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E.M. Thurman

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

At least 91 records · Page 5Linked to original sources

Assessing aquifer contamination risk using immunoassay: Trace analysis of atrazine in unsaturated zone sediments

The vulnerability of a shallow aquifer in south-central Kansas to contamination by atrazine (2-chloro-4-ethylamino-6-isopropylamines-triazine) was assessed by analyzing unsaturated zone soil and sediment samples from about 60 dryland and irrigated sites using an ultrasensitive immunoassay (detection level of 0.02 µg/kg) with verification by gas chromatography/mass spectrometry (GC/MS). Samples were collected at depths of 0 to 1.2 m (i.e., the root zone), 1.2 to 1.8 m, and 1.8 to 3.0 m during two time periods-prior to planting and after harvest of crops. About 75% of the samples contained detectable concentrations of parent atrazine. At the shallow sampling depth, atrazine concentrations ranged from 0.5 to approximately 12 µg/kg. Atrazine concentrations at the intermediate (1.2-1.8 m) depth generally were <1.0 µg/kg, with most of the concentrations <0.10 µg/kg, which suggests substantial degradation of parent atrazine in the root zone. Likewise, atrazine concentrations front the deepest (1.8-3.0 m) depth ranged from <0.02 to 0.33 µg/kg. The metabolite deethylatrazine (2-amino-4-chloro-6- isopropylamine-s-triazine) was detected by GC/MS only in 2 of 60 samples with concentrations of 1.4 and 1.5 µg/kg. The reconnaissance survey shows that, in spite of atrazine use ranging from 1 to 5 or more years, there does not appear to he a significant buildup of parent compound below the root zone. Therefore, the unsaturated zone does not appear to be a major storage compartment of atrazine contamination for the underlying shallow aquifer.

Journal of Environmental Quality

Glutathione conjugation and contaminant transformation

The recent identification of a novel sulfonated metabolite of alachlor in groundwater and metolachlor in soil is likely the result of glutathione conjugation. Glutathione conjugation is an important biochemical reaction that leads, in the case of alachlor, to the formation of a rather difficult to detect, water-soluble, and therefore highly mobile, sulfonated metabolite. Research from weed science, toxicology, and biochemistry is discussed to support the hypothesis that glutathione conjugation is a potentially important detoxification pathway carried out by aquatic and terrestrial plants and soil microorganisms. A brief review of the biochemical basis for glutathione conjugation is presented. We recommend that multidisciplinary research focus on the occurrence and expression of glutathione and its attendant enzymes in plants and microorganisms, relationships between electrophilic substrate structure and enzyme activity, and the potential exploitation of plants and microorganisms that are competent in glutathione conjugation for phytoremediation and bioremediation.

Environmental Science & Technology

Acetochlor in the hydrologic system in the midwestern United States, 1994

The herbicide acetochlor [2-chloro- N -(ethoxymethyl)- N -(2-ethyl-6-methylphenyl)acetamide] was given conditional registration in the United States by the U.S. Environmental Protection Agency in March 1994. This registration provided a rare opportunity to investigate the occurrence of a pesticide during its first season of extensive use in the midwestern United States. Water samples collected and analyzed by the U.S. Geological Survey during 1994 documented the distribution of acetochlor in the hydrologic system; it was detected in 29% of the rain samples from four sites in Iowa, 17% of the stream samples from 51 sites across nine states, and 0% of the groundwater samples from 38 wells across eight states. Acetochlor exhibited concentration increases in rain and streams following its application to corn in the midwestern United States, with 75% of the rainwater and 35% of the stream samples having acetochlor detected during this time period. Acetochlor concentrations in rain decreased as the growing season progressed. Based on the limited data collected for this study, it is anticipated that acetochlor concentrations will have a seasonal pattern in rain and streams similar to those of other acetanilide herbicides examined. Possible explanations for the absence of acetochlor in groundwater for this study include the rapid degradation of acetochlor in the soil zone, insufficient time for this first extensive use of acetochlor to have reached the aquifers sampled, and the possible lack of acetochlor use in the recharge areas for the wells examined.

Environmental Science & Technology

Occurrence of alachlor and its sulfonated metabolite in rivers and reservoirs of the midwestern United States: The importance of sulfonation in the transport of chloroacetanilide herbicides

Alachlor and its metabolite, 2-[(2',6'-diethylphenyl)- (methoxymethyl)amino]-2-oxoethanesulfonate (ESA), were identified in 76 reservoirs in the midwestern United States using immunoassay, liquid chromatography, and gas chromatography/mass spectrometry. The median concentration of ESA (0.48 ??g/L) exceeded the median concentration of alachlor (<0.05 ??g/L), with highest values in the upper Midwest. ESA also was detected in the Mississippi River from the mouth to the headwaters at concentrations of 0.2-1.5 ??g/L, exceeding the concentration of alachlor. In a field runoff study, alachlor rapidly formed ESA. It is hypothesized that a glutathione conjugate forms, which later oxidizes in soil to ESA. The removal of the chlorine atom lessens the toxicity of the parent compound and increases runoff potential. It is hypothesized further that sulfonic acid metabolites of other chloroacetanilides, including acetochlor, butachlor, metolachlor, and propachlor, also occur in surface water.

Midwest

Identification of a new sulfonic acid metabolite of metolachlor in soil

An ethanesulfonic acid metabolite of metolachlor (metolachlor ESA) was identified in soil-sample extracts by negative-ion, fast-atom bombardment mass spectrometry (FAB-MS) and FAB tandem mass spectrometry (FAB-MS/MS). Production fragments from MS/MS analysis of the deprotonated molecular ion of metolachlor ESA in the soil extract can be reconciled with the structure of the synthesized standard. The elemental compositions of the (M - H)- ions of the metolachlor ESA standard and the soil-sample extracts were confirmed by high-resolution mass spectrometry. A dissipation study revealed that metolachlor ESA is formed in soil under field conditions corresponding to a decrease in the concentration of the parent herbicide, metolachlor. The identification of the sulfonated metabolite of metolachlor suggests that the glutathione conjugation pathway is a common detoxification pathway shared by chloroacetanilide herbicides.

Environmental Science & Technology

The deethylatrazine/atrazine ratio as an indicator of the onset of the spring flush of herbicides into surface water of the Midwestern United States

The ratio of deethylatrazine to atrazine (DAR) may be used to record the first major runoff of herbicides from non-point-source corn fields to surface water in the Midwestern United States. The DAR dramatically decreases from ∼0.5 to < 0.1 upon application of herbicide and the first major runoff event of a basin. The DAR then gradually increases to values of approximately 0.4–0.6 during the harvest season. Furthermore, the DAR may be used in studies of surface water movement to give a temporal indicator of water moving into reservoirs for possible storage of herbicides. It is hypothesized that deethylatrazine, which accounts for only 6% of the degradation of atrazine, becomes a significant metabolite in surface water (∼ 50% of parent compound) because of its selective removal from soil. This removal process may be an important concept for consideration in studies of herbicide contamination of rivers and reservoirs.

International Journal of Environmental Analytical

Concentrations of selected herbicides, herbicide metabolites, and nutrients in outflow from selected midwestern reservoirs, April 1992 through September 1993

This data set consists of digital aquifer boundaries for the High Plains aquifer in the central United States. The High Plains aquifer extends from south of 32 degrees to almost 45 degrees north latitude and from 96 degrees 30 minutes to almost 104 degrees west longitude. The area covers 174,000 square miles and is present in Texas, Oklahoma, New Mexico, Kansas, Colorado, Nebraska, Wyoming, and South Dakota. This digital data set was created by digitizing the aquifer boundaries from a 1:1,000,000 base map created by the High Plains RASA project (Gutentag and others, 1984).

Texas, Oklahoma, New Mexico, Kansas, Colorado, Neb

Water-quality data for nutrients, pesticides, and volatile organic compounds in near-surface aquifers of the midcontinental United States, 1992-1994

Water samples were collected from 175 wells in 12 Midcontinental States (Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota, Missouri, Nebraska, North Dakota, Ohio, South Dakota, Wisconsin) from 1992 through 1994 to determine the spatial distribution of nutrients, pesticides, and volatile organic compounds in ground water, and to document the potential effects of the historic flooding that occurred during 1993 on ground- water quality. Concentrations of nitrate greater than the 0.05 mg/L reporting limit were found in 69.1 percent of the water samples, and nitrate concentrations exceeded the U.S. Environmental Protection Agency maximum contaminant limit of 10 mg/L in 9.6 percent of the 249 samples analyzed for nitrate. Pesticides or pesticide metabolites were detected in 72.4 percent of the 210 pesticide analyses, and 28 different compounds were found. Concentrations of multiple pesticide compounds above analytical reporting limits were found in water from about 60 percent of the wells sampled. Although pesticides were frequently detected, only one sample had a pesticide concentration that exceeded a maximum contaminant level for drinking water. The most frequently detected compounds, however, were pesticide metabolites for which maximum contaminant levels have not yet been established. Volatile organic compounds were detected in 13.5 percent of the 155 samples analyzed for these compounds. Only one sample had concentrations of volatile organic compounds that exceeded a maximum contaminant level for drinking water.

Open-File Report

Pesticides in near-surface aquifers: An assessment using highly sensitive analytical methods and tritium

In 1992, the U.S. Geological Survey (USGS) determined the distribution of pesticides in near-surface aquifers of the midwestern USA to be much more widespread than originally determined during a 1991 USGS study. The frequency of pesticide detection increased from 28.4% during the 1991 study to 59.0% during the 1992 study. This increase in pesticide detection was primarily the result of a more sensitive analytical method that used reporting limits as much as 20 times lower than previously available and a threefold increase in the number of pesticide metabolites analyzed. No pesticide concentrations exceeded the U.S. Environmental Protection Agency's (USEPAs) maximum contaminant levels or health advisory levels for drinking water. However, five of the six most frequently detected compounds during 1992 were pesticide metabolites that currently do not have drinking water standards determined. The frequent presence of pesticide metabolites for this study documents the importance of obtaining information on these compounds to understand the fate and transport of pesticides in the hydrologic system. It appears that the 56 parent compounds analyzed follow similar pathways through the hydrologic system as atrazine. When atrazine was detected by routine or sensitive analytical methods, there was an increased likelihood of detecting additional parent compounds. As expected, the frequency of pesticide detection was highly dependent on the analytical reporting limit. The number of atrazine detections more than doubled as the reporting limit decreased from 0.10 to 0.01 &micro;g/L. The 1992 data provided no indication that the frequency of pesticide detection would level off as improved analytical methods provide concentrations below 0.003 &micro;g/L. A relation was determined between groundwater age and the frequency of pesticide detection, with 15.8% of the samples composed of pre-1953 water and 70.3% of the samples of post-1953 water having a detection of at least one pesticide or metabolite. Pre-1953 water is less likely to contain pesticides because it tends to predate the use of pesticides to increase crop production in the Midwest. Pre-1953 water was more likely to occur in the near-surface bedrock aquifers (50.0%) than in the near-surface unconsolidated aquifers (9.1%) sampled.

Journal of Environmental Quality

Data on selected herbicides and two triazine metabolites in precipitation of the Midwestern and Northeastern United States, 1990-91

Weekly precipitation (rain and snow) samples were collected from 81 National Atmospheric Deposition Program/National Trends Network sites in the Midwestern and Northeastern United States for the analysis of herbicides. In addition, five high- elevation background sites along the Rocky Mountains and in Alaska were sampled to provide data on herbicides in precipitation at sites far from the study area. The study began in March 1990 and continued through September 1991. The precipitation samples were shipped to the Central Analytical Laboratory operated by the Illinois State Water Survey for analyses of inorganic compounds. Subsamples of the precipitation were shipped to the U.S. Geological Survey laboratory in Lawrence, Kansas, for the analysis of 11 herbicides and 2 triazines metabolites. This report provides descriptions of the study area, sample-collection methods, laboratory methods, and quality assurance. The report also includes a compilation of herbicide concentration data from both enzyme-linked immunosorbent assay and gas chromatography/mass spectrometry methods. Laboratory analyses consisted of 6,230 samples that were analyzed by enzyme-linked immunosorbent assay using alachlor and atrazine microtiter plates and 2,341 samples that were confirmed by gas chromatography/mass spectrometry analysis. Graphical and statistical comparisons of the two analytical methods are given in this report. Data from this study have been useful in determining the spatial and temporal distribution of herbicide concentrations and deposition in precipitation of over a 26-State area of the Midwestern and Northeastern United States. The data also provide evidence of long-range atmospheric transport of herbicides and triazine metabolites.

Open-File Report

Application of mixed-mode, solid-phase extraction in environmental and clinical chemistry. Combining hydrogen-bonding, cation-exchange and Van der Waals interactions

Silica- and styrene-divinylbenzene-based mixed-mode resins that contain C8, C18 and sulphonated cation-exchange groups were compared for their efficiency in isolation of neutral triazine compounds from water and of the basic drug, benzoylecgonine, from urine. The triazine compounds were isolated by a combination of Van der Waals and hydrogen-bonding interactions, and benzoylecgonine was isolated by Van der Waals interactions and cation exchange. All analytes were eluted with a polar organic solvent contaning 2% ammonium hydroxide. Larger recoveries (95%) were achieved on copolymerized mixed-mode resins where C18 and sulfonic acid are in closer proximity than on 'blended' mixed-mode resins (60-70% recovery).

Journal of Chromatography A

Hydrogeologic, water-quality, and land-use data for the reconnaissance of herbicides and nitrate in near-surface aquifers of the Midcontinental United States, 1991

Water samples were collected during the spring and summer of 1991 from 303 wells penetrating near-surface unconsolidated and bedrock aquifers of the midcontinental United States. Samples were analyzed for 11 herbicides, 2 dealkylated atrazine metabolites, and 4 nutrients. Specific conductance, pH, and dissolved-oxygen concentrations of the ground water were measured onsite. Ancillary data on well construction, hydrogeology, and land use also were obtained for each well.

Open-File Report

Reconnaissance data for selected herbicides, two atrazine metabolities, and nitrate in surface water of the Midwestern United States, 1989-90

Water-quality data were collected from 147 rivers and streams during 1989-90 to assess selected preemergent herbicides, two atrazine metabolites, and nitrate in 10 Midwestern States. This report includes a description of the sampling design, data collection techniques, laboratory and analytical methods, and a compilation of constituent concentrations and quality-assurance data. All water samples were collected by depth-integrating techniques at three to five locations across the wetted perimeter of each stream. Sites were sampled three times in l989--before application of herbi- cides, during the first major runoff after appli- cation of herbicides, and in the fall during a low-flow period when ground water contributed to most of the streamflow. About 50 sites were selected by a stratified random procedure and resampled for both pre- and post-application herbicide concen- trations in 1990 to verify the 1989 results. Laboratory analyses consisted of both enzyme-linked immunosorbent assay (ELISA) with confirmation by gas chromatography-mass spectrometry (GC/MS). The data are useful in studying herbicide transport, in comparison of the spatial distribution of the post-application concentrations of 11 herbicides and 2 atrazine metabolites (deethylatrazine and deisopropylatrazine) in streams and rivers at a regional scale. It is also useful in examination of annual persistence of herbicides and two metabolites in surface water, and in the assessment of atrazine metabolites as indicators of surface- and ground- water interaction. The reconnaissance data are contained in this report and are also available on computer diskette from the U.S. Geological Survey in Lawrence, Kansas.

Open-File Report