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.

Irrigation with Water Contaminated by Sugarcane Pesticides and Vinasse Can Inhibit Seed Germination and Crops Initial Growth.

Sugarcane crops are dependent on chemicals for maintaining plantations. Therefore, environmental consequences concern adjacent areas that can be affected by contaminants in common use, including pesticides and vinasse (i.e., a by-product from the ethanol industry). This study aimed to evaluate phytotoxicity through two plant bioassays with water from mesocosms contaminated with the herbicide 2,4-D (447.0 µg L-1), the insecticide fipronil (63.5 µg L-1), and sugarcane vinasse (1.3%). First, the germination test (4 d) with Eruca sativa L. assessed water samples collected three times after the contamination (2 h, 14 d, and 30 d), considering germination, shoot, and root growth. The results from this bioassay indicated higher phytotoxicity for 2,4-D as it fully inhibited the shoot and root growth even in low concentrations (0.2 µg L-1). However, no significant effect was reported for fipronil and vinasse. Also, the 2,4-D effects drastically decreased due to an expressive concentration reduction (99.4% after 30 d in mixture with vinasse). Second, the irrigation test with Phaseolus vulgaris L. and Zea mays L. considered shoot and root growth and biomass under 21 days after plants emergence. The herbicide 2,4-D inhibited the initial growth of tested species, especially the roots (up to 45% inhibition). Furthermore, sugarcane vinasse caused harmful effects on plant growth (up to 31% inhibition). Therefore, our data showed that these contaminants could inhibit plant germination and initial growth under our tested conditions. These evaluations can endorse risk assessments and water management in sugarcane crops surrounding areas.

Acartia tonsa Dana 1849 as a Model Organism: Considerations on Acclimation in Ecotoxicological Assays.

The copepod Acartia tonsa was standardized as model organism in acute toxicity bioassays due to its key position in coastal food chains and high sensitivity. Once bioassays are performed according to a protocol their results may become tools for the protection of aquatic ecosystems. However, there are divergences in bioassays methods using A. tonsa. This study aimed to investigate: (i) the need for acclimation of A. tonsa collected from the environment for use in acute toxicological bioassays; and (ii) differences in sensitivity between copepods collected from the environment and laboratory-grown copepods. Laboratory-grown copepods are more sensitive to SDS than A. tonsa from the environment. The acclimation time of 30 h helped organisms to recover from stress of collection/handling and changing environment/conditions. Therefore, laboratory-grown copepods showed to be more sensitive than organisms from environment; and for ecotoxicological bioassays acclimating A. tonsa collected from the environment for 30 h can be adopted.

Functional responses of Hyalella meinerti after exposure to environmentally realistic concentrations of 2,4-D, fipronil, and vinasse (individually and in mixture).

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.

Could some procedures commonly used in bioassays with the copepod Acartia tonsa Dana 1849 distort results?

Many organizations have suggested the use of the Calanoid copepod Acartia tonsa in protocols for acute toxicity tests. Nevertheless, these protocols present some problems, such as using 60-180µm meshes to separate specific stages of A. tonsa or carrying out the tests using small volumes that reflect high densities of A. tonsa that do not occur in nature, which could lead to distorted results. In addition, ecotoxicological studies may use statistical approaches that are inadequate for the type of data being analysed. For these reasons, some methodological approaches for bioassays using A. tonsa need to be clarified and revised. In this study, we present information about (i) the retention of copepodite stages of A. tonsa on 180, 330 and 500µm net meshes; (ii) tested storage volumes of 1 organism per 5, 10 or 20mL in each test container (TC); and (iii) considerations about the statistics employed. The results demonstrated that a net mesh of 180µm is capable of retaining all copepodite stages (CI to CVI), contrasting with the recommendation of using a 180µm mesh to separate out adults only. Coarser meshes (330 and 500µm) can also retain different proportions of all copepodite stages, but cannot separate out one developmental stage only. Twenty-five millilitres of medium in an open TC, commonly employed in bioassays simulating densities of 1 organism 5mL-1, completely evaporated, and the results showed that the TCs need to be covered (e.g., PVC film) and filled with a minimum of 100mL of culture medium (simulating densities of 1 organism 20mL-1) to avoid evaporation and increases in salinity. The current use of ANOVA in ecotoxicological studies with proportions of surviving organisms should also be reconsidered since the data are discrete and have a binomial distribution; general linear models (GLMs) are considered more adequate. The information presented here suggests some adjustments that hopefully will enable the improvement of the procedures and methods employed in studies of acute toxicity using the copepod A. tonsa.