1 research outputs found
Molybdenum Burial Mechanism in Sulfidic Sediments: Iron-Sulfide Pathway
Relative
to continental crust, sediments underlying sulfidic marine
waters are molybdenum-rich, a property preserved in the rock record
and useful for characterizing paleoenvironments. The enrichment mechanism
is not agreed upon but is attributed at least partly to deposition
of Fe–Mo–S compounds, which are as yet uncharacterized.
Here, we determine the composition and stability of colloidal Fe–Mo–S
precipitates formed at mildly basic pH and H<sub>2</sub>SÂ(aq) >
10<sup>–5</sup> M. The first product consists simply of FeMoS<sub>4</sub>, with <i>K</i><sub>sp</sub> = 10<sup>–14.95</sup>. Within hours, FeMoS<sub>4</sub> irreversibly transforms by internal
self-reduction to a MoÂ(IV) product of similar composition. The reduced
product is insoluble in 1 M HCl but soluble in concentrated HNO<sub>3</sub>, implying that it would be recovered with pyrite in a common
assay of sediments. X-ray absorption fine structure data show that
MoÂ(IV) in the colloids is coordinated by a split first shell of about
five sulfur atoms at average distances of 2.31 and 2.46 Ã… and
in its second shell by an iron atom at about 2.80 Ã…. These properties
resemble those determined for Mo in modern anoxic lake sediments and
in Phanerozoic black shales. The atomic environment around Mo suggests
that the colloidal products may be inorganic polymers containing cuboid,
Fe<sub>2</sub>Mo<sub>2</sub>S<sub>4</sub><sup>4+</sup> cores. Such
materials are so far unreported by mineralogists, although a rare
mineral, jordisite, may be a related, but more Mo-rich material. The
low solubility of FeMoS<sub>4</sub> makes it a feasible precipitate
in euxinic waters like those in the modern Black Sea. We propose that
colloids similar to those studied here could account for Mo-enrichment
in euxinic basin sediments and black shales