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The Archean metasedimentary succession of the Witwatersrand basin, South Africa, hosts the largest Au deposit in the world. Gold mineralization is mostly concentrated in conglomerate horizons, or "reefs," and is tightly associated with pyrite. Trace element zoning of pyrite from the Ventersdorp Contact Reef, studied by X-ray elemental (As, Ni, Co, and Pb) maps, electron microprobe analysis, and laser ablation-inductively coupled plasma-mass spectrometry, indicates successive stages of pyrite formation, each characterized by different textures and trace element composition (As = 2.2 wt %, Ni = 1.37 wt %, Co = 1.98 wt %). Four generations have been distinguished: generation 1 is detrital and includes compact (nonporous), porous, and laminated pyrite; generations 2 to 4 are postsedimentary/authigenic. Generation 4 pyrite formed at near-peak metamorphic conditions (T = 270°-350°C, chlorite geothermometry). Porous and concentrically laminated pyrite grains (generation 1) are particularly enriched in Au (average 6.4 ppm, maximum 70 ppm), in addition to Sb, Tl, Pb, Mn, Mo, Cu, and Ag, in comparison with compact pyrite types of all generations. In these grains, Au, occurring as "invisible gold," and other trace elements might be finely dispersed with the phyllosilicates filling the pyrite pores. Trace element composition of porous and concentrically laminated pyrite is reminiscent of pyrite known to form in suboxic to anoxic environments (black shales). The presence of Au in detrital pyrite indicates an early introduction of Au in the Ventersdorp Contact Reef. Gold is also present as secondary inclusions of electrum associated with the last pyrite generation (generation 4), together with sphalerite, chalcopyrite, galena, and pyrrhotite. © 2013 Society of Economic Geologists, Inc.

Olympic Dam is a supergiant Fe oxide Cu-U-Au-Ag ore deposit (~9 × 109 t) that is also enriched in rare earth elements (REEs) and fluorine (F). The immediate host to the ore is hydrothermal breccia within granite and volcanic rocks of a Mesoproterozoic silicic large igneous province. Analyses of melt inclusions in quartz phenocrysts in rhyolite show that the silicic magmas of this province were unusually rich in F (up to 1.3 wt%). Fluorite and other F-rich minerals that crystallized from these magmas provided a gigantic reservoir of F. As a result, the Olympic Dam ore-forming fluid was F-rich and had exceptional capacity to transport diverse elements. Further, we infer that hydrofluoric acid, the most corrosive acid known, contributed to hydrothermal breccia formation by dissolution that in turn increased permeability and accelerated the rate of fluid-rock interaction. It is no accident that the world's largest hydrothermal ore deposit occurs in an F-rich silicic large igneous province.

Rhyolites of the Mesoproterozoic Gawler Range Volcanics (GRV) of South Australia are characterised by high concentrations of some trace elements (REE, Y, HFSE, Rb and F, in particular). Whole rock geochemical data suggest that these elements were incompatible during magma crystallisation. Accessory minerals (fluorite, zircon, REE-F-carbonate, Ti oxide, apatite, and titanite) can account for most of the trace element content of the rocks. These minerals occur in vesicles, micromiaroles, lithophysal vugs and in interstices between major mineral phases (quartz and feldspar as both phenocrysts and groundmass). Such textural evidence indicates that accessory minerals crystallised late in the history of the magma and that they were deposited from a volatile-rich (fluid) phase. These features are explained by the following sequence of events: 1) F dissolved in the magma lowered the crystallisation temperature of accessory minerals, causing trace elements (REE, Y, and HFSE) to behave as incompatible elements. 2) Protracted crystallisation of major mineral phases (quartz, feldspar, and oxides) formed a volatile- and trace element-enriched residual liquid. 3) A volatile element (H2O, F, and CO2)-rich phase (late-stage magmatic fluid) evolved from the magma. High concentration of fluorine and other complexing agents in this phase allowed trace elements to be transported in solution. 4) Accessory minerals crystallised from such a phase in vesicles, micromiaroles and interstices between the major mineral phases. © 2010 Elsevier B.V.

The composite Biella pluton is part of an Oligocene volcano-plutonic complex whose origin is connected to the Alpine subduction-collision processes and that emplaced at shallow crustal levels within the eclogite-facies rocks of the Austroalpine Sesia-Lanzo Zone. In the roof zone of the pluton, small satellite igneous bodies are set within the Sesia-Lanzo country rocks, close to the main Biella pluton, and range in composition from quartz alkali feldspar syenite, quartz monzodiorite and monzogabbro, to quartz diorite and gabbronorite. Their geochemical features, including the REE patterns, are coherent with the calc-alkaline to shoshonitic affinity recognized in the whole volcano-plutonic complex. Field and petrographic data suggest that these bodies represent earlier crystallization/differentiation products of the Biella primary magma(s), which underwent contact metamorphic recrystallization during the multistage emplacement of the main pluton. Tourmaline-bearing hydrothermal breccias and different types of hydrothermal veins (including quartz-plagioclase-, quartz-tourmaline- and ankerite-quartz-sulphides-bearing veins) occur within both the intrusive rocks (satellite bodies + the main pluton) and their Sesia-Lanzo Zone country rocks. Both field relationships and vein assemblages suggest a close connection between the late-magmatic evolution of the Biella pluton and the multistage, boron-rich hydrothermal activity.