Perfluoroalkane Sulfonic Acids Research Articles

Concentration and health risk assessment of per- and polyfluoroalkyl substances in cosmetic and personal care products

Per and polyfluoroalkyl substances (PFAS) are toxicologically concerning because of their potential to bioaccumulate and their persistence in the environment and the human body. We determined PFAS levels in cosmetic and personal care products and assessed their health risks. We investigated the trends in concentrations and types of PFAS contaminants in cosmetic and personal care products before and after perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were added to the list of persistent organic pollutants. The total PFAS concentration ranged from 1.98 to 706.75 ng g−1. The hazard quotients (HQs) for PFOA, PFOS and perfluorobutanesulfonic acid (PFBS) were lower than 1, indicating no appreciable risk to consumers. Assuming the simultaneous use of all product types and the worst-case scenario for calculations, perfluoroalkyl carboxylic acids and perfluoroalkane sulfonic acids (PFSAs) also had hazard indices lower than 1. We found that adverse effects are unlikely to occur when each type of cosmetic is used separately, or even when all product types are used together. Nevertheless, the persistence and bioaccumulation characteristics of additional PFAS present in cosmetics continue to be a cause for concern. Further research is necessary to investigate the long-term impacts of using such cosmetics and the associated risks to human health.

Bioaccumulation of legacy and emerging per- and polyfluoroalkyl substances in hydroponic lettuce and risk assessment for human exposure

Reclaimed water for irrigation or hydroponic cultivation provides exposure pathways for per- and polyfluoroalkyl substances (PFAS) to enter the human food chain. This study employed hydroponic methods to investigate the behavior of legacy PFAS and emerging chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs) in lettuce grown under environment-related exposure levels and assessed the human exposure risks from consuming contaminated lettuce. Overall, PFAS in lettuce were concentration-dependent, with long-chain PFAS tending to accumulate in roots and short-chain PFAS accumulating more in shoots. The enrichment of PFAS in lettuce was jointly influenced by their chain length and polar functional groups. Specifically, the root concentration factors (RCFs) of PFAS generally increased with increasing chain length, and RCF values of most perfluoroalkanesulfonic acids (PFSAs) were significantly higher than those of perfluoroalkyl carboxylic acids (PFCAs) with the same chain length (p < 0.01), while the translocation factors (TFs) exhibited opposite trends. RCF values of perfluorooctane sulfonate (PFOS) and its alternatives, Cl-PFESAs, were ranked as follows: 8:2 Cl-PFESA (mean: 139) > 6:2 Cl-PFESA (28.6) > PFOS (25.7), which was attributed to the increased molecular size and hydrophobicity resulting from the insertion of ether bonds and additional CF2 in 8:2 Cl-PFESA. Notably, TF value of 8:2 Cl-PFESA (mean: 0.007) was the smallest among all PFAS, indicating 8:2 Cl-PFESA was difficult to transfer to nutritional compartments. Adults and children would exceed the most conservative health-based reference dose (RfD) by consuming approximately 15.9–148 g and 7.92–74.0 g of contaminated lettuce per day, implying high health risks.

Occurrence, Concentration, and Distribution of 35 PFASs and Their Precursors Retained in 20 Stormwater Biofilters.

Current knowledge about the fate and transport behaviors of per- and polyfluoroalkyl substances (PFASs) in urban stormwater biofilter facilities is very limited. C5-14,16 perfluoroalkyl carboxylic acids [perfluorinated carboxylic acids (PFCAs)], C4,8,10 perfluoroalkanesulfonic acids (PFSAs), methyl-perfluorooctane sulfonamide acetic acid (MeFOSAA, a PFSA precursor), and unknown C6-8 PFCA and perfluorooctanesulfonic acid precursors were frequently found in bioretention media and forebay sediments at Σ35PFAS concentrations of <0.03-19 and 0.064-16 μg/kg-DW, respectively. Unknown C6-8 PFCA precursor concentrations were up to ten times higher than the corresponding PFCAs, especially at forebays and biofilters' top layer. No significant trend could be attributed to PFAS and precursor concentrations versus depth of filter media, though PFAS concentrations were 2-3 times higher in the upper layers on average (significant difference between the upper (0-5 cm) and deepest (35-50 cm) layer). PFASs had a similar spatial concentration distribution in each filter media (no clear difference between short- and long-chain PFASs). Commercial land use and organic matter were important factors explaining the concentration variations among the biofilters and between the sampling depths, respectively. Given the comparable PFAS accumulations in deeper and superficial layers and possible increased mobility after precursor biotransformation, designing shallow-depth, nonamended sand biofilters or maintaining only the top layer may be insufficient for stormwater PFAS management.

Design of deep eutectic solvents for multiple perfluoroalkyl substances removal: Energy-based screening and mechanism elucidation

The current landscape of perfluoroalkyl substances (PFAS) extraction methodologies presents significant challenges, particularly for multiple PFAS with different carbon chain lengths. This study introduced an energy-driven strategic approach for screening deep eutectic solvents (DESs) to effectively remove a diverse range of PFAS, including perfluoroalkylcarboxylic acids (PFCAs), perfluoroalkanesulfonic acids (PFSAs), and perfluoroalkyl amides (FAAs), from contaminated environments (total 13 target compounds). Utilizing energy-based screening, we identified DES candidates with high affinity for a spectrum of PFAS compounds from 1234 potential starting materials of eutectic systems. Key findings revealed the superior removal efficiency of tributylphosphineoxide/2-methylpiperazine system, exceeding 99 % for various PFAS with different carbon chain lengths in real environmental water samples. Additionally, we elucidated the molecular interactions between DESs and PFAS through ab initio molecular dynamics (AIMD) simulations, providing valuable insights into the mechanisms governing the removal process. The mechanism of extraction involves hydrogen bond network topology and structural organization, with DESs capable of extracting PFAS while maintaining a weakly aggregated state of target molecules and minimizing the impact on the intrinsic structures of DES. The proposed system forms a dynamic, complementary, and flexible non-covalent interaction network structure with PFAS. The study advances the understanding of DES as a designable, effective, and sustainable alternative to conventional solvents for PFAS remediation, offering a significant contribution to environmental chemistry and green technology.

In Vitro and In Silico Analysis of the Bindings between Legacy and Novel Per- and Polyfluoroalkyl Substances and Human Serum Albumin.

Per- and polyfluoroalkyl substances (PFASs) are emerging contaminants of concern that can enter the human body through a variety of pathways and thereby cause harmful effects. Exposure of pregnant women to PFASs could even affect both the mother and the child. Human serum albumin (HSA) is considered to be the primary transport protein for a variety of substances in body fluids. It can be bound to different contaminants and might result in possible effects on human health. Yet, few studies are available on the binding affinity of legacy PFASs and their novel alternatives to HSA. In this study, the binding mechanisms of HSA to both legacy PFASs and their novel alternatives were investigated using fluorescence spectroscopy, together with further molecular docking. The results show that all the target PFASs were statically quenched against HSA with binding ratios of 1:1. The binding constants of long-chain PFASs and novel alternatives of perfluoroalkanesulfonic acids (PFSAs) were greater than 102, whereas those of short-chain PFASs alternatives and novel alternatives of perfluorocarboxylic acids (PFCAs) were less than 102. In general, the binding affinities of PFCAs on HSA were less than that of PFSAs, while the binding affinities of short-chain PFASs alternatives on HSA were smaller than those of long-chain PFASs and their novel alternatives. Therefore, bindings to HSA could be considered as an important influencing factor for the bioaccumulation of legacy and novel PFASs in the human body.

Field test of thermally activated persulfate for remediation of PFASs co-contaminated with chlorinated aliphatic hydrocarbons in groundwater

The co-occurrence of per- and polyfluoroalkyl substances (PFASs) and chlorinated aliphatic hydrocarbons (CAHs) in groundwater has drawn increased attention in recent years. No studies have been conducted concerning the oxidative degradation of PFASs and/or CAHs by in situ thermally activated persulfate (TAP) in groundwater, primarily due to the difficulty in cost-effectively achieving the desired temperature in the field. In this study, the effects and mechanisms of PFASs degradation by in situ TAP at a site with PFASs and CAHs co-contaminants were investigated. The target temperature of 40.0–70.0 °C was achieved in groundwater, and persulfate was effectively distributed in the demonstration area – the combination of which ensured the degradation of PFASs and CAHs co-contaminants by in situ TAP. It was demonstrated that the reductions of perfluoroalkyl carboxylic acids (PFCAs) concentration in all monitoring wells were in the range of 43.7 %–66.0 % by in situ TAP compared to those maximum rebound values in groundwater, whereas no effective perfluoroalkane sulfonic acids (PFSAs) degradation was observed. The conversion of perfluoroalkyl acids (PFAAs) precursors was one of the main factors leading to the increase in PFCAs concentrations in groundwater during in situ TAP. CAHs were effectively degraded in most monitoring wells, and furthermore, no inhibitory effects of CAHs and Cl− on the degradation of PFASs were observed due to the presence of sufficient persulfate. Additionally, there were significant increases in SO42− concentrations and reductions of pH values in groundwater due to in situ TAP, warranting their long-term monitoring in groundwater. The integrated field and laboratory investigations demonstrated that the reductions in PFCAs and CAHs concentrations can be achieved by the oxidative degradation of in situ TAP.

Elaborating the Occurrence and Distribution of Per- and Polyfluoroalkyl Substances in Rivers and Sediment around a Typical Aging Landfill in China.

Per- and polyfluoroalkyl substances (PFASs) are bioaccumulative and widely distributed persistent organic pollutants (POPs). Understanding the distribution of and ecological risks posed by PFASs is critical, particularly for PFAS emissions and accumulation from a common urban pollution source. The transformation characteristics and ecological risks of PFASs from a typical aging municipal landfill leachate were systematically monitored and assessed over five years in this study. The results showed that the total PFAS concentrations (ΣPFASs) in the rivers were between 26.4 and 464.3 ng/L, whereas in sediment, ΣPFASs ranged from 9.5 to 58.5 ng/g (w/w). The presence of perfluorooctanoic acid (PFOA) was the most prominent PFAS in both water (39.4-152.3 ng/L) and sediment (1.1-56.1 ng/g). In a five-year monitoring study, the concentration of PFASs in the aging landfill decreased by 23.3%, with higher mean concentrations observed during summer (307.6 ng/L) compared to winter (250.4 ng/L). As for the pollution distribution, the suspended particulate matter-water partition coefficient (log Kd) of carboxylic acid (PFCAs) and perfluoroalkane sulfonic acids (PFSAs) ranged from 1.53 to 2.65, and from 1.77 to 2.82, respectively. PFSAs and long-chain PFCAs exhibited a greater propensity for sediment association compared to short-chain PFCAs. An ecological risk assessment of four typical PFASs, PFOA, perfluorooctane sulfonate (PFOS), perfluorobutanoic acid (PFBA), and perfluorobutane sulfonic acid (PFBS), utilizing the hazard quotient method revealed that the rivers surrounding the typical aging landfill exhibited a low contamination risk for PFOA, while no ecological risks were associated with the other three FPASs. This study contributes to an enhanced comprehension of the occurrence, distribution, and risk of PFASs in the rivers in rivers and sediment surrounding a typical aging landfill site in China, thereby providing crucial reference information for ensuring water quality safety.

Efficient and fast remediation of soil contaminated by per- and polyfluoroalkyl substances (PFAS) by high-frequency heating

This study presents a novel thermal technology (high-frequency heating, HFH) for the decontamination of soil containing per- and polyfluoroalkyl substances (PFAS) and aqueous film-forming foams (AFFFs). Ultra-fast degradation of short-chain PFAS, long-chain homologs, precursors, legacy PFAS, emerging PFAS was achieved in a matter of minutes. The concentrations of PFAS and the soil type had a negligible impact on degradation efficiency, possibly due to the ultra-fast degradation rate overwhelming potential differences. Under the current HFH experiment setup, we achieved near-complete degradation (e.g., >99.9%) after 1 min for perfluoroalkyl carboxylic acids and perfluoroalkyl ether carboxylic acids and 2 min for perfluoroalkanesulfonic acids. Polyfluoroalkyl precursors in AFFFs were found to degrade completely within 1 min of HFH; no residual cationic, zwitterionic, anionic, or non-ionic intermediate products were detected following the treatment. The gaseous byproducts were considered. Most of gaseous organofluorine products of PFAS at low-and-moderate temperatures disappeared when temperatures reached 890 °C, which is in the temperature zone of HFH. For the first time, we demonstrated minimal loss of PFAS in water during the boiling process, indicating a low risk of PFAS entering the atmosphere with the water vapor. The findings highlight HFH its potential as a promising remediation tool for PFAS-contaminated soils.

Evaluation of the adsorption behavior of mixed perfluoroalkyl and polyfluoroalkyl substances onto granular activated carbon and styrene‐divinylbenzene resins

AbstractBecause of the remarkable chemical structure of perfluoroalkyl and polyfluoroalkyl substances (PFAS), as well as the complex conditions of water, selecting an appropriate adsorbent for treating PFAS is critical. Adsorption needs to be environmentally friendly, low cost, and consider the types of adsorbents that work well in mixed PFAS solutions. In the present study, we used mixed PFAS to estimate the PFAS activity. This research aimed to evaluate and compare the efficacy of the adsorption of PFAS from water using different adsorbents: granular activated carbon (GAC), IRA 910 (strong anion resin), and DOWEX MB‐50 (mixed exchange resin). Batch adsorption isotherms and kinetic studies were performed for perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and perfluorohexane sulfonic acid (PFHxS). Freundlich models consistently described the kinetic behavior with a high correlation coefficient (R2 &gt; 0.98). PFAS adsorption capacities on GAC and IRA910 were dependent on the chain length (PFOS &gt; PFOA &gt; PFHxS). The adsorption capacity of DOWEX MB‐50 decreased because of the sulfonate effects (PFOS &gt; PFHxS &gt; PFOA). The rate constants (k2) that represented the adsorption of PFAS on different adsorbents observed within 96 h were accurately determined by the pseudo‐second‐order (PSO) model. GAC achieved followed the relationship k2(PFOS) &gt; k2(PFOA) &gt; k2(PFHxS). Furthermore, k2 of IRA910 decreased in the order of k2(PFOA) &gt; k2(PFOS) &gt; k2(PFHxS), implying that IRA910 promoted hydrophobicity more significantly on the adsorption of PFCAs than perfluoroalkane (‐alkyl) sulfonic acids. The kinetics of DOWEX MB‐50 revealed k2(PFHxS) &gt; k2(PFOS) &gt; k2(PFOA) because gel‐type resins like DOWEX MB‐50 are more suitable for shorter‐chain PFAS. Further investigation is needed to determine the effect of organic matter under natural conditions and evaluate adsorptive selection caused by operational complexities.

The significance of fluorinated compound chain length, treatment technology, and influent composition on per- and polyfluoroalkyl substances removal in worldwide wastewater treatment plants.

Wastewater treatment plants (WWTPs) are deemed major conveyors and point sources of per- and polyfluoroalkyl substances (PFAS) to the environment. This statistical meta-analysis of existing literature from the past 15 years focused on the significance of treatment type for PFAS removal efficiencies and the influence of PFAS sources (domestic vs. industrial) on their removal. Different sampling events, WWTPs across the world, different treatment technologies, configurations, and processes, as well as different PFAS classes and compounds were considered. This study evaluated 13 PFAS analyzed predominantly in 161 WWTPs across the world. The statistical test results revealed that these 13 frequently detected and reported PFAS can be divided into four groups based on their behavior during wastewater treatment, namely (1) C6-10 perfluorocarboxylic acids (PFCAs), (2) C4,5,11,12 PFCAs, (3) C4,6,8 perfluoroalkane sulfonic acids (PFSAs), and (4) C10 PFSA. In this study, biological treatments such as (1) membrane bioreactors, (2) combination of two or more biological treatments, and (3) biofilm processes revealed the highest PFAS removals, although the addition of a tertiary treatment actually had a nonbeneficial effect on PFAS removal. Moreover, a strong statistical correlation was observed between industrial wastewater sources and the presence of high influent PFAS concentrations in the receiving WWTPs. This indicates that industrial sources were the main contributors of the PFAS load in the analyzed WWTPs. Integr Environ Assess Manag 2024;20:59-69. © 2023 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Horizontal and Vertical Distribution of Perfluoroalkyl Acids (PFAAs) in the Water Column of the Atlantic Ocean.

Perfluoroalkyl acids (PFAAs) are widely distributed in the oceans which are their largest global reservoir, but knowledge is limited about their vertical distribution and fate. This study measured the concentrations of PFAAs (perfluoroalkyl carboxylic acids (PFCAs) with 6 to 11 carbons and perfluoroalkanesulfonic acids (PFSAs) with 6 and 8 carbons) in the surface and deep ocean. Seawater depth profiles from the surface to a 5000 m depth at 28 sampling stations were collected in the Atlantic Ocean from ∼50° N to ∼50° S. The results demonstrated PFAA input from the Mediterranean Sea and the English Channel. Elevated PFAA concentrations were observed at the eastern edge of the Northern Atlantic Subtropical Gyre, suggesting that persistent contaminants may accumulate in ocean gyres. The median ΣPFAA surface concentration in the Northern Hemisphere (n = 17) was 105 pg L-1, while for the Southern Hemisphere (n = 11) it was 28 pg L-1. Generally, PFAA concentrations decreased with increasing distance to the coast and increasing depth. The C6-C9 PFCAs and C6 and C8 PFSAs dominated in surface waters, while longer-chain PFAAs (C10-C11 PFCAs) peaked at intermediate depths (500-1500 m). This profile may be explained by stronger sedimentation of longer-chain PFAAs, as they sorb more strongly to particulate organic matter.

Estimated Transfer of Perfluoroalkyl Substances (PFAS) from Maternal Serum to Breast Milk in Women Highly Exposed from Contaminated Drinking Water: A Study in the Ronneby Mother–Child Cohort

Infancy perfluoroalkyl substances (PFAS) exposure from breastfeeding is partially determined by the transfer efficiencies (TEs) of PFAS from maternal serum into breast milk. However, to our knowledge there are no studies of such TEs in highly exposed populations. We estimated the TEs of PFAS from maternal serum into colostrum and breast milk in a cohort of women with a wide range of PFAS exposures. The Ronneby Mother-Child Cohort was established in 2015 after PFAS contamination was discovered in the public drinking water of Ronneby, Sweden. We measured seven PFAS in matched samples of maternal serum at delivery and colostrum and breast milk. We calculated the TE (in percentage) as the ratio of PFAS in colostrum or breast milk to serum multiplied by 100 and evaluated whether TEs varied by PFAS, lactation stage, or exposure level using a series of linear mixed-effects models with a random intercept for each woman. This study included 126 mothers. PFAS associated with firefighting foams [i.e., perfluorohexane sulfonic acid (PFHxS) and perfluorooctane sulfonic acid (PFOS)] were substantially elevated in the serum, colostrum, and breast milk samples of highly exposed women in the cohort and showed strong correlation. PFHxS and PFOS also contributed the largest fraction of total PFAS on average in colostrum and breast milk. Median TEs varied from 0.9% to 4.3% and were higher for perfluoroalkyl carboxylic acids, including perfluorooctanoic acid, than perfluoroalkane sulfonic acids, including PFHxS and PFOS. TEs varied by exposure level, but there was not a consistent pattern in this variation. PFAS concentrations in the colostrum and breast milk of highly exposed women were higher than the concentrations in low-exposed women, and TEs were of a similar magnitude across exposure categories. This implies that breastfeeding may be an important route of PFAS exposure for breastfeeding infants with highly exposed mothers, although the relative contribution of breastfeeding vs. prenatal transplacental transfer remains to be clarified. https://doi.org/10.1289/EHP11292.

Insights into the per- and polyfluoroalkyl substances-contaminated paper mill processing discharge: Detection, phytotoxicity, bioaccumulative profiling, and health risk verification

Per- and polyfluoroalkyl substances (PFASs), a new class of contaminants of emerging concern in different water sources and industrial discharges, have been highlighted, mainly ascribed to the high mobility, persistent, and bioaccumulative behaviors. In this work, the analytical detection of PFASs in the paper mill processing discharge (PMPD), physicochemical parameters, tannin and lignin, and phenolic content were carried out. The phytotoxicity evaluation and bioaccumulative profiles of PMPD-assisted irrigation have been conducted using a soilless cultivation system. The cytotoxicity, genotoxicity and human exposure risk were ascertained via in vitro assay on the human hepatocellular carcinoma (HepG2) cell and the estimation of daily intake, respectively. PFASs were quantitatively detected at the mean concentration of 2712.72 ng/L, consisted of mainly perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs), perfluoroalkane sulfonamidoacetic acids (FASAAs), perfluoroalkane sulfonamides (FASAs), and fluorotelomer sulfonic acids (FTSAs). Significant reductions of the physical elongation, dry weight, and chlorophylls up to 33.49%, 31.71%, and 52.17% were recorded. Profound increase in the proline (101.81%), hydrogen peroxide (55.56%), superoxide anion (67.86%), lipid peroxidation (43.91%), and protein oxidation (32.31%), and up-regulation of antioxidant enzymes activities have been quantified. Bioaccumulation and translocation of PFASs revealed a concentration-, chain length- and functional group-dependent trend within different plant compartments. PFASs-contaminated PMPD treatments induced dose-dependent cell viability reduction and DNA damage in the HepG2 cell. The findings have highlighted that PMPD could be an underestimated source of PFASs, which represents a sharp threat to plants and public health via the water-food crop-human continuum. Future studies gearing towards the genomic profiling of PFASs in different plant species are suggested.

Spatiotemporal and life history related trends of per- and polyfluoroalkyl substances in Indo-Pacific finless porpoises from south China sea (2007–2020)

Per- and polyfluoroalkyl substances (PFASs) levels in Indo-Pacific finless porpoises (Neophocaena phocaenoides) in the Pearl River Estuary (PRE), near the most economically developed region in China, have not been characterized. We measured the hepatic concentrations of twelve PFASs, including nine perfluoroalkyl carboxylic acids (PFCAs) and three perfluoroalkane sulfonic acids (PFSAs) in the finless porpoises (n = 21) collected from the PRE between 2007 and 2020. The average level of PFSAs was more than 2-times higher than that of PFCAs. The order of six dominant PFASs was perfluorooctane sulfonate (PFOS) > perfluoroundecanoic acid (PFUdA) > perfluorodecanoic acid (PFDA) > perfluorotridecanoic acid (PFTrDA) > perfluorononanoic acid (PFNA) > perfluorododecanoic acid (PFDoDA). The levels of Hepatic PFOS of 29% samples exceeded the no observable adverse effect level (NOAEL) values. The concentration of PFASs in males was significant higher than in females. PFASs levels were significantly negatively correlated with body length in males and positively correlated in females. PFASs levels in the PRE finless porpoises were lower than in humpback dolphins possibly due to different foraging habitat toward the coast and the consumption of less fish. PFCAs levels in finless porpoises from the western PRE were higher compared to Hong Kong, possibly due to the high-intensity sources of terrestrial anthropogenic pollutants. Significant increasing spatiotemporal trends of PFSAs, PFCAs and PFASs were found in finless porpoises from 2007 to 2020, suggesting a continuously increased risk of PFASs exposure for PRE cetaceans in the last decade.

Occurrence, fate and risk assessment of per- and polyfluoroalkyl substances in wastewater treatment plants in Shaanxi, China

Wastewater treatment plants (WWTPs) are considered as major sinks for per- and polyfluoroalkyl substances (PFASs). However, conventional WWTPs with low efficiency are also a secondary point source of PFASs entering the environment. Herein, a large-scale investigation of PFASs was conducted in 44 WWTPs throughout Shaanxi Province in the transitional zone between North and South China. The composition profiles of target PFASs differed between wastewater and sludge samples. Perfluorobutanoic acid was dominant in wastewater influent and effluent samples, with maximum concentrations of 59.8 and 11.4 ng/L, respectively. Perfluorooctane sulfonic acid occurred predominantly in sludge samples, with a maximum concentration of 73.2 ng/g. Through wastewater treatment, short-chain PFASs with an even number of carbon atoms were mostly removed, whereas short-chain PFASs with an odd number of carbon atoms were primarily discharged into receiving water. Long-chain PFASs (perfluoroalkyl carboxylic acids: C ≥ 8; perfluoroalkane sulfonic acids: C ≥ 6) were not removed efficiently and secondary production might occur during treatment. Based on the risk quotient, PFASs residues in wastewater effluent posed minimal ecological risk, but the residues in sludge posed low to high potential risk. The mass loadings of PFASs discharged through wastewater and sludge were 15.5 and 3.74 kg/year, respectively, from all WWTPs in Shaanxi Province.

Evaluating the Distribution of Perfluoroalkyl Substances in Rice Paddy Lysimeter with an Andosol.

The properties of potential emerging persistent contaminants, perfluoroalkyl substances (PFAS), in an andosol rice paddy lysimeter were analyzed to determine their mobility and leaching behavior regarding carbon chain length and functional groups. For this purpose, simulated contaminated water (ΣPFAS = 1,185,719 ng/L) was used in the lysimeter. The results showed that PFAS distribution in the paddy soil lysimeter was influenced by the migration of these substances into irrigation water and their adsorption into the soil. PFHxS (C6) and PFOS (C8), which are the main components of the simulated contaminated water, were mostly captured in the soil layers of the low-humic andosol layer (0–35 cm). PFAS distribution may depend on soil properties, such as total carbon (TC) content. Compared with perfluoroalkane sulfonic acids (PFSAs), the distribution of perfluoroalkyl carboxylic acids (PFCAs) in soil showed significant variation. The remaining PFCAs were distributed across all layers of the lysimeter, except for the longer-chain PFCAs. Moreover, the PFSA distribution was directly correlated with the carbon chain number, whereby longer- and shorter-chain PFSAs accumulated in the top and bottom soil layers, respectively. This study provides detailed information on the distribution, leaching, uptake, and accumulation of individual PFAS in andosol paddy fields in Japan.

Radical Reactions of Vinyl Triflates and its Derivatives

Vinyl triflates are valuable precursors for vinyl cations, vinyl carbenes, and electrophiles for transition-metal-catalyzed cross-coupling reactions. However, in these reactions, the trifluoromethyl group is not installed in the final products. The radical reactions of vinyl triflates were limited until our beginning. We initially achieved the synthesis of α-trifluoromethylated ketones from vinyl triflates using triethyl borane as a radical initiator. Since the reaction proceeds chemoselectivity toward the conjugated vinyl triflates, we achieved the chemo- and regio-selective trifluoromethylation of 1,3-bis(vinyl triflates). We developed one-pot trifluoromethylation from aryl alkynes with perfluoroalkanesulfonic acids in the presence of AIBN as a radical initiator. In addition, a crossover experiment and DFT calculations support that the reaction proceeds through an intermolecular pathway. The radical reaction of vinyl triflates in the presence of alkenes afforded γ-trifluoromethylated ketones. We also developed a one-pot triflation-trifluoromethylation-triflation of imines leading trifluoromethyl-substituted vinyl trifluoromethanesulfonic amides.

Stabilization of per- and polyfluoroalkyl substances (PFAS) in sewage sludge using different sorbents

Sewage sludge is known to contain a wide range of per- and polyfluoroalkyl substances (PFAS). To test the feasibility of stabilizing PFAS in sludge, we spiked two known amounts of six perfluorinated carboxylic acids (PFCAs, C6 – C11), three perfluoroalkane sulfonic acids (PFSAs, C4 – C8), and GenX to the sludge and amended it with biochar, granular activated carbon (GAC), or one RemBind® product (100 or 100X) at different doses. Our results showed that RemBind® 100X had the best stabilization performance, followed by GAC and RemBind® 100. Biochar had little effect on decreasing leaching of PFAS. Compared to control sludge without any sorbents at an initial PFAS concentration of 30 µg/kg, the treatment by RemBind® 100X at 2 wt.% after 35 days led to decrease of a ∑PFAS leaching by 89% in the water and 85% in the SPLP leachates. At 300 µg/kg, a similar trend was observed as well. RemBind® 100X, GAC, and RemBind® 100 at a dose of 1 wt.% stabilized PFAS and resulted in significantly lower leachable ∑PFAS than that at a dose of 0.1 wt.%, indicating the dose-effect of sorbents on PFAS stabilization in sludge. During the experimental duration of 115 days, the leachable PFAS gradually increased with time for those with GAC but fluctuated in the water leachate of the sludge with RemBind® 100X, implying a dynamic adsorption/desorption process and potential degradation of PFAS precursors occurring during the incubation. Overall, this study demonstrated the positive effect of sorbent addition toward decreasing PFAS leaching by water and acidic water. The fact that the stabilized PFAS can be extracted well by basic methanol, although this may happen rarely in reality, raises the question of remediation end point, which deserves to be further investigated.

Insights into the Competitive Mechanisms of Per- and Polyfluoroalkyl Substances Partition in Liver and Blood.

Some per- and polyfluoroalkyl substances (PFASs) tend to be accumulated in liver and cause hepatotoxicity. However, the difficulty to directly measure liver concentrations of PFASs in humans hampers our understanding of their hepatotoxicity and mechanisms of action. We investigated the partitioning of 11 PFASs between liver and blood in male CD-1 mice. Although accumulation of the perfluoroalkanesulfonic acids (PFSAs) in mice serum was higher than their carboxylic acids (PFCAs) counterparts as expected, the liver-blood partition coefficients (RL/S) of PFSAs were lower than the PFCAs RL/S, implying a competition between liver and blood. The in vitro experiments further indicated that the partitioning was dominantly determined by their competitive binding between human liver fatty acid binding protein (hL-FABP) and serum albumin (HSA). The binding affinities (Kd) of PFASs to both proteins were measured. The correlations between the RL/S and log Kd(hL-FABP)/log Kd(HSA) were stronger than those with log Kd(hL-FABP) alone, magnifying that the partitioning was dominantly controlled by competitive binding between hL-FABP and HSA. Therefore, the liver concentrations of the selected PFASs in humans could be predicted from the available serum concentrations, which is important for assessing their hepatotoxicity.

Quantitation of linear and branched perfluoroalkane sulfonic acids (PFSAs) in women and infants during pregnancy and lactation.

Per- and polyfluoroalkyl substances (PFAS) are associated with negative health effects, and exposure during fetal life and infancy are of concern. A subgroup of PFAS, linear and branched perfluoroalkane sulfonic acids (PFSA), have significant differences in biochemical reactions, bioaccumulation and potential toxic exposure effects, and data on transfer of PFSA isomers from mother to baby through placenta or in breastmilk are scarce. The objective was to investigate differences in branched and linear PFSA isomers in never-pregnant, pregnant and postpartum women and infants. Serum concentrations of branched and linear, perfluorohexane sulfonate (PFHxS), perfluoroheptane sulfonate (PFHpS) and perfluorooctane sulfonate (PFOS) were measured in never-pregnant women (n=158), pregnant and postpartum women (n=114) and their infants (n=94) at age six months. There was a linear relation between maternal PFSA concentrations in pregnancy week 18 and the infant at age six months. The PFSA concentrations in maternal and infant serum varied with a factor up to 20. The maternal branched/ linear PFHxS ratio increased in the latter part of pregnancy (+45%) and remained high postpartum, and was substantially lower in the infants. Branched/linear PFHpS ratio increased during pregnancy and was highest in the infants, while the branched/linear PFOS ratio decreased in the mothers and was high in the infants. The linear relations between PFSA concentrations in infants aged six months and mothers in pregnancy week 18 confirm that pregnancy and lactation are major excretion routes for PFSA, but accumulate in the infant. The observed great variability in PFSA burden among mothers and infants, as well as the reduced maternal transfer of branched PFHxS isoforms and increased transfer of branched PFOS isoforms compared to the respective linear isoforms to the infant, might impact adverse health effects associated with PFSA exposure, but this should be confirmed in future studies.