Zinc stable isotopes in seafloor hydrothermal vent fluids and chimneys

Many of the heaviest and lightest natural zinc (Zn) isotope ratios have been discovered in hydrothermal ore deposits. However, the processes responsible for fractionating Zn isotopes in hydrothermal systems are poorly understood. In order to better assess the total range of Zn isotopes in hydrothermal systems and to understand the factors which are responsible for this isotopic fractionation, we have measured Zn isotopes in seafloor hydrothermal fluids from numerous vents at 9–10°N and 21°N on the East Pacific Rise (EPR), the TAG hydrothermal field on the Mid-Atlantic Ridge, and in the Guaymas Basin. Fluid δ66Zn values measured at these sites range from + 0.00‰ to + 1.04‰. Of the many physical and chemical parameters examined, only temperature was found to correlate with fluid δ66Zn values. Lower temperature fluids (< 250 °C) had both heavier and more variable δ66Zn values compared to higher temperature fluids from the same hydrothermal fields. We suggest that subsurface cooling of hydrothermal fluids leads to precipitation of isotopically light sphalerite (Zn sulfide), and that this process is a primary cause of Zn isotope variation in hydrothermal fluids. Thermodynamic calculations carried out to determine saturation state of sphalerite in the vent fluids support this hypothesis with isotopically heaviest Zn found in fluids that were calculated to be saturated with respect to sphalerite. We have also measured Zn isotopes in chimney sulfides recovered from a high-temperature (383 °C) and a low-temperature (203 °C) vent at 9–10°N on the EPR and, in both cases, found that the δ66Zn of chimney minerals was lighter or similar to the fluid δ66Zn. The first measurements of Zn isotopes in hydrothermal fluids have revealed large variations in hydrothermal fluid δ66Zn, and suggest that subsurface Zn sulfide precipitation is a primary factor in causing variations in fluid δ66Zn. By understanding how chemical processes that occur beneath the seafloor affect hydrothermal fluid δ66Zn, Zn isotopes may be used as a tracer for studying hydrothermal processes.