Comparing illicit drug use in 19 European cities through sewage analysis Thomas, K.V.; Bijlsma, L.; Castiglioni, S.; Covaci, A.; Emke, E.; Grabic, R.; Hernández, F.; Karolak, S.; Kasprzyk-Hordern, B.; Lindberg, R.H.; Meierjohann, A.; Ort, C.; Pico, Y.; Quintana, J.; Reid, M.; Rieckermann, J.; Terzic, S.; van Nuijs, A.L.N.; de Voogt, W.P. Published in:Science of the Total Environment DOI:10.1016/j.scitotenv.2012.06.069 Link to publicationCitation for published version (APA): Thomas, K. V., Bijlsma, L., Castiglioni, S., Covaci, A., Emke, E., Grabic, R., ... de Voogt, P. (2012) General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: https://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. The analysis of sewage for urinary biomarkers of illicit drugs is a promising and complementary approach for estimating the use of these substances in the general population. For the first time, this approach was simultaneously applied in 19 European cities, making it possible to directly compare illicit drug loads in Europe over a 1-week period. An inter-laboratory comparison study was performed to evaluate the analytical performance of the participating laboratories. Raw 24-hour composite sewage samples were collected from 19 European cities during a single week in March 2011 and analyzed for the urinary biomarkers of cocaine, amphetamine, ecstasy, methamphetamine and cannabis using in-house optimized and validated analytical methods. The load of each substance used in each city was back-calculated from the measured concentrations. The data show distinct temporal and spatial patterns in drug use across Europe. Cocaine use was higher in Western and Central Europe and lower in Northern and Eastern Europe. The extrapolated total daily use of cocaine in Europe during the study period was equivalent to 356 kg/day. High per capita ecstasy loads were observed in Dutch cities, as well as in Antwerp and London. In general, cocaine and ecstasy loads were significantly elevated during the weekend compared to weekdays. Per-capita loads of methamphetamine were highest in Helsinki and Turku, Oslo and Budweis, while the per capita loads of cannabis were similar throughout Europe. This study shows that a standardized analysis for illicit drug urinary biomarkers in sewage can be applied to estimate and compare the use of these substances at local and intern...

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AimsTo perform wastewater analyses to assess spatial differences and temporal changes of illicit drug use in a large European population. Design Analyses of raw wastewater over a 1-week period in 2012 and 2013. Setting and Participants Catchment areas of wastewater treatment plants (WWTPs) across Europe, as follows: 2012: 25 WWTPs in 11 countries (23 cities, total population 11.50 million); 2013: 47 WWTPs in 21 countries (42 cities, total population 24.74 million). Measurements Excretion products of five illicit drugs (cocaine, amphetamine, ecstasy, methamphetamine, cannabis) were quantified in wastewater samples using methods based on liquid chromatography coupled to mass spectrometry. Findings Spatial differences were assessed and confirmed to vary greatly across European metropolitan areas. In general, results were in agreement with traditional surveillance data, where available. While temporal changes were substantial in individual cities and years (P ranging from insignificant to <10 −3 ), overall means were relatively stable. The overall mean of methamphetamine was an exception (apparent decline in 2012), as it was influenced mainly by four cities. Conclusions Wastewater analysis performed across Europe provides complementary evidence on illicit drug consumption and generally concurs with traditional surveillance data. Wastewater analysis can measure total illicit drug use more quickly and regularly than is the current norm for national surveys, and creates estimates where such data does not exist.

Sewer pipelines, although primarily designed for sewage transport, can also be considered as bioreactors. In-sewer processes may lead to significant variations of chemical loadings from source release points to the treatment plant influent. In this study, we assessed in-sewer utilization of growth substrates (primary metabolic processes) and transformation of illicit drug biomarkers (secondary metabolic processes) by suspended biomass. Sixteen drug biomarkers were targeted, including mephedrone, methadone, cocaine, heroin, codeine, and tetrahydrocannabinol (THC) and their major human metabolites. Batch experiments were performed under aerobic and anaerobic conditions using raw wastewater. Abiotic biomarker transformation and partitioning to suspended solids and reactor wall were separately investigated under both redox conditions. A process model was identified by combining and extending the Wastewater Aerobic/anaerobic Transformations in Sewers (WATS) model and Activated Sludge Model for Xenobiotics (ASM-X). Kinetic and stoichiometric model parameters were estimated using experimental data via the Bayesian optimization method DREAM. Results suggest that biomarker transformation significantly differs from aerobic to anaerobic conditions, and abiotic conversion is the dominant mechanism for many of the selected substances. Notably, an explicit description of biomass growth during batch experiments was crucial to avoid significant overestimation (up to 385%) of aerobic biotransformation rate constants. Predictions of in-sewer transformation provided here can reduce the uncertainty in the estimation of drug consumption as part of wastewater-based epidemiological studies.

An extensive study on the presence of illicit drugs and pharmaceuticals with potential for abuse in sewage waters was made for the first time in the Netherlands. A total number of 24 target drugs were investigated in influent and effluent wastewater using liquid chromatography coupled to a high resolution Orbitrap mass spectrometer. This powerful analyzer has allowed not only the detection and identification of the compounds under investigation, but also their quantification at very low levels, which is highly innovative in the field of drugs of abuse. Samples were taken from five sewage treatment plants (STPs) during a whole week. The selected STPs served four cities of different size and an international airport. Daily variances of drug loads were demonstrated and removal efficiencies calculated for each drug and STP individually. Twelve target compounds were found in at least one influent or effluent, and highest concentrations were observed in influents collected from more urbanized areas. The compounds more frequently detected were amphetamine, benzoylecgonine, cocaine and THCCOOH together with the pharmaceuticals codeine, oxazepam and temazepam. Established week trends in consumption of drugs showed distinct differences between individual drugs. A slightly different occurrence pattern was observed in wastewaters from the airport. Thus, methamphetamine was only detected at Schiphol, a fact that was interpreted to be caused by consumption of this drug by travelers. Despite the fact that the Netherlands has frequently been criticized for its liberal drug policy the results from this study did not reveal higher drug consumption than found elsewhere, with the exception of cannabis. KeywordsIllicit drugs of abuse, accurate mass, linear ion trap (LTQ FT) Orbitrap mass spectrometry, sewage water, STP removal efficiency. 2/22

Background and aims Wastewater‐based epidemiology is an additional indicator of drug use that is gaining reliability to complement the current established panel of indicators. The aims of this study were to: (i) assess spatial and temporal trends of population‐normalized mass loads of benzoylecgonine, amphetamine, methamphetamine and 3,4‐methylenedioxymethamphetamine (MDMA) in raw wastewater over 7 years (2011–17); (ii) address overall drug use by estimating the average number of combined doses consumed per day in each city; and (iii) compare these with existing prevalence and seizure data. Design Analysis of daily raw wastewater composite samples collected over 1 week per year from 2011 to 2017. Setting and Participants Catchment areas of 143 wastewater treatment plants in 120 cities in 37 countries. Measurements Parent substances (amphetamine, methamphetamine and MDMA) and the metabolites of cocaine (benzoylecgonine) and of Δ9‐tetrahydrocannabinol (11‐nor‐9‐carboxy‐Δ9‐tetrahydrocannabinol) were measured in wastewater using liquid chromatography–tandem mass spectrometry. Daily mass loads (mg/day) were normalized to catchment population (mg/1000 people/day) and converted to the number of combined doses consumed per day. Spatial differences were assessed world‐wide, and temporal trends were discerned at European level by comparing 2011–13 drug loads versus 2014–17 loads. Findings Benzoylecgonine was the stimulant metabolite detected at higher loads in southern and western Europe, and amphetamine, MDMA and methamphetamine in East and North–Central Europe. In other continents, methamphetamine showed the highest levels in the United States and Australia and benzoylecgonine in South America. During the reporting period, benzoylecgonine loads increased in general across Europe, amphetamine and methamphetamine levels fluctuated and MDMA underwent an intermittent upsurge. Conclusions The analysis of wastewater to quantify drug loads provides near real‐time drug use estimates that globally correspond to prevalence and seizure data.

The analysis of illicit drugs in urban wastewater is the basis of wastewater‐based epidemiology (WBE), and has received much scientific attention because the concentrations measured can be used as a new non‐intrusive tool to provide evidence‐based and real‐time estimates of community‐wide drug consumption. Moreover, WBE allows monitoring patterns and spatial and temporal trends of drug use. Although information and expertise from other disciplines is required to refine and effectively apply WBE, analytical chemistry is the fundamental driver in this field. The use of advanced analytical techniques, commonly based on combined chromatography—mass spectrometry, is mandatory because the very low analyte concentration and the complexity of samples (raw wastewater) make quantification and identification/confirmation of illicit drug biomarkers (IDBs) troublesome. We review the most‐recent literature available (mostly from the last 5 years) on the determination of IDBs in wastewater with particular emphasis on the different analytical strategies applied. The predominance of liquid chromatography coupled to tandem mass spectrometry to quantify target IDBs and the essence to produce reliable and comparable results is illustrated. Accordingly, the importance to perform inter‐laboratory exercises and the need to analyze appropriate quality controls in each sample sequence is highlighted. Other crucial steps in WBE, such as sample collection and sample pre‐treatment, are briefly and carefully discussed. The article further focuses on the potential of high‐resolution mass spectrometry. Different approaches for target and non‐target analysis are discussed, and the interest to perform experiments under laboratory‐controlled conditions, as a complementary tool to investigate related compounds (e.g., minor metabolites and/or transformation products in wastewater) is treated. The article ends up with the trends and future perspectives in this field from the authors’ point of view. © 2016 by The Authors. Mass Spectrometry Reviews published by Wiley Periodicals, Inc. Mass Spec Rev 37:258–280, 2018

In-sewer transformation of drug biomarkers (excreted parent drugs and metabolites) can be influenced by the presence of biomass in suspended form as well as attached to sewer walls (biofilms). Biofilms are likely the most abundant and biologically active biomass fraction in sewers. In this study, 16 drug biomarkers were selected, including the parent forms and the major human metabolites of mephedrone, methadone, cocaine, heroin, codeine, and tetrahydrocannabinol (THC). Transformation and sorption of these substances were assessed in targeted batch experiments using laboratory-scale biofilm reactors operated under aerobic and anaerobic conditions. A one-dimensional model was developed to simulate diffusive transport, abiotic and biotic transformation, and partitioning of drug biomarkers. Model calibration to experimental results allowed estimating biotransformation rate constants in sewer biofilms, which were compared to those obtained for suspended biomass. Our results suggest that sewer biofilms can enhance the biotransformation kinetics of most selected compounds. Through scenario simulations, we demonstrated that the estimation of biotransformation rate constants in biofilm can be significantly biased if the boundary layer thickness is not accurately estimated. This study complements our previous investigation on the transformation and sorption of drug biomarkers in the presence of only suspended biomass in untreated sewage. A better understanding of the role of sewer biofilms-also relative to the in-sewer suspended solids-and improved prediction of associated fate processes can result in more accurate estimation of daily drug consumption in urban areas in wastewater-based epidemiological assessments.