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Olivine/melt partitioning of the transition metal cations, Fe 2+ , Mn 2+ , Co 2+ , and Ni 2+ , together with Mg 2+  and Ca 2+ , has been examined experimentally as a function of melt composition at ambient pressure. Melt structure was inferred from bulk-chemical composition, existing structural data, and 57Fe resonant absorption Mössbauer spectroscopy. Under isothermal conditions, K olivine/melt  D(i-Mg)  = (C i /C Mg )olivine/(C i /C Mg ) melt , is an exponential function of melt NBO/T for i = Ca 2+ , Mn 2+ , Co 2+ , and Ni 2+ . For i = Fe 2+ , the relationship is parabolic with maximum K olivine/melt  D(Fe2+-Mg)  lt-values at NBO/T near 1. At constant melt NBO/T, K olivine/melt  D(i-Mg)  increases systematically with decreasing cation radius, an effect that is more pronounced the more polymerized the melt. The K olivine/melt  D(i-Mg)  melt is also a positive and linear function of Na/(Na + Ca) of Al-free melts. This latter effect results from changes in Qn-species abundance governed by Na/(Na + Ca) of the melts. The enthalpy of the exchange equilibrium, i olivine  + Mg melt  = i melt  + Mg olivine , derived from the temperature-dependence of K olivine/melt  D(i-Mg) , is also a positive function of the ionic radius of the cation. The relationship of enthalpy to melt polymerization also depends on cation radius. The K olivine/melt  D(Fe2+-Mg)  lt does not, however, follow this trend possibly because the bond distance, dFe 2+ -O, in the melts depends on melt composition.

Partitioning of calcium, magnesium, and transition metals between olivine and melt governed by the structure of the silicate melt at ambient pressure