Oxygen chemical diffusion in three basaltic liquids at elevated temperatures and pressures

The diffusivity of oxygen has been measured in three basaltic liquids from 1280 to 1450°C and 4 to 21 kilobars using a solid media piston-cylinder apparatus. The measurements were done by monitoring the reduction of ferric iron in previously oxidized spheres of basalt melt. The compositions studied were olivine nephelinite, alkali basalt, and 1921 Kilauea tholeiite.The isobaric temperature dependence of oxygen diffusivity is adequately described by Arrhenius relationships for the three liquids studied. Arrhenius activation energies were determined at 12 kilobars for olivine nephelinite (62± 6 kcal/mole) and tholeiite (51 ± 4 kcal/mole) and at 4, 12, and 20 kilobars for alkali basalt (70 ± 7, 86 ± 6, and 71 ± 14 kcal/mole, respectively). The Arrhenius parameters for the three compositions define a compensation law which is indistinguishable from those for oxygen diffusion in simple silicate melts (DUNN, 1982) and for divalent cation diffusion in basaltic melts (Hofmann, 1980). These results suggest that the principal species contributing to the total diffusivity of oxygen is the oxide anion (O^2?).The isothermal pressure dependence of oxygen diffusion is complex and quite different from that observed for cationic diffusion in silicate melts. All three compositions show a sharp decrease in oxygen diffusivity at approximately the same pressure as the change in the liquidus phase from olivine to pyroxene, but otherwise the pressure dependence can be described by Arrhenius type equations. The equations yield negative activation volumes for the olivine nehpelinite and the alkali basalt. The activation volumes determined for the tholeiite are near zero at low pressure and positive at high pressure. A negative activation volume represents a decrease in the average size of the principal diffusing species.The results of this study are consistent with a melt model which includes both continuous changes in the relative proportions of the various anionic species in the melt with pressure and the occurrence of anionic disproportionation reactions within narrow pressure ranges.