Synthesis of Water-Dispersible Poly(dimethylsiloxane) and Its Potential Application in the Paper Coating Industry as an Alternative for PFAS-Coated Paper and Single-Use Plastics.

Polyethylene-, polyvinylidene chloride-, and per- and polyfluoroalkyl substance-coated paper generate microplastics or fluorochemicals in the environment. Here, we report an approach for the development of oil-resistant papers using an environmentally friendly, fluorine-free, water-dispersible poly(dimethylsiloxane) (PDMS) coating on kraft paper. Carboxylic-functionalized PDMS (PDMS-COOH) was synthesized and subsequently neutralized with ammonium bicarbonate to obtain a waterborne emulsion, which was then coated onto kraft paper. The water resistance of the coated paper was determined via Cobb60 measurements. The Cobb60 value was reduced to 2.70 ± 0.14 g/m2 as compared to 87.6 ± 5.1 g/m2 for uncoated paper, suggesting a remarkable improvement in water resistance. Similarly, oil resistance was found to be 12/12 on the kit test scale versus 0/12 for uncoated paper. In addition, the coated paper retained 70-90% of its inherent mechanical properties, and more importantly, the coated paper was recycled via pulp recovery using a standard protocol with a 91.1% yield.

Environmental Fate of Cl-PFPECAs: Accumulation of Novel and Legacy Perfluoroalkyl Compounds in Real-World Vegetation and Subsoils.

Per- and polyfluoroalkyl substances (PFAS) are globally distributed and potentially toxic compounds. We report accumulation of chloroperfluoropolyethercarboxylates (Cl-PFPECAs) and perfluorocarboxylates (PFCAs) in vegetation and subsoils in New Jersey. Lower molecular weight Cl-PFPECAs, containing 7-10 fluorinated carbons, and PFCAs containing 3-6 fluorinated carbons were enriched in vegetation relative to surface soils. Subsoils were dominated by lower molecular weight Cl-PFPECAs, a divergence from surface soils. Contrastingly, PFCA homologue profiles in subsoils were similar to surface soils, likely reflecting temporal-use patterns. Accumulation factors (AFs) for vegetation and subsoils decreased with increasing CF2, 6-13 for vegetation and 8-13 in subsoils. In vegetation, for PFCAs having CF2 = 3-6, AFs diminished with increasing CF2 as a more sensitive function than for longer chains. Considering that PFAS manufacturing has transitioned from long-chain chemistry to short-chain, this elevated vegetative accumulation of short-chain PFAS suggests the potential for unanticipated PFAS exposure levels globally in human and/or wildlife populations. This inverse relationship between AFs and CF2-count in terrestrial vegetation is opposite the positive relationship reported in aquatic vegetation suggesting aquatic food webs may be preferentially enriched in long-chain PFAS. AFs normalized to soil-water concentrations increased with chain length for CF2 = 6-13 in vegetation but remained inversely related to chain length for CF2 = 3-6, reflecting a fundamental change in vegetation affinity for short chains compared to long.

Warming Affects Bioconcentration and Bioaccumulation of Per- and Polyfluoroalkyl Substances by Pelagic and Benthic Organisms in a Water-Sediment System.

Warming and exposure to emerging global pollutants, such as per- and polyfluoroalkyl substances (PFAS), are significant stressors in the aquatic ecosystem. However, little is known about the warming effect on the bioaccumulation of PFAS in aquatic organisms. In this study, the pelagic organisms Daphnia magna and zebrafish, and the benthic organism Chironomus plumosus were exposed to 13 PFAS in a sediment-water system with a known amount of each PFAS at different temperatures (16, 20, and 24 °C). The results showed that the steady-state body burden (Cb-ss) of PFAS in pelagic organisms increased with increasing temperatures, mainly attributed to increased water concentrations. The uptake rate constant (ku) and elimination rate constant (ke) in pelagic organisms increased with increasing temperature. In contrast, warming did not significantly change or even mitigate Cb-ss of PFAS in the benthic organism Chironomus plumosus, except for PFPeA and PFHpA, which was consistent with declined sediment concentrations. The mitigation could be explained by the decreased bioaccumulation factor due to a more significant percent increase in ke than ku, especially for long-chain PFAS. This study suggests that the warming effect on the PFAS concentration varies among different media, which should be considered for their ecological risk assessment under climate change.

Associations of per- and polyfluoroalkyl substances and their alternatives with bone mineral density levels and osteoporosis prevalence: A community-based population study in Guangzhou, Southern China.

BACKGROUND: Evidence concerning associations of per- and polyfluoroalkyl substances (PFASs) exposure with bone mineral density (BMD) and osteoporosis is scarce. Additionally, no study has examined the effects of PFAS isomers and alternatives on bone health. OBJECTIVES: To evaluate the associations of PFASs and PFAS alternatives with BMD levels and osteoporosis prevalence. METHODS: A total of 1260 healthy adults from southern China were enrolled. Serum concentrations of 32 legacy PFASs, PFAS isomers, and alternatives were measured using modified liquid chromatography-tandem mass spectrometry. Logistic and linear regression models were applied to evaluate the associations of PFASs with osteoporosis prevalence and BMD levels, respectively, adjusting for confounding factors. We performed stratified analyses to assess potential effect modifications of age and sex. We further used sensitivity analyses to testify the robustness of the main findings. RESULTS: There were 204 (16.2 %) participants diagnosed with osteoporosis. Eleven of the studied PFASs (i.e., PFHpA, PFOA, PFBS, PFHpS, total-PFHxS, n-PFHxS, br-PFHxS, br-PFOS, 1m-PFOS, Σ3 + 4 + 5m-PFOS, and 6:2 Cl-PFESA) showed significant and inverse associations with BMD levels (mean differences ranged from -6.47 to -26.07 per one ln-unit increase in the PFASs). Additionally, we observed that each one ln-unit increase in PFHpA was significantly associated a 23 % (OR = 1.23, 95 % CI = 1.04, 1.45) greater odds of osteoporosis. The above associations were consistent in several sensitivity analyses we performed. Stratified analyses showed stronger associations among women and younger compared to their counterparts. CONCLUSIONS: Our findings suggested that greater PFAS exposure is associated with poorer bone health, especially in women and younger people.

Joint effects of per- and polyfluoroalkyl substance alternatives and heavy metals on renal health: A community-based population study in China.

BACKGROUND: Previous studies have indicated that chlorinated polyfluorinated ether sulfonic acids (Cl-PFESAs), when used as an alternative to per- and polyfluoroalkyl substances (PFASs), result in kidney toxicity. However, their co-exposure with heavy metals, has not yet been described. OBJECTIVES: To explore the joint effects of Cl-PFESAs and heavy metal exposure on renal health in Chinese adults, and identify specific pollutants driving the associations. METHODS: Our sample consists of 1312 adults from a cross-sectional survey of general communities in Guangzhou, China. We measured Cl-PFESAs, legacy PFASs (perfluorooctanoic acid [PFOA] and perfluorooctane sulfonated [PFOS]), and heavy metals (arsenic, cadmium, and lead). The relationship between single pollutant and glomerular filtration rate (eGFR) and the odds ratio (OR) of chronic kidney disease (CKD) was studied using Generalized additive models (GAMs). Bayesian Kernel Machine Regression (BKMR) models were applied to assess joint effects of Cl-PFESAs and heavy metals. Additionally, we conducted a sex-specific analysis to determine the modification effect of this variable. RESULTS: In single pollutant models, CI-PFESAs, PFOA, PFOS and arsenic were negatively associated with eGFR. Additionally, PFOA and heavy metals were positively correlated with the OR of CKD. For example, the estimated change with 95% confidence intervals (CI) of eGFR at from the highest quantile of 6:2 Cl-PFESA versus the lowest quantile was -5.65 ng/mL (95% CI: -8.21, -3.10). Sex played a role in modifying the association between 8:2 Cl-PFESA, PFOS and eGFR. In BKMR models, pollutant mixtures had a negative joint association with eGFR and a positive joint effect on CKD, especially in women. Arsenic appeared to be the primary contributing pollutant. CONCLUSION: We provide epidemiological evidence that Cl-PFESAs independently and jointly with heavy metals impaired kidney health. More population-based human and animal studies are needed to confirm our results.

Association of emerging and legacy per- and polyfluoroalkyl substances with unexplained recurrent spontaneous abortion.

Emerging per- and polyfluoroalkyl substances (PFAS) alternatives are increasingly used in daily life. Although legacy PFAS have been associated with miscarriage in previous studies, it remains unknown whether exposure to emerging and legacy PFAS has any impact on the risk of unexplained recurrent spontaneous abortion (URSA). We conducted a case-control study with 464 URSA cases who had at least 2 unexplained miscarriages and 440 normal controls who had at least one normal livebirth. Concentrations of 21 PFAS in plasma, including three emerging PFAS alternatives, eight linear and branched PFAS isomers, four short-chain PFAS, and six legacy PFAS, were measured by ultra-performance liquid chromatography coupled with a tandem mass spectrometry (UPLC-MS/MS). Multiple logistic regression was applied to evaluate the relationship between PFAS and URSA risk. Perfluorooctanoic acid (PFOA, median: 6.18 ng/mL), perfluorooctane sulfonate (PFOS, median: 4.10 ng/mL), and 6:2 chlorinated perfluoroalkyl ether sulfonic acid (6:2 Cl-PFESA, median: 2.27 ng/mL) were the predominant PFAS in the controls. Exposure to 6:2 Cl-PFESA [adjusted odds ratio (aOR) = 1.18 (95% CI: 1.00, 1.39)] and hexafluoropropylene oxide dimer acid (HFPO-DA) [aOR = 1.35 (95% CI: 1.15, 1.59)] were significantly associated with increased risks of URSA. Women with older age (>30 years old) had a stronger association between PFAS and URSA. Our results suggest that emerging PFAS alternatives may be an important risk factor for URSA.

Environmental Fate of Cl-PFPECAs: Predicting the Formation of PFAS Transformation Products in New Jersey Soils.

Although next-generation per- and polyfluorinated substances (PFAS) were designed and implemented as safer and environmentally degradable alternatives to "forever" legacy PFAS, there is little evidence to support the actual transformation of these compounds and less evidence of the safety of transformed products in the environment. Multiple congeners of one such PFAS alternative, the chloro-perfluoropolyether carboxylates (Cl-PFPECAs), have been found in New Jersey soils surrounding a manufacturing facility. These compounds are ideal candidates for investigating environmental transformation due to the existence of potential reaction centers including a chlorinated carbon and ether linkages. Transformation products of the chemical structures of this class of compounds were predicted based on analogous PFAS transformation pathways documented in peer-reviewed literature. Potential reaction products were used as the basis for high-resolution mass-spectrometric suspect screening of the soils. Suspected transformation products of multiple congeners, the Cl-PFPECAs, including H-PFPECAs, epox-PFPECAs, and diOH-PFPECAs, were tentatively observed in these screenings. Although ether linkages have been hypothesized as potential reaction centers under environmental conditions, to date, no documentation of ether scission has been identified. Despite exhaustive scrutiny of the high-resolution data for our Cl-PFPECA-laden soils, we found no evidence of ether scission.

6:2 Chlorinated polyfluoroalkyl ether sulfonate as perfluorooctanesulfonate alternative in the electroplating industry and the receiving environment.

Electroplating industry is an important application field of per- and polyfluoroalkyl substances (PFASs) as the chromium mist suppressants. 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2 Cl-PFAES) and perfluorooctanesulfonate (PFOS) have been the two widely used mist suppressants, and after the ban of PFOS, 6:2 Cl-PFAES will become the dominant suppressant. The behavior and mechanisms of 6:2 Cl-PFAES in the electroplating industry and the receiving environment were studied and compared with PFOS. 6:2 Cl-PFAES behaved similarly with PFOS due to their similar chemical structure. However, some difference exists for the relatively stronger hydrophobicity of 6:2 Cl-PFAES. Up to 35.7 mg/L of PFOS and 13.4 mg/L of 6:2 Cl-PFAES were found in the industrial wastewater influents, and were effectively reduced to 0.3-0.8 mg/L by the interaction with chromium hydroxide through hydrophobic interaction and ligand exchange. The stronger hydrophobicity of 6:2 Cl-PFAES than PFOS resulted in its accumulation in the surface of foams and comparable or less removal during the industrial and municipal wastewater treatment. 6:2 Cl-PFAES exhibited higher bioaccumulation potential than PFOS in the surface water. 6:2 Cl-PFAES emitted by both mists and water may pose health risks to humans. More attentions towards 6:2 Cl-PFAES are needed after the replacement of PFOS by it in the electroplating industry as a global contaminant of emerging concerns.

Per- and perfluoroalkyl substances alternatives, mixtures and liver function in adults: A community-based population study in China.

Experimental evidence has shown that per- and polyfluoroalkyl substances (PFAS) alternatives and mixtures may exert hepatotoxic effects in animals. However, epidemiological evidence is limited. This research aimed to explore associations of PFAS and the alternatives with liver function in a general adult population. The study participants consisted of 1,303 adults from a community-based cross-sectional investigation in Guangzhou, China, from November 2018 to August 2019. We selected 13 PFAS with detection rates > 85% in serum samples and focused on perfluorooctane-sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and their alternatives [6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA), 8:2 Cl-PFESA, and perfluorohexanoic acid (PFHxA)] as predictors of outcome. Six liver function biomarkers (ALB, ALT, AST, GGT, ALP, and DBIL) were chosen as outcomes. We applied regression models with restricted cubic spline function to explore correlations between single PFAS and liver function and inspected the combined effect of PFAS mixtures on liver by applying Bayesian kernel machine regression (BKMR). We discovered positive associations among PFAS and liver function biomarkers except for ALP. For example, compared with the 25th percentile of PFAS concentration, the level of ALT increased by 12.36% (95% CI: 7.91%, 16.98%) for ln-6:2 Cl-PFESA, 5.59% (95% CI: 2.35%, 8.92%) for ln-8:2 Cl-PFESA, 3.56% (95% CI: -0.39%, 7.68%) for ln-PFHxA, 13.91% (95% CI: 8.93%, 19.13%) for ln-PFOA, and 14.25% (95% CI: 9.91%, 18.77%) for ln-PFOS at their 75th percentile. In addition, higher exposed serum PFAS was found to be correlated with greater odds of abnormal liver function. Analysis from BKMR models also showed an adverse association between PFAS mixtures and liver function. The combined effect of the PFAS mixture appeared to be non-interactive, in which PFOS was the main contributor to the overall effect. Our findings provide evidence of associations between PFAS alternatives, PFAS mixtures, and liver function in the general adult population.

Associations between both legacy and alternative per- and polyfluoroalkyl substances and glucose-homeostasis: The Isomers of C8 health project in China.

BACKGROUND: Epidemiological studies on the associations of legacy per- and polyfluoroalkyl substances (PFASs) and glucose homeostasis remain discordant. Understanding of PFAS alternatives is limited, and few studies have reported joint associations of PFASs and PFAS alternatives. OBJECTIVES: To investigate associations of novel PFAS alternatives (chlorinated perfluoroalkyl ether sulfonic acids, Cl-PFESAs and perfluorobutanoic acid, PFBA) and two legacy PFASs (Perfluorooctanoic acid, PFOA and perfluorooctane sulfonate, PFOS) with glucose-homeostasis markers and explore joint associations of 13 legacy and alternative PFASs with the selected outcomes. METHODS: We used cross-sectional data of 1,038 adults from the Isomers of C8 Health Project in China. Associations of PFASs and PFAS alternatives with glucose-homeostasis were explored in single-pollutant models using generalized linear models with natural cubic splines for PFASs. Bayesian Kernel Machine Regression (BKMR) models were applied to assess joint associations of exposures and outcomes. Sex-specific analyses were also conducted to evaluate effect modification. RESULTS: After adjusting for confounders, both legacy (PFOA, PFOS) and alternative (Cl-PFESAs and PFBA) PFASs were positively associated with glucose-homeostasis markers in single-pollutant models. For example, in the total study population, estimated changes with 95% confidence intervals (CI) of fasting glucose at the 95th percentile of 6:2Cl-PFESA and PFOS against the thresholds were 0.90 (95% CI: 0.59, 1.21) and 0.44 (95% CI: 0.26, 0.62). Positive joint associations were found in BKMR models with 6:2Cl-PFESA contributing most. Sex-specific associations existed in both single- and multi-pollutant models. CONCLUSIONS: Legacy and alternative PFASs were positively associated with glucose-homeostasis markers. 6:2Cl-PFESA was the primary contributor. Sex-specific associations were also identified. These results indicate that joint associations and effect modification should be considered in risk assessment. However, further studies are recommended to strengthen our findings and to elucidate the mechanisms of action of legacy and alternative PFASs.

Prenatal and postnatal exposure to emerging and legacy per-/polyfluoroalkyl substances: Levels and transfer in maternal serum, cord serum, and breast milk.

Gestation and lactation are critical and vulnerable stages for fetuses and newborns. During these periods, per-/polyfluoroalkyl substances (PFASs) accumulated in mothers can be transferred to newborns through placenta and/or breastfeeding, causing potential health risks. To investigate the pre- and postnatal PFAS exposure of newborns, we analyzed 21 emerging and legacy PFASs in 60 sets of matched maternal serum, cord serum, and breast milk samples. In serum, perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), and 6:2 chlorinated polyfluorinated ether sulfonates (6:2 Cl-PFESA) were the most predominant PFASs, while PFOA, PFOS and 6:2 fluorotelomer phosphate diester (6:2 diPAP) contributed most to breast milk. For most PFASs, the levels followed the order of maternal serum > cord serum > breast milk. The 6:2 Cl-PFESA was positively associated with birth weight and ponderal index (p < 0.05). The breastfeeding transfer efficiencies (RBM, median: 0.02-0.10) of most PFASs were 1-2 orders of magnitude lower than transplacental transfer efficiencies (RCM, median: 0.40-1.45), except for perfluorobutanesulfonic acid (PFBS) showing high transfer efficiency both through placenta (median at 0.89) and breastfeeding (median at 0.86). The one-month postnatal exposure to PFASs via breastfeeding was much higher than prenatal exposure in utero. This study enhances the understanding of transplacental and breastfeeding transfer of PFASs and provides assessments of prenatal and postnatal exposure of newborns to emerging and legacy PFASs.

Exposure assessment of PFAS-contaminated sites using avian eggs as a biomonitoring tool: A frame of reference and a case study in the Po River valley (Northern Italy).

For many years, eggs of diverse bird species have been used as monitoring tools in studies investigating perfluoroalkyl substances (PFAS) contamination, especially in marine and remote areas. Avian eggs are a suitable monitoring matrix because they are relatively easy to collect and their yolks store diverse maternally transferred PFAS. Moreover, the concentrations of PFAS detected in the eggs are a good proxy for maternal exposure and allow the assessment of the potential risk for birds. These features support the use of avian eggs as a key monitoring tool in exposure assessment of PFAS-contaminated sites. We first review the recent application of avian eggs in PFAS monitoring in environmental risk assessment schemes, highlighting strengths and limitations and suggesting which criteria should be considered when selecting a proper study species and structuring the sampling and analytical protocol. Eventually, we report findings from a field study realized in 2020 near a perfluoropolymer factory site in the upper Po plain (Northern Italy), revealing an unprecedented contamination level of PFOA and C6O4 in three species of wild passerines. In future, long-term monitoring of PFAS contamination using avian eggs should be maintained, to provide crucial information on the temporal trend of fluorochemical production and waste disposal, while facilitating early identification of emerging PFAS as well as the quantification of their biomagnification across the trophic web. Integr Environ Assess Manag 2021;17:733-745. © 2021 SETAC.

Novel and legacy poly- and perfluoroalkyl substances (PFASs) in indoor dust from urban, industrial, and e-waste dismantling areas: The emergence of PFAS alternatives in China.

With the phase out of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), the composition profiles of poly- and perfluoroalkyl substance (PFAS) in our living environment are unclear. In this study, 25 PFASs were analyzed in indoor dust samples collected from urban, industrial, and e-waste dismantling areas in China. PFOS alternatives, including 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA) (median: 5.52 ng/g) and 8:2 chlorinated polyfluorinated ether sulfonate (8:2 Cl-PFESA) (1.81 ng/g), were frequently detected. By contrast, PFOA alternatives, such as hexafluoropropylene oxide dimer acid (HPFO-DA, Gen-X) and ammonium 4,8-dioxa-3H-perfluorononanoate (ADONA), were not found in any of the dust samples. As expected, all legacy PFASs were widely observed in indoor dust, and 4 PFAS precursors were also detected. Dust concentrations of 6:2 Cl-PFESA were strongly correlated (p < 0.05) with those of 8:2 Cl-PFESA regardless of sampling sites. 6:2 Cl-PFESA was also significantly associated with that of PFOS in industrial and e-waste (p < 0.01) areas. Association analysis suggested that the sources of PFOS and its alternatives are common or related. Although ∑Cl-PFESA concentration was lower than that of PFOS (17.4 ng/g), industrial areas had the highest 6:2 Cl-PFESA/PFOS ratio (0.63). Composition profiles of PFASs in the industrial area showed the forefront of fluorine change. Thus, the present findings suggested that Cl-PFESAs are widely used as PFOS alternatives in China, and high levels of human Cl-PFESA exposure are expected in the future. Short-chain PFASs (C4-C7) were the predominant PFASs found in dust samples, contributing to over 40% of ∑total PFASs. Furthermore, perfluoro-1-butanesulfonate/PFOS and perfluoro-n-butanoic acid (PFBA)/PFOA ratios were 2.8 and 0.72, respectively. These findings suggested shifting to the short-chain PFASs in the environment in China. To the authors knowledge this is the first study to document the levels of 6:2 Cl-PFESA, 8:2 Cl-PFESA in indoor dust.

High trans-placental transfer of perfluoroalkyl substances alternatives in the matched maternal-cord blood serum: Evidence from a birth cohort study.

BACKGROUND: Recent studies suggest that perfluoroalkyl substances (PFAS) and PFAS alternatives can cross the placental barrier. However, little is known on the differential patterns of trans-placental transfer (TPT) among conventional PFAS and PFAS alternatives in epidemiological study. OBJECTIVES: We aimed to characterize comprehensive TPT patterns in conventional PFAS and PFAS alternatives using matched maternal-cord blood serum from a birth cohort. METHODS: A total of 424 mother-fetus pairs were recruited from the Maoming Birth Cohort during 2015-2018. We detected 20 PFAS in cord and maternal serum using an ultraperformance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). TPT of PFAS was calculated via cord to maternal serum concentration ratios. RESULTS: Both of PFOS alternatives (chlorinated polyfluorinated ether sulfonates, Cl-PFESAs) and PFOA short-chain alternative (perfluorobutanoic acid, PFBA) were widely detected in the cord and maternal serum. In cord serum, the predominant PFAS was PFOS (1.93 ng/mL), followed by PFBA (1.45 ng/mL), PFOA (0.75 ng/mL) and 6:2 Cl-PFESA (0.32 ng/mL). We found that the PFAS alternatives had higher TPT than PFOS and PFOA, such as PFBA vs. PFOA (median: 1.41 vs. 0.73, P < 0.001) and 8:2 Cl-PFESA vs. PFOS (median: 0.98 vs. 0.42, P < 0.001). Moreover, the TPT of 8:2 Cl-PFESA was higher than the precursor, linear and isomeric PFOS, respectively (P < 0.01). Furthermore, we found a U-shaped pattern for TPT in perfluorocarboxylic acid compounds (PFCAs) across different length of carbon chain. CONCLUSION: Our findings suggest that PFAS alternatives may be more easily across the placenta than conventional PFAS. Given the widespread usage of PFAS alternatives, our results indicate that more research is needed to assess the potential health risks of prenatal exposure to PFAS alternatives in children.

A review of sources, multimedia distribution and health risks of novel fluorinated alternatives.

Per- and polyfluoroalkyl substances (PFASs) are a class of emerging persistent organic pollutants (POPs). They are widely used in industrial and consumer applications. Due to their persistence, bioaccumulation, long-distance migration and toxicity, it is important to find new compounds that can replace PFASs. The present review investigated the sources, fates and environmental effects of alternative PFAS compounds using surveys have been conducted over the past several years. Concentrations of PFAS alternatives in various environmental media, as well as human tissues, are summarized based on the available data. The results showed that hexafluoropropylene oxide dimer (HFPO-DA), hexafluoropropylene trimer acids (HFPO-TA), and 6:2 chlorinated polyfluorinated ether sulfonic acid (6:2 Cl-PFESA) have become the dominant global perfluorinated pollutants. Currently, there are a few toxicity assessments of these novel fluorinated alternatives, showing that they have systemic multiple organ toxicities. PFAS alternatives exhibited comparable or even more serious potential toxicity than legacy PFASs, indicating that these fluorinated alternatives are also harmful to the environment. Therefore, these alternatives require additional toxicological studies to confirm whether they can be used for a long time.

Per- and polyfluoroalkyl substances (PFASs) in precipitation from mainland China: Contributions of unknown precursors and short-chain (C2C3) perfluoroalkyl carboxylic acids.

A nationwide survey was conducted on per- and polyfluoroalkyl substances (PFASs) in precipitation across mainland China. Twenty-two PFASs, including precursors to perfluoroalkyl acids (pre-PFAAs), were investigated in thirty-nine precipitation samples collected from twenty-eight cities. Trifluoroacetate (TFA), perfluorooctanoic acid, and perfluorooctane sulfonic acid (PFOS) were ubiquitous in precipitation. TFA displayed the highest concentrations (8.8-1.8 × 103 ng/L), which were particularly elevated in coastal cities. 6:2 chlorinated polyfluorinated ether sulfonic acid, an alternative to PFOS, was detected for the first time in precipitation at a frequency of 43%. Polyfluoroalkyl phosphoric acid diesters and 6:2 fluorotelomer sulfonic acid were also occasionally detected. PFAS fluxes in the northeastern area (C4C12; 2.0 × 102-3.4 × 103 ng/m2/d) with major PFAS manufacturing facilities were higher than those in the southwestern area (63-1.7 × 103 ng/m2/d). Using total oxidizable precursor (TOP) assay, the occurrence of unknown pre-PFAAs was for the first time uncovered in precipitation with maximum estimated fluxes of C6 and C8 pre-PFAAs at 3.1 × 103 and 4.3 × 103 ng/m2/d, respectively. The relative contribution of ultrashort-chain PFCAs (C2C3) ranged from 22% to 91% of ∑PFASs, while unknown pre-PFAAs accounted for 6%-56% of the total molar concentrations of PFASs. This bears critical concerns on underestimation of PFAS mass load from precipitation to surface environment ascribed to monitoring data solely on known PFASs. Unknown precursors of PFAAs in the atmosphere are yet to be identified for their chemical structures and relevant environmental risks as well.