PMID- 34624656 OWN - NLM STAT- MEDLINE DCOM- 20211111 LR - 20221207 IS - 1879-2448 (Electronic) IS - 0043-1354 (Linking) VI - 206 DP - 2021 Nov 1 TI - Source identification of amphetamine-like stimulants in Spanish wastewater through enantiomeric profiling. PG - 117719 LID - S0043-1354(21)00913-1 [pii] LID - 10.1016/j.watres.2021.117719 [doi] AB - Amphetamine (AMP), methamphetamine (MAMP) and 3,4-methylenedioxymethamphetamine (MDMA) occur in wastewater not only as a result of illicit consumption, but also, in some cases, from prescription drug use or by direct drug disposal into the sewage system. Enantiomeric profiling of these chiral drugs could give more insight into the origin of their occurrence. In this manuscript, a new analytical methodology for the enantiomeric analysis of amphetamine-like substances in wastewater has been developed. The method consists of a solid-phase extraction (SPE) followed by liquid chromatography-triple quadrupole-tandem mass spectrometry (LC-MS/MS), which showed low quantification limits in the 2.4-5.5 ng L(-1) range. The LC-MS/MS method was first applied to characterize a total of 38 solid street drug samples anonymously provided by consumers. The results of these analysis showed that AMP and MDMA trafficked into Spain are synthesized as racemate, while MAMP is exclusively produced as the S(+)-enantiomer. Then, the analytical method was employed to analyse urban wastewater samples collected from the wastewater treatment plants (WWTPs) of five different cities in 2018 and 2019. Consumption estimated through normalized population loads in wastewater showed an increased pattern of AMP use in the Basque Country. Furthermore, the enantiomeric profiling of wastewater samples was contrasted to lisdexamfetamine (LIS) and selegiline (SEL) prescription figures, two pharmaceuticals which metabolize to S(+)-AMP, and to R(-)-AMP and R(-)-MAMP, respectively. From this analysis, and considering uncertainties derived from metabolism and adherence to treatment, it was concluded that LIS is a relevant source of AMP in those cases with low wastewater loads, i.e. up to a maximum of 60% of AMP detected in wastewater in some samples could originate from LIS prescription, while SEL does not represent a significant source of AMP nor MAMP. Finally, removal efficiencies could be evaluated for the WWTP (serving ca. 860,000 inhabitants) with higher AMP influent concentrations. The removal of AMP was satisfactory with rates higher than 99%, whereas MDMA showed an average removal of approximately 60%, accompanied by an enrichment of R(-)-MDMA. CI - Copyright (c) 2021. Published by Elsevier Ltd. FAU - Estevez-Danta, Andrea AU - Estevez-Danta A AD - Department of Analytical Chemistry, Nutrition and Food Sciences, Institute of Research on Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de Compostela, Constantino Candeira S/N, Santiago de Compostela 15782, Spain. FAU - Montes, Rosa AU - Montes R AD - Department of Analytical Chemistry, Nutrition and Food Sciences, Institute of Research on Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de Compostela, Constantino Candeira S/N, Santiago de Compostela 15782, Spain. Electronic address: rosamaria.montes@usc.es. FAU - Bijlsma, Lubertus AU - Bijlsma L AD - Environmental and Public Health Analytical Chemistry, Research Institute for Pesticides and Water, University Jaume I, Castellon, Spain. FAU - Cela, Rafael AU - Cela R AD - Department of Analytical Chemistry, Nutrition and Food Sciences, Institute of Research on Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de Compostela, Constantino Candeira S/N, Santiago de Compostela 15782, Spain. FAU - Celma, Alberto AU - Celma A AD - Environmental and Public Health Analytical Chemistry, Research Institute for Pesticides and Water, University Jaume I, Castellon, Spain. FAU - Gonzalez-Marino, Iria AU - Gonzalez-Marino I AD - Department of Analytical Chemistry, Nutrition and Food Sciences, Institute of Research on Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de Compostela, Constantino Candeira S/N, Santiago de Compostela 15782, Spain; Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Chemical Sciences, University of Salamanca, Salamanca, Spain. FAU - Miro, Manuel AU - Miro M AD - FI-TRACE group, Department of Chemistry, University of the Balearic Islands, Palma de Mallorca, Spain. FAU - Gutmann, Vanessa AU - Gutmann V AD - Department of Analytical Chemistry, Nutrition and Food Sciences, Institute of Research on Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de Compostela, Constantino Candeira S/N, Santiago de Compostela 15782, Spain. FAU - de San Roman-Landa, Unai Perez AU - de San Roman-Landa UP AD - Asociacion Ai Laket!! Elkartea, Vitoria-Gasteiz, Spain. FAU - Prieto, Ailette AU - Prieto A AD - Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country, Bilbao, Spain; Research Centre for Experimental Marine Biology and Biotechnology, University of the Basque Country (PiE-UPV/EHU), Plentzia, Basque Country 48620, Spain. FAU - Ventura, Mireia AU - Ventura M AD - Energy Control, Asociacion Bienestar y Desarrollo, Barcelona, Spain. FAU - Rodil, Rosario AU - Rodil R AD - Department of Analytical Chemistry, Nutrition and Food Sciences, Institute of Research on Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de Compostela, Constantino Candeira S/N, Santiago de Compostela 15782, Spain. FAU - Quintana, Jose Benito AU - Quintana JB AD - Department of Analytical Chemistry, Nutrition and Food Sciences, Institute of Research on Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de Compostela, Constantino Candeira S/N, Santiago de Compostela 15782, Spain. Electronic address: jb.quintana@usc.es. LA - eng PT - Journal Article DEP - 20210929 PL - England TA - Water Res JT - Water research JID - 0105072 RN - 0 (Waste Water) RN - 0 (Water Pollutants, Chemical) RN - CK833KGX7E (Amphetamine) SB - IM MH - Amphetamine MH - Chromatography, Liquid MH - Tandem Mass Spectrometry MH - *Wastewater MH - *Water Pollutants, Chemical/analysis OTO - NOTNLM OT - Chiral drugs OT - Drug abuse OT - Enantiomers OT - Prescription OT - Sewage OT - Wastewater-based epidemiology EDAT- 2021/10/09 06:00 MHDA- 2021/11/12 06:00 CRDT- 2021/10/08 20:23 PHST- 2021/04/29 00:00 [received] PHST- 2021/09/22 00:00 [revised] PHST- 2021/09/24 00:00 [accepted] PHST- 2021/10/09 06:00 [pubmed] PHST- 2021/11/12 06:00 [medline] PHST- 2021/10/08 20:23 [entrez] AID - S0043-1354(21)00913-1 [pii] AID - 10.1016/j.watres.2021.117719 [doi] PST - ppublish SO - Water Res. 2021 Nov 1;206:117719. doi: 10.1016/j.watres.2021.117719. Epub 2021 Sep 29.