Mechanisms of Fe(II)-Catalyzed Transformation of Fe(III)-(Oxyhydr)oxides
EMSL Project ID
49381
Abstract
Interaction of aqueous Fe(II) with major Fe(III)-oxides and oxyhydroxides yields the enigmatic catalytically reactive "sorbed Fe(II)" species and apparent facile recrystallization of even the most stable forms of these minerals. Such phenomena exemplify a broad category of poorly understood redox-active mineral/fluid interfaces where fundamental understanding remains limited, despite far-reaching implications for interpreting redox geochemistry in most subsurface and aquatic environments. This subtask has established a working model of recrystallization: Fe(II) adsorbs to and transfers electrons across the interface yielding lattice Fe(III) addition, coupled by electron conduction to remote Fe(III) reduction and Fe(II) release elsewhere from the lattice. However, the model is challenged by unfavorable energetics and kinetics of Fe(II)/Fe(III) interfacial electron transfer, limitations in linking macroscopic isotopic tracer observations to microscopic processes, and the fact that the recrystallization process has never been observed in situ. We propose multiscale research on Fe(II)-catalyzed transformations of goethite, hematite, and ferrihydrite, using Fe/O isotope-resolved tomographic mapping of recrystallization fronts in individual crystallites, liquid cell TEM of particle recrystallization in situ, and advanced molecular simulation of up to whole particle recrystallization incorporating the collective electron and atom exchange dynamics. We will unveil the important elementary steps, the operative length scales for conduction-based recrystallization, and relationships between interfacial electron transfer, surface structure, and mineral semiconducting properties. The long-term vision is to translate insights to other redox autocatalytic mineral/fluid interfacial systems.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2016-10-01
End Date
2018-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Collins RN, and KM Rosso. 2017. "Mechanisms and Rates of U(VI) Reduction by Fe(II) in Homogeneous Aqueous Solution and the Role of U(V) Disproportionation." Journal of Physical Chemistry A 121(35):6603-6613. doi:10.1021/acs.jpca.7b05965
Huang X., X. Hou, X. Zhang, K.M. Rosso, and L. Zhang. 2018. "Facet-Dependent Contaminant Removal Properties of Hematite Nanocrystals and Their Environmental Implications." Environmental Science Nano 5, no. 8:1790-1806. PNNL-SA-132769. doi:10.1039/c8en00548f
Klyukin K., K.M. Rosso, and V.Y. Alexandrov. 2018. "Iron Dissolution from Goethite (alpha-FeOOH) Surfaces in Water by Ab Initio Enhanced Free-Energy Simulations." Journal of Physical Chemistry C. PNNL-SA-138228. [Unpublished]
Liu J ,Pearce C I,Shi L ,Wang Z ,Shi Z ,Arenholz E ,Rosso K M 2016. "Particle size effect and the mechanism of hematite reduction by the outer membrane cytochrome OmcA of Shewanella oneidensis MR-1" Geochimica et Cosmochimica Acta 193():160-175. 10.1016/j.gca.2016.08.022
McBriarty ME, GF von Rudorff, J Stubbs, P Eng, J Blumberger, and KM Rosso. 2017. "Dynamic stabilization of metal oxide-water interfaces." Journal of the American Chemical Society 139(7):2581-2584. doi:10.1021/jacs.6b13096
McBriarty ME, J Stubbs, P Eng, and KM Rosso. 2018. "Potential-specific structure at the hematite-electrolyte interface." Advanced Functional Materials 28(8):Article No. 1705618. doi:10.1002/adfm.201705618
Probing size-dependent electrokinetics of hematite aggregates
Qafoku O, CI Pearce, A Neumann, L Kovarik, M Zhu, ES Ilton, ME Bowden, CT Resch, BW Arey, E Arenholz, AR Felmy, and KM Rosso. 2017. "Tc(VII) and Cr(VI) Interaction with a Naturally Reduced Ferruginous Smectite from the Redox Transition Zone." Environmental Science & Technology 51(16):9042-9052. doi:10.1021/acs.est.7b02191
Stoerzinger KA, CI Pearce, TC Droubay, V Shutthanandan, A Shavorskiy, H Bluhm, and KM Rosso. 2017. "Impact of Ti Incorporation on Hydroxylation and Wetting of Fe3O4." Journal of Physical Chemistry C 121(35):19288-19295. doi:10.1021/acs.jpcc.7b06258
Taylor SD, J Liu, BW Arey, DK Schreiber, DE Perea, and KM Rosso. 2018. "Resolving Iron(II) Sorption and Oxidative Growth on Hematite (001) Using Atom Probe Tomography." Journal of Physical Chemistry C 122(7):3903-3914. doi:10.1021/acs.jpcc.7b11989
Taylor S.D., J. Liu, X. Zhang, B.W. Arey, L. Kovarik, D.K. Schreiber, and D.E. Perea, et al. 2019. "Visualizing the iron atom exchange front in the Fe(II)-catalyzed recrystallization of goethite by atom probe tomography." Proceedings of the National Academy of Sciences (PNAS). 116, no. 8:2866-2874. PNNL-SA-138345. doi:10.1073/pnas.1816620116
Zarzycki PP, and KM Rosso. 2017. "Stochastic Simulation of Isotopic Exchange Mechanisms for Fe(II)-Catalyzed Recrystallization of Goethite." Environmental Science & Technology 51(13):7552–7559. doi:10.1021/acs.est.7b01491
Zarzycki P.P., and K.M. Rosso. 2018. "Surface Charge Effects on Fe(II) Sorption and Oxidation at (110) Goethite Surfaces." Journal of Physical Chemistry C 122, no. 18:10059-10066. PNNL-SA-136329. doi:10.1021/acs.jpcc.8b02099