Degradation of atrazine, glyphosate, and 2,4-D in soils collected from two contrasting crop rotations in Southwest Chaco, Argentina.

Argentina stands as one of the leading consumers of herbicides. In a laboratory incubation experiment, the persistence and production of degradation metabolites of Atrazine, 2,4-D, and Glyphosate were investigated in a loamy clay soil under two contrasting agricultural practices: continuous soybean cultivation (T1) and intensified rotations with grasses and legumes (T2). The soils were collected from a long-term no-till trial replicating the influence of the meteorological conditions in the productive region. The soil was enriched with diluted concentrations of 6.71, 9.95, and 24 mg a.i./kg-1 of soil for the respective herbicides, equivalent to annual doses commonly used in the productive region. Samples were taken at intervals of 0, 0.5, 1, 2, 4, 6, 8, 16, 32, and 64 days, and analysis was conducted using high-resolution liquid chromatography UPLC MS/MS. An optimal fit to the first-order kinetic model was observed for each herbicide in both rotations, resulting in relatively short half-lives. Intensified crop sequences favored the production of biotic degradation metabolites. The impact of the high frequency of soybean cultivation revealed a trend of soil acidification and a reduced biological contribution to attenuation processes in soil contamination.

Glyphosate, AMPA, and metsulfuron-methyl retention in the main horizons of a Typic Argiudoll.

Retention is one of the processes controlling the behavior and fate of pesticides in soil. The objective of this work was to evaluate the adsorption and desorption of glyphosate, AMPA, and metsulfuron-methyl in the main horizons of a Typic Argiudoll destined for agricultural use. For this purpose, the batch equilibrium method was used at a range of concentrations for each compound. Desorption was performed in three consecutive steps after the adsorption experiment. The results obtained showed strong adsorption of glyphosate and AMPA in the three horizons, following the trend B > A > C, with weak desorption. Metsulfuron-methyl, on the other hand, showed weak adsorption in the three horizons, following the trend A > B > C, with relevant desorption. Our results allow us to identify metsulfuron-methyl as the compound that poses the greatest environmental risk in terms of the potential contamination of other areas and groundwater. However, despite their strong adsorption and weak desorption, glyphosate and AMPA also represent potential contaminants of other environmental matrices.

Multiresidues of pesticides in the particulate matter (PM10) emitted by rural soils of the semiarid pampas, Argentina. A potential source of air pollution.

The aim of this work was to evaluate the presence of 40 pesticides in the PM10 emitted by rural soils of the semiarid region of Argentina. Six agricultural soils for grain production under no till and with high use of pesticides (AG), 5 agricultural soils for forage and grain production under conventional tillage (AFG) and 5 unpaved rural roads (RR) were sampled. The PM10 was generated using the Easy Dust Generator and it was collected with an electrostatic precipitator. The presence of 20 herbicides, 14 insecticides and 6 fungicides was analyzed in the soil and in the PM10. More than 70% of the pesticides analyzed were detected in the soil and in the PM10. All agricultural soils and 87% of RR soils showed at least one residue of pesticides. Multiresidues of pesticides were found in the 100% of PM10 emitted by rural soils. The mean number of pesticides was higher in the PM10 (7) than in the soil (5). Some pesticides were not detected in the soils but they were detected in the PM10 (triticonazole, carbofuran, metsulfuron methyl) and vice versa. In general, the concentrations of herbicides were higher in the PM10 than in the soil, while the concentrations of insecticides and fungicides were lower in the PM10 than in the soil. These results suggest that the concentrations of pesticide in the PM10 (inhalable fraction) should be used instead the concentrations of pesticide in the soil to calculate the exposure factor to pesticides by dust inhalation. This study provides the initial evidence of the presence of multiple pesticide residues in PM10 emitted by rural soils under different land management. Also confirms that the PM10 is a potential source of air contamination with pesticides. Future studies should be driven to measure the concentrations of pesticides and their dynamics in the PM10.

First evidence of glyphosate and aminomethylphosphonic acid (AMPA) in the respirable dust (PM10) emitted from unpaved rural roads of Argentina.

The aim of this work was to compare the concentration of glyphosate and AMPA in the PM10 and the actual PM10 emission from agricultural soils and unpaved roads, located inside and outside farm fields. To determine the actual PM10 emission by wind erosion, the actual wind erosion was estimated using the Wind Erosion Equation, and the PM10 emission efficiency was measured with the Easy Dust Generator. PM10 was collected in an electrostatic precipitator coupled to the Easy Dust Generator. Actual PM10 emission was 11.5 g ha-1 year-1 in agricultural soils and 4711.4 g ha-1 year-1 in unpaved roads. The high value of actual PM10 emission in unpaved roads was due to their high actual wind erosion and the high PM10 emission efficiency, while the low value in agricultural soils was due to their low actual wind erosion. Content of glyphosate in the PM10 ranged from 59 to 359 µg kg-1 in agricultural soils, from 382 to 454 µg kg-1 in unpaved roads inside farm fields, and from 39 to 639 µg kg-1 in unpaved roads outside farm fields. Content of AMPA in the PM10 ranged from 387 to 7228 µg kg-1 in agricultural soils, from 900 to 4138 µg kg-1 in unpaved roads inside farm fields, and 98 to 500 µg kg-1 in unpaved roads outside farm fields. AMPA concentration in PM10 was higher than that of glyphosate due to the longer persistence of AMPA than glyphosate. Glyphosate and AMPA concentrations in PM10 were higher than in soil, which is an additional risk that should be considered when the effect of PM10 emitted by agricultural soils and unpaved roads on human health are evaluated. Our results show that the amount and chemical composition of PM10 emitted by wind erosion from unpaved roads should be studied in other regions.

Ecological risk assessment of current-use pesticides and biocides in soils, sediments and surface water of a mixed land-use basin of the Pampas region, Argentina.

The present study aimed to assess the ecological risk of 30 current-use agricultural pesticides and biocides in the soil, sediments and aquatic organisms of a mixed land-use basin located in the Depressed Pampas Region of Argentina. Risk Quotients (RQs) were used to evaluate the chronic risk in soil and aquatic organisms, while Toxic Units (TUs) were used to assess the acute risk in sediment-dwelling organisms and aquatic biota. Acetochlor, hydroxy-atrazine, glyphosate, AMPA, metolachlor, imidacloprid and tebuconazole were the only pesticide residues detected (>30%) and quantified in all the matrices evaluated. Glyphosate and AMPA showed the highest concentrations, being their mean and maximum levels 27.90-176.00 µg kg-1 and 270-712.50 µg kg-1 in soils, 8.28-32.0 µg kg-1 and 6.85-17.50 µg kg-1 in sediments, and 1.88-4.36 µg L-1 and 0.66-1.03 µg L-1 in surface water. The RQs in soils showed high chronic risk, mainly due to AMPA and imidacloprid. The TUs in sediments showed acute risk in dwelling organisms, mainly due to glyphosate and imidacloprid. RQs assessment showed a range of chronic risk levels according to the site/sampling event, with higher contribution of atrazine and its metabolites, and acetochlor, whereas TUs assessment showed no acute risk in aquatic biota. In contrast to Europe, in Argentina, there are no restrictions regarding the use of atrazine, acetochlor, imidacloprid and glyphosate to protect aquatic life. Thus, it is recommended that the current Argentine pesticide regulations should be modified to prevent ecological risk and protect ecosystems.

Contribution of soluble and particulate-matter fractions to the total glyphosate and AMPA load in water bodies associated with horticulture.

Glyphosate-based herbicides are used in horticulture to prepare the soil for planting and to remove weeds surrounding greenhouses. Superficial runoff from production units can lead to glyphosate reaching nearby water bodies. Previous publications reported glyphosate's high affinity for suspended solids. The aim of the present work was to investigate the occurrence and concentrations of glyphosate and aminomethylphosphonic acid (AMPA) in soluble and suspended-particulate-matter fractions within the basin of the Carnaval-Stream, a water body traversing a horticultural greenbelt. Glyphosate and AMPA were detected in 67% and 83% of the samples, occurring in both fractions simultaneously at respective maximum concentrations of 17.0 and 4.5 µg.L1 in the soluble fraction and 35,620 and 19,586 µg.kg1 in the particulates. Although the calculated partition coefficients Kd confirmed that these compounds had tended to be associated with the particulate matter, the soluble glyphosate and AMPA contributed, on the average, to more than 90% of the total water volume. Although the analysis of suspended particulates is considered a more sensitive strategy for glyphosate and AMPA detection in surface water, these results demonstrate the need to analyze the soluble phase. The continual occurrence throughout a 3-year sampling was sufficient evidence demonstrating the use of glyphosate in horticulture.

Carbamazepine Degradation Mediated by Light in the Presence of Humic Substances-Coated Magnetite Nanoparticles.

The use of iron-based nanomaterials for environmental remediation processes has recently received considerable attention. Here, we employed core-shell magnetite-humic acids nanoparticles as a heterogeneous photosensitizer and iron source in photo-Fenton reaction for the degradation of the psychiatric drug carbamazepine (CBZ). CBZ showed low photodegradation rates in the presence of the magnetic nanoparticles, whereas the addition of hydrogen peroxide at pH = 3 to the system drastically increased the abatement of the contaminant. The measured Fe2+ and Fe3+ profiles point to the generation of Fe3+ at the surface of the nanoparticles, indicating a heterogeneous oxidation of the contaminant mediated by hydroxyl radicals. Products with a higher transformation degree were observed in the photo-Fenton procedure and support the attack of the HO• radical on the CBZ molecule. Promising results encourage the use of the nanoparticles as efficient iron sources with enhanced magnet-sensitive properties, suitable for applications in photo-Fenton treatments for the purification of wastewater.

Glyphosate and AMPA, "pseudo-persistent" pollutants under real-world agricultural management practices in the Mesopotamic Pampas agroecosystem, Argentina.

In the Pampas, public concern has strongly risen because of the intensive use of glyphosate for weed control and fallow associated with biotech crops. The present study was aimed to evaluate the occurrence and concentration of the herbicide and its main metabolite (AMPA) in soil and other environmental compartments of the mentioned agroecosystem, including groundwater, in relation to real-world agricultural management practices in the region. Occurrence was almost ubiquitous in solid matrices (83-100%) with maximum concentrations among the higher reported in the world (soil: 8105 and 38939; sediment: 3294 and 7219; suspended particulate matter (SPM): 584 and 475 µg/kg of glyphosate and AMPA). Lower detection frequency was observed in surface water (27-55%) with maximum concentrations in whole water of 1.80 and 1.90 µg/L of glyphosate and AMPA, indicating that SPM analysis would be more sensitive for detection in the aquatic ecosystem. No detectable concentrations of glyphosate or AMPA were observed in groundwater. Glyphosate soil concentrations were better correlated with the total cumulative dose and total number of applications than the last spraying event dose, and an increment of 1 mg glyphosate/kg soil every 5 spraying events was estimated. Findings allow to infer that, under current practices, application rates are higher than dissipation rates. Hence, glyphosate and AMPA should be considered "pseudo-persistent" pollutants and a revisions of management procedures, monitoring programs, and ecological risk for soil and sediments should be also recommended.

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. © 2017 SETAC.

Occurrence of glyphosate and AMPA in an agricultural watershed from the southeastern region of Argentina.

Glyphosate (GLY) and AMPA concentrations were determined in sandy soil profiles, during pre- and post-application events in two agricultural soybean fields (S1 and S2). Streamwater and sediment samples were also analyzed. Post-application sampling was carried out one month later from the event. Concentrations of GLY+AMPA in surface soils (0-5 cm depth) during pre-application period showed values 20-fold higher (0.093-0.163 µg/g d.w.) than control area (0.005 µg/g d.w.). After application event soils showed markedly higher pesticide concentrations. A predominance of AMPA (80%) was observed in S1 (early application), while 34% in S2 for surface soils. GLY+AMPA concentrations decreased with depth and correlated strongly with organic carbon (r between 0.74 and 0.88, p<0.05) and pH (r between -0.81 and -0.76, p<0.001). The slight enrichment of pesticides observed from 25 cm depth to deeper layer, in addition to the alkaline pH along the profile, is of high concern about groundwater contamination. Sediments from pre-application period showed relatively lower pesticide levels (0.0053-0.0263 µg/g d.w.) than surface soil with a predominance of glyphosate, indicating a limited degradation. Levels of contaminants (mainly AMPA) in streamwater (ND-0.5 ng/mL) denote the low persistence of these compounds. However, a direct relationship in AMPA concentration was observed between sediment and streamwater. Despite the known relatively short half-life of glyphosate in soils, GLY+AMPA occurrence is registered in almost all matrices at different sampling times (pre- and post-application events). The physicochemical characteristics (organic carbon, texture, pH) and structure of soils and sediment in addition to the time elapsed from application determined the behavior of these contaminants in the environment. As a whole, the results warn us about vertical transport trough soil profile with the possibility of reaching groundwater.

Atrazine and metribuzin sorption in soils of the Argentinean humid pampas.

Laboratory studies were conducted to determine the influence of surface and subsurface properties of three representative soils of the humid pampas of Argentina on atrazine and metribuzin sorption. Atrazine and metribuzin sorption isotherms were constructed for each soil at four depths. Sorption affinity of herbicides was approximated by the Freundlich constant (K(f)), distribution coefficient (Kd), and the normalized Kd based on organic carbon content (K(oc)). Multiple regression of the sorption constants against selected soil properties indicated that organic carbon content (OC) and silt were related positively and negatively, respectively, to atrazine K(f) coefficient (r2 = 0.93), while Kd coefficient of atrazine was related positively to organic carbon content and negatively to both silt and cation exchange capacity (CEC) (r2 = 0.96). For metribuzin, only organic matter content was related positively to Kr coefficient (r2 = 0.51). Lower K(f) values for atrazine were obtained for all soils with increasing depth, indicating lesser sorption at greater depths. Metribuzin sorption was quite similar across all depths. Sorption constant K(f) of atrazine ranged from 2.06 to 7.82, while metribuzin K(f) values ranged from 1.8 to 3.52 and were lower than atrazine for all soils and depths, indicating a greater leaching potential across the soil profile.

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 world's 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.

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.