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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Zam Is a Redox-Regulated Member of the RNB-Family Required for Optimal Photosynthesis in Cyanobacteria

The zam gene mediating resistance to acetazolamide in cyanobacteria was discovered thirty years ago during a drug tolerance screen. We use phylogenetics to show that Zam proteins are distributed across cyanobacteria and that they form their own unique clade of the ribonuclease II/R (RNB) family. Despite being RNB family members, multiple sequence alignments reveal that Zam proteins lack conservation and exhibit extreme degeneracy in the canonical active site—raising questions about their cellular function(s). Several known phenotypes arise from the deletion of zam, including drug resistance, slower growth, and altered pigmentation. Using room-temperature and low-temperature fluorescence and absorption spectroscopy, we show that deletion of zam results in decreased phycocyanin synthesis rates, altered PSI:PSII ratios, and an increase in coupling between the phycobilisome and PSII. Conserved cysteines within Zam are identified and assayed for function using in vitro and in vivo methods. We show that these cysteines are essential for Zam function, with mutation of either residue to serine causing phenotypes identical to the deletion of Zam. Redox regulation of Zam activity based on the reversible oxidation-reduction of a disulfide bond involving these cysteine residues could provide a mechanism to integrate the ‘central dogma’ with photosynthesis in cyanobacteria.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Visualizing energy transfer between redox-active colloids

Redox-active colloids (RACs) represent a novel class of energy carriers that exchange electrical energy upon contact. Understanding contact-mediated electron transfer dynamics in RACs offers insights into physical contact events in colloidal suspensions and enables quantification of electrical energy transport in nonconjugated polymers. Redox-based electron transport was directly observed in monolayers of micron-sized RACs containing ethyl-viologen side groups via fluorescence microscopy through an unexpected nonlinear electrofluorochromism that is quantitatively coupled to the redox state of the colloid. Via imaging studies, using this electrofluorochromism, the apparent charge transfer diffusion coefficient D CT of the RAC was easily determined. The visualization of energy transport within suspensions of redox-active colloids was also demonstrated. Our work elucidates fundamental mechanisms of energy transport in colloidal systems, informs the development of next-generation redox flow batteries, and may inspire new designs of smart active soft matter including conductive polymers for applications ranging from electrochemical sensors and organic electronics to colloidal robotics.

Qu, Alan Subing [Univ. of Illinois at Urbana-Champ↗
DOE OSTI2025

High-resolution X-ray structure of Gln143Asn manganese superoxide dismutase captures multiple hydrogen peroxide-binding sites

Human mitochondrial manganese superoxide dismutase (MnSOD) converts superoxide into hydrogen peroxide and molecular oxygen, serving as a key defence against oxidative damage. Despite extensive studies, the full structural characterization of H 2 O 2 -binding sites in MnSOD remains largely unexplored. Previous H 2 O 2 -soaked MnSOD structures have identified two distinct H 2 O 2 -binding sites: one directly ligated to the catalytic manganese (LIG position) and another at the active-site gateway (PEO position) between the second-shell residues Tyr34 and His30. In this study, a kinetically impaired Gln143Asn MnSOD variant is used to trap and explore additional H 2 O 2 -binding sites beyond the second-shell solvent gate. In the wild-type enzyme, Gln143 mediates proton transfers with the manganese-bound solvent (WAT1) to drive redox cycling of the metal, which is necessary for effective superoxide dismutation. Substitution with Asn stalls catalysis because the increased distance from WAT1 disrupts critical proton-coupled electron-transfer (PCET) events, and the redox cycling of the active-site metal is impaired. This, in turn, stalls the electrostatic cycling of positive charge on the enzyme surface and enhances the likelihood of trapping transient H 2 O 2 -bound states in this variant. The results reveal several H 2 O 2 molecules leading up to the active site, in addition to the canonical LIG and PEO positions.

Dasgupta, Medhanjali [University of Nebraska Medic↗
DOE OSTI2024

Nuclear Fuel and Pu Redox Studies from The Glenn T. Seaborg Institute at Idaho National Laboratory

The Glenn T. Seaborg Institute at Idaho National Laboratory (INL-GTSI) focuses on advancing fundamental research in the actinide sciences by providing unique opportunities to early career scientists and engineers to gain experience studying the actinide elements and their associated systems. The INL-GTSI is built from three focus areas that are based on the expertise and supporting infrastructure at INL and include solid state chemistry and physics, solution phase chemistry and physics, and forensic and isotope science. INL is the lead Laboratory for nuclear energy research and development in the U. S. and the research on nuclear fuels performed under the INL-GTSI gives good examples of solid state studies. Uranium-Molybdenum (U-Mo) alloys are leading fuel candidates for conversion of high performance research and test reactors to low-enriched fuels. During irradiation, generated fission gas accumulates into bubbles and self-organizes into a gas bubble superlattice (GBS) that effectively stores fission gases and inhibits fuel swelling. A study on the early self- organizing behavior of the GBS shows that not only grain boundaries but the interfaces between the U-Mo matrix and uranium carbide (UC) impurities are important to GBS formation.[1] In solution, understanding the complex redox behavior of plutonium in aqueous environments is critical for establishing optimized nuclear waste reprocessing solvent systems and storage tank environments. INL-GTSI researchers have produced an experimentally validated multi-scale model of the gamma radiation induced behavior of plutonium ions in concentrated aqueous HNO3 solutions.[2] Here, gamma radiation effected only minimal steady state changes in the redox distribution of the plutonium oxidation states. The redox cycling between Pu(IV) and Pu(III) is demonstrated to be mediated by the •OH/NO3• radical oxidation of Pu(III) and the H2O2/HNO3 driven reduction of Pu(IV). The INL-GTSI offers young researchers the unique chance to work directly with actinide bearing materials in a U. S. National Laboratory environment. Further topical areas of interest to the INL-GTSI include, but are not limited to, fundamental actinide properties, structure/property (electronic, magnetic, thermal) relations, actinide quantum criticality, f- electron interactions, electron correlations, computational studies, new phases, defect effects, interface interactions, isotope production and separation, forensic analytical chemistry, structure and dynamic properties of actinides in non-aqueous media, separations chemistry and kinetics for advanced nuclear fuel cycles, radiation effects, and innovative and advanced ligand design for complexation of the actinides.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

A Carborane-Derived Proton-Coupled Electron Transfer Reagent

Reagents capable of concerted proton–electron transfer (CPET) reactions can access reaction pathways with lower reaction barriers compared to stepwise pathways involving electron transfer (ET) and proton transfer (PT). To realize reductive multielectron/proton transformations involving CPET, one approach that has shown recent promise involves coupling a cobaltocene ET site with a protonated arylamine Brønsted acid PT site. This strategy colocalizes the electron/proton in a matter compatible with a CPET step and net reductive electrocatalysis. To probe the generality of such an approach a class of C,C'-diaryl-ocarboranes is herein explored as a conceptual substitute for the cobaltocene subunit, with an arylamine linkage still serving as a colocalized Brønsted base suitable for protonation. The featured ocarborane (PhCbPh N ) can be reduced and protonated to generate an N–H bond with a weak effective bond dissociation free energy (BDFE eff ) of 31 kcal/mol, estimated with measured thermodynamic data. This N–H bond is among the lowest measured element–H bonds for analyzed nonmetal compounds. Distinct solid-state crystal structures of the one- and two-electron reduced forms of diaryl-o-carboranes are disclosed to gain insight into their well-behaved redox characteristics. The singly reduced, protonated form of the diaryl-o-carborane can mediate multi-ET/PT reductions of azoarenes, diphenylfumarate, and nitrotoluene. In contrast to the aforementioned cobaltocene system, available mechanistic data disclosed herein support these reactions occurring by a rate-limiting ET step and not a CPET step. A relevant hydrogen evolution reaction (HER) reaction was also studied, with data pointing to a PT/ ET/PT mechanism, where the reduced carborane core is itself highly stable to protonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Characterizing Electron Flow through Catechol‐Graphene Composite Hydrogels

Abstract Electronic materials that allow the controlled flow of electrons in aqueous media are required for emerging applications that require biocompatibility, safety, and/or sustainability. Here, a composite hydrogel film composed of graphene and catechol is electrofabricated, and that this composite offers synergistic properties is reported. Graphene confers metal‐like conductivity and enables charge‐storage through an electrical double layer mechanism. Catechol confers redox‐activity and enables charge‐storage through a redox mechanism. Importantly, there are two functional populations of catechols: conducting‐catechols (presumably in intimate contact with graphene) allow direct electron‐transfer; and non‐conducting‐catechols (presumably physically separated from graphene) require diffusible mediators to enable electron‐transfer. Using a variety of spectroelectrochemical measurements, that the capacity of the composite for charge‐storage increases in proportion to the extent by which the catechol‐groups can undergo redox‐state switching is demonstrated. To illustrate the broad relevance of this work, how the redox‐state switching can be related to both the charge storage of energy materials and the memory of molecular electronic materials is discussed. The authors believe this work is significant because it demonstrates that: conducting and redox‐active components enable distinctly different mechanisms for charge‐storage and electron‐transfer; these components act synergistically; and mediators provide unique opportunities to extend the capabilities of electronic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Resin Assisted Capture Coupled with Isobaric Tandem Mass Tag Labeling for Multiplexed Quantification of Protein Thiol Oxidation

Reversible oxidative modifications on protein thiols have recently emerged as important mediators of cellular function. Herein we describe the detailed procedure of a quantitative redox proteomics method that utilizes resin-assisted capture (RAC) in combination with tandem mass tag (TMT) isobaric labeling and liquid chromatography-tandem mass spectrometry (LC-MS/MS) to allow multiplexed stochiometric quantification of oxidized protein thiols at the proteome level. The site-specific quantitative information on oxidized cysteine residues provides additional insight into the functional impacts of such modifications. The workflow is adaptable across many sample types including cultured cells (e.g. mammalian, prokaryotic) and whole tissues (e.g. heart, lung, muscle) which are initially lysed/homogenized with free thiols being alkylated to prevent artificial oxidation. The oxidized protein thiols are then reduced and captured by a thiol affinity resin which streamlines and simplifies the workflow steps by allowing the proceeding digestion, labeling, and washing procedures to be performed without additional transfer of proteins/peptides. Finally, labeled peptides are eluted and analyzed by LC-MS/MS to reveal comprehensive stoichiometric changes related to thiol oxidation across the entire proteome. This method greatly improves our understanding of the role of redox dependent regulation under physiological and pathophysiological states related to protein thiol oxidation.

RAC, TMT, thiol redox proteomics, cysteine, PTM st↗
DOE OSTI2025

The role of AdhE mutations in Thermoanaerobacterium saccharolyticum

ABSTRACT Thermoanaerobacterium saccharolyticum is a thermophilic anaerobic bacterium that natively ferments a variety of hemicellulose substrates to organic acids and alcohols. It has recently been engineered to produce ethanol at high yield and titer; however, it uses a unique metabolic pathway for ethanol production that is poorly characterized. One of the distinctive aspects of this pathway is the presence of acetyl-CoA as an intermediate metabolite. In this organism, acetyl-CoA is converted to ethanol by a bifunctional AdhE enzyme. This enzyme has been a frequent target for mutations, and in many cases, the function of these mutations was unknown. Using a combination of genetic modifications, enzyme assays, and computational analysis, we have developed a better understanding of how mutations in AdhE affect ethanol production in the engineered homoethanologen strain. We identify a set of approximately interchangeable AdhE mutations (G544D, T597K, T597I, and T605I), whose function is to disrupt the activity of the alcohol dehydrogenase (ADH) domain of AdhE. This reduces NADH-linked ADH activity, which dramatically increases ethanol tolerance and changes the overall stoichiometry of acetaldehyde to ethanol conversion. Furthermore, our improved understanding of the function of these AdhE mutations calls into question a proposed feature of AdhE enzymes known as substrate channeling—direct transfer of acetaldehyde between the two domains of the AdhE enzyme. This improved the understanding of the role of AdhE mutations in T. saccharolyticum and provides deeper insights into the function of the unique ethanol production pathway in this organism. IMPORTANCE Many anaerobic bacteria maintain redox equilibrium by producing reduced organic compounds such as ethanol. The final two steps of ethanol production are mediated by a bifunctional enzyme, AdhE, and this enzyme is a frequent target of mutations in strains engineered for increased ethanol production. Paradoxically, these mutations increase ethanol production by eliminating the activity of one domain of the AdhE enzyme (the ADH domain). This provides additional support for a redox-imbalance theory of alcohol tolerance, which challenges the prevailing hypothesis that alcohol tolerance is associated with cell membrane effects.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Redox enzyme-embedded pyrene-poly(ethylenimine) hydrogel electrode for electrosynthesis

Devices, systems, and compositions of matter involving enzyme-mediated bioelectrocatalysis are disclosed and described. An enzyme electrode can include an electrode, a bioelectric material coupled to the electrode, the bioelectric material further including a water-permeable polymer matrix, a planar linker covalently coupled to the water-permeable polymer matrix and noncovalently coupled to the electrode, and electrochemically active oxidoreductase enzyme molecules functionally embedded in the water-permeable polymer matrix.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Sulfide electrolyte additive enables multi-ionic transfer pathways in alkaline iron redox

Traditional alkaline iron (Fe) batteries rely on the conversion reaction between Fe and Fe(OH) 2 but suffer from hydrogen generation upon Fe formation on charging. Fe 2+ /Fe 3+ redox is a promising anode reaction for alkaline Fe batteries, as it alleviates the formation of hydrogen gas during charging. However, achieving complete Fe 2+ /Fe 3+ redox with a one-electron transfer reaction is challenging due to the formation of electrochemically inert Fe 3 O 4 materials. Here, we demonstrate that an alkaline sulfide-containing electrolyte facilitates the reversible multi-ion transfer and transport pathways within (and beyond) the Fe 2+ /Fe 3+ redox system, including Fe(OH) 2 /Fe 3 O 4 conversion, intercalation of hydrosulfide into layered Fe(OH) 2 , and hydrogen deposition, mediated by hydroxyl ions, hydrosulfide anions, and protons, respectively. This multi-ionic charge storage mechanism delivers a compelling discharge capacity of up to 330 mA h g −1 , as determined by chronopotentiometry measurements at a current density of 0.1 A g −1 , exceeding the theoretical iron redox capacity solely relying on Fe 2+ /Fe 3+ redox (∼299 mA h g −1 ). Our study will highlight the potential of alkaline iron redox as a green anode reaction for various aqueous energy storage systems by utilizing a scalable and low-concentration hydrosulfide electrolyte additive.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Supported Organochromium Ethylene Oligomerization Enabled by Surface Lithiation

Here, in this work, supported organochromium ethylene polymerization catalysts have been tuned to mediate ethylene oligomerization via surface lithiation, which provides a generalizable protocol to control stereoelectronics and redox states of surface organometallic active sites. The homoleptic chromium(IV) alkyl complex Cr(CH 2 SiMe 3 ) 4 was grafted on high-surface-area anatase titania (TiO 2 ) nanoparticles as well as on silica to produce Cr/TiO 2 and Cr/SiO 2 , respectively. Treatment of these materials with excess n-butyllithium led to the reduced chromium complexes Cr/Li x TiO 2 and Cr/Li/SiO 2 , each of which still retains one hydrocarbyl ligand on chromium. A set of heterogeneous complexes were studied by electron paramagnetic resonance and X-ray absorption spectroscopy, which indicate a reduction in the oxidation state of the major chromium species to Cr II upon lithiation. Cr/Li x TiO 2 converts ethylene to hexenes with a high selectivity (>80%), which was persistent over 10 days at 80 °C, achieving >950 turnovers. The exclusive formation of C 4 and C 6 olefins, preferring the trimerization product, without a statistical (Flory–Schulz) distribution is characteristic of the oxidative cyclization oligomerization mechanism rather than the traditional Cossee–Arlman mechanism, whereas Cr/Li/SiO 2 produced a mixture of trimerization and polymerization products, suggesting site heterogeneity in the silica-based material. On the other hand, the unreduced chromium(IV) materials as well as low lithium-containing Cr/Li x TiO 2 (x < 0.16) exclusively produced ultrahigh molecular weight polyethylene, determined by differential scanning calorimetry and gel permeation chromatography analysis, likely formed via a linear-insertion mechanism, with a crossover from the polymerization to oligomerization regime observed at ~16% Li intercalation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Tunable Conversion of Poly(Acrylic Acid) to Vinyl Methyl Ether Copolymers via Electrochemical Decarboxylation

Recognizing the potential of polymer-to-polymer transformations for plastics valorization, a new electrochemical strategy for the decarboxylative functionalization of polyacrylates has been developed. In contrast to most electrochemical approaches to plastic waste valorization that use small-molecule mediators or only form deconstruction products, this report describes one of the first direct electrochemical redox upconversions of a commodity polymer and involves activation of poly(acrylic acid), a material commonly found in disposable diapers and other personal hygiene products. Via electrochemical decarboxylation, poly(acrylic acid) is converted to methyl ether-containing copolymers. Although methods to prepare the 1:1 regularly alternating poly(vinyl methyl ether-alt-maleic anhydride) are known, routes to generate copolymers with variable levels of vinyl methyl ether and acrylate moieties are unknown, but such polymers may have utility in similar applications, such as dentifrices. Tunable conversions with up to 62 mol% vinyl methyl ether content were achieved via controlled-current electrolyses at >100 mA. This approach enables efficient access to copolymers with broad range of comonomer content from a common waste polymer starting material.

Dauzvardis, Fabian [University of Delaware, Newark↗
DOE OSTI2020

Nucleophilic Thiols Reductively Cleave Ether Linkages in Lignin Model Polymers and Lignin

Lignin may serve as a renewable feedstock for the production of chemicals and fuels if mild, scalable processes for its depolymerization can be devised. The use of small organic thiols represents a bioinspired strategy to cleave the β–O–4 bond, the most common linkage in lignin. In the present study, synthetic β–O–4 linked polymers were treated with organic thiols, yielding up to 90 % cleaved monomer products. Lignin extracted from poplar was also treated with organic thiols resulting in molecular weight reductions as high as 65 % (Mn) in oxidized lignin. Thiol–based cleavage of other lignin linkages was also explored in small–molecule model systems to uncover additional potential pathways by which thiols might depolymerize lignin. The success of thiol–mediated cleavage on model dimers, polymers, and biomass–derived lignin illustrates the potential utility of small redox–active molecules to penetrate complex polymer matrices for depolymerization and subsequent valorization of lignin into fuels and chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Single-Molecule Detection of the Encounter and Productive Electron Transfer Complexes of a Photosynthetic Reaction Center

Small, diffusible redox proteins play an essential role in electron transfer (ET) in respiration and photosynthesis, sustaining life on Earth by shuttling electrons between membrane-bound complexes via finely tuned and reversible interactions. Ensemble kinetic studies show transient ET complexes form in two distinct stages: an “encounter” complex largely mediated by electrostatic interactions, which subsequently, through subtle reorganization of the binding interface, forms a “productive” ET complex stabilized by additional hydrophobic interactions around the redox-active cofactors. Here, using single-molecule force spectroscopy (SMFS) we dissected the transient ET complexes formed between the photosynthetic reaction center-light harvesting complex 1 (RC-LH1) of Rhodobacter sphaeroides and its native electron donor cytochrome c 2 (cyt c 2 ). Importantly, SMFS resolves the distribution of interaction forces into low (~150 pN) and high (~330 pN) components, with the former more susceptible to salt concentration and to alteration of key charged residues on the RC. Thus, the low force component is suggested to reflect the contribution of electrostatic interactions in forming the initial encounter complex, whereas the high force component reflects the additional stabilization provided by hydrophobic interactions to the productive ET complex. Employing molecular dynamics simulations, we resolve five intermediate states that comprise the encounter, productive ET and leaving complexes, predicting a weak interaction between cyt c 2 and the LH1 ring near the RC-L subunit that could lie along the exit path for oxidized cyt c 2 . The multimodal nature of the interactions of ET complexes captured here may have wider implications for ET in all domains of life.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Effect of Intermediate Semiconducting TiOx Thin Films on Nanoparticle-Mediated Electron Transfer: Electrooxidation of CO

The concept of nanoparticle-mediated electron transfer (eT) across insulating thin films was elucidated theoretically by Allongue and Chazalviel in 2011. In their model, metal nanoparticles (NPs) are immobilized atop passivating, self-assembled monolayers (SAMs). They found that under certain conditions, related to the thickness of the SAM and the size of the NPs, efficient faradaic oxidation and reduction reactions could proceed at the NP surface. In the absence of NPs, however, eT was suppressed by the insulating SAM thin films. Allongue and Chazalviel concluded that, within certain bounds, eT is mediated by fast tunneling between the conductive electrode and the metal NPs, while the kinetics of the redox reaction are controlled by the NPs. This understanding has been confirmed using a variety of experimental models. The theory is based on electron tunneling; therefore, the nature of the intervening medium (the insulator in prior studies) should not affect the eT rate. In the present manuscript, however, we show that the theory breaks down under certain electrochemical conditions when the medium between conductors is an n-type semiconductor. Specifically, we find that in the presence of either Au or Pt NPs immobilized on a thin film of TiOx, CO electrooxidation does not proceed. In contrast, the exact same systems lead to the efficient reduction of oxygen. At present, we are unable to explain this finding within the context of the model of Allongue and Chazalviel.

Galyamova, Aigerim↗
DOE OSTI2022

Real-space measurement of orbital electron populations for Li 1-x CoO 2

The operation of lithium-ion batteries involves electron removal from and filling into the redox orbitals of cathode materials, experimentally probing the orbital electron population thus is highly desirable to resolve the redox processes and charge compensation mechanism. Here, we combine quantitative convergent-beam electron diffraction with high-energy synchrotron powder X-ray diffraction to quantify the orbital populations of Co and O in the archetypal cathode material LiCoO 2 . The results indicate that removing Li ions from LiCoO 2 decreases Co t 2g orbital population, and the intensified covalency of Co–O bond upon delithiation enables charge transfer from O 2p orbital to Co e g orbital, leading to increased Co e g orbital population and oxygen oxidation. Theoretical calculations verify these experimental findings, which not only provide an intuitive picture of the redox reaction process in real space, but also offer a guidance for designing high-capacity electrodes by mediating the covalency of the TM–O interactions.

25 ENERGY STORAGE↗
DOE OSTI2025

Cryptic cycling by electroactive bacterioplankton in Trout Bog Lake

The potential for extracellular electron transfer (EET) is a prevailing genomic feature of humic lake bacterioplankton. However, there has been little evidence for the substantial ecological contribution predicted by genetics. We hypothesized that anoxygenic phototrophic electrotrophs and accompanying heterotrophic electrogens cycle dissolved organic matter (DOM) between oxidized and reduced states. We predicted that such bacterioplankton would exhibit diel-scale oscillations due to the light dependency of photosynthesis. Using Trout Bog Lake in Wisconsin, USA, as our model ecosystem, we profiled the water column with depth-discrete metagenomic, physiochemical, and electrochemical analyses. We observed variation in oxidation reduction potential (ORP) in response to sunlight, initiating at depths populated by anoxygenic phototrophs with EET genes. We developed an automated buoy to measure electric current flow between many pairs of electrodes simultaneously, observing correlation in electron consumption to sunlight. Our results, combined with published metatranscriptomic analysis, indicate the occurrence of electron cycling between phototrophic oxidation (electrotrophic metabolism) by Chlorobium and anaerobic respiration (electrogenic metabolism) by Geothrix, involving DOM. We also repeatedly observed gradual seasonal increases in hypolimnion ORP throughout summer. These diel and seasonal patterns imply that electroactive DOM mediates the ecology of electroactive bacteria in lakes, controlling humic lake methane emissions.IMPORTANCEWe investigated the physical, chemical, and redox characteristics of a bog lake and electrodes hung therein to test the hypothesis that dissolved organic matter is being cycled between oxidized and reduced states by electroactive bacterioplankton powered by phototrophy. To do so, we performed field-based analyses on multiple timescales using both established and novel instrumentation. We paired these analyses with recently developed bioinformatics pipelines for metagenomics data to investigate genes that enable electroactive metabolism and accompanying metabolisms. Our results are consistent with our hypothesis and yet upend some of our other expectations. Our findings have implications for understanding greenhouse gas emissions from lakes, including electroactivity as an integral part of lake metabolism throughout more of the anoxic parts of lakes and for a longer portion of the summer than expected. Our results also give a sense of what electroactivity occurs at given depths and provide a strong basis for future studies.

carbon emissions↗