Herbicides in Rainfall Across the Midwestern and Northeastern United States, 1990-91
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Fact Sheet↗
Geology topics
E. Michael Thurman
Publications and source records attributed to E. Michael Thurman.
Postflood occurrence of selected agricultural chemicals and volatile organic compounds in near-surface unconsolidated aquifers in the upper Mississippi River basin, 1993
The historic stream flooding and intense rainfall across the upper Mississippi River Basin during summer 1993 had an immediate effect on near-surface unconsolidated aquifers by raising the water levels closer to the land surface . The objective of this study was to determine if this flooding also had immediate effects on groundwater quality . Water samples were collected during September and October 1993 from 110 wells completed in near-surface unconsolidated aquifers and were analyzed for herbicides, herbicide metabolites, inorganic nutrients, and volatile organic compounds. The results of these samples were compared with those obtained during summer 1991 or 1992. The difference was not statistically significant in the frequency of herbicide detection, total herbicide concentration, nitrate concentration, or the frequency of volatile organic compound detection between water samples collected in 1991 and 1992 and those collected in 1993 when all 110 wells were considered collectively . However, water samples from the Missouri River alluvial aquifer had a fourfold increase in the frequency of herbicide detection . There also appears to be a relation between increases in total herbicide concentration and the occurrence of stream flooding near a well. Water samples from wells that had at least a 20-percent increase in dissolved-oxygen concentration had the greatest frequency of substantial changes in total herbicide concentration and substantial increases in nitrate concentration . Increased dissolved-oxygen concentration could indicate areas where recharge has increased as a result of extensive stream flooding and intense rainfall . An inverse relation was determined between well depth and changes (increase or decrease) in total herbicide concentration . Water in shallow wells more quickly reflect changes in water quality in response to changes in recharge. Significantly more urban residential and industrial land use was within a 30-meter radius of the well for wells in which volatile organic compounds were detected. Because water moves more slowly along ground-water flow paths compared with surface-water runoff, additional information is required to determine long-term effects of the 1993 flood on ground-water quality.
upper Mississippi River basin↗
Determination of atrazine in rainfall and surface water by enzyme immunoassay
Rainwater and surface water from four sites in Germany (Bavaria and Lower Saxony) were analyzed for atrazine by enzyme immunoassay from June 1990 until October 1992. The limit of quantification of the immunoassay was 0.02 μg/L with a middle of the test at 0.2 μg/L. About 60 % of the samples contained measurable amounts of atrazine. Seasonal trends were observed, with the highest concentration in the summer months of up to 4 μg/L for rainwater and up to 15 μg/L for surface waters. The highest concentrations were found in agricultural areas, while in the investigated national parks up to 0.56 μg/L could be detected in rain water. This points to long-range atmospheric transport from agricultural areas to pristine national parks. Samples from forest stands usually showed higher atrazine concentrations than samples from open fields. Deposition rates of 10 – 50 μg/m 2 · yr were observed in the national parks and 10–180 μg/m 2 · yr at the agricultural sites. Comparison of results obtained by enzyme immunoassay and GC/MS showed a good correlation of r = 0.95.
Environmental Science and Pollution Research↗
Herbicides and nitrate in near-surface aquifers in the midcontinental United States, 1991
The occurrence and distribution of selected herbicides, atrazine metabolites, and nitrate were determined for near-surface aquifers (within 50 feet of land surface) in the corn- and soybean-producing region of the midcontinental United States. The study region included all or parts of Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota, Missouri, Nebraska, North Dakota, Ohio, South Dakota, and Wisconsin. Water samples were collected during the spring and summer of 1991 from 303 wells completed in near-surface unconsolidated and near-surface bedrock aquifers. At least one herbicide or atrazine metabolite was detected in 24 percent of 579 water samples analyzed for herbicides, based on a reporting limit of 0.05 microgram per liter. However, no herbicide concentration exceeded the U.S. Environmental Protection Agency's maximum contaminant levels or health advisory levels for drinking water. The most frequently detected herbicide compound was desethylatrazine, an atrazine metabolite (18.1 percent), followed by atrazine (17.4 percent); deisopropylatrazine, an atrazine metabolite (5.7 percent); prometon (5.0 percent); metolachlor (2.7 percent); alachlor (1.7 percent); simazine (1.0 percent); metribuzin (1.0 percent); and cyanazine (0.7 percent). The herbicides ametryn, prometryn, propazine, and terbutryn were not detected during this study. Nitrate concentrations equal to or greater than 3.0 milligrams per liter (excess nitrate) were detected in 29 percent of the 599 nitrate analyses, and ammonium concentrations equal to or greater than 0.01 milligram per liter were detected in 78 percent of the 584 ammonium analyses. Nitrate concentrations equal to or greater than the U.S. Environmental Protection Agency's maximum contaminant level for drinking water of 10 milligrams per liter were found in 6 percent of the samples. The frequency of herbicide detection was, in part, affected by the analytical method's reporting limit. Results from this study show that the frequency of atrazine detection increases as the reporting limit decreases. Herbicide metabolite concentrations are critical to understanding the detection of herbicide residues. The frequency of detection of atrazine residue (atrazine + desethylatrazine + deisopropylatrazine) was 22.1 percent, which was more than the frequency of detection of atrazine alone (17.4 percent). Prometon was detected more frequently than every other herbicide except atrazine. The prometon appears to be derived from areas of nonagricultural land use, such as golf courses and residential areas. Herbicides and excess nitrate were both rarely detected in the eastern part of the study region, even though this is an area of intense herbicide and nitrogen-fertilizer use. Hydrogeologic factors, land use, agricultural practices, local features, and water chemistry were analyzed for possible relation to herbicide and excess-nitrate detections. Herbicides and excess nitrate were detected more frequently in near-surface unconsolidated aquifers than in nearsurface bedrock aquifers. The depth to the top of the aquifer was inversely related to the frequency of detection of herbicides and excess nitrate. The proximity of streams to sampled wells also affected the frequency of herbicide detection. Significant seasonal differences were determined for the frequency of herbicide detection, but not for the frequency of excess nitrate.
Illinois, Indiana, Iowa, Kansas, Michigan, Minneso↗
Occurrence and transport of agricultural chemicals in the Mississippi River basin, July through August 1993
Heavy rainfall and severe flooding in the upper Mississippi River Basin from mid-June through early August 1993 flushed extraordinarily large amounts of agricultural chemicals (herbicides and nitrate) into the Mississippi River, many of its tributaries, and, ultimately, the Gulf of Mexico. Even though extremely high streamflows were recorded during the flood in 1993, concentrations of herbicides, such as atrazine, alachlor, cyanazine, and metolachlor, were similar to the maximum concentrations measured during spring and summer 1991 and 1992. It was anticipated that the higher streamflows during the flood would dilute the concentrations of herbicides that are usually flushed into streams in late spring and summer. Instead, concentrations were similar to those measured during much lower flows, but the daily loads of herbicides transported in some reaches of the Mississippi River were higher than those measured in 1991 and 1992. The total atrazine load transported to the Gulf of Mexico from April through August 1993 (539,000 kilograms) was about 80 percent higher than that for the same period in 1991 and 235 percent higher than for the same period in 1992. The concentrations of atrazine and cyanazine in a few individual samples exceeded health-based limits for drinking water. However, because drinking-water regulations are based on the average of at least four quarterly samples, the annual average concentrations in the Mississippi River probably will not exceed these limits for 1993. Nitrate concentrations were similar to those measured during spring and summer 1991 and 1992. The loads of nitrate-nitrogen transported into the Gulf of Mexico during July and August 1993 were as much as 5,734 metric tons per day. These loads generally are similar to those measured in spring 1991 and 1992 but larger than those measured in summer 1991 and 1992. The total nitrate-nitrogen load transported to the Gulf of Mexico from April through August 1993 (827,000 metric tons) was about 37 percent larger than that for this same period in 1991 and 112 percent larger than that for the same period in 1992. The transport of extraordinarily high loads of nitrate and large amounts of fresh-water into the Gulf of Mexico during midsummer when primary production is highest could increase phytoplankton biomass and affect the gulf ecosystem along the Louisiana coast.
Mississippi River↗
Geochemical heterogeneity in a sand and gravel aquifer: Effect of sediment mineralogy and particle size on the sorption of chlorobenzenes
The effect of particle size, mineralogy and sediment organic carbon (SOC) on sorption of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5–25% of the bulk sediment. Although SOC content of the bulk sediment is <0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.
Journal of Contaminant Hydrology↗
Source of atrazine and desethylatrazine in a river, during base flow
A budget of atrazine and desethylatrazine loads was computed for a 116-kilometer reach of the Cedar River in Iowa to determine where these compounds enter the river during base-flow conditions. Loads were determined by measuring discharge and concentrations of the compounds for four main-stem sites along the Cedar River and for 27 tributaries on September 20-22, 1989. Tributaries contributed 17 percent of the increased atrazine load and 24 percent of the increased desethylatrazine load measured between the extreme upstream and downstream sites on the Cedar River. The remaining 76 to 83 percent of the increased loads were attributed to input along the groundwater's main stem. The ground-water samples were collected at depths from 1 to 2 meters beneath the river bottom where the ground water was determined to be moving toward the river. The sources of atrazine and desethylatrazine detected in the ground water may include bank storage of river water or ground-water recharge originating at some distance from the river.
Conference Paper↗
Herbicides in streams. Midwestern United States
Results from a 2-year study of 149 streams geographically distributed across the corn-producing region of 10 midwestern States show that detectable concentrations of herbicides persist year round in most streams. Some herbicides exceeded proposed maximum contaminant levels for drinking water for periods of several weeks to several months following application. Atrazine was the most frequently detected and most persistent herbicide measured, followed by desethylatrazine and metolachlor. The seasonal distribution of atrazine indicates that aquifers contributing base flow to many of the streams are contaminated with herbicides.
Conference Paper↗
Biogeochemistry of aquatic humic substances in Thoreau's Bog, Concord, Massachusetts
Thoreau's Bog is an ombrotrophic floating—mat Sphagnum bog developed in a glacial kettlehole and surrounded by a red maple swamp. Concentrations of dissolved organic carbon in the porewater of the bog average 36 mg/L and are greatest near the surface, especially during late summer. This distribution suggest that the upper layer of living and dead Sphagnum and moderately humified peat is the major site of dissolved organic material production in the bog. The dissolved organic material consists mainly of aquatic fulvic acid (67%) and hydrophilic acids (20%); these organic acids control the pH (typically 4 or somewhat lower) of the bogwater. The elemental, amino acid, carbohydrate, and carboxylic acid contents of fulvic acid from the bog are similar to those of aquatic fulvic acid from the nearby Shawsheen River, although the phenolic hydroxyl content of fulvic acid from Thoreau's Bog is higher. The hydrophilic acids have greater amino acid, carbohydrate, and carboxylic acid contents than the fulvic acid, consistent with the hypothesis that hydrophilic acids are more labile intermediate compounds in the formation of fulvic acid.
Massachusetts↗
Complexation of copper by aquatic humic substances from different environments
The copper-complexing properties of aquatic humic substances isolated from eighteen different environments were characterized by potentiometric titration, using a cupric ion selective electrode. Potentiometric data were analyzed using FITEQL, a computer program for the determination of chemical equilibrium constants from experimental data. All the aquatic humic substances could be modelled as having two types of Cu(II)-binding sites: one with K equal to about 10 6 and a concentration of 1.0 ± 0.4 × 10 −6 M(mg C) −1 and another with K equal to about 10 8 and a concentration of 2.6 ± 1.6 × 10 −7 M(mg C) −1 . A method is described for estimating the Cu(II)-binding sites associated with dissolved humic substances in natural water based on a measurement of dissolved organic carbon, which may be helpful in evaluating chemical processes controlling speciation of Cu and bioavailability of Cu to aquatic organisms.
Science of the Total Environment↗