Photoelectron-promoted metabolism of sulphate-reducing microorganisms in substrate-depleted environments.

Sulphate-reducing microorganisms, or SRMs, are crucial to organic decomposition, the sulphur cycle, and the formation of pyrite. Despite their low energy-yielding metabolism and intense competition with other microorganisms, their ability to thrive in natural habitats often lacking sufficient substrates remains an enigma. This study delves into how Desulfovibrio desulfuricans G20, a representative SRM, utilizes photoelectrons from extracellular sphalerite (ZnS), a semiconducting mineral that often coexists with SRMs, for its metabolism and energy production. Batch experiments with sphalerite reveal that the initial rate and extent of sulphate reduction by G20 increased by 3.6 and 3.2 times respectively under light conditions compared to darkness, when lactate was not added. Analyses of microbial photoelectrochemical, transcriptomic, and metabolomic data suggest that in the absence of lactate, G20 extracts photoelectrons from extracellular sphalerite through cytochromes, nanowires, and electron shuttles. Genes encoding movement and biofilm formation are upregulated, suggesting that G20 might sense redox potential gradients and migrate towards sphalerite to acquire photoelectrons. This process enhances the intracellular electron transfer activity, sulphur metabolism, and ATP production of G20, which becomes dominant under conditions of carbon starvation and extends cell viability in such environments. This mechanism could be a vital strategy for SRMs to survive in energy-limited environments and contribute to sulphur cycling.

Enhanced Rock Weathering as a Source of Metals to Promote Methanogenesis and Counteract CO2 Sequestration.

Enhanced weathering of (ultra)mafic rocks has been proposed as a promising approach to sequester atmospheric CO2 and mitigate climate change. However, these silicate rocks contain varying amounts of trace metals, which are essential cofactors of metallaenzymes in methanogens. We found that weathering of crushed peridotite and basalt significantly promoted the growth and methanogenesis of a model methanogen─Methanosarcina acetivorans C2A under the condition of excess substrate. The released trace metals from peridotite and basalt, especially Fe, Ni, and Co, accounted for the promotion effect. Observation at different spatial scales showed a close association between the rocks and cells. Proteomic analysis revealed that rock amendment significantly enhanced the expression of core metalloenzymes in the methylotrophic methanogenesis pathway. Our study uncovers a previously unrecognized but important negative effect of enhanced rock weathering on methane production, which may counteract the carbon sequestration effort.

Oxidation of Biogenic U(IV) in the Presence of Bioreduced Clay Minerals and Organic Ligands.

Bioreduction of soluble U(VI) to sparingly soluble U(IV) is proposed as an effective approach to remediating uranium contamination. However, the stability of biogenic U(IV) in natural environments remains unclear. We conducted U(IV) reoxidation experiments following U(VI) bioreduction in the presence of ubiquitous clay minerals and organic ligands. Bioreduced Fe-rich nontronite (rNAu-2) and Fe-poor montmorillonite (rSWy-2) enhanced U(IV) oxidation through shuttling electrons between oxygen and U(IV). Ethylenediaminetetraacetic acid (EDTA), citrate, and siderophore desferrioxamine B (DFOB) promoted U(IV) oxidation via complexation with U(IV). In the presence of both rNAu-2 and EDTA, the rate of U(IV) oxidation was between those in the presence of rNAu-2 and EDTA, due to a clay/ligand-induced change of U(IV) speciation. However, the rate of U(IV) oxidation in other combinations of reduced clay and ligands was higher than their individual ones because both promoted U(IV) oxidation. Unexpectedly, the copresence of rNAu-2/rSWy-2 and DFOB inhibited U(IV) oxidation, possibly due to (1) blockage of the electron transport pathway by DFOB, (2) inability of DFOB-complexed Fe(III) to oxidize U(IV), and (3) stability of the U(IV)-DFOB complex in the clay interlayers. These findings provide novel insights into the stability of U(IV) in the environment and have important implications for the remediation of uranium contamination.

An Ancient Respiratory System in the Widespread Sedimentary Archaea Thermoprofundales.

Thermoprofundales, formerly Marine Benthic Group D (MBG-D), is a ubiquitous archaeal lineage found in sedimentary environments worldwide. However, its taxonomic classification, metabolic pathways, and evolutionary history are largely unexplored because of its uncultivability and limited number of sequenced genomes. In this study, phylogenomic analysis and average amino acid identity values of a collection of 146 Thermoprofundales genomes revealed five Thermoprofundales subgroups (A-E) with distinct habitat preferences. Most of the microorganisms from Subgroups B and D were thermophiles inhabiting hydrothermal vents and hot spring sediments, whereas those from Subgroup E were adapted to surface environments where sunlight is available. H2 production may be featured in Thermoprofundales as evidenced by a gene cluster encoding the ancient membrane-bound hydrogenase (MBH) complex. Interestingly, a unique structure separating the MBH gene cluster into two modular units was observed exclusively in the genomes of Subgroup E, which included a peripheral arm encoding the [NiFe] hydrogenase domain and a membrane arm encoding the Na+/H+ antiporter domain. These two modular structures were confirmed to function independently by detecting the H2-evolving activity in vitro and salt tolerance to 0.2 M NaCl in vivo, respectively. The peripheral arm of Subgroup E resembles the proposed common ancestral respiratory complex of modern respiratory systems, which plays a key role in the early evolution of life. In addition, molecular dating analysis revealed that Thermoprofundales is an early emerging archaeal lineage among the extant MBH-containing microorganisms, indicating new insights into the evolution of this ubiquitous archaea lineage.

Effects of Organic Ligands on the Antibacterial Activity of Reduced Iron-Containing Clay Minerals: Higher Extracellular Hydroxyl Radical Production Yet Lower Bactericidal Activity.

Reduced iron-containing clay (RIC) minerals have been documented to exhibit antibacterial activity through a synergistic action of extracellular membrane attack and intracellular oxidation of cellular components. However, the relative importance between extracellular and intracellular processes has remained elusive. Here, metal-chelating organic ligands (lactate, oxalate, citrate, and ethylene diaminetetraacetic acid (EDTA)) were amended to the bactericidal assays such that the importance of the two processes could be evaluated. Reduced nontronite (rNAu-2) was used as a model clay mineral to produce extracellular hydroxyl radical (•OH) upon oxygenation. The presence of Fe-chelating ligands increased •OH yield by 3-5 times. Consequently, bacterial cell membrane attack was enhanced, yet the antibacterial activity of RIC diminished. Additional experiments revealed that the ligands inhibited soluble metal ions from adsorption onto the bacterial cell membrane and/or penetration into the cytoplasm. Consequently, intracellular Fe concentration for the ligand-treated group was nearly 2 orders of magnitude lower than that for no-ligand control, which greatly decreased intracellular accumulation of reactive oxygen species (ROS) and increased cell survival. These results highlight that destruction of intracellular contents (proteins and DNA) is more important than oxidative degradation of membrane lipids and cell envelope proteins in causing bacterial cell death by RIC.

Vanadate Bio-Detoxification Driven by Pyrrhotite with Secondary Mineral Formation.

Vanadium(V) is a redox-sensitive heavy-metal contaminant whose environmental mobility is strongly influenced by pyrrhotite, a widely distributed iron sulfide mineral. However, relatively little is known about microbially mediated vanadate [V(V)] reduction characteristics driven by pyrrhotite and concomitant mineral dynamics in this process. This study demonstrated efficient V(V) bioreduction during 210 d of operation, with a lifespan about 10 times longer than abiotic control, especially in a stable period when the V(V) removal efficiency reached 44.1 ± 13.8%. Pyrrhotite oxidation coupled to V(V) reduction could be achieved by an enriched single autotroph (e.g., Thiobacillus and Thermomonas) independently. Autotrophs (e.g., Sulfurifustis) gained energy from pyrrhotite oxidation to synthesize organic intermediates, which were utilized by the heterotrophic V(V) reducing bacteria such as Anaerolinea, Bacillus, and Pseudomonas to sustain V(V) reduction. V(V) was reduced to insoluble tetravalent V, while pyrrhotite oxidation mainly produced Fe(III) and SO42-. Secondary minerals including mackinawite (FeS) and greigite (Fe3S4) were produced synchronously, resulting from further transformations of Fe(III) and SO42- by sulfate reducing bacteria (e.g., Desulfatiglans) and magnetotactic bacteria (e.g., Nitrospira). This study provides new insights into the biogeochemical behavior of V under pyrrhotite effects and reveals the previously overlooked mineralogical dynamics in V(V) reduction bioprocesses driven by Fe(II)-bearing minerals.

Mineral-Bound Trace Metals as Cofactors for Anaerobic Biological Nitrogen Fixation.

Nitrogenase is the only known biological enzyme capable of reducing N2 to bioavailable NH3. Most nitrogenases use Mo as a metallocofactor, while alternative cofactors V and Fe are also viable. Both geological and bioinformatic evidence suggest an ancient origin of Mo-based nitrogenase in the Archean, despite the low concentration of dissolved Mo in the Archean oceans. This apparent paradox would be resolvable if mineral-bound Mo were bioavailable for nitrogen fixation by ancient diazotrophs. In this study, the bioavailability of mineral-bound Mo, V, and Fe was determined by incubating an obligately anaerobic diazotroph Clostridium kluyveri with Mo-, V-, and Fe-bearing minerals (molybdenite, cavansite, and ferrihydrite, respectively) and basalt under diazotrophic conditions. The results showed that C. kluyveri utilized mineral-associated metals to express nitrogenase genes and fix nitrogen, as measured by the reverse transcription quantitative polymerase chain reaction and acetylene reduction assay, respectively. C. kluyveri secreted chelating molecules to extract metals from the minerals. As a result of microbial weathering, mineral surface chemistry significantly changed, likely due to surface coating by microbial exudates for metal extraction. These results provide important support for the ancient origin of Mo-based nitrogenase, with profound implications for coevolution of the biosphere and geosphere.

Inhibition of Extracellular Enzyme Activity by Reactive Oxygen Species upon Oxygenation of Reduced Iron-Bearing Minerals.

The dual roles of minerals in inhibiting and prolonging extracellular enzyme activity in soils and sediments are governed by enzyme adsorption to mineral surfaces. Oxygenation of mineral-bound Fe(II) generates reactive oxygen species (ROS), yet it is unknown whether and how this process alters the activity and functional lifespan of extracellular enzymes. Here, the effect of mineral-bound Fe(II) oxidation on the hydrolytic activity of a cellulose-degrading enzyme ß-glucosidase (BG) was studied using two pre-reduced Fe-bearing clay minerals (nontronite and montmorillonite) and one pre-reduced iron oxide (magnetite) at pH 5 and 7. Under anoxic conditions, BG adsorption to mineral surfaces decreased its activity but prolonged its lifespan. Under oxic conditions, ROS was produced, with the amount of •OH, the most abundant ROS, being positively correlated with the extent of structural Fe(II) oxidation in reduced minerals. •OH decreased BG activity and shortened its lifespan via conformational change and structural decomposition of BG. These results suggest that under oxic conditions, the ROS-induced inhibitory role of Fe(II)-bearing minerals outweighed their adsorption-induced protective role in controlling enzyme activity. These results disclose a previously unknown mechanism of extracellular enzyme inactivation, which have pivotal implications for predicting the active enzyme pool in redox-oscillating environments.

Enhanced Oxidation of Cr(III)-Fe(III) Hydroxides by Oxygen in Dark and Alkaline Environments: Roles of Fe/Cr Ratio and Siderophore.

The current understanding of Cr(III)-Fe(III) hydroxide (Cr1-xFex(OH)3) oxidation in the dark is primarily focused on strong oxidants, yet the role of oxygen has generally been overlooked. Meanwhile, the effects of organic ligands on the Cr(III) oxidation are poorly known. Herein, we determined the kinetics of Cr1-xFex(OH)3 oxidation by oxygen in the dark as a function of pH and Fe/Cr ratio with/without the presence of a representative organic ligand-siderophore. Results showed that the Cr(III) oxidation rate increased linearly with increasing pH and Fe/Cr ratio. Thermodynamic calculations suggested that the enhanced Cr1-xFex(OH)3 oxidation with increasing pH was primarily due to the decreased ΔG value (i.e., the Gibbs free energy change) at higher pH. The decreased redox potentials (Eh) of Cr1-xFex(OH)3 suspensions with increasing Fe/Cr ratio accounted for the enhanced Cr(III) oxidation of iron-rich Cr1-xFex(OH)3. The siderophore greatly accelerated the Cr1-xFex(OH)3 oxidation at alkaline pH by promoting the formation of soluble organically complexed Cr(III), which can be oxidized readily by oxygen via mineral-surface catalyzed oxidation. Overall, this study highlights the specific role of oxygen and its synergistic role with the siderophore in the oxidation of solid Cr1-xFex(OH)3, which should be taken into consideration in assessing the long-term stability of Cr(III)-Fe(III) hydroxides.

Promotion of Humic Acid Transformation by Abiotic and Biotic Fe Redox Cycling in Nontronite.

The redox activity of Fe-bearing minerals is coupled with the transformation of organic matter (OM) in redox dynamic environments, but the underlying mechanism remains unclear. In this work, a Fe redox cycling experiment of nontronite (NAu-2), an Fe-rich smectite, was performed via combined abiotic and biotic methods, and the accompanying transformation of humic acid (HA) as a representative OM was investigated. Chemical reduction and subsequent abiotic reoxidation of NAu-2 produced abundant hydroxyl radicals (thereafter termed as ·OH) that effectively transformed the chemical and molecular composition of HA. More importantly, transformed HA served as a more premium electron donor/carbon source to couple with subsequent biological reduction of Fe(III) in reoxidized NAu-2 by Geobacter sulfurreducens, a model Fe-reducing bacterium. Destruction of aromatic structures and formation of carboxylates were mechanisms responsible for transforming HA into an energetically more bioavailable substrate. Relative to unaltered HA, transformed HA increased the extent of the bioreduction by 105%, and Fe(III) reduction was coupled with oxidation and even mineralization of transformed HA, resulting in bleached HA and formation of microbial products and cell debris. ·OH transformation slightly decreased the electron shuttling capacity of HA in bioreduction. Our results provide a mechanistic explanation for rapid OM mineralization driven by Fe redox cycling in redox-fluctuating environments.

Vanadium in the Environment: Biogeochemistry and Bioremediation.

Vanadium(V) is a highly toxic multivalent, redox-sensitive element. It is widely distributed in the environment and employed in various industrial applications. Interactions between V and (micro)organisms have recently garnered considerable attention. This Review discusses the biogeochemical cycling of V and its corresponding bioremediation strategies. Anthropogenic activities have resulted in elevated environmental V concentrations compared to natural emissions. The global distributions of V in the atmosphere, soils, water bodies, and sediments are outlined here, with notable prevalence in Europe. Soluble V(V) predominantly exists in the environment and exhibits high mobility and chemical reactivity. The transport of V within environmental media and across food chains is also discussed. Microbially mediated V transformation is evaluated to shed light on the primary mechanisms underlying microbial V(V) reduction, namely electron transfer and enzymatic catalysis. Additionally, this Review highlights bioremediation strategies by exploring their geochemical influences and technical implementation methods. The identified knowledge gaps include the particulate speciation of V and its associated environmental behaviors as well as the biogeochemical processes of V in marine environments. Finally, challenges for future research are reported, including the screening of V hyperaccumulators and V(V)-reducing microbes and field tests for bioremediation approaches.

Goethite Formed in the Periplasmic Space of Pseudomonas sp. JM-7 during Fe Cycling Enhances Its Denitrification in Water.

Denitrification-driven Fe(II) oxidation is an important microbial metabolism that connects iron and nitrogen cycling in the environment. The formation of Fe(III) minerals in the periplasmic space has a significant effect on microbial metabolism and electron transfer, but direct evidence of iron ions entering the periplasm and resulting in periplasmic mineral precipitation and electron conduction properties has yet to be conclusively determined. Here, we investigated the pathways and amounts of iron, with different valence states and morphologies, entering the periplasmic space of the denitrifier Pseudomonas sp. JM-7 (P. JM-7), and the possible effects on the electron transfer and the denitrifying ability. When consistently provided with Fe(II) ions (from siderite (FeCO3)), the dissolved Fe(II) ions entered the periplasmic space and were oxidized to Fe(III), leading to the formation of a 25 nm thick crystalline goethite crust, which functioned as a semiconductor, accelerating the transfer of electrons from the intracellular to the extracellular matrix. This consequently doubled the denitrification rate and increased the electron transport capacity by 4-30 times (0.015-0.04 µA). However, as the Fe(II) concentration further increased to above 4 mM, the Fe(II) ions tended to preferentially nucleate, oxidize, and crystallize on the outer surface of P. JM-7, leading to the formation of a densely crystallized goethite layer, which significantly slowed down the metabolism of P. JM-7. In contrast to the Fe(II) conditions, regardless of the initial concentration of Fe(III), it was challenging for Fe(III) ions to form goethite in the periplasmic space. This work has shed light on the likely effects of iron on environmental microorganisms, improved our understanding of globally significant iron and nitrogen geochemical cycles in water, and expanded our ability to study and control these important processes.

Amine-Functionalized A-Center Sphalerite for Selective and Efficient Destruction of Perfluorooctanoic Acid.

Perfluorochemicals (PFCs), especially perfluorooctanoic acid (PFOA), have contaminated the ground and surface waters throughout the world. Efficient removal of PFCs from contaminated waters has been a major challenge. This study developed a novel UV-based reaction system to achieve fast PFOA adsorption and decomposition without addition of sacrificial chemicals by using synthetic photocatalyst sphalerite (ZnS-[N]) with sufficient surface amination and defects. The obtained ZnS-[N] has the capability of both reduction and oxidation due to the suitable band gap and photo-generated hole-trapping properties created by surface defects. The cooperated organic amine functional groups on the surface of ZnS-[N] play a crucial role in the selective adsorption of PFOA, which guarantee the efficient destruction of PFOA subsequently, and 1 µg L-1 PFOA could be degraded to <70 ng L-1 after 3 h in the presence of 0.75 g L-1 ZnS-[N] under 500 W UV irradiation. In this process, the photogenerated electrons (reduction) and holes (oxidation) on the ZnS-[N] surface work in a synergistic manner to achieve complete defluorination of PFOA. This study not only provides promising green technology for PFC-pollution remediation but also highlights the significance of developing a target system capable of both reduction and oxidation for PFC degradation.

Microorganisms Accelerate REE Mineralization in Supergene Environments.

Exogenic deposits are an important source of rare earth elements (REEs), especially heavy REEs (HREEs). It is generally accepted that microorganisms are able to dissolve minerals and mobilize elements in supergene environments. However, little is known about the roles of microorganisms in the formation of exogenic deposits such as regolith-hosted REE deposits that are of HREE enrichment and provide over 90% of global HREE demand. In this study, we characterized the microbial community composition and diversity along a complete weathering profile drilled from a regolith-hosted REE deposit in Southeastern China and report the striking contributions of microorganisms to the enrichment of REEs and fractionation between HREEs and light REEs (LREEs). Our results provide evidence that the variations in REE contents are correlated with microbial community along the profile. Both fungi and bacteria contributed to the accumulation of REEs, whereas bacteria played a key role in the fractionation between HREEs and LREEs. Taking advantage of bacteria strains isolated from the profile, Gram-positive bacteria affiliated with Bacillus and Micrococcus preferentially adsorbed HREEs, and teichoic acids in the cell wall served as the main sites for HREE adsorption, leading to an enrichment of HREEs in the deposit. The present study provides the first database of microbial community in regolith-hosted REE deposits. These findings not only elucidate the crucial contribution of fungi and bacteria in the supergene REE mineralization but also provide insights into efficient utilization of mineral resources via a biological pathway. IMPORTANCE Understanding the role of microorganisms in the formation of regolith-hosted rare earth element (REE) deposits is beneficial for improving the metallogenic theory and deposit exploitation, given that such deposits absolutely exist in subtropical regions with strong microbial activities. Little is known of the microbial community composition and its contribution to REE mineralization in this kind of deposit. Using a combination of high-throughput sequencing, batch adsorption experiments, and spectroscopic characterization, the functional microorganisms contributing to REE enrichment and fractionation are disclosed. For bacteria, the surface carboxyl and phosphate groups are active sites for REE adsorption, while teichoic acids in the cell walls of G+ bacteria lead to REE fractionation. The above-mentioned findings not only unravel the importance of microorganisms in the formation of supergene REE deposits but also provide experimental evidence for the bioutilization of REE resources.

Effect of Ga1-xInxAs1-yPy Al-free asymmetric barrier on GaAs-based 808-nm laser diode.

A GaInAsP/GaAs/GaAsP Al-free laser with asymmetric potential barriers is designed theoretically to prevent carrier leakage. The band alignment demonstrates that a high height of the potential barrier decreases the leakage current. The internal quantum efficiency increases by increasing the injection efficiency, which is attributed to the decreasing electron potential barrier heights. Moreover, the threshold current and operating voltage decrease by adopting a novel barrier so that the output power and power conversion efficiency (PCE) increase. When the injection current is 5 kA/cm2, the PCE is 77.82% and the output power is 13.21 W. The physical mechanism of potential barrier heights affecting carrier transport is investigated, which will provide a theoretical basis for optimizing laser diodes.

Incomplete denitrification phenotypes in diverse Thermus species from diverse geothermal spring sediments and adjacent soils in southwest China.

A few members of the bacterial genus Thermus have been shown to be incomplete denitrifiers, terminating with nitrite (NO2-) or nitrous oxide (N2O). However, the denitrification abilities of the genus as a whole remain poorly characterized. Here, we describe diverse denitrification phenotypes and genotypes of a collection of 24 strains representing ten species, all isolated from a variety of geothermal systems in China. Confirmed terminal products of nitrate reduction were nitrite or N2O, while nitric oxide (NO) was inferred as the terminal product in some strains. Most strains produced N2O; complete denitrification was not observed. Denitrification phenotypes were largely consistent with the presence of denitrification genes, and strains of the same species often had the same denitrification phenotypes and largely syntenous denitrification gene clusters. Genes for nirS and nirK coexisted in three Thermus brockianus and three Thermus oshimai genomes, which is a unique hallmark of some denitrifying Thermus strains and may be ecologically important. These results show that incomplete denitrification phenotypes are prominent, but variable, within and between Thermus species. The incomplete denitrification phenotypes described here suggest Thermus species may play important roles in consortial denitrification in high-temperature terrestrial biotopes where sufficient supply of oxidized inorganic nitrogen exists.

Optimization of PEC and photocathodic protection performance of TiO2/CuInS2heterojunction photoanodes.

The establishment of heterojunction is a powerful strategy to enhance the photoresponse performance of photoanode. Here, TiO2/CuInS2(T/CIS) composites were prepared via a two-step hydrothermal method, and their morphologies were controlled by adjusting the reaction time. The absorption spectra show that CuInS2can significantly improve the absorption of visible light. The T/CIS2 (2 h reaction time) photoanode exhibited the most outstanding photoelectrochemical (PEC) performance, with a photocurrent density of 168% that of the pure TiO2photoanode. Under simulated sunlight, this photoanode can supply a protective photocurrent of 0.49 mA cm-2and a protective voltage of 0.36 V to stainless steel (304ss), which are about 4 and 2 times those of the TiO2sample. The enhancement in the photocathodic protection performance is attributed to enlarged visible light absorbance and higher charge separation rate. This study demonstrates that the TiO2/CuInS2photoanode is a promising candidate for application in photoinduced cathodic protection of metallic materials.

Cr(VI) Reduction by Siderophore Alone and in Combination with Reduced Clay Minerals.

Siderophores and iron-containing clays are known to influence the transformation of chromium in the environment. The role of clays in hexavalent chromium [Cr(VI)] reduction has been reported extensively. However, the mechanisms of Cr(VI) reduction by siderophores and their combination with iron-bearing clays are poorly known. Herein, we report the kinetics and products of Cr(VI) reduction by a siderophore alone or in combination with reduced clays. Results showed that Cr(VI) reduction by a tri-hydroxamate siderophore─desferrioxamine B (DFOB)─at a pH of 6 was achieved by one-electron transfer via the formation of Cr(V) intermediate. The formed Cr(V) was further reduced to organically complexed Cr(III). The Cr(VI) reduction rate and extent in the presence of both DFOB and reduced clays unexpectedly decreased relative to that with reduced clays alone, despite both serving as Cr(VI) reductants. The interaction between DFOB and clays (e.g., adsorption/intercalation, dissolution, and/or oxidation) was primarily responsible for Cr(VI) reduction inhibition. The extent of inhibition increased at higher DFOB concentrations in the presence of iron-rich nontronite but decreased in the presence of iron-poor montmorillonite, which may be related to their different Cr(VI) reduction mechanisms. This study highlights the importance of siderophores in chromium transformation and its impact on the reactivity of iron-bearing clays toward heavy metal reduction in the environment.

Combined Effects of Fe(III)-Bearing Nontronite and Organic Ligands on Biogenic U(IV) Oxidation.

Bioreduction of soluble U(VI) to sparingly soluble U(IV) solids was proposed as a remediation method for uranium contamination. Therefore, the stability and longevity of biogenic U(IV) are critical to the success of uranium remediation. However, co-occurrence of clay minerals and organic ligands could potentially reoxidize U(IV) to U(VI). Herein, we report a combined effect of Fe(III)-rich nontronite (NAu-2) and environmentally prevalent organic ligands on reoxidation of biogenic U(IV) at circumneutral pH. After 30 days of incubation, structural Fe(III) in NAu-2 oxidized 45.50% U(IV) with an initial rate of 2.7 × 10-3 mol m-2 d-1. Addition of citrate and ethylenediaminetetraacetic acid (EDTA) greatly promoted the oxidative dissolution of U(IV) by structural Fe(III) in NAu-2, primarily through the formation of aqueous ligand-U(IV) complexes. In contrast, a model siderophore, desferrioxamine B (DFOB), partially inhibited U(IV) oxidation due to the formation of stable DFOB-Fe3+ complexes. The resulting U(VI) species intercalated into an NAu-2 interlayer or adsorbed onto an NAu-2 surface. Our results highlight the importance of organic ligands in oxidative dissolution of U(IV) minerals by Fe(III)-bearing clay minerals and have important implications for the design of nuclear waste storage and remediation strategies, especially in clay- and organic-rich environments.

Effect of Siderophore DFOB on U(VI) Adsorption to Clay Mineral and Its Subsequent Reduction by an Iron-Reducing Bacterium.

Uranium mining and nuclear fuel production have led to significant U contamination. Past studies have focused on the bioreduction of soluble U(VI) to insoluble U(IV) as a remediation method. However, U(IV) is susceptible to reoxidation and remobilization when conditions change. Here, we demonstrate that a combination of adsorption and bioreduction of U(VI) in the presence of an organic ligand (siderophore desferrioxamine B, DFOB) and the Fe-rich clay mineral nontronite partially alleviated this problem. DFOB greatly facilitated U(VI) adsorption into the interlayer of nontronite as a stable U(VI)-DFOB complex. This complex was likely reduced by bioreduction intermediates such as the Fe(II)-DFOB complex and/or through electron transfer within a ternary Fe(II)-DFOB-U(VI) complex. Bioreduction with DFOB alone resulted in a mobile aqueous U(IV)-DFOB complex, but in the presence of both DFOB and nontronite U(IV) was sequestered into a solid. These results provide novel insights into the mechanisms of U(VI) bioreduction and the stability of U and have important implications for understanding U biogeochemistry in the environment and for developing a sustainable U remediation approach.