The fate and transport of a variety of chemicals migrating from industrial and municipal waste disposal sites, or applied to agricultural lands, is increasingly becoming a concern. Once released into the subsurface, these chemicals arc subject to a large number of simultaneous physical, chemical, and biological processes, including sorption-desorption, volatilization, and degradation. Depending upon the type of organic chemical involved, transport may also be subject to multiphase flow that involves partitioning of the chemical between different fluid phases. Many models of varying degree of complexity and dimensionality have been developed during the past several decades to quantify the basic physicochemical processes affecting transport in the unsaturated zone. Models for variably saturated water flow, solute transport, aqueous chemistry, and cation exchange were initially developed mostly independently of each other, and only recently has there been a significant effort to couple the different processes involved. Also, most solute transport models in the past considered only one solute. For example, the processes of adsorption- desorption and cation exchange were often accounted for by using relatively simple linear or nonlinear Freundlich isotherms such that all reactions between the solid and liquid phases were forced to be lumped into a single distribution coefficient, and possibly a nonlinear exponent. Other processes such as precipitation-dissolution, biodegradation, volatilization, or radioactive decay were generally simulated by means of simple first- and/or zero-order rate processes. These simplifying approaches were needed to keep the mathematics relatively simple in view of the limitations of previously available computers. The problem of coupling models for water flow and solute transport with multicomponent chemical equilibrium and nonequilibrium models is now increasingly being addressed, facilitated by the introduction of more powerful computers, development of more advanced numerical techniques, and improved understanding of the underlying transport processes. One major frustrating issue facing soil scientists and hydrologists in dealing with the unsaturated zone, both in terms of modeling and experimentation, is the overwhelming heterogeneity of the subsurface environment.
UNSATURATED ZONE CALCITE 813C EVIDENCE OF SOUTHERN NEVADA CLIMATES DURING THE PAST 9 MILLION YEARS