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This study evaluated the effects of environmental contamination caused by pasture intensification and pasture-sugarcane conversion on oxidative stress, biotransformation, esterase enzymes, and development of Scinax fuscovarious and Physalaemus nattereri. Tadpoles were exposed in mesocosms allocated in three treatments: (1) untreated extensive pasture (EP); (2) intensive-pasture conversion (IP) (2,4-D herbicide + fertilizers); and (3) pasture-sugarcane conversion (SC) (fipronil + 2,4-D + fertilizers). After 7 days of exposure, IP reduced catalase (CAT) and increased malondialdehyde (MDA) levels in P. nattereri, while this treatment decreased glucose-6-phosphate dehydrogenase (G6PDH) and CAT activities in S. fuscovarious. SC decreased CAT, G6PDH, and glutathione S-transferase (GST) activities in P. nattereri. In S. fuscovarius, SC reduced G6PDH, acetylcholinesterase (AChE), and carboxylesterase (CbE) activities. MDA was raised in both tadpole species exposed to SC, evidencing oxidative stress. Integrated biomarker responses showed higher scores in both species exposed to SC. Our results warn that management practices currently applied to sugarcane cultivation in Brazil can negatively impact the functional responses of amphibians at natural systems. [ABSTRACT FROM AUTHOR]

Brazil is the largest producer of sugarcane and the world's top pesticide market. Therefore, environmental consequences are of concern. The aim of the present study was to evaluate the acute and chronic toxicity of pesticide formulations largely used in sugarcane crops: the herbicide DMA® 806 BR (a.i. 2,4-D) and the insecticide Regent® 800 WG (a.i. fipronil), isolated and in mixture, to the Neotropical cladoceran Ceriodaphnia silvestrii. Toxicity tests with the individual formulated products indicated 48h-EC50 values of 169 ± 18 mg a.i./L for 2,4-D and 3.9 ± 0.50 µg a.i./L for fipronil. In the chronic tests, the 8d-EC50 values for reproduction were 55 mg a.i./L (NOEC/LOEC: 50/60 mg a.i./L) and 1.6 µg a.i./L (NOEC/LOEC: 0.40/0.80 µg a.i./L) for 2,4-D and fipronil, respectively. A significant decrease in reproduction of C. silvestrii in all concentrations tested of fipronil, except at the lowest, was observed. Regarding 2,4-D, the organisms had total inhibition of reproduction in the two highest concentrations. Probably your energy reallocation was focused (trade-off) only on its survival. The acute pesticide mixture toxicity (immobility) revealed a dose level dependent deviation with antagonism at low and synergism at high concentrations. For chronic mixture (reproduction) toxicity, antagonism occurred as a result of the interaction of the pesticides. Based on our results and concentrations measured in Brazilian water bodies, fipronil represents ecological risks for causing direct toxic effects on C. silvestrii. These results are worrisome given that agricultural production is likely to increase in the coming years. [ABSTRACT FROM AUTHOR]

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Expansion of sugarcane crops may have contributed to the increased contamination of native habitats in Brazil. Several species of amphibians inhabit ponds formed in flooded farmlands, where pesticide concentrations are usually high. This study evaluated the ecotoxicological effects of the sugarcane pesticides fipronil and 2,4-D, as well as the fertilizer vinasse (isolated and mixed), on physiological responses of Leptodactylus fuscus and Lithobates catesbeianus tadpoles. In situ assays were conducted in mesocosms with concentrations based on the doses recommended by the manufacturer. Vinasse (1.3% dilution) caused 100% tadpoles' mortality immediately after its application. Fipronil and/or 2,4-D altered antioxidant and biotransformation responses, induced neurotoxicity and changed lipid contents in tadpoles. A multivariate approach indicated that the mixture of pesticides induced most of the sublethal effects in both tadpole species, in addition to the isolated fipronil in L. fuscus. Fipronil alone increased glucose-6-phosphate dehydrogenase (G6PDH) activity, decreased acetylcholinesterase (AChE) and total lipid contents, and altered some individual lipid classes (e.g., free fatty acids and acetone-mobile polar lipids) in L. fuscus. The interaction between fipronil and 2,4-D in this species were more evident for lipid contents, although enzymatic alterations in G6PDH, AChE and glutathione-S-transferase (GST) were also observed. In L. catesbeianus , the mixture of pesticides reduced triglycerides and total lipids, as well as increased GST and decreased AChE activities. The detoxifying enzyme carboxylesterase was reduced by 2,4-D (alone or in mixture) in both species. Isolated pesticides also modulated specific lipid classes, suggesting their disruptive action on energy metabolism of tadpoles. Our study showed that fipronil, 2,4-D, and vinasse, individually or mixed, can be harmful to amphibians during their larval phase, causing mortality or impairing their functional responses. [Display omitted] • Environmentally relevant dose of vinasse caused 100% tadpole mortality. • Fipronil and/or 2,4-D disrupted energy metabolism in tadpoles. • Neurotoxicity of fipronil and 2,4-D in tadpoles was indicated by AChE inhibitions. • Mixture of pesticides induced several sublethal effects in both tadpole species. [ABSTRACT FROM AUTHOR]

Increased use of pesticides in conventional agriculture implies potential risks to the environment. In aquatic ecosystems, benthic organisms may be exposed to pesticides via contaminated water and sediment, leading to several potential cascading effects on the food web. The aim of this study was to assess the functional implications of environmental realistic concentrations of the herbicide 2,4-D and the insecticide fipronil (alone and in combination) to the native tropical chironomid Chironomus sancticaroli. These two pesticides are widely applied to different crops and have frequently been detected (together) in surface water bodies in Brazil and elsewhere. Commercial products containing fipronil (Regent® 800WG) and 2,4-D (DMA® 806BR) were evaluated in 8-day toxicity tests for their effects on larval survival, growth (body length and biomass), head capsule width, development, and mentum deformities. Fipronil decreased the larval survival at the highest test concentration and the effective concentrations (EC) after eight days of exposure were: EC 10 = 0.48 µg L−1 (0.395–0.565), EC 20 = 1.06 µg L−1 (0.607–1.513), and EC 50 = 3.70 µg L−1 (1.664–5.736). All sublethal test concentrations of fipronil decreased the larval growth, causing reductions in biomass up to 72%. The two highest test concentrations of fipronil decreased the head capsule width and after exposure to 3.7 µg fipronil L−1, only half of the larvae reached the fourth instar. The incidence of deformities was increased by fipronil in a concentration dependent manner with an increase ranging from 23% to 75%. The highest test concentration of 2.4-D (426 µg L−1) decreased the head capsule width, but larval development was unaffected at all concentrations evaluated. In the mixture tests, antagonism was observed at lower fipronil concentrations and synergism at higher fipronil concentrations for growth. The incidence of deformities rose with increasing fipronil concentrations. The results showed that environmental realistic concentrations of fipronil may have serious ecological implications for C. sancticaroli populations and that a mixture with the herbicide 2,4-D can have synergistic effects, potentiating the risks to the aquatic ecosystem. • Fipronil affected survival, growth, and development rates of Chironomus sancticaroli. • Percentage of larvae with mentum deformity and worn teeth was increased by fipronil. • 2,4-D synergized the effects of fipronil at environmentally relevant concentrations. • More severe deformities were associated with higher concentrations of fipronil. [ABSTRACT FROM AUTHOR]

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. [Display omitted] • Dissipation of pesticides in mesocosm systems was influenced by treatments. • Degradation products were quantified in the mesocosm samples after the application. • Deposition of pesticides in the sediment was observed. • The risk assessment in a more representative environmental scenario was carried out. • Significant toxicological effects were observed in the different organisms. [ABSTRACT FROM AUTHOR]

Changes in land use have led to important modifications in aquatic ecosystems around the world. In Brazil, extensive pastures are being converted to sugarcane crops to avoid deforestation, while the remaining pastures are being intensified to compensate for the loss of area. In this study, the hypothesis that conventional soil management practices conducted on intensive pasture and sugarcane crops increase the availability of contaminants in freshwater was tested. Thirteen mesocosms embedded in extensive pasture (EP), intensive pasture (IP), and sugarcane crops (C) systems were monitored for 392 days. The monitoring included the measurement of in situ parameters (pH, dissolved oxygen, electrical conductivity, turbidity, and chlorophyll), nutrients (total nitrogen, nitrite, nitrate, ammonium ion, total phosphorus, total dissolved phosphorus, inorganic phosphorus, and silicate), and metals (aluminum, cadmium, copper, manganese, nickel, lead, potassium, and zinc). Soil management practices were performed in IP and C treatments at full-scale (tillage, application of fertilizers, vinasse and pesticides, and cattle pasture). The patterns observed for each treatment were obtained developing Principal Component Analysis over time. The mesocosms in the EP treatment did not experience large variations in water quality over time since no soil management was performed in this treatment. However, we found that fertilizer and vinasse application was the major precursor to the deterioration of water quality over time. After the first fertilizer application, we found eight and 16 times higher concentrations of total phosphorus, and seven and 45 times higher concentrations of total nitrogen in the IP and C treatments, respectively, in comparison to their concentration in the EP treatment. The application of vinasse in sugarcane crop increased water conductivity, potassium, and manganese concentrations in mesocosms. Dissolved oxygen and pH values decreased over time in all treatments. Overall, soil management practices resulted in greater deterioration of water quality in the sugarcane treatment than in the intensive pasture. [Display omitted] • Soil fertilization increases the concentrations of nitrogenous and phosphorous elements in freshwater. • Vinasse increases potassium and manganese concentrations in freshwater. • Conventional agriculture practices lead to deterioration of water quality over time. • Soil management in sugarcane crops resulted in a higher concentration of nutrients and metals than in intesive pastures. [ABSTRACT FROM AUTHOR]

• After contamination, contaminated treatments (except the herbicide alone) caused 100% mortality up to seven days post application (p.a.). • The mixture of the three compounds had an acute effect until the end of the sampling (75 days p.a.), making it impossible to evaluate the chronic effects of this treatment. • pH and conductivity were the chemical factors of big influence for in situ toxicity (both highly modified by the presence of vinasse). With the growing use of agrochemicals in Brazil, there is also a growing need for more realistic toxicity assessments that aid in understanding the potential risks of environmental-realistic agrochemical (mixture) exposures in the natural ecosystems. The aim of the present study was therefore to evaluate the lethal and sublethal effects of environmental realistic (single and mixture) concentrations of the pesticides DMA® 806 BR (active ingredient - a.i. 2,4-D) and Regent® 800 WG (a.i. fipronil) and sugarcane vinasse to the Neotropical cladoceran Ceriodaphnia silvestrii. This evaluation was carried out through lethal (survival), sublethal (reproduction and intrinsic rates of population increase - r) and post-exposure (feeding rate and also reproduction) tests conducted in situ and with water from mesocosms contaminated with the recommended doses of these compounds. The results showed high acute toxicity for treatments containing fipronil and vinasse when acting in isolation, with survival rates only returning to control values on the last sampling day (75 days post application). Reproduction of surviving cladocerans was reduced in all treatments until the end of the experiment and were potentiated effect in the mixture of the three test compounds. The intrinsic rates of population increase were reduced in all treatments except the single 2,4-D treatment. Post-exposure feeding rate and reproduction, however, were not impaired under the conditions analyzed. The results show the high toxicity of recommended doses of fipronil and vinasse (and especially their mixture) and the importance of evaluating the risks of agrochemical mixtures at environmental-realistic concentrations. [ABSTRACT FROM AUTHOR]

• Fipronil caused lethal effects in Hyalella meinerti even 89 days-post contamination. • 2,4-D, fipronil and vinasse decreased reproduction and behaviour of amphipods. • 2,4-D and fipronil had possible synergic effects in mixture exposures. • No survival of H. meinerti was recorded in the mixtures of pesticides and vinasse. • Low oxygen concentrations on in situ exposures increased pesticides and vinasse toxicities. Sugarcane crops management in Brazil includes the use of pesticides, as well as alternative organic fertilizers such as vinasse obtained from waste of the ethanol industry. In order to assess the effects of the environmental contamination generated by such sugarcane practices, this study was aimed to investigate the effects of the pesticides 2,4-Dichlorophenoxyacetic acid (2,4-D) and fipronil, as well as vinasse, on the survival, behavior, and reproduction of the native epibenthic macroinvertebrate Hyalella meinerti through in situ and laboratory experiments. In situ assays were conducted in mesocosms with six treatments, i.e. untreated control, 2,4-D, fipronil, and vinasse, the mixture of the two pesticides, and both pesticides mixed with vinasse. Survival, swimming behavior, and reproduction were evaluated over time post contamination, from 0−96 h (T1) and 7–14 days (T2) through in situ experiments and 30–44 days (T3) and 75–89 days (T4) post contamination by laboratory bioassays with mesocosm water. In the T1 period, survival of H. meinerti was registered only in controls and mesocosms treated with 2,4-D. In the T2 period, treatments containing fipronil and vinasse (isolated or in both mixture treatments) still caused 100 % of mortality. Survival was recorded only in 2,4-D and control treatments, whereas reproduction only occurred in the control. In the T3 period, no survival occurred to fipronil and both mixture treatments. Vinasse and 2,4-D decreased total reproduction in comparison to control. In the T4 period, amphipods survival was detected when exposed to fipronil and its mixture with 2,4-D. However, these same treatments decreased the amplexus rates and total reproduction, with synergism denoted for the pesticide mixture. The swimming activity of males, females, and couples was decreased in surviving organisms exposed to 2,4-D, fipronil, vinasse, and the mixture of pesticides along all experimental periods. Our study showed that the application of fipronil, 2,4-D, and vinasse isolated or mixed at realistic concentrations of actual sugarcane management practices may negatively impact functional responses of indigenous amphipods in natural aquatic systems. [ABSTRACT FROM AUTHOR]