Fish inhabiting rice field: Bioaccumulation, oxidative stress and neurotoxic effects after pesticides application

The present study aimed to evaluate the biological effects triggered by the application of a current-use mixture of pesticides (the herbicide glyphosate, the insecticide bifenthrin, BF, and the fungicides azoxystrobin, AZ, and cyproconazole, CYP) on two native fish (Markiana nigripinnis and Astyanax lacustris) inhabiting a rice field. We analyzed pesticide residues in water, sediment and fish samples 21 days before and after a fumigation event. Additionally, organismic indices, oxidative stress and neurotoxicity biomarkers in fish at both sampling periods were compared. After fumigation, glyphosate, BF, AZ and CYP were detected in water and sediment samples, being also bioaccumulated in both fish species. A decreasing condition factor in A. lacustris and a higher liver somatic index in M. nigripinnis were observed as well. Overall, results showed that, after the application of the pesticide mixture, antioxidant mechanisms failed to prevent oxidative damage in the liver and gills of M. nigripinnis. Meanwhile, A. lacustris showed a different response: an inhibition of the antioxidant defenses without tissue lipid oxidative damage. Furthermore, acetylcholinesterase activity after spraying was significantly reduced in brain and muscle tissues of A. lacustris and in the brain of M. nigripinnis. Our results show that current-use pesticides, like glyphosate, BF, AZ and CYP, pose health risks on native fish populations inhabiting rice fields.Fil: Rossi, Andrea Silvana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; ArgentinaFil: Fantón, Noelia Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; ArgentinaFil: Michlig, Melina Paola. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Repetti, María Rosa. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; ArgentinaFil: Cazenave, Jimena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; Argentin

¿Compartimos la vida con los plaguicidas?

Los plaguicidas presentan toxicidad no solo para la plaga que combaten sino también, en distintos grados, impactan con efectos negativos a la naturaleza y al hombre. Esta controversia suscita tensiones entre la producción y la sociedad, conduciendo a la necesidad de adoptar prácticas productivas más sustentables, menos agresivas con el ambiente y la salud de las poblaciones. También moviliza la implementación de legislaciones y acciones para mantener los riesgos bajo control. La preocupación que este escenario ha motivado en la ciencia de nuestro país y nuestra región, se manifiesta en los múltiples estudios, recomendaciones y acciones encaminadas a brindar mejoras y soluciones a todo nivel. Aquí seleccionamos algunos casos de estudio desarrolla- dos en nuestro centro, que ejemplifican sobre la ocurrencia de residuos de plaguicidas en ambientes y alimentos producidos en la provincia de Santa Fe.Fil: Repetti, María Rosa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química; ArgentinaFil: Michlig, Nicolás. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química; ArgentinaFil: Demonte, Luisina Delma. Universidad Nacional del Litoral. Facultad de Ingeniería Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Centro de Estudios Fotosintéticos y Bioquímicos. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Centro de Estudios Fotosintéticos y Bioquímicos; ArgentinaFil: Michlig, Melina Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química; ArgentinaFil: Beldomenico, Horacio Ramon. Universidad Nacional del Litoral. Facultad de Ingeniería Química; Argentin

Sublethal exposure to imidacloprid in commercial Apis mellifera colonies in early spring: performance of honey bees and insecticide transference between in-hive products

Honey bees have an important role in ecosystems as pollinators. However, in recent years, bee populations have declined, with habitat destruction, pesticide use, and climate change contributing to the decline. One of the most important risk factors is the use of neurotoxic pesticides, such as neonicotinoids. The aim of this work was to study the effects of imidacloprid in commercial Apis mellifera L. colonies artificially fed with syrups spiked with this insecticide and its possible transfer among in-hive products such as honey and larvae. For this purpose, 30 colonies were placed in the same apiary; once a week for 7 weeks in early spring, each colony was fed with 0.5 L of syrup with the following doses of imidacloprid: 0, 15, 30, 120, and 240 µg kg−1. The colony strength was evaluated by monitoring: the number of adult bees and brood combs, queenlessness, unhealthy colonies (by detection of Nosema spp. spores and European foulbrood), as well as pollen and honey storage. Worker bees, larvae, honey, and beeswax were sampled to evaluate imidacloprid transfer within the hive. Trends in the persistence of the compound showed that up to 60% of the parent (not metabolized) was stored in honey, and the absence of residues in the larvae suggests that they were not exposed. Another result showed a certain impact in the honey reserves and honey yield with a reduction of this resource in the colonies exposed to imidacloprid.EEA RafaelaFil: Michlig, Melina Paola. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos (PRINARC); ArgentinaFil: Michlig, Melina Paola. Consejo Nacional de Investigaciones Científicas Técnicas; ArgentinaFil: Pacini, Adriana Cecilia. Instituto Nacional de Tecnología Agropecuaria. Estación Experimental Agropecuaria Rafaela. Instituto de Investigación de la Cadena Láctea (IDICAL); ArgentinaFil: Pacini, Adriana Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Investigación de la Cadena Láctea (IDICAL); ArgentinaFil: Merke, Julieta. Instituto Nacional de Tecnología Agropecuaria. Estación Experimental Agropecuaria Rafaela. Instituto de Investigación de la Cadena Láctea (IDICAL); ArgentinaFil: Merke, Julieta. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Investigación de la Cadena Láctea (IDICAL); ArgentinaFil: Orellano, Emanuel. Instituto Nacional de Tecnología Agropecuaria. Estación Experimental Agropecuaria Rafaela. Instituto de Investigación de la Cadena Láctea (IDICAL); ArgentinaFil: Orellano, Emanuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Investigación de la Cadena Láctea (IDICAL); ArgentinaFil: Brasca, Melina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos (PRINARC); ArgentinaFil: Brasca, Melina. Consejo Nacional de Investigaciones Científicas Técnicas; ArgentinaFil: Repetti, María Rosa. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos (PRINARC); Argentin

Zooplankton shifts from headwater to lowland streams: Insights into the role of water quality to assist the protection and restoration of agricultural waterways

Despite the critical importance of zooplankton for many ecological processes, knowledge of its structure and distribution patterns in small streams subject to intensive land uses remains limited. Here we analysed changes in zooplankton community and composition in 10 sites located in streams from first-order to sixteenth-order, according to Shreve's classification, in a small catchment influenced by intensive agriculture. Using univariate and multivariate methods, we investigated the extent to which local scale environmental factors explained the spatial patterns of zooplankton community. We found that environmental conditions of headwaters differed markedly from those of lowland streams, especially with respect to nutrient levels, which were higher in the former than the latter. Zooplankton community was mainly composed by microphagous rotifers, and the overall species composition differed with the stream order. While zooplankton diversity and evenness increased with stream order and correlated negatively with nutrient level, zooplankton abundance and biomass showed the opposite trend. The mechanistic processes creating these patterns remain unknown but are likely linked to the effects of greater water mixing and dilution in lowland streams, as well as ecological processes such as predation and resource diversification. No clear pattern was found for presence or concentrations of pesticides in relation to the stream order. However, water quality seemed to be an important factor influencing zooplankton assemblages, which were significantly associated with pesticides and trophic state variables. Our findings suggest that agricultural pollution is impacting the zooplankton community, which may have implications for the food webs and overall health of the stream systems.Fil: Gutierrez, María Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas; ArgentinaFil: Mayora, Gisela Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; ArgentinaFil: Licursi, Magdalena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; ArgentinaFil: Michlig, Melina Paola. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; ArgentinaFil: Repetti, María Rosa. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; ArgentinaFil: Negro, Carlos Leandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas; Argentin

Determination of imidacloprid in beehive samples by UHPLC-MS/MS

Imidacloprid is a systemic insecticide belonging to the neonicotinoid family. It was the first neonicotinoid introduced in the mid-1990s, and since then, its use has grown rapidly to control pests in a variety of agricultural crops. Several studies have shown that neonicotinoids translocate to the nectar and pollen of treated plants, which represents a potential risk to pollinators. Therefore, an open-field feeding study was carried out. For this purpose, 30 beehives of Apis mellifera L. were installed in the same apiary. All colonies were in similar health and population conditions when assays were started. For seven weeks, colonies were fed with sucrose syrup with different concentrations of imidacloprid: 15, 30, 120 and 240 μg kg −1 . Thus, the assays were divided into four treatments and a witness (Control) with no added imidacloprid. To check the hives’ exposure to imidacloprid and evaluate its distribution, sampling of adult worker bees and larvae was performed before, during and after the whole feeding period (7 weeks). Furthermore, in the 15th week, honey and beeswax (honeycomb) samples were collected from the brood chamber and honey super of all hives. Analytical methodologies for sample preparation based on the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) procedure were optimized and validated. After soaking the bees and honey samples and the extraction using acetonitrile with MgSO 4 and NaCl salts, a dispersive solid-phase extraction (d-SPE) step with MgSO 4 , PSA and C18 was applied. Melted beeswax was subjected to an acetonitrile extraction, followed by freeze-out and d-SPE with PSA and C18. Extracts were evaluated in a UHPLC-MS/MS system. LOQ (μg kg −1 ) values were 0.25, 0.50 and 1 for honey, bees and beeswax, respectively. Satisfactory recovery performance was achieved with relative standard deviation ≤20%. Residue concentrations of imidacloprid in samples showed correlation with the doses supplied, indicating exposure of the beehives to the insecticide. Honey stored approximately 60% of the loaded imidacloprid through syrup feeding.Fil: Michlig, Melina Paola. Universidad Nacional del Litoral; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Merke, Julieta. Instituto Nacional de Tecnología Agropecuaria. Centro Regional Santa Fe. Estación Experimental Agropecuaria Rafaela; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Pacini, Adriana Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Instituto Nacional de Tecnología Agropecuaria. Centro Regional Buenos Aires; ArgentinaFil: Orellano, Ramiro Emanuel. Instituto Nacional de Tecnología Agropecuaria. Centro Regional Buenos Aires; ArgentinaFil: Beldomenico, Horacio Ramon. Universidad Nacional del Litoral. Facultad de Ingeniería Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Repetti, María Rosa. Universidad Nacional del Litoral. Facultad de Ingeniería Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Cocktails of pesticide residues in Prochilodus lineatus fish of the Salado River (South America): First record of high concentrations of polar herbicides

Muscle and viscera (gills-liver) of the fish Prochilodus lineatus were obtained from four sites of lower course of Salado river and one site at Santa Fe river near to its confluence with Salado river from Santa Fe (Argentina) between December 2021 and February 2022. Sediment samples were also obtained from the same sites. All samples were analyzed for pesticide residues following the QuEChERS method to quantify 136 compounds by UHPLC-ESI-MS/MS and GC-EI-MS/MS. Overall, muscle fish tissue showed very high concentrations (maximum concentrations detected) of the insecticide cypermethrin (204 μg/kg), polar herbicides (glyphosate; 187 μg/kg and its degradation product (aminomethylphosphonic acid) AMPA; 3116 μg/kg, and glufosinate-ammonium; 677 μg/kg), and the fungicide pyraclostrobin (50 μg/kg). In viscera samples, high values of cypermethrin (506 μg/kg), chlorpyrifos (78 μg/kg), and lambdacyhalothrin (73 μg/kg) were the main pesticides found. Mean residues concentrations detected among sites were not significantly different neither in muscle nor viscera of P. lineatus in most of the cases. Exceptionally, the southernmost studied site of the Lower Salado river showed significant differences in concentration of residues found in muscle, due to high concentrations of glyphosate and glufosinate-amonium (KW = 11.879 and KW = 13.013, respectively, P < 0.05). Other norther Lower Salado river site showed significant higher AMPA concentration in fish viscera than in the rest of the studied sites (KW = 12.86 P < 0.05). Some sediment samples showed low levels of herbicides such as glyphosate (24 μg/kg) and fungicides. However, the world highest levels of polar herbicides were recorded in fish muscle. The results of this study highlight the need for periodic monitoring due to the high concentration of pesticides and its potential risk in a very important commercial freshwater fish from Argentina, which is consumed locally and exported to other countries for human consumption.Fil: Lajmanovich, Rafael Carlos. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Saneamiento Ambiental. Cátedra de Ecotoxicología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Repetti, María Rosa. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; ArgentinaFil: Cuzziol Boccioni, Ana Paula. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Saneamiento Ambiental. Cátedra de Ecotoxicología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Michlig, Melina Paola. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Demonte, Luisina Delma. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Attademo, Andres Maximiliano. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Peltzer, Paola. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentin

Effect of crop sequence on water runoff and soil and herbicides losses

La evaluación del efecto de los sistemas agrícolas sobre el ambiente es fundamental para minimizar sus impactos negativos. Este estudio evalúa las pérdidas de agua, sedimentos y herbicidas por escurrimiento en distintas secuencias agrícolas, luego de una precipitación próxima a la pulverización. Fue realizado en parcelas de escurrimiento bajo lluvia natural, en INTA Paraná. Las secuencias de cultivo evaluadas fueron: soja continua (S), soja continua con trigo como cultivo de cobertura (CC-S) y trigo/soja (T/S) bajo siembra directa, las cuales fueron pulverizadas con glifosato y cletodim. Considerando el total de los datos analizados, los porcentajes perdidos en escurrimiento de glifosato y cletodim respecto a lo aplicado oscilaron entre 5,3-13,5% y 2,6-5,9%, respectivamente. Las pérdidas de suelo y AMPA (concentración) fueron mayores para S. Se resalta la importancia de las condiciones meteorológicas posteriores a las pulverizaciones para reducir el riesgo de aportes difusos de agroquímicos hacia cuerpos de agua.Assessing agricultural systems effects on the environment is essential to minimize any negative impact. This study evaluates water, sediments and herbicides losses by runoff on different crop sequences due to a precipitation event following spraying of herbicides. Measurements were conducted in natural-rainfall runoff plots at INTA Paraná. Crop sequences were: soybean monoculture (S), soybean monoculture with wheat as cover crop (CC-S), and both wheat / soybean as cash crops (T / S). All sequences were sprayed with glyphosate and clethodim before soybean´s sowing. Compared to the amount applied, the proportion of glyphosate and clethodim in runoff ranged between 5.3-13.5% and 2.6-5.9%, respectively. Losses of soil and AMPA (concentration) were greatest for S. The results highlight the importance of checking meteorological forecast conditions before spraying of herbicides to reduce nonpoint pollution of water bodies.Fil: Seehaus, Mariela Soledad. Instituto Nacional de Tecnología Agropecuaria; ArgentinaFil: Sasal, María Carolina. Instituto Nacional de Tecnología Agropecuaria; ArgentinaFil: Van Opstal, Natalia. Instituto Nacional de Tecnología Agropecuaria; ArgentinaFil: Gabioud, Emmanuel Adrián. Instituto Nacional de Tecnología Agropecuaria; ArgentinaFil: Wilson, Marcelo Germán. Instituto Nacional de Tecnología Agropecuaria; ArgentinaFil: Wingeyer, Ana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; ArgentinaFil: Michlig, Melina Paola. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; ArgentinaFil: Repetti, María Rosa. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Investigación y Análisis de Residuos y Contaminantes Químicos; Argentin

Microplastics and plastic additives as contaminants of emerging concern: A multi-biomarker approach using Rhinella arenarum tadpoles

Polyethylene microplastics (PE-MPs), a whitish thermoplastic polymer with numerous applications, is one of the materials most widely used in the industrial sector, whereas tetrabromobisphenol A (TBBPA) is a brominated flame retardant. The aim of this study was to analyze the effects of PE-MPs and TBBPA on Rhinella arenarum tadpoles at the laboratory scale. Tadpoles were chronically exposed (30 days) to four treatments: PE-MPs (60 mg L−1), TBBPA (10 µg L−1), their mixture (PE-MPs + TBBPA), and dechlorinated water as negative control (CO). Biomarkers of enzymatic activity (acetylcholinesterase, AChE; carboxylesterase, CbE; glutathione reductase, GR; and glutathione-S-transferase, GST), hepatic physiological alteration (alkaline phosphatase; ALP activity, and cholesterol; CHOL level), and endocrine disruption through thyroid hormone (T4) levels were assessed. In addition, intestine and liver were histomorphologically evaluated. AChE activity in tadpoles was significantly inhibited after exposure to PE-MPs and TBBPA with respect to CO. In addition, CbE, GR, and ALP activities showed higher values in the mixture of PE-MPs+  TBBPA treatment than in CO, whereas CHOL level was higher in TBBPA and PE-MPs+  TBBPA treatments than in CO. GST activity did not show significant differences between treatments and CO. T4 levels increased significantly in all treatments with respect to CO. The intestinal structure of tadpoles exposed to PE-MPs and PE-MPs+  TBBPA showed signs of mechanical damage. The intestinal wall of tadpoles under PE-MPs, TBBPA and PE-MPs+  TBBPA treatments was thicker than that of CO individuals. The analysis of liver histology demonstrated the hepatotoxicity caused by PE-MPs+  TBBPA. This study provides quantitative evidence of the harmful effects of PE-MPs, TBBPA and their mixture on enzymatic and hormonal activities, and histological evidence of intestinal wall hypertrophy and liver damage of R. arenarum tadpoles