Linear Perfluorooctane Sulfonate Research Articles

Overall and individual associations between per- and polyfluoroalkyl substances and liver function indices and the metabolic mechanism

Per- and polyfluoroalkyl substances (PFAS) can disrupt liver homeostasis. Studies have shown that a single exposure to PFAS may provoke abnormal liver function; however, few studies have investigated the overall effect of PFAS mixtures. We aimed to investigate associations between exposure to PFAS mixtures and liver function indices and explore the relevant mechanisms. This study included 278 adult males from Guangzhou, China. Serum metabolite profiles were analyzed using untargeted metabolomics. We applied weighted quantile sum (WQS) regression as well as Bayesian kernel machine regression (BKMR) to analyze the association of nine PFAS mixtures with 14 liver function indices. PFAS mixtures were positively associated with apolipoprotein B (APOB) and gamma-glutamyltransferase (GGT) and negatively associated with direct bilirubin (DBIL) and total bilirubin (TBIL) in both the WQS and BKMR analyses. In addition, Spearman’s correlation test showed individual PFAS correlated with APOB, GGT, TBIL, and DBIL, while there’s little correlation between individual PFAS and other liver function indices. In linear regression analysis, PFHxS, PFOS, PFHpS, PFNA, PFDA, and PFUdA were associated with APOB; PFOA, PFDA, PFOS, PFNA, and PFUdA were associated with GGT. Subsequently, a metabolome-wide association study and mediation analysis were combined to explore metabolites that mediate these associations. The mechanisms linking PFAS to APOB and GGT are mainly related with amino acid and glycerophospholipid metabolism. High-dimensional mediation analysis showed that glycerophospholipids are the main markers of the association between PFAS and APOB, and that (R)-dihydromaleimide, Ile Leu, (R)-(+)-2-pyrrolidone-5-carboxylic acid, and L-glutamate are the main markers of the association between PFAS and GGT. In summary, overall associations between PFAS and specific indices of liver function were found using two statistical methods; the metabolic pathways and markers identified here may serve to prompt more detailed study in animal-based systems, as well as a similar detailed analysis in other populations.

Occurrence of perfluoroalkyl substances in cow's, goat's and sheep's milk - dietary intake and risk assessment.

Milk from cows, goats and sheep was analysed in terms of content of fourteen perfluoroalkyl substances (PFASs). Altogether, 73 milk samples from cows (n = 38), goats (n = 20) and sheep (n = 15) were collected from various regions of Poland. Concentrations of analytes were determined using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The lower-bound sum of four PFAS (∑4 PFASs) concentrations (perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid, perfluorononanoic acid and perfluorohexanesulfonic acid) were highest in sheep's (0.0055 μg/kg), lower in goat's (0.0046 μg/kg), and lowest in cow's milk (0.0008 μg/kg). Goat's and sheep's milk was statistically significantly more contaminated than cow's milk. None of the samples exceeded the indicative values set by Commission Recommendation (EU) 2022/1431, and even the maximum detected concentrations were an order of magnitude lower. The most frequently detected was linear PFOS, which was found in 33%, 76% and 93% of cow's, goat's and sheep's milk samples, respectively. Based on mean upper-bound ∑4 PFAS concentrations and average milk consumption, the estimated intake of ∑4 PFASs ranged from 0.153 to 0.266 ng/kg body weight (b.w.) for children and from 0.050 to 0.88 ng/kg b.w. for adults, which indicates that exposure is very low and is merely <7% of the tolerable weekly intake (TWI) for children and <2% of the TWI for adults. Regardless of the milk type, the intake of PFASs via consumption of Polish milk does not contribute significantly to the overall PFAS intake of either adults or children.

Physiological effects of PFAS exposure in seabird chicks: A multi-species study of thyroid hormone triiodothyronine, body condition and telomere length in South Western France

There is growing evidence that poly and perfluoroalkyl substances (PFAS) exposure leads to the disruption of thyroid hormones including thyroxine (T4) and triiodothyronine (T3), and may affect telomeres, repetitive nucleotide sequences which protect chromosome ends. Many seabird species are long-lived top predators thus exhibit high contaminant levels, and PFAS-disrupting effects on their physiology have been documented especially in relation to the endocrine system in adults. On the contrary, studies on the developmental period (i.e., chicks), during which exposure to environmental contaminants may have a greater impact on physiological traits, remain scarce to this date. We carried out a multi-species study with the aim to assess whether and to which extent chicks of four gull species (herring gull, great and lesser black-backed gull, yellow-legged gull) in South Western France are contaminated by PFAS, and to bring further evidence about their potential physiological consequences. Linear PFOS showed concentrations of concern as it was generally >10 times higher than the other PFAS, and exceeded a threshold toxicity level (calculated from previous studies in birds) in almost all sampled chicks. Nonetheless, in herring gull male chicks, total T3 levels were significantly and negatively associated with perfluorodecanoate (PFDA) and perfluorododecanoate (PFDoDA) and positively associated with perfluorotetradecanoate (PFTeDA) in female chicks. Total T3 levels were also positively associated with PFDoDA in great black backed gull male chicks and with perfluorotridecanoate (PFTrDA) in lesser black backed gull chicks. In lesser and great black-backed gulls, both females and males showed significant negative associations between several PFAS and their body condition, and a positive association between telomere length and L-PFOS in the yellow-legged gull was also found. These results corroborate previous findings and need to be further explored as they suggest that PFAS may interfere with the physiological status of chicks during the developmental period, potentially inducing long-lasting consequences.

Antibiotic induced restructuring of the gut microbiota does not affect oral uptake and accumulation of perfluorooctane sulfonic acid (PFOS) in rats

Perfluorooctane sulfonic acid (PFOS) is a manmade legacy compound belonging to the group of persistent per- and polyfluorinated substances (PFAS). While many adverse health effects of PFOS have been identified, knowledge about its effect on the intestinal microbiota is scarce. The microbial community inhabiting the gut of mammals plays an important role in health, for instance by affecting the uptake, excretion, and bioavailability of some xenobiotic toxicants. Here, we investigated (i) the effect of vancomycin-mediated microbiota modulation on the uptake of PFOS in adult Sprague-Dawley rats, and (ii) the effects of PFOS exposure on the rat microbiota composition. Four groups of twelve rats were exposed daily for 7 days with either 3 mg/kg PFOS plus 8 mg/kg vancomycin, only PFOS, only vancomycin, or a corn oil control. Vancomycin-induced modulation of the gut microbiota composition did not affect uptake of branched and linear PFOS over a period of 7 days, measured in serum samples. 16S rRNA amplicon sequencing of faecal and intestinal samples revealed that vancomycin treatment lowered microbial alpha-diversity, while PFOS increased the microbial diversity in vancomycin-treated as well as in non-antibiotic treated animals, possibly because an observed decrease in the Enterobacteriaceae abundance allows other microbial species to propagate. Colonic short-chain fatty acids were significantly lower in vancomycin-treated animals but remained unaffected by PFOS. Our results suggest that PFOS exposure may disturb the intestinal microbiota, but that antibiotic-induced modulation of the intestinal ecosystem does not affect systemic uptake of PFOS in rats.

Decreased levels of perfluoroalkyl substances in patients receiving hemodialysis treatment

Perfluoroalkyl substances (PFAS) have been reported to be harmful to multiple organs in the human body. Based on a previous study suggesting that hemodialysis (HD) may be a means of eliminating PFAS from the human body, we aimed to compare the serum PFAS concentrations of patients undergoing regular HD, patients with chronic kidney disease (CKD) and controls. Additionally, we also investigated the correlation between PFAS and biochemical data, as well as concurrent comorbidities. We recruited 301 participants who had been on maintenance dialysis for >90 days, 20 participants with stage 5 non-dialysis CKD, and 55 control participants who did not have a diagnosis of kidney disease, with a mean creatinine level of 0.77 mg/dl. Eight different PFAS, namely perfluorooctanoic acid (PFOA), total and linear perfluorooctanesulfonic acid (PFOS), perfluoroheptanoic acid (PFHpA), perfluorohexanesulfonic acid (PFHxS), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA), were measured using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Spearman correlation and multivariable linear regression with 5 % false discovery rate were used to evaluate the relationships between PFAS and clinical parameters in HD patients and controls. Circulating concentrations of seven PFAS, including total and linear PFOS (T-PFOS and L-PFOS) PFDA, PFNA, PFHxS, PFOA, and PFUnDA, were significantly lower in the HD group compared to the CKD and control group. For the interplay between biochemical data and PFAS, all of the studied PFAS were positively correlated with aspartate aminotransferase, alanine aminotransferase, glucose, blood urea nitrogen, ferritin, and vitamin D in the controls, while in HD patients, the PFAS were all positively correlated with albumin, uric acid, iron, and vitamin D. These findings may offer valuable insights for future studies seeking to eliminate PFAS.

Perfluoroalkyl substances in Baltic fish – the risk to consumers

Perfluoroalkyl substances (PFASs) were investigated in five Baltic fish species (sprat, herring, salmon, trout, and cod). Each species’ median lower bound (LB) concentration of ∑14 PFASs was as follows: in sprat it was 3.54 µg/kg wet weight (w.w.), in cod 2.15 µg/kg w.w., in salmon 2.10 µg/kg w.w., in trout 2.03 µg/kg w.w. and in herring 1.74 µg/kg w.w.. Regarding the species’ median LB of ∑4 PFASs (perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorohexane sulfonic acid (PFHxS)), sprat was the most contaminated with 2.90 µg/kg w.w. and herring was the least with 1.17 µg/kg w.w.. Among all PFASs, PFOS was found in the highest concentrations (range 0.04–9.16 µg/kg w.w.) and the percentage share in the total concentration of ∑14 PFASs was between 56 and 73%. The average proportion of linear PFOS (L-PFOS) in the total PFOS (branched and linear) was the highest in salmon at 89% and trout at 87%, and in the other three species it ranged from 75 to 80%. Different consumption scenarios were assumed and the intake of PFASs was calculated for children and adults. Dietary intake via fish consumption was 3.20–25.13 ng/kg of body weight (b.w.) for children and 1.68–8.30 ng/kg b.w. for adults. Baltic fish caught along Polish coastal areas are a significant source of PFASs, especially for children.

Abstract P172: Per- and Polyfluoroalkyl Substances (PFASs), Apolipoprotein and the Risk of Coronary Heart Disease: A Case-Control Pilot Study

The association of PFASs with blood lipids, lipoproteins and apolipoproteins, and coronary heart disease (CHD) risk are inconsistent in previous studies. The aim of current study is to examine the potential association between plasma PFASs, blood lipoproteins and their subspecies defined by apolipoproteins, and whether PFASs are associated with CHD risk.A case-control study was conducted in 100 men and 102 women aged 45-70 years. We leveraged 101 participants from HPFS and NHS who were initially free of cardiovascular disease and developed a fatal or non-fatal myocardial infarction during follow-up, and randomly matched controls in a 1:1 ratio for age, smoking status, and date of blood draw. Seven plasma PFASs measurements were examined at baseline, including perfluorohexane sulfonic acid (PFHxS), perfluorooctanoic acid (PFOA), total perfluorooctane sulfonic acid (PFOS), branched PFOS (brPFOS), linear PFOS (nPFOS), perfluorononanoic acid (PFNA), and perfluorodecanoic acid (PFDA), with all mean CVs &lt;20%. Pearson correlation was applied to study the relationship between PFASs, lipoproteins and subspecies; Conditional logistic regression model was conducted to test the association between PFASs and CHD risk; a mediating effect model was used to assess how blood lipids and apolipoprotein subspecies mediate the association between PFASs and CHD risk.After multivariable adjustments, we did not find significant associations between PFAS and lipids, except for PFHxS and high-density lipoprotein cholesterol (HDL-C) with a significant positive association (r=0.19, p=0.046). For subspecies with apolipoprotein (apo) C-III, we observed non-significant inverse associations between plasma PFAS concentrations and the subspecies of HDL-C, low-density lipoprotein cholesterol (LDL-C) and VLDL-C that contain only apoC-III. For those without ApoC-III, the directions of most associations are positive. Strong associations were demonstrated between PFNA, PFDA and HDL-C with ApoE (r=0.42, p=0.00004; r=0.27, p=0.004, respectively). In addition, elevated PFOS concentrations were associated with higher relative risk of CHD (HR=1.04, p=0.02), especially for branched PFOS (HR=1.18, p=0.003), and these association were largely dose dependent (PFOS: p for linearity = 0.009; brPFOS: 0.0007). Mediation analysis illustrated no mediating effect regarding blood lipids and apolipoprotein subspecies on the association of interest, except for HDL-C on the association between PFOS, nPFOS and CHD risk (%mediated=25%, p=0.03; %mediated=36%, p=0.03, separately).Our results suggest that there is a linear positive dose-response relationship between PFOS and CHD risk, but the association is probably not mediated by subspecies with/without Apo C-III or Apo E.

Prenatal Exposure to Legacy and Alternative Per- and Polyfluoroalkyl Substances and Neuropsychological Development Trajectories over the First 3 Years of Life.

The neurotoxic effects of prenatal exposure to per- and polyfluoroalkyl substances (PFAS) on offspring animals are well-documented. However, epidemiological evidence for legacy PFAS is inconclusive, and for alternative PFAS, it is little known. In this investigation, we selected 718 mother-child pairs from the Chinese Maoming Birth Cohort Study and measured 17 legacy and alternative PFAS in the third-trimester serum. Neuropsychological developments (communication, gross motor function, fine motor function, problem solving ability, and personal-social skills) were assessed at 3, 6, 12, 18, 24, and 36 months using the Ages and Stages Questionnaires 3rd edition. Trajectories of each subscale were classified into persistently low and persistently high groups via group-based trajectory modeling. Logistic regression and grouped weighted quantile sum were fitted to assess the potential effects of individual PFAS and their mixtures, respectively. Higher linear PFHxS levels were associated with elevated odds for the persistently low trajectories of communication (OR = 1.73; 95% CI: 1.12, 2.66) and problem solving ability (OR = 2.11; 95% CI: 1.14, 3.90). Similar findings were observed for linear PFOS, 1m-PFOS, PFDA, PFDoDA, PFUnDA, and legacy PFAS mixture. However, no association was observed for alternative PFAS and their mixture. We provided insights into the longitudinal links between prenatal legacy/alternative PFAS exposure and neuropsychological development trajectories over the first 3 years of life.

Occurrences of legacy and emerging per- and polyfluoroalkyl substances in human milk in China: Results of the third National Human Milk Survey (2017-2020).

Per- and polyfluoroalkyl substances (PFAS) are persistent organic pollutants widely contaminated and exposed in humans. China is a major manufacturer and consumer of these chemicals. To characterize the occurrences, geographical variations, temporal trends, and exposure risks of legacy and emerging PFAS in perinatal women and their children in China, 30 PFAS were measured in 100 pooled human milk samples consisting of 3531 individual samples collected from 100 sites in 24 provinces during the 2017-2020 National Human Milk Survey. Linear-perfluorooctanoic acid (L-PFOA, 151pg/mL) and linear-perfluorooctane sulfonate (L-PFOS, 57.0pg/mL) were the predominant PFAS in human milk, followed by 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA, 25.9pg/mL). The geographic variation trend of PFOA was different from PFOS and Cl-PFESA, and a special geographic trend of perfluoropentanesulfonate (PFPeS) was observed. Comparison of National Human Milk surveys from different periods showed a sharp decrease of PFAS exposure in old industrial areas including Shanghai and Liaoning, but higher PFAS exposure observed in Shandong and Hubei indicated a possible domestic shift of PFAS manufacture to these areas. Worldwide comparison of PFAS in human milk indicated high PFOA exposure in China. Risk assessments for mothers and breastfeeding infants showed that PFAS exposure is of concern in China.

Perfluoroalkyl Acids in Follicular Fluid and Embryo Quality during IVF: A Prospective IVF Cohort in China.

Perfluoroalkyl acids (PFAA) have been measured in ovarian follicular fluid from women using in vitro fertilization (IVF), although associations between follicular fluid PFAA and IVF outcomes have been inconsistent. We investigated the association between follicular fluid PFAA and embryo quality in women undergoing IVF. We prospectively enrolled 729 women undergoing IVF treatment in Guangxi province, China, from July 2018 to December 2018. We measured 32 PFAA, including branched isomers, in follicular fluid using ultra-performance liquid chromatography coupled to tandem mass spectrometry. We applied restricted cubic splines, linear regression, and log-binominal regression models to investigate associations between follicular fluid PFAA and embryo quality, adjusting for confounding variables and investigated oocyte maturity as an intervening variable using causal mediation analysis. We further estimated the overall effect of the PFAA mixture on outcomes using Bayesian kernel machine regression (BKMR). We detected 8 of 32 measured PFAA in of follicular fluid samples. Higher PFAA concentrations were associated with fewer high-quality embryos from IVF. The high-quality embryo rates at the 50th percentile of linear perfluoro-1-octanesulfonate acid (n-PFOS), all branched PFOS isomers (Br-PFOS) and linear perfluoro--octanoic acid (n-PFOA) were [95% confidence interval (CI): , ], (95% CI: , ) and (95% CI: , ) lower, respectively, than the high quality embryo rates at the reference 10th percentile of PFAA. Oocyte maturity mediated 11.76% (95% CI: 3.18, 31.80%) and 14.28% (95% CI: 2.95, 31.27%) of the n-PFOS and n-PFOA associations, respectively. The results of the BKMR models showed a negative association between the PFAA mixture and the probability of high-quality embryos, with branched PFOS isomers having posterior inclusion probabilities of 1 and accounting for the majority of the association. Exposure to higher PFAA concentrations in follicular fluid was associated with poorer embryo quality during IVF. Branched PFOS isomers may have a stronger effect than linear PFOS isomers. More studies are needed to confirm these findings and to directly estimate the effects on pregnancy and live-birth outcomes. https://doi.org/10.1289/EHP10857.

Isomer-Specific Serum Concentrations of Perfluorooctane Sulfonic Acid among U.S. Adults: Results from the National Health and Nutrition Examination Survey (NHANES) and the Study of Women's Health Across the Nation Multi-Pollutant Study (SWAN-MPS).

Electrochemical fluorination manufacture of perfluorooctane sulfonic acid (PFOS), one of the most studied per- and polyfluoroalkyl substances, produces mixtures of linear and branched isomers, but little is known about human exposure to linear or branched PFOS isomers. We examined determinants affecting isomer-specific patterns of PFOS in serum in two adult populations in the United States, the National Health and Nutrition Examination Survey (NHANES) and the Study of Women's Health Across the Nation Multi-Pollutant Study (SWAN-MPS). After adjusting for demographic variables, fish consumption (in both populations), a glomerular filtration rate above 90 mL/min/1.73 m2 (observed in NHANES; not tested in SWAN-MPS), premenopausal status (only observed in SWAN-MPS), and less consumption of processed food (observed in SWAN-MPS; not tested in NHANES) were associated with a higher proportion of linear PFOS. Non-Hispanic Black and Asian participants were likely to have a higher proportion of linear PFOS than non-Hispanic White participants in both populations. Our findings suggest that isomer-specific patterns of PFOS serum concentrations in humans vary depending on population characteristics that affect PFOS exposure and excretion. Consideration of specific PFOS isomers in future human biomonitoring and epidemiologic studies can provide useful insight to better understand PFOS exposure.

Perfluoroalkyl substances in hen eggs from different types of husbandry.

Poultry eggs from cage, ecological and free range production were analyzed in terms of perfluoroalkyl substances (PFASs). Taking into account all fourteen analyzed compounds, perfluorobutanoic acid (PFBA) reach the highest concentrations (mean 0.23, 0.24, 0.27μg/kg wet weight (w.w) for organic, cage and free range eggs respectively. Taking into account the lower bound sum of four PFASs: PFOS, PFOA, PFNA, PFHxS which according to EFSA, made up half of the lower bound exposure to PFASs, organic eggs were the most contaminated (0.10μg/kg wet weight) followed by free range (0.04μg/kg wet weight) and battery cage (0.00μg/kg wet weight). The percentage share in the lower bound concentration indicates the dominant role of PFOS (37-100%). Linear PFOS accounted for 71-92% of the sum of linear and branched PFOS. Estimates of PFOS, PFOA, PFNA, PFHxS intake via eggs based lower-bound concentrations were 0.00-0.65ng/kg b. w for children and 0.00-0.21ng/kg b. w for adults which corresponds to 0-15% of the tolerable weekly intake (TWI) and 0-5% TWI for children and adult respectively.

Serum per- and polyfluoroalkyl substance concentrations in four municipal US fire departments.

Firefighters have occupational and environmental exposures to per- and polyfluoroalkyl substances (PFAS). The goal of this study was to compare serum PFAS concentrations across multiple United States fire departments to National Health and Nutrition Examination Survey (NHANES) participants. Nine serum PFAS were compared in 290 firefighters from four municipal fire departments (coded A-D) and three NHANES participants matched to each firefighter on sex, ethnicity, age, and PFAS collection year. Only Departments A and C had sufficient women study participants (25 and six, respectively) to compare with NHANES. In male firefighters compared with NHANES, geometric mean perfluorohexane sulfonate (PFHxS) was elevated in Departments A-C, sum of branched perfluoromethylheptane sulfonate isomers (Sm-PFOS) was elevated in all four departments, linear perfluorooctane sulfonate (n-PFOS) was elevated in Departments B and C, linear perfluorooctanoate (n-PFOA) was elevated in Departments B-D, and perfluorononanoate (PFNA) was elevated in Departments B-D, but lower in A. In male firefighters compared with NHANES, perfluoroundecanoate (PFUnDA) was more frequently detected in Departments B and D, and 2-(N-methyl-perfluorooctane sulfonamido) acetate (MeFOSAA) was less frequently detected in Departments B-D. In female firefighters compared with NHANES, PFHxS and Sm-PFOS concentrations were elevated in Departments A and C. Other PFAS concentrations were elevated and/or reduced in only one department or not significantly different from NHANES in any department. Serum PFHxS, Sm-PFOS, n-PFOS, n-PFOA, and PFNA concentrations were increased in at least two of four fire departments in comparison to NHANES.

Sorption of Perfluorooctane Sulfonic Acid Including Its Isomers to Soils: Effects of pH, Natural Organic Matter and Na2SO4

Perfluorooctane sulfonic acid (PFOS) has been produced in large quantities for the use in various applications. As a consequence, PFOS is ubiquitous in the environment. Managing transportation of PFOS requires a clear understanding of PFOS mobilization in soils and their interactions with different soil components. The current study investigated a pH-dependent sorption of PFOS isomers onto soil and the effect of dissolved humic substances and Na2SO4. Sorption experiments of PFOS isomers was conducted on top and subsoils to assess their capacity to retain PFOS. Topsoil and subsoil samples were sampled from two areas in Kvarntorp, Kumla, Sweden. Sorption experiments were performed by shaking a mixture of soil and soil solutions spiked with PFOS isomers. One way ANOVA showed that linear PFOS (L-PFOS) and branched PFOS (Br-PFOS) isomers showed different sorption behavior onto soils. Calculated logarithmic partition coefficients revealed that L-PFOS is readily sorbed onto soils sampled at area 1) at very low pH (&amp;lt;4.5) whereas it was the least sorbed onto soils collected at area 2) under the studied pH range. Electrostatic interactions governed the sorption of PFOS isomers during acidic conditions whereas other mechanism controlled the sorption during neutral to alkaline conditions. The presence of humic acid enhanced the sorption of all PFOS isomers whereas fulvic acid inhibited their sorption onto soil. Sorption results revealed that the topsoil had a high capacity to sorb all PFOS isomers compared to the subsoil from the same area. For soils collected from an area covered by young oak trees, a high sorption on the topsoil was attributed to a high organic content [measured as loss on ignition (LOI)] and cation exchange capacity (CEC). However, there was no correlation between sorption capacity and LOI or CEC content for soil collected from another area covered by spruce forest. This suggested that the sorption on latter soils was controlled by other physicochemical properties.

Estimation of Transport Parameters of Perfluoroalkyl Acids (PFAAs) in Unsaturated Porous Media: Critical Experimental and Modeling Improvements.

Predicting the transport of perfluoroalkyl acids (PFAAs) in the vadose zone is critically important for PFAA site cleanup and risk mitigation. PFAAs exhibit several unusual and poorly understood transport behaviors, including partitioning to the air-water interface, which is currently the subject of debate. This study develops a novel use of quasi-saturated (residual air saturation) column experiments to estimate chemical partitioning parameters of both linear and branched perfluorooctane sulfonate (PFOS) in unsaturated soils. The ratio of linear-to-branched air-water interfacial partitioning constants for all six experiments was 1.62 ± 0.24, indicating significantly greater partitioning of linear PFOS isomers at the air-water interface. Standard breakthrough curve analysis and numerical inversion of HYDRUS models support the application of a Freundlich isotherm for PFOS air-water interfacial partitioning below a critical reference concentration (CRC). Data from this study and previously reported unsaturated column data on perfluorooctanoate (PFOA) were reevaluated to examine unsaturated systems for transport nonidealities. This reanalysis suggests both transport nonidealities and Freundlich isotherm behavior for PFOA below the CRC using drainage-based column methods, contrary to the assertions of the original authors. Finally, a combined Freundlich-Langmuir isotherm was proposed to describe PFAA air-water interfacial partitioning across the full range of relevant PFAA concentrations.

Perfluorinated alkyl substances in Canadian human milk as part of the Maternal-Infant Research on Environmental Chemicals (MIREC) study

Perfluorinated alkyl substances (PFAS) were determined in human milk samples (n = 664) from participants in the Maternal-Infant Research on Environmental Chemicals (MIREC) study. ΣPFAS concentrations (sum of seven PFAS) ranged from 3.1 ng L−1 to 603 ng L−1, with a median concentration of 106 ng L−1 in the Canadian mothers' milk analyzed. These data comprise the first pan-Canadian dataset of PFAS in human milk. Perfluorooctanoic acid (PFOA) and linear perfluorooctanesulfonate (L-PFOS) were the dominant contributors to ΣPFAS in human milk samples. An inverse relationship between ΣPFAS concentrations and age was observed (Spearman correlation - 0.184). Primiparous women had elevated PFAS concentrations in milk relative to women who had children previously (p < 0.001). In contrast, the region of maternal birth did not influence ΣPFAS concentrations (p = 0.156). Although China and Norway have observed consistently detectable levels of perfluoroundecanoic acid (PFUdA) in human milk, PFAS with long carbon chains (n ≥ 11) were not present above method detection limits in Canadian human milk samples analyzed as part of the MIREC study. In conclusion, despite the presence of low levels of environmental contaminants in human milk, Health Canada supports breastfeeding due to the benefits to both infants and mothers.

Perfluoroalkyl Substances and Incident Natural Menopause in Midlife Women: The Mediating Role of Sex Hormones.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) have been associated with earlier natural menopause; however, the underlying mechanisms are not well understood, particularly the extent to which this relationship is mediated by sex hormones. We analyzed data (1999-2017) on 1,120 premenopausal women from the Study of Women's Health Across the Nation (SWAN). Causal mediation analysis was applied to quantify the degree to which follicle-stimulating hormone (FSH) and estradiol levels could mediate the associations between PFAS and incident natural menopause. Participants with higher PFAS concentrations had shorter times to natural menopause, with a relative survival of 0.82 (95% confidence interval (CI): 0.69, 0.96) for linear perfluorooctane sulfonate (n-PFOS), 0.84 (95% CI: 0.69, 1.00) for sum of branched-chain perfluorooctane sulfonate (Sm-PFOS), 0.79 (95% CI: 0.66, 0.93) for linear-chain perfluorooctanoate (n-PFOA), and 0.84 (95% CI: 0.71, 0.97) for perfluorononanoate (PFNA), comparing the highest tertile of PFAS concentrations with the lowest. The proportion of the effect mediated through FSH was 8.5% (95% CI: -11.7, 24.0) for n-PFOS, 13.2% (95% CI: 0.0, 24.5) for Sm-PFOS, 26.9% (95% CI: 15.6, 38.4) for n-PFOA, and 21.7% (6.8, 37.0) for PFNA. No significant mediation by estradiol was observed. The effect of PFAS on natural menopause may be partially explained by variations in FSH concentrations.

Simultaneous determination of perfluorooctanoic acid and perfluorooctanesulfonic acid in Korean sera using LC-MS/MS

Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) are synthetic chemicals that have been used in various industries and household products. These can easily accumulate in the human body, causing adverse effects on human health. In this study, a high-performance liquid chromatography-tandem mass spectrometry method was developed and validated for the simultaneous analysis of PFOA and linear PFOS in human serum. Owing to a lack of PFOA- and PFOS-free human serum, 13C8-PFOA and 13C8-PFOS were used as surrogate analytes for quantification. A sensitive and selective sample preparation method was developed and optimized by combining solid-phase extraction and protein precipitation method. The lower limit of quantification was 0.05 ng/mL, and the analytical response was linear up to 10 ng/mL for both PFOA and linear PFOS. Chromatographic separation of the linear PFOS from branched isomers was achieved within 5.5 min. The method was validated at various concentrations and afforded acceptable accuracy and precision values. After validation, the method was successfully applied to evaluate the exposure levels of PFOA and linear PFOS in the Korean population. The serum concentrations of PFOA and linear PFOS were 0.42–28.3 ng/mL and 0.81–57.6 ng/mL, respectively. The median concentration of linear PFOS was approximately 2.6-fold higher than that of PFOA. The concentration of PFOA was higher in women than men (p < 0.05) and that of linear PFOS was not significantly different between men and women. Therefore, a sensitive, selective, and reliable bioanalytical method was developed and validated. This method can potentially be applied to biomonitoring studies involving PFOA and linear PFOS.

Per-and polyfluoroalkyl substances, epigenetic ageand DNA methylation: across-sectional study of firefighters.

Background: Per- and polyfluoroalkyl substances (PFASs) are persistent chemicals that firefighters encounter. Epigenetic modifications, including DNA methylation, could serve as PFASstoxicity biomarkers. Methods: With a sample size of197 firefighters, we quantified theserum concentrations of nine PFASs, blood leukocyte DNA methylation and epigenetic age indicators via the EPIC array. We examined theassociations between PFASswith epigenetic age, site- and region-specific DNA methylation, adjusting for confounders. Results: Perfluorohexane sulfonate, perfluorooctanoate (PFOA)and the sum of branched isomers of perfluorooctane sulfonate (Sm-PFOS) were associated with accelerated epigenetic age. Branched PFOA, linear PFOS, perfluorononanoate, perfluorodecanoateand perfluoroundecanoate were associated with differentially methylated loci and regions. Conclusion: PFASs concentrations areassociated with accelerated epigenetic age and locus-specific DNA methylation. The implications for PFASs toxicity merit further investigation.

Urban proximity while breeding is not a predictor of perfluoroalkyl substance contamination in the eggs of brown pelicans

Identifying sources of exposure to chemical stressors is difficult when both target organisms and stressors are highly mobile. While previous studies have demonstrated that populations of some organisms proximal to urban centers may display increased burdens of human-created chemicals compared to more distal populations, this relationship may not be universal when applied to organisms and stressors capable of transboundary movements. We examined eggs of brown pelicans (Pelecanus occidentalis), a nearshore seabird with daily movements ranging from local to 50 km and annual migrations ranging from year-round residency to 1500 km. Thirty-six eggs from three breeding colonies located at increasing distances to a major urban center (Charleston, South Carolina, USA) were analyzed for concentrations of per- and polyfluoroalkyl substances (PFAS). Areas of high use for each colony during the breeding season were also assessed via the tracking of adult pelicans from each colony using GPS-PTT satellite transmitters and overlapped with measures of relative urbanization via land cover data. We report potentially significant ∑PFAS concentrations in the eggs of pelicans (175.4 ± 120.1 ng/g w wt. SD), driven largely by linear perfluorooctane sulfonate (n-PFOS) (48–546 ng/g w wt.). Residues of the precursor compound perfluorooctane sulfonamide (FOSA) were also present in pelican eggs, suggesting continued exposure of local wildlife beyond implemented phaseouts of some PFAS. For most analytes, egg concentrations did not exhibit a significant spatial structure despite some differentiation in high-use areas unlike similar data for another regional apex predator, the bottlenose dolphin (Tursiops truncatus). We suggest that the partially migratory nature of brown pelicans during the non-breeding season, combined with daily ranges that may extend to 50 km from local point sources, may have homogenized exposure across individuals. Charleston likely remains a major source for PFAS in the overall region, however, given the high concentrations observed as well as known releases of PFAS in the nearshore environment.