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Aquatic communities are increasingly exposed to complex mixtures of contaminants, mainly pesticides due to the impact of agricultural activity. The aim of this study was to evaluate the toxicity of an eight-pesticide cocktail on larvae of the South American common toad, Rinella arenarum. The cocktail represents a realistic mixture of insecticides (cypermethrin, chlorpyrifos and lambda-cyhalothrin), herbicides (glyphosate, glufosinate ammonium, prometryn and metolachlor), and a fungicide (pyraclostrobin) previously found in aquatic organisms (Prochilodus lineatus) from the Salado River Basin, an area with strong agricultural pressure. Computational simulations through the Density Functional Tight-Binding method indicated a strong spontaneous trend toward the formation of the cocktail, suggesting that it may act as a novel xenobiotic entity in the environment. The cocktail effects were evaluated in early-developing and premetamorphic larvae, at feasible concentrations found in real scenarios. The mixture led to high mortality and teratogenicity in early-developing larvae. Premetamorphic larvae showed endocrine disruption, oxidative stress, and impairments in detoxification and hepatic functioning. Neurotoxicity, genotoxicity, cardiotoxicity and high mortality under stress conditions were also observed in exposed larvae. This novel evaluation highlights the ecotoxicological risk for aquatic organisms exposed to complex mixtures and underscores the need to consider cocktail effects in studies regarding ecosystems health.

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The aim of this study was to formulate novel biomixtures with the ability to dissipate globally used pesticides. For this, an effective stabilization of two wastes, poultry litter and activated sewage sludge, was achieved through a combination of composting and vermicomposting, with the aid of the earthworm Eisenia fetida. Hence, two different mixtures were prepared combining the wastes with and without the addition of sewage sludge, and their physicochemical and microbiological characterization was examined during both processes. Earthworms reproduction was promoted by more than fourteen times the initial number of individuals introduced. This step made it possible to obtain substrates rich in organic matter, stable and non-pathogenic. The resulting vermicomposted substrates (V-C1 and V-C2) were used to produce two different biomixtures with wheat stubble (WS) and soil (S): SWSV-C1 and SWSV-C2, and they were tested for the remediation of a solution of five pesticides (2,4-D, cypermethrin, imidacloprid, acetochlor and dimethoate) in a 119-days assay. Comparisons were made with a WS-only biomixture (SWS) and a soil control. All biomixtures were more successful in dissipating the pesticides than soil; 2,4-D, dimethoate, and acetochlor degradation reached more than 99% in the three biomixtures after 28-56 days of assay. Biomixtures containing either vermicomposts acted faster than SWS, particularly for 2,4-D, dimethoate and cypermethrin. The total microbial activity was found to be higher in the two biomixtures containing vermicompost, which can be linked to their enhanced performance in the degradation of pesticides. Although the germination of Lactuca sativa proved that neither of the three spent biomixtures were phytotoxic at the end (germination index >60%), only SWSV-C1 and SWSV-C2 proved to be safe for the survival of E. fetida. This work confirms that vermicompost improves the success of biomixtures, not only in terms of pesticide removal, but also providing non-toxic spent biomixtures.

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Biobeds are presented as an alternative for good pesticide wastewater management on farms. This work proposes a new test for in-situ biomonitoring of pesticide detoxification in biobeds. It is based on the assessment of visually appreciable injuries to Eisenia fetida. The severity of the injury to each exposed individual is assessed from the morphological changes observed in comparison with the patterns established in seven categories and, an injury index is calculated. A linear relationship between the proposed injury index and the pesticide concentration was determined for each pesticide sprayed individually in the biomixture. The five pesticides used were atrazine, prometryn, clethodim, haloxyfop-P-methyl and dicamba. In addition, a multiple linear regression model (i.e., a multivariate response surface) was fitted, which showed a good generalization capacity. The sensitivity range of the injury test was tested from 0.01 to 630 mg kg-1 as the total pesticide concentration. This index is then used to monitor the detoxification of these pesticides in a biomixture (composed of wheat stubble, river waste, and soil, 50:25:25% by volume) over 210 days. The results are compared with standardized tests (Eisenia fetida avoidance test and Lactuca sativa seed germination test) carried out on the same biomixture. The results are also compared with data on the removal of pesticides. The injury test showed a better correlation with the removal of pesticides than the avoidance test and seed germination test. This simple and inexpensive test has proved to be useful for decontamination in-situ monitoring in biobeds.

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We experimentally assessed the impact of the application of herbicides and fertilizers derived from agricultural activity through the individual and simultaneous addition of glyphosate, atrazine, and nutrients (nitrogen 'N' and phosphorus 'P') on the biofilm community and their resilience when the experimental factors were removed. We hypothesize that i) the presence of agrochemicals negatively affects the biofilm community leading to the simplification of the community structure; ii) the individual or simultaneous addition of herbicides and nutrients produces differential responses in the biofilm; and iii) the degree of biofilm recovery differs according to the treatment applied. Environmentally relevant concentrations of glyphosate (0.7 mgL-1), atrazine (44 µgL-1), phosphorus (1 mg P L-1 [KH2PO4]), and nitrogen (3 mg N L-1[NaNO3]) were used. Chlorophyll a, ash-free dry weight, abundance of main biofilm groups and nutrient contents in biofilm were analyzed. At initial exposure time, all treatments were dominated by Cyanobacteria; through the exposure period, it was observed a progressive replacement by Bacillariophyceae. This replacement occurred on day 3 for the control and was differentially delayed in all herbicides and/or nutrient treatments in which the abundance of cyanobacteria remains significant yet in T5. A significant correlation was observed between the abundance of cyanobacteria and the concentration of atrazine, suggesting that this group is less sensitive than diatoms. The presence of agrochemicals exerted differential effects on the different algal groups. Herbicides contributed to phosphorus and nitrogen inputs. The most frequently observed interactions between experimental factors (nutrients and herbicides) was additivity excepting for species richness (antagonistic effect). In the final recovery time, no significant differences were found between the treatments and the control in most of the evaluated parameters, evincing the resilience of the community.

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The Espinal region (Entre Ríos, Argentina) has suffered land use changes caused by expansion of the agricultural frontier. This expansion has led to an increased use of pesticides. This study is aimed at better understanding the spatial distribution of pesticides in surface water of the Estacas stream, a representative basin of the Espinal region, associated with crop production. The location and proportion of area with soybean, maize, and wheat crops in each catchment area of the basin were estimated, and surface water samples were taken to perform a pesticide screening during a period of one year. Soybean represented approximately 71% of the total cultivated area of the basin, whereas maize and wheat accounted for 15% and 14%, respectively. The analysis of 125 analytes showed the presence of 19 pesticides. The pesticide load maps showed that atrazine was detected in an area of relatively low catchment compared to other pesticides as glyphosate, which is applied in all the agricultural fields of the basin. The load of metolachlor and S-metolachlor covered a large area of the basin. The highest recorded concentrations of these pesticides were 86 µg L-1 of atrazine, 24 µg L-1 of metolachlor, 19 µg L-1 of glyphosate, and 15 µg L-1 of S-metolachlor. The results allow better understanding the environmental distribution of pesticides associated with pest control in the crops of the basin studied, the doses and times of application, and the variation in the rainfall in the basin. This study provides relevant information about how aquatic ecosystems in agricultural basins receive the diffuse contribution of pesticides, representing potential sources of water pollution. Also, the results allow supporting the design of agricultural practices and politics to improve land-use planning for the development of sustainable basins.

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The effect of water activity (aW; 0.87, 0.90, 0.92, 0.94, 0.96, 0.98 and 0.99), temperature (15, 25, and 30 °C), incubation time (5, 10, 14, and 21 days), and their interactions on mycelial growth and aflatoxin production in a chickpea-based medium by three Aspergillus flavus strains isolated from chickpea grains in Argentina was evaluated. Maximum growth rates were obtained at the highest aW (0.99) and 30 °C, with growth decreasing as the aW of the medium was reduced. Maximum levels of aflatoxins were produced at 0.99 aW and 25 °C after 5 days of incubation for two strains, and at 25 °C and 0.96 aW after 21 days of incubation for the third strain. The aflatoxin concentrations varied considerably depending on the aW and temperature interactions assayed. Two-dimensional profiles of aW by temperature interactions were developed from these data to identify areas where conditions indicate a significant risk from aflatoxin accumulation on chickpea. This study provides useful baseline data on conditions representing a high and a low risk for contamination of chickpea by aflatoxins which is of greater concern because this pulse is destined mainly for human consumption.

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Land use changes have led to the degradation of multiple ecosystem services and affected the quality of aquatic ecosystems. The aims of this study were (i) to assess the expansion of the agricultural border over the native forest of an Argentinean stream basin and (ii) to characterize the surface water quality, considering physicochemical parameters, and pesticide concentrations. The agricultural frontier expansion was estimated through the analysis of satellite image coverage. Samples of surface water were taken bimonthly for 2 years. The native forest cover decreased from 72% in 1987 to 60% in 2017 due to the sustained increase in agricultural activities. In surface water, the concentrations of cations decreased: Na > Ca > K > Mg, whereas those of anions decreased: HCO3 > > Cl > SO4 > PO4. The 84 surface water samples analyzed revealed 25 pesticides, including herbicides (44%), insecticides (28%), and fungicides (28%). Herbicides were detected in more than 60% of the samples. 2,4-D, atrazine, cyproconazole, diazinon, glyphosate, AMPA, and metolachlor were detected in all the study sites and sometimes, 2,4-D, atrazine, dicamba, and metolachlor concentrations exceeded the guideline levels. The high sampling frequency of this study and the two annual cycles of crops in the basin enabled sensing of pesticide molecules and concentrations that had not been previously detected, indicating diffuse contamination. These findings signal an emergent challenge on the Espinal agro-ecosystem integrity due to changes in land use.

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An increase in the spatial variability of rainfall is expected due to climate change. This implies increasing rainfall rates during spring and summer in the Pampas region, Argentina, period of maximum application of agrochemicals, which might cause an increase in pesticides and nutrients carried to surface water systems, as runoff by rainfall is one of the main pathways for diffuse pollution. The crops phenological stage can also affect pesticide and nutrient runoff since the applied agrochemicals and soil cover differ in each stage. In this study, we assessed the influence of rainfall and seasonal crop practices on water quality (nutrient and pesticide concentrations) in three streams in the Pampas region, Argentina. Five sampling campaigns were performed before and after three rainfall events during two different seasons of crop practices (SCP1, SCP2) and the physicochemical characteristics of the stream and runoff water were analyzed. The pesticide concentrations in the streams presented a general increase immediately after the rainfall event. Water quality was also affected, as an increase in ammonium, soluble reactive phosphorus (SRP), biological oxygen demand (BOD), and turbidity was observed. The crops phenological stage influenced pesticide and nutrient types and concentrations detected in the streams. During SCP1, mainly characterized by chemical fallow and sowing of soybean and vegetative growth and flowering of corn, ammonium, SRP, BOD, turbidity, and some pesticides, such as metolachlor, showed significantly higher results than those found in SCP2 (grain filling and vegetative growth of soybean and corn sowing). The pesticide concentrations detected in runoff water depended mostly on the pesticide solubility, the lateral slope of the streams, and the percentage of woody riparian vegetation cover. The results obtained show the relevance of assessing the influence of rainfall and crops phenological stages on the dynamics of surface water and on pesticide and nutrient runoff for environmental monitoring.

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The effects of exposure to the herbicide Dicamba (DIC) on tadpoles of two amphibian species, Scinax nasicus and Elachistocleis bicolor, were assessed. Mortality and biochemical sublethal effects were evaluated using acetylcholinesterase (AChE), glutathione S-transferase (GST), glutathione reductase (GR), aspartate aminotransferase (AST), and alanine aminotransferase (ALT) activities and thyroid hormone (T4) levels. The LC50 value at 48h was 0.859 mg L-1 for S. nasicus and 0.221 mg L-1 for E. bicolor tadpoles. After exposure to sublethal DIC concentrations for 48 h, GST activity increased in S. nasicus but significantly decreased in E. bicolor with respect to controls. GR activity decreased only in S. nasicus at all the tested DIC concentrations. AChE activity was significantly inhibited in both S. nasicus and E. bicolor tadpoles at 48 h. DIC also caused significant changes in transamination, as evidenced by an increase in AST and ALT activities in both amphibian species. T4 levels were higher in DIC-treated tadpoles of both species than in controls. The DIC-induced biochemical alterations in glutathione system enzymes and transaminases indicate lesions in liver tissues and cellular function. Moreover, the observed AChE inhibition could lead to the accumulation of acetylcholine, excessively stimulating postsynaptic receptors, and the increase in T4 levels in both species may indicate an overactive thyroid. The commercial DIC formulation showed a high biotoxicity in the two amphibian native species after short-term exposure, controversially differing from the toxicity level indicated in the official fact sheet data. This fact highlights the need for an urgent re-categorization and reevaluation of DIC toxicity in native species.

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Argentina, together with the USA and Brazil, produces approximately 80% of the total worldwide glyphosate loadings. The development of a simplified ultra-high performance liquid chromatographic tandem mass spectrometric method (UHPLC-MS/MS) for the determination of glyphosate, aminomethylphosphonic acid (AMPA) and glufosinate in water is described, including studies of several alternatives of 9-fluorenylmethylchloroformate (FMOC-Cl) derivatization and pretreatment steps. The proposed method includes acidification and neutralization of a low sample volume (3 mL), 2 hours derivatization step, cleanup with dichloromethane, followed by reverse phase UHPLC-MS/MS determination of the analytes. Figures of merit were satisfactory in terms of linearity, selectivity, accuracy and intermediate precision (%REC 70-105% with RSD < 15%). Limits of quantification (LOQ) were suitable for monitoring purposes (0.6, 0.2, 0.1 µg/L for glyphosate, AMPA and glufosinate respectively). The validated methodology was applied for the analysis of livestock wells waters from 40 dairy farms located in the central region of Argentina. Glyphosate and AMPA were quantified in 15% and 53% of the analyzed samples with concentrations ranging from 0.6-11.3 µg/L and 0.2-6.5 µg/L respectively. Greater concentrations of glyphosate were also verified in waters from open-reservoir tanks, which are directly exposed to the farm environment. In these cases glyphosate and AMPA occurrence increased, being quantified in the 33% and 61% of the samples with values ranging 0.6-21.2 µg/L and 0.2-4.2 µg/L respectively. Also in this case glufosinate was found in 52% samples at

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The aim of this study was to evaluate the relationship between glyphosate and phosphate fertilizer application and their contribution to surface water runoff contamination. The study was performed in Aquic Argiudoll soil (Tezanos Pinto series). Four treatments were assessed on three dates of rainfall simulation after fertilizer and herbicide application. The soluble phosphorus in runoff water was determined by a colorimetric method. For the determination of glyphosate and aminomethylphosphonic acid (AMPA), a method based on fluorenylmethyloxycarbonyl (FMOC) group derivatization, solid phase extraction (SPE) purification, and ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was employed. The application of phosphorus fertilizer resulted in an increased loss of glyphosate by runoff after 1 day of application. These results suggest the need for further study to understand the interactions and to determine appropriate application timing with the goal of reducing the pollution risk by runoff.

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We examined the bioaccumulation of α- and ß-endosulfan and endosulfan sulfate in tissues from the crab Zilchiopsis collastinensis. There was more endosulfan accumulated in the hepatopancreas (from <2 to 467.8 ng g(-1)) than in the gonads (from <2 to 52.1 ng g(-1)) or muscles (<2 ng g(-1)). The endosulfan concentrations in the hepatopancreas decreased over time and with the endosulfan dilution (p < 0.05). In the gonads there was little bioaccumulation, which did not vary over time (p > 0.05). The hepatopancreas is a dynamic organ that is able to depurate itself, whereas the gonads act as a sink for pesticides.

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