Iron Bioremediation in Acidic Abandoned Coalmine Drainage Includes Nitrate Reduction Indirectly Oxidizing Iron
Poster for the Gordon Research Conference Applied and Environmental Microbiology, July 16-21 2023, South Hadley, MA.
Vietmeier, Anna↗
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Impact of zero valent iron aging on reductive removal of technetium-99
Zero valent iron (ZVI) is a promising material for reductive removal of technetium from industrial waste streams. An example application of this method could be to treatment of low activity aqueous waste that is currently stored in tanks at the Hanford site. However, there is still a lack of understanding of the useful lifetime of ZVI for treatment and the changes in reductive removal of Tc over time. In this research, we studied the reductive removal of Tc from aqueous solutions by ZVI aged with up to 30 days by contact with 0.08 M NaCl solutions. These results show that ZVI could be used to remove Tc(VII) from aqueous solutions by its reduction to the less soluble and relatively immobile Tc(IV) with greater than 99% removal in three hours. Still, greater than 90% of Tc is removed with ZVI aging up to one week. However, after 10 days of aging of zero valent iron, a significant decrease in removal of Tc occurs (55% removal at three hours) followed by negligible removal after aging for two weeks or more which is consistent with formation of iron oxides on the surface. Further, these results correlate with XRD and FTIR analysis showing an increase in magnetite followed by maghemite and goethite with aging time.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Formation of Zerovalent Iron in Iron-Reducing Cultures of Methanosarcina barkeri
Methanogenic archaea have been shown to reduce iron from ferric [Fe(III)] to ferrous [Fe(II)] state, but minerals that form during iron reduction by different methanogens remain to be characterized. Here, we show that zerovalent iron (ZVI) minerals, ferrite [α-Fe(0)] and austenite [γ-Fe(0)], appear in the X-ray diffraction spectra minutes after the addition of ferrihydrite to the cultures of a methanogenic archaeon, Methanosarcina barkeri (M. barkeri). M. barkeri cells and redox-active, nonenzymatic soluble organic compounds in organic-rich spent culture supernatants can promote the formation of ZVI; the latter compounds also likely stabilize ZVI. Methanogenic microbes that inhabit organic- and Fe(III)-rich anaerobic environments may similarly reduce Fe(III) to Fe(II) and ZVI, with implications for the preservation of paleomagnetic signals during sediment diagenesis and potential applications in the protection of iron metals against corrosion and in the green synthesis of ZVI.
54 ENVIRONMENTAL SCIENCES↗
New molecular components of high and low affinity iron import systems in Drosophila
The high abundance and molecular versatility of iron have led to its universal presence in biological systems, yet its absorption is exceptionally challenging. Animals and yeasts use divalent metal transporters to import iron, but yeasts also employ the multicopper oxidase Fet3p for high-affinity iron uptake when iron-starved. Using long-term iron depletion in Drosophila, we identified four components involved in iron absorption: Multicopper oxidase-4 (Mco4), a Fet3p ortholog, is essential for surviving iron starvation, whereas the cytochrome b561 enzymes Fire (Ferric Iron Reductase) and Fire-like, as well as cytochrome b5 protein Firewood, are required for iron absorption under normal conditions. This study reports the presence of a high-affinity iron uptake system in an animal, a cytochrome b5 electron donor for ferric iron reduction, and intestinal ferric reductases, and provides a valuable resource for further exploration of genes involved in iron homeostasis, transport, and absorption.
Iron↗
Reduction kinetics of hematite powder using argon/hydrogen plasma with prospects for near net shaping of sustainable iron
Direct reduction of iron ore using hydrogen plasma is being explored as a potential solution to decarbonize the iron and steel sector. The current state-of-the-art demonstrated reduction of hematite pellets via hydrogen plasma using Ar + 10% H 2 but had slow reduction kinetics, requiring 30 minutes of plasma exposure for complete reduction. Here we show that using hematite in a powder form, easily obtainable from beneficiated ore, results in 10× faster kinetics using plasma generated from Ar + 2% H 2 shielding gas compared to the current state-of-the art. Additionally, the increased kinetics using powders and a dilute hydrogen concentration can enable the use of advanced manufacturing techniques like blown powder directed energy deposition using a plasma tungsten arc welding torch to manufacture near net shape components directly from the ore concentrates. This ore to part approach will also reduce the emissions associated with downstream processes like rolling, forging, and machining, thereby further aiding in the sectorial decarbonization efforts.
36 MATERIALS SCIENCE↗
Microbial community dynamics and cycling of plutonium and iron in a seasonally stratified and radiologically contaminated pond
Plutonium (Pu) cycling and mobility in the environment can be impacted by the iron cycle and microbial community dynamics. We investigated the spatial and temporal changes of the microbiome in an iron (Fe)-rich, plutonium-contaminated, monomictic reservoir (Pond B, Savannah River Site, South Carolina, USA). The microbial community composition varied with depth during seasonal thermal stratification and was strongly correlated with redox. During stratification, Fe(II) oxidizers (e.g., Ferrovum, Rhodoferax, Chlorobium) were most abundant in the hypoxic/anoxic zones, while Fe(III) reducers (e.g., Geothrix, Geobacter) dominated the deep, anoxic zone. Sulfate reducers and methanogens were present in the anoxic layer, likely contributing to iron and plutonium cycling. Multinomial regression of predicted functions/pathways identified metabolisms highly associated with stratification (within the top 5%), including iron reduction, methanogenesis, C1 compound utilization, fermentation, and aromatic compound degradation. Two sediment cores collected at the Inlet and Outlet of the pond were dominated by putative fermenters and organic matter (OM) degraders. Overall, microbiome analyses revealed the potential for three microbial impacts on the plutonium and iron biogeochemical cycles: (1) plutonium bioaccumulation throughout the water column, (2) Pu–Fe-OM-aggregate formation by Fe(II) oxidizers under microaerophilic/aerobic conditions, and (3) Pu–Fe-OM-aggregate or sediment reductive dissolution and organic matter degradation in the deep, anoxic waters.
54 ENVIRONMENTAL SCIENCES↗
Anaerobic methane oxidation coupled to manganese reduction by members of the Methanoperedenaceae
Abstract Anaerobic oxidation of methane (AOM) is a major biological process that reduces global methane emission to the atmosphere. Anaerobic methanotrophic archaea (ANME) mediate this process through the coupling of methane oxidation to different electron acceptors, or in concert with a syntrophic bacterial partner. Recently, ANME belonging to the archaeal family Methanoperedenaceae (formerly known as ANME-2d) were shown to be capable of AOM coupled to nitrate and iron reduction. Here, a freshwater sediment bioreactor fed with methane and Mn(IV) oxides (birnessite) resulted in a microbial community dominated by two novel members of the Methanoperedenaceae, with biochemical profiling of the system demonstrating Mn(IV)-dependent AOM. Genomic and transcriptomic analyses revealed the expression of key genes involved in methane oxidation and several shared multiheme c-type cytochromes (MHCs) that were differentially expressed, indicating the likely use of different extracellular electron transfer pathways. We propose the names “Candidatus Methanoperedens manganicus” and “Candidatus Methanoperedens manganireducens” for the two newly described Methanoperedenaceae species. This study demonstrates the ability of members of the Methanoperedenaceae to couple AOM to the reduction of Mn(IV) oxides, which suggests their potential role in linking methane and manganese cycling in the environment.
54 ENVIRONMENTAL SCIENCES↗
Dispersion of sulfur creates a valuable new growth medium formulation that enables earlier sulfur oxidation in relation to iron oxidation in Acidithiobacillus ferrooxidans cultures
Abstract Acidithiobacillus ferrooxidans is an acidophilic chemolithoautotroph that is commonly reported to exhibit diauxic population growth behavior where ferrous iron is oxidized before elemental sulfur when both are available, despite the higher energy content of sulfur. We have discovered sulfur dispersion formulations that enables sulfur oxidation before ferrous iron oxidation. The oxidation of dispersed sulfur can lower the culture pH within days below the range where aerobic ferrous iron oxidation can occur. Thus, ferric iron reduction can be observed quickly which had previously been reported over extended incubation periods with untreated sulfur. Therefore, we demonstrate that this substrate utilization pattern is strongly dependent on the cell loading in relation to sulfur concentration, sulfur surface hydrophobicity, and the pH of the culture. Our dispersed sulfur formulation, lig‐sulfur, can be used to support the rapid antibiotic selection of plasmid‐transformed cells, which is not possible in liquid cultures where ferrous iron is the main source of energy for these acidophiles. Furthermore, we find that media containing lig‐sulfur supports higher production of green fluorescent protein compared to media containing ferrous iron. The use of dispersed sulfur is a valuable new tool for the development of engineered A. ferrooxidans strains and it provides a new method to control iron and sulfur oxidation behaviors.
Inaba, Yuta↗
Exploring the kinetics of actinyl–EDTA reduction by ferrous iron using quantum-mechanical calculations
Here, the reduction of An(VI) (An = U, Np, and Pu) to An(IV) significantly decreases its solubility and mobility. This reaction can be hindered by complexation with inorganic (e.g., carbonate) or organic ligands. Ethylenediaminetetraacetic acid (EDTA) is one such organic ligand that forms stable complexes with actinides. Therefore, it may enhance the mobility of actinides. However, the redox kinetics and mechanisms of actinyl (An(V/VI)O 2 +/2+ )–EDTA are not well characterized yet and are thus studied here using quantum-mechanical calculations. The principle is to approach the actinyl–EDTA and Fe 2+ (reductant) in small incremental steps and calculate the system energy at each distance. The overall reaction is then delineated into sub-processes (encounter frequency in bulk solution, formation of outer-sphere complex, transition from outer- to inner-sphere complex, and electron transfer), and reaction rates are determined for each sub-process. The formation of outer-sphere complexes occurs rapidly in microseconds to seconds over a wide range of actinyl concentrations (pM to μM); in contrast, the transition to the inner-sphere complex is relatively slow (milliseconds to a few seconds). Immediate electron transfer to form the pentavalent actinide is observed along the reaction path for Np(VI) and Pu(VI), but not for U(VI). Surprisingly, in acidic conditions, one of the carboxylic groups gets protonated in EDTA of [UO 2 (edta)] 2- rather than one of the amino groups. This process-based series of calculations can be applied to any redox reaction and allows the prediction of changes to the rate law and rate-limiting step in a more fundamental way for different environments
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Interactions between molecular-scale biogeochemical processes and hyporheic exchange for understanding coupled Fe-S-C cycling in iron-rich riparian wetlands (Final Technical Report)
Riparian wetlands are dynamic interfaces that exert strong control over water quality, contaminant mobility, and greenhouse gas emissions. These systems are characterized by hyporheic exchange between oxic surface water and anoxic groundwater, which generates steep redox gradients and promotes spatially and temporally variable microbial activity. Despite growing recognition of tightly coupled iron (Fe), sulfur (S), and carbon (C) cycling in these environments, the mechanisms governing these interactions—particularly under low-sulfate freshwater conditions—remain poorly constrained. This project developed a mechanistic understanding of how hydrologic variability and microbial processes interact to control Fe–S–C cycling in iron-rich riparian wetlands. Using a multi-scale and multi-method approach integrating field observations, geochemical and spectroscopic analyses, metagenomics, and reactive transport modeling, we demonstrate that “cryptic” sulfur cycling—rapid sulfur transformations involving intermediate-valence species—plays a dominant and previously underrecognized role in freshwater wetlands. These processes persist despite low sulfate concentrations and significantly influence iron reduction, carbon mineralization, and methane dynamics. The results show that cryptic sulfur cycling enhances dissolved Fe 2+ production, regulates methane concentrations, and is strongly controlled by climate-driven hydrologic fluxes. By linking hydroclimate, subsurface flow, and biogeochemical reactions, this work provides a predictive framework for understanding how wetland systems respond to environmental change, with direct implications for water quality and carbon cycling.
54 ENVIRONMENTAL SCIENCES↗
Novel Remediation of Mercury-Contaminated Sediments Using Manganese Oxide and Activated Carbon Amendments - 20394
Mercury contamination in sediments poses a challenging remediation problem because of its ability to biogeochemically cycle and biomagnify in the food chain as methylmercury from low resident sediment and porewater concentrations. One mitigation approach is to lower the overall rate of net methylmercury production by creating conditions unfavorable for sulfate and iron reduction or methanogenesis, the primary pathways for methylation of inorganic mercury. Manganese oxides and other redox-active amendments are a promising and novel in situ amendment technology aimed at reducing net methylation of mercury though control of redox conditions in mercury-contaminated sediment-water systems. This paper reviews the thermodynamic and kinetic framework for this remediation technology, presents experimental and spectroscopic data illustrating the approach using solid manganese oxides, and discusses potential advantages, disadvantages, and applications. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Redox Mechanisms and Migration Tendencies in Earth-Abundant 0.7Li 2 MnO 3 ·0.3LiFeO 2 Cathodes: Coupling Spin-Resolved X-ray Absorption Near Edge and X-ray Absorption Fine Structure Spectroscopies
We report the use of iron 1s3p resonant X-ray emission processes to conduct spin-selective, high-energy resolution fluorescence detected X-ray absorption near-edge spectroscopy (HERFD-XANES) on an iron-containing, lithium- and manganese-rich, fully earth-abundant cathode material, Li 1.3 Mn 0.5 Fe 0.2 O 2 (0.7Li 2 MnO 3 ·0.3LiFeO 2 ). Coupling this technique with conventional Mn K-edge XANES and detailed extended X-ray absorption fine structure (EXAFS) analysis from both the Mn and Fe vantage points, we gain fundamental insights into the redox processes and migration tendencies of transition metals in this cathode material at the bulk level. We show that during the first charge, Fe 3+ undergoes oxidation to form Fe 4+ prior to the activation plateau. Toward the end of activation, a significant fraction of the iron is present as tetrahedral Fe 3+ . This observation reveals that iron migration from octahedral to tetrahedral sites and iron reduction are initiated during activation. Upon first discharge from the activated state, a continuous and overlapping reduction of both Fe and Mn is observed, with Fe largely restored back as an octahedrally coordinated Fe 3+ . The manganese local environment gradually changes to a distorted cooperative Jahn–Teller Mn 3+ structure during discharge, with the clear presence of two Mn–O as well as two Mn–Mn correlation distances at 2.0 V. The significant reduction of manganese in the very first discharge is distinctly different from that seen in typical nickel-based lithium-manganese-rich materials but is similar to that observed for pure Li 2 MnO 3 . In conclusion, these findings shed light on key structure–property correlations in the cathode material and point to a causative relationship between the redox mechanisms as well as structural changes endured by the material and relatively poor performance during extended electrochemical cycling.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
High-Resolution XFEL Structure of the Soluble Methane Monooxygenase Hydroxylase Complex with its Regulatory Component at Ambient Temperature in Two Oxidation States
Soluble methane monooxygenase (sMMO) is a multicomponent metalloenzyme that catalyzes the conversion of methane to methanol at ambient temperature using a nonheme, oxygen-bridged dinuclear iron cluster in the active site. Structural changes in the hydroxylase component (sMMOH) containing the diiron cluster caused by complex formation with a regulatory component (MMOB) and by iron reduction are important for the regulation of O 2 activation and substrate hydroxylation. Structural studies of metalloenzymes using traditional synchrotron-based X-ray crystallography are often complicated by partial X-ray-induced photoreduction of the metal center, thereby obviating determination of the structure of the enzyme in pure oxidation states. Here, microcrystals of the sMMOH:MMOB complex from Methylosinus trichosporium OB3b were serially exposed to X-ray free electron laser (XFEL) pulses, where the ≤35 fs duration of exposure of an individual crystal yields diffraction data before photoreduction-induced structural changes can manifest. Merging diffraction patterns obtained from thousands of crystals generates radiation damage-free, 1.95 Å resolution crystal structures for the fully oxidized and fully reduced states of the sMMOH:MMOB complex for the first time. The results provide new insight into the manner by which the diiron cluster and the active site environment are reorganized by the regulatory protein component in order to enhance the steps of oxygen activation and methane oxidation. Furthermore, this study also emphasizes the value of XFEL and serial femtosecond crystallography (SFX) methods for investigating the structures of metalloenzymes with radiation sensitive metal active sites.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Iron XANES measurements of carbonates and phyllosilicates in CM chondrites: A record of redox conditions during aqueous alteration
Multiple generations of calcite and dolomite precipitated in CM chondrites during ice melting events that led to episodes of liquid water. Models and laboratory analysis have suggested a long-term transition from oxidizing to reducing conditions during aqueous alteration on the CM parent body. We found that synchrotron X-ray absorption near edge spectroscopy (XANES) can detect relative differences in the oxidation state of trace iron within these carbonates. In CM chondrites, previous work interpreted Mn abundance in calcite as an indicator of relatively early or late formation, and dolomite is understood to form relatively late. In the CM1 chondrite Meteorite Hills 01070, XANES maps reveal that Mn-poor calcite contains more oxidized iron relative to Mn-rich calcite. While these measurements of carbonates support increasing iron reduction with progressive aqueous alteration in MET 01070, comparison among different CM chondrites suggests a complex picture of redox evolution. In addition to carbonates, we performed XANES measurements of the phyllosilicate-rich matrix of Allan Hills 83,100. Pre-edge centroid analysis indicates that this CM1/2 has an oxidation state similar to typical CM2 chondrites. While additional measurements are warranted to confirm the full span of redox trends in CM carbonates, our data do not support a correlation between redox state and petrologic type.
Bailey, Elizabeth [Univ. of California, Santa Cruz↗
Stability of a Ni/NiF 2 Reference Electrode with a Metallic Membrane for Use in Molten Fluoride Salts
In this study, an experimental high-temperature fluoride salt reference electrode (RE) developed by HiFunda LLC was tested in molten FLiNaK at 550 °C. The high-temperature reference electrode (HTRE), based on the Ni/NiF 2 redox couple, was tested over a period of 13 d for short-term stability, long-term stability, and electrochemical analysis capabilities. The HTRE was tested using open circuit potentiometry (OCP), cyclic voltammetry (CV), square wave voltammetry (SWV), and electrochemical impedance spectroscopy (EIS). The HTRE reference potential was measured against changes in salt composition by increasing FeF 2 concentrations in the melt across six additions from 0 to 0.1 mol% FeF 2 . The long-term stability of the electrode was then tested over ten days at a constant composition of 0.1 mol% FeF 2 . OCP, SWV, and CV were used to calculate an average potential drift between 7–10 mV per day. Using CV and SWV, the number of electrons transferred for iron reduction and the diffusion coefficient of Fe 2+ were measured.
Electrochemistry↗
Safety Review of the Hydrogen Components of a Reference Design of the Wind-H2-Green Steel/Ammonia Project
The Department of Energy Hydrogen Fuel Cell Technology Office and Wind Energy Technologies Office’s Wind-H2-Green Steel/Ammonia project is an initiative to demonstrate the feasibility and efficacy of GW-scale integrated energy systems. The team designed reference facilities that utilize wind- and solar-produced hydrogen for industrial steel and ammonia production. This novel concept warranted review of safety codes and standards as they apply to the designs and the identification of codes and standards as they apply to the designs and the identification of codes and standards gaps. This report reviews hydrogen production and storage codes and standards using reference design specifications from a Minnesota steel plant. Requirements, recommendations, and exclusions for the system were identified. Observed gaps included non-specific salt cavern storage requirements, electrolyzer capacity beyond regulated ranges, and lack of requirements for iron reduction via hydrogen. This report will aide future project design efforts and may provide a basis for safety reviews in new designs for industrial facilities with hydrogen production integration.
08 HYDROGEN↗
Safety Review of the Hydrogen Components of a Reference Design of the Wind-H2-Green Steel/Ammonia Project
The Department of Energy Hydrogen Fuel Cell Technology Office and Wind Energy Technologies Office's Wind-H2-Green Steel/Ammonia project is an initiative to demonstrate the feasibility and efficacy of GW-scale integrated energy systems. The team designed reference facilities that utilize wind- and solar-produced hydrogen for industrial steel and ammonia production. This novel concept warranted review of safety codes and standards as they apply to the designs and the identification of codes and standards gaps. This report reviews hydrogen production and storage codes and standards using reference design specifications from a Minnesota steel plant. Requirements, recommendations, and exclusions for the system were identified. Observed gaps included non-specific salt cavern storage requirements, electrolyzer capacity beyond regulated ranges, and lack of requirements for iron reduction via hydrogen. This report will aide future project design efforts and may provide a basis for safety reviews in new designs for industrial facilities with hydrogen production integration.
08 HYDROGEN↗
Small molecule dye for molecular imaging and photothermal therapy
Disclosed is a small molecule dye for use in imaging in the near-infrared window, namely between 1000 nm-1700 nm wavelength. The present dyes are also useful for photoacoustic imaging and photothermal therapy. The dyes have a structure of a D-A-D (donor-acceptor-donor) fluorescent compound core and side chains rendering the compounds water soluble and easily conjugated to hydrophilic polymers and/or targeting ligands. Further disclosed is compound, CH1055 that can be PEGylated, conjugated to a targeting ligand, or conjugated to taurine. Key steps utilized to assemble the core structure of the target included a cross-Suzuki coupling reaction, iron reduction and N-thionylaniline induced ring closure. Four carboxylic acid groups were introduced into the donor-acceptor-donor (D-A-D) type fluorescent compound to impart a certain aqueous solubility and to allow facile conjugation to targeting ligands.
Cheng, Zhen↗