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Repartitioning of co-precipitated Mo(VI) during Fe(II) and S(-II) driven ferrihydrite transformation

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dc.contributor.authorSchoepfer, Valerie
dc.contributor.authorLindsay, Matthew B. J.
dc.date.accessioned2022-10-26T16:46:09Z
dc.date.available2022-10-26T16:46:09Z
dc.date.issued2022-08-29
dc.descriptionCopyright © 2022 Elsevier B.V. All rights reserved.en_US
dc.description.abstractMolybdenum is an essential element for most biological systems. Biosynthesis of Mo-enzymes that support global biogeochemical cycles of N, C, and S depends upon bioavailable molybdate (MoO42−). Interactions with Fe(III) (oxyhydr)oxides can limit Mo bioavailability in aerobic environments, while redox-driven mineral transformations can enhance Mo sequestration. Here, we examine Mo repartitioning during Fe(II) and S(-II) driven ferrihydrite transformation under anaerobic conditions. We reacted Mo(VI) co-precipitated 2-line ferrihydrite with Fe(II)(aq) or S( II)(aq) and monitored geochemical and mineralogical changes over time. Inductively coupled plasma–mass spectrometry (ICP–MS) and synchrotron powder X-ray diffraction (XRD) results revealed rapid Fe(II)(aq) and S(-II)(aq) uptake and limited Mo release during extensive ferrihydrite transformation to goethite [α-FeOOH] and lepidocrocite [γ-FeOOH] in the Fe(II) and S( II) experiments. Transmission electron microscopy–selected area electron diffraction (TEM-SAED), coupled with Mo LIII-edge and K-edge X-ray absorption near edge structure (XANES) spectroscopy, revealed partial Mo(VI) reduction and precipitation of kamiokite [Fe2MoIV3O8] and sidwillite [MoVIO3‧2H2O] in both experiments. Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Mo K-edge revealed Mo-O, Mo-Fe and Mo-Mo bonding consistent with kamiokite precipitation in both Fe(II) and S(-II) experiments, and the absence of Mo-S bonding in the S(-II) experiments. Similar Mo(VI) repartitioning pathways during Fe(II) and S( II) driven ferrihydrite transformation suggests that: (i) Fe(II) served as the electron donor for ferrihydrite transformation in both experiments, with Fe(II)(aq) likely produced in situ via ferrihydrite sulfidation in the S( II) experiments; and (ii) co-precipitation inhibited Mo release and limited subsequent interactions S(-II)(aq) during ferrihydrite transformation. Overall, our findings indicate that initial association with FeOx phases can strongly influence Mo sequestration pathways in anaerobic environments.en_US
dc.description.sponsorshipFunding was provided by the Natural Sciences and Engineering Research Council of Canada (NSERC) through a Discovery Grant (Grant No. RGPIN-2020-05172) held by MBJL. VAS is a Fellow in the NSERC CREATE to INSPIRE program. A portion of the research described in this paper was performed at the Canadian Light Source, which is supported by the Canada Foundation for Innovation, NSERC, the University of Saskatchewan, the Government of Saskatchewan, Western Economic Diversification Canada, the National Research Council Canada, and the Canadian Institutes of Health Research.en_US
dc.description.versionPeer Revieweden_US
dc.identifier.citationSchoepfer, V.A, & Lindsay, M.B.J. (2022). Repartitioning of co-precipitated Mo(VI) during Fe(II) and S(-II) driven ferrihydrite transformation. Chemical Geology, 610. https://doi.org/10.1016/j.chemgeo.2022.121075en_US
dc.identifier.doi10.1016/j.chemgeo.2022.121075
dc.identifier.urihttps://hdl.handle.net/10388/14273
dc.language.isoenen_US
dc.publisherElsevieren_US
dc.rightsAttribution-NonCommercial-NoDerivs 2.5 Canada*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/2.5/ca/*
dc.subjectMo(VI) reductionen_US
dc.subjectferrihydriteen_US
dc.subjectsidwilliteen_US
dc.subjectkamiokiteen_US
dc.subjectferruginousen_US
dc.subjectsulfidicen_US
dc.titleRepartitioning of co-precipitated Mo(VI) during Fe(II) and S(-II) driven ferrihydrite transformationen_US
dc.typeArticleen_US

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