Fate and toxicity of 2,4-D and fipronil in mesocosm systems.

2,4-D and fipronil are among Brazil's most used pesticides. The presence of these substances in surface waters is a concern for the aquatic ecosystem health. Thus, understanding the behavior of these substances under environmentally relevant conditions is essential for an effective risk assessment. This study aimed to determine the degradation profiles of 2,4-D and fipronil after controlled application in aquatic mesocosm systems under influencing factors such as environmental aspects and vinasse application, evaluate pesticide dissipation at the water-sediment interface, and perform an environmental risk assessment in water and sediment compartments. Mesocosm systems were divided into six different treatments, namely: control (C), vinasse application (V), 2,4-D application (D), fipronil application (F), mixture of 2,4-D and fipronil application (M), and mixture of 2,4-D and fipronil with vinasse application (MV). Pesticide application was performed according to typical Brazilian sugarcane management procedures, and the experimental systems were monitored for 150 days. Pesticide dissipation kinetics was modeled using first-order reaction models. The estimated half-life times of 2,4-D were 18.2 days for individual application, 50.2 days for combined application, and 9.6 days for combined application with vinasse. For fipronil, the respective half-life times were 11.7, 13.8, and 24.5 days. The dynamics of pesticides in surface waters resulted in the deposition of these compounds in the sediment. Also, fipronil transformation products fipronil-sulfide and fipronil-sulfone were quantified in water 21 days after pesticide application. Finally, performed risk assessments showed significant potential risk to environmental health, with RQ values for 2,4-D up to 1359 in freshwater and 98 in sediment, and RQ values for fipronil up to 22,078 in freshwater and 2582 in sediment.

Atrazine and its degradation products in drinking water source and supply: Risk assessment for environmental and human health in Campinas, Brazil.

Atrazine is a broad-spectrum herbicide widely used worldwide to control grassy and broadleaf weeds. Atrazine's popularity is attributable to its cost-effectiveness and reliable performance. Relatedly, it is also an important micropollutant with a potential negative impact on biodiversity and human health. Atrazine has long been regularly detected in several environmental compartments, and its widespread use has resulted in ubiquitous and unpreventable contamination. Among pesticides sold in Brazil, atrazine has remained among the top-ranked active ingredients for the last several years. Thus, this study aimed to evaluate the occurrence of atrazine and three degradation products (hydroxyatrazine, desisopropylatrazine, and desethylatrazine) in surface water (Capivari and Atibaia rivers) and treated water, monthly sampling from two drinking water treatment plants in Campinas (São Paulo, Brazil). An analytical method using solid-phase extraction (SPE) and liquid chromatography tandem mass spectrometry (LC-MS/MS) was developed to determine target compounds simultaneously. The method presented instrument quantification limits from 0.5 to 4.0 ng mL-1 and recovery values from 80 to 112%, with a maximum relative standard deviation of 6%. All analytes had a detection frequency of 100% from 2 to 2744 ng L-1. Statistical analysis showed no analyte removal after conventional water treatment. Also, the Capivari River showed greater analyte concentration than the Atibaia River. Performed risk assessments according to current Brazilian standards showed no human and environmental health risks. However, other risk assessment approaches may indicate potential risks, advocating for further research and ongoing surveillance.

Ecological risk assessment of pesticides in urban streams of the Brazilian Amazon.

The use of pesticides in households and peri-urban areas of the Amazon has increased notably during the last years. Yet, the presence of these contaminants in Amazonian freshwater ecosystems remains unexplored. Here, we assessed the exposure to 18 pesticides and 5 transformation products in the Amazon River and in the urban streams of Manaus, Santarém, Macapá, and Belém (Brazil). Pesticide concentrations were analyzed by liquid and gas chromatography methods. Ecological risks were assessed following a two-tiered approach. First, hazard quotients and an overall hazard index were calculated using toxicity data for standard test species of primary producers, invertebrates, and fish. Second, the pesticides showing moderate-to-high ecological risks in the first tier were evaluated using Species Sensitivity Distributions (SSDs). Our study shows that pesticides are widespread in urban and peri-urban areas of the Brazilian Amazon. The frequency of detection was higher in urban streams than in the Amazon River, with some samples taken in Manaus, Santarém, and Belém containing up to 8 compounds. Most pesticides were measured at relatively low concentrations (ng L-1), except for malathion, carbendazim and the bulk concentration of chlorpyrifos, which were monitored at concentrations above 100 ng L-1. Based on the first-tier assessment, we found moderate-to-high risks for freshwater invertebrates for malathion, chlorpyrifos, and chlorpyrifos-methyl, and moderate risks for malathion to fish. The risk assessment performed with SSDs indicated high risks of malathion and chlorpyrifos-methyl in urban areas, with up to 15% and 5% of invertebrate species potentially affected, respectively. The bulk concentrations of chlorpyrifos resulted in high risks in some urban areas (14-22% of species affected) and in areas of the main river (32-44%) impacted by agriculture. We conclude that pesticide residues may contribute to a biodiversity impact in the Amazon and should be further monitored in urban and peri-urban areas, particularly after heavy rainfall events.