Distribution Of Polyfluoroalkyl Substances Research Articles

Modulation of irrigation-induced microbial nitrogen‑iron redox to per- and polyfluoroalkyl substances' water-soil interface release in paddy fields: Activation or immobilization?

Understanding the modulation of paddy field irrigation to the migration of per- and polyfluoroalkyl substances (PFAS) at the water-soil interface is pivotal for the management of PFAS pollution in paddy soil and surrounding surface water environments. In flooded soils, soil organic matter was transformed into aromatic protein-like dissolved organic matter (DOM). Meanwhile, Na+, K+, and Mg2+ were translocated into extracellular polymeric substances (EPS) under the catalysis of cation channel enzymes (p < 0.05), provided ion bridging for the binding of DOM and PFAS, and accelerated the accumulation of C4–C9 PFAS in overlying water (41.79–99.14 %). Short-chain PFAS's accumulation in soil solution of drought soils was stimulated by microorganisms secreting soluble microbial by-product-like DOM (53.15–97.96 %). Furthermore, PFAS's distribution in flood soils was dominated by bacterial denitrification and iron-reduction, whereas iron-oxidation and ammoxidation controlled that in drought soils. The transformation of organic carbon including CO and COC caused by irrigation-induced redox modulated PFAS cross-media translocation. Iron‑nitrogen redox in flooded paddy soils immobilized the PFAS's migration into overlying water (p < 0.05). Our findings have profound implications for PFAS's pollution control, surface water environmental protection, and rice production security in paddy fields.

Simulating PFAS transport in effluent-irrigated farmland using PRZM5, LEACHM, and HYDRUS-1D models.

Application of wastewater effluent to agricultural lands can serve as a sustainable approach to meet irrigation and nutrient needs for crop production. While nitrogen and phosphorous loadings can be effectively managed, concerns have been raised regarding the fate of emerging contaminants, including per- and polyfluoroalkyl substances (PFAS), which are widely detected in wastewater effluent. The objective of this paper was to evaluate the ability of three unsaturated flow and transport models, Pesticide Root Zone Model 5 (PRZM5), LEACHM, and HYDRUS-1D, to predict the distribution of PFAS in the soil profile at the Pennsylvania State University Living Filter site, which has received daily wastewater effluent applications for several decades. The models were modified to include adsorption at the air-water interface (AWI), which has been shown to be an important factor governing PFAS transport and phase distribution in the vadose zone. Simulations showed that PRZM5 did not accurately reproduce the observed perfluorooctanesulfonic acid (PFOS) behavior, which was attributed to the "tipping bucket" approach used for water flow that results in the disappearance of AWI during water flow. In contrast, both LEACHM and HYDRUS-1D captured the observed retention of PFOS and perfluorooctanoic acid (PFOA) over a 50-year simulation period. Due to differences in the approach used to calculate the AWI area, LEACHM predicted greater accumulation of PFOS and PFOA at the AWI compared to HYDRUS-1D. These findings indicate that mathematical models that directly account for unsaturated water flow and adsorption at the AWI are able to provide reasonable predictions of long-term PFAS leaching resulting from land application of wastewater effluent.

Fate of per- and polyfluoroalkyl substances at a 40-year dedicated municipal biosolids land disposal site

The fate of per- and polyfluoroalkyl substances (PFAS) was evaluated at a site where municipal biosolids have been applied annually for 38 years as a waste management strategy. Soil cores (1.8 m in 30-cm sections), groundwater from four wells, and biosolids applied in 2022 were analyzed for PFAS (54 targeted, 17 semi-quantified) using liquid chromatography high resolution mass spectrometry including suspect screening. Total PFAS concentrations decreased with soil depth from 1700 ng/g to 2.06 ng/g. PFAS distribution in 2022 biosolids were 60 mol% perfluoroalkyl acid (PFAA) precursors and intermediates. The surface soil was dominated by long-chain PFAAs (67–76 mol%) reflecting precursor degradation after biosolids application. Presence of semi-quantified intermediates further reflects precursor degradation in surface soil. Long-chain PFAAs diminished with depth while short-chain PFAAs increased with up to 98 and 96 mol% short-chain PFAAs in the bottom depth and groundwater, respectively. PFAS distribution with depth is consistent with chain-length dependent sorption-impacted transport and the high organic carbon content of the surface soil (15.2 % OC) which subsequently decreased with depth (~2–3 % OC at >60 cm). High organic carbon content in the upper horizon is likely from decades of high biosolids application rates, which contributed to minimizing leaching of long-chain PFAS. While the well within the dedicated land disposal is not drinking water, for comparison only, PFAS concentrations in this well only marginally exceeded the EU drinking water directive for total PFAS and a few individual short-chain PFAS, but did exceed tenfold, the USEPA drinking water standard for PFOA.

Comparing occurrence of per- and polyfluoroalkyl substances (PFAS) in municipal biosolids and industrial wastewater sludge: A City of Los Angeles study

Biosolids and sludge are what remain after the liquid fraction of wastewater is separated during wastewater treatment. These high organic content matrices are known to contain organic contaminants, a few of which are the hazardous and environmentally persistent per- and polyfluoroalkyl substances (PFAS). The current study investigates whether sludge from a treatment facility serving mostly industrial establishments and biosolids from a facility serving mostly domestic dwellings retain these ‘forever chemicals’ similarly. Using 31 markers covering different classes of PFAS, the sludge was found to contain higher levels of PFAS (869 ± 791 ng/g; 21 of 31) than biosolids (31 ± 7 ng/g, 11 of 31). The most abundant overall was perfluorooctane sulfonic acid (PFOS), mostly in sludge (range: 71–1300 ng/g versus 0–18 ng/g in biosolids). The large PFAS concentration variability in sludge was seasonal and sinusoidal. Sludge, additionally, contained all long chain PFAS, precursors (mostly surfactant ingredients and their transformation byproducts) and short chain PFAS (perhaps because of higher moisture content). By regression, the sludge is shown to consistently contain twice as much PFAS as biosolids when the same amounts are exposed to increasing levels of PFAS. Factors observed to cause differential PFAS retention between sludge and biosolids were moisture (98.6 % and 72.1 %, respectively), chain length, input quality (industrial versus residential) and functional group. Sulfonic acids for instance are one C atom shorter than carboxylates with similar occurrence in sludge and biosolids. More studies are needed to define the roles that organic carbon of sludge/biosolids, water chemistry, temperature and factors not considered here play in partitioning PFAS between the two matrices with respect to inputs. Existing Koc values could not help in explaining observed trends, but the ratio of biosolids-to-influent concentrations was found to correlate positively with PFAS size. Using influent in the ratio, and not effluent, is novel. SynopsisSludge and biosolids are soil amendments; they contain hazardous and persistent PFAS. Methods of decoupling PFAS from these matrices start with understanding matrix-driven PFAS partitioning as shown here.

Distribution and bioaccumulation of per- and polyfluoroalkyl substances (PFASs) in the Kuroshio Extension region of Northwest Pacific Ocean

Per- and polyfluoroalkyl substances (PFASs) are prevalently present in oceans, posing potential health risks to organisms and humans. However, information of PFAS distribution in remote open oceans is limited. In the Kuroshio Extension region of Northwest Pacific Ocean (6 stations), samples of 84 seawater (0–5800 m), 9 sediments, and 9 organisms were taken, and 25, 10, and 15 out of 29 PFASs were identified, respectively, with perfluorooctanoic acid (PFOA) and perfluorooctane sulfonates (PFOS) as the most dominant PFASs. In seawater, ΣPFASs concentration decreased from the Kuroshio region (4.47 ng/L) to the Oyashio region (3.15 ng/L), and decreased with increasing seawater depth under the function of biological and physical pumps. Additionally, 12 precursors and emerging PFASs, including perfluorooctane sulfonamide (FOSA, 0.20 ng/L), were detected. In sediment, PFASs (5.92–12.97 pg/g) were identified at depths exceeding 5000 m, including 3 precursors (e.g., FOSA, 0.82 pg/g). ΣPFASs contents were 27.12, 31.47 and 36.97 ng/g (dry weight) in brown algae (Phaeophyceae), barnacles (Balanus), and lanternfish (Myctophiformes), respectively, in which two precursors (e.g., FOSA, 0.09–0.12 ng/g) were also identified. A correlation with the trophic position was found for PFOA bioaccumulation. These findings provide useful information on PFAS distribution in the global open ocean environments.

Interaction and coexistence characteristics of dissolved organic matter and toxic metals with per- and polyfluoroalkyl substances in landfill leachate

Landfill leachate-containing per- and polyfluoroalkyl substances (PFAS) is both an important ‘sink’ and a ‘source’ of secondary pollution, posing serious threaten to surrounding environments. To date, the pollution characteristics of PFAS in landfill leachate, and the coexistence and interaction between PFAS and other leachate contaminants, such as dissolved organic matter (DOM) and toxic metals remains unclear. Herein, our results showed that 17 target PFAS, with concentrations ranged from 1804 to 43309 ng/L, were detected in landfill leachates. The main PFAS were short-chain and even-chain substances represented by perfluorobutanoic acid (PFBA) and perfluorobutane sulfonic acid (PFBS). Leachate derived DOM is mainly composed of protein-like and humic-like substance, among which the total contribution of protein-like substance is as high as 73.7%. Correlation analysis results showed that the distribution of PFAS was strongly correlated with the substituted functional groups (e.g., carboxyl and hydroxyl) on the aromatic ring of humic-like substance (C2 and E253/E203) and autochthonous metabolism by microbial activities (FI). Furthermore, Mn element showed a significantly strong correlation with PFAS. Both organic and inorganic substances positively correlated with toxic metals. Our findings are helpful to understand the environmental fate of PFAS, and contribute to decision-making regarding DOM, toxic metals, and PFAS management in landfill.

Assessment of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) Mass Flux and Distributions in a Lake System Using Sediment Bed Passive Flux Meters and Ceramic Dosimeters

AbstractPer‐ and polyfluoroalkyl substances (PFAS) are persistent in the environment due to their chemical stability and can spread quickly in a lake system due to mixing. Passive samplers allow for time‐weighted average concentration monitoring and the ability to detect low concentrations, which are difficult to measure with conventional grab sampling. This study demonstrates the feasibility of deploying both ceramic dosimeters and Sediment Bed Passive Flux Meters (SBPFMs) to assess time integrated PFAS concentrations and fluxes, respectively, at a historically contaminated PFAS lake near Baden‐Baden, Germany. Long‐term surface water grab samples resulted in the detection of PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFBS, PFHxS, and PFOS at a total concentration of approximately 1 μg/L. Dosimeters were deployed for 66 and 126 d, resulting in detected concentrations ranging from approximately 250 to 380 ng/L and 120 to 460 ng/L, respectively. The 66 d deployment resulted in the detection of PFPeA, PFHxA, PFHpA, and PFOA, whereas the 126 d deployment additionally detected PFBA, PFNA, PFDA, PFUnDA, PFDoDA, PFTeDA, PFBS, PFPeS, PFOS, PFNS, and PFDS. SBPFMs resulted in the detection of PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFUnA, PFTrDA, and PFBS and the determination of a total mass discharge of 5.6 g/d into the lake. Overall, dosimeters and SBPFMs are more sensitive than grab samples at detecting PFAS at low concentrations and can be used to better understand spatial distribution of PFAS in a lake system.

High-Resolution Depth-Discrete Analysis of PFAS Distribution and Leaching for a Vadose-Zone Source at an AFFF-Impacted Site.

The long-term leaching of polyfluoroalkyl substances (PFAS) within the vadose zone of an AFFF application site for which the depth to groundwater is approximately 100 m was investigated by characterizing the vertical distribution of PFAS in a high spatial resolution. The great majority (99%) of PFAS mass resides in the upper 3 m of the vadose zone. The depths to which each PFAS migrated, quantified by moment analysis, is an inverse function of molar volume, demonstrating chromatographic separation. The PFAS were operationally categorized into three chain-length groups based on the three general patterns of retention observed. The longest-chain (>∼335 cm3/mol molar volume) PFAS remained within the uppermost section of the core, exhibiting minimal leaching. Conversely, the shortest-chain (<∼220 cm3/mol) PFAS accumulated at the bottom of the interval, which coincides with the onset of a calcic horizon. PFAS with intermediate-chain lengths were distributed along the length of the core, exhibiting differential magnitudes of leaching. The minimal or differential leaching observed for the longest- and intermediate-chain-length PFAS, respectively, demonstrates that retention processes significantly impacted migration. The accumulation of shorter-chain PFAS at the bottom of the core is hypothesized to result from limited deep infiltration and potential-enhanced retention associated with the calcic horizon.

Occurrence and Fate of Per- and Polyfluoroalkyl Substances (PFAS) in Atmosphere: Size-Dependent Gas-Particle Partitioning, Precipitation Scavenging, and Amplification.

The concerns about the fate of per- and polyfluoroalkyl substances (PFAS) in the atmosphere are continuously growing. In this study, size-fractionated particles, gas, and rainwater samples were simultaneously collected in Shijiazhuang, China, to investigate the multiphase distribution of PFAS in the atmosphere. Perfluoroalkyl carboxylic acids (PFCAs) dominated the total concentration of PFAS in atmospheric media. A strong positive relationship (0.79 < R2 < 0.99) was observed between the concentration of PFCAs and organic matter fraction (fOM) in different particle size fractions, while no such relationship for perfluoroalkyl sulfonic acids (PFSAs) and fOM, suggesting fOM may be an important factor influencing the size-dependent distribution of PFCAs. Temperature played a key role in the gas-particle partitioning of PFAS, while it did not significantly affect their particle-size-dependent distribution. The associative concentration fluctuation of particle and particle-bound PFAS during precipitation suggested that precipitation scavenging was an important mechanism for the removal of PFAS from the atmosphere. Furthermore, temporary increases in atmospheric PFAS concentrations were observed during the precipitation. Fugacity ratios of PFAS in rainwater and gas phase (log fR/fG ranged between 2.0 and 6.6) indicated a strong trend for PFAS to diffuse from the rainwater to the gas phase during the precipitation, which may explain that the concentration of PFAS in the gas phase continued to increase even at the end of the precipitation.

Bioaccumulation and trophic transfer of per- and polyfluoroalkyl substances in a subtropical mangrove estuary food web

Mangrove estuaries are an important land-sea transitional ecosystem that is currently under various pollution pressures, while there is a lack of research on per- and polyfluoroalkyl substances (PFAS) in the organisms of mangrove estuaries. In this study, we investigated the distribution and seasonal variation of PFAS in the tissues of organisms from a mangrove estuary. The PFAS concentrations in fish tissues varied from 0.45 ng/g ww to 17.67 ng/g ww and followed the order of viscera > head > carcass > muscle, with the highest tissue burden found in the fish carcass (39.59 ng). The log BAF values of PFDoDA, PFUnDA, and PFDA in the whole fish exceeded 3.70, indicating significant bioaccumulation. The trophic transfer of PFAS in the mangrove estuary food web showed a dilution effect, which was mainly influenced by the spatial heterogeneity of PFAS distribution in the estuarine environment, and demonstrated that the gradient dilution of PFAS in the estuary habitat environment can disguise the PFAS bio-magnification in estuarine organisms, and the larger the swimming ranges of organisms, the more pronounced the bio-dilution effect. The PFOA-equivalent HRs of category A and B fish were 3.48–5.17 and 2.59–4.01, respectively, indicating that mangrove estuarine residents had a high PFAS exposure risk through the intake of estuarine fish.

Overview of Per- and Polyfluoroalkyl Substances (PFAS), Their Applications, Sources, and Potential Impacts on Human Health

Per- and polyfluoroalkyl substances (PFAS) belong to a group of synthetic compounds that have recently raised concerns about human health and environmental quality due to their great prevalence, degradation resistance, and potential toxicity. This review focuses on the applications of PFAS and their effects on human health. Specific emphasis has been laid on (i) the application/use of PFAS, (ii) sources and distribution of PFAS in diverse environmental compartments, and (iii) the impact of PFAS on human health. Significant health effects on humans are associated with exposure to PFAS, i.e., immunotoxicity, thyroid and kidney disorders, cancer, etc. Conclusions obtained from PFAS studies demonstrate that inadequate evidence should not be used to justify delaying risk reduction steps for PFAS alternatives. PFAS can be determined in different environmental matrices using both traditional analytical approaches, i.e., liquid chromatography coupled with mass spectrometry (LC-MS/MS) and semi-quantitative and passive sampling, and advanced analytical methods with colorimetric, spectrofluorimetric, and electrochemical detection. Traditional methods are costly and not broadly available, while the emerging, cost-effective methods are less sensitive and unable to meet regulatory exposure limits. There is still a significant number of studies to be performed to fully comprehend the real contamination by PFAS.

Biological effects of perfluoroalkyl substances on running water ecosystems: A case study in Beiluo River, China

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are emerging contaminants that pose a threat to the biodiversity of the Beiluo River, a polluted watercourse on the Loess Plateau impacted by diverse human activities. However, the occurrence, spatial distribution, and substitution characteristics of PFASs in this region remain unclear. This study aimed to unravel PFAS distribution patterns and their impact on the aquatic ecosystems of the Beiluo River Basin. The total PFAS concentration in the area ranged from 16.64–35.70 ng/L, with predominantly perfluorocarboxylic acids (PFCAs) and perfluorosulfonic acids (PFSAs), collectively contributing 94%. The Mantel test revealed threats to aquatic communities from both legacy long-chain (perfluorooctanoic acid and sodium perfluorooctane sulfonic acid) and emerging (6:2 fluorotelomer sulfonic acid, 2-Perfluorohexyl ethanoic acid, and hexafluoropropylene oxide dimer acid (Gen-X)) PFSAs. The canonical correspondence analysis ordination indicated that trace quantities of emerging PFASs, specifically 2-Perfluorohexyl ethanoic acid and hexafluoropropylene oxide dimer acid (Gen-X), significantly influenced geographical variations in aquatic communities. In conclusion, this study underscores the importance of comprehensively exploring the ecological implications and potential risks associated with PFASs in the Beiluo River Basin.

Profile of per- and polyfluoroalkyl substances, source appointment, and determinants in Argentinean postpartum women

BackgroundPer- and polyfluoroalkyl substances (PFAS) are a group of synthetic chemicals with potential adverse health effects. Information concerning PFAS concentrations in relation to pregnancy is scarce in South America and non-existent in Argentina. AimWe aimed to investigate an extended maternal PFAS profile herein serum concentrations in a regional and global view, source appointment, and determinants in Argentinean women. MethodsA cross-sectional study with a sampling period from 2011 to 2012 included 689 women from Ushuaia and Salta in Argentina. Serum samples collected two days postpartum were analyzed by ultra-high pressure liquid chromatography coupled to electrospray negative ionisation tandem-quadrupole mass-spectrometry. Principal Component Analysis (PCA) following absolute principal component score-multiple linear regression (APCS-MLR) was used for PFAS source appointments. Determinants of PFAS were explored through a MLR approach. A review of previous studies within the same period was conducted to compare with present levels. ResultsArgentinean PFAS concentrations were the lowest worldwide, with PFOS (0.74 ng/mL) and PFOA (0.11 ng/mL) as the dominant substances. Detection frequencies largely aligned with the compared studies, indicating the worldwide PFAS distribution considering the restrictions. The PCA revealed region-specific loading patterns of two component groups of PFAS, a mixture of replaced and legacy substances in Ushuaia and long-chain in Salta. This might relate to a mix of non-diet and diet exposure in Ushuaia and diet in Salta. Region, age, lactation, parity, household members, migration, bottled water, and freshwater fish were among the determinants of various PFAS. ConclusionThis is the first study to monitor human PFAS exposure in Argentina. Maternal PFAS concentrations were the lowest observed worldwide in the same period. Exposure contributions are suggested to be affected by restrictions and substitutions. Given the limited population-based studies and the emergence of PFAS, it is essential to conduct further monitoring of PFAS in Argentina and South America.

Research Progress on Distribution, Transportation, and Control of Per- and Polyfluoroalkyl Substances in Chinese Soils

Per- and polyfluoroalkyl substances (PFAS) are a class of persistent organic pollutants that have attracted much attention in recent years, which has the characteristics of diverse species, refractory degradation, long-distance transportation, easy bioaccumulation, etc. The distribution, accumulation, and potential toxicity of PFAS in water and organisms have received extensive attention worldwide. However, studies on PFAS distribution and transportation in soil are still hovering at a preliminary stage. The PFAS pollution surveys in Chinese soils are mainly concentrated in the economically developed eastern regions. The types and concentrations of PFAS in soils are directly related to the industrial types, atmospheric deposition, and human activities in these surveyed areas, which are similar to foreign soil surveys. Traditional perfluoro carboxylic acid (PFCAs) and perfluoro octane sulfonate (PFSAs) are the most important types of PFAS in Chinese soils. This study reviewed the distribution characteristics, transportation pathways, and influencing factors of PFAS in Chinese soils, as well as domestic and foreign control policies on PFAS pollution. Meanwhile, this study further pointed out the shortcomings of the current research on the distribution and control of PFAS in soil in order to provide a reference for the investigation, research, and control of PFAS pollution in Chinese soils.

Background concentrations and spatial distribution of PFAS in surface waters and sediments of the greater Melbourne area, Australia

A survey of per- and polyfluoroalkyl substances (PFAS) was conducted in Melbourne, Australia to determine background concentrations in residential, industrial, municipal wastewater treatment plants, and rural land uses. Surface water and sediment samples collected from 65 sites with different catchment land uses were analysed for thirty-three PFAS. Twenty-two out of thirty-three targeted PFAS were detected, with at least one PFAS species was detected in 98% water samples and 8% sediment samples. One site was determined to have point-source pollution from an airport (surface water Σ33PFAS = 4261 ng/L) and was excluded from statistical analyses. The median Σ33PFAS concentration in surface water was 63.5 ng/L and the average was 78.6 ng/L (range < DL-526 ng/L). PFAS species with the highest median concentrations were PFBA (11.3 ng/L), PFHxA (9.2 ng/L), PFOA (8.3 ng/L), PFOS (8.0 ng/L), PFPeA (7.5 ng/L), PFHpA (3.2 ng/L), and PFHxS (2.9 ng/L).The average Σ4PFAS in sediments was 0.35 ng/g d.w. (range = <DL-6.7 ng/g) and the congeners detected were PFOS, N-MeFOSAA, N-EtFOSAA, and N-EtFOSE. Significantly higher concentrations of all PFAS were found in urban areas than rural, except for PFBA which was evenly dispersed throughout all areas. Short-chain perfluoroalkyl carboxylic acids (PFCAs), PFBA, PFPeA, PFHxA, PFHpA, and the PFSA, PFBS were evenly dispersed throughout urban and industrial areas. PFOA, PFNA, and PFDA were higher, but not significantly, in residential catchments than industrial catchments. Industrial areas had significantly higher concentrations of perfluoroalkyl sulfonic acids (PFSAs), PFPeS, PFHxS, and PFOS, and 6:2 FTS than other urbanised areas. The distribution of PFAS throughout catchment types in this study displayed similar trends to other studies including findings of PFBA in background areas. Ongoing monitoring of defined catchments is recommended to improve understanding of PFAS sources and changes in environmental profiles, and to assess the implications of its occurrence throughout the environment.

Studying mixture effects on uptake and tissue distribution of PFAS in zebrafish (Danio rerio) using physiologically based kinetic (PBK) modelling

Per- and polyfluoroalkyl substances (PFAS) are ubiquitously distributed in the aquatic environment. They include persistent, mobile, bioaccumulative, and toxic chemicals and it is therefore critical to increase our understanding on their adsorption, distribution, metabolism, excretion (ADME). The current study focused on uptake of seven emerging PFAS in zebrafish (Danio rerio) and their potential maternal transfer. In addition, we aimed at increasing our understanding on mixture effects on ADME by developing a physiologically based kinetic (PBK) model capable of handling co-exposure scenarios of any number of chemicals. All studied chemicals were taken up in the fish to varying degrees, whereas only perfluorononanoate (PFNA) and perfluorooctanoate (PFOA) were quantified in all analysed tissues. Perfluorooctane sulfonamide (FOSA) was measured at concerningly high concentrations in the brain (Cmax over 15 μg/g) but also in the liver and ovaries. All studied PFAS were maternally transferred to the eggs, with FOSA and 6:2 perfluorooctane sulfonate (6,2 FTSA) showing significant (p < 0.02) signs of elimination from the embryos during the first 6 days of development, while perfluorobutane sulfonate (PFBS), PFNA, and perfluorohexane sulfonate (PFHxS) were not eliminated in embryos during this time-frame. The mixture PBK model resulted in >85 % of predictions within a 10-fold error and 60 % of predictions within a 3-fold error. At studied levels of PFAS exposure, competitive binding was not a critical factor for PFAS kinetics. Gill surface pH influenced uptake for some carboxylates but not the sulfonates. The developed PBK model provides an important tool in understanding kinetics under complex mixture scenarios and this use of New Approach Methodologies (NAMs) is critical in future risk assessment of chemicals and early warning systems.

Distribution of select per- and polyfluoroalkyl substances at a chemical manufacturing plant

Per- and polyfluoroalkyl substances (PFAS) are used in various industrial products; however, they pose serious health risks. In this study, soil, soil gas, and groundwater samples were collected at a PFAS manufacturing facility in New Jersey, USA, to determine the presence and distribution of PFASs from the soil surface to groundwater and at various distances from the presumed source. Fluorotelomer alcohols (FTOHs) were detected in soil (< 0.26–36.15 ng/g) and soil gas (160–12,000 E µg/m3), while perfluorinated carboxylic acids (PFCAs) were found in soil (4.3–810 ng/g), soil gas (<0.10–180 µg/m3), and groundwater (37–49 µg/L). FTOH and PFCA concentrations decreased as the distance from the presumed source increased, suggesting that PFCAs are likely to migrate in groundwater, whereas FTOHs primarily move in the vapor phase. The presence of PFAS in the groundwater, soil, and soil gas samples indicate its potential for vapor intrusion; thus, some PFAS may contribute to indoor air inhalation exposure. To the best of our knowledge, this is the first report on the quantification of volatile PFAS in soil gas at a PFAS manufacturing facility.

Cloth-Air Partitioning of Neutral Per- and Polyfluoroalkyl Substances (PFAS) in North Carolina Homes during the Indoor PFAS Assessment (IPA) Campaign.

Partitioning of per- and polyfluoroalkyl substances (PFAS) to indoor materials, including clothing, may prolong the residence time of PFAS indoors and contribute to exposure. During the Indoor PFAS Assessment (IPA) Campaign, we measured concentrations of nine neutral PFAS in air and cotton cloth in 11 homes in North Carolina, for up to 9 months. Fluorotelomer alcohols (i.e., 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH) are the dominant target species in indoor air, with concentrations ranging from 1.8 to 49 ng m-3, 1.2 to 53 ng m-3, and 0.21 to 5.7 ng m-3, respectively. In cloth, perfluorooctane sulfonamidoethanols (i.e., MeFOSE and EtFOSE) accumulated most significantly over time, reaching concentrations of up to 0.26 ng cm-2 and 0.24 ng cm-2, respectively. From paired measurements of neutral PFAS in air and suspended cloth, we derived cloth-air partition coefficients (Kca) for 6:2, 8:2, and 10:2 FTOH; ethylperfluorooctane sulfonamide (EtFOSA); MeFOSE; and EtFOSE. Mean log(Kca) values range from 4.7 to 6.6 and are positively correlated with the octanol-air partition coefficient. We investigated the effect of the cloth storage method on PFAS accumulation and the influence of home characteristics on air concentrations. Temperature had the overall greatest effect. This study provides valuable insights into PFAS distribution, fate, and exposure indoors.

Paired Liver:Plasma PFAS Concentration Ratios from Adolescents in the Teen-LABS Study and Derivation of Empirical and Mass Balance Models to Predict and Explain Liver PFAS Accumulation.

Animal studies have pointed at the liver as a hotspot for per- and polyfluoroalkyl substances (PFAS) accumulation and toxicity; however, these findings have not been replicated in human populations. We measured concentrations of seven PFAS in matched liver and plasma samples collected at the time of bariatric surgery from 64 adolescents in the Teen-Longitudinal Assessment of Bariatric Surgery (Teen-LABS) study. Liver:plasma concentration ratios were perfectly explained (r2 > 0.99) in a multilinear regression (MLR) model based on toxicokinetic (TK) descriptors consisting of binding to tissue constituents and membrane permeabilities. Of the seven matched plasma and liver PFAS concentrations compared in this study, the liver:plasma concentration ratio of perfluoroheptanoic acid (PFHpA) was considerably higher than the liver:plasma concentration ratio of other PFAS congeners. Comparing the MLR model with an equilibrium mass balance model (MBM) suggested that complex kinetic transport processes are driving the unexpectedly high liver:plasma concentration ratio of PFHpA. Intratissue MBM modeling pointed to membrane lipids as the tissue constituents that drive the liver accumulation of long-chain, hydrophobic PFAS, whereas albumin binding of hydrophobic PFAS dominated PFAS distribution in plasma. The liver:plasma concentration data set, empirical MLR model, and mechanistic MBM modeling allow the prediction of liver from plasma concentrations measured in human cohort studies. Our study demonstrates that combining biomonitoring data with mechanistic modeling can identify underlying mechanisms of internal distribution and specific target organ toxicity of PFAS in humans.

Emission of Per- and Polyfluoroalkyl Substances from a Waste-to-Energy Plant─Occurrence in Ashes, Treated Process Water, and First Observation in Flue Gas.

Per- and polyfluoroalkyl substances (PFASs) are a large group of compounds commonly used as industrial chemicals and constituents of consumer products, e.g., as surfactants and surface protectors. When products containing PFASs reach their end of life, some end up in waste streams sent to waste-to-energy (WtE) plants. However, the fate of PFASs in WtE processes is largely unknown, as is their potential to enter the environment via ash, gypsum, treated process water, and flue gas. This study forms part of a comprehensive investigation of the occurrence and distribution of PFASs in WtE residues. Sampling was performed during incineration of two different waste mixes: normal municipal solid waste incineration (MSWI) and incineration of a waste mix with 5-8 wt % sewage sludge added to the MSWI (referred to as Sludge:MSWI). PFASs were identified in all examined residues, with short-chain (C4-C7) perfluorocarboxylic acids being the most abundant. Total levels of extractable PFASs were higher during Sludge:MSWI than during MSWI, with the total annual release estimated to be 47 and 13 g, respectively. Furthermore, PFASs were detected in flue gas for the first time (4.0-5.6 ng m-3). Our results demonstrate that some PFASs are not fully degraded by the high temperatures during WtE conversion and can be emitted from the plant via ash, gypsum, treated process water, and flue gas.