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1.
Proc Natl Acad Sci U S A ; 121(31): e2400525121, 2024 Jul 30.
Article in English | MEDLINE | ID: mdl-39042683

ABSTRACT

Per- and polyfluoroalkyl substances (PFAS), particularly the perfluorinated ones, are recalcitrant to biodegradation. By integrating an enrichment culture of reductive defluorination with biocompatible electrodes for the electrochemical process, a deeper defluorination of a C6-perfluorinated unsaturated PFAS was achieved compared to the biological or electrochemical system alone. Two synergies in the bioelectrochemical system were identified: i) The in-series microbial-electrochemical defluorination and ii) the electrochemically enabled microbial defluorination of intermediates. These synergies at the material-microbe interfaces surpassed the limitation of microbial defluorination and further turned the biotransformation end products into less fluorinated products, which could be less toxic and more biodegradable in the environment. This material-microbe hybrid system brings opportunities in the bioremediation of PFAS driven by renewable electricity and warrants future research on mechanistic understanding of defluorinating and electroactive microorganisms at the material-microbe interface for system optimizations.


Subject(s)
Biodegradation, Environmental , Anaerobiosis , Halogenation , Electrodes/microbiology , Fluorocarbons/metabolism , Fluorocarbons/chemistry , Electrochemical Techniques/methods , Bacteria/metabolism
2.
Int J Cancer ; 154(6): 979-991, 2024 Mar 15.
Article in English | MEDLINE | ID: mdl-37902275

ABSTRACT

Human exposure to per- and polyfluoroalkyl substances (PFAS) occurs globally through contaminated food, dust, and drinking water. Studies of PFAS and thyroid cancer have been limited. We conducted a nested case-control study of prediagnostic serum levels of 19 PFAS and papillary thyroid cancer (400 cases, 400 controls) in the Finnish Maternity Cohort (pregnancies 1986-2010; follow-up through 2016), individually matched on sample year and age. We used conditional logistic regression to estimate odds ratios (OR) and 95% confidence intervals (CI) for log2 transformed and categorical exposures, overall and stratified by calendar period, birth cohort, and median age at diagnosis. We adjusted for other PFAS with Spearman correlation rho = 0.3-0.6. Seven PFAS, including perfluoroctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), N-ethyl-perfluorooctane sulfonamidoacetic acid (EtFOSAA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluorohexane sulfonic acid (PFHxS) were detected in >50% of women. These PFAS were not associated with risk of thyroid cancer, except for PFHxS, which was inversely associated (OR log2 = 0.82, 95% CI: 0.70-0.97). We observed suggestive but imprecise increased risks associated with PFOA, PFOS, and EtFOSAA for those diagnosed at ages <40 years, whereas associations were null or inverse among those diagnosed at 40+ years (P-interaction: .02, .08, .13, respectively). There was little evidence of other interactions. These results show no clear association between PFAS and papillary thyroid cancer risk. Future work would benefit from evaluation of these relationships among those with higher exposure levels and during periods of early development when the thyroid gland may be more susceptible to environmental harms.


Subject(s)
Alkanesulfonic Acids , Environmental Pollutants , Fluorocarbons , Sulfonic Acids , Thyroid Neoplasms , Humans , Female , Pregnancy , Thyroid Cancer, Papillary/epidemiology , Case-Control Studies , Finland/epidemiology , Fluorocarbons/adverse effects , Thyroid Neoplasms/epidemiology , Thyroid Neoplasms/etiology
3.
Am J Epidemiol ; 193(8): 1182-1196, 2024 Aug 05.
Article in English | MEDLINE | ID: mdl-38400646

ABSTRACT

We synthesized the epidemiologic evidence on the associations between per- and polyfluoroalkyl substances (PFAS) exposure and breast cancer risk. Our systematic review and meta-analysis included 18 and 11 articles, respectively, covering studies up to February 2023. The summary relative risks (RRs) estimated by random-effects meta-analyses did not support an association between PFAS and overall breast cancer risk (eg, a natural log (ln)-unit increase in serum/plasma concentrations [ng/mL] for perfluorooctanoate [PFOA] RR = 0.95; 95% CI, 0.77-1.18; perfluorooctane sulfonate [PFOS] RR = 0.98; 95% CI, 0.87-1.11). However, when limiting to studies that assessed exposures prior to a breast cancer diagnosis, we observed a positive association with PFOA (a ln-unit increase, RR = 1.16; 95% CI, 0.96-1.40). We also observed some possible heterogeneous associations by tumor estrogen and progesterone receptor status among postmenopausal breast cancer cases. No meaningful changes were observed after excluding the studies with high risk of bias (Tier 3). Based on the evaluation tool developed by the National Toxicology Program, given the heterogeneity across studies and the variability in timing of exposure measurements, the epidemiologic evidence needed to determine the association between PFAS exposure and breast cancer remains inadequate. Our findings support the need for future studies with improved study designs to determine this association.


Subject(s)
Breast Neoplasms , Caprylates , Environmental Exposure , Fluorocarbons , Humans , Breast Neoplasms/epidemiology , Breast Neoplasms/chemically induced , Breast Neoplasms/blood , Fluorocarbons/blood , Fluorocarbons/adverse effects , Female , Caprylates/blood , Environmental Exposure/adverse effects , Alkanesulfonic Acids/blood , Epidemiologic Studies
4.
Toxicol Appl Pharmacol ; 491: 117047, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39111555

ABSTRACT

Per- and polyfluoroalkyl substances (PFAS) bioaccumulate in different organ systems, including bone. While existing research highlights the adverse impact of PFAS on bone density, a critical gap remains in understanding the specific effects on the bone marrow microenvironment, especially the bone marrow adipose tissue (BMAT). Changes in BMAT have been linked to various health consequences, such as the development of osteoporosis and the progression of metastatic tumors in bone. Studies presented herein demonstrate that exposure to a mixture of five environmentally relevant PFAS compounds promotes marrow adipogenesis in vitro and in vivo. We show that among the components of the mixture, PFHxS, an alternative to PFOS, has the highest propensity to accumulate in bone and effectively promote marrow adipogenesis. Utilizing RNAseq approaches, we identified the peroxisome proliferator-activated receptor (PPAR) signaling as a top pathway modulated by PFHxS exposure. Furthermore, we provide results suggesting the activation and involvement of PPAR-gamma (PPARγ) in PFHxS-mediated bone marrow adipogenesis, especially in combination with high-fat diet. In conclusion, our findings demonstrate the potential impact of elevated PFHxS levels, particularly in occupational settings, on bone health, and specifically bone marrow adiposity. This study contributes new insights into the health risks of PFHxS exposure, urging further research on the relationship between environmental factors, diet, and adipose tissue dynamics.


Subject(s)
Adipogenesis , Bone Marrow , Fluorocarbons , Mice, Inbred C57BL , PPAR gamma , Sulfonic Acids , Adipogenesis/drug effects , Animals , Fluorocarbons/toxicity , Mice , Bone Marrow/drug effects , Bone Marrow/metabolism , PPAR gamma/metabolism , Sulfonic Acids/toxicity , Male , Signal Transduction/drug effects , Bone Marrow Cells/drug effects , Bone Marrow Cells/pathology , Adipose Tissue/drug effects , Adipose Tissue/metabolism
5.
Toxicol Appl Pharmacol ; 490: 117044, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39074624

ABSTRACT

BACKGROUND: Many studies have reported that prenatal exposure to Per- and Polyfluoroalkyl Substances (PFASs) can disrupt immune function. However, little is known about the effects of PFASs on immune molecules. The study analyzed the association between prenatal exposure to mixed and single PFASs and plasma immune molecules in three-year-old children. METHODS: Ten PFASs were measured in umbilical cord serum, while peripheral blood samples were collected at age three to measure immune molecules. Associations between exposure to individual and combined PFASs and immune molecules were analyzed using Generalized Linear Models and Weighted Quantile Sum (WQS) regression. RESULTS: (1) Interleukin-4 (IL-4) increased by 23.85% (95% CI:2.99,48.94) with each doubling of Perfluorooctanoic Acid (PFOA), and Interleukin-6 (IL-6) increased by 39.07% (95%CI:4.06,85.86) with Perfluorotridecanoic Acid (PFTrDA). Elevated PFOA and Perfluorononanoic Acid (PFNA) were correlated with increases of 34.06% (95% CI: 6.41, 70.28) and 24.41% (95% CI: 0.99, 53.27) in Eotaxin-3, respectively. Additionally, the doubling of Perfluorohexane Sulfonic Acid (PFHxS) was associated with a 9.51% decrease in Periostin (95% CI: -17.84, -0.33). (2) The WQS analysis revealed that mixed PFASs were associated with increased IL-6 (ß = 0.37, 95%CI:0.04,0.69), mainly driven by PFTrDA, PFNA, and 8:2 Chlorinated Perfluoroethyl Sulfonamide (8:2 Cl-PFESA). Moreover, mixed PFASs were linked to an increase in Eotaxin-3 (ß = 0.32, 95% CI: 0.09,0.55), primarily influenced by PFOA, PFTrDA, and Perfluorododecanoic Acid (PFDoDA). CONCLUSIONS: Prenatal PFASs exposure significantly alters the levels of immune molecules in three-year-old children, highlighting the importance of understanding environmental impacts on early immune development.


Subject(s)
Fluorocarbons , Prenatal Exposure Delayed Effects , Humans , Female , Fluorocarbons/blood , Fluorocarbons/toxicity , Child, Preschool , Pregnancy , Prenatal Exposure Delayed Effects/blood , Prenatal Exposure Delayed Effects/immunology , Prenatal Exposure Delayed Effects/chemically induced , China/epidemiology , Male , Environmental Pollutants/blood , Fetal Blood/immunology , Fetal Blood/chemistry , Caprylates/blood , Caprylates/toxicity , Interleukin-6/blood , Interleukin-4/blood , Decanoic Acids/blood , Decanoic Acids/toxicity , Alkanesulfonic Acids/blood , Alkanesulfonic Acids/toxicity , Adult , Maternal Exposure/adverse effects
6.
Environ Sci Technol ; 58(37): 16291-16301, 2024 Sep 17.
Article in English | MEDLINE | ID: mdl-39226190

ABSTRACT

Previous studies regarding the associations between perfluoroalkyl and polyfluoroalkyl substances (PFAS) and autism spectrum disorder (ASD) have yielded inconsistent results, with the underlying mechanisms remaining unknown. In this study, we quantified 13 PFAS in cord serum samples from 396 neonates and followed the children at age 4 to assess ASD-related symptoms. Our findings revealed associations between certain PFAS and ASD-related symptoms, with a doubling of perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA) concentrations associated with respective increases of 1.79, 1.62, and 1.45 units in language-related symptoms and PFDA exhibiting an association with higher score of sensory stimuli. Nonlinear associations were observed in the associations of 6:2 chlorinated polyfluorinated ether sulfonate (Cl-PFAES) and 8:2 Cl-PFAES with ASD-related symptoms. Employing weighted quantile sum (WQS) regression, we observed significant mixture effects of multiple PFAS on all domains of ASD-related symptoms, with PFNA emerging as the most substantial contributor. Assuming causality, we found that 39-40% of the estimated effect of long-chain PFAS (PFUnDA and PFDoDA) exposure on sensory stimuli was mediated by androstenedione. This study provides novel epidemiological data about prenatal PFAS mixture exposure and ASD-related symptoms.


Subject(s)
Autism Spectrum Disorder , Fluorocarbons , Prenatal Exposure Delayed Effects , Humans , Female , Autism Spectrum Disorder/epidemiology , Pregnancy , Child, Preschool , Male , Infant, Newborn , Decanoic Acids
7.
Environ Sci Technol ; 58(35): 15779-15789, 2024 Sep 03.
Article in English | MEDLINE | ID: mdl-39168926

ABSTRACT

The Yangtze River Estuary is the terminal sink of terrestrial per- and polyfluoroalkyl substances (PFAS) from the Yangtze River, while the environmental fate characteristics of legacy and emerging PFAS around this region have rarely been discussed. Here, 24 targeted PFAS in seawater, sediments, suspended particulate matter (SPM), and plankton in the offshore region adjacent to this estuary were investigated. The three dominant PFAS in all phases were perfluorooctanoic acid (PFOA, 23.8-61.9%), perfluorobutanoic acid (PFBA, 23.6-42.8%), and perfluoro(2-methyl-3-oxahexanoic) acid (HFPO-DA, 6.1-12.1%), and perfluoro-1-butane sulfonamide (FBSA, 0.1-7.3%) was first detected. The horizontal distributions of PFAS were dependent on salinity and disturbed by multiple water masses, while the vertical variations could be explained by their different partitioning characteristics in the water-SPM-sediment system (partition coefficients, Log Kd and Log Koc) and plankton (bioaccumulation factors, Log BAF). Although physical mixing was the major driver for PFAS settling (>83.7%), the absolute settling amount caused by the biological pump was still high (150.00-41994.65 ng m-2 day-1). More importantly, we found unexpected high Log Kd values of PFBA (2.24-4.55) and HFPO-DA (2.26-4.67), equal to PFOA (2.28-4.72), which brought concerns about their environmental persistence. Considering the increased detection of short-chain and emerging PFAS, more comprehensive environmental behaviors analysis is required urgently.


Subject(s)
Environmental Monitoring , Estuaries , Rivers , Water Pollutants, Chemical , Rivers/chemistry , Water Pollutants, Chemical/analysis , Fluorocarbons , Seawater/chemistry , China , Geologic Sediments/chemistry
8.
Environ Sci Technol ; 2024 Sep 09.
Article in English | MEDLINE | ID: mdl-39250774

ABSTRACT

Firefighting foam is a significant source of per- and polyfluoroalkyl substances (PFAS) pollution, yet the PFAS profiles in foam formulations, particularly in China, remain unclear. Here, using target and nontarget analyses, we investigated 50 target PFAS in firefighting foams currently utilized in China, identified novel PFAS, and discovered new end products through a total oxidizable precursor (TOP) assay. We identified a total of 54 PFAS compounds (spanning 34 classes and containing seven novel PFAS) with total PFAS concentrations of 0.03-21.21 mM. Among seven novel PFAS, four PFAS met persistence, bioaccumulation, and toxicity criteria, and another PFAS had the highest ToxPi score among the identified 54 PFAS. Moreover, the predominant PFAS varied significantly in the studied foams and differed markedly from those used in other countries. After the TOP assay, nontarget analysis uncovered 1.1-55.5% more PFAS precursors and 8.25-55.5% more fluorine equivalents compared to traditional target analysis combined with TOP assay. Specifically, three double-bond perfluorinated alcohols were identified for the first time as end products of the TOP assay. This study provides crucial information for pollution control and risk assessment associated with PFAS in firefighting foam applications and emphasizes the importance of combining nontarget analysis with TOP assay in uncovering unknown PFAS precursors.

9.
Environ Sci Technol ; 58(21): 9314-9327, 2024 May 28.
Article in English | MEDLINE | ID: mdl-38709515

ABSTRACT

Globally implemented ecological risk assessment (ERA) guidelines marginalize hormesis, a biphasic dose-response relationship characterized by low-dose stimulation and high-dose inhibition. The present study illuminated the promise of hormesis as a scientific dose-response model for ERA of per- and polyfluoroalkyl substances (PFAS) represented by perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). A total of 266 hormetic dose-response relationships were recompiled from 1237 observations, covering 30 species from nine representative taxonomic groups. The standardized hormetic amplitudes followed the log-normal probability distribution, being subject to the limits of biological plasticity but independent of stress inducers. The SHapley Additive exPlanations algorithm revealed that the target endpoint was the most important variable explaining the hormetic amplitudes. Subsequently, quantitative frameworks were established to incorporate hormesis into the predicted no-effect concentration levels, with a lower induction dose and a zero-equivalent point but a broader hormetic zone for PFOS. Realistically, 10,117 observed concentrations of PFOA and PFOS were gathered worldwide, 4% of which fell within hormetic zones, highlighting the environmental relevance of hormesis. Additionally, the hormesis induction potential was identified in other legacy and emerging PFAS as well as their alternatives and mixtures. Collectively, it is time to incorporate the hormesis concept into PFAS studies to facilitate more realistic risk characterizations.


Subject(s)
Hormesis , Risk Assessment , Water Pollutants, Chemical , Fluorocarbons , Alkanesulfonic Acids , Caprylates
10.
Environ Sci Technol ; 58(29): 12875-12887, 2024 Jul 23.
Article in English | MEDLINE | ID: mdl-38980177

ABSTRACT

There has been widespread concern about the health hazards of per- and polyfluoroalkyl substances (PFAS), which may be the risk factor for hyperuricemia with evidence still insufficient in the general population in China. Here, we conducted a nationwide study involving 9,580 adults aged 18 years or older from 2017 to 2018, measured serum concentrations of uric acid and PFAS (PFOA, PFOS, 6:2 Cl-PFESA, PFNA, PFHxS) in participants, to assess the associations of individual PFAS with hyperuricemia, and estimated a joint effect of PFAS mixtures. We found positive associations of higher serum PFAS with elevated odds of hyperuricemia in Chinese adults, with the greatest contribution from PFOA (69.37%). The nonmonotonic dose-response (NMDR) relationships were observed for 6:2 Cl-PFESA and PFHxS with hyperuricemia. Participants with less marine fish consumption, overweight, and obesity may be the sensitive groups to the effects of PFAS on hyperuricemia. We highlight the potential health hazards of legacy long-chain PFAS (PFOA) once again because of the higher weights of joint effects. This study also provides more evidence about the NMDR relationships in PFAS with hyperuricemia and emphasizes a theoretical basis for public health planning to reduce the health hazards of PFAS in sensitive groups.


Subject(s)
Hyperuricemia , Hyperuricemia/epidemiology , Hyperuricemia/blood , Humans , Cross-Sectional Studies , Adult , Male , Female , Fluorocarbons/blood , Middle Aged , China/epidemiology , Uric Acid/blood
11.
Environ Sci Technol ; 58(3): 1648-1658, 2024 Jan 23.
Article in English | MEDLINE | ID: mdl-38175212

ABSTRACT

The semiconductor industry has claimed that perfluorooctanesulfonate (PFOS), a persistent per- and polyfluoroalkyl substance (PFAS), has been eliminated from semiconductor production; however, information about the use of alternative compounds remains limited. This study aimed to develop a nontarget approach to discovering diverse PFAS substitutions used in semiconductor manufacturing. A distinct fragment-based approach has been established to identify the hydrophobic and hydrophilic features of acidic and neutral fluorosurfactants through fragments and neutral losses, including those outside the homologous series. Ten sewage samples from 5 semiconductor plants were analyzed with target and nontarget analysis. Among the 20 identified PFAS spanning 12 subclasses, 15 were reported in semiconductor sewage for the first time. The dominant identified PFAS compounds were C4 sulfonamido derivatives, including perfluorobutane sulfonamido ethanol (FBSE), perfluorobutane sulfonamide (FBSA), and perfluorobutane sulfonamido diethanol (FBSEE diol), with maximum concentrations of 482 µg/L, 141 µg/L, and 83.5 µg/L in sewage, respectively. Subsequently, three ultrashort chain perfluoroalkyl acids (PFAAs) were identified in all samples, ranging from 0.004 to 19.9 µg/L. Three effluent samples from the associated industrial wastewater treatment plants (WWTPs) were further analyzed. This finding, that the C4 sulfonamido acetic acid series constitutes a significant portion (65%-82%) of effluents from WWTP3 and WWTP4, emphasizes the conversion of fluorinated alcohols to fluorinated acids during aerobic treatment. The identification of the intermediate metabolites of FBSEE diol, further supported by our laboratory batch studies, prompts the proposal of a novel metabolic pathway for FBSEE diol. The total amount of perfluorobutane sulfonamido derivatives reached 1934 µg/L (90%), while that of PFAAs, which have typically received attention, was only 205 µg/L (10%). This suggests that perfluorobutane sulfonamido derivatives are emerging as a new trend in fluorosurfactants used in the semiconductor industry, serving as PFAS precursors and contributing to the release of their metabolites into the environment.


Subject(s)
Fluorocarbons , Water Pollutants, Chemical , Sewage/chemistry , Surface-Active Agents , Water Pollutants, Chemical/analysis , Fluorocarbons/analysis
12.
Environ Sci Technol ; 58(13): 5670-5684, 2024 Apr 02.
Article in English | MEDLINE | ID: mdl-38501683

ABSTRACT

PFASs are linked to serious health and environmental concerns. Among their widespread applications, PFASs are known to be used in food packaging and directly contribute to human exposure. However, information about PFASs in food packaging is scattered. Therefore, we systematically map the evidence on PFASs detected in migrates and extracts of food contact materials and provide an overview of available hazard and biomonitoring data. Based on the FCCmigex database, 68 PFASs have been identified in various food contact materials, including paper, plastic, and coated metal, by targeted and untargeted analyses. 87% of these PFASs belong to the perfluorocarboxylic acids and fluorotelomer-based compounds. Trends in chain length demonstrate that long-chain perfluoroalkyl acids continue to be found, despite years of global efforts to reduce the use of these substances. We utilized ToxPi to illustrate that hazard data are available for only 57% of the PFASs that have been detected in food packaging. For those PFASs for which toxicity testing has been performed, many adverse outcomes have been reported. The data and knowledge gaps presented here support international proposals to restrict PFASs as a group, including their use in food contact materials, to protect human and environmental health.


Subject(s)
Fluorocarbons , Water Pollutants, Chemical , Humans , Fluorocarbons/analysis , Food Packaging , Food , Water Pollutants, Chemical/analysis
13.
Environ Sci Technol ; 2024 Oct 03.
Article in English | MEDLINE | ID: mdl-39363531

ABSTRACT

To date, considerable knowledge and data gaps regarding the occurrence, environmental levels, and fate of polymeric perfluoroalkyl and polyfluoroalkyl substances (PFAS) exist. In the present study availability, accumulation, and transformation of C4- and C8-fluoroalkylsulfonamide (FASA)-based copolymers were assessed in laboratory-grown earthworms (Eisenia fetida, triplicate of exposure tests and control). Further, a field study on earthworms (18 pooled samples) in sludge-amended soil was conducted to assess the environmental impact of sludge-amended soil with regard to the FASA-based copolymers, together with the applied sludge (n = 3), and the field soils during the period (n = 4). In the laboratory study, the FASA-based copolymers were taken up by the earthworms in concentrations between 19 and 33 ng/g of dw for the C8- and between 767 and 1735 ng/g of dw for the C4-FASA-based copolymer. Higher biota soil accumulation factors (BAFs) were observed for the copolymer with a longer perfluorinated side-chain length (C8, average BAF value of 0.7) compared to the copolymer with a shorter side-chain length (C4, average BAF value of 0.02). Perfluorooctane sulfonamidoacetates (FOSAAs) and perfluorooctane sulfonamide (FOSA), including both branched and linear isomers, were detected after exposure to the C8-FASA-based copolymer. Two metabolites were detected in the earthworms exposed to the C4-FASA-based copolymer: perfluorobutanesulfonamide (FBSA) and perfluorobutanesulfonic acid (PFBS). Although the presence of other monomers or impurities in the copolymer formulation cannot be ruled out, the present laboratory study suggests that the FASA-based copolymers may be an indirect source of lower molecular weight PFAS in the environment through transformation. Elevated levels of C8-FASA-based copolymer were found in the field sludge-amended soil compared to nontreated soil (32 versus 11 ng/g d.w.), and higher concentrations of PFAS in earthworms living in sludge-amended soil compared to nontreated soil (566 versus 103 ng/g d.w.) were observed. These findings imply that the application of sludge is a potential pathway of PFAS to the environment.

14.
Environ Sci Technol ; 2024 Sep 13.
Article in English | MEDLINE | ID: mdl-39271478

ABSTRACT

Granular activated carbon (GAC) adsorption is frequently used to remove recalcitrant organic micropollutants (MPs) from water. The overarching aim of this research was to develop machine learning (ML) models to predict GAC performance from adsorbent, adsorbate, and background water matrix properties. For model calibration, MP breakthrough curves were compiled and analyzed to determine the bed volumes of water that can be treated until MP breakthrough reaches ten percent of the influent MP concentration (BV10). Over 400 data points were split into training, validation, and testing sets. Seventeen variables describing MP, background water matrix, and GAC properties were explored in ML models to predict log10-transformed BV10 values. Using the ML models on the testing set, predicted BV10 values exhibited mean absolute errors of ∼0.12 log units and were highly correlated with experimentally determined values (R2 ≥ 0.88). The top three drivers influencing BV10 predictions were the air-hexadecane partition coefficient and hydrogen bond acidity (Abraham parameters L and A) of the MPs and the dissolved organic carbon concentration of the GAC influent water. The model can be used to rapidly estimate the GAC bed life, select effective GAC products for a given treatment scenario, and explore the suitability of GAC treatment for remediating emerging MPs.

15.
Environ Sci Technol ; 58(4): 2089-2101, 2024 Jan 30.
Article in English | MEDLINE | ID: mdl-38231021

ABSTRACT

North American river otters (Lontra canadensis) are top predators in riverine ecosystems and are vulnerable to per- and polyfluoroalkyl substance (PFAS) exposure. Little is known about the magnitude of exposure and tissue distribution of PFAS in river otters. We measured 45 PFAS in various tissues of 42 river otters collected from several watersheds in the state of West Virginia, USA. The median concentrations of ∑All (sum concentration of 45 PFAS) varied among tissues in the following decreasing order: liver (931 ng/g wet weight) > bile > pancreas > lung > kidney > blood > brain > muscle. Perfluoroalkylsulfonates (PFSAs) were the predominant compounds accounting for 58-75% of the total concentrations, followed by perfluoroalkyl carboxylates (PFCAs; 21-35%). 8:2 fluorotelomer sulfonate (8:2 FTS), 10:2 FTS, and 6:2 chlorinated polyfluoroalkyl ether sulfonate were frequently found in the liver (50-90%) and bile (96-100%), whereas hexafluoropropylene oxide dimer acid (HFPO-DA) was rarely found. The hepatic concentrations of ∑All in river otters collected downstream of a fluoropolymer production facility located along the Ohio River were 2-fold higher than those in other watersheds. The median whole body burden of ∑All was calculated to be 1580 µg. PFOS and perfluorooctanoic acid (PFOA) concentrations in whole blood of some river otters exceeded the human toxicity reference values, which warrant further studies.


Subject(s)
Fluorocarbons , Otters , Water Pollutants, Chemical , Animals , Humans , West Virginia , Ecosystem , Fluorocarbons/analysis , Liver , Water Pollutants, Chemical/analysis
16.
Environ Sci Technol ; 58(17): 7480-7492, 2024 Apr 30.
Article in English | MEDLINE | ID: mdl-38639388

ABSTRACT

Microbial transformation of per- and polyfluoroalkyl substances (PFAS), including fluorotelomer-derived PFAS, by native microbial communities in the environment has been widely documented. However, few studies have identified the key microorganisms and their roles during the PFAS biotransformation processes. This study was undertaken to gain more insight into the structure and function of soil microbial communities that are relevant to PFAS biotransformation. We collected 16S rRNA gene sequencing data from 8:2 fluorotelomer alcohol and 6:2 fluorotelomer sulfonate biotransformation studies conducted in soil microcosms under various redox conditions. Through co-occurrence network analysis, several genera, including Variovorax, Rhodococcus, and Cupriavidus, were found to likely play important roles in the biotransformation of fluorotelomers. Additionally, a metagenomic prediction approach (PICRUSt2) identified functional genes, including 6-oxocyclohex-1-ene-carbonyl-CoA hydrolase, cyclohexa-1,5-dienecarbonyl-CoA hydratase, and a fluoride-proton antiporter gene, that may be involved in defluorination. This study pioneers the application of these bioinformatics tools in the analysis of PFAS biotransformation-related sequencing data. Our findings serve as a foundational reference for investigating enzymatic mechanisms of microbial defluorination that may facilitate the development of efficient microbial consortia and/or pure microbial strains for PFAS biotransformation.


Subject(s)
Biotransformation , Soil Microbiology , RNA, Ribosomal, 16S/genetics , Soil/chemistry , Soil Pollutants/metabolism , Fluorocarbons/metabolism
17.
Environ Sci Technol ; 58(15): 6616-6627, 2024 Apr 16.
Article in English | MEDLINE | ID: mdl-38569050

ABSTRACT

While the extent of environmental contamination by per- and polyfluoroalkyl substances (PFAS) has mobilized considerable efforts around the globe in recent years, publicly available data on PFAS in Europe were very limited. In an unprecedented experiment of "expert-reviewed journalism" involving 29 journalists and seven scientific advisers, a cross-border collaborative project, the "Forever Pollution Project" (FPP), drew on both scientific methods and investigative journalism techniques such as open-source intelligence (OSINT) and freedom of information (FOI) requests to map contamination across Europe, making public data that previously had existed as "unseen science". The FPP identified 22,934 known contamination sites, including 20 PFAS manufacturing facilities, and 21,426 "presumptive contamination sites", including 13,745 sites presumably contaminated with fluorinated aqueous film-forming foam (AFFF) discharge, 2911 industrial facilities, and 4752 sites related to PFAS-containing waste. Additionally, the FPP identified 231 "known PFAS users", a new category for sites with an intermediate level of evidence of PFAS use and considered likely to be contamination sources. However, the true extent of contamination in Europe remains significantly underestimated due to a lack of comprehensive geolocation, sampling, and publicly available data. This model of knowledge production and dissemination offers lessons for researchers, policymakers, and journalists about cross-field collaborations and data transparency.


Subject(s)
Fluorocarbons , Water Pollutants, Chemical , Fluorocarbons/analysis , Water Pollutants, Chemical/analysis , Environmental Pollution , Europe , Commerce
18.
Environ Sci Technol ; 58(19): 8215-8227, 2024 May 14.
Article in English | MEDLINE | ID: mdl-38687897

ABSTRACT

Per- and polyfluoroalkyl substances (PFAS) are extensively utilized in varieties of products and tend to accumulate in the human body including umbilical cord blood and embryos/fetuses. In this study, we conducted an assessment and comparison of the potential early developmental toxicity of perfluorooctanoic acid (PFOA), undecafluorohexanoic acid (PFHxA), heptafluorobutyric acid, perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate, and perfluorobutyric acid at noncytotoxic concentrations relevant to human exposure using models based on human embryonic stem cells in both three-dimensional embryoid body (EB) and monolayer differentiation configurations. All six compounds influenced the determination of cell fate by disrupting the expression of associated markers in both models and, in some instances, even led to alterations in the formation of cystic EBs. The expression of cilia-related gene IFT122 was significantly inhibited. Additionally, PFOS and PFOA inhibited ciliogenesis, while PFOA specifically reduced the cilia length. Transcriptome analysis revealed that PFOS altered 1054 genes and disrupted crucial signaling pathways such as WNT and TGF-ß, which play integral roles in cilia transduction and are critical for early embryonic development. These results provide precise and comprehensive insights into the potential adverse health effects of these six PFAS compounds directly concerning early human embryonic development.


Subject(s)
Fluorocarbons , Human Embryonic Stem Cells , Humans , Human Embryonic Stem Cells/drug effects , Fluorocarbons/toxicity , Cell Differentiation/drug effects
19.
Environ Sci Technol ; 58(23): 10195-10206, 2024 Jun 11.
Article in English | MEDLINE | ID: mdl-38800846

ABSTRACT

Concentrations of 33 PFASs were determined in 20 Eurasian otters, sampled 2015-2019, along a transect away from a factory, which used PFOA in PTFE manufacture. Despite cessation of usage in 2012, PFOA concentrations remained high near the factory (>298 µg/kg ww <20 km from factory) and declined with increasing distance (<57 µg/kg ww >150 km away). Long-chain legacy PFASs dominated the Σ33PFAS profile, particularly PFOS, PFOA, PFDA, and PFNA. Replacement compounds, PFECHS, F-53B, PFBSA, PFBS, PFHpA, and 8:2 FTS, were detected in ≥19 otters, this being the first report of PFBSA and PFECHS in the species. Concentrations of replacement PFASs were generally lower than legacy compounds (max: 70.3 µg/kg ww and 4,640 µg/kg ww, respectively). Our study underscores the utility of otters as sentinels for evaluating mitigation success and highlights the value of continued monitoring to provide insights into the longevity of spatial associations with historic sources. Lower concentrations of replacement, than legacy, PFASs likely reflect their lower bioaccumulation potential, and more recent introduction. Continued PFAS use will inevitably lead to increased environmental and human exposure if not controlled. Further research is needed on fate, toxicity, and bioaccumulation of replacement compounds.


Subject(s)
Environmental Monitoring , Otters , Water Pollutants, Chemical , Animals , Water Pollutants, Chemical/analysis , Fresh Water , Fluorocarbons/analysis
20.
Environ Sci Technol ; 58(5): 2446-2457, 2024 Feb 06.
Article in English | MEDLINE | ID: mdl-38178542

ABSTRACT

The 6:2 fluorotelomer sulfonamide (6:2 FTSAm)-based compounds signify a prominent group of per- and polyfluoroalkyl substances (PFAS) widely used in contemporary aqueous film-forming foam (AFFF) formulations. Despite their widespread presence, the biotransformation behavior of these compounds in wastewater treatment plants remains uncertain. This study investigated the biotransformation of 6:2 FTSAm-based amine oxide (6:2 FTNO), alkylbetaine (6:2 FTAB), and 6:2 fluorotelomer sulfonic acid (6:2 FTSA) in aerobic sludge over a 100-day incubation period. The biotransformation of 6:2 fluorotelomer sulfonamide alkylamine (6:2 FTAA), a primary intermediate product of 6:2 FTNO, was indirectly assessed. Their stability was ranked based on the estimated half-lives (t1/2): 6:2 FTAB (no obvious products were detected) ≫ 6:2 FTSA (t1/2 ≈28.8 days) > 6:2 FTAA (t1/2 ≈11.5 days) > 6:2 FTNO (t1/2 ≈1.2 days). Seven transformation products of 6:2 FTSA and 15 products of 6:2 FTNO were identified through nontarget and suspect screening using high-resolution mass spectrometry. The transformation pathways of 6:2 FTNO and 6:2 FTSA in aerobic sludge were proposed. Interestingly, 6:2 FTSAm was hardly hydrolyzed to 6:2 FTSA and further biotransformed to perfluoroalkyl carboxylic acids (PFCAs). Furthermore, the novel pathways for the generation of perfluoroheptanoic acid (PFHpA) from 6:2 FTSA were revealed.


Subject(s)
Fluorocarbons , Water Pollutants, Chemical , Sewage/chemistry , Oxides , Amines , Fluorocarbons/analysis , Biotransformation , Sulfonamides/metabolism , Water Pollutants, Chemical/analysis
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