This contribution provides an overview of available experimental, thermodynamic, and molecular data on Au aqueous speciation, solubility, and partitioning in major types of geological fluids in the Earth's crust, from low-temperature aqueous solution to supercritical hydrothermal-magmatic fluids, vapours, and silicate melts. Critical revisions of these data allow generation of a set of thermodynamic properties of the AuOH, AuCl ⁻ ₂ , AuHS, and Au(HS) ⁻ ₂ complexes dominant in aqueous hydrothermal solutions; however, other complexes involving different sulphur forms, chloride, and alkali metals may operate in high-temperature sulphur-rich fluids, vapours, and melts. The large affinity of Au for reduced sulphur is responsible for Au enrichment in S-rich vapours and sulphide melts, which are important gold sources for hydrothermal deposits. Thermodynamic, speciation, and partitioning data, and their comparison with Au and S contents in natural fluid inclusions from magmatic-hydrothermal gold deposits, provide new constraints on the major physical-chemical parameters (temperature, pressure, salinity, acidity, redox) and ubiquitous fluid components (sulphur, carbon dioxide, arsenic) affecting Au concentration, transport, precipitation, and fractionation from other metals in the crust. The availability and speciation of sulphur and their changes with the fluid and melt evolution are the key factors controlling gold behaviour in most geological situations.

Porphyry systems supply most copper and significant gold to our economy. Recent studies indicate that they are frequently associated with high Sr/Y magmatic rocks, but the meaning of this association remains elusive. Understanding the association between high Sr/Y magmatic rocks and porphyry-type deposits is essential to develop genetic models that can be used for exploration purposes. Here we present results on a Pleistocene volcano of Ecuador that highlight the behaviour of copper in magmas with variable (but generally high) Sr/Y values. We provide indirect evidence for Cu partitioning into a fluid phase exsolved at depths of ~15 km from high Sr/Y (>70) andesitic magmas before sulphide saturation. This lends support to the hypothesis that large amounts of Cu- and S-bearing fluids can be accumulated into and released from a long-lived high Sr/Y deep andesitic reservoir to a shallower magmatic-hydrothermal system with the potential of generating large porphyry-type deposits.

Hydrothermal ore deposits are large geochemical anomalies of sulfur and metals in the Earth9s 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.

Porphyry-related base metal vein and replacement mineralization (i.e., Cordilleran polymetallic mineralization) in the Morococha district, central Peru, is part of a large magmatic-hydrothermal system associated with the emplacement of several late Miocene porphyry intrusions and formation of important Cu-Mo mineralization. Zn-Pb-Ag-Cu veins overprint the giant Toromocho porphyry Cu-Mo deposit in the center of the district and display a typical concentric base metal zonation (Cu → Zn, Pb → Ag) covering an area of approximately 50km².

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in combination with near-infrared microscopy of fluid inclusions hosted by ore minerals that are opaque to visible light can provide the composition of ore-precipitating fluids. We applied the two techniques to well-constrained fluid inclusion assemblages hosted by pyrite, enargite, and quartz to trace the source and evolution of the fluids in high-sulfidation epithermal veins overprinting a porphyry copper deposit at Rosia Poieni, Romania. Despite some analytical limitations caused by the sulfide host minerals, the data demonstrate that fluids trapped in apparently cogenetic quartz and ore minerals are chemically different. Systematic changes in major and trace element ratios between liquid-vapor, vapor-rich, and brine fluid inclusion assemblages in the three minerals record an evolving fluid source at the porphyry to epithermal transition. Regarding their Cs/(Na + K) ratios, most of epithermal quartz-hosted fluid inclusion assemblages form a well-defined cluster, which coincides with the narrow range of the porphyry-stage fluids trapped in early quartz of the porphyry stockwork veins. Their Cu/(Na + K) ratios are 10 to 100 times lower compared to the pyrite-hosted inclusions and correspond to the lowest Cu/(Na + K) ratios recorded for the porphyry-stage fluids. By contrast, pyrite-hosted, vapor-rich fluid inclusions have the highest Cu/(Na + K) similar to the highest Cu/(Na + K) ratios measured in the porphyry-stage fluid inclusions. The results led to the conclusion that the gangue and ore minerals in the high-sulfidation epithermal veins at Rosia Poieni formed by successive pulses of chemically distinct hydrothermal fluids that were successively exsolved from residual melt batches of a progressively crystallizing magma at greater depth. These results are consistent with detailed textural observations, but petrography alone could not have led to this unambiguous conclusion