Isotope Tracers in Catchment Hydrology

PART I. BASIC PRINCIPLES. Chapter 1: Fundamentals of Small Catchment Hydrology ( J.M. Buttle). Introduction to Small Catchments. The Catchment Water Balance. General components of the water balance. Precipitation, interception, net precipitation, Snowmelt. Infiltration and soil water storage. Evaporation and evapotranspiration. Storage in lakes, wetlands and stream channels. Runoff outputs via streamflow. Mechanisms of stormflow generation. Groundwater flow. Questions of Spatial and Temporal Scale in Catchment Hydrology. Use of Isotopes in Catchment Research. Evaporation, evapotranspiration, interception. Pore-water mixing (the mobile-immobile water issue). Soil and groundwater recharge rates. Soil water, groundwater and surface water residence times. Storm runoff components. Water sources versus water flowpaths. Sources of solutes. New Research Directions. Summary. Chapter 2: Fundamentals of Isotope Geochemistry (C. Kendall and E.A. Caldwell). Introduction. Fundamentals of Isotope Geochemistry. Definitions. Terminology. Standards. Stable Isotope Fractionation. Properties of isotopic molecules. Fractionation accompanying chemical reactions and phase changes. The Rayleigh equations. Isotopic fractionation in open and closed systems. Biological fractionations. Sample Collection, Analysis, and Quality Assurance. Sampling guidelines. Analytical methods and instrumentation. Quality assurance of contract laboratories. Applications of Isotope Tracers in Catchment Hydrology. Water isotope hydrology. Solute isotope biogeochemistry. Mixing. Isotopically labeled materials. Stable isotopes in geochemical modeling. Use of a multi-isotope approach for the determination of flowpaths. Summary. PART II. PROCESSES AFFECTING ISOTOPIC COMPOSITIONS. Chapter 3: Isotopic Variations in Precipitation (N.L. Ingraham). Introduction. Global hydrologic cycle. Natural Fractionation of Isotopes in Precipitation. Co-variance of hydrogen and oxygen isotopes in precipitation. Systematics of Isotope Variations in Precipitation. System fractionation. Unique types of precipitation. Observed effects. Temporal variation in precipitation. Geographic variation in precipitation in convective systems. Continental effect in precipitation. Dependence of rain on ambient temperature. Exchange with atmospheric vapor. Evaporation on the canopy. Mesoscale Circulation and Storm Trajectories. Tritium. Origin. Recent elevated levels and decline. Observed terrestrial and marine distributions. Uses of tritium in catchment basin research. Implications for Catchment Basin Research. Scale issues. Sample collection. Summary. Chapter 4: Isotopic Fractionation in Snow Cover (L.W. Cooper). Introduction. Isotopic Changes to a Snowpack. Changes during snow accumulation. Changes during snowmelt. Isotopic water balance and evaporation. Catchment scale and runoff considerations. Future Directions for Research. Chapter 5:Isotopic Exchange in Soil Water (C.J. Barnes, J.V. Turner). Introduction. General discussion of isotopes. Analytical considerations. Soil-water extraction techniques. Processes Leading to Soil Water Concentration Variations: Meteorological Inputs. Processes Leading to Soil Water Concentration Variations: Evaporation. Introduction. Saturated soils. Unsaturated soils. Unsteady evaporation. Temperature effects. Oxygen-18/deuterium relationship. Further modifications due to salinity and transpiration. New Research Directions. Summary. Chapter 6: Plants, Isotopes and Water Use: a Catchment-Scale Perspective. (T.E. Dawson, J.R. Ehleringer). Introduction. Plants and catchment-level processes. Working premise concerning plants, isotopes and water use. Water Uptake and Water Transport in Plants. Background. Measurements of water uptake and transport by plants. Stomatal Regulation of Water Movement in the Soil-Plant-Atmosphere Continuum. Water movement and the regulatory role of plants: the leaf-level. Water movement and the regulatory role of plants: the stand-level. Water Sources and Water Use by Plants: Case Studies Using Stable Isotopes. Riparian forest communities. Arid and semi-arid plant communities. Temperate forest communities. Coastal plant communities. Current Issues Involving Plants and Catchment-Scale Hydrologic Processes. Invasive plants and site water balance. Stream diversions and riparian manipulations. Deforestation, reforestation and desertification. Long-term Record of Water Use by Plants. Merging the Study of Stable Isotopes in Water with Studies of Water Uptake and Water Use in Plants and the Hydrology of Catchments. Chapter 7: Isotopes in Groundwater Hydrology (R. Gonfiantini, K. Fröhlich, L. Araguás-Araguás, K. Rozanski).Introduction. Isotopic Variations in Waters Recharging the Aquifers. The isotopic composition of precipitation. The isotopic composition of surface waters. Isotopic Effects in the Unsaturated Zone. Mechanisms of infiltration. Water movement in the unsaturated zone. Dissolution processes. Shallow Aquifers. Recharge by precipitation. Recharge from surface waters. Hydrodynamical models of shallow groundwater systems based on isotopic data. Deep Groundwater. Groundwater movement in confined aquifers. Groundwater age. Interconnections between aquifers. Geothermal groundwaters. Groundwater Studies in Catchments. Present situation and case study examples. Research trends and needs. Chapter 8: Lithogenic and Cosmogenic Tracers in Catchment Hydrology (G.J. Nimz). Introduction. Processes that Affect Lithogenic and Cosmogenic Isotopic Compositions in Hydrologic Systems. Lithogenic and cosmogenic solutes used in hydrologic analysis. Origin of lithogenic nuclides in natural waters: mineral reactions. Origin of lithogenic nuclides in natural waters: trace element exchange. Origin of isotopic variations: radiogenic nuclides. Origin of isotopic variations: the mineral weathering sequence. Origin of isotopic variations: uranium isotopes and alpha recoil. Origin of isotopic variations: cosmogenic nuclides. Origin of isotopic variations: fission products. Hydrologic application of cosmogenic nuclides. The Application of Lithogenic and Cosmogenic Nuclides to Catchment Hydrology. Input: precipitation, dry deposition, and throughfall. The shallow system: hydrograph separation, weathering, and arid-region infiltration. Evaporation / transpiration. The deep system: groundwater flow. System (basin) closure: mixing of water masses. Streamflow: mass balance within the catchment. Lithogenic and cosmogenic nuclides: summary. New Directions in Lithogenic and Cosmogenic Nuclides. The other geologic giant: neodymium. Lithogenic elements with fractionating isotopes. New directions in catchment hydrology for cosmogenic nuclides. Lithogenic and Cosmogenic Tracers in Catchment Hydrology: Concluding Remarks. Chapter 9: Dissolved Gases in Subsurface Hydrology (D.K. Solomon, P.G. Cook, W.E. Sanford). Introduction. Occurrence and Transport of Dissolved Gases. Shallow Groundwater Dating. ³H/³He. Chlorofluorocarbons. ⁸⁵ Kr. Radiogenic ⁴He. Field examples of groundwater dating. Groundwater Surface-Water Interactions. ⁴He. ²²²Rn. Injected Dissolved Gas Tracers. Field example: noble gas tracer experiment. Future Directions. PART III. CASE STUDIES IN ISOTOPE HYDROLOGY. Chapter 10: Oxygen and Hydrogen Isotopes in Rainfall-Runoff Studies (D.P. Genereux, R.P. Hooper). Introduction. Hydrograph Separation. Terminology. Requirements and assumptions in hydrograph separation. Findings and examples. Scale dependence of fpe values. Intra-component variability in tracer concentrations. Recommendations for field studies. New Directions. Subsurface mixing and residence time. Use of isotopes in model calibration. Conclusions. Chapter 11: High Rainfall, Response-Dominated Catchments: A Comparative Study of Experiments in Tropical Northeast Queensland with Temperate New Zealand (M. Bonell, C.J. Barnes, C.R. Grant, A. Howard, J. Burns). Introduction. Previous Studies in High Rainfall, Response - Dominated Catchments. The Maimai catchments. Linkages between the Maimai and Babinda studies. Physical Background. Experimental Methods. Precipitation. Streamflow. Hillslope instrumentation. Results: Event of February 16, 1991. Antecedent catchment storage and rainfall-runoff of sample storm. Matric and hydraulic potential changes on sample slope transects. Hydrograph analysis. Stream Hydrograph Analysis and Isotopic Response. Event analysis - general considerations. Soil and groundwater isotopic changes. How High Rainfall Catchments Work. The Babinda model. The secondary store issue. New water dominance at Babinda vs old water dominance at Maimai. Future Research Directions. Chapter 12: Snowmelt-Dominated Systems (A. Rodhe). Introduction. Basic hydrological processes. Global geographical distribution. Isotopic characteristics of snowmelt. Hydrograph Separation Studies. Historical studies. Recent studies with more complete characterization. Vertical Unsaturated Flow. Estimates of groundwater recharge and particle velocity. Piston flow versus macropore flow. Transit times and flow pattern from lysimeter studies. Flow pattern in two and three dimensions. Implications for catchment flow studies. Conclusions and Future Research Directions. Chapter 13: Arid Catchments (N.L. Ingraham, E.A. Caldwell, B.Th. Verhagen). Introduction. The Use of Isotopes in Arid Catchment Studies. Precipitation. Lakes. Rivers. Rivers displaying isotopic enrichment. Rivers without isotopic enrichment. Soil water. Infiltration and recharge in arid regions. Groundwater. The 'd' value in arid groundwater. Sampling. Precipitation. Surface water. Soil water. Non-Traditional Techniques. Strontium. ³He/Tritium. Chlorine-36. Noble Gases. Chlorofluorocarbons. Future Directions. Chapter 14: Groundwater and Surface-Water Interactions in Riparian and Lake-Dominated Systems (J.F. Walker, D.P. Krabbenhoft). Introduction. Importance of lake-dominated systems. Dominant hydrological processes. Previous Studies in Lake Systems. Estimating Groundwater Exchange with Lakes. Stable-isotope mass-balance method. Index-lake method. Wisconsin WEBB Case Study. Study area. Study design. Isotopic flow-system progression. Isotopic complexity. Concluding Remarks. PART IV. CASE STUDIES IN ISOTOPE GEOCHEMISTRY. Chapter 15: Use of Stable Isotopes in Evaluating Sulfur Biogeochemistry of Forest Ecosystems (M.J. Mitchell, H.R. Krouse, B. Mayer, A.C. Stam, Y. Zhang). Introduction: Forest Ecosystem Sulfur Dynamics. Controls on Sulfur Isotope Composition. Isotope fractionation. Atmospheric sources of sulfur. Geological sources of sulfur. Sulfur isotopes in the hydrosphere. Sulfur isotopes in soil and terrestrial vegetation. Natural Abundance Studies. Hubbard Brook Experimental Forest, New Hampshire. Bear Brook Watershed, Maine. Experimental Lakes Area, Ontario, Canada. Rocky Mountains, Colorado and Wyoming. Black Forest, Germany .Applied Tracer Studies. Hubbard Brook Experimental Forest, New Hampshire. Bear Brook Watershed, Maine. West Whitecourt, Alberta, Canada. Bavaria, Germany. Höglwald, Germany. Black Forest, Germany. Skjervatjern Catchment, Norway. Lake Gordsjön Catchment, Sweden. New Research Directions. Summary. Chapter 16: Tracing Nitrogen Sources and Cycles in Catchments (C. Kendall). Introduction. Fundamentals of nitrogen isotopes. Methods. The Nitrogen Cycle. Isotopic fractionations. Processes affecting N isotopic compositions. &dgr;¹⁵N Values of Nitrogen Sources and Reservoirs.Atmospheric sources. Fertilizers. Animal waste. Plants. Soils. Groundwaters. &dgr;¹⁸O Values of Nitrate Sources and Reservoirs. Atmospheric nitrate. Synthetic fertilizers and reagents. Microbial nitrate. Other processes affecting nitrate &dgr;⁸O values. Tracing Sources and Cycling of Nitrate. Mixing. Denitrification. Application Studies. Agricultural and urban sources of nitrate. Sources of N in acid-rain affected forested catchments Nitrogen-limited systems. Labeled-tracer studies. Food web studies. New Frontiers. Applications of the dual isotope method. Tracing sources and sinks for DOM. Applications of compound-specific isotope ratio mass spectrometry. Use of isotopic techniques to assess impacts of changes inland-management practices and landuse on water quality. Use of a multi-isotope or multi-tracer approach. Development of linked hydrologic/geochemical models. Summary. Chapter 17: Carbon Cycling in Terrestrial Environments (Y. Wang, T.G. Huntington, L.J. Osher, L.I. Wassenaar, S.E. Trumbore, R.G. Amundson, J.W. Harden, D.M. McKnight, S.L. Schiff, G.R. Aiken, W.B. Lyons, R.O. Aravena, J.S. Baron). Introduction. Carbon Isotopes and Terminology. Carbon Dynamics in Soils. ¹⁴C age of soil organic matter. Use of ¹⁴C to study C turnover in soils. The use of ¹³C to study C turnover in soils. Use of carbon isotopes in understanding carbon dynamics in peatlands. Isotope Studies of Dissolved Organic Matter in Groundwater. Stable carbon isotopes. Nitrogen, sulfur and hydrogen isotopes. Radiocarbon in DOC. Isotope Study of DOC in Lacustrine Environments. Isotope Studies and the Carbon Budget. Chapter 18: Tracing of Weathering Reactions and Water Flowpaths: A Multi-isotope Approach. (T.D. Bullen, C. Kendall). Introduction. Rationale for using water and solute isotopes as tracers in catchments. Theoretical bases of the strontium, lead and carbon isotope systems. Geological/environmental factors leading to successful tracing with solute isotopes Influences on Isotopic Composition of Sr, Pb and C in Catchment Waters. Lithologic controls on the isotopic composition of strontium and lead. Atmospheric/anthropogenic inputs of Sr, Pb, and C. Effects of organic and inorganic cycling on isotopic composition of carbon. Multi-Isotope Studies at Selected Watersheds.The combined use of O, H and Sr isotopes to understand differences in chemical evolution along different flowpaths in a sandy aquifer in northern Wisconsin. Sr, Pb and C isotopes as surrogate tracers of water movement at a catchment nested in calc-silicate rocks, Sleepers River, Vermont. C and Sr isotopes as tracers of sources of carbonate alkalinity at Catoctin Mountain, Maryland. Synthesis: an isotopic view of a catchment. Additional Solute Isotope Tracers: Li, B, Fe. Summary. Chapter 19: Erosion, Weathering, and Sedimentation. (P.R. Bierman, A. Albrecht, M.H. Bothner, E.T. Brown, T.D. Bullen, L.B. Gray, L. Turpin).
Introduction. In Situ Produced Cosmogenic Nuclides. Cosmogenic nuclides in exposed outcrops.
Cosmogenic nuclides in sediments. Case studies.
Atmospheric Nuclides: ²¹⁰Pb. Methods. Interpretation. Applications. Combined Approaches To Catchment Landscape Analysis: ¹³⁷Cs and ²¹⁰Pb. Lake sediments. Soils. Water samples. Case studies. Tracing of Sediment Sources and Identification of Erosion Processes. Using Natural and Anthropogenic Radionuclides. Nuclides of importance. Case studies. Sr and Weathering. Weathering and ⁸⁷Sr/ ⁸⁶Sr. Typical ⁸⁷Sr/⁸⁶Sr ratios. Sr isotopes as tracers of solute sources. Chapter 20: Applications of Uranium- and Thorium-Series Radionuclides in Catchment Hydrology Studies. (T.F. Kraemer, D.P. Genereux). Introduction. Review of Fundamental Concepts. Decay chains and radioactive equilibrium. Physical and chemical processes that redistribute U and Th series radionuclides. Radon Techniques in Catchment Hydrology. General considerations, mixing models. Mixing model without correction for volatilization. Mixing model with degassing correction through stagnant film model. Mixing model with degassing correction through an injected tracer. Mixing model, with partitioning of water inflow into different sources. Radium Isotopic Techniques in Catchment Hydrology. General considerations. Radium as a tracer for groundwater input to an estuary system. Use of ²²⁸Ra and ²²⁶Ra in quantifying groundwater input to a stream: conservative mixing. Use of ²²⁸Ra and ²²⁶Ra in quantifying groundwater input to a stream: non-conservative mixing. Use of ²²⁸Ra and ²²⁶Ra in quantifying three end-member conservative mixing. Using ²²⁴Ra and ²²⁸Ra to determine residence time of water in short-residence time reservoirs. Using radium isotopes to identify the source of water issuing from springs. New Research Directions. PART V. SYNTHESIS. Chapter 21: Modeling of Isotopes and Hydrogeochemical Responses in Catchment Hydrology. (J.V. Turner, C.J. Barnes). Introduction. Some definitions and terms. Limitations of the Mass Balance Hydrograph Separation Approach. Mass balance hydrograph separation models. Estimation of Transit Times - System Response Functions of Catchments. System response functions. System response functions based on the IUH. Application of system response functions based on the Instantaneous Unit Hydrograph. Identifying "old" and "new" water in terms of system response functions. Time series approaches to system response functions. Kalman filtering and residence times. Comparisons of Models of Isotopic and Chemical Hydrograph Separation. New Research Directions. Chapter 22: Isotopes as Indicators of Environmental Change (J.B. Shanley, E. Pendall, C. Kendall, L.R. Stevens, R.L. Michel, P.J. Phillips, R.M. Forester, D.L. Naftz, B. Liu, L. Stern, B.B. Wolfe, C.P. Chamberlain, S.W. Leavitt, T.H.E. Heaton, B. Mayer, L.D. Cecil, W.B. Lyons, B.G. Katz, J.L. Betancourt, D.M. McKnight, J.D. Blum, T.W.D. Edwards, H.R. House, E. Ito, R.O. Aravena, J.F. Whelan). Introduction. Direct and proxy records of environmental change. Recent Environmental Change Indicators. Groundwater dating. Direct use of water isotopes to infer recent global change. Changes in land use deduced from tracer studies. Isotope tracers for tracking migratory patterns of birds. Changes in atmospheric deposition. Paleo-Climatic Indicators. Groundwater as an archive of paleo-climatic information. Continental glaciers. Clay minerals, oxides, and hydroxides. Pedogenic carbonates. Paleoenvironmental reconstruction from stable isotopes in
tree rings and plant fossils. Lacustrine environments: organics. Lacustrine environments: authigenic carbonates. Lacustrine environments: ostracodes. New Research Directions. Summary.

A web page for this book is located at URL http://wwwrcamnl.wr.usgs.gov/isoig/isopubs/. This page includes copies of the table of contents and the index, colored versions of selected non-copyrighted figures that can be downloaded for teaching purposes, a list of errata, selected portions of the non-copyrighted chapters and other useful isotope-related information. These listings will be searchable on-line.