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Embryos and fetuses are of major concern due to their high vulnerability. Previous studies demonstrated that human exposure to per- and polyfluoroalkyl substances (PFAS) may be underestimated because only a limited number of known PFAS can be measured. This investigation studied the total PFAS exposure by measuring the extractable organofluorine (EOF) in pooled maternal serum, placental tissue, and cord serum samples (total number of pooled samples: n = 45). The EOF was analyzed using combustion ion chromatography, and the concentrations of known PFAS were determined using ultraperformance liquid chromatography coupled with a tandem mass spectrometer. Using a mass balance analysis approach, the amount of unknown PFAS was estimated between the levels of known PFAS and EOF. The EOF levels ranged from 2.85 to 7.17 ng F/mL (21 PFAS were quantified) in the maternal serum, from 1.02 to 1.85 ng F/g (23 PFAS were quantified) in the placental tissue, and from 1.2 to 2.10 ng F/mL (18 PFAS were quantified) in the cord serum. An average of 24, 51, and 9% of EOF is unidentified in the maternal serum, placental tissue, and cord serum, respectively. The results show that the levels of unidentified EOF are higher in the placental tissue, suggesting accumulation or potential transformation of precursors in the placenta., Please provide a synopsis

Since the detection of per- and polyfluoroalkyl substances (PFAS) in humans and different environmental media in the last two decades, this substance group has attracted a lot of attention as well as increasing concerns. The fluorine mass balance approach, by comparing the levels of targeted PFAS after conversion to fluorine equivalents with those of extractable organic fluorine (EOF), showed the presence of unidentified organofluorine in different environmental samples. Out of the thousands of PFAS in existence, only a very small fraction is included in routine analysis. In recent years, liquid chromatography coupled with tandem-mass spectrometry (LC-MS/MS) has demonstrated the ability to analytically cover a wide spectrum of PFAS. In contrast, conventional extraction methods developed 10 to 15 years ago were only evaluated for a limited number of PFAS. The aim of the present study was to evaluate the advantages and disadvantages of three different extraction methods, adapted from the literatures without further optimization (ion-pair liquid-liquid extraction, solid-phase extraction (SPE), using hydrophilic-lipophilic (HLB) or weak anion exchange (WAX) sorbents), for human biomonitoring of 61 PFAS in serum and placental tissue samples. In addition, levels of EOF were compared among these extraction methods via spiked samples. Results showed that performance, in terms of recovery, differed between the extraction methods for different PFAS; different extraction methods resulted in different EOF concentrations indicating that the choice of extraction method is important for target PFAS and EOF analysis. Results of maternal serum samples, analyzed in two different laboratories using two different extraction methods, showed an accordance of 107.6% (± 21.3); the detected perfluoroalkyl acids (PFAAs) in maternal and cord serum samples were in the range of 0.076 to 2.9 ng/mL. Graphical abstract Supplementary Information The online version contains supplementary material available at 10.1007/s00216-020-03041-5.

Perfluorooctane sulfonic acid (PFOS) is a ubiquitous environmental pollutant. In humans, PFOS exposure has been associated with a number of adverse health outcomes, including reduced birth weight. Whether PFOS is capable of affecting angiogenesis and thus possibly fetal development is unknown. Therefore, we investigated 1) the metabolic activity of PFOS-exposed endothelial cells (human umbilical vein endothelial cells, HUVECs), fibroblasts (normal colon fibroblasts, NCFs), and epithelial cells (human colorectal carcinoma cells, HCT116), 2) PFOS-specific inhibition of vascular endothelial growth factor receptor (VEGFR)2 stimulation in KDR/NFAT-RE HEK293 cells, and 3) the antiangiogenic potential of PFOS in a 3D in vitro angiogenesis model of HUVECs and NCFs. In terms of metabolic activity, endothelial cells (HUVECs) were much more sensitive to PFOS than fibroblasts (NCFs) or epithelial cells (HCT116). VEGFR2 signaling in KDR/NFAT-RE HEK293 cells decreased with increasing PFOS concentrations. In co-culture (angiogenesis assay), PFOS treatment resulted in a dose-dependent reduction in tip and branch formation, tip length (μm), and total structural area (μm2) with stable metabolic activity of HUVECs up to high concentrations. We conclude that PFOS possesses antiangiogenic properties. Inhibition of VEGFR2 signaling indicates a possible mechanism of action that can be linked to an existing Adverse Outcome Pathway (AOP43) containing the AO reduced birth weight. Further studies are needed to confirm PFOS-specific adverse effects on angiogenesis, placental perfusion, and fetal growth.

Several thousands of highly persistent per- and polyfluoroalkyl substances (PFAS) exist and it is therefore challenging to analytically determine a larger spectrum of these compounds simultaneously in one sample. It is even more difficult to efficiently remove mobile PFAS in wastewater treatment plants (WWTPs) to protect the receiving waters. The total oxidizable precursor (TOP) assay is an approach that enables the detection of the total PFAS content in a sample via oxidation of precursors, followed by subsequent analysis of the perfluoroalkyl acid (PFAA) concentration before and after oxidative processes. Activated carbon combined with a preceding ozonation step is considered a promising tool for the removal of micropollutants but considering PFAS removal efficiencies in effluents for this process combination more information is required. The focus of the study was to implement and assess the TOP assay with ozone as oxidizing agent to estimate the total PFAS content in a WWTP effluent. Additionally, granular activated carbon (GAC) and powdered activated carbon (PAC) with a preceding ozonation step was tested for the removal efficiencies for 22 PFAS. For the TOP assay the obtained accordance in molarity using spiked tap water as quality control was 95.2% (15 mg O3/L) and 99.1% (6 mg O3/L). Applying the TOP assay, an estimated total PFAS content of 840 ng/L was determined in the respective effluent, which was 91.1% higher than obtained by target PFAS analysis, implying the presence of unknown precursors not included in common monitoring. While all treatment techniques that included ozone or a preceding ozonation step solely transformed precursors and long-chain perfluoroalkyl acids (PFAA, i.e., >C9) to shorter congeners, PAC was the only tested water treatment application that was able to remove 19.3% of the total PFAS molarity.

The study aims to simultaneously control micropollutants and bromate formations by using ozonation and peroxone process. The batch experiments were run with variations in specific ozone dose (SOD) and hydrogen peroxide-to-ozone (H2O2/O3) ratio. Based on the removal by ozonation and peroxone, micropollutants were categorized into three groups: non-reactive compounds (i.e. amidotrizoate), moderately reactive compounds (i.e. metoprolol, acesulfame potassium, bezafibrate, and benzotriazole), and highly reactive compounds (i.e. carbamazepine and diclofenac). For ozonation and peroxone process, the removals for highly reactive compounds and moderately reactive compounds were 82–99% and 29–99%, respectively. The removal of amidotrizoate was not observed in this study. The effect of ozonation on micropollutant removals was similar to the peroxone process. However, differences in bromate formation were observed. Bromate formation depended on the SOD, while addition of hydrogen peroxide suppressed the bromate formation. The peroxone process at the H2O2/O3 ratio of 0.3 was recommended to bromide-containing water below 100 µg·L−1 for simultaneous control of micropollutants and bromate. Enhancement in micropollutant removals, except for the non-reactive groups, was achieved with either higher SOD or the addition of hydrogen peroxide to ozonation. The micropollutant removal predicted from the second-order kinetic reaction with ozone and •OH exposures was higher than the observed data.

Perfluoroalkyl (PFAS) substances are widespread in the environment and in organisms. The fact that exposure to PFAS is associated with elevated cholesterol levels is a major concern for human health. Previous investigations, in which bovine serum albumin was frequently studied, indicate that PFOS, PFOA and PFNA bind to serum albumin. However, it is critical to know whether these and other PFAS have a preference for the protein or the lipid fraction in native human blood fractions. For this reason, blood samples from four young healthy volunteers (two women, two men, 23–31 years old) were used for protein size separation and fractionation by the Cohn method in combination with serial ultracentrifugation. The plasma fractions were analyzed for 11 PFAS using high-performance tandem mass spectrometry (HPLC-MS/MS). Although the data are based on a small sample, they clearly show that albumin is the most important carrier protein for PFOS, PFOA, PFHxS, PFNA and PFDA in native human plasma. These five compounds have very little or no affinity for lipoproteins. The confirmation of their transport through albumin is important for the epidemiology of PFAS. The present results must be verified by the examination of a larger number of persons. Keywords: Albumin, Human plasma, perfluoroalkyl substances (PFAS)