Removal of acephate and methamidophos from water: Coagulation and adsorptive treatment approaches.

Pesticides has transformed the agricultural industry, primarily by enhancing productivity. However, the indiscriminate use of such compounds can adversely affect human health and disrupt ecosystem balance. Limited knowledge exists regarding the removal of these compounds from water, particularly for organophosphate pesticides when employing conventional treatment technologies. Therefore, this study aimed to assess the removal of acephate (ACE) and methamidophos (MET) - considered priority pesticides in Brazil - from waters with high and low turbidity during the clarification process carried out with aluminum sulfate (AS) and ferric chloride (FC), either alone or combined with powdered activated carbon (PAC) adsorption. All water samples were submitted to solid phase extraction (SPE C18 cartridges) prior to acephate and methamidophos analysis by HPLC MS/MS. The clarification process with either AS or FC coagulant did not efficiently remove acephate or methamidophos and maximum average removal (27 %) was observed with waters of high turbidity when using ferric chloride as coagulant. Addition of mineral PAC was also ineffective for removing both pesticides. However, the use of vegetable PAC (10 mg/L) resulted in better removal percentages, up to 80%, but only for methamidophos. The limited removal rates were attributed to the high hydrophilicity of acephate and methamidophos, along with their neutral charge at coagulation pH. These factors hinder the interaction of such organophosphorus pesticides with the flocs formed during coagulation as well as with PAC surface.

Coastal plastic pollution: A global perspective.

Coastal ecosystems have ecological importance worldwide and require control and prevention measures to mitigate human pollution. The objective of this study was to perform a systematic review to provide a comprehensive overview of the global issue of coastal plastic pollution. 689 articles were eligible for qualitative synthesis and 31 were considered for quantitative analysis. There was an exponential increase in articles addressing coastal plastic pollution over the past 50 years. Studies were mainly carried out on beaches, and plastic bottles were the most found item, followed by cigarette butts. Polyethylene was the predominant plastic polymer, and white microplastic fragments stood out. China published most articles on the topic and Brazil had the highest number of sites sampled. Meta-analysis had significant effect sizes based on the reported data. These findings carry significant implications for environmental policies, waste management practices, and targeted awareness campaigns aimed at mitigating plastic pollution.

Identification of metabolites generated in the biotransformation process by the Danio rerio (zebrafish) exposed to the fungicide tebuconazole.

Tebuconazole is a triazole fungicide widely used in agricultural crops for control of multiple fungal, mainly foliar and soil-borne diseases. Due to its intense use, this pesticide has been detected on aquatic matrices in different countries, which makes it necessary to identify metabolites capable to be used in its exposure monitoring. The aim of this work was to evaluate tebuconazole metabolites in zebrafish water tanks using liquid chromatography coupled to a high-resolution mass spectrometer (LCHRMS) to highlight analytical targets to monitor tebuconazole exposure in aquatic environments. Two Phase I metabolites, TEB-OH and TEB-COOH, and one Phase II metabolite, TEB-S, were identified. Target metabolomics pointed TEB-S as the most important metabolite for discrimination between treatment and negative control group and potential surrogate for detection and monitoring of tebuconazole exposure in aquatic environments. To the best of our knowledge, this is the first study to suggest the sulphation of tebuconazole (TEB-S) by zebrafish metabolism. Moreover, the use of water samples proved to be a promising approach when compared to the usual biological matrices (e.g. plasma) for evaluating the exposure of aquatic animals to tebuconazole because it is a clean and easy to obtain matrix. Water samples presented a higher concentration of metabolites when compared to plasma samples. The results suggest the applicability of this assay model for the identification of potential biomarkers for monitoring the presence of xenobiotics in water.

Occurrence and environmental risk assessment of 22 pesticides in Brazilian freshwaters.

Pesticide contamination in water resources is a global threat. Although usually found at low concentrations, pesticides raise considerable toxicological concerns, mainly when mixtures are considered. The occurrence of 22 pesticides (2,4 D, alachlor, aldicarb, aldrin, atrazine, carbendazim, carbofuran, chlordane, chlorpyrifos, DDT, diuron, glyphosate, lindane, mancozeb, methamidophos, metolachlor, molinate, profenofos, simazine, tebuconazole, terbufos, and trifluralin) was investigated, through consolidated database information, in surface freshwaters of Brazil. Moreover, scenarios of environmental risk assessment considering isolated compounds and mixtures were performed, as well as a meta-analytic approach for toxicity purposes. Pesticides in freshwater have been reported from 719 cities (12.9% of Brazilian cities), where 179 (3.2%) showed pesticide occurrence above the limit of detection or quantification. Considering cities with more than five quantified, 16 cities were prone to environmental risks considering individual risks. However, the number increased to 117 cities when the pesticide mixture was considered. The mixture risk was driven by atrazine, chlorpyrifos, and DDT. The national maximum acceptable concentrations (MAC) for nearly all pesticides are higher than the predicted no-effect concentration (PNEC) for the species evaluated, except aldrin. Our results show the need to consider mixtures in the environmental risk assessment to avoid underestimation and review MAC to protect aquatic ecosystems. The results presented here may guide the revision of the national environmental legislation to ensure the protection of Brazilian aquatic ecosystems.

Chironomus sancticaroli (Diptera: Chironomidae) in ecotoxicology: laboratory cultures and tests.

Chironomus sancticaroli is a tropical species, easy to grow and to maintain in laboratory cultures. It has a fast reproduction cycle, under adequate conditions, around 30 days, allowing it to have many generations per year, an important criterion for selecting a test organism in ecotoxicology. Its life stages include: eggs, four larval instars (one planktonic and three benthic), pupa and adult (midges) This study aimed to: (1) review the methods for C. sancticaroli cultivation and its use in ecotoxicological tests, (2) establish a laboratory culture of C. sancticaroli, presenting the difficulties and discussing the ways to overcome them. Early 4th instar larvae was the most used in acute studies, while the 1st instar larvae (early 1st instar) was the most used in chronic studies; 96 h and 28 days were the most frequent durations in acute and chronic studies, respectively. The most common endpoints evaluated were organisms' survival and development, and most of the ecotoxicological studies using C. sancticaroli were performed in laboratory. Most of the tested contaminants were pesticides and these had the most adverse effects on organisms. Most mesocosms with environmental contaminated samples did not show adverse effects on C. sancticaroli. Chronic and field studies as well as those testing the effects of the mixture contaminants on C. sancticaroli were still deficient. Keeping the laboratory environment and equipment effectively sanitized was important as well as maintaining stabilized conditions of temperature, photoperiod, physical, chemical and biological water quality in cultures.

Glyphosate concentrations in global freshwaters: are aquatic organisms at risk?

Glyphosate is the most used herbicide worldwide. Many studies have reported glyphosate risks to aquatic organisms of different trophic levels. Moreover, evidence suggests flaws in countries' legislation that may imply the non-protection of aquatic species exposed to glyphosate. Therefore, we aimed to investigate glyphosate concentrations in freshwater ecosystems worldwide based on a systematic literature review, to discuss the results considering each country's legislation, and to assess the relative tolerance and risk for aquatic species. Only articles providing in situ concentrations of glyphosate in freshwater systems were included in our study. In total, 73 articles met the inclusion criteria and were used in our analysis. The studies comprised freshwater ecosystems from 21 countries. Most countries evaluated (90%) did not have restrictive legislation for aquatic glyphosate concentrations, resulting in a potential non-protection of aquatic organisms. Glyphosate may pose a moderate to high risk in 95% of the countries investigated, reaching a maximum concentration of 105 mg L-1. Additionally, the risk analysis showed that glyphosate concentrations below 0.1 µg L-1 represent a low risk, whereas glyphosate concentrations above 1 µg L-1, which is below the limit established by some countries' legislation, represent a high risk to aquatic organisms. Therefore, we strongly recommend a revision of the countries' legislation for glyphosate concentration in freshwater systems.

Three-bestseller pesticides in Brazil: Freshwater concentrations and potential environmental risks.

Agricultural production in Brazil is favored by weather conditions and by the large amount of available land. Therefore, currently, Brazil is the second largest exporter of agricultural products globally. Pesticides are widely used in Brazilian crops due to their high efficiency, their low cost, and permissive legislation. However, pesticides tend to reach water resources threatening organisms and the water quality. Thereby, we aimed to review the surface freshwater concentrations of the three-bestseller pesticides in Brazil (glyphosate, 2,4D, and atrazine), and discuss the results with sales, legislation, toxicity and potential risks. For that, we performed a systematic review of quantitative studies of glyphosate, atrazine, and 2,4D in Brazilian freshwater and included monitoring data provided by the Brazilian Ministry of Health in our analysis. Finally, we calculated the risk assessment for the three pesticides. Only a few scientific studies reported concentrations of either of the three-bestseller pesticides in Brazilian freshwaters. Between 2009 and 2018, an increase in the sales of 2,4D, atrazine, and glyphosate was observed. It was not possible to evaluate the relation between concentrations and sales, due to limited number of studies, lack of standard criteria for sampling, individual environmental properties, and type of pesticide. Atrazine showed a higher toxicity compared to 2,4D and glyphosate. Regarding the environmental risks, 65%, 72%, and 94% of the Brazilian states had a medium to high risk to 2,4D, atrazine, and glyphosate, respectively. Finally, 80% of the Brazilian states evaluated showed a high environmental risk considering a mixture of the three pesticides. Although most of the environmental concentrations registered were below the allowed limits according to the Brazilian legislation, they are already enough to pose a high risk for the aquatic ecosystems. We, therefore, strongly recommend a revaluation of the maximum allowed values in the national surface freshwater Brazilian legislation.