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E.M. Thurman

Publications and source records attributed to E.M. Thurman.

At least 37 records · Page 2Linked to original sources

Herbicide and degradate flux in the Yazoo River Basin

During 1996-1997, water samples were collected from five sites in the Yazoo River Basin and analysed for 14 herbicides and nine degradates. These included acetochlor, alachlor, atrazine, cyanazine, fluometuron, metolachlor, metribuzin, molinate, norflurazon, prometryn, propanil, propazine, simazine, trifluralin, three degradates of fluometuron, two degradates of atrazine, one degradate of cyanazine, norflurazon, prometryn, and propanil. Fluxes generally were higher in 1997 than in 1996 due to a greater rainfall in 1997 than 1996. Fluxes were much larger from streams in the alluvial plain (an area of very productive farmland) than from the Skuna River in the bluff hills (an area of small farms, pasture, and forest). Adding the flux of the atrazine degradates to the atrazine flux increased the total atrazine flux by an average of 14.5%. The fluometuron degradates added about 10% to the total fluometuron flux, and adding the norflurazon degradate flux to the norflurazon flux increased the flux by 82% in 1996 and by 171% in 1997.

International Journal of Environmental Analytical ↗

Herbicides and degradates in shallow aquifers of Illinois: Spatial and temporal trends

During the fall of 2000, the occurrence was examined of 16 herbicides and 13 herbicide degradates in samples from 55 wells in shallow aquifers underlying grain producing regions of Illinois. Herbicide compounds with concentrations above 0.05 μg/L were detected in 56 percent of the samples. No concentrations exceeded regulatory drinking water standards. The six most frequently detected compounds were degradates. Water age was an important factor in determining vulnerability of ground water to transport of herbicide compounds. Unconsolidated aquifers, which were indicated to generally contain younger ground water than bedrock aquifers, had a higher occurrence of herbicides (73 percent of samples) than bedrock aquifers (22 percent). Temporal analysis to determine if changes in concentrations of selected herbicides and degradates could be observed over a near decadal period indicated a decrease in detection frequency (25 to 18 percent) between samplings in 1991 and 2000. Over this period, significant differences in concentrations were observed for atrazine (decrease) and total acetochlor (increase). The increase in acetochlor compound concentrations corresponds to an increase in acetochlor use during the study period, while the decrease in atrazine concentrations corresponds to relatively consistent use of atrazine. Changes in frequency of herbicide detection and concentration do not appear related to changes in land use near sampled wells.

Illinois↗

Summary of significant results from studies of triazine herbicides and their degradation products in surface water, ground water, and precipitation in the midwestern United States during the 1990s

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.

Midwest region↗

Combination of LC/TOF-MS and LC/Ion Trap MS/MS for the Identification of Diphenhydramine in Sediment Samples

Diphenhydramine (Benadryl) is a popular over-the-counter antihistaminic medication used for the treatment of allergies. After consumption, excretion, and subsequent discharge from wastewater treatment plants, it is possible that diphenhydramine will be found in environmental sediments due to its hydrophobicity (log P = 3.27). This work describes a methodology for the first unequivocal determination of diphenhydramine bound to environmental sediments. The drug is removed from the sediments by accelerated solvent extraction and then analyzed by liquid chromatography with a time-of-flight mass spectrometer and an ion trap mass spectrometer. This combination of techniques provided unequivocal identification and confirmation of diphenhydramine in two sediment samples. The accurate mass measurements of the protonated molecules were m/z 256.1703 and 256.1696 compared to the calculated mass of m/z 256.1701, resulting in errors of 0.8 and 2.3 ppm. This mass accuracy was sufficient to verify the elemental composition of diphenhydramine in each sample. Furthermore, accurate mass measurements of the primary fragment ion were obtained. This work is the first application of time-of-flight mass spectrometry for the identification of diphenhydramine and shows the accumulation of an over-the-counter medication in aquatic sediments at five different locations.

Analytical Chemistry↗

Herbicide concentrations in the Mississippi River basin: The importance of chloroacetanilide herbicide degradates

The proportion of chloroacetanilide herbicide degradates, specifically the ethane sulfonic (ESA) and oxanilic (OA) acids, averaged 70% of the total herbicide concentration in samples from the Upper Mississippi River. In samples from the Missouri River and the Ohio River, the proportion of chloroacetanilide degradates in the total herbicide concentration was much less, 24% and 41%, respectively. The amount of tile drainage throughout the Mississippi River Basin appeared to be related to the occurrence and distribution of chloroacetanilide degradates in water samples. Pesticide concentrations in streams of the Mississippi River Basin have been well characterized. However, recent research demonstrates that in order to more fully understand the fate and transport of pesticides, the major pesticide degradates need to be included in the analysis. From March 1999 through May 2001, water samples from four major junctures of the Mississippi River Basin were collected and analyzed for a suite of herbicides and their degradate compounds. Each sampling site was selected to represent a major part of the Mississippi River: upper and lower Mississippi, Missouri and Ohio Rivers. Each basin has unique landscape variables, geology, hydrology, precipitation, and land use, which is reflected in the pesticide content at the most downstream sample site near the mouth of the Mississippi River. Atrazine was the most frequently detected herbicide (detected in 97% of the samples), followed by metolachlor (60%), and acetochlor (31%). The most frequently detected degradates were metolachlor ESA (69%), followed by deethylatrazine (62%), metolachlor OA (37%), and alachlor ESA (37%). Metolachlor ESA was detected more frequently than its parent compound (69 vs. 60%), as was alachlor ESA (37 vs. 9%). After an improvement was made in the analytical method, metolachlor ESA was detected in every sample, metolachlor OA in 89% of the samples, alachlor ESA in 84%, acetochlor ESA in 71%, and acetochlor OA in 66%.

Mississippi River Basin↗

Herbicides and herbicide degradation products in upper midwest agricultural streams during august base-flow conditions

Herbicide concentrations in streams of the U.S. Midwest have been shown to decrease through the growing season due to a variety of chemical and physical factors. The occurrence of herbicide degradation products at the end of the growing season is not well known. This study was conducted to document the occurrence of commonly used herbicides and their degradation products in Illinois, Iowa, and Minnesota streams during base-flow conditions in August 1997. Atrazine, the most frequently detected herbicide (94%), was present at relatively low concentrations (median 0.17 μg L −1 ). Metolachlor was detected in 59% and cyanazine in 37% of the samples. Seven of nine compounds detected in more than 50% of the samples were degradation products. The total concentration of the degradation products (median of 4.4 μg L −1 ) was significantly greater than the total concentration of parent compounds (median of 0.26 μg L −1 ). Atrazine compounds were present less frequently and in significantly smaller concentrations in streams draining watersheds with soils developed on less permeable tills than in watersheds with soils developed on more permeable loess. The detection and concentration of triazine compounds was negatively correlated with antecedent rainfall (April–July). In contrast, acetanalide compounds were positively correlated with antecedant rainfall in late spring and early summer that may transport the acetanalide degradates into ground water and subsequently into nearby streams. The distribution of atrazine degradation products suggests regional differences in atrazine degradation processes.

Midwest region↗

Reconnaissance data for glyphosate, other selected herbicides, their degradation products, and antibiotics in 51 streams in nine midwestern states, 2002

Since 1989, the U.S. Geological Survey has conducted periodic reconnaissance studies of streams in the Midwestern United States to determine the geographic and seasonal distribution of herbicide compounds. These studies have documented that large amounts of acetochlor, alachlor, atrazine, cyanazine, metolachlor, and their degradation products are flushed into streams during post-application runoff. Additional studies show that peak herbicide concentrations tend to occur during the first runoff after herbicide application and that herbicide flushes can occur during runoff for several weeks to months following application. Since the first stream study conducted in 1989, several significant changes in herbicide use have occurred. The most substantial change is the tripling in the use of glyphosate during the past 5 years. Over this same time period (1997-2001), usage of acetochlor and atrazine increased slightly, whereas alachlor, cyanazine, and metolachlor usage decreased. During 2002, 154 samples were collected from 51 streams in nine Midwestern States during three periods of runoff. This report provides a compilation of the analytical results of five laboratory methods. Results show that glyphosate was detected in 55 (36 percent) of the samples, and aminomethylphosphonic acid (a degradation product of glyphosate) was detected in 107 (69 percent) of the samples. Atrazine, the most frequently detected herbicide, was found in 93 percent of the samples, followed by metolachlor, found in 73 percent of the samples; metolachlor ethanesulfonic acid (ESA) and oxanilic acid (OXA) were the most frequently detected herbicide degradation products, both being found in more than 95 percent of the samples. The data presented here are valuable for comparison with results from the earlier reconnaissance studies.

Minnesota, Wisconsin, Iowa, Illinois, Indiana, Ohi↗

Work plan for determining the occurrence of glyphosate, its transformation product AMPA, other herbicide compounds, and antibiotics in midwestern United States streams, 2002

Changes in herbicide use in the Midwestern United States have been substantial over the last 5 years. Most significant is a tripling in the use of glyphosate (N-[phosphonomethyl]glycin). Over this same time period (1997­2001), atrazine use increased by 20 percent and acetochlor use increased by 10 percent, while cyanazine use decreased by 99 percent, alachlor use decreased by 70 percent, and metolachlor use decreased by 55 percent. Previous studies have documented that herbicide flushes occur in midwestern streams during runoff events for several weeks to several months following application, and that herbicide concentrations in midwestern streams during flushing events are related to rates of herbicide use. The objective of this study is to determine the distribution of glyphosate and its primary transformation product aminomethylphosphonic acid (AMPA) in midwestern streams during post-application and harvest-season runoff events. Water samples will be collected in 2002 during two post-herbicide-application runoff events and one harvest-season runoff event from 53 sites on streams in the Midwestern United States. All samples will be analyzed at the U.S. Geological Survey Organic Geochemistry Research Laboratory in Lawrence, Kansas, for glyphosate and 20 other herbicides. Samples will also be analyzed for a glyphosate transformation product (AMPA) and 26 other herbicide transformation products, using GC/MS or HPLC/MS. Selected samples will be analyzed for 36 antibiotics or antibiotic transformational products. Results from this study will represent the first broad-scale investigation of glyphosate and AMPA in U.S. water resources.

Midwest region↗

Water-quality assessment of the eastern Iowa Basins: Selected pesticides and pesticide degradates in streams, 1996-98

Water samples were collected in streams of the Eastern Iowa Basins study unit from 1996 to 1998 as part of the U.S. Geological Survey’s National Water-Quality Assessment (NAWQA) Program. More than 350 samples were collected to document the occurrence, distribution, and transport of pesticides and pesticide degradates. The Eastern Iowa Basins study unit encompasses about 50,500 square kilometers (19,500 square miles) in eastern Iowa and southern Minnesota and is drained by four major rivers—the Wapsipinicon, Cedar, Iowa, and Skunk—which flow into the Mississippi River at the eastern border of Iowa. The most commonly detected pesticides— acetochlor, alachlor, atrazine, cyanazine, and metolachlor—were those most heavily used on crops during the study. Atrazine and metolachlor were detected in 100 percent, and acetochlor, alachlor and cyanazine were detected in more than 70 percent of all surface-water samples. Four pesticide degradates—metolachlor ethane sulfonic acid, alachlor ethane sulfonic acid, metolachlor oxanilic acid, and acetochlor ethane sulfonic acid were detected in more than 75 percent of the samples. Only one nonagricultural herbicide, prometon, was detected in more than 80 percent of the samples. Carbofuran, the most commonly detected insecticide, was found in 16 percent of all samples. Mixtures of pesticide compounds commonly occurred in the samples. Five or more parent pesticide compounds were detected in 50 percent of the samples. Four or more pesticide degradates were detected in 68 percent and seven or more pesticide degradates were detected in 17 percent of the samples. Acetochlor, alachlor, atrazine, cyanazine, and metolachlor were generally present at low concentrations; median concentrations ranged from 0.01 to 0.22 microgram per liter. However, median concentrations for the pesticide degra-dates, 0.07 to 3.7 micrograms per liter, were larger than their parent compounds. Acetochlor, alachlor, atrazine, cyanazine, and metolachlor pesticide compounds were detected at an order of magnitude or higher in the late spring and summer than at other times of the year. Pesticide concentrations generally peak following application in May and June and decrease during the growing season. A small secondary peak of atrazine, acetochlor, alachlor, cyanazine, and metolachlor concentrations occurred in late winter at all sites. The seasonal patterns for the triazine (atrazine and cyanazine) degradates were similar to the parent compounds (increasing in the spring), but the triazine degra-dates often had higher median concentrations than their parent compounds in the fall and winter. The chloroacetanilide (acetochlor, alachlor, and metolachlor) degradates did not follow a strong seasonal pattern like their parent compounds. In general, the chloroacetanilide degradates had constant and higher median concentrations when compared to their parent compounds throughout the year. The median concentrations for the chloroacetanilide pesticide degradates were often an order of magnitude higher than their parent compounds. Concentrations of pesticides varied by land-form region. Atrazine and cyanazine and their degradates were present in significantly greater concentrations in streams of the Southern Iowa Drift Plain than streams of either the Des Moines Lobe or the Iowan Surface.

Iowa, Minnesota↗

River discharge measurements by using helicopter-mounted radar

The United States Geological Survey and the University of Washington collaborated on a series of initial experiments on the Lewis, Toutle, and Cowlitz Rivers during September 2000 and a detailed experiment on the Cowlitz River during May 2001 to determine the feasibility of using helicopter-mounted radar to measure river discharge. Surface velocities were measured using a pulsed Doppler radar, and river depth was measured using ground-penetrating radar. Surface velocities were converted to mean velocities, and horizontal registration of both velocity and depth measurements enabled the calculation of river discharge. The magnitude of the uncertainty in velocity and depth indicate that the method error is in the range of 5 percent. The results of this experiment indicate that helicopter-mounted radar can make the rapid, accurate discharge measurements that are needed in remote locations and during regional floods.

Washington↗

Linker-assisted immunoassay and liquid chromatography/mass spectrometry for the analysis of glyphosate

A novel, sensitive, linker-assisted enzyme-linked immunosorbent assay (L'ELISA) was compared to on-line solidphase extraction (SPE) with high-performance liquid chromatography/mass spectrometry (HPLC/MS) for the analysis of glyphosate in surface water and groundwater samples. The L'ELISA used succinic anhydride to derivatize glyphosate, which mimics the epitotic attachment of glyphosate to horseradish peroxidase hapten. Thus, L'ELISA recognized the derivatized glyphosate more effectively (detection limit of 0.1 μg/L) and with increased sensitivity (10-100 times) over conventional ELISA and showed the potential for other applications. The precision and accuracy of L'ELISA then was compared with on-line SPE/HPLC/MS, which detected glyphosate and its degradate derivatized with 9-fluorenylmethyl chloroformate using negative-ion electrospray (detection limit 0.1 μg/L, relative standard deviation ±15%). Derivatization efficiency and matrix effects were minimized by adding an isotope-labeled glyphosate (2- 13 C 15 N). The accuracy of L'ELISA gave a false positive rate of 18% between 0.1 and 1.0 μg/L and a false positive rate of only 1% above 1.0 μg/L. The relative standard deviation was ±20%. The correlation of L'ELISA and HPLC/MS for 66 surface water and groundwater samples was 0.97 with a slope of 1.28, with many detections of glyphosate and its degradate in surface water but not in groundwater.

Analytical Chemistry↗

Prediction of capacity factors for aqueous organic solutes adsorbed on a porous acrylic resin

The capacity factors of 20 aromatic, allphatic, and allcycllc organic solutes with carboxyl, hydroxyl, amine, and methyl functional groups were determined on Amberlite XAD-8, a porous acrylic resin. The logarithm of the capacity factor, k' , correlated inversely with the logarithm of the aqueous molar solubility with significance of less than 0.001. The log k' -log solubility relationship may be used to predict the capacity of any organic solute for XAD-8 using only the solubility of the solute. The prediction is useful as a guide for determining the proper ratio of sample to column size In the preconcentration of organic solutes from water. The inverse relationship of solubility and capacity is due to the unfavorable entropy of solution of organic solutes which affects both solubility and sorption.

Analytical Chemistry↗

Herbicides in surface waters of the midwestern United States: The effect of spring flush

Approximately three-fourths of all preemergent herbicides used in the United States are applied to row crops over a 12-state area, called the "corn belt" (I). The application of these compounds may cause widespread degradation of water quality (2). Because herbicides are water soluble, there is the potential for leaching into groundwater and surface water (3, 4), as well as aerial transport and Occurrence in precipitation (5). Monitoring studies in the Midwest have shown widespread detection of herbicides in groundwater and in surface water (3,4); however, little is known about the regional impact of herbicide application (6). The objective of our research was to assess the mag. nitude and persistence of herbicide runoff in the spring flush at the regional scale.

Environmental Science & Technology↗

Herbicide transport in rivers: Importance of hydrology and geochemistry in nonpoint-source contamination

Alachlor, atrazine, cyanazine, metolachlor, and metribuzin were measured at six sites during 1984 and 1985 in large subbasins within the Cedar River, IA. A computer model separated the Cedar River discharge hydrograph into groundwater and overland-flow components. The concentration of herbicides in the river when groundwater was the major flow component was less than 1.0 μ g/L and averaged 0.2 μ g/L. The maximum concentrations of herbicides occurred when overland flow was the major component of river discharge, exceeding 50 pg/L for total herbicides. About 6% of the annual river load of atrazine was transported with the groundwater component, while 94% was transported with overland flow. From 1.5 to 5% of the atrazine applied during the year was transported from the basin. Atrazine concentrations in the river in- creased according to the discharge divided by the drainage area. This correlation indicates that rivers with large normalized 2-year peak flows have the potential to transport large concentrations of herbicides. A diagrammatic model of nonpoint-source transport of herbicides was developed that suggests that sorbed transport from fields occurs during episodes of overland flow with rapid dissolution of herbicides downstream.

Iowa↗

Reduction of nonpoint source contamination of surface water and groundwater by starch encapsulation of herbicides

The loss of the preemergent herbicide atrazine in surface runoff from experimental field plots growing corn (Zea mays L.) was significantly reduced using a starchencapsulated formulation versus a conventional powdered formulation. Field edge losses of starch-encapsulated atrazine were described as following a Rayleigh distribution totaling 1.8% of applied herbicide compared to exponential powdered atrazine losses of 2.9% applied - a 40% decrease. This has important implications for the reduction of nonpoint source contamination of surface water by agricultural chemicals. Unsaturated zone release of starchencapsulated atrazine was gradual, but comparable weed control was maintained. Deethylatrazine was a major dealkylated metabolite from each formulation, and deisopropylatrazine was a minor metabolite. The determination of soil partition coefficients for deethylatrazine and deisopropylatrazine (0.4 and 0.3, respectively), aqueous solubilities (3200 and 670 mg/L, respectively), and melting points (133 and 177 C, respectively) confirmed that the dealkylated metabolites should move more rapidly through the soil profile to groundwater than atrazine.

Environmental Science & Technology↗