Gold colloids occur in black smoker fluids from the Niua South hydrothermal vent field, Lau Basin (South Pacific Ocean), confirming the long-standing hypothesis that gold may undergo colloidal transport in hydrothermal fluids. Six black smoker vents, varying in temperature from 250 °C to 325 °C, were sampled; the 325 °C vent was boiling at the time of sampling and the 250 °C fluids were diffusely venting. Native gold particles ranging from <50 nm to 2 µm were identified in 4 of the fluid samples and were also observed to precipitate on the sampler during collection from the boiling vent. Total gold concentrations (dissolved and particulate) in the fluid samples range from 1.6 to 5.4 nM in the high-temperature, focused flow vents. Although the gold concentrations in the focused flow fluids are relatively high, they are lower than potential solubilities prior to boiling and indicate that precipitation was boiling induced, with sulfide lost upon boiling to exsolution and metal sulfide formation. Gold concentrations reach 26.7 nM in the 250 °C diffuse flow sample, and abundant native gold particles were also found in the fluids and associated sulfide chimney and are interpreted to be a product of colloid accumulation and growth following initial precipitation upon boiling. These results indicate that colloid-driven precipitation as a result of boiling, the persistence of colloids after boiling, and the accumulation of colloids in diffuse flow fluids are important mechanisms for the enrichment of gold in seafloor hydrothermal systems. 1 GSA Data Repository item 2018008, Figure DR1 (map of Niua), Figure DR2 (photograph of the tarnish that developed during sampling), Figure DR3 (additional SEM/EDS), Figure DR4 (temperature, pressure, and boiling of fluids at Niua), Figure DR5 (calculated solubilities for Au at Niua). and Table DR1 (fluid concentration and location of fluid collection),
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 ƒO 2 (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 ƒO 2 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 d...
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