Microbial Dissimilatory Iron Reduction Research Articles

The fate of Arsenic associated with the transformation of iron oxides in soils: The mineralogical evidence

The influence of iron (oxyhydr)oxides on the transformation and migration of arsenic(As) has garnered significant attention. Previous work has largely focused on the transformation of iron oxides related to As fate at molecular and mechanistic levels. However, studies examining the interplay between As concentration and iron oxides transformation within complex soil system are sparse. This study investigates the transformation of iron oxides in soils with varying As concentration during microbial dissimilatory iron reduction (DIR), employing humic acid (HA) as electron shuttle and assesses the impact on As speciation transformation. Comparative analyses indicate that in soils with high As concentration (>1000 mg/kg), the secondary transformation of iron (oxyhydr)oxides to other forms, such as the conversion of ferrihydrite to goethite and lepidocrocite, or schwertmannite to goethite, is impeded. Consequently, the formation of goethite and lepidocrocite, which would typically re-stabilize As, is inhibited, leading to elevated release of As(III). On the other hand, an increase in magnetite formation in soils with low As concentration (<100 mg/kg) appears to re-stabilize As effectively. Furthermore, the formation of new secondary iron (oxyhydr)oxides in soils with As concentration <200 mg/kg enhances fraction F5, which subsequently contributes to the re-immobilization of As, sequestering it within the soil matrix. This process results in a lower release of As(III) from soils with As concentration below 200 mg/kg. These findings enhance the understanding of the interdependent relationship between the transformation of iron oxides and the fate of As in complex soil systems.

Trace elements, C–O isotopes and U–Pb geochronology of the Minas Supergroup in the Segredo deposit, Quadrilátero Ferrífero, Brazil

The metasedimentary succession of the Minas Supergroup in the Quadrilátero Ferrífero (QFe) region, eastern Brazil, contains important, up to 400 m thick Lake Superior-type Banded Iron Formation (BIF) of the Cauê Formation. These are superposed by dolomitic carbonates of the Gandarela Formation, deposited ca. 2.4 Ga ago and thus probably registering the Great Oxygenation Event (GOE) of the Paleoproterozoic.The Segredo BIF deposit is located in the SW part of the QFe. The structural complexity and the discontinuity of layers challenge local studies on the sedimentary evolution of the Minas Basin. In the Segredo deposit, the stratigraphic sequence of the Minas Supergroup is exposed in the overturned limb of Fábrica Synform, that refold the Dom Bosco Synform.Based on the geological mapping and the study of a 480-m deep drill core, a lithostratigraphic review of the area is proposed, with stacking of the Itabira, Piracicaba, Sabará and Itacolomi groups, from the bottom up.The Itabira Group comprises BIF, intraformational metaconglomerate and dolostone with lateral and vertical interlayering. The chemical and isotopic data from the Cauê and Gandarela formations are defined by variations of the trace element and C-isotopic signatures. The intraformational metaconglomerate is interpreted as gravity flow products at the edges of the carbonate platform.Dolomitic BIFs show positive Eu anomalies and low terrigenous content, thus confirming the contribution of seawater hydrothermal fluids during the precipitation of BIF and carbonates. Negative Ce anomalies reflect a locally oxygenated ocean during precipitation of the Gandarela Formation carbonates.The carbon isotope stratigraphy is marked by δ13C values from around −1.5‰ in the Cauê BIF and around 0‰ in the Gandarela dolomites, indicating normal seawater conditions and deposition probably before the global Lomagundi event. The negatively fractionated values obtained for the Cauê BIF are consistent with previous studies suggesting the operation of microbial Dissimilatory Iron Reduction as an important process in BIF formation.Above the Gandarela carbonates, the occurrence of the Sabará Group through an angular unconformity is for the first time confirmed in the region by the occurrence of detrital sedimentary facies and by U–Pb geochronological data (younger detrital zircon at ca. 2.1 Ga).

Facet Dependence of Biosynthesis of Vivianite from Iron Oxides by Geobacter sulfurreducens.

Vivianite plays an important role in alleviating the phosphorus crisis and phosphorus pollution. The dissimilatory iron reduction has been found to trigger the biosynthesis of vivianite in soil environments, but the mechanism behind this remains largely unexplored. Herein, by regulating the crystal surfaces of iron oxides, we explored the influence of different crystal surface structures on the synthesis of vivianite driven by microbial dissimilatory iron reduction. The results showed that different crystal faces significantly affect the reduction and dissolution of iron oxides by microorganisms and the subsequent formation of vivianite. In general, goethite is more easily reduced by Geobacter sulfurreducens than hematite. Compared with Hem_{100} and Goe_L{110}, Hem_{001} and Goe_H{110} have higher initial reduction rates (approximately 2.25 and 1.5 times, respectively) and final Fe(II) content (approximately 1.56 and 1.20 times, respectively). In addition, in the presence of sufficient PO43-, Fe(II) combined to produce phosphorus crystal products. The final phosphorus recoveries of Hem_{001} and Goe_H{110} systems were about 5.2 and 13.6%, which were 1.3 and 1.6 times of those of Hem_{100} and Goe_L{110}, respectively. Material characterization analyses indicated that these phosphorous crystal products are vivianite and that different iron oxide crystal surfaces significantly affected the size of the vivianite crystals. This study demonstrates that different crystal faces can affect the biological reduction dissolution of iron oxides and the secondary biological mineralization process driven by dissimilatory iron reduction.

Microbial utilization of recently fixed, plant-derived organic carbon in shallow Holocene and Pleistocene aquifers in Bangladesh

The presence of dissolved arsenic in shallow aquifers of Bangladesh is widely accepted to require microbial dissimilatory iron-reduction in anoxic aquifers utilizing organic carbon as an electron donor. However, the various potential sources of this carbon, and whether organic carbon sources vary with sediment age (i.e. < 12 kyr-old Holocene vs older Pleistocene sediments) are still poorly understood. To shed light on these questions, natural abundance radiocarbon signatures of in situ microbial phospholipids fatty acids (PLFA), concentrations of sterol biomarkers, and aqueous [Cl-] and [Br-] were compared in two Bangladesh aquifers; a shallow (11–15 m) aquifer low in dissolved arsenic containing oxidized (orange) Pleistocene sands, Dopar Tek (DT), and a shallow (6–21 m) aquifer high in dissolved arsenic containing reduced (grey) Holocene sands, Desert Island (DI). Radiocarbon signatures of PLFA (Δ14CPLFA = −30 to −63 ‰ and +9 to +25 ‰, respectively) indicate microbial utilization of carbon fixed from the atmosphere within the last several decades, the drawdown of which into the shallow portions of both the Pleistocene Dopar Tek and Holocene Desert Island aquifers was likely enhanced by regional pumping activities. Similar results were previously obtained for two other Holocene aquifers in the same region, but to our knowledge this is the first time modern PLFA has been extracted from Pleistocene sediments. At both sites, high proportions of phytosterols, low sewage contamination indices (SCI < 0.7), and generally low Cl/Br ratios (averaging 434 and 544 at Desert Island and Dopar Tek respectively), are consistent with predominantly plant-derived organic carbon inputs. This contrasts with sewage-derived input inferred from higher sewage contamination index values (>0.7) previously observed at the two other shallow Holocene aquifers in the same region. Overall, our observations show that microbial communities within shallow aquifers, including those of Pleistocene age, utilize very recently fixed organic carbon associated with both plant and/or sewage origin. The microbial utilization of organic carbon fixed within the past several decades, likely derived from plants, in the anaerobic Pleistocene, has not, as of yet, led to iron reduction that would be sufficient to increase arsenic concentrations in groundwater. However, the observed microbial utilization of recently fixed carbon within all Bangladesh aquifers studied to date, indicates that pumping enhanced drawdown represents a potential risk to any systems where it might occur.

Complex iron and sulphate reducing Cretaceous sedimentary system revealed by extreme isotope values

AbstractThe iron and sulphur isotope compositions of sedimentary pyrites have been extensively used as a proxy for microbial metabolisms and redox evolution of the oceans. We illustrate the benefit of in‐situ and coupled study of Fe and S isotopes on sedimentary pyrites from late mid‐Cretaceous sediments from the Central Apennines, Italy. We report extremely low δ56Fe values for sedimentary pyrites (as low as −4.7‰) and unusual high δ34S values (as high as +88.9‰). We propose a model that explains these extreme values but also the large range of pyrite δ34S and δ56Fe values as well as the considerable microscale variations in this values. These isotopic compositions were likely produced by microbial dissimilatory iron reduction in the shelf sediment, transportation of Fe2+ via an iron shuttle, production of heavy SO4 by pyrite precipitation in the water column, diffusion and advection of SO4 and H2S, and finally bacterial sulphate reduction.

An in-situ bio-remediation of nitrobenzene in stimulated aquifer using emulsified vegetable oil

Widespread nitrobenzene (NB) contamination in groundwater requires an economical and effective remediation technology. In situ microbial reactive zone enhanced by injecting emulsified vegetable oil (EVO) is an effective method for remediating NB-contaminated groundwater, which can be reduced to aniline (AN) effectively in the reactive zone. However, the bio-mechanism of NB remediation in a real contaminated site is still unclear. Thus, a 3-D tank was established to conduct a pilot-scale experiment and the bacterial communities in the tank were analyzed by 16S rDNA high-throughput sequencing. The results suggested that the injection of EVO can stimulate some certain microorganisms to grow, and reduce NB though biological and biochemical processes. There were three degradation pathways of NB: (1) direct oxidation by Pseudomonas; (2) direct mineralization by Clostridium sensu stricto; and (3) coupled reduction of NB through microbial dissimilatory iron reduction by Geobacter and Arthrobacter. Among these pathways, the coupled reduction process is the main degradation pathway.

Depositional and Environmental Constraints on the Late Neoarchean Dagushan Deposit (Anshan-Benxi Area, North China Craton): An Algoma-Type Banded Iron Formation

Abstract The late Neoarchean, ~2.53 to 2.51 Ga Dagushan banded iron formation (BIF), is a typical Algoma-type BIF located in the northeast part of the North China craton. Despite having undergone upper greenschist to lower amphibolite facies metamorphism, the Dagushan BIF retains evidence of varied depositional facies, making it an ideal archive to evaluate the paleomarine environment and the paragenesis of the ore minerals. A transition from oxide to silicate to carbonate facies BIF is evident in a northward direction. The mineralogical composition shifts from magnetite and quartz in the south through a magnetite-quartz-cummingtonite/stilpnomelane assemblage in the transition zone to magnetite-siderite in the north. Such a distinct distribution of mineralogical facies correlates well with the depositional environment of the BIF. The carbonate facies BIFs formed in a near-shore, proximal environment, whereas the oxide and silicate facies BIF assemblages formed in deeper waters, distal to the paleoshoreline. The BIF samples display characteristic seawater-like rare earth element + yttrium (REE + Y) profiles with positive La and Y anomalies and heavy REE enrichment relative to the light REEs when normalized to post-Archean Australian shale. Positive Eu anomalies suggest a high-temperature hydrothermal contribution to the BIF. The absence of a negative Ce anomaly in nearly all samples, coupled with positive δ56Fe in magnetite in all mineralogical facies, indicates a dominantly anoxic water column contemporaneous with deposition of the BIF. At ~2.53 Ga in the Anshan area, seawater was mostly anoxic and rich in ferrous iron. Dissolved ferrous iron in upwelling hydrothermal fluids was oxidized and precipitated as Fe(III) oxyhydroxides in the photic zone leading to BIF formation. Proximal to hydrothermal vents, magnetite formed via the reaction of Fe(III) oxyhydroxides and aqueous Fe(II) supplied from the hydrothermal fluids and microbial dissimilatory iron reduction (DIR) coupled to organic carbon oxidation. Proximal to a paleoshoreline, siderite formed through DIR, as evidenced by the depleted δ13C values and the presence of graphite. Silicates, such as stilpnomelane and cummingtonite, are considered to be the metamorphic products of early diagenetic silicates (e.g., nontronite) that formed in the water column from admixtures of Fe(III) oxyhydroxides and amorphous silica.

Hematite facet-mediated microbial dissimilatory iron reduction and production of reactive oxygen species during aerobic oxidation

Microbial dissimilatory iron reduction and aerobic oxidation affect the biogeochemical cycles of many elements. Although the processes have been widely studied, the underlying mechanisms, and especially how the surface structures of iron oxides affect these redox processes, are poorly understood. Therefore, {001} facet-dominated hematite nanoplates (HNP) and {100} facet-dominated hematite nanorods (HNR) were used to explore the effects of surface structure on the microbial dissimilatory iron reduction and aerobic oxidation processes. During the reduction stage, the production of total Fe(II) normalized by specific surface area (SSA) was higher for HNP than HNR due to steric effects and the ligand-bound conformation of the connection between iron on different exposed facets and electron donors from microorganisms. However, during the aerobic oxidation stage, both the SSA- and Fe(II)-normalized reactive oxygen species (ROS), including hydrogen peroxide (H2O2) and hydroxyl radical (•OH), were higher for HNR than HNP. Theoretical calculation results showed that the {100} facets exhibited a lower activation energy barrier for oxygen reduction reaction than {001} facets, supporting the experimental observation that {100} facet-dominated HNR had a higher ROS production efficiency than {001} facet-dominated HNP. These results indicated that surface characteristics not only mediated the microbial reduction of Fe(III) but also affected the aerobic oxidation of microbially reduced Fe(II). Accessibility of electron donors to surface iron atom determined the reduction of Fe(III), and activation energy barrier for oxygen reduction by surface Fe(II) dominated the ROS production during the redox processes. This study advances our understanding of the mechanisms through which ROS are produced by iron (oxyhydr)oxides during microbial dissimilatory iron reduction and aerobic oxidation processes.

Iron and Carbon Isotope Constraints on the Formation Pathway of Iron-Rich Carbonates within the Dagushan Iron Formation, North China Craton

Banded iron formations (BIFs) are enigmatic chemical sedimentary rocks that chronicle the geochemical and microbial cycling of iron and carbon in the Precambrian. However, the formation pathways of Fe carbonate, namely siderite, remain disputed. Here, we provide photomicrographs, Fe, C and O isotope of siderite, and organic C isotope of the whole rock from the ~2.52 Ga Dagushan BIF in the Anshan area, China, to discuss the origin of siderite. There are small magnetite grains that occur as inclusions within siderite, suggesting a diagenetic origin of the siderite. Moreover, the siderites have a wide range of iron isotope compositions (δ56FeSd) from −0.180‰ to +0.463‰, and a relatively negative C isotope composition (δ13CSd = −6.20‰ to −1.57‰). These results are compatible with the reduction of an Fe(III)-oxyhydroxide precursor to dissolved Fe(II) through microbial dissimilatory iron reduction (DIR) during early diagenesis. Partial reduction of the precursor and possible mixing with seawater Fe(II) could explain the presence of siderite with negative δ56Fe, while sustained reaction of residual Fe(III)-oxyhydroxide could have produced siderite with positive δ56Fe values. Bicarbonate derived from both DIR and seawater may have provided a C source for siderite formation. Our results suggest that microbial respiration played an important role in the formation of siderite in the late Archean Dagushan BIF.

Effects of Dissolved Organic Matter on the Bioavailability of Heavy Metals During Microbial Dissimilatory Iron Reduction: A Review.

Dissolved organic matter (DOM), a type of mixture containing complex structures and interactions, has important effects on environmental processes such as the complexation and interface reactions of soil heavy metals. Furthermore, microbial dissimilatory iron reduction (DIR), a key process of soil biogeochemical cycle, is closely related to the migration and transformation of heavy metals and causes the release of DOM by carbon-ferrihydrite associations. This chapter considers the structural properties and characterization techniques of DOM and its interaction with microbial dissimilated iron. The effect of DOM on microbial DIR is specifically manifested as driving force properties, coprecipitation, complexation, and electronic shuttle properties. The study, in addition, further explored the influence of pH, microorganisms, salinity, and light conditions, mechanism of DOM and microbial DIR on the toxicity and bioavailability of different heavy metals. The action mechanism of these factors on heavy metals can be summarized as adsorption coprecipitation, methylation, and redox. Based on the findings of the review, future research is expected to focus on: (1) The combination of DOM functional group structure analysis with high-resolution mass spectrometry technology and electrochemical methods to determine the electron supply in the mechanism of DOM action on DIR; (2) Impact of DOM on differences in structure and functions of plant rhizosphere in heavy metal contaminated soil; and (3) Bioavailability of DOM-dissociative iron-reducing bacteria-heavy metal ternary binding on rhizosphere heavy metals under dynamic changes of water level from the perspective of the differences in DOM properties, such as polarity, molecular weight, and functional group.

The formation of marine red beds and iron cycling on the Mesoproterozoic North China Platform

Abstract Marine red beds (MRBs) are common in sedimentary records, but their genesis and environmental implications remain controversial. Genetic models proposed for MRBs variably invoke diagenetic or primary enrichments of iron, with vastly different implications for the redox state of the contemporaneous water column. The Xiamaling Formation (ca. 1.4 Ga) in the North China Platform hosts MRBs that offer insights into the iron cycling and redox conditions during the Mesoproterozoic Era. In the Xiamaling MRBs, well-preserved, nanometer-sized flaky hematite particles are randomly dispersed in the clay (illite) matrix, within the pressure shadow of rigid detrital grains. The presence of hematite flake aggregates with multiple face-to-edge (“cardhouse”) contacts indicates that the hematite particles were deposited as loosely bound, primary iron oxyhydroxide flocs. No greenalite or other ferrous iron precursor minerals have been identified in the MRBs. Early diagenetic ankerite concretions hosted in the MRBs show non-zero I/(Ca+Mg) values and positive Ce anomalies (&amp;gt;1.3), suggesting active redox cycling of iodine and manganese and therefore the presence of molecular oxygen in the porewater and likely in the water column during their formation. These observations support the hypothesis that iron oxyhydroxide precipitation occurred in moderately oxygenated marine waters above storm wave base (likely &amp;lt;100 m). Continentally sourced iron reactivated through microbial dissimilatory iron reduction, and distal hydrothermal fluids may have supplied Fe(II) for the iron oxyhydroxide precipitation. The accumulation of the Xiamaling MRBs may imply a slight increase of seawater oxygenation and the existence of long-lasting adjacent ferruginous water mass.

The reduction of nitrobenzene by extracellular electron transfer facilitated by Fe-bearing biochar derived from sewage sludge

In this work, the incorporation of Fe-bearing sludge-derived biochar greatly enhanced both biotic and abiotic reduction of nitrobenzene (NB) to aniline, which was attributed to the concomitant microbial dissimilatory iron reduction. Biogenic Fe(II) produced by Geobacter sulfurreducens dominated the anaerobic reduction of NB following the pseudo-first-order kinetic. Besides, the increase of pyrolysis temperature from 600 to 900 ℃ to generate biochar resulted in an accelerated removal rate of NB in Geobacter-biochar combined system. The morphology and structural characterization of biochar with G. sulfurreducens confirmed the formation of conductive bacteria-biochar aggregates. Electrochemical measurements suggested the presence of graphitized domains and quinone-like moieties in biochar as redox-active centers, which might play an important role in accelerating electron transfer for microbial dissimilatory iron reduction and NB degradation. This study provides a feasible way of using Fe-bearing sludge as a valuable feedstock for biochar generation and its application with electrochemically active bacteria for the bioremediation of nitroaromatic compounds-polluted wastewater.

The Carboniferous Shikebutai Iron Deposit in Western Tianshan, Northwestern China: Petrology, Fe-O-C-Si Isotopes, and Implications for Iron Pathways

Abstract Submarine volcanic-hosted iron deposits are important sources of iron ore in northwestern China. Here we present the petrological characteristics and coupled Fe-O, C, and Si isotope data of iron ores from the Shikebutai submarine volcanic-hosted hematite deposit in the Western Tianshan region. Several stratiform and lenticular hematite-dominated orebodies occur in Carboniferous submarine volcano-sedimentary sequences in this region. The ores are mainly composed of hematite, quartz, and minor siderite with distinct alternating iron-rich and silica-rich bands. The hematite shows δ56Fe and δ18O values in the range of –0.31 to 0.80‰ and 2.2 to 7.0‰, respectively, and the jasper yields δ30Si values of –1.90 to –1.20‰. Iron and Si were both derived from hydrothermal fluids related to submarine magmatism/volcanism. The Fe-bearing minerals in the Shikebutai deposit define distinct formation pathways. Hematite is the primary dehydrated Fe(III) oxyhydroxide, and the Fe isotope data indicate fractionation resulting from the partial oxidation of Fe(II). The O isotope data reflect inheritance from the submarine hydrothermal fluids source. Jasper was produced during coprecipitation of silica adsorbed onto the Fe(III) oxyhydroxides. The siderite-rich iron ore/volcaniclastic rock samples with a high and variable total organic carbon content (0.14–5.57%) show negative δ13C values (–3.0 to –1.1‰) and light δ56Fe values (–1.11 to –0.84‰). Our isotope data, together with the common occurrence of hematite inclusions in siderite, suggest that siderite was mainly produced by microbial dissimilatory iron reduction during diagenesis. The geologic, petrological, and isotopic data suggest that the Carboniferous Shikebutai deposit was precipitated through chemical and biogenic processes.

Hematite Crystallization in the Presence of Organic Matter: Impact on Crystal Properties and Bacterial Dissolution

Microbial dissimilatory iron reduction (DIR) is a widespread process in oxygen-poor sediments and waters, where it regulates Fe and C cycling and contributes to nutrient and trace metal distributio...

Is microbial reduction of Fe (III) in podzolic soils influencing C release?

Fe(III) oxides stabilize soil organic matter by forming Fe organo-mineral associations (Fe-OMA). Under anoxic conditions, Fe-OMA may be destabilized by microbial dissimilatory iron reduction that releases aqueous Fe(II) and also possibly adsorbed or co-precipitated organic matter. Soil spodic horizons that accumulate Fe-OMA are ideal natural materials to study such impact. Here, we study three spodic horizons from pedons (P) of increasing age: P-270 yrs, P-330 yrs and P-530 yrs. Their contents of total carbon and short range ordered (SRO) Fe oxides increase with soil age from, respectively, 1486 to 3618 and 13 to 249 μmol g−1. The samples were incubated for 96 h under anoxic conditions, with and without Shewanella putrefaciens (a model dissimilatory Fe(III)-reducing bacteria) in a minimal medium devoid of any pH buffer and external electron donor. The concentration of dissolved Fe(II), total Fe and organic C was monitored at 9 time steps. With increasing age, both the rate and extent of microbial Fe(III) reduction increased after S. putrefaciens addition. In P-270 yrs, P-330 yrs and P-530 yrs, respectively, the microbial reduction rates were 0.004, 0.026 and 0.114 fmol Fe(II) h−1 cell−1 while the amounts of released Fe(II) were 0.23, 0.32 and 1.98 μmol Fe(II) g−1, both being strongly correlated with SRO Fe oxides content. Dissolved organic carbon (DOC) was released with or without S. putrefaciens in all samples (up to 73 μmol OC g−1 after 96 h in P-530 yrs). Adding S. putrefaciens significantly increased DOC release, but only in P-270 yrs. Podzol development thus increases the impact of anoxia on Fe(II) release since organic matter accumulation impedes Fe oxide crystallization, thereby amplifying Fe availability for Fe reducing microbes. The evolution of Fe oxide content and crystallinity thus affects the fate of both C and Fe in soils.

Potential of Crystalline and Amorphous Ferric Oxides for Biostimulation of Anaerobic Digestion

Iron oxides have been widely investigated to accelerate the conversion of organic wastes to methane. However, the potential mechanism involved with different types of iron oxides is a controversial topic. In this study, crystalline Fe2O3 and amorphous Fe (OH)3 were respectively supplemented to explore the effects of the crystal form of Fe(III) on anaerobic digestion. The results showed that the addition of Fe2O3 and Fe(OH)3 both significantly enhanced COD removal and biomethanation compared with the control. The reason was related to that the supplement of Fe(OH)3 induced an efficient microbial dissimilatory iron reduction to enhance the decomposition of complex organics into simples. Consistently, 28.3% of Fe(OH)3 dosed at the initial stage were reduced into Fe(II), while no obvious iron reduction was observed with the Fe2O3 supplement. Interestingly, Fe2O3 significantly stimulated the secretion of protein and humic acid-like substances in EPS, leading to an electron-transfer capacity higher than that for Fe(OH)3 and control reactors, which seemed to be an important reason for the improved anaerobic performance. The gene function prediction also showed a different degree of expression of functional genes involved in amino-acid, polysaccharides, and inorganic ion transport and metabolism in the presence of Fe2O3 and Fe(OH)3. This study helped to give a more comprehensive insight for the mechanisms of ferric oxides on the improvement of anaerobic digestion.

Mechanism on emulsified vegetable oil stimulating nitrobenzene degradation coupled with dissimilatory iron reduction in aquifer media

Microbial dissimilatory iron reduction could remediate reducible pollutants in groundwater, such as nitrobenzene (NB). But the natural attenuation rate in aquifer is limited. To stimulate this process, emulsified vegetable oil (EVO) was injected as a remediation agent. The mechanism of this process was studied. Results showed that the addition of EVO made iron easier used by microorganisms and thus promoted dissimilatory iron reduction. The readily used Fe(III) served as electron acceptor and was reduced to Fe(II). Fe(II) supplied electrons to NB, with NB reduced to aniline. Sulphide in the aquifer media also donated electrons and oxidized to polysulfide, then forming precipitates with Fe(II) to the surface of aquifer media, and thus slowing down the electron supplying of EVO and forming permanent efficiency for NB remediation. The work helps to complete a systematic understanding of NB remediation process under stimulation of EVO.

Anoxic to suboxic Mesoproterozoic ocean: Evidence from iron isotope and geochemistry of siderite in the Banded Iron Formations from North Qilian, NW China

Banded Iron Formations (BIFs) provide important constraints on geochemical cycling of Fe and ancient marine environment. Globally, the formation of BIFs peaked during late Archean and early Paleoproterozoic, with limited reappearance during Neoproterozoic. Here we investigate a rare example of Mesoproterozoic (ca. 1.3 Ga) BIFs from Jingtieshan in the North Qilian region of NW China. We present rare earth element and yttrium (REE + Y) compositions together with iron isotope features of siderite from the BIFs, and integrate these with our published data on carbon isotope compositions from the siderite-rich BIFs (including carbonate facies BIFs and mixed carbonate-oxide facies BIFs). Siderite from the BIFs shows REE + Y characteristics that are consistent with submarine hydrothermal fluids mixed with seawater, including positive Eu/Eu∗ anomalies and high Y/Ho ratios. The siderite also displays homogeneous iron isotope compositions (δ56Fe range from −0.71‰ to −0.41‰, one sample down to −1.62‰) and moderate negative carbon isotope compositions (δ13C values = −8.40‰ to −3.0‰). These findings argue against the traditional view that siderite associated with BIFs was formed through microbial dissimilatory iron reduction (DIR). Instead, siderite from Jingtieshan BIFs is in equilibrium with submarine hydrothermal fluids and seawater suggesting an inorganic origin, and was directly precipitated from the CO2 and Fe oversaturated water column, with only insignificant role for DIR. These Mesoproterozoic BIFs are also characterized by Ce anomalies, and the siderite falls within the pe–log [S]T and (PO2)–(PCO2) stability fields, suggesting that the BIFs were deposited in an anoxic to suboxic ocean. The results from our study suggest the presence of iron-rich Mesoproterozoic deep ocean in the North Qilian area.

Silicon isotope fractionation during microbial reduction of Fe(III)–Si gels under Archean seawater conditions and implications for iron formation genesis

Microbial dissimilatory iron reduction (DIR) is a deeply rooted metabolism in the Bacteria and Archaea. In the Archean and Proterozoic, the most likely electron acceptor for DIR in marine environments was Fe(III)–Si gels. It has been recently suggested that the Fe and Si cycles were coupled through sorption of aqueous Si to iron oxides/hydroxides, and through release of Si during DIR. Evidence for the close association of the Fe and Si cycles comes from banded iron formations (BIFs), which consist of alternating bands of Fe-bearing minerals and quartz (chert). Although there has been extensive study of the stable Fe isotope fractionations produced by DIR of Fe(III)–Si gels, as well as studies of stable Fe isotope fractionations in analogous abiologic systems, no studies to date have investigated stable Si isotope fractionations produced by DIR.In this study, the stable Si isotope fractionations produced by microbial reduction of Fe(III)–Si gels were investigated in simulated artificial Archean seawater (AAS), using the marine iron-reducing bacterium Desulfuromonas acetoxidans. Microbial reduction produced very large 30Si/28Si isotope fractionations between the solid and aqueous phase at ∼23°C, where Δ30Sisolid–aqueous isotope fractionations of −3.35±0.16‰ and −3.46±0.09‰ were produced in two replicate experiments at 32% Fe(III) reduction (solid-phase Fe(II)/FeTotal=0.32). This isotopic fractionation was substantially greater than that observed in two abiologic controls that had solid-phase Fe(II)/FeTotal=0.02–0.03, which produced Δ30Sisolid–aqueous isotope fractionations of −2.83±0.24‰ and −2.65±0.28‰. In a companion study, the equilibrium Δ30Sisolid–aqueous isotope fractionation was determined to be −2.3‰ for solid-phase Fe(II)/FeTotal=0. Collectively, these results highlight the importance of Fe(II) in Fe–Si gels in producing large changes in Si isotope fractionations. These results suggest that DIR should produce highly negative δ30Si values in quartz that is the product of diagenetic reactions associated with Fe–Si gels. Such Si isotope compositions would be expected to be associated with Fe-bearing minerals that contain Fe(II), indicative of reduction, such as magnetite. Support for this model comes from recent in situ Si isotope studies of oxide-facies BIFs, where quartz in magnetite-rich samples have significantly more negative δ30Si values than quartz in hematite-rich samples.

Biologically recycled continental iron is a major component in banded iron formations

Banded iron formations (BIFs) record a time of extensive Fe deposition in the Precambrian oceans, but the sources and pathways for metals in BIFs remain controversial. Here, we present Fe- and Nd-isotope data that indicate two sources of Fe for the large BIF units deposited 2.5 billion y ago. High-εNd and -δ(56)Fe signatures in some BIF samples record a hydrothermal component, but correlated decreases in εNd- and δ(56)Fe values reflect contributions from a continental component. The continental Fe source is best explained by Fe mobilization on the continental margin by microbial dissimilatory iron reduction (DIR) and confirms for the first time, to our knowledge, a microbially driven Fe shuttle for the largest BIFs on Earth. Detailed sampling at various scales shows that the proportions of hydrothermal and continental Fe sources were invariant over periods of 10(0)-10(3) y, indicating that there was no seasonal control, although Fe sources varied on longer timescales of 10(5)-10(6) y, suggesting a control by marine basin circulation. These results show that Fe sources and pathways for BIFs reflect the interplay between abiologic (hydrothermal) and biologic processes, where the latter reflects DIR that operated on a basin-wide scale in the Archean.