Formation of massive sulfide deposits on oceanic ridge crests: Incremental reaction models for mixing between hydrothermal solutions and seawater

Abstract

Equilibrium path calculations have been used to model mixing between hot (350°C) hydrothermal solutions and ambient seawater, in an attempt to simulate mineral precipitation at seafloor vents. These calculations predict temperatures of precipitation, paragenetic sequence of minerals, and chemical composition of chimney deposits associated with vents on the seafloor at 21°N, EPR. Assuming sulfate-sulfide disequilibrium during mixing, the paragenetic sequence revealed is: chalcopyrite, anhydrite, pyrrhotite, pyrite, sphalerite, graphite, and barite. When sulfate-sulfide equilibria is permitted during mixing, however, reduction of small amounts of sulfate results in early precipitation of pyrite and a sequence of Cu-rich sulfide minerals (chalcopyrite-bornite-chalcocite-covellite). This sequence is analogous to that observed in thin chimney walls. The calculations indicate that sulfide mineral precipitation occurs in response to both cooling and change in composition of the hydrothermal solutions as a result of mixing. Varying the amount of mixing with respect to temperature, simulating conductive heating of seawater prior to mixing, results in only minor variations in the sequence and abundance of precipitated phases. Anhydrite precipitation during mixing occurs early, which is consistent with formation of an anhydrite leading edge of chimney structures. Similarly, extrapolation of warm spring data from Galapagos to zero SO 4 concentration suggests anhydrite formation due to mixing with seawater beneath the seafloor, most likely below the level of reactive calcareous sediments. Subsequent interaction of the mixed hydrothermal solution with those sediments results in elevated and variable Ca concentrations estimated for end-member solutions from the Galapagos. Precipitation of Mg hydroxide sulfate hydrate in the walls of the vent chimneys at 21°N, EPR, occurs as a result of conductive heating of ambient seawater with only very minor amounts of mixing. In contrast, precipitation of amorphous silica in the vents must be due to conductive cooling of the hydrothermal solutions. Thus, incremental reaction calculations demonstrate that reactions occurring in and associated with venting ridge crest hydrothermal solutions can be effectively modeled using the thermodynamic data and reaction modeling codes available today. Departures from equilibrium required to accurately model the mixing process are easily accommodated and consistent with data from the vents and vent forming materials.