Determining Timescales for Groundwater Flow and Solute Transport

  • Peter G. Cook
  • John-Karl Böhlke


One of the principal uses of environmental tracers is for determining the ages of soil waters and groundwaters. (We may refer to this as ‘hydrochronology’by analogy with the dating of solid materials known as geochronology.) Information on soil water and groundwater age enables timescales for a range of subsurface processes to be determined. For example, ‘groundwater stratigraphy’is used increasingly to decipher past recharge rates and conditions in unconfined aquifers, in much the same way that sedimentary stratigraphy yields information about past depositional environments. The use of environmental tracers to determine water ages allows groundwater recharge rates and flow velocities to be determined independently, and commonly more accurately, than with traditional hydraulic methods where hydraulic properties of aquifers are poorly known or spatially variable. Studies of groundwater residence times in association with groundwater contamination studies can enable historic release rates of contaminants and contaminant transport rates to be determined. Where input rates are known, measurements of groundwater contaminant concentrations, together with groundwater dating, can sometimes be used for estimating chemical reaction rates. The combination of these dating methods with stable isotope measurements has sometimes allowed changes in contaminant sources over time to be determined.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Adar E.M. and Neuman S.P. (1988) Estimation of spatial recharge distribution using environmental isotopes and hydrochemical data, II. Application to Aravaipa Valley in southern Arizona, U.S.A. J. Hydrol. 97, 279–302.CrossRefGoogle Scholar
  2. Allison G.B. and Holmes J.W. (1973) The environmental tritium concentration of underground water and its hydrological interpretation. J. Hydrol. 19, 131–143.CrossRefGoogle Scholar
  3. Allison G.B. and Hughes M.W. (1975) The use of environmental tritium to estimate recharge to a South-Australian aquifer. J. Hydrol. 26, 245–254.CrossRefGoogle Scholar
  4. Andrews J.N. and Lee D.J. (1979) Inert gases in groundwater from the Bunter Sandstone of England as indicators of age and palaeoclimatic trends. J. Hydrol. 41, 233–252.CrossRefGoogle Scholar
  5. Appel C.A. and Reilly T.E. (1994) Summary of selected computer programs produced by the U.S. Geological Survey for simulation of ground-water flow and quality. U.S. Geological Survey Circular 1104, 98 pp.Google Scholar
  6. Appelo C.A.J. and Postma D. (1996) Geochemistry, Groundwater and Pollution. Balkema, Rotterdam, 536 pp.Google Scholar
  7. Begemann F. and Libby W.F. (1957) Continental water balance, ground water inventory and storage times, surface ocean mixing rates and world-wide water circulation patterns from cosmic-ray and bomb tritium. Geochim. Cosmochim. Acta 12, 277–296.CrossRefGoogle Scholar
  8. Bentley H.W., Phillips F.M., Davis S.N., Habermehl M.A., Airey P.L., Calf G.E., Elmore D., Gove H.E. and Torgersen T. (1986) Chlorine 36 dating of very old groundwater. 1. The Great Artesian Basin, Australia. Water Resour. Res. 22(13), 1991–2001.CrossRefGoogle Scholar
  9. Böhlke J.K. and Denver J.M. (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 Resour. Res. 31(9), 2319–2339.CrossRefGoogle Scholar
  10. Böhlke J.K., Revesz K., Busenberg E., Deak J., Deseo E. and Stute M. (1997) Groundwater record of halocarbon transport by the Danube River. Environ. Sci. Technol. 31(11), 3293–3299.CrossRefGoogle Scholar
  11. Böttcher J., Strebel O. and Duynisveld W.H.M. (1989) Kinetik und Modellierung gekoppelter Stoffumsetzungen im Grundwasser eines Lockergesteins-Aquifers. Geologisches Jahrbuch 51C, 3–40.Google Scholar
  12. Böttcher J., Strebel O., Voerkelius S. and Schmidt H.-L. (1990) Using isotope fractionation of nitrate-nitrogen and nitrate-oxygen for evaluation of microbial denitrification in a sandy aquifer. J. Hydrol. 114, 413–424.CrossRefGoogle Scholar
  13. Burt T.P. and Trudgill S.T. (1993) Nitrate in Groundwater. In Nitrate. Processes, Patterns, and Management, eds. T.P. Burt, A.L. Heathwaite and S.T. Trudgill, pp.213–238. John Wiley and Sons, Chichester.Google Scholar
  14. Busenberg E. and Plummer L.N. (1996) Concentrations of chlorofluorocarbons and other gases in ground water at Mirror Lake, New Hampshire. In U.S. Geological Survey Toxic Substances Program. Proceedings of the technical meeting, September 20-24, 1993, Colorado Springs, Colorado, eds. D. W. Morganwalp and D. A. Aronson, pp. 151–158. U.S. Geological Survey, Water Resources Investigations Report 94-4015.Google Scholar
  15. Campana M.E. and Simpson E.S. (1984) Groundwater residence times and recharge rates using a discrete-state compartment model and 14C data. J. Hydrol. 72, 171–185.CrossRefGoogle Scholar
  16. Chappelle F.H., Zelibor J.L., Grimes D.J. and Knobel L.L. (1987) Bacteria in deep coastal plain sediments of Maryland: a possible source of CO2 to groundwater. Water Resour. Res. 23(8), 1625–1632.CrossRefGoogle Scholar
  17. Cleveland W.S. (1979) Robust locally weighted regression and smoothing scatterplots. J. Amer. Statist. Assn. 74, 829–836.CrossRefGoogle Scholar
  18. Cook P.G. and Solomon D.K. (1995) Transport of atmospheric trace gases to the water table: implications for groundwater dating with chlorofluorocarbons and krypton 85. Water Resour. Res. 31(2), 263–270.CrossRefGoogle Scholar
  19. Cook P.G., Solomon D.K., Plummer L.N., Busenberg E. and Schiff S.L. (1995) Chlorofluorocarbons as tracers of groundwater transport processes in a shallow, silty sand aquifer. Water Resour. Res. 31(3), 425–434.CrossRefGoogle Scholar
  20. Copenhaver S.A., Krishnaswami S., Turekian K.K., Epler N. and Cochran J.K. (1993) Retardation of 238U and 232Th decay chain radionuclides in Long Island and Connecticut aquifers. Geochim. Cosmochim. Acta 57, 597–603.CrossRefGoogle Scholar
  21. Coplen T.B. (1993) Uses of environmental isotopes. In Regional Ground-Water Quality, ed. W.M. Alley, pp. 227–253. Van Nostrand Reinhold, New York, N.Y.Google Scholar
  22. Davis S.N. and Murphy E. (1987) Dating ground water and the evaluation of repositories for radioactive waste. U.S. Nuclear Regulatory Commission, Report NUREG/CR-4912. U.S. Nuclear Regulatory Commission, Washington, 181 pp.Google Scholar
  23. Dincer T., Al-Mugrin A. and Zimmermann U. (1974) Study of the infiltration and recharge through the sand dunes in arid zones with special reference to the stable isotopes and thermonuclear tritium. J. Hydrol. 23(1), 79–109.CrossRefGoogle Scholar
  24. Dincer T. and Payne B.R. (1971) An environmental isotope study of the south-western karst region of Turkey. J. Hydrol. 14, 233–258.CrossRefGoogle Scholar
  25. Dunkle S.A., Plummer L.N., Denver J.M., Hamilton P.A., Michel R.L. and Coplen T.B. (1993) Chlorofluorocarbons (CC13F and CC12F2) as dating tools and hydrologic tracers in shallow groundwater of the Delmarva Peninsula, Atlantic Coastal Plain, United States. Water Resour. Res. 29(12), 3837–3860.CrossRefGoogle Scholar
  26. Edmunds W.M., Walton N.R.G., Howard M.P.J. and Jacovides J. (1981) Geochemical estimation of aquifer recharge. British Geological Survey, Report WD/OS/80/17.Google Scholar
  27. Ekwurzel B., Schlosser P., Smethie Jr. W.M., Plummer L.N., Busenberg E., Michel R.L., Weppernig R. and Stute M. (1994) Dating of shallow groundwater: comparison of the transient tracers 3H/3He, chlorofluorocarbons, and 85Kr. Water Resour. Res. 30(6), 1693–1708.CrossRefGoogle Scholar
  28. Eriksson E. (1958) The possible use of tritium for estimating groundwater storage. Tellus 10, 472–478.CrossRefGoogle Scholar
  29. Focazio M.J., Plummer L.N., Böhlke J.K., Busenberg E., Bachman L.J. and Powars D.S. (1998) Preliminary estimates of residence times and apparent ages of ground water in the Chesapeake Bay watershed, and water-quality data from a survey of springs. US Geological Survey, Water Resources Investigations Report 97-4225, 75 pp.Google Scholar
  30. Fontes J.-C. (1980) Environmental isotopes in groundwater hydrology. In Handbook of Environmental Isotope Geochemistry, Vol. 1, eds. P. Fritz and J.-C. Fontes, pp.75–140. Elsevier, Amsterdam.Google Scholar
  31. Gelhar L.W. and Wilson J.L. (1974) Ground-water quality modeling. Ground Water 12(6), 399–408.CrossRefGoogle Scholar
  32. Geyh M.A. and Backhaus G. (1979) Hydrodynamic aspects of carbon-14 groundwater dating. Isotope Hydrology 1978, Vol. II, pp. 631–643. IAEA, Vienna.Google Scholar
  33. Haitjema H.M. (1995) On the residence time distribution in idealized groundwatersheds. J. Hydrol. 172, 127–146.CrossRefGoogle Scholar
  34. Howard K.W.F. (1985) Denitrification in a major limestone aquifer. J. Hydrol. 76, 265–280.CrossRefGoogle Scholar
  35. Johnston C.T., Cook P.G., Frape S.K., Plummer L.N., Busenberg E. and Blackport R.J. (1998) Ground water age and nitrate distribution within a glacial aquifer beneath a thick unsaturated zone. Ground Water 36(1), 171–180.CrossRefGoogle Scholar
  36. Kendall C., Sklash M.G. and Bullen T.D. (1995) Isotope tracers of water and solute sources in catchments. In Solute Modelling in Catchment Systems, ed. S.T. Trudgill, pp.261–303. Wiley, Chichester.Google Scholar
  37. Krishnaswami S., Graustein W.C., Turekian K.K. and Dowd J.F. (1982) Radium, thorium and radioactive lead isotopes in groundwaters: application to the in situ determination of adsorption-desorption rate constants and retardation factors. Water Resour. Res. 18(6), 1633–1675.CrossRefGoogle Scholar
  38. Leaney F.W. and Allison G.B. (1986) Carbon-14 and stable isotope data for an area in the Murray Basin: its use in estimating recharge. J. Hydrol. 88, 129–145.CrossRefGoogle Scholar
  39. Lerner D.N. and Papatolios K.T. (1993) A simple analytical approach for predicting nitrate concentrations in pumped ground water. Ground Water 31(3), 370–375.CrossRefGoogle Scholar
  40. Letolle R. and Olive P. (1983) Isotopes as pollution tracers. In Guidebook on Nuclear Techniques in Hydrology. Tech. Rep. No. 91, pp. 411–422. IAEA, Vienna.Google Scholar
  41. Libra R.D., Hallberg G.R. and Hoyer B.E. (1987) Impacts of agricultural chemicals on groundwater quality in Iowa. In Ground Water Quality and Agricultural Practices, ed. D.M. Fairchild, pp. 185–217. Lewis, Chelsea.Google Scholar
  42. Maloszewski P., Rauert W., Stichler W. and Herrman A. (1983) Application of flow models to an Alpine catchment area using tritium and deuterium data. J. Hydrol. 66, 319–330.CrossRefGoogle Scholar
  43. Maloszewski P. and Zuber A. (1982) Determining the turnover time of groundwater systems with the aid of environmental tracers. 1. Models and their applicability. J. Hydrol. 57, 207–231.CrossRefGoogle Scholar
  44. Maloszewski P. and Zuber A. (1996) Lumped parameter models for the interpretation of environmental tracer data. In Manual on Mathematical Models in Isotope Hydrogeology. IAEA-TECDOC 910, pp. 9–50. IAEA, Vienna.Google Scholar
  45. Mazor E. (1972) Paleotemperatures and other hydrological parameters deduced from noble gases dissolved in ground waters: Jordan Rift Valley, Israel. Geochim. Cosmochim. Acta 36, 1321–1336.CrossRefGoogle Scholar
  46. Mazor E. and Bosch A. (1992) Helium as a semi-quantitative tool for groundwater dating in the range of 1041—108 years. In Isotopes of Noble Gases as Tracers in Environmental Studies, pp. 163–178. IAEA, Vienna.Google Scholar
  47. Modica E., Buxton H.T. and Plummer L.N. (1998) Evaluating the source and residence times of groundwater seepage to streams, New Jersey Coastal Plain. Water Resour. Res. 34(11), 2797–2810.CrossRefGoogle Scholar
  48. Nydal R. and Lövseth K. (1996) Carbon-14 measurments in atmospheric CO2 from northern and southern hemisphere sites, 1962-1993. ORNL/CDIAC-93 NDP-057. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, Oak Ridge, Tennessee.CrossRefGoogle Scholar
  49. Pearson Jr. F.J. and White D.E. (1967) Carbon 14 ages and flow rates of water in Carrizo Sand, Atascosa County, Texas. Water Resour. Res. 3(1), 251–261.CrossRefGoogle Scholar
  50. Phillips F.M., Mattick J.L., Duval T.A., Elmore D. and Kubik P.W. (1988) Chlorine 36 and tritium from nuclear weapons fallout as tracers for long-term liquid and vapor movement in desert soils. Water Resour. Res. 24(11), 1877–1891.CrossRefGoogle Scholar
  51. Phillips F.M., Tansey M.K., Peeters L.A., Cheng S. and Long A. (1989) An isotopic investigation of groundwater in the central San Juan Basin, New Mexico: carbon 14 dating as a basis for numerical flow modeling. Water Resour. Res. 25(10), 2259–2273.CrossRefGoogle Scholar
  52. Plummer L.N., Busby J.F., Lee R.W. and Hanshaw B.B. (1990) Geochemical modeling of the Madison aquifer in parts of Montana, Wyoming, and South Dakota. Water Resour. Res. 26(9), 1981–2014.CrossRefGoogle Scholar
  53. Portniaguine O. and Solomon D.K. (1998) Parameter estimation using groundwater age and head data, Cape Cod, Massachusetts. Water Resour. Res. 34(4), 637–645.CrossRefGoogle Scholar
  54. Postma D., Boesen C., Kristiansen H. and Larsen F. (1991) Nitrate reduction in an unconfined sandy aquifer: water chemistry, reduction processes, and geochemical modeling. Water Resour. Res. 27(8), 2027–2045.CrossRefGoogle Scholar
  55. Przewlocki K. and Yurtsever Y. (1974) Some conceptual mathematical models and digital simulation approach in the use of tracers in hydrological systems. Isotope Techniques in Groundwater Hydrology 1974, Vol. II, pp. 425–450. IAEA, Vienna.Google Scholar
  56. Raats P.A.C. (1981) Residence times of water and solutes within and below the root zone. Agric. Water Manage. 4(1), 63–82.CrossRefGoogle Scholar
  57. Reilly T.E., Plummer L.N., Phillips P.J. and Busenberg E. (1994) The use of simulation and multiple environmental tracers to quantify groundwater flow in a shallow aquifer. Water Resour. Res. 30(2), 421–433.CrossRefGoogle Scholar
  58. Robertson W.D. and Cherry J.A. (1989) Tritium as an indicator of recharge and dispersion in a groundwater system in Central Ontario. Water Resour. Res. 25(6), 1097–1109.CrossRefGoogle Scholar
  59. Robertson W.D., Cherry J.A. and Schiff S.L. (1989) Atmospheric sulfur deposition 1950–1985 inferred from sulfate in groundwater. Water Resour. Res. 25(6), 1111–1123.CrossRefGoogle Scholar
  60. Robertson W.D. and Schiff S.L. (1994) Fractionation of sulphur isotopes during biogenic sulphate reduction below a sandy forested recharge area in south-central Canada. J. Hydrol. 158, 123–134.CrossRefGoogle Scholar
  61. Sanford W.E. and Buapeng S. (1996) A comparison of groundwater ages based on 14C data and three dimensional advective transport modelling of the Lower Chao Phraya Basin: effects of palaeohydrology and implications for water resources development in Thailand. Isotopes in Water Resources Management, Vol. 2, pp. 383–394. IAEA, Vienna.Google Scholar
  62. Scanion B.R. (1992) Evaluation of liquid and vapor water flow in desert soils based on chlorine 36 and tritium tracers and nonisothermal flow simulations. Water Resour. Res. 28(1), 285–297.CrossRefGoogle Scholar
  63. Schlosser P., Stute M., Sonntag C. and Munnich K. (1989) Tritiogenic 3He in shallow groundwater. Earth Planet. Sci. Lett. 94, 245–256.CrossRefGoogle Scholar
  64. Shapiro S.D. (1998) Evaluation of the 3H-3He dating technique in complex hydrologic environments. Unpubl. PhD thesis, Columbia University, 253 pp.Google Scholar
  65. Sheets R.A., Bair E.S. and Rowe G.L. (1998) Use of 3H/3He ages to evaluate and improve groundwater flow models in a complex buried-valley aquifer. Water Resour. Res. 34(5), 1077–1089.CrossRefGoogle Scholar
  66. Smith D.B., Wearn P.L., Richards H.J. and Rowe P.C. (1970) Water movement in the unsaturated zone of high and low permeability strata by measuring natural tritium. Isotope Hydrology 1970, pp.73–87. IAEA, Vienna.Google Scholar
  67. Solomon D.K., Poreda R.J., Cook P.G. and Hunt A. (1995) Site characterization using 3H/3He ground-water ages, Cape Cod, MA. Ground Water 33(6), 988–996.CrossRefGoogle Scholar
  68. Solomon D.K., Hunt A. and Poreda R.J. (1996) Source of radiogenic helium 4 in shallow aquifers: implications for dating young groundwater. Water Resour. Res. 32(6), 1805–1813.CrossRefGoogle Scholar
  69. Strack O.D.L. (1989) Groundwater Mechanics. Prentice-Hall, Englewood Cliffs, New Jersey.Google Scholar
  70. Strebel O., Böttcher J. and Fritz P. (1990) Use of isotope fractionation of sulfate-sulfur and sulfate-oxygen to assess bacterial desulfurication in a sandy aquifer. J. Hydrol. 121, 155–172.CrossRefGoogle Scholar
  71. Stute M. and Schlosser P. (1993) Principles and applications of the noble gas paleothermometer. In Climate Change in Continental Isotopic Records, eds. P.K. Swart, K.C. Lohmann, J. McKenzie and S. Savin, pp.89–100. American Geophysical Union, Geophysical Monograph 78.Google Scholar
  72. Sudicky E.A. and Frind E.O. (1981) Carbon 14 dating of groundwater in confined aquifers: implications of aquitard diffusion. Water Resour. Res. 17(4), 1060–1064.CrossRefGoogle Scholar
  73. Szabo Z., Rice D.E., Plummer L.N., Busenberg E. and Drenkard S. (1996) Age dating of shallow groundwater with chlorofluorocarbons, tritium/helium3, and flow path analysis, southern New Jersey coastal plain. Water Resour. Res. 32(4), 1023–1038.CrossRefGoogle Scholar
  74. Tenu A., Noto P., Cortecci G. and Nuti S. (1975) Environmental isotopic study of the Barremian — Jurassic aquifer in South Dobrogea (Roumania). J. Hydrol. 26, 185–198.CrossRefGoogle Scholar
  75. Thorstenson D.C., Weeks E.P., Haas H. and Fisher D.W. (1983) Distribution of gaseous 12CO2, 13CO2, and 14CO2 in the sub-soil unsaturated zone of the western US Great Plains. Radiocarbon 25(2), 315–346.Google Scholar
  76. Torgersen T. and Clarke W.B. (1985) Helium accumulation in groundwater, I: An evaluation of sources and the continental flux of crustal 4He in the Great Artesian Basin, Australia Geochim. Cosmochim. Acta 49, 1211–1218.CrossRefGoogle Scholar
  77. Tyler S.W. and Walker G.R. (1994) Root zone effects on tracer migration in arid zones. Soil Sci. Soc. Amer. J. 58(1), 25–31.CrossRefGoogle Scholar
  78. Verhagen B.T. (1992) Detailed geohydrology with environmental isotopes. A case study at Serowe, Botswana. Isotope Techniques in Water Resources Development 1991, pp. 345–362. IAEA, Vienna.Google Scholar
  79. Vogel J.C. (1967) Investigation of groundwater flow with radiocarbon. Isotopes in Hydrology, pp. 355–369 IAEA, Vienna.Google Scholar
  80. Vogel J.C., Talma A.S. and Heaton T.H.E. (1981) Gaseous nitrogen as evidence for denitrification in groundwater. J. Hydrol. 50, 191–200.CrossRefGoogle Scholar
  81. Walker G.R. and Cook P.G. (1991) The importance of considering diffusion when using carbon-14 to estimate groundwater recharge to an unconfined aquifer. J. Hydrol. 128, 41–48.CrossRefGoogle Scholar
  82. Warner M.J. and Weiss R.F. (1985) Solubilities of chlorofluorocarbons 11 and 12 in water and seawater. Deep-Sea Res. 32, 1485–1497.CrossRefGoogle Scholar
  83. Weeks E.P., Earp D.E. and Thompson G.M (1982) Use of atmospheric fluorocarbons F-11 and F-12 to determine the diffusion parameters of the unsaturated zone in the Southern High Plains of Texas. Water Resour. Res. 18(5), 1365–1378.CrossRefGoogle Scholar
  84. Wilhelm E., Battino R. and Wilcock R.J. (1977) Low-pressure solubility of gases in liquid water. Chem. Rev. 77, 219–262.CrossRefGoogle Scholar
  85. Wilson G.B., Andrews J.N. and Bath A.H. (1990) Dissolved gas evidence for denitrification in the Lincolnshire Limestone groundwaters, eastern England. J. Hydrol. 113, 51–60.CrossRefGoogle Scholar
  86. Yurtsever Y. and Payne B.R. (1986) Mathematical models based on compartmental simulation approach for quantitative interpretation of tracer data in hydrological systems. 5th Int. Symp. Underground Water Tracing, pp.341–353. Institute of Geology and Mineral Exploration, Athens.Google Scholar
  87. Zhao X., Fritzel T.L.B., Quinodoz H.A.M., Bethke C.M. and Torgersen T. (1998) Controls on the distribution and isotopic composition of helium in deep ground-water flows. Geology 26, 291–294.CrossRefGoogle Scholar
  88. Zimmerman U., Münnich K.O., Roether W., Kreutz W., Schubach K. and Siegel O. (1966) Tracers determine movement of soil moisture and evapotranspiration. Science 152, 346–347.CrossRefGoogle Scholar
  89. Zuber A. (1986) Mathematical models for the interpretation of environmental radioisotopes in groundwater systems. In Handbook of Environmental Isotope Geochemistry, Vol. 2, eds. P. Fritz and J.-C. Fontes, pp. 1–59. Elsevier, Amsterdam.Google Scholar

Copyright information

© Springer Science+Business Media New York 2000

Authors and Affiliations

  • Peter G. Cook
    • 1
  • John-Karl Böhlke
    • 2
  1. 1.CSIRO Land and WaterGlen OsmondAustralia
  2. 2.US Geological SurveyRestonUSA

Personalised recommendations