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Hexafluoropropylene oxide (GenX) is a kind of substitute to PFOA, which has been listed in the Stockholm Convention. In this study, GenX was attempted to be degraded using a boron-doped diamond anode in the electrochemical oxidation system. The effects of operating parameters, including current density (0.5-10 mA/cm2), initial pH (3.0-11.49), initial concentration of GenX (20-150 mg/L), electrode distances (0.5-2 cm), electrolyte types (Na2SO4, NaCl, NaNO3 and NaHCO3) and Na2SO4 electrolyte concentration (40-80 mm), on GenX were studied. GenX can almost completely be degraded under the optimal operating parameters after 180 min of electrolysis. Free radical quenching experiments were carried out to investigate the effects of hydroxyl radicals and sulphate radicals on the degradation of GenX. The degradation intermediates were identified based on the ultra-high performance liquid chromatography equipped with a tandem mass spectrometer, and the degradation mechanisms were also proposed. Finally, the toxicities of GenX and its degradation products were evaluated using the QSAR models. The novelty is that the degradation mechanisms of the high concentration GenX (100 mg/L) were elucidated based on the free radical quenching experiments and the intermediates detected, when the degradation ratio reached 100%.

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BACKGROUND: Perfluorinated compounds (PFCs) are a class of widely manufactured and used emerging persistent pollutants. The recent discovered new class of macrocycles pillararenes have garnered significant attention for the applications in environmental pollutant adsorption, with abundant π electron cavities, a symmetrical rigid structure, and host-guest recognition capabilities. RESULTS: In this work, we designed and synthesized novel cationic pillar [n]arenes magnetic nanoparticles (CWPA5@MNPs), and investigated its adsorption performance and mechanism as a type of new adsorbent for the enrichment of PFCs. The results indicate that CWPA5@MNPs exhibits selectively strong affinity for perfluorooctane sulfonate (PFOS) and long-chain (C9-C14) perfluorocarboxylic acids (PFCAs), with the adsorption efficiency exceeding 80 % within 12 min. The maximum adsorption capacity of CWPA5@MNPs for PFOS was measured to be 29.02 mg/g. CWPA5@MNPs can be rapidly isolated from the solution using external magnets, offering a quick and easy separation. Consequently, this study established a CWPA5@MNPs-assisted magnetic solid-phase extraction (MSPE) coupled with high-performance liquid chromatography-tandem mass spectrometry (CWPA5@MNPs-MSPE-HPLC-MS/MS) method for the rapid detection of trace levels of PFCs in environmental water samples. The analysis of 7 PFCs yielded recovery rates ranging from 86.1 % to 107.5 %, with intraday and interday relative standard deviations (RSD) of 3.6-6.4 % and 1.3-7.0 %, respectively. SIGNIFICANCE AND NOVELTY: The study reveals the synthesis and application of novel cationic pillar [n]arenes magnetic nanoparticles (CWPA5@MNPs) as highly efficient adsorbents for selective perfluorinated compounds (PFCs) in water samples. It demonstrates the potential of the newly developed CWPA5@MNPs-MSPE-HPLC-MS/MS method for the quantitative analysis of PFCs in environment, with high sensitivity, accuracy and stability.

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Perfluorinated compounds (PFCs), as an important class of environmental pollutants, have chemical and structural similarities that make their detection a great technical challenge. This study synthesized three species of metal-organic frameworks (MOFs) using different lanthanide metal ions or organic ligands, which were integrated into a fluorescent sensor array. This innovative approach offers a straightforward, rapid, and precise detection strategy for PFCs. Different ionization properties and fluorinated hydrophobic tails of PFCs lead to different electrostatic attraction and hydrophobic effects between PFCs and sensing elements, which become the basis for differential sensing. Furthermore, the fluorescence signal is more convenient to collect, making the sensor array simple to complete the identification. Combined with pattern recognition methods, the array successfully identified seven kinds of PFCs and mixtures with a classification accuracy of 100 % and a detection limit as low as 51 nM. Finally, the utility of the sensor array in river water sample analysis was verified. The strategy provides an effective method for identifying and determining PFCs and offers new opportunities for developing sensor arrays based on lanthanide MOFs.

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In a previous in vivo study, adult male fathead minnows (Pimephales promelas) were exposed via water for 4 days to 1H,1H,8H,8H-perfluorooctane-1,8-diol (FC8-diol). The present study expands on the evaluation of molecular responses to this perfluoro-alcohol by analyzing 26 male fathead minnow liver RNA samples from that study (five from each test concentration: 0, 0.018, 0.051, 0.171, and 0.463 mg FC8-diol/L) using fathead minnow EcoToxChips Ver. 1.0. EcoToxChips are a quantitative polymerase chain reaction array that allows for simultaneous measurement of >375 species-specific genes of toxicological interest. Data were analyzed with the online tool EcoToxXplorer. Among the genes analyzed, 62 and 96 were significantly up- and downregulated, respectively, by one or more FC8-diol treatments. Gene expression results from the previous study were validated, showing an upregulation of vitellogenin mRNA (vtg) and downregulation of insulin-like growth factor 1 mRNA (igf1). Additional genes related to estrogen receptor activation including esr2a (estrogen receptor 2a) and esrrb (estrogen related receptor beta) were also affected, providing further confirmation of the estrogenic nature of FC8-diol. Furthermore, genes involved in biological pathways related to lipid and carbohydrate metabolism, innate immune response, endocrine reproduction, and endocrine thyroid were significantly affected. These results both add confidence in the use of the EcoToxChip tool for inferring chemical mode(s) of action and provide further insights into the possible biological effects of FC8-diol. Environ Toxicol Chem 2024;00:1-9. © 2024 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

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Wastewater treatment plants have been recognized as important sinks for per- and polyfluoroalkyl substances (PFAS) because of their ineffectiveness in removing them reflecting both water and sewage sludge discharge routes. Hydrothermal treatment represents an alternative technology for treating sludge to recover energy and other valuable products. In this study, 15 PFAS were determined in sludge and hydrochar substrates using sonication-solid phase extraction procedure and analyzed using LC-Orbitrap-High Resolution-MS/MS. The method was fully validated, exhibiting very good linearity, recoveries in the range of 48 to 126 %, low detection and quantification limits with expanded uncertainty and precision below 32 % and 21.9 %, respectively. The method was applied to sludge samples from the WWTP of Ioannina city (Greece), as well as to hydrothermally treated samples under various conditions. The most abundant PFAS were PFHxA (0.5-38.3 ng g-1) and PFOS (4.4-22.1 ng g-1). Finally, the hydrothermally treated sludge samples spiked with PFAS presented removal efficiencies for total PFAS of 86.9 %, 91.8 % and 95.7 % at three spiking levels namely 10, 50 and 200 ng g-1, respectively. Results indicated that PFCAs were almost completely removed, except for PFOA, while the concentrations of PFSAs increased in the produced hydrochar with the formation of several intermediates, as detected by HR-LC-MS/MS. The results of this study demonstrate the effect of hydrothermal treatment to the fate of PFAS in sewage sludge and contribute for further studies on design and scale up of hydrothermal carbonization technology as a management option for safer disposal of municipal wastewater sludge.

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This study investigated the concentrations and profiles of 19 perfluoroalkyl substances (PFASs) in the muscle and liver of four freshwater species from Lake Trasimeno (Italy): Anguilla anguilla (European eel), Carassius auratus (goldfish), Perca fluviatilis (European perch), and Procambarus clarkii (red swamp crayfish). In livers, the amount of PFASs ranged from 3.1 to 10 µg kg-1, significantly higher than that in muscle (0.032-1.7 µg kg-1). The predominant PFASs were perfluorooctane sulfonic acid (PFOS) and long-chain carboxylic acids (C8-C14). Short-chain compounds (C4-C5), as well as the long-chain sulfonic acids (C9-C12), were not quantified. The contamination patterns were similar among species with few differences, suggesting the influence of species-specific accumulation. The PFAS concentrations in livers were comparable among species, while in muscle, the higher values were measured in European eel, followed by goldfish, European perch, and red swamp crayfish. The levels were generally lower than those reported for fish from Northern Italian lakes and rivers. The concentrations of regulated PFASs were lower than the maximum limits set by Regulation EU 2023/915 and did not exceed the Environmental Quality Standards (PFOS in biota). This study provides the first valuable insights on PFASs in freshwater species from Lake Trasimeno.

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This study investigated the pollution of perfluorinated compounds (PFCs) in sediments from the main stream of the Yangtze River, the longest river in Asia. Totally, 13 of 15 PFASs were detected in the sediments and the total concentrations ranged from 0.058 ng/g to 0.89 ng/g dry weight (dw), with dominant contaminants by perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). Concentrations of PFASs in the downstream were higher than those of upstream and midstream. Four main sources were analysed using the Unmix model, textile treatments and food packaging dominantly accounted for approximately half of the total sources, followed by metal electroplating (26.8%), fluoropolymer products (16.3%) and fluororesin coatings (7.4%). Total organic carbon (TOC), total nitrogen (TN) and grain size had significant correlation with the concentration of PFASs in sediments, indicating that the physical and chemical parameters could directly affect the adsorption process of PFASs. In addition, anthropogenic factors such as urbanization rate and per capita GDP also had a direct impact on the distribution of PFASs. Environmental risk assessment showed that PFOS posed low to medium risks to the Yangtze River, indicating that sustained attentions were needed.

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Short-chain Perfluorinated compounds (PFCs), used as substitutes for highly toxic long-chain PFCs, are increasingly entering the aquatic environment. However, the toxicity of short-chain PFCs in the environment is still controversial. This study investigated the effects of short-chain perfluorobutanesulfonic acid (PFBS) at different concentrations (2.5, 6, 14.4, 36, and 90 mg/L) on M. aeruginosa growth under 12-day exposure and explored the molecular mechanism of toxicity using transcriptomics. The results showed that M. aeruginosa exhibited hormetic effects after exposure to PFBS. Low PFBS concentrations stimulated algal growth, whereas high PFBS concentrations inhibited it, and this inhibitory effect became progressively more pronounced with increasing PFBS exposure concentrations. Transcriptomics showed that PFBS promoted the pathways of photosynthesis, glycolysis, energy metabolism and peptidoglycan synthesis, providing the energy required for cell growth and maintaining cellular morphology. PFBS, on the other hand, caused growth inhibition in algae mainly through oxidative stress, streptomycin synthesis, and genetic damage. Our findings provide new insights into the toxicity and underlying mechanism of short-chain PFCs on algae and inform the understanding of the hormetic effect of short-chain PFCs, which are crucial for assessing their ecological risks in aquatic environments.

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"GenX" [ammonium perfluoro (2-methyl-3-oxahexanoate] was developed as a replacement chemical for toxic perfluorinated compounds to be used in product manufacturing. Here, we assessed developmental, mitochondrial, and behavioral toxicity endpoints in zebrafish embryos/larvae exposed to GenX. GenX exerted low toxicity to zebrafish embryos/larvae up to 20 mg/L. GenX did not affect mitochondrial oxidative phosphorylation nor ATP levels. ROS levels were reduced in larvae fish exposed to 10 and 100 µg/L, indicative of an antioxidant defense; however, ROS levels were elevated in fish exposed to 1000 µg/L. Increased expression of cox1 and sod2 in GenX exposed 7-day larvae was noted. GenX (0.1 or 1 µg/L) altered transcripts associated with neurotoxicity (elavl3, gfap, gap43, manf, and tubb). Locomotor activity of larvae was reduced by 100 µg/L GenX, but only in light periods. Perturbations of anxiety-related behaviors in larvae were not observed with GenX exposure. These data inform risk assessments for long-lived perfluorinated chemicals of concern.

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INTRODUCTION: Evidence of the adverse metabolic health effects of perfluoroalkyl and polyfluoroalkyl substances (PFAS) is increasing. However, the impact of PFAS on cardiovascular diseases remains controversial. This meta-analysis aimed to analyze the impact of PFAS on the stroke risk. CONTENT: Databases were searched for studies published up to November 1, 2022, which report the association between stroke and exposure to at least one of four main PFAS (perfluorooctanoic acid [PFOA], perfluorooctanesulfonic acid [PFOS], perfluorononanoic acid [PFNA], and perfluorohexane sulfonic acid [PFHxS]). Data extraction and quality assessment were performed according to the Newcastle-Ottawa scale. SUMMARY AND OUTLOOK: Four studies were included in this systematic review. Multivariate adjusted odds ratios (ORs) for incident stroke per 1-log unit increment in each serum PFAS were combined in the meta-analysis. The risk of development of stroke was not significantly associated with PFOA, PFOS, or PFNA exposure (PFOA: pooled odds ratio [OR]=1.001, 95 % confidence interval [CI]=0.975-1.028, p=0.934; PFOS: pooled OR=0.994, 95 % CI=0.972-1.017, p=0.601; PFNA: pooled OR=1.016, 95 % CI=0.920-1.123, p=0.752), whereas a moderately lower risk was associated with PFHxS exposure without statistical significance (pooled OR=0.953, 95 % CI=0.908-1.001, p=0.054). PFOA, PFOS, and PFNA exposure showed a neutral association, while PFHxS showed a possible inverse association with the risk of stroke. Therefore, this finding should be interpreted with caution. Further prospective observational studies with PFAS mixture analyses are warranted.

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Perfluorinated compounds (PFCs) and their short-chain derivatives are contaminants found globally. Adsorption research on volatile perfluorinated compounds (VPFCs), which are the main PFCs substances that undergo transfer and migration, is particularly important. In this study, new fluorine-containing tail materials (FCTMs) were prepared by combining fluorine-containing tail organic compounds with modified glass fibers. The adsorption effects of these FCTMs were generally stronger than that of pure activated glass fibers without fluorine- tailed, with an adsorption efficiency of up to 86% based on F-F interactions. The results showed that the FCTMs had improved desorption efficiency and reusability, and higher adsorption efficiency compared with that of polyurethane foam. FTGF was applied to the active sampler, and the indoor adsorption of perfluorovaleric acid was up to 2.45 ng/m3. The adsorption kinetics and isotherm simulation results showed that the adsorption process of typical perfluorinated compounds conformed to the second-order kinetics and Langmuir model. Furthermore, Nuclear Magnetic Resonance (NMR) results showed that the chemical shift in the fluorine spectrum was significantly changed by F-F interactions. This research provides basic theoretical data for the study of VPFCs, especially short-chain VPFCs, facilitating improved scientific support for the gas phase analysis of VPFCs in the environment.

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BACKGROUND: Precocious puberty (PP) in girls is traditionally defined as the onset of breast development before the age of 8 years. The specific biomarkers of premature thelarche (PT) and central precocious puberty (CPP) girls are uncertain, and little is known about their metabolic characteristics driven by perfluorinated compounds (PFCs) and clinical phenotype. This study aimed to screen specific biomarkers of PT and CPP and elucidate their underlying pathogenesis. The relationships of clinical phenotype-serum PFCs-metabolic characteristics were also explored to reveal the relationship between PFCs and the occurrence and development of PT and CPP. METHODS: Nuclear magnetic resonance (NMR)-based cross-metabolomics strategy was performed on serum from 146 PP (including 30 CPP, 40 PT, and 76 unspecified PP) girls and 64 healthy girls (including 36 prepubertal and 28 adolescent). Specific biomarkers were screened by the uni- and multivariate statistical analyses. The relationships between serum PFCs and clinical phenotype were performed by correlation analysis and weighted gene co-expression network analysis to explore the link of clinical phenotype-PFCs-metabolic characteristics in PT and CPP. RESULTS: The disordered trend of pyruvate and butyrate metabolisms (metabolites mapped as formate, ethanol, and 3-hydroxybutyrate) were shared and kept almost consistent in PT and CPP. Eight and eleven specific biomarkers were screened for PT and CPP, respectively. The area under curve of specific biomarker combination was 0.721 in CPP vs. prepubertal, 0.972 in PT vs. prepubertal, 0.646 in CPP vs. prepubertal integrated adolescent, and 0.822 in PT vs. prepubertal integrated adolescent, respectively. Perfluoro-n-heptanoic acid and perfluoro-n-hexanoic acid were statistically different between PT and CPP. Estradiol and prolactin were significantly correlated with PFCs in CPP and PT. Clinical phenotypes and PFCs drive the metabolic characteristics and cause metabolic disturbances in CPP and PT. CONCLUSIONS: The elevation of formate, ethanol, and 3-hydroxybutyrate may serve as the early diagnostic indicator for PP in girls. But the stratification of PP still needs to be further determined based on the specific biomarkers. Specific biomarkers of CPP and PT exhibited good sensitivity and can facilitate the classification diagnosis of CPP and PT. PFC exposure is associated with endocrine homeostasis imbalance. PFC exposure and/or endocrine disturbance directly or indirectly drive metabolic changes and form overall metabolic network perturbations in CPP and PT.

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Perfluorinated compounds (PFCs) are man-made chemicals used in the manufacture of many products with water and dirt repellent properties. Many diseases have been proved to be related to the exposure of PFCs, including breast fibroadenoma, hepatocellular carcinoma, breast cancer and leydig cell adenoma. However, whether the PFCs promote the progression of prostate cancer remains unclear. In this work, through comprehensive bioinformatics analysis, we discovered the correlation between the prostate cancer and five PFCs using Comparative Toxicogenomics Database (CTD), Gene Expression Omnibus (GEO) and The Cancer Genome Atlas (TCGA) databases. In addition, further analysis showed that several PFCs-related genes demonstrated strong prognostic value for prostate cancer patients. The survival analysis and receiver operating characteristic (ROC) curves revealed that PFCs-related genes based prognostic model held great predictive value for the prognosis of prostate cancer, which could potentially serve as an independent risk factor in the future. In vitro experiments verified the promotive role of perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) in the growth of prostate cancer cells. This study provided novel insights into understanding the role of PFCs in prostate cancer and brought attention to the environmental association with cancer risks and progression.

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Perfluorinated compounds (PFCs) are widely used in textiles, fire protection, metal electroplating, and semiconductor production owing to their hydrophobic and oil-repellent characteristics. However, they are also persistent organic pollutants. The uncontrolled discharge of PFCs into the environment has led to serious global pollution. PFCs pose severe reproductive, neural, immune, and other threats to human health by accumulating through the food chain. Thus, the development and application of high-performance extraction materials has become a research hotspot in efforts to achieve the accurate detection of trace PFCs in environmental waters. Most traditional PFC adsorbents present a number of disadvantages, such as low adsorption selectivity, slow diffusion, and poor reusability. Covalent organic frameworks (COFs) are crystalline polymers with ordered porous structures, large specific surface areas, and high chemical and thermal stability. These frameworks can easily be functionalized for the desired purpose. In this paper, spherical amino-functionalized COFs (denoted COF-NH2) were fabricated via a two-step method to effectively enrich/remove PFCs from water. First, vinyl covalent organic framework (Vinyl COF) was synthesized at room temperature using 1,4-diradical-2,5-divinylbenzene (Dva) and 1,3,5-tris(4-aminophenyl)benzene (Tab) as building blocks. Then, thioether-bridged aromatic amine-functionalized spherical COF-NH2 was synthesized through a thiol-alkenyl click reaction using 4-aminothiophenol as the functional monomer. COF-NH2 showed good dispersion in water owing to its abundant amino groups, forming multiple hydrogen bonds with the F atoms of PFCs. The synergistic hydrophobic interactions between the organic skeleton of the COF and alkyl carbon chains of the PFCs led to enhanced adsorption efficiency. The produced Vinyl COF and COF-NH2 were characterized by Fourier transform infrared spectroscopy (FT-IR), field-emission scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), and Brunner-Emmet-Teller (BET) measurements. The results confirmed that spherical COF-NH2 materials with a homogeneous size distribution were successfully fabricated. The obtained COF-NH2 microspheres had a diameter of approximately 500 nm and exhibited high thermal stability as well as a large specific surface area and pore volume. The adsorption kinetics, isotherm adsorption models, pH effects, and regeneration properties of COF-NH2 were also investigated, and the results indicated that the adsorption of PFCs by COF-NH2 conformed to the pseudo-second-order kinetic and Langmuir isotherm adsorption models. The obtained COF-NH2 microspheres can be applied over a wide pH range, and the best adsorption effect was achieved in neutral and alkaline environments. After five cycles of regeneration and reuse, the COF-NH2 microspheres retained their good adsorption efficiency for PFCs. The adsorption mechanism was mainly attributed to the synergistic effect of hydrogen bonding and hydrophobic interactions between COF-NH2 and the PFCs. The extraction efficiencies of the microspheres toward five PFCs (perfluorobutyric acid, perfluorovaleric acid, perfluorohexanoic acid, perfluorooctanoic acid, and perfluorononanoic acid) in tap and Pearl River water samples were between 91.76% and 98.59%, with relative standard deviations (RSDs) (n=3) varying from 0.82% to 3.8%; these findings indicate that the obtained COF-NH2 is promising for the extraction of PFCs from complex water samples. Given their uniform size distribution, high thermal stability, good adsorption performance, and reusability, the novel spherical COF-NH2 materials developed in this study may be used as solid-phase extraction materials or filled into liquid chromatographic columns for the enrichment, separation, and detection of PFCs in complex samples.

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The fate and transport behavior of microplastics (MPs), emerging colloidal contaminant ubiquitous in natural environments, would be greatly affected by other copresent pollutants. PFOA (emerging surfactant pollutant) would interact with MPs after encounter with them in natural environments, which could alter the transport behavior of both pollutants. Relevant knowledge is still lacking, affecting accurate prediction the fate and distribution of these two emerging contaminants in natural porous media. The cotransport behavior of different surface charged MPs (negatively/positively charged, CMPs/AMPs) with PFOA (three concentrations ranging from 0.1 to 10 mg/L) in porous media in both 10 and 50 mM NaCl solutions thus was investigated in the present study. We found PFOA inhibited CMPs transport in porous media, while enhanced AMPs transport. The mechanisms leading to the altered transport of CMPs/AMPs caused by PFOA were found to be different. The decreased electrostatic repulsion between CMPs-sand induced by the decreased CMPs negative zeta potentials via the adsorption of PFOA led to the inhibited transport of CMPs in CMPs-PFOA suspension. The enhanced electrostatic repulsion between AMPs-sand due to the decreased positive charge of AMPs via the adsorption of PFOA together with steric repulsion induced by suspended PFOA resulted in the increased transport of AMPs in AMPs-PFOA suspension. Meanwhile, we found that the adsorption onto MPs surfaces also impacted the transport of PFOA. Due to the lower mobility of MPs than PFOA, the presence of MPs despite their surface charge decreased the transport of PFOA of all examined concentrations in quartz sand columns. This study demonstrates that when MPs and PFOA are co-existing in environments, their interaction with each other will alter the fate and transport behavior of both pollutants in porous media and the alteration is highly correlated with the amount of PFOA adsorbed onto MPs and original surface properties of MPs.

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Per- and polyfluoroalkyl substances (PFAS) have been extensively produced and used as surfactants and repellents for decades. To date, the global contamination pattern of PFAS in marine biota has seldomly been reviewed. Seabirds are ideal biomonitoring tools to study environmental contaminants and their effects. Here, we compiled and synthesized reported PFAS concentrations in various seabird species to reflect spatiotemporal patterns and exposure risks of major PFAS on a global ocean scale. Perfluorooctane sulfonic acid (PFOS) was the most studied PFAS in seabirds, which showed the highest level in eggs of common guillemots (U. aalge) from the Baltic Sea, followed by great cormorants (P. carbo) from the North Sea and double-crested cormorants (P.auritus) from the San Francisco Bay, whereas the lowest were those reported for Antarctic seabirds. The temporal pattern showed an overall higher level of PFOS in the late 1990s and early 2000s, consistent with the phase-out of perfluorooctane sulfonyl fluoride-based products. Maximum liver PFOS concentrations in several species such as cormorants and fulmars from Europe and North America exceeded the estimated toxicity reference values. Systematic evaluations using representative species and long time-series are necessary to understand contamination patterns in seabirds in South America, Africa, and Asia where information is lacking. In addition, limited research has been conducted on the identification and toxic effects of novel substitutes such as fluorotelomers and ether PFAS (F-53B, Gen-X etc.) in seabirds. Further research, including multi-omics analysis, is needed to comprehensively characterize the exposure and toxicological profiles of PFAS in seabirds and other wildlife.

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

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Exposure to per- and polyfluoroalkyl substances (PFAS) through the environment can lead to harmful health outcomes and the development of disease. However, little is known about how PFAS impact underlying biology that contributes to these adverse health effects. The metabolome represents the end product of cellular processes and has been used previously to understand physiological changes that lead to disease. In this study, we investigated whether exposure to PFAS was associated with the global, untargeted metabolome. In a cohort of 459 pregnant mothers and 401 children, we quantified plasma concentrations of six individual PFAS- PFOA, PFOS, PFHXS, PFDEA, and PFNA- and performed plasma metabolomic profiling by UPLC-MS. In adjusted linear regression analysis, we found associations between plasma PFAS and perturbations in lipid and amino acid metabolites in both mothers and children. In mothers, metabolites of 19 lipid pathways and 8 amino acid pathways were significantly associated with PFAS exposure at an FDR<0.05 threshold; in children, metabolites of 28 lipid pathways and 10 amino acid pathways exhibited significant associations at FDR<0.05 with PFAS exposure. Our investigation found that metabolites of the Sphingomyelin, Lysophospholipid, Long Chain Polyunsaturated Fatty Acid (n3 and n6), Fatty Acid- Dicarboxylate, and Urea Cycle showed the most significant associations with PFAS, suggesting these may be particular pathways of interest in the physiological response to PFAS. To our knowledge, this is the first study to characterize associations between the global metabolome and PFAS across multiple periods in the life course to understand impacts on underlying biology, and the findings presented here are relevant in understanding how PFAS disrupt normal biological function and may ultimately give rise to harmful health effects.

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Novel magnetic and fluorinated porous carbons (M-FPCs) with high fluorine content, large pore volume and specific surface area were first prepared by carbonizing and further fluorinating Fe-Zr bimetal-organic frameworks. The M-FPCs exhibit excellent adsorption performance toward perfluorinated compounds (PFCs), and the maximal adsorption capacity ranges from 518.1 to 919.3 mg g-1 for various PFCs. Based on this property, an environmental analytical method of dispersive solid-phase extraction (DSPE) using M-FPCs as adsorbents coupled with ultra-high-performance liquid chromatography-mass spectrometry (UPLC-MS) was developed for the detection of trace PFCs. The linear range was as wide as 10-200 ng L-1, and low limit of detection (0.02-0.16 ng L-1) and good precision (relative standard deviation less than 6.11% for intra-day and inter-day) were achieved. This method was applied to the detection of trace PFCs in environmental water and soil samples with satisfactory results.

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Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are emerging pollutants that threaten food safety. Herein, a rapid, accurate, and selective method for determination of PFOA and PFOS in milk was established by using new molecularly imprinted phenolic resin (MIP-PR) as the adsorbent of dispersive filter extraction (DFE) combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS). MIP-PR was synthesized at room-temperature using m-aminophenol, glutaraldehyde, and perfluorononanoic acid as the monomers, cross-linkers, and virtual templates, respectively, and exhibited rapid mass transfer (30 s), high selectivity (imprinted factors > 3.7), and large adsorption capacity (>54.6 mg/g). Compared with reported methods, the developed MIP-PR-DFE method is fast, selective, inexpensive, and shows good purification and enrichment efficiency. The proposed MIP-PR-DFE-LC-MS/MS exhibited low limits of detection (0.006-0.022 ng/mL), high recoveries (94.7-109 %), and good precision (RSDs ≤ 9.5 %). This study provides a new idea for the development of imprinted resin adsorbents for perfluorinated compound, and a new method for sample pretreatment for monitoring of PFOA and PFOS in food.

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