Sulfur and chlorine in nakhlite clinopyroxenes: Source region concentrations and magmatic evolution

The volatile concentrations of the martian mantle and martian magmas remain important questions due to their role in petrogenesis and planetary habitability. The sulfur and chlorine concentrations, and their spatial distribution, in clinopyroxenes from nakhlites MIL 03346, Nakhla, and NWA 998 were measured to provide insight into these volatiles in the parental melts and source regions of nakhlites, and to constrain the evolution of the nakhlite melts. Sulfur and chlorine in four clinopyroxene crystals from MIL 03346, four from Nakhla, and five from NWA 998 were measured in crystal cores and rims by synchrotron X-ray fluorescence using beamline I18 at the Diamond Light Source. Portions of two crystals from MIL 03346 and one from Nakhla were mapped for S and Cl; a few reconnaissance analyses of Cl and F in MIL 03346 and Nakhla were made by ion microprobe. Clinopyroxene cores in Nakhla and NWA 998 contain ~10 ppm S, ~10 ppm Cl and ~74 ppm F (only Nakhla analyzed), whereas the cores of MIL 03346 contain ~10 ppm S, ~5 ppm Cl and ~53 ppm F. Using the volatile concentrations in the cores combined with previously determined partition coefficients we calculate that these clinopyroxenes crystallized from evolved basaltic melts containing ~500 ppm S, ~500-1900 ppm Cl, and 160-420 ppm F. These evolved melts can be used to calculate primitive melts in equilibrium with martian peridotite and the concentrations of S, Cl and F in the mantle source region of the nakhlite melts. Depending upon the extent of melting (5-30%) necessary to produce the primary melts associated with nakhlites, our calculations indicate that the nakhlite source region has a S concentration between 20 (5% melting) to 120 ppm (30% melting), Cl between 16 and 97 ppm, and F between 14 and 48 ppm. These concentrations in the nakhlite magma source region are similar to previous estimates for the martian mantle; our calculated source region concentrations of F and Cl agree best with previous estimates if the martian mantle undergoes 10-20% melting to produce primary magmas that evolve to be parental to nakhlites. However, our maximum estimated sulfur concentration of the source (calculated for 30% melting) is near previous minimum estimates for the martian mantle, suggesting the possibility that the nakhlite source region is depleted in sulfur relative to much of Mars' mantle. Mapping the spatial distribution of volatiles in three clinopyroxene crystals demonstrates that S and Cl concentrations of the evolving melts changed significantly from the core to the rim, particularly those in MIL 03346. Increasing S and Cl concentrations between the core and rim of MIL 03346 crystals are attributed to incorporation of additional volatiles through assimilation, but the Nakhla crystal shows no such evidence. However, concentrations of Cl and S at some outer crystal rims of one MIL 03346 crystal decrease, most probably due to volatile degassing during the final stages of clinopyroxene growth.