Skip to main content
Log in

Sources of nitrate contamination and age of water in large karstic springs of Florida

  • Original Article
  • Published:
Environmental Geology

Abstract

In response to concerns about the steady increase in nitrate concentrations over the past several decades in many of Florida’s first magnitude spring waters (discharge ≥2.8 m3/s), multiple isotopic and other chemical tracers were analyzed in water samples from 12 large springs to assess sources and timescales of nitrate contamination. Nitrate-N concentrations in spring waters ranged from 0.50 to 4.2 mg/L, and δ15N values of nitrate in spring waters ranged from 2.6 to 7.9 per mil. Most δ15N values were below 6 per mil indicating that inorganic fertilizers were the dominant source of nitrogen in these waters. Apparent ages of groundwater discharging from springs ranged from 5 to about 35 years, based on multi-tracer analyses (CFC-12, CFC-113, SF6, 3H/3He) and a piston flow assumption; however, apparent tracer ages generally were not concordant. The most reliable spring-water ages appear to be based on tritium and 3He data, because concentrations of CFCs and SF6 in several spring waters were much higher than would be expected from equilibration with modern atmospheric concentrations. Data for all tracers were most consistent with output curves for exponential and binary mixing models that represent mixtures of water in the Upper Floridan aquifer recharged since the early 1960s. Given that groundwater transit times are on the order of decades and are related to the prolonged input of nitrogen from multiple sources to the aquifer, nitrate could persist in groundwater that flows toward springs for several decades due to slow transport of solutes through the aquifer matrix.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9a,b
Fig. 10a,b
Fig. 11

Similar content being viewed by others

References

  • Aeschbach-Hertig W, Schlosser P, Stute M, Simpson HJ, Ludin A, Clark JF (1998) A 3H/3He study of groundwater flow in a fractured bedrock aquifer. Groundwater 36:661–670

    CAS  Google Scholar 

  • Anderson JR, Hardy EE, Roach JT, Witmer RE (1976) A land use and land cover classification system for use with remote sensor data. U.S. Geological Survey Professional Paper 964, 28 pp

  • Andrews WJ (1994) Nitrate in groundwater and spring water near four dairy farms in north Florida 1990–93. U.S. Geological Survey Water-Resources Investigations Report 94–4162, 63 pp

  • Böhlke JK (2002) Groundwater recharge and agricultural contamination. Hydrogeology J 10:153–179

    Article  Google Scholar 

  • Böhlke JK, Denver JM (1995) Combined use of groundwater dating, chemical and isotopic analyses to resolve the history and fate of nitrate contamination in two agricultural watersheds, Atlantic coastal plain, Maryland. Water Resources Research 31:2319–2339

    Article  Google Scholar 

  • Burg A, Heaton THE (1998) The relationship between the nitrate concentration and hydrology of a small chalk spring, Israel. J Hydrology 204:68–82

    Article  Google Scholar 

  • Busenberg E, Plummer LN (1992) Use of chlorofluoromethanes (CCl3F and CCl2F2) as hydrologic tracers and age-dating tools: example- the alluvium and terrace system of central Oklahoma. Water Resources Research 28:2257–2283

    Article  CAS  Google Scholar 

  • Busenberg E, Plummer LN (2000) Dating young groundwater with sulfur hexafluoride-- Natural and anthropogenic sources of SF6. Water Resources Research 36:3011–3030

    Article  CAS  Google Scholar 

  • Busenberg E, Weeks E, Plummer LN, Bartholemay RC (1993) Age dating groundwater by use of chlorofluorocarbons (CCl3F and CCl2F2), and distribution of chlorofluorocarbons in the unsaturated zone, Snake River Plain aquifer, Idaho National Engineering Laboratory, Idaho. U.S. Geological Survey Water Resources Investigations Report 93–4054, 47 pp

  • Bush PW, Johnston RH (1988) Groundwater hydraulics, regional flow, and groundwater development of the Floridan aquifer system in Florida and parts of Georgia, South Carolina, and Alabama. U.S. Geological Survey Professional Paper 1403-C, 80 pp

  • Buzek F, Kadlecova R, Zak K (1998) Nitrate pollution of a karstic groundwater system. In: Isotope Techniques in the Study of Environmental Change, International Atomic Energy Agency Report 1024, Vienna, Austria, pp 453–464

  • Chelette AR, Pratt TR, Godin J (2002a) Florida Springs Initiative FY2001–2002 Final Report. Northwest Florida Water Management District Technical File Report 02–01, 6 pp

  • Chelette AR, Pratt, TR, Katz BG (2002b) Nitrate loading as an indicator of nonpoint source pollution in the lower St. Marks-Wakulla Rivers watershed. Northwest Florida Water Management District Water Resources Special Report 02–1, 138 pp

  • Cook PG, Böhlke JK (1999) Determining timescales for groundwater flow and solute transport. In: Cook PG, Herczeg AL (eds) Environmental Tracers in Subsurface Hydrology. Kluwer Academic Publishers, Boston, pp 1–30

  • Coxon C (1999) Agricuturally induced impacts. In: Drew D, Hotzl H (eds) Karst hydrogeology and human activities. Balkema, Rotterdam, pp 37–80

  • Crandall CA, Katz BG, Hirten JJ (1999) Hydrochemical evidence for mixing of river water and groundwater during high-flow conditions, lower Suwannee River Basin, Florida. Hydrogeology J 7:454–467

    Article  Google Scholar 

  • Davis JH (1996) Hydrogeologic investigation and simulation of ground-water flow in the Upper Floridan aquifer of north-central Florida and southwestern Georgia and delineation of contributing areas for selected city of Tallahassee, Florida, water-supply wells. U.S. Geological Survey Water-Resources Investigations Report 95–4296, 55 pp

  • Dietrich PG, Hebert D (1997) Regional discharge of a Triassic artesian karst aquifer: Mixing and age of spring waters in the Thuringian basin, Germany, estimated by isotope methods: In: Gunay G, Johnson AI (eds) Karst Waters and Environmental Impacts. Balkemia, Rotterdam, pp 221–229

  • Dincer T, Payne BR (1971) An environmental isotope study of the southwestern karst region of Turkey. J Hydrology 14:233–258

    Article  Google Scholar 

  • Faulkner GL (1973) Geohydrology of the Cross-Florida Barge Canal area with special reference to the Ocala vicinity. U.S. Geological Survey Water-Resources Investigations, 73–1, 117 pp

  • Focazio MJ, Plummer LN, Böhlke JK, Busenberg E, Bachman LJ, Powars DS (1998) Preliminary estimates of residence times and apparent ages of groundwater in the Chesapeake Bay Watershed, and water-quality data from a survey of springs. U.S. Geological Survey Water-Resources Investigations Report 97–4225, 75 pp

  • Fogg GE, Rolston DE, Decker DL, Louie DT, Grismer ME (1998) Spatial variation in nitrogen isotope values beneath nitrate contamination sources. Groundwater 36:418–426

    CAS  Google Scholar 

  • Gormly JR, Spalding RF (1979) Sources and concentrations of nitrate-nitrogen in groundwater of the central Platte region, Nebraska. Groundwater 17:291–301

    CAS  Google Scholar 

  • Grubbs JW (1998) Recharge rates to the Upper Floridan aquifer in the Suwannee River Water Management District, Florida. U.S. Geological Survey Water Resources Investigations Report 97–4283, 30 pp

  • Heaton THE, Vogel JC (1981) Excess air in groundwater. J Hydrology 50:201–216

    Article  CAS  Google Scholar 

  • Heaton THE (1986) Isotopic studies of nitrogen pollution in the hydrosphere and atmosphere: A review. Chemical Geology 59:87–102

    CAS  Google Scholar 

  • Hornsby D, Ceryak R (1999) Springs of the Suwannee River Basin in Florida. Suwannee River Water Management District Report WR99–02, 178 pp

  • Hornsby D, Mattson R (1998) Surface water quality and biological monitoring network. Suwannee River Water Management District Annual Report WR-98–02

  • Hübner H (1986) Isotope effects of nitrogen in the soil and biosphere. In: Fritz P, Fontes JC (eds) Handbook of Environmental Geochemistry, vol. 2, The Terrestrial Environment B. Elsevier, New York, pp 361–425

  • Jones GW, Upchurch SB, Champion KM (1996) Origin of nitrate in groundwater discharging from Rainbow Springs, Marion County, Florida. Southwest Florida Water Management District, Ambient Ground-Water Quality Monitoring Program, 155 pp

  • Katz BG (1992) Hydrochemistry of the Upper Floridan aquifer in Florida. U.S. Geological Survey Water Resources Investigations Report 91–4196, 37 pp

  • Katz BG, Hornsby HD, Böhlke JK, Mokray MF (1999) Sources and chronology of nitrate contamination in spring waters, Suwannee River Basin, Florida. U.S. Geological Survey Water-Resources Investigations Report 99–4252, 54 pp

  • Katz BG, Hornsby HD, Böhlke JK (2001) Timescales for nitrate contamination of spring waters, northern Florida, USA. Chemical Geology 179:167–186

    Article  CAS  Google Scholar 

  • Katz BG, Chelette AR, Pratt TR (2004) Use of chemical and isotopic tracers to assess nitrate contamination and groundwater age, Woodville Karst Plain, USA. J Hydrology 289:36–61

    Article  CAS  Google Scholar 

  • Kendall C, Aravena R (1999) Nitrogen isotopes in groundwater systems. In: Cook P, Herczeg AL (eds) Environmental Tracers in Subsurface Hydrology. Kluwer, Boston, Ch. 9, pp 261–298

  • Kincaid TR (1998) River water intrusion to the unconfined Floridan aquifer. Environmental and Engineering Geoscience 4:361–374

    Google Scholar 

  • Kincaid TR (1999) Morphologic and fractal characterization of saturated karstic caves. Ph.D dissertation, University of Wyoming, 174 pp

  • Kreitler CW (1975) Determining the source of nitrate in groundwater by nitrogen isotope studies. Univ. Of Texas, Austin, Texas Bur Econ Geol Rep Invest No 83, 57 pp

  • Ludin A, Weppernig R. Bonisch G, Schlosser P (1998) Mass spectrometric measurement of helium isotopes and tritium. Lamont-Doherty Earth Observatory, Palisades, NY, Technical Report 98–06

  • Maloszewski P, Zuber A (1982) Determining the turnover time of groundwater systems with the aid of environmental tracers 1. Models and their applicability. J Hydrology 57:207–231

    Article  CAS  Google Scholar 

  • Maloszewski P, Zuber A (1996) Lumped parameter models for the interpretation of environmental tracer data. In: Manual on Mathematical Models in Isotope Hydrology. IAEA-TECDOC 910, IAEA, Vienna, pp 9–50

  • Mariotti A, Landreau A, Simon B (1988) N isotope biogeochemistry and natural denitrification processed in groundwater: application to the chalk aquifer of northern France. Geochimica et Cosmochimica Acta 52:1869–1878

    Article  CAS  Google Scholar 

  • Michel RM (1989) Tritium deposition in the continental United States 1953–1983. U.S. Geological Survey Water Resources Investigations Report 89–4072, 46 pp

  • Osmond JK, Buie BF, Rydell HS, Kaufman MI, Wallick EI (1971) Uranium and tritium as natural tracers in the Floridan aquifer. Florida Water Resources Research Center Publication No. 14, University of Florida, Gainesville, 66 pp

  • Pittman JR, Hatzell HH, Oaksford ET (1997) Spring contributions to water quantity and nitrate loads in the Suwannee River during base flow in July 1995. U.S. Geological Survey Water-Resources Investigations Report 97–4152, 12 pp

  • Plummer LN, Busenberg E, Drenkard S, Schlosser P, Ekwurzel B, Weppernig R, McConnell JB, Michel RL (1998) Flow of river water into a karstic limestone aquifer. 2. Dating the young fraction in groundwater mixtures in the Upper Floridan aquifer near Valdosta, Georgia. Applied Geochemistry 13:1017–1043

    Article  CAS  Google Scholar 

  • Plummer LN, Busenberg E (1999) Chlorofluorocarbons. In: Cook PG, Herczeg A (eds) Environmental Tracers in Subsurface Hydrology, Ch. 15, Kluwer Academic Press, Boston, pp 441–478

  • Plummer LN, Busenberg E, Böhlke JK, Nelms DL, Drenkard S, Michel RL, Schlosser P (2001) Groundwater residence times in Shenandoah National Park, Blue Ridge Mountains, Virginia, USA: a multitracer approach. Chemical Geology 179:93–111

    Article  CAS  Google Scholar 

  • Reilly TE, Plummer LN, Phillips PJ, Busenberg E (1994) The use of simulation and multiple environmental tracers to quantify groundwater flow in a shallow aquifer. Water Resources Research 30:421–433

    Article  Google Scholar 

  • Rosenau JC, Faulkner GL, Hendry CW Jr, Hull RW (1977) Springs of Florida. Florida Bureau of Geology Bulletin No. 31, 461 pp

  • Schlosser P, Stute M, Dorr H, Sonntag C, Munnich KO (1988) Tritium/3He dating of shallow groundwater. Earth Planetary Science Letters 89:353–362

    Article  CAS  Google Scholar 

  • Schlosser P, Stute M, Sonntag C, Munnich KO (1989) Tritiogenic 3He in shallow groundwater. Earth Planetary Science Letters 94:245–256

    Article  CAS  Google Scholar 

  • Scott TM, Means GH, Means RC, Meegan RP (2002) First magnitude springs of Florida. Florida Geological Survey Open File Report No. 85, 138 pp

  • Sepulveda N (2002) Simulation of ground-water flow in the intermediate and Floridan aquifer systems in peninsular Florida. U.S. Geological Survey Water-Resources Investigations Report 02–4009, 130 pp

  • Solomon DK, Sudicky EA (1991) Tritium and helium-3 isotope ratios for direct estimation of spatial variations in groundwater recharge. Water Resources Research 27:2309–2319

    Article  Google Scholar 

  • Stringfield VT (1936) Artesian water in the Florida peninsula. U.S. Geological Survey Water-Supply Paper 773-C, pp 115-195

  • Stute M, Schlosser P (1999) Atmospheric noble gases. In: Cook PG, Herczeg AL (eds) Environmental Tracers in Subsurface Hydrology. Kluwer, Boston, pp 349–377

  • Thatcher LL (1962) The distribution of tritium fallout in precipitation over North America. Bulletin International Association of Hydrological Sciences 7:48–58

    Google Scholar 

  • Toth J (1963) A theoretical analysis of groundwater flow in small drainage basins. J Geophysical Research 68:4795–4812

    Google Scholar 

  • Wilson WL, Skiles WC (1988) Aquifer characterization by quantitative dye tracing at Ginnie Spring, northern Florida. In: Proceedings of the Second Conference on Environmental Problems in Karst Terranes and Their Solutions. The Association of Groundwater Scientists and Engineers, Dublin, OH, pp 121-141

  • Zoellmann K, Kinzelbach W, Fulda C (2001) Environmental tracer transport (3H and SF6) in the saturated and unsaturated zones and its use in nitrate pollution management. J Hydrology 240:187–205

    Article  CAS  Google Scholar 

  • Zuber A (1986) Mathematical models for the interpretation of environmental radioisotopes in groundwater systems. In: Fritz P, Fontes JC (eds) Handbook of Environmental Geochemistry, Vol. 2: The terrestrial environment. Elsevier, Amsterdam, pp 1–59

  • Zuber A, Michalczyk Z Maloszewski P (2001) Great tritium ages explain the occurrence of good-quality groundwater in a phreatic aquifer of an urban area, Lublin, Poland. Hydrogeology J 9:451–460

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This study was funded jointly by the Florida Department of Environmental Protection and the USGS. The authors thank J. Hannon and J.K. Böhlke for nitrogen isotope analyses; E. Busenberg, L.N. Plummer, J. Wayland, and G. Casile for CFCs and SF6 analyses; P. Schlosser for H, Ne and He isotope analyses; and G. Casile, D. Munroe, K. Champion, and C. Tomlinson for water sampling assistance; W. Zwanka, G. Jones, A. Chelette, A. Sepulveda and T.R. Pratt for preliminary delineation of springsheds; and L.N. Plummer, G. Phelps, and P.E. LaMoreaux for their comments that were helpful in revising this manuscript.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to B. G. Katz.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Katz, B.G. Sources of nitrate contamination and age of water in large karstic springs of Florida. Env Geol 46, 689–706 (2004). https://doi.org/10.1007/s00254-004-1061-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00254-004-1061-9

Keywords

Navigation