Thematic Articles

Case Hardening: Turning Weathering Rinds into Protective Shells

Case hardening is the process by which the outer shell of an exposed rock surface hardens due to near-surface diagenesis. Rock coatings and weathering rinds are distinct phenomena: rock coatings accrete on surfaces; weathering rinds derive from mineral dissolution and mechanical fracturing of the outer millimeters of a rock to create porosity. Ongoing reaction with rain, dew, or melted snow results in the downward migration of rock-coating components into weathering-rind pores. Initially, pore infilling protects the outer surface of the rock from flaking. As case hardening progresses, however, ongoing mineral dissolution underneath the case-hardened zone eventually leads to detachment. This sudden loss can destroy rock art, the surfaces of stone monuments, and facing stones of buildings.

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Mineral Surface Coatings: Environmental Records at the Nanoscale

Past and present (a)biotic soil processes can be preserved by mineral surface coatings, which can sequester contaminants in soils and sediments. The coatings can contain complex assemblages of nanometer-size minerals and organic components. The formation, composition, and morphology of these complex mineral assemblages depend on, and hence reflect, the mineralogical and chemical composition of the substrate they develop on and the environmental factors in the surrounding soils and sediments. Mineral surface coatings typically contain complex and variable porosities, many with regions of limited fluid flow. Low-flow conditions, combined with different nanometer-size phases in the interior of mineral surface coatings, allow coatings to sequester contaminant-bearing solutes, complexes, and nanoparticles.

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Coatings on Rocks and Minerals: Interface Between the Lithosphere and the Biosphere, Hydrosphere, and Atmosphere

Coatings occur along interfaces between rocks and minerals and their environment. Coatings result from the wide variety of reactions and/or processes that occur at the interface between the lithosphere and the biosphere, hydrosphere, and atmosphere. Such coatings are biochemically, mineralogically and isotopically complex and have the potential to record changes in their immediate environment. The transition between a coating and its underlying host is abrupt and defined by a sharp interface at the nanoscale. Articles in this issue highlight new and exciting research in the field of coatings, focussing on coatings formed in deserts, soils, sediments, oceans, and on rocks from Mars.

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Sedimentary 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.

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Chalcophile Elements and Sulfides in the Upper Mantle

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.

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Volcanic Sulfides and Outgassing

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.

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Sulfide Minerals in Hydrothermal Deposits

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.

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Magmatic Sulfide Ore Deposits

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.

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Mineralogy of Sulfides

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.

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Volcanoes: Characteristics, Tipping Points, and those Pesky Unknown Unknowns

The geological record of volcanic eruptions suggests that scientists are some way from being able to forecast eruptions at many of the world’s volcanoes. There are three reasons for this. First, continuing geological discoveries show that our knowledge is incomplete. Second, knowledge is limited about why, how, and when volcanic unrest turns into eruptions, and over what timescales. Third, there are imbalances between the studies of past eruptions, and the geophysical techniques and observations on modern events, versus the information needed or demanded by society. Scientists do not yet know whether there are other, presently unknown, factors that are important in controlling eruptions, or if there is an inherent unknowability about some volcanic systems.

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