Manganese scavenging and oxidation at hydrothermal vents and in vent plumes

Hydrothermal vents provide a major source of dissolved Mn(II) to the oceans, where concentrations range from 5 mM within the 350°C hot smokers to just above ambient seawater concentration in far field vent plumes. The Mn(II)-rich environments within warm vents and vent plumes provide a suitable habitat for Mn(II) oxidizing bacteria. In order to compare rates of scavenging and oxidation of Mn(II) proximally within vent fields (<30 m from venting water and temperatures <16°C) and distally within vent plumes, and to determine the relative contribution of microbes, incubation experiments using ⁵⁴Mn as a radiotracer were conducted in situ and on collected water samples from three hydrothermal vent locations: the Guaymas basin (GB), the Galapagos spreading center (GA), and the Endeavor Ridge of the Juan de Fuca spreading center (JDF). Both the adsorbed and oxidized fractions of the total ⁵⁴Mn scavenged were determined and found to often be significant (as high as 65 and 74%, respectively). Manganese scavenging rates were generally higher in in situ incubations than in incubations conducted on board ship. Inhibition of ⁵⁴Mn scavenging by sodium azide provided evidence for microbially mediated Mn(II) uptake and oxidation in waters both proximal (GA and GB) and distal to the vents (GA and JDF), even at distances as great as 17 km from the ridge axis at JDF. The highest manganese scavenging rates were observed within the vent fields (up to 2.5 nM/day). The residence times of dissolved Mn(II) were shorter in the GB and GA vent fields (26 and 28 days) than in the JDF vent field (1.4 years). This difference may be due to different mechanisms of Mn(II) precipitation in operation. At the GA vent field Mn(II) precipitation was often strongly inhibited by sodium azide and therefore apparently due to microbial activity. In contrast, Mn(II) scavenging within the JDF vent field was not significantly affected by sodium azide. Because ⁵⁴Mn scavenging in the JDF vent field was dependent on the presence of oxygen and a much larger fraction of the total ⁵⁴Mn scavenged was adsorbed than oxidized, manganese scavenging appears to occur primarily by an abiological mechanism, perhaps coprecipitation with iron oxyhydroxides. In comparison to the vent fields, Mn(II) scavenging rates were lower within the vent plumes (<0.6 nM/ day for GA and <0.2 nM/day for JDF), whereas residence times were not significantly different (as low as 34 days for GA and 1.0 years for JDF). The short residence times (90 and 118 days) and high microbial activity measured in bottom waters beneath the vent plumes at GA and JDF probably resulted from enhanced scavenging by manganate-coated bacteria that settled out from the vent plume and accumulated near the bottom. Therefore, bacteria not only enhance the scavenging of Mn within vent waters, but also facilitate Mn deposition to the sediments.