Thermodynamics of the oxygen isotope fractionation involving plagioclase

The thermodynamic relationship between the oxygen isotope fractionation properties of plagioclase and its composition has been derived by treating plagioclase as a "reciprocal solution" consisting of independent cationic and anionic substitutions, namely (NaAl)⁵⁺⇄(CaSi)⁵⁺ and ¹⁸O⇄¹⁶O. The results show that the logarithm of the oxygen isotope fractionation factor, α, between plagioclase and a coexisting phase varies linearly with the anorthite content of plagioclase. The proportionality constant is given by the oxygen isotope fractionation factor between albite and anorthite, and has been derived from the experimental data of two groups of workers, O'Neil and Taylor [2] and Matsuhisa et al. [3], on the isotopic fractionation between each plagioclase end-member and aqueous solutions. It is found that O'Neil and Taylor's data on isotopic exchange of plagioclase end-members with only 2-3 M chloride solution, rather than with both pure water and the chloride solution, lead essentially to zero intercept of the ln α(Ab-An) vs. 1/T² relation, in accord with Bottinga and Javoy's [10] conclusion about the oxygen isotope fractionation between two anhydrous silicates at T>500°C.