The quantification of illicit drug and pharmaceutical residues in sewage has been shown to be a valuable tool that complements existing approaches in monitoring the patterns and trends of drug use. ...The present work delineates the development of a novel analytical tool and dynamic workflow for the analysis of a wide range of substances in sewage-based samples. The validated method can simultaneously quantify 51 target psychoactive substances and pharmaceuticals in sewage-based samples using an off-line automated solid phase extraction (SPE-DEX) method, using Oasis HLB disks, followed by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC-QTOF) in MSe. Quantification and matrix effect corrections were overcome with the use of 25 isotopic labeled internal standards (ILIS). Recoveries were generally greater than 60% and the limits of quantification were in the low nanogram-per-liter range (0.4–187 ng L−1). The emergence of new psychoactive substances (NPS) on the drug scene poses a specific analytical challenge since their market is highly dynamic with new compounds continuously entering the market. Suspect screening using high-resolution mass spectrometry (HRMS) simultaneously allowed the unequivocal identification of NPS based on a mass accuracy criteria of 5 ppm (of the molecular ion and at least two fragments) and retention time (2.5% tolerance) using the UNIFI screening platform. Applying MSe data against a suspect screening database of over 1000 drugs and metabolites, this method becomes a broad and reliable tool to detect and confirm NPS occurrence. This was demonstrated through the HRMS analysis of three different sewage-based sample types; influent wastewater, passive sampler extracts and pooled urine samples resulting in the concurrent quantification of known psychoactive substances and the identification of NPS and pharmaceuticals.
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•A novel reiterative workflow based on three identification levels for the determination of drugs in sewage-based samples.•Validation of a multi-residue method for the determination of 51 drugs, pharmaceuticals and metabolites by SPE-UHPLC-QTOF.•Applicability for three different sewage-based samples: wastewater, passive samplers and pooled urine samples.•Dynamic procedure which enables the addition of new compounds based on experimental results.
Eight organic UV filters and stabilizers were quantitatively determined in wastewater sludge and effluent, landfill leachate, sediments, and marine and freshwater biota. Crab, prawn and cod from ...Oslofjord, and perch, whitefish and burbot from Lake Mjøsa were selected in order to evaluate the potential for trophic accumulation. All of the cod livers analysed were contaminated with at least 1 UV filter, and a maximum concentration of almost 12μg/g wet weight for octocrylene (OC) was measured in one individual. 80% of the cod livers contained OC, and approximately 50% of cod liver and prawn samples contained benzophenone (BP3). Lower concentrations and detection frequencies were observed in freshwater species and the data of most interest is the 4 individual whitefish that contained both BP3 and ethylhexylmethoxycinnamate (EHMC) with maximum concentrations of almost 200ng/g wet weight. The data shows a difference in the loads of UV filters entering receiving water dependent on the extent of wastewater treatment. Primary screening alone is insufficient for the removal of selected UV filters (BP3, Padimate, EHMC, OC, UV-234, UV-327, UV-328, UV-329). Likely due in part to the hydrophobic nature of the majority of the UV filters studied, particulate loading and organic carbon content appear to be related to concentrations of UV filters in landfill leachate and an order of magnitude difference in these parameters correlates with an order of magnitude difference in the effluent concentrations of selected UV filters (Fig. 2). From the data, it is possible that under certain low flow conditions selected organic UV filters may pose a risk to surface waters but under the present conditions the risk is low, but some UV filters will potentially accumulate through the trophic food chain.
•Total organic UV filter wastewater effluent loadings were up to 800ng/day/1000 population.•The occurrence of BP3, EHMC, Padimate, OC, UV-327 and UV-238 in selected biota suggests the potential to bioaccumulate.•Risk quotients were <1 for BP3, EHMC, OC, UV-327 and UV-328, indicating low risk to receiving waters.
According to estimates put forward in multiple studies, tire and road wear particles are one of the largest sources to microplastic contamination in the environment. There are large uncertainties ...associated with local emissions and transport of tire and road wear particles into environmental compartments, highlighting an urgent need to provide more data on inventories and fluxes of these particles. To our knowledge, the present paper is the first published data on mass concentrations and snow mass load of tire and polymer-modified road wear particles in snow. Roadside snow and meltwater from three different types of roads (peri-urban, urban highway and urban) were analysed by Pyrolysis Gas Chromatography Mass Spectrometry. Tire particle mass concentrations in snow (76.0–14,500 mg/L meltwater), and snow mass loads (222–109,000 mg/m2) varied widely. The concentration ranges of polymer-modified particles were 14.8–9550 mg/L and 50.0–28,800 mg/m2 in snow and meltwater, respectively. Comparing the levels of tire and PMB particles to the total mass of particles, showed that tire and PMB-particles combined only contribute to 5.7% (meltwater) and 5.2% (mass load) of the total mass concentration of particles. The large variation between sites in the study was investigated using redundancy analysis of the possible explanatory variables. Contradictory to previous road studies, speed limit was found to be one of the most important variables explaining the variation in mass concentrations, and not Annual Average Daily Traffic. All identified variables explained 69% and 66%, for meltwater and mass load concentrations, respectively. The results show that roadside snow contain total suspended solids in concentrations far exceeding release limits of tunnel and road runoff, as well as tire particles in concentrations comparable to levels previously reported to cause toxicity effects in organisms. These findings strongly indicate that roadside snow should be treated before release into the environment.
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•TRWP is estimated to be one of the largest sources of MP to the environment.•Mass data of TRWP are limited and not before presented for roadside snow.•Roadside snow from various road types were analysed with Pyr-GC/MS.•Concentrations of TRWP showed large variations between and within road types.•Speed and AADT explained the main variation observed.
Nontarget analysis is considered one of the most comprehensive tools for the identification of unknown compounds in a complex sample analyzed via liquid chromatography coupled to high-resolution mass ...spectrometry (LC–HRMS). Due to the complexity of the data generated via LC–HRMS, the data-dependent acquisition mode, which produces the MS2 spectra of a limited number of the precursor ions, has been one of the most common approaches used during nontarget screening. However, data-independent acquisition mode produces highly complex spectra that require proper deconvolution and library search algorithms. We have developed a deconvolution algorithm and a universal library search algorithm (ULSA) for the analysis of complex spectra generated via data-independent acquisition. These algorithms were validated and tested using both semisynthetic and real environmental data. A total of 6000 randomly selected spectra from MassBank were introduced across the total ion chromatograms of 15 sludge extracts at three levels of background complexity for the validation of the algorithms via semisynthetic data. The deconvolution algorithm successfully extracted more than 60% of the added ions in the analytical signal for 95% of processed spectra (i.e., 3 complexity levels multiplied by 6000 spectra). The ULSA ranked the correct spectra among the top three for more than 95% of cases. We further tested the algorithms with 5 wastewater effluent extracts for 59 artificial unknown analytes (i.e., their presence or absence was confirmed via target analysis). These algorithms did not produce any cases of false identifications while correctly identifying ∼70% of the total inquiries. The implications, capabilities, and the limitations of both algorithms are further discussed.
The European and U.S. chemical agencies have listed approximately 800k chemicals about which knowledge of potential risks to human health and the environment is lacking. Filling these data gaps ...experimentally is impossible, so
approaches and prediction are essential. Many existing models are however limited by assumptions (e.g., linearity and continuity) and small training sets. In this study, we present a supervised direct classification model that connects molecular descriptors to toxicity. Categories can be driven by either data (using
-means clustering) or defined by regulation. This was tested via 907 experimentally defined 96 h LC
values for acute fish toxicity. Our classification model explained ≈90% of the variance in our data for the training set and ≈80% for the test set. This strategy gave a 5-fold decrease in the frequency of incorrect categorization compared to a quantitative structure-activity relationship (QSAR) regression model. Our model was subsequently employed to predict the toxicity categories of ≈32k chemicals. A comparison between the model-based applicability domain (AD) and the training set AD was performed, suggesting that the training set-based AD is a more adequate way to avoid extrapolation when using such models. The better performance of our direct classification model compared to that of QSAR methods makes this approach a viable tool for assessing the hazards and risks of chemicals.
In this article, a dataset from a collaborative non-target screening trial organised by the NORMAN Association is used to review the state-of-the-art and discuss future perspectives of non-target ...screening using high-resolution mass spectrometry in water analysis. A total of 18 institutes from 12 European countries analysed an extract of the same water sample collected from the River Danube with either one or both of liquid and gas chromatography coupled with mass spectrometry detection. This article focuses mainly on the use of high resolution screening techniques with target, suspect, and non-target workflows to identify substances in environmental samples. Specific examples are given to emphasise major challenges including isobaric and co-eluting substances, dependence on target and suspect lists, formula assignment, the use of retention information, and the confidence of identification. Approaches and methods applicable to unit resolution data are also discussed. Although most substances were identified using high resolution data with target and suspect-screening approaches, some participants proposed tentative non-target identifications. This comprehensive dataset revealed that non-target analytical techniques are already substantially harmonised between the participants, but the data processing remains time-consuming. Although the objective of a “fully-automated identification workflow” remains elusive in the short term, important steps in this direction have been taken, exemplified by the growing popularity of suspect screening approaches. Major recommendations to improve non-target screening include better integration and connection of desired features into software packages, the exchange of target and suspect lists, and the contribution of more spectra from standard substances into (openly accessible) databases.
Graphical Abstract
Matrix of identification approach versus identification confidence
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.
•8-iso-PGF2α was for the first time quantitatively analysed in sewage by IAC–LC–HRMS.•IAC allows efficient removal of matrix components and sufficient sensitivity.•8-iso-PGF2α was found to be stable ...in wastewater at least for 24h.•β-Glucuronidase treatment is essential to analyse total 8-iso-PGF2α in wastewater.
A reliable oxidative stress biomarker, 8-iso-prostaglandin F2α (8-iso-PGF2α), was for the first time quantitatively analysed in wastewater using an analytical method consisting of liquid chromatography–high resolution mass spectrometry coupled to immunoaffinity clean-up (IAC-LC-HRMS). Factors influencing the method's robustness were investigated, including analyte stability in sewage and enzymatic deconjugation with β-glucuronidase. The IAC-LC-HRMS method was linear over the range of 0.1–100ng/mL with correlation coefficient (R2) of 0.999. The quantification limits were sufficiently low to detect 8-iso-PGF2α in sewage (method quantification limit of 0.3ng/L) and precision, expressed as relative standard deviation was less than 7% and the accuracy expressed as relative recovery was in the 103–113% range. As a result, the application of the method to 24-h composite wastewater samples from Oslo showed 8-iso-PGF2α concentrations of 18.9–23.3ng/L for 8 days in March 2015. This study demonstrates a standard method to analyse 8-iso-PGF2α in sewage that will contribute to the further investigation of the potential use of 8-iso-PGF2α as a sewage biomarker for assessing the status of community health.
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