Significance of highly siderophile element and Re–Os isotope systematics in global carbonatites

The systematics of highly siderophile elements (HSE) in carbonatites have rarely been investigated although carbonatite melts are among key metasomatic agents in the Earth's mantle. Thus, establishing the Os isotope systematics of carbonatites is of prime importance because carbonatite metasomatism might play a determining role in driving 187Os/188Os signature of the Earth's mantle as a consequence of extreme mobility of carbonatite liquids. In this study, a suite of carbonatites from continental settings was analyzed for HSE abundances and ReOs isotope systematics, combined with detailed petrography of sulfide phases, to provide constraints on the HSE behavior during the formation of carbonatite melts, the role of sulfides in distribution of HSE and the reliability of ReOs isotope compositions. All investigated carbonatites display low ΣHSE <1 ppb whereby calciocarbonatites exhibit supra-chondritic OsN/IrN ratios from ~1.4 to 15, in contrast to magnesiocarbonatites and Mg/Fe-rich carbonatites showing exclusively sub-chondritic OsN/IrN. We posit that preferential removal of Os over Ir during the segregation of calcite-normative melts from the co-existing S-rich silicate melts is the main driver of Os/Ir elemental fractionation. The present-day 187Os/188Os ratios in carbonatites range from mildly unradiogenic (~0.124) to extremely radiogenic values (~115–152), with 187Os/188Os(i) ratios spanning from negative to highly radiogenic (~17) values, paralleled by highly variable 187Re/188Os ratios between 0.096 and ~ 26,000, and without any clear relationship to the carbonatite type or emplacement age. The ReOs systematics of carbonatites appear to be significantly modified by hydrothermal processes resulting in either removal of both Re and Os, or Re addition and, consequently, commonly negative calculated γOs values, which may indicate a rather limited potential of the ReOs systematics to evaluate the nature of carbonatite melts. Conversely, limited ReOs data for the samples that were likely not affected by late-stage perturbation indicate a largely radiogenic 187Os/188Os nature of carbonatite melts. Nevertheless, carbonatite melts may, in part, be responsible for the radiogenic γOs values commonly observed in mantle-derived silicate melts influenced by carbonatite-like metasomatism.