Perfluoroalkyl Acids Precursors Research Articles

Tissue-specific distribution and bioaccumulation of perfluoroalkyl acids, isomers, alternatives, and precursors in citrus trees of contaminated fields: Implication for risk assessment

The ingestion of fruits containing perfluoroalkyl acids (PFAAs) presents potential hazards to human health. This study aimed to fill knowledge gaps concerning the tissue-specific distribution patterns and bioaccumulation behavior of PFAAs and their isomers, alternatives, and precursors (collectively as per-/polyfluoroalkyl substances, PFASs) within citrus trees growing in contaminated fields. It also assessed the potential contribution of precursor degradation to human exposure risk of PFASs. High concentrations of total target PFASs (∑PFASstarget, 92.45–7496.16 ng/g dw) and precursors measured through the total oxidizable precursor (TOP) assay (130.80–13979.21 ng/g dw) were found in citrus tree tissues, and short-chain PFASs constituted the primary components. The total PFASs concentrations followed the order of leaves > fruits > branches, bark > wood, and peel > pulp > seeds. The average contamination burden of peel (∑PFASstarget: 57.75%; precursors: 71.15%) was highest among fruit tissues. Bioaccumulation factors (BAFs) and translocation potentials of short-chain, branched, or carboxylate-based PFASs exceeded those of their relatively hydrophobic counterparts, while ether-based PFASs showed lower BAFs than similar PFAAs in above-ground tissues of citrus trees. In the risk assessment of residents consuming contaminated citruses, precursor degradation contributed approximately 36.07% to total PFASs exposure, and therefore should not be ignored.

Effective stabilization of per- and polyfluoroalkyl substances (PFAS) precursors in wastewater treatment sludge by surfactant-modified clay

The application of biosolids or treated sewage sludge containing per- and polyfluoroalkyl substances (PFAS) in agricultural lands and the disposal of sludge in landfills pose high risks to humans and the environment. Although PFAS precursors have not been regulated yet, their potential transformation to highly regulated perfluoroalkyl acids (PFAAs) may enable them to serve as a long-term source and make remediation of PFAAs a continuing task. Therefore, treating precursors in sewage sludge is even more, certainly not less, critical than treating or removing PFAAs. In this study, a green surfactant-modified clay sorbent was evaluated for its efficacy in stabilizing two representative PFAA precursors in sludge, e.g., N-ethyl perfluorooctane sulfonamido acetic acid (N-EtFOSAA) and 6:2 fluorotelomer sulfonic acid (6:2 FTSA), in comparison with unmodified clay and powdered activated carbon (PAC). Results showed N-EtFOSAA and 6:2 FTSA exhibited distinct adsorption behaviors in the sludge without sorbents due to their different physicochemical properties, such as hydrophobicity and functional groups. Among the three sorbents, the modified clay reduced the water leachability of N-EtFOSAA and 6:2 FTSA by 91.5% and 95.4%, respectively, compared to controls without amendments at the end of the experiment (47 days). Within the same duration, PAC decreased the water leachability of N-EtFOSAA and 6:2 FTSA by 60.6% and 37.3%, respectively. At the same time, the unmodified clay demonstrated a poor stabilization effect and even promoted the leaching of precursors. These findings suggested that the modified clay had the potential for stabilization of precursors, while negatively charged and/or hydrophilic sorbents, such as the unmodified clay, should be avoided in the stabilization process. These results could provide valuable information for developing effective amendments for stabilizing PFAS in sludge or biosolids. Future research should evaluate the long-term effect of the stabilization approach using actual sludge from wastewater treatment facilities.

Legacy and Emerging Per- and Polyfluoroalkyl Substances Surveillance in Bufo gargarizans from Inlet Watersheds of Chaohu Lake, China: Tissue Distribution and Bioaccumulation Potential.

Amphibians are sensitive biomonitors of environmental pollutants but reports regarding per- and polyfluoroalkyl substances (PFAS), a class of synthetic organofluorine substances, are limited. In this study, samples of water and Chinese toads (Bufo gargarizo) were collected in Chaohu Lake, China. Tissue-specific bioaccumulation characteristics of 39 PFAS, including 19 perfluoroalkyl acids (PFAAs), 8 emerging PFAS, and 12 PFAA precursors, were investigated, and the levels of some biochemical indicators were determined. The highest PFAS concentrations were found in the liver [215.97 ng/g dry weight (dw)] of Chinese toads, followed by gonads (135.42 ng/g dw) and intestine (114.08 ng/g dw). A similar tissue distribution profile was found between legacy and emerging PFAS in the toads, and the occurrence of two emerging PFAS, 2,3,3,3-tetrafluoro-2-propanoate (HFPO-DA) and 6:2 hydrogen-substituted polyfluorooctane ether sulfonate (6:2 H-PFESA) in the amphibians were for the first time reported. Field-based bioaccumulation factors of HFPO-DA were higher than perfluorooctanoic acid, indicating the higher bioaccumulation potential of this emerging PFAS than the legacy C8 compound. Males had significantly higher gonad PFAS levels than females while estradiol levels in gonads increased with increasing concentrations of certain PFAS (e.g., 6:2 H-PFESA), implying that PFAS may trigger estrogenic effects in the toads, especially for male toads.

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.

Per- and polyfluoroalkyl substances (PFAS) in surface sediments: Occurrence, patterns, spatial distribution and contribution of unattributed precursors in French aquatic environments

While perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) are ubiquitous in aquatic environments, non-targeted methods have recently revealed the presence of numerous unidentified per- and polyfluoroalkyl substances (PFAS). Besides those methods, the total oxidizable precursor (TOP) assay has proved useful to estimate the contribution of unattributed perfluoroalkyl acids precursors (pre-PFAAs). In this study, an optimized extraction method was developed to examine the spatial distribution of 36 targeted PFAS in surface sediments collected at French nationwide scale (n = 43), including neutral, anionic and zwitterionic molecules. In addition, a TOP assay procedure was implemented to estimate the contribution of unattributed pre-PFAAs in these samples. Conversion yields of targeted pre-PFAAs were determined for the first time under realistic conditions and led to differences in oxidation profiles compared to the common spiked ultra-pure water method. PFAS were detected in 86 % of samples and ∑PFAStargeted was in the range < Limit of Detection – 23 ng g−1 dry weight (dw) (median: 1.3 ng g−1 dw), with ∑pre-PFAAstargeted representing on average 29 ± 26 % of ∑PFAS. Among pre-PFAAs, compounds of emerging interest such as the fluorotelomer sulfonamidoalkyl betaines 6:2 FTAB and 8:2 FTAB were respectively detected in 38 % and 24 % of samples, with levels similar to those of L-PFOS (<0.36–2.2, <0.50–6.8 and < 0.08–5.1 ng g−1 dw, respectively). A hierarchical cluster analysis coupled with a geographic information system-based approach revealed similarities between groups of sampling sites. For instance, elevated contribution of FTABs were associated with the proximity to airport activities where betaine-based aqueous film-forming foam (AFFFs) might have been used. In addition, unattributed pre-PFAAs were strongly correlated with ∑PFAStargeted and they accounted for 58 % of ∑PFAS (median value); they were generally found in larger quantity near industrial and urban areas where the highest ∑PFAStargeted were also observed.

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.

Total oxidizable precursors assay for PFAS in human serum

Per- and polyfluoroalkyl substances (PFAS) are a class of chemicals including over 4700 substances. As a limited number of PFAS is routinely analyzed in human serum, complementary analytical methods are required to characterize the overlooked fraction. A promising tool is the total oxidizable precursors (TOP) assay to look for precursors by oxidation to perfluoroalkyl acids (PFAA). The TOP assay was originally developed for large volumes of water and had to be adapted for 250 μL of human serum. Optimization of the method was performed on serum samples spiked with model precursors. Oxidative conditions similar to previous TOP assay methods were not sufficient for complete oxidation of model precursors. Prolonged heating time (24 h) and higher oxidant amount (95 mg of Na2S2O8 per 225 μL of serum) were needed for complete conversion of the model precursors and accomplishing PFAA yields of 35–100 %. As some precursors are not fully converted to PFAA, the TOP assay can only provide semi-quantitative estimates of oxidizable precursors in human serum. However, the TOP assay can be used to give indications about the identity of unknown precursors by evaluating the oxidation products, including perfluoroalkyl sulfonic acids (PFSA) and perfluoroalkyl ether carboxylic acids (PFECA). The optimized TOP assay for human serum opens the possibility for high-throughput screening of human serum for undetected PFAA precursors.

PFAS and Precursor Bioaccumulation in Freshwater Recreational Fish: Implications for Fish Advisories.

Per- and polyfluoroalkyl substances (PFAS) are a diverse class of fluorinated anthropogenic chemicals that include perfluoroalkyl acids (PFAA), which are widely used in modern commerce. Many products and environmental samples contain abundant precursors that can degrade into terminal PFAA associated with adverse health effects. Fish consumption is an important dietary exposure source for PFAS that bioaccumulate in food webs. However, little is known about bioaccumulation of PFAA precursors. Here, we identify and quantify PFAS in recreational fish species collected from surface waters across New Hampshire, US, using a toolbox of analytical methods. Targeted analysis of paired water and tissue samples suggests that many precursors below detection in water have a higher bioaccumulation potential than their terminal PFAA. Perfluorobutane sulfonamide (FBSA), a short-chain precursor produced by electrochemical fluorination, was detected in all fish samples analyzed for this compound. The total oxidizable precursor assay interpreted using Bayesian inference revealed fish muscle tissue contained additional, short-chain precursors in high concentration samples. Suspect screening analysis indicated these were perfluoroalkyl sulfonamide precursors with three and five perfluorinated carbons. Fish consumption advisories are primarily being developed for perfluorooctane sulfonate (PFOS), but this work reinforces the need for risk evaluations to consider additional bioaccumulative PFAS, including perfluoroalkyl sulfonamide precursors.

Oysters for legacy and emerging per- and polyfluoroalkyl substances (PFASs) monitoring in estuarine and coastal waters: Phase distribution and bioconcentration profile

Per- and polyfluoroalkyl substances (PFASs) are a diverse group of widely used anthropogenic chemicals that are environmentally persistent and bioaccumulative, especially in aquatic ecosystem. The heavily industrialized and urbanized Greater Bay Area in China represents a notable contamination source for PFASs, which may potentially influence the health of local oysters as a keystone species in local ecosystems and a popular seafood. In this study, samples of oysters and their surrounding waters were collected from the littoral zones of the Pearl River Estuary (PRE), China during winter 2020, where 44 PFASs, including 19 perfluoroalkyl acids (PFAAs), 8 emerging PFASs, and 17 PFAA precursors (or intermediates), were analyzed. Total PFAS concentrations ranged 13.8−58.8 ng/L in the dissolved phase, 3.60−11.2 ng/g dry weight (dw) in the suspended particulate matter (SPM), and 0.969−1.98 ng/g dw in the oysters. Most short-chain PFASs were present in the dissolved phase (>95%), while long-chain PFASs generally showed higher concentrations in the SPM. Log field-based bioconcentration factors (BCFs) of long-chain PFASs increased linearly (r = 0.95, p < 0.01) with increasing estimated log membrane−water (Dmw) and protein−water (Dpw) distribution coefficients. Perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA) exhibited higher measured BCFs than those estimated by their Dmw and Dpw. Considering the widespread occurrence of their precursors, the contribution of precursor transformation was likely to be a significant source of PFHxA and PFHpA. Oysters from the PRE littoral zones posed low risks to human health associated with PFAS consumption, which might be underestimated due to limited toxicity data available for PFAA precursors and emerging PFASs. This study sheds light on the practicality of applying oysters as biomonitors for timely PFAS monitoring in coastal environments.

How Well Do Product Labels Indicate the Presence of PFAS in Consumer Items Used by Children and Adolescents?

PFAS are persistent and toxic chemicals used in many commercial and industrial applications that are often added to consumer products, including those used by children and adolescents, to impart water and stain resistance. Since product labels rarely list chemical additives, including PFAS, we evaluated whether other information on product labels can be used by consumers to select products without PFAS. We selected 93 items marketed to or often used by children and adolescents across three product types (furnishings, apparel, bedding) and five labeling groups representing different combinations of water and/or stain resistance and “green” (including “nontoxic”) assurances. We screened all products for total fluorine (F) and analyzed solvent extracts from a subset (n = 61) for 36 targeted PFAS and from a smaller subset (n = 30) for perfluoroalkyl acids (PFAAs) generated by precursor oxidation using the total oxidizable precursor (TOP) assay. Products advertised as water- and/or stain-resistant had more frequent detections and higher concentrations of total F than those without such claims, and targeted PFAS were detected only in products labeled as water- and/or stain-resistant. Concentrations of PFAAs generated by precursor oxidation using the TOP assay often exceeded pre-oxidation concentrations, suggesting that PFAA precursors contribute to solvent-extractable PFAS from products. Among products advertised as water- and/or stain-resistant, detection frequencies and concentrations of targeted PFAS were similar regardless of green assurances. This study illustrates many nonessential uses of PFAS in products used by children and adolescents and suggests that while water- and stain-resistant assurances can identify products likely to contain PFAS, current green assurances do not consistently indicate the absence of PFAS.

Electrochemical Transformations of Perfluoroalkyl Acid (PFAA) Precursors and PFAAs in Landfill Leachates

Landfill leachates possess a countless number of chemical classes of potential environmental and human concern, including per- and polyfluoroalkyl substances (PFAS). While detection and biodegradation studies of PFAS in leachates have been conducted previously, the degradation of precursors of perfluoroalkyl acids (PFAAs) in landfill leachates with oxidative technologies has not been addressed. Thus, information regarding the oxidative transformations of PFAA precursors typically present in leachates is lacking. Target and suspect PFAS were identified in a landfill leachate, and their concentrations during electrochemical treatment were quantified over time. Liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF) measurements of the leachate showed a total PFAS concentration of 157 ± 10 nmol/L that included 53 PFAS and 19 different classes. Multiple PFAS are reported for the first time in landfill leachates. The molar composition of the leachate was comprised of 33% PFAAs, 7% electrochemical fluorination (ECF) precursors, and 60% fluorotelomer (FT) precursors. Further analysis with total oxidizable precursor (TOP) assay revealed an additional concentration of precursors that was not identified with LC-QToF. The evaluation of the intermediate and final products generated during the electrochemical treatment showed evidence of known electrochemical degradation pathways. However, this is the first study to have more evidence for electrochemical pathways in landfill leachates. In brief, sulfonamide-based precursors and fluorotelomer-based precursors were electrochemically transformed into perfluoroalkyl carboxylic acids (PFCAs) during treatment of the leachate.

Hydrothermal liquefaction of sewage sludge – effect of four reagents on relevant parameters related to biocrude and PFAS

Catalytic hydrothermal liquefaction (HTL) can convert wet biomass into crude-like oil and has potential to degrade pollutants during the thermal depolymerization process. To avoid negative environmental impacts from per- and polyfluoroalkyl substances (PFAS) in sewage sludge after its final disposal, we comprehensively evaluated catalytic destruction of PFAS in sludge through HTL. The results showed that adding red mud to HTL was beneficial for the biocrude yield and significantly increased the carbon conversion efficiency and energy recovery of the hydrothermal process. HTL at 300 °C for 2 h degraded > 96% of spiked perfluorooctanoic acid (PFOA). The mass of spiked perfluorobutanesulfonic acid (PFBS) and perfluorooctanesulfonic acid (PFOS) and pre-existing perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA), however, increased in the HTL product streams. The remaining PFAS after HTL mainly stayed in the biocrude phase. Our findings indicated that HTL under the studied condition was not able to degrade all PFAS existed in sewage sludge. Although adding red mud could improve the HTL performance with respect to biocrude, this reagent did not improve the removal of perfluoroalkyl acids (PFAAs). As a matter of fact, the hydrothermal process amended with the selected reagents resulted in increased mass of PFBS, PFHxA, and PFHpA in the HTL products due to degradation of PFAA precursors. Thus, other treatment approaches for PFAS removal from sewage sludge need to be identified to prevent possible contamination of environments receiving PFAS-containing sludge.

Spatial and temporal trends of perfluoroalkyl acids in water bodies: A case study in Taihu Lake, China (2009–2021)

Perfluoroalkyl acids (PFAAs) have been ubiquitously detected in water bodies and are a cause of great public concern due to their adverse effects. This study investigated the long-term temporal-spatial trends of PFAAs in the water bodies of the entire Taihu Lake, and predicted PFAA concentrations for 2024. A field investigation conducted in 2021 and previous data allowed to derive trends over a broad temporal-spatial scale, which is often not feasible in short-term studies. In the 2009–2021 period, the most quantifiable PFAAs increased, among which perfluorooctanoic acid and perfluorohexanoic acid were predominant. As of 2021, the mean total concentration of ten PFAAs (∑10PFAA) showed a distinct spatial decreasing trend, moving from north to south within the lake, and similar spatial distribution patterns were also noted in other years. The main PFAA input and most serious contamination were concentrated in the northern region, due to the riverine inputs and clustering of PFAA-related industries. The ∑10PFAA concentration in the wet season was greater and presented a more uniform distribution pattern than that in the dry season, possibly due to the combined effects of the degradation of PFAA precursors, water inflow, rainfall, shipping activities, and a shallow water column. From 2009 to 2021 the ∑10PFAA concentration of the entire lake showed an increasing trend, but the rate of increase was significantly reduced. In addition, a grey model predicted that the mean ∑10PFAA concentration in the entire Taihu Lake will reach 431 ng/L in 2024, and the northern region will be affected by a more serious PFAA pollution in the future because it exhibited a high mean ∑10PFAA concentration of 426 ng/L in 2021. These findings provide novel insights into the temporal-spatial distribution of PFAAs in Taihu Lake, and could help regulators to formulate policy decisions in response to PFAA pollution.

Release of Per- and Polyfluoroalkyl Substances from Aqueous Film-Forming Foam Impacted Soils.

Per- and polyfluoroalkyl substances (PFASs) are highly mobile in the saturated subsurface, yet aqueous film-forming foam (AFFF)-impacted source zones appear to be long lasting PFAS reservoirs. This study examined the release of over one hundred anionic and zwitterionic PFASs from two AFFF-impacted surface soils under saturated conditions with packed soil columns. Perfluoroalkyl acids (PFAAs) were released more rapidly than their polyfluorinated precursors, while anionic PFASs that were present in partially uncharged states were released more slowly than PFASs that were present entirely as anions, as were zwitterionic PFASs with terminal cationic functional groups when compared with analogous zwitterions with only anionic terminal groups. Nonideal transport was observed in both per- and polyfluorinated classes, as soil column effluent concentrations of slowly released PFASs increased by up to 107-fold with sustained artificial groundwater flow. A flow-interruption experiment suggested the influence of rate-limited desorption on diverse PFAS classes, including PFAAs with as few as four perfluorinated carbons. These results suggest that during infiltration the slow, rate-limited desorption of anionic and zwitterionic PFAA precursors may result in these compounds comprising an increasingly large fraction of the remaining PFASs in AFFF-impacted surface soils.

Treatment of PFAS-containing landfill leachate using an enhanced contact plasma reactor

A bench-scale plasma reactor was used to degrade poly- and perfluoroalkyl substances (PFAS) in landfill leachate samples obtained from three different locations. In the leachate samples before treatment, five long-chain, six short-chain perfluoroalkyl acids (PFAAs) and eight PFAA precursors were detected in a wide concentration range (~102 to 105 ng/L; total oxidizable precursors (TOP) ~106 ng/L). The concentration of perfluorooctane sulfonate (PFOS) plus perfluorooctanoic acid (PFOA) ranged between 2000 and 3000 ng/L. Plasma-based water treatment of 500 mL samples resulted in faster removal rates for longer-chain than shorter chain length PFAAs. Both PFOS and PFOA were removed to below United States Environmental Protection Agency’s (USEPA’s) health advisory concentration level (HAL) concentrations (<70 ng/L) in 10–75 min; 90% PFOA and PFOS removal was achieved in 10 min. Long-chain and short-chain PFAAs were removed by >99.9% and 10–99.9%, respectively. The removal rate constant (kPFOA+PFOS) for combined PFOA and PFOS ranged between 0.20 and 0.34 min-1. Overall, 60 ± 2% of the TOP concentration and 34 ± 2% of the TOC were removed. No effect of non-PFAS co-contaminants (e.g., total initial organic carbon concentration ~2000 mg/L) on the degradation efficiency was observed. Short-chain PFAA removal efficacy was enhanced by adding a cationic surfactant (cetrimonium bromide). Overall, the results indicate that plasma-based technology may be a viable technology for the treatment of PFAS-contaminated landfill leachates.

An exploratory analysis of poly- and per-fluoroalkyl substances in pet food packaging from the United States

Poly- and per-fluoroalkyl substances (PFAS) were reported to be used in food packaging to impart water and oil repellency. Little is known, however, with regard to the occurrence of PFAS in pet food packaging. In this study, 37 pet food packaging and 11 pet foods were analyzed for the determination of 13 perfluoroalkyl acids (PFAA), including nine perfluoroalkyl carboxylic acids (PFCA; C 4 - C 12 ) and four perfluoroalkyl sulfonic acids (PFSA; C 4 - C 10 ). Furthermore, samples were extracted in organic solvents (methanol and ethyl acetate) and an aliquot of the extract was analyzed using total oxidizable precursor (TOP) assay to determine the occurrence of PFAS precursors that may be present in packaging. PFSA concentrations were below their respective limits of detection. Plastic food packaging samples contained ∑ PFCA (sum of 9 PFCAs) concentrations an order of magnitude higher (range: <LOD-60.0 ng/g; mean: 11.8 ng/g), following oxidation of extracts by the TOP assay, than those measured prior to oxidation (range: <LOD-10.3 ng/g; mean: 1.28 ng/g). Similarly, pet food contained approximately an order of magnitude higher ∑ PFCA concentrations (range: 0.600–14.3 ng/g; mean: 5.71 ng/g) following oxidation than those measured prior to oxidation (range: <LOD-3.67 ng/g; mean: 0.89 ng/g). Higher ∑ PFCA concentrations following the TOP assay suggested the occurrence of PFAA precursors in food packaging. Fluorotelomer alcohols were suspected to contribute to higher PFCA concentrations measured following the oxidation of extracts of food packaging. • Perfluoroalkyl substances were measured in pet packaging and pet food. • Total oxidizable precursor (TOP) assay was applied in the analysis. • ∑ PFCAs concentrations in packaging before and after the TOP assay were 1.99 and 11.0 ng/g, respectively. • Precursors that were oxidized to PFBA were found in pet food and packaging.

Biotransformation of perfluoroalkyl acid precursors from various environmental systems: advances and perspectives.

Perfluoroalkyl acids (PFAAs) are widely used in industrial production and daily life because of their unique physicochemical properties, such as their hydrophobicity, oleophobicity, surface activity, and thermal stability. Perfluorosulfonic acids (PFSAs) and perfluorocarboxylic acids (PFCAs) are the most studied PFAAs due to their global occurrence. PFAAs are environmentally persistent, toxic, and the long-chain homologs are also bioaccumulative. Exposure to PFAAs may arise directly from emission or indirectly via the environmental release and degradation of PFAA precursors. Precursors themselves or their conversion intermediates can present deleterious effects, including hepatotoxicity, reproductive toxicity, developmental toxicity, and genetic toxicity. Therefore, exposure to PFAA precursors constitutes a potential hazard for environmental contamination. In order to comprehensively evaluate the environmental fate and effects of PFAA precursors and their connection with PFSAs and PFCAs, we review environmental biodegradability studies carried out with microbial strains, activated sludge, plants, and earthworms over the past decade. In particular, we review perfluorooctyl-sulfonamide-based precursors, including perfluroooctane sulfonamide (FOSA) and its N-ethyl derivative (EtFOSA), N-ethyl perfluorooctane sulfonamido ethanol (EtFOSE), and EtFOSE-based phosphate diester (DiSAmPAP). Fluorotelomerization-based precursors are also reviewed, including fluorotelomer alcohols (FTOH), fluorotelomer sulfonates (FTSA), and a suite of their transformation products. Though limited information is currently available on zwitterionic PFAS precursors, a preliminary review of data available for 6:2 fluorotelomer sulfonamide betaine (FTAB) was also conducted. Furthermore, we update and refine the recent knowledge on biotransformation strategies with a focus on metabolic pathways and mechanisms involved in the biotransformation of PFAA precursors. The biotransformation of PFAA precursors mainly involves the cleavage of carbon-fluorine (C-F) bonds and the degradation of non-fluorinated functional groups via oxidation, dealkylation, and defluorination to form shorter-chained PFAAs. Based on the existing research, the current problems and future research directions on the biotransformation of PFAA precursors are proposed.

Formation and partitioning behaviour of perfluoroalkyl acids (PFAAs) in waste activated sludge during anaerobic digestion

The formation and fate of perfluoroalkyl acids (PFAAs) in sludge during anaerobic digestion (AD) is of global importance since the sludge is a significant source of PFAAs to the environment. The formation of PFAAs from polyfluorinated compounds, namely PFAA precursors, is poorly understood in AD. This study aims to investigate the formation of PFAAs from precursors and their partitioning behaviour in waste activated sludge (WAS) during AD process. To achieve this, three isotope-labelled PFAAs were spiked and monitored along with indigenous PFAAs and precursors over eight weeks in a laboratory-scale anaerobic digester, fed with sludge from a local wastewater treatment plant and operated with a hydraulic retention time of 12 days under 35 ℃. In addition to isotope-labelled PFAAs, twelve native PFAAs and eight polyfluorinated compounds were detected in the feed and digested sludges. A mass-balance model, validated by the spiking experiment, was applied to predict the concentrations of PFAAs and precursors assuming no formation/degradation in AD. The measured concentrations of short-chain PFAAs (perfluoroalkyl carboxylates (PFCAs): C < 8; perfluoroalkane sulfonates (PFSAs): C < 6) in the AD sludge were significantly (p < 0.05) higher than the model-predicted concentrations, indicating the formation of these PFAAs from precursors in AD. In contrast, the formation of long-chain PFAAs (PFCAs: C ≥ 8; PFSAs: C ≥ 6) was not observed. Moreover, the degradation of two polyfluoroalkyl phosphates (PAPs) (6:2 PAP and 6:2/8:2 diPAP) occurred, evidenced by their measured concentrations that were statistically lower than the mass-balance predictions. Further, the AD process reduced the amount of PFAAs absorbed/adsorbed to sludge, particularly for the long-chain ones, due to the breakdown of solids.

Characterizing and Comparing Per- and Polyfluoroalkyl Substances in Commercially Available Biosolid and Organic Non-Biosolid-Based Products.

There is increasing concern over the presence of per- and polyfluoroalkyl substances (PFAS) in biosolids, while sales in commercially available biosolid-based products used as soil amendments are also increasing. Here, the occurrence of 17 perfluoroalkyl acids (PFAAs) present in 13 commercially available biosolid-based products, six organic composts (manure, mushroom, peat, and untreated wood), and one food and yard waste compost were studied. The PFAA concentration ranges observed are as follows: biosolid-based products (9.0-199 μg/kg) > food and yard waste (18.5 μg/kg) > other organic products (0.1-1.1 μg/kg). Analysis of 2014, 2016, and 2018 bags produced from one product line showed a temporal decrease in the total PFAAs (181, 101, and 74 μg/kg, respectively). The total oxidizable precursor (TOP) assay revealed the presence of PFAA precursors in the biosolid-based products at much higher levels, when the soluble carbon was removed by the ENVI-Carb clean-up prior to the TOP assay. Time-of-flight mass spectrometry confirmed the presence of three sulfonamides, two fluorotelomer sulfonates, and several polyfluoroalkyl phosphate diesters. Pore-water concentrations of water-saturated products were primarily of short-chain PFAAs and increased with increasing PFAA concentrations in the products. A strong positive log-linear correlation between organic carbon (OC)-normalized PFAA partition coefficients and the number of CFn units indicates that OC is a good predictor of PFAA release concentrations.

Total oxidizable precursor assay in the determination of perfluoroalkyl acids in textiles collected from the United States

Per- and polyfluoroalkyl substances (PFASs) are used in specialty/functional textiles to impart oil, water, and stain repellency. Little is known, however, with regard to the occurrence of PFASs in textiles including infant clothing. In this study, 13 perfluoroalkyl acids (PFAAs), comprising four perfluoroalkyl sulfonic acids (PFSAs; C4–C10) and nine perfluoroalkyl carboxylic acids (PFCAs; C4–C12) were determined in 160 textile samples collected from the United States. Two extraction methods, one involving a simple solvent extraction (i.e., before oxidation) and the other with an oxidative treatment (i.e., after oxidation) of textile extracts, were used. The sum concentrations of 13 PFAAs (i.e., ∑PFAA) in textile extracts before oxidation ranged from <LOD to 63.7 μg/m2 (<LOD–285 ng/g), with a mean value of 3.18 μg/m2 (14.2 ng/g). ∑PFAA concentrations were the highest in flame retarded textiles (n = 23; mean: 13.3 μg/m2; 59.4 ng/g), followed by water repellent textiles (n = 56; 2.88 μg/m2; 12.9 ng/g) and infant clothes (n = 81; 0.521 μg/m2; 2.33 ng/g). C4–C10 PFCAs accounted for at least three-quarters of the ∑PFAA content in our textile samples. Textile extracts analyzed after oxidative treatment exhibited ∑PFAA concentrations 10-fold higher than those in extracts analyzed prior to oxidation, which suggested that PFAA precursors are used in textiles. Precursors that generated C4–C5 PFCAs, upon oxidation, were more prevalent than those that yielded PFOA. The calculated dermal exposure doses in infants of PFAAs present in clothes were at least 1–2 orders of magnitude below the reference doses proposed by the United States Environmental Protection Agency. This is the first time that the oxidative treatment was applied in the analysis of PFASs in textiles, and our results suggest the existence of PFCA precursors in textiles.