ABSTRACT
Synthetic organic chemicals, including pesticides, pharmaceuticals, and industrial compounds, pose a growing threat to marine ecosystems. Despite their potential impact, data on the co-occurrence of these contaminants in multiple compartments, including surface water, bottom water, porewater, and sediment in the marine environment remains limited. Such information is critical for assessing coastal chemical status, establishing environmental quality benchmarks, and conducting comprehensive environmental risk assessments. In this study, we describe a multifaceted monitoring campaign targeting pesticides, pharmaceuticals, surfactants, additives, and plasticizers among other synthetic chemicals in four sampling sites. One site was located in the small Coliumo bay affected by urban settlements and tourism in central-south and additionally, we sampled three sites, Caucahue Channel, affected by urban settlements and salmon farming in northern Patagonia in Chile. Surface water, bottom water, porewater, and adjacent sediment samples were collected for target screening analysis in LC- and GC-HRMS platforms. Our results show the detection of up to 83 chemicals in surface water, 71 in bottom water, 101 in porewater, and 244 in sediments. To enhance data utility and reuse potential, we provide valuable information on the mode of action and molecular targets of the identified chemicals. This comprehensive dataset contributes to defining pollution fingerprints in coastal areas of the Global South, including remote regions in Patagonia. It serves as a critical resource for future research including marine chemical risk assessment, policymaking, and the advancement of environmental protection in these regions.
ABSTRACT
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.
ABSTRACT
Water resources play a crucial role in sustaining life on earth yet chemicals of emerging concern (CECs) arising from extensive human applications are an increasing threat towards their existence. In this study, we examined the occurrence, removal and potential risk of CECs found in rivers and wastewater treatment plants (WWTPs) in western Kenya. Samples were prepared by solid-phase extraction and analysed using high performance liquid chromatography-mass spectrometry with a target list of 785 compounds. Out of these, 333 and 352 (influent 322, effluent 265) compounds were quantified in rivers and wastewater respectively, with pharmaceuticals, industrial compounds, and pesticides being frequently detected in both rivers and WWTPs. Compounds with highest concentrations included saccharin (9.9 µg/L), metformin (7.5 µg/L), and oxypurinol (6.5 µg/L) in rivers whereas caffeine (280 µg/L), deoxycholic acid (179 µg/L), 2-oxindole (10.9 µg/L) and ibuprofen (8.1 µg/L) were found at high concentrations in WWTPs. Based on the types of crops grown, samples from maize growing regions recorded the highest number of pesticides (75) which coincided with the spraying season. The WWTP showed the capacity to eliminate some compounds although the removal efficiencies varied greatly with 204 compounds exhibiting an average removal efficiency exceeding 50 %. Based on the risk assessment, crustaceans had the highest potential risk for toxicity with toxic unit (TU) values up to 5.4 driven primarily by diazinon and dichlorvos followed by algae (TU up to 0.07) and fish (TU up to 0.01) in rivers. A similar trend was observed in WWTP with diazinon (TU up to 5.5), diuron (TU up to 0.07) and carbendazim (TU up to 0.006) driving the risk for crustaceans, algae and fish respectively. These findings highlight the significance of surface water and WWTPs as sources and sinks of CECs in the environment translating to potential risks on aquatic organisms and humans.
Subject(s)
Environmental Monitoring , Rivers , Waste Disposal, Fluid , Wastewater , Water Pollutants, Chemical , Kenya , Water Pollutants, Chemical/analysis , Wastewater/chemistry , Risk Assessment , Rivers/chemistry , Pesticides/analysis , AnimalsABSTRACT
The release of chemicals into the environment presents a significant threat to aquatic ecosystems dependent on the proximity to emission sources and seasonal dynamics of emission and mobilization. While spatial-temporal information on water pollution in Europe is increasing, there are substantial knowledge gaps on seasonal pollution dynamics in tropical countries. Thus, we took Lake Victoria South Basin in western Kenya as a case study to identify spatial and seasonal hot spots of contamination, quantified toxic risks to different groups of organisms, and identified seasonal risk drivers. For this purpose, we analyzed grab water samples from five rivers with agricultural and wastewater treatment plants in their catchment in four different seasons. We used liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) with a target list of 785 organic micropollutants. A total of 307 compounds were detected with concentrations ranging from 0.3 ng/L to 6.6 µg/L. Using a Toxic Unit (TU) approach based on mixture toxicity to standard test organisms, crustaceans were identified as the most affected group followed by algae and fish. For crustaceans, chronic risk thresholds were exceeded in 96 % of all the samples, while 56 % of all samples are expected to be acutely toxic, with the highest risk in February during the dry season. High toxic unit values for algae and fish were recorded in July dry season and May wet season. Diazinon, imidacloprid, clothianidin and pirimiphos-methyl were the major drivers for crustacean toxicity while triclosan and different herbicide mixtures drive risks to algae in dry and wet seasons, respectively. A total of 18 chemicals were found to exceed acute and chronic environmental risk thresholds. With this study, strong spatial-temporal patterns of pollution, risks and risk drivers could be confirmed informing prioritization of monitoring and abatement to enhance water quality and reduce toxic risks.
ABSTRACT
Chemical pollution of the aquatic environment is nowadays characterised by increasing levels of anthropogenic organic compounds at low concentrations and is recognised as one of the main drivers of the deteriorated ecological state of European waterbodies. To improve the understanding of the impact of chemical pollution in surface waters, a combined approach of chemical and bioanalytical testing is considered necessary for effective ecologically oriented water management. For this dataset, six 25-L water samples were collected at six sampling sites along the Holtemme River in Central Germany using large-volume solid phase extraction. All samples were analysed by targeted high-resolution liquid chromatography-mass spectrometry (LC-MS) and a selected bioanalytical test battery using effect-based methods. These methods included cytotoxicity assessment, several mechanism-specific CALUXâ tests to identify endocrine and oxidative stress-related effects and the fish embryo acute toxicity test to investigate (sub)lethal effects in the model species Danio rerio. This approach provided a dataset that offers a longitudinal characterisation of the chemical pollution and ecotoxicological impacts. The combination of chemical analysis and effect-based analysis is valuable for future studies as it will help researchers, risk assessors and authorities to identify hot spots of chemical pollution, monitor environmental quality standards and recommend mitigation strategies.
ABSTRACT
Native and invasive species often occupy similar ecological niches and environments where they face comparable risks from chemical exposure. Sometimes, invasive species are phylogenetically related to native species, e.g. they may come from the same family and have potentially similar sensitivities to environmental stressors due to phylogenetic conservatism and ecological similarity. However, empirical studies that aim to understand the nuanced impacts of chemicals on the full range of closely related species are rare, yet they would help to comprehend patterns of current biodiversity loss and species turnover. Behavioral sublethal endpoints are of increasing ecotoxicological interest. Therefore, we investigated behavioral responses (i.e., change in movement behavior) of the four dominant amphipod species in the Rhine-Main area (central Germany) when exposed to the neonicotinoid thiacloprid. Moreover, beyond species-specific behavioral responses, ecological interactions (e.g. parasitation with Acanthocephala) play a crucial role in shaping behavior, and we have considered these infections in our analysis. Our findings revealed distinct baseline behaviors and species-specific responses to thiacloprid exposure. Notably, Gammarus fossarum exhibited biphasic behavioral changes with hyperactivity at low concentrations that decreased at higher concentrations. Whereas Gammarus pulex, Gammarus roeselii and the invasive species Dikerogammarus villosus, showed no or weaker behavioral responses. This may partly explain why G. fossarum disappears in chemically polluted regions while the other species persist there to a certain degree. But it also shows that potential pre-exposure in the habitat may influence behavioral responses of the other amphipod species, because habituation occurs, and potential hyperactivity would be harmful to individuals in the habitat. The observed responses were further influenced by acanthocephalan parasites, which altered baseline behavior in G. roeselii and enhanced the behavioral response to thiacloprid exposure. Our results underscore the intricate and diverse nature of responses among closely related amphipod species, highlighting their unique vulnerabilities in anthropogenically impacted freshwater ecosystems.
Subject(s)
Amphipoda , Introduced Species , Neonicotinoids , Water Pollutants, Chemical , Animals , Amphipoda/drug effects , Amphipoda/physiology , Neonicotinoids/toxicity , Water Pollutants, Chemical/toxicity , Insecticides/toxicity , Germany , Behavior, Animal/drug effects , ThiazinesABSTRACT
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.
Subject(s)
Environmental Exposure , Environmental Monitoring , Humans , Environmental Exposure/analysis , Environmental Monitoring/methods , Environmental Monitoring/standards , Environmental Pollutants/analysis , Hazardous Substances/analysis , Mass Spectrometry/methods , Risk Assessment/methodsABSTRACT
Liquid chromatography (LC) or gas chromatography (GC) coupled to high-resolution mass spectrometry (HRMS) is a versatile analytical method for the analysis of thousands of chemical pollutants that can be found in environmental and biological samples. While the tools for handling such complex datasets have improved, there are still no fully automated workflows for targeted screening analysis. Here we present an R-based workflow that is able to cope with challenging data like noisy ion chromatograms, retention time shifts, and multiple peak patterns. The workflow can be applied to batches of HRMS data recorded after GC with electron ionization (GC-EI) and LC coupled to electrospray ionization in both negative and positive mode (LC-ESIneg/LC-ESIpos) to perform peak annotation and quantitation fully unsupervised. We used Orbitrap HRMS data of surface water extracts to compare the Automated Target Screening (ATS) workflow with data evaluations performed with the vendor software TraceFinder and the established semi-automated analysis workflow in the MZmine software. The ATS approach increased the overall evaluation performance of the peak annotation compared to the established MZmine module without the need for any post-hoc corrections. The overall accuracy increased from 0.80 to 0.86 (LC-ESIpos), from 0.77 to 0.83 (LC-ESIneg), and from 0.67 to 0.76 (GC-EI). The mean average percentage errors for quantification of ATS were around 30% compared to the manual quantification with TraceFinder. The ATS workflow enables time-efficient analysis of GC- and LC-HRMS data and accelerates and improves the applicability of target screening in studies with a large number of analytes and sample sizes without the need for manual intervention.
Subject(s)
Workflow , Mass Spectrometry/methods , Software , Automation , Chromatography, Liquid/methods , Gas Chromatography-Mass Spectrometry/methods , Water Pollutants, Chemical/analysisABSTRACT
Environmental risk assessments strategies that account for the complexity of exposures are needed in order to evaluate the toxic pressure of emerging chemicals, which also provide suggestions for risk mitigation and management, if necessary. Currently, most studies on the co-occurrence and environmental impacts of chemicals of emerging concern (CECs) are conducted in countries of the Global North, leaving massive knowledge gaps in countries of the Global South. In this study, we implement a multi-scenario risk assessment strategy to improve the assessment of both the exposure and hazard components in the chemical risk assessment process. Our strategy incorporates a systematic consideration and weighting of CECs that were not detected, as well as an evaluation of the uncertainties associated with Quantitative Structure-Activity Relationships (QSARs) predictions for chronic ecotoxicity. Furthermore, we present a novel approach to identifying mixture risk drivers. To expand our knowledge beyond well-studied aquatic ecosystems, we applied this multi-scenario strategy to the River Aconcagua basin of Central Chile. The analysis revealed that the concentrations of CECs exceeded acceptable risk thresholds for selected organism groups and the most vulnerable taxonomic groups. Streams flowing through agricultural areas and sites near the river mouth exhibited the highest risks. Notably, the eight risk drivers among the 153 co-occurring chemicals accounted for 66-92 % of the observed risks in the river basin. Six of them are pesticides and pharmaceuticals, chemical classes known for their high biological activity in specific target organisms.
Subject(s)
Environmental Monitoring , Water Pollutants, Chemical , Water Pollutants, Chemical/analysis , Ecosystem , Rivers/chemistry , Chile , Risk AssessmentABSTRACT
Chemicals in the aquatic environment can be harmful to organisms and ecosystems. Knowledge on effect concentrations as well as on mechanisms and modes of interaction with biological molecules and signaling pathways is necessary to perform chemical risk assessment and identify toxic compounds. To this end, we developed criteria and a pipeline for harvesting and summarizing effect concentrations from the US ECOTOX database for the three aquatic species groups algae, crustaceans, and fish and researched the modes of action of more than 3,300 environmentally relevant chemicals in literature and databases. We provide a curated dataset ready to be used for risk assessment based on monitoring data and the first comprehensive collection and categorization of modes of action of environmental chemicals. Authorities, regulators, and scientists can use this data for the grouping of chemicals, the establishment of meaningful assessment groups, and the development of in vitro and in silico approaches for chemical testing and assessment.
ABSTRACT
Controlling and minimising background contamination is crucial for maintaining a high quality of samples in human biomonitoring targeting organic chemicals. We assessed the contamination of three previous types and one newly introduced medical-grade type of sample tubes used for storing human body fluids at the German Environmental Specimen Bank. Aqueous extracts from these tubes were analysed by non-targeted liquid chromatography-high resolution mass spectrometry (LC-HRMS) before and after a dedicated cleaning procedure. After peak detection using MZmine, Bayesian hypothesis testing was used to group peaks into those originating either from instrumental and laboratory background contamination, or actual tube contaminants, based on if their peak height was reduced, increased or not affected by the cleaning procedure. For all four tube types 80-90% of the 2475 peaks (1549 in positive and 926 in negative mode) were assigned to laboratory/instrumental background, which we have to consider as potential sample tube contaminants. Among the tube contaminants, results suggest a considerable difference in the contaminant peak inventory and the absolute level of contamination among the different sample tube types. The cleaning procedure did not affect the largest fraction of peaks (50-70%). For the medical grade tubes, the removal of contaminants by the cleaning procedure was strongest compared to the previous tubes, but in all cases a small fraction increased in intensity after cleaning, probably due to a release of oligomers or additives. The identified laboratory background contaminants were mainly semi-volatile polymer additives such as phthalates and phosphate esters. A few compounds could be assigned solely as tube-specific contaminants, such as N,N-dibutylformamide and several constituents of the oligomeric light stabiliser Tinuvin-622. A cleaning procedure before use is an effective way to standardise the used sample tubes and minimises the background contamination, and therefore increases sample quality and therewith analytical results.
Subject(s)
Biological Monitoring , Phthalic Acids , Humans , Chromatography, Liquid/methods , Bayes Theorem , Liquid Chromatography-Mass Spectrometry , Phthalic Acids/analysisABSTRACT
PURPOSE: A prospective, single-arm, open-label, multicenter, first-in-human, early feasibility study was completed to evaluate the safety and performance of the GPX Embolic Device (Fluidx, Salt Lake City, Utah), a novel liquid embolic agent, for use in the peripheral vasculature when deep distal embolization is desired. MATERIALS AND METHODS: The early feasibility study evaluated the use of the device in the peripheral vasculature. Enrollment consisted of 17 patients with diverse embolization needs requiring deep distal vessel/vessel bed occlusion. Technical success, freedom from adverse events (AEs), and handling/performance characteristics were assessed with follow-up at 30 days. RESULTS: The trial enrolled 17 patients requiring distal vascular penetration of the embolic agent, including 7 with renal angiomyolipomas, 4 with renal cell carcinomas (primary and secondary), 4 with portal veins needing embolization, 1 with pelvic sarcoma, and 1 with polycystic kidney. In all cases (100%), technical success was achieved with target regions fully occluded on the first angiogram (taken immediately after delivery). Furthermore, the material received high usability ratings, as measured by a postprocedural investigator questionnaire. Most patients (15/17, 88.2%) were free from device-related severe AEs, and there were no unanticipated AEs during the study. Each patient completed a 30-day follow-up evaluation, and sites remained fully occluded in each case where imaging was available (6 [35.3%] of 17 patients had follow-up imaging where all sites were deemed occluded [100%] with a mean of 30.2 days after the procedure). CONCLUSIONS: The results of this first-in-human, early feasibility study demonstrate that the GPX Embolic Device may provide safe and effective embolization for arterial or venous applications where deep distal penetration is desired.
Subject(s)
Embolism , Embolization, Therapeutic , Ionic Liquids , Humans , Embolization, Therapeutic/adverse effects , Embolization, Therapeutic/methods , Prospective Studies , Treatment OutcomeABSTRACT
There is increasing awareness that chemical pollution of freshwater systems with complex mixtures of chemicals from domestic sources, agriculture and industry may cause a substantial chemical footprint on water organisms, pushing aquatic ecosystems outside the safe operating space. The present study defines chemical footprints as the risk that chemicals or chemical mixtures will have adverse effects on a specific group of organisms. The aim is to characterise these chemical footprints in European streams based on a unique and uniform screening of more than 600 chemicals in 445 surface water samples, and to derive site- and compound-specific information for management prioritisation purposes. In total, 504 pesticides, biocides, pharmaceuticals and other compounds have been detected, including frequently occurring and site-specific compounds with concentrations up to 74 µg/L. Key finding is that three-quarter of the investigated sites in 22 European river basins exceed established thresholds for chemical footprints in freshwater, leading to expected acute or chronic impacts on aquatic organisms. The largest footprints were recorded on invertebrates, followed by algae and fish. More than 70 chemicals exceed thresholds of chronic impacts on invertebrates. For all organism groups, pesticides and biocides were the main drivers of chemical footprints, while mixture impacts were particularly relevant for invertebrates. No clear significant correlation was found between chemical footprints and the urban discharge fractions, suggesting that effluent-specific quality rather than the total load of treated wastewater in the aquatic environment and the contribution of diffuse sources, e.g. from agriculture, determine chemical footprints.
Subject(s)
Disinfectants , Pesticides , Water Pollutants, Chemical , Animals , Rivers/chemistry , Ecosystem , Water Pollutants, Chemical/analysis , Invertebrates , Pesticides/analysis , Aquatic Organisms , Water , Environmental MonitoringABSTRACT
Plastics are produced with a staggering array of chemical compounds, with many being known to possess hazardous properties, and others lacking comprehensive hazard data. Furthermore, non-intentionally added substances can contaminate plastics at various stages of their lifecycle, resulting in recycled materials containing an unknown number of chemical compounds at unknown concentrations. While some national and regional regulations exist for permissible concentrations of hazardous chemicals in specific plastic products, less than 1 % of plastics chemicals are subject to international regulation [1]. There are currently no policies mandating transparent reporting of chemicals throughout the plastics value chain or comprehensive monitoring of chemicals in recycled materials. The dataset presented here provides the chemical analysis of 28 samples of recycled High-Density Polyethylene (HDPE) pellets obtained from various regions of the Global South, along with a reference sample of virgin HDPE. The analysis comprises both Target and Non-Targeted Screening approaches, employing Liquid Chromatography-High-Resolution Mass Spectrometry (LC-HRMS) and Gas Chromatography-High-Resolution Mass Spectrometry (GC-HRMS). In total, 491 organic compounds were detected and quantified, with an additional 170 compounds tentatively annotated. These compounds span various classes, including pesticides, pharmaceuticals, industrial chemicals, plastic additives. The results highlight the prevalence of certain chemicals, such as N-ethyl-o-Toluesulfonamide, commonly used in HDPE processing, found in high concentrations. The paper provides a dataset advancing knowledge of the complex chemical composition associated with recycled plastics.
ABSTRACT
Human biomonitoring studies are important for understanding adverse health outcomes caused by exposure to chemicals. Complex mixtures of chemicals detected in blood - the blood exposome - may serve as proxies for systemic exposure. Ideally, several analytical methods are combined with in vitro bioassays to capture chemical mixtures as diverse as possible. How many and which (bio)analyses can be performed is limited by the sample volume and compatibility of extraction and (bio)analytical methods. We compared the extraction efficacy of three extraction methods using pooled human plasma spiked with >400 organic chemicals. Passive equilibrium sampling (PES) with polydimethylsiloxane (PDMS) followed by solid phase extraction (PES + SPE), SPE alone (SPE), and solvent precipitation (SolvPrec) were compared for chemical recovery in LC-HRMS and GC-HRMS as well as effect recovery in four mammalian cell lines (AhR-CALUX, SH-SY5Y, AREc32, PPARγ-BLA). The mean chemical recoveries were 38% for PES + SPE, 27% for SPE, and 61% for SolvPrec. PES + SPE enhanced the mean chemical recovery compared to SPE, especially for neutral hydrophobic chemicals. PES + SPE and SolvPrec had effect recoveries of 100-200% in all four cell lines, outperforming SPE, which had 30-100% effect recovery. Although SolvPrec has the best chemical recoveries, it does not remove matrix like inorganics or lipids, which might pose problems for some (bio)analytical methods. PES + SPE is the most promising method for sample preparation in human biomonitoring as it combines good recoveries with cleanup, enrichment, and potential for high throughput.
Subject(s)
Neuroblastoma , Animals , Humans , Organic Chemicals , Biological Assay/methods , Solid Phase Extraction/methods , MammalsABSTRACT
Chemical pollution caused by synthetic organic chemicals at low concentrations in the environment poses a growing threat to the ecological status of aquatic ecosystems. These chemicals are regularly released into surface waters through both treated and untreated effluents from wastewater treatment plants (WWTPs), agricultural runoff, and industrial discharges. Consequently, they accumulate in surface waters, distribute amongst environmental compartments according to their physicochemical properties, and cause adverse effects on aquatic organisms. Unfortunately, there is a lack of data regarding the occurrence of synthetic organic chemicals, henceforth micropollutants, in South American freshwater ecosystems, especially in Chile. To address this research gap, we present a comprehensive dataset comprising concentrations of 153 emerging chemicals, including pesticides, pharmaceutical and personal care products (PPCPs), surfactants, and industrial chemicals. These chemicals were found to co-occur in surface waters within Central Chile, specifically in the River Aconcagua Basin. Our sampling strategy involved collecting surface water samples from streams and rivers with diverse land uses, such as agriculture, urban areas, and natural reserves. For sample extraction, we employed an on-site large-volume solid phase extraction (LVSPE) device. The resulting environmental extracts were then subjected to wide-scope chemical target screening using gas chromatography and liquid chromatography high-resolution mass spectrometry (GC- and LC-HRMS). The dataset we present holds significant value in assessing the chemical status of water bodies. It enables comparative analysis of pollution fingerprints associated with emerging chemicals across different freshwater systems. Moreover, the data can be reused for environmental risk assessment studies. Its utilisation will contribute to a better understanding of the impact and extent of chemical pollution in aquatic ecosystems, facilitating the development of effective mitigation strategies.
ABSTRACT
Aquatic environments are polluted with a multitude of organic micropollutants, which challenges risk assessment due the complexity and diversity of pollutant mixtures. The recognition that certain source-specific background pollution occurs ubiquitously in the aquatic environment might be one way forward to approach mixture risk assessment. To investigate this hypothesis, we prepared one typical and representative WWTP effluent mixture of organic micropollutants (EWERBmix) comprised of 81 compounds selected according to their high frequency of occurrence and toxic potential. Toxicological relevant effects of this reference mixture were measured in eight organism- and cell-based bioassays and compared with predicted mixture effects, which were calculated based on effect data of single chemicals retrieved from literature or different databases, and via quantitative structure-activity relationships (QSARs). The results show that the EWERBmix supports the identification of substances which should be considered in future monitoring efforts. It provides measures to estimate wastewater background concentrations in rivers under consideration of respective dilution factors, and to assess the extent of mixture risks to be expected from European WWTP effluents. The EWERBmix presents a reasonable proxy for regulatory authorities to develop and implement assessment approaches and regulatory measures to address mixture risks. The highlighted data gaps should be considered for prioritization of effect testing of most prevalent and relevant individual organic micropollutants of WWTP effluent background pollution. The here provided approach and EWERBmix are available for authorities and scientists for further investigations. The approach presented can furthermore serve as a roadmap guiding the development of archetypic background mixtures for other sources, geographical settings and chemical compounds, e.g. inorganic pollutants.
Subject(s)
Environmental Pollutants , Databases, Factual , Environmental Pollution , Geography , Quantitative Structure-Activity RelationshipABSTRACT
Acetylcholinesterase (AChE) inhibitors are an important class of neuroactive chemicals that are often detected in aquatic and terrestrial environments. The correct functionality of the AChE enzyme is linked to many important physiological processes such as locomotion and respiration. Consequently, it is necessary to develop new analytical strategies to identify harmful AChE inhibitors in the environment. It has been shown that mixture effects and oxidative stress may jeopardize the application of in vivo assays for the identification of AChE inhibitors in the environment. To confirm that in vivo AChE assays can be successfully applied when dealing with complex mixtures, an extract from river water impacted by non-treated wastewater was bio-tested using the acute toxicity fish embryo test (FET) and AChE inhibition assay with zebrafish. The zebrafish FET showed high sensitivity for the extract (LC10 = relative extraction factor 2.8) and we observed a significant inhibition of the AChE (40%, p < 0.01) after 4-day exposure. Furthermore, the extract was chromatographically fractionated into a total of 26 fractions to dilute the mixture effect and separate compounds according to their physico-chemical properties. As expected, non-specific acute effects (i.e., mortality) disappeared or evenly spread among the fractions, while AChE inhibition was still detected in five fractions. Chemical analysis did not detect any known AChE inhibitors in these active fractions. These results confirm that the AChE assay with Danio rerio can be applied for the detection of neuroactive effects induced in complex environmental samples, but also, they highlight the need to increase analytical and identification techniques for the detection of neurotoxic substances.
Subject(s)
Water Pollutants, Chemical , Zebrafish , Animals , Acetylcholinesterase , Rivers/chemistry , Serbia , Water Pollutants, Chemical/analysis , Cholinesterase Inhibitors/toxicity , Embryo, NonmammalianABSTRACT
Monitoring methodologies reflecting the long-term quality and contamination of surface waters are needed to obtain a representative picture of pollution and identify risk drivers. This study sets a baseline for characterizing chemical pollution in the Danube River using an innovative approach, combining continuous three-months use of passive sampling technology with comprehensive chemical (747 chemicals) and bioanalytical (seven in vitro bioassays) assessment during the Joint Danube Survey (JDS4). This is one of the world's largest investigative surface-water monitoring efforts in the longest river in the European Union, which water after riverbank filtration is broadly used for drinking water production. Two types of passive samplers, silicone rubber (SR) sheets for hydrophobic compounds and AttractSPETM HLB disks for hydrophilic compounds, were deployed at nine sites for approximately 100 days. The Danube River pollution was dominated by industrial compounds in SR samplers and by industrial compounds together with pharmaceuticals and personal care products in HLB samplers. Comparison of the Estimated Environmental Concentrations with Predicted No-Effect Concentrations revealed that at the studied sites, at least one (SR) and 4-7 (HLB) compound(s) exceeded the risk quotient of 1. We also detected AhR-mediated activity, oxidative stress response, peroxisome proliferator-activated receptor gamma-mediated activity, estrogenic, androgenic, and anti-androgenic activities using in vitro bioassays. A significant portion of the AhR-mediated and estrogenic activities could be explained by detected analytes at several sites, while for the other bioassays and other sites, much of the activity remained unexplained. The effect-based trigger values for estrogenic and anti-androgenic activities were exceeded at some sites. The identified drivers of mixture in vitro effects deserve further attention in ecotoxicological and environmental pollution research. This novel approach using long-term passive sampling provides a representative benchmark of pollution and effect potentials of chemical mixtures for future water quality monitoring of the Danube River and other large water bodies.
Subject(s)
Water Pollutants, Chemical , Water Quality , Environmental Monitoring/methods , Water Pollutants, Chemical/toxicity , Water Pollutants, Chemical/analysis , Androgen Antagonists , Ecotoxicology , Estrone , Rivers/chemistryABSTRACT
Plastic waste is considered a major threat for terrestrial, marine and freshwater ecosystems. Ingestion of primary or secondary microparticles resulting from plastic degradation can lead to their trophic transfer raising serious health concerns. In this study, the effect of amine and carboxy functionalized polystyrene microparticles on the physiology of daphnids was investigated with a combination of phenotypic and metabolic endpoints. Carboxy functionalized microparticles showed higher toxicity in acute exposures compared to their amine counterparts. Accumulation of both microparticles in animal gut was confirmed by stereo-microscopy as well as fluorescent microscopy which showed no presence of particles in the rest of the animal. Fluorescence based quantification of microparticles extracted from animal lysates validated their concentration-dependent uptake. Additionally, exposure of daphnids to amine and carboxy functionalized microparticles resulted in increased activities of key enzymes related to metabolism and detoxification. Finally, significant metabolic perturbations were discovered following exposure to microplastics. These findings suggest that polystyrene microparticles can hinder organism performance of the freshwater species and highlight the importance of seeking for holistic and physiological endpoints for pollution assessment.