Experimental study of trace element partitioning between lunar orthopyroxene and anhydrous silicate melt: Effects of lithium and iron

Orthopyroxene (Opx) was present during a significant portion of crystallisation of the lunar magma ocean, but its influence on co-existing melt trace element contents is not well quantified. We performed high-pressure (P, 1.1 to 3.2 GPa). high-temperature (T, 1400 to 1600 C) experiments on synthetic Fe-rich compositions at reducing conditions relevant to the lunar mantle to constrain trace element partitioning between Opx and anhydrous silicate melts. Opx-melt partition coefficients (DOpx-melt) for a wide range of trace elements (LILE: Li, Ba; REE: La, Ce, Nd, Sm, Dy, Eu, Er, Tm Y, Yb, Lu; HFSE: Zr, Nb, Hf, Ta,Th, U); and transition metals (Sc, V. Mn, Co, Mo) show only very minor variations across the considered P-T range. REE partition coefficients increase from D-La(opx-melt) = 0.0014 +/- 0.0008 to D-Lu(opx-melt) = 0.051 +/- 0.007. D values for highly charged elements vary from D-Th(opx-melt) = 0.0013 +/- 0.0008 through D-Nb(opx-melt) = 0.0018 +/- 0.0006 and D-U(opx-melt) = 0.0015 +/- 0.0006 to D-Ti(opx-melt) = 0.068 +/- 0.0010. D-Lu(opx-melt)/D-Hf(opx-melt) values of 6.3 +/- 2.4 are at the high end of reported values for minerals that played a role during crystallisation of the lunar magma ocean, and higher than previously reported for Opx under identical oxygen fugacity conditions, implying Opx-rich cumulates in the lunar mantle have highly superchondritic Lu-Hf ratios. Lattice strain modelling of our REE partitioning data suggests that varying the concentration of divalent Fe in Opx very slightly decreases the ideal cation radius for M3+ elements entering the M2 site, r(0)(M2), whereas the partitioning of M3+ elements entering the M1 site is unaffected. A subtle increase in the maximum partition coefficient for M3+ elements entering both the M1 and M2 sites with decreasing T is identified, when experiments carried out at similar reducing oxygen fugacities are considered. The presence of Li at concentrations of up to similar to 350 ppm does not have a measureable effect on the Opx-melt partitioning behaviour of REE or any other element, showing that charge-balancing of M3+, M4+ and M5+ elements in Opx is likely dominated by a vacancy mechanism. (C) 2011 Elsevier B.V. All rights reserved.