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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.
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Biotransformação , Microbiologia do Solo , RNA Ribossômico 16S/genética , Solo/química , Poluentes do Solo/metabolismo , Fluorocarbonos/metabolismoRESUMO
Indicators of male fertility are in decline globally, but the underlying causes, including the role of environmental exposures, are unclear. This study aimed to examine organic chemical pollutants in seminal plasma, including both known priority environmental chemicals and less studied chemicals, to identify uncharacterized male reproductive environmental toxicants. Semen samples were collected from 100 individuals and assessed for sperm concentration, percent motility, and total motile sperm. Targeted and nontargeted organic pollutant exposures were measured from seminal plasma using gas chromatography, which showed widespread detection of organic pollutants in seminal plasma across all exposure classes. We used principal component pursuit (PCP) on our targeted panel and derived one component (driven by etriadizole) associated with total motile sperm (p < 0.001) and concentration (p = 0.03). This was confirmed by the exposome-wide association models using individual chemicals, where etriadizole was negatively associated with total motile sperm (FDR q = 0.01) and concentration (q = 0.07). Using PCP on 814 nontargeted spectral peaks identified a component that was associated with total motile sperm (p = 0.001). Bayesian kernel machine regression identified one principal driver of this association, which was analytically confirmed to be N-nitrosodiethylamine. These findings are promising and consistent with experimental evidence showing that etridiazole and N-nitrosodiethylamine may be reproductive toxicants.
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Poluentes Ambientais , Sêmen , Sêmen/química , Sêmen/efeitos dos fármacos , Masculino , Humanos , Expossoma , Adulto , Exposição AmbientalRESUMO
In the modern "omics" era, measurement of the human exposome is a critical missing link between genetic drivers and disease outcomes. High-resolution mass spectrometry (HRMS), routinely used in proteomics and metabolomics, has emerged as a leading technology to broadly profile chemical exposure agents and related biomolecules for accurate mass measurement, high sensitivity, rapid data acquisition, and increased resolution of chemical space. Non-targeted approaches are increasingly accessible, supporting a shift from conventional hypothesis-driven, quantitation-centric targeted analyses toward data-driven, hypothesis-generating chemical exposome-wide profiling. However, HRMS-based exposomics encounters unique challenges. New analytical and computational infrastructures are needed to expand the analysis coverage through streamlined, scalable, and harmonized workflows and data pipelines that permit longitudinal chemical exposome tracking, retrospective validation, and multi-omics integration for meaningful health-oriented inferences. In this article, we survey the literature on state-of-the-art HRMS-based technologies, review current analytical workflows and informatic pipelines, and provide an up-to-date reference on exposomic approaches for chemists, toxicologists, epidemiologists, care providers, and stakeholders in health sciences and medicine. We propose efforts to benchmark fit-for-purpose platforms for expanding coverage of chemical space, including gas/liquid chromatography-HRMS (GC-HRMS and LC-HRMS), and discuss opportunities, challenges, and strategies to advance the burgeoning field of the exposome.
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Espectrometria de Massas , Humanos , Espectrometria de Massas/métodos , Expossoma , Metabolômica , Proteômica/métodos , Exposição AmbientalRESUMO
Aqueous film-forming foams (AFFFs) have been extensively used for extinguishing hydrocarbon-fuel fires at military sites, airports, and fire-training areas. Despite being a significant source of per- and polyfluoroalkyl substances (PFAS), our understanding of PFAS occurrence in AFFF formulations and AFFF-impacted environments is limited, as is the impact of microbial transformation on the environment fate of AFFF-derived PFAS. This literature review compiles PFAS concentrations in electrochemical fluorination (ECF)- and fluorotelomer (FT)-based AFFFs and provides an overview of PFAS occurrence in AFFF-impacted environments. Our analysis reveals that AFFF use is a predominant point source of PFAS contamination, including primary precursors (polyfluoroalkyl substances as AFFF components), secondary precursors (polyfluoroalkyl transformation products of primary precursors), and perfluoroalkyl acids (PFAAs). Moreover, there are discrepancies between PFAS concentration profiles in AFFFs and those measured in AFFF-impacted media. For example, primary precursors constitute 52.6 % and 99.5 % of PFAS mass in ECF- and FT-based AFFFs, respectively, whereas they represent only 0.7 % total mass in AFFF-impacted groundwater. Conversely, secondary precursors, which constitute <1 % of PFAS in AFFFs, represent 4.0-27.8 % of PFAS in AFFF-impacted environments. The observed differences in PFAS levels between AFFFs and environmental samples are likely due to in-situ biotransformation processes. Biotransformation rates and pathways reported for AFFF-derived primary and secondary precursors varied among different classes of precursors, consistent with the PFAS occurrence in AFFF-impacted environments. For example, readily biodegradable primary precursors, N-dimethyl ammonio propyl perfluoroalkane sulfonamide (AmPr-FASA) and n:2 fluorotelomer thioether amido sulfonate (n:2 FtTAoS), were rarely detected in AFFF-impacted environments. In contrast, key secondary precursors, perfluoroalkane sulfonamides (FASAs) and n:2 fluorotelomer sulfonate (n:2 FTS), were widely detected, which was attributed to their resistance to biotransformation. Key knowledge gaps and future research priorities are presented to better understand the occurrence, fate, and transport of AFFF-derived PFAS in the environment and to design more effective remediation strategies.
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Molecular data storage offers the intriguing possibility of higher theoretical density and longer lifetimes than today's electronic memory devices. Some demonstrations have used deoxyribonucleic acid (DNA), but bottlenecks in nucleic acid synthesis continue to make DNA data storage orders of magnitude more expensive than electronic storage media. Additionally, despite its potential for long-term storage, DNA faces durability challenges from environmental degradation. In this work, we demonstrate nongenomic molecular data storage using molecular libraries redirected from chemical waste streams. This approach requires no synthetic effort and can be implemented by using molecules that have a minimal associated cost. While the technique is agnostic about the exact molecular content of its inputs, we confirmed that some sources contained poly fluoroalkyl substances (PFAS), which persist for long periods in the natural environment and could offer extremely durable information storage as well as environmental benefits. These demonstrations provide a perspective on some of the valuable possibilities for nongenomic molecular information systems.
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Short chain per- and polyfluoroalkyl substances (PFAS), including hexafluoropropylene oxide dimer acid (GenX) and perfluorobutane sulfonate (PFBS), are replacement chemicals for environmentally persistent, long-chain PFAS. Although GenX and PFBS have been detected in surface and ground water worldwide, few studies provide information on the metabolic alterations or risks associated with their exposures. In this study, larval zebrafish were used to investigate the toxicity of early-life exposure to GenX or PFBS. Zebrafish were chronically exposed from 4 h post-fertilization (hpf) to 6 days post-fertilization (dpf) to 150 µM GenX or 95.0 µM PFBS. Ultra-high-performance liquid chromatography paired with high-resolution mass spectrometry was used to quantify uptake of GenX and PFBS into zebrafish larvae and perform targeted and untargeted metabolomics. Our results indicate that PFBS was 20.4 % more readily absorbed into the zebrafish larvae compared to GenX. Additionally, PFBS exposure significantly altered 13 targeted metabolites and 21 metabolic pathways, while GenX exposure significantly altered 1 targeted metabolite and 17 metabolic pathways. Exposure to GenX, and to an even greater extent PFBS, resulted in a number of altered metabolic pathways in the amino acid metabolism, with other significant alterations in the carbohydrate, lipid, cofactors and vitamins, nucleotide, and xenobiotics metabolisms. Our results indicate that GenX and PFBS impact the zebrafish metabolome, with implications of global metabolic dysregulation, particularly in metabolic pathways relating to growth and development.
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Metabolômica , Poluentes Químicos da Água , Peixe-Zebra , Animais , Peixe-Zebra/metabolismo , Poluentes Químicos da Água/toxicidade , Fluorocarbonos/toxicidade , Larva/efeitos dos fármacos , Larva/metabolismo , Larva/crescimento & desenvolvimento , Metaboloma/efeitos dos fármacosRESUMO
Nearly all per- and polyfluoroalkyl substances (PFAS) biotransformation studies reported to date have been limited to laboratory-scale batch reactors. The fate and transport of PFAS in systems that more closely represent field conditions, i.e., in saturated porous media under flowing conditions, remain largely unexplored. This study investigated the biotransformation of 6:2 fluorotelomer sulfonate (6:2 FTS), a representative PFAS of widespread environmental occurrence, in one-dimensional water-saturated flow-through columns packed with soil obtained from a PFAS-contaminated site. The 305-day column experiments demonstrated that 6:2 FTS biotransformation was rate-limited, where a decrease in pore-water velocity from 3.7 to 2.4 cm/day, resulted in a 21.7-26.1 % decrease in effluent concentrations of 6:2 FTS and higher yields (1.0-1.4 mol% vs. 0.3 mol%) of late-stage biotransformation products (C4C7 perfluoroalkyl carboxylates). Flow interruptions (2 and 7 days) were found to enhance 6:2 FTS biotransformation during the 6-7 pore volumes following flow resumption. Model-fitted 6:2 FTS column biotransformation rates (0.039-0.041 cmw3/gs/d) were â¼3.5 times smaller than those observed in microcosms (0.137 cmw3/gs/d). Additionally, during column experiments, planktonic microbial communities remained relatively stable, whereas the composition of the attached microbial communities shifted along the flow path, which may have been attributed to oxygen availability and the toxicity of 6:2 FTS and associated biotransformation products. Genus Pseudomonas dominated in planktonic microbial communities, while in the attached microbial communities, Rhodococcus decreased and Pelotomaculum increased along the flow path, suggesting their potential involvement in early- and late-stage 6:2 FTS biotransformation, respectively. Overall, this study highlights the importance of incorporating realistic environmental conditions into experimental systems to obtain a more representative assessment of in-situ PFAS biotransformation.
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Fluorocarbonos , Microbiota , Poluentes Químicos da Água , Fluorocarbonos/análise , Biotransformação , Alcanossulfonatos/metabolismo , Água , Poluentes Químicos da Água/análiseRESUMO
Aqueous film forming foams (AFFFs) have been used to extinguish fires since the 1960s, leading to widespread subsurface contamination by per- and polyfluoroalkyl substances (PFAS), an essential component of AFFF. This study presents 1-D simulations of PFAS migration in the vadose zone resulting from AFFF releases. Simulation scenarios used soil profiles from three US Air Force (USAF) installations, encompassing a range of climatic conditions and hydrogeologic environments. A three-component mixture, representative of major constituents of AFFF, facilitated the exploration of competitive and synergistic effects of co-constituents on PFAS migration. To accurately capture unsaturated transport of PFAS in porous media, the model considers (1) surfactant-induced flow, (2) non-linear sorption to the solid phase, (3) competitive accumulation at the air-water interface, and (4) the moisture-dependence of the air-water interfacial area. Defined PFAS releases were consistent with fire training exercises, emergency responses, and accidental spills of record. Simulation results illustrate the importance of hydrogeologic, climatic, geochemical, and AFFF release conditions on PFAS transport and retention. Comparison of field observations and model simulations for Ellsworth AFB indicate that much of the PFOA and PFOS mass is associated with the air-water interface and the solid phase, which limits their migration potential in the vadose zone. Results also show that rates of migration in the aqueous phase are largely controlled by hydrogeologic properties, including recharge rates and hydraulic conductivity. AFFF spill scenarios varying in volume, concentration, and frequency reveal the importance of release characteristics in determining rates of PFAS migration and concentration peaks. Variability is attributed to non-linear sorption processes, where, contrary to simple linear partitioning formulations, transport is strongly affected by the concentration of PFAS species. Simulations also demonstrate the importance of modeling the AFFF as a mixture since competitive interfacial accumulation effects are shown to enhance the mobility of less surface-active PFAS compounds.
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Introduction: Exposure to endocrine disrupting chemicals (EDCs), such as phthalates, can negatively impact maternal and child health, contributing to impaired fetal growth, preterm birth, and pregnancy complications, as well as increased downstream risks of cardiometabolic disease and breast cancer. Notably, women of color (WOC) are the largest consumers of personal care products, which are a common source of EDC exposure. Methods: The Let's Reclaim Our Ancestral Roots (Let's R.O.A.R) Pilot Study developed an educational intervention delivered during pregnancy to promote reduced use of phthalate-containing hair care products (HCPs). This mixed-methods study included: (1) a quantitative analysis and (2) a qualitative analysis of the educational sessions and the semi-structured focus groups to evaluate the factors that influenced the hair care practices and product choices of WOC at various stages of life, including their current pregnancy (hereafter referred to as the hair journey). During the sessions, participants learned about EDCs (with a focus on phthalates), the unequal burden of exposure for WOC, adverse implications of exposure, and exposure reduction strategies. Focus group sessions provided insight into participants' hair journeys from childhood to the current pregnancy and explored factors during their hair product selection process. All sessions were transcribed and imported into NVivo Version 12 for coding and thematic analysis. Results: A total of 46 individuals were enrolled in the study, and 31 participated in an educational session. This current work synthesizes the qualitative analysis of this study. We identified two important life stages (before and after gaining agency over hair care practices and product choices) and three dominant themes related to HCP use: (1) products that impacted the hair journey, which involved all mentions of hair products, (2) factors that influenced the hair journey, which included individuals or entities that shaped participants' hair experiences, and (3) the relationship between hair and sense of self, where sense of self was defined as the alignment of one's inner and outer beauty. Conclusion: The themes intersected and impacted the participants' hair journey. Cultural integration was a sub-theme that overlapped within the dominant themes and participants discussed the effect of traditions on their hair experiences.