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By B. Berkowitz, et al.

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Extra resources for Contaminant Geochemistry

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2 Subsurface Aqueous Solutions The aqueous solution here refers to free water in the subsurface having a composition affected by the interaction between the incoming water and the solid and gaseous phases. This composition is achieved under a dynamic equilibrium with natural processes and may be disturbed by anthropogenic activities. The chemical composition of the subsurface aqueous solution at a given time is the end product of all the reactions to which the liquid water has been exposed. The thermodynamic properties of subsurface aqueous solutions are expressed in terms of a single species solution activity coefficient for each molecular constituent.

The chemical potential of a pure species i, µi0(P, T), is a measure of the activity of compound i in its standard state, that is, pure organic liquid at the same pressure (P) and temperature (T). The term µi0(P, T) is referred to as the standard state chemical potential. From Eq. 9, it is seen that the chemical potential of a species in an ideal solution is lower than the chemical potential of the pure component. Usually, only very dilute solutions can be considered ideal. In most aqueous solutions, ions are stabilized because they are solvated by water molecules.

Other reactions are spontaneous because they lead to an increase in the disorder of the system (∆S > 0). Calculations of ∆H and ∆S can be used to probe the driving force behind a particular reaction. 2 Equilibrium A system is in equilibrium when all acting influences are cancelled by others, resulting in a stable, balanced, or unchanging system in relation to its surroundings. In the subsurface, equilibrium can be defined in terms of thermal, chemical, or mechanical equilibrium. Usually, in the subsurface, changes occur slowly over geological time scales, so that a state of equilibrium is never reached.

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