Identifying pesticides of high concern for ecosystem, plant, animal, and human health: A comprehensive field study across Europe and Argentina.

The widespread and excessive use of pesticides in modern agricultural practices has caused pesticide contamination of the environment, animals, and humans, with confirmed serious health consequences. This study aimed to identify the 20 most critical substances based on an analysis of detection frequency (DF) and median concentrations (MC) across environmental and biological matrices. A sampling campaign was conducted across 10 case study sites in Europe and 1 in Argentina, each encompassing conventional and organic farming systems. We analysed 209 active substances in a total of 4609 samples. All substances ranked among the 20 most critical were detected in silicon wristbands worn by humans and animals and indoor dust from both farming systems. Five of them were detected in all environmental matrices. Overall, higher values of DF and MC, including in the blood plasma of animals and humans, were recorded in samples of conventional compared to organic farms. The differences between farming systems were greater in the environmental samples and less in animal and human samples. Ten substances were detected in animal blood plasma from conventional farms and eight in animal blood plasma from organic farms. Two of those, detected in both farming systems, are classified as hazardous for mammals (acute). Five substances detected in animal blood plasma from organic farms and seven detected in animal blood plasma from conventional farms are classified as hazardous for mammals (dietary). Three substances detected in human blood plasma are classified as carcinogens. Seven of the substances detected in human blood plasma are classified as endocrine disruptors. Six substances, of which five were detected in human blood plasma, are hazardous for reproduction/development. Efforts are needed to elucidate the unknown effects of mixtures, and it is crucial that such research also considers biocides and banned substances, which constitute a baseline of contamination that adds to the effect of substances used in agriculture.

Long-term vinasse application enhanced the initial dissipation of atrazine and ametryn in a sugarcane field in Tucumán, Argentina.

The production of sugarcane bioethanol generates large volumes of vinasse, an effluent whose final disposal can produce an environmental impact that is of concern. The long-term disposal of vinasse in sugarcane fields could challenge crop management, such as the performance of traditional herbicides, by changing soil properties. This study aimed to evaluate the effect of long-term vinasse application on the field and the dissipation of atrazine and ametryn herbicides in a subtropical sugarcane agroecosystem, and to discuss the potential processes involved in it. Vinasse affected soil properties by increasing pH (12%), electrical conductivity (160%), and soil organic carbon (25%) at 0-10 cm depth of soil. Differences in the herbicide calculated sorption coefficient (Kd) varied according to the pedotransfer function applied and the herbicide type (atrazine or ametryn). During the first seven days after herbicide application, the soil underwent long-term vinasse application and increased atrazine and ametryn dissipation 45% and 33%, respectively, compared with the conventional fertilization scheme (control). The Pesticide Root Zone Model revealed that dissipation was mediated mainly by the degradation process rather than transport or other processes. The long-term application of vinasse in a typical sugarcane field of Tucumán, Argentina decreased the potential groundwater pollution of triazines and, adversely, reduced their bioavailability for weed control. For this, the present study presents original information about how long-term treatment with vinasse may require an adaptation of conventional management practices such as the application of herbicides in Argentina and other sugarcane-producing regions. Integr Environ Assess Manag 2023;00:1-12. © 2023 SETAC.

Epilithic biofilms as a discriminating matrix for long-term and growing season pesticide contamination in the aquatic environment: Emphasis on glyphosate and metabolite AMPA.

The indiscriminate use of pesticides represents high ecological risk in aquatic systems. Recently, the inclusion of epilithic biofilms as a reactive matrix has shown potential in diagnosing the health of water resources. The objective of this study was to use multiple matrices (water, suspended sediments, and biofilms) to discriminate contamination degrees in catchments with long and recent history of intensive pesticide use and to monitor growing season pesticides transfer to watercourses. Two catchments were monitored: one representative of "modern agriculture" in a subtropical environment, and another representative of recent agricultural expansion over the Pampa Biome in subtropical Brazil. Glyphosate and AMPA were accumulated in the biofilms and were detected at all sites and at all monitoring times, in concentrations ranging from 195 to 7673 µg kg-1 and from 225 to 4180 µg kg-1, respectively. Similarly, the fungicide tebuconazole has always been found in biofilms. The biofilms made it possible to discriminate the long-term history of pesticide use in the catchments and even to identify the influx pulses of pesticides immediately after their application to crops, which was not possible with active water sampling and even with suspended sediment monitoring. It is strongly recommended that, in regions with intensive cultivation of soybeans and other genetically modified crops, the presence of glyphosate and its metabolite AMPA be permanently monitored, a practice still very scarce in the literature.

Monensin occurrence in surface water and its impact on aquatic biota in a stream of the southeast Pampas, Argentina.

Monensin is an ionophore antibiotic used as a feed additive and growth promoter in cattle production worldwide. The occurrence of monensin in aquatic surficial ecosystems is of concern due to its possible detrimental effects on human health and native biota. Argentina is one of the most important cattle beef producers worldwide; however, there is little knowledge on the environmental occurrence of monensin and the associated risks to aquatic biota. In this study, we developed a method for the extraction and quantification of monensin in surface water; then, we evaluated the occurrence of monensin in a stream impacted by different animal husbandry's operations, and then, we analyzed the ecological implications of monensin residues on aquatic organisms using the risk quotient (RQ) method. Sampling was carried out on August 2017 from the headwaters to the floodplain of the El Pantanoso stream, Buenos Aires province, Argentina. Monensin detection frequency was 75% (n = 20). The median level was 0.40 µg/L and the maximum concentration was 4.70 µg/L. The main input of monensin was from a cattle slaughterhouse, an activity that has not been considered before in the literature as a source of emission of veterinary pharmaceuticals into the environment. The RQ assessment showed that monensin levels could have potential negative effects on aquatic biota in the sampling site closest to the cattle slaughterhouse. The data obtained in this study shows that monensin was present in El Pantanoso surface waters at levels of high ecotoxicological risk to aquatic biota.

Indiscriminate use of glyphosate impregnates river epilithic biofilms in southern Brazil.

Epilithic biofilms are communities of microorganisms composed mainly of microbial cells, extracellular polymeric substances from the metabolism of microorganisms, and inorganic materials. Biofilms are a useful tool to assess the impact of anthropic action on aquatic environments including the presence of pesticide residues such as glyphosate. The present work seeks to monitor the occurrence of glyphosate and AMPA residues in epilithic biofilms occurring in a watershed. For this, epilithic biofilm samples were collected in the Guaporé River watershed in the fall and spring seasons of 2016 at eight points. Physicochemical properties of the water and biofilms were determined. The determination of glyphosate and AMPA was performed using an ultra-high performance liquid chromatograph coupled to a tandem mass spectrometer. The concentrations of glyphosate and AMPA detected in epilithic biofilms vary with the season (from 90 to 305 µg kg-1 for glyphosate and from 50 to 240 µg kg-1 for AMPA, in fall and spring, respectively) and are strongly influenced by the amount of herbicide applications. Protected locations and those with poor access not demonstrate the presence of these contaminants. In the other seven points of the Guaporé River watershed, glyphosate was detected in concentrations ranging from 10 to 305 µg kg-1, and concentrations of AMPA ranged from 50 to 670 µg kg-1. An overview of the contamination in the Guaporé watershed shows that the most affected areas are located in the Marau sub-watershed, which are strongly influenced by the presence of the city of Marau. This confirms the indiscriminate use of glyphosate in the urban area (weed control, domestic gardens and horticulture) and constitutes a problem for human and animal health. The results showed that biofilms can accumulate glyphosate resulting from the contamination of water courses and are sensitive to the sources of pollution and pesticides present in rivers.