Use of chemical and isotopic tracers to assess nitrate contamination and ground-water age, Woodville Karst Plain, USA

Concerns regarding ground-water contamination in the Woodville Karst Plain have arisen due to a steady increase in nitrate-N concentrations (0.25-0.90 mg/l) during the past 30 years in Wakulla Springs, a large regional discharge point for water (9.6 m3/s) from the Upper Floridan aquifer (UFA). Multiple isotopic and chemical tracers were used with geochemical and lumped-parameter models (exponential mixing (EM), dispersion, and combined exponential piston flow) to assess: (1) the sources and extent of nitrate contamination of ground water and springs, and (2) mean transit times (ages) of ground water. Delta 15N-NO3 values (1.7-13.8???) indicated that nitrate in ground water originated from localized sources of inorganic fertilizer and human/animal wastes. Nitrate in spring waters (??15N-NO3=5.3-8.9???) originated from both inorganic and organic N sources. Nitrate-N concentrations (<0.02-16 mg/l) were highly variable both spatially and vertically in the oxic UFA, based on water samples from 46 wells and four springs collected from 1997 to 2000. During high-flow conditions, spring waters had decreased nitrate and increased DOC concentrations that resulted from mixtures of 20-95% surface water. Although higher nitrate-N concentrations (>1.0 mg/l) were associated with shallow wells (open intervals less than 15 m below land surface), elevated nitrate concentrations in deeper wells are consistent with mixtures of water from shallow and deep zones in the UFA as indicated from geochemical mixing models and the distribution of mean transit times (5-90 years) estimated using lumped-parameter flow models. Ground water with mean transit times of 10 years or less tended to have higher dissolved organic carbon concentrations, lower dissolved solids, and lower calcite saturation indices than older waters, indicating mixing with nearby surface water that directly recharges the aquifer through sinkholes. Significantly higher values of pH, magnesium, dolomite saturation index, and phosphate in springs and deep water (>45 m) relative to a shallow zone (<45 m) were associated with longer ground-water transit times (50-90 years). Chemical differences with depth in the aquifer result from deep regional flow of water recharged through low permeability sediments (clays and clayey sands of the Hawthorn Formation) that overlie the UFA upgradient from the karst plain.