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Introduction: Pollution has emerged as a significant threat to humanity, necessitating a thorough evaluation of its impacts. As a result, various methods for human biomonitoring have been proposed as vital tools for assessing, managing, and mitigating exposure risks. Among these methods, urine stands out as the most commonly analyzed biological sample and the primary matrix for biomonitoring studies. Objectives: This review concentrates on exploring the literature concerning residual pesticide determination in urine, utilizing liquid and gas chromatography coupled with mass spectrometry, and its practical applications. Method: The examination focused on methods developed since 2010. Additionally, applications reported between 2015 and 2022 were thoroughly reviewed, utilizing Web of Science as a primary resource. Synthesis: Recent advancements in chromatography-mass spectrometry technology have significantly enhanced the development of multi-residue methods. These determinations are now capable of simultaneously detecting numerous pesticide residues from various chemical and use classes. Furthermore, these methods encompass analytes from a variety of environmental contaminants, offering a comprehensive approach to biomonitoring. These methodologies have been employed across diverse perspectives, including toxicological studies, assessing pesticide exposure in the general population, occupational exposure among farmers, pest control workers, horticulturists, and florists, as well as investigating consequences during pregnancy and childhood, neurodevelopmental impacts, and reproductive disorders. Future directions: Such strategies were essential in examining the health risks associated with exposure to complex mixtures, including pesticides and other relevant compounds, thereby painting a broader and more accurate picture of human exposure. Moreover, the implementation of integrated strategies, involving international research initiatives and biomonitoring programs, is crucial to optimize resource utilization, enhancing efficiency in health risk assessment.

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Diflubenzuron (DFB) and pyriproxyfen (PPF) are larvicides used in crops to control insect plagues. However, these pesticides are known to impact non-target organisms like fish and mammals. Here, we aimed at assessing the embryotoxicity of purified DFB, PPF, and their mixtures in a non-target organism-zebrafish. Zebrafish embryos were exposed to different concentrations for 120 h: 0.025, 0.125, 0.25, 1.25, 2.5, and 10 mg/L of purified PPF and purified DFB, while we used 0.025 mg/L PPF + 10 mg/L DFB (Mix A), 0.125 mg/L PPF + 10 mg/L DFB (Mix B), and 0.25 mg/L PPF + 10 mg/L DFB (Mix C) for the mixtures of PPF + DFB. We observed mortality, teratogenicity, and cardiotoxicity. For the neurotoxicity tests and evaluation of reactive oxygen species (ROS) levels in the brain, embryos were exposed for 120 h to 0.379 and 0.754 mg/L of PPF and 0.025 and 0.125 mg/L of DFB. We established the LC50 for PPF as 3.79 mg/L, while the LC50 for DFB was not determinable. Survival and hatching were affected by PPF concentrations above 0.125 mg/L, DFB concentrations above 1.25 mg/L, and the lower pesticide mixtures. PPF exposure and mixtures induced different types of malformations, while a higher number of malformations were observed for the mixtures, suggesting a potentiating effect. Pesticides diminished avoidance responses and increased the levels of ROS across all concentrations, indicating neurotoxicity. Our findings underscore the detrimental impact of PPF and DFB exposure, spanning from biochemistry to morphology. There is a critical need to reconsider the global use of these pesticides and transition to more ecologically friendly forms of pest control, raising an alarm regarding repercussions on human and animal health and well-being.

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2,4-dichlorophenoxyacetic acid (2,4-D) is a widely used herbicide worldwide and is frequently found in water samples. This knowledge has prompted studies on its effects on non-target organisms, revealing significant alterations to liver structure and function. In this review, we evaluated the literature on the hepatotoxicity of 2,4-D, focusing on morphological damages, toxicity biomarkers and affected liver functions. Searches were conducted on PubMed, Web of Science and Scopus and 83 articles were selected after curation. Among these studies, 72% used in vivo models and 30% used in vitro models. Additionally, 48% used the active ingredient, and 35% used commercial formulations in exposure experiments. The most affected biomarkers were related to a decrease in antioxidant capacity through alterations in the activities of catalase, superoxide dismutase and the levels of malondialdehyde. Changes in energy metabolism, lipids, liver function, and xenobiotic metabolism were also identified. Furthermore, studies about the effects of 2,4-D in mixtures with other pesticides were found, as well as hepatoprotection trials. The reviewed data indicate the essential role of reduction in antioxidant capacity and oxidative stress in 2,4-D-induced hepatotoxicity. However, the mechanism of action of the herbicide is still not fully understood and further research in this area is necessary.

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Common bean (Phaseolus vulgaris L.) is an important crop for food security and for national economics for several countries worldwide. One of the most important factors of risk in common bean production is the fungal disease anthracnose caused by Colletotrichum lindemuthianum, which, in some cases, causes complete yield losses; this kind of plant disease is usually managed through the application of chemical products such as fungicides that are commonly not accepted by society. This rejection is based on the relationship of pesticides with health damage and environmental contamination. In order to help in solving these drawbacks, the present work proposes the use of electrochemically activated salt solutions (EASSs) as a safer pathogen control agent in crops, due to it having shown an elicitor and biostimulant effect on plants. With this background, this manuscript presents in vitro results of the evaluation of the inhibitory effect for multiple bean pathogens and in vivo results of EASS in the common bean-Colletotrichum pathosystem by evaluation of the infection severity and defense activation, such as secondary metabolite production and antioxidant activity. EASS presence in growth media had a strong inhibitory effect at the beginning of experiments for some of the evaluated fungi. EASSs showed an effect against the development of the disease when applied in specific doses to prevent distress in plants.

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The excessive application of pesticides and fertilizers has generated losses in biological diversity, environmental pollution, and harmful effects on human health. Under this context, nanotechnology constitutes an innovative tool to alleviate these problems. Notably, applying nanocarriers as controlled release systems (CRSs) for agrochemicals can overcome the limitations of conventional products. A CRS for agrochemicals is an eco-friendly strategy for the ecosystem and human health. Nanopesticides based on synthetic and natural polymers, nanoemulsions, lipid nanoparticles, and nanofibers reduce phytopathogens and plant diseases. Nanoproducts designed with an environmentally responsive, controlled release offer great potential to create formulations that respond to specific environmental stimuli. The formulation of nanofertilizers is focused on enhancing the action of nutrients and growth stimulators, which show an improved nutrient release with site-specific action using nanohydroxyapatite, nanoclays, chitosan nanoparticles, mesoporous silica nanoparticles, and amorphous calcium phosphate. However, despite the noticeable results for nanopesticides and nanofertilizers, research still needs to be improved. Here, we review the relevant antecedents in this topic and discuss limitations and future challenges.

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This study aimed to evaluate glyphosate (GLY) and aminomethylphosphonic acid (AMPA) toxicity at 65, 650, and 6500 µg L-1 to the initial stages of development of Steindachneridion melanodermatum, an endangered endemic species from the Iguaçu River, assessing hatching, survival, total larval length, deformities, oxidative stress biochemical biomarkers, and neurotoxicity. Overall, looking at the sum of responses through the integrated biomarker response, the species was more sensitive to AMPA than GLY, especially at the lower concentration of 65 µg L-1, which induced mortality, deformities, underdevelopment, and oxidative stress. Considering the risk of exposure and the importance of conservation of the highly endemic ichthyofauna of this basin, it is urgent to investigate and regulate both GLY and AMPA levels at the Iguaçu River to protect not only this species, but the entire ecosystem.

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The objective was to compare the types and concentrations of pesticides allowed in the water potability standard for human supply in Brazil with other countries considered to be the largest consumers of pesticides in dollars invested in purchase/trade. This is a descriptive and documentary study, with data collection in regulations available in official government websites in Brazil, USA, China, Japan, France, Germany, Canada, Argentina, India, Italy, and World Health Organization (WHO). Since Germany, France and Italy are part of the European Union (EU), the legislative resolution of the European Parliament was adopted. Pesticides number and maximum permitted values (MPV) differ between the countries and WHO. In the Brazilian ordinance there are forty pesticides, a number like the USA, Canada, China, and WHO, but that represents only 8% of the total pesticides registered for agricultural use in Brazil. When comparing the ordinance of Brazil with EU the values are only the same for Aldrin + Dieldrin. For other, amounts between 2 and 5000 times more are allowed in Brazil. Brazilian regulations do not establish a total value for the mixture of pesticides in water, only individual limits, which together can reach 1677.13 µg/L, while in EU standards it is only 0.5 µg/L. The study showed discrepancies of the pesticides allowed in water potability standard of the Brazil with other countries, but features 12 pesticides with the same concentrations as WHO guidelines, thus, a worldwide standardization in water potability regulations is necessary to promote health and reducing risk of exposure.

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Brazil is the third largest exporter of fruits and vegetables in the world and, consequently, uses large amounts of pesticides. Food contamination with pesticide residues (PRs) is a serious concern, especially in developing countries. Several research reports revealed that some Brazilian farmers spray pesticides on fruits and vegetables in large quantities, generating PRs after harvest. Thus, ingestion of food contaminated with PRs can cause adverse health effects. Based on information obtained through a systematic review of essential information from 33 articles, we studied the assessment of potential health risks associated with fruit and vegetable consumption in children and adults from Brazilian states. This study identified 111 PRs belonging to different chemical groups, mainly organophosphates and organochlorines, in 26 fruit and vegetable samples consumed and exported by Brazil. Sixteen of these PRs were above the Maximum Residue Limit (MRL) established by local and international legislation. We did not identify severe acute and chronic dietary risks, but the highest risk values were observed in São Paulo and Santa Catarina, associated with the consumption of tomatoes and sweet peppers due to the high concentrations of organophosphates. A high long-term health risk is associated with the consumption of oranges in São Paulo and grapes in Bahia due to chlorothalonil and procymidone. We also identified that 26 PRs are considered carcinogenic by the United States Environmental Protection Agency (US EPA), and the carcinogenic risk analysis revealed no severe risk in any Brazilian state investigated due to the cumulative hazard index (HI) < 1. However, the highest HI values were in São Paulo due to acephate and carbaryl in sweet pepper and in Bahia due to dichlorvos. This information can help regulatory authorities define new guidelines for pesticide residue limits in fruits and vegetables commonly consumed and exported from Brazil and monitor the quality of commercial formulations.

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Repeated presence of strawberries amongst produce with pesticide residues results in questionings related to the risks involved by its consumption. Deterministic and probabilistic risk assessment methods might be used depending on the available data. In the present study, both methods were used to estimate risks of pesticide intake by strawberry consumption. Strawberry samples along two years were analyzed via the multiresidue method. Results of active ingredients (a.i.) concentrations were organized and used for calculations for intake estimates. On the deterministic method, intake was calculated based on the data of a.i. concentration and consumption data coming from an online questionnaire and body weight between 5 and 70 kg. On the probabilistic method, the concentrations of a.i. and body weight of 60 kg were evaluated in two scenarios: a) consumption data from an online questionnaire or b) consumption data retrieved from Family Budget Survey of the Brazilian Institute of Geography and Statistics. In the 62 strawberry samples, 38 a.i. were quantified and in 25 samples the residue analyses were considered satisfactory and 37 had an unsatisfactory outcome. In the deterministic approach, 23% of the a.i. had a calculated intake higher than the acceptable daily intake (ADI) and risk concentrated in body weights between 5 and 30 kg. The risk is low when considering a body weight of 60 kg. All a.i. tested in the first scenario of the probabilistic method pointed towards some possibility of intake being higher than the ADI. In the second scenario, only the a.i. procymidone exceeded the ADI.

A frequente presença do morango entre os alimentos com resíduos de agrotóxicos acima do limite máximo ou não autorizados gera uma série de questionamentos em relação aos riscos envolvidos no seu consumo. Nos processos de avaliação do riscopodemserutilizadosmétodosdeterminísticos e probabilísticosdependendo dos dados disponíveis. O objetivodestetrabalhofoiconduzirumaavaliaçãodeterminística e probabilística do risco de ingestão de agrotóxicosatravés do consumo de morangos. Para tanto, 62 amostras de morangosforamanalisadasatravés do método de multiresíduos entre osanos de 2018 e 2019. Osresultados de concentração dos ingredientesativosforamorganizados e utilizados para oscálculos de estimativa da ingestão. No métododeterminísticoaingestãofoicalculada com base nos dados de concentração dos ingredientesativos das amostras de morangos, dados de consumoprovenientes de um questionário online e pesos corporais entre 5 e 70 kg. No métodoprobabilísticoforamutilizadosos dados de concentração dos ingredientesativos das amostras e peso corporal de 60 kg noscenários um e dois, onde, no primeiro, os dados de consumoutilizadosforamos dados do questionário e no segundoos dados de consumo de morangoprovenientes da Pesquisa de OrçamentosFamiliares. Nas 62 amostras de morangoanalisadasforamdetectados 38 ingredientesativos, sendo 25 amostrasconsideradassatisfatórias, e 37 insatisfatórias. Entre osingredientesativosdetectados, 40% nãotêmseuusoautorizado para a cultura. Na avaliaçãodeterminística, 23% dos ingredientesativosapresentaramingestãocalculada superior a ingestãodiáriaaceitávelempelomenos um cenário, estando o riscoconcentradonos pesos corporais entre 5 e 30 kg, sendo o riscobaixoquandoconsiderado o peso corporal de 60 kg. Todososingredientesativostestados no primeirocenário da avaliaçãoprobabilísticaapresentaramalgumapossibilidade de aingestãoser superior a ingestãodiáriaaceitável, enquanto que para o segundocenárioapenas o ingredienteativoprocimidonasuperou a ingestãodiáriaaceitável. Entre osmodelosestudados, o primeirocenário da avaliaçãoprobabilísticafoi o que apresentou a maiorprobabilidade de provocarintoxicação e procimidonafoi o ingredienteativomaisfrequentementedetectadonasamostras, e que apresentou as maiores chances de oferecerrisco à saúde.

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ABSTRACT: Repeated presence of strawberries amongst produce with pesticide residues results in questionings related to the risks involved by its consumption. Deterministic and probabilistic risk assessment methods might be used depending on the available data. In the present study, both methods were used to estimate risks of pesticide intake by strawberry consumption. Strawberry samples along two years were analyzed via the multiresidue method. Results of active ingredients (a.i.) concentrations were organized and used for calculations for intake estimates. On the deterministic method, intake was calculated based on the data of a.i. concentration and consumption data coming from an online questionnaire and body weight between 5 and 70 kg. On the probabilistic method, the concentrations of a.i. and body weight of 60 kg were evaluated in two scenarios: a) consumption data from an online questionnaire or b) consumption data retrieved from Family Budget Survey of the Brazilian Institute of Geography and Statistics. In the 62 strawberry samples, 38 a.i. were quantified and in 25 samples the residue analyses were considered satisfactory and 37 had an unsatisfactory outcome. In the deterministic approach, 23% of the a.i. had a calculated intake higher than the acceptable daily intake (ADI) and risk concentrated in body weights between 5 and 30 kg. The risk is low when considering a body weight of 60 kg. All a.i. tested in the first scenario of the probabilistic method pointed towards some possibility of intake being higher than the ADI. In the second scenario, only the a.i. procymidone exceeded the ADI.

RESUMO: A frequente presença do morango entre os alimentos com resíduos de agrotóxicos acima do limite máximo ou não autorizados gera uma série de questionamentos em relação aos riscos envolvidos no seu consumo. Nos processos de avaliação do riscopodemserutilizadosmétodosdeterminísticos e probabilísticosdependendo dos dados disponíveis. O objetivodestetrabalhofoiconduzirumaavaliaçãodeterminística e probabilística do risco de ingestão de agrotóxicosatravés do consumo de morangos. Para tanto, 62 amostras de morangosforamanalisadasatravés do método de multiresíduos entre osanos de 2018 e 2019. Osresultados de concentração dos ingredientesativosforamorganizados e utilizados para oscálculos de estimativa da ingestão. No métododeterminísticoaingestãofoicalculada com base nos dados de concentração dos ingredientesativos das amostras de morangos, dados de consumoprovenientes de um questionário online e pesos corporais entre 5 e 70 kg. No métodoprobabilísticoforamutilizadosos dados de concentração dos ingredientesativos das amostras e peso corporal de 60 kg noscenários um e dois, onde, no primeiro, os dados de consumoutilizadosforamos dados do questionário e no segundoos dados de consumo de morangoprovenientes da Pesquisa de OrçamentosFamiliares. Nas 62 amostras de morangoanalisadasforamdetectados 38 ingredientesativos, sendo 25 amostrasconsideradassatisfatórias, e 37 insatisfatórias. Entre osingredientesativosdetectados, 40% nãotêmseuusoautorizado para a cultura. Na avaliaçãodeterminística, 23% dos ingredientesativosapresentaramingestãocalculada superior a ingestãodiáriaaceitávelempelomenos um cenário, estando o riscoconcentradonos pesos corporais entre 5 e 30 kg, sendo o riscobaixoquandoconsiderado o peso corporal de 60 kg. Todososingredientesativostestados no primeirocenário da avaliaçãoprobabilísticaapresentaramalgumapossibilidade de aingestãoser superior a ingestãodiáriaaceitável, enquanto que para o segundocenárioapenas o ingredienteativoprocimidonasuperou a ingestãodiáriaaceitável. Entre osmodelosestudados, o primeirocenário da avaliaçãoprobabilísticafoi o que apresentou a maiorprobabilidade de provocarintoxicação e procimidonafoi o ingredienteativomaisfrequentementedetectadonasamostras, e que apresentou as maiores chances de oferecerrisco à saúde.

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The environmental risks of pesticides found in surface waters of an important agricultural basin in Brazil were estimated by adopting two approaches: individual pesticides risk quotients (RQ) and concentration addition model for pesticide mixtures (∑RQs) contained in each water sample. Monitoring was carried out in the Mogi Guaçu River basin, Brazil, from October 2017 to May 2018. Four sampling points were selected in the Mogi Guaçu River and seven in its tributaries A multiresidue method with solid-phase extraction and subsequent analysis by UPLC-ESI-QqQ-MS/MS was developed to quantify 19 pesticides. Herbicides, except for simazine, presented the highest detection frequencies with values above 70%. Tebuthiuron was found in all 55 analyzed samples, presenting the highest concentration (6437 ng L-1) over the monitoring period. Fungicides and insecticides showed similar detection frequency (DF) values, ranging from 1.8% to 21.8%. Tebuconazole and carbofuran were the fungicides and insecticides most frequently detected, respectively. January 2018 sampling showed the highest total concentration of pesticides, differing from March 2018 and May 2018 (p < 0.05). The MG2 > TMG8 > MG1 > TMG6 sites showed the highest concentration total of pesticides while MG4 > TMG4 > TMG3 (p < 0.05) sites showed the lowest values: MG4 > TMG4 > TMG3 (p < 0.05). Most pesticide occurrences presented no risks to aquatic organisms. Only 19 out of the 175 pesticide occurrences > LOQ presented individual risks to aquatic biota. Contrary to the results obtained by the individual risk assessment, most pesticide mixtures presented risks to aquatic biota. In 36 out of the 55 samples analyzed during monitoring, pesticide mixtures presented risks to aquatic life.

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Biosensors are a simple, low-cost, and reliable way to detect pesticides in food matrices to ensure consumer food safety. This systematic review lists which nanomaterials, biorecognition materials, transduction methods, pesticides, and foods have recently been studied with biosensors associated with analytical performance. A systematic search was performed in the Scopus (n = 388), Web of Science (n = 790), and Science Direct (n = 181) databases over the period 2016-2021. After checking the eligibility criteria, 57 articles were considered in this study. The most common use of nanomaterials (NMs) in these selected studies is noble metals in isolation, such as gold and silver, with 8.47% and 6.68%, respectively, followed by carbon-based NMs, with 20.34%, and nanohybrids, with 47.45%, which combine two or more NMs, uniting unique properties of each material involved, especially the noble metals. Regarding the types of transducers, the most used were electrochemical, fluorescent, and colorimetric, representing 71.18%, 13.55%, and 8.47%, respectively. The sensitivity of the biosensor is directly connected to the choice of NM and transducer. All biosensors developed in the selected investigations had a limit of detection (LODs) lower than the Codex Alimentarius maximum residue limit and were efficient in detecting pesticides in food. The pesticides malathion, chlorpyrifos, and paraoxon have received the greatest attention for their effects on various food matrices, primarily fruits, vegetables, and their derivatives. Finally, we discuss studies that used biosensor detection systems devices and those that could detect multi-residues in the field as a low-cost and rapid technique, particularly in areas with limited resources.

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Esta pesquisa buscou analisar os casos de intoxicações por organofosforados e carbamatos, presentes em agrotóxicos e pesticidas, registrados na base de dados do Centro de Informação e Assistência Toxicológica do Paraná (CIATox/PR). Trata-se de estudo retrospectivo em que foram avaliadas variáveis sociodemográficas e clínicas relacionadas à intoxicação, à forma de exposição, à causa e ao desfecho. Para a análise estatística foram utilizados testes de Kolmogorov-Smirnov, Shapiro-Wilk, Qui-Quadrado e Teste Exato de Fisher, considerando p<0,05. A amostra foi composta por 426 casos, sendo 218 (51,2%) mulheres. O principal agente foi raticida clandestino em 278 (65,2%) pacientes. A principal circunstância das intoxicações foi tentativa de suicídio com 293 (68,8%) casos. Houve predominância de exposição via oral (89,9%) e zona urbana em 349 (81,9%) casos, a maioria considerados leves (52,6%) e assistidos em serviços médicos (66,4%). Cerca de 327 (76,8%) indivíduos apresentavam manifestações clínicas. O tempo decorrido entre a exposição e o contato com o CIATox/PR foi maior nos casos considerados graves (p= 0,041). A atropina foi utilizada em 94 (49%) pacientes intoxicados por carbamatos, em 31 (33,3%) por organofosforados e em 84 (59,6%) por outros inibidores da colinesterase não especificados. Duas mulheres e um adolescente apresentaram desfecho fatal, tendo em comum a ingesta intencional de "chumbinho". A casuística predominante nesta série histórica foi paciente do sexo feminino, faixa etária adulta, residente na região metropolitana, exposta a agrotóxico por via oral, sintomática, classificada como gravidade leve, sem necessidade de atropina, contudo ocorreram três casos com desfecho para o óbito.

This research aimed to analyze the cases of poisoning by organophosphates and carbamates, present in agrochemicals and pesticides, registered in the database of the Information and Toxicological Assistance Center of Paraná (CIATox/PR). This is a retrospective study in which sociodemographic and clinical variables related to intoxication, form of exposure, cause and outcome were evaluated. For the statistical analysis, the Kolmogorov-Smirnov, Shapiro-Wilk, Chi-Square and Fisher's Exact Test were used, considering p<0.05. The sample consisted of 426 cases, 218 (51.2%) of which were women. The main agent was clandestine rodenticide in 278 (65.2%) patients. The main circumstance of intoxication was a suicide attempt with 293 (68.8%) cases. There was a predominance of oral exposure (89.9%) and urban areas in 349 (81.9%) cases, most considered mild (52.6%) and assisted in medical services (66.4%). About 327 (76.8%) individuals had clinical manifestations. The time elapsed between exposure and contact with CIATox/PR was longer in cases considered severe (p=0.041). Atropine was used in 94 (49%) patients intoxicated by carbamates, in 31 (33.3%) by organophosphates and in 84 (59.6%) by other unspecified cholinesterase inhibitors. Two women and one teenager had a fatal outcome, having in common the intentional ingestion of "chumbinho". The predominant casuistry in this historical series was a female patient, adult age, living in the metropolitan region, exposed to pesticides orally, symptomatic, classified as mild severity, without the need for atropine, however, there were three cases with an outcome of death.

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Nanopesticides are nanostructures with two to three dimensions between 1 to 200 nm, used to carry agrochemical ingredients (AcI). Because of their unique properties, the loading of AcI into nanoparticles offers benefits when compared to free pesticides. However, with the fast development of new engineered nanoparticles for pests' control, a new type of environmental waste is being produced. This paper describes the nanopesticides sources, the harmful environmental and health effects arising from pesticide exposure. The potential ameliorative impact of nanoparticles on agricultural productivity and ecosystem challenges are extensively discussed. Strategies for controlled release and stimuli-responsive systems for slow, sustained, and targeted AcI and genetic material delivery are reported. Special attention to different nanoparticles source, the environmental behavior of nanopesticides in the crop setting, and the most recent advancements and nanopesticides representative research from experimental results are revised. This review also addresses some issues and concerns in developing, formulating and toxicity pesticide products for environmentally friendly and sustainable agriculture.

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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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Continuous fungicide spraying is required to eliminate fungal pathogens on grapes. However, this practice is associated with several risks, including contamination and environmental imbalance, as well as toxicity to operators and the induction of resistance in pathogens. In addition, a strong correlation has been reported between the presence of fungicides and the occurrence of issues during alcoholic fermentation, resulting in negative impacts on the sensory quality of the final products. Numerous studies have evaluated residue concentrations of phytosanitary products in grapes, juices, and wines, and a significant number of studies have assessed the impact of different agrochemicals on bioprocesses. However, a review compiling the key results of these studies is currently lacking. This review incorporates results obtained in the last decade from research on the presence of fungicide residues, including azoxystrobin, boscalid, captan, copper, fenhexamid, folpet, pyraclostrobin, pyrimethanil and tebuconazole, and their effects on fermentation kinetics. Practical solutions to mitigate these problems, both in vineyards and industry, are also presented and discussed. This review highlights the constant high fungicidal agent concentrations (greater than 1 or 2 mg L-1) used throughout the winemaking process, with the impact of residues being of particular concern, especially with regard to their effect on yeast activity and the fermentation process. Thus, the adoption of methodologies that allow winemakers to control and trace these residues is an important step in avoiding or reducing fermentation problems throughout the winemaking process.[Figure: see text].

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Agricultural expansion and intensification has led globally to a rapid landscape structure change and high agrochemical use resulting in habitat loss and degraded environmental quality. Co-occurrence of landscape change and agrochemical contamination threatens biodiversity and might have interactive effects especially for organisms with complex life-cycles such as amphibians. We evaluated effects of landscape structure and agrochemical contamination at different spatial scales on anurans in Entre Rios, Argentina. We selected 35 independent stream headwaters along an agricultural expansion and intensification gradient. We conducted anuran call surveys from spring 2012 to summer 2013 and obtained detection-non detection data to estimate mean richness and focal species occupancy. We quantified forest area and riparian forest width at two spatial scales (sub-basin and local reach scale). We measured nutrients and pesticides in water and sediment. We evaluated anuran response to landscape and contamination variables using GLMs for richness and single season single-species occupancy models for focal species. Anuran diversity increased with forest area and riparian forest width, and decreased at sites with herbicide and nutrient contamination, particularly glyphosate; 2,4-D and nitrates. Also, most focal frog species responded mainly to basin forest and 2,4-D. Negative effects of agrochemical contamination on anuran diversity was mitigated in areas with larger basin forest cover. Agricultural management should ensure the reduction of herbicide and fertilizer use, the sparing of adequate forested habitat within drainage areas, and preservation of riparian forests around anuran breeding habitat to reduce and mitigate the negative effects of agrochemical contamination on anurans diversity in agroecosystems.

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In Argentina, periurban agriculture is performed by farmers with inadequate training in the use of pesticides and chemical fertilizers, developing horticulture with serious soil deterioration. The aim of this work was to monitor bacterial diversity of a horticultural soil (S) and a reference soil (R) as quality index for the design of future restoration strategies. As crops changed together with the agrochemical applications, sample collection was before harvest for strawberries, post-harvest for red peppers, pre-harvest broccoli crop and of a resting soil in treatment with poultry litter as a fertilizing amendment. Bacterial diversity was analysed by the use of high throughput sequencing of the V1-V3 region of the 16S rRNA gene. Analysis of R soils seemed relatively constant in time, enriched in Alphaproteobacteria and Acidobacteria consistent with a reference to soil health. The effect of the intensive use of S soils was proved by differences in Chloroflexi, Bacteroidetes and Proteobacteria relative abundances. The main evidence of the alteration of S soils was the increase in Bacteroidetes and Betaproteobacteria. A weak recuperation trend of S soil microbiota was registered during a post-harvest inactive period. A strong influence of the soil use routine-consisting in high crop rotation and short time-rest cycles-on microbial community structure was verified. These results indicate the microbiota perturbation, caused by the intense use of periurban agriculture soils and will contribute for further actions to improve environment quality.

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The magnetic adsorbent prepared with hydrocalumite-iron oxide (HC/Fe) modified with dodecyl sulfate (DS) was examined for the removal of the agrichemicals atrazine (ATZ) and chlorpyrifos (CPF) from aqueous solution. The adsorbent HC-DS/Fe was characterized by infrared spectroscopy (IR), Raman spectroscopy, X-ray diffractometry (XRD) and atomic absorption spectrometry. The effects of adsorbent dosage, contact time, pH and initial concentration of ATZ and CPF were evaluated. HC-DS/Fe presented a maximum adsorption capacity for ATZ of 4.5 mg g-1 (30 min) and for CPF of 72.9 mg g-1 (210 min) at 25 °C. HC-DS/Fe can be readily removed from the aqueous solution by magnetization because of its magnetic properties. The free energy variation for HC-DS/Fe during the adsorption of the ATZ was -48.78 to -53.91 kJ mol-1 and for the CPF of -55.79 to -59.28 kJ mol-1, suggesting the spontaneity of the adsorption process. The positive value of △H suggests an endothermic process for the interaction of ATZ and CPF by HC-DS/Fe. This adsorbent showed satisfactory results when used in the treatment of a sample of river water, fortified with the agrichemicals chlorpyrifos, atrazine, thiamethoxam and acetamiprid.

Assuntos

RESUMO

Glyphosate (GLY)-dicamba (DIC) and GLY-flurochloridone (FLC) are herbicide mixtures which are widely used for treating fallow containing glyphosate resistant weeds. The aim of this study was to evaluate the acute toxic effects and the prevailing interactions on stage 36 tadpoles of the anuran species Rhinella arenarum when exposed to equitoxic and non-equitoxic combinations of these herbicide combinations. Experiments were realized using the following combinations of commercial formulations: 48% GLY-based Credit® + 57.71% DIC-based Banvel® and 48% GLY-based Credit® + 25% FLC-based Twin Pack Gold®. GLY-DIC and GLY-FLC equitoxic mixtures were assayed mixing each constituent with an equivalent individual toxicity able to induce the same lethality effect. After 96 h of exposure, GLY-DIC and GLY-FLC equitoxic mixtures presented toxic unit 50 values (TU50 96h) of 1.74 (confidence interval: 1.58-1.92) and 1.54 (confidence interval: 1.46-1.62) respectively, indicating the presence of a weak antagonistic interaction as TU values were greater than 1. For their part, most non-equitoxic combinations of GLY-DIC and GLY-FLC tested did not significantly differ from additivity, the only exception being when DIC and FLC were fixed at 0.33 TUs, where a weak antagonism was observed. Overall, results indicate that the toxicity of both GLY-DIC and GLY-FLC mixtures to R. arenarum tadpoles vary from additive to slightly antagonistic, depending on the proportion of constituting herbicide formulations present in the mixture.

Assuntos