Metasomatic oxidation of upper mantle periodotite

Examination of Fe³⁺ in metasomatized spinel peridotite xenoliths reveals new information about metasomatic redox processes. Composite xenoliths from Dish Hill, California possess remnants of magmatic dikes which were the sources of the silicate fluids responsible for metasomatism of the peridotite part of the same xenoliths. Mössbauer spectra of mineral separates taken at several distances from the dike remnants provide data on Fe³⁺ contents of minerals in the metasomatized peridotite. Clinopyroxenes contain 33% of total iron (Fe_T) as Fe³⁺ (Fe³⁺/Fe_T=0.33); orthopyroxenes contain 0.06–0.09 Fe³⁺/Fe_T; spinels contain 0.30–0.40 Fe³⁺/Fe_T; olivines contain 0.01–0.06 Fe³⁺/Fe_T; and metasomatic amphibole in the peridotite contains 0.85–0.90 Fe³⁺/Fe_T. In each mineral, Fe³⁺ and Fe²⁺ cations per formula unit (p.f.u.) decrease with distance from the dike, but the Fe³⁺/Fe_T ratios of each mineral do not vary. Clinopyroxene, spinel, and olivine Fe³⁺/Fe_T ratios are significantly higher than in unmetasomatized spinel peridotites. Metasomatic changes in Fe³⁺/Fe_T ratios in each mineral are controlled by the oxygen fugacity of the system, but the mechanism by which each phase accommodates this ratio is affected by crystal chemistry, kinetics, rock mode, fluid composition, fluid/rock ratio, and fluid-mineral partition coefficients. Ratio increases in pyroxene and spinel occur by exchange reactions involving diffusion of Fe³⁺ into existing mineral grains rather than by oxidation of existing Fe²⁺ in peridotite mineral grains. The very high Fe³⁺/Fe_T ratio in the metasomatic amphibole may be a function of the high Fe³⁺/Fe_T of the metasomatic fluid, crystal chemical limitations on the amount of Fe³⁺ that could be accommodated by the pyroxene, spinel, and olivine of the peridotite, and the ability of the amphibole structure to accommodate large amounts of 3 + valence cations. In the samples studied, metasomatic amphibole accounts for half of the bulk-rock Fe₂O₃. This suggests that patent metasomatism may produce a greater change in the redox state of mantle peridotite than cryptic metasomatism. Comparison of the metasomatized samples with unmetasomatized peridotites reveals that both Fe²⁺ and Fe³⁺ cations p.f.u. were increased during metasomatism and 50% or more of iron added was Fe³⁺. With increasing distance from the dike, the ratio of added Fe³⁺ to added Fe²⁺ increases. The high Fe³⁺/Fe_T of amphibole and phlogopite in the dikes and in the peridotite, and the high ratios of added Fe³⁺/added Fe²⁺ in pyroxenes and spinel suggest that the Fe³⁺/Fe_T ratio of the metasomatic silicate fluid was high. As the fluid perolated through and reacted with the peridotite, Fe³⁺ and C–O–H volatile species were concentrated in the fluid, increasing the fluid Fe³⁺/Fe_T.