The effect of chromite crystallization on the distribution of osmium, iridium, ruthenium and rhodium in picritic magmas : an example from the Emeishan Large Igneous Province, Southwestern China

The positive correlations between whole-rock concentrations of Cr and Os, Ir and Ru (referred to collectively as iridium-like platinum-group elements, IPGE) in both sulphide-poor plutonic and volcanic rocks suggest that chromite contributes to the collection of these elements during the early stages of sulphide-undersaturated magma differentiation. However, it is not clear whether these correlations are the result of IPGE partitioning into chromite or whether other minerals are involved. Positive correlations between MgO and IPGE have been observed, suggesting that these elements could be incorporated into olivine as well as into chromite. Alternatively, given the siderophile nature of IPGE, they may crystallize as discrete minerals together with chromite, as suggested by the presence of platinum-group minerals in chromite-rich rocks such as mantle podiform and crustal stratiform chromitites. To investigate the effect of chromite crystallization on the distribution of IPGE and Rh in picritic magmas, we have determined the content of these elements in chromites from the Emeishan Large Igneous Province (southwestern China) by in situ laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The time-resolved analysis signals are generally uniform, indicating that the IPGE and Rh are homogeneously distributed within the chromite crystals. The median concentrations are 30 ppb Os, 23 ppb Ir, 248 ppb Ru and 21 ppb Rh. The incorporation of Rh in chromites appears to be influenced by the oxidation state of the magma from which they crystallize because there is a positive correlation between the degree of inversion of the chromite structure [expressed by Fe3+/(Cr + Al + Fe3+)] and the Rh content of the analyzed crystals. In contrast, the enrichments of Os, Ir and Ru in chromites appear to be controlled by other parameters such as temperature or the S content of the magma. Based on empirical calculations, we determined that partition coefficients between chromite and melt are higher for Ru (127) than for Os (23), Ir (27) and Rh (32). Despite these high partition coefficients, mass-balance calculations show that chromite does not account for all the IPGE and Rh concentrations in the rocks, with chromite accounting for maxima of 84, 49, 22 and 20% of the whole-rock Ru, Rh, Ir and Os budgets, respectively. In situ LA-ICP-MS and scanning electron microscopy analyses reveal the presence of micrometric-sized PGE-rich minerals, including laurite (RuS2), Os–Ir ± Ru alloys, sperrylite (PtAs2) and Pt–Fe (± IPGE and Rh) alloys, in association with chromite crystals. The presence of these minerals may account for the balance of IPGE and Rh. Alternatively, if IPGE and Rh are compatible with olivine, the balance may be accounted for by the large amount of olivine crystals found in the Emeishan picrites. Based on numerical modelling, we conclude that chromite, olivine and platinum-group minerals all contribute to the collection of IPGE and Rh during the early stages of picritic magma differentiation. Also, we establish that the preferential incorporation of Ru into chromite is responsible for the negative Ru anomalies observed in the PGE patterns of the Emeishan flood basalts. On the other hand, the relative importance of olivine and platinum-group minerals in controlling IPGE and Rh remains uncertain and is a key subject for further investigation