Development of a USE/d-SPE and targeted DIA-Orbitrap-MS acquisition methodology for the analysis of wastewater-derived organic pollutants in fish tissues and body fluids

Pharmaceuticals (PhACs) are partially removed during wastewater treatment and end up in the receiving waters. As a result, aquatic biota is continuously exposed to a wide range of potentially hazardous contaminants such as PhACs. Therefore, fish could be a good bio indicator to give a direct measure of the occurrence of PhACs in the aquatic environment. In this study, a robust analytical method has been optimized and validated for the determination of 81 organic compounds, mainly PhACs, in seven wild fish tissue types (liver, muscle, pancreas, kidney, skin, heart, and brain) and two body fluids (plasma and bile). Solid samples extraction was performed combining a procedure based on bead beating tissue homogenization plus ultrasound extraction followed by dispersive solid-phase extraction (dSPE) clean-up using zirconia and C18 sorbents for solid matrices, whereas bile and plasma were diluted. The key aspects of this method are: • The method facilitated the simultaneous extraction of 81 PhACs of a wide range of polarity (logP from -4.9 to 5.6) in tissues with variable lipid content. • The validation was performed using Cyprinus carpio at 20 ng g-1 and 200 ng g-1 for solid tissues, 50 ng mL-1 and 500 ng mL-1 for plasma, and 100 ng mL-1 and 1000 ng mL-1 for bile. Analyte detection was performed in LC-HRMS Q-Exactive Orbitrap system with full scan and targeted data-independent acquisition (DIA) mode for high-confidence and sensitive quantitation in either (+) or (-) ESI mode. • The majority of compounds presented recoveries between 40% and 70% and relative standard deviations (RSD) below 30%.

This study has been financially supported by the Spanish national TRAPPER project (CICLIC, RTI2018-097158-B-C33). This work was supported by the “Agencia Estatal de Investigación” from the Spanish Ministry of Science and Innovation and the IDAEA-CSIC, a Centre of Excellence Severo Ochoa (CEX2018-000794-S), and through the SYNERGY Project “Environmental risk of complex mixtures of emerging persistent and mobile chemicals in aquatic ecosystems (MixPersiRisk)” financed with Severo Ochoa funds.

Peer reviewed