Concentrations Of Perfluoroalkyl Carboxylates Research Articles

Per- and polyfluoroalkyl substances (PFAS) in Canadian municipal wastewater and biosolids: Recent patterns and time trends 2009 to 2021

The concentrations of per- and polyfluoroalkyl substances (PFAS) were determined in raw influent, final effluent, and treated biosolids at Canadian wastewater treatment plants (WWTPs) to evaluate the fate of PFAS through liquid and solids trains of typical treatment process types used in Canada and to assess time trends of PFAS in wastewater between 2009 and 2021. Data for 42 PFAS in samples collected from 27 WWTP across Canada were used to assess current concentrations and 48 WWTPs were included in the time trends analysis. Although regulated and phased-out of production by industry since the early 2000s and late 2000s/early2010s, respectively, perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and other long-chain PFAS continue to be widely detected in Canadian wastewater and biosolids. Short-chain PFAS that are not currently regulated in Canada were also widely detected. In general, elevated concentrations of several PFAS were observed at WWTPs that receive landfill leachate. Except for PFOS, concentrations of long-chain perfluoroalkyl carboxylates (PFCAs) and perfluoroalkane sulfonates (PFSAs) generally decreased over time in influent, effluent, and biosolids, which is attributable to industrial production phase-outs and regulations. Concentrations of PFOS did not decrease over time in wastewater media. This indicates that regulatory action and industrial phase-outs of PFOS are slow to be reflected in wastewater. Concentrations of short-chain PFCAs in wastewater influent and effluent consistently increased between 2009 and 2021, which reflect the use of short-chain PFAS as replacements for phased-out and regulated longer-chained PFAS. Short-chain PFAS were infrequently detected in biosolids. Continued periodic monitoring of PFAS in wastewater matrices in Canada and throughout the world is recommended to track the effectiveness of regulatory actions, particularly activities to address the broad class of PFAS.

Perfluoroalkyl Substances in Seabird Eggs from Canada's Pacific Coast: Temporal Trends (1973-2019) and Interspecific Patterns.

Whether perfluoroalkyl sulfonates (PFSAs) and perfluoroalkyl carboxylates (PFCAs) are responding to legislative restrictions and showing decreasing trends in top marine predators that range across the eastern North Pacific Ocean is unclear. Here, we examined longer-term temporal trends (1973-2019) of 4 PFSAs and 13 PFCAs, as well stable isotopes of δ13C and δ15N, in the eggs of 4 seabird species sampled along a nearshore-offshore gradient; double-crested cormorants (Nannopterum auritum), pelagic cormorants (Urile pelagicus), rhinoceros auklets (Cerorhinca monocerata), and Leach's storm-petrels (Hydrobates leucorhous) from the Pacific coast of British Columbia, Canada. PFOS was the most abundant PFSA (79-94%) detected in all eggs regardless of colony and year, with the highest concentrations, on average, measured in auklet eggs (mean = 58 ng g-1, range = 11-286 ng g-1 ww). Perfluoroundecanoic acid (PFUdA) and perfluorotridecanoic acid (PFTriDA) were the dominant long-chain PFCAs (≥30% combined). The majority of PFSAs (including PFOS) are statistically declining (p < 0.001) in the eggs of all 4 species with PFOS half-lives ranging from 2.6 to 7.8 years. Concentrations of long-chain PFCAs exhibited a trajectory comprised of linear increases and second-order declines, suggesting that the rate of uptake of PFCAs is slowing or leveling off. These trends are consistent with the voluntarily ceased production of PFSAs by 3M circa 2000-2003 and are among the first from the northeast Pacific to indicate a positive response to several regulations and restrictions on PFCAs from facility emissions and product content.

Perfluoroalkyl substances (PFASs) in white whales (Delphinapterus leucas) from Svalbard – A comparison of concentrations in plasma sampled 15 years apart

The objective of the present study was to investigate recent concentrations of perfluoroalkyl substances (PFASs) in white whales (Delphinapterus leucas) from Svalbard and compare them to concentrations found in white whales sampled from that same area 15 years ago. Plasma collected from live-captured white whales from two time periods (2013–2014, n = 9, and 1996–2001, n = 11) were analysed for 19 different PFASs. The 11 PFASs detected included seven C8–C14 perfluoroalkyl carboxylates (PFCAs) and three C6–C8 perfluoroalkyl sulfonates (PFSAs) as well as perfluorooctane sulfonamide (FOSA). Recent plasma concentrations (2013–2014) of the dominant PFAS in white whales, perfluorooctane sulfonate (PFOS; geometric mean = 22.8 ng/mL), was close to an order of magnitude lower than reported in polar bears (Ursus maritimus) from Svalbard. PFOS concentrations in white whales were about half the concentrations in harbour (Phoca vitulina) and ringed (Pusa hispida) seals, similar to hooded seals (Cystophora cristata) and higher than in walruses (Odobenus rosmarus) from that same area. From 1996 to 2001 to 2013–2014, plasma concentrations of PFOS decreased by 44%, whereas four C9-12 PFCAs and total PFCAs increased by 35–141%. These results follow a similar trend to what has been reported in other studies of Arctic marine mammals from Svalbard. The most dramatic change has been the decline of PFOS concentrations since 2000, corresponding to the production phase-out of PFOS and related compounds in many countries around the year 2000 and a global restriction on these substances in 2009. Still, the continued dominance of PFOS in white whales, and increasing concentration trends for several PFCAs, even though exposure is relatively low, calls for continued monitoring of concentrations of both PFCAs and PFSAs and investigation of biological effects.

Poly- and perfluoroalkyl substance concentrations in human breast milk and their associations with postnatal infant growth

Perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates are widespread in human breast milk. However, the occurrence of chlorinated polyfluorinated ether sulfonates (Cl-PFESAs) and fluorotelomer alcohols (FTOHs) in breast milk and their effects on postnatal growth of infants through breast milk consumption are still not well known. This study characterized the occurrence of 16 poly- and perfluoroalkyl substances (PFASs) in breast milk from 174 women in Hangzhou, China and investigated the association between lactation exposure to these PFASs through breast milk consumption and the postnatal growth of infants. Our results showed that perfluorooctanoate (mean 87 pg/mL) was the predominant PFAS in breast milk, followed by perfluorohexanoate (41 pg/mL), 6:2 Cl-PFESA (28 pg/mL), and perfluorooctane sulfonate (25 pg/mL). The occurrence and levels of Cl-PFESAs in Chinese breast milk were firstly reported in the current study. The 8:2 and 10:2 FTOH were detected in half of breast milk samples, with the mean concentration of 9.0 pg/mL and 10 pg/mL, respectively. Breast milk concentrations of C8-C10 PFCAs and 6:2 Cl-PFESA were negatively correlated with infant's length gain rate. Exposed to higher levels of 8:2 FTOH were correlated with decreased infant's weight gain rate. Daily intakes of PFASs via the consumption of breast milk were calculated for infants. Overall, this study firstly demonstrated that lactation exposure to C8-C10 PFCAs, 8:2 FTOH, and 6:2 Cl-PFESA through breast milk consumption may affect the postnatal growth of infants.

Atmospheric perfluoroalkyl acid occurrence and isomer profiles in Beijing, China

The airborne occurrence, isomer profiles, and phase distribution of perfluoroalkyl acids (PFAAs), including perfluoroalkyl carboxylates (PFCAs) and sulfonates (PFSAs), have received little scientific attention to date. Here we collected gaseous and particulate phase (PM2.5) samples in China, between June and November 2013, using alkalized annular denuders and downstream filters toavoid sampling artefacts associated with traditional air sampling. We analysed the concentrations of 18 linear PFAAs and the branched isomers of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). Concentrations of total PFAAs were dominated by PFCAs, with a range of 6.6–610 pg/m3 in the gaseous phase and 2.3–290 pg/m3 in the particulate phase. Concentrations of total PFCAs were higher in summer than winter in both phases. Branched PFOA isomers accounted for 10–22% of total PFOA in the gaseous phase and 13–24% in the particulate phase, which is close to, but slightly lower than, their abundance in the commercial PFOA mixtures manufactured using the electrochemical fluorination (ECF) process. In contract, branched PFOS isomers accounted for 26-63% of total PFOS in the gaseous phase and 39-77% in the particulate phase, which is much higher than their abundance in commercial PFOS mixtures manufactured by ECF. Most PFCAs had mean particle-associated fractions (Φ) higher than 0.5. PFHxS had a much higher mean Φ (0.65) than linear PFOS (0.31). We hypothesise that PFAAs observed in Beijing air may originate from the local water bodies through processes such as aerosol generation, although transformation of precursors also contribute.

Integrating total oxidizable precursor assay data to evaluate fate and transport of PFASs

AbstractFate and transport of per‐ and polyfluoroalkyl substances (PFASs) are complex and are not well understood. Among this class of emerging contaminants, perfluoroalkyl acids (PFAAs) comprising perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs) are being studied more frequently than polyfluorinated compounds. PFAAs are persistent in the environment, recalcitrant to biological degradation, and, therefore, widespread. Previous studies have indicated that some PFASs bioaccumulate. The fate and transport of PFAAs can be complicated by the presence of PFAA precursors. The PFAA precursors are defined in this article as those fluorinated chemicals that can be potentially transformed abiotically or biotically into terminal PFCA or PFSA products. Due to potential biotransformation in the environment, PFAA precursors can influence the temporal and lateral distribution of PFAAs in the environment. Presently, only a very small number of PFAA precursors can be quantitatively analyzed by commercial laboratories. For instance, N‐ethyl perfluorooctanesulfonamidoacetic acid and N‐methyl perfluorooctanesulfonamidoacetic acid are the only two precursors included in the most commonly applied PFAS analytical method, U.S. Environmental Protection Agency Method 537. The current commercial laboratory methodologies primarily quantify between 14 and 31 PFASs. As an alternative, a total oxidizable precursor assay (TOPA) was developed to quantify the measurable PFSA and PFCA concentrations after aggressive oxidation converting PFAA precursors abiotically into PFCAs. The difference between PFAA concentrations before and after oxidation can be used to estimate the amount of oxidizable PFAA precursors in the sample. This is one of the first articles that utilized TOPA data to help interpret PFAS fate and transport in the environment.

Diet and metabolic state are the main factors determining concentrations of perfluoroalkyl substances in female polar bears from Svalbard

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 C8-C13 perfluoroalkyl carboxylates (PFCAs) in 112 plasma samples obtained in April and September 2012–2013. Nitrogen and carbon stable isotope ratios (δ15N, δ13C) 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 C8-C10 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.

Elevated levels of short carbon-chain PFCAs in breast milk among Korean women: Current status and potential challenges

Breast milks can be contaminated with perfluoroalkyl substances (PFASs). Exposure to PFASs during early stages of life may lead to adverse health effects among breastfed infants. To date, perfluorootanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been most frequently measured PFASs in breast milks worldwide. Information on shorter carbon-chain PFASs in breast milk is scarce. In this study, breast milks were sampled from 264 Korean lactating women, and measured for seventeen PFASs, including ten perfluoroalkyl carboxylates (PFCAs), four perfluoroalkyl sulfonates, and three perfluoroalkyl sulfonamides. PFOA and PFOS were detected in 98.5% of the breast milk samples, with median concentrations of 0.072 and 0.050ng/mL, respectively. Perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), and perfluoroheptanoic acid (PFHpA) were detected in higher frequencies, ranging between 67.4% and 81.8%. The concentrations of short carbon-chain PFCAs in breast milk such as PFPeA and PFHxA were the highest ever reported to date, and were comparable to that of PFOS. Concentrations of shorter chain PFCA in breast milk tended to be higher among the women with longer lactation period, while those of PFOA showed the opposite trend, suggesting a possibility that breastfeeding might be an important route of excretion for PFOA among lactating women. Fish consumption and the use of consumer products, e.g., skin care products, cosmetics and non-stick coated cooking utensils, were identified as significant predictors of PFAS concentrations in breast milk. Health risks associated with PFOA and PFOS exposure through breastfeeding were estimated negligible, however, risks of the short carbon-chain PFCAs could not be assessed because of lack of relevant toxicological information. Further efforts for source identification and exposure management measures for shorter chain PFCAs are necessary.

Spatial and temporal trends in perfluoroalkyl substances (PFASs) in ringed seals (Pusa hispida) from Svalbard

This study investigates concentrations of perfluoroalkyl carboxylates (PFCAs), perfluoroalkyl sulfonates (PFSAs) and perfluoroalkane sulfonamides (FASA) in plasma from ringed seals sampled in the period 1990–2010 (n = 71) in Svalbard, Norway. Perfluorooctane sulfonate was dominant among the perfluoroalkyl substances. PFCAs were dominated by perfluoroundecanoate followed by perfluorononanoate. C4C8 PFCAs and perfluorooctane sulfonamide (FOSA) were detected in ≤42% of the samples. PFSA and PFCA concentrations were higher in seals sampled from Kongsfjorden, a fjord influenced by strong inflows of Atlantic Water compared to seals from fjords dominated by Arctic Water (e.g. Billefjorden). Sex, age and body condition of the seals did not influence PFAS concentrations. Due to the confounding effect of year and sampling area, temporal trends were assessed only in seals sampled from Kongsfjorden (5 years, n = 51). PFHxS and PFOS concentrations did not show significant linear trends during the whole study period, but a decrease was observed since 2004. Concentrations of all of the detected PFCAs (C9C13 PFCAs) increased until 2004 after which they have declined or stabilized.

Perfluoroalkyl substance concentrations in a terrestrial raptor: relationships to environmental conditions and individual traits.

Accumulation of persistent organic pollutants (POPs) in wildlife may be influenced by the physical and biotic environment, and concentrations vary greatly among areas, seasons, and individuals. Different hypotheses about sources of variation in perfluoroalkyl substance (PFAS) concentrations were examined in eggs (n = 107) of tawny owls (Strix aluco) collected over a 24-yr period (1986-2009) in Norway. Predictor variables included the North Atlantic Oscillation (NAO), temperature, snow, food availability (vole abundance), and individual traits such as age, body condition, and clutch size. Concentrations of both perfluoro-octane sulfonate (PFOS) and perfluoroalkyl carboxylates (PFCAs) varied several fold in the population, both inter- and intra-annually. Moreover, individuals laid eggs with several times higher or lower PFAS concentrations within few years (1 yr-5 yr). After controlling for temporal trends (i.e., declining PFOS and increasing PFCA concentrations), both PFOS and PFCAs were positively associated to the winter NAO in the previous year (NAOy - 1 ), suggesting that atmospheric transport may be affecting the input of PFASs to the local ecosystem. Perfluoro-octane sulfonate was negatively related to temperature, but the pattern was complex as there was an interaction between temperature and the feeding conditions. The PFOS accumulation was highest in years with high vole abundance and low to medium temperatures. For PFCAs, there was an interaction between NAOy - 1 and feeding conditions, suggesting that strong air transport toward Norway and high consumption of voles led to a moderate increase in PFCA accumulation. The individual traits, however, had very little impact on the concentrations of PFASs in the eggs. The present study thus suggests that annual variation in environmental conditions influences the concentrations of PFASs in a terrestrial raptor such as the tawny owl.

Tissue-Specific Concentrations and Patterns of Perfluoroalkyl Carboxylates and Sulfonates in East Greenland Polar Bears

Several perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs) of varying chain length are bioaccumulative in biota. However, wildlife reports have focused on liver and with very little examination of other tissues, and thus there is a limited understanding of their distribution and potential effects in the mammalian body. In the present study, the comparative accumulation of C(6) to C(15) PFCAs, C(4), C(6), C(8) and C(10) PFSAs, and select precursors were examined in the liver, blood, muscle, adipose, and brain of 20 polar bears (Ursus maritimus) from Scoresby Sound, Central East Greenland. Overall, PFSA and PFCA concentrations were highest in liver followed by blood > brain > muscle ≈ adipose. Liver and blood samples contained proportionally more of the shorter/medium chain length (C(6) to C(11)) PFCAs, whereas adipose and brain samples were dominated by longer chain (C(13) to C(15)) PFCAs. PFCAs with lower lipophilicities accumulated more in the liver, whereas the brain accumulated PFCAs with higher lipophilicities. The concentration ratios (±SE) between perfluorooctane sulfonate and its precursor perfluorooctane sulfonamide varied among tissues from 9 (±1):1 (muscle) to 36 (±7):1 (liver). PFCA and PFSA patterns in polar bears indicate that the pharmacokinetics of these compounds are to some extent tissue-specific, and are the result of several factors that may include differing protein interactions throughout the body.

Temporal Trends and Pattern of Polyfluoroalkyl Compounds in Tawny Owl (Strix aluco) Eggs from Norway, 1986−2009

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in tawny owl (Strix aluco) eggs collected in Central Norway over a period of 24 years (1986-2009). Concentrations of 12 PFCs, including C(6)-C(8), C(10) perfluoroalkyl sulfonates (PFSAs), perfluorooctane sulfonamide (PFOSA), and C(8)-C(14) perfluoroalkyl carboxylates (PFCAs), were measured, whereas saturated and unsaturated fluorotelomer carboxylates and shorter chain PFSAs and PFCAs were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (geometric mean 10.1 ng/g wet weight (ww)), followed by perfluorotridecanoate (PFTriDA) (0.36 ng/g ww) and perfluoroundecanoate (PFUnDA) (0.19 ng/g ww). Significant decreasing concentrations were found for PFOS with an annual decrease of 1.6% (1986-2009), while, conversely, the C(10)-C(13) PFCA concentrations increase significantly with an annual increase of 4.2-12% (1986-2009). Consequently, the contribution of PFOS to the ∑PFCs decreased, whereas the contribution of the ∑PFCAs increased over the time. Toxicological implications for tawny owls are limited, but the maximal PFOS concentration found in this stu0dy is about 20 times lower than the predicted avian no effect concentration (PNEC) which suggest adverse effects caused by PFOS are unlikely. However, tawny owls are exposed to a mixture of various PFCs, and PFCA concentrations still increase.

Perfluoroalkyl contaminants in liver tissue from East Greenland polar bears (Ursus maritimus)

Perfluoroalkyl substances were determined in polar bears (Ursus maritimus) collected in East Greenland (69 degrees 00'N to 74 degrees 00"N) to compare with other populations and to examine effects of age and gender on concentrations of these contaminants. Hepatic tissue (n = 29) was analyzed for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorohexane sulfonate, heptadecafluorooctane sulfonamide (PFOSA), and perfluoroalkyl carboxylates (PFCAs) with C9-C15 perfluorinated carbon chains by liquid chromatography tandem mass spectrometry. Concentrations of PFOS found in samples from East Greenland (mean = 2,470+/-1,320 ng/g wet weight) were similar to Hudson Bay, Canada, and both populations had significantly greater concentrations than those reported for Alaska, suggesting a spatial trend. Male bears showed a significant increase in concentration up to age six for PFCAs with C10-C14 carbon chains (r2 > or = 0.50, p < or = 0.05). Significant correlations were found between adjacent chain length PFCAs, (e.g., PFNA to PFDA: p < 0.05; r2 = 0.90). This may indicate a common source for these chemicals, although the specifics of source and mode of transport are unknown. No significant correlations were found between concentrations of PFCAs in liver tissue and previously reported polychlorinated biphenyl (PCB) congeners analyzed in fat samples from the same bears.

Identification of long-chain perfluorinated acids in biota from the Canadian Arctic.

Recently it was discovered that humans and animals from various urban and remote global locations contained a novel class of persistent fluorinated contaminants, the most pervasive of which was perfluorooctane sulfonate (PFOS). Lower concentrations of perfluorooctanoate, perfluorohexane sulfonate, and heptadecafluorooctane sulfonamide have also been detected in various samples. Although longer perfluoroalkyl carboxylates (PFCAs) are used in industry and have been detected in fish following a spill of aqueous film forming foam, no studies have been conducted to examine the widespread occurrence of long-chain PFCAs (e.g., CF3(CF2)xCOO-, where x > 6). To provide a preliminary assessment of fluorinated contaminants, including PFCAs, in the Canadian Arctic, polar bears, ringed seals, arctic fox, mink, common loons, northern fulmars, black guillemots, and fish were collected at various locations in the circumpolar region. PFOS was the major contaminant detected in most samples and in polar bear liver was the most prominent organohalogen (mean PFOS = 3.1 microg/g wet weight) compared to individual polychlorinated biphenyl congeners, chlordane, or hexachlorocyclohexane-related chemicals in fat. Using two independent mass spectral techniques, it was confirmed that all samples also contained ng/g concentrations of a homologous series of PFCAs, ranging in length from 9 to 15 carbons. Sum concentrations of PFCAs (sum(PFCAs)) were lower than total PFOS equivalents (sum(PFOS)) in all samples except for mink. In mink, perfluorononanoate (PFNA) concentrations exceeded PFOS concentrations, indicating that PFNA and other PFCAs should be considered in future risk assessments. Mammals feeding at higher trophic levels had greater concentrations of PFOS and PFCAs than mammals feeding at lower trophic positions. In general, odd-length PFCAs exceeded the concentration of even-length PFCAs, and concentrations decreased with increasing chain length in mammals. PFOS and PFCA concentrations were much lower for animals living in the Canadian Arctic than for the same species living in mid-latitude regions of the United States. Future studies should continue to monitor all fluorinated contaminants and examine the absolute and relative toxicities for this novel suite of PFCAs.