Formation of Zn- and Fe-sulfides near hydrothermal vents at the Eastern Lau Spreading Center: implications for sulfide bioavailability to chemoautotrophs

In June 2005, diffuse-flow (< 50°C) and high-temperature (> 250°C) vent fluids were collected from four field sites along the ELSC ridge axis. Total and filtered Zn and Fe concentrations were quantified in the vent fluid samples using voltammetric and spectrometric analyses. The results indicated north-to-south variability in vent fluid composition. In the high temperature vent fluids, the ratio of total Fe to total Zn varied from 39 at Kilo Moana, the most northern site, to less than 7 at the other three sites. The concentrations of total Zn, Fe, and acid-volatile sulfide indicated that oversaturation and precipitation of sphalerite (ZnS(s)) and pyrite (FeS2(s)) were possible during cooling of the vent fluids as they mixed with the surrounding seawater. In contrast, most samples were undersaturated with respect to mackinawite (FeS(s)). The reactivity of Zn(II) in the filtered samples was tested by adding Cu(II) to the samples to induce metal-exchange reactions. In a portion of the samples, the concentration of labile Zn2+ increased after the addition of Cu(II), indicating the presence of strongly-bound Zn(II) species such as ZnS clusters and nanoparticles.Results of this study suggest that Zn is important to sulfide speciation at ELSC vent habitats, particularly at the southern sites where Zn concentrations increase relative to Fe. As the hydrothermal fluids mix with the ambient seawater, Zn-sulfide clusters and nanoparticles are likely preventing sulfide oxidation by O2 and reducing bioavailability of S(-II) to organisms.Deep-sea hydrothermal vents in the Pacific Ocean support productive ecosystems that rely on symbiotic relationships between chemoautotrophic microorganisms and macroinvertebrates [1,2]. Many of these chemoautotrophs utilize inorganic sulfide as the electron source for carbon fixation. As a result, primary productivity in these ecosystems can be controlled by sulfide that enters the surrounding seawater environment from hydrothermal fluid release [