Magnetite activities across the MgAl2O4-Fe3O4 spinel join,with application to thermobarometric estimates of upper mantle oxygen fugacity

The activity of Fe₃O₄ component in MgAl₂O₄-Fe₃O₄ spinels has been measured at 900° and 1000° C and 1 atm total pressure using a zirconia oxygen electrolyte. As previously reported for the dilute Fe₃O₄ concentration region (Mattioli and Wood 1986a), magnetite activity at 1000° C is greater than at 900° C at constant Fe₃O₄ mole fraction, for compositions across the MgAl₂O₄-Fe₃O₄ join between 20 and 80 mol% Fe₃O₄ component. The 1-atm solvus crest lies between 900° and 1000° C and, at 900° C the limbs are at Fe₃O₄ mole fractions of 0.2 and 0.6 approximately.Application of the O'Neill and Navrotsky (1983, 1984) cation distribution model indicates that the unusual activity — composition behavior of Fe₃O₄ is caused by changes in the equilibrium state of disorder of mixed MgAl₂O₄-Fe₃O₄ spinels relative to the disordered Fe₃O₄ standard state. In addition, both stoichiometric volumes (Mattioli et al. 1987) and activities across the MgAl₂O₄-Fe₃O₄ join suggest that short range order is significant for this binary. Excess free energy terms must be added to ideal Fe₃O₄ activities formulated from equilibrium cation distributions in complex MgAl₂O₄-Fe₃O₄ spinels in order to increase Fe₃O₄ activities to values consistent with observation and to generate the apparent region of immiscibility at 900° C.We have applied our activity data to the estimation of upper mantle spinel-lherzolite oxygen fugacities. We calculated that minimum 's are about 2 log units below the synthetic QFM buffer at 15 kbar total pressure for Fe₃O₄ concentration of 2 mol%, in a Cr-free spinel phase. If a preliminary calibration of an additional 25 mol% Fe²⁺-substitution as FeCr₂O₄ or FeAl₂O₄ component is incorporated into Fe₃O₄ activity, then olivine-orthopyroxene-spinel assemblages of depleted-Type 1-spinel-lherzolite xenoliths indicate 's close to QFM at 15 kbar. This is in good agreement with previous thermobarometric estimates and in sharp contrast to 1 atm intrinsic measurements near IW.     

The solubility of alumina in orthopyroxene coexisting with garnet

The solubility of alumina in complex orthopyroxenes crystallised in equilibrium with garnet has been determined over the pressure-temperature range 8–30 Kb and 800–1250° C. The results are in good agreement with predictions made using the simple thermodynamic model of Wood and Banno (1973). The model has been refined using a combination of the new data on orthopyroxenes of about En₆₀Fs₄₀ (with variable calcium content) and previously published data on more magnesian systems. Given analyses of coexisting Orthopyroxene and garnet in natural assemblages it is possible to calculate a P-T curve for the rock which should, in most cases, be accurate to within 2 or 3 kbar.