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The reaction kinetics and reaction pathway of methadone and its main human metabolite, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) in chlorine containing waters were investigated by direct injection of individual reaction time aliquots in a liquid chromatography-quadrupole-time-of-flight-mass spectrometry (LC-QTOF-MS) system. Factors potentially affecting the rate of the reaction were evaluated in detail by means of a Box-Behnken experimental design in which methadone and EDDP were considered separately. Sample pH and chlorine concentration turned out to be the two significant variables, enhancing the kinetics with an increase in their values. Transformation products (TPs) were first searched over sample chromatograms by comparing control, blank and time zero samples to aliquots stopped at different reaction times. Their tentative identity was further inferred by generating their empirical formulae from their accurate single MS spectra and, subsequently, by interpreting their fragmentation pattern from their tandem MS (MS/MS) spectra. In total, 8 TPs, arising from intra-molecular cyclation, dehydrogenation, oxidation and chlorination, could be detected in the case of methadone, one of them being the EDDP and another 3 coming from EDDP, so being common to both the precursor drug and its metabolite. A tentative transformation pathway was proposed, and the reaction was evaluated under potential real circumstances by chlorinating two different river samples. In this way, it was possible to demonstrate that its extension is highly affected by the content of dissolved organic matter, so both compounds were highly or completely transformed in samples with a low anthropogenic impact, whereas they were considerably more stable in waters with a high concentration of organic matter. Finally, the ecotoxicity of precursors and transformation species was predicted by software tools, revealing that, in some cases, the toxicological responses displayed by the TPs were up to 100 times higher than those of methadone. [ABSTRACT FROM AUTHOR]

Highlights: [•] THCCOOH reacts very quickly with aqueous chlorine. [•] Half-life lower than 2min even at low chlorine doses (0.2mgL−1). [•] Seven by-products identified by LC–QTOF-MS. [•] By-products can be more toxic than THCCOOH. [•] Reaction can also take place in real surface waters. [ABSTRACT FROM AUTHOR]

Abstract: An assessment of the sewage occurrence and biodegradability of seven parabens and three halogenated derivatives of methyl paraben (MeP) is presented. Several wastewater samples were collected at three different wastewater treatment plants (WWTPs) during April and May 2010, concentrated by solid-phase extraction (SPE) and analysed by liquid chromatography-electrospray-quadrupole-time-of-flight mass spectrometry (LC-QTOF-MS). The performance of the QTOF system proved to be comparable to triple-quadrupole instruments in terms of quantitative capabilities, with good linearity (R 2 > 0.99 in the 5–500 ng mL−1 range), repeatability (RSD < 5.6%) and LODs (0.3–4.0 ng L−1 after SPE). MeP and n-propyl paraben (n-PrP) were the most frequently detected and the most abundant analytes in raw wastewater (0.3–10 μg L−1), in accordance with the data displayed in the bibliography and reflecting their wider use in cosmetic formulations. Samples were also evaluated in search for potential halogenated by-products of parabens, formed as a result of their reaction with residual chlorine contained in tap water. Monochloro- and dichloro-methyl paraben (ClMeP and Cl2MeP) were found and quantified in raw wastewater at levels between 0.01 and 0.1 μg L−1. Halogenated derivatives of n-PrP could not be quantified due to the lack of standards; nevertheless, the monochlorinated species (ClPrP) was identified in several samples from its accurate precursor and product ions mass/charge ratios (m/z). Removal efficiencies of parabens and MeP chlorinated by-products in WWTPs exceeded 90%, with the lowest percentages corresponding to the latter species. This trend was confirmed by an activated sludge biodegradation batch test, where non-halogenated parabens had half-lives lower than 4 days, whereas halogenated derivatives of MeP turned out to be more persistent, with up to 10 days of half-life in the case of dihalogenated derivatives. A further stability test performed with raw wastewater also showed that parabens degrade rapidly in real sewage, with half-lives lower than 10 h for n-butyl-paraben, while dihalogenated species again turned out to be more stable, with half-lives longer than a week. [Copyright &y& Elsevier]

Consumption of 3,4-methylendioxymethamphetamine (MDMA) has been always estimated by measuring the parent substance through chemical analysis of wastewater. However, this may result in an overestimation of the use if the substance is directly disposed in sinks or toilets. Using specific urinary metabolites may overcome this limitation. This study investigated for the first time the suitability of a panel of MDMA metabolites as biomarkers of consumption, considering the specific criteria recently proposed, i.e. being detectable and stable in wastewater, being excreted in a known percentage in urine, and having human excretion as the sole source. A new analytical method was developed and validated for the extraction and analysis of MDMA and three of its main metabolites in wastewater. 24-h composite raw wastewater samples from three European cities were analysed and MDMA use was back-calculated. Results from single MDMA loads, 4-hydroxy-3-methoxymethamphetamine (HMMA) loads and from the sum of MDMA, HMMA and 4-hydroxy-3-methoxyamphetamine (HMA) loads were in line with the well-known recreational use of this drug: consumption was higher during the weekend in all cities. HMMA and HMA turned out to be suitable biomarkers of consumption; however, concentrations measured in wastewater did not resemble the expected pharmacokinetic profiles, quite likely due to the very limited information available on excretion profiles. Different options were tested to back-calculate MDMA use, including the sum of MDMA and its metabolites, to balance the biases associated with each single substance. Nevertheless, additional pharmacokinetic studies are urgently needed in order to get more accurate excretion rates and, therefore, improve the estimates of MDMA use. [ABSTRACT FROM AUTHOR]

The information obtained from the chemical analysis of specific human excretion products (biomarkers) in urban wastewater can be used to estimate the exposure or consumption of the population under investigation to a defined substance. A proper biomarker can provide relevant information about lifestyle habits, health and wellbeing, but its selection is not an easy task as it should fulfil several specific requirements in order to be successfully employed. This paper aims to summarize the current knowledge related to the most relevant biomarkers used so far. In addition, some potential wastewater biomarkers that could be used for future applications were evaluated. For this purpose, representative chemical classes have been chosen and grouped in four main categories: (i) those that provide estimates of lifestyle factors and substance use, (ii) those used to estimate the exposure to toxicants present in the environment and food, (iii) those that have the potential to provide information about public health and illness and (iv) those used to estimate the population size. To facilitate the evaluation of the eligibility of a compound as a biomarker, information, when available, on stability in urine and wastewater and pharmacokinetic data (i.e. metabolism and urinary excretion profile) has been reviewed. Finally, several needs and recommendations for future research are proposed. [ABSTRACT FROM AUTHOR]

• Enantiomeric analysis of street drug samples and wastewater. • Amphetamine and MDMA sold as racemates, methamphetamine sold as pure enantiomer. • High loads of amphetamine in Basque wastewater due to illicit abuse. • Lisdexamfetamine prescription contributes to amphetamine loads in other locations. • Enantioselective removal during wastewater treatment. 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. [Display omitted] [ABSTRACT FROM AUTHOR]

Background: In this study, an alternative and complementary method to those approaches currently used to estimate alcohol consumption by the population is described. This method, known as wastewater-based epidemiology (WBE), allows back-calculating the alcohol consumption rate in a given population from the concentrations of a selected biomarker measured in wastewater.Methods: Composite (24-h) wastewater samples were collected at the inlet of 17 wastewater treatment plants located in 13 Spanish cities for seven consecutive days in 2018. The sampled area covered 12.8% of the Spanish population. Wastewater samples were analyzed to determine the concentration of ethyl sulfate, the biomarker used to back-calculate alcohol consumption.Results: Alcohol consumption ranged from 4.5 to 46 mL/day/inhabitant. Differences in consumption were statistically significant among the investigated cities and between weekdays and weekends. WBE-derived estimates of alcohol consumption were comparable to those reported by its corresponding region in the Spanish National Health Survey in most cases. At the national level, comparable results were obtained between the WBE-derived annual consumption rate (5.7 ± 1.2 L ethanol per capita (aged 15+)) and that reported by the National Health Survey (4.7 L ethanol per capita (aged 15+)).Conclusions: This is the largest WBE study carried out to date in Spain to estimate alcohol consumption rates. It confirms that this approach is useful for establishing spatial and temporal patterns of alcohol consumption, which could contribute to the development of health care management plans and policies. Contrary to established methods, it allows obtaining information in a fast and relatively economical way. [ABSTRACT FROM AUTHOR]