The knowledge of molybdenum speciation under hydrothermal conditions is a key for understanding the formation of porphyry deposits which are the primary source of Mo. Previous studies have revealed a complex speciation of Mo including (hydrogen)molybdate ions, their ion pairs with alkalis, oxy-chloride species, and thiomolybdate complexes. However, these available data are unable to account for the observed massive transport of Mo in porphyry-related fluids revealed by fluid inclusion analyses demonstrating 100s ppm of Mo (e.g., Kouzmanov and Pokrovski, 2012). A potential missing ligand for Mo may be the trisulfur radical ion, which is predicted to be abundant in sulfate-sulfide rich acidic-to-neutral porphyry-like fluids.
We performed X-ray absorption spectroscopy (XAS) measurements at the Mo K-edge (20.0 keV) in a hydrothermal autoclave available at BM30 of ESRF synchrotron (Testemale et al., 2005) to study the molybdenite solubility in model S3•- rich aqueous solutions at 300°C and 500 bar. We found that Mo can be efficiently transported by S3•--bearing fluids at concentrations of several ppm, whereas the available data on OH-Cl-S complexes predict negligibly small (<100 ppb) Mo concentrations at our conditions. Work is in progress to extend the experiments to wider T-P-composition range of porphyry fluids and to quantitatively assess the role of S3•- in Mo transport by geological fluids.
K. Kouzmanov and G.S. Pokrovski, Soc. Econ. Geol. Spec. Pub. 16 (573–618), 2012; D. Testemale et al., Rev. Sci. Instr. 76 (043905), 2005.
Funding: Deutsche Forschungsgemeinschaft WI 2000/25-1, KL 1368/13-1, SCHM 2415/6-1, ESRF ES-1050.