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A novel analytical workflow for suspect screening of organic acidic contaminants in drinking water is presented, featuring selective extraction by silica-based strong anion-exchange solid-phase extraction, mixed-mode liquid chromatography-high resolution accurate mass spectrometry (LC-HRMS), peak detection, feature reduction and compound identification. The novel use of an ammonium bicarbonate-based elution solvent extended strong anion-exchange solid-phase extraction applicability to LC-HRMS of strong acids. This approach performed with consistently higher recovery and repeatability (88 ± 7 % at 500 ng L-1), improved selectivity and lower matrix interference (mean = 12 %) over a generic mixed-mode weak anion exchange SPE method. In addition, a novel filter for reducing full-scan features from fulvic and humic acids was successfully introduced, reducing workload and potential for false positives. The workflow was then applied to 10 London municipal drinking water samples, revealing the presence of 22 confirmed and 37 tentatively identified substances. Several poorly investigated and potentially harmful compounds were found which included halogenated hydroxy-cyclopentene-diones and dibromomethanesulfonic acid. Some of these compounds have been reported as mutagenic in test systems and thus their presence here requires further investigation. Overall, this approach demonstrated that employing selective extraction improved detection and helped shortlist suspects and potentially toxic chemical contaminants with higher confidence.

Despite being a developed country in the European Union (EU), knowledge of the nature and extent of contamination of water bodies with contaminants of emerging concern (CECs) in Ireland is limited. In this study, >140 CECs including pharmaceuticals, pesticides and personal care products were monitored in monthly samples of wastewater treatment plant (WWTP) influent, effluent and receiving surface waters at both an urban and a rural location (72 samples in total) in Ireland over a 12-month period in 2018-2019. In total, 58 CECs were detected, including several EU Water Framework Directive Watch List compounds. Of all classes, the highest concentrations were measured for pharmaceuticals across all media, i.e., propranolol in surface waters (134 ng·L-1), hydrochlorothiazide in effluent (1067 ng·L-1) and venlafaxine in influent wastewater (8273 ng·L-1). Overall, high wastewater treatment removal was observed and a further reduction in CEC occurrence and concentration was measured via dilution in the receiving river environment. Lastly, an environmental risk assessment (ERA) was performed using risk quotients (RQ), which revealed that in surface waters, total RQ for all CECs was an order of magnitude lower than in effluents. The majority of CECs in surface waters posed a lower risk except E2 and EE2 which presented a medium risk (RQs of 3.5 and 1.1, respectively) in the rural area. This work represents the most comprehensive CEC monitoring dataset to date for Ireland which allowed for an ERA prioritisation to be performed for the first time.

Z-drugs, benzodiazepines and ketamine are classes of psychotropic drugs prescribed for treating anxiety, sleep disorders and depression with known side effects including an elevated risk of addiction and substance misuse. Both groups of these drugs have a strong potential for misuse, which has escalated over the years and was hypothesized here to have been exacerbated during the COVID-19 pandemic. Wastewater-based epidemiology (WBE) constitutes a fast, easy, and relatively inexpensive approach to epidemiological surveys for understanding the incidence and frequency of uses of these drugs. In this study, we analyzed wastewater (n = 376) from 50 cities across the United States and Mexico from July to October 2020 to estimate drug use rates during a pandemic event. Both time and flow proportional composite and grab samples of untreated municipal wastewater were analyzed using solid-phase extraction followed by liquid chromatography-tandem mass spectrometry to determine loadings of alprazolam, clonazepam, diazepam, ketamine, lorazepam, nordiazepam, temazepam, zolpidem, and zaleplon in raw wastewater. Simultaneously, prescription data of the aforementioned drugs were extracted from the Medicaid database from 2019 to 2021. Results showed high detection frequencies of ketamine (90 %), lorazepam (87 %), clonazepam (76 %) and temazepam (73 %) across both Mexico and United States and comparatively lower detection frequencies for zaleplon (22 %), zolpidem (9 %), nordiazepam (

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., This study was supported by the following countries, institutions and projects Australia: Thyne Reid foundation; Canada: Natural Sciences and Engineering Research Council of Canada (NSERC); Iceland: The Icelandic Research Fund (Grant number 163049–051); Slovenia: Slovene Research Agency (funding Project L1–9191); Spain: MINECO/AEI projects (CTM2014–56628‐C3–2‐R, CTQ2015–65603‐P, CTM2016–81935‐REDT, CTM2017–84763‐C3–2‐R), Galician Council of Culture, Education and Universities (ED481D 2017/003); UK: Environmental Sustainability Knowledge Transfer Network, Engineering and Physical Sciences Research Council and Thermo Fisher Scientific (CASE industrial scholarship for K. Munro, Ref.: EP/J502029/1). European Monitoring Centre for Drugs and Drug Addiction (EMCDDA); EU International Training Network SEWPROF (Marie Curie‐FP7‐PEOPLE, grant number 317205); COST Action ES1307 supported by COST (European Cooperation in Science and Technology); WATCH (Wastewater Analysis of Traces of illicit drug‐related Chemicals for law enforcement and public Health DG migration and Home affairs ‐ HOME/2015/ISFP/PR/DRUG/0062). Sampling support and provision of catchment information Austria: Klemens Geiger and Michael Schlapp; Belgium: Jonathan Phariseau, Bart Coene, Luc Van Os, Peter Nys, Dieter Lemaire, Jean‐François Mougel, Patrick Vantroyen and Karel Claes; Croatia: Marin Ganjto; Czech Republic: Jiri Stara and Robert Hrich Brněnské; France: Véronique Bremont; Italy: Roberto Mazzini and Francesca Pizza (Milan), Francesco Avolio (Bologna), Fabrizio Moratto and Sergio Ghezzi (Gorizia), Rosanna Brienza and Simona Panariello (Potenza), Pier Paolo Abis and Antonia Attanasio (Bari), Antonella Cicala (Palermo); Norway: Pia Ryrfors; Portugal: João Goulão, José Martins, Pedro Alvaro and Fátima Paixão; Slovakia: Silvia Antalová and Jozef Tichy; Spain: Begoña Martínez López, Cristian Mesa, Santiago Querol Rodriguez, Fernando Llavador, Enrique Albors and Gloria Fayos; the Netherlands: Alex Veltman, Peter Theijssen, Peter van Dijk, Stefan Wijers, Mark Stevens, Ferry de Wilde. Analytical support Australia: Maulik Ghetia; Cyprus: Popi Karaolia; Greece: Nikoilaos Raikos; Spain: Ana Maria Botero‐Coy, Clara Boix, Alberto Celma, Jorge Pitarch, Inés Racamonde and Eddie Fonseca; Italy: Emma Gracia‐Lor, Nikolaos I. Rousis and Noelia Salgueiro‐Gonzalez. Data repository and data screening Eawag: Harald von Waldow; EMCDDA: Renate Hochwieser, Liesbeth Vandam, João Matias and Federica Mathis.

The occurrence of pharmaceutical and illicit drug residues potentially arising from combined sewer overflows (CSOs) in the Central London portion of the Thames Estuary is presented. Approximately 39 million tonnes of untreated sewage enter the River Thames at 57 CSO points annually. Differential analysis of influents and effluents in a major wastewater treatment plant identified seven potential drug-related CSO markers based on removal rates. Three were present in influent at concentrations1 μg L

The application of new sorbent-film coated passive samplers for capture of bulk commercial and military explosives vapours in operationally relevant spaces such as luggage, rooms, vehicles and shipping containers is presented. Samplers were easily integrated with in-service detection technologies with little/no sample preparation required. Ethylene glycol dinitrate (EGDN) was detected within 4 h in a container holding a suitcase packed with 0.2 kg Perunit 28E. Within a 22,000 dm3 room, 1 kg of concealed Seguridad was detected within 24 h and in an adjoining room within 7 days. Exposed samplers also successfully captured components of 1 kg TNT after 72 h and 1 kg concealed Perunit 28E after 6 h in both a furnished room and a large, partially filled shipping container. For the latter, samplers captured detectable residues outside the container after 24 h and were stable during wet weather for 72 h. A one-week trial at three operationally relevant venues including a university, a theatre and a government building revealed a nuisance positive rate of

A new thin-film passive sampler is presented as a low resource dependent and discrete continuous monitoring solution for explosives-related vapours. Using 15 mid-high vapour pressure explosives-related compounds as probes, combinations of four thermally stable substrates and six film-based sorbents were evaluated. Meta-aramid and phenylene oxide-based materials showed the best recoveries from small voids (~70%). Analysis was performed using liquid chromatography-high resolution accurate mass spectrometry which also enabled tentative identification of new targets from the acquired data. Preliminary uptake kinetics experiments revealed plateau concentrations on the device were reached between 3–5 days. Compounds used in improvised explosive devices, such as triacetone triperoxide, were detected within 1 hour and were stably retained by the sampler for up to 7 days. Sampler performance was consistent for 22 months after manufacture. Lastly, its direct integration with currently in-service explosives screening equipment including ion mobility spectrometry and thermal desorption mass spectrometry is presented. Following exposure to several open environments and targeted interferences, sampler performance was subsequently assessed and potential interferences identified. High-security building and area monitoring for concealed explosives using such cost-effective and discrete passive samplers can add extra assurance to search routines while minimising any additional burden on personnel or everyday site operation.

Pharmaceuticals have been considered ‘contaminants of emerging concern’ for more than 20 years. In that time, many laboratory studies have sought to identify hazard and assess risk in the aquatic environment, whilst field studies have searched for targeted candidates and occurrence trends using advanced analytical techniques. However, a lack of a systematic approach to the detection and quantification of pharmaceuticals has provided a fragmented literature of serendipitous approaches. Evaluation of the extent of the risk for the plethora of human and veterinary pharmaceuticals available requires the reliable measurement of trace levels of contaminants across different environmental compartments (water, sediment, biota - of which biota has been largely neglected). The focus on pharmaceutical concentrations in surface waters and other exposure media have therefore limited both the characterisation of the exposome in aquatic wildlife and the understanding of cause and effect relationships. Here, we compile the current analytical approaches and available occurrence and accumulation data in biota to review the current state of research in the field. Our analysis provides evidence in support of the ‘Matthew Effect’ and raises critical questions about the use of targeted analyte lists for biomonitoring. We provide six recommendations to stimulate and improve future research avenues., Graphical abstract Image 1, Highlights • Occurrence and accumulation of pharmaceuticals in aquatic fauna is presented. • Evidence of the Matthew Effect from biased pharmaceutical pre-selection. • Field versus laboratory derived accumulation factors showed a large disparity. • Specific accumulation is pronounced for liver and bile over other tissues. • Recommendations for advancements within environmental toxicology are proposed., The determination of the pharmaceutical exposome in aquatic fauna is critical to understanding the extent of contamination and the potential risk in the environment.

Methods were developed to assess uptake and elimination kinetics in Gammarus pulex of nine pharmaceuticals (sulfamethazine, carbamazepine, diazepam, temazepam, trimethoprim, warfarin, metoprolol, nifedipine and propranolol) using targeted LC-MS/MS to determine bioconcentration factors (BCFs) using a 96 h toxicokinetic exposure and depuration period. The derived BCFs for these pharmaceuticals did not trigger any regulatory thresholds and ranged from 0 to 73 L kg−1 (sulfamethazine showed no bioconcentration). Metabolism of chemicals can affect accurate BCF determination through parameterisation of the kinetic models. The added selectivity of LC-MS/MS allowed us to develop confirmatory methods to monitor the biotransformation of propranolol, carbamazepine and diazepam in G. pulex. Varying concentrations of the biotransformed products; 4-hydroxypropranolol sulphate, carbamazepine-10,11-epoxide, nordiazepam, oxazepam and temazepam were measured following exposure of the precursor compounds. For diazepam, the biotransformation product nordiazepam was present at higher concentrations than the parent compound at 94 ng g−1 dw. Overall, the results indicate that pharmaceutical accumulation is low in these freshwater amphipods, which can potentially be explained by the rapid biotransformation and excretion., Graphical abstract Image 1, Highlights • Bioconcentration factors of 9 pharmaceuticals in G. pulex ranged from 0 to 73 L kg−1 • G. pulex are capable of pharmaceutical biotransformation. • Five pharmaceutical metabolites were determined up to 94.5 ng g−1 • Biotransformation can affect BCFtotal estimates if metabolites are not accounted for.

Modeling and prediction of polar organic chemical integrative sampler (POCIS) sampling rates (Rs) for 73 compounds using artificial neural networks (ANNs) is presented for the first time. Two models were constructed: the first was developed ab initio using a genetic algorithm (GSD-model) to shortlist 24 descriptors covering constitutional, topological, geometrical and physicochemical properties and the second model was adapted for Rs prediction from a previous chromatographic retention model (RTD-model). Mechanistic evaluation of descriptors showed that models did not require comprehensive a priori information to predict Rs. Average predicted errors for the verification and blind test sets were 0.03 ± 0.02 L d(-1) (RTD-model) and 0.03 ± 0.03 L d(-1) (GSD-model) relative to experimentally determined Rs. Prediction variability in replicated models was the same or less than for measured Rs. Networks were externally validated using a measured Rs data set of six benzodiazepines. The RTD-model performed best in comparison to the GSD-model for these compounds (average absolute errors of 0.0145 ± 0.008 L d(-1) and 0.0437 ± 0.02 L d(-1), respectively). Improvements to generalizability of modeling approaches will be reliant on the need for standardized guidelines for Rs measurement. The use of in silico tools for Rs determination represents a more economical approach than laboratory calibrations.

Quantitative measurement of drug consumption biomarkers in wastewater can provide objective information on community drug use patterns and trends. This study presents the measurement of alcohol consumption in 20 cities across 11 countries through the use of wastewater-based epidemiology (WBE), and reports the application of these data for the risk assessment of alcohol on a population scale using the margin of exposure (MOE) approach. Raw 24-h composite wastewater samples were collected over a one-week period from 20 cities following a common protocol. For each sample a specific and stable alcohol consumption biomarker, ethyl sulfate (EtS) was determined by liquid chromatography coupled to tandem mass spectrometry. The EtS concentrations were used for estimation of per capita alcohol consumption in each city, which was further compared with international reports and applied for risk assessment by MOE. The average per capita consumption in 20 cities ranged between 6.4 and 44.3L/day/1000 inhabitants. An increase in alcohol consumption during the weekend occurred in all cities, however the level of this increase was found to differ. In contrast to conventional data (sales statistics and interviews), WBE revealed geographical differences in the level and pattern of actual alcohol consumption at an inter-city level. All the sampled cities were in the "high risk" category (MOE10) and the average MOE for the whole population studied was 2.5. These results allowed direct comparisons of alcohol consumption levels, patterns and risks among the cities. This study shows that WBE can provide timely and complementary information on alcohol use and alcohol associated risks in terms of exposure at the community level.