Adsorption of Tetrathiomolybdate to Iron Sulfides and Its Impact on Iron Sulfide Transformations

Nathan Miller, Maura Dougherty, Ruochen Du, Tyler Sauers, Candice Yan, Jonathan E. Pines, Kate L. Meyers, Y. M. Dang, Emily Nagle, Ziqin Ni, Tipsiri Pungsrisai, Maxwell T. Wetherington, Trent P. Vorlicek, Katherine E. Plass, Jennifer L. Morford

Research output: Contribution to journalArticlepeer-review

Abstract

Molybdenum (Mo) in marine sediments has been used as a paleoproxy to provide evidence for past oceanic euxinic and sulfidic conditions through its association with pyrite. Here, we examine the adsorption of Mo to the pyrite precursors mackinawite and greigite and assess the robustness of this association during iron sulfide phase transformations. Tetrathiomolybdate (MoS42-) adsorption experiments were done using mackinawite and greigite that had been characterized using powder X-ray diffraction and Raman spectroscopy. Adsorption of tetrathiomolybdate to mackinawite and to a primarily greigite mixture was similar. Both showed little change to the mineral phase upon adsorption. Relative to previously published data on pyrite, there was a much greater amount of Mo adsorption and a different mode of adsorption. A mackinawite/greigite mixture was also synthesized through an alternative method that more closely mimicked environmental conditions with a brief in situ aging to form an initial phase of iron sulfide, likely highly disordered mackinawite, and the near-immediate addition of MoS42-. X-ray photoelectron spectroscopy results support the adsorption of tetrathiomolybdate and its concomitant reduction to Mo(IV). The Mo-adsorbed mackinawite/greigite mixture was transformed through heating into a greigite/pyrite mixture while monitoring Mo release to the aqueous phase. Here, the sorption of Mo on the solid phase promoted the transformation of mackinawite into pyrite upon heating without diagenetic loss of Mo to the aqueous phase. These results support the early capture of MoS42- to less-stable forms of iron sulfide with negligible diagenetic loss during subsequent transformation. This work continues to point to Mo(VI) as a plausible oxidant of FeS to FeS2 within natural euxinic settings.

Original languageEnglish (US)
Pages (from-to)2246-2260
Number of pages15
JournalACS Earth and Space Chemistry
Volume4
Issue number12
DOIs
StatePublished - Dec 17 2020

All Science Journal Classification (ASJC) codes

  • Geochemistry and Petrology
  • Atmospheric Science
  • Space and Planetary Science

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