The U.S. Geological Survey method (0-2141-09) presented is approved for the determination of glyphosate, its degradation product aminomethylphosphonic acid (AMPA), and glufosinate in water. It was was validated to demonstrate the method detection levels (MDL), compare isotope dilution to standard addition, and evaluate method and compound stability. The original method USGS analytical method 0-2136-01 was developed using liquid chromatography/mass spectrometry and quantitation by standard addition. Lower method detection levels and increased specificity were achieved in the modified method, 0-2141-09, by using liquid chromatography/tandem mass spectrometry (LC/MS/MS). The use of isotope dilution for glyphosate and AMPA and pseudo isotope dilution of glufosinate in place of standard addition was evaluated. Stable-isotope labeled AMPA and glyphosate were used as the isotope dilution standards. In addition, the stability of glyphosate and AMPA was studied in raw filtered and derivatized water samples. The stable-isotope labeled glyphosate and AMPA standards were added to each water sample and the samples then derivatized with 9-fluorenylmethylchloroformate. After derivatization, samples were concentrated using automated online solid-phase extraction (SPE) followed by elution in-line with the LC mobile phase; the compounds separated and then were analyzed by LC/MS/MS using electrospray ionization in negative-ion mode with multiple-reaction monitoring. The deprotonated derivatized parent molecule and two daughter-ion transition pairs were identified and optimized for glyphosate, AMPA, glufosinate, and the glyphosate and AMPA stable-isotope labeled internal standards. Quantitative comparison between standard addition and isotope dilution was conducted using 473 samples analyzed between April 2004 and June 2006. The mean percent difference and relative standard deviation between the two quantitation methods was 7.6 plus or minus 6.30 (n = 179), AMPA 9.6 plus or minus 8.35 (n = 206), and glufosinate 9.3 plus or minus 9.16 (n = 16). The analytical variation of the method, comparison of quantitation by isotope dilution and multipoint linear regressed standard curves, and method detection levels were evaluated by analyzing six sets of distilled-water, groundwater, and surface-water samples spiked in duplicate at 0.0, 0.05, 0.10 and 0.50 microgram per liter and analyzed on 6 different days during 1 month. The grand means of the normalized concentration percentage recovery for glyphosate, AMPA, and glufosinate among all three matrices and spiked concentrations ranged from 99 to 114 plus or minus 2 to 7 percent of the expected spiked concentration. The grand mean of the percentage difference between concentrations calculated by standard addition and linear regressed multipoint standard curves ranged from 8 to 15 plus or minus 2 to 9 percent for the three compounds. The method reporting levels calculated from all the 0.05- microgram per liter spiked samples were 0.02 microgram per liter for all three compounds. Compound stability experiments were conducted on 10 samples derivatized four times for periods between 136 to 269 days. The glyphosate and AMPA concentrations remained relatively constant in samples held up to 136 days before derivatization. The half life of glyphosate varied from 169 to 223 days in the underivatized samples. Derivatized samples were analyzed the day after derivitization, and again 54 and 64 days after derivatization. The derivatized samples analyzed at days 52 and 64 were within 20 percent of the concentrations of the derivatized samples analyzed the day after derivatization.

A number of major studies to analyze triazine herbicides and their degradation products (i.e., metabolites) in water have been carried out by the United States Geological Survey (USGS), Water Resources Division, in the Toxic Substances Hydrology Program. These studies investigated four major water resources - groundwater, surface water, reservoirs, and precipitation.Reconnaissance studies of groundwater wells in the midwestern United States identified the relationship between land use, groundwater age, and concentration and occurrence of herbicides and their degradation products in groundwater. The studies also described the frequency of herbicide detection in relation to analytical reporting limits, groundwater age in relation to the frequency of herbicide detections, and the persistence of degradation products. Studies revealed that pre-1953 groundwater (before most herbicides were used on a large scale) had a much lower herbicide detection frequency than post-1953 (similar to 16% versus 70%). This is logical since the percentage of detections that occur in groundwater is a function of the detection limit of the method used and more sensitive methods continue to be developed. Parent herbicides are not detected as frequently in groundwater as are degradation products. Finally, herbicides that have a long half-life are detected more frequently in groundwater.Surface water runoff studies in the midwestern United States began in 1989. A reconnaissance study of 147 streams was conducted to determine the geographic and seasonal distribution of herbicides. The data showed that herbicides were flushed from cropland and were transported through the surface water system as pulses in response to late spring and early summer precipitation. Median concentrations of atrazine and cyanazine increased by one order of magnitude and then decreased to near pre-planting levels by harvest sampling. Deethylatrazine (DEA) and deisopropylatrazine (DIA) also occurred in samples, indicating either that some of the parent herbicides remained from the previous year or there was early pre-plant atrazine application before the sampling period. The data also show that the ratio of DEA to atrazine (called the DAR), which has been used as an indicator of atrazine from non-point sources, may be used also as a tracer of movement into rivers. The concentrations of these degradation products vary with the hydrologic conditions of the basin and the timing of runoff. Also, changes in herbicide usage and best management practices have significantly decreased the amount of atrazine and cyanazine concentrations found in surface water. Trends for atrazine concentrations show a median of 10.9 micrograms per liter (mu g/L) in 1989, 5.54 mu g/L in 1995, and 4.27 mu g/L in 1998. There was also a decrease of cyanazine concentration in surface water over years with a median of 2.65 mu g/L in 1989, 1.35 mu g/L in 1995, and 0.44 mu g/L in 1998.The third major water resource study involved 76 reservoirs located in 11 midwestern states. These studies determined the occurrence and temporal distribution of herbicides and their degradation products in the outflow from selected reservoirs in the upper Midwest; they also explored whether the occurrence of herbicides in the reservoir outflow could be related to drainage-basin characteristics, water and land use, herbicide use, and climate. It was found that reservoirs are repositories for herbicides from midwestern streams and that herbicides and their degradation products were detected more frequently throughout the year in reservoirs than in streams. Reservoirs hold runoff from cropland causing herbicide concentrations to decrease downstream, and they dampen the pulse of herbicides that occur during the spring flush.The fourth major water resource examined by these studies was precipitation. The area studied included 26 states from the upper Midwest (where herbicide use is prevalent) and the Northeast. The results identified the occurrence and temporal distribution of triazine herbicides and their degradation products in the Midwest. The highest concentrations occurred following herbicide application to cropland. From mid-April to mid-July in 1990 and 1991, volume-weighted concentrations of 0.2-0.4 mu g/L for atrazine were typical throughout the Midwest, and volume-weighted concentrations as large as 0.6-0.9 mu g/L occurred in precipitation at several sites. Atrazine was detected most often, followed by DEA, cyanazine, and DIA. Herbicide deposits were greatest in areas where herbicide use was high and decreased with distance from the Midwest.

The U.S. Geological Survey conducted a number of studies from 2001 through 2006 to investigate and document the occurrence, fate, and transport of glyphosate, its degradation product, aminomethylphosphonic acid (AMPA), and glufosinate in 2,135 ground- and surface-water samples, 14 rainfall samples, and 193 soil samples. Analytical methods were developed to detect and measure glyphosate, AMPA, and glufosinate in water, rainfall, and soil. Results show that AMPA was detected more frequently and occurred at similar or higher concentrations than the parent compound, glyphosate, whereas glufosinate was seldom found in the environment. Glyphosate and AMPA were detected more frequently in surface water than in ground water. Trace levels of glyphosate and AMPA may persist in the soil from year to year. The methods and data described in this report are useful to researchers and regulators interested in the occurrence, fate, and transport of glyphosate and AMPA in the environment.

An analytical method for the determination of isoxaflutole and its sequential degradation products, diketonitrile and a benzoic acid analogue, in filtered water with varying matrices was developed by the U.S. Geological Survey Organic Geochemistry Research Group in Lawrence, Kansas. Four different water-sample matrices fortified at 0.02 and 0.10 ug/L (micrograms per liter) are extracted by vacuum manifold solid-phase extraction and analyzed by liquid chromatography/tandem mass spectrometry using electrospray ionization in negative-ion mode with multiple-reaction monitoring (MRM). Analytical conditions for mass spectrometry detection are optimized, and quantitation is carried out using the following MRM molecular-hydrogen (precursor) ion and product (p) ion transition pairs: 357.9 (precursor), 78.9 (p), and 277.6 (p) for isoxaflutole and diketonitrile, and 267.0 (precursor), 159.0 (p), and 223.1 (p) for benzoic acid. 2,4-dichlorophenoxyacetic acid-d3 is used as the internal standard, and alachlor ethanesulfonic acid-d5 is used as the surrogate standard. Compound detection limits and reporting levels are calculated using U.S. Environmental Protection Agency procedures. The mean solid-phase extraction recovery values ranged from 104 to 108 percent with relative standard deviation percentages ranging from 4.0 to 10.6 percent. The combined mean percentage concentration normalized to the theoretical spiked concentration of four water matrices analyzed eight times at 0.02 and 0.10 ug/L (seven times for the reagent-water matrix at 0.02 ug/L) ranged from approximately 75 to 101 percent with relative standard deviation percentages ranging from approximately 3 to 26 percent for isoxaflutole, diketonitrile, and benzoic acid. The method detection limit (MDL) for isoxaflutole and diketonitrile is 0.003 ug/L and 0.004 ug/L for benzoic acid. Method reporting levels (MRLs) are 0.011, 0.010, and 0.012 ug/L for isoxaflutole, diketonitrile, and benzoic acid, respectively. On the basis of the calculated MRLs and MDLs and evaluation of the signal-to-noise ratios for each compound, the MRLs and MDLs are set at 0.010 and 0.003 ug/L, respectively, for all three compounds.

Isoxaflutole (IXF), a newer low application rate herbicide, was introduced for weed control in corn (Zea mays) to use as an alternative to widely applied herbicides such as atrazine. The transport of IXF in streamwater has not been well-studied. The fate and transport of IXF and two of its degradation products was studied in 10 Iowa rivers during 2004. IXF rapidly degrades to the herbicidally active diketonitrile (DKN), which degrades to a biologically inactive benzoic acid (BA) analogue. IXF was detected in only four, DKN in 56, and BA in 43 of 75 samples. The concentrations of DKN and BA were approximately 2 orders of magnitude less than those of the commonly detected triazine and acetamide herbicides and their degradation products. Concentrations of IXF, DKN, and BA were highest during the May through June postplanting period. The concentration ratio of BA/DKN was similar to the deethylatrazine/atrazine ratio with smaller ratios occurring during May and June. The relative temporal variation of DKN and BA was similar to that observed for atrazine and deethylatrazine. This study shows that low application rate herbicides can have similar temporal transport patterns in streamwater as compared to more widely applied herbicides but at lower concentrations.

During 2004, a study to document the occurrence of herbicides and herbicide degradation products was conducted for 10 major Iowa rivers draining to the Missouri and Mississippi Rivers. Seventy-five water-quality samples were collected to measure isoxaflutole, acetamide, and triazine herbicides and their herbicide degradation products. An analytical method to measure isoxaflutole and its degradation products, diketonitrile and benzoic acid, was developed by the U.S. Geological Survey Organic Geochemistry Research Laboratory in Lawrence, Kansas, using vacuum manifold solid-phase extraction and liquid chromatography/mass spectrometry/mass spectrometry and is described in this report. Isoxaflutole, a low application rate preemergence herbicide for control of annual broadleaf weeds, is used extensively in Iowa. Findings from the study documented in this report indicate that isoxaflutole was designed to degrade quickly to diketonitrile, which appears to be more stable, and then to benzoic acid. Of the 75 samples collected to measure isoxaflutole, there were four detections of isoxaflutole, 53 detections of diketonitrile, and 41 detections of benzoic acid. Also, results of acetamide and triazine water-quality samples correlate with past studies, which indicate that herbicide degradation products are detected more frequently and often at higher concentrations in surface water than their parent compounds. In addition to analysis of isoxaflutole and its degradation products, samples were analyzed by the USGS National Water-Quality Laboratory schedule 2001 for about 52 pesticides and their degradation products.

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In accordance with the mission of the U.S. Geological Survey (USGS) Toxic Substances Hydrology Program, a pesticide study was conducted during 2003–04 to determine the occurrence of the fungicide chlorothalonil and its degradation products at 22 surface-water sites in five Southern States. Water-quality samples were collected during the peanut-growing season (June–September) in 2003. During the peanut-growing season in 2004, samples were collected after large storms.An analytical method was developed at the USGS Organic Geochemistry Research Laboratory in Lawrence, Kansas, to measure chlorothalonil and its degradation products by liquid chromatography/mass spectrometry (LC/MS). Chlorothalonil was detected in 4 of the 113 surface-water samples. The primary degradation product of chlorothalonil, 4-hydroxy-chlorothalonil, was detected in 26 of the 113 samples with concentrations ranging from 0.002 to 0.930 microgram per liter. The chlorothalonil degradation products, 1-amide-4-hydroxy-chorothalonil and 1,3-diamide-chlorothalonil, were detected in one water sample each at 0.020 and 0.161 microgram per liter, respectively.The USGS Methods and Research Development Group, Lakewood, Colorado, developed a custom method for chlorothalonil using gas chromatography/mass spectrometry (GC/MS) in an effort to achieve a lower laboratory reporting level (LRL) than the USGS National Water-Quality Laboratory (NWQL) schedule 2060, which analyzes the compound chlorothalonil at a LRL of 0.035 µg/L. The group succeeded in achieving a lower GC/MS reporting level of 0.01 µg/L. Chlorothalonil was detected in 5 of 68 water samples analyzed using the custom GC/MS method, whereas chlorothalonil was detected in 2 of 21 water samples analyzed using NWQL schedule 2060.In addition to analysis of chlorothalonil and its degradation products, samples were analyzed using the USGS NWQL schedules 2001 and 2060 for about 114 pesticides and their degradation products. Samples also were analyzed for dissolved organic carbon, suspended sediment, and percentage of silt- and clay-sized particles.Overall, it was found that chlorothalonil was detected only infrequently and at relatively low concentrations. Chlorothalonil’s major degradation product, 4-hydroxy-chlorothalonil, was detected most frequently, occurred generally at higher concentrations in water samples than did the parent fungicide, and the data from this study reaffirmed that it is the dominant degradation product of chlorothalonil in the peanut-growing environment.

Nonpoint-source contamination of water resources from triazine herbicides has been a major water-quality issue during the 1990s in the United States. To address this issue, studies of surface water, ground water, and precipitation have been carried out by the U.S. Geological Survey in the Midwestern United States. Reconnaissance studies of 147 streams were conducted to determine the geographic and seasonal distribution of atrazine, cyanazine, propazine, and simazine. These studies showed that high concentrations of herbicides were flushed from cropland and transported through the stream system as pulses in response to spring and summer rainfall. The studies also revealed the persistence of herbicides and their degradation products in streams. An investigation of 76 reservoirs showed that the occurrence and temporal distribution of herbicides and their degradation products in reservoir outflow could be related to reservoir and drainage-basin characteristics, water and land use, herbicide use, and climate. Significant findings showed that concentrations of atrazine and its degradation products remained elevated all summer and into the fall and that recently applied atrazine mixed with atrazine applied the previous year as water moved through a reservoir. Reconnaissance studies of 303 ground-water wells were completed to determine hydrogeological and seasonal occurrence, concentration, and distribution of herbicides and their degradation products. Samples collected from across the Midwestern United States consistently revealed that triazine herbicide degradation products commonly were found more frequently than their parent herbicide and that ground-water age could be an important factor in explaining variations in herbicide contamination. A final study investigated precipitation in the Midwestern United States, northeast to the Atlantic Ocean, and northward to the Canadian border. It found that the highest herbicide concentrations in precipitation occurred following herbicide application to cropland. Atrazine was detected most often, followed by deethylatrazine, cyanazine, and deisoproplyatrazine. Mass deposition of herbicides by precipitation was greatest in areas where herbicide use was intense and decreased with distance from the Midwest. Findings of the 1990s studies include an improved understanding of the occurrence, persistence, chemistry, and transport of triazine herbicides and their degradation products in the hydrologic environment. A significant increase in knowledge of triazine herbicides and development and improvement of analytical methods were accomplished in the past decade. The results produced are not only significant for the present (2005) but provide an important data set for future use.

This fact sheet introduces a study of the nonpoint-source occurrence of pesticides in water of the cotton-growing areas of the Southern United States with special emphasis on the Mississippi Embayment (fig.1).This study is being conducted by the U.S.

Water samples were collected from nine streams in five Midwestern States during 1990 and from two of the nine streams during 1991-92 to determine the concentration, temporal distribution, and transport of 11 agricultural herbicides, two triazine metabolites, and nutrients during storm runoff.This report presents a description of the sampling plan, data-collection techniques, laboratory methods, and a compilation of herbicide and nutrient concentration and quality-assurance data.Samples were collected at nine sites during April through August 1990 by a combination of manual sampling and automatic samplers.Automatic samplers were programmed to collect samples during baseflow conditions and when runoff from precipitation occurred.Sampling was continued at two sites during March 1991 through April 1992 using the same sampling procedures used in 1990.Approximately 2,000 samples were collected from the nine sites in 1990, and about 400 samples were collected from two sites in 1991-92.Laboratory analyses consisted of microtitre-plate enzyme-linked immunosorbent assay for triazine and chloroacetanilide herbicides and confirmation of selected samples by gas chromatography/mass spectrometry.The data have been useful in studying herbicide and nutrient transport, in showing that atrazine and cyanazine are the major triazine herbicides and that alachlor and metolachlor are the primary chloroacetanilide herbicides present in water samples, and in examining the annual persistence of herbicides in surface water.Introduction 1 CO distilled water and sample water prior to collection of the filtrate.All samples were chilled immediately.Herbicide samples were shipped to the USGS laboratory in Lawrence, Kansas, for immunoassay and GC/MS analysis (Thurman and others , 1990).Nutrient samples were shipped to the USGS laboratory in Arvada, Colorado, for analysis (Fishman and Friedman, 1989). Laboratory MethodsHerbicide sample bottles received at