Analysis and distribution of per- and polyfluoroalkyl substances in decidua and villi placenta explants.

Placenta mediates the transfer of nutrients, oxygen and drugs from mother to fetus. It is constituted by two cellular layers separated by the intervillous space: the outer is in direct contact with maternal blood (decidua placenta), and the inner (villi) directly in contact with the fetus. Environmental contaminants, such as per- and polyfluoroalkyl substances (PFAS) also demonstrated the ability to cross the tissue multiple layers, posing at risk the health of the fetus. The aim of the present study was to analyse the PFAS amount in decidua and villi placenta explants and to study differences in their distribution among the two side of this organ. The determination of 23 PFAS was carried out by liquid chromatography coupled to high-resolution accurate mass spectrometry (LC-HRAM). Our research included women who delivered at term between 2021 and 2022. Our data indicated that all samples contained at least one PFAS, demonstrating the ubiquitarian presence of these compounds in our population. A high occurrence of PFOS, PFOA and PFHxS, followed by PFHxA, PFBS and PFUnA was found. The fluorotelomer 6:2 FTS was also present in more than 40% of samples and this represent the first data on placenta explants. Mean and median PFAS values for decidual explants were 0.5 ng/g and 0.4 ng/g (SD 0.3), while for villi explants mean and median values were 0.6 ng/g and 0.4 ng/g (SD 0.4). A different pattern of accumulation was observed between villi and decidual explants for PFOS, PFOA and PFUnA (villi > decidua) and PFHxA, PFHxS, PFBS and 6:2 FTS (decidua > villi). Even if the mechanism of this selectively accumuation is not yet understood, molecular degree of ionization and its lipophilicity could at least in part explain this difference. This study expands the limited data describing PFAS levels in the placenta and pose attention on PFAS exposure during pregnancy.

Per- and polyfluoroalkyl substances (PFAS) presence in food: Comparison among fresh, frozen and ready-to-eat vegetables.

There is a worldwide discussion to provide safety limits in food for per- and polyfluoroalkyl substances (PFAS), a group of persistent contaminants associated to human disease. Processed food is more at risk of containing increased amounts of PFAS as a consequence of intentionally or non-intentionally contamination during manipulation and packaging. Among food products, also vegetables can be submitted to industrial manipulation; therefore, a different PFAS content correlated to the level of vegetables processing is conceivable. This study assessed the amount and type of PFAS present in fresh, frozen and ready-to-eat vegetables. Differences have been observed between the three groups of samples in the average PFAS content; the difference between ready-to eat and frozen vegetables resulted statistically significative. Organic vegetables displayed a lower total amount of PFAS respect to the traditional counterpart. The impact of industrial manipulation remains to be cleared, but pesticides use during cultivation could be considered a source of PFAS contamination.

Automated sample preparation and analysis by gas chromatography tandem mass spectrometry (GC-MS/MS) for the determination of 3- and 2-monochloropropanediol (MCPD) esters and glycidol esters in edible oils.

The potentially carcinogenic process contaminant 3- and 2-monochloropropanediol esters (2-MCPD and 3-MCPD esters) and glycidyl esters (GEs) are under study in refined oils and foodstuffs. Legislation set recommended total daily intake (TDI) for 3-MCPD of 0.8 µg/kg and as low as reasonably achievable (ALARA) for glycidol. Usually, the so far adopted method for the determination of these contaminants relay on numerous and time-consuming steps for sample preparation (AOCS methods) and on GC-MS detection. The obtained sensitivities and the number of processable samples are thus limited. In this optic, new reliable methods that allow for the fast and sensitive determination of these contaminants in edible oils may be considered an improvement of the overall strategy of tackling the problem. In this paper a new automated method for sample preparation and detection by GC-MS/MS is presented and validated. Data on sensitivity (LOD at 1.5, 2.2 and 3 ng/g for 3-MCPD, 2-MCPD, 3-MBPD (deriving from glycidol), respectively), linearity across low and high calibration ranges and precision showed to be fit-for-purposes. Finally, the methodology was applied to ten extra virgin oil samples and one sample of sunflower seeds oil.

Determination of perfluoroalkyl substances (PFAS) in human hair by liquid chromatography-high accurate mass spectrometry (LC-QTOF).

Biomonitoring of perfluoroalkyl substances (PFASs) in hair is conventionally achieved by SPE extraction and liquid chromatography-triple quadrupole analysis, with sensitivities in the range of ng/g. The aim of this study was to develop and validate a rapid method to detect 20 perfluoroalkyl substances (PFASs) in human hair from general populations by SPE purification and liquid-chromatography coupled to accurate mass measurement (LC-QTOF). The obtained sensitivities (LOQ), linearity and RSD accuracies were respectively in the range of 0.07-0.5 ng/g, 0.1 (or 0.2 or 0.5)-10 ng/g, 1-16%. To verify the applicability of the method, 11 hair samples from volunteers were tested. The detected PFAS were PFBA (range 0.24-14.6 ng/g), PFBS (0.496 ng/g), PFOA (range 0.08-0.178 ng/g) and PFOS (

Rapid detection of asperphenamate in a hay batch associated with constipation and deaths in dairy cattle. The application of DART-HRMS to veterinary forensic toxicology.

Direct analysis in real time (DART) coupled to high-resolution mass spectrometry (HRMS) was applied for the first time to veterinary forensic toxicology to investigate the presence of toxic compounds in hay after an episode of acute intoxication in a dairy cattle farm. In addition to gross field necropsy and histological examination, microbial cultures, and heavy metals analysis, the molecular fingerprinting of the suspected hay batch was investigated by DART-HRMS. DART-HRMS revealed a distinct signal of m/z 507.2289 in the hay batch thought to be associated with the digestive complications. A search on chemical structure databases matched the ion with asperphenamate, a toxin produced by Penicillium spp. and Aspergillus spp. Liquid Chromatography-HMRS analysis and electrospray-HRMS-MS/MS of the hay extracts further characterized the structure and confirmed the identification of the compound as asperphenamate. Asperphenamate is fungal metabolite which can have cytotoxic and antitumor activity in humans, and it is classified as acute toxicant and harmful if swallowed.