Distribution Of Polyfluoroalkyl Substances Research Articles

Nationwide distribution of per- and polyfluoroalkyl substances (PFAS) in road dust from India

In India, information on the occurrence and distribution of legacy and emerging per- and polyfluoroalkyl substances (PFAS) is deficient. In the present study, nationwide 79 road dust samples were collected from 12 states and 1 union territory for the analysis of 34 PFAS. Overall, total concentrations of 21 quantified PFAS (∑21PFAS) ranged 23–861 pg/g (median: 116 pg/g), with perfluorooctane sulfonic acid (PFOS) being predominant (median: 19.9 pg/g). Short to long chain perfluoroalkyl carboxylic acids (PFCAs; C4 − C18) were detected, where the concentrations of PFAS decreased with the increase in PFAS carbon chain length. ∑21PFAS was highest in road dust from urban area (n = 27; median: 230 pg/g), followed by suburban (n = 21; median: 126 pg/g) and rural areas (n = 31; median: 76 pg/g), suggesting environmental impacts of industriallization and urbanization on PFAS distribution. PFAS composition in rural road dust was significantly different from those in suburban and urban samples (p < 0.01). Regarding 4 geographical regions of India, PFAS in road dust showed spatial difference where higher concentrations were found in South India compared to other regions. ∑21PFAS were positively associated with city-wise population of India (rs = 0.40, p < 0.01). Strong to moderate positive correlation was observed between ∑21PFAS, fluorotelomer sulfonic acids, and PFCAs (rs = 0.23, 0.30, and 0.28, respectively; p < 0.05) and the total state-wise vehicles in India, suggesting that vehicles exhaust or non-exhaust (e.g., vehicle tire debris and polishing material) might contribute to the PFAS occurrence in Indian road dust. Toddlers (2–5 years) had the highest estimated daily intake of ∑PFAS via road dust ingestion under average-case and worst-case scenarios (0.55 and 1.16 pg/kg bw/day, respectively). This is the first time to evaluate PFAS in Indian road dust nationwide, aiding to provide first-hand data for human exposure to PFAS in India.

Prevalence of per- and polyfluoroalkyl substances (PFASs) in marine seafood from the Gulf of Guinea

PFASs are ubiquitous in the global environment due to their wide use, persistence and bioaccumulation, and are of concern for human health. This study investigated the levels of PFASs in seafood with a view to provide knowledge on the occurrence of PFASs in marine resources and to evaluate seafood safety and human health risk via dietary exposure to coastal communities in the Gulf of Guinea, where there is currently very little data. The sum of targeted PFASs was between 91 and 1510 pg g-l ww (mean 465 ± 313 pg g-l ww), with PFOS and long-chain PFCAs prevailing. The concentrations of PFASs in the three species of croakers were species- and location-dependent, with habitat and anthropogenic pressure as likely drivers of the differences. Significantly higher contamination levels were found in male croakers. The trophic transfer and biomagnification of PFASs from shrimps to croakers was evidenced for PFOS and long-chain PFCAs (with a significant increase of contaminants from the prey to the predator). The calculated estimated daily intakes (EDIs) and hazard ratio (HR) for PFOS in croakers (whole fish and muscles) and shrimp were lower than the European Food and Safety Agency's recommended level for PFOS (1.8 ng kg−1 day−1) and below the HR safety threshold value of 1. From the results, based on present safety limits, PFOS levels in croakers and shrimps from the Gulf of Guinea do not pose immediate health risks to the human population. This study provides the first insight regarding the distribution of PFASs in seafood from the tropical NE Atlantic region of the Gulf of Guinea and highlights the need for further monitoring across the Gulf.

PFAS surveillance in abiotic matrices within vital aquatic habitats throughout Florida

Per- and polyfluoroalkyl substances (PFAS) are a group of manufactured chemicals that are resistant to degradation and thus persistent in the environment. The presence, uptake, and accumulation of PFAS is dependent upon the physiochemical properties of the PFAS and matrix, as well as the environmental conditions since the time of release. The objective of this study was to measure the extent of PFAS contamination in surface water and sediment from nine vulnerable aquatic systems throughout Florida. PFAS were detected at all sampling locations with sediment exhibiting greater PFAS concentrations when compared to surface water. At most locations, elevated concentrations of PFAS were identified around areas of increased human activity, such as airports, military bases, and wastewater effluents. The results from the present study highlight the ubiquitous presence of PFAS in vital Florida waterways and filled an important gap in understanding the distribution of PFAS in dynamic, yet vulnerable, aquatic environments.

Visualization of the Distribution of PFOS and PFHxS in Concrete by DESI MSI

Firefighting training grounds (FTGs) may serve as a potential secondary source for the release of per- and polyfluoroalkyl substances (PFAS) due to historic use of aqueous film-forming foams (AFFFs). Understanding the heterogenicity and vertical distribution of PFAS in AFFF-impacted concrete is important for risk management and potential remediation. This study assessed whether desorption electrospray ionization mass spectrometry imaging (DESI MSI) can be used to analyze PFAS in a concrete core from an AFFF-impacted FTG to provide the vertical distribution of PFAS. PFOS and PFHxS were detected and observed to be distributed in the core mapped by DESI MSI in a manner consistent with data obtained using a conventional method of drilling samples along the depth of a concrete core (i.e., core sidewall drilling) followed by extraction into methanol and analysis by liquid chromatography mass spectrometry. Visualization by DESI MSI provided the mass distribution in greater detail at a resolution of 30–200 μm pixel size. DESI can provide location mapping at PFAS concentrations of >2.7 pg/mm2 (PFHxS) and 3.6 pg/mm2 (PFOS) with a spatial resolution much greater than that of the previously used core sidewall drilling method.

Variations of the Level, Profile, and Distribution of PFAS around POSF Manufacturing Facilities in China: An Overlooked Source of PFCA.

The occurrence of per- and polyfluoroalkyl substances (PFAS) was investigated inside two manufacturing facilities in China. Levels, profiles, and spatial distribution of the detected PFAS were found to be distinctly site-specific and influenced by the area's historic function, production structure of the plant, downpour-induced accidental pollution, and variations in the adsorption and transport of compounds. Very high concentrations of PFAS [mainly C4 and C8 perfluoroalkyl sulfonic acids (PFSAs)] were found in topsoil and groundwater from both plants, with the highest values of 4.89 × 106 μg/kg dw and 1.10 × 104 μg/L, respectively. Elevated concentrations of perfluoroalkyl carboxylic acids (PFCAs) in this study were attributed to their unintentional formation during the electrochemical fluorination process, which might be an overlooked source of PFCA. PFAS generally showed decreasing trends from shallow layers to the bottom of the soil core and demonstrated some downward migrations at different soil depths with time, and C4-C8 PFAS presented a deeper seepage than their long-chain homologues. Total organic carbon appeared to be more important for PFAS sorption to the topsoil than to the soil core. Workers were at potential risk of exposure to perfluorooctanesulfonic acid via soil at production and storage related sites. This study provides a critical reference for the systematic control of PFAS pollution around manufacturing facilities and a proof for an overlooked source of PFCA.

Residue Distribution and Daily Exposure of Per- and Polyfluoroalkyl Substances in Indica and Japonica Rice.

Per- and polyfluoroalkyl substances (PFAS) have excellent chemical stability but have adverse environmental impacts of concern. Furthermore, bioaccumulation of PFAS in rice varieties─which is the essential staple food crop in Asia─has not been verified. Therefore, we cultivated Indica (Kasalath) and Japonica rice (Koshihikari) in the same Andosol (volcanic ash soil) paddy field and analyzed the air, rainwater, irrigated water, soil, and rice plants for 32 PFAS residues, throughout the cultivation to human consumption. During the rice cultivation period, the cultivation environment in atmospheric particulate matter (PM) constituted perfluoroalkyl carboxylic acids (PFCAs), with minimal perfluorinated sulfonic acids (PFSAs). Furthermore, perfluorooctanesulfonic acid (PFOS) migrates at a PM > 10 to drop in a cultivation field and was conducive to leakage and accumulation of PFCAs in air particles in the field environment. Moreover, precipitation was a sources of irrigation water contamination, and cultivated soil with a high carbon content could capture PFSAs and PFCAs (over C10). There were no major differences in residual PFAS trends in the rice varieties, but the distribution of PFAS in the growing soil, air, and rainwater differed. The edible white rice part was mainly affected by irrigation water in both varieties. Monte Carlo simulations of daily exposure assessments of PFOS, PFOA, and perfluorononanic acid showed similar results for Indians consuming Indica rice and Japanese consuming Japonica rice. The results indicate that the ultratrace PFAS residue concentrations and their daily exposure were not cultivar-specific.

Exposure of children and adolescents from Northeastern Slovenia to per- and polyfluoroalkyl substances

Per- and polyfluoroalkyl substances (PFAS) are of high concern for the environment, wildlife, and human health due to their persistence and potential to cause adverse health effects. Despite political measures to restrict the production and distribution of PFAS and to limit the exposure of populations, PFAS can be measured at commonly high detection frequencies in human samples.Thus, this pilot study aimed to determine the serum concentrations of PFPA, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFHxS, PFHpS, PFOS, PFHxA, PFDoDA, and PFBS in 113 girls and 112 boys (age 7–10 and 12–15) from Northeastern Slovenia - a rural area characterized by agricultural activities - and to identify potential sources of exposure using questionnaire data. PFAS were analysed by liquid chromatography coupled to mass spectrometry after phospholipid removal.9 out of 12 analytes were detected at detection frequencies above 30%, with the highest geometric means (GM) being observed for PFOS (GM 1.9 ng/mL) > PFOA (GM 1.0 ng/mL) > PFHxS (GM 0.3 ng/mL) = PFNA (GM 0.3 ng/mL). We identified the participants’ socio-economic status, age, sex, sampling region, public water supply, and the consumption of fish and seafood, cereals, and locally produced fruits, vegetables, and mushrooms as the predominant determinants of exposure. Furthermore, we compared our results with the serum and plasma concentrations reported for similar age groups in other studies and concluded that PFAS exposure in this highly agricultural area in Slovenia is notably low. This is the first study systematic HBM study of PFAS exposure in Slovenia, although it was conducted on a limited number of participants representative of rural and agricultural areas, it represents a good basis for upgrading the approach to a nationwide HBM study.

High density polyethylene (HDPE) and thermoplastic polyurethane (TPU) wristbands as personal passive samplers monitoring per- and polyfluoroalkyl substances (PFASs) exposure to postgraduate students

Per- and polyfluoroalkyl substances (PFASs) present adverse effects for human health, which result in strong needs for reliable tools monitoring personal exposure to PFASs. This study manufactured two wristbands of high density polyethylene (HDPE) and thermoplastic polyurethane (TPU), and used the wristbands to monitor PFASs personal exposure. The analytical method was developed to measure 32 PFASs in the paired HDPE and TPU wristbands worn by 60 postgraduates. Twenty-nine of 32 PFASs were detected and hexafluoropropylene oxide dimer acid (HFPO-DA) was predominant individual PFASs with median concentrations of 337 and 554 pg/g for HDPE and TPU wristbands respectively. The gender and grade of students had moderate effects on PFASs distribution in the wristbands. Higher PFASs levels were determined in the two wristbands worn by the male students compared to the females, and the greatest PFASs concentration was observed in the wristbands worn by the first-year postgraduates, follow by second- and third-year postgraduates. Additionally, significant correlations between paired HDPE and TPU wristbands were observed for perfluorobutanoic acid (PFBA), perfluorohexane sulfonic acid (PFHxS), perfluoroheptane sulfonic acid (PFHpS), perfluorooctane sulfonic acid (PFOS), and HFPO-DA. These results suggest that HDPE and TPU wristbands can be used as effective tools for monitoring personal PFAS exposure.

A novel method for extraction, clean-up and analysis of per- and polyfluoroalkyl substances (PFAS) in different plant matrices using LC-MS/MS

Per- and polyfluoroalkyl substances (PFAS) are chemicals of concern due to their persistence, bioaccumulation, and toxic properties. PFAS accumulation in plants poses a risk of human and animal exposure due to consumption of the affected plants, but also allows plants to be used in remediation of PFAS-contaminated soils and groundwater. Therefore, effective extraction, cleanup, and analytical methods for measuring PFAS concentrations in plants are fundamental for research on animal and environmental health. PFAS analysis in plant matrices is complex, due to high matrix interference, and scarcity of methods for analyzing different classes of PFAS. In this study, a simple sample preparation method for PFAS analysis in various plant tissues (leaves, needles, twigs, stems, roots from 10 different species) was developed and validated. Instrumental analysis was performed using liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The method was optimized considering six different extraction conditions and three different cleanup techniques. Methanol as extraction solvent, combined with 1 g ENVI carb cartridges, showed best performance among all extraction conditions and cleanup techniques tested. Method validation showed good recovery (90–120%), high within-day and between-day precision (<20% relative standard deviation), and low method detection limit (0.04–4.8 ng g−1 dry weight (dw)) for different plant matrices. In tests of the method on soil and different plant tissues of silver birch (Betula pendula) and Norway spruce (Picea abies) at a PFAS-contaminated site, 16 of 24 target PFAS were detected in plants and 17 in soil. ƩPFAS concentration in soil was 43 ng g−1 dw. PFAS distribution in silver birch tissues ranged from 7.1 ng g−1 dw in roots to 64 ng g−1 dw in leaves, and in Norway spruce from 14 ng g−1 dw in roots to 16 ng g−1 dw in needles. This novel method for PFAS analysis in plants can be valuable in future monitoring, process understanding, remediation, and risk assessments.

Distribution of per- and poly-fluoroalkyl substances and their precursors in human blood

Many studies have examined per- and poly-fluoroalkyl substances (PFASs) in human blood. However, the distribution of PFASs in human blood remains not well known, especially for perfluorooctane sulfonate (PFOS) precursors. In this study, human blood samples (n = 162) were collected from general Chinese population, and then the isomer-specific partitioning of PFASs between human plasma and red blood cells (RBCs) were investigated. Perfluorooctanoate (PFOA) and PFOS were consistently the predominant PFASs in both human plasma and RBCs. In human blood, among C4–C7 perfluoroalkyl carboxylates (PFCAs), the calculated mean mass fraction in plasma (Fp) values increased from 0.76 to 0.82 with the increasing chain length. C7–C13 PFCAs exhibited a trend of gradually decreasing mean Fp with chain length. Among PFAS precursors, 6:2 fluorotelomer phosphate diester had the highest mean Fp value (0.87 ± 0.11). Calculated Fp values of N-methyl perfluorooctanesulfonamide (N-MeFOSA) and N-ethyl perfluorooctanesulfonamide (N-EtFOSA) were 0.66 ± 0.13 and 0.70 ± 0.12, respectively. Individual branched isomers consistently had greater Fp values than their corresponding linear isomers for PFOA, PFHxS, and perfluoroctane sulfonamide. To our knowledge, this study first reports the distribution of N-MeFOSA and N-EtFOSA in human blood, contributing to the better understanding of the occurrence and fate of PFASs in humans.

Concentration and distribution of metals, total fluorine, per- and poly-fluoroalkyl substances (PFAS) in vertical soil profiles in industrialized areas.

The widespread usage of per- and poly-fluoroalkyl substances (PFAS) has caused great concern due to their potential toxicology to human and environmental health. However, there have been limited investigations on the vertical distribution of PFAS in fluorine (F) contaminated soils. In this study, the spatial and vertical distribution of metals, total F, and PFAS in the soil profiles were investigated at different areas in an industrial city. The higher F concentrations in the farmland soils with intensive agricultural activities suggested the impacts of soil tillage. The ΣPFAS concentrations ranged from 0.187 to 1.852ngg-1 in all soil samples, with PFOA as the dominant pollutant, which accounted for 17.2%-51.6% of the ΣPFAS in all samples. Highest level of PFAS was found in the shallow layer of the soil profiles. The long-chain PFAS such as PFUdA and PFTeDA tended to remain in the topsoil, while the short-chains (PFBA, PFPeA, and PFHxA) have migrated to depth of 100cm in the vertical soil profile. The application of F-enriched phosphorus fertilizers and atmospheric deposition may be important sources of F and PFAS in soils in this area. Correlation analysis indicated that most of PFAS have similar common sources, and the significantly positive correlation between Zn and PFAS suggested they may share similar sources. This study highlights the need for further work to monitor the PFAS level in soil environments in industrialized areas, in addition to focusing on soil metal and F pollution.

Survey of per- and polyfluoroalkyl substances (PFAS) in surface water collected in Pensacola, FL

As the persistence of per- and polyfluoroalkyl substances (PFAS) become a global concern, information about the occurrence and characteristics of PFAS in estuarine and marine ecosystems is poorly represented. In this study, the presence of 51 PFAS were monitored in the Pensacola Bay System (PBS), Florida, USA. Due to the presence of many potential PFAS sources in close proximity to the PBS (e.g., military bases, industries, airports and several firefighting stations), the distribution and concentration of PFAS in this estuarine environment provides insights into the fate of these complex compounds as well as the possible impacts on coastal systems. Surface water was collected and analyzed from 45 different sites via Strata-X-AW cartridge extractions and ultra-high pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis. Recoveries for many PFAS (13/51) were >60% (mean 77 %), with relative standard deviations below 20%, except for N-methylperfluoro-1-octanesulfonamidoacetic acid (N-MeFOSAA) (22%). Of the perfluoroalkyl carboxylic acids (PFCAs), which comprised the majority of PFAS detected: perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA) were present in all samples; however, perfluoropentanoic acid (PFPeA) was the individual PFAS with the highest concentration of this group (51.9 ng.L−1, at site 81). The PFAS detected at the highest concentrations were perfluoroalkyl sulfonic acids (PFSA), with perfluorooctane sulfonic acid (PFOS) having the highest detected concentration (269 ng.L−1, at site 81). At all sites, at least eight or more PFAS were quantified. Past and current use of PFAS-containing materials and their fate in areas surrounding military bases, airports, and industries, require more in-depth monitoring efforts to better determine the need for regulation, management, and/or remediation. Here, sites located close to areas suspected of PFAS use had elevated concentrations. For example, one coastal location near an airfield had a ΣPFAS of 677 ng.L−1. Expansion from these ongoing efforts will focus on assessment of PFAS-related effects in local wildlife and evaluating the distribution of PFAS at these “hotspot” sites during large episodic weather events, a critically understudied phenomenon regarding PFAS and vulnerable coastal environments.

Insight into the uptake and translocation of per- and polyfluoroalkyl substances in hydroponically grown lettuce.

The prevalence of per- and polyfluoroalkyl substances (PFASs) in agricultural soils has raised concerns regarding the health risks associated with the consumption of PFAS-contaminated agricultural products. The present study investigated the uptake and translocation of nine PFASs in lettuce using a hydroponic setting. During the uptake experiments, long-chain PFASs (≥ C8) exhibited greater accumulations in lettuce roots, while short-chain PFASs (≤ C7) manifested preferential transport to the shoots. The average root concentration factors of PFASs were positively correlated with their log Kow values. A significantly negative relationship was found between the average translocation factors of PFASs and their molecular volume. Sorption of long-chain PFASs by lettuce roots was enhanced after heating the roots to increase the cell membrane permeability. The accumulation of perfluorododecanoic acid increased significantly in shoots of lettuce plants without roots as compared to whole lettuce plants. Results of the present study indicate that sorption to root surface tissues and efficiency in passing through the root Casparian strip are two important factors that affect the uptake and distribution of PFASs within plants.

Uptake of individual and mixed per- and polyfluoroalkyl substances (PFAS) by soybean and their effects on functional genes related to nitrification, denitrification, and nitrogen fixation

In this study, we set up a soil-microbe-soybean system spiked with PFOA, PFOS, or a PFAS mixture of eight PFAS and investigated the distribution of PFAS in the system and impacts on the abundance and expression level of genes involved in the nitrogen (N) cycle. When soybean was exposed to the PFAS mixtures, synergistic uptake by shoots was detected. PFAS exhibited remarkable impacts on abundance of nitrification and denitrification genes in both bulk soil and rhizosphere as well as expression of N fixation gene in soybean nodules. The abundance of nitrification genes AOA and AOB amoA and denitrification gene nirK was significantly reduced (p < 0.05) in almost all treatments in bulk soil, except PFOA at 10 μg/kg. The abundance of other functional genes, such as nirS and norZ was affected differently depending on PFAS concentrations and sample location, either bulk soil or the rhizosphere. Interestingly, the N fixation gene nifH in soybean nodules was overexpressed by a PFAS mixture at 100 μg/kg. Hence, this work provided in-depth knowledge regarding the distribution of PFAS and their impacts on the N cycle for the studied system. Results from this study provide insights on assessing risks posed by individual or mixed PFAS to soybean.

Occurrence of per- and polyfluoroalkyl substances (PFAS) in municipal solid waste landfill leachates from western China.

Landfill leachate has been documented as a significant source of trace organic pollutants, comprising an expansive family of per- and polyfluoroalkyl substances (PFAS). This study presents the findings on the distribution of 13 perfluoroalkyl carboxylates (PFCAs) and 4 perfluoroalkyl sulfonates (PFSAs) in leachates from 6 municipal solid waste (MSW) landfills in western China. The total concentrations of 17 PFAS in sampled leachates ranged from 1805 to 43,310ng/L, and 15 compounds were detected in all samples. The short-chain compounds perfluorobutane sulfonate (PFBS, mean mass fraction 23.1%) and perfluorobutyric acid (PFBA, mean mass fraction 20.6%) were dominant. There were higher PFAS concentrations in leachates from operating landfills (mean: 12,194ng/L) compared to closed landfills (mean: 2747ng/L), but there was no significant difference between young (< 10years) and old landfills (> 10years). Moderate to weak correlations were observed between PFAS concentrations and leachate properties, e.g., TN, NH4+-N, TOC, and pH. This is the first report on the distribution of PFAS in landfill leachates from western China. The results have identified landfill leachate as an underestimated source of PFAS in the environment and have contributed to a more comprehensive evaluation on PFAS presence across China.

Per- and poly-fluoroalkyl substances in sediments from the water-level-fluctuation zone of the Three Gorges Reservoir, China: Contamination characteristics, source apportionment, and mass inventory and loadings

Sixteen paired surface sediment samples (0–5 cm, n = 32) covering upstream to downstream of water-level-fluctuation zone of Three Gorges Reservoir, China were collected in March 2018 (following six months of submergence) and September 2018 (after six months of exposure). Seventeen per- and poly-fluoroalkyl substances (PFASs) were quantified to evaluate contamination characteristics, apportion source categories and estimate mass inventory and loadings. The concentration of ΣPFASs ranged from 0.26 to 0.82 ng·g−1 at high water-level (HWL) and 0.46–1.53 ng·g−1 at low water-level (LWL). Perfluorooctanoic acid (PFOA, mean: 0.32 ng·g−1) and perfluorooctane sulfonate (PFOS, mean: 0.12 ng·g−1) dominated, accounting 44.9% and 16.3% of the total PFASs, respectively. The distribution of PFASs was more influenced by anthropogenic activities than physicochemical parameters of the sediments. Positive matrix factorization (PMF) identified PFOA-based products was the major sources (40.1% and 38.6%, respectively). Besides, the direct sources of PFOA-, PFOS-, PFNA-and PFBA-based products played the predominant role, while the indirect degradation of precursors contributed relatively little. The sediment (0–5 cm) mass inventory of PFASs at LWL (57.5 kg) was higher than HWL (39.3 kg). The annual mass loadings of the total PFASs, PFOA, PFOS, perfluoroundecanoic acid (PFUdA) and perfluorononanoic acid (PFNA) from the upstream to the middle-lower reaches of Yangtze River were 27.4 kg, 11.1 kg, 4.63 kg, 2.89 kg and 2.57 kg, respectively. This study could provide the basic datasets of PFASs in surface sediments of the TGR, and also indicate an important transport of PFASs from upstream to the lower reaches, which should be further studied as well.

Bioaccumulation of polyfluoroalkyl substances in the Lake Huron aquatic food web

Polyfluoroalkyl substances (PFAS) are a group of fluorinated organic chemicals that have been produced for industrial and commercial application since the 1950s. PFAS are highly persistent and ubiquitous in water, sediment, and biota. Toxic effects of PFAS on humans and the ecosystem have increased scientific and public concern. To better understand the distribution of PFAS in the Laurentian Great Lakes, carbon (12C and 13C) and nitrogen (14N and 15N) stable isotope enrichment, fatty acid profiles, and PFAS were measured in the Lake Huron (LH) aquatic food web. The trophic level of the organisms was estimated using δ15N and found to be a determinant of PFAS biomagnification. The δ13C and fatty acid profiles were used to assess the carbon/energy flow pathway and predator-prey relationships, respectively. The δ13C, δ15N, and fatty acids were used to elucidate the trophodynamics and understand the PFAS trophic transfer in the LH aquatic food web. Perfluorooctanesulfonic acid (PFOS) was the dominant PFAS observed, followed by C9 - C11 perfluorinated carboxylic acids (PFCA). The highest PFOS concentrations (45 ± 11 ng/g, wet weight (wwt)) were detected in lake trout (Salvelinus namaycush), while the highest total PFCA concentrations (sum of C4 – C16 PFCAs) were detected in deepwater sculpin (Myoxocephalus thompsonii). With the exception of perfluorooctanoic acid (PFOA), C8-C14 PFAS biomagnification factors (BMFs) were found to be generally greater than 1, suggesting PFAS biomagnification from prey to predator. Trophic magnification factors (TMFs) of C8-C14 PFCA were found to be independent of compound hydrophobicity.

Predicting the impact of salt mixtures on the air-water interfacial behavior of PFAS

Salts are known to have strong impacts on environmental behavior of per- and polyfluoroalkyl substances (PFAS) including air-water interfacial adsorption. Multivalent salts impact interfacial adsorption to a greater extent than monovalent salts. Models to make a priori predictions of PFAS interfacial adsorption in the presence of multiple salts with different ionic charges are needed given the need to predict PFAS environmental fate. This study further develops a mass-action model to predict the interfacial behavior of PFAS as a function of both salt valency and concentration. The model is validated using surface tension data for a series of monovalent and divalent salt mixtures over a wide range of ionic strengths (i.e., from no added salt to 0.5 M) as well as comparison to data from literature. This model highlights the disproportionate impact of multivalent salts on interfacial adsorption and the practical utility of the model for predicting interfacial adsorption in the presence of multiple monovalent and multivalent inorganic salts. Results suggest that failure to account for divalent salt, even when concentrations are much smaller than monovalent salt, under most environmentally relevant aqueous phase conditions will result in significant underpredictions of PFAS interfacial adsorption. Simple examples of PFAS distribution in a range of salt conditions in the vadose zone and in aerated-water treatment reactors highlight the predictive utility of the model.

Perfluoroalkyl Substance Contamination Levels of Pike (Esox lucius L.) and Roach (Rutilus rutilus L.) from Selected Masurian Lakes in Eastern Europe.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are of increased concern because of their bioaccumulation in humans and the biota, the health risk they pose to humans and other animals, and their persistence in the environment. In the present study, the occurrence of PFAS in selected tissues from pike (Esox lucius L.) and roach (Rutilus rutilus L.) collected from two lakes in the Masurian Lake District (Poland) in eastern Europe was addressed. Ten PFAS were analyzed in the tissue of the brain, liver, kidneys, gonads, and muscles by micro-high-performance liquid chromatography coupled with tandem mass spectrometry. Only perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid, and perfluorodecanoic acid were detected above the limit of quantification. Concentrations in pike and roach from Ełckie Lake and Hańcza Lake were estimated to be 14/27 and 4.4/3.2 ng/g wet weight, respectively. The contributions of PFOS and PFOA to the sum of PFAS calculated for particular tissues for each fish species were higher than those of the other analyzed compounds: PFOS was found to be predominant in fish from Ełckie Lake, whereas PFOA predominated in fish from Hańcza Lake. It was noted that PFAS concentrations in tissues declined in the following order: kidney > gonads ≈ brain > liver > muscle. The sum of the greatest estimated PFAS concentration was 9.7 ng/g wet weight in kidneys of pike collected from Hańcza Lake. No correlation was noted between PFAS concentration and fish size. The information provided in our study gives a better understanding of the potential dependencies in PFAS distribution and accumulation in biota. Environ Toxicol Chem 2021;40:3317-3327. © 2021 SETAC.

Transcriptional effects of binary combinations of PFAS in FaO cells

Per- and polyfluoroalkyl substances (PFAS) represent a large class of structurally diverse chemicals of increasing public concern, mostly due to their chemical stability and undetermined toxicity profiles. In laboratory animals, adverse effects implicated for certain PFAS, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in particular, include liver toxicity and the associated metabolic dysregulation, immune and thyroid alterations, reproductive toxicity, and selected tumors. The broad commercialization and environmental distribution of PFAS has drawn attention to the need for understanding risks associated with combined exposure to multiple PFAS in complex mixtures. The purpose of this investigation is to determine whether binary combinations of PFAS elicit a molecular response that is either greater than or less than the sum of the individual responses. Exposure of FaO rat hepatoma cells for 24 h to 25 μM–200 μM of the 4- and 8-carbon perfluorocarboxylic acids (PFBA and PFOA) or the 4, 6, and 8-carbon perfluorosulfonic acids (PFBS, PFHxS, and PFOS, respectively) individually caused a dose-dependent increase in PPARα-regulated expression of peroxisomal bifunctional enzyme (Ehhadh). Potency increased with carbon number, with the carboxylates eliciting a greater transcriptional response than the corresponding sulfonates. Combined exposure to PFOA and PFBA produced an effect that was significantly less than the sum of the individual responses. The response to the combination of PFOA and PFOS produced a summative effect at concentrations that were not cytotoxic. Combined exposures to PFOS and either PFBS or PFHxS at low noncytotoxic concentrations produced a transcriptional effect that was significantly less than the sum of the individual effects. The results demonstrate that among the five structurally related perfluoroalkyl acids included in this investigation, PPARα transcriptional activation in response to combined binary exposures is consistently at or below that predicted by the sum of the individual effects.