Spatio-temporal assessment of illicit drug use at large scale: evidence from 7 years of international wastewater monitoring.

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.

Sorbent Film-Coated Passive Samplers for Explosives Vapour Detection Part B: Deployment in Semi-Operational Environments and Alternative Applications.

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 <1.4% (n = 72). Finally, two alternative applications are presented for extraction of liquid samples and use a particulate contact swab showing flexibility for a range of different search activities.

Sorbent Film-Coated Passive Samplers for Explosives Vapour Detection Part A: Materials Optimisation and Integration with Analytical Technologies.

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.

Assessing the reliability of uptake and elimination kinetics modelling approaches for estimating bioconcentration factors in the freshwater invertebrate, Gammarus pulex.

This study considers whether the current standard toxicokinetic methods are an accurate and applicable assessment of xenobiotic exposure in an aquatic freshwater invertebrate. An in vivo exposure examined the uptake and elimination kinetics for eight pharmaceutical compounds in the amphipod crustacean, Gammarus pulex by measuring their concentrations in both biological material and in the exposure medium over a 96 h period. Selected pharmaceuticals included two anti-inflammatories (diclofenac and ibuprofen), two beta-blockers (propranolol and metoprolol), an anti-depressant (imipramine), an anti-histamine (ranitidine) and two beta-agonists (formoterol and terbutaline). Kinetic bioconcentration factors (BCFs) for the selected pharmaceuticals were derived from a first-order one-compartment model using either the simultaneous or sequential modelling methods. Using the simultaneous method for parameter estimation, BCF values ranged from 12 to 212. In contrast, the sequential method for parameter estimation resulted in bioconcentration factors ranging from 19 to 4533. Observed toxicokinetic plots showed statistically significant lack-of-fits and further interrogation of the models revealed a decreasing trend in the uptake rate constant over time for ranitidine, diclofenac, imipramine, metoprolol, formoterol and terbutaline. Previous published toxicokinetic data for 14 organic micro-pollutants were also assessed and similar trends were identified to those observed in this study. The decreasing trend of the uptake rate constant over time highlights the need to interpret modelled data more comprehensively to ensure uncertainties associated with uptake and elimination parameters for determining bioconcentration factors are minimised.

Gradient liquid chromatographic retention time prediction for suspect screening applications: A critical assessment of a generalised artificial neural network-based approach across 10 multi-residue reversed-phase analytical methods.

For the first time, the performance of a generalised artificial neural network (ANN) approach for the prediction of 2492 chromatographic retention times (tR) is presented for a total of 1117 chemically diverse compounds present in a range of complex matrices and across 10 gradient reversed-phase liquid chromatography-(high resolution) mass spectrometry methods. Probabilistic, generalised regression, radial basis function as well as 2- and 3-layer multilayer perceptron-type neural networks were investigated to determine the most robust and accurate model for this purpose. Multi-layer perceptrons most frequently yielded the best correlations in 8 out of 10 methods. Averaged correlations of predicted versus measured tR across all methods were R(2)=0.918, 0.924 and 0.898 for the training, verification and test sets respectively. Predictions of blind test compounds (n=8-84 cases) resulted in an average absolute accuracy of 1.02±0.54min for all methods. Within this variation, absolute accuracy was observed to marginally improve for shorter runtimes, but was found to be relatively consistent with respect to analyte retention ranges (~5%). Finally, optimised and replicated network dependency on molecular descriptor data is presented and critically discussed across all methods. Overall, ANNs were considered especially suitable for suspects screening applications and could potentially be utilised in bracketed-type analyses in combination with high resolution mass spectrometry.

Pharmaceuticals in the freshwater invertebrate, Gammarus pulex, determined using pulverised liquid extraction, solid phase extraction and liquid chromatography-tandem mass spectrometry.

The development, characterisation and application of a new analytical method for multi-residue PPCP determination in the freshwater amphipod, Gammarus pulex are presented. Analysis was performed using pulverised liquid extraction (PuLE), solid phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Qualitative method performance offered excellent limits of detection at <20 ng g(-1) for 18 out of 29 compounds. For quantitative application, linearity and precision were considered acceptable for 10 compounds across the ng-µg g(-1) range (R2≥0.99; ≤20% relative standard deviation respectively). The method was applied to the analysis of G. pulex and river water sourced from six tributaries of the River Thames. Carbamazepine, diazepam, nimesulide, trimethoprim and warfarin were determined in G. pulex samples at low ng g(-1) (dry weight) concentrations across these sites. Temazepam and diclofenac were also detected, but were not quantifiable. Six pharmaceuticals were quantified in surface waters across the eight sites at concentrations ranging from 3 to 344 ng L(-1). The possibility for confirmatory detection and subsequent quantification of pharmaceutical residues in benthic organisms such as G. pulex will enable further understanding on the susceptibility and ecological effects of PPCPs in the aquatic environment.