Effect of sulfur speciation on chemical and physical properties of very reduced mercurian melts

The NASA MESSENGER mission revealed that lavas on Mercury are enriched in sulfur (1.5-4 wt.%) compared with other terrestrial planets (<0.1 wt.%), a result of high S solubility under its very low oxygen fugacity (estimated fO(2) between IW-3 and IW-7). Due to decreasing O availability at these low fO(2) conditions, and an abundance of S2- , the latter acts as an important anion. This changes the partitioning behaviour of many elements (e.g. Fe, Mg, and Ca) and modifies the physical properties of silicate melts. To further understand S solubility and speciation in reduced magmas, we have analysed 11 high pressure experiments run at 1 GPa in a piston cylinder at temperatures of 1250-1475 degrees C andf O-2 between IW-2.5 to IW-7.5. S K-Edge XANES is used to determine coordination chemistry and oxidation state of S species in highly reduced quenched silicate melts. As fO(2) decreases from IW-2 to IW-7, S speciation goes through two major changes. At similar to IW-2, FeS, FeCr2S4, Na2S, and MnS species are destabilized, CaS (with minor Na2S) becomes the dominant S species. At similar to IW-4, Na2S is destabilized, MgS becomes the dominant S species, with lesser amounts of CaS. The changes in S speciation at low fO(2) affect the activities of SiO2, MgO and CaO in the melt, stabilizing enstatite at the expense of forsterite, and destabilizing plagioclase and clinopyroxene. These shifts cause the initial layering of Mercury's solidified magma ocean to be enstatite-rich and plagioclase poor. Our results on S speciation at low fO(2) are also applicable to the petrologic evolution of enstatite chondrite parent bodies and perhaps early Earth. (C) 2020 Elsevier Ltd. All rights reserved.