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D. A. Goolsby

Publications and source records attributed to D. A. Goolsby.

At least 19 recordsLinked to original sources

Cyanazine, atrazine, and their metabolites as geochemical indicators of contaminant transport in the Mississippi River

The geochemical transport of cyanazine and its metabolite cyanazine amide (CAM) was compared to atrazine and its metabolite deethylatrazine (DEA) at three sites in the Mississippi River basin during 1992 and six sites during 1993. The floods of 1993 caused an uninterrupted exponential decline in herbicide concentrations; whereas, in 1992 herbicide concentrations varied mostly in response to two discrete discharge pulses in the spring and midsummer and were stable during an extended period of summer low-flow. Concentration half-lives calculated from the 1993 data for atrazine were approximately twice those of cyanazine at all sites. The half-life for atrazine and cyanazine was shortest, 22 and 14 days, respectively at the Mississippi River at Clinton, Ill. -- the farthest upstream site -- and longest, 42 and 22 days, respectively, at the Baton Rouge, La. site -- the farthest downstream site. The concentration of CAM exceeded the concentration of DEA through September at all sites where the mean ratio of atrazine-to-cyanazine (ACR) was less than 4.0. The ratio of CAM-to-cyanazine (CAMCR) increased from 0.2 to more than 1.0 and the ratio of DEA-to-atrazine (DAR) increased from less than 0.1 to 0.3 from application in May through early to mid- July. Temporal changes in the CAMCR were used to identify pre- and post-application "slugs" of water transported along the reaches of the Mississippi River.

Arkansas, Illinois, Kentucky, Louisiana, Mississip↗

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↗

Regression models of herbicide concentrations in outflow from reservoirs in the midwestern USA, 1992-1993

Reservoirs are used to store water for public water supply, flood control, irrigation, recreation, hydropower, and wildlife habitat, but also often store undesirable substances such as herbicides. The outflow from 76 reservoirs in the midwestern USA, was sampled four times in 1992 and four times in 1993. At least one herbicide was detected in 82.6 percent of all samples, and atrazine was detected in 82.1 percent of all samples. Herbicide properties; topography, land use, herbicide use, and soil type in the contributing drainage area; residence time of water in reservoirs; and timing of inflow, release, and rainfall all can affect the concentration of herbicides in reservoirs. A GIS was used to quantify characteristics of land use, agricultural chemical use, climatic conditions, topographic character, and soil type by reservoir drainage basins. Multiple linear and logistic regression equations were used to model mean herbicide concentrations in reservoir outflow as a function of these characteristics. Results demonstrate a strong association between mean herbicide concentrations in reservoir outflow and herbicide use rates within associated drainage basins. Results also demonstrate the importance of including soils and basin hydrologic characteristics in models used to estimate mean herbicide concentrations.

Journal of the American Water Resources Associatio↗

Test hold in aquifer with many water-bearing zones at Jacksonville, Florida

One of the deepest water ‐exploration wells in the southeastern United States was completed in 1966 at Jacksonville , Florida . It was drilled to a depth of nearly 2,500 feet to supply geologic and hydrologic information on the deeper unexplored part of the Floridan aquifer . This aquifer consists of a series of water producing zones separated by nonproducing zones . An important new fresh‐ water producing zone was found, and the contact between the fresh water and salt water was located. The well was completed in three separate zones so that it could be used to monitor the the deeper part of the aquifer to detect any salt‐ water encroachment. This paper describes the objectives, techniques, and results of drilling the test well.

Florida↗

Occurrence of selected herbicides and herbicide degradation products in Iowa's Ground Water, 1995

Herbicide compounds were prevalent in ground water across Iowa, being detected in 70% of the 106 municipal wells sampled during the summer of 1995. Herbicide degradation products were three of the four most frequently detected compounds for this study. The degradation product alachlor ethanesulfonic acid was the most frequently detected compound (65.1%), followed by atrazine (40.6%), and the degradation products deethylatrazine (34.9%), and cyanazine amide (19.8%). The corn herbicide acetochlor, first registered for widespread use in the United States in March 1994, was detected in a single water sample. No reported herbicide compound concentrations for this study exceeded currem U.S. Environmental Protection Agency's maximum contaminant levels or health advisory levels for drinking water, although the herbicide degradation products examined have yet to have such levels established. The occurrence of herbicide compounds had a significant, inverse relation to well depth and a significant, positive relation to dissolved-oxygen concentration. It is felt that both well depth and dissolved oxygen are acting as rough surrogates to ground-water age, with younger ground water being more likely to contain herbicide compounds. The occurrence of herbicide compounds was substantially different among the major aquifer types across Iowa, being detected in 82.5% of the alluvial, 81.8% of the bedrock/ karst region, 40.0% of the glacial-drift, and 25.0% of the bedrock/nonkarst region aquifers. The observed distribution was partially attributed to variations in general ground-water age among these aquifer types. A significant, inverse relation was determined between total herbicide compound concentrations in ground water and the average soil slope within a 2-km radius of sampled wells. Steeper soil slopes may increase the likelihood of surface runoff occurring rather than ground-water infiltration–decreasing the transport of herbicide compounds to ground water. As expected, a significant positive relation was determined between intensity of herbicide use and herbicide concentrations in ground water.

Iowa↗

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↗

A reconnaissance study of herbicides and their metabolites in surface water of the midwestern united states using immunoassay and gas chromatography/mass spectrometry

Preemergent herbicides and their metabolites, particularly atrazine, deethylatrazine, and metolachlor, persisted from 1989 to 1990 in the majority of rivers and streams in the midwestern United States. In spring, after the application of herbicides, the concentrations of atrazine, alachlor, and simazine were frequently 3-10 times greater than the U.S. Environmental Protection Agency maximum contaminant level (MCL). The concentration of herbicides exceeded the MCLs both singly and in combination. Two major degradation products of atrazine (deisopropylatrazine and deethylatrazine) also were found in many of the streams. The order of persistence of the herbicides and their metabolites in surface water was atrazine > deethylatrazine > metolachlor > alachlor > deisopropylatrazine > cyanazine. Storm runoff collected at several sites exceeded the MCL multiple times during the summer months as a function of stream discharge, with increased concentrations during times of increased streamflow. It is proposed that metabolites of atrazine may be used as indicators of surface-water movement into adjacent alluvial aquifers.

Environmental Science & Technology↗

Long-term changes in consentrations and flux fo nitrogen in the Mississippi River Basin, USA

Current and historical data show that nitrogen concentrations and flux in the Mississippi River Basin have increased significantly during the past 100 years. Most of the increase observed in the lower Mississippi River has occurred since the early 1970s and is due almost entirely to an increase in nitrate. The current (1980-99) average annual nitrogen (N) flux from the Mississippi Basin to the Gulf of Mexico is about 1 555 500 t year-1, of which about 62% is nitrate-N. The remaining 38% is organic nitrogen and a small amount of ammonium. The current (1980-99) average nitrate flux to the Gulf is almost three times larger than it was during 1955-70. This increased supply of nitrogen to the Gulf is believed to be partly responsible for the increasing size of a large hypoxic zone that develops along the Louisiana-Texas shelf each summer. This zone of oxygen-depleted water has doubled in areal extent since it was first measured in 1985. The increase in annual nitrate flux to the Gulf can be largely explained by three factors: Increased fertilizer use, annual variability in precipitation and increased streamflow, and the year-to-year variability in the amount of nitrogen available in the soil-ground water system for leaching to streams. The predominant source areas for the nitrogen transported to the Gulf of Mexico are basins draining southern Minnesota, Iowa, Illinois, Indiana, and Ohio. Basins in this region yield 1801 to 3050 kg N km-2 year-1 to streams, several times the N yield of basins outside this region.

Hydrological Processes↗

Nitrogen input to the Gulf of Mexico

Historical streamflow and concentration data were used in regression models to estimate the annual flux of nitrogen (N) to the Gulf of Mexico and to determine where the nitrogen originates within the Mississippi Basin. Results show that for 1980-1996 the mean annual total N flux to the Gulf of Mexico was 1 568 000 t yr-1. The flux was about 61% nitrate N, 37% organic N, and 2% ammonium N. The flux of nitrate N to the Gulf has approximately tripled in the last 30 years with most of the increase occurring between 1970 and 1983. The mean annual N flux has changed little since the early 1980s, but large year-to-year variations in N flux occur because of variations in precipitation. During wet years the N flux can increase by 50% or more due to flushing of nitrate N that has accumulated in the soils and unsaturated zones in the basin. The principal source areas of N are basins in southern Minnesota, Iowa, Illinois, Indiana, and Ohio that drain agricultural land. Basins in this region yield 1500 to more than 3100 kg N km-2 yr-1 to streams, several times the N yield of basins outside this region.

Mississippi–Atchafalaya River basin↗

Differentiating nonpoint sources of deisopropylatrazine in surface water using discrimination diagrams

Pesticide degradates account for a significant portion of the pesticide load in surface water. Because pesticides with similar structures may degrade to the same degradate, it is important to distinguish between different sources of parent compounds that have different regulatory and environmental implications. A discrimination diagram, which is a sample plot of chemical data that differentiates between different parent compounds, was used for the first time to distinguish whether sources other than atrazine (6-chloro- N 2 -ethyl- N 4 -isopropyl-1,3,5-triazine-2,4-diamine) contributed the chlorinated degradate, deisopropylatrazine (DIA; 6-chloro- N -ethyl-1,3,5-triazine-2,4-diamine) to the Iroquois and Delaware Rivers. The concentration ratio of deisopropylatrazine to deethylatrazine [6-chloro- N -(1-methylethyl)-1,3,5-triazine-2,4-diamine], called the D 2 R, was used to discriminate atrazine as a source of DIA from other parent sources, such as 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). The ratio of atrazine to cyanazine (ACR) used in conjunction with the D 2 R showed that after atrazine, cyanazine was the main contributor of DIA in surface water. The D 2 R also showed that cyanazine, and to a much lesser extent simazine, contributed a considerable amount (∼40%) of the DIA that was transported during the flood of the Mississippi River in 1993. The D 2 R may continue to be a useful discriminator in determining changes in the nonpoint sources of DIA in surface water as cyanazine is currently being removed from the market.

Kansas↗

Nitrogen flux and sources in the Mississippi River Basin

Nitrogen from the Mississippi River Basin is believed to be at least partly responsible for the large zone of oxygen-depleted water that develops in the Gulf of Mexico each summer. Historical data show that concentrations of nitrate in the Mississippi River and some of its tributaries have increased by factors of 2 to more than 5 since the early 1900s. We have used the historical streamflow and concentration data in regression models to estimate the annual flux of nitrogen (N) to the Gulf of Mexico and to determine where the nitrogen originates within the Mississippi Basin. Results show that for 1980–1996 the mean annual total N flux to the Gulf of Mexico was 1 568 000 t/year. The flux was approximately 61% nitrate as N, 37% organic N, and 2% ammonium as N. The flux of nitrate to the Gulf has approximately tripled in the last 30 years with most of the increase occurring between 1970 and 1983. The mean annual N flux has changed little since the early 1980s, but large year-to-year variations in N flux occur because of variations in precipitation. During wet years the N flux can increase by 50% or more due to flushing of nitrate that has accumulated in the soils and unsaturated zones in the basin. The principal source areas of N are basins in southern Minnesota, Iowa, Illinois, Indiana, and Ohio that drain agricultural land. Basins in this region yield 800 to more than 3100 kg total N/km 2 per year to streams, several times the N yield of basins outside this region. Assuming conservative transport of N in the Mississippi River, streams draining Iowa and Illinois contribute on average approximately 35% of the total N discharged by the Mississippi River to the Gulf of Mexico. In years with high precipitation they can contribute a larger percentage.

Science of Total Environment↗

Atmospheric nitrogen in the Mississippi River Basin: Amissions, deposition and transport

Atmospheric deposition of nitrogen has been cited as a major factor in the nitrogen saturation of forests in the north-eastern United States and as a contributor to the eutrophication of coastal waters, including the Gulf of Mexico near the mouth of the Mississippi River. Sources of nitrogen emissions and the resulting spatial patterns of nitrogen deposition within the Mississippi River Basin, however, have not been fully documented. An assessment of atmospheric nitrogen in the Mississippi River Basin was therefore conducted in 1998-1999 to: (1) evaluate the forms in which nitrogen is deposited from the atmosphere; (2) quantify the spatial distribution of atmospheric nitrogen deposition throughout the basin; and (3) relate locations of emission sources to spatial deposition patterns to evaluate atmospheric transport. Deposition data collected through the NADP/NTN (National Atmospheric Deposition Program/National Trends Network) and CASTNet (Clean Air Status and Trends Network) were used for this analysis. NO(x) Tier 1 emission data by county was obtained for 1992 from the US Environmental Protection Agency (Emissions Trends Viewer CD, 1985-1995, version 1.0, September 1996) and NH3 emissions data was derived from the 1992 Census of Agriculture (US Department of Commerce. Census of Agriculture, US Summary and County Level Data, US Department of Commerce, Bureau of the Census. Geographic Area series, 1995:1b) or the National Agricultural Statistics Service (US Department of Agriculture. National Agricultural Statistics Service Historical Data. Accessed 7/98 at URL, 1998. http://www.usda.gov/nass/pubs/hisdata.htm). The highest rates of wet deposition of NO3- were in the north-eastern part of the basin, downwind of electric utility plants and urban areas, whereas the highest rates of wet deposition of NH4+ were in Iowa, near the center of intensive agricultural activities in the Midwest. The lowest rates of atmospheric nitrogen deposition were on the western (windward) side of the basin, which suggests that most of the nitrogen deposited within the basin is derived from internal sources. Atmospheric transport eastward across the basin boundary is greater for NO3- than NH4+, but a significant amount of NH4+ is likely to be transported out of the basin through the formation of (NH4)2SO4 and NH4NO3 particles - a process that greatly increases the atmospheric residence time of NH4+. This process is also a likely factor in the atmospheric transport of nitrogen from the Midwest to upland forest regions in the North-East, such as the western Adirondack region of New York, where NH4+ constitutes 38% of the total wet deposition of N.

Science of Total Environment↗

Pesticides in the atmosphere of the Mississippi River Valley, part I: Rain

Weekly composite rainfall samples were collected in three paired urban and agricultural regions of the Midwestern United States and along the Mississippi River during April–September 1995. The paired sampling sites were located in Mississippi, Iowa, and Minnesota. A background site, removed from dense urban and agriculture areas, was located near Lake Superior in Michigan. Herbicides were the predominant type of pesticide detected at every site. Each sample was analyzed for 47 compounds and 23 of 26 herbicides, 13 of 18 insecticides, and three of three related transformation products were detected in one or more sample from each paired site. The detection frequency of herbicides and insecticides were nearly equivalent at the paired Iowa and Minnesota sites. In Mississippi, herbicides were detected more frequently at the agricultural site and insecticides were detected more frequently at the urban site. The highest total wet depositional amounts (μg pesticide/m 2 per season) occurred at the agricultural sites in Mississippi (1980 μg/m 2 ) and Iowa (490 μg/m 2 ) and at the urban site in Iowa (696 μg/m 2 ). Herbicides accounted for the majority of the wet depositional loading at the Iowa and Minnesota sites, but methyl parathion (1740 μg/m 2 ) was the dominant compound contributing to the total loading at the agricultural site in Mississippi. Atrazine, CIAT (a transformation product of atrazine and propazine) and dacthal were detected most frequently (76, 53, and 53%, respectively) at the background site indicating their propensity for long-range atmospheric transport.

Mississippi River Valley↗

Pesticides in the atmosphere of the Mississippi River Valley, part II: Air

Weekly composite air samples were collected from early April through to mid-September 1995 at three paired urban and agricultural sites along the Mississippi River region of the Midwestern United States. The paired sampling sites were located in Mississippi, Iowa, and Minnesota. A background site, removed from dense urban and agricultural areas, was located on the shore of Lake Superior in Michigan. Each sample was analyzed for 49 compounds; of these, 21 of 26 herbicides, 13 of 19 insecticides, and 4 of 4 related transformation products were detected during the study, with most pesticides detected in more than one sample. The maximum number of pesticides detected in an air sample was 18. Herbicides were the predominant type of pesticide detected at every site. Detection frequencies of most herbicides were similar at the urban and agricultural sites in Iowa and Minnesota. In Mississippi, herbicides generally were detected more frequently at the agricultural site. The insecticides chlorpyrifos, diazinon, and carbaryl, which are used in agricultural and non-agricultural settings, were detected more frequently in urban sites than agricultural sites in Mississippi and Iowa. Methyl parathion was detected in 70% of the samples from the Mississippi agricultural site and at the highest concentration (62 ng/m 3 air) of any insecticide measured in the study. At the background site, dacthal (100%), atrazine (35%), cyanazine (22%), and the (primarily atrazine) triazine transformation products CIAT (35%) and CEAT (17%) were detected most frequently, suggesting their potential for long-range atmospheric transport.

Mississippi River Valley↗

Occurrence of pesticides in rain and air in urban and agricultural areas of Mississippi, April-September 1995

In April 1995, the US Geological Survey began a study to determine the occurrence and temporal distribution of 49 pesticides and pesticide metabolites in air and rain samples from an urban and an agricultural sampling site in Mississippi. The study was a joint effort between the National Water-Quality Assessment and the Toxic Substances Programs and was part of a larger study examining the occurrence and temporal distribution of pesticides in air and rain in the Mississippi River basin. Concurrent high-volume air and wet-only deposition samples were collected weekly. The air samplers consisted of a glass-fiber filter to collect particles and tandem polyurethane foam plugs to collect gas-phase pesticides. Every rain and air sample collected from the urban and agricultural sites had detectable levels of multiple pesticides. The magnitude of the total concentration was 5-10 times higher at the agricultural site as compared to the urban site. The pesticide with the highest concentration in rain at both sites was methyl parathion. The pesticide with the highest concentration in the air samples from the agricultural site was also methyl parathion, but from the urban site the highest concentration was diazinon followed closely by chlorpyrifos. More than two decades since p,p'-DDT was banned from use in the United States, p,p'-DDE, a metabolite of p,p'-DDT, was detected in every air sample collected from the agricultural site and in more than half of the air samples from the urban site.

Mississippi↗