Influence of magnetite stoichiometry on U VI reduction

Drew E. Latta, Christopher A. Gorski, Maxim I. Boyanov, Edward J. O'Loughlin, Kenneth M. Kemner, Michelle M. Scherer

Research output: Contribution to journalArticlepeer-review

125 Scopus citations


Hexavalent uranium (U VI) can be reduced enzymatically by various microbes and abiotically by Fe 2+-bearing minerals, including magnetite, of interest because of its formation from Fe 3+ (oxy)hydroxides via dissimilatory iron reduction. Magnetite is also a corrosion product of iron metal in suboxic and anoxic conditions and is likely to form during corrosion of steel waste containers holding uranium-containing spent nuclear fuel. Previous work indicated discrepancies in the extent of U VI reduction by magnetite. Here, we demonstrate that the stoichiometry (the bulk Fe 2+/Fe 3+ ratio, x) of magnetite can, in part, explain the observed discrepancies. In our studies, magnetite stoichiometry significantly influenced the extent of U VI reduction by magnetite. Stoichiometric and partially oxidized magnetites with x ≥ 0.38 reduced U VI to U IV in UO 2 (uraninite) nanoparticles, whereas with more oxidized magnetites (x < 0.38) and maghemite (x = 0), sorbed U VI was the dominant phase observed. Furthermore, as with our chemically synthesized magnetites (x ≥ 0.38), nanoparticulate UO 2 was formed from reduction of U VI in a heat-killed suspension of biogenic magnetite (x = 0.43). X-ray absorption and Mössbauer spectroscopy results indicate that reduction of U VI to U IV is coupled to oxidation of Fe 2+ in magnetite. The addition of aqueous Fe 2+ to suspensions of oxidized magnetite resulted in reduction of U VI to UO 2, consistent with our previous finding that Fe 2+ taken up from solution increased the magnetite stoichiometry. Our results suggest that magnetite stoichiometry and the ability of aqueous Fe 2+ to recharge magnetite are important factors in reduction of U VI in the subsurface.

Original languageEnglish (US)
Pages (from-to)778-786
Number of pages9
JournalEnvironmental Science and Technology
Issue number2
StatePublished - Jan 17 2012

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Environmental Chemistry


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