Ag isotopic and chalcophile element evolution of the terrestrial and martian mantles during accretion: new constraints from Bi, Pd, and Ag metal-silicate partitioning.

The Earth’s timing of accretion and acquisition of moderately volatile compounds is uncertain. Hafnium-W and Mn-Cr isotopic data can bracket the timing of early planetary differentiation and core formation. The Ag-Pd system has also been utilized but its application has been limited by a lack of high pressure and temperature metal-silicate partitioning for Pd and Ag. Be-cause Ag (and Bi) are volatile chalcophile siderophile elements, understanding their early distribution can constrain the origin of volatile elements in differentiated bodies and planets. Unfortunately, neither Ag or Bi have been studied across the wide range of pressure and temperature conditions that are relevant to accretion and core-mantle differentiation. Here, new high-pressure and temperature multi-anvil metal-silicate equilibrium experiments for Bi and Ag have been carried out at conditions relevant to planetary accretion and metal silicate differentiation that allow a more refined and complete understanding of element partitioning during core formation. The new metal-silicate partitioning data utilized to predict the distributions of Bi, Pd, and Ag at conditions of accretion for Earth and Mars and show that the Pd/Ag ratio is significantly fractionated during accretion, allowing for the production of detectable 107Ag anomalies produced while 107Pd (half life = 6.5 M.y.) was still extant. Application of the new partitioning results to Earth shows that D(Bi) and D(Ag) (D = metal/silicate concentration ratio) are lowered due to the effect of pressure and Si alloyed in the metallic liquid, resulting in higher predicted mantle Bi and Ag abundances than in the bulk silicate Earth (BSE), as well as high and variable Pd/Ag. The unradiogenic Ag isotopic composition of the BSE could have been generated by early accretion of volatile-poor (high Pd/Ag) precursors, followed by later accretion of volatile–rich (low Pd/Ag) material, in agreement with earlier studies of Pd-Ag and Mn-Cr (Schönbächler et al., 2010). However, these main accretion phases would have to be followed by segregation of a sulfide liquid (at least 1.5% of magma ocean) at high pressures (>30 GPa), to explain the PUM Bi, Pd, and Ag, as well as Au, Pt, Cu and Ni concentrations as proposed previously. If the early accreted bulk Earth was volatile depleted with high Pd/Ag ratios, portions of the mantle may contain ancient domains that developed positive 107Ag isotopic anomalies (as also argued by noble gases, Nd, W, and Os isotopes). In comparison, Bi, Pd, and Ag concentrations in the martian mantle could have been set by simple metal-silicate equilibrium. Mars accreted and differentiated relatively rapidly, while also developing a deep magma ocean with a high Pd/Ag ratio that could have evolved positive 107Ag anomalies, in contrast to Earth. Measurements on shergottites may reveal these predicted Ag isotopic anomalies.