Eduardo De Gerónimo

Environmental fate of glyphosate and aminomethylphosphonic acid in surface waters and soil of agricultural basins

Argentinian agricultural production is fundamentally based on a technological package that combines no-till and glyphosate in the cultivation of transgenic crops. Transgenic crops (soybean, maize and cotton) occupy 23 million hectares. This means that glyphosate is the most employed herbicide in the country, where 180-200 million liters are applied every year. The aim of this work is to study the environmental fate of glyphosate and its major degradation product, aminomethylphosphonic acid (AMPA), in surface water and soil of agricultural basins. Sixteen agricultural sites and forty-four streams in the agricultural basins were sampled three times during 2012. The samples were analyzed by UPLC-MS/MS ESI(+/-). In cultivated soils, glyphosate was detected in concentrations between 35 and 1502 μg kg(-1), while AMPA concentration ranged from 299 to 2256 μg kg(-1). In the surface water studied, the presence of glyphosate and AMPA was detected in about 15% and 12% of the samples analyzed, respectively. In suspended particulate matter, glyphosate was found in 67% while AMPA was present in 20% of the samples. In streams sediment glyphosate and AMPA were also detected in 66% and 88.5% of the samples respectively. This study is, to our knowledge, the first dealing with glyphosate fate in agricultural soils in Argentina. In the present study, it was demonstrated that glyphosate and AMPA are present in soils under agricultural activity. It was also found that in stream samples the presence of glyphosate and AMPA is relatively more frequent in suspended particulate matter and sediment than in water.

Presence of pesticides in surface water from four sub-basins in Argentina.

Argentina has 31 million hectares given over to agriculture comprising 2.2% of the worlds total area under cultivation (Stock Exchange of Rosario, Argentina). Despite the intensity of this agricultural activity, data on pesticide pollution in surface water are rather scarce. In this sense, the aim of this work is to determine the presence of pesticides in surface water of four agricultural sub-basins of Argentine. An environmental monitoring was carried out to determine the impact of twenty-nine pesticides used in agricultural activities on the surface water quality of agricultural areas within the San Vicente, Azul, Buenos Aires southeast and Mista stream sub-basins. The samples were analyzed by solid-phase extraction (SPE) using OASIS HLB 60 mg cartridges and ultra-high-pressure liquid chromatography coupled to tandem mass spectrometry (UHPLC/MSMS) that provided good analytical quality parameters. The southeast of Buenos Aires was the site with the highest frequency of pesticides detection, followed by Azul and San Vicente microbasins. The most detected pesticides, considering all surface water samples, were atrazine, tebuconazole and diethyltoluamide with maximum concentration levels of 1.4, 0.035, and 0.701 μg L(-1), respectively. The results obtained for all basins studied show the presence of residual pesticides in surface waters according the different agricultural activities developed.

Spatial and temporal trends and flow dynamics of glyphosate and other pesticides within an agricultural watershed in Argentina

In the present study, we evaluated the spatial and temporal trends of current-use pesticides in surface water and sediments as well as their relationship with hydrological stream dynamics within the agricultural watershed of El Crespo stream (Buenos Aires Province, Argentina). We sampled 2 contrasting sites: site 1 (upstream), surrounded by agricultural lands, and site 2 (downstream), surrounded by natural grasslands. Most of the applied pesticides (glyphosate, 2,4-D, atrazine, tebuconazole, and imidacloprid) were detected at high frequencies in surface water samples at both sites. However, only glyphosate and aminomethylphosphonic acid (AMPA) were present at high concentrations and had a significant spatial-temporal trend. The highest concentrations were found during spring 2014 at site 1, in association with the intense rains that occurred in that season. The fact that glyphosate and AMPA concentrations were higher than the rest of the studied compounds is closely related to the land use within the watershed, as glyphosate was the most applied herbicide during the fallow period of glyphosate-resistant crops (soybean, maize). The pesticide mixture had a significant spatial-temporal trend, reaching the highest levels during storm flow events in spring 2014. The intensive rains in spring 2014 could be the main factor influencing stream hydrology and pesticide behavior at El Crespo watershed. The estimated annual pesticide losses were 3.11 g/ha at site 1 and 0.72 g/ha at site 2. This result indicates that an attenuation process could be decreasing pesticide loads during downstream transport from site 1 to site 2. Environ Toxicol Chem 2017;36:3206-3216.

A simple and rapid analytical methodology based on liquid chromatography-tandem mass spectrometry for monitoring pesticide residues in soils from Argentina

A rapid analytical methodology has been developed for multi-residue determination of pesticides in soils using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) with a triple quadrupole analyzer. Soil samples were collected from 12 representative agricultural areas in Argentina, and 18 pesticides were selected on the basis of their use. Special attention was paid to minimize sample preparation, making easier the method application to routine analysis. Several extraction procedures were tested, performing a careful study on matrix effects. The method finally proposed (extraction with acetonitrile and a subsequent 2-fold dilution with water without any clean-up step) was fully validated at 0.05 and 0.5 mg kg−1 on the basis of European SANCO 12571/2013 and 825/00 guidelines. The method applicability and robustness were demonstrated by analysis of quality control (QC) samples, consisting of eleven soils spiked at 0.5 mg kg−1. These soil samples were collected from different experimental plots, and were very diverse in their physico-chemical characteristics. The methodology developed is of easy application, there is low consumption of solvents and reagents, and no clean-up is required despite the complexity of the soil matrix. In the near future, the method developed will be used to monitor the presence of pesticides in large agricultural areas of Argentina.

Non-point source pollution of glyphosate and AMPA in a rural basin from the southeast Pampas, Argentina

We measured the occurrence and seasonal variations of glyphosate and its metabolite, aminomethylphosphonic acid (AMPA), in different environmental compartments within the limits of an agricultural basin. This topic is of high relevance since glyphosate is the most applied pesticide in agricultural systems worldwide. We were able to quantify the seasonal variations of glyphosate that result mainly from endo-drift inputs, that is, from direct spraying either onto genetically modified (GM) crops (i.e., soybean and maize) or onto weeds in no-till practices. We found that both glyphosate and AMPA accumulate in soil, but the metabolite accumulates to a greater extent due to its higher persistence. Knowing that glyphosate and AMPA were present in soils (> 93% of detection for both compounds), we aimed to study the dispersion to other environmental compartments (surface water, stream sediments, and groundwater), in order to establish the degree of non-point source pollution. Also, we assessed the relationship between the water-table depth and glyphosate and AMPA levels in groundwater. All of the studied compartments had variable levels of glyphosate and AMPA. The highest frequency of detections was found in the stream sediments samples (glyphosate 95%, AMPA 100%), followed by surface water (glyphosate 28%, AMPA 50%) and then groundwater (glyphosate 24%, AMPA 33%). Despite glyphosate being considered a molecule with low vertical mobility in soils, we found that its detection in groundwater was strongly associated with the month where glyphosate concentration in soil was the highest. However, we did not find a direct relation between groundwater table depth and glyphosate or AMPA detections. This is the first simultaneous study of glyphosate and AMPA seasonal variations in soil, groundwater, surface water, and sediments within a rural basin.

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.

Soil microbial communities and glyphosate decay in soils with different herbicide application history

This study evaluates the glyphosate dissipation under field conditions in three types of soil, and aims to determine the importance of the following factors in the environmental persistence of herbicide: i) soil bacterial communities, ii) soil physicochemical properties, iii) previous exposure to the herbicide. A soil without previous record of GP application (P0) and two agricultural soils, with 5 and >10years of GP exposure (A5 and A10) were subjected to the application of glyphosate at doses of 3mg·kg-1. The concentration of GP and AMPA was determined over time and the dynamics of soil bacterial communities was evaluated using 16S ARN ribosomal gene amplicon-sequencing. The GP exposure history affected the rate but not the extent of GP biodegradation. The herbicide was degraded rapidly, but P0 soil showed a dissipation rate significantly lower than soils with agricultural history. In P0 soil, a significant increase in the relative abundance of Bacteroidetes was observed in response to herbicide application. More generally, all soils displayed shifts in bacterial community structure, which nevertheless could not be clearly associated to glyphosate dissipation, suggesting the presence of redundant bacteria populations of potential degraders. Yet the application of the herbicide prompted a partial disruption of the bacterial association network of unexposed soil. On the other hand, higher values of linear (Kd) and nonlinear (Kf) sorption coefficient in P0 point to the relevance of cation exchange capacity (CEC), clay and organic matter to the capacity of soil to adsorb the herbicide, suggesting that bioavailability was a key factor for the persistence of GP and AMPA. These results contribute to understand the relationship between bacterial taxa exposed to the herbicide, and the importance of soil properties as predictors of the possible rate of degradation and persistence of glyphosate in soil.