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The rapid increase in the production and global use of chemicals and their mixtures has raised concerns about their potential impact on human and environmental health. With advances in analytical techniques, in particular, high-resolution mass spectrometry (HRMS), thousands of compounds and transformation products with potential adverse effects can now be detected in environmental samples. However, identifying and prioritizing the toxicity drivers among these compounds remain a significant challenge. Effect-directed analysis (EDA) emerged as an important tool to address this challenge, combining biotesting, sample fractionation, and chemical analysis to unravel toxicity drivers in complex mixtures. Traditional EDA workflows are labor-intensive and time-consuming, hindering large-scale applications. The concept of high-throughput (HT) EDA has recently gained traction as a means of accelerating these workflows. Key features of HT-EDA include the combination of microfractionation and downscaled bioassays, automation of sample preparation and biotesting, and efficient data processing workflows supported by novel computational tools. In addition to microplate-based fractionation, high-performance thin-layer chromatography (HPTLC) offers an interesting alternative to HPLC in HT-EDA. This review provides an updated perspective on the state-of-the-art in HT-EDA, and novel methods/tools that can be incorporated into HT-EDA workflows. It also discusses recent studies on HT-EDA, HT bioassays, and computational prioritization tools, along with considerations regarding HPTLC. By identifying current gaps in HT-EDA and proposing new approaches to overcome them, this review aims to bring HT-EDA a step closer to monitoring applications.
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This study investigates human exposure to per- and polyfluoroalkyl substances (PFAS) via drinking water and evaluates human health risks. An analytical method for 56 target PFAS, including ultrashort-chain (C2-C3) and branched isomers, was developed. The limit of detection (LOD) ranged from 0.009 to 0.1 ng/L, except for trifluoroacetic-acid and perfluoropropanoic-acid with higher LODs of 35 and 0.24 ng/L, respectively. The method was applied to raw and produced drinking water from 18 Dutch locations, including groundwater or surface water as source, and applied various treatment processes. Ultrashort-chain (300 to 1100 ng/L) followed by the group of perfluoroalkyl-carboxylic-acids (PFCA, ≥C4) (0.4 to 95.1 ng/L) were dominant. PFCA and perfluoroalkyl-sulfonic-acid (≥C4), including precursors, showed significantly higher levels in drinking water produced from surface water. However, no significant difference was found for ultrashort PFAS, indicating the need for groundwater protection. Negative removal of PFAS occasionally observed for advanced treatment indicates desorption and/or degradation of precursors. The proportion of branched isomers was higher in raw and produced drinking water as compared to industrial production. Drinking water produced from surface water, except for a few locations, exceed non-binding provisional guideline values proposed; however, all produced drinking waters met the recent soon-to-be binding drinking-water-directive requirements.
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Ácidos Alcanossulfônicos , Água Potável , Fluorocarbonos , Água Subterrânea , Poluentes Químicos da Água , Humanos , Água Potável/análise , Água Potável/química , Monitoramento Ambiental/métodos , Poluentes Químicos da Água/análise , Água Subterrânea/química , Fluorocarbonos/análise , Ácidos Carboxílicos , Ácidos Alcanossulfônicos/análiseRESUMO
Monitoring of microplastics in environmental samples is relevant to the scientific world, as well as to environmental agencies and water authorities, in particular considering increasing efforts to decrease emissions and the growing concern of governments and the public. Therefore, rapid accurate detection and identification of microplastics including polymers, despite their degradation in the environment, is crucial. The degradation has a significant impact on the infrared spectra of the microplastics and can impede the identification process. This work presents a novel approach to addressing the problem of identification of weathered microplastics. A quantum cascade laser (LDIR) was used to record the infrared spectra of various polymeric particles (81,291 individual particles). Using a combination of pristine and weathered particles, two supervised machine learning (ML) models, namely Subspace k-Nearest Neighbor (Sub-kNN) and Boosted Decision Tree (BDT), were trained to recognize the spectrum characteristics of labeled particles and then used to identify unlabeled samples, with an identification accuracy of 89.7% and 77.1% using 10-fold cross validation. About 90% of the samples could be identified via the Sub-kNN or BDT models. Subsequently, a non-supervised ML model, namely, Density-based Spatial Clustering of Applications with Noise (DBSCAN), was used to cluster samples which could not be labeled from the supervised ML model. This enabled the detection of additional subgroups of microplastics. Manual labelling can then be carried out on a selection of spectra per group (e.g., centroids of each cluster), hence accelerating the identification process and allowing to add new labeled samples to the initial supervised ML. Although expert efforts are still needed, the proposed method greatly lowers labeling efforts by using the combined supervised and unsupervised learning models. In the future, the use of deep neural networks could further boost the implementation of these kinds of approaches for polymer and microplastic identification in environmental settings.
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Microplásticos , Poluentes Químicos da Água , Monitoramento Ambiental/métodos , Lasers Semicondutores , Aprendizado de Máquina , Plásticos , Polímeros , Poluentes Químicos da Água/análiseRESUMO
The COVID-19 pandemic has brought new momentum to 'wastewater-based epidemiology' (WBE). This approach can be applied to monitor the levels of antibiotic-resistant genes (ARGs), which in terms are used to make inferences about the burden of antimicrobial resistance (AMR) in human settlements. However, there is still little information about temporal variability in ARG levels measured in wastewater streams and how these influence the inferences made about the occurrence of AMR in communities. The goal of this study was hence to gain insights into the variability in ARG levels measured in the influent and effluent of two wastewater treatment plants in The Netherlands and link these to levels of antibiotic residues measured in the same samples. Eleven antibiotics were detected, together with all selected ARGs, except for VanB. Among the measured antibiotics, significant positive correlations (p > 0.70) with the corresponding resistance genes and some non-corresponding ARGs were found. Mass loads varied up to a factor of 35 between days and in concomitance with rainfall. Adequate sampling schemes need to be designed to ensure that conclusions are drawn from valid and representative data. Additionally, we advocate for the use of mass loads to interpret levels of AMR measured in wastewater.
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COVID-19 , Purificação da Água , Antibacterianos/farmacologia , Resistência Microbiana a Medicamentos/genética , Genes Bacterianos , Humanos , Pandemias , Eliminação de Resíduos Líquidos , Águas Residuárias/químicaRESUMO
LC-HRMS-based nontarget screening (NTS) has become the method of choice to monitor organic micropollutants (OMPs) in drinking water and its sources. OMPs are identified by matching experimental fragmentation (MS2) spectra with library or in silico-predicted spectra. This requires informative experimental spectra and prioritization to reduce feature numbers, currently performed post data acquisition. Here, we propose a different prioritization strategy to ensure high-quality MS2 spectra for OMPs that pose an environmental or human health risk. This online prioritization triggers MS2 events based on detection of suspect list entries or isotopic patterns in the full scan or an additional MS2 event based on fragment ion(s)/patterns detected in a first MS2 spectrum. Triggers were determined using cheminformatics; potentially toxic compounds were selected based on the presence of structural alerts, in silico-fragmented, and recurring fragments and mass shifts characteristic for a given structural alert identified. After MS acquisition parameter optimization, performance of the online prioritization was experimentally examined. Triggered methods led to increased percentages of MS2 spectra and additional MS2 spectra for compounds with a structural alert. Application to surface water samples resulted in additional MS2 spectra of potentially toxic compounds, facilitating more confident identification and emphasizing the method's potential to improve monitoring studies.
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Água Potável , Poluentes Químicos da Água , Quimioinformática , Cromatografia Líquida , Água Potável/análise , Humanos , Espectrometria de Massas , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidadeRESUMO
At the individual level, exposure to contaminants is generally assessed through the analysis of specific biomarkers in biological matrices. However, these studies are costly and logistically demanding, limiting their applicability to monitor population-wide exposure over time and space. By focusing on a selection of exposure biomarkers to phosphorus flame retardants and plasticizers (PFRs), this study aims to explore the possibility of using wastewater as a complementary source of information about exposure. Wastewater samples were collected from five cities in Europe and analyzed using a previously established method. Substantial differences in biomarker levels were observed between the investigated catchments, suggesting differences in exposure. Time trends in biomarkers observed between 2013 and 2016 were found to agree with results from human biomonitoring studies and reports about production volumes. Using Monte Carlo simulations, average urinary concentrations were estimated. These were generally higher compared to results from human biomonitoring studies. Various explanations for these differences were formulated (i.e., other excretion routes, external sources and different sampling approaches). Obtained results show that wastewater analysis provides unique information about geographical and temporal differences in exposure, which would be difficult to gather using other monitoring tools.
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Retardadores de Chama , Cidades , Monitoramento Ambiental , Europa (Continente) , Humanos , Fósforo , Plastificantes , Águas ResiduáriasRESUMO
Organophosphate flame retardants and plasticizers (PFRs) are a group of chemicals widely added to consumer products. PFRs are quickly metabolized in the human body into two types of metabolites, (1) dialkyl and diaryl phosphate esters (DAPs), such as diphenyl phosphate (DPHP) and bis(1,3-dichloro-2-propyl) phosphate (BDCIPP); and (2) hydroxylated PFRs (HO-PFRs), such as 1-hydroxy-2-propyl bis(1-chloro-2-propyl) phosphate (BCIPHIPP) and 2-hydroxyethyl bis(2-butoxyethyl) phosphate (BBOEHEP). Existing analytical methods usually focus on DAPs; therefore, human biomonitoring data on HO-PFRs remain scarce. In this study, an analytical procedure was developed for the simultaneous quantification of multiple PFR metabolites in human urine, covering eight DAPs and six HO-PFRs. Sample preparation was optimized to include all target compounds using Bond-Elut C18 solid-phase extraction cartridges, followed by instrumental analysis based on liquid-chromatography coupled to tandem mass spectrometry (LC-MS/MS). Method performance was validated according to established guidelines and satisfactory results were obtained for all metabolites in terms of recovery, linearity, limits of quantification, precision, and accuracy. Recoveries ranged from 87 to 112%. Method detection limits from 0.002 ng/mL for 2-ethyl-5-hydroxyhexyl diphenyl phosphate (5-HO-EHDPHP) to 0.66 ng/mL for 4-hydroxyphenyl phenyl phosphate (4-HO-DPHP). Seven PFR metabolites were frequently detected in a small biomonitoring study (n = 14), among them bis(1,3-dichloro-2-propyl) phosphate (BDCIPP), di-n-butyl phosphate (DNBP), 5-HO-EHDPHP, and BBOEHEP. Highest mean concentrations were found for DPHP, 2-ethylhexyl phenyl phosphate (EHPHP), and BCIPHIPP, while 4-HO-DPHP, 5-HO-EHDPHP, and EHPHP were detected in urine for the first time. Overall, the obtained results demonstrate that the developed method can be used for the simultaneous determination of 14 urinary biomarkers of exposure to PFRs. Graphical abstract á .
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Biomarcadores/urina , Retardadores de Chama , Plastificantes/química , Cromatografia Líquida/métodos , Monitoramento Ambiental , Poluentes Ambientais/urina , Humanos , Espectrometria de Massas em Tandem/métodosRESUMO
Tobacco smoking remains an important public health issue worldwide. Assessment of exposure to tobacco-related toxicants and carcinogens at the population level is thus an essential population health indicator. This can be achieved by wastewater-based epidemiology (WBE), which relies on the analysis of biomarkers in wastewater. However, required analytical methods for the simultaneous measurement of tobacco-related toxicants and carcinogens in wastewater are not available. In this study, a new analytical procedure was developed and validated to measure tobacco-related alkaloids, carcinogens, and their metabolites in raw wastewater, including anabasine (ANABA), anatabine (ANATA), cotinine (COT), trans-3'-hydroxycotinine (COT-OH), N-nitrosoanabasine (NAB), N-nitrosoanatabine (NAT), N-nitrosonornicotine (NNN), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL), NNAL-N-ß-glucuronide, and NNAL-O-ß-glucuronide. Different parameters were optimized for the solid-phase extraction procedure and instrumental analysis using liquid chromatography-tandem mass spectrometry. The optimized method was fully validated, resulting in acceptable within-run and between-run precision (<8% and <10% relative standard deviation, respectively) and accuracy (<9% and <13% bias, respectively). Method quantification limits were at 0.5-120 ng/L in wastewater. Target analytes were stable in wastewater at 4 and 20 °C over 24 h. The developed method was applied to wastewater samples from two Belgian cities. Average concentrations of COT, COT-OH, ANATA, ANABA, and NAT were 5200, 2600, 30, 10, and 0.6 ng/L, respectively, while NAB, NNN, NNK, and NNAL were not detected in the samples. With the developed robust analytical method, our study provided the first insight into the population exposure to both toxicants and carcinogens resulting from tobacco use.
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Carcinógenos/química , Cromatografia Líquida/métodos , Nicotiana/química , Espectrometria de Massas em Tandem/métodos , Águas Residuárias/química , Poluentes Químicos da Água/química , Biomarcadores/análise , Carcinógenos/toxicidade , Humanos , Poluentes Químicos da Água/toxicidadeRESUMO
Phosphorus flame retardants and plasticizers (PFRs) are increasingly used in consumer goods, from which they can leach and pose potential threats to human health. Monitoring human exposure to these compounds is thus highly relevant. Current assessment of exposure through analysis of biological matrices is, however, tedious as well as logistically and financially demanding. Analysis of selected biomarkers of exposure to PFRs in wastewater could be a simple and complementary approach to monitoring, over space and time, exposure at the population level. An analytical procedure, based on solid-phase extraction (SPE) and liquid chromatography coupled to tandem mass spectrometry, was developed and validated to monitor the occurrence in wastewater of human exposure biomarkers of 2-ethylhexyldiphenyl phosphate (EHDPHP), tris(2-butoxyethyl) phosphate (TBOEP), triphenyl phosphate (TPHP), tris(2-chloroisopropyl) phosphate (TCIPP), and tris(2-chloroethyl) phosphate (TCEP). Various SPE sorbents and extraction protocols were evaluated, and for the optimized method, absolute extraction recoveries ranged between 46% and 100%. Accuracy and precision were satisfactory for the selected compounds. Method detection limits ranged from 1.6 to 19 ng L-1. Biomarkers of exposure to PFRs were measured for the first time in influent wastewater. Concentrations in samples collected in Belgium ranged from below the limit of quantitation to 1072 ng L-1, with 2-ethylhexyl phenyl phosphate (EHPHP) and TCEP being the most abundant. Per capita loads of target biomarkers varied greatly, suggesting potential differences in exposure between the investigated communities. The developed method allowed implementation of the concepts of human biomonitoring at the community scale, opening the possibility to assess population-wide exposure to PFRs.
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Fluctuations in ammonium (NH4+), measured as NH4-N loads using an ion-selective electrode installed at the inlet of a sewage treatment plant, showed a distinctive pattern which was associated to weekly (i.e., commuters) and seasonal (i.e., holidays) fluctuations of the population. Moreover, population size estimates based on NH4-N loads were lower compared to census data. Diurnal profiles of benzoylecgonine (BE) and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH) were shown to be strongly correlated to NH4-N. Characteristic patterns, which reflect the prolonged nocturnal activity of people during the weekend, could be observed for BE, cocaine, and a major metabolite of MDMA (i.e., 4-hydroxy-3-methoxymethamphetamine). Additional 24 h composite samples were collected between February and September 2013. Per-capita loads (i.e., grams per day per 1000 inhabitants) were computed using census data and NH4-N measurements. Normalization with NH4-N did not modify the overall pattern, suggesting that the magnitude of fluctuations in the size of the population is negligible compared to those of illicit drug loads. Results show that fluctuations in the size of the population over longer periods of time or during major events can be monitored using NH4-N loads: either using raw NH4-N loads or population size estimates based on NH4-N loads, if information about site-specific NH4-N population equivalents is available.
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Compostos de Amônio/análise , Monitoramento de Medicamentos , Métodos Epidemiológicos , Drogas Ilícitas/análise , Densidade Demográfica , Águas Residuárias/química , Cocaína/análogos & derivados , Cocaína/análise , Humanos , Fatores de TempoRESUMO
Wastewater-based epidemiology (WBE) can provide objective and timely information on the use of new psychoactive substances (NPS), originally designed as legal alternatives of internationally controlled drugs. NPS have rapidly emerged on the global drug market, posing a challenge to drug policy and constituting a risk to public health. In this study, a WBE approach was applied to monitor the use of more than 300 NPS, together with fentanyl and its main metabolite norfentanyl, in influent wastewater collected from 12 European cities during March-June 2021. Quantitative and qualitative analysis of NPS in composite 24 h influent wastewater samples were based on solid phase extraction and liquid chromatography-mass spectrometry. In-sample stability tests demonstrated the suitability of most investigated biomarkers, except for a few synthetic opioids, synthetic cannabinoids and phenetylamines. Fentanyl, norfentanyl and eight NPS were quantified in influent wastewater and at least three substances were found in each city, demonstrating their use in Europe. N,N-dimethyltryptamine and 3-methylmethcathinone (3-MMC) were the most common NPS found, with the latter having the highest mass loads (up to 24.8 mg/day/1000 inhabitants). Seven additional substances, belonging to five categories of NPS, were identified in different cities. Spatial trends of NPS use were observed between cities and countries, and a changing weekly profile of use was observed for 3-MMC. WBE is a useful tool to rapidly evaluate emerging trends of NPS use, complementing common indicators (i.e. population surveys, seizures) and helping to establish measures for public health protection.
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Psicotrópicos , Águas Residuárias , Psicotrópicos/análise , Europa (Continente) , Cidades , Fentanila/análiseRESUMO
The chemical burden on the environment and human population is increasing. Consequently, regulatory risk assessment must keep pace to manage, reduce, and prevent adverse impacts on human and environmental health associated with hazardous chemicals. Surveillance of chemicals of known, emerging, or potential future concern, entering the environment-food-human continuum is needed to document the reality of risks posed by chemicals on ecosystem and human health from a one health perspective, feed into early warning systems and support public policies for exposure mitigation provisions and safe and sustainable by design strategies. The use of less-conventional sampling strategies and integration of full-scan, high-resolution mass spectrometry and effect-directed analysis in environmental and human monitoring programmes have the potential to enhance the screening and identification of a wider range of chemicals of known, emerging or potential future concern. Here, we outline the key needs and recommendations identified within the European Partnership for Assessment of Risks from Chemicals (PARC) project for leveraging these innovative methodologies to support the development of next-generation chemical risk assessment.
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Exposição Ambiental , Monitoramento Ambiental , Humanos , Exposição Ambiental/análise , Monitoramento Ambiental/métodos , Monitoramento Ambiental/normas , Poluentes Ambientais/análise , Substâncias Perigosas/análise , Espectrometria de Massas/métodos , Medição de Risco/métodosRESUMO
Wastewater-based epidemiology (WBE) has been proven to be a useful tool in monitoring public health-related issues such as drug use, and disease. By sampling wastewater and applying WBE methods, wastewater-detectable pathogens such as viruses can be cheaply and effectively monitored, tracking people who might be missed or under-represented in traditional disease surveillance. There is a gap in current knowledge in combining hydraulic modeling with WBE. Recent literature has also identified a gap in combining machine learning with WBE for the detection of viral outbreaks. In this study, we loosely coupled a physically-based hydraulic model of pathogen introduction and transport with a machine learning model to track and trace the source of a pathogen within a sewer network and to evaluate its usefulness under various conditions. The methodology developed was applied to a hypothetical sewer network for the rapid detection of disease hotspots of the disease caused by the SARS-CoV-2 virus. Results showed that the machine learning model's ability to recognize hotspots is promising, but requires a high time-resolution of monitoring data and is highly sensitive to the sewer system's physical layout and properties such as flow velocity, the pathogen sampling procedure, and the model's boundary conditions. The methodology proposed and developed in this paper opens new possibilities for WBE, suggesting a rapid back-tracing of human-excreted biomarkers based on only sampling at the outlet or other key points, but would require high-frequency, contaminant-specific sensor systems that are not available currently.
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This study aimed to identify antimicrobial contaminants in the aquatic environment with effect-directed analysis. Wastewater influent, effluent, and surface water (up- and downstream of the discharge location) were sampled at two study sites. The samples were enriched, subjected to high-resolution fractionation, and the resulting 80 fractions were tested in an antibiotics bioassay. The resulting bioactive fractions guided the suspect and nontargeted identification strategy in the high-resolution mass spectrometry data that was recorded in parallel. Chemical features were annotated with reference databases, assessed on annotation quality, and assigned identification confidence levels. To identify antibiotic metabolites, Phase I metabolites were predicted in silico for over 500 antibiotics and included as a suspect list. Predicted retention times and fragmentation patterns reduced the number of annotations to consider for confirmation testing. Overall, the bioactivity of three fractions could be explained by the identified antibiotics (clarithromycin and azithromycin) and an antibiotic metabolite (14-OH(R) clarithromycin), explaining 78% of the bioactivity measured at one study site. The applied identification strategy successfully identified antibiotic metabolites in the aquatic environment, emphasizing the need to include the toxic effects of bioactive metabolites in environmental risk assessments.
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Anti-Infecciosos , Poluentes Químicos da Água , Águas Residuárias , Claritromicina , Poluentes Químicos da Água/análise , Monitoramento Ambiental/métodos , Antibacterianos/análise , Anti-Infecciosos/análiseRESUMO
WBE has now become a complimentary tool in SARS-CoV-2 surveillance. This was preceded by the established application of WBE to assess the consumption of illicit drugs in communities. It is now timely to build on this and take the opportunity to expand WBE to enable comprehensive assessment of community exposure to chemical stressors and their mixtures. The goal of WBE is to quantify community exposure, discover exposure-outcome associations, and trigger policy, technological or societal intervention strategies with the overarching aim of exposure prevention and public health promotion. To achieve WBE's full potential, the following key aspects require further action: (1) Integration of WBE-HBM (human biomonitoring) initiatives that provide comprehensive community-individual multichemical exposure assessment. (2) Global WBE monitoring campaigns to provide much needed data on exposure in low- and middle-income countries (LMICs) and fill in the gaps in knowledge especially in the underrepresented highly urbanised as well as rural settings in LMICs. (3) Combining WBE with One Health actions to enable effective interventions. (4) Advancements in new analytical tools and methodologies for WBE progression to enable biomarker selection for exposure studies, and to provide sensitive and selective multiresidue analysis for trace multi-biomarker quantification in a complex wastewater matrix. Most of all, further developments of WBE needs to be undertaken by co-design with key stakeholder groups: government organisations, health authorities and private sector.
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COVID-19 , Saúde Única , Humanos , Vigilância Epidemiológica Baseada em Águas Residuárias , Monitoramento Biológico , SARS-CoV-2 , Biomarcadores/análiseRESUMO
Despite high vaccination rates in the Netherlands, severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) continues to circulate. Longitudinal sewage surveillance was implemented along with the notification of cases as two parts of the surveillance pyramid to validate the use of sewage for surveillance, as an early warning tool, and to measure the effect of interventions. Sewage samples were collected from nine neighborhoods between September 2020 and November 2021. Comparative analysis and modeling were performed to understand the correlation between wastewater and case trends. Using high resolution sampling, normalization of wastewater SARS-CoV-2 concentrations, and 'normalization' of reported positive tests for testing delay and intensity, the incidence of reported positive tests could be modeled based on sewage data, and trends in both surveillance systems coincided. The high collinearity implied that high levels of viral shedding around the onset of disease largely determined SARS-CoV-2 levels in wastewater, and that the observed relationship was independent of variants of concern and vaccination levels. Sewage surveillance alongside a large-scale testing effort where 58 % of a municipality was tested, indicated a five-fold difference in the number of SARS-CoV-2-positive individuals and reported cases through standard testing. Where trends in reported positive cases were biased due to testing delay and testing behavior, wastewater surveillance can objectively display SARS-CoV-2 dynamics for both small and large locations and is sensitive enough to measure small variations in the number of infected individuals within or between neighborhoods. With the transition to a post-acute phase of the pandemic, sewage surveillance can help to keep track of re-emergence, but continued validation studies are needed to assess the predictive value of sewage surveillance with new variants. Our findings and model aid in interpreting SARS-CoV-2 surveillance data for public health decision-making and show its potential as one of the pillars of future surveillance of (re)emerging viruses.
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COVID-19 , Humanos , COVID-19/epidemiologia , SARS-CoV-2 , Águas Residuárias , Vigilância Epidemiológica Baseada em Águas Residuárias , EsgotosRESUMO
Monitoring of SARS-CoV-2 in wastewater (WW) is a promising tool for epidemiological surveillance, correlating not only viral RNA levels with the infection dynamics within the population, but also to viral diversity. However, the complex mixture of viral lineages in WW samples makes tracking of specific variants or lineages circulating in the population a challenging task. We sequenced sewage samples of 9 WW-catchment areas within the city of Rotterdam, used specific signature mutations from individual SARS-CoV-2 lineages to estimate their relative abundances in WW and compared them against those observed in clinical genomic surveillance of infected individuals between September 2020 and December 2021. We showed that especially for dominant lineages, the median of the frequencies of signature mutations coincides with the occurrence of those lineages in Rotterdam's clinical genomic surveillance. This, along with digital droplet RT-PCR targeting signature mutations of specific variants of concern (VOCs), showed that several VOCs emerged, became dominant and were replaced by the next VOC in Rotterdam at different time points during the study. In addition, single nucleotide variant (SNV) analysis provided evidence that spatio-temporal clusters can also be discerned from WW samples. We were able to detect specific SNVs in sewage, including one resulting in the Q183H amino acid change in the Spike gene, that was not captured by clinical genomic surveillance. Our results highlight the potential use of WW samples for genomic surveillance, increasing the set of epidemiological tools to monitor SARS-CoV-2 diversity.
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COVID-19 , Águas Residuárias , Humanos , SARS-CoV-2/genética , Esgotos , COVID-19/epidemiologiaRESUMO
Wastewater-based epidemiology (WBE) is increasingly being recognized as a powerful tool for detecting and monitoring SARS-CoV-2 trends at a population level. This study looked to extend the use of WBE to explore the effectiveness of nonpharmaceutical interventions (NPIs) that have been used in response to COVID-19 and compare the results to the effect of such interventions on COVID-19 hospitalizations. A data-driven approach demonstrated that trends of SARS-CoV-2 RNA in wastewater, from Amsterdam and Utrecht (The Netherlands), precede hospitalizations by at least 3-9 days. Additionally, the effect of NPIs can be seen in wastewater and hospitalizations after 20 and 24 days, respectively. Changepoint analysis indicated that the closure of schools and universities significantly reduced the level of SARS-CoV-2 RNA in wastewater and COVID-19 hospitalizations. Regression modeling suggested the stay-at-home policy is an effective intervention for reducing the level of SARS-CoV-2 RNA in wastewater, whereas the closure of workplaces significantly reduced hospitalizations in both Dutch cities. This study demonstrates how WBE can be used to inform public health decisions and anticipate future strain on healthcare facilities in major cities but also indicates a need for higher temporal resolution of wastewater sampling.
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3,4-Methylenedioxymethamphetamine (MDMA) and amphetamine are commonly used psychoactive stimulants. Illegal manufacture of these substances, mainly located in the Netherlands and Belgium, generates large amounts of chemical waste which is disposed in the environment or released in sewer systems. Retrospective analysis of high-resolution mass spectrometry (HRMS) data was implemented to detect synthesis markers of MDMA and amphetamine production in wastewater samples. Specifically, suspect and non-target screening, combined with a prioritization approach based on similarity measures between detected features and mass loads of MDMA and amphetamine was implemented. Two hundred and thirty-five 24 h-composite wastewater samples collected from a treatment plant in the Netherlands between 2016 and 2018 were analyzed by liquid chromatography coupled to high-resolution mass spectrometry. Samples were initially separated into two groups (i.e., baseline consumption versus dumping) based on daily loads of MDMA and amphetamine. Significance testing and fold-changes were used to find differences between features in the two groups. Then, associations between peak areas of all features and MDMA or amphetamine loads were investigated across the whole time series using various measures (Euclidian distance, Pearson's correlation coefficient, Spearman's rank correlation coefficient, distance correlation and maximum information coefficient). This unsupervised and unbiased approach was used for prioritization of features and allowed the selection of 28 presumed markers of production of MDMA and amphetamine. These markers could potentially be used to detect dumps in sewer systems, help in determining the synthesis route and track down the waste in the environment.