Fate and transport of glyphosate and aminomethylphosphonic acid in surface waters of agricultural basins.
TL;DR: Glyphosate use in a watershed results in some occurrence in surface water; however, the watersheds most at risk for the offsite transport of glyphosate are those with high application rates, rainfall that results in overland runoff and a flow route that does not include transport through the soil.
Abstract: BACKGROUND: Glyphosate [N-(phosphonomethyl)glycine] is a herbicide used widely throughout the world in the production of many crops and is heavily used on soybeans, corn and cotton. Glyphosate is used in almost all agricultural areas of the United States, and the agricultural use of glyphosate has increased from less than 10000 Mg in 1992 to more than 80000 Mg in 2007. The greatest intensity of glyphosate use is in the midwestern United States, where applications are predominantly to genetically modified corn and soybeans. In spite of the increase in usage across the United States, the characterization of the transport of glyphosate and its degradate aminomethylphosphonicacid (AMPA) on a watershed scale is lacking. RESULTS: Glyphosate and AMPA were frequently detected in the surface waters of four agricultural basins. The frequency and magnitude of detections varied across basins, and the load, as a percentage of use, ranged from 0.009 to 0.86% and could be related to three general characteristics: source strength, rainfall runoff andflow route. CONCLUSIONS: Glyphosate use in a watershed results in some occurrence in surface water; however, the watersheds most at risk for the offsite transport of glyphosate are those with high application rates, rainfall that results in overland runoff and a flow route that does not include transport through the soil. c � 2011 Society of Chemical Industry
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TL;DR: An analytical approach was developed to develop an analytical approach to study the environmental fate of AAPs and identified N-(methylamino)methanephosphonic acid (MAMPA) was identified for the first time as the product of decomposition of the examined aminopolyphosphonates.
Abstract: Aminopolyphosphonates (AAPs) are commonly used industrial complexones of metal ions, which upon the action of biotic and abiotic factors undergo a breakdown and release their substructures. Despite the low toxicity of AAPs towards vertebrates, products of their transformations, especially those that contain phosphorus and nitrogen, can affect algal communities. To verify whether such chemical entities are present in water ecosystems, much effort has been made in developing fast, inexpensive, and reliable methods for analyzing phosphonates. However, unfortunately, the methods described thus far require time-consuming sample pretreatment and offer relatively high values of the limit of detection (LOD). The aim of this study was to develop an analytical approach to study the environmental fate of AAPs. Four phosphonic acids, N,N-bis(phosphonomethyl)glycine (GBMP), aminotris(methylenephosphonic) acid (ATMP), hexamethylenediamine-N,N,N′,N′-tetrakis(methylphosphonic) acid (HDTMP), and diethylenetriamine penta(methylenephosphonic) acid (DTPMP) were selected and examined in a water matrix. In addition, the susceptibility of these compounds to biotransformations was tested in colonies of five freshwater cyanobacteria—microorganisms responsible for the so-called blooms in the water. Our efforts to track the AAP decomposition were based on derivatization of N-alkyl moieties with p-toluenesulfonyl chloride (tosylation) followed by chromatographic (HPLC-UV) separation of derivatives. This approach allowed us to determine seven products of the breakdown of popular phosphonate chelators, in nanomolar concentrations and in one step. It should be noted that the LOD of four of those products, aminemethylphosphonic acid (AMPA), N-phosphomethyl glycine (NPMG), N-(methyl)aminemethanephosphonic acid (MAMPA), and N-(methyl) glycine (SAR), was set below the concentration of 50 nM. Among those substances, N-(methylamino)methanephosphonic acid (MAMPA) was identified for the first time as the product of decomposition of the examined aminopolyphosphonates.
8 citations
Cites background from "Fate and transport of glyphosate an..."
...For example, N-phosphonomethyl glycine and AMPA have been detected in Mississippi River basin at levels above 0.1 μg L−1 Responsible editor: Vitor Manuel Oliveira Vasconcelos * Jacek Lipok jacek.lipok@uni.opole.pl 1 Faculty of Chemistry, Opole University, Oleska 48, 45-052 Opole, Poland (Coupe et al. 2012)....
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...…N-phosphonomethyl glycine and AMPA have been detected in Mississippi River basin at levels above 0.1 μg L−1 Responsible editor: Vitor Manuel Oliveira Vasconcelos * Jacek Lipok jacek.lipok@uni.opole.pl 1 Faculty of Chemistry, Opole University, Oleska 48, 45-052 Opole, Poland (Coupe et al. 2012)....
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...Demand for organophosphonates has intensified in recent years because thousands of tons of these compounds are consumed by industry, agriculture, and households each year (Benbrook 2016, Coupe et al. 2012, Studnik et al. 2015)....
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TL;DR: The relative toxicity of glyphosate (GLY) and its metabolite aminomethylphosphonic acid (AMPA) to zebrafish were compared in this paper , where the larvae were exposed to one dose of either GLY (0.1, 1, or 10 μM), AMPA (0., 1, 1 or 10μM), or a 1 μM mixture for 7-days post-fertilization.
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TL;DR: In this paper, a case study on long-term no-tillage farming systems in Brazil, where Glyphosate (GLY) has been applied for more than 35 years, was presented.
Abstract: With the growing global concern on pesticide management, the relationship between its environmental recalcitrance, food security and human health has never been more relevant. Pesticides residues are known to cause significant environmental contamination. Here, we present a case study on long-term no-tillage farming systems in Brazil, where Glyphosate (GLY) has been applied for more than 35 years. GLY and its main breakdown product, aminomethylphosphonic acid (AMPA) were determined in topsoil (0–10 cm) samples from no-tillage fields and nearby subtropical secondary forests by high-performance liquid chromatography coupled with a fluorescence detector. In addition, the presence of carbamates, organochlorines, organophosphates and triazines were also screened for. GLY and AMPA were present in all soil samples, reaching values higher than those described for soils so far in the literature. A significant decrease for AMPA was observed only between the secondary forest and the farm's middle slope for site B. GLY and AMPA were observed respectively at peak concentrations of 66.38 and 26.03 mg/kg soil. GLY was strongly associated with forest soil properties, while AMPA associated more with no-tillage soil properties. Soil texture was a significant factor contributing to discrimination of the results as clay and sand contents affect GLY and AMPA retention in soils. This was the first study to report DDT and metabolites in consolidated no-tillage soils in Brazil (a pesticide fully banned since 2009). Based on human risk assessment conducted herein and the potential risk of GLY to local soil communities, this study offers a baseline for future studies on potential adverse effects on soil biota, and mechanistic studies.
8 citations
TL;DR: It is reported that glyphosate affects developmental stages and demonstrates toxicity and damage in zebrafish, and glyphosate causes damage in the embryonic, larval and adult stages of this species.
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TL;DR: In this paper, the null hypothesis that nitrification and the distribution of archaeal and bacterial nitrifying communities would not be impacted by long-term applications of the herbicide, glyphosate, to glyphosate-resistant (gR) and non-glyphosate-resistant corn (nongR) under conventional tillage (CT) and reduced-tillage (RT) systems was tested.
Abstract: We tested the null hypothesis that nitrification and the distribution of archaeal and bacterial nitrifying communities would not be impacted by long-term applications of the herbicide, glyphosate, to glyphosate-resistant (gR) and non-glyphosate-resistant corn (nongR) under conventional tillage (CT) and reduced tillage (RT) systems. Bulk and rhizosphere soil nitrification poten-tial rates and quantification of amoA genes of archaeal (AOA) and bacterial (AOB) communities were undertaken. In 2013, the nitrification rate of nongR corn with no glyphosate application treatment associated with bulk and rhi-zosphere soils under RT displayed greater (P < 0.05) nitrification rates than gR corn with glyphosate applications. In 2014, the nitrification rate of the rhizosphere soil under RT in gR corn with no glyphosate application treat-ment was greater (P < 0.05) than other rhizosphere soil treatments. Ratios between archaeal and bacterial amoA genes indicated distinct dominance of AOA communities in the rhizosphere soil. The ratios between AOA and AOB amoA genes in bulk soil were more balanced. Regression analyses indicated more significant correlations between nitrification potential determinations and bulk soil nutrients ratios, nutrient acquisition ratios, and microbial com-munities than between analogous rhizosphere soil characteristics. Compared to non-glyphosate treatments, glyphosate applications appeared to disrupt rhizosphere nutrient, exoenzymatic, and microbial relationships. glyphosate applications had an inconsistent inhibitory effect on the nitrification process. In contrast to bulk soil, rhizosphere soil nitrifying communities were most likely in competition with corn roots for ammonia-n, and were thus dominat-ed by more oligotrophic archaeal nitrifiers compared to bacterial nitrifiers.
8 citations
Cites background from "Fate and transport of glyphosate an..."
...Published online January 4, 2018 1372 Soil Science Society of America Journal Glyphosate is a xenobiotic compound with a half-life in soil ranging between 1.7 and 142 d (Coupe et al., 2011)....
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References
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TL;DR: Glyphosate-based weed control products are among the most widely used broad-spectrum herbicides in the world and have been extensively investigated for their potential to produce adverse effects in nontarget organisms as discussed by the authors.
Abstract: Glyphosate-based weed control products are among the most widely used broad-spectrum herbicides in the world. The herbicidal properties of glyphosate were discovered in 1970, and commercial formulations for nonselective weed control were first introduced in 1974 (Franz et al. 1997). Formulations of glyphosate, including Roundup® Herbicide (RU)1 (Monsanto Company, St. Louis, MO), have been extensively investigated for their potential to produce adverse effects in nontarget organisms. Governmental regulatory agencies, international organizations, and others have reviewed and assessed the available scientific data for glyphosate formulations and independently judged their safety. Conclusions from three major organizations are publicly available and indicate RU can be used with minimal risk to the environment (Agriculture Canada 1991; USEPA 1993a; WHO 1994). Several review publications are available on the fate and effects of RU or glyphosate in the environment (Carlisle and Trevors 1988;Smith and Oehme 1992 ; Malik et al. 1989;Rueppel et al. 1977; Sullivan and Sullivan 1997;Forestry Canada, 1989). In addition, several books have been published about the environmental and human health considerations of glyphosate and its formulations (Grossbard and Atkinson 1985; Franz et al. 1997). In addition, RU and other glyphosate formulations have been selected for use in a number of weed control programs for state and local jurisdictions in the United States. Many of these uses require that ecological risk assessments be conducted in the form of Environmental Impact Statements or Environmental Assessments. These documents are comprehensive and specific to local use situations. Documents are available for risk assessments in Texas, Washington, Oregon, Pennsylvania, New York, Virginia, and other states (USDA 1989;USDA 1992;USDA 1996;USDA 1997;USDI 1989; Washington State DOT 1993).
883 citations
TL;DR: The literature on pesticide losses in runoff waters from agricultural fields is reviewed in this paper, where the majority of commercial pesticides, total losses are 0.5%0 or less of the amounts applied, unless severe rainfall conditions occur within 1-2 weeks after application.
Abstract: The literature on pesticide losses in runoff waters from agricultural fields is reviewed. For the majority of commercial pesticides, total losses are 0.5%0 or less of the amounts applied, unless severe rainfall conditions occur within 1–2 weeks after application. Exceptions are the organochlorine insecticides, which may lose about 1% regardless of weather pattern because of their long persistence; and soil surface-applied, wettable-powder formulations of herbicides, which may lose up to 5%, depending on weather and slope, because of the ease of washoff of the powder.Pesticides with solubilities of 10 ppm or higher are lost mainly in the water phase of runoff, and erosion control practices will have little effect on such losses. Organochlorine pesticides, paraquat, and arsenical pesticides, however, are important cases of pesticides which are strongly adsorbed by sediments, and erosion control can be important in controlling losses of these compounds.The behavior and fate of pesticides in streams receiving runoff is generally not known. Information on such factors as time and distance of impact of a given runoff event, ability of local ecosystems to recover from transient pesticide concentrations, and dissipation or concentration processes in aquatic ecosystems will have to be obtained before “edge-of-field” pesticide losses can be related to water quality in receiving waters.
753 citations
TL;DR: Glyphosate [N-(phosphonomethyl)glycine] was readily bound to kaolinite, illite, and bentonite clay and to charcoal and muck but not to ethyl cellulose as mentioned in this paper.
Abstract: Glyphosate [N-(phosphonomethyl)glycine] was readily bound to kaolinite, illite, and bentonite clay and to charcoal and muck but not to ethyl cellulose. Fe+++ and Al+++-saturated clays and organic matter adsorbed more glyphosate than Na+ or Ca+-saturated clays and organic matter. Glyphosate appears to be bound to the soil through the phosphonic acid moiety as phosphate in the soil competed with 14C-glyphosate for adsorption sites. Glyphosate mobility in the soil was very limited and was affected by pH, phosphate level, and soil type. The 14C-glyphosate was biodegraded in soil to 14CO2 possibly by co-metabolism. Potentiometric titrations of the compound gave pKa values of 2, 2.6, 5.6, and 10.6.
444 citations
TL;DR: Glyphosate-resistant crops have promoted the adoption of reduced- or no-tillage agriculture in the USA and Argentina, providing a substantial environmental benefit and the development and use of failsafe introgression barriers in crops with such linked genes is needed.
Abstract: Glyphosate [N-(phosphonomethyl) glycine]-resistant crops (GRCs), canola (Brassica napus L.), cotton (Gossypium hirsutum L.), maize (Zea mays L.), and soybean [Glycine max (L.) Merr.] have been commercialized and grown extensively in the Western Hemisphere and, to a lesser extent, elsewhere. Glyphosate-resistant cotton and soybean have become dominant in those countries where their planting is permitted. Effects of glyphosate on contamination of soil, water, and air are minimal, compared to some of the herbicides that they replace. No risks have been found with food or feed safety or nutritional value in products from currently available GRCs. Glyphosate-resistant crops have promoted the adoption of reduced- or no-tillage agriculture in the USA and Argentina, providing a substantial environmental benefit. Weed species in GRC fields have shifted to those that can more successfully withstand glyphosate and to those that avoid the time of its application. Three weed species have evolved resistance to glyphosate in GRCs. Glyphosate-resistant crops have greater potential to become problems as volunteer crops than do conventional crops. Glyphosate resistance transgenes have been found in fields of canola that are supposed to be non-transgenic. Under some circumstances, the largest risk of GRCs may be transgene flow (introgression) from GRCs to related species that might become problems in natural ecosystems. Glyphosate resistance transgenes themselves are highly unlikely to be a risk in wild plant populations, but when linked to transgenes that may impart fitness benefits outside of agriculture (e.g., insect resistance), natural ecosystems could be affected. The development and use of failsafe introgression barriers in crops with such linked genes is needed.
387 citations
TL;DR: In this paper, the Soil and Water Assessment Tool (SWAT) water quality model is designed to assess nonpoint and point source pollution and was recently modified for tile drainage.
Abstract: The presence of subsurface tile drainage systems can facilitate nutrient and pesticide transport, thereby contributing to environmental pollution. The Soil and Water Assessment Tool (SWAT) water quality model is designed to assess nonpoint and point source pollution and was recently modified for tile drainage. Over 25% of the nation's cropland required improved drainage. In this study, the model's ability to validate the tile drainage component is evaluated with nine years of hydrologic monitoring data collected from the South Fork watershed in Iowa, since about 80% of this watershed is tile drained. This watershed is a Conservation Effects Assessment Program benchmark watershed and typifies one of the more intensively managed agricultural areas in the Midwest. Comparison of measured and predicted values demonstrated that inclusion of the tile drainage system is imperative for obtaining a realistic watershed water balance. Two calibration/validation scenarios tested if the results differed in how the data set was divided. The optimum scenario results for the simulated monthly and daily flows had Nash-Sutcliffe efficiency (ENS) values during the calibration/validation (1995-1998/1999-2004) periods of 0.9/0.7 and 0.5/0.4, respectively. The second scenario results for the simulated monthly and daily flows had ENS values during the calibration/validation (1995-2000/2001-2004) periods of 0.8/0.5 and 0.7/0.2, respectively. The optimum scenario reflects the distribution of peak rainfall events represented in both the calibration and validation periods. The year 2000, being extremely dry, negatively impacted both the calibration and validation results. Each water budget component of the model gave reasonable output, which reveals that this model can be used for the assessment of tile drainage with its associated practices. Water yield results were significantly different for the simulations with and without the tile flow component (25.1% and 16.9%, expressed as a percent of precipitation). The results suggest that the SWAT2005 version modified for tile drainage is a promising tool to evaluate streamflow in tile-drained regions when the calibration period contains streamflows representing a wide range of rainfall events.
209 citations