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Automated method to determine pharmaceutical compounds in wastewater using on-line solid-phase extraction coupled to LC-MS/MS

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Abstract

An automated method was developed using on-line solid-phase extraction (SPE) as a sample preparation step, coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS), for determination of pharmaceutical compounds in wastewater samples at nanograms per liter to micrograms per liter concentration levels. This method is suitable for use in routine analysis, especially in environmental applications, avoiding cross-contamination and requiring minimal sample handling. Results can be obtained rapidly, with a chromatographic run time of only 24 min (including sample preparation and chromatographic analysis). Using a 50 μL injection volume, the method was validated according to international guidelines, considering parameters included in terms of method detection (MDL) and quantification limit (MQL), linearity, inter-day and intra-day precisions, and matrix effects. Assessment of chromatographic efficiency considered peak resolution and asymmetry, and carryover was evaluated to ensure analytical reliability and the ability to reuse the SPE cartridge. The intra- and inter-day precisions were lower than 10 and 17%, respectively. The MDL values ranged from 1×10-6 to 1 μg L-1, while the MQL values were from 0.001 to 3 μg L-1. Matrix effects were minimized by isotope dilution calibration. Application of the method to 20 wastewater samples showed that caffeine was the most frequently detected compound, with the highest concentration of 715 μg L-1, while other pharmaceutical compounds were detected in fewer samples and at lower concentrations (up to 8.51 μg L-1).

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Funding

The authors received funding from Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP, grants 16/03369-3, 18/11700-7, 18/22393-8, and INCT-DATREM 14/50945-4), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, grant 465571/2014-0), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES, 88887136426/2017/00), and Instituto de Química – Universidade Estadual Paulista (IQ/UNESP).

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  1. National Institute for Alternative Technologies of Detection, Toxicological Evaluation and Removal of Micropollutants and Radioactives (INCT-DATREM), Institute of Chemistry, São Paulo State University, P.O. Box 355, Araraquara, SP, 14800-060, Brazil

    César Augusto Marasco Júnior, Bianca Ferreira da Silva, Rafaela Silva Lamarca & Paulo Clairmont Feitosa de Lima Gomes

  2. College of Veterinary Medicine, Department of Physiological Sciences, University of Florida, P.O. Box 490, Gainesville, FL, 32601, USA

    Bianca Ferreira da Silva

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  1. César Augusto Marasco Júnior
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Marasco Júnior, C.A., da Silva, B.F., Lamarca, R.S. et al. Automated method to determine pharmaceutical compounds in wastewater using on-line solid-phase extraction coupled to LC-MS/MS. Anal Bioanal Chem 413, 5147–5160 (2021). https://doi.org/10.1007/s00216-021-03481-7

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