Thermodynamic controls on element partitioning between titanomagnetite and andesitic-dacitic silicate melts

Titanomagnetite-melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO(2)) and temperature (T) in an andesitic-dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite-melt partitioning of the divalent cations (Mg2+, Mn2+, Co2+, Ni2+, Zn2+) and Cu2+/Cu+ with increasing fO(2) between 0.2 and 3.7 log units above the fayalite-magnetite-quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral-melt partitioning of divalent cations, a more rigorous justification of magnetite-melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO(2) implies a reciprocal relationship between a(Fe2+O) and a(Fe3+O1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite-melt partitioning of divalent cations with fO(2) in magnetite- rich spinel. As a result of this, titanomagnetite-melt partitioning of divalent cations is indirectly sensitive to changes in fO(2) in silicic, but less so in mafic bulk systems.