Spatial distribution of pesticides in surface water of the Estacas stream (Argentine Espinal region) associated with crop production.

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.

Wastewater-Based Epidemiology: Detection of SARS-CoV-2 RNA in Different Stages of Domestic Wastewater Treatment in Santa Fe, Argentina.

The COVID-19 pandemic affected human life at every level. In this study, we analyzed genetic markers (N and ORF1ab, RNA genes) of SARS-CoV-2 in domestic wastewaters (DWW) in San Justo City (Santa Fe, Argentina), using reverse transcription-quantitative real-time PCR. Out of the 30 analyzed samples, 30% were positive for SARS-CoV-2 RNA. Of the total positive samples, 77% correspond to untreated DWW, 23% to pre-chlorination, and no SARS-CoV-2 RNA was registered at the post-chlorination sampling site. The viral loads of N and OFR1ab genes decreased significantly along the treatment process, and the increase in the number of viral copies of the N gene could anticipate, by 6 days, the number of clinical cases in the population. The concentration of chlorine recommended by the WHO (≥ 0.5 mg L-1 after at least 30 min of contact time at pH 8.0) successfully removed SARS-CoV-2 RNA from DWW. The efficiency of wastewater-based epidemiology (WBE) confirms the need to control and increase DWW treatment systems on a regional and global scale. This work could contribute to building a network for WBE to monitor SARS-CoV-2 in wastewaters during the pandemic waves and the epidemic remission phase. Supplementary Information: The online version contains supplementary material available at 10.1007/s11270-022-05772-w.

Quality of the surface water of a basin affected by the expansion of the agricultural frontier over the native forest in the Argentine Espinal region.

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.

Effect of rainfall runoff from agricultural areas and seasonal crop practices on zooplankton community in Pampean streams, Argentina.

Extreme climatic events are considered one of the main consequences of climate change. In the Pampas region, Argentina, an intensification of rainfall is expected during the periods of maximum agrochemical application. This study assesses the main factors determining the zooplankton community attributes in three streams belonging to the agricultural Pampas region, Argentina, and the effect of rainfall and seasonal crop practices on the zooplankton community composition. Sampling campaigns were performed before and after three rainfall events during two seasonal crop practices: (1) soybean chemical fallow-sowing and corn vegetative growth-flowering, (2) soybean vegetative growth-grain filling and corn sowing. The runoff in agricultural areas affected the zooplankton community attributes and composition. The biological oxygen demand, turbidity, and conductivity were the main water quality variables affecting the zooplankton community attributes. The increase of these variables after rainfall or during pre-emergence crop practices favoured the zooplankton groups most tolerant to eutrophication such as Bdelloidea, Chydoridae, Moinidae, and Sididae. Factors such as rainfall and seasonal crop practices must be considered in environmental monitoring design.

Influence of rainfall and seasonal crop practices on nutrient and pesticide runoff from soybean dominated agricultural areas in Pampean streams, Argentina.

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.

Synergy between glyphosate and cypermethrin formulations on zooplankton: evidences from a single-specie test and a community mesocosm experiment.

Agrochemicals can reach freshwater bodies by drift, leaching, or runoff, where they constitute complex mixtures. Given that glyphosate and cypermethrin are within the most worldwide used pesticides, they are likely to co-occur in freshwater bodies. The aim of this study was to analyze the interaction between glyphosate and cypermethrin formulations on the cladoceran Ceriodaphnia dubia (Richard 1894) through an acute toxicity test and on a zooplankton assemblage through a mesocosm (30 L) experiment. The 24-h LC50 of both isolated pesticides and their equitoxic mixture was obtained for C. dubia. The mesocosm was performed by exposing a zooplankton assemblage to both pesticides isolated and in combination. The acute toxicity of the equitoxic mixture in C. dubia was 3 and 4 times higher than the isolated toxicity of glyphosate and cypermethrin, respectively. The total toxic units of the mixture were 0.53, indicating a synergistic interaction. In the mesocosm experiment, both pesticides also interacted causing a synergistic negative effect in Cladocera and Copepoda abundances. No interactions between pesticides were found for Rotifera; therefore, the mixture effect was considered additive. It is suggested to continue analyzing pesticide mixture effects on the basis of complementary scales of analysis to reach more environmentally relevant information.

Second-, third- and fourth-generation quinolones: Ecotoxicity effects on Daphnia and Ceriodaphnia species.

We conducted the first complete toxicological study of six quinolones, including acute, chronic, and recovery assays on Daphnia magna and Ceriodaphnia dubia. The assayed quinolones were second-generation ciprofloxacin (CIP), norfloxacin (NOR), enrofloxacin (ENR), and marbofloxacin (MAR); third-generation levofloxacin (LEV), and fourth-generation moxifloxacin (MOX). The median lethal concentrations (LC50) obtained for both species by acute ecotoxicity assay ranged from 14 to 73 mg L-1 and from 3 to 23 mg L-1 at 48 and 72 h, respectively; while the median effective concentration (EC50) ranged from 4 to 28 mg L-1 in the chronic ecotoxicity assays. C. dubia surviving the chronic exposure assay was monitored in recovery assays free of quinolones. A fluorometric method was used to confirm that there was no significant loss of quinolone concentrations during the acute assays. We also used this method to show that quinolone concentrations fell below 80% of the nominal value after 9-11 d if exposure solutions were not renewed. This study on the ecotoxicological and chemical behavior of quinolones in two cladoceran species fills a data gap about how these emerging contaminants affect nontarget aquatic organisms and how long they persist in the environment.

How can interspecific interactions in freshwater benthic macroinvertebrates modify trace element availability from sediment?

This study aimed to assess how bioturbation by freshwater benthic macroinvertebrates with different biological traits alone or in combination could modify trace elements (TE) fate between sediment and water, and if water TE concentration and animal TE content impair their body stores. Three macroinvertebrate species were exposed to TE contaminated sediment for 7 days: the omnivorous Echinogammarus berilloni (Amphipoda), the sediment feeding Tubifex tubifex (Oligochaeta) and the filter feeding Pisidium sp. (Bivalvia). Treatments were one without invertebrates (control), two with amphipods or mussels alone, and the combinations amphipod-mussel, and amphipod-mussel-worms. Water TE concentration increased significantly in 2 or 3 species mesocosms, concerning mainly Rare Earth Elements, Cr, U and Pb, known to be associated to the colloidal phase. By contrast, water soluble TE were not affected by animals. For both, amphipods and mussels, TE body content increased with the number of coexisting species. For amphipods, this increase concerned both, soluble and colloid-associated TE, possibly due to intense contact and feeding from sediment and predation on tubificids. TE bioaccumulation in mussel was less important and characterized by soluble TE, with water filtration as most plausible uptake route. Protein, triglyceride and Whole Body Energy Budget increased in amphipods with the number of coexisting species (probably by feeding on mussels' feces and tubificids) whereas triglycerides declined in mussels (presumably filtration was disturbed by amphipods). This study highlights interspecific interactions as key drivers explaining both: TE bioturbation, depending on their water solubility or colloidal association, and the exposure/contamination of species through another species activity.

Effect of metals on Daphnia magna and cladocerans representatives of the Argentinean fluvial littoral.

Chronic toxicity tests were conducted to assess the effect of Cu, Cr and Pb on Moinodaphnia macleayi and Ceriodaphnia dubia -two cladoceran species from the Argentinian Fluvial Littoral Zone (AFLZ)- and Daphnia magna -an holarctic species-. The specimens were exposed to three concentrations of each metal. As endpoints, the number of living and dead organisms, molts, neonates released, and the age of first reproduction were recorded. Chronic assays showed that Cu significantly affected the analyzed life history traits in the three species. The lowest Pb and Cr concentrations did not affect survival, molting or fecundity in D. magna. Conversely, in M. macleayi and C. dubia, survival, molting and fecundity showed highly significant differences in all the concentrations tested compared to control assay. The present study stresses the importance of using biological parameters as bioindicators, as well as the study species from the Southern Hemisphere to assess metal pollution.

Infodisruptions in predator-prey interactions: xenobiotics alter microcrustaceans responses to fish infochemicals.

Chemical communication is one of the most important ecological phenomena promoting the maintenance of ecosystem dynamics. In predator-prey interactions, mediation signals allow prey to detect their predators and can be crucial in the process of avoiding them. Since organisms in many natural waterbodies are often subjected to anthropogenic stressors, it is hypothesised that low concentrations of xenobiotic compounds can disturb this chemical communication, acting as infodisruptors. This study analyzes whether two anthropogenic pollutants (chromium and an insecticide) interfere in two freshwater predator-prey interactions, by altering the behavioural responses of a cladoceran and a copepod species to a fish chemical cue. The concentrations tested were lower than those considered innocuous under international water quality guidelines, and two types of behaviour were analysed: escape ability and depth selection in an artificial water column. Both species tested demonstrated a higher escape ability when exposed to the cue than when they were not exposed. Xenobiotics modified the responses of the copepod in opposite ways: chromium inhibited this behaviour and the insecticide prompted a higher than expected level of escape ability. The depth selection patterns were different between N. conifer and C. dubia. Fish kairomones did not modify them, however chromium and the insecticide caused important alterations in both cases. Such disruptions would be detrimental to the organisms' life cycle trajectories, which, in natural systems, would cause longterm damage in trophic structure and in evolutionary processes.

Microcrustaceans escape behavior as an early bioindicator of copper, chromium and endosulfan toxicity.

The purpose of this work was to experimentally analyze the impact of copper, chromium and a commercial pesticide with endosulfan on the escape behavior of two copepods (Notodiaptomus conifer, Argyrodiaptomus falcifer) and three cladocerans (Daphnia magna, Pseudosida variabilis and Ceriodaphnia dubia). The experimental assays were carried out using a novel hydraulic devise designed to mimic three-speed predator capture behavior. Two concentrations, one "high" and one "low", were employed and the exposure time was 15 (±5) minutes. With two exceptions, the species exposed to heavy metals manifested higher ability to escape than controls. Both concentrations of the pesticide reduced the escape ability of cladocerans but copepods responded, in general, in a similar manner as for heavy metals. The immediate apparent advantage of low and early toxic effects is discussed and the high sensitivity of the escape behavior suggests that it could be a complementary endpoint to be used in future ecotoxicological tests.

Exposure to sublethal chromium and endosulfan alter the diel vertical migration (DVM) in freshwater zooplankton crustaceans.

Among zooplankton behaviors, diel migrations constitute one of the most effective predator avoidance strategy and confer metabolic and demographic advantages. We aim to examine whether sublethal concentrations of two widespread pollutants (a pesticide with endosulfan and chromium as potassium dichromate) alter the depth selection, vertical migration and grouping of five freshwater species: Argyrodiaptomus falcifer, Notodiaptomus conifer, Pseudosida variabilis, Ceriodaphnia dubia and Daphnia magna. In a series of experimental assays, performed with 150 cm length transparent tubes, we analyzed the ascents and descents movements through periods of 24 h. Among controls, the copepods showed a tendency to remain closest to the surface, however, N. conifer registered a downward movement of 18.14 cm between 06:00 and 12:00. The cladoceran P. variabilis occupied the deeper position (85 cm), C. dubia showed a tendency to hike to the surface at 06:00 (57.7 cm) descending to lower levels at 18:00. D. magna showed a constant movement of ascent between 00:00 and 18:00, making an average travel of 29.4 cm. When subjected to pollutants, these behaviors were altered. It is hypothesized that a reduction in swimming activity and disorientation would be the main cause of such alterations. The high sensitivity of this endpoint sugests it to be adecuate as a complement in future standard toxicity tests.

Efecto de los metales sobre microcrustáceos de agua dulce. Avances metodológicos y potencialidad de cladóceros y copépodos como organismos test / Effects of metals on freshwater microcrustaceans. Metodological advances and potentiality of cladocerans and copepods as test organisms

El incremento de los metales en los cuerpos de agua dulce a causa de las actividades antropogénicas genera importantes alteraciones sobre la biota. Esta revisión analiza los efectos adversos de varios metales de relevancia ecotoxicológica sobre los microcrustáceos zooplanctónicos (cladóceros y copépodos), los avances experimentales en esta línea y las ventajas de cada grupo como organismos test. En general, la necesidad de obtener indicadores más sensibles y representativos que los tradicionales, promovió lineamientos hacia estudios subcrónicos, interspecíficos y multigeneracionales. Por otra parte, la tendencia actual hacia el estudio de mezclas de sustancias y los efectos indirectos permite adquirir una visión más integral del problema. El impacto sobre las poblaciones es muy variable, dependiendo de la naturaleza del metal, las características del medio, el tiempo de exposición, las condiciones de cultivo y aspectos genéticos. Sin embargo, la mayoría de los trabajos se centran en pocas especies, dejando vacancias en el conocimiento de las representantes de cada región particular. Si bien algunos atributos de los cladóceros y copépodos como el tamaño, la morfología y el rol ecológico los tornan buenos indicadores, las diferencias en el desarrollo, reproducción y estrategias de perpetuación confieren ventajas a un grupo sobre otro.

The increase of metals in fresh water systems due to anthropogenic activities cause important alterations on the biota. The present review analyze the adverse effects of various metals of ecotoxicological relevance on microcrustaceans zooplankton species (cladocerans and copepods), the experimental advances and the advantages of each group as test organisms. In general, the need to obtain more sensitive and representative indicators than the tradicional ones leads to subchronic, interespecific and multigenerational studies. Additionally, the analysis of mixtures as well as their indirect effects allows to acquire more integral knowledges of the impact of contaminants. The toxic effects are different, depending on the nature of metals, the physicochemical characteristics of the water, exposutre time and genetic traits. However, most works are focused on few species, leading vacant areas on the knowledge of the representatives of every particular region. Despite some cladocerans and copepods atributes make them good bioindicators (size, morphology and ecological role), differences of development, reproduction and perpetuation strategies bring advantages to one group on another.

Efectos de la contaminación por metales pesados sobre la comunidad bentónica de la cuenca del arroyo Cululú (río salado del norte Argentina) / Effects of heavy metals contamination on the benthic community in the arroyo Cululú basin (río salado del norte Argentina)

Se determinó la incidencia de los efluentes industriales con alto contenido de metales pesados en la calidad físico-química de los sedimentos de fondo de la cuenca del Arroyo Cululú, a través del análisis de la estructura de la comunidad macrozoobentónica. En tres muestreos estacionales se estudiaron seis ambientes de la cuenca del río Salado del Norte en su tramo inferior, en los que se realizaron análisis físicos y químicos de sedimentos de fondo, análisis de densidad y riqueza de organismos, diversidad de especies y afinidad entre comunidades. Pudieron establecerse relaciones entre la estructura y composición de la comunidad macrozoobentónica, las variables ambientales estudiadas y la concentración de metales pesados (Cr T, Cr VI, Cu, Cd y Pb) en sedimentos de fondo. La comunidad del ambiente no contaminado presentó mayor densidad y un ensamble de especies diferente al de los otros ambientes. Los metales pesados actuaron como factores perturbadores, determinando que la comunidad macrozoobentónica de sitios contaminados sea diferente a la del sitio de referencia

Efectos del efluente de curtiembre sobre ceriodaphnia dubia crustacea cladocera en condiciones experimentales / Effects of tannery waste water on ceriodaphnia dubia crustacea cladocera under experimental conditions

El objetivo de este estudio es evaluar empíricamente los efectos de distintas concentraciones de efluente de curtiembre con alto contenido de Cr y sulfuro sobre los atributos de historia de vida y parámetros poblacionales de ceriodaphnia dubia Richard 1894 (crustaceas, clodocera) en bioensayos crónicos. Se encontró que el efluente afectó significativamente a la sobrevivencia, la fecundidad, número de mudas y camadas de C. dubia. Se incrementó el tiempo intermudas y se retrasó la edad de la primera reproducción con el aumento en la concentración de efluente, no produciendo crías en concentraciones >1ml.l-¹. R0 fue <1 en concentraciones >0,6ml.l de efluente, lo que indica un umbral máximo de concentración para el establecimiento y mantenimiento de poblaciones zooplanctónicas en el ambiente. Se destaca la importancia de incrementar el empleo de especies de muy amplia distribución así como el uso de parámetros poblacionales integrados en estudios ecotoxicológicos. Se discute la importancia de desarrollar bioensayos sometiendo a los organismos de prueba a la acción de efluentes complejos por el mayor realismo que aportan

Respuesta de una comunidad zooplanctónica de agua dulce a la aplicación de cromo en clausuras experimentales / Reponse of a zooplanktonic freshwater community to chromium application in experimental enclosures

Se evaluó el impacto del cromo, muy utilizado en Argentina en industrias de curtiembre, sobre la estructura del zooplancton del río Paraná mediante un experimento en estanques de 150 litros, durante 5 semanas, con un control y 4 tratamientos (2 aplicaciones de 0,1; 0,4; 0,7 y 1,0mg.l-1 K2Cr2O7), todos replicados. Se evaluó diversidad riqueza de especies y densidad del zooplancton, temperatura, pH, conductividad, O2 disuelto, Cr total y Cr (VI), y la capacidad de repoblamiento. Diferencias en la densidad de zoopláncteres entre tratamiento fueron evaluados con ANOVA de medidas repetidas. El Cr tuvo un importante efecto negativo sobre el zooplancton. La densidad disminuyó significativamente con el incremento en la concentración de Cr, así como la riqueza de especies y diversidad específica en la mayoría de los tratamientos. El repoblamiento sólo ocurrió en el tanque con la concentración menor. Se discuten las ventajas adaptativas de organismos con reproducción sexual, y se analiza la posible acción del Cr por vía trófica y su efecto sobre la estructura de tamaño de la comunidad. Se destaca la importancia de investigar el efecto de bajos niveles de Cr sobre comunidades de ecosistemas perturbados