Non-target screening in water analysis: recent trends of data evaluation, quality assurance, and their future perspectives.

This trend article provides an overview of recent advancements in Non-Target Screening (NTS) for water quality assessment, focusing on new methods in data evaluation, qualification, quantification, and quality assurance (QA/QC). It highlights the evolution in NTS data processing, where open-source platforms address challenges in result comparability and data complexity. Advanced chemometrics and machine learning (ML) are pivotal for trend identification and correlation analysis, with a growing emphasis on automated workflows and robust classification models. The article also discusses the rigorous QA/QC measures essential in NTS, such as internal standards, batch effect monitoring, and matrix effect assessment. It examines the progress in quantitative NTS (qNTS), noting advancements in ionization efficiency-based quantification and predictive modeling despite challenges in sample variability and analytical standards. Selected studies illustrate NTS's role in water analysis, combining high-resolution mass spectrometry with chromatographic techniques for enhanced chemical exposure assessment. The article addresses chemical identification and prioritization challenges, highlighting the integration of database searches and computational tools for efficiency. Finally, the article outlines the future research needs in NTS, including establishing comprehensive guidelines, improving QA/QC measures, and reporting results. It underscores the potential to integrate multivariate chemometrics, AI/ML tools, and multi-way methods into NTS workflows and combine various data sources to understand ecosystem health and protection comprehensively.

Assessing the effect of ß-glucan diets on innate immune response of tilapia macrophages against trichlorfon exposure: an in vitro study.

The widespread use of pesticides in some areas where fish species such as tilapia are farmed may cause damage to the environment and affect commercial fish and therefore, human health. Water leaching with the pesticide trichlorfon, during the fumigation season in the field, can affect water quality in fish farms and consequently affect fish health. At the same time, the use of immunomodulatory compounds such as ß-glucan supplied in the diet has become widespread in fish farms as it has been shown that improves the overall immune response. The present research examines the immunomodulatory impacts observed in macrophages of Nile tilapia (Oreochromis niloticus) after being fed a diet supplemented with ß-glucan for 15 days, followed by their in vitro exposure to trichlorfon, an organophosphate pesticide, at concentrations of 100 and 500 µg mL-1 for 24 h. The results showed that ß-glucan diet improved the viability of cells exposed to trichlorfon and their antioxidant capacity. However, ß-glucan did not counteract the effects of the pesticide as for the ability to protect against bacterial infection. From the present results, it can be concluded that ß-glucan feeding exerted a protective role against oxidative damage in cells, but it was not enough to reduce the deleterious effects of trichlorfon on the microbicidal capacity of macrophages exposed to this pesticide.

Chlorpyrifos-mediated mitochondrial calcium overload induces EPC cell apoptosis via ROS/AMPK/ULK1.

Chlorpyrifos (CPF) is a typical organophosphate insecticide known to has serious toxicological effects on aquatic animals and causes many environmental contamination problems. To assess the effects of CPF on the epithelioma papulosum cyprini (EPC) cells of the common carps from the point of calcium ion (Ca2+) transport, the CPF-exposed EPC models were primarily established, and both AO/EB staining and Annexin V/PI assay with flow cytometry analysis were subsequently implemented to identify that CPF-induced EPC cell apoptosis, in consistent with the up-regulated expression of BAX, Cyt-c, CASP3 and CASP9, and down-regulated BCL-2 expression. Then, Mag-Fluo-4 AM, Fluo-4 AM and Rhod-2 AM staining probes were co-stained with ER-Tracker Red and Mito-Tracker Green applied to image cellular Ca2+ flux, illuminating Ca2+ depleted from ER and flux into mitochondria, resulting in ER stress and mitochondrial dysfunction. Additionally, 2-Aminoethyl Diphenylborinate (2-APB), 4-Phenylbutyric acid (4-PBA) and Dorsomorphin (Compound C) were performed as the inhibitor of Ca2+ transition, ER stress and AMPK phosphorylation, suggesting CPF-mediated Ca2+ overload triggered ER stress. And the over-generation of Mito-ROS intensified oxidative stress, promoting the phosphorylation of AMPK and deteriorating cell apoptotic death. The results of this study demonstrated Ca2+ overload-dependent mitochondrial dysfunction engages in the CPF-induced apoptosis, providing a novel concept for investigating the toxicity of CPF as environmental pollution on aquatic organisms.

Evaluation of effect of hazardous contaminants in areas for the abstraction of drinking water.

The lower portion of Taquari River is influenced by compounds from anthropic activities causing concern about the drinking water supplied to cities in the region. The study objective was to investigate the presence of contaminants at drinking water abstraction sites, defining the mutagenic effects of these stressors as an ecosystem quality parameter and its possible effects on human health. Geographic Information System techniques were used to investigate sources of contamination and it was found that agricultural activities predominated with a few medium and high potential pollutant agricultural activities, besides a soil area that was contaminated and undergoing an intervention process. Mutagenic effects were evaluated by Salmonella/microsome assay using TA98, TA97a, TA100, YG1041 and YG1042 strains in the presence and absence of metabolic activation (S9). Mutagenesis found in organic sediment extracts and surface water samples showed the prevalence of direct-acting mutagens at the drinking water abstraction sites. Taquari (Ta032, the sampling points were named according to the initial letters of the river (Ta), followed by the number of kilometers from the mouth) showed the highest mutagenic potency in sediment, while Ta063, at Bom Retiro do Sul, presented it in the water sample. In the Triunfo region (Ta011) there were significant responses in sediment and in water samples. The samples at General Câmara (Ta006) showed the least presence of contaminants. The Allium cepa test applied to sediments in natura showed significant micronucleus induction in Ta032 in accordance with the Salmonella/microssome assay. The test performed on Danio rerio embryos (FET) in the in natura water samples did not present significant responses. Chemical analyses of polycyclic aromatic hydrocarbons and metals already identified as chemical markers in the area indicated a small contribution to the mutagenic potency, calling attention to the fact that other direct-acting pollutants may be present at the drinking water abstraction sites.

Amphibian (Euphlyctis cyanophlyctis) in vitro ovarian culture system to assess impact of aquatic agrochemical contaminants on female reproduction.

The present study is an attempt to screen impacts of aquatic agrochemical contaminants (acephate, atrazine and cypermethrin) on development and growth of follicles, in in vitro-cultured ovarian fragments of frog (Euphlyctis cyanophlyctis). Ovarian lobes removed surgically from gravid females were cut into small pieces and cultured in vitro in presence of graded (0.01 or 0.1 µg/ml of culture medium) concentrations of test chemicals or estradiol-17ß (positive controls) or culture medium alone (controls) in quadruplicate sets at 23 ± 1 °C temperature for 20 days in a humidified sterile chamber. On 21st day, they were fixed in Bouin's fluid and used for differential follicle counting (n = 3 sets) and histology (n = 1 set). In vitro exposure of ovarian fragments to test chemicals caused a decline in previtellogenic follicles, maintenance of large yolky follicles, incorporation of brown granules into early vitellogenic follicles and decrease in follicular atresia compared to corresponding controls. These results suggest that ovarian follicles are greatly sensitive to chemical exposure during their transition from previtellogenic to vitellogenic growth phase and in vitro ovarian culture system may be used as a tool to assess the effects of aquatic agrochemical contaminants on ovarian function.

Low adsorption affinity of athabasca oil sands naphthenic acid fraction compounds to a peat-mineral mixture.

Much of the toxicity in oil sands process-affected water in Athabasca oil sands tailings has been attributed to naphthenic acids (NAs) and associated naphthenic acid fraction compounds (NAFCs). Previous work has characterized the environmental behaviour and fate of these compounds, particularly in the context of constructed treatment wetlands. There is evidence that wetlands can attenuate NAFCs in natural and engineered contexts, but relative contributions of chemical, biotic, and physical adsorption with sequestration require deconvolution. In this work, the objective was to evaluate the extent to which prospective wetland substrate material may adsorb NAFCs using a peat-mineral mix (PMM) sourced from the Athabasca Oil Sands Region (AOSR). The PMM and NAFCs were first mixed and then equilibrated across a range of NAFC concentrations (5-500 mg/L) with moderate ionic strength and hardness (∼200 ppm combined Ca2+ and Mg2+) that approximate wetland water chemistry. Under these experimental conditions, low sorption of NAFCs to PMM was observed, where sorbed concentrations of NAFCs were approximately zero mg/kg at equilibrium. When NAFCs and PMM were mixed and equilibrated together at environmentally relevant concentrations, formula diversity increased more than could be explained by combining constituent spectra. The TOC present in this PMM was largely cellulose-derived, with low levels of thermally recalcitrant carbon (e.g., lignin, black carbon). The apparent enhancement of the concentration and diversity of components in PMM/NAFCs mixtures are likely related to aqueous solubility of some PMM-derived organic materials, as post-hoc combination of dissolved components from PMM and NAFCs cannot replicate enhanced complexity observed when the two components are agitated and equilibrated together.

Marine mesocosm system: A reliable tool for testing bioaccumulation and effects of seawater enrichment with dissolved iron in reef organisms.

In 2015, a marine mesocosm facility was designed and implemented by the Coral Vivo Project in its research station (Porto Seguro, Bahia State, Brazil) to initially study the effects of global impacts, especially ocean warming and acidification, on coral reefs. However, local impacts, including seawater contamination with metal(loid)s, are considered as a major threat to coral reefs. Also, in 2015, the largest disaster involving a mining dam occurred in Brazil. Iron (Fe) mining tailings originated from the dam failure affected not only freshwater ecosystems (rivers, lakes and lagoons), but also adjacent beaches, mangroves, restingas, reefs and other marine systems. Seawater, sediments and biota were contaminated with metal(loid)s, especially Fe, arsenic (As), mercury (Hg) and manganese (Mn). Therefore, we aimed to adapt the marine mesocosm facility of the Coral Vivo Project to evaluate the bioaccumulation and biological impacts of increasing concentrations of dissolved Fe on a diversity of reef organisms. Results obtained indicate a great versatility and reliability of the marine mesocosm system for application in biological and ecological studies on the isolated effect of seawater dissolved Fe on reef organisms of different functional groups simultaneously.•Studies involving seawater enrichment with dissolved Fe can be performed using a marine mesocosm system.•The marine mesocosm is a reliable tool to study the isolated effects of metal(loid)s on reef organisms.

Toxicity of antifouling biocides on planktonic and benthic neotropical species.

Organotin-based (OTs: TBT and TPT) antifouling paints have been banned worldwide, but recent inputs have been detected in tropical coastal areas. However, there is a lack of studies evaluating the toxicity of both legacy and their substitute antifouling booster biocides (e.g., Irgarol and diuron) on neotropical species. Therefore, the acute toxicity of four antifouling biocides (TBT, TPT, Irgarol, and diuron) was investigated using the marine planktonic organisms Acartia tonsa and Mysidopsis juniae, the estuarine tanaid Monokalliapseudes schubarti (water exposure), and the burrowing amphipod Tiburonella viscana (spiked sediment exposure). Results confirmed the high toxicity of the OTs, especially to planktonic species, being about two orders of magnitude higher than Irgarol and diuron. Toxic effects of antifouling compounds were observed at levels currently found in tropical coastal zones, representing a threat to planktonic and benthic invertebrates. Furthermore, deterministic PNECmarine sediment values suggest that environmental hazards in tropical regions may be higher due to the higher sensitivity of tropical organisms. Since regulations on antifouling biocides are still restricted to a few countries, more ecotoxicological studies are needed to derivate environmental quality standards based on realistic scenarios. The present study brings essential contributions regarding the ecological risks of these substances in tropical and subtropical zones.

Use of Riparian Spiders as Sentinels of Persistent and Bioavailable Chemical Contaminants in Aquatic Ecosystems: A Review.

Aquatic ecosystems around the world are contaminated with a wide range of anthropogenic chemicals, including metals and organic pollutants, that originate from point and nonpoint sources. Many of these chemical contaminants have complex environmental cycles, are persistent and bioavailable, can be incorporated into aquatic food webs, and pose a threat to the health of wildlife and humans. Identifying appropriate sentinels that reflect bioavailability is critical to assessing and managing aquatic ecosystems impacted by contaminants. The objective of the present study is to review research on riparian spiders as sentinels of persistent and bioavailable chemical contaminants in aquatic ecosystems. Our review of the literature on riparian spiders as sentinels suggests that significant progress has been made during the last two decades of research. We identified 55 published studies conducted around the world in which riparian spiders (primarily of the families Tetragnathidae, Araneidae, Lycosidae, and Pisauridae) were used as sentinels of chemical contamination of lotic, lentic, and estuarine systems. For several contaminants, such as polychlorinated biphenyls (PCBs), Hg, and Se, it is now clear that riparian spiders are appropriate sentinels. However, many contaminants and factors that could impact chemical concentrations in riparian spiders have not been well characterized. Further study of riparian spiders and their potential role as sentinels is critical because it would allow for development of national-scale programs that utilize riparian spiders as sentinels to monitor chemical contaminants in aquatic ecosystems. A riparian spider sentinel program in the United States would be complementary to existing national sentinel programs, including those for fish and immature dragonflies. Environ Toxicol Chem 2022;41:499-514. © 2021 SETAC.

Evaluation of a full-scale wastewater treatment plant with ozonation and different post-treatments using a broad range of in vitro and in vivo bioassays.

Micropollutants present in the effluent of wastewater treatment plants (WWTPs) after biological treatment are largely eliminated by effective advanced technologies such as ozonation. Discharge of contaminants into freshwater ecosystems can thus be minimized, while simultaneously protecting drinking water resources. However, ozonation can lead to reactive and potentially toxic transformation products. To remove these, the Swiss Federal Office for the Environment recommends additional "post-treatment" of ozonated WWTP effluent using sand filtration, but other treatments may be similarly effective. In this study, 48 h composite wastewater samples were collected before and after full-scale ozonation, and after post-treatments (full-scale sand filtration, pilot-scale fresh and pre-loaded granular activated carbon, and fixed and moving beds). Ecotoxicological tests were performed to quantify the changes in water quality following different treatment steps. These included standard in vitro bioassays for the detection of endocrine, genotoxic and mutagenic effects, as well as toxicity to green algae and bacteria, and flow-through in vivo bioassays using oligochaetes and early life stages of rainbow trout. Results show that ozonation reduced a number of ecotoxicological effects of biologically treated wastewater by 66 - 93%: It improved growth and photosynthesis of green algae, decreased toxicity to luminescent bacteria, reduced concentrations of hormonally active contaminants and significantly changed expression of biomarker genes in rainbow trout liver. Bioassay results showed that ozonation did not produce problematic levels of reaction products overall. Small increases in toxicity observed in a few samples were reduced or eliminated by post-treatments. However, only relatively fresh granular activated carbon (analyzed at 13,000 - 20,000 bed volumes) significantly reduced effects additionally (by up to 66%) compared to ozonation alone. Inhibition of algal photosynthesis, rainbow trout liver histopathology and biomarker gene expression proved to be sufficiently sensitive endpoints to detect the change in water quality achieved by post-treatment.

Toxicological impacts of micro(nano)plastics in the benthic environment.

Micro(nano)plastics (MNPs) have sparked growing public and scientific concerns as emerging pollutants in recent decades, due to their small size and potential for significant ecological and human health impacts. Understanding the toxicological effects of MNPs on aquatic organisms is of great importance; however, most of the available research on aquatic organisms has focused on the pelagic organisms, and studies on benthic organisms are lacking yet. Being bottom-dwelling creatures, benthos perhaps confronts more extreme pressure from MNPs. Therefore, this review summarizes the current literature on the impacts of MNPs on benthic organisms to reveal their toxicity on the survival, growth, development and reproductive systems. MNPs can accumulate in various tissues of benthos and probably cause tissue-specific damage, resulting in genotoxicity and reproductive toxicity to benthic organisms. And, in severe cases, they may also pass on the adverse effects to the next generations. The complexity of co-exposure to MNPs with other aquatic contaminants is also highlighted. Furthermore, we have comprehensively discussed the internal and external factors affecting the toxicity of MNPs in benthic organisms. Additionally, we also presented the current research gaps and potential future challenges, providing overall background information for a thorough understanding of the toxic effects of MNPs in the benthic aquatic ecosystem.

Aquatic environment remediation by atomic layer deposition-based multi-functional materials: A review.

Water pollution still poses significant threats to the ecosystem and human health today. The adsorption, advanced oxidation and membranes filtration have been extensively investigated and utilized for aquatic contaminants remediation, and their efficiency is closely correlated with the advanced materials design and fabrication (e.g. adsorbents, catalysts and membranes). Thanks to uniform deposition, three-dimensional conformity and process controllability, the atomic layer deposition (ALD) has emerged as a promising strategy for fabrication of these multifunctional materials, arising their successful application in aquatic contaminants remediation. Therefore, a timely review on ALD-based water treatment materials is highly important to summarize the current opportunity and elucidate unaddressed problems in this field. Herein, in this review, the advantages of ALD process, the superiority of ALD-based materials and the corresponding decontamination performance were analyzed comprehensively, highlighting key advantages offered by this technology.

Technical design and optimisation of polymer inclusion membranes (PIMs) for sample pre-treatment and passive sampling - A review.

This review reports on the increasing interest in technical designs, calibration, and application of PIM-based devices in sample pre-treatment and passive sampling in environmental water monitoring from 2010 to 2021. With regards to passive sampling, devices are calibrated in a laboratory setup using either a dip-in or flow-through approach before environmental application. In sample preparation, the device set-ups can be offline, online or in a continuous flow separation device connected to a flow injection analysis system. The PIMs have also demonstrated potential in both these offline and online separations; however, there is still a draw-back of low diffusion coefficients obtained in these PIM set-ups. Electro-driven membrane (EME) extraction has demonstrated better performance as well as improved analyte flux. Critical in electro-driven membrane extraction is applying correct voltage that may not compromise the PIM performance due to leaching of components to the aqueous solutions. Further, besides different PIM configurations and designs being developed, PIM based extractions are central to PIM components (base polymer, carrier and plasticizer). As such, recent studies have also focused on improving PIM stability by investigating use of various PIM components, incorporating nano additives into the PIM composition, and investigating novel green PIM synthetic routes. All these aspects are covered in this review. Further, some recent studies that have demonstrated the ability to eliminate effects of flow patterns and membrane biofouling in PIM based applications are also included.

Biocatalytic degradation/redefining "removal" fate of pharmaceutically active compounds and antibiotics in the aquatic environment.

Recently, the increasing concentration and persistent appearance of antibiotics traces in the water streams are considered an issue of high concern. In this context, an array of antibiotics has been categorized as pollutants of emerging concern due to their complex and highly stable bioactivity, indiscriminate usage with ultimate release into water bodies, and notable persistence in environmental matrices. Moreover, antibiotics traces containing household sewage/drain waste and pharmaceutical wastewater effluents contain a range of bioactive/toxic organic compounds, inorganic salts, pharmaceutically-active ingredients, or a mixture of all, which possesses negative influences ranging from ecological pollution to damage biodiversity. Moreover, their uncontrolled and undesirable bioaccumulation also poses a potential threat to target and non-target organisms in the environment. Aiming to tackle this issue effectively, various detection, quantification, degradation, and redefining "removal" processes have been proposed and investigated based on physical, chemical, and biological strategies. Though both useful and side effects of antibiotics on humans and animals are usually investigated thoroughly following safety and toxicity measures, however, their direct or indirect environmental impacts are not well reviewed yet. Owing to the considerable research gap, the environmental perfectives of antibiotics traces and their effects on target and non-target populations have now become the topic of research interest. Based on literature evidence, over the past several years, numerous individual studies have been performed and published covering various aspects of antibiotics. However, a comprehensive compilation on enzyme-based degradation of antibiotics is still lacking and requires careful consideration. Hence, this review summarizes up-to-date literature on enzymes as biocatalytic systems, explicitly, free as well as immobilized forms and their effective exploitation for the degradation of various antibiotics traces and other pharmaceutically-active compounds present in the water bodies. It is further envisioned that the enzyme-based strategies, for antibiotics degradation or removal, discussed herein, will help readers for a better understanding of antibiotics persistence in the environment along with the associated risks and removal measures. In summary, the current research thrust presented in this review will additionally evoke researcher to engineer robust and sustainable processes to effectively remediate antibiotics-contaminated environmental matrices.