng/g) contained the highest PFAA burden followed by (in descending order): liver (median, 11.6ng/g), kidney (median, 9.04ng/g), spleen (median, 5.92ng/g), adipose (median, 2.54ng/g), and muscle (median, 1.11ng/g). Loskop Dam tilapia have been affected by an inflammatory disease of the adipose tissue known as pansteatitis, so this study also aimed to investigate relationships between PFAA tissue concentrations and incidence of pansteatitis or fish health status. Results revealed that healthy tilapia exhibited an overall higher (p-value<0.05) PFAA burden than pansteatitis-affected tilapia across all tissues. Further analysis showed that organs previously noted in the literature to contain the highest PFAA concentrations, such as kidney, liver, and plasma, were the organs driving the difference in PFAA burden between the two tilapia groups. Care must be taken in the interpretations we draw from not only the results of our study, but also other PFAA measurements made on populations (human and wildlife alike) under differing health status., (Copyright © 2017. Published by Elsevier B.V.)

Concentrations of perfluorooctane sulfonate (PFOS) in San Francisco Bay (SF Bay) wildlife have historically been among the highest reported globally. To track continuing exposures to PFASs and assess the impact of the 2002 phase-out of production of PFOS and related chemicals in the US, nine perfluoroalkyl carboxylic acids (PFCAs; C4-C12), three perfluoroalkyl sulfonic acids (PFSAs; C4, C6, C8) and perfluorooctane sulfonamide (PFOSA, a PFOS precursor) were measured in SF Bay cormorant eggs in 2012 and harbor seal serum sampled between 2009 and 2014. PFOS remained the dominant perfluoroalkyl acid (PFAA) in both cormorant eggs (36.1-466 ng/g) and seals (12.6-796 ng/g) from 2012 and 2014, respectively. Concentrations in seal and bird eggs from the South Bay have declined approximately 70% in both matrices. To elucidate potential pathways of exposure, prey fish, sediments and wastewater effluent were analyzed for PFASs, and in the case of sediment and effluent, a suite of PFAA precursors. PFOS was the dominant PFAA in prey fish and sediment. In effluent, different mixtures of PFAAs were measured, with PFOS, PFHxA, and PFOA detected in the highest concentrations. Polyfluoroalkyl phosphate diesters (PFCA-precursors) were observed at concentrations over an order of magnitude higher than PFCAs in sediment, highlighting their importance as a potential, on-going source of PFCAs to SF Bay wildlife. These findings suggest that the PFOS phase-out has resulted in reduced burdens to wildlife in SF Bay, but that exposure to diverse and incompletely characterized PFASs continues., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Perfluoroalkyl substances (PFASs) have been detected in organisms worldwide, including Polar Regions. The polar bear (Ursus maritimus), the top predator of Arctic marine ecosystems, accumulates high concentrations of PFASs, which may be harmful to their health. The aim of this study was to investigate which factors (habitat quality, season, year, diet, metabolic state [i.e. feeding/fasting], breeding status and age) predict PFAS concentrations in female polar bears captured on Svalbard (Norway). We analysed two perfluoroalkyl sulfonates (PFSAs: PFHxS and PFOS) and C 8 -C 13 perfluoroalkyl carboxylates (PFCAs) in 112 plasma samples obtained in April and September 2012-2013. Nitrogen and carbon stable isotope ratios (δ 15 N, δ 13 C) in red blood cells and plasma, and fatty acid profiles in adipose tissue were used as proxies for diet. We determined habitat quality based on movement patterns, capture position and resource selection functions, which are models that predict the probability of use of a resource unit. Plasma urea to creatinine ratios were used as proxies for metabolic state (i.e. feeding or fasting state). Results were obtained from a conditional model averaging of 42 general linear mixed models. Diet was the most important predictor of PFAS concentrations. PFAS concentrations were positively related to trophic level and marine diet input. High PFAS concentrations in females feeding on the eastern part of Svalbard, where the habitat quality was higher than on the western coast, were likely related to diet and possibly to abiotic factors. Concentrations of PFSAs and C 8 -C 10 PFCAs were higher in fasting than in feeding polar bears and PFOS was higher in females with cubs of the year than in solitary females. Our findings suggest that female polar bears that are exposed to the highest levels of PFAS are those 1) feeding on high trophic level sea ice-associated prey, 2) fasting and 3) with small cubs., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Perfluoroalkyl acids (PFAAs) are highly persistent substances which have been detected in wildlife around the world, including birds. Although bird eggs have often been used to determine and monitor PFAAs levels in the marine environment, this has rarely been done in the terrestrial environment. In the present study we examined the concentrations and composition profile of 12 PFAAs (4 perfluoroalkyl sulfonic acids (PFSAs) and 8 perfluoroalkyl carboxylic acids (PFCAs) in the eggs of great tits (Parus major) collected at a fluorochemical plant and in three other areas, representing a gradient in distance from the pollution source (from 1 to 70 km), in Antwerp, Belgium. The PFSA concentrations measured at the site of the fluorochemical plant were among the highest ever reported in eggs with median concentrations of 10380 ng/g (extrapolated), 99.3 ng/g and 47.7 ng/g for PFOS, PFHxS and PFDS respectively. Furthermore, the median concentration of 19.8 ng/g for PFOA was also among the highest ever reported in bird eggs. Although these concentrations decreased sharply with distance from the fluorochemical plant, levels found in the adjacent sites were still high compared to what has been reported in literature. Moreover, based on what is known in literature, it is likely that these concentrations may cause toxicological effects. PFOS was the dominant contributor to the PFSA and PFAAs (63.4-97.6%) profile at each site, whereas for PFCAs this was PFOA at the plant site and the nearest locations (41.0-52.8%) but PFDoA (37.7%) at the farthest location. Although there is some evidence that PFAAs concentrations close to the plant site are decreasing in comparison with earlier measurements, which may be due to the phase out of PFOS, more research is necessary to understand the extent of the toxicological effects in the vicinity of this PFAAs hotspot., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Perfluoroalkyl substances (PFAS) have recently received increased research attention, particularly concerning aquatic organisms and in regions of exposure to aqueous film forming foams (AFFFs). Air Force bases historically applied AFFFs in the interest of fire training exercises and have since expressed concern for PFAS contamination in biota from water bodies surrounding former fire training areas. Six PFAS were monitored, including perfluorooctane sulfonate (PFOS), in aquatic species from 8 bayou locations at Barksdale Air Force Base in Bossier City, Louisiana (USA) over the course of 1 yr. The focus was to evaluate temporal and spatial variability in PFAS concentrations from historic use of AFFF. The PFOS concentrations in fish peaked in early summer, and also increased significantly downstream of former fire training areas. Benthic organisms had lower PFOS concentrations than pelagic species, contrary to previous literature observations. Bioconcentration factors varied with time but were reduced compared with previously reported literature values. The highest concentration of PFOS in whole fish was 9349 ng/g dry weight, with 15% of samples exceeding what is believed to be the maximum whole fish concentration reported to date of 1500 ng/g wet weight. Further studies are ongoing, to measure PFAS in larger fish and tissue-specific partitioning data to compare with the current whole fish values. The high concentrations presently observed could have effects on higher trophic level organisms in this system or pose a potential risk to humans consuming contaminated fish. Environ Toxicol Chem 2017;36:2022-2029. © 2016 SETAC., (© 2016 SETAC.)

Different from typical hydrophobic organic contaminants (HOCs), perfluoroalkyl acids (PFAAs) are more soluble in water and less partitioned to soil than the HOCs. It remains unclear whether and to what extent PFAAs could be sequestrated in soil. In this study, sequential extraction of PFAAs in soil and bioaccumulation of PFAAs in earthworm were carried out to understand the sequestration and bioavailability of PFAAs in soils with different soil organic matter (SOM) and aged for different time periods (7 and 47d). Sequestration occurred in different degrees depending on the amount and compositions of SOM in soil, structural properties of PFAAs and aging time. Surprisingly, in one peat soil with high fraction of organic carbon (f oc , 59%), the PFAAs were completely sequestrated in the soil. Aging might lead to further sequestration of PFAAs in soil with relatively lower f oc . As a consequence of sequestration, the bioavailability of PFAAs in peat soils was reduced 3-10 times compared to that in the plain farmland soil. However, the sequestrated PFAAs were still bioaccumulative in earthworms to some extent. The results indicated that the risk of PFAAs in field soil with high content of SOM could be underestimated if only free PFAAs using mild solvent extraction were monitored., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The concentrations of 11 perfluorinated alkyl acids (PFAAs) were measured in the livers of foxes (Vulpes vulpes) from Germany, a primarily carnivorous species, and chamois (Rupicapra rupicapra) from Austria, an herbivorous species. Perfluorooctanesulfonate (PFOS) at concentrations [all results refer to wet weight (ww)] of 3.2-320 µg/kg were detected in all 40 fox livers tested, yielding an arithmetic mean of 46.6 µg/kg and a median of 29.8 µg/kg. Long-chain PFAAs were detected at concentrations of 1.7 µg/kg perfluorononanoic acid (PFNA) to 2.4 µg/kg perfluorodecanoic acid (PFDA) and perfluorododecanoic acid (PFDoDA). Of the short-chain PFAAs tested, only perfluorohexanoic acid (PFHxA) was found in 1 fox liver at a concentration of 1.4 µg/kg, and perfluorohexane sulfonate (PFHxS) was found in 2 fox livers at a concentration of 1 µg/kg each. PFOS and PFNA concentrations higher than limit of quantification (LOQ) were detected in 90.9 and 81.8 % of chamois livers, respectively. The arithmetic mean for PFOS concentrations was 2.2 µg/kg (median 2.4 µg/kg), a factor of 21 (median factor of 12) lower than in fox livers. The arithmetic mean for PFNA concentrations was 2.0 µg/kg (median 1.9 µg/kg). Perfluorobutanoic acid, PFHxA, perfluorooctanoic acid, perfluorobutanesulfonate, and PFHxS were not detected at concentrations higher than the LOQ in any of the samples. The various results are compared with one another and with the results of other studies of herbivorous, carnivorous, and omnivorous wild animals. The highest concentrations of PFAA, in particular PFOS, were found in omnivorous animals followed by carnivores. The lowest levels were present in herbivores.

Gammarids were exposed to sediments from a deposition site located on the Rhône River (France) downstream of a fluoropolymer manufacturing plant. Gammarids accumulated to various extents four long-chain perfluoroalkyl carboxylic acids (PFCAs) from C9 to C13, one sulfonate, perfluorooctane sulfonate (PFOS) and three of its precursors (the perflurooctane sulfonamide (FOSA), the N-methyl perfluorooctane sulfonamidoacetic acid (MeFOSAA), the N-ethyl perfluorooctane sulfonamidoacetic acid (EtFOSAA) and the 6:2 fluorotelomer sulfonic acid (6:2 FTSA). Whatever the compound, the steady state was not achieved after a 3-week exposure; elimination was almost complete after a 3-week depuration period for perfluorononanoic acid (PFNA), PFOS, the three precursors and the 6:2FTSA. However, this was not the case for long-chain PFCAs, whose elimination rates decreased with increasing chain length. PFAS accumulation in gammarids occurred via the trophic and respiratory pathways, in proportions varying with the carbon chain length and the terminal moiety., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Polychlorinated biphenyls (PCBs) and perfluorinated carboxylates and sulfonates (PFASs) are persistent pollutants in sediment that can potentially bioaccumulate in aquatic organisms. The current study investigates variation in the accumulation of PCBs and PFASs in laboratory-cultured Hexagenia spp., Lumbriculus variegatus and Pimephales promelas from contaminated field-collected sediment using 28-day tests. BSAF(lipid) (lipid-normalized biota-sediment accumulation factor) values for total concentration of PCBs were greater in Hexagenia spp. relative to L. variegatus and P. promelas. The distribution of congeners contributing to the total concentration of PCBs in tissue varied among the three species. Trichlorobiphenyl congeners composed the greatest proportion of the total concentration of PCBs in L. variegatus while tetra- and pentabiphenyl congeners dominated in Hexagenia spp. and P. promelas. Perfluorooctane sulfonate (PFOS) was present in all three species at concentrations greater than all other PFASs analyzed. Hexagenia spp. also produced the greatest BSAF(lipid) and BSAF(ww) (non-lipid-normalized biota-sediment accumulation factor) values for PFOS relative to the other two species. However, this was not the case for all PFASs. The trend of BSAF values and number of carbon atoms in the perfluoroalkyl chain of perfluorinated carboxylates varied among the three species but was similar for perfluorinated sulfonates. Differences in the dominant pathways of exposure (e.g., water, sediment ingestion) likely explain a large proportion of the variation in accumulation observed across the three species., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Chemicals of emerging concern (CECs) in the basin of the Laurentian Great Lakes of North America include per- and poly-fluoroalkyl substances (PFASs) classified as perfluoroalkyl acids. We investigated several PFASs, and specifically 13 C4-C16 perfluorinated carboxylic acids (PFCAs), 4 (C4, C6, C8 and C10) perfluorinated sulfonates (PFSAs), perfluoro-4-ethylcyclohexane sulfonate (PFEtCHxS) and selected precursors (e.g. perfluorobutane sulfonamide and perfluorooctane sulfonamide) in herring gull (Larus argentatus) eggs collected in 2012-2013 from 19 Canadian and U.S. colony sites across the Great Lakes. C6, C8 and C10 PFSAs, PFEtCHxS, and C7-14 and C16 PFCAs were quantifiable at >97% of the 114 egg samples. PFEtCHxS concentrations ranged from n.d. to 3.1ng/g ww (highest in Lake Michigan eggs). Mean Σ4PFSA (92 to 97% perfluorooctane sulfonate (PFOS)) and Σ9PFCA concentration ranges were 44 to 740 and 4.8 to 118ng/g ww, respectively. Σ4PFSA showed a clear increasing concentration trend from the northwest to the southeast colonies. Also, Σ4PFCA to Σ9PFSA concentration ratios in gull eggs were greater in eggs from Lake Superior relative to colonies in the other lakes. PFOS concentrations in some egg samples were greater than some of the known lowest observed effect concentrations (LOECs) measured and reported in captive bird model studies. This study showed the increasing complexity of PFAS-CECs, and emphasized the importance of continuing monitoring of bioaccumulative PFAS in Great Lakes herring gulls., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Perfluorooctanoic acid (PFOA) is widely used in the manufacture of many industrial and household products. To assess the potential environmental risk of PFOA, its accumulation, translocation and phytotoxic effects were investigated using the model plant species Arabidopsis thaliana. Exposure to 18 μM PFOA-F in agar plates did not affect plant growth, but 181-1811 μM PFOA-F inhibited root and shoot growth. PFOA was more phytotoxic on shoot growth than NaF at the equivalent F concentration, with the latter having 3.9-7.6 times higher EC50 for shoot biomass than PFOA. PFOA was efficiently translocated from roots to shoots, where it existed as intact PFOA molecules without transformation evidenced by the (19)F NMR spectra. PFOA caused a significant increase in the concentration of H2O2 and malondialdehyde (MDA) in shoots, indicating that oxidative stress is a likely cause of PFOA phytotoxicity., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Fluorinated fire-fighting foams may be released into the environment during fire-fighting activities, raising concerns due to the potential environmental and health impacts for some fluorinated organics. The current study investigated (1) the biodegradability of three fluorinated fire-fighting foams, and (2) the applicability of current standard measures used to assess biodegradability of fluorinated fire-fighting foams. The biodegradability of three fluorinated fire-fighting foams was evaluated using a 28-day dissolved organic carbon (DOC) Die-Away Test. It was found that all three materials, diluted in water, achieved 77-96% biodegradability, meeting the criteria for "ready biodegradability". Defluorination of the fluorinated organics in the foam during biodegradation was measured using ion chromatography. It was found that the fluorine liberated was 1-2 orders of magnitude less than the estimated initial amount, indicating incomplete degradation of fluorinated organics, and incomplete CF bond breakage. Published biodegradability data may utilize biochemical oxygen demand (BOD), chemical oxygen demand (COD), and total organic carbon (TOC) metrics to quantify organics. COD and TOC of four fluorinated compounds were measured and compared to the calculated carbon content or theoretical oxygen demand. It was found that the standard dichromate-based COD test did not provide an accurate measure of fluorinated organic content. Thus published biodegradability data using COD for fluorinated organics quantification must be critically evaluated for validity. The TOC measurements correlated to an average of 91% of carbon content for the four fluorinated test substances, and TOC is recommended for use as an analytical parameter in fluorinated organics biodegradability tests., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study summarizes results on levels of 25 perfluoroalkyl substances (PFASs), three hexabromocyclododecane isomers (HBCDs), tetrabromobisphenol A (TBBPA), three brominated phenols and four hydroxylated derivates of polybrominated diphenyl ethers (OH-PBDEs) in 59fish samples collected in nine localities on two major rivers from the Czech Republic. To identify potential sources of these chemicals, several sampling sites located close to highly industrialized areas were also involved. The major PFAS representatives, perfluorooctane sulfonate (PFOS), C9-C14 perfluoroalkyl carboxylic acids (PFCAs) and perfluorooctane sulfonamide (FOSA) were detected in 100% fish samples. The concentration ranges of individual substances in the respective groups of PFASs were as follows: 0.572-61.3ngg(-)(1) wet weight (ww) for Tot-PFOS, 0.007-0.121ngg(-)(1)ww for perfluoroalkane sulfonates (PFSAs) (without PFOS isomers), 0.007-22.0ngg(-)(1)ww for PFCAs and 0.026-7.76ngg(-)(1)ww for FOSA. The highest contents of ∑PFASs (51.9ngg(-)(1)ww and 47.8ngg(-)(1)ww) were measured in fish muscle tissue from the locality Trmice situated on the Bílina River and Verdek on the Labe River, where chemical and/or textile industry is located. From 11 targeted BFRs, five compounds (α-HBCD, β-HBCD, γ-HBCD, TBBPA and 2,4,6-tribromophenol (TBP)) were determined in analyzed samples. The concentration ranged as follows: 3.15-1211ngg(-)(1) lipid weight (lw) for ∑HBCD, 4.99-203ngg(-)(1)lw for TBBPA and 1.76-107ngg(-)(1)lw for 2,4,6-TBP., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

This study investigates concentrations of 18 perfluoroalkyl substances (PFAS) in blood plasma of adult lactating Weddell seals (Leptonychotes weddellii) (n = 10) from McMurdo Sound, Antarctica. Perfluoroundecanoic acid (PFUnDA) was detected in all samples at concentrations ranging from 0.08 to 0.23 ng/ml. Perfluorooctane sulfonate (PFOS), perfluorohexanoate (PFHxA) and perfluorotridecanoate (PFTriDA) were sporadically detected, while the remaining compounds were below the limit of detection. This is the first report of detectible concentrations of PFASs in an endemic Antarctic marine mammal species. We suggest that the pollutants have been subjected to long range atmospheric transportation and/or derive from a local source. A review of these and published data indicate that perfluoroalkyl carboxylates (PFCAs) dominate in biotic PFAS patterns in species feeding south of the Antarctic Circumpolar Current (ACC), whereas PFOS was the major PFAS detected in species feeding predominantly north of the current., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The occurrence and sources of 21 perfluoroalkyl substances (PFASs: C4-C14, C16, C18 carboxylate, C4, C6-C8 and C10 sulfonates and C8 sulfonamide) were determined in water, sediment, and biota of the Llobregat River basin (NE Spain). Analytes were extracted by solid phase extraction (SPE) and determined by liquid chromatography triple quadrupole mass spectrometer (LC-QqQ-MS). All samples were contaminated with at least one PFAS, being the most frequently found perfluorobutanoate (PFBA), perfluorooctanoate (PFOA) and perfluorooctane sulfonate (L-PFOS). In general, mean PFAS concentrations measured in sediments (0.01-3.67 ng g(-1)) and biota (0.79-431 μg kg(-1)) samples were higher than those found in water (0.01-233 ng L(-1)). L-PFOS presented very high levels in biota and water, particularly in the Anoia River where a maximum concentration of 2.71 μg L(-1) was related to important industrial activities. However, this pollution does not extend down the Llobregat River according to cumulated values. None of the hazard quotients (HQ) calculated indicate potential risk for the different tropic levels considered (algae, Daphnia sp. and fish). According to Maximum Allowable Concentration (MAC) proposed by the European Commission (L-PFOS) and to Provisional Health Advisory (PHA) values (PFOA, L-PFOS) established by the United States Environmental Protection Agency (US EPA), only two water samples exceeded PHA concentration for L-PFOS., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Perfluorinated compounds (PFCs) have recently received scientific and regulatory attention due to their broad environmental distribution, persistence, bioaccumulative potential, and toxicity. Studies suggest that fish consumption may be a source of human exposure to perfluorooctane sulfonate (PFOS) or long-chain perfluorocarboxylic acids. Most PFC fish tissue literature focuses on marine fish and waters outside of the United States (U.S.). To broaden assessments in U.S. fish, a characterization of PFCs in freshwater fish was initiated on a national scale using an unequal probability design during the U.S. Environmental Protection Agency's (EPA's) 2008-2009 National Rivers and Streams Assessment (NRSA) and the Great Lakes Human Health Fish Tissue Study component of the 2010 EPA National Coastal Condition Assessment (NCCA/GL). Fish were collected from randomly selected locations--164 urban river sites and 157 nearshore Great Lake sites. The probability design allowed extrapolation to the sampled population of 17,059 km in urban rivers and a nearshore area of 11,091 km(2) in the Great Lakes. Fillets were analyzed for 13 PFCs using high-performance liquid chromatography tandem mass spectrometry. Results showed that PFOS dominated in frequency of occurrence, followed by three other longer-chain PFCs (perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid). Maximum PFOS concentrations were 127 and 80 ng/g in urban river samples and Great Lakes samples, respectively. The range of NRSA PFOS detections was similar to literature accounts from targeted riverine fish sampling. NCCA/GL PFOS levels were lower than those reported by other Great Lakes researchers, but generally higher than values in targeted inland lake studies. The probability design allowed development of cumulative distribution functions (CDFs) to quantify PFOS concentrations versus the sampled population, and the application of fish consumption advisory guidance to the CDFs resulted in an estimation of the proportion of urban rivers and the Great Lakes that exceed human health protection thresholds., (Copyright © 2014. Published by Elsevier B.V.)

While the literature has reported a widespread occurrence of perfluoroalkyl substances (PFASs) in marine biota, very limited studies have been dedicated to the southern hemisphere. Hepatic concentrations of nine PFAAs were analysed in 49 stranded stingrays from eastern Australia using liquid chromatograph coupled with tandem mass spectrometry and relationships with biological parameters (i.e. body size, age and sex) were investigated. Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) were the predominant compounds quantified, with hepatic concentrations varying from 2 to 117 and from 0.2 to 19 ng·g(-1) w.w., respectively. A negative correlation between the concentration of PFASs in the livers of 32 blue-spotted stingrays and the body size/age was found. This relationship was independent of the animal's sex. We postulate that the dependence on body size is related to differing uptake kinetics of the chemicals, after the sting rays were exposed to an increased level of the contaminants in their environment. Such a pollution event could be related to a severe flood event that occurred at this location a few months before the samples' collection. Our results indicate that the influence of the body size/age should be taken into account when estimating bioaccumulation parameters from environmental measurements or exposure levels of biota to PFASs., (Copyright © 2014. Published by Elsevier B.V.)

Water, sediment, plankton, and blood and liver tissues of crucian carp (Carassius auratus) and mandarin fish (Siniperca scherzeri) were collected from six major rivers and lakes in South Korea (including Namhan River, Bukhan River, Nakdong River, Nam River, Yeongsan River and Sangsa Lake) and analyzed for perfluorinated alkyl substances (PFASs). Perfluorooctane sulfonate (PFOS) was consistently detected at the greatest concentrations in all media surveyed with the maximum concentration in water of 15 ng L(-1) and in biota of 234 ng mL(-1) (fish blood). A general ascending order of PFAS concentration of water0.80, p<0.001) were observed between PFOS concentration in blood and liver tissues of both crucian carp and mandarin fish. This result suggests that blood can be used for nonlethal monitoring of PFOS in fish. Overall, the rank order of mean bioconcentration factors (BCFs) of PFOS in biota was; phytoplankton (196 L/kg)

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., (© 2014 SETAC.)

Crop uptake of perfluoroalkyl acids (PFAAs) from biosolids-amended soil has been identified as a potential pathway for PFAA entry into the terrestrial food chain. This study compared the uptake of PFAAs in greenhouse-grown radish (Raphanus sativus), celery (Apium graveolens var. dulce), tomato (Lycopersicon lycopersicum), and sugar snap pea (Pisum sativum var. macrocarpon) from an industrially impacted biosolids-amended soil, a municipal biosolids-amended soil, and a control soil. Individual concentrations of PFAAs, on a dry weight basis, in mature, edible portions of crops grown in soil amended with PFAA industrially impacted biosolids were highest for perfluorooctanoate (PFOA; 67 ng/g) in radish root, perfluorobutanoate (PFBA; 232 ng/g) in celery shoot, and PFBA (150 ng/g) in pea fruit. Comparatively, PFAA concentrations in edible compartments of crops grown in the municipal biosolids-amended soil and in the control soil were less than 25 ng/g. Bioaccumulation factors (BAFs) were calculated for the root, shoot, and fruit compartments (as applicable) of all crops grown in the industrially impacted soil. BAFs were highest for PFBA in the shoots of all crops, as well as in the fruit compartment of pea. Root-soil concentration factors (RCFs) for tomato and pea were independent of PFAA chain length, while radish and celery RCFs showed a slight decrease with increasing chain length. Shoot-soil concentration factors (SCFs) for all crops showed a decrease with increasing chain length (0.11 to 0.36 log decrease per CF2 group). The biggest decrease (0.54-0.58 log decrease per CF2 group) was seen in fruit-soil concentration factors (FCFs). Crop anatomy and PFAA properties were utilized to explain data trends. In general, fruit crops were found to accumulate fewer long-chain PFAAs than shoot or root crops presumably due to an increasing number of biological barriers as the contaminant is transported throughout the plant (roots to shoots to fruits). These data were incorporated into a preliminary conceptual framework for PFAA accumulation in edible crops. In addition, these data suggest that edible crops grown in soils conventionally amended for nutrients with biosolids (that are not impacted by PFAA industries) are unlikely a significant source of long-chain PFAA exposure to humans.

The current article maps perfluoroalkyl acids (PFAAs) contamination in the largest Science Park of Taiwan. The occurrence of ten target PFAAs in the effluent of an industrial wastewater treatment plant (IWWTP), its receiving rivers, rainwater, sediment, and the muscles and livers of fish was investigated. All target PFAAs were found in effluent of IWWTP, in which perfluorooctane sulfonate (PFOS) (6,930 ng/L), perfluorohexyl sulfonate (PFHxS) (2,662 ng/L) and perfluorooctanoic acid (PFOA) (3,298 ng/L) were the major constituents. Concentrations of PFBS and PFOS in the IWWTP downstream areas have exceeded safe concentration levels of avian and aquatic life, indicating a potential risk to wildlife in those areas. In sediment samples, predominant contaminants were PFOS (1.5-78 ng/g), PFOA (0.5-5.6 ng/g), and perfluorododecanoic acid (PFDoA) (nd-5.4 ng/g). In biological tissue samples, concentrations as high as 28,933 ng/g of PFOS were detected in tilapia and catfish liver samples. A positive correlation for log (C sediment/C water) and log (C tissue/C water) was found. The concentration and proportion (percentage of all PFAAs) of PFOS found in biotissue samples from the Keya River (which receives industrial wastewater) were found to be much greater (200 times) than those of samples from the Keelung River (which receives mainly domestic wastewater). These findings suggest that the receiving aquatic environments and, in turn, the human food chain can be significantly influenced by industrial discharges.

While (N-ethyl perfluorooctanesulfonamido)ethanol (FOSE) -based phosphate diester (diSPAP) has been proposed as a candidate precursor of perfluorooctanesulfonate (PFOS), its potential biotransformation to PFOS has not been verified. Metabolism of diSPAP was investigated in Japanese medaka ( Oryzias latipes ) after exposure in water for 10 days, followed by 10 days of depuration. Branched isomers of diSPAP (B-diSPAP) were preferentially enriched in medaka exposed to diSPAP, with the proportion of branched isomers (BF) ranging from 0.56 to 0.80, which was significantly greater than that in the water to which the medaka were exposed (0.36) (p < 0.001). This enrichment was due primarily to preferential uptake of B-diSPAP. PFOS together with perfluorooctanesulfonamide (PFOSA), N-ethyl perfluorooctanesulfonamide (NEtFOSA), 2-(perfluorooctanesulfonamido)acetic acid (FOSAA), NEtFOSAA, FOSE, and NEtFOSE were detected in medaka exposed to diSPAP, which indicated the potential for biotransformation of diSPAP to PFOS via multiple intermediates. Due to preferential metabolism of branched isomers, FOSAA and PFOSA exhibited greater BF values (>0.5) than those of NEtFOSA, NEtFOSAA, and NEtFOSE (<0.2). Such preferential metabolism of branched isomers along the primary pathway of metabolism and preferential accumulation of B-diSPAP led to enrichment of branched PFOS (B-PFOS) in medaka. Enrichment of B-PFOS was greater for 3-, 4-, and 5-perfluoromethyl PFOS (P3MPFOS, P4MPFOS, and P5MPFOS), for which values of BF were 0.58 ± 0.07, 0.62 ± 0.06, and 0.61 ± 0.05 (day 6), respectively; these values are 5.8-, 7.8-, and 6.4-fold greater than those of technical PFOS. This work provides evidence on the isomer-specific accumulation of PFOS from diSPAP and will be helpful to track indirect sources of PFOS in the future.

Perfluorinatedalkyl acids (PFAAs) are of growing concern due to possible health effects on humans. Exposure assessments indicate that fish consumption is one of the major sources of perfluorooctane sulfonate (PFOS) exposure to humans, one of the major PFASs, whereas concerns of overestimation of this exposure source have been raised. Therefore, PFAAs concentrations in fish from the North Atlantic (Icelandic fishing grounds) in the flesh of different fish species were investigated along with more detailed analyses of tissue concentrations in cod (Gadus morhua) and lumpfish (Cyclopterus lumpus). Further, fish feed was investigated as a possible source of PFAAs in aquaculture by examining fish meal as feed ingredient. No PFAAs were detected in the edible part of all fish samples, except for PFOS in pollock (Pollachius virens, 0,05 ng/g wet weight). PFOS was the only PFAA detected in the fish meal samples with the exception of PFOSA in blue whiting (Micromesistius poutassou) meal (0,45 ng/g dry weight (d.w.)), where the PFOS concentration was 1,3-13 ng/g d.w. in the capelin (Mallotus villosus) and mackerel (Scomber scombrus) meal samples. The conclusions of the study are that fish commonly consumed from the Icelandic fishing grounds are unlikely to be an important source of PFAAs exposure.

The exposure and effects of perfluoroalkyl substances (PFASs) were studied at eight locations in Minnesota and Wisconsin between 2007 and 2011 using tree swallows (Tachycineta bicolor). Concentrations of PFASs were quantified as were reproductive success end points. The sample egg method was used wherein an egg sample is collected, and the hatching success of the remaining eggs in the nest is assessed. The association between PFAS exposure and reproductive success was assessed by site comparisons, logistic regression analysis, and multistate modeling, a technique not previously used in this context. There was a negative association between concentrations of perfluorooctane sulfonate (PFOS) in eggs and hatching success. The concentration at which effects became evident (150-200 ng/g wet weight) was far lower than effect levels found in laboratory feeding trials or egg-injection studies of other avian species. This discrepancy was likely because behavioral effects and other extrinsic factors are not accounted for in these laboratory studies and the possibility that tree swallows are unusually sensitive to PFASs. The results from multistate modeling and simple logistic regression analyses were nearly identical. Multistate modeling provides a better method to examine possible effects of additional covariates and assessment of models using Akaike information criteria analyses. There was a credible association between PFOS concentrations in plasma and eggs, so extrapolation between these two commonly sampled tissues can be performed.

Profiles of seven compounds of perfluoro-alkyl substances (PFASs) were compared among three species of top predators from the Danish North Sea: the white-beaked dolphin (Lagenorhynchus albirostris), the harbor porpoise (Phocoena phocoena), and the harbor seal (Phoca vitulina). The seals had higher total burdens (757.8 ng g(-1) ww) than the dolphins (439.9 ng g(-1) ww) and the porpoises (355.8 ng g(-1) ww), probably a reflection of feeding closer to the shore and thus contamination sources. The most striking difference among the species was the relative contribution of perfluorooctanesulfonamide (PFOSA) to the profiles; the seals (0.1%) had much lower levels than porpoises (8.3%) and dolphins (26.0%). In combination with the values obtained from the literature, this result indicates that Carnivora species including Pinnipedia have a much higher capacity of transforming PFOSA to perfluorooctane sulfonic acid (PFOS) than cetacean species. Another notable difference among the species was that the two smaller species (seals and porpoises) with supposedly higher metabolic rates had lower concentrations of the perfluorinated carboxylic acids, which are generally more easily excreted than perfluorinated sulfonamides. Species-specific characteristics should be recognized when PFAS contamination in marine mammals is investigated, for example, several previous studies of PFASs in cetaceans have not quantified PFOSA.

Beef and dairy products may be important vectors of human exposure to perfluoroalkyl acids (PFAAs), but the understanding of how PFAAs are accumulated and transferred through agricultural food chains is very limited. Here, the bioaccumulation of PFAAs in dairy cows receiving naturally contaminated feed and drinking water was investigated by conducting a mass balance of PFAAs for a herd of dairy cows in a barn on a typical Swedish dairy farm. It was assumed that the cows were able to reach steady state with their dietary intake of PFAAs. Perfluorooctane sulfonic acid (PFOS) and perfluoroalkyl carboxylic acids (PFCAs) with 8 to 12 carbons were detected in cow tissue samples (liver, muscle, and blood) at concentrations up to 130 ng kg(-1). Mass balance calculations demonstrated an agreement between total intake and excretion within a factor of 1.5 and consumption of silage was identified as the dominant intake pathway for all PFAAs. Biomagnification factors (BMFs) were highly tissue and homologue specific. While BMFs of PFOS and PFCAs with 9 and 10 fluorinated carbons in liver ranged from 10 to 20, perfluorooctanoic acid (PFOA) was not biomagnified (BMF<1) in any of the investigated tissues. Biotransfer factors (BTFs; defined as the concentration in tissue divided by the total daily intake) were calculated for muscle and milk. Log BTFs ranged from -1.95 to -1.15 day kg(-1) with the highest BTF observed for PFOS in muscle. Overall, the results of this study suggest that long-chain PFAAs have a relatively high potential for transfer to milk and beef from the diet of dairy cows. However, a low input of PFAAs to terrestrial systems via atmospheric deposition and low bioavailability of PFAAs in soil limits the amount of PFAAs that enter terrestrial agricultural food chains in background contaminated environments and makes this pathway less important than aquatic exposure pathways. The BTFs estimated here provide a useful tool for predicting human exposure to PFAAs via milk and beef under different contamination scenarios.