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• ZnS-X%[N] with adjustable surface amine functional groups and Zn defects. • ZnS-X%[N] could efficiently adsorb PFAS. • The adsorbed PFAS are subsequently degraded under UV irradiation. • The regulatory mechanism of CTAB on ZnS photocatalytic performance was investigated. Perfluorinated alkylated substances (PFAS), as a category of persistent organic pollutants, have garnered extensive concern due to their resilience against environmental degradation. Herein, we developed an amine-functionalized sphalerite (ZnS) with adjustable surface amine functional groups and Zn defects (ZnS-X%[N]) by in situ coprecipitation and simple hydrothermal method in the presence of cetyltrimethylammonium bromide (CTAB). This material demonstrated efficient PFAS adsorption and subsequent photo-induced degradation under UV irradiation. The characterization results by TEM, BET, FTIR, XPS and EPR revealed that CTAB primarily influences ZnS by modulating surface amine functionalities, zinc defect density, and enhancing its photoreductive capacity. Adsorption and kinetic degradation experiments further showed that a medium CTAB concentration in ZnS-40%[N] achieves highest PFAS adsorption capacity (C max : 0.201 mol kg-1), and the corresponding decomposition rate was the fastest (k de : 1.53; k df : 1.19). This efficacy is attributed to the ZnS-40%[N]'s ideal adsorptive sites and surface shallow defects. Moreover, theoretical simulation also supports the above experimental inference. Overall, ZnS-X%[N] exhibits a synergistic effect on PFAS adsorption and degradation, showcasing its potential for environmental adaptability and practical application. [ABSTRACT FROM AUTHOR]

Persistent organic pollutants, such as perfluorinated alkylated substances (PFASs) and brominated flame retardants (BFRs) are widespread in the environment and most of them are bioaccumulated in wildlife and humans. The present study is the first investigation to reveal the PFAS and BFR levels of serum samples in the adult population of the Czech Republic. Altogether, 300 serum samples from blood donors in four cities were examined. In all samples 19 PFASs and 33 BFRs, including some of their metabolites, were targeted. The analyses were performed using ultra high performance liquid chromatography coupled with tandem mass spectrometry or gas chromatography with mass spectrometry (according to the type of analyte). PFASs, with the carbon chain length C6 and higher, dominated in all samples. Perfluorooctanesulfonate (PFOS; median: 2.43ng/mL), perfluorooctanoic acid (PFOA; median: 0.756ng/mL), perfluorodecanoic acid (PFDA; median: 0.145ng/mL) and perfluorohexanesulfonate (PFHxS; median: 0.184ng/mL) were detected in 100% of samples. Perfluorononanoic acid (PFNA; median: 0.325ng/mL) and perfluoroundecanoic acid (PFUdA; median: 0.058ng/mL) in 99.7% and 96.0% of samples, respectively. We observed statistically significant associations (p<0.05) between selected PFAS concentrations and the locality, gender, age of donors and education level. None of the BFRs was detected above the LOQ in more than 9% of the samples. The most frequently detected representatives of this group were congeners of polybrominated diphenyl ethers, namely BDE-47 (in 8.7%; range: 0.496-5.44ng/g lipid weight (l.w.)), BDE-99 (in 6.0%; range: 0.706-9.46ng/g l.w.), BDE-153 (in 7.3%; range: 0.736-6.44ng/g l.w.) and BDE-209 (in 7.0%; range: 13.7-2693ng/g l.w.). [ABSTRACT FROM AUTHOR]

A perfluorinated alkylated substances (PFAS) biomonitoring study was conducted in European eel ( Anguilla anguilla ) in Italy for the first time. Perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) concentrations were assessed in the organs of 35 wild eels from two locations, the highly impacted Po River and the Comacchio Lagoon along the north-western Adriatic coast. PFAS were extracted by ion-pairing liquid extraction procedure and measured using high performance liquid chromatography with electrospray ionization tandem mass spectrometry. There were no significant differences in mean PFAS concentrations ( p > 0.05) between samples from the two sites. PFOS and PFOA were detectable (>0.4 ng g −1 wet weight, w.w) in 73% and 31% of the total samples, respectively. PFOS concentrations ranged from <0.4 to 6.28 ng g −1 w.w and PFOA from <0.4 to 92.77 ng g −1 w.w. The highest PFAS levels were observed in blood and the lowest in muscle. Histology showed macrophage aggregates and hepatocytic vacuolation in some liver samples. No tissue anomalies were seen in the gonads, suggesting no reproductive impairment. The PFAS contamination levels observed were comparable to, or lower than, those reported in fish in other European countries, seeming to indicate that PFAS pollution of the study area is not remarkable. [ABSTRACT FROM AUTHOR]

Abstract: A previously developed and validated methodology based on liquid chromatography coupled to high resolution mass spectrometry was used for determine the concentration levels of 14 perfluoroalkylated substances (PFASs) in a set of 48 breast milk samples collected from French women in the frame of the ELFE pilot study. In accordance with other similar studies conducted at european and international levels, PFOS, PFOA, and PFHxS were detected and quantified in most of the analyzed samples (90%, 98% and 100%, respectively), and appeared as major contributors to the total PFAS exposure (38%, 37%, 25%, respectively), whereas the other targeted PFAS were very rarely, if not, found at the limits of detection of the method. Also in agreement with other published data, the concentration levels measured for the detected substances varied from <0.05 to 0.33μg/L for PFOS (median=0.079), from <0.05 to 0.22μg/L for PFOA (median=0.075), and from 0.04 to 0.07μg/L for PFHxS (median=0.050). On the basis of this relatively limited data set, no statistically significant relation was observed between these exposure levels and developmental outcomes, in particular the weight at birth. Similarly, no relation was observed between the measured PFAS levels and various socio-demographical parameters including the consumption of seafood, alcohol, smoking, or socio-economical level. These results suggest a need for further research and better knowledge regarding the sources, pharmacokinetics, and factors of exposure for other substances belonging to this class of emerging contaminants. [Copyright &y& Elsevier]

Abstract: The present study documents development and validation of a novel approach for determination of 23 perfluorinated alkylated substances (PFASs) in food of animal origin represented by milk and fish. The list of target analytes comprises four classes of PFASs, both ionic and non-ionic: 11 perfluorocarboxylic acids (PFCAs), 4 perfluorosulphonic acids (PFSAs), 5 perfluorosulphonamides (FOSAs) and 3 perfluorophosphonic acids (PFPAs). Fast sample preparation procedure is based on an extraction of target analytes with acetonitrile (MeCN) and their transfer (supported by inorganic salts and acidification) into the organic phase. Removing of matrix co-extracts by a simple dispersive solid phase extraction (SPE) employing ENVI-Carb and C18 sorbents is followed by an efficient sample pre-concentration performed by acetonitrile evaporation and subsequent dilution of residue in a small volume of methanol (matrix equivalent in the final extracts was 16 and 8gmL−1, for milk and fish respectively). Using modern instrumentation consisting of ultra-high performance liquid chromatography (UHPLC) hyphenated with a tandem mass spectrometer (MS/MS), limits of quantification (LOQs) as low as 0.001–0.006μgkg−1 for milk and 0.002–0.013μgkg−1 for fish can be achieved. Under these conditions, a wide spectrum of PFASs, including minor representatives, can be determined which enables collecting data required for human exposure studies. The pilot study employing the new method for examination of milk and canned fish samples was realized. Whereas in majority of canned fish products a wide spectrum of PFCAs, perfluorooctanesulphonic acid (PFOS) and perfluoro-1-octanesulphonamide (PFOSA) was detected, only in a few milk samples very low concentrations (LOQ levels) of PFOS and perfluorooctansulphonic acid (PFDS) were found. [Copyright &y& Elsevier]

Abstract: Polybrominated diphenyl ethers (PBDEs), perfluorinated alkylated substances (PFAS), and metals were monitored in tile drainage and groundwater following liquid (LMB) and dewatered municipal biosolid (DMB) applications to silty-clay loam agricultural field plots. LMB was applied (93,500Lha−1) in late fall 2005 via surface spreading on un-tilled soil (SSLMB), and a one-pass aerator-based pre-tillage prior to surface spreading (AerWay SSD) (A). The DMB was applied (8Mgdwha−1) in early summer 2006 on the same plots by injecting DMB beneath the soil surface (DI), and surface spreading on un-tilled soil (SSDMB). Key PBDE congeners (BDE-47, -99, -100, -153, -154, -183, -209) comprising 97% of total PBDE in LMB, had maximum tile effluent concentrations ranging from 6 to 320ngL−1 during application-induced tile flow. SSLMB application-induced tile mass loads for these PBDE congeners were significantly higher than those for control (C) plots (no LMB) (p <0.05), but not A plots (p >0.05). PBDE mass loss via tile (0–2h post-application) as a percent of mass applied was ~0.04–0.1% and ~0.8–1.7% for A and SSLMB, respectively. Total PBDE loading to soil via LMB and DMB application was 0.0018 and 0.02kg total PBDE ha−1 yr−1, respectively. Total PBDE concentration in soil (0–0.2m) after both applications was 115ngg−1 dw, (sampled 599days and 340 days post LMB and DMB applications respectively). Of all the PFAS compounds, only PFOS (max concentration=17ngL−1) and PFOA (12ngL−1) were found above detectable limits in tile drainage from the application plots. Mass loads of metals in tile for the LMB application-induced tile hydrograph event, and post-application concentrations of metals in groundwater, showed significant (p <0.05) land application treatment effects (SSLMB >A>C for tile and SSLMB and A>C for groundwater for most results). Following DMB application, no significant differences in metal mass loads in tile were found between SSDMB and DI treatments (PBDE/PFAS were not measured). But for many metals (Cu, Se, Cd, Mo, Hg and Pb) both SSDMB and DI loads were significantly higher than those from C, but only during <100days post DMB application. Clearly, pre-tilling the soil (e.g., A) prior to surface application of LMB will reduce application-based PBDE and metal contamination to tile drainage and shallow groundwater. Directly injecting DMB in soil does not significantly increase metal loading to tile drains relative to SSDMB, thus, DI should be considered a DMB land application option. [Copyright &y& Elsevier]

Abstract: Perfluorinated alkylated substances (PFAS) are of global interest due to their occurrence and persistency in the environment. This study includes surface waters and sediments for the analysis of eleven PFAS. The PFAS studied can be grouped in perfluoroalkyl carboxylates (PFCAs), perfluoroalkyl sulfonates (PFS) and perfluoroalkyl sulfonamides (PFSA). The two most important compounds are perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). These two substances showed the most significant values for surface water samples with maximum concentrations of 21ngl−1 for PFOA and 37ngl−1 for PFOS. Sediment samples from seven Austrian lakes and the river Danube were studied. Whereas PFSA and PFS were not detected in any sediment sample PFCAs were detected in most of the lake samples in concentrations up to 1.7μgkg−1 dry wt. PFOA, perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA) were detected in all Danube river sediment samples in concentrations varying from 0.1 up to 5.1μgkg−1 dry wt. For the various sampling points the proportional mass flows deriving from wastewater discharges were calculated. Whereas only up to 10% of the average flow is discharged wastewater up to more than 50% of the PFAS mass flows in the rivers can be attributed to wastewater discharges. Besides wastewater different other pathways as emissions from point sources, further degradation of precursor products, runoff from contaminated sites or surface runoff as well as dry and wet deposition have to be considered as relevant sources for PFAS contamination in surface waters. [Copyright &y& Elsevier]