From a validated targeted method to a retrospective UHPLC-HRMS non-targeted analysis unveiling COVID-19-related contaminants in clams. Have we bias in marine model organisms for ecotoxicological studies?

This study explores a retrospective non-targeted analysis (NTA), based on Ultra High-Performance Liquid Chromatography coupled to High-Resolution Mass Spectrometry (UHPLC-HRMS), to assess hidden chemicals of emerging concern (CECs) in marine model organisms. Conventional ecotoxicological studies do not include evaluating the natural habitats of the collected organisms, missing the possibility of highlighting unexpected pollutants, and thus compromising the correctness and reliability of the experimental results. In this paper we reprocessed samples previously collected from the Venice Lagoon for ecotoxicological studies and used for targeted analysis of three bisphenols-related compounds (i.e. BPS, BPF and BPAF) on seawater and specimens of the clam Ruditapes philippinarum. Results from the validation were the following: accuracy, expressed as percentage recoveries (R%), in the range 80%

Integrated environmental assessment of a diversion-project-type urban water source considering the risks of novel and legacy contaminants.

The water diversion project is an effective engineering approach to overcome water scarcity as a water source for the area. However, the complex environmental conditions of long-distance water diversion bring many uncertainties for water security. In this study, we assessed the pollution condition and risk levels of emerging contaminants and traditional contaminants in the water and soil along a water diversion project in Tianjin. Then, we assessed the influence of eco-economic characteristics on environmental conditions and established a comprehensive assessment framework of water source sustainability by analytic hierarchy process (AHP). The results showed that excessive nutrient elements and heavy metal pollution mainly contributed to environmental problems in the water source area. Contrary to pollution assessment, the soil ecosystem was more subject to environmental pressure due to atmospheric deposition. The health risk assessment indicated that all contaminants had negligible non-carcinogenic risks for adults, with arsenic being considered a priority pollutant. The statistical analysis results indicated land use allocation was the most important factor in the environmental management of the water source area. According to the result of the integrated environmental assessment, the main characteristics of pressure zones were high pollution levels and human activity intensity. It is urgent to control agricultural pollution and allocate land use rationally for water source pressure zones. By considering the risks of traditional and emerging contaminants in water and soil, this study could support urban water source management and the sustainable development of the water diversion project.

Comparing the performance of microbial electrochemical assisted and aerated treatment wetlands in pilot-scale: Removal of major pollutants and organic micropollutants.

The combination of treatment wetlands (TWs) with microbial electrochemical technologies (MET) is often studied in the lab to improve the performance and decrease the footprint of TWs. In this article we evaluated the long-term performance of four pilot-scale vertical sub-surface flow TWs for major pollutants' and organic micropollutants' removal from domestic wastewater. Three of them were filled with electroconductive material and operated under saturated (MET SAT), unsaturated (MET UNSAT) and unsaturated-saturated (MET HYBRID) conditions while the fourth one was a saturated intensified aerated system (AEW) filled with gravel. The MET-TWs achieved significant removals of COD (>78 %) with no clogging issues at the maximum applied OLR (249 g COD m-3 d-1) while under these loading conditions TSS removal exceeded 84 %. Among all electroactive TWs, UNSAT could remove 25 g NH4-N m-3 d-1 through nitrification when peak ammonium loading rate was applied; however this removal was significantly lower than AEW (35 g NH4-N m-3d-1). No important removal of P was observed in all systems with the exception of MET-SAT were precipitation reactions of P with iron occurred when anaerobic pretreated wastewater was used. The removal of the sum of studied organic micropollutants ranged between 70 ± 18 % (MET UNSAT) to 91 ± 4 % (AEW) and improved with feeding pulses increase. Moderate to high removal of specific microcontaminants was observed depending on the target compound, the studied system and the operational conditions. AEW and MET HYBRID systems complied with the limits set by EU for wastewater discharge to non-sensitive water bodies and for Class B water reuse. Scale-up calculations for a settlement of 500 PE showed that these systems require much less area per PE (0.51 m2 PE-1) comparing to conventional TWs while the operational cost was calculated to 0.07 € m-3 for the AEW and 0.02 € m-3 for the MET HYBRID.

A review on hazards and treatment methods of released antibiotics in hospitals wastewater during the COVID-19 pandemic.

Drugs and related goods are widely used in order to promote public health and the quality of life. One of the most serious environmental challenges affecting public health is the ongoing presence of antibiotics in the effluents generated by pharmaceutical industries and hospitals. Antibiotics cannot be entirely removed from wastewater using the traditional wastewater treatment methods. Unmetabolized antibiotics generated by humans can be found in urban and livestock effluent. The antibiotic present in effluent contributes to issues with resistance to antibiotics and the creation of superbugs. Over the recent 2 years, the coronavirus disease 2019 pandemic has substantially boosted hospital waste volume. In this situation, a detailed literature review was conducted to highlight the harmful effects of untreated hospital waste and outline the best approaches to manage it. Approximately 50 to 70% of the emerging contaminants prevalent in the hospital wastewater can be removed using traditional treatment strategies. This paper emphasizes the numerous treatment approaches for effectively eliminating emerging contaminants and antibiotics from hospital wastewater and provides an overview of global hospital wastewater legislation and guidelines on hospital wastewater administration. Around 90% of ECs might be eliminated by biological or physical treatment techniques when used in conjunction with modern oxidation techniques. According to this research, hybrid methods are the best approach for removing antibiotics and ECs from hospital wastewater. The document outlines the many features of effective hospital waste management and might be helpful during and after the coronavirus disease 2019 outbreak, when waste creation on all hospitals throughout the globe has considerably increased.

A data-driven approach to identifying PFAS water sampling priorities in Colorado, United States.

BACKGROUND: Per and polyfluoroalkyl substances (PFAS), a class of environmentally and biologically persistent chemicals, have been used across many industries since the middle of the 20th century. Some PFAS have been linked to adverse health effects. OBJECTIVE: Our objective was to incorporate known and potential PFAS sources, physical characteristics of the environment, and existing PFAS water sampling results into a PFAS risk prediction map that may be used to develop a PFAS water sampling prioritization plan for the Colorado Department of Public Health and Environment (CDPHE). METHODS: We used random forest classification to develop a predictive surface of potential groundwater contamination from two PFAS, perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA). The model predicted PFAS risk at locations without sampling data into one of three risk categories after being "trained" with existing PFAS water sampling data. We used prediction results, variable importance ranking, and population characteristics to develop recommendations for sampling prioritization. RESULTS: Sensitivity and precision ranged from 58% to 90% in the final models, depending on the risk category. The model and prioritization approach identified private wells in specific census blocks, as well as schools, mobile home parks, and public water systems that rely on groundwater as priority sampling locations. We also identified data gaps including areas of the state with limited sampling and potential source types that need further investigation. IMPACT STATEMENT: This work uses random forest classification to predict the risk of groundwater contamination from two per- and polyfluoroalkyl substances (PFAS) across the state of Colorado, United States. We developed the prediction model using data on known and potential PFAS sources and physical characteristics of the environment, and "trained" the model using existing PFAS water sampling results. This data-driven approach identifies opportunities for PFAS water sampling prioritization as well as information gaps that, if filled, could improve model predictions. This work provides decision-makers information to effectively use limited resources towards protection of populations most susceptible to the impacts of PFAS exposure.

3-Methyl Thiophene-Modified Boron-Doped Diamond (BDD) Electrodes as Efficient Catalysts for Phenol Detection-A Case Study for the Detection of Gallic Acid in Three Specific Tea Types.

Polymer modification has been established as a cost-effective, simple, in situ method for overcoming some of the inherent disadvantages of boron-doped diamond (BDD) electrodes, and its application has been extended to reliable, low-cost environmental monitoring solutions. The present review focuses on modifying BDD electrodes with semi-conductive polymers acting as redox mediators. This article reports on the development of a 3-methyl thiophene-modified boron-doped diamond (BDD/P3MT) sensor for the electrochemical determination of total phenolic compounds (TPCs) in tea samples, using gallic acid (GA) as a marker. GA is a significant polyphenol with various biological activities, making its quantification crucial. Thus, a simple, fast, and sensitive GA sensor was fabricated using the electroanalytical square wave voltammetry (SWV) technique. The sensor utilizes a semi-conductive polymer, 3-methyl thiophene, as a redox mediator to enhance BDD's sensitivity and selectivity. Electrochemical synthesis was used for polymer deposition, allowing for greater purity and avoiding solubility problems. The BDD/P3MT sensor exhibits good electrochemical properties, including rapid charge transfer and a large electrochemical area, enabling GA detection with a limit of detection of 11 mg/L. The sensor's response was correlated with TPCs measured by the Folin-Ciocalteu method. Square wave voltammetry (SWV) showed a good linear relationship between peak currents and GA concentrations in a wide linear range of 3-71 mg/L under optimal conditions. The BDD/P3MT sensor accurately measured TPCs in green tea, rooibos tea, and black tea samples, with green tea exhibiting the highest TPC levels. The results demonstrate the potential of the modified BDD electrode for the rapid and accurate detection of phenolic compounds in tea, with implications for quality control and antioxidant activity assessments. The prolific publications of the past decade have established BDD electrodes as robust BDD sensors for quantifying polyphenols. Fruits, vegetables, nuts, plant-derived beverages such as tea and wine, traditional Eastern remedies and various herbal nutritional supplements contain phenolic chemicals. The safety concerns of contaminated food intake are significant health concerns worldwide, as there exists a critical nexus between food safety, nutrition, and food security. It has been well established that green tea polyphenol consumption promotes positive health effects. Despite their potential benefits, consuming high amounts of these polyphenols has sparked debate due to concerns over potential negative consequences.

The Mass Spectrometric Ortho Effect for Distinguishing the Coeluting Isomers of Polychlorinated Biphenyls and the Coeluting Isomers of Polybrominated Biphenyls: Qualitative and Quantitative Aspects.

Polychlorinated biphenyls (PCBs) and polybrominated biphenyls (PBBs) are persistent organic pollutants still widespread in the environment and in the food chain. Both groups of these synthetic xenobiotics consist of 209 possible congeners depending on the number and position of halogens. PCBs with the same number of chlorine atoms and PBBs with the same number of bromine atoms are isomers: ten different degrees of halogenation are allowed, which results in a lot of existing isomers for both groups. The isomers have perfect correspondence in the number and type of atoms with differences only in positioning, so their mass spectra are expected to be identical with a consequent significant analytical problem in the event of coelution of the chromatographic peaks. This is not always the case, since the mass spectrometric ortho effect is capable of effectively discriminating many coeluting PCB or PBB isomers, although not all possible ones. The present paper investigates, for the first time, the reliability of qualitative and quantitative analysis by using the ortho effect: this was conducted through targeted experimental measurements on real samples of food by using different detectors. In this context, it is shown how to recognize the presence of a PCB that does not have the ortho effect when coeluting with an isomer that has. This is an important aspect that has never been studied until now. The ortho effect is extremely simple to operate once the ordinary GC-MS runs have been performed: the analyst only needs to recheck the mass spectrum for measuring the intensity of the first dehalogenation ion. The topic is of practical relevance since two different isomers can have different health hazards, and the presence of a very toxic isomer could be masked by a less toxic one. The same mass spectrometric ortho effect also deals with PXBs (i.e., mixed poly-brominated/chlorinated biphenyls), which are emerging contaminants.

One-pot fabrication of task specific magnetic adsorbent for the efficient isolation and capture of liquid-crystal monomers pollutants in waters prior to chromatographic quantification.

BACKGROUND: Liquid crystal monomers (LCMs) have been classified as emerging organic pollutants. Efficient isolation and extraction is a critical step in the determination, and then knowing the occurrence and distribution of LCMs in environmental waters. However, the reported sample preparation techniques still suffer some dilemmas such as using large amount of organic solvent, low extraction capacity, tedious operation procedure and employment of expensive extraction column. To circumvent the disadvantages, new extraction format and adsorbent with quickness, less consumption of organic solvent, superior extraction performance and low cost should be developed for the analysis of LCMs. RESULTS: Using 1H,1H,2H,2H-heptadecafluorodecyl acrylate and 9-vinylanthracene as mixed functional monomers, a task specific magnetic adsorbent (TSMA) was prepared by one-pot hydrothermal technique for the highly efficient capture of LCMs under magnetic solid phase extraction (MSPE) format. Due to the abundant functional groups, the developed TSMA/MSPE presented satisfactory capture performance towards LCMs. Satisfactory enrichment factors (132-212) and high adsorption capacity (18 mg/g) were obtained. Additionally, the relevant adsorption mechanism was studied by the combination of density functional theory calculation and experiments about adsorption kinetics and adsorption isotherm. Under the beneficial conditions, a sensitive and reliable method for the monitoring of studied LCMs in environmental waters was established by the combination of TSMA/MSPE with HPLC equipped with diode array detector (DAD). The achieved limits of detection and spiked recoveries were 0.0025-0.0061 µg/L and 81.0-112 %, respectively. Finally, the developed method was employed to monitor LCMs levels in the North Creek watershed of Jiulong River. SIGNIFICANCE AND NOVELTY: The current study provided a new adsorbent for quick and efficient capture of LCMs at trace levels. In addition, a sensitive, reliable and anti-intereference method for the monitoring of trace LCMs in actual waters was established. Moreover, for the first, the contents, occurrence and distribution of LCMs in North Creek watershed was investigated based on the developed method.

Occurrence of pharmaceutical residues in drinking water: a systematic review.

The aim of the present paper was to give a complete picture on the drinking water contamination by pharmaceutical residues all over the world. For this purpose, a systematic review was carried out for identifying all available research reporting original data resulting by sampling campaign and analysis of "real" drinking water samples to detect pharmaceutical residues. The investigated databases were PubMed, Scopus, and Web of Science. A total of 124 studies were included; among these, 33 did not find target analytes (all below the limit of detection), while the remaining 91 studies reported the presence for one or more compounds, in concentrations ranging from a few units to a few tens of nanograms. The majority of the studies were performed in Europe and the most represented categories were nonsteroidal anti-inflammatory drugs and analgesics. The most common analytical approach used is the preparation and analysis of the samples by solid-phase extraction and chromatography coupled to mass spectrometry. The main implications resulting from our review are the need for (a) further studies aimed to allow more accurate environmental, wildlife, and human health risk assessments and (b) developing integrated policies promoting less environmentally persistent drugs, the reduction of pharmaceuticals in livestock breeding, and the update of wastewater and drinking water treatment plants for a better removal of drugs and their metabolites.

Intercorrelations of Chlorinated Paraffins, Dechloranes, and Legacy Persistent Organic Pollutants in 10 Species of Marine Mammals from Norway, in Light of Dietary Niche.

Short-, medium-, and long-chain chlorinated paraffins (CPs) (SCCPs, MCCPs, and LCCPs) and dechloranes are chemicals of emerging concern; however, little is known of their bioaccumulative potential compared to legacy contaminants in marine mammals. Here, we analyzed SCCPs, MCCPs, LCCPs, 7 dechloranes, 4 emerging brominated flame retardants, and 64 legacy contaminants, including polychlorinated biphenyls (PCBs), in the blubber of 46 individual marine mammals, representing 10 species, from Norway. Dietary niche was modeled based on stable isotopes of nitrogen and carbon in the skin/muscle to assess the contaminant accumulation in relation to diet. SCCPs and dechlorane-602 were strongly positively correlated with legacy contaminants and highest in killer (Orcinus orca) and sperm (Physeter macrocephalus) whales (median SCCPs: 160 ng/g lw; 230 ng/g lw and median dechlorane-602: 3.8 ng/g lw; 2.0 ng/g lw, respectively). In contrast, MCCPs and LCCPs were only weakly correlated to recalcitrant legacy contaminants and were highest in common minke whales (Balaenoptera acutorostrata; median MCCPs: 480 ng/g lw and LCCPs: 240 ng/g lw). The total contaminant load in all species was dominated by PCBs and legacy chlorinated pesticides (63-98%), and MCCPs dominated the total CP load (42-68%, except 11% in the long-finned pilot whale Globicephala melas). Surprisingly, we found no relation between contaminant concentrations and dietary niche, suggesting that other large species differences may be masking effects of diet such as lifespan or biotransformation and elimination capacities. CP and dechlorane concentrations were higher than in other marine mammals from the (sub)Arctic, and they were present in a killer whale neonate, indicating bioaccumulative properties and a potential for maternal transfer in these predominantly unregulated chemicals.

On-site evaluation of DGT passive sampling for quantitatively measuring per- and polyfluoroalkyl substances in a river-estuary-sea water system.

The passive sampling technique of diffusive gradients in thin-films (DGT) is promising for monitoring emerging contaminants such as per- and polyfluoroalkyl substances (PFAS). It is urgent to evaluate the impacts of salinity and exposure time on DGT sampling before it can be set as a standard method. Herein, DGT sampler based on the binding gel of weak anion exchanger (WAX) resin was deployed in a representative water system of the Xiaoqing river-estuary-sea for representative sampling windows (<1 day to 28 days) with high pH (8.18 ± 0.04 to 8.51 ± 0.17) and wide ranges of salinity (0.95 ± 0.07‰ to 14.37 ± 3.92‰), total dissolved solids (1.20 ± 0.09 g/L to 15.29 ± 3.91 g/L) and dissolved organic matter (2.8-32 mg/L). The results showed that the WAX-DGT sampler exhibited good performance for most target PFAS except for short-chain perfluorocarboxylates (C ≤ 5) in 14 days. When the exposure time was over 14 days, biofouling of the sampler may deflect the mass accumulation of the PFAS in the sampler. Salinity played an important role in the mass binding of PFAS by DGT. The shorter the carbon chain of the compound, the greater the influence of the salinity. PFAS with carboxyl groups had greater affinities for the biofouled membrane filter than those with sulfonic groups. In the river-estuary-sea system, where PFAS concentrations changed dynamically, the temporal resolution of the monitoring strategy has been demonstrated to be more important than spatial resolution. DGT provided a better integral of PFAS exposure than grab sampling in the dynamic water system and offered equivalent sensitivity of grab sampling with exposure time <10 d and greater sensitivity with exposure time ≥10 d. Thus, DGT has the advantage of providing high temporal resolution monitoring. This study provided support for the standardization of the DGT technique.

CrAss-like phages are suitable indicators of antibiotic resistance genes found in abundance in fecally polluted samples.

Antibiotic resistance genes (ARGs) have been extensively observed in bacterial DNA, and more recently, in phage particles from various water sources and food items. The pivotal role played by ARG transmission in the proliferation of antibiotic resistance and emergence of new resistant strains calls for a thorough understanding of the underlying mechanisms. The aim of this study was to assess the suitability of the prototypical p-crAssphage, a proposed indicator of human fecal contamination, and the recently isolated crAssBcn phages, both belonging to the Crassvirales group, as potential indicators of ARGs. These crAss-like phages were evaluated alongside specific ARGs (blaTEM, blaCTX-M-1, blaCTX-M-9, blaVIM, blaOXA-48, qnrA, qnrS, tetW and sul1) within the total DNA and phage DNA fractions in water and food samples containing different levels of fecal pollution. In samples with high fecal load (>103 CFU/g or ml of E. coli or somatic coliphages), such as wastewater and sludge, positive correlations were found between both types of crAss-like phages and ARGs in both DNA fractions. The strongest correlation was observed between sul1 and crAssBcn phages (rho = 0.90) in sludge samples, followed by blaCTX-M-9 and p-crAssphage (rho = 0.86) in sewage samples, both in the phage DNA fraction. The use of crAssphage and crAssBcn as indicators of ARGs, considered to be emerging environmental contaminants of anthropogenic origin, is supported by their close association with the human gut. Monitoring ARGs can help to mitigate their dissemination and prevent the emergence of new resistant bacterial strains, thus safeguarding public health.

Homogeneous to heterogeneous redox mediator enhancing ferrate(VI) oxidation of sulfamethoxazole: Role of ferrate(VI) activation and electron shuttle.

Ferrate (Fe(VI)) is a promising oxidant for water remediation, yet it has limited reactivity towards certain recalcitrant but important emerging contaminants, such as sulfamethoxazole. Here, this study demonstrates that nitroxide redox mediators, specifically 9-azabicyclo[3.3.1]nonasne N-oxyl (ABNO), can catalyze Fe(VI) reaction with sulfamethoxazole by functioning both as Fe(VI) activator and electron shuttle. The underlying mechanism is explained as: (i) Fe(VI) activation: a series of one-electron transfers between Fe(VI) and ABNO produces highly reactive Fe(V)/Fe(IV) and ABNO+; (ii) electron shuttle: the newly formed active ABNO+ reacts with the sulfamethoxazole, contributing to its removal. Concurrently, ABNOH is generated and subsequently converted back to ABNO by reactive species, thereby completing the redox cycle. The as-developed heterogeneous redox mediator, ABNO@SiO2, retained its catalytic properties and effectively catalyzed Fe(VI) to remove sulfamethoxazole at environmentally relevant pH levels.

Occurrence and potential ecological risks of PFAS in Pampulha Lake, Brazil, a UNESCO world heritage site.

Per- and polyfluoroalkyl substances (PFAS) comprise >4000 synthetic substances used in industrial applications and consumer products. PFAS used daily in households and manufacturing plants end up in domestic sewage, and industrial effluents can be discharged to surface water. Urban watersheds located in low and middle-income countries (LMIC), which lack sanitation infrastructure, are potential recipients of waste containing PFAS. Yet, only a few studies report PFAS occurrence in urban reservoirs and lakes, especially those located in the Global South due to resource limitations. This is the first study aimed to assess PFAS occurrence and ecological risks in Pampulha Lake, Brazil, a site which represents the reality of many other urban watersheds in LMIC as it is surrounded by densely populated areas and manufacturing plants. Surface water samples were collected monthly for 1 year from four sampling points at Pampulha Lake. Sample analysis was based on US Environmental Protection Agency Method 1633, which employs solid phase extraction followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Species sensitivity distribution (SSD) curves were built to identify potentially susceptible species based on detected water concentrations. Bioaccumulation was estimated for fish tissue. Short-chain (perfluorobutanesulfonic acid, PFBS and perfluorohexanoic acid, PFHxA) and long-chain PFAS (perfluorodecanoic acid, PFDA; perfluorooctanoic acid, PFOA; perfluorododecanoic acid, PFDoA; and perfluorooctanesulfonic acid, PFOS) were detected at the µg L-1 range. Total PFAS concentrations in the wet season were generally higher than in the dry season, likely due to limited capacity of the treatment plant processing water from tributaries which receive raw sewage. More than 5 % of aquatic species are potentially susceptible to chronic effects of PFOS at detected concentrations (0.2-2.2 µg L-1). Predicted bioaccumulation of PFOS in fish was above advisory diet intake levels for humans. Results emphasize the need for studies related to PFAS occurrence in watersheds located in LMIC.

Derivation of water quality criteria for paraquat, bisphenol A and carbamazepine using quantitative structure-activity relationship and species sensitivity distribution (QSAR-SSD).

The risk assessment of an expanding array of emerging contaminants in aquatic ecosystems and the establishment of water quality criteria rely on species sensitivity distribution (SSD), necessitating ample multi-trophic toxicity data. Computational methods, such as quantitative structure-activity relationship (QSAR), enable the prediction of specific toxicity data, thus mitigating the need for costly experimental testing and exposure risk assessment. In this study, robust QSAR models for four aquatic species (Rana pipiens, Crassostrea virginica, Asellus aquaticus, and Lepomis macrochirus) were developed using leave-one-out (LOO) screening variables and the partial least squares algorithm to predict toxicity data for paraquat, bisphenol A, and carbamazepine. These predicted data can be integrated with experimental data to construct SSD models and derive hazardous concentration for 5 % of species (HC5) for the criterion maximum concentration. The chronic water quality criterion for paraquat, bisphenol A, and carbamazepine were determined at 6.7, 11.1, and 3.5 µg/L, respectively. The QSAR-SSD approach presents a viable and cost-effective method for deriving water quality criteria for other emerging contaminants.

Bioconcentration of pharmaceuticals by aquatic flora in an Australian river system.

Pharmaceuticals are emerging contaminants in the environment and are a ubiquitous presence in rivers downstream of wastewater treatment plant outfalls. Questions remain about the persistence of pharmaceuticals in rivers, and the uptake and bioconcentration of pharmaceuticals by aquatic plants. Our study took place in the Yarrowee/Leigh/Barwon River system in southeastern Australia. We quantified the concentrations of five pharmaceuticals (carbamazepine, primidone, propranolol, tramadol, and venlafaxine) in surface water at five sites along a 144-km stretch of river, downstream of the presumed primary point source (a wastewater treatment plant outfall). We quantified pharmaceuticals in the leaves of two aquatic plant species (Phragmites australis and Vallisneria australis) sampled at each site, and calculated bioconcentration factors. All five pharmaceuticals were detected in surface waters, and the highest detected concentration exceeded 500 ng.L-1 (tramadol). Four of the pharmaceuticals (all except tramadol) were detected and quantified at all sites, including the furthest site from the outfall (144 km). Carbamazepine showed less attenuation with distance from the outfall than the other pharmaceuticals. Carbamazepine and venlafaxine were quantified in the leaves of both aquatic plant species (range: 10-31 ng.g-1), and there was evidence that bioconcentration factors increased with decreasing surface water concentrations. The study demonstrates the potential long-distance persistence of pharmaceuticals in river systems, and the bioconcentration of pharmaceuticals by aquatic plants in natural ecosystems. These phenomena deserve greater attention as aquatic plants are a potential point of transfer of pharmaceuticals from aquatic ecosystems to terrestrial food webs.

Acute exposure to environmentally relevant concentrations of pharmaceutical pollutants induces neurobehavioral toxicity in zebrafish (Danio rerio).

Pharmaceutical waste from point and non-point sources enters, persists, or disseminates in the environment and is known as environmentally persistent pharmaceutical pollutants. Understanding the impacts of pharmaceutical pollutants on the environment and health is essential. This study investigates the behavioral impacts of pharmaceutical pollutants on aquatic organisms and delineates the possible nexus of oxidative stress. The male zebrafish were exposed to four major representative pharmaceutical pollutants, viz., acetaminophen, carbamazepine, metformin, and trimethoprim at environmentally relevant concentrations individually as well as in a mixture for seven days. Substantial alterations in social interaction, aggressive nature, novel tank exploration, and light and dark zone preferences were recorded and the degree varied to different pharmaceutical pollutants. The activity of oxidative stress markers, superoxide dismutase, glutathione-S-transferase, and catalase, was found to be suppressed to 66-20%, 42-25%, and 59-20% respectively with the elevated malondialdehyde generation (180-260%) compared to control. The activity level of acetylcholine esterase was found to be increased to 200-500% across all treatment groups. Despite the synergistic impacts of pharmaceutical pollutants on the whole system that could not be ascertained, this comprehensive study highlights their toxicity nature to induce neurobehavioral toxicity in zebrafish through oxidative stress mechanisms and altered cholinergic systems.

Occurrence and Environmental Risk Assessment of Contaminants of Emerging Concern in Brazilian Surface Waters.

We investigated the occurrence and the environmental risk of eight contaminants of emerging concern (CECs; acetaminophen, naproxen, diclofenac, methylparaben, 17ß-estradiol, sulfathiazole, sulfadimethoxine, and sulfamethazine) in three Brazilian water bodies, namely, the Monjolinho River Basin (São Paulo State), the Mogi Guaçu River (São Paulo State), and the Itapecuru River (Maranhão State) in three sampling campaigns. The CECs were only quantified in surface water samples collected at the Monjolinho River Basin. Acetaminophen, naproxen, and methylparaben were detected in the range of <200 to 575.9 ng L-1, <200 to 224.7 ng L-1, and <200 to 303.6 ng L-1, respectively. The detection frequencies of the three measured compounds were between 33% and 67%. The highest concentrations of CECs were associated with intense urbanization and untreated sewage discharge. Furthermore, CEC concentrations were significantly correlated with total organic carbon, electrical conductivity, and dissolved oxygen levels, suggesting that domestic pollution from urban areas is an important source in the distribution of CECs in the Monjolinho River Basin. The environmental risk assessment indicated a high risk for acetaminophen (risk quotient [RQ] values between 2.1 and 5.8), a medium risk for naproxen (RQs between 0.6 and 0.7), and a low risk for methylparaben (RQs < 0.1) to the freshwater biota of the Monjolinho River Basin. Our findings show potential threats of CECs in Brazilian water bodies, especially in vulnerable areas, and reinforce the need for improvements in environmental regulations to include monitoring and control of these compounds in aquatic systems. Environ Toxicol Chem 2024;00:1-12. © 2024 SETAC.

[Identification and Derivation of Emerging Contaminants in the Roof Rainwater Confluence].

To identify emerging contaminants （ECs） in rainwater is a topic that has gradually received widespread attention. Rainwater resources, specifically urban roofs, play a crucial role in utilizing rainwater efficiently by understanding the occurrence and migration characteristics of pollutants in precipitation. This study selected a typical roof and studied the differences in rainwater quality and pollution occurrence at different collection stages during six rainfall events from March to May in 2023. Principal component analysis （PCA） and correlation analysis were used to explore the distribution, migration, and transformation of ECs in the collection process of roof rainwater. The findings revealed the presence of 44/54 ECs in wet deposition, dry and wet deposition, and roof runoff processes, with a total concentration range of 63.0 to 432.4 ng·L-1 and an average concentration of 166.8 ng·L-1. Notably, bisphenol A （BPA） exhibited the highest concentration, ranging from 14.7 to 265.6 ng·L-1, with an average concentration of 62.5 ng·L-1, followed by ofloxacin （OFX） and ethylhexyl methoxycinnamate （EHMC）, with detected concentrations up to 45.5 ng·L-1 and 44.8 ng·L-1. Dissolved organic matter （DOM）, nitrogen pollutants, and particulate matter were important factors affecting the occurrence characteristics of ECs, with a mantel correlation coefficient of up to 0.98 （P<0.01）. Based on the analysis of different rainfall events and collection stages, variations were observed in the accumulation pathways and contribution ratios of different pollutants. The wet deposition exhibited the highest content of ECs in the initial stage, whereas the dry and wet deposition and roof runoff processes displayed higher ECs content in the later stages. Additionally, the average ECs contribution rates of dry and wet deposition to roof runoff were 21.48% and 78.52%, respectively. Due to the influence of roof material and surface roughness retention performance, over 30% of ECs, including pharmaceuticals and personal care products （PPCPs）, endocrine-disrupting compounds （EDCs）, and pesticides, were deposited on the roof during the runoff collection. The results of this research can provide the theoretical foundation and technical support for the identification and control of ECs in urban roof runoff and for the safe storage of rainwater.

Impacts of cattle management and agricultural practices on water quality through different approaches: physicochemical and ecotoxicological parameters.

The intensification of livestock farming can pose risks to the environment due to the increased use of veterinary products and the generation of waste in confined areas. The quality of water bodies near livestock establishments (Areco River (A) and Doblado stream (D), San Antonio de Areco, Buenos Aires, Argentina) was studied by physicochemical parameters, metals, pesticides, emerging contaminants, and lethal and sublethal toxicity (neurotoxicity and oxidative stress) in larvae of the native amphibian Rhinella arenarum. Six sites were selected: upstream (S1A and S1D), at the level (S2A and S2D), and downstream (S3A and S3D) from the establishments. A low concentration of dissolved oxygen was observed in Doblado stream (< 2.34 mg/L). Cu, Mn, V, and Zn exceeded the limits for the protection of aquatic life at various sites. Between 24 and 34 pesticides were detected in all sites, with 2,4-D, atrazine, and metolachlor being the most recurrent. In water and sediment, the concentrations of ivermectin (S2A, 1.32 µg/L and 58.18 µg/kg; S2D, 0.8 µg/L and 85.22 µg/kg) and oxytetracycline (S2A, < 1 mg/L and < 1 mg/kg; S2D, 11.8 mg/L and 39 mg/kg) were higher at sites near the establishments. All sites caused between 30 and 38.3% of lethality and produced neurotoxicity and alterations in the reduced glutathione content. Moreover, larvae exposed to samples from all sites incorporated ivermectin. These results demonstrate the degradation of the studied sites in relation to the agricultural activities of the area, highlighting the need to take measures to protect and preserve aquatic ecosystems.