Microbial Fe Reduction Research Articles

Asymmetrical changes of electron-donating and electron-accepting capacities of natural organic matter during its interaction with Fe oxyhydroxides

The electron gain and loss of natural organic matter (NOM) plays an important role in the biogeochemical cycling of element and contaminant attenuation. The electron-donating capacity (EDC) and electron-accepting capacity (EAC) of NOM determine its electron exchange ability. However, the influences of bonded matrices on EDC and EAC of NOM remain unclear. Here we investigated the variations in EDC and EAC of NOM during its interaction with Fe oxyhydroxides. Compared to original NOM, the presence of Fe oxyhydroxides slightly decreased the EDC of dissolved NOM by 0.58–2.08 mmol e−/g C and of adsorbed NOM by 0.33–2.67 mmol e−/g C. However, the EAC of dissolved NOM and adsorbed NOM significantly (p < 0.05) increased by 1.92–14.17 and 3.08–36.67 mmol e−/g C, respectively. The excessive increase of EAC was mainly attributed to changes in NOM chemical components, particularly increases in oxidative components such as Fe(III) and quinonoid carbonyls, rather than changes in EDC. For dissolved NOM, the heightened EAC was mainly attributed to the complexation of Fe(III) by carboxyl in NOM. For adsorbed NOM, the boosted EAC was predominantly linked to the enrichment of quinonoid carbonyl through the selective molecular fractionation and the oxidative polymerization of polyphenols in NOM. Our finding highlights the previously overlooked phenomenon of asymmetrical changes of EDC and EAC of NOM during its interaction with Fe oxyhydroxides. The increased EAC could potentially affect various biogeochemical processes, such as methane production, anaerobic ammonium oxidation and microbial Fe(III) reduction.

Activated carbon as a strong DOM adsorbent mitigates antimony and arsenic release in flooded mining-impacted soils

In Southern China, the co-occurrence of arsenic (As) and antimony (Sb) contamination in soils around Sb mines presents an environmental challenge. During the flooding period of mining-impacted soils, anaerobic reduction of iron (Fe) oxides enhances the mobilization and bioavailability of Sb and As, further elevating the risk of Sb and As entering the food chain. To address this problem, activated carbon (AC) and biochar (BC) were applied to remediate flooded mining-impacted soils. Our results explored that AC can significantly decrease mobilization by 9–97 % for Sb and 9–67 % for As through inhibiting Fe(III) mineral reduction and dissolution in flooded soils. In contrast, there was no significant effect of BC. This was attributed to the strong adsorption of soil dissolved organic matter (DOM) by AC compared to BC, while DOM as electron shuttle is crucial for microbial Fe(III) reduction. Consequently, the DOM sequestration by AC effectively mitigates Sb and As leaching in contaminated mining soils.

Bioproduction of cerium-bearing magnetite and application to improve carbon-black supported platinum catalysts

BackgroundBiogeochemical processing of metals including the fabrication of novel nanomaterials from metal contaminated waste streams by microbial cells is an area of intense interest in the environmental sciences.ResultsHere we focus on the fate of Ce during the microbial reduction of a suite of Ce-bearing ferrihydrites with between 0.2 and 4.2 mol% Ce. Cerium K-edge X-ray absorption near edge structure (XANES) analyses showed that trivalent and tetravalent cerium co-existed, with a higher proportion of tetravalent cerium observed with increasing Ce-bearing of the ferrihydrite. The subsurface metal-reducing bacterium Geobacter sulfurreducens was used to bioreduce Ce-bearing ferrihydrite, and with 0.2 mol% and 0.5 mol% Ce, an Fe(II)-bearing mineral, magnetite (Fe(II)(III)2O4), formed alongside a small amount of goethite (FeOOH). At higher Ce-doping (1.4 mol% and 4.2 mol%) Fe(III) bioreduction was inhibited and goethite dominated the final products. During microbial Fe(III) reduction Ce was not released to solution, suggesting Ce remained associated with the Fe minerals during redox cycling, even at high Ce loadings. In addition, Fe L2,3 X-ray magnetic circular dichroism (XMCD) analyses suggested that Ce partially incorporated into the Fe(III) crystallographic sites in the magnetite. The use of Ce-bearing biomagnetite prepared in this study was tested for hydrogen fuel cell catalyst applications. Platinum/carbon black electrodes were fabricated, containing 10% biomagnetite with 0.2 mol% Ce in the catalyst. The addition of bioreduced Ce-magnetite improved the electrode durability when compared to a normal Pt/CB catalyst.ConclusionDifferent concentrations of Ce can inhibit the bioreduction of Fe(III) minerals, resulting in the formation of different bioreduction products. Bioprocessing of Fe-minerals to form Ce-containing magnetite (potentially from waste sources) offers a sustainable route to the production of fuel cell catalysts with improved performance.Graphical

The Influences of O2 Availability on the Microbial Activities and Fe Transformations in the Iron Formation Caves of the Southern Espinhaço Range, Brazil

Over 3000 iron formation caves (IFCs) have formed in erosion-resistant Fe(III)-rich rocks throughout Brazil. Microbial Fe(III) reduction occurs in IFCs, where a microbe-rich, Fe(III)-depleted paste (sub muros) is found behind an Fe(III)-(hydr)oxide crust in the ceiling/walls. Microbial Fe(III) reduction in sub muros appears to be responsible for the transformation of Fe(III) to more soluble Fe(II), which is removed, leading to cave formation. This process of biospeleogenesis is likely controlled by O2 availability, which is linked to seasonal changes. Here, we studied the effects of alternating anoxia/oxia on the microbial community and on Fe solubility in banded iron formation (BIF), a rock type consisting of layered Fe(III)-oxide and silicate. Incubations of synthetic pore water, pulverized BIF, and sub muros were prepared and incubated under anoxia, during which BIF-Fe(III) reduction proceeded. During the Fe(III) reduction period, Firmicutes and/or Alphaproteobacteria were enriched, and genes involved in Fe(III) and sulfate reduction were detected in the metagenomes. Fe(II) oxidation genes, which were detected in the fresh sub muros, were not found. Upon the addition of atmospheric O2, Fe(III) reduction was arrested, and incomplete Fe(II) oxidation occurred. Betaproteobacteria, Gammaproteobacteria, and Chloroflexi increased in relative abundance following aeration, and Fe(III) reduction genes were still identified. Our results demonstrate that the sub muros microbial community retains the ability to reduce Fe(III) and drive speleogenesis despite fluctuations in O2 levels.

LATE ARCHEAN SHELF-TO-BASIN IRON SHUTTLE CONTRIBUTES TO THE FORMATION OF THE WORLD-CLASS DATAIGOU BANDED IRON FORMATION

Abstract Banded iron formations (BIFs) are among the few chemical sedimentary archives that capture the biogeo-chemical evolution of Fe cycling and the redox evolution of the early Earth. Although biologically recycled continental Fe has been previously proposed to be a significant source of Fe in BIFs deposited from a stratified ocean at the onset of the Great Oxidation Event (GOE; ~2.5–2.2 Ga), constraining Fe sources and pathways in Archean BIFs remains challenging. Here we present major and trace element and Fe-Nd-Cr isotope data for the largest BIF (i.e., Dataigou) in China to test whether a benthic Fe shuttle was operative during deposition of pre-GOE BIFs. The absence of true, shale-normalized Ce anomalies, coupled with unfractionated Cr and positive Fe isotope compositions, suggests that BIF deposition occurred in an anoxic water column under reducing atmospheric conditions, whereas positive Eu anomalies indicate a significant input from a high-temperature hydrothermal source. Based on a significant correlation between initial Nd and Fe isotope data, we suggest that two Fe sources were periodically mixed and resulted in deposition of the Dataigou BIF. Here, we suggest the following sources: (1) hydrothermal fluids from sea-floor systems (low εNd(t) and high δ56Fe), derived from the interaction of fluids with underlying, older continental crust, and (2) a benthic Fe flux (high εNd(t) and low δ56Fe), generated by microbial Fe(III) reduction in coastal sediments during weathering of a nearby depleted landmass. Results presented here confirm, for the first time, that a microbially driven Fe shuttle was operational and supplied Fe on a basin-wide scale in the absence of atmospheric oxygen.

Ammonium-Enhanced Arsenic Mobilization from Aquifer Sediments.

Ammonium-related pathways are important for groundwater arsenic (As) enrichment, especially via microbial Fe(III) reduction coupled with anaerobic ammonium oxidation; however, the key pathways (and microorganisms) underpinning ammonium-induced Fe(III) reduction and their contributions to As mobilization in groundwater are still unknown. To address this gap, aquifer sediments hosting high As groundwater from the western Hetao Basin were incubated with 15N-labeled ammonium and external organic carbon sources (including glucose, lactate, and lactate/acetate). Decreases in ammonium concentrations were positively correlated with increases in the total produced Fe(II) (Fe(II)tot) and released As. The molar ratios of Fe(II)tot to oxidized ammonium ranged from 3.1 to 3.7 for all incubations, and the δ15N values of N2 from the headspace increased in 15N-labeled ammonium-treated series, suggesting N2 as the key end product of ammonium oxidation. The addition of ammonium increased the As release by 16.1% to 49.6%, which was more pronounced when copresented with organic electron donors. Genome-resolved metagenomic analyses (326 good-quality MAGs) suggested that ammonium-induced Fe(III) reduction in this system required syntrophic metabolic interactions between bacterial Fe(III) reduction and archaeal ammonium oxidation. The current results highlight the significance of syntrophic ammonium-stimulated Fe(III) reduction in driving As mobilization, which is underestimated in high As groundwater.

In-situ reactivation and reuse of micronsized sulfidated zero-valent iron using SRB-enriched culture: A sustainable PRB technology

Sulfidated zero-valent iron (S-ZVI) is an attractive material of permeable reactive barriers (PRBs) for the remediation of contaminated groundwater. However, S-ZVI is prone to be passivated due to the oxidation of reactive and conductive iron sulfide (FeSx) shell and the formation of inactive and non-conductive ferric (hydr)oxides, which serve as electron transfer barriers to hinder the electron flow from Fe° core to contaminants. This study thus proposed a novel approach for in-situ reactivation and reuse of micronsized S-ZVI (S-mZVI) in PRB using sulfate-reducing bacteria (SRB) enriched culture to realize long-lasting remediation of Cr(VI)-contaminated groundwater. S-mZVI were passivated after reactions with Cr(VI) due to the formation of electron transfer barriers (mainly inactive and non-conductive Fe(III) (hyd)oxides, which increased the polarization resistance from 16.38 to 27.38 kΩ cm2 and hindered the electron transfer from the Fe° core. Interestingly, the passivated S-mZVI was efficiently reactivated by providing the SRB-enriched culture and organic carbon within 12 h, and the Cr(VI) removal capacity of S-mZVI in the three use cycles increased to 37.4 mg Cr/g, which was 2.1 times higher than that of the virgin S-mZVI. After biological reactivation, the Rp of reactivated S-mZVI decreased to 12.30 kΩ cm2. SRB-mediated reactivation removed the electron transfer barriers via biotic and abiotic reduction of Fe(III) (hyd)oxides. Especially, the microbial Fe(III) reduction mediated by FmnA-dmkA-fmnB-pplA-ndh2-eetAB-dmkB protein family enhanced the Fe2+ release from the surface and the subsequent re-formation of reactive and conductive FeSx shell. A long-term PRB column test further demonstrated the feasibility of in-situ biological reactivation and reuse of S-mZVI for enhanced Cr(VI)-contaminated groundwater remediation. Within 64 days, the Cr(VI) removal capacity of S-mZVI in the four use cycles increased by 3.2 times, compared to the virgin one. The bio-reactivation using the SRB-enriched culture and sulfate locally-available in groundwater will reduce the chemical and maintenance costs associated with the frequent replacement of reactive ZVI-based materials. The PRB technology based on the bio-renewable S-mZVI can be a sustainable alternative to the conventional PRBs for the long-lasting and low-cost remediation of groundwater contaminated by oxidative pollutants.

Physico-chemical properties of illite in the organic matter (OM)-rich claystone of Nankai Trough contrast with coeval OM-poor claystone: IODP Expedition 348

Naturally occurring microbially induced smectite-to-illite (Sm-I) reaction is of great interest to understand the control for the conventional Sm-I transformation, the source of bioavailable iron (Fe) in sediments, and the evolution of the microbial community in the deep biosphere. Direct comparisons of physico-chemical properties of illite-like phases including collapsed high-charge smectite and transient phase, and mature illite were performed for the organic matter (OM)-rich claystone in contrast with those of coeval OM-poor claystone (2163 m–2217 m below sea floor) buried at Nankai Trough (Integrated Ocean Discovery Program Site C0002). These clay layers are interbedded with 70°–90° dipping angle, such that they have nearly identical burial conditions of temperature, time, and fluid geochemistry except for OM content, one of the significant controls that can fuel heterotrophic microbial Fe (III) reduction. Unlike the abiotic Sm-I reaction, the local variations in the crystal structure, elemental composition, and oxidation states of Fe for the illite and illite-like phases in the OM-rich claystone suggest that illitization is promoted through the reduction of structural Fe (III) in smectite by microbial activity, however the effects of OM cannot be ruled out.

Wetland soil organic carbon balance is reversed by old carbon and iron oxide additions.

Iron (Fe) oxides can stabilize organic carbon (OC) through adsorption and co-precipitation, while microbial Fe reduction can disrupt Fe-bound OC (Fe-OC) and further increase OC mineralization. The net effects of OC preservation and mineralization mediated by Fe oxides are still unclear, especially for old carbon (formed from plant litters over millions of years) and crystalline Fe oxides. Accelerating the recovery of wetland carbon sinks is critical for mitigating climate change and achieving carbon neutrality. Quantifying the net effect of Fe-mediated OC mineralization and preservation is vital for understanding the role of crystalline Fe oxides in carbon cycling and promoting the recovery of soil carbon sinks. Here, we explored the OC balances mediated by hematite (Hem) and lignite addition (Lig) to freshwater wetland (FW, rich in C and Fe) and saline-alkaline wetland (SW, poor in C and Fe) soil slurries, incubated under anaerobic conditions. Results showed that Lig caused net OC accumulation (FW: 5.9 ± 3.6 mg g-1; SW: 8.3 ± 3.2 mg g-1), while Hem caused dramatic OC loss, particularly in the FW soils. Hem inhibited microbial Fe(III) reduction by decreasing the relative abundance of Fe respiration reducers, while substantially enhancing OC mineralization through the shift in the microbial community structure of FW soils. Lig resulted in carbon emission, but its contribution to preservation by the formation of Fe-OC was far higher than that which caused OC loss. We concluded that crystalline Fe oxide addition solely favored the increase of OC mineralization by adjusting the microbial community structure, while old carbon enriched with an aromatic and alkyl promoted Fe-OC formation and further increased OC persistence. Our findings could be employed for wetland restoration, particularly for the recovery of soil carbon sinks.

Effects of Fe(III) (hydr)oxide mineralogy on the development of microbial communities originating from soil, surface water, groundwater, and aerosols

Microbial Fe(III) reduction is a key component of the iron cycle in natural environments. However, the susceptibility of Fe(III) (hydr)oxides to microbial reduction varies depending on the mineral's crystallinity, and the type of Fe(III) (hydr)oxide in turn will affect the composition of the microbial community. We created microcosm reactors with microbial communities from four different sources (soil, surface water, groundwater, and aerosols), three Fe(III) (hydr)oxides (lepidocrocite, goethite, and hematite) as electron acceptors, and acetate as an electron donor to investigate the shaping effect of Fe(III) mineral type on the development of microbial communities. During a 10-month incubation, changes in microbial community composition, Fe(III) reduction, and acetate utilization were monitored. Overall, there was greater reduction of lepidocrocite than of goethite and hematite, and the development of microbial communities originating from the same source diverged when supplied with different Fe(III) (hydr)oxides. Furthermore, each Fe(III) mineral was associated with unique taxa that emerged from different sources. This study illustrates the taxonomic diversity of Fe(III)-reducing microbes from a broad range of natural environments.

Potential natural attenuation of petroleum hydrocarbons in fuel contaminated soils: Focusing on anaerobic fuel biodegradation involving microbial Fe(III) reduction

Liquid fossil fuels, collectively known as total petroleum hydrocarbons (TPHs), are highly toxic and frequently leak into subsurface environments due to anthropogenic activities. As an in-situ biological remedial option for TPH contamination, aerobic TPH biodegradation is limited due to oxygen's low solubility in water, and because it is consumed quickly by aerobic bacteria. Thus, we investigated the potential of anaerobic TPH degradation by indigenous fermenting bacteria and Fe(III)-reducing bacteria. Twenty 6–10 m soil cores were collected from a closed military base subject to ongoing TPH contamination since the 1980s. Physicochemical and microbial properties were determined at 0.5-m intervals in each core. To assess the relationship between TPH degradation and microbial Fe(III) reduction, soil samples were grouped into high-TPH (>500 mg kg−1) and high-Fe(II) (>450 mg kg−1), high-TPH and low-Fe(II), low-TPH and high-Fe(II), and low-TPH and low-Fe(II) groups. Alpha diversity was significantly lower in high-TPH groups than in low-TPH groups, suggesting that high TPH concentrations exerted a strong selective pressure on bacterial communities. In the high-TPH and low-Fe(II) group, fermenting bacteria, including Microgenomatia and Chlamydiae, were more abundant, suggesting that TPH biodegradation occurred via fermentation. In the high-TPH and high-Fe(II) group, Fe(III)-reducing bacteria, including Geobacter and Zoogloea, were more abundant, suggesting that microbial Fe(III) reduction enhances TPH biodegradation. In contrast, the fermenting and/or Fe(III)-reducing bacteria were not statistically abundant in the low-TPH groups.

Fe(II) oxidation after microbial Fe(III) reduction does not cause Cd release

Fe(II) oxidation after microbial Fe(III) reduction does not cause Cd release

Immobilization of zinc and cadmium by biochar-based sulfidated nanoscale zero-valent iron in a co-contaminated soil: Performance, mechanism, and microbial response

Mining and smelting of mineral resources causes excessive accumulation of potentially toxic metals (PTMs) in surrounding soils. Here, biochar-based sulfidated nanoscale zero-valent iron (SNZVI/BC) was designed via a one-step liquid phase reduction method to immobilize cadmium (Cd) and zinc (Zn) in a copolluted arable soil. A 60 d soil incubation experiment revealed that Cd and Zn immobilization efficiency by 6 % SNZVI/BC (25.2–26.2 %) was higher than those by individual SNZVI (13.9–18.0 %) or biochar (14.0–19.3 %) based on the changes in diethylene triamine pentaacetic acid (DTPA)-extractable PTM concentrations in soils, exhibiting a synergistic effect. Cd2+ or Zn2+ replaced isomorphously Fe2+ in amorphous ferrous sulfide, as revealed by XRD, XPS, and high-resolution TEM-EDS, forming metal sulfide precipitates and thus immobilizing PTMs. PTM immobilization was further enhanced by adsorption by biochar and oxidation products (Fe2O3 and Fe3O4) of SNZVI via precipitation and surface complexation. SNZVI/BC also increased the concentration of dissolved organic carbon and soil pH, thus stimulating the abundances of beneficial bacteria, i.e., Bacilli, Clostridia, and Desulfuromonadia. These functional bacteria further facilitated microbial Fe(III) reduction, production of ammonium and available potassium, and immobilization of PTMs in soils. The predicted function of the soil microbial community was improved after supplementation with SNZVI/BC. Overall, SNZVI/BC could be a promising functional material that not only immobilized PTMs but also enhanced available nutrients in cocontaminated soils.

Biochar promoted microbial iron reduction in competition with methanogenesis in anaerobic digestion

Microbial Fe (III) reduction generally could outcompete methanogenesis due to its thermodynamic advantage, while the low bioavailability of Fe (III) compounds limits this process in the anaerobic digestion system, which could result in the low recovery of vivianite. Therefore, this study investigated the competition between Fe (III) reduction and methanogenesis in the presence of different biochar (pyrochar and hydrochar). The results showed that pyrochar obtained at 500 °C (P5) resulted in the highest Fe (III) reduction (80.3%) compared to the control experiment (29.1%). P5 also decreased methane production by 9.4%. Both conductivity and surface oxygen-containing functional groups contributed to the promotion of direct electron transfer for Fe (III) reduction. Genomic-centric metatranscriptomics analysis showed that P5 led to the highest enrichment of Geobacter soli A19 and induced the significant expression of out membrane cytochrome c and pilA in Geobacter soli A19, which was related to higher Fe (III) reduction.

Resolving dynamic mineral-organic interactions in the rhizosphere by combining in-situ microsensors with plant-soil reactive transport modeling

Associations between minerals and organic matter represent one of the most important carbon storage mechanisms in soils. Plant roots are major sources of soil carbon, and resolving the dynamics and dominance of microbial consumption versus mineral sorption of root-derived carbon is critical to understanding soil carbon storage. Here we integrate in-situ rhizosphere microsensor and plant physiological measurements with a 3-D plant-soil reactive transport model to explore the fate of dissolved organic carbon (DOC) in the rhizosphere, particularly its microbial consumption and interaction with Fe oxide minerals. Over several days, microdialysis probes at the root-soil interface of growing Vicia faba roots in live soil, revealed clear diel patterns of DOC concentration in the pore water. Daytime DOC spikes coincided with peaks in leaf-level photosynthesis rates and were accompanied by declining redox potential and dissolved oxygen as well as increasing pH in the rhizosphere. Incorporating microsensor data into our modeling framework showed that the measured rapid loss of DOC after each mid-day spike could not be explained by consumption via aerobic respiration, nor via anaerobic respiration dominated by Fe oxide reduction. Rather, in the model, a large fraction of rhizosphere DOC was rapidly immobilized each day by adsorption to Fe oxides. Further, modeled microbial Fe reduction (fueled by DOC) did not mobilize significant organic carbon from Fe oxides during the day. Instead, the model predicted equilibrium desorption of organic carbon from Fe oxides at night. This new mechanistic modeling framework, which couples aboveground plant physiological measurements with non-destructive high-resolution monitoring of rhizosphere processes, has great potential for exploring the dynamics and balance of the various microbial reactions and mineral interactions controlling carbon storage in soils.

Microbe-Mineral Interactions between Asbestos and Thermophilic Chemolithoautotrophic Anaerobes.

The Fe content and the morphometry of asbestos are two major factors linked to its toxicity. This study explored the use of microbe-mineral interactions between asbestos (and asbestos-like) minerals and thermophilic chemolithoautotrophic microorganisms as possible mineral dissolution treatments targeting their toxic properties. The removal of Fe from crocidolite was tested through chemolithoautotrophic Fe(III) reduction activities at 60°C. Chrysotile and tremolite-actinolite were tested for dissolution and potential release of elements like Si and Mg through biosilicification processes at 75°C. Our results show that chemolithoautotrophic Fe(III) reduction activities by Deferrisoma palaeochoriense were supported with crocidolite as the sole source of Fe(III) used as a terminal electron acceptor during respiration. Microbial Fe(III) reduction activities resulted in higher Fe release rates from crocidolite in comparison to previous studies on Fe leaching from crocidolite through Fe assimilation activities by soil fungi. Evidence of biosilicification in Thermovibrio ammonificans did not correspond with increased Si and Mg release from chrysotile or tremolite-actinolite dissolution. However, overall Si and Mg release from chrysotile into our experimental medium outmatched previously reported capabilities for Si and Mg release from chrysotile by fungi. Differences in the profiles of elements released from chrysotile and tremolite-actinolite during microbe-mineral experiments with T. ammonificans underscored the relevance of underlying crystallochemical differences in driving mineral dissolution and elemental bioavailability. Experimental studies targeting the interactions between chemolithoautotrophs and asbestos (or asbestos-like) minerals offer new access to the mechanisms behind crystallochemical mineral alterations and their role in the development of tailored asbestos treatments. IMPORTANCE We explored the potential of chemosynthetic microorganisms growing at high temperatures to induce the release of key elements (mainly iron, silicon, and magnesium) involved in the known toxic properties (iron content and fibrous mineral shapes) of asbestos minerals. We show for the first time that the microbial respiration of iron from amphibole asbestos releases some of the iron contained in the mineral while supporting microbial growth. Another microorganism imposed on the two main types of asbestos minerals (serpentines and amphiboles) resulted in distinct elemental release profiles for each type of asbestos during mineral dissolution. Despite evidence of microbially mediated dissolution in all minerals, none of the microorganisms tested disrupted the structure of the asbestos mineral fibers. Further constraints on the relationships between elemental release rates, amount of starting asbestos, reaction volumes, and incubation times will be required to better compare asbestos dissolution treatments studied to date.

Environmental and microbial influence on chemistry and dolomite formation in an ancient lake, Green River Formation (Eocene), Uinta basin, Utah, U.S.A.

ABSTRACT Integrated stratigraphic, petrographic, and geochemical data allow interpretation of biogeochemical and mineralization processes in paleoenvironmental context of ancient lacustrine environments. These indicate that lake chemistry, microbial processes, and organic matter (OM) strongly influenced dolomite formation in near-surface environments throughout deposition of the Green River Formation (Eocene, Uinta basin, Utah). The lower Green River Formation consists of interbedded fluvio-deltaic siliciclastics, paleosols, carbonate mud, coated-grain carbonates, mollusk and ostracod limestones, and microbialites all landward of profundal OM-bearing illitic mudrocks. Calcite, dolomite, Fe-dolomite, and authigenic feldspars are common. Carbonate δ18O and δ13C are covariant, and positive excursions of carbonate δ13C (up to 6.9‰ VPDB) and organic-matter δ15N (up to 13.9‰ V-AIR) occur in profundal OM-bearing mudrocks. The upper Green River Formation consists mainly of laminated OM-lean and OM-rich dolomitic muds (i.e., “oil-shales”). Zoned dolomite crystals with Mg-calcite centers and Fe-dolomite rims are widespread in addition to authigenic feldspars and Na-carbonates. Carbonate δ13C-enrichment (up to 15.8‰ VPDB), and organic-matter δ15N-enrichment (up to 18.4‰ V-AIR) occur in these OM-rich dolomite muds. Organic-matter δ13C is relatively invariable (mean = –29.3‰ VPDB) and does not covary with carbonate δ13C. Trends in mineralogy, organic-matter abundance, and stable isotopes result from changing hydrologic systems, paleoclimate, lake chemistry and microbial processes coincident with the Early Eocene Climate Optimum. The lower Green River Formation paleo-lake was smaller in area and volume, heavily influenced by meteoric fluvial input, variably oxygenated, and ranged from neutral and fresh to alkaline and saline. Especially in littoral environments with abundant microbialites, dolomite formed through recrystallization of precursor carbonate involving both replacement of precursor carbonate and direct precipitation as cements and overgrowths. The upper Green River Formation paleo-lake was more expansive with widespread low-oxygen, nutrient-rich, and alkaline saline environments with increased planktic organic-matter productivity. Microbial decay of organic matter in low-oxygen environments produced alkaline lake waters through methanogenesis, possible denitrification, and bacterial sulfate reduction to a limited degree. This favored precipitation of widespread dolomite, as well as Na-carbonates, authigenic feldspars, and analcime from lake water and phreatic pore water. Extracellular polymeric substances (EPS) excreted by microbial communities provided favorable nucleation sites for Mg-carbonate, allowing kinetic barriers of low-temperature dolomite formation to be overcome. Cycling of pH due to turnover of organic matter and associated microbial processes potentially bolstered EPS generation and abiotic environmental conditions favorable to dolomite precipitation. It is likely that metastable precursor carbonate was recrystallized to ordered dolomite, but it is possible that direct precipitation occurred. Fe-dolomite overgrowths precipitated after dolomite where microbial Fe reduction occurred in stagnant, oxygen-depleted, alkaline pore waters.

Role of microbial iron reduction in arsenic metabolism from soil particle size fractions in simulated human gastrointestinal tract

Gut microbiota provides protection against arsenic (As) induced toxicity, and As metabolism is considered an important part of risk assessment associated with soil As exposures. However, little is known about microbial iron(III) reduction and its role in metabolism of soil-bound As in the human gut. Here, we determined the dissolution and transformation of As and Fe from incidental ingestion of contaminated soils as a function of particle size (<250 μm, 100–250 μm, 50–100 μm and < 50 μm). Colon incubation with human gut microbiota yielded a high degree of As reduction and methylation of up to 53.4 and 0.074 μg/(log CFU/mL)/hr, respectively; methylation percentage increased with increasing soil organic matter and decreasing soil pore size. We also found significant microbial Fe(III) reduction and high levels of Fe(II) (48 %−100 % of total soluble Fe) may promote the capacity of As methylation. Although no statistical change in Fe phases was observed with low Fe dissolution and high molar Fe/As ratios, higher As bioaccessibility of colon phase (avg. 29.4 %) was mainly contributed from reductive dissolution of As(V)-bearing Fe(III) (oxy)hydroxides. Our results suggest that As mobility and biotransformation by human gut microbiota (carrying arrA and arsC genes) are strongly controlled by microbial Fe(III) reduction coupled with soil particle size. This will expand our knowledge on oral bioavailability of soil As and health risks from exposure to contaminated soils.

Flavins enhance the hydroxyl radical production from FeCO3 oxygenation for organic pollutant degradation

Hydroxyl radical (•OH) produced from Fe(II) oxidation has a great influence on element transformation and the natural attenuation of contaminants. Although the rules and mechanisms of •OH production from Fe(II) oxidation have been extensively studied, the influence of coexisting compounds of flavins, which are widespread in subsurface environments and could mediate microbial Fe(III) reduction to generate Fe(II), on •OH production remains unclear. Here, we reveal that reduced/oxidized riboflavin (RBFH2/RBF) significantly enhances •OH production from FeCO3 oxidation by oxygen (O2) within laboratory air at circumneutral pH conditions, but has no evident influence on other Fe(II) species. For instance, for oxygenation of 2 g/L FeCO3 at pH 7.3, the •OH accumulation within 180 min is 32.9 μM, while it increases to 72.3 and 72.6 μM with the addition of 20 μM RBFH2 and RBF, respectively. The mechanisms of •OH production enhancement are related to the complexation ability of RBF and the redox activity of RBFH2. Without RBFH2/RBF, •OH is primarily generated from the oxidation of structural Fe(II) by O2, followed by adsorbed Fe(II). With the addition of RBFH2/RBF, RBF chelates adsorbed Fe(II) and structural Fe(II) to form Fe(II)-RBF complex, thereby elevating •OH yield. Hence, •OH production is first attributed to the oxidation of structural Fe(II) and Fe(II)-RBF complex and secondarily to the oxidation of adsorbed Fe(II) in FeCO3-RBFH2/RBF systems. Besides, the oxidation of RBFH2 secondarily contributes to •OH generation in the presence of RBFH2. For pollutant removal, the removal efficiency of sulfamethoxazole increases from 20% to 39% and 38% after the addition of 20 μM RBFH2 and RBF in FeCO3 suspension, respectively. The finding reveals the neglected catalytic effects of RBFH2/RBF in •OH production from FeCO3 oxidation by O2.

Growth and genome-based insights of Fe(III) reduction of the high-temperature and NaCl-tolerant Shewanella xiamenensis from Changqing oilfield of China.

A facultative anaerobe bacterium Shewanella xiamenensis CQ-Y1 was isolated from the wastewater of Changqing oilfield in Shaanxi Province of China. Shewanella is the important dissimilatory metal-reducing bacteria. It exhibited a well potential application in biodegradation and bioremediation. Genome sequencing, assembling and functional annotation were conducted to explore the genome information of CQ-Y1. The effect of temperatures and NaCl concentrations on the CQ-Y1 growth and Fe(III) reduction were investigated by UV visible spectrophotometry, SEM and XRD. Genomic analysis revealed its complete genome was a circular chromosome of 4,710,887 bp with a GC content of 46.50% and 4,110 CDSs genes, 86 tRNAs and 26 rRNAs. It contains genes encoding for Na+/H+ antiporter, K+/Cl- transporter, heat shock protein associated with NaCl and high-temperature resistance. The presence of genes related to flavin, Cytochrome c, siderophore, and other related proteins supported Fe(III) reduction. In addition, CQ-Y1 could survive at 10% NaCl (w/v) and 45°C, and temperature showed more pronounced effects than NaCl concentration on the bacterial growth. The maximum Fe(III) reduction ratio of CQ-Y1 reached 70.1% at 30°C without NaCl, and the reduction reaction remained active at 40°C with 3% NaCl (w/v). NaCl concentration was more effective than temperature on microbial Fe(III) reduction. And the reduction products under high temperature and high NaCl conditions were characterized as Fe3(PO4)2, FeCl2 and Fe(OH)2. Accordingly, a Fe(III) reduction mechanism of CQ-Y1 mediated by Cytochrome c and flavin was hypothesised. These findings could provide information for a better understanding of the origin and evolution of genomic and metabolic diversity of S. xiamenensis.