Contaminant Geochemistry by B. Berkowitz, et al.

By B. Berkowitz, et al.

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The composition of the subsurface liquid phase varies over time, mainly due to recharge with rainwater, irrigation water, or the fluctuation of the water table (groundwater) level. In addition, disposal and discharge of wastes and effluents and the application of agrochemicals are key sources of pollution into the subsurface, contributing significant changes to the composition of the liquid phase. 1 Near Solid Phase Water Water molecules that are oriented preferentially with the polar axis perpendicular to the solid surface, in the vicinity of a solid surface, are considered near solid phase water.

In most aqueous solutions, ions are stabilized because they are solvated by water molecules. As the ionic strength is increased, ions interact with each other. Thus, when calculating the chemical potential of species i, a term that takes into account the deviation from ideal conditions is added. This term is called an excess term and can be either positive or negative. The term usually is written as RT lnγi, where γi is the activity coefficient of component i. The complete expression for the chemical potential of species i then becomes µ i = µ i0 ( P, T ) + RT ln xi + RT ln γ i = µ i0 ( P, T ) + RT ln( xi γ i ).

It was shown that the primary solvation shell of a monovalent cation contains between three and six water molecules that exchange relatively rapidly with the surrounding bulk liquid. A secondary solvation shell, if it exists, is very weakly developed. The primary solvation shell of a bivalent cation contains between six and eight water molecules, which exchange rapidly with the surrounding bulk liquid. A secondary solvation shell containing about 15 water molecules develops as the cation concentration decreases, and it also moves with the cation as a unit.

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