Development of Innovative Methods for the Analysis of Emerging Contaminants: focus on Performance Enhancing Compounds in Various Matrices

This PhD project involved the development of analytical methodologies for the assessment of Emerging organic Contaminants (EC) in various matrices. Hence, the sampling, the sample treatment and the analysis of each matrix selected were investigated. The matrices studied in this work were: dietary supplements (DS) and similar products, human hairs, wastewaters and seawaters. The types of samples involved were, thus, very different and specific procedures have to be developed for each of them. Firstly, the extraction of EC from DS was optimized through a Design of Experiments (DoE) approach, as well as their instrumental analysis. DS were subjected to a Salt-Assisted Liquid-Liquid Extraction (SALLE) and the diluted extracts were analyzed through Hydrophilic Liquid Chromatography (HILIC) coupled with tandem Mass Spectrometry (MS). Secondly, a totally new way to extract solid samples was developed: the Moka-Pot Extraction (MPE). Exploiting the high-pressure high-temperature solid-liquid extraction that occurs within Moka, good extraction efficiencies could be obtained and optimal conditions were again found through the multivariate approach (DoE). This strategy was then widened to analytes not included in the original study and applied to samples presenting slightly different matrices. Among them, some products were found to contain relevant amounts of banned Performance Enhancing Compounds, thus being disallowed for athletes. Also a matrix of biological interest, like hairs, was studied. A quick methanolic extraction assisted by ultrasonication was developed to obtain a multi-class extraction protocol, with a wide chemical coverage of EC presenting different physico-chemical properties. It was successfully applied to dozens of real samples, enabling the quantification of many EC. A relevant part of the project involved the employment of passive samplers (compared to spot sampling) to monitor the contamination in wastewaters and seawaters. The processing protocol of the selected passive samplers (Polar Organic Chemicals Integrative Samplers – POCIS) was carefully studied and the best conditions were applied to real samples. The various sampling campaigns allowed to get several snapshots of the contamination levels of the sites of interest during the periods investigated. Finally, a structural modification of POCIS (involving a different material as the protective layer for the inner sorbent) was also tested and employed in field deployments, allowing a comparison with the results obtained by standard POCIS configuration.