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Wastewater-based epidemiology (WBE) using viral nucleic acids to predict community viral outbreaks has many challenges, including interferences from the wastewater matrix. Liquid chromatography with tandem mass spectrometry (LC–MS/MS) monitoring of pharmaceutically active compounds, such as antivirals and over-the-counter drugs commonly used to relieve the symptoms of infection, could complement information provided by molecular techniques. For instance, residues of drugs associated with managing Covid-19 symptoms, including azithromycin, chloroquine, hydroxychloroquine, and lopinavir, have been detected in influent wastewater. A significant correlation can be observed between the total of Covid-19–related drugs detected and the 5-day rolling averages of reported cases. Spikes in acetaminophen concentrations can also be observed a couple of weeks before a spike in SARS-CoV-2 RNA copies in wastewater, suggesting that over-the-counter analgesic concentrations in raw sewage may be used to complement viral RNA data as an early-warning system for effective management of viral outbreaks at the community level. Sample preparation and analysis of pharmaceuticals in wastewater present unique challenges and are discussed in this article.

Sphingolipids are key signaling lipids and their dysregulation has been associated with various cellular processes. We have previously shown significant changes in sphingolipids in therapy-induced senescence, a state of cell cycle arrest as a response to chemotherapy, including the accumulation of ceramides, and provided evidence suggesting that ceramide processing is important for this process. Herein, we conducted a focused small molecule inhibitor screen targeting the sphingolipid pathway, which highlighted a new lipid regulator of therapy-induced senescence. Among the inhibitors tested, the inhibition of ceramide kinase by NVP-231 reduced the levels of senescent cells. Ceramide kinase knockdown exhibited similar effects, strongly supporting the involvement of ceramide kinase during this process. We showed that ceramide-1-phosphate was upregulated in therapy-induced senescence and that NVP-231 reduced ceramide-1-phosphate levels in different cell line models of therapy-induced senescence. Finally, ceramide-1-phosphate addition to NVP-231-treated cells reversed the effects of NVP-231 during senescence. Overall, our results identify a previously unknown lipid player in therapy-induced senescence and highlight a potential targetable enzyme to reduce the levels of therapy-induced senescent cells.

Antibiotic resistant bacteria and antibiotic resistance genes are important environmental contaminants. Nonetheless, what drives the evolution, spread and transmission of antibiotic resistance dissemination is still poorly understood. The abundance of antibiotic resistant bacteria and antibiotic resistance genes is often elevated in human impacted areas, especially in environments receiving faecal wastes, or in the presence of complex mixtures of chemical contaminants, such as pharmaceuticals and personal care products (PPCPs). Self-replication, mutation, horizontal gene transfer and adaptation to different environmental conditions contribute to the persistence and proliferation of antibiotic resistant bacteria in habitats under strong anthropogenic influence. This review will discuss the interplay between chemical contaminants and antibiotic resistant bacteria and respective genes, specifically in reference to co-occurrence, potential biostimulation and selective pressure effects, and will overview mitigation by existing man-made and natural barriers. Evidence and strategies to improve the assessment of human-health risks due to environmental antibiotic resistance are also debated. This article is protected by copyright. All rights reserved. Environ Toxicol Chem 2022;00:0-0. © 2022 SETAC.

The advent of new data acquisition and handling techniques has opened the door to alternative and more comprehensive approaches to environmental monitoring that will improve our capacity to understand and manage environmental systems. Researchers have recently begun using machine learning (ML) techniques to analyze complex environmental systems and their associated data. Herein, we provide an overview of data analytics frameworks suitable for various Environmental Science and Engineering (ESE) research applications. We present current applications of ML algorithms within the ESE domain using three representative case studies: (1) Metagenomic data analysis for characterizing and tracking antimicrobial resistance in the environment; (2) Nontarget analysis for environmental pollutant profiling; and (3) Detection of anomalies in continuous data generated by engineered water systems. We conclude by proposing a path to advance incorporation of data analytics approaches in ESE research and application.

Antibiotic use in animal husbandry is a potential entryway for antibiotics and antibiotic resistance genes (ARGs) to enter the environment through manure fertilizer application. The potential of anaerobic digestion (AD) to remove antibiotics and ARGs was investigated through tetracycline (TC) and sulfadimethoxine (SDM) additions into dairy manure digested for 44 d. This was the first study to evaluate antibiotics at concentrations quantified on-farm and relevant to field applications of manure. Triplicate treatments included a 1 mg L-1 TC spike, a 10 mg L-1 TC spike, a 1 mg L-1 SDM spike (SDM 1), a 10 mg L-1 SDM spike, a mixture of TC and SDM at 1 mg L-1 each (TC+SDM 1), and a manure-only treatment. The SDM spikes were reduced by >99% reduction during the AD processing, but TC additions had variable reductions (0-96%). Molecular analyses showed that decreases in tetM gene copies correlated with declines in TC; however, reductions in SDM concentration did not correlate with decreases in sul1 gene copy concentrations. The AD reactors containing 10 mg L-1 of TC and 10 mg L-1 of SDM both had CH4 production reductions of 7.8%, whereas no CH4 reduction was observed in other treatments (1 mg L-1 treatments). The study results were the first to confirm that AD can remove SDM when adding at concentrations observed in on-farm manure (

Garlic, an Allium vegetable, contains rich flavonoids organosulfur compounds (OSCs) that have potent anticancer properties. The aim of the review is to provide an overview of the different types of garlic, their active compounds, and the potential anticancer benefits with a focus on antioxidant activity. Animal and cell line studies have provided convincing evidence that garlic and its organosulfur compounds inhibit carcinogenesis through a number of events including induction of apoptosis, inhibiting cellular proliferation, scavenging radical oxygen species (ROS), increasing the activities of enzymes such as glutathione S-transferase, and reducing tumor size. Epidemiological studies showed compelling evidence that garlic consumption is associated with decreased risk of colorectal cancer, but inconsistent evidence for stomach, breast, and prostate cancers. Studies also suggest that the presence and potency of garlic OSCs varies with respect to the preparation and form of garlic. Further epidemiological studies with information on garlic form consumed or preparation methods and molecular studies regarding its antioxidant mechanisms, such as increasing enzymatic and nonenzymatic antioxidants levels, are warranted.

An on-farm solid-liquid separator (SLS) and rotary drum composter (RD) manure treatment system was monitored for its impact on antibiotic residues and antibiotic resistance genes (ARGs). Administered antibiotics were tracked, and treatment system mass flows were quantified. Total amounts of antibiotic residues and ARGs were calculated from measured concentrations and mass flows. Only oxytetracycline (OTC) and sulfadimethoxine (SDM) were detected in the manure treatment system influent. No β-lactams were measured despite comprising ∼25% of the antibiotics administered. Nearly 80% of OTC and >90% of SDM partitioned into SLS liquid effluent (SL). The RD reduced the mass of OTC remaining in the SLS solid effluent (SS) significantly by 50%, whereas the mass of SDM appeared to increase after RD treatment. All four ARGs tested were detected in influent, with >70% of the sul1, blaOXA-1 , and intI1 genes (normalized by the 16S ribosomal RNA gene) partitioning into the SL. In contrast, about eight times more normalized tetO gene copies partitioned into the SS than in the SL. All ARGs remaining in the SS were significantly reduced by the RD treatment, with a noteworthy 98% reduction in normalized tetO gene copies. This study provides insight into on-farm levels of antibiotic residues and ARGs in dairy manure, their partitioning during SLS treatment, and their fate after a high-temperature RD treatment reaching 72.2 ± 0.18 °C near the outlet. It also notes the importance of mass-flow standardization of data, and the need to work towards standardization of manure system sampling protocols for antibiotic residues and ARGs.

Pharmaceuticals and personal care products (PPCPs) can enter agricultural fields through wastewater irrigation, biosolid amendments, or urine fertilization. Numerous studies have assessed the risk of PPCP contamination, however there are no standardized methodologies for sample treatment, making the interpretation of results challenging. Various time periods between sampling and analysis have been reported (shipping, storage, etc.), but literature is lacking in the evaluation of PPCP degradation amidst this process. This study assessed the stability of 20 pharmaceuticals (200 μg L−1) in soil and crops stored at −40 °C for 7, 30, and 310 days. After 310 days, caffeine, meprobamate, trimethoprim, primidone, carbamazepine, anhydro-erythromycin and dilantin were found to be stable (≥75% recovery) in all matrices. On the other hand, acetaminophen, amitriptyline, bupropion, lamotrigine, sulfamethoxazole, naproxen, ibuprofen, and paroxetine were unstable after 30 days in at least one of the matrices investigated. Due to variations in analyte stability, fortification with isotopically-labelled surrogates at the point of sample collection was evaluated in comparison to fortification after shipment and storage, immediately prior to extraction. Chromatographic peak areas of stable analytes were found to be reproducible (±15%) in field-fortified samples, indicating that no additional error occurred during sample handling under field conditions despite having a less controlled environment. Unstable analytes revealed notable differences in peak areas between fortification times, suggesting that fortification immediately after sample collection is crucial to account for analyte losses during shipping and storage, resulting in accurate quantification of PPCPs.

Cartagena Bay is an estuarine system located in the Caribbean Sea (Colombia, South America), that receives fresh water from Canal del Dique, which is connected to the Magdalena River, the most important river of Colombia, with some of the most prominent Colombian cities located in its watershed, which has a high sediment yield. An analysis of persistent organic pollutants and heavy metals was carried out on marine sediments from Cartagena Bay. Cartagena Bay sediments deployed the occurrence of total levels of pesticides (thiocarbamates, bromacil, triazines, organochlorines, and organophosphorus), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs), in sediments ranging from 0.83–33.67 ng/g dry-weight, 0.05–0.34 ng/g dry-weight, and 0.06–19.58 ng/g dry-weight, respectively. Their concentrations were lower than those reported in NOAA Screening Quick Reference Tables. DDTs and PCBs are banned organochlorine compounds, since, even at low levels, their presence in sediments represents a threat to aquatic organisms and, therefore, to human health through the trophic chain. Sediments showed high concentrations of strontium (50–959.6 mg/kg). All metals evaluated in the marine sediments were found in the S6 sampling point; this was near tannery and hydrocarbon industries (Pb 37.1 mg/kg, Cr 137.2 mg/kg, Cd 1.7 mg/kg, Cu 64.4 mg/kg, As 13.1 mg/kg, Sr 318.9 mg/kg); these results exceeded the accepted values of threshold effect levels (TEL) used as an indicator of their potential risk on marine life.

Wastewater-based surveillance (WBS) for disease monitoring is highly promising but requires consistent methodologies that incorporate predetermined objectives, targets, and metrics. Herein, we describe a comprehensive metagenomics-based approach for global surveillance of antibiotic resistance in sewage that enables assessment of 1) which antibiotic resistance genes (ARGs) are shared across regions/communities; 2) which ARGs are discriminatory; and 3) factors associated with overall trends in ARGs, such as antibiotic concentrations. Across an internationally sourced transect of sewage samples collected using a centralized, standardized protocol, ARG relative abundances (16S rRNA gene-normalized) were highest in Hong Kong and India and lowest in Sweden and Switzerland, reflecting national policy, measured antibiotic concentrations, and metal resistance genes. Asian versus European/US resistomes were distinct, with macrolide-lincosamide-streptogramin, phenicol, quinolone, and tetracycline versus multidrug resistance ARGs being discriminatory, respectively. Regional trends in measured antibiotic concentrations differed from trends expected from public sales data. This could reflect unaccounted uses, captured only by the WBS approach. If properly benchmarked, antibiotic WBS might complement public sales and consumption statistics in the future. The WBS approach defined herein demonstrates multisite comparability and sensitivity to local/regional factors. This material is based upon work supported by the U.S. National Science Foundation (NSF) Award OISE: 1545756. Additional funding to D.G.J.L. was provided by the Swedish research council VR (2018-05771) and the Region Västra Götaland under the ALF agreement (grant number ALFGBG-717901). Funding for H.B. was provided by the Swiss National Science Foundation under the NRP72 “Antimicrobial resistance”, grant 167116. Published version

Per- and poly-fluorinated substances (PFASs) are organic pollutants that have been linked to numerous health effects, including diabetes, cancers, and dysregulation of the endocrine system. This study aims to develop a liquid chromatography with tandem mass spectrometry (LC-MS/MS) assay to measure changes in 17 hormones in H295R cell line (a steroid producing adrenocortical cells) upon exposure to PFASs. Due to the challenges in the analysis of steroid hormones using electrospray ionization MS, a chemical derivatization method was employed to achieve 0.07-2 μg/L detection limits in LC-MS/MS. Furthermore, a 10-fold concentration factor through solid-phase extraction (SPE) allows for consistent sub-parts per billion detections. Optimization of the derivatization conditions showed doubly-derivatized products in some hormone analytes, including progesterone, corticosterone, and cortisol, and gave improved ionization efficiency up to 20-fold higher signal than the singly-derivatized product. The use of SPE for sample cleanup to analyze hormones from cellular media using weak anion exchange sorbent yielded 80-100% recovery for the 17 targeted hormones. The method was validated by exposing H295R cells to two known endocrine disruptors, forskolin and prochloraz, which showed expected changes in hormones. An initial exposure of H295R cells with various PFAS standards and their mixtures at 1 μM showed significant increases in progestogens with some PFAS treatments, which include PFBS, PFHxA, PFOS, PFDA, and PFDS. In addition, modest changes in hormone levels were observed in cells treated with other sulfonated or carboxylated headgroup PFASs. This sensitive LC-MS/MS method for hormone analysis in H295R cells will allow for the investigations of the alterations in the hormone production caused by exposure to various environmental insults in cell-based assays and other

The fate, effects, and treatment of per- and polyfluoroalkyl substances (PFAS), an anthropogenic class of chemicals used in industrial and commercial production, are topics of great interest in recent research and news cycles. This interest stems from the ubiquity of PFAS in the global environment as well as their significant toxicological effects in humans and wildlife. Research on toxicity, sequestration, removal, and degradation of PFAS has grown rapidly, leading to a flood of valuable knowledge that can get swamped out in the perpetual rise in the number of publications. Selected papers from the Journal of Hazardous Materials between January 2018 and May 2022 on the toxicity, sequestration, and degradation of PFAS are reviewed in this article and made available as open-access publications for one year, in order to facilitate the distribution of critical knowledge surrounding PFAS. This review discusses routes of toxicity as observed in mammalian and cellular models, and the observed human health effects in exposed communities. Studies that evaluate of toxicity through in-silico approaches are highlighted in this paper. Removal of PFAS through modified carbon sorbents, nanoparticles, and anion exchange materials are discussed while comparing treatment efficiencies for different classes of PFAS. Finally, various biotic and abiotic degradation techniques, and the pathways and mechanisms involved are reviewed to provide a better understanding on the removal efficiencies and cost effectiveness of existing treatment strategies.

Land application of treated sewage sludge (also known as biosolids) is considered a sustainable route of disposal because it reduces waste loading into landfills while improving soil health. However, this waste management practice can introduce contaminants from biosolids, such as per- and polyfluoroalkyl substances (PFAS), into the environment. PFAS have been observed to be taken up by plants, accumulate in humans and animals, and have been linked to various negative health effects. There is limited information on the nature and amounts of PFAS introduced from biosolids that have undergone different treatment processes. Therefore, this study developed analytical techniques to improve the characterization of PFAS in complex biosolid samples. Different clean-up techniques were evaluated and applied to waste-activated sludge (WAS) and lime-stabilized primary solids (PS) prior to targeted analysis and suspect screening of biosolid samples. Using liquid chromatography with high-resolution mass spectrometry, a workflow was developed to achieve parallel quantitative targeted analysis and qualitative suspect screening. This study found that concentrations of individual PFAS (27 targeted analytes) can range from 0.6 to 84.6 ng/g in WAS (average total PFAS = 241.4 ng/g) and from 1.6 to 33.8 ng/g in PS (average total PFAS = 72.1 ng/g). The suspect screening workflow identified seven additional PFAS in the biosolid samples, five of which have not been previously reported in environmental samples. Some of the newly identified compounds are a short-chain polyfluorinated carboxylate (a PFOS replacement), a diphosphate ester (a PFOA precursor), a possible transformation product of carboxylate PFAS, and an imidohydrazide which contains a sulfonate and benzene ring.

Effluents from ten full-scale municipal wastewater treatment plants (WWTPs) that discharge into the Hudson River, surface waters, and wild-caught fish samples were analyzed using liquid chromatography with tandem mass spectrometry (LC/MS/MS) to examine the influence of wastewater discharge on the concentrations of contaminants of emerging concern (CECs) and their ecological impacts on fish. Analysis was based on targeted detection of 41 pharmaceuticals, and non-targeted analysis (suspect screening) of CECs. Biological effects of treated WWTP effluents were assessed using a larval zebrafish (Danio rerio) swimming behavior assay. Concentrations of residues in surface waters were determined in grab samples and polar organic chemical integrative samplers (POCIS). In addition, vitellogenin peptides, used as biomarkers of endocrine disruption, were quantified using LC/MS/MS in the wild-caught fish plasma samples. Overall, 94 chemical residues were identified, including 63 pharmaceuticals, 10 industrial chemicals, and 21 pesticides. Eight targeted pharmaceuticals were detected in 100% of effluent samples with median detections of: bupropion (194 ng/L), carbamazepine (91 ng/L), ciprofloxacin (190 ng/L), citalopram (172 ng/L), desvenlafaxine (667 ng/L), iopamidol (3790 ng/L), primidone (86 ng/L), and venlafaxine (231 ng/L). Over 30 chemical residues were detected in wild-caught fish tissues. Notably, zebrafish larvae exposed to chemical extracts of effluents from 9 of 10 WWTPs, in at least one season, were significantly hyperactive. Vitellogenin expression in male or immature fish occurred 2.8 times more frequently in fish collected from the Hudson River as compared to a reference site receiving no direct effluent input. Due to the low concentrations of pharmaceuticals detected in effluents, it is likely that chemicals other than pharmaceuticals measured are responsible for the behavioral changes observed. The combined use of POCIS and non-target analysis demonstrated significant increase in the chemical coverage for CEC detection, providing a better insight on the impacts of WWTP effluents and agricultural practices on surface water quality.

Per- and polyfluoroalkyl substances (PFASs) are exceptionally stable chemicals due to their strong C F bonds. Nanoscale zero-valent iron (nZVI) particles have the potential to remove and degrade PFASs through redox activity. In this study, we deposited nZVI onto two-dimensional reduced graphene oxide (rGO) nanosheets and tested these synthesized rGO-nZVI nanohybrid (NH) for the treatment of a mixture of short- and long-chain PFASs in water with and without H2O2. All PFASs were removed at a higher efficiency by the rGO-nZVI NH than by the parent materials rGO and nZVI. Notably, the long-chain PFASs were removed at a faster rate than the short-chain PFASs. After a 10 min exposure to the rGO-nZVI NH without H2O2, the long-chain PFASs (perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA)) were removed by 85 % and 39 %, respectively, while short-chain PFASs (perfluoropentane sulfonic acid and perfluoropentanoic acid) were removed by 19 % and 18 %, respectively. The addition of H2O2 enhanced the PFAS treatment performance by 10–18 %, which can be attributed to the generation of reactive oxygen species by the rGO-nZVI NH. Liquid chromatography high-resolution mass spectrometry analysis confirmed the formation of unique shorter chain and partially defluorinated PFAS-Fe complexes from both PFOS and PFOA.

United States dairy operations use antibiotics (primarily β-lactams and tetracyclines) to manage bacterial diseases in dairy cattle. Antibiotic residues, antibiotic-resistant bacteria (ARB), and antibiotic resistance genes (ARG) can be found in dairy manure and may contribute to the spread of antibiotic resistance (AR). Although β-lactam residues are rarely detected in dairy manure, tetracycline residues are common and perhaps persistent. Generally,15% of bacterial pathogen dairy manure isolates are ARB, although resistance to some antibiotics (e.g., tetracycline) can be higher. Based on available data, the prevalence of medically important ARB on dairy operations is generally static or may be declining for antibiotic-resistant Staphylococcus spp. Over 60 ARG can be found in dairy manure (including β-lactam and tetracycline resistance genes), although correlations with antibiotic usage, residues, and ARB have been inconsistent, possibly because of sampling and analytical limitations. Manure treatment systems have not been specifically designed to mitigate AR, though certain treatments have some capacity to do so. Generally, well-managed aerobic compost treatments reaching higher peak temperatures (60°C) are more effective at mitigating antibiotic residues than static stockpiles, although this depends on the antibiotic residue and their interactions. Similarly, thermophilic anaerobic digesters operating under steady-state conditions may be more effective at mitigating antibiotic residues than mesophilic or irregularly operated digesters or anaerobic lagoons. The number of ARB may decline during composting and digestion or be enriched as the bacterial communities in these systems shift, affecting relative ARG abundance or acquire ARG during treatment. Antibiotic resistance genes often persist through these systems, although optimal management and higher operating temperature may facilitate their mitigation. Less is known about other manure treatments, although separation technologies may be unique in their ability to partition antibiotic residues based on sorption and solubility properties. Needed areas of study include determining natural levels of AR in dairy systems, standardizing and optimizing analytical techniques, and more studies of operating on-farm systems, so that treatment system performance and actual human health risks associated with levels of antibiotic residues, ARB, and ARG found in dairy manure can be accurately assessed.

An anionic iron(II) tetrahedral molecular cage (FeMOP) was studied for its ability to interact with various per- and polyfluoroalkyl substances (PFASs) in aqueous media. Liquid chromatography tandem mass spectrometry revealed that longer-chain-length (more than six carbons) perfluorocarboxylic, -sulfonic, and fluorotelomers were removed from solution. In contrast, the steric bulk of N-ethyl substituted fluorosulfonamido acetic acid PFASs hindered association with the cage. Solution binding studies in D2O using 19F nuclear magnetic resonance (NMR) titrations and a Job plot show a 1:1 binding stoichiometry for perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA) with an association constant (Ka) of

Wastewater treatment plants (WWTPs) have been considered as hotspots for pharmaceutical residues, such as antidepressants, antimicrobials and active ingredients of over-the-counter drugs. Despite evidence of ecotoxicological effects of these microcontaminants on exposed fish in the aquatic systems, there is currently no regulation in terms of the levels of pharmaceutical residues allowable for release into the environment. Depending on the extent of treatment employed in WWTPs removal of pharmaceutical residues are highly variable. This study compares the removal efficiencies for several antimicrobials, antidepressants, and other pharmaceuticals at different stages of the wastewater treatment process of seven WWTPs that employ varying treatment technologies including biological, physical, advanced chemical oxidation, and a combination of two or more of these technologies. The concentrations of the pharmaceuticals were measured by liquid chromatography/mass spectrometry at multiple points during the course of treatment. Additionally, the ecotoxicological effects of the WWTP effluents were also evaluated based on the behavioral effects in larval zebrafish. It was found that biological treatment process provided negative to low removal ( 95% overall removal) for 14 out of 15, and 9 out of 11 compounds detected in WWTP influents, respectively. Notably, the final effluents of the seven WWTPs in this study did not show any significant behavioral alterations in zebrafish, indicating that despite differences in removal efficiencies all the treatment processes investigated are sufficient in preventing short-term biological effects.

Engineered nanomaterials, like graphene with tunable adsorption sites and nanoscale zero-valent iron (nZVI) with unique redox chemistry, offer great prospects for removing pharmaceutical and personal care products (PPCPs) through adsorption and catalytic advanced oxidation processes (AOPs) in comparison to bulk materials. Although PPCPs are found as a complex mixture in wastewater and in the environment, most studies regarding nano-enabled PPCP removal reported results with only one PPCP at a time and typically at high initial concentrations. In this study, we utilized reduced graphene oxide (rGO) as a support for nZVI to synthesize rGO–nZVI nanohybrids (NHs) and used rGO–nZVI NHs for the removal of a complex mixture of 12 diverse PPCPs that includes antibiotic, anti-inflammatory, anti-seizure, and antidepressant pharmaceuticals, which are recalcitrant in the environment. We also tested the removal of PPCPs at their individual environmentally relevant concentrations at the ppb level. The rGO–nZVI NH was synergistically utilized as both an adsorbent and a heterogeneous Fenton catalyst (for AOPs) in the presence of H2O2 to remove ∼95–99% of environmentally relevant concentrations (200 ppb) of PPCPs within 10 minutes. Even in the absence of H2O2, the hybridization resulted in better adsorptive properties (14–72% more removal) of the rGO–nZVI NHs compared to the parent nanomaterials (rGO or nZVI) for various PPCPs in the mixture, removing ∼82–99% of PPCPs, at the end of 30 minutes, with comparatively slower kinetics (∼3–5.5 times) than in the presence of H2O2. Hydrophobic PPCPs were removed faster and more PPCPs were removed by both adsorption and AOPs. The potential of utilizing rGO–nZVI NHs in drinking/wastewater treatment systems, or even in point-of-use systems where necessary, was substantiated by the enhanced and fast PPCP removal capacity of nanohybrids.

Metabolomics, the global profiling of metabolite composition, is a powerful technique that can be applied to answer a diverse set of research questions concerning effects of toxicants on organisms. It has recently emerged as a tool to understand complex environmental perturbations in biological systems, especially at sub-lethal concentrations. Organisms can be affected by different stressors such as xenobiotics or increase in concentration of natural compounds such as nitrogen, phosphorous, and sulfur. Metabolomics has facilitated a better understanding of the effects of these perturbations on organisms such as plants, animals, and humans providing phenotypic and biological information in a high throughput manner. In this review, we will discuss recent applications of metabolomics to study the ecological effects of different environmental perturbations, including nanoparticles, pharmaceuticals and personal care products, pesticides, as well as the changes in natural compounds found in the environment with a focus on plant systems.

Alors que divers organismes internationaux ont récemment proposé des plans pour la création de systèmes de surveillance de la résistance antimicrobienne (RAM), la plupart des PRMF ne disposent pas des infrastructures et des ressources pour le faire efficacement. La RAM est donc un problème majeur d’équité en matière de santé, mais aussi un exemple de la connexion dans notre monde unique: les populations les plus à risque disposent des mécanismes de surveillance et de confinement les plus médiocres; dans le même temps, la migration mondiale, les voyages et le commerce nous rendent tous vulnérables. Les mesures que nous utilisons actuellement ne capturent pas de manière significative l'impact potentiel de la RAM aux niveaux sanitaire, économique et sociétal plus large. La surveillance mondiale de la RAM devrait inclure une surveillance étroite de l'utilisation d'antibiotiques chez les animaux, ainsi que les concentrations de divers produits chimiques libérés dans l'environnement. En fin de compte, les efforts coordonnés de divers scientifiques et parties prenantes, dans diverses disciplines et dans le monde, sont essentiels pour relever les défis pressants de la RAM mondiale croissante.

Wastewater-based epidemiology (WBE) for disease monitoring is highly promising, but requires consistent methodologies that incorporate predetermined objectives, targets, and metrics. We demonstrate a comprehensive metagenomics-based approach for global surveillance of antibiotic resistance in sewage, enabling assessment of: 1) which antibiotic resistance genes (ARGs) are shared across regions/communities; 2) which ARGs are discriminatory; and 3) factors associated with overall trends including antibiotic concentrations in sewage. Across an internationally-sourced transect of sewage samples collected using a centralized, standardized protocol, ARG relative abundances (16S rRNA gene-normalized) were highest in Hong Kong and India and lowest in Sweden and Switzerland, reflecting national policy, measured antibiotic concentrations, and metal resistance genes. Asian versus European/US resistomes were distinct, with macrolide-lincosamide-streptogramin, phenicol, quinolone, and tetracycline versus multidrug resistance ARGs being discriminatory, respectively. Sales data were not predictive of antibiotics measured in sewage, emphasizing need for direct measurements. The WBE approach defined herein demonstrates multi-site comparability and sensitivity to local/regional factors.

Wastewater treatment plants (WWTPs) receive a confluence of sewage containing antimicrobials, antibiotic resistant bacteria, antibiotic resistance genes (ARGs), and pathogens and thus are a key point of interest for antibiotic resistance surveillance. WWTP monitoring has the potential to inform with respect to the antibiotic resistance status of the community served as well as the potential for ARGs to escape treatment. However, there is lack of agreement regarding suitable sampling frequencies and monitoring targets to facilitate comparison within and among individual WWTPs. The objective of this study was to comprehensively evaluate patterns in metagenomic-derived indicators of antibiotic resistance through various stages of treatment at a conventional WWTP for the purpose of informing local monitoring approaches that are also informative for global comparison. Relative abundance of total ARGs decreased by ∼50% from the influent to the effluent, with each sampling location defined by a unique resistome (i.e., total ARG) composition. However, 90% of the ARGs found in the effluent were also detected in the influent, while the effluent ARG-pathogen taxonomic linkage patterns identified in assembled metagenomes were more similar to patterns in regional clinical surveillance data than the patterns identified in the influent. Analysis of core and discriminatory resistomes and general ARG trends across the eight sampling events (i.e., tendency to be removed, increase, decrease, or be found in the effluent only), along with quantification of ARGs of clinical concern, aided in identifying candidate ARGs for surveillance. Relative resistome risk characterization further provided a comprehensive metric for predicting the relative mobility of ARGs and likelihood of being carried in pathogens and can help to prioritize where to focus future monitoring and mitigation. Most antibiotics that were subject to regional resistance testing were also found in the WWTP, with the total antibiotic load decreasing by ∼40–50%, but no strong correlations were found between antibiotics and corresponding ARGs. Overall, this study provides insight into how metagenomic data can be collected and analyzed for surveillance of antibiotic resistance at WWTPs, suggesting that effluent is a beneficial monitoring point with relevance both to the local clinical condition and for assessing efficacy of wastewater treatment in reducing risk of disseminating antibiotic resistance. Published version

This study quantified the potential of farm-scale composting to degrade antibiotics in dairy manure. The compost windrow, consisting of sick cow bedding from a 1000-cow US dairy farm, was managed using the dairy farm’s typical practices and monitored for tetracycline and nutrient composition. Samples were collected over 33 days, which was the time from compost pile formation to land application as fertilizer, and analyzed for solids, antibiotics, and nutrient content. Average tetracycline concentrations at the beginning of the study (452 ng/g DW) were lower than at the end of composting (689 ng/g DW), illustrating that antibiotic degradation was not greater than degradation of the compost solids. Total Kjeldahl nitrogen (TKN) increased from 15.3 to 18.4 g/kg during the composting period due to decreases in solids and likely inhibition of N-mineralization due to the presence of antibiotics. The results indicated that antibiotics were not completely degraded when using the farm’s compost pile management techniques, with antibiotics possibly impacting nitrogen transformation in the compost, which should be considered in nutrient management when using sick cow bedding. Additionally, the results showed that antibiotic degradation during farm-scale composting can vary from reported laboratory-scale due to differences in management, composting duration, and temporal conditions, illustrating the need for more extensive on-farm research including common farm practices and real-world conditions.

RATIONALE Silicone wristbands have emerged as valuable passive samplers for monitoring of personal exposure to environmental contaminants in the rapidly developing field of exposomics. Once deployed, silicone wristbands collect and hold a wealth of chemical information that can be interrogated using high-resolution mass spectrometry (HRMS) to provide a broad coverage of chemical mixtures. METHODS Gas chromatography coupled to Orbitrap™ mass spectrometry (GC/Orbitrap™ MS) was used to simultaneously perform suspect screening (using in-house database) and unknown screening (using vendor databases) of extracts from wristbands worn by volunteers. The goal of this study was to optimize a workflow that allows detection of low levels of priority pollutants, with high reliability. In this regard, a data processing workflow for GC/Orbitrap™ MS was developed using a mixture of 123 environmentally relevant standards consisting of pesticides, flame retardants, organophosphate esters, and polycyclic aromatic hydrocarbons as test compounds. RESULTS The optimized unknown screening workflow using a search index threshold of 750 resulted in positive identification of 70 analytes in validation samples, and a reduction in the number of false positives by over 50%. An average of 26 compounds with high confidence identification, 7 level 1 compounds and 19 level 2 compounds, were observed in worn wristbands. The data were further analyzed via suspect screening and retrospective suspect screening to identify an additional 36 compounds. CONCLUSIONS This study provides three important findings: (1) a clear evidence of the importance of sample cleanup in addressing complex sample matrices for unknown analysis, (2) a valuable workflow for the identification of unknown contaminants in silicone wristband samplers using electron ionization HRMS data, and (3) a novel application of GC/Orbitrap™ MS for the unknown analysis of organic contaminants that can be used in exposomics studies.

The role of heterotrophic and nitrifying microorganisms in the (co-)metabolic biotransformation of 10 pharmaceutically active compounds (PhACs) was investigated. To this aim, biotransformation assays were performed with heterotrophic and nitrifying sludge developed separately in a two-stage full-scale activated sludge system. Each stage was operated at different inflow wastewater characteristics and sludge retention times (on average 8 d and 35 d). The biotransformation capacity of each sludge was evaluated in the absence of primary substrate and in the presence of acetate and ammonium, to independently elucidate the co-metabolic role of heterotrophs and nitrifiers present in both sludges. Trimethoprim, diclofenac and carbamazepine were recalcitrant (removal < 5% after 1 d; biotransformation rate < 50 µg/g VSS·d) under all the tested conditions. High concentrations of caffeine, acetaminophen and iopromide were quickly biotransformed (> 80% after 1 d; > 800 µg/g VSS·d) in the absence of primary substrates. The heterotrophic sludge only showed a co-metabolic effect towards erythromycin, which increased its biotransformation rate between 43% and 53% when acetate and ammonium were supplied. In contrast, when stimulated, nitrifiers and slow-growing heterotrophs present in the nitrifying sludge co-metabolically biotransformed acetaminophen, ibuprofen and naproxen to a significant extent. Sulfamethoxazole was recalcitrant, except when the nitrifying sludge was fed with acetate (> 800 µg/g VSS·d), suggesting that slow-growing heterotrophs co-metabolically biotransformed it. This study provides evidence that biotransformation of PhACs depends on several metabolic activities, as the heterotrophic activity of the nitrifying sludge, which are not only determined by the SRT but also by the feeding composition This research was supported by the UB RENEW (Research and Education in eNergy, Environment and Water) grant, the Spanish Ministry of Economy and Competitiveness COMETT Project (CTQ2016-80847-R). Authors from Universidade de Santiago de Compostela belong to CRETUS Strategic Partnership (ED431E 2018/01) and to the Galicia Competitive Research Group (GRC ED431C 2017/29), programs co-funded by the Fondo Europeo de Desarrollo Regional (FEDER) and Xunta de Galicia 2023-01-22 SI

The vast number of chemicals potentially reaching aquatic environment pose a challenge in maintaining the quality of water resources. However, best management practices to improve water quality are typically focused on reducing nutrient transport without assessing how these practices may impact the occurrence of micropollutants. The potential for co-management of nutrients and organic micropollutants exists, but few studies have comprehensively evaluated the suite of contaminants associated with different water quality management practices (riparian zone restoration, stormwater management, etc.). Furthermore, most studies dealing with the determination of micropollutants in environmental samples include only a limited number of target analytes, leaving many contaminants undetected. To address this limitation, there has been a gradual shift in environmental monitoring from using target analysis to either suspect screening analysis (SSA) or non-targeted analysis (NTA), which relies on accurate mass measurements, mass spectral fragmentation patterns, and retention time information obtained using liquid chromatography coupled to high-resolution mass spectrometry. The work presented in this paper focuses on a wide-scope detection of micropollutants in surface water samples from the Potomac River watershed (United States). An in-house database composed of 1039 compounds based on experimental analysis of primary standards was established, and SSA workflow was optimized and applied to determine the presence of micropollutants in surface water. A total of 103 micropollutants were detected in the samples, some of which are contaminants that were not previously monitored and belong to various classes such as pharmaceuticals, personal care products, per-and polyfluoroalkyl substances and other persistent industrial chemicals. The impact of best management practices being implemented for nitrogen and phosphorus reductions were also assessed for their potential to reduce micropollutant transport. This work illustrates the advantages of suspect screening methods to determine a large number of micropollutants in environmental samples and reveals the potential to co-manage a diverse array of micropollutants based on shared transport and transformation mechanisms in watersheds., Highlights • In-house suspect screening database that include 1039 micropollutants was developed • Suspect screening analysis (SSA) workflow was optimized to increase chemical coverage • SSA detected 103 micropollutants in the samples collected from Potomac watershed • BMPs result in co-management of nutrients and micropollutants transport