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Minerals
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Redox Reactivity of Iron Minerals in the Geosphere, 2nd Edition
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Redox Reactivity of Iron Minerals in the Geosphere, 2nd Edition

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Environmental Mineralogy and Biogeochemistry".

Deadline for manuscript submissions: 20 April 2025 | Viewed by 2924

Special Issue Editors

Dr. Edward J. O'Loughlin

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Guest Editor
Biogeochemical Processes Group, Biosciences Division, Argonne National Laboratory, Building 203, Room E-137, 9700 South Cass Avenue, Argonne, IL 60439, USA
Interests: biogeochemistry; geomicrobiology; geochemistry; biomineralization; microbial transformations of minerals
Special Issues, Collections and Topics in MDPI journals
Dr. Lucie Stetten

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Guest Editor
Biogeochemical Processes Group, Biosciences Division, Argonne National Laboratory, Building 203, Room E-113, 9700 South Cass Avenue, Argonne, IL 60439, USA
Interests: biogeochemistry; mineralogy; nutrients and contaminants fate; chemical speciation; X-ray spectroscopy
Dr. Maxim I. Boyanov

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Guest Editor
Institute of Chemical Engineering, Bulgarian Academy of Sciences, Sofia 1103, Bulgaria
Interests: synchrotron X-ray methods; redox transformations; contaminant transport; complexation mechanisms; surface processes; nanoprecipitation

Special Issue Information

Dear Colleagues,

Iron is a highly abundant element in the lithosphere, and Fe oxides, Fe-bearing phyllosilicate minerals, Fe sulfides, and other Fe-bearing minerals are common constituents of soils and sediments. As such, redox-active Fe-bearing minerals are key players in electron transfer reactions involved in the biogeochemical cycling of elements and the transformation of organic and inorganic contaminants in both natural and engineered redox dynamic environments.

We invite contributions relatking to, but not limited to, laboratory and field studies of the transformations of Fe-bearing minerals via abiotic and microbially-driven redox reactions; the coupling of redox reactions of Fe-bearing minerals with the biogeochemical cycling of critical elements (e.g., N, P, and S); and the impacts of Fe redox reactions on contaminant transformation, fate, and transport in aquatic and terrestrial environments. We especially encourage multidisciplinary studies that use cutting-edge approaches such as advanced imaging and spectroscopic techniques, isotopic analysis, and omics-based molecular microbiology.

Dr. Edward J. O'Loughlin
Dr. Lucie Stetten
Dr. Maxim I. Boyanov
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Minerals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • biomineralization
  • iron oxides
  • iron sulfides
  • transformation
  • contaminants
  • mineralization

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Related Special Issue

Published Papers (3 papers)

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Research

12 pages, 1105 KiB  
Article
Cyanide Storage on Ferroan Brucite (MgxFe1−x(OH)2): Implications for Prebiotic Chemistry
by Ellie K. Hara and Alexis S. Templeton
Minerals 2025, 15(2), 141; https://doi.org/10.3390/min15020141 - 31 Jan 2025
Viewed by 386
Abstract
Cyanide is a crucial reagent for the synthesis of biomolecules in prebiotic chemistry. However, effective organic synthesis requires cyanide to be concentrated. One proposed mechanism for cyanide storage and concentration on Early Earth involves the formation of aqueous ferrocyanide complexes. In basic pH [...] Read more.
Cyanide is a crucial reagent for the synthesis of biomolecules in prebiotic chemistry. However, effective organic synthesis requires cyanide to be concentrated. One proposed mechanism for cyanide storage and concentration on Early Earth involves the formation of aqueous ferrocyanide complexes. In basic pH conditions, cyanide will spontaneously form ferrocyanide complexes in the presence of aqueous Fe(II). While ferrocyanide aqueous complex formation is well defined, the potential for Fe(II)-bearing minerals to react with cyanide to form ferrocyanide complexes or store cyanide on the mineral surface has yet to be explored under prebiotically relevant conditions. In this study, we demonstrate that when cyanide interacts with ferroan brucite (MgxFe1−x(OH)2), cyanide will both form aqueous and mineral-surface-adsorbed ferrocyanide implying that there are two reservoirs that cyanide will partition into. In addition, we found that cyanide decreased the amount of hydrogen gas produced by the oxidation of ferroan brucite, indicating that cyanide alters the mineral’s redox reactivity. The cyanide adsorbed on brucite can be released by a decrease in pH, which leads to the dissolution of ferroan brucite, thus releasing the adsorbed cyanide. Our findings suggest that iron-bearing minerals may represent an overlooked storage reservoir of cyanide on Hadean Earth, potentially playing a significant role in cyanide availability for prebiotic chemistry. Full article
(This article belongs to the Special Issue Redox Reactivity of Iron Minerals in the Geosphere, 2nd Edition)
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14 pages, 4423 KiB  
Article
Effect of CO2 Concentration on the Microbial Activity of Orenia metallireducens (Strain Z6) in Surface Inert Materials
by Shuyi Li, Wentao Song, Juan Liu, Maxim I. Boyanov, Edward J. O’Loughlin, Kenneth M. Kemner, Robert A. Sanford, Hongbo Shao, Qi Feng, Yu He, Yiran Dong and Liang Shi
Minerals 2025, 15(2), 112; https://doi.org/10.3390/min15020112 - 24 Jan 2025
Viewed by 340
Abstract
Carbon dioxide (CO2) sequestration has garnered widespread attention as a key strategy for mitigating CO2 emissions and combating the greenhouse effect. However, the mechanisms underlying the interactions between CO2, widespread siliceous minerals and biological processes remain unclear. The [...] Read more.
Carbon dioxide (CO2) sequestration has garnered widespread attention as a key strategy for mitigating CO2 emissions and combating the greenhouse effect. However, the mechanisms underlying the interactions between CO2, widespread siliceous minerals and biological processes remain unclear. The present study explored the potential impacts of different CO2 concentrations on microbial activity, environmental conditions and their feedback on the fate of CO2. A total of 20 experimental conditions was created, with the variables including different natural and synthetic siliceous minerals (e.g., quartz sand and a type of commercial glass beads), the presence or absence of the iron-reducing microorganism Orenia metallireducens (strain Z6) and varying CO2 concentrations (0%, 20%, 50%, 100%) in the presence of ferrihydrite and pyruvate. Geochemical, microbial and mineralogical analyses revealed that elevated CO2 concentrations significantly inhibited microbial Fe(III) reduction and pyruvate metabolism. Interestingly, compared to cultures without mineral amendments or those with glass beads alone, the addition of quartz sand enabled strain Z6 to better withstand the environmental stress caused by elevated CO2, promoting pyruvate fermentation and iron reduction. In addition to an increased pH, the formation of siderite, hematite and vivianite was also observed in the bioactive systems. Although both glass beads and quartz sand were primarily composed of silica, differences in the mineral structure, elemental composition and acid neutralization capacity rendered quartz sand more chemically active and unexpectedly led to greater CO2 sequestration. Full article
(This article belongs to the Special Issue Redox Reactivity of Iron Minerals in the Geosphere, 2nd Edition)
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15 pages, 2827 KiB  
Article
Interactions of Perrhenate (Re(VII)O4−) with Fe(II)-Bearing Minerals
by Anthony W. N. Kilber, Maxim I. Boyanov, Kenneth M. Kemner and Edward J. O’Loughlin
Minerals 2024, 14(2), 181; https://doi.org/10.3390/min14020181 - 7 Feb 2024
Cited by 3 | Viewed by 1560
Abstract
Rhenium (Re) is an extremely rare element, with a crustal abundance of approximately 0.4 parts per billion (ppb) and a sea water concentration of 8.3 parts per trillion (ppt). However, Re concentrations in anoxic marine sediments range from 2 to 184 ppb, which [...] Read more.
Rhenium (Re) is an extremely rare element, with a crustal abundance of approximately 0.4 parts per billion (ppb) and a sea water concentration of 8.3 parts per trillion (ppt). However, Re concentrations in anoxic marine sediments range from 2 to 184 ppb, which is attributed to reduction of the highly soluble perrhenate ion (Re(VII)O4−) to insoluble Re(IV) species. Anoxic sediments typically contain Fe(II) and sulfide species, which could potentially reduce Re(VII) to Re(IV). In this study, we examined the interactions of KReO4 with magnetite (Fe3O4), siderite (FeCO3), vivianite (Fe3(PO4)2•8H2O), green rust (mixed Fe(II)/Fe(III) layered double hydroxide), mackinawite (FeS), and chemically reduced nontronite (NAu-1) using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy to determine the valence state and speciation of Re. Uptake of Re by green rust was rapid, with ~50% associated with the solids within 2 days. In contrast, there was <10% uptake by the other Fe(II) phases over 48 days. Reduction of Re(VII) to Re(IV) was only observed in the presence of green rust, producing clusters of bidentate-coordinated Re(IV)O6 octahedra.. These results suggest that except for green rust, the potential for other Fe(II)-bearing minerals to act as reductants for ReO4− in sedimentary environments requires further investigation. Full article
(This article belongs to the Special Issue Redox Reactivity of Iron Minerals in the Geosphere, 2nd Edition)
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