Molybdenum (Mo) and tungsten (W) are redox-sensitive elements that exhibit contrasting geochemical behaviors under different redox and/or sulfidic conditions despite belonging to the same group in the periodic table. In this study, the geochemistry of Mo and W in a sediment-porewater system was investigated using a core sample collected from sediment containing hydrothermal minerals (Izena Hole, Okinawa, Japan). The Mo contents in the sediment and the porewater were quantified to calculate the partition coefficient K-d (concentration ratio of the solid phase to the aqueous phase) for Mo. However, the W concentration in the porewater was exceedingly low to be detected. Thus, we also conducted laboratory experiments simulating the sediment-porewater system to clarify the partitioning behaviors of Mo and W under redox conditions. X-ray absorption near-edge structure (XANES) spectra were obtained to determine the chemical species of Mo and W in sediment at different depths to understand the chemical processes of Mo and W. In particular, high-sensitivity XANES spectroscopy using wavelength-dispersive fluorescence mode was applied to W L-3 edge XANES spectra to reduce the interference signals from coexistent elements (Zn and Ni). This step thereby facilitating the identification of oxygen- and sulfur-coordinated species for W in the sediments.
The collected core sample covered a broad range of redox conditions under various hydrogen sulfide (H2S) concentrations depending on the depth. The presence of iron oxides in the upper layer suggested an oxic condition above within 4 cm depth below the seafloor (cmbsf). Iron and Zn sulfide minerals were found in deeper layers (16-24 cmbsf) and indicated the reductive conditions formed in such layer. Hydrogen sulfide was also observed in the porewater of the deeper layer. Analyses for Mo in the natural sediments, as well as XANES analyses, revealed that the K-d was higher in the deeper layer, with high pyrite and H2S contents, than in the upper layer. These results implied that Mo was removed from the porewater under reductive and/or sulfidic conditions. The chemical species of Mo was also an oxygen-coordinated species in the upper layer (0-8 cmbsf). Meanwhile, the detection of sulfide in the deeper layer suggests that Mo sulfidation is an important reaction in Mo enrichment in sediments.
On the other hand, at all the depths, W formed oxygen-coordinated species in the sediment. The subtle change of K-d for W with depth suggested that H2S did not affect the W adsorption in our samples. Hence, the Mo/W ratio in the sediments increased with the development of reducing conditions and vice versa in the coexistent porewater. Speciation analysis revealed that the high stability of oxygen-coordinated species of W was responsible for the variations of the Mo/W ratio under various redox conditions.