Human exposure and mass balance distribution during procymidone application in horticultural greenhouses

The purpose of this study was to analyze the impact of procymidone application in periurban horticultural greenhouses, especially on workers (applicators and assistants) and soil and plastic mulching, when mechanically pressurized application systems were employed. The mean Potential Dermal Exposure (PDE) was measured using the Whole Body Dosimetry technique. The PDE for the applicators was 188 mL h−1 ± 103 mL h−1, and 14.7 mL h−1 ± 6.3 mL h−1 for the assistants. In the first case, the most exposed body sections were the upper right and left (46.8 mL h−1 ± 23.4 mL h−1; 47.0 mL h−1 ± 23.5 mL h−1) and lower (20.8 mL h−1 ± 10.4 mL h−1; 17.3 mL h−1 ± 8.7 mL h−1) legs, while in the case of assistants, hands and legs were the most impacted limbs. Regarding the Margin of Safety (MOS) during the mix and load stage, two of three pesticide preparations resulted unsafe, while for the applicators, six of six spraying operations were unsafe. For the assistants, five of five operations were safe, but three of them were close to the safety limit. Procymidone distribution between drift (0.03% ± 0.07 %), applicator (0.20% ± 0.15 %), polyethylene mulching (8.5% ± 4.5 %) and soil (3.0% ± 1.1 %) was determined with respect to the total pesticide applied. Procymidone soil impact was also evaluated using Eisenia andrei behavioral tests, finding positive correlations between procymidone application and avoidance and reproduction tests.Fil: Fitó Friedrichs, Gretel Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; ArgentinaFil: Berenstein, Giselle Anahí. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; ArgentinaFil: Nasello, María Soledad. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; ArgentinaFil: Dutra Alcoba, Yohana Yisel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; ArgentinaFil: Hughes, Enrique Alejandro. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; ArgentinaFil: Basack, Silvana Beatriz. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; ArgentinaFil: Montserrat, Javier Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; Argentin

Combined effects of technical grade fenitrothion, humic acids and particulate matter on cholinesterase activity in freshwater invertebrates

Purpose: The relative sensitivity of two freshwater invertebrate organisms to the organophosphorus insecticide fenitrothion was assessed by measuring cholinesterase (ChE) activity, a wellknown biomarker of both exposure and effect to organophosphorus pesticides. The influence of different concentrations of humic acids (HAs) and particulate matter on fenitrothion bioavailability was assessed in the more sensitive species. Materials and methods: The selected invertebrates were the dwelling feeding oligochaete Lumbriculus variegatus and the pulmonate gastropod Biomphalaria glabrata. Acute 48- h bioassays were performed exposing organisms to different fenitrothion concentrations. The concentrations that induced 50 % inhibition of enzyme activity (EC50) were calculated. Fenitrothion bioavailability was investigated using different concentrations of commercial HA or particulate matter. Sand and a diverse selection of chromatographic resins that have been proposed as analogues of natural sediments were selected. For these experiments, animals were exposed to a fenitrothion value similar to the EC50. Results and discussion: The 48-h EC50 values were 12±2 and 23±3 μgl−1 for L. variegatus and B. glabrata, respectively. Depending on HA concentration and the characteristics of particles, ChE activity was similar or higher than the value recorded for animals exposed only to the pesticide in aqueous solution. Conclusion: The results indicated that L. variegatus was the more sensitive species of the two. In this species, fenitrothion bioavailability did not increase due to the presence of either different HA concentrations or particulate matter. The experimental approach may constitute a useful tool to predict the influence of dissolved organic matter and sediment particles on fenitrothion bioavailability and toxicity to nontarget aquatic invertebrates.Fil: Cánepa, Alejandro. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Toxicología y Química Legal; ArgentinaFil: Basack, Silvana Beatriz. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Toxicología y Química Legal; ArgentinaFil: Casabe, Norma Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales; ArgentinaFil: Verrengia Guerrero, Noemí Rosario. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Toxicología y Química Legal; Argentin

Dolomite used in phosphate water treatment: Desorption processes, recovery, reuse and final disposition

Desorption is a method that contributes to two important aspects for the sustainability of the water treatments that involve adsorption processes: a) the regeneration of the adsorbent making it reusable in several efficient cycles and, b) the recovery of the adsorbate. In previous studies, it was shown that dolomite constituted an efficient adsorbent of phosphates from aqueous solutions. Once the adsorbent saturation is achieved, it becomes useless for further uses, generating waste, a new environmental problem if it could not be properly disposed. In this work, the main objectives were to study the phosphate desorption process for the recovery and reuse of dolomite and to evaluate the possibilities of a final disposal of exhausted dolomite for agricultural soil improvement and applying the desorbed phosphate as fertilizer. The most efficient agent for the desorption process was 1 M NH 4 Cl. Ultrasound evidenced a negative effect on desorption. The pseudo-second order model fitted better the experimental data and the equilibrium time was 30 min. Up to four efficient adsorption-desorption cycles were obtained. Phosphate bioavailability of exhausted dolomite was assessed with autochthonous microorganisms. The obtained extracts were used in Lactuca sativa growth experiments, establishing that they are not phytotoxic and otherwise, could promote the vegetal growth.Fil: Piol, María Natalia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ingeniería; ArgentinaFil: Paricoto, María. Universidad de Buenos Aires. Facultad de Ingeniería; ArgentinaFil: Saralegui, Andrea Beatriz. Universidad Nacional de General Sarmiento. Instituto de Ciencias; ArgentinaFil: Basack, Silvana Beatriz. Universidad de Buenos Aires. Facultad de Ingeniería; ArgentinaFil: Vullo, Diana Lia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ingeniería; ArgentinaFil: Boeykens, Susana Patricia. Universidad Nacional de General Sarmiento. Instituto de Ciencias; Argentin

Environmental fate of dibutylphthalate in agricultural plastics: Photodegradation, migration and ecotoxicological impact on soil

Phthalic acid esters (PAEs) were determined in polyethylene covers used in horticultural production units located at Moreno and La Plata districts (Buenos Aires, Argentina), detecting 0.69–8.75 mg PAEs kg−1 plastic in greenhouse and tunnel films. The PAEs found were diisobutylphthalate (DIBP), dibutylphthalate (DBP) and diethylhexylphthalate (DEHP). DBP was chosen as a model molecule to carry out the photochemical degradation studies that led to the formation of monobutylphthalate (MBP) and phthalic acid (PA). DBP, MBP and PA migration from plastic covers was studied, finding that while DBP and MBP moved to soil and atmosphere in short times (<48 h), PA remained in the agricultural covers. Further experiments with DBP were made to explore the effect on migration of temperature (20 °C, 50 °C), film thickness (25 μm, 100 μm) and plastic ageing by solarization, observing that temperature increase, film thickness reduction and ageing by solarization favored DBP migration to the environment. DBP and MBP impact on soil were evaluated by avoidance and reproduction tests using Eisenia andrei as bioindicator. Both compounds reduced cocoon viability decreasing the number of juveniles at the lowest concentration assayed (0.1 mg kg−1 of soil). At higher DBP and MBP concentrations the reproductive parameters (number of total cocoons, hatchability and number of juveniles) also showed alterations compared with the controls. Carboxylesterases (CaE), cholinesterases (ChE) and glutathion-S-transferases (GST) activities were analyzed in E. andrei exposed to DBP; cholinesterases activities were reduced at 1 and 10 mg DBP kg−1 soil, and glutathione S-transferases activities were increased at 10 mg DBP kg−1 soil while no effect was observed on carboxylesterases activities. These results emphasize the need to continue studying the impact of PAEs and their photodegradation products on the environment.Fil: Berenstein, Giselle Anahí. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de General Sarmiento. Instituto de Ciencias; ArgentinaFil: Hughes, Enrique Alejandro. Universidad Nacional de General Sarmiento. Instituto de Ciencias; ArgentinaFil: Zalts, Anita. Universidad Nacional de General Sarmiento. Instituto de Ciencias; ArgentinaFil: Basack, Silvana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de General Sarmiento. Instituto de Ciencias; ArgentinaFil: Bonesi, Sergio Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; ArgentinaFil: Montserrat, Javier Marcelo. Universidad Nacional de General Sarmiento. Instituto de Ciencias; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Improvement of laboratory skills of Chemical and Civil Engineering students using an interdisciplinary service-learning project for water quality and supply assessment in low-income homes

The University of Buenos Aires (UBA) develops the UBANEX program, focused on service-learning projects for students involving social, environmental and public health concerns. One of the proposals was a collaborative project between UBA and the National University of General Sarmiento. Based on the hypothesis that students’ voluntary involvement in social concerns improves their attitudes towards themselves and learning, the aim was to focus on the development of social and professional skills by implementing an interdisciplinary work for water quality and supply assessment in low-income homes from a southern district of the Buenos Aires Metropolitan Area. Eighteen volunteers—Chemical and Civil Engineering students—were recruited during August–December 2016. Tasks were distributed according to their interests: survey making, sampling, lab analysis, infrastructure checking, etc. Volunteers were surveyed in social involvement, lab skills, data compilation and analysis, leading to a final report with recommendations for a proper water use. The survey results compiled their feedback: 72% admitted an update on water quality problems, 60% learned new lab techniques and were able to analyze results, 89% supported the University’s involvement in social concerns and 56% expanded their opinion about the professional field. The students confirmed their interest in participating in the next UBANEX project.Fil: Piol, María Natalia. Universidad de Buenos Aires. Facultad de Ingeniería. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Saralegui, Andrea Beatriz. Universidad de Buenos Aires. Facultad de Ingeniería. Departamento de Química; ArgentinaFil: Orero, Gabriela Leonor. Universidad de Buenos Aires. Facultad de Arquitectura, Diseño y Urbanismo; ArgentinaFil: Boeykens, Susana Patricia. Universidad de Buenos Aires. Facultad de Ingeniería. Departamento de Química; ArgentinaFil: Basack, Silvana Beatriz. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; ArgentinaFil: Vullo, Diana Lia. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Comparative toxicity of two glyphosate-based formulations to Eisenia andrei under laboratory conditions

Glyphosate-based products are the leading post-emergent agricultural herbicides in the world, particularly in association with glyphosate tolerant crops. However, studies on the effects of glyphosate-based formulations on terrestrial receptors are scarce. This study was conducted to evaluate the comparative toxicity of two glyphosate-based products: Roundup FG (monoammonium salt, 72% acid equivalent, glyphosate-A) and Mon 8750 (monoammonium salt, 85.4% acid equivalent, glyphosate-B), towards the earthworm Eisenia andrei. Median lethal concentration (LC50) showed that glyphosate-A was 4.5-fold more toxic than glyphosate-B. Sublethal concentrations caused a concentration-dependent weight loss, consistent with the reported effect of glyphosate as uncoupler of oxidative phosphorylation. Glyphosate-A showed deleterious effects on DNA and lysosomal damage at concentrations close to the applied environmental concentrations (14.4μg ae cm-2). With glyphosate-B toxic effects were observed at higher doses, close to its LC50, suggesting that the higher toxicity of formulate A could be attributed to the effects of some of the so-called "inert ingredients", either due to a direct intrinsic toxicity, or to an enhancement in the bioavailability and/or bioaccumulation of the active ingredient. Our results highlight the importance of ecotoxicological assessment not only of the active ingredients, but also of the different formulations usually employed in agricultural practices.Fil: Piola, Lucas. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Toxicología y Química Legal; ArgentinaFil: Fuchs, Julio Silvio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Toxicología y Química Legal; ArgentinaFil: Oneto, Maria Luisa. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Toxicología y Química Legal; ArgentinaFil: Basack, Silvana Beatriz. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Toxicología y Química Legal; ArgentinaFil: Kesten, Eva Marta. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Toxicología y Química Legal; ArgentinaFil: Casabe, Norma Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Toxicología y Química Legal; Argentin

Thermal paper as a potential source of bisphenol A for humans and the environment: migration and ecotoxicological impact

The objective of this work was to evaluate thermal paper (TP) tickets used in Argentina as a potential source of bisphenol A (BPA) that could impact humans and the environment. BPA in TP was measured by HPLC ranging from 11.1 to 30.5 mg BPAg−1. In order to estimate the impact on humans, dermal BPA estimated daily intake was calculated as being 79.3 ± 19.5 μgd−1 for workers and 1.6 ± 0.4 μgd−1 for the general population. To evaluate TP’s impact on the environment, BPA migration from TP to water and soil was studied. In the case of water, 99.6% of the BPA tickets content migrated in 30 h, while 78.0% moved into the soil in 96 h. BPA degradation kinetics in soil and water were also carried out; while in soil 61.9% of BPA degraded in 120 h, no degradation was observed up to 120 h in tap or river water. Additionally, ecotoxicological effects of BPA on the earthworm Eisenia andrei, a representative terrestrial indicator, were studied performing bioassays on lethality, avoidance, and reproductive and enzymatic activity. BPA showed to be very toxic to E. andrei (LC50 value in contact paper test of 17 μgcm−2, 95% confidence interval 6–46 μgcm−2, 24 h exposure) and also caused an increase of total cocoons for earthworms exposed to 10 and 50 mg BPA kg−1 soil. Evasion response was observed at a concentration of 50 mg BPA kg−1 soil, while no effect was observed on cholinesterases, carboxylesterases, and glutathione S-transferases activities (1, 10, and 50 mg BPA kg−1 soil). Finally, a simple BPA degradation technology using water peroxide and radish (Raphanus sativus) tissue as catalyst was explored as a simple and domestic potential treatment to avoid BPA migration to the environment.Fil: Nasello, María Soledad. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; ArgentinaFil: Beiguel, Erica Patricia. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; ArgentinaFil: Fitó Friedrichs, Gretel Alejandra. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Irala, Carmen. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; ArgentinaFil: Berenstein, Giselle Anahí. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Basack, Silvana Beatriz. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; ArgentinaFil: Montserrat, Javier Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de General Sarmiento. Instituto de Ciencias. Área de Química; Argentin

Biomarcadores para a avaliação dos efeitos de clorpirifós em minhocas e em parâmetros funcionais do solo

The objective of this work was to evaluate the effects of chlorpyrifos on earthworms and on soil functional parameters. An integrated laboratory-field study was performed in a wheat field in Argentina, sprayed with chlorpyrifos at two recommended application rates (240 or 960 g ha-1 a.i.). Laboratory tests included neutral red retention time, comet assay (single cell gel electrophoresis), and avoidance behavior, each using the earthworm Eisenia andrei exposed in soil collected 1 or 14 days after pesticide application, and the bait-lamina test. Field tests assessed organic matter breakdown using the litterbag and bait-lamina assays. Earthworm populations in the field were assessed using formalin application and hand-sorting. The neutral red retention time and comet assays were sensitive biomarkers to the effects of chlorpyrifos on the earthworm E. andrei; however, the earthworm avoidance test was not sufficiently robust to assess these effects. Feeding activity of soil biota, assessed by the bait lamina test, was significantly inhibited by chlorpyrifos after 97 days, but recovered by the 118th day of the test. Litterbag test showed no significant differences in comparison to controls. Earthworm abundance in the field was too low to adequately test the sensitivity of this assessment endpoint.O objetivo deste trabalho foi avaliar os efeitos do clorpirifós sobre as minhocas e sobre parâmetros funcionais do solo. Foi executado um estudo integrado campo-laboratório, em uma plantação de trigo na Argentina, onde foi aplicado clorpirifós em duas doses recomendadas (240 ou 960 g ha-1 a.i.). Os ensaios laboratoriais incluíram tempo de retenção do vermelho-neutro, ensaio cometa (eletroforese em gel de célula única) e teste de fuga, cada um com a minhoca Eisenia andrei exposta aos solos coletados 1 e 14 dias após tratamentos, e teste com a lâmina-isca. Nos bioensaios de campo, avaliou-se a decomposição da matéria orgânica em sacolas com alfafa e com a lâmina-isca. As populações de minhocas foram avaliadas no campo com uso do método de extração com formalina e remoção manual. O tempo de retenção do vermelho-neutro e o ensaio cometa foram biomarcadores sensíveis aos efeitos do clorpirifós na minhoca E. andrei; porém, o comportamento de fuga não foi eficiente para avaliar tais efeitos. A atividade alimentar da biota do solo, avaliada pelo teste de lâmina-isca, foi significativamente inibida pelo clorpirifós após 97 dias, mas recuperou-se no 118o dia do teste. O teste de sacolas com alfafa não mostrou diferenças significativas em comparação aos controles. A abundância das minhocas em campo foi muito baixa, para testar adequadamente a sensibilidade desta variável

Biomarkers for the assessment of chlorpyrifos effects on earthworms and on soil functional parameters

The objective of this work was to evaluate the effects of chlorpyrifos on earthworms and on soil functional parameters. An integrated laboratory-field study was performed in a wheat field in Argentina, sprayed with chlorpyrifos at two recommended application rates (240 or 960 g ha-1 style='vertical-align:baseline'> a.i.). Laboratory tests included neutral red retention time, comet assay (single cell gel electrophoresis), and avoidance behavior, each using the earthworm Eisenia andrei exposed in soil collected 1 or 14 days after pesticide application, and the bait-lamina test. Field tests assessed organic matter breakdown using the litterbag and bait-lamina assays. Earthworm populations in the field were assessed using formalin application and hand-sorting. The neutral red retention time and comet assays were sensitive biomarkers to the effects of chlorpyrifos on the earthworm E. andrei; however, the earthworm avoidance test was not sufficiently robust to assess these effects. Feeding activity of soil biota, assessed by the bait lamina test, was significantly inhibited by chlorpyrifos after 97 days, but recovered by the 118th day of the test. Litterbag test showed no significant differences in comparison to controls. Earthworm abundance in the field was too low to adequately test the sensitivity of this assessment endpoint