Ecotoxicity of doped zinc oxide nanoparticles: Perspectives on environmental safety.

Studies on the ecotoxicity of doped zinc oxide nanoparticles (ZnO NPs) are recent, with the first publications starting in 2010. In this sense, this is the first study that comprehensively reviews the ecotoxicological effects of ZnO NPs doped with lanthanide elements to fill this literature gap. This research explores a multifaceted question at the intersection of nanotechnology, toxicology, and environmental science. Different types of dopants commonly used for ZnO doping were investigated in this review, focusing on the ecotoxicological effects of lanthanides as dopants. Bacteria were the main class of organisms used in ecotoxicological studies, since antimicrobial activity of these nanomaterials is extensively explored to combat the imminent problem of resistant bacteria, in addition to enabling the safe use of these nanomaterials for biomedical applications. Doping appears to exhibit greater efficacy when compared to undoped ZnO NPs in terms of antimicrobial effects; however, it cannot be said that it has no impact on non-target organisms. An extensive examination of the literature also establishes the importance and need to evaluate the effects of doped ZnO NPs on organisms from different environmental compartments in order to identify their potential impacts. We underscore the dearth of research information regarding the environmental toxicity/ecotoxicity of doped ZnO nanoparticles across various ecological levels, thereby limiting the extrapolation of findings to humans or other complex models. Therefore, we emphasize the urgency of a multi-parameter assessment for the development of sanitary and environmentally safe nanotechnologies.

Five years after the collapse of the Fundão Dam: lessons from temporal monitoring of chemistry and acute toxicity.

In November 2015, the Fundão Dam break released millions of tons of metal-rich tailings into the Doce River Basin (DRB), causing catastrophic damage and potential ecological effects that reached the Atlantic Ocean. This study aimed to evaluate the geochemistry and toxicity of water and sediments collected in the DRB from 2015 to 2019 and to determine the spatial and temporal trends. Water and sediment samples were analyzed for metals and As by inductively coupled plasma optical emission spectrometry (ICP-OES), and acute toxicity for Daphnia similis or D. magna. Results were explored using geochemical indices and correlation analyzes. Overall, higher concentrations of metals and As in water and sediments were observed immediately after dam breakage, but the levels exhibited a decreasing trend over time, although the levels of some elements such as As and Mn remained high in the upper DRB. The geochemical indices indicated mostly low to moderate contamination, and the enrichment factor (EF) demonstrated a higher enrichment of Mn in the upper DRB. Acute toxicity to water fleas (D. similis and D. magna) was occasionally observed in waters and sediments, but the reference samples were toxic, and the short-term effects were not correlated with metals and As. Overall, the results showed limited bioavailability of metals and As and a decreasing trend in their concentrations, indicating an ongoing recovery process in DRB. These results are important to decision-making regarding the disaster and actions for environmental restoration.

Assessing the pollution and ecotoxicological status of the Iguaçu River, southern Brazil: A review.

The degradation of water resources available for human consumption is increasing with the continuous release of chemicals into aquatic environments and their inefficient removal in wastewater treatment. Several watersheds in Brazil, such as the Iguaçu River, are affected by multiple sources of pollution and lack information about their pollution status. The Iguaçu River basin (IRB) has great socioeconomic and environmental relevance to both the supply of water resources and its considerable hydroelectric potential, as well as for the high rate of endemism of its ichthyofauna. Also, the IRB is home to large conservation units, such as the Iguaçu National Park, recognized by UNESCO as a natural World Heritage Site. Thus, this article discusses the chemical pollution in the IRB approaching: (i) the main sources of pollution; (ii) the occurrence of inorganic and organic micropollutants; (iii) the available ecotoxicological data; and (iv) the socioeconomic impacts in three regions of the upper, middle, and lower IRB. Different studies have reported relevant levels of emerging contaminants, persistent organic pollutants, toxic metals, and polycyclic aromatic hydrocarbons detected in the water and sediment samples, especially in the upper IRB region, associated with domestic and industrial effluents. Additionally, significant concentrations of pesticides and toxic metals were also detected in the lower IRB, revealing that agricultural practices are also relevant sources of chemicals for this watershed. More recently, studies indicated an association between fish pathologies and the detection of micropollutants in the water and sediments in the IRB. The identification of the main sources of pollutants, associated with the distribution of hazardous chemicals in the IRB, and their potential effects on the biota, as described in this review, represent an important strategy to support water management by public authorities for reducing risks to the local endemic biodiversity and exposed human populations. Integr Environ Assess Manag 2024;00:1-26. © 2023 SETAC.

Linking MS1 and MS2 signals in positive and negative modes of LC-HRMS in untargeted metabolomics using the ROIMCR approach.

Data-independent acquisition (DIA) mode in liquid chromatography (LC) high-resolution mass spectrometry (HRMS) has emerged as a powerful strategy in untargeted metabolomics for detecting a broad range of metabolites. However, the use of this approach also represents a challenge in the analysis of the large datasets generated. The regions of interest (ROI) multivariate curve resolution (MCR) approach can help in the identification and characterization of unknown metabolites in their mixtures by linking their MS1 and MS2 DIA spectral signals. In this study, it is proposed for the first time the analysis of MS1 and MS2 DIA signals in positive and negative electrospray ionization modes simultaneously to increase the coverage of possible metabolites present in biological systems. In this work, this approach has been tested for the detection and identification of the amino acids present in a standard mixture solution and in fish embryo samples. The ROIMCR analysis allowed for the identification of all amino acids present in the analyzed mixtures in both positive and negative modes. The methodology allowed for the direct linking and correspondence between the MS signals in their different acquisition modes. Overall, this approach confirmed the advantages and possibilities of performing the proposed ROIMCR simultaneous analysis of mass spectrometry signals in their differing acquisition modes in untargeted metabolomics studies.

Sublethal effects of the herbicides atrazine and glyphosate at environmentally relevant concentrations on South American catfish (Rhamdia quelen) embryos.

The objective of this work was to evaluate the effects following exposure (96 h) of South American catfish (R. quelen) embryos to active ingredients and commercial formulations from atrazine and glyphosate, isolated and in mixtures, at environmentally relevant concentrations. While the survival rates were not affected, sublethal effects were evidenced after exposure. The most frequent deformities were fin damage and axial and thoracic damage. The mixture of active ingredients caused an increase in SOD and GST, differing from the treatment with the mixture of commercial formulations. The activity of AChE was significantly reduced following the treatment with the active ingredient atrazine and in the mixture of active ingredients. In general, herbicide mixtures were responsible for causing more toxic effects to R. quelen embryos. Therefore, these responses showed to be suitable biomarkers of herbicides' exposure, in addition to generating more environmentally relevant baseline data for re-stablishing safety levels of these substances in aquatic bodies.

From molecular endpoints to modeling longer-term effects in fish embryos exposed to the elutriate from Doce River.

Sediments represent a major sink and also a main source of contaminants to aquatic environments. An environmental disaster from a mining dam breakage in 2015 in South-East Brazil re-suspended complex mixtures of chemicals deposited in the sediment, spreading contaminants along the Doce River Basin (DRB) major river course. While high levels of contaminants in sediment were well described, toxicological effects in aquatic organisms were poorly investigated. Thus, the effects of these potentially toxic chemicals were assessed in the present study through different endpoints (biochemical to populational levels) in fish embryos of the South-American silver catfish exposed to elutriates from different sites of the DRB. Despite no significant mortality observed, our results showed that exposure to the elutriates, especially those from the closest site to the dam collapse, caused higher deformities rates and DNA damage in the fish embryos than in the control group. Multivariate analysis showed that these sublethal effects may be related to the high levels of metals introduced by mining activities, compromising long-term survival and reproduction success. In addition, it was possible to observe the influence of other sources of pollutants along the river. According to our data, the mathematical model simulated a significant impact on the population density at longer-term exposure, for the sites that showed the most prominent toxicity responses. The fish embryo toxicity test proved to be an effective assay to assess the ecotoxicological effects of the pollutants from a major river contaminated by a mining dam collapse and showed that the survival rate per se was not a suitable endpoint to assess the toxicity of the pollutants. As a consequence, we contributed to shed a light on a potential underestimated impact of pollutants in sediments of the DRB on the native organisms at distinct biological levels of organizations.

Ecotoxicity of losartan potassium in aquatic organisms of different trophic levels.

The intensive use of the antihypertensive losartan potassium (LOS) has culminated in its high occurrence in aquatic environments. However, insufficient studies had investigated its effects in non-target organisms. In this study, ecotoxicity of LOS was assessed in aquatic organisms from distinct trophic levels (Desmodesmus subspicatus, Daphnia magna, and Astyanax altiparanae). Genotoxicity was assessed by the comet assay in D. magna and A. altiparanae, and biochemical biomarkers for the fish. LOS was more toxic to D. subspicatus (EC50(72h) = 27.93 mg L-1) than D. magna (EC50 = 303.69 mg L-1). Subsequently, this drug showed to induce more DNA damage in D. magna than A. altiparanae, when exposed to 2.5 mg L-1. No significant stress responses were observed by the fish biomarkers, suggesting that higher trophic levels organisms are more tolerant to LOS toxicity. LOS showed relatively low toxic potential for a short period of exposure, but with different patterns of toxicity for the organisms from distinct trophic levels, contributing to further risk assessment of LOS.

Sublethal effects of triclosan and triclocarban at environmental concentrations in silver catfish (Rhamdia quelen) embryos.

Although banished in some countries, triclosan (TCS) and triclocarban (TCC) have been detected in surface waters in concentrations ranging from ng L-1 to µg L-1 and have shown to affect non-target organisms posing risk to aquatic ecosystems. However, the majority of the studies consider higher levels of these chemicals and single exposure effects to investigate their potential risks, rather than using environmentally relevant concentrations and their binary mixture. In this study, the toxicity of TCS and TCC, and their binary mixture was assessed in catfish embryos (Rhamdia quelen, a south American native species) exposed to environmental concentrations during 96 h. Organisms were evaluated through the endpoints of developmental abnormalities (spine, fin, facial/cranial and thorax), biochemical biomarkers related to oxidative stress responses: catalase (CAT), superoxide dismutase (SOD), glutathione-S-transferase (GST) activities, protein carbonylation (PCO) and neurotoxicity by acetylcholinesterase activity (AChE). The data showed that TCS caused fin abnormalities, decrease of SOD activity and increase of AChE activity in the catfish embryos of 96hpf. On the other hand, TCC and the binary mixture showed a higher abnormality index for the 96hpf embryos, and an induction of CAT and GST activities for the mixture treatment. The results obtained were able to show potential, but not severe, toxicity of TCS and TCC even in low concentrations and a short period of exposure. The relevance of studies approaching real scenarios of exposure should be reinforced, considering environmental concentrations of chemicals, interactions of contaminants in complex mixtures and the use of a native species such as R. quelen exposed during initial stages of development.

The applied indicators of water quality may underestimate the risk of chemical exposure to human population in reservoirs utilized for human supply-Southern Brazil.

The knowledge concerning associations between chronic chemical exposure and many disorders with complex etiology involving gene-environment interactions is increasing, and new methods must be developed to improve water quality monitoring. The complexity of chemical mixtures in polluted aquatic environments makes the evaluation of toxic potential in those sites difficult, but the use of biomarkers and bioindicators has been recognized as a reliable tool to assess risk of exposure to biota and also the human population. In order to evaluate the use of fish and biomarkers to assess toxic potential and bioavailability of chemicals in human-related hydric resources, an in situ experiment was accomplished in two water reservoirs designated for human supply, which were previously evaluated by the local environmental regulatory agency through a set of physical, chemical, and classical biological parameters. Molecular, biochemical, and morphological biomarkers were performed in caged Oreochromis niloticus kept for 6 months in the studied reservoirs to assess potentially useful biomarkers to evaluate the quality of water for human supply. Chemical analysis of toxic metals in liver and muscle and polycyclic aromatic hydrocarbons (PAHs) in bile was considered to assess the bioavailability of pollutants and highlight human activity impact. The reservoir previously classified by a governmental agency as less impacted presented more risk of exposure to biota. These results were supported by chemical analysis, vitellogenin expression, histopathological findings (gonads, liver, and gills), as well as indicators of neurotoxic effects and oxidative stress in liver. The inclusion of some biomarkers as parameters in regulatory monitoring programs in reservoirs designated for human supply is strongly suggested to evaluate the risks of exposure to the human population. Thus, a revision of the traditional biological and physicochemical analysis utilized to establish the conditions of water quality is necessary.

Mercury distribution in target organs and biochemical responses after subchronic and trophic exposure to neotropical fish Hoplias malabaricus.

In the present study, we investigated the mercury distribution, mercury bioaccumulation, and oxidative parameters in the Neotropical fish Hoplias malabaricus after trophic exposure. Forty-three individuals were distributed into three groups (two exposed and one control) and trophically exposed to fourteen doses of methylmercury each 5 days, totalizing the doses of 1.05 µg g⁻¹ (M1.05) and 10.5 µg g⁻¹ (M10.5 group). Autometallography technique revealed the presence of mercury in the intestinal epithelia, hepatocytes, and renal tubule cells. Mercury distribution was dose-dependent in the three organs: intestine, liver, and kidney. Reduced glutathione concentration, glutathione peroxidase, catalase, and glutathione S-transferase significantly decreased in the liver of M1.05, but glutathione reductase increased and lipid peroxidation levels were not altered. In the M10.5, most biomarkers were not altered; only catalase activity decreased. Hepatic and muscle mercury bioaccumulation was dose-dependent, but was not influenced by fish sex. The mercury localization and bioaccumulation corroborates some histopathological findings in this fish species (previously verified by Mela et al. in Ecotoxicol Environ Saf 68:426-435, 2007). However, the results of redox biomarkers did not explain histopathological findings previously reported in M10.5. Thus, fish accommodation to the stressor may reestablish antioxidant status at the highest dose, but not avoid cell injury.

Water quality assessment of the Tubarão River through chemical analysis and biomarkers in the Neotropical fish Geophagus brasiliensis.

The Tubarão River rises in Santa Catarina, Brazil, and has been historically affected by coal mining activities around its springhead. To evaluate its water conditions, an investigation regarding a possible decontamination gradient associated with the increased river flow toward the estuary, as well as the influence of seasonality over this gradient was performed through a series of biomarkers (vitellogenin, comet assay, lipid peroxidation, protein carbonylation, gluthatione, gluthatione S-transferase, acetylcholinesterase, light microscopy in liver, and scanning electron microscopy in gills) and chemical analysis (polycyclic aromatic hydrocarbons (PAHs) in bile and metal analysis in sediment) in the cichlid Geophagus brasiliensis. Two collections (summer and winter) were made in four distinct sites along the river, while sediments were sampled between those seasons. As expected, the contamination linked exclusively to mining activities was not observed, possibly due to punctual inputs of contaminants. The decontamination gradient was not observed, although seasonality seemed to have a critical role in the responses of biomarkers and availability of contaminants. In the summer, the fish presented higher histopathological damages and lower concentrations of PAHs, while in the winter they showed both higher genetic damage and accumulation of PAHs. The Tubarão suffers impacts from diverse activities, representing health risks for wild and human populations.

Monitoring water quality in reservoirs for human supply through multi-biomarker evaluation in tropical fish.

Paraíba do Sul River is located at a very densely inhabited region of Brazil crossing the three most industrialized states of the country (São Paulo, Minas Gerais and Rio de Janeiro states). As a result, industrial and farming residues as well as urban sewage are frequently disposed without appropriate treatment. The current study aimed at investigating the water quality in three reservoirs along the Paraíba do Sul River (Ilha dos Pombos, Santa Cecília and Santa Branca), through physiological, morphological, biochemical, and genetic biomarkers. The bioindicator chosen was the catfish Pimelodus maculatus, sampled during the dry (June 2008) and rainy (February 2009) seasons. Also, some water physicochemical parameters were analyzed from the sampling sites, but displayed no alterations according to the Brazilian Agency for Water Quality Legislation. Branchial carbonic anhydrase activity was inhibited in the dry season, while renal carbonic anhydrase activity was inhibited in the rainy season in the Santa Branca reservoir, indicating disturbance of osmoregulatory and acid-base regulation processes. Histopathological alterations were observed in the gills (neoplasic and tissue hyperplasia processes) and liver (necrosis), indicating serious damage to the functional integrity of these organs. A high incidence of melanomacrophage centers was observed in the liver, suggesting an intense immune response in all reservoirs. Acetylcholinesterase and catalase activity showed also differences corroborating some morphological results. Likewise, the induction of the micronucleus and DNA damage indicate genotoxicity, but mainly in the Santa Branca reservoir. Thus, the health status of P. maculatus warrants caution in the use of the water from the 3 reservoirs for direct human consumption, particularly after the accidental spill of endosulfan in November 2008, three months before the rainy season sampling.