The effect of melt composition and oxygen fugacity on manganese partitioning between apatite and silicate melt

Oxygen fugacity and melt composition are both known to have a strong influence on the partitioning of trace elements between coexisting minerals and melt. Previous work has suggested that Mn partitioning between apatite and silicate melt may be strongly affected by oxygen fugacity and could, therefore, act as an oxybarometer. Here, we present a new study on the partitioning of Mn between apatite and melt at high temperature (1400–1250 °C) and 1 GPa pressure, for various melt compositions and oxygen fugacities (NNO +4.7 to NNO -10). We find that there is no demonstrable variation in the partition coefficient for Mn between apatite and silicate melt (DMnAp-m) across the range of fO2 conditions studied here. Instead, we find that DMnAp-m varies significantly with melt composition and that in particular, the proportion of non-bridging oxygens strongly influences partitioning of Mn between apatite and melt. We propose that variations in the Mn content of natural apatite, previously thought to reflect variations in fO2, are instead related to the degree of melt polymerisation. These findings are consistent with the results of Mn K-edge XANES spectroscopy, which demonstrate that Mn in coexisting apatite and silicate glass is present predominantly as Mn2+ regardless of fO2. Furthermore, XANES spectra from a series of silicate glasses synthesised at various oxygen fugacities demonstrate that Mn2+ is the predominant species, and that the average Mn oxidation state does not vary over a wide range of fO2-T conditions.