The detailed mechanisms of gold precipitation in high- and low-sulfidation deposits are complex and vary depending on the

geological setting and nature of fluids involved (Cooke and Simmons, 2000). The following section briefly considers gold precipitation mechanisms as applicable to epithermal deposits, although the principles discussed here also apply to other gold deposit types. The reader is encouraged to read the relevant sections on metal solubility and precipitation mechanisms in Chapter 3 (sections 3.4 and 3.5) before continuing with this section. Anionic species, or ligands, of chloride (Cl ) and sulfide (specifically HS) are regarded as being essential in order to solubilize gold in aqueous solutions (Seward and Barnes, 1997). In reduced, near-neutral pH, aqueous solutions Au is likely to be transported as the Au(HS) 2 complex and this is also likely to be the preferred medium for the movement of gold in low-sulfidation environments. By contrast, at higher temperatures (300 C) and for solutions that are both more acidic and saline, gold is preferentially transported as the Au(Cl)2 complex, and this mode of transport probably applies to high-sulfidation environments. Since the mechanism whereby gold is transported could be fundamentally different in the two epithermal deposit types, it follows that the chemical and physical controls that precipitate the gold from the hydrothermal fluids are also likely to differ. For low-sulfidation deposits gold precipitation is relatively straightforward and is linked to one, or both, of the two processes that characterize fluid evolution in this environment, namely boiling and fluid mixing. Boiling of an ore fluid in this case will result in loss of H2S to the vapor phase, which causes destabilization of the Au(HS) 2 complex and precipitation of Au, as described in equation [2.7] (after Cooke and Simmons, 2000): Au(HS)2 H0.5H2 Au 2H2S [2.7] Mixing of an oxidized meteoric water with the same ore fluid would also have the effect of precipitating gold, as shown in equation [2.8]: Evidence for boiling-induced Au precipitation is provided from modern geothermal systems that exploit steam to drive electricity-generating turbines, such as at Broadlands in New Zealand (Cooke and Simmons, 2000). It is well known in these power stations that the siliceous scale that plates the inside of pipes and accompanies the flashing of water to steam is often enriched in both Au and Ag. In actual low-sulfidation deposits the narrow vertical interval over which vein-hosted mineralization occurs (such as at Hishikari; Box 2.4) is another indication that boiling acts as a fundamental control on ore precipitation. Although it is clear that fluid mixing also plays a role, in deposits such as Creede in Colorado, the evidence for a widespread role for this mechanism is less clear (Cooke and Simmons, 2000). For high-sulfidation deposits the Au deposition mechanisms are less well understood and more complex, since it is feasible to transport gold, not only as a Au(Cl) 2 complex, as suggested above, but also as a bisulfide complex (Au(HS)) in fluids with a high sulfur activity. It is also considered possible that Au is transported together with Cu in the vapor phase (see section 2.4.2 above). If gold is transported as a bisulfide complex in high-sulfidation environments then the precipitation mechanisms are also likely to be related to boiling and fluid mixing, as for low-sulfidation systems. If, on the other hand, gold is transported as a chloride complex, then boiling and extraction of oxidized sulfur species (SO2 or SO4 2) into the vapor phase will have little effect on its stability. Fluid mixing, between a hot, acidic and saline Au(Cl)2 bearing ore fluid and a cooler, neutral meteoric solution, could, however, be an important precipitation mechanism, since it will have the effect of increasing pH and decreasing salinity (by dilution) of the ore fluid. Studies at Lepanto, for example, indicate that fluid mixing did occur with variations in the ratio of magmatic to meteoric fluids ranging from 9:1 to 1:1 over the ore deposit (Hedenquist et al., 1998). Arribas et al. (1995) have provided a model for the formation of high-sulfidation epithermal systems that reflects the complexities related to possible variations of gold speciation in this environment. The model envisages two stages of ore formation. The first involves degassing of hot, acid rich magmatic vapors that are responsible for intense leaching of the host rock to form the porous vuggy quartz zone in the fumarolic conduit and the advanced argillic alteration halo around it (Figure 2.23a). The vapor phases could also mix with meteoric waters to form an acid sulfate fluid that has a low Au solubility, but is also implicated in the alteration process. The secondary porosity and permeability created during this alteration process is considered to be a necessary preparatory stage for the influx of later metal-bearing fluids. Subsequent ore deposition can occur in one of two ways. A hot, acidic, and saline ore fluid, carrying gold as a Au(Cl) 2 complex, could be derived directly from the subjacent magma and move directly up into the alteration zone. Ore precipitation would occur as a result of mixing and dilution of this fluid by cooler meteoric waters (Figure 2.23b). Alternatively, it is suggested that Cu and Au are initially removed from the magma in the vapor phase and that these metal charged gases mix with heated ground waters circulating around the intrusion to form a low salinity fluid in which gold is transported as Au(HS). This fluid would then precipitate metals by boiling in the near surface environment, or mixing with meteoric waters, or both (Figure 2.23b).