Divining gold in seafloor polymetallic massive sulfide systems

Hydrothermal fluids on the modern seafloor are important carriers of base and precious metals in a wide range of volcanic and tectonic settings. The concentrations and distribution, especially of gold and silver, in associated seafloor massive sulfide (SMS) deposits are strongly influenced by variable source rocks, fluid chemistry, and precipitation mechanisms. Compositional data of 130 SMS deposits around the world show a large range of gold and silver grades, in part reflecting strong buffering of the hydrothermal fluids by their host rocks. Geochemical reaction-path modeling shows that in most cases the investigated hydrothermal fluids are undersaturated with gold and silver, and solubilities can be orders of magnitude higher than the Au and Ag concentrations measured in the corresponding fluids. Precipitation of gold during conductive cooling of mid-ocean ridge black smoker (MOR) fluids occurs at low temperatures but can be very rapid, with > 90% of the gold deposited in the first 25 °C of cooling below ~ 150 °C. The result is a Zn–Au polymetallic assemblage with Au and Ag deposited at the same time together with Pb and sulfosalts. In ultramafic-dominated (UM) systems, the strongly reduced hydrothermal fluids promote the deposition of gold at higher temperatures and explain the correlation between gold and copper in these deposits. In this case, the lower stability of the AuHS° complex at low ƒO2 (buffered by fayalite, magnetite, and quartz) results in gold deposition at > 250 °C with early bornite and chalcopyrite and before sphalerite and silver, producing a high-temperature Cu–Au assemblage. In sediment-hosted (SED) systems, the much higher pH stabilizes Au(HS)2− and keeps gold in solution to very low temperatures, after the precipitation of chalcopyrite, sphalerite, and galena, resulting in Au-poor polymetallic sulfides and very late-stage deposition of gold, commonly with amorphous silica. In arc-related (ARC) systems, gold deposition occurs at somewhat higher temperatures than in the MOR case, in part because the fluids start with higher gold concentrations. This can be explained by probable direct magmatic contributions, and the high ƒO2 of the fluids, which promotes the solubility of gold at the source. During cooling, gold precipitates at about 160 °C with sphalerite, tennantite, silver, and galena, resulting in an Au-rich polymetallic sulfide assemblage. The mixing of hydrothermal fluids with seawater generally causes oxidation and eventually a decrease in the pH at a mixing ratio of 1:1, causing an initial increase in the solubility of gold and silver. This can delay gold deposition from aqueous species to very low temperatures. These complex systematics make prediction of Au and Ag grades difficult. However, important new data are coming to light on the actual concentrations of the precious metals in hydrothermal fluids. In particular, the input of magmatic volatiles and leaching of pre-existing gold can lead to significant increases in the Au and Ag concentrations of the venting fluids and earlier deposition. In several cases, it appears that at least part of the gold load is present as nanoparticles in suspension, allowing bulk gold concentrations that may be far in excess of liquid saturation. Boiling at the seafloor is now widely observed, even at great water depths close to the critical point of seawater. Model calculations of phase separation during boiling show the competing effects on gold solubility of H2, H2S, and CO2 partitioning into the vapor, which can result in highly variable gold-to-base metal ratios in the deposits. Flashing of the vent fluids into steam at high temperatures is also commonly observed and can lead to spectacular Au grades, with a strong Cu–Au association in the deepest and hottest vents.