Donald A. Goolsby

Eutrophication: Nitrate flux in the Mississippi River

Increased delivery of biologically available nitrogen to estuaries and coastal oceans in recent decades has been linked to eutrophication and seasonal hypoxia in the northern Gulf of Mexico and elsewhere. We have developed a model that accounts for 95% of annual variation in delivery of nitrate to the Gulf of Mexico by the Mississippi River in 1960–98. Retrospective analysis indicates that this nitrate flux could have been reduced by 33% if the use of nitrogen-containing fertilizer in the Mississippi River basin had been cut by 12%.

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/km2 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.

Formation and transport of deethylatrazine and deisopropylatrazine in surface water

Field disappearance studies and a regional study of nine rivers in the Midwest Corn Belt show that deethylatrazine (DEA; 2-amino-4-chloro-6-isopropylamino-s-triazine) and deisopropylatrazine (DIA; 2-amino-4-chloro-6-ethylaminos-triazine) occur frequently in surface water that has received runoff from two parent triazine herbicides, atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) and cyanazine (2-chloro-4-ethylamino-6-methylpropionitrileamino-s-triazine). The concentration of DEA and DIA in surface water varies with the hydrologic conditions of the basin and the timing of runoff, with maximum concentrations reaching 5 μg/L (DEA+DIA)

Mississippi Basin nitrogen flux believed to cause Gulf hypoxia

An expanding hypoxic zone develops each spring and summer on the Louisiana-Texas shelf of the Gulf of Mexico, and nitrogen from the Mississippi River Basin has been implicated as one of the principal causes. Hypoxic conditions, which occur when dissolved oxygen concentrations are less than 2 mg/L, can cause stress or death in bottom-dwelling organisms that cannot leave the zone. The mid-summer extent of the hypoxic zone has more than doubled since it was first systematically mapped in 1985 [Rabalais et al., 1999]. The largest hypoxic zone measured to date occurred in 1999, when it reached ∼20,000 km2, about the size of the state of New Jersey [Rabalais, 1999].

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 (microg pesticide/m2 per season) occurred at the agricultural sites in Mississippi (1980 microg/m2) and Iowa (490 microg/m2) and at the urban site in Iowa (696 microg/m2). Herbicides accounted for the majority of the wet depositional loading at the Iowa and Minnesota sites, but methyl parathion (1740 microg/m2) 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.

Occurrence and load of selected herbicides and metabolites in the lower Mississippi River

Analyses of water samples collected from the Mississippi River at Baton Rouge, Louisiana, during 1991-1997 indicate that hundreds of metric tons of herbicides and herbicide metabolites are being discharged annually to the Gulf of Mexico. Atrazine, metolachlor, and the ethane-sulfonic acid metabolite of alachlor (alachlor ESA) were the most frequently detected herbicides and, in general, were present in the largest concentrations. Almost 80% of the annual herbicide load to the Gulf of Mexico occurred during the growing season from May to August. The concentrations and loads of alachlor in the Mississippi River decreased dramatically after 1993 in response to decreased use in the basin. In contrast, the concentrations and loads of acetochlor increased after 1994, reflecting its role as a replacement for alachlor. The peak annual herbicide load occurred in 1993, when approximately 640 metric tons (t) of atrazine, 320 t of cyanazine, 215 t of metolachlor, 53 t of simazine, and 50 t of alachlor were discharged to the Gulf of Mexico. The annual loads of atrazine and cyanazine were generally 1-2% of the amount annually applied in the Mississippi River drainage basin; the annual loads of acetochlor, alachlor, and metolachlor were generally less than 1%. Despite a reduction in atrazine use, historical data do not indicate a long-term downward trend in the atrazine load to the Gulf of Mexico. Although a relation (r2 = 0.62) exists between the atrazine load and stream discharge during May to August, variations in herbicide use and rainfall patterns within subbasins can have a large effect on herbicide loads in the Mississippi River Basin and probably explain a large part of the annual variation in atrazine load to the Gulf of Mexico.

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.

Atmospheric nitrogen in the Mississippi River Basin--emissions, 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. NOx 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.

Statistical modeling of agricultural chemical occurrence in midwestern rivers

Abstract 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 river 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 ( R 2 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 ( R 2 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.