Target analysis and suspect screening of UV filters, parabens and other chemicals used in personal care products in human cord blood: Prenatal exposure by mother-fetus transfer.

Prenatal exposure to certain organic chemicals like pesticides and phenols has been lifelong associated with birth outcomes and health disorders. Many personal care product (PCP) ingredients have similar properties or structures to those chemicals. Previous studies have documented the occurrence of UV filters (UVFs) and paraben preservatives (PBs) in the placenta, but observational studies concerning PCPs chemicals and foetal exposure are particularly scarce. Thus, this work aimed to assess the presence of a wide range of PCPs chemicals using target and suspect screening in the umbilical cord blood of new born babies to evaluate their potential transfer to the fetus. To do so, we analysed 69 umbilical cord blood plasma samples from a mother-child cohort from Barcelona (Spain). We quantified 8 benzophenone-type UVFs and their metabolites, and 4 PBs using validated analytical methodologies based on target screening using liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Then, we screened for additional 3246 substances using high-resolution mass spectrometry (HRMS) and advanced suspect analysis strategies. Six UVFs and three parabens were detected in the plasma with frequencies between 1.4% and 17.4% and concentrations up to 53.3 ng/mL (benzophenone-2). Thirteen additional chemicals were tentatively identified in the suspect screening, and ten were further confirmed with the corresponding standards. Among them, we found the organic solvent N-methyl-2-pyrrolidone, the chelating agent 8-hydroxyquinoline, and the antioxidant 2,2'-methylenebis(4-methyl-6-tert-butylphenol), which have been demonstrated to display reproductive toxicity. UVFs and PBs presence in the umbilical cord blood demonstrates mother-fetus transfer through the placental barrier and prenatal exposure to these PCPs chemicals, which may lead to adverse effects in the early stages of fetal development. Considering the small cohort used in this study, the reported results should be interpreted as a preliminary reference for the background umbilical cord transfer levels of the target PCPs chemicals. Further research is needed to determine the long-term consequences of prenatal exposure to PCPs chemicals.

Development of a sensitive analytical method for the simultaneous analysis of Benzophenone-type UV filters and paraben preservatives in umbilical cord blood.

UV filters and parabens are compounds used in large quantities in modern societies and have become ubiquitous in the environment. They are considered compounds of emerging concern due to the unwanted effects they cause in the environment and their bioaccumulation potential in humans. Considering their endocrine disrupting activity and their so far unknown effects in newborns, a continuous monitoring of these substances is required. In this work, we developed and validated a new sensitive methodology for the analysis of 8 UV filters and metabolites, and 4 parabens in umbilical cord blood samples. The method consisted of a liquid-liquid extraction and phase separation by freezing. Then, the organic extract was further analyzed at alkaline pH using liquid chromatography coupled to tandem-mass spectrometry (LC-MS/MS) using a QqLIT hybrid mass spectrometer as analyzer. The low limits of detection achieved (0.01-0.42 ng/mL) allowed the reliable simultaneous quantification of UV filters and parabens in this complex biological matrix.•Simple, fast and sensitive analysis of UV filters and parabens in cord blood samples.•First simultaneous analysis of UV filters and parabens in cord blood.•Allows the evaluation of perinatal transfer of UV filters and parabens from the mother to the fetus.

Transformation products of amoxicillin and ampicillin after photolysis in aqueous matrices: Identification and kinetics.

Antibiotics are widely used in human medicine and veterinary production. Residues of these compounds reach the water sources through waste or direct application (e.g. aquaculture). The constant input of the parent drugs and their transformation products into the environment leads these pharmaceuticals to be considered as emerging pollutants. For some molecules, the pathway of degradation and formation in products is less known. To assess the impact of these substances in the environment and in the human health, it is necessary to elucidate the transformation products and their kinetic of degradation to evaluate the possible risks. In the present report, the characterization and the degradation kinetic of two widely used ß-lactams antibiotics - amoxicillin and ampicillin - was evaluated. Surface water samples containing these antibiotics were submitted to photolysis and analyzed by liquid chromatography coupled to mass spectrometry with Orbitrap detection in order to establish the profile of degradation and the formation of transformation products. Results showed that the degradation of amoxicillin and ampicillin is almost complete and reach their maximum at 48 h in river water. Moreover, a database containing >65 transformation products of amoxicillin and ampicillin was build and real samples of industrial wastewater were analyzed to investigate the occurrence of amoxicillin, ampicillin and their transformation products.

UV filters and benzotriazoles in urban aquatic ecosystems: The footprint of daily use products.

The increased use of beauty and other daily use products, in particular those containing UV filters (UV-Fs) and benzotriazoles, results in their introduction in significant amounts into the aquatic environment. In this study, we aim to assess the occurrence and impact of UV-Fs and benzotriazoles in aquatic ecosystems in the metropolitan area of Barcelona, Spain. River water samples from the Llobregat and Besòs Rivers were analysed together with sediment, suspended particulate matter, and wastewater samples from 6 wastewater treatment plants (WWTPs) along their basins. The analysis of 6 UV-Fs and 2 benzotriazoles in water samples was performed using an automatized on-line solid phase extraction coupled to liquid chromatography tandem mass spectrometry (SPE-HPLC-MS/MS) method. The analysis of the target compounds in the suspended solids and in the sediments was performed by HPLC-MS/MS. The analysis of the water samples showed the ubiquitous presence of UV-Fs. Benzotriazole (BZT; partition coefficient octanol-water Log Kow=1.23) and methylbenzotriazole (MeBZT; Log Kow=1.89) had the highest levels in both river water and wastewater. Removal rates in the selected WWTPs were highly variable (4-100%). Concentrations of lipophilic UV-Fs (Log Kow 4.95-7.53) in suspended particulate matter from wastewaters were high (up to 1,031,868.2ngg-1dry weight (dw)), whereas in sediment the concentrations were always below 300ng g-1 dw. The risk assessment expressed in terms of hazard quotients (HQs) revealed that most UV-Fs were not likely to produce adverse ecotoxicological effects against the living organisms assayed in river waters and influent wastewaters at the concentrations observed. However, HQs above 1 were obtained for BZT and MeBZT in effluent wastewaters discharged to the river.

Determination of parabens and benzophenone-type UV filters in human placenta. First description of the existence of benzyl paraben and benzophenone-4.

UV filters and parabens (PBs) are chemicals used in daily personal care and hygiene products to protect materials and humans from the adverse effects of UV radiation and to preserve the integrity of the formulation, respectively. Several studies highlight their widespread environmental occurrence and endocrine disrupting effects. However, little is known about human exposure to these compounds. The objective of this study was to investigate the exposure of human embryos and foetuses to endocrine disrupting UV filters and PBs. Placentas from volunteer mothers in Barcelona were collected at delivery after informed, written consent by the pregnant women. UV filters and parabens were analysed by liquid chromatography-tandem mass spectrometry. The excellent performance of the method allowed measuring the target compounds in human placental tissue at low ng/g fresh weight level. The detection frequency of the selected compounds was in the range 17-100%. Benzophenone-1, methyl paraben, butyl paraben and benzyl paraben were detected in all samples. The highest measured concentration corresponded to methyl paraben, 11.77ng/g fresh weight. Reported concentrations of benzophenone-4 and benzyl paraben constitute the first evidence about their accumulation in placenta. The results obtained corroborate that foetuses are exposed to a wide diversity of UV filters and PBs via the placenta.

Analytical quality assurance in veterinary drug residue analysis methods: matrix effects determination and monitoring for sulfonamides analysis.

In residue analysis of veterinary drugs in foodstuff, matrix effects are one of the most critical points. This work present a discuss considering approaches used to estimate, minimize and monitoring matrix effects in bioanalytical methods. Qualitative and quantitative methods for estimation of matrix effects such as post-column infusion, slopes ratios analysis, calibration curves (mathematical and statistical analysis) and control chart monitoring are discussed using real data. Matrix effects varying in a wide range depending of the analyte and the sample preparation method: pressurized liquid extraction for liver samples show matrix effects from 15.5 to 59.2% while a ultrasound-assisted extraction provide values from 21.7 to 64.3%. The matrix influence was also evaluated: for sulfamethazine analysis, losses of signal were varying from -37 to -96% for fish and eggs, respectively. Advantages and drawbacks are also discussed considering a workflow for matrix effects assessment proposed and applied to real data from sulfonamides residues analysis.

Ozonation and peroxone oxidation of benzophenone-3 in water: effect of operational parameters and identification of intermediate products.

The goal of this study was to bring forward new data and insights with respect to the effect of operational variables and reaction pathways during ozonation and peroxone oxidation of the UV filter compound benzophenone-3 (BP3) in water. A systematic parameter study, investigating the effect of the ozone inlet concentration, temperature, pH, H(2)O(2) and t-butanol addition in a lab-scale bubble reactor, showed the promising potential of ozonation towards BP3 degradation. pH showed to be a major process parameter, with half-life times (5.1-15.0 min) being more than two times shorter at pH10 compared to neutral and acid conditions. This indicates the important role of hydroxyl radicals as supported by the addition of H(2)O(2) and t-butanol as HO promoter and scavenger, respectively. Ozonation intermediate products were identified by liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (HPLC-QqTOF-MS/MS). Demethylation and non-selective HO attack proved to be the major reaction mechanisms. Where available, identified intermediates were confirmed using analytical standards, and concentration profiles along the ozonation process were determined through selective targeted MS/MS analysis. Benzophenone-1 (BP1), also being a UV-filter compound, and 2,2'-dihydroxy-4-methoxybenzophenone (DHMB) revealed to be the major BP3 degradation products, showing a maximum concentration at about the half-life time of BP3.