WRIR 99-4252


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Katz, B.G., Hornsby, H.D., Bohlke, J.F., and Mokray, M.F., 1999, Sources and chronology of nitrate contamination in spring waters, Suwannee River Basin, Florida: Water-Resources Investigations 99-4252, 54 p.

ABSTRACT:

A multi-tracer approach, which consisted of analyzing water samples for n aturally occurring chemical and isotopic indicators, was used to better understand sources and chronology of nitrate contamination in spring wate rs discharging to the Suwannee and Santa Fe Rivers in northern Florida. Dur ing 1997 and 1998, as part of a cooperative study between the Suwannee River Water Management District and the U.S. Geological Survey, water samples were collected and analyzed from 24 springs and two wells for major ions, nutrients, dissolved organic carbon, and selected environmental isotopes [18O/16O, D/H, 13C/12C, 15N/14N]. To better understand when nitrate entered the ground-water system, water samples were analyzed for chlorofluorocarbons (CFCs; CCl3F, CCl2F2, and C2Cl3F3) and tritium (3H); in this way, the apparent ages and residence times of spring waters and water from shallow zones in the Upper Floridan aquifer were determined. In addition to information obtained from the use of isotopic and other chemical tracers, information on changes in land-use activities in the basin during 1954-97 were used to estimate nitrogen inputs from nonpoint sources for five counties in the basin.

Changes in nitrate concentrations in spring waters with time were compared with estimated nitrogen inputs for Lafayette and Suwannee Counties. Agricultural activities [cropland farming, animal farming operations (beef and dairy cows, poultry, and swine)] along with atmospheric deposition have contributed large quantities of nitrogen to ground water in the Suwannee River Basin in northern Florida. Changes in agricultural land use during the past 40 years in Alachua, Columbia, Gilchrist, Lafayette, and Suwannee Counties have contributed variable amounts of nitrogen to the ground-water system. During 1955-97, total estimated nitrogen from all nonpoint sources (fertilizers, animal wastes, atmospheric deposition, and septic tanks) increased continuously in Gilchrist and Lafayette Counties. In Suwannee, Alachua, and Columbia Counties, estimated nitrogen inputs from all nonpoint sources peaked in the late 1970's corresponding to the peak use in fertilizer during this time. Fertilizer use in Columbia, Gilchrist, Lafayette, and Suwannee Counties increased substantially during 1993-97.

The heavy use of fertilizers in the basin is corroborated by nitrogen isotope data. Values of d15N of nitrate (d15N-NO3) in spring waters range from 2.7 per mil (SUW718971) to 10.6 per mil (Poe Spring) with a median of 5.4 per mil. The range of values indicates that nitrate in the sampled spring waters most likely originates from a mixture of inorganic (fertilizers) and organic (animal wastes) sources; however, higher d15N values for Poe and Lafayette Blue Springs indicate that an organic source of nitrogen probably is contributing nitrate to these spring waters. Water samples from two wells sampled in Lafayette County have high d15N-NO3 values of 11.0 and 12.1 per mil, indicating the predominance of an organic source of nitrate. These two wells are located near dairy and poultry farms, where leachate from animal wastes may contribute nitrate to ground water. Dissolved-gas data (nitrogen, argon, and oxygen) indicate that denitrification has not removed large amounts of nitrate from the ground-water system. Thus, variations in d15N-NO3 values of spring waters can be attributed to variations in d15N-NO3 values of ground-water recharge, and can be used to obtain information about source(s) of nitrate.

Extending the use of age-dating techniques (CFCs and 3H) to spring waters in complex karst systems required the use of several different approaches for estimating age and residence time of ground water discharging to springs. These approaches included the use of a simple reservoir model, a piston-flow model, an exponential model, and a binary-mixing model. When age data (CFC-11, CFC-113, and 3H) are combined for all springs, models that incorporate exponential mixtures seem to provide reliable estimates of average residence times of ground water discharging to springs. Whereas, data for some individual springs fit a binary-mixing model with more than 50 percent young water (recharged within the past 5 years), data from other individual springs fit a piston-flow model with a water age of about 25 years. The young ages of several spring waters (such as SUW718971, SUW725971, and Ginnie Spring) indicate the high vulnerability of the springs to contamination. For most springs, CFCs suggest that a large fraction of the water is more than 20 years old. Springs with lower flows tend to have young ages (shallow ground-water flow systems), whereas springs with higher flows tend to have older ages (deep ground-water flow systems).

The chemical composition of spring waters can be used as a qualitative indicator of age and ground-water residence time. Nitrate-nitrogen concentrations and dissolved oxygen in spring waters are inversely related to the apparent ages of spring waters and ground-water residence time in the basin. Silica concentrations increase as the age of spring waters increase.

Long-term trends in nitrate concentrations in selected spring waters were compared with estimated inputs of nitrogen from various sources in Suwannee and Lafayette Counties. In both counties, trends in nitrate concentrations in spring waters closely followed the estimated contribution of nitrogen from fertilizers. Decreasing nitrate concentrations in spring waters from Suwannee County followed the decrease in estimated fertilizer use from the mid-1970's to the early 1990's. Increasing nitrate concentrations in sprin g waters from Lafayette County followed the steady increase in fertilizer use from the early 1960's to the mid-1990's

The relation between the concentration of nitrate in ground water and the amount of nitrogen that is added to a ground-water contributing area for a spring is controlled by complex interactions among hydrogeologic, land-use, and climatic factors, as well as several other land-management factors. Spring waters represent mixtures of converging flow paths that contain ground water with a range of ages. Even if nitrogen inputs were reduced substantially, it may take decades for nitrate concentrations in the ground-water system to return to near background levels.