The effect of titanium and phosphorus on ferric/ferrous ratio in silicate melts: an experimental study

Abstract

The effect of TiO2 and P2O5 on the ferric/ferrous ratio in silicate melts was investigated in model silicate melts at air conditions in the temperature range 1,400–1,550 °C at 1-atm total pressure. The base composition of the anorthite–diopside eutectic composition was modified with 10 wt % Fe2O3 and variable amounts of TiO2 (up to 30 wt %) or P2O5 (up to 20 wt %). Some compositions also contained higher SiO2 concentrations to compare the role of SiO2, TiO2, and P2O5 on the Fe3+/Fe2+ ratio. The ferric/ferrous ratio in experimental glasses was analyzed using a wet chemical technique with colorimetric detection of ferrous iron. It is shown that at constant temperature, an increase in SiO2, TiO2, and P2O5 content results in a decrease in the ferric/ferrous ratio. The effects of TiO2 and SiO2 on the Fe3+/Fe2+ ratio was found to be almost identical. In contrast, adding P2O5 was found to decrease ferric/ferrous ratio much more effectively than adding silica. The results were compared with the predictions from the published empirical equations forecasting Fe3+/Fe2+ ratio. It was demonstrated that the effects of TiO2 are minor but that the effects of P2O5 should be included in models to better describe ferric/ferrous ratio in phosphorus-bearing silicate melts. Based on our observations, the determination of the prevailing fO2 in magmas from the Fe3+/Fe2+ ratio in natural glasses using empirical equations published so far is discussed critically.