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D. A. Goolsby

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

At least 37 records · Page 2Linked to original sources

Changes in herbicide concentrations in Midwestern streams in relation to changes in use, 1989-1998

Water samples were collected from Midwestern streams in 1994–1995 and 1998 as part of a study to help determine if changes in herbicide use resulted in changes in herbicide concentrations since a previous reconnaissance study in 1989–1990. Sites were sampled during the first significant runoff period after the application of pre-emergent herbicides in 1989–1990, 1994–1995, and 1998. Samples were analyzed for selected herbicides, two atrazine metabolites, three cyanazine metabolites, and one alachlor metabolite. In the Midwestern USA, alachlor use was much greater in 1989 than in 1995, whereas acetochlor was not used in 1989 but was commonly used in 1995. The use of atrazine, cyanazine, and metolachlor was approximately the same in 1989 and 1995. The median concentrations of atrazine, alachlor, cyanazine, and metolachlor were substantially higher in 1989–1990 than in 1994–1995 or 1998. The median acetochlor concentration was higher in 1998 than in 1994 or 1995.

Science of Total Environment↗

Are shifts in herbicide use reflected in concentration changes in Midwestern rivers?

In many Midwestern rivers, elevated concentrations of herbicides occur during runoff events for 1-3 months following application. The highest or 'peak' herbicide concentration often occurs during one of these runoff events. Herbicide concentrations in rivers are affected by a number of factors, including herbicide use patterns within the associated basin. Changing agricultural practices, reductions in recommended and permitted herbicide applications, shifts to new herbicides, and greater environmental awareness in the agricultural community have resulted in changes to herbicide use patterns. In the Midwestern United States, alachlor use was much larger in 1989 than in 1995, while acetochlor was not used in 1989, and commonly used in 1995. Use of atrazine, cyanazine, and metolachlor was about the same in 1989 and 1995. Herbicide concentrations were measured in samples from 53 Midwestern rivers during the first major runoff event that occurred after herbicide application (postapplication) in 1989, 1990, 1994, and 1995. The median concentrations of atrazine, alachlor, cyanazine, metribuzin, metolachlor, propazine, and simazine all were significantly higher in 1989/90 than in 1994/95. The median acetochlor concentration was higher in 1995 than in 1994. Estimated daily yields for all herbicides and degradation products measured, with the exception of acetochlor, were higher in 1989/90 than in 1994/95. The differences in concentration and yield do not always parallel changes in herbicide use, suggesting that other changes in herbicide or crop management are affecting concentrations in Midwestern rivers during runoff events.In many Midwestern rivers, elevated concentrations of herbicides occur during runoff events for 1-3 months following application. The highest or `peak' herbicide concentration often occurs during one of these runoff events. Herbicide concentrations in rivers are affected by a number of factors, including herbicide use patterns within the associated basin. Changing agricultural practices, reductions in recommended and permitted herbicide applications, shifts to new herbicides, and greater environmental awareness in the agricultural community have resulted in changes to herbicide use patterns. In the Midwestern United States, alachlor use was much larger in 1989 than in 1995, while acetochlor was not used in 1989, and commonly used in 1995. Use of atrazine, cyanazine, and metolachlor was about the same in 1989 and 1995. Herbicide concentrations were measured in samples from 53 Midwestern rivers during the first major runoff event that occurred after herbicide application (postapplication) in 1989, 1990, 1994, and 1995. The median concentrations of atrazine, alachlor, cyanazine, metribuzin, metolachlor, propazine, and simazine all were significantly higher in 1989/90 than in 1994/95. The median acetochlor concentration was higher in 1995 than in 1994. Estimated daily yields for all herbicides and degradation products measured, with the exception of acetochlor, were higher in 1989/90 than in 1994/95. The differences in concentration and yield do not always parallel changes in herbicide use, suggesting that other changes in herbicide or crop management are affecting concentrations in Midwestern rivers during runoff events.

Environmental Science & Technology↗

Seasonal and annual load of herbicides from the Mississippi River Basin to the Gulf of Mexico

Water samples collected from rivers in the Mississippi River Basin were analyzed for selected herbicides to evaluate their discharge to the Gulf of Mexico and to identify their predominant source areas within the basin. Samples were collected from the Mississippi River at Baton Rouge, LA from 1991 to 1997 and from sites on the upper Mississippi, the Missouri, and the Ohio Rivers from 1996 to 1997. Atrazine, metolachlor, and alachlor ESA (an alachlor metabolite) were the most frequently detected herbicides in the Mississippi River at Baton Rouge, and, in general, were present in the largest concentrations. The peak annual herbicide load was in 1993 when about 640 metric tons of atrazine, 320 metric tons of cyanazine, 215 metric tons of metolachlor, 53 metric tons of simazine, and 50 metric tons of alachlor were discharged to the Gulf of Mexico. The annual load of atrazine and cyanazine was generally 1−3% of the amount annually applied in the Mississippi River drainage basin; the annual load of acetochlor, alachlor, and metolachlor was generally less than 1%. During 1996−1997 the Ohio River contributed about 50% of the discharge and 50% or more of the herbicide load to the Gulf of Mexico.

Environmental Science & Technology↗

Occurrence and transport of acetochlor in streams of the Mississippi River Basin

The herbicide acetochlor [2-chloro- N -(ethoxymethyl)- N -(2-ethyl-6-methylphenyl) acetamide] was first used on corn ( Zea mays L.) in the USA during the growing season of 1994. By 1996, it was the third most heavily used corn herbicide in the midwestern USA. During the growing season of 1997, 78% of 375 samples collected at 32 stream sites in the Mississippi River Basin contained detectable concentrations of acetochlor. However, concentrations in only 2% of the samples exceeded 2/µg/L, the maximum annual average concentration allowable in public water supplies derived primarily from surface water. The largest acetochlor concentrations were detected in streams draining basins in parts of Illinois, Indiana, and Iowa. The median concentration of acetochlor in streams was about 10% that of atrazine (6-chloro- N -ethyl- N -isopropyl-1,3,5-triazine-2,4-diamine), about 25% that of metolachlor [2-chloro- N -(2-ethyl-6-methylphenyl)- N -(2-methoxy-1-methylethyl) acetamide], about 50% that of cyanazine [2-[[4-chloro-6-(ethylamino)-l,3,5-triazin-2-yl]amino]-2-methylpropionitrile], and about threefold that of alachlor [2-chloro-2′,6′-diethyl- N -(methoxymethyl) acetanilide]. Load estimates indicate that, during the growing season of 1997, agricultural subbasins draining areas of Illinois, Indiana, and Iowa contributed about 37 000 kg, or 74%, of the 50 000 kg of acetochlor measured in streams of the Mississippi River Basin.

Journal of Environmental Quality↗

Evaluation of microtiter-plate enzyme-linked immunosorbent assay for the analysis of triazine and chloroacetanilide herbicides in rainfall

Triazine and chloroacetanilide concentrations in rainfall samples collected from a 23-state region of the United States were analyzed with microtiter-plate enzyme-linked immunosorbent assay (ELISA). Thirty-six percent of rainfall samples (2072 out of 5691) were confirmed using gas chro matography/mass spectrometry (GC/MS) to evaluate the operating performance of ELISA as a screening test. Comparison of ELISA to GC/MS results showed that the two ELISA methods accurately reported GC/MS results ( m = 1), but with more variability evident with the triazine than with the chloroacetanilide ELISA. Bayes's rule, a standardized method to report the results of screening tests, indicated that the two ELISA methods yielded comparable predictive values (80%), but the triazine ELISA yielded a false-positive rate of 11.8% and the chloroacetanilide ELISA yielded a false-negative rate of 23.1%. The false-positive rate for the triazine ELISA may arise from cross reactivity with an unknown triazine or metabolite. The false-negative rate of the chloroacetanilide ELISA probably resulted from a combination of low sensitivity at the reporting limit of 0.15 μg/L and a distribution characterized by 75% of the samples at or below the reporting limit of 0.15 μg/L.

Environmental Science & Technology↗

Herbicides in ground water of the Midwest: A regional study of shallow aquifers, 1991-94

The intensive herbicide use associated with the 'Corn Belt' marks the Midwestern United States as a region where herbicide contamination of ground water could be a problem. To better understand the regional occurrence of herbicides in shallow aquifers of the Midwest, a sampling network of 303 wells across 12 States was developed. The results documented relatively widespread, low-level concentrations of herbicides in the shallow aquifers sampled. The most frequently detected compounds, however, were the transformation products of these herbicides. A relation was determined between herbicide occurrence and the general age of the ground water sampled. Water that recharged ground water within the past 40 years was much more likely to contain herbicides than water recharged earlier.

Midwest↗

Herbicides and their metabolites in rainfall: Origin, transport, and deposition patterns across the midwestern and northeastern United States, 1990-1991

Herbicides were detected in rainfall throughout the midwestern and northeastern United States during late spring and summer of 1990 and 1991. Herbicide concentrations exhibited distinct geographic and seasonal patterns. The highest concentrations occurred in midwestern cornbelt states following herbicide application to cropland. Volume-weighted concentrations of 0.2−0.4 μg/L for atrazine and alachlor were typical in this area during mid-April through mid-July, and weighted concentrations as large as 0.6−0.9 μg/L occurred at several sites. Concentrations of 1−3 μg/L were measured in a few individual samples. Atrazine was detected most often followed by alachlor, deethylatrazine, metolachlor, cyanazine, and deisopropylatrazine. The high ratio (∼0.5) of deethylatrazine to atrazine in rainfall suggests atmospheric degradation of atrazine. Mass deposition of herbicides was greatest in areas where herbicide use was high and decreased with distance from the cornbelt. Estimated deposition rates for both atrazine and alachlor ranged from more than 240 μg m - 2 yr - 1 for some areas in the midwestern states to less than 10 μg m - 2 yr - 1 for the New England states. The estimated annual deposition of atrazine on the Great Lakes ranged from about 12 to 63 μg m - 2 yr - 1 . The total amounts of atrazine and alachlor deposited annually in rainfall in the study area represent about 0.6% of the atrazine and 0.4% of the alachlor applied annually to crops in the study area.

Environmental Science & Technology↗

Statistical modeling of agricultural chemical occurrence in midwestern rivers

Agricultural chemicals in surface water may constitute a human health risk or have adverse effects on aquatic life. Recent research on unregulated rivers in the midwestern USA documents that elevated concentrations of herbicides occur for 1-4 months following application in late spring and early summer. In contrast, nitrate concentrations in unregulated rivers are elevated during fall, winter, and spring months. Natural and anthropogenic variables of fiver drainage basins, such as soil permeability, amount of agricultural chemicals applied, or percentage of land planted in corn, affect agricultural chemical concentration and mass transport in rivers. Presented is an analysis of selected data on agricultural chemicals collected for three regional studies conducted by the US Geological Survey. Statistical techniques such as multiple linear and logistic regression were used to identify natural and anthropogenic variables of drainage basins that have strong relations to agricultural chemical concentrations and mass transport measured in rivers. A geographic information system (GIS) was used to manage and analyze spatial data. Statistical models were developed that estimated the concentration, annual transport, and annual mean concentration of selected agricultural chemicals in midwestern rivers. Multiple linear regression models were not very successful (R2 from 0.162 to 0.517) in explaining the variance in observed agricultural chemical concentrations during post-planting runoff. Logistic regression models were somewhat more successful, correctly matching the observed concentration category in 61-80% of observations. Linear and multiple linear regression models were moderately successful (R2 from 0.522 to 0.995) in explaining the variance in observed annual transport and annual mean concentration of agricultural chemicals. Explanatory variables that were commonly significant in the regression models include estimates of agricultural chemical use, crop acreage, soil characteristics, and basin topography.

Journal of Hydrology↗

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↗

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↗

Occurrence of selected pesticides and their metabolites in near-surface aquifers of the midwestern United States

The occurrence and distribution of selected pesticides and their metabolites were investigated through the collection of 837 water-quality samples from 303 wells across the Midwest. Results of this study showed that five of the six most frequently detected compounds were pesticide metabolites. Thus, it was common for a metabolite to be found more frequently in groundwater than its parent compound. The metabolite alachlor ethanesulfonic acid (alachlor-ESA; 2-[(2,6-diethylphenyl)(methoxymethyl)amino]-2-oxoethanesulfonic acid) was detected almost 10 times as frequently and at much higher concentrations than its parent compound alachlor (2-chloro-2&lsquo;,6&lsquo;-diethyl- N -(methoxymethyl)acetamide). The median detectable atrazine (2-chloro-4-ethylamino-6- isopropylamino- s -triazine) concentration was almost half that of atrazine residue (atrazine plus the two atrazine metabolites analyzed). Cyanazine amide [2-chloro-4-(1-carbamoyl-1-methylethylamino)-6-ethylamino- s -triazine] was detected almost twice as frequently as cyanazine (2-chloro-4-ethylamino-6-methylpropionitrileamino- s -triazine). Results show that information on pesticide metabolites is necessary to understand the environmental fate of pesticides. Consequently, if pesticide metabolites are not quantified, the effects of chemical use on groundwater quality would be substantially underestimated. Thus, continued research is needed to identify major degradation pathways for all pesticides and to develop analytical methods to determine their concentrations in water and other environmental media.

Environmental Science & Technology↗

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↗

A regional monitoring network to investigate the occurrence of agricultural chemicals in near-surface aquifers of the midcontinental USA

Previous state and national surveys conducted in the mid-continental USA have produced a wide range in results regarding the occurrence of agricultural chemicals in groundwater. At least some of these differences can be attributed to inconsistencies between the surveys, such as different analytical reporting limits. The US Geological Survey has designed a sampling network that is geographically and hydrogeologically representative of near-surface aquifers in the corn- and soybean-producing region of the midcontinental USA. More than 800 water quality samples have been collected from the network since 1991. Six of the seven most frequently detected compounds from this study were herbicide metabolites. A direct relation was determined between tritium content to herbicide and nitrate contamination. The unconsolidated aquifers sampled were found to be more susceptible to herbicide and nitrate contamination than the bedrock aquifers. Knowledge of the regional occurrence and distribution of agricultural chemicals acquired through the study of data collected at network sites will assist policy makers and planners with decisions regarding the protection of drinking-water supplies.

Conference Paper↗