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The recent application of non-targeted analysis (NTA) techniques in environmental monitoring has revealed numerous novel fluorinated species in surface water, wildlife, and humans in the Cape Fear River (CFR) region of North Carolina. In this study, we have re-examined archived alligator, striped bass, horse, and dog serum as well as archived seabird tissue data from previously reported exposure studies in order to extend the panel of detected novel PFAS. In this study, the compounds CF3-(OCF2)x-COOH, x = 6, 7, 8 (Abbreviated PFO6TeDA, PFO7HxDA, PFO8OcDA, respectively), and 6H-Perfluoro-3-oxa,4-methylhexanesulfonic acid (Nafion byproduct 6) were detected for the first time in environmental tissues even though these analytes were not previously detected in the CFR. Analytical standards were available for PFO6TeDA and Nafion Byproduct 6, and therefore, were quantitated in investigated tissues. PFO7HxDA and PFO8OcDA had no available standards and were semi-quantitated using NTA techniques. Of note, PFO6TeDA, PFO7HxDA, and PFO8OcDA were observed in alligator, bass, and seabird but not horse and dog. PFO6TeDA was detected at the highest frequency in all investigated tissues with PFO7HxDA and PFO8OcDA detected at lower frequencies. No Nafion Byproduct 6 values are reported in serum due to poor analytical reproducibility of the measurements. Seabird tissue to blood ratios suggests PFO6TeDA is highest in the heart, kidney, and liver and lowest in the brain. Overall, additional studies are needed to fully understand the potential impact of these additional novel PFAS on both wildlife and humans in the CFR region.
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With increasing public awareness of PFAS, and their presence in biological and environmental media across the globe, comes a matching increase in the number of PFAS monitoring studies. As more matrices and sample cohorts are examined, there are more opportunities for matrix interferents to appear as PFAS where there are none (i.e., "seeing ghosts"), impacting subsequent reports. Addressing these ghosts is vital for the research community, as proper analytical measurements are necessary for decision-makers to understand the presence, levels, and potential risks associated with PFAS and protect human and environmental health. To date, PFAS interference has been identified in several matrices (e.g., food, shellfish, blood, tissue); however, additional unidentified interferents are likely to be observed as PFAS research continues to expand. Therefore, the aim of this commentary is several fold: (1) to create and support a publicly available dataset of all currently known PFAS analytical interferents, (2) to allow for the expansion of that dataset as more sources of interference are identified, and (3) to advise the wider scientific community on how to both identify and eliminate current or new analytical interference in PFAS analyses.
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Fluorocarburos , Contaminantes Químicos del Agua , Humanos , Contaminantes Químicos del Agua/análisis , Fluorocarburos/análisis , Alimentos Marinos/análisis , Mariscos/análisis , Membrana EritrocíticaRESUMEN
BACKGROUND: A fluorochemical facility near Fayetteville, North Carolina, emitted per- and polyfluoroalkyl ether acids (PFEAs), a subgroup of per- and polyfluoroalkyl substances (PFAS), to air. OBJECTIVE: Analyze PFAS in private wells near the facility and in blood from well users to assess relationships between PFEA levels in water and serum. METHODS: In 2019, we recruited private well users into the GenX Exposure Study and collected well water and blood samples. We targeted 26 PFAS (11 PFEAs) in water and 27 PFAS (9 PFEAs) in serum using liquid chromatography-mass spectrometry. We used regression modeling to explore relationships between water and serum PFAS. For the only PFEA detected frequently in water and serum, Nafion byproduct 2, we used generalized estimating equation (GEE) models to assess well water exposure metrics and then adjusted for covariates that may influence Nafion byproduct 2 serum concentrations. RESULTS: We enrolled 153 participants ages 6 and older (median = 56 years) using 84 private wells. Most wells (74%) had ≥6 detectable PFEAs; median ∑PFEAs was 842 ng/L (interquartile range = 197-1760 ng/L). Low molecular weight PFEAs (PMPA, HFPO-DA [GenX], PEPA, PFO2HxA) were frequently detected in well water, had the highest median concentrations, but were not detectable in serum. Nafion byproduct 2 was detected in 73% of wells (median = 14 ng/L) and 56% of serum samples (median = 0.2 ng/mL). Cumulative dose (well concentration × duration at address) was positively associated with Nafion byproduct 2 serum levels and explained the most variability (10%). In the adjusted model, cumulative dose was associated with higher Nafion byproduct 2 serum levels while time outside the home was associated with lower levels. IMPACT: PFAS are a large class of synthetic, fluorinated chemicals. Fluorochemical facilities are important sources of environmental PFAS contamination globally. The fluorochemical industry is producing derivatives of perfluoroalkyl acids, including per- and polyfluoroalkyl ether acids (PFEAs). PFEAs have been detected in various environmental samples but information on PFEA-exposed populations is limited. While serum biomonitoring is often used for PFAS exposure assessment, serum biomarkers were not good measures of long-term exposure to low molecular weight PFEAs in a private well community. Environmental measurements and other approaches besides serum monitoring will be needed to better characterize PFEA exposure.
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Éter , Polímeros de Fluorocarbono , Fluorocarburos , Propionatos , Humanos , Suero , North Carolina , Éteres de Etila , ÉteresRESUMEN
Central North Carolina (NC) is highly contaminated with per- and polyfluoroalkyl substances (PFAS), in part due to local fluorochemical production. Little is known about the exposure profiles and long-term health impacts for humans and animals that live in nearby communities. In this study, serum PFAS concentrations were determined using liquid chromatography high-resolution mass spectrometry and diagnostic clinical chemistry endpoints were assessed for 31 dogs and 32 horses that reside in Gray's Creek NC at households with documented PFAS contamination in their drinking water. PFAS were detected in every sample, with 12 of the 20 PFAS detected in ≥50% of samples from each species. The average total PFAS concentrations in horses were lower compared to dogs who had higher concentrations of PFOS (dogs 2.9 ng/mL; horses 1.8 ng/mL), PFHxS (dogs 1.43 ng/mL, horses < LOD), and PFOA (dogs 0.37 ng/mL; horses 0.10 ng/mL). Regression analysis highlighted alkaline phosphatase, glucose, and globulin proteins in dogs and gamma glutamyl transferase in horses as potential biomarkers associated with PFAS exposure. Overall, the results of this study support the utility of companion animal and livestock species as sentinels of PFAS exposure differences inside and outside of the home. As in humans, renal and hepatic health in domestic animals may be sensitive to long-term PFAS exposures.
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Ácidos Alcanesulfónicos , Agua Potable , Contaminantes Ambientales , Fluorocarburos , Contaminantes Químicos del Agua , Humanos , Perros , Caballos , Animales , North Carolina , Fluorocarburos/análisis , Contaminantes Químicos del Agua/análisis , Agua Potable/análisis , Agua Potable/química , Biomarcadores , Ácidos Alcanesulfónicos/análisis , Contaminantes Ambientales/análisisRESUMEN
The shift away from PFOS and PFOA production in the past 20 years towards shorter chain and replacement PFAS has led to the environmental release of complex mixtures of emerging PFAS for which bioaccumulation potential and toxicology are largely unknown. The rate at which emerging PFAS can be prioritized for research in these complex mixtures is often limited by the lack of available chemical standards. We developed a study design that rapidly assesses which emerging PFAS in an environmentally derived mixture have the potential for mammalian bioaccumulation and thus prioritize these emerging chemicals for standard synthesis and toxicity testing. Surface water was collected at an impacted site downstream of an industrial fluorochemical manufacturing outfall and concentrated 100-fold via weak anion exchange, solid-phase extraction. The concentrated extract contained 13 previously identified emerging PFAS, including hexafluoropropylene oxide-dimer acid (HFPO-DA). BALB/c mice were orally dosed with surface water concentrate once a day for seven days. Twenty-four hours after the last dose, liver, serum, urine, and feces were collected and the emerging PFAS were semi-quantified based on peak area counts. Of the 13 emerging PFAS, Nafion byproduct-2 (Nafion BP2), Hydro-EVE, PFO4DA, and PFO5DoA had the largest increases in percent composition when comparing serum and liver to the dosing solution, suggesting that these PFAS may have the highest bioaccumulation potential. This finding supports other studies that detected bioaccumulation of the same four PFAS in human serum collected from communities with contaminated drinking water. In the future, the Rapid Assessment Bioaccumulation Screening (RABS) study design can be extended to other complex industrial chemical mixtures impacting surface water in order to better inform chemical prioritization for acquisition and in vitro/in vivo toxicity testing of the potential pollutants.
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Ácidos Alcanesulfónicos , Agua Potable , Fluorocarburos , Contaminantes Químicos del Agua , Ácidos Alcanesulfónicos/toxicidad , Animales , Bioacumulación , Mezclas Complejas , Fluorocarburos/análisis , Humanos , Mamíferos , Ratones , Contaminantes Químicos del Agua/toxicidadRESUMEN
Pansteatitis is the leading cause for the decline in Nile crocodile populations and the sporadic mortality of fish in the Olifants River System, South Africa. To determine the prevalence of this disease in lentic systems, Mozambique tilapia, Oreochromis mossambicus, were collected from Lake Loskop, Lake Flag Boshielo, Phalaborwa Barrage and Lake Luphephe-Nwanedi. The former three impoundments are located within the main stem of the Olifants River, while the latter, which is geographically isolated and situated in the Limpopo River System, served as a reference site. Mesenteric adipose, liver, serosa of the swim bladder, gill and the skeletal muscle of fish sampled were examined for gross and microscopic evidence of pansteatitis. Microscopically observed changes were used to statistically compare pansteatitis prevalence between samples and sites. Based on histopathological evaluation, the adipose tissue in the liver, swim bladder serosa and coelom from severely debilitated individuals showed the most significant pathological changes. Lesions indicative of steatitis were observed in fish collected from Lake Loskop (75%), Lake Flag Boshielo (22%) and Lake Luphephe-Nwanedi (15%). Further investigation is warranted to understand the pervasiveness and mechanisms driving pathological changes of pansteatitis at Lake Flag Boshielo, Phalaborwa Barrage and Lake Luphephe-Nwanedi.
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Enfermedades de los Peces/patología , Esteatitis/patología , Tilapia , Tejido Adiposo/patología , Sacos Aéreos/patología , Animales , Lagos , Hígado/patología , Ríos , SudáfricaRESUMEN
INTRODUCTION: Lipidomics is an emerging field with great promise for biomarker and mechanistic studies due to lipids diverse biological roles. Clinical research applying lipidomics is drastically increasing, with research methods and tools developed for clinical applications equally promising for wildlife studies. OBJECTIVES: Limited research to date has applied lipidomics, especially of the intact lipidome, to wildlife studies. Therefore, we examine the application of lipidomics for in situ studies on Mozambique tilapia (Oreochromis mossambicus) in Loskop Dam, South Africa. Wide-scale mortality events of aquatic life associated with an environmentally-derived inflammatory disease, pansteatitis, have occurred in this area. METHODS: The lipidome of adipose tissue (n = 31) and plasma (n = 51) from tilapia collected from Loskop Dam were characterized using state of the art liquid chromatography coupled to high-resolution tandem mass spectrometry. RESULTS: Lipid profiles reflected pansteatitis severity and were significantly different between diseased and healthy individuals. Over 13 classes of lipids associated with inflammation, cell death, and/or oxidative damage were upregulated in pansteatitis-affected adipose tissue, including ether-lipids, short-chained triglyceride oxidation products, sphingolipids, and acylcarnitines. Ceramides showed a 1000-fold increase in the most affected adipose tissues and were sensitive to disease severity. In plasma, triglycerides were found to be downregulated in pansteatitis-affected tilapia. CONCLUSION: Intact lipidomics provided useful mechanistic data and possible biomarkers of pansteatitis. Lipids pointed to upregulated inflammatory pathways, and ceramides serve as promising biomarker candidates for pansteatitis. As comprehensive coverage of the lipidome aids in the elucidation of possible disease mechanisms, application of lipidomics could be applied to the understanding of other environmentally-derived inflammatory conditions, such as those caused by obesogens.