Journal of Environmental Quality 30:329-336 (2001)
© 2001 American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America
ARTICLE
SYMPOSIUM PAPER
Nitrogen Input to the Gulf of Mexico
Donald A. Goolsbya,
William A. Battaglina,
Brent T. Aulenbachb and
Richard P. Hooperc
a U.S. Geological Survey, MS406, DFC, Lakewood, CO 80225
b USGS, Atlanta, GA 30360
c USGS, Northborough, MA 01532
Corresponding author (wbattagl{at}usgs.gov)
Received for publication July 14, 2000.
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ABSTRACT
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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 1568000 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.
Abbreviations: MARB, Mississippi–Atchafalaya River basin
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INTRODUCTION
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THE Mississippi–Atchafalaya River basin shown in Fig. 1 drains an area of nearly 3208700 km2 or about 41% of the conterminous United States. It is the largest river basin in North America and the third largest river basin in the world (van der Leeden et al., 1990). Only the Amazon River basin in South America and the Congo River basin in Africa are larger. The basin drains all or parts of 30 states and extends from the Appalachian Mountains in western Pennsylvania and New York to the Rocky Mountains in western Montana, and from southern Canada to the Gulf of Mexico. About 58% of the basin is cropland. Other significant land uses and their percentage of the basin include woodland (18%), range and barren land (21%), wetlands and water (2.4%), and urban land (0.6%). About 70 million people live within the Mississippi basin, and it contains one of the most productive farming regions in the world. The central part of the basin produces the majority of the corn, soybean, wheat, cattle, and hogs produced in the United States. Because of the intensive agriculture, the majority of all fertilizers and pesticides used in the United States are applied to cropland within the basin. In addition, the central part of the basin was subjected to extensive agricultural drainage during 1870–1920 and 1945–1960 (Zucker and Brown, 1998) in order to make the land suitable for producing crops. The climate, land use, soils, and population vary widely across the Mississippi River Basin. The annual runoff ranges from less than 5 cm yr-1 in the arid western part of the basin to more than 60 cm yr-1 in the humid eastern part.
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Fig. 1. Map of the Mississippi–Atchafalaya River basin showing the average annual total nitrogen yields from 42 interior basins, 1980
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The Mississippi and Atchafalaya Rivers are the primary riverine sources of freshwater and nutrients discharged to the Gulf of Mexico. The combined mean annual streamflow for the Mississippi and Atchafalaya Rivers since 1980 is nearly 22000 m3 s-1 and represents about 80% of the estimated freshwater discharge from the United States to the Gulf (Dunn, 1996). These two rivers also account for an estimated 90% of total nitrogen (N) flux discharged annually to the Gulf (Dunn, 1996). Nitrogen, along with other nutrients, leads to increased production of algae in the Gulf and has been implicated as a possible cause of hypoxia (dissolved oxygen concentrations less than 2 mg L-1) in a large zone of bottom water in the Gulf along the Louisiana–Texas coast (Rabalais et al., 1996, 1998).
In this paper, historical data are used to estimate the annual flux of nitrogen to the Gulf of Mexico and to determine which parts of the Mississippi Basin contribute disproportionately large amounts of nitrogen to the Mississippi River.
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METHODS
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Historical data on streamflow and concentrations of dissolved nitrite plus nitrate (hereafter nitrate N) and total N (total organic N plus ammonium N plus nitrate) were used in regression models to estimate the daily and annual flux of nitrogen from the Mississippi–Atchafalaya River basin (MARB) to the Gulf of Mexico. Nitrate N concentrations have been measured numerous times each year since 1955, and total N concentrations have been measured since 1975 in the lower Mississippi River at St. Francisville, La. To determine the source areas of the nitrogen transported to the Gulf, regression models were also developed for 42 smaller interior basins within the MARB (Fig. 1). These 42 basins, in aggregate, comprise about 70% of the MARB. Nitrate N and total N fluxes were estimated for these basins for the period 1980 to 1996.
Regression Model Structure
Multiple regression models were developed to relate the flux (loads) of nitrate N and total N to stream discharge. Consistent with many past studies (e.g., Cohn et al., 1992), a seven-parameter model was developed of the form:
where ln [ ] is the natural logarithm of the argument in brackets; 
is the flux of the solute (C·Q); C is the solute concentration; Q is the daily average streamflow; 
is a centering term (a constant) related to the mean discharge of the data set and is used to ensure that the linear and quadratic flow terms (see Cohn et al., 1992 for derivation) are independent; T is time, expressed in decimal years; 
is a centering term (a constant) related to the mean sampling date of the data set and is used to ensure that the linear and quadratic time terms are independent (see Cohn et al., 1992 for derivation); 
is the error term; and ß0...ß6 are the fitted parameters in the multiple regression model.
This model captures the dependence of concentration on discharge, season (the sine and cosine terms), and any long-term trend. Quadratic terms were included to account for curvature that remained after transformation. Model parameters were estimated using the SAS system (SAS Institute, 1990). Standard diagnostics (e.g., plots of observed vs. predicted values, and various residual plots) were calculated and examined for all models. All terms were retained in the models, even if the model parameters were not significant, to simplify calculation of models across all sites and solutes. Daily streamflow was not measured at Sites 17 and 21 (Fig. 1) and streamflow from a nearby gauging station was used in the regression model to estimate nutrient flux. For six sites (4, 27, 35, 36, 39, and 42; Fig. 1), continuous measurement of streamflow was not available. For these sites, the annual flux was estimated using the average of the instantaneous discharge measurements made when samples were collected and flow-weighted average nutrient concentrations.
Daily fluxes estimated from the models were summed over time to provide annual and long-term average flux estimates from the 42 basins and to the Gulf of Mexico. Nutrient yields (mass per unit area per unit time) were calculated for each basin by dividing the annual fluxes by the basin drainage area. This normalized the fluxes so that comparisons could be made among basins of varying size.
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RESULTS AND DISCUSSION
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Historical Nitrogen Concentrations
Some of the earliest data available on nitrogen concentrations were published in U.S. Geological Survey (USGS) Water-Supply Paper 194 (Leighton, 1907). This report contains testimony pertaining to a lawsuit heard by the U.S. Supreme Court in 1905 on pollution of the Illinois and Mississippi Rivers by Chicago sewage. It also contains data on hundreds of analyses for nitrate N, nitrite, ammonia, and organic nitrogen in samples from the Illinois River basin and Mississippi River in the vicinity of St. Louis, MO, during 1897–1902. Historical nutrient data are also available from a study conducted by the USGS during 1906–1907. In this study water samples were collected each day for about a year from 62 major rivers in the eastern one-half of the United States. These included several sites on the Mississippi River from Minneapolis, MN to New Orleans, LA, and sites on rivers in Arkansas, Illinois, Indiana, Iowa, Minnesota, Ohio, and Pennsylvania. The daily samples were composited at about 10-d intervals and analyzed for numerous solutes, including nitrate N. Results of these analyses have been published in at least two USGS reports (Dole, 1909; Clarke, 1924). The USGS National Water Information System database provided additional data on nitrate N concentrations in the Mississippi River and for several rivers in Iowa for 1944 to 1996.
While the historical nitrate N concentrations probably do not represent natural background conditions, they do provide a baseline from which changes that have occurred in the past 90 to 100 years can be determined. A summary of historical nitrate N concentrations in a few interior basins in the MARB from the late 1890s to about 1965 are presented in Table 1. Mean concentrations for samples collected from these same streams during 1980–1996 near where the historical samples were obtained are shown for comparison. These data clearly show that the concentration of nitrate N in the Mississippi River and some of its tributaries has increased substantially in the last 100 years. The mean nitrate N concentrations in the rivers shown in Table 1 have increased by factors of two to more than five.
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Table 1. Historical and current (1980–1996) mean nitrate N concentrations in the Mississippi River basin [n, number of samples]
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The longest uninterrupted data set on nitrate N concentrations in the MARB is from the lower Mississippi River at St. Francisville (Fig. 1). Numerous samples have been collected at this site each year since 1954. From 1954 to 1967 samples were collected each day and composited at 10- to 30-d intervals for analysis. Compositing was discontinued in late 1967 and all subsequent analyses were on discrete samples collected periodically. The St. Francisville data set has been used extensively by scientists to estimate nitrate N flux to the Gulf of Mexico and determine long-term changes in Mississippi River water quality (Turner and Rabalais, 1991; Bratkovich et al., 1994; Dunn, 1996; Rabalais et al., 1996; Goolsby et al., 1997). The long-term pattern in nitrate N concentrations at this site is shown in Fig. 2
. The average mean annual nitrate N concentration at St. Francisville during 1980–1996 was more than double the average concentration during 1955–1970. The average minimum and maximum annual concentrations also more than doubled.
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Fig. 2. Long-term patterns in nitrate concentrations in the lower Mississippi River at St. Francisville, La
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Current Nitrogen Concentrations
The two principal forms in which nitrogen occurs in streams of the MARB are nitrate N and organic nitrogen (dissolved and particulate). Substantial amounts of ammonia also may occur in some stream reaches, particularly downstream from sources of human and animal wastes. However, ammonia is quickly transformed to nitrate N and concentrations are generally much less than 0.1 mg N L-1 in the lower reaches of the Mississippi River (Antweiler et al., 1995). Trace amounts of nitrite also occur briefly during the oxidation of ammonia to nitrate N, which is the end product of the aerobic biochemical oxidation of organic nitrogen and ammonia in soil and water. Nitrate N is the most soluble and mobile form of nitrogen and is easily leached by precipitation into ground water, subsurface tile drainage, and streams. The distribution of nitrate N from 1980–1996 at the sites representing the 42 interior basins is shown in the boxplots in Fig. 3A
. There are two distinctly different groups of basins. Twelve basins have median nitrate N concentrations ranging from about 2.5 mg N L-1 to more than 6 mg N L-1, while the remaining 30 basins have medians of less than 1.5 mg N L-1. Figure 3A also shows that the maximum nitrate N concentration at several of these sites occasionally exceeds the USEPA drinking water standard of 10 mg N L-1. The high nitrate N concentrations are associated with basins having either a high percentage of land in row crop (corn, soybean, or sorghum) or a high population density (people per km2). Basin 20 (Raccoon River, IA) had the highest median nitrate N concentration (6.2 mg N L-1) and the highest percent cropland (74%). Basins 5 and 6 in Ohio and Basin 22 in Illinois have the highest population densities (100 to more than 300 people per km2) and more than 45% of the basin areas are in row crops. The extent of row cropland expressed as a percent of the basin area for the 12 basins with highest median nitrate N concentrations ranged from 44 to 74. The percent of row cropland in the remaining 30 basins ranged from 0.1 to 35.
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Fig. 3. Boxplots showing the distribution of (A) nitrate plus nitrite, and (B) total organic nitrogen concentrations in 42 interior basins for 1980–1996
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Figure 3B shows the distribution of total organic nitrogen (dissolved and particulate). Median values range from less than 0.5 mg N L-1 to about 1.5 mg N L-1. The highest concentrations are associated with high population density, high cropland percentage, and/or high suspended-sediment concentrations. Median concentrations of ammonia N (not shown in figures) were less than 0.2 mg L-1 in all 42 basins except the upper Illinois River (Basin 22). This basin is dominated by municipal wastes from the Chicago area, and the river water contains significant amounts of ammonia N (median is about 0.5 mg N L-1).
Nitrate N concentrations in basins where the supply of nitrogen in soils is abundant can vary seasonally over a large range (less than 0.1 mg N L-1 to more than 10 mg N L-1) in response to climatic and hydrologic conditions. Concentrations in streams tend to be highest in the late winter and spring when streamflow is highest and lowest in the late summer and fall when streamflow is low. This direct relationship between concentration and streamflow indicates that most of the nitrate N in these streams is from nonpoint sources. If the nitrate N was predominantly from point sources, concentrations would decrease as streamflow increased due to dilution. Instead, nitrate N concentrations in streams increase in response to rainfall or snowmelt that leaches nitrate N that has accumulated in the soil. Scientific evidence suggests that nitrogen levels can build up in soils during dry years from mineralization processes and reduced uptake by crops, and nitrogen can be flushed out in larger than normal amounts in succeeding wet years (Randall et al., 1997). Nitrate can enter streams through agricultural drains, ground water discharge, and direct runoff. Nitrate concentrations generally decrease in the summer and fall as streamflow and subsurface tile drainage decrease. Assimilation of nitrogen by agricultural crops on the land and aquatic plants in streams also aids in decreasing the nitrate concentrations in streams during summer months.
Agricultural drainage plays a major role in transporting nitrate from cropland to streams in the MARB. More than 20 million hectares, mostly cropland, have been drained through use of subsurface tile drainage, ditches, and streams in Illinois, Indiana, Iowa, Ohio, Minnesota, Missouri, and Wisconsin (USDA, 1987). This practice "short-circuits" the flow of water by draining the top of the saturated zone directly into streams, and eventually the Mississippi River. This drainage practice can result in the leaching of large amounts of nitrate N that are stored in the soil zone and unsaturated zone. Nitrate N concentrations in agricultural drains can be very high—20 to 40 mg N L-1 or more (David et al., 1997; Randall et al., 1997; Fenelon, 1998; Gentry et al., 1998; Zucker and Brown, 1998).
Flux of Nitrogen to the Gulf of Mexico
The mean annual flux of nitrogen compounds from the MARB to the Gulf of Mexico for 1980–1996 is summarized in Table 2. This period includes the drought of 1988–1989, when fluxes were very low, and the flood of 1993, when the flux was very high. The mean annual flux of all forms of nitrogen was 1568000 t yr-1. This is within 2% of the flux estimate of 1597000 t yr-1 by Dunn (1996) for 1972–1993 and about 14% less than the 1982–1987 estimate of 1824000 t yr-1 made by Turner and Rabalais (1991). About three-quarters of the nitrogen flux from the MARB enters the Gulf of Mexico via the Mississippi River channel and the remainder discharges through the Atchafalaya River. However, nearly all of the nitrogen discharging from the Atchafalaya River is diverted into the Atchafalaya from the Mississippi River in northern Louisiana. The total N flux is about 61% nitrate N, 2% ammonia N, and the remaining 37% is dissolved and particulate organic N. The flux of ammonia N and the fraction of organic nitrogen present in dissolved and particulate forms was estimated from concentration data.
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Table 2. Mean annual flux of nitrogen from the Mississippi– Atchafalaya River basin to the Gulf of Mexico, 1980–1996. (Flux measured in the Mississippi River at St. Francisville, LA, and the Atchafalaya River at Melville, LA.)
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The annual flux of nitrate N to the Gulf increased significantly over the period 1955–1996, as shown in Fig. 4
. This increase in flux parallels the increase in concentration shown in Fig. 2. A Kendall's tau test for trend (Helsel and Hirsch, 1992) shows the increase in nitrate N flux to be highly significant (p < 0.001), with a trend slope of about 19000 t yr-1. During 1955–1970 nitrate N flux averaged 328000 t yr-1. However, during 1980–1996 the nitrate N flux averaged 952700 t yr-1, almost a threefold increase. Nearly all of this increase occurred between 1970 and 1983. There is no statistically significant trend, upward or downward, in nitrate N from 1980 to 1996, even if the flood year of 1993 is removed.
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Fig. 4. Bar chart of the annual flux of nitrate and organic nitrogen from the Mississippi–Atchafalaya River basin to the Gulf of Mexico, 1955–1996
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All of the increase in total N that has occurred since 1972 (Fig. 4) can be attributed to the increase in nitrate N. The large year-to-year differences in flux are caused by variations in streamflow. The flux of nitrate N was relatively low during the drought years of 1988–1989 (500000–600000 t), but was high (>1500000 t) during the flood year of 1993. Nitrate N flux was also high during 1979 and during 1982–1986, when streamflow was abnormally high.
It should also be noted that streamflow in the MARB generally increased during the 1955–1996 period (Fig. 4) and this could account for part of the increase in nitrate N flux. The average annual streamflow was 30% higher during 1980–1996 than during 1955–1970. A Kendall's tau test on the mean annual streamflow during 1955–1996 showed a statistically significant upward trend (p = 0.001) with a slope of 158 m3 s-1 yr-1. The higher streamflow in the later time period could influence nitrate N flux in two ways. First, the volume of flow would be larger and more nitrate N should be transported unless concentrations decreased, which does not appear to be the case. Second, the higher precipitation would leach more accumulated nitrate N from soils in the basin and would actually cause nitrate N concentrations to increase, as was previously discussed. The combination of higher concentrations and higher streamflow in the 1980–1996 period would produce significant increases in nitrate N flux.
Sources of Nitrogen
The spatial patterns in the average annual total N yields in the MARB are shown graphically in Fig. 1 for the 42 interior basins. The total N in most of these basins was composed largely of nitrate N. Nitrate N yields, therefore, have a spatial pattern very similar to that of total N. The distributions of the annual yields of total N for the 42 basins are shown in Fig. 5
for the 1980–1996 period. The highest average annual total N yields ranged from 1500 to more than 3100 kg N km-2 yr-1 and occurred in a band extending from southwestern Minnesota across Iowa, Illinois, Indiana, and Ohio (Fig. 1). Annual average total N yields were 2750, 2290, 2020, 3090, and 1850 kg N km-2 yr-1 in the Cedar, Iowa, Skunk, Raccoon, and Des Moines River basins in Iowa (Basins 17–21); 3120 and 1650 kg N km-2 yr-1 in the Illinois River basin (22–23); 1580 kg N km-2 yr-1 in the Wabash River basin (8); and 1980 kg N km-2 yr-1 in the Great Miami basin in Ohio (6). Other basins adjacent to these, but not shown in the figures because of insufficient data, may have had similar yields. The maximum annual total N yield from some of these basins exceeded 6000 kg N km-2 yr-1 (Fig. 5) during years with high streamflow. The total N discharged from these five rivers alone accounted for as much as 20% of the nitrogen discharge from the MARB during average years and more than 30% during flood years such as 1993, assuming instream denitrification losses in the lower Mississippi River were not significant. The nitrogen discharged from all streams draining the states of Iowa and Illinois during average years is estimated to account for about 35% of the nitrogen discharged to the Gulf. Total N yields were generally less than 1000 kg N km-2 yr-1 in basins south of the Ohio River and were generally less than 500 kg N km-2 yr-1 in the Missouri, Arkansas, and lower Mississippi basin. Many of the drier basins in the western part of the MARB had total N yields less than 100 kg N km-2 yr-1.
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Fig. 5. Boxplots showing the distribution of the annual total nitrogen yields for 42 interior basins, 1980–1996. Dashes (-) show the median yields for several sites where other statistics could not be computed
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The large range in annual yields of total N shown in Fig. 5 can be attributed largely to year-to-year variations in precipitation and leaching of nitrogen from nonpoint sources. During dry years, there is little rainfall to transport soluble nitrogen (nitrate N) from the soil and unsaturated zone to streams. Under these conditions nitrogen yields were very low, and nitrogen inputs from point sources may dominate in some streams. During periods of high precipitation, nitrate N that has accumulated in the soil is flushed into streams via subsurface tile drainage, ground water discharge, and overland flow; thus, yields are high. Basins with large point-source inputs, such as the Upper Illinois River (22), with more than 300 people per km2, exhibit a different distribution in average annual yields (Fig. 5). The minimum annual yield is very high (greater than 2000 kg N km-2 yr-1) because of sustained year-round direct inputs of N from point sources. The range in yields is small because point source inputs are not greatly affected by precipitation. Several other basins, with above average population densities, such as the Scioto (5), Great Miami (6), Wabash (8), and the Rock (16) show this same pattern but to a lesser extent.
The nitrogen flux and yield estimates presented in the forgoing discussion represent the amounts of nitrogen delivered to larger rivers, usually the Ohio, Missouri, or Mississippi, and subsequently to the Gulf of Mexico. They do not account for any instream losses such as denitrification or deposition in sediment in reservoirs or flood plains. These processes would not substantially affect our estimates of nitrogen flux from the MARB to the Gulf of Mexico. However, if denitrification is significant in large rivers, this could affect our estimates of the relative contributions from basins within the MARB. The relative contribution of nitrogen to the Gulf by the furthest upstream basins could be overestimated, and the relative contribution by the furthest downstream basins could be underestimated.
Two lines of evidence suggest instream nitrogen losses in large rivers are small. First, the aggregate annual nitrogen yield near the mouths of the Ohio, lower Missouri, and upper and lower Mississippi basins (826 kg N km-2 yr-1), an area of 1668400 km2, is similar to the aggregate average annual nitrogen yield near the mouths of 30 interior basins (880 kg N km-2 yr-1) that comprise 62% of the area of the large basins. The upper Missouri and Arkansas basins were excluded from this calculation because they contain large amounts of drainage area with low precipitation and low runoff rates and very low nitrogen yields. Also, the Upper Missouri basin contains large reservoirs with long hydraulic residence times and could trap and store nitrogen in bottom sediments in the form of organic N. This small difference in yields, about 6%, is well within the standard errors, and is an indication that no significant denitrification occurs between the outlets of the interior basins and the outlets of the large rivers.
The second line of evidence is based on the results of a model that Howarth et al. (1996) applied to rivers draining to the North Atlantic Ocean. The model relates nitrogen loss, which is largely denitrification, to the ratio of mean water depth to water residence time of rivers. The deeper the rivers are, the less time nitrate N in the water column is in contact with benthic zones where denitrification could occur. They suggest that 5 to 20% of the nitrogen inputs to streams might be lost through denitrification in larger rivers. The large rivers in the MARB should be near the low end of these denitrification estimates. There is also some short-term removal of nitrogen in algal and plant biomass that is deposited in the bottoms of streams and reservoirs. However, much of the nitrogen should be accounted for in the long-term flux estimates if nitrogen is later released in dissolved or particulate forms. The rate at which dissolved and particulate nitrogen is released is dependent on many factors and is not well known. The above discussion suggests that most (>90%) of the nitrogen that enters the Ohio, lower Missouri, and Mississippi Rivers is eventually discharged to the Gulf of Mexico. Denitrification may result in significant losses of nitrogen in streams smaller and shallower than those used in this analysis. If this is true, then nitrogen yields in smaller watersheds could be significantly higher than those reported here for the 42 interior basins.
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L. E. Osterman, R. Z. Poore, P. W. Swarzenski, and R. E. Turner
Reconstructing a 180 yr record of natural and anthropogenic induced low-oxygen conditions from Louisiana continental shelf sediments
Geology,
April 1, 2005;
33(4):
329 - 332.
[Abstract]
[Full Text]
[PDF]
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D. Q. Kellogg, A. J. Gold, P. M. Groffman, K. Addy, M. H. Stolt, and G. Blazejewski
In Situ Ground Water Denitrification in Stratified, Permeable Soils Underlying Riparian Wetlands
J. Environ. Qual.,
March 1, 2005;
34(2):
524 - 533.
[Abstract]
[Full Text]
[PDF]
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D. B. Jaynes, D. L. Dinnes, D. W. Meek, D. L. Karlen, C. A. Cambardella, and T. S. Colvin
Using the Late Spring Nitrate Test to Reduce Nitrate Loss within a Watershed
J. Environ. Qual.,
March 1, 2004;
33(2):
669 - 677.
[Abstract]
[Full Text]
[PDF]
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G. F. McIsaac, M. B. David, G. Z. Gertner, and D. A. Goolsby
Relating Net Nitrogen Input in the Mississippi River Basin to Nitrate Flux in the Lower Mississippi River: A Comparison of Approaches
J. Environ. Qual.,
September 1, 2002;
31(5):
1610 - 1622.
[Abstract]
[Full Text]
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TOP
ABSTRACT
INTRODUCTION
