Sulfides

Sedimentary sulfides constitute over 95% of the sulfide on the surface of the planet, and their formation, preservation and destruction largely determines the surface environment. The sulfide in sediments is mainly derived from the products of sulfate-reducing bacteria, which are currently responsible for oxidizing over half the organic matter flux reaching sediments. Pyrite is the mineral overwhelmingly produced. The geochemistry of pyrite, both in terms of its isotopic composition and its trace-element loading, has varied dramatically over geologic time. As such, it is a major source of our current understanding about the nature of the early Earth and of the Earth’s subsequent geochemical and biological evolution.

Sulfides are among the most important petrogenetic agents in magmatic systems. They are ubiquitous in most upper-mantle rock types, common as inclusions in diamonds and they host significant amounts of geochemically and economically important chalcophile (‘sulfur-loving’) elements, such as Cu, Ni, Pb, In, Au and the platinum-group elements. Despite their low abundance (<< 1% of the bulk rock), residual sulfides have a disproportionate control over the chalcophile element budget in upper mantle lithologies, as well as that of melts derived from the Earth’s mantle.

Sulfides are a major potential repository for magmatic metals and sulfur. In relatively reduced magmas, there may be a dynamic interplay between sulfide liquids and magma degassing as magmas ascend/erupt. Sulfide-bubble aggregates may segregate to shallow levels. Exsolved fluids may oxidize sulfides to produce SO2 gas and metals, which can vent to the atmosphere with chalcophile metal ratios reflecting those in their parent sulfide liquids. Sulfide breakdown and/or sequestration timing and balance define the role of sulfides in both ore formation and the environmental impacts of volcanic eruptions, including during the evolution of large igneous provinces, which are key periods of heightened volcanism during Earth history.

Hydrothermal ore deposits are large geochemical anomalies of sulfur and metals in the Earth’s crust that have formed at <1 to ~8 km depth. Sulfide minerals in hydrothermal deposits are the primary economic source of metals used by society, which occur as major, minor and trace elements. Sulfides also play a key role during magmatic crystallization in concentrating metals that subsequently may (or may not) be supplied to hydrothermal fluids. Precipitation of sulfides that themselves may have little economic value, like pyrite, may trigger the deposition of more valuable metals (e.g. Au) by destabilizing the metal-bearing sulfur complexes. We review why, where and how sulfide minerals in hydrothermal systems precipitate.

Magmatic sulfide ore deposits are products of natural smelting: concentration of immiscible sulfide liquid (‘matte’), enriched in chalcophile elements, derived from silicate magmas (‘slags’). Sulfide ore deposits occupy a spectrum from accumulated pools of matte within small igneous intrusions or lava flows, mined primarily for Ni and Cu, to stratiform layers of weakly disseminated sulfides within large mafic–ultramafic intrusions, mined for platinum-group elements. One of the world’s most valuable deposits, the Platreef in the Bushveld Complex (South Africa) has aspects of both of these end members. Natural matte compositions vary widely between and within deposits, and these compositions are controlled largely by the relative volumes of matte and slag that interact with one another.

Metal sulfides are the most important group of ore minerals. Here, we review what is known about their compositions, crystal structures, phase relations and parageneses. Much less is known about their surface chemistry, their biogeochemistry, or the formation and behaviour of ‘nanoparticle’ sulfides, whether formed abiotically or biogenically.