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Geology topics

E.M. Thurman

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

At least 19 recordsLinked to original sources

Groundwater as a nonpoint source of atrazine and deethylatrazine in a river during base flow conditions

Alluvial groundwater adjacent to the main stem river is the principal nonpoint source of atrazine and deethylatrazine in the Cedar River of Iowa after the river has been in base flow conditions for 5 days. Between two sites along a 116-km reach of the Cedar River, tributaries contributed about 25% of the increase in the atrazine and deethylatrazine load, whereas groundwater from the alluvial aquifer contributed at least 75% of the increase in load. Within the study area, tributaries aggregate almost all of the discharge from tile drains, and yet the tributaries still only contribute 25% of the increase in loads in the main stem river. At an unfamned study site adjacent to the Cedar River, the sources of atrazine and deethylatrazine in the alluvial groundwater are bank storage of river water and groundwater recharge from areas distant from the river. Atrazine and deethylatrazine associated with bank storage water will provide larger concentrations to the river during early base flow conditions. After the depletion of bank storage, stable and smaller concentrations of atrazine and deethylatrazine, originating from groundwater recharge, continue to be discharged from the alluvial aquifer to the river; thus these results indicate that alluvial aquifers are an important nonpoint source of atrazine and deethylatrazine in rivers during base flow.

Iowa

Organic geochemistry and sources of natural aquatic foams

Aquatic foams and stream-water samples were collected from two pristine sites for humic substances isolation and characterization. Biomarker compounds identified in foam and stream humic substances included phospholipid fatty acids, steroids, and lignin. Results showed that foams had a 10 to 20 fold greater DOC concentration and were enriched in humic substances (90% by weight of DOC) that showed increased hydrophobicity, aliphatic character, and compositional complexity compared to host stream humic substances (55 to 81% by weight of DOC). Foam humic substances also were enriched in humic acid (36 to 83% by weight) compared to host stream humic substances (10 to 14% by weight). Biomarkers, which contributed less than 5% by weight to the DOC pool, indicated higher plants, bacteria, algae, fungi, and diatoms as DOC sources. It is proposed that aquatic foams may be important media for the concentration and transport of organic substances in the aquatic environment.

ACS Symposium Series

Source and transport of desethylatrazine and desisopropylatrazine to groundwater of the midwestern United States

Based on usage of the parent compounds and studies of their dissipation in corn fields, atrazine (6-chloro-N-ethyl-N'-(1-methylethyl-1,3,5-triazine-2,4-diamine)), cyanazine (2-[[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino]-2-methylpropionitrile), and simazine (6-chloro-N,N'diethyl-1,3,5-triazine-2,4-diamine) are thought to be the important contributors of desethylatrazine (6-chloro-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine) or DEA and desisopropylatrazine(6-chloro-N-ethyl)-1,3,5-triazine-2,4-diamine) or DIA to ground water. Atrazine degrades to both DEA and DIA by dealkylation. DEA is transported through the unsaturated zone more readily than DIA because of the more rapid degradation of DIA in the shallow unsaturated zone. Both cyanazine and simazine degrade to DIA by dealkylation, and DIA may be an indicator of leaching and subsequent degradation from both parent compounds. Because cyanazine has an acid intermediate that is mobile in the unsaturated zone, it may be an important source for DIA transport to ground water. Based on a regional survey of ground water of the Midwest during the Spring and Summer of 1991, DEA occurs most frequently with detections of DEA (15.4%) > atrazine (14.7%) > DIA (4%) > simazine (0.7%) > cyanazine (0.3%) > propazine (no detections). The DEA to atrazine ratio (DAR) is an indicator of atrazine source and transport, with the lowest ratios indicating most rapid transport.

ACS Symposium Series

Herbicides and transformation products in surface waters of the Midwestern United States

Most herbicides applied to crops are adsorbed by plants or transformed (degraded) in the soil, but small fractions are lost from fields and either move to streams in overland runoff, near surface flow, or subsurface drains, or they infiltrate slowly to ground water. Herbicide transformation products (TPs) can be more or less mobile and more or less toxic in the environment than their source herbicides. To obtain information on the concentrations of selected herbicides and TPs in surface waters of the Midwestern United States, 151 water samples were collected from 71 streams and five reservoir outflows in 1998. These samples were analyzed for 13 herbicides and 10 herbicide TPs. Herbicide TPs were found to occur as frequently or more frequently than source herbicides and at concentrations that were often larger than their source herbicides. Most samples contained a mixture of more than 10 different herbicides or TPs. The ratios of TPs to herbicide concentrations can be used to determine the source of herbicides in streams. Results of a two-component mixing model suggest that on average 90 percent or more of the herbicide mass in Midwestern streams during early summer runoff events originates from the runoff and 10 percent or less comes from increased ground water discharge.

Journal of the American Water Resources Associatio

Terbuthylazine and deethylterbuthylazine in rain and surface water: Determination by enzyme immunoassay and gas chromatography/mass spectrometry

Rain and surface water samples from Southern Germany were investigated from 1991 to 1995 for terbuthylazine and one of its major metabolites, deethylterbuthylazine. The concentrations observed were compared to the concentrations found for atrazine and deethylatrazine in the same water samples. Concentrations ranged from < 0.02 μg/L to 0.7 μg/L for terbuthylazine and from < 0.02 μg/L to 0.6 μg/L for deethylterbuthylazine, compared to concentrations of < 0.02 μg/L to 3 μg/L and < 0.02 μg/L to 0.5 μg/L for atrazine and deethylatrazine, respectively. The ratios of metabolite concentrations to parent compound concentrations were calculated for deethylterbuthylazine to terbuthylazine ( DTR ) and deethylatrazine to atrazine ( DAR ). In rain water, DTR of 0.8…3.0 and DAR of 0.3… 1.9 were determined with mean values of 0.9… 1.7 for DTR and 0.6…0.9 for DAR in the different years. The ratios increased during summer periods. The highest ratios were observed in samples from forest stands, showing that degradation of the herbicide has occurred during transport between the source and the sampling site. The DTR in rain water were about 50… 100% higher than the DAR . This indicates a higher degradation rate of terbuthylazine during atmospheric transport. In surface water, DTR of 0.3… 1.2 with mean values of 0.5…0.8 and DAR of 0.2…2.2 with mean values of 0.2… 1.3 were observed. The ratios increased from June to September.

Acta Hydrochimica et Hydrobiologica

Urban contributions of glyphosate and its degradate AMPA to streams in the United States

Glyphosate is the most widely used herbicide in the world, being routinely applied to control weeds in both agricultural and urban settings. Microbial degradation of glyphosate produces aminomethyl phosphonic acid (AMPA). The high polarity and water-solubility of glyphosate and AMPA has, until recently, made their analysis in water samples problematic. Thus, compared to other herbicides (e.g. atrazine) there are relatively few studies on the environmental occurrence of glyphosate and AMPA. In 2002, treated effluent samples were collected from 10 wastewater treatment plants (WWTPs) to study the occurrence of glyphosate and AMPA. Stream samples were collected upstream and downstream of the 10 WWTPs. Two reference streams were also sampled. The results document the apparent contribution of WWTP effluent to stream concentrations of glyphosate and AMPA, with roughly a two-fold increase in their frequencies of detection between stream samples collected upstream and those collected downstream of the WWTPs. Thus, urban use of glyphosate contributes to glyphosate and AMPA concentrations in streams in the United States. Overall, AMPA was detected much more frequently (67.5%) compared to glyphosate (17.5%).

Science of the Total Environment

Widespread detection of N, N-diethyl-m-toluamide in U.S. streams: Comparison with concentrations of pesticides, personal care products, and other organic wastewater compounds

One of the most frequently detected organic chemicals in a nationwide study concerning the effects of wastewater on stream water quality conducted in the year 2000 was the widely used insect repellant N , N -diethyl- m -toluamide (DEET). It was detected at levels of 0.02 &mu;g/L or greater in 73% of the stream sites sampled, with the selection of sampling sites being biased toward streams thought to be subject to wastewater contamination (i.e., downstream from intense urbanization and livestock production). Although DEET frequently was detected at all sites, the median concentration was low (0.05 &mu;g/L). The highest concentrations of DEET were found in streams from the urban areas (maximum concentration, 1.1 &mu;g/L). The results of the present study suggest that the movement of DEET to streams through wastewater-treatment systems is an important mechanism that might lead to the exposure of aquatic organisms to this chemical.

Environmental Toxicology and Chemistry

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

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 &mu;g L &minus;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 &mu;g L &minus;1 ) was significantly greater than the total concentration of parent compounds (median of 0.26 &mu;g L &minus;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&ndash;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 (1997&shy;2001), 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&rsquo;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&mdash;the Wapsipinicon, Cedar, Iowa, and Skunk&mdash;which flow into the Mississippi River at the eastern border of Iowa. The most commonly detected pesticides&mdash; acetochlor, alachlor, atrazine, cyanazine, and metolachlor&mdash;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&mdash;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