Perfluoroalkyl Sulfonic Acids Research Articles

A pilot study of per- and polyfluoroalkyl substances in automotive lubricant oils from the United States

Abstract Per- and polyfluoroalkyl substances (PFASs) were reported to be used as additives in automotive lubricant oils and hydraulic fluids, to reduce surface tension, prevent fires and evaporation. Little is known, however, with regard to the occurrence of PFASs in automotive lubricants. In this study, concentrations and profiles of 13 perfluoroalkyl acids (PFAAs), encompassing nine perfluoroalkyl carboxylic acids (PFCAs; C4–C12) and four perfluoroalkyl sulfonic acids (PFSAs; C4–C10), were determined in 18 automotive lubricants purchased in the United States. The lubricant extracts were analyzed before and after oxidization, to measure PFAAs and their precursors, using the total oxidizable precursor (TOP) assay. Following oxidation, lubricant extracts yielded ∑ PFAA concentrations up to two orders of magnitude higher (range: 196–8300 ng/g; mean: 1840 ng/g) than those measured prior to oxidation (5.96–344 ng/g; 71.6 ng/g), which suggested the presence of notable amounts of PFAA precursors. Long-chain PFCAs (C8–C12;​ ∼ 70% of total) were the major PFASs detected (prior to oxidation). The mean molar increase in the concentration (pM/g) upon oxidation of lubricant extracts varied among the nine PFCAs in the following decreasing order: C4 (1350) > C12 (670) > C11 (570) = C5 (570) > C10 (460) > C9 (300) > C7 (140) = C6 (140) > C8 (110). Principal component analysis of PFCA profiles revealed that PFAAs originate from their respective precursors.

Destruction of Per- and Polyfluoroalkyl Substances (PFASs) in Aqueous Film-Forming Foam (AFFF) with UV-Sulfite Photoreductive Treatment.

Ultraviolet photochemical reaction of sulfite (SO32-) photosensitizer generates strongly reducing hydrated electrons (eaq-; NHE = -2.9 V) that have been shown to effectively degrade individual per- and polyfluoroalkyl substances (PFASs), including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). However, treatment of complex PFAS mixtures in aqueous film-forming foam (AFFF) remains largely unknown. Here, UV-sulfite was applied to a diluted AFFF to characterize eaq- reactions with 15 PFASs identified by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) targeted analysis. Results show that reactivity varies widely among PFASs, but reaction rates observed for individual PFASs in AFFF are similar to rates observed in single-solute experiments. While some structures, including long-chain perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) were readily degraded, other structures, most notably short-chain PFSAs and fluorotelomer sulfonic acids (FTSs), were more recalcitrant. This finding is consistent with results showing incomplete fluoride ion release (up to 53% of the F content in AFFF) during reactions. Furthermore, results show that selected PFSAs, PFCAs, and FTSs can form as transient intermediates or unreactive end-products via eaq- reactions with precursor structures in AFFF. These results indicate that while UV-sulfite treatment can be effective for treating PFOS and PFOA to meet health advisory levels, remediation of the wider range of PFASs in AFFF will prove more challenging.

Per- and polyfluoroalkyl substances in paired dust and carpets from childcare centers

Carpets can be a significant source of per- and polyfluoroalkyl substances (PFASs) in the indoor environment and may be an especially important source of exposure for children and toddlers. Most previous studies focused on measuring indoor dust only. In this study, we measured PFAS concentrations in paired carpet and dust samples from 18 California childcare centers in 2018 to investigate carpet as a contributor to PFASs in dust. Median total PFAS concentrations (∑PFASs) in carpets and dust were 471 ng/g and 523 ng/g, respectively. 6:2 FTOH and 6:2 FTSA were the two dominant PFASs, collectively accounting for over 50% of the ∑PFASs in both media. Other frequently detected PFASs included C4–C14 perfluoroalkylcarboxylic acids, C4–C8 perfluoroalkylsulfonic acids, PFDS, 4:2 FTSA, 8:2 FTSA, FOSA, MeFOSE, EtFOSE, 8:2 FTOH, and 10:2 FTOH. We found strong associations between PFAS levels in carpet and dust pairs, suggesting that carpets can be a source and a sink for PFASs. The estimated total perfluoroalkyl acids (PFAA) intake via dust ingestion for children was 0.023, 0.096, and 1.9 ng/kg body weight/day in the low-, intermediate-, and high-exposure scenarios, respectively. Our data suggest that PFASs of emerging concern are playing an increasingly important role in indoor exposure to PFASs.

Application of zero-valent iron coupled with biochar for removal of perfluoroalkyl carboxylic and sulfonic acids from water under ambient environmental conditions

Advanced oxidation and reduction processes have been intensively investigated as potential methods to promote the decomposition of perfluoroalkyl substances (PFASs). However, extreme operational conditions such as highly acidic pH, high temperature, and high pressure are required to promote degradation reactions, which makes these technologies costly and less feasible for full-scale applications. The objective of this study was to evaluate the effectiveness of zero-valent iron (ZVI) alone and a mixture of ZVI and biochar (ZVI + BC) for removal of seven target PFASs from water under ambient environmental conditions. Target PFASs included three perfluoroalkyl carboxylic acids (PFCAs) [perfluorooctanoic acid (PFOA, C8-PFCA), perfluoroheptanoic acid (C7-PFCA), and perfluorohexanoic acid (C6-PFCA)] and four perfluoroalkyl sulfonic acids (PFSAs) [perfluorooctane sulfonic acid (PFOS, C8-PFSA), perfluoroheptane sulfonic acid (C7-PFSA), perfluorohexane sulfonic acid (C6-PFSA), and perfluorobutane sulfonic acid (C4-PFSA)]. Batch test results show that PFSAs (up to 94% removal) were more effectively removed than PFCAs (up to 60% removal) when utilizing either ZVI or (ZVI + BC). About 20–60% of input PFOA (~18,550 μg L−1) and 90–94% of input PFOS (~18,580 μg L−1) were removed by ZVI alone or the mixture of (ZVI + BC). The removal efficiencies of PFCAs and PFSAs by reactive media increased with increasing chain length, from 0 to 17% for short-chain PFCAs (C6–C7) and 20 to 70% for short-chain PFSAs (C4–C7). About 5–10% of input PFOA and PFOS was partially defluorinated by ZVI alone as indicated by F− release; however, the defluorination efficiency may be underestimated due to the sorption of F− by the reactive media. Overall, the reactive mixture (ZVI + BC) may be an effective and environmentally sustainable material for removing PFASs from water under ambient environmental conditions.

Origin and organ-specific bioaccumulation pattern of perfluorinated alkyl substances in crabs

Consumption of seafood is a major contributor to perfluorinated alkyl substances (PFASs) exposure. Crabs contain high levels of PFASs, and different PFASs are concentrated in their tissues depending on their habitat. Despite South Korea importing huge quantities of crabs, no investigation has been conducted on the effect of PFAS exposure. This study investigated the risk of exposure to PFASs when ingesting crabs. To determine the risk of exposure, 19 different PFAS species were measured in the edible parts (body, legs, offal, and eggs) of crabs originating from South Korea (n = 17), China (n = 14), India (n = 7), and Pakistan (n = 31), which were distributed in the fish markets of South Korea. The results revealed that, in contrast to short-chain PFASs, long-chain PFASs (PFCAs≥8, PFSAs≥6, and perfluorooactane sulfonamidoacetic acids (FOSAAs)≥8) were detected in crab samples from all four countries of origin, and in all the edible parts except for the legs. Perfluorooctanoic acid (PFOA; 16.9 ng/g in South Korea, 9.42 ng/g in China) and perfluoro-n-tridecanoic acid (PFTrDA; 5.35 ng/g in South Korea, 2.40 ng/g in China) were the predominant perfluoroalkyl carboxylic acids (PFCAs) detected in the crabs originating from South Korea and China, and perfluorooctane sulfonic acid (PFOS; 7.02 ng/g in Pakistan, 5.88 ng/g in India) was the predominant perfluoroalkyl sulfonic acids (PFSAs) detected in crabs originating from Pakistan and India. These results indicate that PFASs that are accumulated in crabs differ depending on the ocean from which they originate. The concentrations of PFOA and PFOS were significantly higher in the eggs and offal than in the legs and body of the crab. The average daily intake of PFOA and PFOS in South Koreans ranges from 0.01% to 0.07% based on the tolerable daily intake of EFSA and MFDS. These results establish the PFAS profiles and risk assessment of crabs that are distributed in South Korea.

Transplacental Transfer of Per- and Polyfluoroalkyl Substances Identified in Paired Maternal and Cord Sera Using Suspect and Nontarget Screening

Novel per- and polyfluoroalkyl substances (PFASs) in various environmental media have attracted increasing attention; however, the information regarding PFASs exposure in pregnant women and fetuses is insufficient. In this study, we built and applied suspect and nontarget screening strategies based on the mass difference of the CF2, CF2O, and CH2CF2 units to select potential novel PFASs from 117 paired maternal and cord sera. In total, 10 legacy PFASs and 19 novel PFASs from 10 classes were identified to be above confidence levels 3, among which 14 were not previously reported in human serum. Novel PFASs accounted for a considerable percentage of total PFASs in pregnant women and can be transferred to fetuses at non-negligible concentrations (i.e., 27.9% and 30.3% of total PFAS intensities in maternal and cord sera, respectively). The transplacental transfer efficiency (TTE) of PFASs showed a U-shape trend in the series of perfluoroalkyl carboxylic acids, perfluoroalkyl sulfonic acids, and unsaturated perfluorinated alcohols. The TTE of novel PFASs is suggested to be structure-dependent, based on a flexible docking experiment. This study provides comprehensive TTE information on legacy and novel PFASs for the first time, and additional toxicity studies are needed to evaluate the risk of novel PFASs further.

Novel and legacy per- and polyfluoroalkyl substances in bald eagle eggs from the Great Lakes region

Decades of large-scale production of per- and polyfluoroalkyl substances (PFASs) have resulted in their ubiquitous presence in the environment worldwide. Similarly to other persistent and bioaccumulative organic contaminants, some PFASs, particularly the long-chain congeners, can be biomagnified via food webs, making top predators vulnerable to elevated PFAS exposure. In this study, we measured seven classes of PFASs in bald eagle (Haliaeetus leucocephalus) eggs for the first time. The eggs (n = 22) were collected from the North American Great Lakes in 2000–2012. The ranges of total concentrations of perfluoroalkyl sulfonic acids (∑PFSAs) and perfluoroalkyl carboxylic acids (∑PFCAs) were 30.5–1650 and 5.4–216 ng/g wet weight (ww), respectively. In addition to these traditional PFAS compounds, 6:2 fluorotelomer sulfonic acid (6:2 FTS; median: 15.7 ng/g ww), perfluoro-4-ethylcyclohexanesulfonic acid (PFECHS; 0.22 ng/g ww), and 8-chloro-perfluorooctanesulfonic acid (Cl-PFOS, detected in wildlife for the first time; 0.53 ng/g ww) were also frequently detected. Bald eagle eggs from breeding areas located less than 8 km from a Great Lake shoreline or tributary had significantly greater total PFAS concentrations (∑PFASs) than those from breeding areas located further than 8 km (p < 0.05). In these samples, ∑PFASs rivalled the total concentration of brominated flame retardants, and were significantly greater than those of several other organic contaminants, such as dechlorane-related compounds, organophosphate esters, and flame retardant metabolites.

New directions in perfluoroalkyl sulfonic acid–based proton-exchange membranes

Perfluoroalkyl sulfonic acid (PFSA) polymer membranes have enabled a variety of electrochemical energy storage and conversion devices such as fuel cells and flow batteries and material conversion devices such as electrolyzers to produce hydrogen and chlorine. For decades, a small group of simple copolymers were relied on in these applications. The practical limits for conductivity through lower equivalent weight are being approached for these polymers. Recently, the community has recognized the need for new PFSA ionomers with properties tailored to the specific needs of each application. An emerging area of importance is the manipulation of the diffusion properties of these polymers. For example, fuel cell membranes need to maintain good barrier properties as thicknesses are reduced, while ionomers with increased oxygen diffusion rates are sought for fuel cell electrodes. In recent years, the class of PFSA ionomers has expanded to include new side chain structures, new comonomers, and even hydrocarbon hybrid structures.

Perfluorinated Compounds (PFCs) in Soil of the Pearl River Delta, China: Spatial Distribution, Sources, and Ecological Risk Assessment.

This study investigated the levels, spatial distribution, sources, and ecological risks of 16 perfluorinated compounds (PFCs) in 68 surface soil samples (0-20cm) from 7 cities in the Pearl River Delta (PRD), China. Sixteen target PFCs, including perfluoroalkyl carboxylic acids (PFCAs, C5-C14, C16, and C18) and perfluoroalkyl sulfonic acids (PFSAs, C4, C6, C8, and C10), were analyzed by high-performance liquid chromatography-negative electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS). Concentrations of total PFCs (∑PFCs) ranged from 2.19 to 98.5μgkg-1 (dry weight, dw), with an average of 5.97μgkg-1dw. Perfluorooctane sulfonate (PFOS) was the dominant PFC, accounting for 23.9% of ∑PFCs. The highest ∑PFCs was found in the soil sample collected from Dongguan with a large number of manufacturing industries. There were no significant differences of ∑PFCs among unban, industrial, and agricultural soils, indicating similar pollution sources in soil of the PRD. More than 70% of ∑PFCs in soil of the PRD could be attributed to the four principal components, represented by PFOS and perfluorooctanoic acid (PFOA), perfluoropentanoic acid (PFPeA) and perfluorohexanoic acid (PFHxA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUdA). Ecological risk assessment indicated that PFOA had low risk to soil plants and animals. However, the risk of PFOS to soil plants was relatively high in some studied regions.

Approaches to Integrating the Toxicology and Epidemiology Evidence on PFAS

S05: PFAS Research Reaches its Adolescence: What Have We Learned and Where Are We Going?, Beatrix Theater, August 26, 2019, 10:30 AM - 12:00 PM Per- and polyfluoroalkyl substances (PFASs) have gained wide attention the last two decades. At present 4,600 CAS Registry Numbers are associated with PFASs that may have been on the global market (OECD 2018), while only some very few of these have been studied extensively. Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), belonging respectively to the sub groups of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs), are the best studied PFASs. Under the European REACH regulation, some PFCAs and PFSAs have been identified as substances of very high concern (SVHC), demonstrating a need for undertaking risk assessments. The risk assessment process include several steps, including hazard assessment and identification of the critical effect. The importance of integrating data from both experimental animal studies and human epidemiological studies have been highlighted, as both types of data have specific advantages and disadvantages. However, for many PFASs the amount of data is very limited, making this impossible. In the case of PFOS and PFOA data from both animal studies and human epidemiological studies are available for several endpoints. In this presentation, there will be a discussion on how these complementary types of data can be used in hazard assessments and how to utilize this knowledge for other PFASs where the data, in particular epidemiological data, are more limited or do not exist. However, for some endpoints such as changes in blood lipids, contradictory results have been observed between studies on experimental animals and humans. This, along with differences in exposure and toxicokinetics, needs to be considered when combining data from experimental animal studies and epidemiological studies. Reference OECD. 2018. Toward a New Comprehensive Global Database of Per- and Polyfluoroalkyl Substances (PFASs): Summary Report on Updating the OECD 2007 List of Per- and Polyfluoroalkyl Substances (PFASs). OECD Series on Risk Management No. 39.

Evaluation of perfluoroalkyl substances in field-cultivated vegetables

Perfluoroalkyl substances (PFASs) were investigated in three types of vegetables (fruit, leafy, and root vegetables) that were cultivated and harvested from 2014 to 2017. The cultivated soil was mainly affected by perfluoroalkyl carboxylic acid (PFCAs; 91.8% detection rate) rather than perfluoroalkyl sulfonic acids (PFSAs; 8.2%). The cultivated soil (i.e., a volcanic cohesive soil) had a high total organic carbon (TOC = 3.4%) and therefore showed strong adsorption of long-chain PFASs. Short-chain PFCAs (i.e., under C9) were mainly detected in vegetables; specifically, PFBA showed high concentration in tomato shoots. Principal component analysis (PCA) plots clearly showed that PFASs in vegetables were different from those of cultivated soil, air, and rainwater. Interestingly, the whole potato (i.e., including peel) was in the same group as soil, indicating that the whole potato can easily be affected by the cultivated soil. Energy Dispersive X-ray Spectrometry-Scanning Electron Microscope (EDS-SEM) results showed that presence of unremovable micron-sized cultivated soil particles on the potato surface. Comparing the regional differences between the cultivated area of Tsukuba city (East Japan) and Osaka city (West Japan), PFASs patterns were similar in cucumber but differed in green perilla and potato.

Derivation of a chronic reference dose for perfluorohexane sulfonate (PFHxS) for reproductive toxicity in mice

Perfluorohexane sulfonate (PFHxS) is a six-carbon perfluoroalkyl sulfonic acid that was used as an industrial surfactant, but is now found as an environmental contaminant worldwide. In addition to its use as an industrial surfactant, it is a legacy contaminant from the use of aqueous film-forming foams. Despite its widespread occurrence in the environment and evidence of biological activity associated with PFHxS and similar perfluoroalkyl sulfonic acids in rodents, there is no oral toxicity value currently available from the IRIS Database. To derive an oral reference dose (RfD) for PFHxS, available toxicity studies were reviewed using a weight-of-evidence approach. A 42-day mouse reproductive study was chosen as the critical study for the derivation of the oral RfD. Benchmark dose modeling was utilized to derive a point of departure (POD) for a reduction in litter size. A 95% lower confidence limit on the benchmark dose (BMDL) of 13,900 ng/mL (serum PFHxS) was modeled for a reduction in litter size. An oral RfD for PFHxS of 4.0 ng/kg/d was calculated by conversion of the BMDL to a human equivalent oral dose using a human half-life adjusted dosimetric conversion factor and the application of a total uncertainty factor of 300. Additional research is needed to better characterize the toxicity associated with oral exposure to PFHxS and refine the development of toxicity values.

One-pot fabrication of magnetic fluorinated carbon nanotubes adsorbent for efficient extraction of perfluoroalkyl carboxylic acids and perfluoroalkyl sulfonic acids in environmental water samples

Efficient extraction of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) is challenging due to their highly fluorinated property. Based on the particular characters of PFCAs and PFSAs, a new type of magnetic fluorinated carbon nanotubes adsorbent (MFCA) for magnetic solid phase extraction (MSPE) was fabricated facilely using one-pot hydrothermal approach. The morphology, structure and magnetic properties of the prepared MFCA were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and vibrating sample magnetometry. It was observed that the resultant adsorbent possessed satisfactory superparamagnetism and saturation magnetism. Furthermore, the MFCA exhibited excellent enrichment performance for target PFCAs and PFSAs by means of fluorous-fluorous, hydrophobic and hydrogen bonding interactions. Under the most favorable preparation and extraction conditions, the proposed MFCA/MSPE was combined with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) to quantify ultra trace target analytes in environmental water samples. The limits of detection (S/N = 3) of PFCAs and PFSAs were 0.010–0.036 ng/L and 0.024–0.50 ng/L, respectively. In addition, the introduced approach also displayed other features such as quick extraction procedure, wide linear dynamic ranges, excellent method precision and eco-friendliness. Finally, the concentrations of PFCAs and PFSAs in tap, river, lake and waste water samples were successfully measured by isotope internal standard calibration curve method.

Combined spatial and retrospective analysis of fluoroalkyl chemicals in fluvial sediments reveal changes in levels and patterns over the last 40 years

Bed sediments and a dated sediment core were collected upstream and downstream from the city of Lyon (France) to assess the spatial and temporal trends of contamination by per- and polyfluoroalkyl substances (PFASs) in this section of the Rhône River. Upstream from Lyon, concentrations of total PFASs (ΣPFASs) in sediments are low (between 0.19 and 2.6 ng g−1 dry weight - dw), being characterized by a high proportion of perfluorooctane sulfonate (PFOS). Downstream from Lyon, and also from a fluoropolymer manufacturing plant, ΣPFASs concentrations reach 48.7 ng g−1 dw. A gradual decrease of concentrations is reported at the coring site further downstream (38 km). Based on a dated sediment core, the temporal evolution of PFASs is reconstructed from 1984 to 2013. Prior to 1987, ΣPFASs concentrations were low (≤2 ng g−1 dw), increasing to a maximum of 51 ng g−1 dw in the 1990s and then decreasing from 2002 to the present day (∼10 ng g−1 dw). In terms of the PFAS pattern, the proportion of perfluoroalkyl sulfonic acids (PFSAs) has remained stable since the 1980s (∼10%), whereas large variations are reported for carboxylic acids (PFCAs). Long chain- (C > 8) PFCAs characterized by an even number of perfluorinated carbons represent about 74% of the total PFAS load until 2005. However, from 2005 to 2013, the relative contribution of long chain- (C > 8) PFCAs with an odd number of perfluorinated carbons reaches 80%. Such changes in the PFAS pattern likely highlight a major shift in the industrial production process. This spatial and retrospective study provides valuable insights into the long-term contamination patterns of PFAS chemicals in river basins impacted by both urban and industrial activities.

Occurrences of perfluoroalkyl and polyfluoroalkyl substances in tree bark: Interspecies variability related to chain length

Occurrences of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in tree bark from four species were investigated. Species-dependent congener distribution patterns were firstly reported for perfluorocarboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs). The majority of PFSAs and PFCAs in Chinese red pine bark were C5–C7 PFSAs and perfluorohexanoic acid (PFHxA, containing six carbon atoms, C6), whereas perfluorobutanesulfonic acid (PFBS, C4) and longer chain congeners (PFCAs: C ≥ 7; PFSAs: C ≥ 8) took a larger proportion in the fissured bark from Canadian poplar, Chinese scholartree and weeping willow. The species-dependent congener profiles depended on the structures and chemical compositions of tree bark, as well as the translocation of PFASs within plants. Different tree bark characteristics caused different retention abilities for particle-bound and gaseous PFASs. Particle-bound PFASs retained in the rougher structures of fissured bark led to preferential retention of long chain congeners (the major fraction in the particle phase), while lipid-rich Chinese red pine bark retained more gaseous PFASs (mainly short chain congeners). Besides, the abundance of short chain PFASs in red pine bark was consistent with the chain length-dependent translocation behaviors of PFASs in various plants, suggesting that translocation of PFASs within plants to tree bark may be invovled.

Bioaccumulation and biomagnification of perfluoroalkyl acids and precursors in East Greenland polar bears and their ringed seal prey

The bioaccumulation and biomagnification of 22 major perfluoroalkyl substances (PFAS) were investigated in tissues of polar bears (Ursus maritimus) and their major prey species, the ringed seal (Pusa hispida), from the Scoresby Sound region of East Greenland. In polar bear liver the mean Σ4PFSA (perfluoroalkyl sulfonic acid) concentration (C4, C6, C8 and C10) was 2611 ± 202 ng/g wet weight (ww; 99% perfluorooctane sulfonate (PFOS)) and two orders of magnitude higher than the 20 ± 3 ng/g ww (89% PFOS) concentration in fat. The mean Σ4PFSAs in seal liver was 111 ± 5 ng/g ww (98% PFOS) and three orders of magnitude higher relative to the 0.05 ± 0.01 ng/g ww concentration in blubber (100% perfluorohexane sulfonate). Perfluoro-1-octane sulfonamide (FOSA) was quantifiable in bear (mean 10 ± 1.4 ng/g ww) and seal (mean 0.6 ± 0.1 ng/g ww) liver but not in fat or blubber. The mean Σ13PFCAs (C4–C18; perfluoroalkyl carboxylic acids) in bear liver (924 ± 71 ng/g ww) was much greater than in seal liver (74 ± 6 ng/g ww). In bear fat and seal blubber, the mean Σ13PFCAs were 15 ± 1.9 and 0.9 ± 0.1 ng/g ww, respectively. Longer chain C11 to C14 PFCAs dominated in bear fat and seal blubber (60–80% of Σ13PFCA), whereas shorter-chain C9 to C11 PFCAs dominated in the liver (85–90% of Σ13PFCA). Biomagnification factors (BMFs) were orders of magnitude greater for PFHxS and C9 to C13 PFCAs when based on bear liver to seal blubber rather than bear liver to seal liver, and PFCA (C9 to C13) BMFs decreased with increasing chain length. Seal blubber to bear liver BMFs better reflects the dietary exposure relationship of PFAS between bears and seals.

Spatial Distribution of Perfluorinated Compounds in Atmosphere of the Pearl River Delta, China.

Perfluorinated compounds (PFCs) are of special concern due to their environmental persistence and biotoxicity. In the present study, spatial distribution of PFCs in atmosphere of the Pearl River Delta (PRD) of Southern China was investigated from November 2013 to January 2014. Forty-two air samples were collected using passive air samplers to determine the 13 target analytes, including perfluoroalkyl carboxylic acids (PFCAs, C5-14) and perfluoroalkyl sulfonic acids (PFSAs, C4, C6, and C8). Results showed that the total concentrations of PFCs (ΣPFCs) ranged from 53.7 to 225pgm-3 with an average level of 122 ± 41.5pgm-3, indicating a wide variation on ΣPFCs in atmosphere of the PRD. Perfluorooctane sulfonate (PFOS) was the most abundant PFCs, followed by perfluorooctanoic acid (PFOA), perfluoropentanoic acid (PFPeA), and perfluoroheptanoic acid (PFHpA). PFOS, PFOA, PFPeA, and PFHpA accounted for 26%, 22%, 21%, and 19% of ΣPFCs, respectively. A general decline in ΣPFCs was observed in the atmosphere from south PRD to north PRD. It was likely related to the industrial distribution, population density, and wind direction. In addition, the same order of magnitude of PFOS and lower level of PFOA were observed in this study compared with those in atmosphere sampled in other regions. The lifetime risk indexes on the PFOS and PFOA concentrations were much less than unity, suggesting a lower nononcogenic risk to residents in the PRD.

Column chromatography approach to determine mobility of fluorotelomer sulfonates and polyfluoroalkyl betaines

Betaine-based polyfluoroalkyl surfactants are major perfluoroalkyl and polyfluoroalkyl surfactants (PFASs) found in many aqueous film-forming foams (AFFF) impacted sites, while the transport behavior (i.e., mobility and adsorption) of PFAS-based betaines in groundwater and natural geosorbents interfaces remains unclear. To fill the knowledge gap, partitioning between of 15 AFFF-relevant PFASs, including 3 fluorotelomer sulfonates (FTSAs) and 3 polyfluoroalkyl betaines, and a model soil organic matter (SOM) were systematically assessed using a modified column chromatography approach. Results show that the retention of FTSAs (perfluoroalkyl chain-length of 4, 6, and 8) to SOM are similar to that of corresponding legacy perfluoroalkyl sulfonic acids (PFSAs) with the same chain length; FTSAs also respond to changes in solution chemistry similarly as PFSAs. At a solution pH of 5.9, based on the equilibrium speciation of the betaine-PFASs together with the experimental observations, the predominance of the neutral species over zwitterions gives rise to the relatively higher retention of polyfluoroalkyl betaines than perfluoroalkyl carboxylic acids (PFCAs) of equivalent chain-length. Sorption edges (minimal and maximal logKoc values over a defined pH range) determined for three polyfluoroalkyl betaines are: 1.90–3.81 for perfluorooctaneamide betaine (PFOAB), 2.03–2.65 for perfluoroctane sulfonamide betaine (PFOSB), and < 3.04 for 6:2 fluorotelomer sulfonamide betaine (6:2 FTAB). Moreover, the increase in pH reduces the sorption of all PFASs to SOM. Increasing calcium ion (concentration ranges from 0.5 to 50 mM) has enhanced the sorption of anionic PFASs to SOM but decreased the sorption of the polyfluoroalkyl betaines. These findings are expected to improve the ability to anticipate and predict the possible subsurface locations (i.e., predominantly in groundwater or sorbed to soil) of both novel and legacy PFASs.

Contamination of groundwater with per- and polyfluoroalkyl substances (PFAS) from legacy landfills in an urban re-development precinct

The extent of per- and polyfluoroalkyl substances (PFAS) in groundwater surrounding legacy landfills is currently poorly constrained. Seventeen PFAS were analysed in groundwater surrounding legacy landfills in a major Australian urban re-development precinct. Sampling locations (n = 13) included sites installed directly in waste material and down-gradient from landfills, some of which exhibited evidence of leachate contamination including elevated concentrations of ammonia-N (≤106 mg/L), bicarbonate (≤1,740 mg/L) and dissolved methane (≤10.4 mg/L). Between one and fourteen PFAS were detected at all sites and PFOS, PFHxS, PFOA and PFBS were detected in all samples. The sum of detected PFAS (∑14PFAS) varied from 26 ng/L at an ambient background site to 5,200 ng/L near a potential industrial point-source. PFHxS had the highest median concentration (34 ng/L; range: 2.6–280 ng/L) followed by PFOS (26 ng/L; range: 1.3–4,800 ng/L), PFHxA (19 ng/L; range: <LOQ – 46 ng/L) and PFOA (12 ng/L; range: 1.7–74 ng/L). Positive correlations between ∑14PFAS, PFOA and other perfluoroalkyl carboxylic acids (PFCAs) (e.g. PFHxA) with typical leachate indicators including ammonia-N and bicarbonate were observed. In contrast, no such correlations were found with perfluoroalkyl sulfonic acids (PFSAs) (e.g., PFOS and PFHxS). In addition, a strong positive linear correlation (R2 = 0.69) was found between the proportion of PFOA in the sum of detected perfluorinated alkylated acids (PFOA/∑PFAA) and ammonia-N concentrations in groundwater. This is consistent with previous research showing relatively high PFOA/∑PFAA in municipal landfill leachates, and more conservative behaviour (e.g. less sorption and reactivity) of PFCAs during subsurface transport compared to PFSAs. PFOA/∑PFAA in groundwater may therefore be a useful indicator of municipal landfill-derived PFAA. One site with significantly elevated PFOS and PFHxS concentrations (4,800 and 280 ng/L, respectively) appears to be affected by point-source industrial contamination, as landfill leachate indicators were absent.

Temporal trends of per- and polyfluoroalkyl substances (PFAS) in the influent of two of the largest wastewater treatment plants in Australia

Abstract Per- and polyfluoroalkyl substances (PFAS) are found ubiquitously in wastewater treatment plants (WWTPs) due to their multiple sources in industry and consumer products. In Australia, limited spatial data are available on PFAS levels in WWTPs influent, while no temporal data have been reported. The aim of this study was to investigate the occurrence and temporal trend of PFAS in the influent of two large WWTPs in Australia (WWTP A and B) over a four-year period. Daily influent samples were collected over one week at different seasons from 2014 to 2017. Eleven perfluoroalkyl acids (PFAA) (i.e. seven perfluoroalkyl carboxylic acids (PFCAs) and four perfluoroalkyl sulfonic acids (PFSA)) were detected with mean Σ11PFAA concentrations of 57 ± 3.3–94 ± 17 ng/L at WWTP A, and 31 ± 6.1–142 ± 73 ng/L at WWTP B. The highest mean concentrations were observed for perfluorohexanoate (PFHxA) (20 ± 2 ng/L) in WWTP A, and perfluorooctane sulfonate (PFOS) (17 ± 13 ng/L) in WWTP B. The precursor 6:2 fluorotelomer sulfonate was detected over five sampling periods from Aug 2016 to Oct 2017, with mean concentrations of 37 ± 18–138 ± 51 ng/L for WWTP A and 8.8 ± 4.5–29 ± 5.1 ng/L for WWTP B. Higher concentration of 6:2 FTS (1.8–11 folds) than those of PFOA and PFOS in WWTP A indicate a likely substitution of C8 PFAA by fluorotelomer-based PFAS in this catchment. Temporal trends (annual and seasonal) in per-capita mass load were observed for some PFAA, increasing for PFPeA, PFHxA, PFHpA, PFNA, and PFHxS, while decreasing for PFBS and PFOS in either WWTPs. Notably, elevated levels of PFOS in October 2017 were observed at both WWTPs with the highest per capita mass load of up to 67 μg/day/inhabitant. For some PFAS release trends, longer sampling periods would be required to achieve acceptable statistical power.