Perfluorohexane Sulfonate Research Articles

Determination of trace perfluorinated compounds in environmental water samples by dispersive solid- phase extraction-high performance liquid chromatography-tandem mass spectrometry using carbon nanotube composite materials

In this work, carbon nanotubes (CNTs) on silica rod (SiO2) composite materials were prepared to extract six perfluorinated compounds (PFCs) in real environmental water samples by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The as-synthesized sorbents, hereafter referred to as CNT@SiO2, were employed for dispersive solid-phase extraction (d-SPE). Perfluoroheptanoic acid (PFHpA), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorooctane sulfonate (PFOS), and perfluorodecanoic acid (PFDA) were selected as target analytes. The main extraction parameters were systematically optimized using the single-factor optimization method. The optimum adsorption parameters were as follows: adsorption time of 30 min, sorbent amount of 10 mg, pH 6 and NaCl concentration of 1.7 mol/L for sample solution, and 4 mL acetone as desorption solvent, desorption for 4 min. LC-triple quadrupole MS was conducted to quantify the selected PFCs in water samples. The mobile phase was 5 mmol/L ammonium acetate and methanol, the flow rate was set to 0.4 mL/min, the column temperature was set to 40 ℃, and the injection volume was 5.0 μL. The chromatographic separation system was equipped with a Kinetex C18 column (100 mm×2.1 mm, 1.7 μm). The mass spectrometer was operated with negative electrospray ionization in multi-reaction monitoring mode. CNT@SiO2 was prepared in five batches and used as the d-SPE sorbent, and the relative standard deviations (RSDs) of the PFC recoveries among these five batches ranged from 4.9% to 9.3%. The reusability of the CNT@SiO2 sorbent was assessed. After eight d-SPE cycles using the same sorbent, the RSDs of the PFC recoveries were 3.7%-8.2%. These results indicated that the sorbent had good stability and reusability for d-SPE. Excellent results were achieved under optimal extraction conditions. The method validation results indicated that the linear ranges were 0.4-1000 ng/L for PFNA, PFOS, and PFDA, 0.9-1000 ng/L for PFHpA, 0.7-1000 ng/L for PFHxS, and 0.6-1000 ng/L for PFOA. The correlation coefficients were 0.973-0.997. The limit of detection (LOD) and limit of quantification of the method were 0.10-0.26 ng/L and 0.33-0.87 ng/L, respectively. At 20 ng/L, the RSDs of the intra- and inter-day precisions were 2.73%-7.75% and 3.38%-8.21%, respectively. At 100 ng/L, the RSDs of the intra- and inter-day precisions were 2.95%-8.46% and 4.16%-9.14%, respectively. Finally, at 500 ng/L, the RSDs of the intra- and inter-day precisions were 2.51%-7.48% and 3.59%-9.63%, respectively. The developed method was applied to analyze six PFCs in tap water, barreled drinking water, and river water samples. PFOA and PFOS were determined in tap water at mass concentrations of 5.6 and 8.7 ng/L, respectively. No PFCs were found in barreled drinking water and river water. Satisfactory recoveries of 72.1%-109.6% at low, middle, and high spiking levels were also obtained. In conclusion, the d-SPE-LC-MS/MS method based on CNT@SiO2 composite sorbents is accurate and sensitive. The results of this study demonstrate that CNT@SiO2 is a good choice for the rapid and effective determination of PFCs from water samples. Further exploration of the use of CNT@SiO2 sorbents for the extraction and determination of trace organic pollutions in environmental samples is in progress.

Per- and polyfluoroalkyl substances (PFAS) and immune system-related diseases: results from the Flemish Environment and Health Study (FLEHS) 2008–2014

BackgroundThe successive FLEHS campaigns assess internal exposure to pollutants and associated early biological and health effects in participants of different age groups.Materials and methodsMother–newborn pairs (N = 220 in 2008–2009, age 18–42 years; N = 269 in 2013–2014, age 18–44 years), 197 adolescents 14–15 years (2010–2011), 201 adults 20–40 years (2008–2009) and 205 adults 50–65 years (2014) were recruited. For the various groups of subjects different sets of PFAS were assessed. Perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorobutane sulfonate (PFBS) were determined in cord plasma and peripheral serum as these were the PFAS compounds for which we had access to high quality measurements and which were expected to be present in the highest concentrations. Participants filled out a questionnaire based on the European Community Respiratory Health Survey questionnaire on asthma and allergy. In these cross-sectional studies associations were assessed using stepwise multiple logistic regression, with confounders (including smoking and familial occurrence of the disease) and potential covariates selected on the basis of experience in our previous studies and a literature search. Forest plots of odds ratios summarize the associations between the various PFAS on the one hand and the different immune outcomes on the other hand.ResultsFor several self-reported immune system-related diseases inverse associations with PFAS serum concentrations were observed. These inverse associations were more pronounced in mothers and adults than in adolescents. A significant inverse association was observed in adults and mothers (for mothers based on measurements on cord plasma) between PFNA, PFOS, and PFHxS and asthma (for mothers also for PFOA), in mothers between PFHxS, PFNA and PFOS and allergic rhinitis, in mothers and adults between PFHxS and PFOS and some forms of allergy (for mothers also for PFOA), in adults between PFOA and eczema, and in adolescents between PFOS and systemic allergy.ConclusionInternal exposure to PFAS was associated with changes in immunological processes consistent with what has been reported in the literature. Whereas these changes were observed in many publications to be associated with adverse health effects, our findings suggest that they can also lead to inverse associations with certain immune system-related diseases.

Associations between endocrine disruptor contamination and thyroid hormone homeostasis in Belgian type 1 diabetic children.

Humans are daily exposed to many environmental pollutants, some of which being suspected to be thyroid disruptors. Some populations could be particularly susceptible to thyroid disruption, such like diabetics due to the well-known relation between the thyroid function and the control of carbohydrate homeostasis by pancreas. Therefore, the aim of this study was to investigate the associations between the exposure to several persistent and non-persistent chemicals and thyroid hormones levels in children with type 1 diabetes. Blood and urine sample were collected from 54 children diagnosed for type 1 diabetes mellitus. The concentrations of 7 phthalate metabolites, 4 parabens, 7 bisphenols, benzophenone 3 and triclosan were measured in urine, while 15 organochlorine pesticides, 4 polychlorinated biphenyls (PCBs) and 7 perfluoroalkyl substances were analyzed in serum samples. In the same time, the blood levels of free thyroxine (fT4), thyroid stimulating hormone (TSH) and glycated hemoglobin (Hb1Ac) were determined. We highlighted positive associations between serum perfluorohexane sulfonate and urinary monoethylphthalate levels, and TSH level in blood. We also found that PCB 138 was positively associated to fT4 while urinary levels of bisphenol F were negatively correlated to this hormone. Finally, we observed positive associations between Hb1Ac levels and the contamination by PCB 153 and two urinary phthalate metabolites: mono-2-ethyl-5-hydroxyhexyl phthalate and mono-2-ethyl-5-oxoxyhexyl phthalate. Our results showed that our small cohort of children with type 1 diabetes mellitus is potentially susceptible to thyroid disruptions by some pollutants. Moreover, for these children, both di-(2-ethylhexyl) phthalate metabolites would potentially hamper the glucose homeostasis. Nevertheless, additional studies are mandatory to further explore these findings.

Study on Pollution Characteristics of Perfluoroalkyl Substances (PFASs) in Shallow Groundwater

Perfluoroalkyl substances (PFASs) in shallow groundwater are increasingly being studied due to the global occurrence, environment persistence, bioaccumulation, and potential human health risk. In this research, 16 PFAS (11 perfluorinated carboxylic acids and 5 perfluorinated sulfonic acids) concentrations in groundwater were quantified to obtain information on geographical distribution and PFAS detection pattern for 4 years in South Korea. In the results, groundwater PFAS concentration ranged from non-detectable to average 45.2 ng/L (sum of PFASs). The major PFAS compounds were perfluorooctanoic acid (PFOA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS). The short chain (C < 8) PFASs were more prevalent than long chain (C > 8) PFASs in shallow groundwater. However, the detection patterns of 15 PFASs were different for each aquifer. Subsequently, through a health risk assessment, a non-carcinogenic risk level through ingestion, inhalation, and dermal contact for PFOA and PFOS was determined at 10−1, and it presents the need for PFAS management of groundwater.

Associations of perfluoroalkyl substances (PFAS) with lipid and lipoprotein profiles

BackgroundPerfluoroalkyl substances (PFAS) are man-made chemicals with unique properties that are widely distributed in humans and the environment. Recent studies suggest that PFAS are involved in cholesterol metabolism, however, the mechanisms underlying the associations are poorly understood.ObjectiveWe aimed to evaluate associations of plasma PFAS with detailed lipid and lipoprotein subfractions in an adult population of men and women.MethodsWe measured concentrations of cholesterol and triglycerides in lipoprotein subfractions, apolipoprotein subclasses, as well as fatty acid and different phospholipid measures, using serum proton nuclear magnetic resonance (1H-NMR), and four plasma PFAS using liquid chromatography-mass spectrometry (UHPLC-MS/MS). Measurements were available for 493 participants (all aged 50 years, 50% female). Multivariable linear regression was used to estimate the association of four PFAS with 43 different 1H-NMR measures, with adjustment for body mass index (BMI), smoking, education, and physical activity.ResultsWe found that perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorodecanoic acid (PFDA), but not perfluorohexanesulfonate (PFHxS), concentrations were consistently positively associated with concentrations of cholesterol in lipoprotein subfractions, apolipoproteins, as well as composite fatty acid- and phospholipid profiles. The most consistent associations were found for the relationship of PFAS with total cholesterol in intermediate-density lipoprotein (IDL), across all low-density lipoprotein (LDL) subfractions and small high-density lipoprotein (HDL). Moreover, we found weak to null evidence for an association of any of the measured 13 triglyceride lipoprotein subfractions with PFAS.ConclusionsOur results suggest that plasma PFAS concentrations are associated with cholesterol in small HDL, IDL and all LDL subfractions, as well as apolipoproteins and composite fatty acid and phospholipid profiles but to a lesser extent with triglycerides in lipoproteins. Our findings draw attention to the need for more detailed measurements of lipids across various lipoprotein subfractions and subclasses in assessing the role of PFAS in lipid metabolism.ImpactBy performing an in-depth characterization of circulating cholesterol and triglycerides in lipoprotein subfractions, apolipoprotein, fatty acid, and phospholipid concentrations, this study has expanded upon the limited literature available on the associations of plasma PFAS concentrations beyond clinical routine laboratory testing for lipids.

Per- and polyfluoroalkyl substances in groundwater in Thailand: occurrence, source identification and spatial distribution

Per- and polyfluoroalkyl substances have the potential to leach into groundwater, particularly in areas with potential pollution sources, such as landfills. The composition and distribution of per- and polyfluoroalkyl substances, as well as soil characteristics, are particularly useful for identifying the sources of per- and polyfluoroalkyl substances. The objectives of the present study were to characterise per- and polyfluoroalkyl substance levels in groundwater in Thailand, identify their potential sources and highlight their spatial distribution. Groundwater samples were collected in areas hosting municipal and industrial waste disposal sites. Seven Per- and polyfluoroalkyl substances were extracted from the groundwater samples using the solid-phase extraction technique and analysed by high-performance liquid chromatography-tandem mass spectrometry. These samples contain mostly perfluorooctanoic acid and perfluorooctane sulfonate, with the highest concentrations of 34.96 and 25.88 ng L–1, respectively, obtained from industrial waste disposal site areas. The presence of perfluorohexane sulfonate in most samples from industrial waste disposal site areas suggests its usage as a substitute for perfluorooctane sulfonate-based products. In addition to waste disposal, hierarchical cluster analysis reveals that other sources likely influence the presence of per- and polyfluoroalkyl substances in groundwater in Thailand. Livestock farming and ponds near groundwater wells probably impact per- and polyfluoroalkyl substances levels in the associated groundwater. The spatial distribution of per- and polyfluoroalkyl substances shows that in addition to waste disposal sources, soil characteristics and interactions between their negatively charged components and cations in soils significantly influence the contamination of groundwater in the areas studied.

Spatial and temporal variability of per- and polyfluoroalkyl substances (PFAS) in environmental media of a small pond: Toward an improved understanding of PFAS bioaccumulation in fish

Per- and polyfluoroalkyl substances (PFAS) are highly fluorinated compounds with many industrial applications, for instance as ingredients in fire-suppressing aqueous film-forming foams (AFFF). Several PFAS have been demonstrated to be persistent, bioaccumulative and toxic. This study better characterizes the bioaccumulation of PFAS in freshwater fish through a spatial and temporal analysis of surface water and sediment from a stormwater pond in a former Naval air station (NAS) with historic AFFF use. We sampled environmental media from four locations twice per week for five weeks and sampled fish at the end of the sampling effort. The primary PFAS identified in surface water, sediment, and biota were perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) followed by perfluorooctanoic acid (PFOA) in environmental media and perfluoroheptane sulfonate (PFHpS) in biota. We observed significant temporal variability in surface water concentrations at the pond headwaters following stochastic events such as heavy rainfall for many compounds, particularly PFHxS. Sediment concentrations varied most across sampling locations. In fish, liver tissue presented the highest concentrations for all compounds except PFHxS, which was highest in muscle tissue, suggesting the influence of fine-scale aqueous PFAS fluctuations on tissue distribution. Calculated log bioaccumulation factors (BAFs) ranged from 0.13 to 2.30 for perfluoroalkyl carboxylates (PFCA) and 0.29–4.05 for perfluoroalkane sulfonates (PFSA) and fluctuated greatly with aqueous concentrations. The variability of PFAS concentrations in environmental media necessitates more frequent sampling efforts in field-based studies to better characterize PFAS contamination in aquatic ecosystems as well as exercising caution when considering single time-point BAFs due to uncertainty of system dynamics.

Exposure to perfluoroalkyl and polyfluoroalkyl substances and estimated glomerular filtration rate in adults: a cross-sectional study based on NHANES (2017-2018).

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) may be important environmental risk factors affecting renal function. This study aimed to investigate the relationships between PFASs and estimated glomerular filtration rate (eGFR) in univariate exposure and multivariate co-exposure models of PFASs. A total of 1700 people over 18years from National Health and Nutrition Examination Survey (NHANES) in 2017-2018 were selected as subjects to explore the relationships between eGFR and six PFASs (perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFUA), perfluorodecanoic acid (PFDeA), and perfluorohexane sulfonate (PFHxS)). First, multiple linear regression was used to estimate the association of each PFAS with eGFR, and the joint effect of PFAS mixtures was evaluated by Bayesian kernel machine regression (BKMR). Multiple linear regression analysis showed PFOS (β = - 0.246, p = 0.026) and PFHxS (β = 0.538, p = 0.049) were significantly associated with eGFR in total population. In BKMR analysis, there was joint effect between PFOS and PFHxS for eGFR. And there were the joint effects of multiple PFAS on eGFR, especially the significant joint effect between PFHxS and PFDeA/PFNA/PFUA. Future cohort studies need to explore the association of multiple PFASs and health.

Nitrifying Microorganisms Linked to Biotransformation of Perfluoroalkyl Sulfonamido Precursors from Legacy Aqueous Film-Forming Foams.

Drinking water supplies across the United States have been contaminated by firefighting and fire-training activities that use aqueous film-forming foams (AFFF) containing per- and polyfluoroalkyl substances (PFAS). Much of the AFFF is manufactured using electrochemical fluorination by 3M. Precursors with six perfluorinated carbons (C6) and non-fluorinated amine substituents make up approximately one-third of the PFAS in 3M AFFF. C6 precursors can be transformed through nitrification (microbial oxidation) of amine moieties into perfluorohexane sulfonate (PFHxS), a compound of regulatory concern. Here, we report biotransformation of the most abundant C6 sulfonamido precursors in 3M AFFF with available commercial standards (FHxSA, PFHxSAm, and PFHxSAmS) in microcosms representative of the groundwater/surface water boundary. Results show rapid (<1 day) biosorption to living cells by precursors but slow biotransformation into PFHxS (1-100 pM day-1). The transformation pathway includes one or two nitrification steps and is supported by the detection of key intermediates using high-resolution mass spectrometry. Increasing nitrate concentrations and total abundance of nitrifying taxa occur in parallel with precursor biotransformation. Together, these data provide multiple lines of evidence supporting microbially limited biotransformation of C6 sulfonamido precursors involving ammonia-oxidizing archaea (Nitrososphaeria) and nitrite-oxidizing bacteria (Nitrospina). Further elucidation of interrelationships between precursor biotransformation and nitrogen cycling in ecosystems would help inform site remediation efforts.

Uptake of Per- and Polyfluoroalkyl Substances by Fish, Mussel, and Passive Samplers in Mobile-Laboratory Exposures Using Groundwater from a Contamination Plume at a Historical Fire Training Area, Cape Cod, Massachusetts.

Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive per- and polyfluoroalkyl substances (PFAS) groundwater contamination plume. The potential for PFAS bioconcentration from exposure to the contaminated groundwater, which discharges to surface water bodies, was assessed with mobile-laboratory experiments using groundwater from the contamination plume and a nearby reference location. The on-site continuous-flow 21-day exposures used male and female fathead minnows, freshwater mussels, polar organic chemical integrative samplers (POCIS), and polyethylene tube samplers (PETS) to evaluate biotic and abiotic uptake. The composition of the PFAS-contaminated groundwater was complex and 9 PFAS were detected in the reference groundwater and 17 PFAS were detected in the contaminated groundwater. The summed PFAS concentrations ranged from 120 to 140 ng L-1 in reference groundwater and 6100 to 15,000 ng L-1 in contaminated groundwater. Biotic concentration factors (CFb) for individual PFAS were species, sex, source, and compound-specific and ranged from 2.9 to 1000 L kg-1 in whole-body male fish exposed to contaminated groundwater for 21 days. The fish and mussel CFb generally increased with increasing fluorocarbon chain length and were greater for sulfonates than for carboxylates. The exception was perfluorohexane sulfonate, which deviated from the linear trend and had a 10-fold difference in CFb between sites, possibly because of biotransformation of precursors such as perfluorohexane sulfonamide. Uptake for most PFAS in male fish was linear over time, whereas female fish had bilinear uptake indicated by an initial increase in tissue concentrations followed by a decrease. Uptake of PFAS was less for mussels (maximum CFb = 200) than for fish, and mussel uptake of most PFAS also was bilinear. Although abiotic concentration factors were greater than CFb, and values for POCIS were greater than for PETS, passive samplers were useful for assessing PFAS that potentially bioconcentrate in fish but are present at concentrations below method quantitation limits in water. Passive samplers also accumulate short-chain PFAS that are not bioconcentrated.

Validation of UV/persulfate as a PFAS treatment of industrial wastewater and environmental samples

The contamination of natural water and industrial wastewater with per- and polyfluoroalkyl substances (PFAS) occurs globally. Thus, proper technologies are required to reduce PFAS in the environment and mitigate the adverse effects of these pollutants on human health and the environment. This study used a 23 full factorial design to evaluate the importance of operating factors including the level of persulfate (PS), the initial concentration of PFAS, and the time to the photochemical degradation of PFAS via ultraviolet irradiation at 185/254 nm assisted with persulfate (PS/UV method) in spiked solution. The method was then applied to break down PFAS in industrial wastewater, landfill leachate and groundwater samples using the highest factor levels applied in the 23 full factorial design. The results showed that the three investigated factors played an important role in the degradation of PFAS. The highest PFAS degradation was 57 % perfluorobutanoic acid (PFBA), 80 % perfluorooctanoic acid (PFOA) and 60 % perfluorooctane sulfonate (PFOS) using 10 mg L−1 PFAS, 5 g L−1 PS for 4 h. The defluorination also increased in the presence of PS but decreased in the presence of potassium hydrogen phthalate, nitrates, and chlorides. The PS/UV method decreased the concentration of PFAS in wastewater samples by 20–25 % PFOS and 13–15 % perfluorohexane sulfonate (PFHxS). PFAS degradation in wastewater improved with increasing treatment time. Under the PS/UV treatment, the degradation of major PFAS in groundwater was 94 % 6–2 FTS, 75 % PFOA, 62 % PFOS and 61 % PFHxS. The removal of major compounds in landfill leachate reached up to 12 % PFHxA, 32 % PFPeA, 56 % PFOA and 43 % PFOS. Our study indicated matrix effects leading to decreased PFAS degradation in different contaminated waters. The level of PS should also be controlled to an optimal value because higher levels led to a decrease in treatment efficiency.

Adsorption of PFOS onto graphite intercalated compound and analysis of degradation by-products during electro-chemical oxidation

Perfluorooctane sulfonate (PFOS) is a highly recalcitrant perfluoro chemical belonging to the family of per- and polyfluoroalkyl substances (PFAS). Its adsorption and degradation was demonstrated in a novel PFAS remediation process involving the adsorption onto graphite intercalated compounds (GIC) and the electrochemical oxidation. The Langmuir type of adsorption was characterized by a loading capacity of 53.9 μg PFOS g−1 GIC and a second order kinetics (0.021 g μg−1 min−1). Up to 99% of PFOS was degraded in the process with a half-life of 15 min. The breakdown by-products included short chain perfluoroalkane sulfonates such as Perfluoroheptanesulfonate (PFHpS), Perfluorohexanesulfonate (PFHxS), Perfluoropentanesulfonate (PFPeS) and Perfluorobutanesulfonate (PFBS), but also short chain perfluoro carboxylic acids such as perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and perfluorobutanoic acid (PFBA) indicating different degradation pathways. These by-products could also be broken down but the shorter the chain the slower the degradation rate. This novel combined adsorption and electrochemical process offers an alternative treatment for PFAS contaminated waters.

Erratum: Current Breast Milk PFAS Levels in the United States and Canada: After All This Time, Why Don't We Know More?

Vol. 131, No. 3 ErratumOpen AccessErratum: Current Breast Milk PFAS Levels in the United States and Canada: After All This Time, Why Don’t We Know More?is correction ofCurrent Breast Milk PFAS Levels in the United States and Canada: After All This Time, Why Don’t We Know More? Judy S. LaKind, Marc-André Verner, Rachel D. Rogers, Helen Goeden, Daniel Q. Naiman, Satori A. Marchitti, Geniece M. Lehmann, Erin P. Hines, and Suzanne E. Fenton Judy S. LaKind Search for more papers by this author , Marc-André Verner Search for more papers by this author , Rachel D. Rogers Search for more papers by this author , Helen Goeden Search for more papers by this author , Daniel Q. Naiman Search for more papers by this author , Satori A. Marchitti Search for more papers by this author , Geniece M. Lehmann Search for more papers by this author , Erin P. Hines Search for more papers by this author , and Suzanne E. Fenton https://orcid.org/0000-0002-8956-398X Search for more papers by this author Published:17 March 2023CID: 039001https://doi.org/10.1289/EHP12915AboutSectionsPDF ToolsDownload CitationsTrack Citations ShareShare onFacebookTwitterLinked InReddit During the paper editing process, two values in Table 2 were mistakenly modified. Milk:serum concentration ratios from the “Kärrman et al. 2007” study should be 0.01 for PFOS and 0.01 PFNA. This error affects values in Table 2 only. All calculations were performed with the correct values.The authors regret the error.Table 2 Published milk:serum concentration ratios for PFOA, PFOS, PFHxS, and PFNA.StudyCountryPFOAPFOSPFHxSPFNACariou et al. 2015France0.038 (lowercase italic n equals 10n=10)0.011 (lowercase italic n equals 19n=19)0.012 (lowercase italic n equals 8n=8)—Kärrman et al. 2007Sweden0.12 (lowercase italic n equals 1n=1)0.01 (lowercase italic n equals 12n=12)0.02 (lowercase italic n equals 12n=12)0.01 (lowercase italic n equals 2n=2)Kim et al. 2011Korea0.025 (lowercase italic n equals 17n=17)0.011 (lowercase italic n equals 17n=17)0.008 (lowercase italic n equals 17n=17)—Liu et al. 2011China0.11 (lowercase italic n equals 50n=50)0.02 (lowercase italic n equals 50n=50)—0.05 (lowercase italic n equals 50n=50)Mean0.07330.01300.01330.030Note: lowercase italic n equalsn=number of samples with measured milk and serum concentrations within individual studies. —, no data; PFHxS, perfluorohexane sulfonate; PFNA, perfluorononanoic acid; PFOA, perfluorooctanoic acid; PFOS, perfluorooctane sulfonate.FiguresReferencesRelatedDetailsRelated articlesCurrent Breast Milk PFAS Levels in the United States and Canada: After All This Time, Why Don’t We Know More?23 February 2022Environmental Health Perspectives Vol. 131, No. 3 March 2023Metrics About Article Metrics Publication History Manuscript received17 February 2023Manuscript accepted23 February 2023Originally published17 March 2023 Financial disclosuresPDF download License information EHP is an open-access journal published with support from the National Institute of Environmental Health Sciences, National Institutes of Health. All content is public domain unless otherwise noted. Note to readers with disabilities EHP strives to ensure that all journal content is accessible to all readers. However, some figures and Supplemental Material published in EHP articles may not conform to 508 standards due to the complexity of the information being presented. If you need assistance accessing journal content, please contact [email protected]. Our staff will work with you to assess and meet your accessibility needs within 3 working days.

Role of bioavailability and protein binding of four anionic perfluoroalkyl substances in cell-based bioassays for quantitative in vitro to in vivo extrapolations

Perfluoroalkyl substances (PFAS) are persistent and pose a risk to human health. High throughput screening (HTS) cell-based bioassays may inform risk assessment of PFAS provided that quantitative in vitro to in vivo extrapolation (QIVIVE) can be developed. The QIVIVE ratio is the ratio of nominal (Cnom) or freely dissolved concentration (Cfree) in human blood to Cnom or Cfree in the bioassays. Considering that the concentrations of PFAS in human plasma and in vitro bioassays may vary by orders of magnitude, we tested the hypothesis that anionic PFAS bind to proteins concentration-dependently and therefore the binding differs substantially between human plasma and bioassays, which has an impact on QIVIVE. Solid phase microextraction (SPME) with C18-coated fibers served to quantify the Cfree of four anionic PFAS (perfluorobutanoate (PFBA), perfluorooctanoate (PFOA), perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonate (PFOS)) in the presence of proteins and lipid, medium components, cells and human plasma over five orders of magnitude in concentrations. The C18-SPME method was used to quantify the non-linear binding to proteins, human plasma and medium, and the partition constants to cells. These binding parameters were used to predict Cfree of PFAS in cell bioassays and human plasma by a concentration-dependent mass balance model (MBM). The approach was illustrated with a reporter gene assay indicating activation of the peroxisome proliferator-activated receptor gamma (PPARγ-GeneBLAzer). Blood plasma levels were collected from literature for occupational exposure and the general population. The QIVIVEnom ratios were higher than the QIVIVEfree ratios due to the strong affinity to proteins and large differences in protein contents between human blood and bioassays. For human health risk assessment, the QIVIVEfree ratios of many in vitro assays need to be combined to cover all health relevant endpoints. If Cfree cannot be measured, they can be estimated with the MBM and concentration-dependent distribution ratios.

Perfluorinated compound correlation between human serum and drinking water: Is drinking water a significant contributor?

Perfluorinated compounds (PFASs) are a new artificial chemical. Due to its substantial toxicity and complex degradation in the natural environment, monitoring PFASs has become a hot issue for many researchers. Currently, the relationship between the concentration of PFASs in serum and the concentration of PFASs in drinking water is unclear. This paper aims to study the concentration levels of PFASs in drinking water and residents' serum in a city in northern China and the relationship between them. The results show that the concentration of PFASs in drinking water is low, and the average concentrations of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) were 2.57 ± 0.69 ng/L and 0.30 ng/L, respectively, which were lower than the limits specified in China's newly introduced Standards for drinking water quality (GB 5749-2022). In the serum of residents, PFOA and PFOS were the two PFASs with the highest concentration. Spearman correlation analysis showed that perfluorohexane sulfonate (PFHxS) and PFOS concentrations were positively correlated with age, and PFHxS, PFOA, PFNA, and PFOS varied with sex. At the same time, the correlation analysis also showed no correlation between PFAS in drinking water and serum, indicating that drinking water was not the main factor causing the physical burden of PFAS in residents. The HI method was used to assess the health risks of PFASs to human beings. The risk entropy of all PFASs for human hepatotoxicity and reproductive toxicity is below 1.

Perfluoroalkyl substance exposure is associated with asthma and innate immune cell count in US adolescents stratified by sex.

Exposure to perfluoroalkyl substances (PFAS) may be harmful to humans; however, previous studies have been inconsistent regarding the potential for PFAS-induced immunosuppresion. This study explored the relationship between PFAS exposure and risks of asthma, wheezing, and immunosuppression in 12-19year-olds using the National Health and Nutrition Examination Survey (NHANES) data. Logistic regression models were used to reveal associations between serum PFAS levels and risks of asthma, wheezing, asthma attack, and emergency department visits. Pearson's correlation was used to determine the relationship between serum PFAS levels and leukocyte count. Data were also stratified by sex. We found that medium-low levels of serum perfluorooctane sulfonate (PFOS) (6.90-12.40ng/mL) and serum perfluorooctanoic acid (PFOA) (2.43-3.60ng/mL) were negatively related, respectively, to current asthma and wheezing in boys, and to wheezing in girls. Meanwhile, boys with medium-high levels (1.50-3.00ng/mL) of serum perfluorohexanesulfonate (PFHxS) had a high risk of wheezing. Among asthmatic participants, both medium-high levels (3.75-5.07ng/mL) of serum PFOA and high levels (> 3.92ng/mL) of PFHxS correlated with asthma attacks in boys; likewise, medium-low levels (0.70-0.99ng/mL) of serum PFNA correlated with asthma attacks in girls. Also, PFOA and PFNA levels were weakly positively correlated with basophil count, whereas PFOS levels were weakly negatively correlated with eosinophils in asthmatic boys, indicating that basophils may be important in the immune response to PFAS exposure among asthmatics.

Spatio-temporal trends in livestock exposure to per- and polyfluoroalkyl substances (PFAS) inform risk assessment and management measures

The migration of per- and polyfluoroalkyl substances (PFAS) onto agricultural properties has resulted in the accumulation of PFAS in livestock. The environmental determinants of PFAS accumulation in livestock from the grazing environment are poorly understood, resulting in limited capacity to manage livestock exposure and subsequent transfer of PFAS through the food chain. Analytical- (n = 978 samples of soil, water, pasture, and serum matrices), farm management/practice- and livestock physiology data were collated and interrogated from environmental PFAS investigations across ten farms, from four agro-ecological regions of Victoria (Australia). Statistical analysis identified perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) as key analytes of concern for livestock bioaccumulation. PFOS and PFHxS concentrations in livestock drinking water were positively correlated with serum concentrations while other intake pathways (pasture and soil) had weaker correlations. Seasonal trends in PFAS body burden (serum concentrations) were identified and suggested to be linked to seasonal grazing behaviours and physiological water requirements. The data showed for the first time that livestock exposure to PFAS is dynamic and with relatively short elimination half-lives, there is opportunity for exposure management. Meat from cattle, grazed on PFAS impacted sites, may exceed health-based guideline values for PFAS, especially for markets with low limits (like the European Commission Maximum Limits or EC MLs). This study found that sites with mean livestock drinking water concentrations as low as 0.003 μg PFOS/L may exceed the EC ML for PFOS in cattle meat. Risk assessment can be used to prioritise site cleanup and development of management plans to reduce PFAS body burden by considering timing of stock rotation and/or supplementation of primary exposure sources.

Association between maternal exposure to per- and polyfluoroalkyl substances and serum markers of liver function during pregnancy in China: A mixture-based approach

Previous studies have shown that per- and polyfluoroalkyl substances (PFAS) may have hepatotoxic effects in animals. However, epidemiological evidence in humans, especially pregnant women, is limited. This study aimed to assess the association of single and multiple PFAS exposure with serum markers of liver function in pregnant women. A total of 420 pregnant women from the Guangxi Zhuang Birth Cohort were enrolled from June 2015 to April 2019. Nine PFAS were measured in the maternal serum in early pregnancy. Data for liver function biomarkers, namely, alanine aminotransferase (ALT), aspartate aminotransferase (AST), gamma-glutamyltransferase (GGT), total bilirubin (TBIL), direct bilirubin (DBIL), and indirect bilirubin (IBIL), were obtained from medical records. In generalized linear model (GLM), there was a positive association of perfluorooctane sulfonate (PFOS) with ALT, perfluorodecanoic acid (PFDA) and perfluorobutanesulfonic acid (PFBS) with GGT, and perfluorohexane sulfonate (PFHxS) with TBIL and IBIL. In contrast, there was a negative association of perfluoroheptanoic acid (PFHpA) with TBIL. There were inverse U-shaped relationships of PFUnA with ALT and AST and PFDA with ALT by restricted cubic spline. The weighted quantile sum (WQS) regression model revealed the positive effects of the PFAS mixture on GGT, TBIL, DBIL, and IBIL. Bayesian kernel machine regression (BKMR) analysis confirmed that the PFAS mixture was positively associated with GGT, and PFBS was the main contributor. In addition, the BKMR model showed a positive association of individual PFBS with GGT, individual PFHxS with TBIL and IBIL, and a negative association of individual PFHpA with TBIL. Our findings provide evidence of an association between individual PFAS, PFAS mixture and maternal serum markers of liver function during pregnancy. Additionally, these findings also enhance concerns over PFAS exposure on maternal liver function and PFAS monitoring in pregnancy, reducing the effect of maternal liver dysfunction on maternal and infant health.

Association of per- and polyfluoroalkyl substance exposure with fatty liver disease risk in US adults

Per- and polyfluoroalkyl substances (PFAS) are widespread pollutants with demonstrated hepatotoxicity. Few studies have examined the association between PFAS and fatty liver disease (FLD) risk in an adult population. In this cross-sectional study of participants from the 2017-2018 National Health and Nutrition Examination Survey, serum PFAS were measured, and FLD cases were ascertained by vibration-controlled transient elastography. Logistic regression models were used to examine the association between circulating PFAS levels and FLD risk. Analyses were stratified into non-alcoholic FLD and alcoholic FLD risk groups by alcohol intake status, as well as controlling for other risk factors, including personal demographics, lifestyle factors, and related health factors. Among 1,135 eligible participants, 446 had FLD. For FLD risk, the multivariable-adjusted odds ratio per log-transformed SD increase (ORSD) in perfluorohexane sulfonate (PFHxS) was 1.13 (95% CI 1.01-1.26). The association between PFHxS and FLD appeared stronger among individuals with obesity or high-fat diets (both p interaction <0.05). When limiting the analysis to 212 heavy drinkers (≥2 drinks/day for women and ≥3 drinks/day for men), significantly higher risk of alcoholic FLD was found for higher levels of perfluorooctanoic acid (ORSD 1.79; 95% CI 1.07-2.99), PFHxS (ORSD 2.06; 95% CI 1.17-3.65), and perfluoroheptane sulfonic acid (ORSD 1.44; 95% CI 1.00-2.07), and marginally significant higher risk for total PFAS (ORSD 2.12; 95% CI 0.99-4.54). In never or light drinkers, we did not observe any significant association between PFAS and non-alcoholic FLD. Significant positive associations were found for PFAS with aspartate aminotransferase, gamma-glutamyl transaminase, total bilirubin, and albumin (β ranged from 0.008 to 0.101, all p <0.05). Higher serum PFAS was moderately associated with FLD risk and worse liver function in the general population, and among those with independent risk factors, including heavy alcohol intake, obesity, or high-fat diets, PFAS increased the risk. These results suggest synergistic effects on hepatic steatosis between PFAS exposures as measured through biomonitoring data and lifestyle risk factors in a nationally representative US population. The per- and polyfluoroalkyl substances (PFAS) may convey higher risk for chronic liver disease in humans. Among 1,135 US adults in the 2017-2018 National Health and Nutrition Examination Survey, we found that higher serum PFAS was associated with higher fatty liver disease risk and worse liver function, especially among those with liver disease risk factors, including heavy alcohol intake, obesity, or high-fat diets. Continuously monitoring PFAS in the population and examining how they potentiate risk to the liver are essential.

Association between perfluoroalkyl substances exposure and the prevalence of nonalcoholic fatty liver disease in the different sexes: a study from the National Health and Nutrition Examination Survey 2005-2018.

There is evidence that perfluoroalkyl substances (PFASs) have effects on liver toxicity, and the effects may exhibit sex differences. Our study aims to explore the association between exposure to four PFASs (perfluorooctanoic acid, PFOA; perfluorooctane sulfonate, PFOS; perfluorohexane sulfonate, PFHxS; and perfluorononanoate, PFNA) and the risk of nonalcoholic fatty liver disease (NAFLD) in adults ≥ 20years old in the US population. The data were based on the National Health and Nutrition Examination Survey (NHANES) 2005-2018. We used Poisson regression to explore the association between the four PFASs and NAFLD. We included 3464 participants; of these, 1200 (34.64%) individuals were defined as having NAFLD, and the prevalence of NAFLD was 39.52% in men and 30.40% in women. After Poisson regression, among the premenopausal and postmenopausal and total women, PFOA had a significantly positive association with NAFLD (p < 0.05). After principal component analysis, the "composite PFAS" was associated with NAFLD in postmenopausal and total women, and the RRs (95% CIs) were 1.306 (1.075, 1.586) and 1.161 (1.007, 1.339), respectively. In adults, we found that PFASs were associated with NAFLD, and the associations varied by sex, particularly for PFOA and PFNA, which had a positive association with NAFLD in women.