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 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.
Water Res. 2021 Nov 1;206:117719. doi: 10.1016/j.watres.2021.117719. Epub 2021 Sep 29.
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 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.
安非他命（AMP）、甲基苯丙胺（MAMP）和 3,4-亚甲二氧基甲基苯丙胺（MDMA）不仅由于非法消费，而且在某些情况下，由于处方药物使用或直接将药物排入污水系统，而存在于废水中。对这些手性药物的对映体分析可以更深入地了解它们的来源。在本文中，开发了一种新的分析方法，用于废水中介兴奋剂物质的对映体分析。该方法包括固相萃取（SPE）和液相色谱-三重四极杆串联质谱（LC-MS/MS），其定量下限在 2.4-5.5ng L 范围内。LC-MS/MS 方法首先应用于对 38 个匿名提供给消费者的固体街头毒品样本进行分析。这些分析的结果表明，进入西班牙的 AMP 和 MDMA 是作为外消旋体合成的，而 MAMP 则专门作为 S(+)-对映体合成。然后，该分析方法用于分析 2018 年和 2019 年从五个不同城市的污水处理厂（WWTP）采集的城市废水样本。根据废水中归一化人口负荷估计的消耗量表明，巴斯克地区 AMP 的使用呈增加趋势。此外，将废水样本的对映体分析与利右苯丙胺（LIS）和司来吉兰（SEL）的处方数据进行对比，这两种药物分别代谢为 S(+)-AMP 和 R(-)-AMP 和 R(-)-MAMP。通过该分析，并考虑到代谢和治疗依从性带来的不确定性，可以得出结论，在低废水负荷的情况下，LIS 是 AMP 的一个重要来源，即某些样本中检测到的废水中高达 60%的 AMP 可能来自 LIS 处方，而 SEL 既不是 AMP 也不是 MAMP 的重要来源。最后，还可以评估具有较高 AMP 进水浓度的 WWTP（服务约 860,000 名居民）的去除效率。AMP 的去除率非常令人满意，高于 99%，而 MDMA 的平均去除率约为 60%，同时 R(-)-MDMA 得到了富集。
