Kinetic controls on the sulfide mineralization of komatiite-associated Ni-Cu-(PGE) deposits

Abstract

Genesis of magmatic Ni-Cu-(PGE) deposits involves many interconnected and multiple-scale processes in the fields of thermodynamics, kinetics and fluid dynamics. The main focus of quantitative work on magmatic sulfide ore genesis has been on equilibrium thermodynamics since the initial studies over 50 years ago, while the significance of kinetics and dynamics to sulfide mineralization in dynamic magmatic systems has received little attention. Taking the komatiite-hosted Ni-Cu-(PGE) deposits of the Raglan area as an example, we have developed a quantitative model for assimilation of sulfidic substrates during lava emplacement through the consideration of these three fields. We show that the dominant control on the composition of externally derived sulfide xenomelts throughout their residence within the flowing magma is exerted by relative rates of diffusion of sulfur and metals. In rapid channelized flow of komatiites, the kinetically-controlled extraction of chalcophile elements from silicate melt into externally-derived sulfide droplets released from underlying sediments is the quickest way to produce orebodies with economic value, without the necessity of reaching either sulfide saturation throughout the mass of magma or indeed compositional equilibrium in the magmatic system as our long-held understanding would suggest. The kinetic upgrading of initially metal-poor sulfide xenomelts is enhanced for sulfide droplets of smaller size and increasing downstream distance from the source, approaching to equilibrium mass distribution for the fast-diffusing elements such as Cu during prolonged or especially vigorous processes (e.g., chaotic magma mixing). In this kinetically-driven process, differences in diffusivities between Pt and Pd may account for the anomalous excess Pd/Pt ratios (~2) of disseminated ores from many komatiite-related deposits compared with the compositions of the parental magmas. Sedimentation of sulfide on the bottom of the flowing magma terminates this kinetically-controlled process, while the number density of droplets imposes a restriction on sulfide compositions due to mass conservation. Therefore, sulfide mineralization in komatiite-associated deposits is mostly controlled by diffusion kinetics with additional interactions and restrictions from the dynamics of transport and settling of sulfide droplets. By analogy, multiple cycles of dynamic processes predominate in the conduit-type magmatic deposits. A quantitative grasp of the relative importance of these three fundamental mechanisms, i.e., thermodynamic driving forces, kinetics of diffusive equilibration, and fluid dynamics of transport and deposition, is of great value in understanding ore genesis in complex mineral systems and even the origin of igneous rocks in general.