Perfluorohexane Sulfonate Research Articles

Leachability of per- and poly-fluoroalkyl substances from contaminated concrete.

The historical use and storage of aqueous film-forming foams (AFFF) containing per- and poly-fluoroalkyl substances (PFAS) at a range of sites including airports, defence, and port facilities have resulted in a legacy of contaminated infrastructure such as concrete. Contaminated concrete constitutes an ongoing source of PFAS contamination requiring management to ensure the protection of human health and the environment. In this study, modified Leaching Environmental Assessment Framework (LEAF) and Australian Standard Leaching Procedure (ASLP) were used to examine the leachability of PFAS, specifically, perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorohexanesulfonate (PFHxS) and perfluorohexanoic acid (PFHxA) from AFFF-contaminated concrete collected from an Australian Defence Fire Training Area (FTA). In general, PFAS readily leached from intact contaminated concrete monoliths with the cumulative proportion (%) decreasing in the order: PFHxA (>95%) > PFOS (26-84%) ≈ PFHxS (14-78%) > PFOA (<1-54%). Higher leachability for PFHxA from concrete is consistent with previous findings for solids, however, inconsistent for PFOA with higher retention (lower leachability) in concrete as compared to PFOS. Duration of exposure to water (0.5-48 h) and temperature (25 °C and 50 °C) had little influence on the proportion of PFAS leachability from powdered concrete. A higher proportion of PFAS leached from a <2 mm concrete powder size fraction as compared to 2-20 mm and 20 mm size fractions. This behavior reflects an increase in surface area with decreasing concrete particle size. Reducing the particle size could enhance PFAS removal from waste concrete.

Understanding the effects of per- and polyfluoroalkyl substances on early skin development: Role of ciliogenesis inhibition and altered microtubule dynamics

Per- and polyfluoroalkyl substances (PFAS) are a class of highly stable chemicals, widely used in everyday products, and widespread in the environment, even in pregnant women. While epidemiological studies have linked prenatal exposure to PFAS with atopic dermatitis in children, little is known about their toxic effects on skin development, especially during the embryonic stage. In this study, we utilized human embryonic stem cells to generate non-neural ectoderm (NNE) cells and exposed them to six PFAS (perfluorooctanoic acid (PFOA), undecafluorohexanoic acid (PFHxA), heptafluorobutyric acid (PFBA), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS) and perfluorobutyric acid (PFBS)) during the differentiation process to assess their toxicity to early skin development. Our results showed that PFOS altered the spindle-like morphology of NNE cells to a pebble-like morphology, and disrupted several NNE markers, including KRT16, SMYD1, and WISP1. The six PFAS had a high potential to cause hypohidrotic ectodermal dysplasia (HED) by disrupting the expression levels of HED-relevant genes. Transcriptomic analysis revealed that PFOS treatment produced the highest number (1156) of differentially expressed genes (DEGs) among the six PFAS, including the keratinocyte-related genes KRT6A, KRT17, KRT18, KRT24, KRT40, and KRT81. Additionally, we found that PFOS treatment disturbed several signaling pathways that are involved in regulating skin cell fate decisions and differentiation, including TGF-β, NOTCH, Hedgehog, and Hippo signaling pathways. Interestingly, we discovered that PFOS inhibited, by partially interfering with the expression of cytoskeleton-related genes, the ciliogenesis of NNE cells, which is crucial for the intercellular transduction of the above-mentioned signaling pathways. Overall, our study suggests that PFAS can inhibit ciliogenesis and hamper the transduction of important signaling pathways, leading potential congenital skin diseases. It sheds light on the underlying mechanisms of early embryonic skin developmental toxicity and provides an explanation for the epidemiological data on PFAS. Environmental implicationWe employed a model based on human embryonic stem cells to demonstrate that PFOS has the potential to elevate the risk of hypohidrotic ectodermal dysplasia. This is achieved by targeting cilia, inhibiting ciliogenesis, and subsequently disrupting crucial signaling pathways like TGF-β, NOTCH, Hedgehog, and Hippo, during the early phases of embryonic skin development. Our study highlights the dangers and potential impacts of six PFAS pollutants on human skin development. Additionally, we emphasize the importance of closely considering PFHxA, PFBA, PFHxS, and PFBS, as they have shown the capacity to modify gene expression levels, albeit to a lesser degree.

Per- and Poly-Fluoroalkyl Substances Exposure Is Associated With Later Occurrence of Inflammatory Bowel Disease

Inflammatory bowel disease (IBD) is an immune-mediated inflammatory disease of the intestinal tract of elusive etiology. Environmental chemical exposures are increasingly acknowledged as a potential IBD risk factor. Per- and poly-fluoroalkyl substances (PFASs), a large class of persistent fluorinated organic chemicals used in industrial applications and consumer products such as paints, food packaging, and nonstick cookware, for over 6 decades, may be implicated in IBD etiology. Yet, epidemiological evidence has so far been scarce. Exposures to a few legacy PFASs, including perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorodecanoic (PFDA), and perfluorohexane sulfonate (PFHxS), have been associated with immunotoxicity and increased risk of other immune-mediated diseases,1 but data for their potential association with IBD are conflicting.2,3 Further, the impact of more recently emerging PFAS chemicals on IBD risk has not been studied.

Prenatal Exposure to Poly- and Perfluoroalkyl Substances (2009-2014) and Vaccine Antibody Titers of Measles, Mumps, Rubella, and Varicella in Children Four to Eight Years Old from the Healthy Start Cohort.

Prenatal exposures to certain poly- and perfluoroalkyl substances (PFAS) are associated with reduced humoral responses to some childhood immunizations. We estimated associations between prenatal PFAS exposure and child antibody titers for measles, mumps, rubella (MMR), and varicella after immunization. We measured serum antibody titers of 145 children (4-8 y old) enrolled in the Healthy Start cohort in Colorado, whose mothers had PFAS quantified mid-pregnancy (2009-2014). We used linear and logistic regression models to assess the relationship between five PFAS detected in of mothers and continuous or non-high-censored ("low") antibody titers and quantile g-computation to evaluate the overall effect of the PFAS mixture. Median concentrations of individual PFAS were at or below the median reported among females in the United States. After receiving two vaccine doses, seropositive levels of antibodies were detected among most (93%-100%) children. Each log-unit increase in perfluorononanoate was associated with 2.09 [95% confidence interval (CI): 1.13, 3.87] times higher odds of a low measles titer, and each log-unit increase in perfluorooctanoate was associated with 2.46 (95% CI: 1.28, 4.75) times higher odds of a low mumps titer. Odds ratios for all other PFAS were elevated, but CIs included the null. Each quartile increase in the PFAS mixture was associated with 1.35 (95% CI: 0.80, 2.26) times higher odds of a low measles titer and 1.44 (95% CI: 0.78, 2.64) times higher odds of a low mumps titer. No significant associations were observed between PFAS and varicella or rubella antibodies. In stratified analyses, associations were negative among female children, except for perfluorohexane sulfonate and varicella, whereas they were positive among males. Some prenatal PFAS were associated with lower antibody titers among fully immunized children. The potential for immunotoxic effects of PFAS requires further investigation in a larger study, because exposure is ubiquitous globally. https://doi.org/10.1289/EHP12863.

Hepatic Transcriptome Comparative In Silico Analysis Reveals Similar Pathways and Targets Altered by Legacy and Alternative Per- and Polyfluoroalkyl Substances in Mice.

Per- and poly-fluoroalkyl substances (PFAS) are a large class of fluorinated carbon chains that include legacy PFAS, such as perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorohexane sulfonate (PFHxS). These compounds induce adverse health effects, including hepatotoxicity. Potential alternatives to the legacy PFAS (HFPO-DA (GenX), HFPO4, HFPO-TA, F-53B, 6:2 FTSA, and 6:2 FTCA), as well as a byproduct of PFAS manufacturing (Nafion BP2), are increasingly being found in the environment. The potential hazards of these new alternatives are less well known. To better understand the diversity of molecular targets of the PFAS, we performed a comparative toxicogenomics analysis of the gene expression changes in the livers of mice exposed to these PFAS, and compared these to five activators of PPARα, a common target of many PFAS. Using hierarchical clustering, pathway analysis, and predictive biomarkers, we found that most of the alternative PFAS modulate molecular targets that overlap with legacy PFAS. Only three of the 11 PFAS tested did not appreciably activate PPARα (Nafion BP2, 6:2 FTSA, and 6:2 FTCA). Predictive biomarkers showed that most PFAS (PFHxS, PFOA, PFOS, PFNA, HFPO-TA, F-53B, HFPO4, Nafion BP2) activated CAR. PFNA, PFHxS, PFOA, PFOS, HFPO4, HFPO-TA, F-53B, Nafion BP2, and 6:2 FTSA suppressed STAT5b, activated NRF2, and activated SREBP. There was no apparent relationship between the length of the carbon chain, type of head group, or number of ether linkages and the transcriptomic changes. This work highlights the similarities in molecular targets between the legacy and alternative PFAS.

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

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

Effects of polyamide microplastics on the adsorption of perfluoroalkyl substances in soil

Perfluoroalkyl substances (PFAS) and novel PFAS are continuously detected in soil environments and have attracted increasing attention. The presence of microplastics (MP) in soil systems is of increasing concern worldwide. However, the effects of MP on PFAS adsorption by soil systems remain largely unexplored. In this study, we compared the adsorption behavior of four PFAS on polyamide microplastics (PAMP), polyamide microplastic - soil mixtures (PAMP+soil), and soil to investigate the effects of MP on the adsorption of PFAS in soil. The results show that the four PFAS Perfluorooctanoic acid (PFOA), 6:2 fluorotelomer sulfonic acid (6:2FTSA), Perfluorohexanesulfonate (PFHxS) and Perfluorinated (2-methyl-3-oxohexanoic acid) (GenX) present different adsorption behaviors onto PAMP, PAMP+soil and soil due to their different physicochemical properties. However, similar laws are founded that the adsorption capacity of PAMP, with respect to the four PFAS, is stronger than that of PAMP+soil (20–56 times), followed by that of soil (72–122 times). PAMP amends into soil greatly inhibits the adsorption capacity of PAMP because their surfaces are covered with soil particles or biofilms. The inhibition rate decreases with increasing PAMP dosage. However, the addition of PAMP to soil significantly enhances the adsorption of PFAS compared with that of soil alone. This enhancement indicates that the input of MP into the soil might reduce the mobility of PFAS by improving the adsorption capacity of the soil. Furthermore, the co-culture time of PAMP and soil mixture has a slight impact on adsorption, suggesting that the effect of MP on soil adsorption of PFAS is almost stable. The findings of this study contribute to the understanding of the effects of PAMP in soil on the environmental behavior of PFAS and provide a valuable reference for evaluating the potential risk posed by the co-existence of MP and organic contaminants in soil ecosystems.

Early menarche and other endocrine disrupting effects of per- and polyfluoroalkyl substances (PFAS) in adolescents from Northern Norway. The Fit Futures study

BackgroundPer- and polyfluoroalkyl substances (PFAS) comprise a large group of chemicals that are ubiquitous in the environment and include recognized persistent organic pollutants. The aim of this cross-sectional study was to investigate possible endocrine disrupting effects of different PFAS in adolescents. MethodsSerum concentrations of PFAS, thyroid, parathyroid and steroid hormones were measured in 921 adolescents aged 15–19 years in the Fit Futures study, Northern Norway. The questionnaire included data on self-reported age at menarche and puberty development score (PDS). Multiple linear and logistic regression analyses and principle component analyses (PCA) were used to assess associations of PFAS with hormones concentrations and puberty indices. ResultsIn girls, total PFAS (∑PFAS), perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), perfluorononanoate (PFNA), perfluorodecanoate (PFDA) were positively associated with dehydroepiandrosterone sulfate (DHEAS) and negatively associated with 11-deoxycorticosterone (11-DOC)/DHEAS ratio. In boys, the associations with 11-DOC/DHEAS ratio were positive for ∑PFAS, perfluoroheptanoate (PFHpA), perfluoroheptane sulfonate (PFHpS), PFOA, and PFOS. Perfluoroundecanoate (PFUnDA) was negatively associated with free thyroxine (fT4) and free triiodothyronine (fT3) in boys. PFNA and PFDA were also negatively associated with fT3 in boys. Serum parathyroid hormone concentration (PTH) was negatively associated with ∑PFAS and perfluorohexane sulfonate (PFHxS) in girls, and with PFOS in boys. PFDA and PFUnDA were positively associated with early menarche, while ∑PFAS and PFOA were positively associated with PDS in boys.No associations of PFAS with serum testosterone, follicle-stimulating hormone, or luteinizing hormone were found in either sex. In girls, PFOA was positively associated with free testosterone index (FTI). In boys, PFOA was positively associated with androstendione and 17-OH-progesterone, while PFHpA was positively associated with estradiol. ConclusionsSerum concentrations of several PFAS were associated with parathyroid and steroid hormones in both sexes, and with thyroid hormones in boys, as well as with early menarche in girls and higher PDS in boys.

Evaluating the Effect of Gestational Exposure to Perfluorohexane Sulfonate on Placental Development in Mice Combining Alternative Splicing and Gene Expression Analyses.

Perfluorohexane sulfonate (PFHxS) is a frequently detected per- and polyfluoroalkyl substance in most populations, including in individuals who are pregnant, a period critical for early life development. Despite epidemiological evidence of exposure, developmental toxicity, particularly at realistic human exposures, remains understudied. We evaluated the effect of gestational exposure to human-relevant body burden of PFHxS on fetal and placental development and explored mechanisms of action combining alternative splicing (AS) and gene expression (GE) analyses. Pregnant ICR mice were exposed to 0, 0.03, and from gestational day 7 to day 17 via oral gavage. Upon euthanasia, PFHxS distribution was measured using liquid chromatography-tandem mass spectrometry. Maternal and fetal phenotypes were recorded, and histopathology was examined for placenta impairment. Multiomics was adopted by combining AS and GE analyses to unveil disruptions in mRNA quality and quantity. The key metabolite transporters were validated by quantitative real-time PCR (qRT-PCR) for quantification and three-dimensional (3D) structural simulation by AlphaFold2. Targeted metabolomics based on liquid chromatography-tandem mass spectrometry was used to detect amino acid and amides levels in the placenta. Pups developmentally exposed to PFHxS exhibited signs of intrauterine growth restriction (IUGR), characterized by smaller fetal weight and body length () compared to control mice. PFHxS concentration in maternal plasma was . PFHxS trans-placenta distribution suggested dose-dependent transfer through placental barrier. Histopathology of placenta of exposed dams showed placental dysplasia, manifested with an attenuated labyrinthine layer area and deescalated blood sinus counts and placental vascular development index marker CD34. Combined GE and AS analyses pinpointed differences in genes associated with key biological processes of placental development, proliferation, metabolism, and transport in placenta of exposed dams compared to that of control dams. Further detection of placental key transporter gene expression, protein structure simulation, and amino acid and amide metabolites levels suggested that PFHxS exposure during pregnancy led to impairment of placental amino acid transportation. The findings from this study suggest that exposure to human-relevant very-low-dose PFHxS during pregnancy in mice caused IUGR, likely via downregulating of placental amino acid transporters, thereby impairing placental amino acid transportation, resulting in impairment of placental development. Our findings confirm epidemiological findings and call for future attention on the health risk of this persistent yet ubiquitous chemical in the early developmental stage and provide a new approach for understanding gene expression from both quantitative and qualitative omics approaches in toxicological studies. https://doi.org/10.1289/EHP13217.

Photoelectrochemical sensor for histone deacetylase Sirt1 detection based on Z-scheme heterojunction of CuS–BiVO4 photoactive material and the cyclic etching of MnO2 by NADH

A novel photoelectrochemical (PEC) biosensor was constructed for histone deacetylase Sirt1 detection based on the Z-Scheme heterojunction of CuS–BiVO4 and reduced nicotinamide adenine dinucleotide (NADH) induced cyclic etching of MnO2 triggered by Sirt1 enzyme catalytic histone deacetylation event. Based on the Z-Scheme heterojunction, the photoactivity of the CuS–BiVO4 was improved greatly due to the highly effective separation of the photogenerated electron-hole pairs. In the presence of MnO2 nanosheets on the CuS–BiVO4/ITO electrode surface, the photocurrent decreased due to the inhibition effect of MnO2. However, this inhibition effect was eliminated by the incubation of MnO2/CuS–BiVO4/ITO with NADH, where NADH was produced in the deacetylation process of acetylated peptide catalyzed by Sirt1 with NAD+. The formed NADH etched MnO2, resulting in an increased photocurrent. In this process, NADH was oxidized to produce NAD+, which further involved the deacetylation process. Based on this cycle, the photocurrent of the biosensor was improved greatly and the sensitive and selective detection of Sirt1 was achieved. The biosensor presented a wide linear range from 0.005 to 10 nM with the low detection limit of 3.38 pM (S/N = 3). In addition, the applicability of the developed method was evaluated by investigating the effect of sodium butyrate and perfluorohexane sulfonate on Sirt1 activity.

Gestational hypertension, preeclampsia, and gestational diabetes mellitus after high exposure to perfluoroalkyl substances from drinking water in Ronneby, Sweden

BackgroundLeakage of fire-fighting foam from an airfield caused contamination of the drinking water supplied to a third of the population in Ronneby, resulting in very high serum levels of predominantly perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS). The results of studies investigating the association between exposure to perfluorinated alkyl substances (PFAS) and pregnancy complications are inconsistent, and studies at high exposures of PFOS and PFHxS are lacking. ObjectivesTo investigate the association between exposure to high levels of PFAS and gestational hypertension and preeclampsia, and gestational diabetes mellitus. MethodsWe retrieved data on 27 292 childbirths between 1995 and 2013 from the National Medical Birth Register for women that had a residential address in Blekinge county for at least one year before delivery. Residential history was used as a proxy for exposure by categorizing women into high-, intermediate-, or background exposed based on their residential address during the five-year period before childbirth. Data on confounders were retrieved from administrative registers. The outcomes were defined based on International Classification of Diseases codes. We used logistic regression to estimate odds ratios (OR) for gestational hypertension and preeclampsia, and gestational diabetes mellitus. We also investigated effect modification by fetal sex. ResultsWe found no evidence of increased risk of gestational hypertension and preeclampsia (OR 0.80; CI 0.63–1.03), nor gestational diabetes (OR 1.03; CI 0.67–1.58) after high PFAS exposure. There was no effect modification by fetal sex. DiscussionThis was the first study to investigate the association between high exposure to PFOS and PFHxS and pregnancy complications. The results from this study add important knowledge to public health management as new hotspots with high levels of PFAS are continuously discovered.

Perfluoroalkyl acid depuration from the edible tissues of a migratory recreationally fished species

Environmental emissions of perfluoroalkyl acids (PFAAs) impact estuarine species and the fisheries that rely on them. Migratory estuarine fishes may be captured for consumption in areas distant to known contaminant sources, but exposure risk depends on how quickly contaminants are depurated. This baseline presents the outcomes from a novel experiment simulating the migration of a popular recreational fish species (Dusky Flathead, Platycephalus fuscus) following environmental exposure to PFAAs, and assessing depuration from edible muscle tissues. Over the 33-day experiment, perfluorooctane sulfonate (PFOS) concentrations declined slowly, with modelling suggesting that concentrations fell below the relevant screening value (5.2 μg kg−1) within ∼558 h (285–1372 h; 90 % CI). Low concentrations (<1.2 μg kg−1) of perfluorohexane sulfonate also depurated rapidly. This study provides useful information for assessing potential exposure risk posed by recreationally targeted fish migrating away from contaminated areas. The experimental design employed has a real-world context that is relevant for future studies.

A systematic investigation of single solute, binary and ternary PFAS transport in water-saturated soil using batch and 1-dimensional column studies: Focus on mixture effects

This study aimed to investigate the transport and release of per- and polyfluoroalkyl substances (PFAS), as single solutes and binary and ternary mixtures, and associated competitive sorption effects in water-saturated soil. Batch sorption isotherm and desorption, and one-dimensional miscible displacement studies were conducted. For the batch study, the mixtures exhibited extensive sorption isotherm nonlinearity at aqueous concentrations exceeding 20 µg/L. At and above this threshold, competitive effects significantly decreased PFAS sorption, mostly affecting perfluorooctanoic acid (PFOA) and perfluorohexane sulfonate (PFHxS). Importantly, mixture effects exacerbated isotherm nonlinearity and may increase the leaching of PFAS in subsurface soil and groundwater. Further, up to 100% desorption occurred for single solutes and mixtures, indicating that the studied PFAS were weakly sorbed. For the column study, at influent concentrations (21 – 27 µg/L, depending on PFAS) near the threshold, PFOA and PFHxS breakthrough curves (BTC) generally exhibited equilibrium (nonlinear) transport, whereas perfluorooctane sulfonate (PFOS) exhibited nonequilibrium transport, with minimal or no mixture effects. Nonequilibrium transport of PFOS was driven by rate-limited sorption, especially as flow interruption tests confirmed the absence of physical nonequilibrium. The sorption distribution coefficients (Kd) from moment and frontal analyses, and 2-site modelling of the BTC, were consistent with the batch-derived Kd, although comparatively smaller. Such discrepancies may limit the applicability of batch-derived Kd values for predictive transport modelling purposes. Overall, understanding mixture impacts may aid effective predictive modelling of PFAS transport and leaching, especially in aqueous film forming foam (AFFF)-source zone areas associated with elevated PFAS concentrations. At low or environmental PFAS concentrations, mixture effects can be expected to be play a minor role in influencing PFAS transport.

Evaluation of the Effect of Perfluorohexane Sulfonate on the Proliferation of Human Liver Cells.

Perfluorohexane sulfonate (PFHxS) is a widely detected replacement for legacy long-chain perfluoroalkyl substances (PFAS) in the environment and human blood samples. Its potential toxicity led to its recent classification as a globally regulated persistent organic pollutant. Although animal studies have shown a positive association between PFHxS levels and hepatic steatosis and hepatocellular hypertrophy, the link with liver toxicity, including end-stage liver cancer, remains inconclusive. In this study, we examined the effects of PFHxS on the proliferation of Hep3B (human hepatocellular carcinoma) and SK-Hep1 (human liver sinusoidal endothelial cells). Cells were exposed to different PFHxS concentrations for 24-48 h to assess viability and 12-14 days to measure colony formation. The viability of both cell lines increased at PFHxS concentrations <200 μM, decreased at >400 μM, and was highest at 50 μM. Colony formation increased at <300 μM and decreased at 500 μM PFHxS. Consistent with the effect on cell proliferation, PFHxS increased the expression of proliferating cell nuclear antigen (PCNA) and cell-cycle molecules (CDK2, CDK4, cyclin E, and cyclin D1). In summary, PFHxS exhibited a biphasic effect on liver cell proliferation, promoting survival and proliferation at lower concentrations and being cytotoxic at higher concentrations. This suggests that PFHxS, especially at lower concentrations, might be associated with HCC development and progression.

Presence of Perfluoroalkyl Carboxylic Acids and Sulfonates in Vietnamese Food Contact Materials

Per- and polyfluoroalkyl substances (PFASs) are considered as persistent organic pollutants (POPs), which should be restricted or eliminated. In this study, concentrations of four perfluoroalkyl carboxylic acids (perfluorobutanoic acid PFBA, perfluorohexanoic acid PFHxA, perfluorooctanoic acid PFOA, perfluorodecanoic acid PFDA) and four perfluoroalkyl sulfonates (perfluorobutane sulfonate PFBS, perfluorohexane sulfonate PFHxS, perfluorooctane sulfonate PFOS, perfluorodecane sulfonate PFDS) were analyzed in food contact materials (FCM) collected from Hanoi, Vietnam. A total of 15 FCM samples was obtained including several categories such as instant drink/food boxes, bags, cups, wrappers, and tray. The FCM samples were untrasonic extracted with methanol, concentrated, and filtered before analysis by a liquid chromatography–tandem mass spectrometry (LC-MS/MS) system. Recoveries of native and surrogate standards ranged from 70% to 130% with RSD &lt; 20% in replicated analysis. Method detection limits of PFASs ranged from 0.04 to 0.08 ng/g. Concentrations of S8PFASs ranged from not detected (ND) to 1.46 (average ± SD: 0.417 ± 0.479) ng/g. Detection frequencies of PFASs decreased in the order: PFDA (33%) &gt; PFBA, PFOA, PFHxS, PFOS (27%) &gt; PFDS (13%) &gt; PFHxA (7%) &gt; PFBS (0%). Average concentrations of individual compounds decreased in the order: PFOS &gt; PFDA &gt; PFHxS &gt; PFOA &gt; PFBA &gt; PFHxA &gt; PFDS &gt; PFBS. Relatively low PFAS concentrations found in the FCM samples of this study indicated that these substances were mainly derived from unintentional sources rather than intentionally added to the materials.&#x0D;

Screening for 26 per- and polyfluoroalkyl substances (PFAS) in German drinking waters with support of residents

The occurrence of per- and polyfluoroalkyl substances (PFAS) in water cycles poses a challenge to drinking water quality and safety. In order to counteract the large knowledge gap regarding PFAS in German drinking water, 89 drinking water samples from all over Germany were collected with the help of residents and were analyzed for 26 PFAS by high-performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). The 20 PFAS recently regulated by sum concentration (PFAS∑20), as well as six other PFAS, were quantified by targeted analysis. In all drinking water samples, PFAS∑20 was below the limit of 0.1 μg/L, but the sum concentrations ranged widely from below the limit of quantification up to 80.2 ng/L. The sum concentrations (PFAS∑4) of perfluorohexanesulfonate (PFHxS), perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorononanoate of 20 ng/L were exceeded in two samples. The most frequently detected individual substances were PFOS (in 52% of the samples), perfluorobutanesulfonate (52%), perfluorohexanoate (PFHxA) (44%), perfluoropentanoate (43%) and PFHxS (35%). The highest single concentrations were 23.5 ng/L for PFHxS, 15.3 ng/L for PFOS, and 10.1 ng/L for PFHxA. No regionally elevated concentrations were identified, but some highly urbanized areas showed elevated levels. Concentrations of substitution PFAS, including 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoate and 2,2,3-trifluor-3-[1,1,2,2,3,3-hexafluor-3-(trifluormethoxy)propoxy]-propanoate (anion of ADONA), were very low compared to regulated PFAS. The most frequently detected PFAS were examined for co-occurrences, but no definite correlations could be found.

Are PFBS, PFHxS, and 6:2FTSA more friendly to the soil environment compared to PFOS? A new insight based on ecotoxicity study in soil invertebrates (Eisenia fetida)

As alternatives to perfluorooctane sulfonate (PFOS) with shorter carbon chains or lower proportion of fluorine atoms, perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), and 6:2 fluorotelomer sulfonic acid (6:2FTSA) have been detected in various environmental media. However, it is unclear whether the toxicity of these alternatives is lower than that of PFOS. Therefore, this study investigated the toxicity and differences in PFBS, PFHxS, 6:2FTSA, and PFOS (0.2 mg/kg) after 56 d of exposure using the common invertebrate Eisenia fetida in soil as the test organism. The results showed that although PFOS, PFBS, PFHxS, and 6:2FTSA induced oxidative stress and apoptosis in earthworms and led to developmental and reproductive toxicity in terms of comprehensive toxicity, PFHxS > PFOS > PFBS >6:2FTSA. To reveal the mechanisms underlying the differences in toxicity between the alternatives and PFOS, we conducted molecular docking and transcriptomic analyses. The results indicated that, unlike PFOS, PFBS, and PFHxS, 6:2FTSA did not cause significant changes in antioxidant enzyme activity at the molecular level. Furthermore, PFOS exposure caused disorder in the nervous and metabolic systems of earthworms, and PFHxS disrupted energy balance and triggered inflammatory responses, which may be important reasons for the higher toxicity of these compounds. In contrast, exposure to 6:2FTSA did not result in adverse transcriptomic effects, suggesting that 6:2FTSA exerted the least molecular-scale toxicity in earthworms. The results of this study provide new insights into the environmental safety of using PFBS, PFHxS, and 6:2FTSA as alternatives to PFOS.

Prenatal and Childhood Per- and Polyfluoroalkyl Substance (PFAS) Exposures and Blood Pressure Trajectories From Birth to Late Adolescence in a Prospective US Prebirth Cohort.

Background Evidence is limited regarding the associations of prenatal and childhood per- and polyfluoroalkyl substance (PFAS) exposures with blood pressure (BP) trajectories in children. Methods and Results Participants are from Project Viva, a prospective prebirth cohort in eastern Massachusetts. We measured PFAS in early-pregnancy maternal (median, 9.6 weeks) and midchildhood (median, 7.7 years) plasma samples. We conducted standardized BP measurements at 6 research visits: birth, infancy (median, 6.3 months), early childhood (median, 3.2 years), midchildhood (median, 7.7 years), early adolescence (median, 12.9 years), and late adolescence (median, 17.5 years). We used linear regression to examine associations of individual PFASs with BP at each visit, linear spline mixed-effects regression to model BP trajectories, and a mixture approach to estimate PFAS exposure burden. We included 9036 BP measures from 1506 participants. We observed associations between particular individual prenatal PFASs and child BP at specific time points, for example, prenatal 2-(N-ethyl-perfluorooctane sulfonamido) acetate (EtFOSAA) and 2-(N-methyl-perfluorooctane sulfonamido) acetate (MeFOSAA) with higher systolic BP at birth; prenatal perfluorooctane sulfonate (PFOS) and EtFOSAAwith lower diastolic BP in infancy; and prenatal PFOS, perfluorooctanoate (PFOA), and EtFOSAAwith higher systolic BP at midchildhood. No prenatal or childhood PFAS was consistently associated with BP across all visits. Diastolic BP trajectories from 0 to 20 years differed slightly by prenatal PFOA, perfluorohexane sulfonate (PFHxS), and perfluorononanoate (PFNA)(P values 0.01-0.09). Diastolic BP trajectories from 6 to 20 years differed slightly by midchildhood PFHxS and MeFOSAA(P-values 0.03-0.08). Prenatal or childhood PFAS mixture burden scoreswere not associated with BP. Conclusions We found associations of prenatal and childhood PFAS exposures with BP at specific time points between birth and late adolescence but no consistent associations across all time points or PFAS types.

Temporal decline in serum PFAS concentrations among metropolitan firefighters: Longitudinal study on post-exposure changes following PFAS foam cessation

Firefighters are at a high risk of exposure to per- and polyfluoroalkyl substances (PFAS) due to their frequent use of PFAS-containing foams in training and emergency situations. This longitudinal study aimed to investigate the changes in serum PFAS levels among firefighters following cessation of their exposure to PFAS-containing foams. The study involved 130 firefighters from the South Australian Metropolitan Fire Services (SAMFS), and serum samples were collected at two time points: baseline in 2018–19 and follow-up in 2021–22. Along with the collection of samples, a survey questionnaire was administered to gather information on firefighters' employment and demographic characteristics. Regression models were employed to assess the association between these factors and the outcome variable (annual percentage change in serum PFAS concentration). The results indicated a decline in serum PFAS concentrations over time, with the main contaminants being perfluorooctane sulfonic acid (PFOS), perfluorohexane sulfonate (PFHxS), and perfluorooctanoic acid (PFOA). The median and Interquartile Range (IQR) of total PFAS (∑PFAS) concentration reduced from 21.5 ng/ml (IQR: 11 to 53 ng/ml) at baseline to 15 ng/ml (IQR: 8 to 33 ng/ml) at follow-up. On average, there was an annual reduction of 13%, 7%, and 4.4% in serum concentrations of PFOS, PFHxS, and PFOA, respectively. Firefighters under the age of 55, those who used PFAS in the past ten years, or those who had little to no frequency of PFAS exposure in their previous employment, encountered a significantly higher annual percentage reduction (P < 0.05) in both ∑PFAS and PFOS concentrations. None of the independent variables analysed could significantly predict the annual percentage change in PFOA and PFHxS.This study provides evidence for a declining temporal trend in serum PFAS concentrations among metropolitan firefighters following workplace interventions that involved the removal of PFAS-containing foams.

A Critical Review of Amphibian Per- and Polyfluoroalkyl Substance Ecotoxicity Research Studies: Identification of Screening Levels in Water and Other Useful Resources for Site-Specific Ecological Risk Assessments.

With the goal of aiding risk assessors conducting site-specific risk assessments at per- and polyfluoroalkyl substance (PFAS)-contaminated sites, this critical review synthesizes information on the ecotoxicity of PFAS to amphibians in 10 amphibian species and 16 peer-reviewed publications. The studies in this review consisted of spiked-PFAS chronic toxicity experiments with perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorohexane sulfonate (PFHxS), and 6:2 fluorotelomer sulfonate (6:2 FTS) that evaluated apical endpoints typical of ecological risk-based decision making (survival, growth, and development). Body mass was the most sensitive endpoint, showing clear and biologically meaningful population level adverse effect sizes (≥20% adverse effects). From these results, we recommend chronic no observed effect concentration (NOEC) screening levels of 590 µg/L for PFOS and 130 µg/L for PFOA. At or above recommended chronic lowest observed effect concentration screening levels of 1100 µg/L PFOS and 1400 µg/L PFOA, there is an increased chance of adverse biologically relevant chronic effects. Biologically relevant adverse effects were not observed for PFHxS and 6:2 FTS, so unbounded NOECs of 1300 µg/L PFHxS and 1800 µg/L 6:2 FTS are recommended. Screening levels are also provided for the concentration of PFAS in an amphibian diet, amphibian tissue, and moss substrate. In addition, we recommend bioconcentration factors that can be useful to predict concentrations of PFAS in amphibians using concentrations in water; these values are useful for food web modeling to understand risks to vertebrate wildlife that prey on amphibians. Overall, the present study provides a guide to the wealth of ecotoxicological research on PFAS conducted by our research group and highlights the need for additional work that would improve the understanding of chemical risks to amphibians. Environ Toxicol Chem 2023;00:1-13. © 2023 SETAC.