Iron (Fe) minerals play a crucial role in biogeochemical cycles due to their ubiquity in nature, high adsorption capacity and redox activity towards many other elements. Mixed-valent Fe minerals are unique since they contain Fe(II) and Fe(III). For example, magnetite (Fe(II)Fe(III)2O4) nanoparticles (MNPs) can affect the availability and mobility of nutrients and contaminants. This is due to the high surface area to volume ratio and the presence of Fe(II) and Fe(III), allowing redox transformation of (in‑)organic contaminants. Recent studies have shown that magnetite can serve as an electron source and sink for Fe(II)-oxidizing and Fe(III)-reducing microorganisms, storing and releasing electrons; thus, it functions as a biogeobattery. However, the ability of MNPs to act as biogeobatteries over consecutive redox cycles and the consequences for mineral integrity and identity remain unknown. Here, we show MNPs working as biogeobatteries in two consecutive redox cycles over 41 days. MNPs were first oxidized by the autotrophic nitrate-reducing Fe(II)-oxidizing culture KS and subsequently reduced by the Fe(III)-reducing Geobacter sulfurreducens. In addition to reduced magnetite, we identified the Fe(II) mineral vivianite after reductions, suggesting partial reductive dissolution of MNPs and re-crystallization of Fe2+ with phosphate from the growth medium. Measurements of the Fe(II)/Fe(III) ratio revealed microbial oxidation and reduction for both the first redox cycle (oxidation: 0.29±0.014, reduction: 0.75±0.023) and the second redox cycle (oxidation: 0.30±0.015, reduction: 1.64±0.10). Relative changes in magnetic susceptibility (∆κ in %) revealed greater changes for the second oxidation (–8.7±1.99%) than the first (–3.9±0.19%) but more minor changes for the second reduction (+14.29±0.39%) compared to the first (+25.42±1.31%). Our results suggest that MNPs served as biogeobatteries but became less stable over time, which has significant consequences for associated contaminants, nutrients and bioavailability for Fe-metabolizing microorganisms.

Cretaceous bentonites were collected in outcrop from the Sweetgrass Arch and the Disturbed Belt in Montana. The mixed-layer illite-smectite (I/S) components of the bentonites from the Sweetgrass Arch have from 0 to 25% illite layers and no detectable structurai Fe2+, whereas the samples from the Disturbed Belt have from about 25 to 90% illite layers, and all contain Fe2+. A positive correlation (r = 0.89) exists between the percentage of structural iron that is Fe2+ and the amount of fixed interlayer K in the I/S.

The higher percentage of illite layers in the samples from the Disturbed Belt is attributed to reactions related to elevated temperatures caused by burial beneath thrust sheets. The increase in Fe2+/Fe3+ with increasing percentages of illite layers is tentatively attributed to a redox reaction involving the oxidation of organic matter. Although there is no statistical evidence for an increase in octahedral charge with an increase in illite layers when all the samples are considered together, iron reduction may have contributed as much as 10 to 30% of the increase in total structural charge that occurred in any given sample during metamorphism. The remaining structural charge increase can be attributed to the substitution of Al3+ for Si4+ in the tetrahedral sites.

The uniformity of clay films affects the transport of an anionic electroactive probe through the film. When cations other than Na+ are present in the initial swelling of the film (such as native K+ and Ca2+), or when the native clay is highly charged, internal dislocations of the film, caused by variable stacking domains, enhance the diffusive transport of Fe(CN)63− across the film. This effect is investigated using clay-modified electrodes in which the clays are of variable exchange forms (Na+, Ca2+, or K+) and variable charge. The charge on the clay is determined both by the native form of the clay and by reduction of structural Fe3+. The results suggest that swelling of clays increases in a linear fashion with CEC, at least for minimally charged clays.

A model to compensate the 2:1 layer having excess negative charge owing to the reduction of Fe3+ to Fe2+ by sodium dithionite buffered with citrate-bicarbonate in nontronite, beidellite, and montmorillonite is proposed. This model is based on reassessing published experimental data for Fe-containing smectites and on a recently published structural model for reduced Garfield nontronite. In the reduced state, Fe2+ cations remain six-fold coordinated, and increases of negative charge in the 2:1 layer are compensated by the sorption of Na+ and H+ from solution. Some of the incorporated protons react with structural OH groups to cause dehydroxylation. Also, some protons bond with undersaturated oxygen atoms of the octahedral sheet. The amount of Na+ (p) and H+ (ni) cations incorporated in the structure as a function of the amount of Fe reduction can be described quantitatively by two equations: p = m/(1 + K0mrel) and ni = K0mrel/(1 + K0mrel); with K0 = CEC (9.32 − 1.06mtot + 0.02mtot2), where mtot is the total Fe content in the smectite, m is the Fe2+ content, mrel is the reduction level (m/mtot), CEC is the cation-exchange capacity, and K0 is a constant specific to the smectite. The model can predict, from the chemical composition of a smectite, the modifications of its properties as a function of reduction level. Based on this model, the structural mechanism of Fe3+ reduction in montmorillonite differs from that determined in nontronite and beidellite owing to differences in the distribution of cations over trans- and cis-octahedral sites.

The presence of nitrate and other redox-active anionic contaminants in terrestrial ecosystems poses a significant risk to humans and other forms of life on Earth. The purpose of the present study was to test a potential in situ system, using poly-(D) glucosamine (chitosan) adsorbed to mineral surfaces under redox-active conditions in order to degrade nitrate to lower oxidation states. Chitosan is a linear polysaccharide derived from the chitin found in the shells of shrimp and other shellfish. Five different loadings of chitosan (0, 0.075, 0.25, 0.50, and 1.0 g/L; labeled C0, C1, C2, C3, and C4, respectively) were adsorbed to ferruginous smectite (SWa-1) to form chitosan-SWa-1 composites (CSC) in the pH range 5.8–4. The CSC was then reduced by Na2S2O4 in a citrate-bicarbonate buffered dispersion and washed free of excess salts under inert-atmosphere conditions. Upon addition of the nitrate, the solution pH remained slightly acidic, ranging from 5.5 to 4.7. Samples were analyzed for Fe(II) content, reacted with a NaNO3 solution, and then re-analyzed for structural Fe(II) content. Supernatant solutions were analyzed for nitrate, nitrite, and ammonium. In samples C1 to C4, extensive concentrations of nitrite were observed in the supernatants with a corresponding increase in the reoxidation of structural Fe(II), proving that a coupled redox reaction had occurred between the nitrate and the structural Fe in the clay mineral. The most efficient loading, defined as the largest percentage of adsorbed nitrate reduced to nitrite, occurred in sample C1. The total amount of nitrate reduced and Fe(II) reoxidized followed the trend 0 = C0 < C2 < C3 < C4 ≈ C1. Chitosan showed the potential to reverse the surface charge of constituent clay minerals, thereby enabling the CSC to remove nitrate anions from aqueous mineral systems via redox reactions with structural Fe(II) in clay minerals.

Recent studies postulated the viability of a suite of metabolic pathways in Enceladus’ ocean motivated by the detection of H2 and CO2 in the plumes – evidence for available free energy for methanogenesis driven by hydrothermal activity at the moon's seafloor. However, these have not yet been explored in detail. Here, a range of experiments were performed to investigate whether microbial iron reduction could be a viable metabolic pathway in the ocean by iron-reducing bacteria such as Geobacter sulfurreducens. This study has three main outcomes: (i) the successful reduction of a number of crystalline Fe(III)-bearing minerals predicted to be present at Enceladus was shown to take place to differing extents using acetate as an electron donor; (ii) substantial bacterial growth in a simulated Enceladus ocean medium was demonstrated using acetate and H2(g) separately as electron donors; (iii) microbial iron reduction of ferrihydrite was shown to partially occur at pH 9, the currently accepted value for Enceladus’ ocean, whilst being severely hindered at the ambient ocean temperature of 0°. This study proposes the possibilities for biogeochemical iron cycling in Enceladus’ ocean, suggesting that a strain of iron-reducing bacteria can effectively function under Enceladus-like conditions.