New analytical method for the determination of endocrine disruptors in human faeces using gas chromatography coupled to tandem mass spectrometry.

Endocrine-disrupting chemicals are environmental pollutants that can enter our bodies and cause diverse pathologies. Some bisphenols and parabens have been shown to be capable of modifying proper functioning of the endocrine system. Among other dysfunctions, endocrine-disrupting chemicals can cause changes in intestinal microbiota. Faeces are a convenient matrix that can be useful for identifying the quantity of endocrine disruptors that reach the intestine and the extent to which the organism is exposed to these pollutants. The present work developed a new analytical method to determine 17 compounds belonging to the paraben and bisphenol families found in human faeces. The extraction method was optimized using an ultrasound-assisted extraction technique followed by a clean-up step based on the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) technique. Optimization was performed using the design of experiments technique. In validation analysis, the method was proven to be linear over a wide range. R-squared outcomes were between 95 and 99%. Selectiveness and sensitivity outcomes were acceptable, with detection limits being between 1 and 10 ng g-1 in all cases, whilst quantification limits were between 3 and 25 ng g-1 in all instances, with the exception of bisphenol AF. The method was deemed accurate, with recovery values being close to 100% and relative standard deviations being lower than 15% in all cases. Applicability was examined by analysing 13 samples collected from volunteers (male and female). All samples were contaminated with at least one of the analytes studied. The most commonly found compounds were methylparaben and bisphenol A, which were detected in almost all samples and quantitatively determined in 11 and 12 samples, respectively. Of the 17 compounds analysed, 11 were found in at least one sample. Outcomes demonstrate that faeces can be a good matrix for the determination of exposure to contaminants of interest here.

Determination of ultraviolet filters in human nails using an acid sample digestion followed by ultra-high performance liquid chromatography-mass spectrometry analysis.

Ultraviolet filters (UV-filters) are specific chemicals that absorb and reflect UVA and UVB radiation from the sun. They are regularly used in sunscreens and in other personal care products (PCPs), and in products like plastics, adhesives, toys, or furniture finishes. This work develops and validates a new method to determine concentrations of UV-filters (BP-1, BP-2, BP-3, BP-6, BP-8, 4-OH-BP, THB, AVB) in human nail samples. Nails are easily available and are considered to be suitable indicators of cumulative and continued exposure to harmful chemicals. The treatment of nail samples includes microwave assisted digestion/extraction (MAE) in a methanolic solution of o-phosphoric acid (0.05 mol L-1) followed by analyte determination using ultra-high performance liquid chromatography-mass spectrometry (UHPLC-MS/MS) in multiple reaction monitoring mode. The analytes were separated in less than 10 min. The digestion procedure was optimized using multivariate techniques. Matrix-matched calibration with a pig hoof matrix was used for validating the method. A study of accuracy with spiked blank samples was also conducted. The calculated detection limits varied between 0.2 and 1.5 ng g-1, and quantification limits between 1.0 and 5.0 ng g-1. The trueness of the method was an estimation of the recovery, which was between 90.2% and 112.2%; with an estimated precision (relative standard deviation, % RSD) lower than 12.3% for all UV-filters. Nail samples were obtained from 22 volunteers (male and female). The results showed that BP-1 and BP-3 mainly bioaccumulate in human nails.

Determination of endocrine disrupting chemicals in human nails using an alkaline digestion prior to ultra-high performance liquid chromatography-tandem mass spectrometry.

Rapid industrialization has resulted in a progressive increase in human exposure to hazardous chemicals. The present work develops and validates a new method to determinate 18 endocrine disrupting chemicals (EDCs) in human nail samples. In contrast to other common biological samples, nail sampling is non-invasive and since they take several months to grow out, they are well suited for measuring and reflecting the cumulative exposure to harmful substances in the long term. A digestion of samples with a 0.04 M solution of sodium hydroxide is carried out followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), working in multiple-reaction-monitoring (MRM) mode. The compounds were separated in 8 min. Multivariate optimization strategies were used for the optimization of the parameters that affects the digestion procedure. The validation was developed using a matrix-matched calibration and a recovery assay with spiked samples. The limits of detection and quantification ranged from 0.3 to 1.2 ng g-1 and from 1 to 5 ng g-1, respectively. Recovery rates for spiked samples were between 88% and 113% and the relative standard deviation (% RSD) was lower than 12.7% for all studied EDCs. The method was applied for the analysis of these compounds in human nail samples from volunteers. All samples tested positive for several of the analyzed EDCs.