Trace element partitioning in basaltic systems as a function of oxygen fugacity

Along with temperature, pressure and melt chemistry, magmatic oxygen fugacity (fO2) has an important influence on liquid and solid differentiation trends and melt structure. To explore the effect of redox conditions on mineral stability and mineral-melt partitioning in basaltic systems we performed equilibrium, one-atmosphere experiments on a picrite at 1200–1110 °C with fO2 ranging from NNO-4 log units to air. Clinopyroxene crystallizes from 1180 °C to near-solidus, along with plagioclase, olivine and spinel. Olivine Mg# increases with increasing fO2, eventually reacting to pigeonite. Spinel is absent under strongly reducing conditions. Mineral-melt partition coefficients (D) of redox-sensitive elements (Cr, Eu, V, Fe) vary systematically with fO2 and, in some cases, temperature (e.g. DCr in clinopyroxene). Clinopyroxene sector zoning is common; sectors along a- and b-axes have higher AlIV, AlVI, Cr and Ti and lower Mg than c-axis sectors. In terms of coupled substitutions, clinopyroxene CaTs (MgSi = AlVIAlIV) prevails under oxidized conditions (≥ NNO), where Fe3+ balances the charge, but is limited under reduced conditions. Overall, AlIV is maximised under high temperature, oxidizing conditions and in slowly grown (a–b) sectors. High AlIV facilitates incorporation of REE (REEAlIV = CaSi), but DREE (except DEu) show no systematic dependence on fO2 across the experimental suite. In sector zoned clinopyroxenes enrichment in REE3+ in Al-rich sectors is quantitatively consistent with the greater availability of suitably-charged M2 lattice sites and the electrostatic energy penalty required to insert REE3+ onto unsuitably-charged M2 sites. By combining our experimental results with published data, we explore the potential for trace element oxybarometry. We show that olivine-melt DV, clinopyroxene-melt DV/DSc and plagioclase-melt DEu/DSr all have potential as oxybarometers and we present expressions for these as a function of fO2 relative to NNO. The crystal chemical sensitivity of heterovalent cation incorporation into clinopyroxene and the melt compositional sensitivity of the Eu2+–Eu3+ redox potential limit the use of clinopyroxene-melt and plagioclase-melt, however, olivine-melt DV affords considerable precision and accuracy as an oxybarometer that is independent of temperature, and crystal and melt composition. Variation of DV and DV/DSc with fO2 for olivine and clinopyroxene contains information on redox speciation of V in coexisting melt. By comparing the redox speciation constraints from partitioning to data from Fe-free synthetic systems and XANES spectroscopy of quenched glasses, we show that homogenous equilibria involving Fe and V species modify V speciation on quench, leading to a net overall reduction in the average vanadium valence. Mineral-melt partitioning of polyvalent species can be a useful probe of redox speciation in Fe-bearing systems that is unaffected by quench effects.