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Continuous time-resolved X-ray diffraction of the biocatalyzed reduction of Mn oxide

¹ Department of Geosciences, Pennsylvania State University, University Park, Pennsylvania 16802, U.S.A.
² Penn State Institutes of Energy and the Environment, Pennsylvania State University, University Park, Pennsylvania 16802, U.S.A.
³ Department of Biochemistry and Molecular Biology, Pennsylvania State University, University Park, Pennsylvania 16802, U.S.A.
⁴ Department of Mineral Sciences, Smithsonian Institution, Washington, D.C. 20013, U.S.A.

Correspondence: ^* E-mail: tfischer{at}geosc.psu.edu

Here we report the first continuous time-resolved X-ray diffraction analysis of a biologically mediated mineral reaction. We incubated total membrane (TM) fractions of the facultative anaerobe Shewanella oneidensis in an anoxic environmental reaction cell with formate (as electron donor via formate dehydrogenase) and powdered birnessite, a layered Mn^3+,4+ oxide common to many soils. Using both synchrotron and conventional X-ray sources, we irradiated the reaction mixtures for up to two weeks and observed bioreduction and dissolution of birnessite and the concomitant precipitation of rhodochrosite [Mn²⁺CO₃] and hausmannite [Mn²⁺Mn₂³⁺O₄]. The high time resolution of these experiments documented systematic changes in crystal structure during the breakdown of birnessite and the emergence of nanocarystalline rhodochrosite. In addition, the relative abundances of birnessite and rhodochrosite were quantified over time for different concentrations of TM fraction, allowing for the determination of rate equations that govern this bioreaction. Importantly, constant irradiation for two weeks did not stop the enzymatic reaction, suggesting that enzymes may be more resilient than whole cells when exposed to X-ray radiation.

Key Words: Mn oxide • biological-mineral interactions • time-resolved XRD • birnessite • rhodochrosite • hausmannite