Tissue distribution, biomagnification, human health risk, and risk mitigation of perfluoroalkyl acids (PFAAs) in the aquatic food web of an urban fringe lake: Insights from urban-rural and seasonal scales.

Perfluoroalkyl acids (PFAAs), renowned for their exceptional physical and chemical properties, are ubiquitous in urban and rural environments. Despite their widespread usage, more knowledge is needed concerning their accumulation and transfer mechanisms within the aquatic food webs of urban fringe lakes, especially across rural-urban and seasonal scales. This study investigated the tissue distribution, bioaccumulation, biomagnification, associated human health risks, and potential risk mitigation strategies of 15 PFAAs within the food web of Luoma Lake, a prototypical urban fringe lake. All targeted PFAAs were detected in samples, with ∑PFAA concentrations ranging from 116.97 to 564.26 ng/g dw in muscles and 26.96-1850.95 ng/g dw in viscera. Spatial variations revealed significantly higher ∑PFAA concentrations in the muscles from the urban subregion (∑PFAA: 359.66 ± 76.48 ng/g dw) compared to the rural subregion (∑PFAA: 328.86 ± 87.51 ng/g dw). Seasonal fluctuations impacted PFAA concentrations in fish and crustacean muscles but exhibited negligible effects on bivalve muscles. Spatial variations only influenced PFAA concentrations in specific viscera (gill, liver, kidney), while seasonal changes had minimal effects on viscera. The organisms demonstrated varying bioaccumulation capacities, with crustaceans displaying the highest bioaccumulation potential, followed by crustaceans and fish. Both spatial and seasonal variations modulated the bioaccumulation patterns of PFAA in muscles, whereas bioaccumulation in viscera was only influenced by seasonal factors. Notably, PFAA biomagnification along the food web was exclusively governed by spatial distribution, remaining unaffected by seasonal changes. The human health risk assessment underscored the potential adverse health impacts of PFOS and PFOA, particularly on young children (aged 2 to <6 years). This study further proposed comprehensive recommendations for mitigating PFAA-induced health risks, encompassing source control, selective consumption, pre-cooking treatments, and strategic cooking method selection. This research provides crucial insights into the ecological behaviors and health implications of PFAA in urban fringe lakes.

Perfluoroalkyl acid precursor or weakly fluorinated organic compound? A proof of concept for oxidative fractionation of PFAS and organofluorines.

Organofluorine mass balance approaches are increasingly applied to investigate the occurrence of per- and polyfluoroalkyl substances (PFAS) and other organofluorines in environmental samples more comprehensively. Usually, complex samples prevent the identification and quantification of every fluorine-containing molecule. Consequently, large unidentified fractions between fluorine sum parameters such as extractable organic fluorine (EOF) and the sum of quantified analytes are frequently reported. We propose using oxidative conversion to separate (unidentified) weakly fluorinated compounds (e.g., pesticides, pharmaceuticals) from PFAA-precursors (perfluoroalkyl chain lengths ≥ C6). We show with three organofluorine model substances (flufenamic acid, diflufenican, pantoprazole) that CF3-groups or aromatic fluorine can be quantitatively converted to inorganic fluoride and trifluoroacetic acid (TFA) by applying PhotoTOP oxidation (UV/TiO2). The principle of fluorine separation in mixtures is demonstrated by the oxidation of the three weakly fluorinated compounds together with the PFAA-precursor 6:2/6:2 fluorotelomer mercaptoalkyl phosphate diester (FTMAP). After oxidation, the products F- and TFA were separated from PFCAs (> C4) by SPE, and the fractions were analyzed individually. Closed mass balances both with and without the addition of organic matrix were achieved. Eventually, the fluorine balance was verified by total fluorine measurements with combustion ion chromatography (CIC). The proposed methods should be considered a proof of concept to potentially explain unidentified fractions of the EOF, especially if compounds with low fluorine content such as pesticides, pharmaceuticals, and their transformation products contribute largely to the EOF. Future studies are needed to show the applicability to the complexity of environmental samples.

Influence of age on the concentrations of perfluoroalkyl acids (PFAA) in the tissues of perch (Percafluviatilis).

Globally, perfluoroalkyl acids (PFAA) are ubiquitous due to their almost unlimited applications in industry and households and are detected in a wide variety of matrices.Aquatic ecosystems are of particular importance due to the spread of PFAA via water fluxes. The majority of published studies describe PFAA concentrations in fish or aquatic mammals, but not the dependence of PFAA concentrations in tissues and organs in fish of different ages. Since this is very important for understanding the accumulation behavior of these substances our study systematically investigates the influence of age on the PFAA concentration in the tissues of 74 perches (Perca fluviatilis), a very popular edible fish. Fish are particularly suitable as indicators of PFAA contamination of water because of their uptake via water (gills and skin) and food (predominantly piscivorous diet). The mean total PFAA concentrations (as the sum of the individual concentrations of 11 compounds) were: 114 µg/kg (kidney), 112 µg/kg (heart), 79.9 µg/kg (liver), 78.4 µg/kg (spleen), 64.6 µg/kg (gills) and 21.7 µg/kg (muscle), with longer-chain compounds accounting for 90% of the substances. Perfluorooctanesulfoic acid (PFOS) accounted for the largest percentage of the total PFAA concentration in all tissues at 43-63%. With the exception of the heart and spleen, a significant increase in total concentrations was observed with increasing age of the perch. The strongest correlation was observed for the kidney, followed by the liver and gills. With regard to their consumption as human nutrition the tolerable weekly PFAA intake of 4.4 ng/kg bodyweight and week for the sum of the 4 EFSA PFAA in adults and children was exceeded many times over (860% and 1600% respectively) with an average fish consumption per week. The maximum PFAA levels set in the E.U. since January 2023 were exceeded five times.

The Total Mass of Per- and Polyfluoroalkyl Substances (PFASs) in California Cosmetics.

Cosmetics make up one of the consumer product categories most widely known to contain perfluoroalkyl and polyfluoroalkyl substances (PFASs), including precursors to perfluorooctanoic acid (PFOA) and other perfluoroalkyl acids (PFAAs). Because of the way cosmetics are used, most of the PFASs present in these products are likely to reach wastewater treatment plants (WWTPs), which suggests that cosmetics may contribute significantly to the load of PFOA and other PFASs at WWTPs. However, the majority of PFASs present as intentional ingredients in cosmetics cannot be quantified with the available analytical methods. To address this issue, we developed a methodology to estimate the total PFAS mass in cosmetics as well as the corresponding mass of total organic fluorine and of fluorinated side chains associated with PFAA precursors, using various ingredient databases and ingredient concentrations reported by manufacturers. Our results indicate that the cosmetics sold in California during a one-year period cumulatively contain 650-56 000 kg of total PFASs, 370-37 000 kg of organic fluorine, and 330-20 000 kg of fluorinated side chains associated with PFAA precursors. Among the 16 product subcategories considered, >90% of the PFAS mass came from shaving creams and gels, hair care products, facial cleansers, sun care products, and lotions and moisturizers, while the sum of all nine makeup subcategories accounted for <3%. Comparing our estimates to available WWTP influent data from the San Francisco Bay Area suggests that cosmetics may account for at least 4% of the precursor-derived PFAAs measured in wastewater. As the first study ever to estimate the total mass of PFASs contained in cosmetics sold in California, our results shed light on the significance of certain cosmetics as a source of PFASs to WWTPs and can inform effective source reduction efforts.

Four Decades of Spatiotemporal Variability of Per- and Polyfluoroalkyl Substances (PFASs) in the Baltic Sea.

Temporal and spatial variability of per- and polyfluoroalkyl substances (PFASs) in herring, cod, eelpout, and guillemot covering four decades and more than 1000 km in the Baltic Sea was investigated to evaluate the effect of PFAS regulations and residence times of PFASs. Overall, PFAS concentrations responded rapidly to recent regulations but with some notable basin- and homologue-specific variability. The well-ventilated Kattegat and Bothnian Bay showed a faster log-linear decrease for most PFASs than the Baltic Proper, which lacks a significant loss mechanism. PFOS and FOSA, for example, have decreased with 0-7% y-1 in the Baltic Proper and 6-16% y-1 in other basins. PFNA and partly PFOA are exceptions and continue to show stagnant or increasing concentrations. Further, we found that Bothnian Bay herring contained the highest concentrations of >C12 perfluoroalkyl carboxylic acids (PFCAs), likely from rivers with high loads of dissolved organic carbon. In the Kattegat, low PFAS concentrations, but a high FOSA fraction, could be due to influence from the North Sea inflow below the halocline and possibly a local source of FOSA and/or isomer-specific biotransformation. This study represents the most comprehensive spatial and temporal investigation of PFASs in Baltic wildlife while providing new insights into cycling of PFASs within the Baltic Sea ecosystem.

Remove legacy perfluoroalkyl acids and emerging per- and polyfluoroalkyl ether acids by single-use and regenerable anion exchange resins: Rapid small-scale column tests and model fits.

Rapid small-scale column tests (RSSCT) are used to study the removal of per- and polyfluoroalkyl substances (PFAS) for drinking water treatment by ion exchange. Breakthroughs of 15 emerging per- and perfluoroalkyl ether acids and six legacy perfluoroalkyl acid analogs are studied using a single-use PFAS-selective anion exchange resin (AER1) and a regenerable, generic anion exchange resin (AER2). The Bohart-Adams model was used to describe and predict breakthrough, with the modeled results reasonably aligned with RSSCT results in most cases, enabling shorter RSSCT duration for future applications. AER1 exhibited high uptake capacity with no breakthrough for 11 of the 21 tested PFAS during the 144,175 BV continuous operation, allowing compliance with the new National Primary Drinking Water Regulation in many application scenarios. AER2 exhibited much faster breakthroughs for most PFAS and is not a promising option for drinking water treatment. However, the summed PFAS capacity via model fit and total PFAS adsorbed via measurement were only <0.01 % of both resin capacities at full breakthrough, suggesting PFAS could only occupy a tiny portion of the ion exchange sites even for the PFAS-selective AER1. Ether group insertion in the PFAS group leads to later breakthrough, and linear isomers were better captured by the resins than the branched isomers. Overall, PFAS uptake capacity increases and kinetics decrease when the PFAS molecular volume increases. Regeneration using 10 % NaCl solutions partially released PFAS from AER2 but not from AER1, with more short-chain PFAS released than long-chain ones. Ether group insertion decreased the PFAS recoveries during the regeneration of AER2. The regenerated resins showed much faster breakthroughs than the pristine resins, making them unfavorable for drinking water treatment applications. Adsorption displacement of short-chain PFAS by long-chain PFAS was observed in pristine AER1, and post-regeneration leaching occurred for both resins, both phenomena making the resins a possible PFAS source in long-term use.

Assessment of Potential Accumulation of Trifluoroacetate in Terminal Lakes.

Trifluoroacetate (TFA) is the anionic form of the shortest perfluorocarboxylic acid (PFCA) and is ubiquitous in the environment at concentrations that are typically much higher than those of other PFCAs. As a stable and nonvolatile anion, it is expected to accumulate in terminal lakes in endorheic basins. This research sampled eight terminal lakes in the Western United States to determine the degree to which TFA is concentrating in these lakes and compare the data to samples collected from three of these lakes 25 years ago. The first observation was that three of the six terminal lakes sampled had higher TFA concentrations than their input streams, while the last two lakes lacked surface water inputs at the sampling time. The TFA concentrations in Mono Lake effectively remained constant over 25 years despite the input stream concentrations increasing 6.5-fold. In contrast, Pyramid Lake concentrations increased approximately the expected amount based on a simplistic analysis of input flows and concentrations. An additional observation was that lakes in basins with agricultural activity appeared to have higher TFA concentrations, which suggests an agricultural input.

Evaluation of per- and polyfluoroalkyl substances (PFAS) released from two Florida landfills based on mass balance analyses.

Per- and polyfluoroalkyl substances (PFAS) have been found at high levels within landfill environments. To assess PFAS distributions, this study aimed to evaluate PFAS mass flux leached from disposed solid waste and within landfill reservoirs by mass balance analyses for two full-scale operational Florida landfills. PFAS mass flux in different aqueous components within landfills were estimated based on PFAS concentrations and water flow rates. For PFAS concentration, 26 PFAS, including 18 perfluoroalkyl acids (PFAAs) and 8 PFAA-precursors, were measured in samples collected from the landfills or estimated based on previous studies. Flow rates of aqueous components (rainfall, evapotranspiration, runoff, stormwater, groundwater, leakage, gas condensate, and leachate) were evaluated through the Hydrologic Evaluation of Landfill Performance model, water balance, and Darcy's Law. Results showed that the average PFAS mass flux leached from the solid waste standardized by area was estimated as 36.8 g/ha-yr, which was approximately 1 % to 3 % of the total amount of PFAS within the solid waste. The majority of PFAS leached from the solid waste (95 % to 97 %) is captured by the leachate collection system, with other aqueous components representing much smaller fractions (stormwater system at 3 % to 5 %, and gas condensate and groundwater at < 1 %). Also, based on the results, we estimate that PFAS releases will likely occur at least over 40 years. Overall, these results can help prioritize components for waste management and PFAS treatment during the anticipated landfill release periods.

Perfluoroalkyl acid precursors in agricultural soil-plant systems: Occurrence, uptake, and biotransformation.

Perfluoroalkyl acid (PFAA) precursors have been used in various consumer and industrial products due to their hydrophobic and oleophobic properties. In recent years, PFAA precursors in agricultural soil-plant systems have received increasing attention as they are susceptible to biotransformation into metabolites with high biotoxicity risks to human health. In this review, we systematically assessed the occurrence of PFAA precursors in agricultural soils, taking into account their sources and biodegradation pathways. In addition, we summarized the findings of the relevant literature on the uptake and biotransformation of PFAA precursors by agricultural plants. The applications of biosolids/composts and pesticides are the main sources of PFAA precursors in agricultural soils. The physicochemical properties of PFAA precursors, soil organic carbon (SOC) contents, and plant species are the key factors influencing plant root uptakes of PFAA precursors from soils. This review revealed, through toxicity assessment, the potential of PFAA precursors to generate metabolites with higher toxicity than the parent precursors. The results of this paper provide a reference for future research on PFAA precursors and their metabolites in soil-plant systems.

Per- and polyfluoroalkyl substances (PFAS) in final treated solids (Biosolids) from 190 Michigan wastewater treatment plants.

Trends in concentration, distribution, and variability of per- and polyfluoroalkyl substances (PFAS) in biosolids are characterized using an extensive dataset of 350 samples from 190 wastewater treatment plants (WWTPs) across Michigan. All samples are comprised of final treated solids generated at the end of the wastewater treatment process. Concentrations of both individual and Σ24 PFAS are lognormally distributed, with Σ24 PFAS concentrations ranging from 1-3200 ng/g and averaging 108 ± 277 ng/g dry wt. PFAS with carboxyl and sulfonic functional groups comprise 29% and 71% of Σ24 PFAS concentrations, respectively, on average. Primary sample variability in concentration is associated with long-chain PFAS with higher tendency for partitioning to biosolids. Short-chain carboxylic compounds, most notably PFHxA, are responsible for secondary concentration variability. Usage of FTSA and PFBS replacements to long-chain sulfonic compounds also contributes to variance in biosolids concentrations. Sulfonamide precursor compounds as a collective group are detected at a similar frequency as PFOS and often have higher concentrations. Trends in PFAS enrichment for individual PFAS vary at least 3 orders-of-magnitude and generally increase with compound hydrophobicity; however, partitioning of PFAS onto solids in WWTPs is a complex process not easily described nor constrained using experimentally-derived partitioning coefficients.

Elevated Levels of Ultrashort- and Short-Chain Perfluoroalkyl Acids in US Homes and People.

Per- and polyfluoroalkyl substances (PFAS) make up a large group of fluorinated organic compounds extensively used in consumer products and industrial applications. Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), the two perfluoroalkyl acids (PFAAs) with 8 carbons in their structure, have been phased out on a global scale because of their high environmental persistence and toxicity. As a result, shorter-chain PFAAs with less than 8 carbons in their structure are being used as their replacements and are now widely detected in the environment, raising concerns about their effects on human health. In this study, 47 PFAAs and their precursors were measured in paired samples of dust and drinking water collected from residential homes in Indiana, United States, and in blood and urine samples collected from the residents of these homes. Ultrashort- (with 2 or 3 carbons [C2-C3]) and short-chain (with 4-7 carbons [C4-C7]) PFAAs were the most abundant in all four matrices and constituted on average 69-100% of the total PFAA concentrations. Specifically, trifluoroacetic acid (TFA, C2) and perfluoropropanoic acid (PFPrA, C3) were the predominant PFAAs in most of the samples. Significant positive correlations (n = 81; r = 0.23-0.42; p < 0.05) were found between TFA, perfluorobutanoic acid (PFBA, C4), and perfluoroheptanoic acid (PFHpA, C7) concentrations in dust or water and those in serum, suggesting dust ingestion and/or drinking water consumption as important exposure pathways for these compounds. This study demonstrates that ultrashort- and short-chain PFAAs are now abundant in the indoor environment and in humans and warrants further research on potential adverse health effects of these exposures.

Fluorine Mass Balance, including Total Fluorine, Extractable Organic Fluorine, Oxidizable Precursors, and Target Per- and Polyfluoroalkyl Substances, in Pooled Human Serum from the Tromsø Population in 1986, 2007, and 2015.

Of the thousands of per- and polyfluoroalkyl substances (PFAS) known to exist, only a small fraction (≤1%) are commonly monitored in humans. This discrepancy has led to concerns that human exposure may be underestimated. Here, we address this problem by applying a comprehensive fluorine mass balance (FMB) approach, including total fluorine (TF), extractable organic fluorine (EOF), total oxidizable precursors (TOP), and selected target PFAS, to human serum samples collected over a period of 28 years (1986, 2007, and 2015) in Tromsø, Norway. While concentrations of TF did not change between sampling years, EOF was significantly higher in 1986 compared to 2007 and 2015. The ∑12PFAS concentrations were highest in 2007 compared to 1986 and 2015, and unidentified EOF (UEOF) decreased from 1986 (46%) to 2007 (10%) and then increased in 2015 (37%). While TF and EOF were not influenced by sex, women had higher UEOF compared to men, opposite to target PFAS. This is the first FMB in human serum to include TOP, and it suggests that precursors with >4 perfluorinated carbon atoms make a minor contribution to EOF (0-4%). Additional tools are therefore needed to identify substances contributing to the UEOF in human serum.

PFAS-CTAB Complexation and Its Role on the Removal of PFAS from a Lab-Prepared Water and a Reverse Osmosis Reject Water Using a Plasma Reactor.

Electrical discharge plasma reactors with argon bubbling can effectively treat long-chain perfluoroalkyl acids (PFAAs) in contaminated water, and the addition of a cationic surfactant cetrimonium bromide (CTAB) is known to enhance the removal of short-chain PFAAs. However, the roles of PFAA chain length, functional group, and water matrix properties on PFAA-CTAB complexation are largely unknown. This work investigated the bulk liquid removal of different PFAAs by CTAB in the absence of plasma. Stepwise addition of CTAB was subsequently used to efficiently treat PFAAs in a lab-prepared water and a reverse osmosis (RO) reject water using an enhanced contact plasma reactor. The results show that CTAB inhibited the bulk liquid removal of long-chain PFAAs in the absence of plasma likely due to the formation of hydrophilic CTAB-PFAA mixed micelles and competition for interfacial access between long-chain PFAAs and CTAB. On the contrary, CTAB enhanced the removal of short- and ultrashort-chain PFAAs by forming hydrophobic complexes. After 6 h of treatment in the plasma reactor with CTAB, PFAAs were 86 to >99% removed from the lab-prepared water and 29 to >99% removed from the RO reject water. This study provides important insights for overcoming mass transfer limitations for PFAA treatment technologies.

Production of perfluoroalkyl acids (PFAAs) from precursors in contaminated agricultural soils: Batch and leaching experiments.

Contamination of soils with per- and polyfluoroalkyl substances (PFAS) (e.g., aqueous film forming foams (AFFFs) or PFAS containing biosolids applied to agricultural soils) can lead to large scale groundwater pollution. For site management, knowledge about the extent and time scales of PFAS contamination is crucial. At such sites, often persistent perfluoroalkyl acids (PFAAs) and so-called precursors, which can be transformed into PFAAs, co-occur. In this study, the release of PFAAs from 14 soil samples from an agricultural site in southwest Germany contaminated via compost/paper sludge was investigated. Rapid leaching of C4-C8 perfluoroalkyl carboxylic acids (PFCA) was observed in saturated column tests, while slowing down with increasing chain-length (≥ C9 PFCAs). Two selected samples were further incubated in batch-tests after removal of existing C4-C8 PFCAs in extensive column leaching tests until a liquid-solid ratio of 10 l/kg. During 60 days of incubation, aqueous concentrations of C4-C8 PFCAs increased linearly by a factor of 29-222, indicating continuous production by transformation of precursors. The potential PFAA-precursor reservoir was estimated by the direct total oxidizable precursor (dTOP) assay. PFCA concentrations after the dTOP increased up to two orders of magnitude. Production rates determined in batch-tests combined with the results of dTOP assay were used to estimate time scales for the duration of C4-C8 PFCAs emission from the contaminated agricultural soils which likely will last for several decades.

Legacy perfluoroalkyl acids and their oxidizable precursors in plasma samples of Norwegian women.

Humans are exposed to perfluoroalkyl acids (PFAA) mainly through direct pathways, such as diet and drinking water, but indirect exposure also occurs when PFAA precursors break down to form legacy PFAA. Exposure to PFAA precursors raises particular concern, as neither the exposure nor the precursors themselves have been well described. In the present study, we aimed to assess the indirect contribution of oxidizable PFAA precursors to the total per- and polyfluoroalkyl substances (PFAS) burden in human plasma following the voluntary phase-out of production of long-chain PFAS. In addition, multiple logistic regression was used to explore associations between selected lifestyle and dietary factors and the oxidizable PFAA precursors fraction. This study included 302 cancer-free participants of the Norwegian Women and Cancer postgenome cohort. PFAS analyses were performed in plasma samples to determine PFAS concentrations before and after oxidation with the Total Oxidizable Precursor (TOP) assay. In pre-TOP analyses, perfluorooctane sulfonic acid (PFOS) was the dominant compound, followed by perfluorooctanoic acid (PFOA).The vast majority (98%) of the study population had increased post-TOP concentrations for at least one PFAA. The formation of PFAA accounted for 12% of the total PFAS burden, with seven PFAA observed post-TOP in at least 30% of study participants. PFHpA, br- PFOA, and PFDA were only detected in post-TOP analyses and showed the highest increase in concentrations. Of the PFAA with increased concentrations, we noted significant associations for year of birth, parity, BMI, and some dietary factors, although they were not consistent between the different PFAA. These results indicate that while the TOP assay might not provide a complete assessment of total PFAS burden in humans, it offers comprehensive assessment of unknown PFAA precursors that might be present in plasma, and it could therefore be implemented as an auxiliary tool in this regard.

Concentration, distribution, and bioconcentration of short- and long-chain perfluoroalkyl substances in the water, suspended particulate matter, and surface sediment of a typical semi-enclosed bay.

This study investigated per- and polyfluoroalkyl substances (PFAS) levels in the surface water, suspended particulate matter (SPM), sediment, and fishes in the Laizhou Bay (LZB) and its inflow river estuaries in dry, normal, and wet seasons. The results demonstrated that the short-chain perfluoroalkyl acids (PFAA) accounted for about 60 % of the total PFAA (∑PFAA) concentration in water, while long-chain PFAA were the dominant compounds in the sediment and SPM. The levels of the ∑PFAA and their precursors decreased from the estuaries to the bay, which implied that terrigenous input (pollutant in land flowed into sea) was the main pollution source of PFAA in the LZB. The PFAAs levels in surface water were ranked as the order of dry > normal > wet season. The distribution coefficients of PFAA showed that the long-chain PFAA were more prone to be adsorbed by sediment and SPM than short-chain PFAA. The increase of ∑PFAA concentrations was in the range of 0.32-36.7 ng·L-1 after the oxidation conversion of water samples. Precursors were the important source of the PFAA in the surface water. The perfluorooctane sulfonate (PFOS) was the dominant compound in fish tissues. These results provide hints for understanding PFAS pollution in LZB.

Underestimation of Per- and Polyfluoroalkyl Substances in Biosolids: Precursor Transformation During Conventional Treatment.

Wastewater treatment plants generate a solid waste known as biosolids. The most common management option for biosolids is to beneficially reuse them as an agricultural amendment, but because of the risk of pathogen exposure, many regulatory bodies require pathogen reduction before biosolids reuse. Per- and polyfluoroalkyl substances (PFAS) are well documented in biosolids, but limited information is available on how biosolids treatment processes impact PFAS. Furthermore, quantification of PFAS has focused on perfluoroalkyl acids (PFAAs) which are a small fraction of thousands of PFAS known to exist. The objective of this study was to quantify 92 PFAS in biosolids collected from eight biosolids treatment facilities before and after four pathogen treatment applications: composting, heat treatment, lime treatment, and anaerobic digestion. Overall, total PFAS concentrations before and after treatment were dominated by PFAA precursor species, in particular, diPAPs which accounted for a majority of the mass of the Σ92PFAS. This differs from historic data that found PFAAs, primarily PFOS, to dominate total PFAS concentrations. Treatment options such as heat treatment and composting changed the ratio of PFAA precursors to PFAAs indicating a transformation of PFAS during treatment. This study finds that PFAA precursors are likely underrepresented by other studies and make up a larger percentage of the total PFAS concentration in biosolids than previously estimated.

Evaluation of per- and polyfluoroalkyl substances (PFAS) in leachate, gas condensate, stormwater and groundwater at landfills.

Per- and polyfluoroalkyl substances (PFAS), found in many consumer products, are commonly disposed of in landfills at the end of their service lives. To identify landfill liquids that should be prioritized for treatment, this study aimed to evaluate PFAS levels in different aqueous samples from landfills and identify relationships between PFAS and landfill characteristics. Twenty-six PFAS including 11 perfluoroalkyl carboxylic acids (PFCAs), 7 perfluoroalkyl sulfonates (PFSAs), and 8 perfluoroalkyl acid precursors (PFAA-precursors) were measured in municipal solid waste (MSW) leachate, construction and demolition debris (CDD) leachate, municipal solid waste incineration (MSWI) ash leachate, gas condensate, stormwater, and groundwater from landfills. Based on the median, results show that PFAS levels in MSW leachate were the highest (10,000 ng L-1), CDD leachate were intermediate (6200 ng L-1), and MSWI ash leachate were the lowest (1300 ng L-1) among the leachates evaluated. PFAS levels in gas condensate (7000 ng L-1) were similar to MSW leachate. PFAS in stormwater and groundwater were low (medians were less than 500 ng L-1). Dominant subgroups included PFCAs and PFAA-precursors in all leachates. PFSAs were also found in CDD leachate, PFAA-precursors in gas condensate, and PFCAs in stormwater and groundwater. Landfill characteristics significantly correlated with ∑26PFAS included waste proportions (percentage of MSWI ash in landfill, |rs| = 0.22), operational status (active or not, |rs| = 0.27) and rainfall (30-d cumulative rainfall, |rs| = 0.39). The results from this study can be used to prioritize which landfills and which reservoir of liquids (and corresponding subgroup of PFAS) to target for PFAS management.

Effect of two sorbents on the distribution and transformation of N-ethyl perfluorooctane sulfonamido acetic acid (N-EtFOSAA) in soil-soybean systems.

The broad application of perfluoroalkyl acid (PFAA) precursors has led to their occurrence in soil, resulting in potential uptake and bioaccumulation in plants. In this study, we investigated the effect of powdered activated carbon (PAC) and montmorillonite on the distribution and transformation of a perfluorooctanesulfonic acid (PFOS) precursor, N-ethyl perfluorooctane sulfonamido acetic acid (N-EtFOSAA), in soil-plant systems. The results showed that N-EtFOSAA at 300 µg/kg was taken up by soybean roots and shoots together with its transformation products (i.e., perfluorooctane sulfonamide (PFOSA), PFOS), while decreasing the biomass of shoots and roots by 47.63% and 61.16%, respectively. PAC amendment significantly reduced the water leachable and methanol extractable N-EtFOSAA and its transformation products in soil. In the presence of soybean and after 60 days, 73.5% of the initially spiked N-EtFOSAA became non-extractable bound residues. Compared to the spiked controls, the PAC addition also decreased the total plant uptake of N-EtFOSAA by 94.96%. In contrast, montmorillonite showed limited stabilization performance for N-EtFOSAA and its transformation products and was ineffective to lower their bioavailability. Overall, the combination of PAC and soybean was found to be effective in immobilizing N-EtFOSAA in soil.

Exposure of a single wild boar population in North Rhine-Westphalia (Germany) to perfluoroalkyl acids.

Perfluoroalkyl acids (PFAA) are among the leading chemical pollutants in the twenty-first century. Of these, perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) have been widely detected in a large number of animal and environmental samples. Wild boars accumulate PFAA in their livers, but it has not yet been clarified to what extent wild boars of the same population accumulate different PFAA in their livers or whether any conclusions can be drawn from any differences found in regard to environmental contamination. In this study, liver samples from wild boars killed during driven hunts in 2019 and 2020 from a defined forest area in North Rhine-Westfalia, Germany were analyzed for 13 different PFAA. A mean load of 493 µg/kg (± 168 µg/kg) PFAA was measured in 2020. Perfluorosulfonic acids accounted for 87% of the total load in both years, with PFOS dominating this group. These results were similar to those of 14 liver samples collected from other regions of Germany for comparison. In addition, the livers of hunted pregnant sows and fetuses were examined. The load of short-chain perfluorocarboxylic acids (< C8) in the fetus liver was as high as that of the sows, whereas the concentrations of long-chain perfluorocarboxylic acids (≥ C8) were lower than in the dams. This result shows for the first time that fetuses take up PFAA from their mothers in utero. Our study shows that PFAA content in wild boar livers is comparably high in all animals in a local population and indicates a need for further research regarding a nationwide background exposure to PFAA in wild boars and their surrounding environment.