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Wigley, T. M. L., & Plummer, L. N. (1976). Mixing of carbonate waters. Geochimica et Cosmochimica Acta, 40(9), 989–995.
Abstract: When mineral solutions of different compositions are mixed, the molalities and activities of individual ions in the mixture are often non-linear functions of their end-member values. This non-linearity is particularly significant in determining mineral saturation levels. Mixtures of saturated solutions may be either undersaturated or supersaturated depending on the end-member compositions and the physical conditions in which end-members and their mixtures exist. In carbonate solutions important non-linear effects occur due to redistribution of carbonate species. In extreme cases this causes mixture pH to be below both the end-member pH values. A simple but precise computer program (WATMIX) has been developed for calculating mixture composition for closed and open system mixing of arbitrary end-members. A number of mixing examples are considered which allow one to isolate three important processes leading to non-linear behaviour: the algebraic effect, the δPCO2 effect, and the ionic strength effect.
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