Assuntos
Ácidos Alcanossulfônicos , Água Potável , Fluorocarbonos , Poluentes Químicos da Água , Água Potável/análise , Exposição Ambiental/análise , Monitoramento Ambiental , Organização Mundial da Saúde , Fluorocarbonos/análise , Ácidos Alcanossulfônicos/análise , Poluentes Químicos da Água/análise , CaprilatosRESUMO
Perfluoroalkyl acids (PFAAs) are continuously accumulated in surface sediments due to extensive and long-term application. However, the mechanisms through which disturbances induced by ship propeller jets at the riverbed cause secondary release of PFAAs from sediments remain unclear. In this study, the effects of different propeller rotational speeds on PFAA migration, release, and distribution in multiphase media were investigated by performing indoor flume experiments combined with particle tracking velocimetry. Moreover, key factors influencing PFAA migration and distribution were identified, and partial least squares regression (PLS) method was applied to develop quantitative prediction models of relationships among hydrodynamics, physicochemical parameters, and PFAA distribution coefficients. The total PFAA concentrations (ΣPFAAs) in overlying water under propeller jet action exhibited transient characteristics and hysteresis with time after the disturbance. In contrast, the ΣPFAAs in suspended particulate matter (SPM) exhibited an upward trend throughout the process with consistent characteristics. The spatial distribution trends of PFAAs in overlying water and SPM at different propeller rotational speeds featured vertical variability and axial consistency. Furthermore, PFAA release from sediments was driven by axial flow velocity (Vx) and Reynolds normal stress Ryy, while PFAA release from porewater was inextricably linked to Reynolds stresses Rxx, Rxy, and Rzz (p < 0.05). PLS regression models showed that variations in Vorticity, dissolved organic carbon, and pH influenced the decreases in PFAA distribution coefficients between SPM and overlying water (KD-SW) as propeller rotational speed increased, except for very long-chain PFAAs (C > 10). The increases in PFAA distribution coefficients between sediment and porewater (KD-SP) were mainly determined by physicochemical parameters of sediments, and the direct effect of hydrodynamics was relatively weak. Our study provides valuable information regarding the migration and distribution of PFAAs in multiphase media under propeller jet disturbance (both during and after disturbance).
Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Poluentes Químicos da Água , Água , Poluentes Químicos da Água/análise , Fluorocarbonos/análise , Material Particulado , Hidrodinâmica , Ácidos Alcanossulfônicos/análise , Monitoramento AmbientalRESUMO
The efficacy of photodynamic therapy (PDT) strictly depends on the availability of molecular oxygen to trigger the light-induced generation of reactive species. Fluorocarbons have an increased ability to dissolve oxygen and are attractive tools for gas delivery. We synthesized three fluorous derivatives of chlorin with peripheral polyfluoroalkyl substituents. These compounds were used as precursors for preparing nanoemulsions with perfluorodecalin as an oxygen depot. Therefore, our formulations contained hydrophobic photosensitizers capable of absorbing monochromatic light in the long wavelength region and the oxygen carrier. These modifications did not alter the photosensitizing characteristics of chlorin such as the generation of singlet oxygen, the major cytocidal species in PDT. Emulsions readily entered HCT116 colon carcinoma cells and accumulated largely in mitochondria. Illumination of cells loaded with emulsions rapidly caused peroxidation of lipids and the loss of the plasma membrane integrity (photonecrosis). Most importantly, in PDT settings, emulsions potently sensitized cells cultured under prolonged (8 weeks) hypoxia as well as cells after oxygen depletion with sodium sulfite (acute hypoxia). The photodamaging potency of emulsions in hypoxia was significantly more pronounced compared to emulsion-free counterparts. Considering a negligible dark cytotoxicity, our materials emerge as efficient and biocompatible instruments for PDT-assisted eradication of hypoxic cells.
Assuntos
Fluorocarbonos , Fotoquimioterapia , Porfirinas , Humanos , Fármacos Fotossensibilizantes/química , Porfirinas/química , Fluorocarbonos/farmacologia , Hipóxia/metabolismo , Oxigênio , Emulsões/química , Linhagem Celular TumoralRESUMO
8:2 perfluoroalkyl phosphate diester (8:2 diPAP) is the main precursor of perfluoroalkyl carboxylic acids, and it has been detected in a wide range of environments. In this study, conventional biochemical and histopathological analyses and transcriptome methods were used to investigate the accumulation and oxidative stress of 8:2 diPAP in Manila clams (Ruditapes philippinarum) as well as the clam's defense mechanisms for the first time. The hepatopancreas was the main target organ for 8:2 diPAP accumulation; the concentration reached 484.0⯱â¯15.5â¯ng/g after 7 days of exposure to 10⯵g/L of 8:2 diPAP, which was 2-100 times higher than that found in other organs. 8:2 diPAP accumulation resulted in significant lipid peroxidation, and the change in malondialdehyde content was highly correlated with 8:2 diPAP accumulation (r > 0.8). The antioxidant enzymes catalase and peroxidase were significantly activated at 7 days of exposure. Although the levels subsequently returned to normal, this restoration was unable to prevent damage. Histopathological analysis showed that 8:2 diPAP exposure resulted in inflammatory damage to the hepatopancreas, which failed to resolve during the recovery period. Transcriptomic analyses showed that the expression of differentially expressed genes had different degrees of positive/negative correlation with antioxidant indicators, and they were significantly enriched in cell death regulatory pathways such as autophagy, apoptosis, and necrosis. The core factor expression results indicated that 8:2 diPAP exposure induced activation of the organismal autophagy factor followed by a shift towards apoptosis. In addition, pathways related to amino acid metabolism and energy metabolism were involved in determining the cell fate of Manila clams. Overall, these results indicated that 8:2 diPAP induced peroxidation of membrane lipids, disturbed physiological processes, and ultimately initiated programmed cell death in Manila clams. The findings of this study provide new insights into the mechanism of toxicity of 8:2 diPAP exposure in marine bivalves.
Assuntos
Bivalves , Fluorocarbonos , Poluentes Químicos da Água , Animais , Antioxidantes/metabolismo , Fosfatos/metabolismo , Poluentes Químicos da Água/toxicidade , Estresse Oxidativo , Fluorocarbonos/análise , Bivalves/metabolismo , Mecanismos de DefesaRESUMO
BACKGROUND: Legacy per- and polyfluoroalkyl substances (PFAS), known for their environmental persistence and bio-accumulative properties, have been phased out in the U.S. due to public health concerns. A newer polymerization aid used in the manufacture of some fluoropolymers, hexafluoropropylene oxide-dimer acid (HFPO-DA), has lower reported bioaccumulation and toxicity, but is a potential neurotoxicant implicated in dopaminergic neurodegeneration. OBJECTIVE: We investigated HFPO-DA's bio-accumulative potential and sex-specific effects on lifespan, locomotion, and brain gene expression in fruit flies. METHODS: We quantified bioaccumulation of HFPO-DA in fruit flies exposed to 8.7 × 104 µg/L of HFPO-DA in the fly media for 14 days via UHPLC-MS. Long-term effect on lifespan was determined by exposing both sexes to 8.7 × 102 - 8.7 × 105 µg/L of HFPO-DA in media. Locomotion was measured following 3, 7, and 14 days of exposures at 8.7 × 101 - 8.7 × 105 µg/L of HFPO-DA in media, and high-throughput 3'-end RNA-sequencing was used to quantify gene expression in fly brains across the same time points. RESULTS: Bioaccumulation of HFPO-DA in fruit flies was not detected. HFPO-DA-induced effects on lifespan, locomotion, and brain gene expression, and lowest adverse effect level (LOAEL) showed sexually dimorphic patterns. Locomotion scores significantly decreased in at least one dose at all time points for females and only at 3-day exposure for males, while brain gene expression exhibited non-monotonic dose-response. Differentially expressed genes correlated to locomotion scores revealed sex-specific numbers of positively and negatively correlated genes per functional category. CONCLUSION: Although HFPO-DA effects on locomotion and survival were significant at doses higher than the US EPA reference dose, the brain transcriptomic profiling reveals sex-specific changes and neurological molecular targets; gene enrichments highlight disproportionately affected categories, including immune response: female-specific co-upregulation suggests potential neuroinflammation. Consistent sex-specific exposure effects necessitate blocking for sex in experimental design during HFPO-DA risk assessment.
Assuntos
Drosophila melanogaster , Fluorocarbonos , Masculino , Animais , Feminino , Drosophila melanogaster/genética , Longevidade/genética , Fluorocarbonos/toxicidade , Expressão Gênica , Encéfalo/metabolismo , LocomoçãoRESUMO
Per-and polyfluoroalkyl substances (PFASs) are present in surface water, tap water, and even commercial drinking water and pose a threat to human health. In this study, the occurrence and transformation of 14 PFASs were studied in large drinking water treatment plants (DWTPs) with Taihu Lake as the source, and the results showed that a total of 10 PFASs were detected in the water samples, indicating that PFAS were widely distributed in drinking water. The total concentration of PFASs in raw water was 127.4 ng·L-1, with the highest concentration being that of pentadecafluorooctanoic acid (PFOA, 49.8 ng·L-1). Pre-ozone caused a reverse increase in the concentration of PFASs, which may have been due to the presence of precursors or conversion from short to long chains. PFASs were not effectively removed by conventional treatment processes, andozone-biological activated carbon (O3-BAC) had a dominant role in the removal of PFASs (20.74%) from DWTPs. O3-BAC, the main removal process for DWTPs, contained high concentrations of PFASs in the backwash water with similar distribution characteristics to the raw water. Using a pilot plant, five common filter backwash water treatment processes were compared, and the results showed that GAC-ultrafiltration could adsorb and retain a certain amount of PFASs while ensuring a high removal rate of turbidity (99.08%). The 3D-EEM analysis indicated that GAC-ultrafiltration could also remove most of the fluorescent micro-pollutants, and for raw water containing high concentrations of PFASs DWTPs, it is practical to use it as a filter backwash water reuse treatment process.
Assuntos
Ácidos Alcanossulfônicos , Água Potável , Fluorocarbonos , Poluentes Químicos da Água , Purificação da Água , Humanos , Água Potável/análise , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Fluorocarbonos/análise , Carvão Vegetal/análise , Ácidos Alcanossulfônicos/análise , Monitoramento AmbientalRESUMO
Legacy per- and polyfluoroalkyl substances (PFASs) have elicited much concern because of their ubiquitous distribution in the environment and the potential hazards they pose to wildlife and human health. Although an increasing number of effective PFAS alternatives are available in the market, these alternatives bring new challenges. This paper comprehensively reviews how PFASs bind to transport proteins (e.g., serum albumin, liver fatty acid transport proteins and organic acid transporters), nuclear receptors (e.g., peroxisome proliferator activated receptors, thyroid hormone receptors and reproductive hormone receptors) and membranes (e.g., cell membrane and mitochondrial membrane). Briefly, the hydrophobic fluorinated carbon chains of PFASs occupy the binding cavities of the target proteins, and the acid groups of PFASs form hydrogen bonds with amino acid residues. Various structural features of PFAS alternatives such as chlorine atom substitution, oxygen atom insertion and a branched structure, introduce variations in their chain length and hydrophobicity, which potentially change the affinity of PFAS alternatives for endogenous proteins. The toxic effects and mechanisms of action of legacy PFASs can be demonstrated and compared with their alternatives using binding models. In future studies, in vitro experiments and in silico quantitative structure-activity relationship modeling should be better integrated to allow more reliable toxicity predictions for both legacy and alternative PFASs.
Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Humanos , Fluorocarbonos/toxicidade , Simulação por Computador , Aminoácidos , Relação Quantitativa Estrutura-AtividadeRESUMO
Perfluoroalkyl substances (PFASs) are a classic environmental endocrine disruptor with carcinogenic risk. Epidemiological studies have shown that PFASs contamination is associated with breast cancer development, but the mechanism remains largely unknown. This study first obtained complex biological information about PFASs-induced breast cancer through the comparative toxicogenomics database (CTD). The Protein-Protein Interaction (PPI) network, Kyoto Encyclopedia of Genes and Genomes (KEGG) and Gene Ontology (GO) analysis were utilized to investigate molecular pathways. The ESR1 and GPER expression levels at different pathological stages and the prognosis of Breast Cancer patients were confirmed using the Cancer Genome Atlas (TCGA) database. Furthermore, we verified this by cellular experiments and the results showed breast cancer cell migration and invasion were promoted by PFOA. Two estrogen receptors (ER), ERα and G protein-coupled estrogen receptor (GPER), mediated the promoting effects of PFOA by activating MAPK/Erk and PI3K/Akt signaling pathways. These pathways were regulated by ERα and GPER in MCF-7 cells or independently by GPER in MDA-MB-231 cells. Overall, our study provides a better overview of the mechanisms associated with PFASs-induced breast cancer development and progression.
Assuntos
Neoplasias da Mama , Fluorocarbonos , Humanos , Feminino , Receptores de Estrogênio/genética , Receptores de Estrogênio/metabolismo , Neoplasias da Mama/metabolismo , Receptor alfa de Estrogênio/genética , Receptor alfa de Estrogênio/metabolismo , Proteínas Proto-Oncogênicas c-akt/metabolismo , Fosfatidilinositol 3-Quinases/metabolismo , Proliferação de Células , Estrogênios/metabolismo , Receptores Acoplados a Proteínas G/genética , Receptores Acoplados a Proteínas G/metabolismo , Transdução de Sinais , Fluorocarbonos/toxicidade , Linhagem Celular TumoralRESUMO
Perfluorooctane sulfonate (PFOS) is a widespread and persistent chemical in the environment. Reports show that PFOS is a potential endocrine disruptor; however, the possible effects of PFOS on placental endocrine function are unclear. This study aimed to investigate the endocrine-disrupting effects of PFOS on the placenta in pregnant rats and its potential mechanism. Pregnant rats from gestational days 4-20 were exposed to 0, 10, and 50 µg/mL PFOS through drinking water followed by analysis of various biochemical parameters. PFOS dose-dependently decreased fetal and placental weight in both sexes, with a specific decrease in weight of labyrinth but not junctional layer. Plasma progesterone (↑166%), aldosterone (↑201%), corticosterone (↑205%), testosterone (↑45%), luteinizing hormone (↑49%) levels were significantly increased, while estradiol (↓27%), prolactin (↓28%) and hCG (↓62%) levels were reduced in groups exposed to higher doses of PFOS. Real-time quantitative reverse transcriptase-polymerase chain reaction analysis revealed a significant increase in mRNA levels of placental steroid biosynthesis enzymes, including Cyp11A1 and 3ß-HSD1 in male placenta and StAR, Cyp11A1, 17ß-HSD1 and 17ß-HSD3 in female placenta of PFOS dams. Cyp19A1 expression in ovaries was significantly decreased in PFOS dams. mRNA levels for placental steroid metabolism enzyme UGT1A1 increased in male but not in female placenta of PFOS dams. These results suggest that the placenta is a target tissue of PFOS and PFOS-induced dysregulation in steroid hormone production might be related to the altered expression of hormone biosynthesis and metabolism enzyme genes in the placenta. This hormone disruption might affect maternal health and fetal growth.
Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Gravidez , Ratos , Feminino , Masculino , Animais , Placenta/metabolismo , Enzima de Clivagem da Cadeia Lateral do Colesterol/genética , Enzima de Clivagem da Cadeia Lateral do Colesterol/metabolismo , Fluorocarbonos/toxicidade , Ácidos Alcanossulfônicos/toxicidade , Estradiol/metabolismo , Esteroides/metabolismoRESUMO
BACKGROUND: Per- and polyfluoroalkyl substances (PFAS) have been previously linked to polycystic ovarian syndrome (PCOS), but only a few legacy PFAS were examined. OBJECTIVES: This study aimed to explore this association with a variety of PFAS, including legacy, branched-chain isomers, and emerging alternatives, as well as a PFAS mixture. METHODS: From 2014 to 2016, we conducted a multicenter, hospital-based case-control study on environmental endocrine disruptors and infertility in China. Three hundred sixty-six women with PCOS-related infertility and 577 control participants without PCOS were included in the current analysis. Twenty-three PFAS, including 3 emerging PFAS alternatives, 6 linear and branched PFAS isomers, 6 short-chain PFAS, and 8 legacy PFAS, were quantified in the plasma. Logistic regression and two multipollutant models [quantile-based g-computation (QGC) and Bayesian kernel machine regression (BKMR) methods] were used to assess the association of individual PFAS and PFAS mixture with PCOS, as well as the potential interactions among the congeners. RESULTS: After adjusting for potential confounders, Each 1-standard deviation higher difference in ln-transformed 6:2 chlorinated perfluoroalkyl ether sulfonic acid (6:2 Cl-PFESA) and hexafluoropropylene oxide dimer acid (HFPO-DA) level was significantly associated with a 29% (95% CI: 1.11, 1.52) and 39% (95% CI:1.16, 1.68) higher odds of PCOS, respectively. Meanwhile, branched isomers of perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) (i.e., br-PFHxS, n-PFOS, 1m-PFOS, Σ3,4,5m-PFOS), short-chain PFAS (i.e., PFPeS and PFHxA) and other legacy PFAS [i.e., total concentrations of PFOS (T-PFOS), and perfluorododecanoic acid (PFDoA)] were significantly associated with increased odds of PCOS. The PFAS mixture was positively related to PCOS in the BKMR model. A similar trend was observed in QGC model, a ln-unit increase in the PFAS mixture was associated with a 20% increased risk of PCOS [adjusted odds ratio (aOR)=1.20 (95% CI: 1.06, 1.37)]. After controlling for other PFAS homologs, 6:2 Cl-PFESA, HFPO-DA, Σ3,4,5m-PFOS, and PFDoA were the major contributors based on the QGC and BKMR models. The associations were more pronounced in overweight/obese women. CONCLUSIONS: In this group of women, environmental exposure to a PFAS mixture was associated with an elevated odds of PCOS, with 6:2 Cl-PFESA, HFPO-DA, Σ3,4,5m-PFOS, and PFDoA being the major contributors, especially in overweight/obese women. https://doi.org/10.1289/EHP11814.
Assuntos
Ácidos Alcanossulfônicos , Poluentes Ambientais , Fluorocarbonos , Infertilidade , Síndrome do Ovário Policístico , Humanos , Feminino , Síndrome do Ovário Policístico/epidemiologia , Estudos de Casos e Controles , Teorema de Bayes , Sobrepeso , Exposição Ambiental , Ácidos Alcanossulfônicos/análise , Alcanossulfonatos/análise , ObesidadeRESUMO
BACKGROUND: Associations between per- and polyfluoroalkyl substances (PFAS) and blood lipid levels in humans were mixed. OBJECTIVES: The objective of this meta-analysis was to summarize associations between PFAS and blood lipids in adults. METHODS: A literature search was conducted on PubMed and Web of Science for articles published through 13 May 2022 that examined associations between PFAS and blood lipids, including total cholesterol (TC), high-density lipoprotein cholesterol (HDL-C), low-density lipoprotein cholesterol (LDL-C), and triacylglycerols (TGs). Inclusion criteria included the presence of associations between five PFAS (PFOA, PFOS, PFHxS, PFDA, and PFNA) and four blood lipid measures (TC, HDL-C, LDL-C, and TGs) in adults. Data on study characteristics and PFAS-lipid associations were extracted. Assessments of individual study quality were performed. Associations of changes of blood lipid levels corresponding to 1 interquartile range (IQR)-unit increase of blood PFAS levels were pooled using random effects models. Dose-response relationships were examined. RESULTS: Twenty-nine publications were included in the present analyses. Every IQR increase of PFOA was significantly associated with a 2.1-mg/dL increase in TC (95% CI: 1.2, 3.0), a 1.3-mg/dL increase in TGs (95% CI: 0.1, 2.4), and a 1.4-mg/dL increase in LDL-C (95% CI: 0.6, 2.2). PFOS was also significantly associated with TC and LDL-C levels, and the corresponding values were 2.6 (95% CI: 1.5, 3.6) and 1.9 (95% CI: 0.9, 3.0), respectively. Associations of PFOS and PFOA with HDL-C levels were largely null. For minor PFAS species, PFHxS was significantly associated with higher levels of HDL-C [0.8 (95% CI: 0.5, 1.2)]. Inverse associations were observed between PFDA and TGs [-5.0 (95% CI: -8.1, -1.9)] and between PFNA and TGs [-1.7 (95% CI: -3.5, -0.02)], whereas a positive association was observed between PFDA and HDL-C [1.4 (95% CI: 0.1, 2.7)]. Nonsignificant nonlinear dose-response relationships were identified for associations of PFOA and PFOS with certain blood lipids. DISCUSSION: PFOA and PFOS were significantly associated with TC and LDL-C levels in adults. Whether these findings may translate into an elevated cardiovascular disease risk associated with PFAS exposure warrants further investigation. https://doi.org/10.1289/EHP11840.
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Ácidos Alcanossulfônicos , Poluentes Ambientais , Fluorocarbonos , Adulto , Humanos , LDL-Colesterol , LipídeosRESUMO
Some contemporary aqueous film-forming foams (AFFFs) contain n:3 and n:1:2 fluorotelomer betaines (FTBs), which are often detected at sites impacted by AFFFs. As new chemical replacements, little is known about their environmental fate. For the first time, we investigated the biotransformation potential of 5:3 and 5:1:2 FTBs and a commercial AFFF that mainly contains n:3 and n:1:2 FTBs (n = 5, 7, 9, 11, and 13). Although some polyfluoroalkyl compounds are precursors to perfluoroalkyl acids, 5:3 and 5:1:2 FTBs exhibited high persistence, with no significant changes even after 120 days of incubation. While the degradation of 5:3 FTB into suspected products such as fluorotelomer acids or perfluoroalkyl carboxylic acids (PFCAs) could not be conclusively confirmed, we did identify a potential biotransformation product, 5:3 fluorotelomer methylamine. Similarly, 5:1:2 FTB did not break down or produce short-chain hydrogen-substituted polyfluoroalkyl acids (n:2 H-FTCA), hydrogen-substituted PFCA (2H-PFCA), or any other products. Incubating the AFFF in four soils with differing properties and microbial communities resulted in 0.023-0.25 mol % PFCAs by day 120. Most of the products are believed to be derived from n:2 fluorotelomers, minor components of the AFFF. Therefore, the findings of the study cannot be fully explained by the current understanding of structure-biodegradability relationships.
Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Betaína , Solo , Poluentes Químicos da Água/análise , Fluorocarbonos/análise , Água , Ácidos Carboxílicos/metabolismoRESUMO
Polyfluoroalkyl phosphate esters (PAPs) are widely used and detected in various environmental media and organisms, but little is known about their behaviors in plants. In this study, the uptake, translocation and transformation of 6:2 and 8:2 diPAP in wheat using hydroponic experiments were investigated. 6:2 diPAP was more easily taken up by roots and translocated to shoots than 8:2 diPAP. Their phase I metabolites were fluorotelomer saturated carboxylates (FTCAs), fluorotelomer unsaturated carboxylates (FTUCAs) and perfluoroalkyl carboxylic acids (PFCAs). PFCAs with even-numbered chain length were the primary phase I terminal metabolites suggesting that they were mainly generated through ß-oxidation. Cysteine and sulfate conjugates were the primary phase II transformation metabolites. The higher levels and ratios of phase II metabolites in the 6:2 diPAP exposure group indicated that the phase I metabolites of 6:2 diPAP were more susceptible to phase II transformation than that of 8:2 diPAP, which was confirmed by density functional theory calculation. Enzyme activity analyses and in vitro experiments demonstrated that cytochrome P450 and alcohol dehydrogenase actively participated in the phase â transformation of diPAPs. Gene expression analyses showed that glutathione S-transferase (GST) was involved in the phase â ¡ transformation, and the subfamily GSTU2 played a dominant role.
Assuntos
Fluorocarbonos , Fosfatos , Fosfatos/metabolismo , Triticum/metabolismo , Biotransformação , Fluorocarbonos/metabolismo , Ácidos CarboxílicosRESUMO
BACKGROUND: Exposure to perfluorinated alkylate substances (PFAS) is associated with harmful effects on human health, including developmental immunotoxicity. This outcome was chosen as the critical effect by the European Food Safety Authority (EFSA), which calculated a new joint reference dose for four PFAS using a Benchmark Dose (BMD) analysis of a study of 1-year old children. However, the U.S. Environmental Protection Agency (EPA) recently proposed much lower exposure limits. METHODS: We explored the BMD methodology for summary and individual data and compared the results with and without grouping for two data sets available. We compared the performance of different dose-response models including a hockey-stick model and a piecewise linear model. We considered different ways of testing the assumption of equal weight-based toxicity of the four PFAS and evaluated more flexible models with exposure indices allowing for differences in toxicity. RESULTS: Results relying on full and decile-based data were in good accordance. However, BMD results for the larger study were lower than observed by EFSA for the smaller study. EFSA derived a lower confidence limit for the BMD of 17.5 ng/mL for the sum of serum-PFAS concentration, while similar calculations in the larger cohort yielded values of about 1.5 ng/mL. As the assumption of equal weight-based toxicity of the four PFAS seems questionable, we confirmed dose-dependencies that allowed potency differences between PFAS. We also found that models linear in the parameters for the BMD analysis showed superior coverage probabilities. In particular, we found the piecewise linear model to be useful for Benchmark analysis. CONCLUSIONS: Both data sets considered could be analyzed on a decile basis without important bias or loss of power. The larger study showed substantially lower BMD results, both for individual PFAS and for joint exposures. Overall, EFSA's proposed tolerable exposure limit appears too high, while the EPA proposal is in better accordance with the results.
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Benchmarking , Fluorocarbonos , Criança , Humanos , Lactente , Benchmarking/métodos , Fluorocarbonos/toxicidadeRESUMO
Per- and polyfluoroalkyl substances (PFAS) are used for their properties such as stain and water resistance. The substances have been associated with adverse health outcomes in both pregnant mothers and infants, including pre-eclampsia and low birthweight. A growing body of research suggests that PFAS are transferred from mother to fetus through the placenta, leading to in utero exposure. A systematic review was performed using the PubMed database to search for studies evaluating determinants of PFAS concentrations in blood matrices of pregnant mothers and neonates shortly after birth. Studies were included in this review if an observational study design was utilized, exposure to at least one PFAS analyte was measured, PFAS were measured in maternal or neonatal matrices, at least one determinant of PFAS concentrations was assessed, and results such as beta estimates were provided. We identified 35 studies for inclusion in the review and evaluated the PFAS and determinant relationships among the factors collected in these studies. Parity, breastfeeding history, maternal race and country of origin, and household income had the strongest and most consistent evidence to support their roles as determinants of certain PFAS concentrations in pregnant mothers. Reported study findings on smoking status, alcohol consumption, and pre-pregnancy body mass index (BMI) suggest that these factors are not important determinants of PFAS concentrations in pregnant mothers or neonates. Further study into informative factors such as consumer product use, detailed dietary information, and consumed water sources as potential determinants of maternal or neonatal PFAS concentrations is needed. Research on determinants of maternal or neonatal PFAS concentrations is critical to estimate past PFAS exposure, build improved exposure models, and further our understanding on dose-response relationships, which can influence epidemiological studies and risk assessment evaluations. Given the potential for adverse outcomes in pregnant mothers and neonates exposed to PFAS, it is important to identify and understand determinants of maternal and neonatal PFAS concentrations to better implement public health interventions in these populations.
Assuntos
Feto , Fluorocarbonos , Feminino , Gravidez , Lactente , Recém-Nascido , Humanos , Índice de Massa Corporal , Mães , Placenta , Estudos Observacionais como AssuntoRESUMO
Concentrations of per and polyfluorinated alkyl substances (PFAS) in drinking water are significantly lower than in vivo levels of the native target hormone. These concentrations are orders of magnitude lower than the hormone in question, particularly when corrected for transactivation. A pregnant woman can excrete about 7,000 µg/day of total estrogens. A low-dose oral contraceptive pill contains 20 µg estradiol. Soy-based baby formula contains phytoestrogens equivalent to a low-dose oral contraceptive pill. A woman on a low-dose oral hormone replacement therapy consumes about 0.5-2 mg/day of one or more estrogens. The levels of endocrine-disrupting substances (EDSs) exposure by oral, respiratory, or dermal routes have the potential to make removing PFAS from drinking water due to its estrogenic activity divert valuable resources. These levels become even less of a threat when their estrogenic potencies are compared with those of the target hormones present as contaminants in water and even more so when compared with levels commonly present in human tissues. The fact that PFAS constitute a tiny fraction compared to exposure to phytoestrogens makes the effort even more insignificant. If PFAS are to be removed from drinking water, it is not due to their estrogenic activity.
Assuntos
Água Potável , Fluorocarbonos , Poluentes Químicos da Água , Gravidez , Feminino , Humanos , Fitoestrógenos , Risco , Estrogênios/análise , Estradiol , Estrona , Anticoncepcionais Orais , Poluentes Químicos da Água/análiseRESUMO
Perfluorooctanoic acid (PFOA) is a part of a large group of anthropogenic, persistent, and bioaccumulative contaminants known as per- and polyfluoroalkyl substances (PFAS) that can be harmful to human health. In this work, we present the first ab initio molecular dynamics (AIMD) study of temperature-dependent degradation dynamics of PFOA on (100) and (110) surfaces of γ-Al2O3. Our results show that PFOA degradation does not occur on the pristine (100) surface, even when carried out at high temperatures. However, introducing an oxygen vacancy on the (100) surface facilitates an ultrafast (<100 fs) defluorination of C-F bonds in PFOA. We also examined degradation dynamics on the (110) surface and found that PFOA interacts strongly with Al(III) centers on the surface of γ-Al2O3, resulting in a stepwise breaking of C-F, C-C, and C-COO bonds. Most importantly, at the end of the degradation process, strong Al-F bonds are formed on the mineralized γ-Al2O3 surface, which prevents further dissociation of fluorine into the surrounding environment. Taken together, our AIMD simulations provide critical reaction mechanisms at a quantum level of detail and highlight the importance of temperature effects, defects, and surface facets for PFOA degradation on reactive surfaces, which have not been systematically explored or analyzed.
Assuntos
Fluorocarbonos , Simulação de Dinâmica Molecular , Humanos , Óxido de Alumínio , Caprilatos/químicaRESUMO
Pyrolysis is the process whereby carbonaceous materials, such as biosolids, are heated between 400°C and 900°C in the absence of oxygen. Three main products are generated: a solid product called biochar, a py-liquid that consists of aqueous phase and non-aqueous phase liquid, and py-gas. The biochar holds value as a beneficial soil amendment and sequesters carbon. The py-liquid is potentially hazardous and needs to be dealt with (including potentially reducing it on-site via catalysis or thermal oxidation). Py-gas can be used on-site for energy recovery. Pyrolysis has gained recent interest due to concern over per- and polyfluoroalkyl substances (PFAS) in biosolids. Although pyrolysis can remove PFAS from biosolids, it has been shown to produce PFAS that reside in py-liquid, and the fate in py-gas remains a knowledge gap. More research is needed to help close the PFAS and fluorine mass balance through pyrolysis influent and effluent products because pyrolysis alone does not destroy all PFAS. The moisture content of biosolids substantially affects the energy balance for pyrolysis. Utilities that already produce a dried biosolids product are in a better position to install pyrolysis. Pyrolysis has both defined benefits (solids reduction, PFAS removal from biosolids, and biochar production) as well as remaining questions (the fate of PFAS in py-gas and py-liquid, mass balance on nutrients, and py-liquid handling options) that will be answered through more pilot and full-scale demonstrations. Regulations and local policies (such as carbon sequestration credits) could affect pyrolysis implementation. Pyrolysis should be considered as an option in the biosolids stabilization toolbox with application being based on individual circumstances of a utility (e.g., energy, moisture content of biosolids, PFAS). PRACTITIONER POINTS: Pyrolysis has known benefits but limited full-scale operational data. Pyrolysis removes PFAS from biochar, but PFAS fate in gas phase is unknown. Moisture content of influent feed solids affects energy balance of pyrolysis. Policy on PFAS, carbon sequestration, or renewable energy could impact pyrolysis.
Assuntos
Fluorocarbonos , Águas Residuárias , Biossólidos , PiróliseRESUMO
BACKGROUND AND AIM: Epidemiological evidence on the association between prenatal exposure to Perfluoroalkyl substances (PFAS) and child cognition remains unclear. Thus, we aimed to investigate whether prenatal exposure to PFAS is associated with intelligence quotient (IQ) in offspring. METHOD: This study population included 2031 mother-child pairs in the Shanghai Birth Cohort (SBC) enrolled during 2013-2016. Ten PFAS were measured by high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS-MS) in maternal plasma samples collected in early gestation between 9 and 16 weeks of gestation. Child IQ was assessed using the Wechsler Preschool and Primary Scales of Intelligence-Fourth Edition (WPPSI-IV) at 4 years of age. Multivariable linear regression models were used to estimate the associations between individual PFAS concentrations (as a continuous variable or categorized into tertiles) and child IQ. A quantile g-computation approach was used to evaluate the joint and independent effects of PFAS on IQ. We also examined whether the associations varied by child sex. RESULTS: We found no significant associations between ln-transformed nine individual PFAS and child full scale IQ (FSIQ) or subscale IQ after adjusting for potential confounders. The observed associations were not modified by child sex. PFAS in tertiles showed the same pattern. Results from quantile g-computation showed that PFAS mixture was not associated with child IQ; perfluorobutane sulfonate was negatively associated with FSIQ (ß, -0.81; 95 % CI: -1.55, -0.07), and perfluorooctane sulfonate was also associated with lower fluid reasoning index scores (ß, -1.61; 95 % CI: -3.07, -0.16) while adjusting for the other PFAS. CONCLUSION: PFAS mixture during early pregnancy was not associated with child IQ. For certain individual PFAS, there were inverse associations with FSIQ or subscale IQ. Considering the evidence is still inconsistent, further research is needed to confirm or refute these results in other populations and to elucidate the potential neurotoxicology of PFAS.
