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Showing papers on "Iron oxide published in 2012"


Journal ArticleDOI
TL;DR: This feature article aims to stress the importance of proper nanostructuring and advanced compositing that would result in improved physicochemical properties of metal oxides, thus making them promising negative electrodes for next-generation LIBs.
Abstract: The search for new electrode materials for lithium-ion batteries (LIBs) has been an important way to satisfy the ever-growing demands for better performance with higher energy/power densities, improved safety and longer cycle life. Nanostructured metal oxides exhibit good electrochemical properties, and they are regarded as promising anode materials for high-performance LIBs. In this feature article, we will focus on three different categories of metal oxides with distinct lithium storage mechanisms: tin dioxide (SnO2), which utilizes alloying/dealloying processes to reversibly store/release lithium ions during charge/discharge; titanium dioxide (TiO2), where lithium ions are inserted/deinserted into/out of the TiO2 crystal framework; and transition metal oxides including iron oxide and cobalt oxide, which react with lithium ions via an unusual conversion reaction. For all three systems, we will emphasize that creating nanomaterials with unique structures could effectively improve the lithium storage properties of these metal oxides. We will also highlight that the lithium storage capability can be further enhanced through designing advanced nanocomposite materials containing metal oxides and other carbonaceous supports. By providing such a rather systematic survey, we aim to stress the importance of proper nanostructuring and advanced compositing that would result in improved physicochemical properties of metal oxides, thus making them promising negative electrodes for next-generation LIBs.

972 citations


Journal ArticleDOI
TL;DR: In situ structural transformation of hollow iron oxide nanoparticles by synchrotron X-ray absorption and diffraction techniques provided clear understanding of the lithium intercalation processes during electrochemical cycling.
Abstract: Material design in terms of their morphologies other than solid nanoparticles can lead to more advanced properties. At the example of iron oxide, we explored the electrochemical properties of hollow nanoparticles with an application as a cathode and anode. Such nanoparticles contain very high concentration of cation vacancies that can be efficiently utilized for reversible Li ion intercalation without structural change. Cycling in high voltage range results in high capacity (∼132 mAh/g at 2.5 V), 99.7% Coulombic efficiency, superior rate performance (133 mAh/g at 3000 mA/g) and excellent stability (no fading at fast rate during more than 500 cycles). Cation vacancies in hollow iron oxide nanoparticles are also found to be responsible for the enhanced capacity in the conversion reactions. We monitored in situ structural transformation of hollow iron oxide nanoparticles by synchrotron X-ray absorption and diffraction techniques that provided us clear understanding of the lithium intercalation processes during electrochemical cycling.

359 citations


Journal ArticleDOI
TL;DR: In this paper, the authors report on the use of synthetic and natural Fe (hydr)oxides as catalysts in environmental remediation procedures using an advanced oxidation process, more specifically the Fentonlike system, which is highly efficient in generating reactive species such as hydroxyl radicals, even at room temperature and under atmospheric pressure.
Abstract: Iron is the fourth most common element by mass in the Earth’s crust and forms compounds in several oxidation states. Iron (hydr)oxides, some of which form inherently and exclusively in the nanometre-size range, are ubiquitous in nature and readily synthesized. These facts add up to render many Fe (hydr)oxides suitable as catalysts, and it is hardly surprising that numerous studies on the applications of Fe (hydr)oxides in catalysis have been published. Moreover, the abundant availability of a natural Fe source from rocks and soils at minimal cost makes the potential use of these as heterogeneous catalyst attractive. Besides those Fe (hydr)oxides that are inherently nanocrystalline (ferrihydrite, Fe5HO8·4H2O, and feroxyhyte, δ′-FeOOH), magnetite (Fe3O4) is often used as a catalyst because it has a permanent magnetization and contains Fe in both the divalent and trivalent states. Hematite, goethite and lepidocrocite have also been used as catalysts in their pure forms, doped with other cations, and as composites with carbon, alumina and zeolites among others. In this review we report on the use of synthetic and natural Fe (hydr)oxides as catalysts in environmental remediation procedures using an advanced oxidation process, more specifically the Fenton-like system, which is highly efficient in generating reactive species such as hydroxyl radicals, even at room temperature and under atmospheric pressure. The catalytic efficiency of Fe (hydr)oxides is strongly affected by factors such as the Fe oxidation state, surface area, isomorphic substitution of Fe by other cations, pH and temperature.

311 citations


Journal ArticleDOI
TL;DR: In this article, the adsorption of Pb(II), 1-naphthol, and 1naphthylamine, as representatives of inorganic and organic pollutants, on GO-iron oxides and reduced graphene oxide (RGO) was investigated.
Abstract: Graphene oxide (GO) and reduced graphene oxide (RGO) were both decorated with iron oxide nanoparticles and were characterized by scanning and transmission electron microscopy, powder X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The adsorption of Pb(II), 1-naphthol, and 1-naphthylamine, as representatives of inorganic and organic pollutants, on GO-iron oxides and RGO-iron oxides was investigated. The results showed that the GO-iron oxide material was a good adsorbent for Pb(II) but not for 1-naphthol and 1-naphthylamine due to oxygen-containing groups on the surface, whereas the RGO-iron oxide material was a good adsorbent for 1-naphthol and 1-naphthylamine but not for Pb(II). The adsorption of 1-naphthol and 1-naphthylamine on RGO-iron oxides was an endothermic and spontaneous process. Both materials can be easily separated by magnetic separation.

293 citations


Journal ArticleDOI
TL;DR: In this paper, the effect of thermal annealing on uncoated and coated magnetite nano-particles has been investigated using transmission electron microscopy (TEM), energy dispersive X-ray (EDX) spectroscopy, infrared (IR) and Raman spectrographic analysis (TGA).

283 citations


Journal ArticleDOI
TL;DR: In this article, an as-synthesized 1,3,5-benzenetricarboxylic (Fe-BTC) metal-organic coordination polymers are synthesized via a simple solvothermal method.
Abstract: Iron and 1,3,5-benzenetricarboxylic (Fe–BTC) metal–organic coordination polymers are synthesized via a simple solvothermal method. The as-synthesized Fe–BTC polymers exhibit gel behavior, which is stable in common organic solvents or in water. The Fe–BTC polymer as an adsorbent for arsenic removal from water is tested. The kinetics and thermodynamics of arsenic adsorption by the Fe–BTC polymer in aqueous solution are investigated comprehensively. The effect of pH on the adsorption is also investigated. Kinetic studies show that the kinetic data are well described by the pseudo-second-order kinetic model. The thermodynamic analysis indicates that the adsorption is spontaneous. The adsorption isotherms can be well described with the Langmuir equation. The Fe–BTC polymers show relatively high arsenic adsorption capacity, more than 6 times that of iron oxide nanoparticles with a size of 50 nm and 36 times that of commercial iron oxide powders. Hence, the as-synthesized Fe–BTC polymers possess relatively high ...

281 citations


Journal ArticleDOI
24 Jan 2012-ACS Nano
TL;DR: In this article, an enhanced photocurrent in a thin-film iron oxide photoanode coated on arrays of Au nanopillars was shown, attributed primarily to the increased optical absorption originating from both surface plasmon resonances and photonic-mode light trapping in the nanostructured topography.
Abstract: Photocatalytic water splitting represents a promising way to produce renewable hydrogen fuel from solar energy. Ultrathin semiconductor electrodes for water splitting are of particular interest because the optical absorption occurs in the region where photogenerated charge carriers can effectively contribute to the chemical reactions on the surface. It is therefore important to manipulate and concentrate the incident light so that more photons can be absorbed within the thin film. Here we show an enhanced photocurrent in a thin-film iron oxide photoanode coated on arrays of Au nanopillars. The enhancement can be attributed primarily to the increased optical absorption originating from both surface plasmon resonances and photonic-mode light trapping in the nanostructured topography. The resonances can be tuned to a desirable wavelength by varying the thickness of the iron oxide layer. A net enhancement as high as 50% was observed over the solar spectrum.

273 citations


Journal ArticleDOI
TL;DR: Owing to the enhanced colloidal stability and the high r(2) relaxivity, it was possible to successfully perform in vivo MR imaging of tumors by intravenous injection of 22-nm-sized WFIONs, using a clinical 3-T MR scanner.
Abstract: The theoretically predicted maximum r(2) relaxivity of iron oxide nanoparticles was achieved by optimizing the overall size of ferrimagnetic iron oxide nanocubes. Uniform-sized iron oxide nanocubes with an edge length of 22 nm, encapsulated with PEG-phospholipids (WFION), exhibited high colloidal stability in aqueous media. In addition, WFIONs are biocompatible and did not affect cell viability at concentrations up to 0.75 mg Fe/ml. Owing to the enhanced colloidal stability and the high r(2) relaxivity (761 mM(-1) s(-1)), it was possible to successfully perform in vivo MR imaging of tumors by intravenous injection of 22-nm-sized WFIONs, using a clinical 3-T MR scanner.

265 citations


Journal ArticleDOI
TL;DR: In this paper, a modified polyol protocol was used to synthesize novel structures of magnetic iron oxide, which look constituted of smaller grains of approximately 11 nm, assembled in a flower-shaped structure.
Abstract: Magnetic nanoparticles exhibit a high potential to selectively treat cancer by hyperthermia provided that high heating capacity can be reached. In this work, we report an efficient synthesis of novel structures of magnetic iron oxide. The particles, obtained by applying a modified “polyol” protocol, present a particular shape: they look constituted of smaller grains of approximately 11 nm, assembled in a flower-shaped structure. These nanoflowers, dispersed in water at physiological pH, present particularly interesting magnetic properties and a great capacity of heating. The value of the specific loss power (SLP) of these nanoflowers is 1 order of magnitude higher than the SLP reported for conventional 11 nm single-domain maghemite nanoparticles in the same condition of field exposure.

241 citations


Journal ArticleDOI
TL;DR: Degradation experiments with various structurally distinct compounds were carried out, indicating a similar selectivity of the heterogeneous Fenton-like system to that known for oxidation with ·OH.

236 citations


Journal ArticleDOI
TL;DR: In this paper, a study was conducted to evaluate hematite, magnetite, goethite, and iron rich laterite soil as arsenic adsorbents, and the results showed that arsenic adsorption occurred over the entire pH range tested (pH 4 − 11).

Journal ArticleDOI
TL;DR: In this article, a new Fe-Mn mixedoxide catalysts were prepared for the low-temperature selective catalytic reduction (SCR) of NOx with ammonia in the presence of excess oxygen.
Abstract: Novel Fe–Mn mixed-oxide catalysts were prepared for the low-temperature selective catalytic reduction (SCR) of NOx with ammonia in the presence of excess oxygen. It was found that Fe(0.4)–MnOx catalyst showed the highest activity, yielding 98.8% NOx conversion and 100% selectivity of N2 at 120 °C at a space velocity of 30 000 h–1. XRD results suggested that a new crystal phase of Fe3Mn3O8 was formed in the Fe–MnOx catalysts. TPR and Raman data showed that there was a strong interaction between the iron oxide and manganese oxide, which is responsible for the formation of the active center―Fe3Mn3O8. Intensive analysis of fresh, used, and regenerated catalysts by XPS revealed that electron transfer between Fen+ and Mnn+ ions in Fe3Mn3O8 may account for the long lifetime of the Fe(0.4)–MnOx catalyst. In addition, the SCR activity was suppressed a little in the presence of SO2 and H2O, but it was reversible after their removal.

Journal ArticleDOI
TL;DR: In this paper, an effective copper removal method using pectin-coated iron oxide magnetic nanocomposite as an adsorbent was described, and the amount of adsorbed Cu(II) increased with increasing pH, followed by decreased pH value after copper uptake, attesting to the ion exchange and electrostatic force mechanism during the adsorption process.

Journal ArticleDOI
05 Jun 2012-ACS Nano
TL;DR: The in vivo fate of PEGylated monodisperse IO nanocrystals and the iron, phospholipid, and oleic acid biodegradation products may influence the cellular environments in the organs and blood that can determine their safety in the body.
Abstract: Thermal decomposition of organometallic precursors has been found to generate highly crystalline iron oxide (IO) nanocrystals that display superior MR contrast and lower polydispersity than IO nanocrystals synthesized by aqueous precipitation. In the present study, the in vivo characteristics of IO nanocrystals prepared by the thermal decomposition route and then coated with a phospholipid containing a pendant poly(ethylene glycol) chain are examined. The size and surface chemistry of the IO nanocrystal influence the biodistibution, the rate of biodegradation and bioclearance, and the biodegradation products. We conclude that the in vivo fate of PEGylated monodisperse IO nanocrystals and the iron, phospholipid, and oleic acid biodegradation products may influence the cellular environments in the organs and blood that can determine their safety in the body.

Journal ArticleDOI
TL;DR: A series of iron-modified Ce/TiO2 catalysts with different Fe/Ti molar ratios were prepared by an impregnation method and used for selective catalytic reaction (SCR) of NOx with NH3.
Abstract: A series of iron-modified Ce/TiO2 catalysts with different Fe/Ti molar ratios were prepared by an impregnation method and used for selective catalytic reaction (SCR) of NOx with NH3. The Fe–Ce/TiO2 catalyst with a Fe/Ti molar ratio of 0.2 had good low-temperature activity and sulfur-poisoning resistance compared with the Ce/TiO2 catalyst. The introduction of Fe could increase the amount of Ce3+ and chemisorbed oxygen species on the catalyst surface and thereafter generate more ionic NH4+ and in situ formed NO2, respectively. In addition, the dispersion of cerium oxide could be improved by the addition of iron, and no visible phase of iron oxide could be observed at low Fe/Ti molar ratios (≤0.2). All of these factors played significant roles in the enhanced catalytic activity, especially the low-temperature activity. Furthermore, mechanisms of the SCR reaction and the SO2 poisoning of the Fe(0.2)–Ce/TiO2 catalyst were studied using in situ diffuse reflectance infrared Fourier transform spectroscopy. Coordi...

Journal ArticleDOI
TL;DR: Electrostatic attraction and oxidation-reduction between chromium and mixed maghemite-magnetite are postulated as mechanisms for the removal of Cr(VI) from aqueous solutions.

Journal ArticleDOI
TL;DR: In this paper, the effects of silica on chemical/structural properties and Fischer-Tropsch synthesis (FTS) performance of iron-based catalysts have been investigated and shown that adding silica significantly changes the adsorption sites of catalysts.

Journal ArticleDOI
TL;DR: In this article, a well-defined hollow interiors can be created inside Prussian Blue (PB) nanoparticles through controlled chemical etching in the presence of poly(vinylpyrrolidone) (Angew. Chem., Int. Ed.2012, 51, 984).
Abstract: Our recent work has demonstrated that well-defined hollow interiors can be created inside Prussian Blue (PB) nanoparticles through controlled chemical etching in the presence of poly(vinylpyrrolidone) (Angew. Chem., Int. Ed.2012, 51, 984). By calcination of these PB nanoparticles as starting precursors, we can successfully synthesize nanoporous iron oxides with hollow interiors. From scanning electron microscopy (SEM) and transmission electron microscopy (TEM), the original hollow cavities of PB nanocubes are shown to be retained after crystal transformation to iron oxides. Also, the obtained hollow iron oxides show a very high surface area because of their nanoporous shells, as illustrated by N2 gas adsorption–desorption analysis. By tuning the applied calcination temperatures and selecting the PB nanoparticles with different hollow cavities, crystalline α-Fe2O3, and γ-Fe2O3 can be selectively formed in the products without formation of any impurity phases. Field-dependent magnetization measurements indi...

Journal ArticleDOI
TL;DR: In this paper, a co-precipitation method using aqueous solution of ferric and ferrous ions with sodium salt was used to synthesize iron oxide nanoparticles.
Abstract: The iron oxide nanoparticles have been synthesized in co-precipitation method using aqueous solution of ferric and ferrous ions with sodium salt. The synthesis of iron-oxide nanoparticles were validated by UV-Visible spectroscopy which showed higher peak at 370 nm as valid standard reference. An average size of iron oxide nanoparticle found by Diffraction Light scattering (DLS) particle size analyser, ranges approximately between 10 nm to 120 nm with mean particle size of 66 nm. The X-ray power diffraction (XRD) analysis revealed the crystallographic structure of magnetic particles. Characterization of the mean particle size and morphology of iron oxide nanoparticles confirmed that the iron oxide nanoparticles are nearly spherical and crystalline in shape. Further the antibacterial effect of iron oxide nanoparticles was evaluated against ten pathogenic bacteria which showed that the nanoparticles have moderate antibacterial activity against both Gram positive and Gram negative pathogenic bacterial strains and retains potential application in pharmaceutical and biomedical industries.

Journal ArticleDOI
TL;DR: In this paper, thin films of hematite (α-Fe2O3) were deposited by the reactive evaporation of iron in an oxygen atmosphere and X-ray diffraction was used to verify the phase of the films and revealed that the films had a polycrystalline structure composed of nano-crystallites.

Journal ArticleDOI
TL;DR: In this article, uniform iron oxide magnetic nanoparticles, with sizes in the range 9-22 nm, have been synthesized by thermal decomposition of an iron oleate complex in 1-octadecene, controlling reaction parameters related to the nucleation and growth processes.
Abstract: Uniform iron oxide magnetic nanoparticles, with sizes in the range 9–22 nm, have been synthesized by thermal decomposition of an iron oleate complex in 1-octadecene, controlling reaction parameters related to the nucleation and growth processes. After transferring to water through a ligand substitution process, nanoparticles display very good magnetic and magneto-thermal properties. The relationship between these properties and the size and size distribution of the particles is discussed. The colloidal stability of the nanoparticles dispersed in common biological buffers has also been studied.

Journal ArticleDOI
01 Sep 2012-Carbon
TL;DR: In this article, superparamagnetic Fe3O4 nanoparticles were anchored on reduced graphene oxide nanosheets by co-precipitation of iron salts in the presence of different amounts of graphene oxide (GO).

Journal ArticleDOI
TL;DR: Internalization of citrate-coated and uncoated superparamagnetic iron oxide nanoparticles by human breast cancer (MCF-7) cells was verified by transmission electron microscopy imaging and metabolic and trypan blue assays manifested their excellent biocompatibility.

Journal ArticleDOI
Shubin Yang1, Yi Sun1, Long Chen1, Yenny Hernandez1, Xinliang Feng1, Klaus Müllen1 
TL;DR: An effective approach is reported for the fabrication of porous iron oxide ribbons by controlling the nucleation and growth of iron precursor onto the graphene surface and followed by an annealing treatment, which exhibits a high reversible capacity and excellent cycle stability for lithium storage.
Abstract: A well-designed nanostructure of transition metal oxides has been regarded as a key to solve their problems of large volume changes during lithium insertion-desertion processes which are associated with pulverization of the electrodes and rapid capacity decay. Here we report an effective approach for the fabrication of porous iron oxide ribbons by controlling the nucleation and growth of iron precursor onto the graphene surface and followed by an annealing treatment. The resultant iron oxide ribbons possess large aspect ratio, porous structure, thin feature and enhanced open-edges. These characteristics are favorable for the fast diffusion of lithium ions and electrons, and meanwhile can effectively accommodate the volume change of iron oxides during the cycling processes. As a consequence, the graphene-induced porous iron oxide ribbons exhibit a high reversible capacity and excellent cycle stability for lithium storage.

Journal ArticleDOI
TL;DR: In this article, the authors highlight the adsorption process by using iron oxide minerals as the adsorbent for arsenic removal from water and highlight the characteristics of arsenic in water and its toxicities.
Abstract: This review highlights the adsorption process by using iron oxide minerals as the adsorbent for arsenic removal from water. It includes the characteristics of arsenic in water and its toxicities, the adsorption process for arsenic removal from contaminated water, iron oxide minerals as the adsorbent, arsenic adsorption capacity on iron oxide minerals, main factors of the adsorption, and arsenic removal from water by the adsorption process, as well as the mechanisms by which arsenic species adsorb on iron oxide minerals.

Journal ArticleDOI
TL;DR: In this article, high-resolution X-ray photoelectron spectroscopy (HR-XPS) was used to study the chemical transformations of arsenite (As(III) enabled by nZVI during the sequestration process.
Abstract: Nanoscale zerovalent iron (nZVI) has shown a high efficacy for removing arsenite (As(III)), a groundwater contaminant of great concern, yet the chemical transformations of As(III) enabled by nZVI during the sequestration process are not well understood. Using high-resolution X-ray photoelectron spectroscopy (HR-XPS), arsenic in multiple valence states was observed for nZVI particles reacted with aqueous As(III), which establishes that nZVI is capable of inducing As(III) oxidation and reduction, a unique attribute imparted by the core–shell nature of nZVI particles. Time-dependent analysis shows that As(III) oxidation was a facile and reversible reaction taking place at the surface of the iron oxide shell, whereas As(III) reduction occurred at a slower rate and led to gradual diffusion and accumulation of reduced arsenic at a subsurface layer near the Fe(0) core. Long-term (146 days) exposure of the arsenic-laden nZVI in an aqueous environment caused progressive depletion of the Fe(0) cores; however, arsen...

Journal ArticleDOI
TL;DR: To predict the PEG-coated nanoparticle behavior in biological media, colloidal stability evaluation was performed to estimate the coating endurance in different conditions and indicated that at neutral pH condition, nanoparticles treated by 3/1 ratio possessed better stability parameters.

Journal ArticleDOI
13 Feb 2012-Langmuir
TL;DR: The results show that following the Mn doping process there is a large increase in affinity and capacity for heavy metals (i.e., Co, Ni, Zn, As, Ag, Cd, Hg, and Tl).
Abstract: A method for tuning the analyte affinity of magnetic, inorganic nanostructured sorbents for heavy metal contaminants is described The manganese-doped iron oxide nanoparticle sorbents have a remarkably high affinity compared to the precursor material Sorbent affinity can be tuned toward an analyte of interest simply by adjustment of the dopant quantity The results show that following the Mn doping process there is a large increase in affinity and capacity for heavy metals (ie, Co, Ni, Zn, As, Ag, Cd, Hg, and Tl) Capacity measurements were carried out for the removal of cadmium from river water and showed significantly higher loading than the relevant commercial sorbents tested for comparison The reduction in Cd concentration from 100 ppb spiked river water to 1 ppb (less than the EPA drinking water limit of 5 ppb for Cd) was achieved following treatment with the Mn-doped iron oxide nanoparticles The Mn-doped iron oxide nanoparticles were able to load ∼1 ppm of Cd followed by complete stripping and

Journal ArticleDOI
TL;DR: It is suggested that in vitro cytotoxicity and genotoxicity induced by metal oxide nanoparticles are not always higher than those induced by their bulk counterparts.
Abstract: Potential differences in the toxicological properties of nanosized and non-nanosized particles have been notably pointed out for titanium dioxide (TiO(2)) particles, which are currently widely produced and used in many industrial areas. Nanoparticles of the iron oxides magnetite (Fe(3)O(4)) and hematite (Fe(2)O(3)) also have many industrial applications but their toxicological properties are less documented than those of TiO(2). In the present study, the in vitro cytotoxicity and genotoxicity of commercially available nanosized and microsized anatase TiO(2), rutile TiO(2), Fe(3)O(4), and Fe(2)O(3) particles were compared in Syrian hamster embryo (SHE) cells. Samples were characterized for chemical composition, primary particle size, crystal phase, shape, and specific surface area. In acellular assays, TiO(2) and iron oxide particles were able to generate reactive oxygen species (ROS). At the same mass dose, all nanoparticles produced higher levels of ROS than their microsized counterparts. Measurement of particle size in the SHE culture medium showed that primary nanoparticles and microparticles are present in the form of micrometric agglomerates of highly poly-dispersed size. Uptake of primary particles and agglomerates by SHE exposed for 24 h was observed for all samples. TiO(2) samples were found to be more cytotoxic than iron oxide samples. Concerning primary size effects, anatase TiO(2), rutile TiO(2), and Fe(2)O(3) nanoparticles induced higher cytotoxicity than their microsized counterparts after 72 h of exposure. Over this treatment time, anatase TiO(2) and Fe(2)O(3) nanoparticles also produced more intracellular ROS compared to the microsized particles. However, similar levels of DNA damage were observed in the comet assay after 24 h of exposure to anatase nanoparticles and microparticles. Rutile microparticles were found to induce more DNA damage than the nanosized particles. However, no significant increase in DNA damage was detected from nanosized and microsized iron oxides. None of the samples tested showed significant induction of micronuclei formation after 24 h of exposure. In agreement with previous size-comparison studies, we suggest that in vitro cytotoxicity and genotoxicity induced by metal oxide nanoparticles are not always higher than those induced by their bulk counterparts.

Journal ArticleDOI
TL;DR: Large-scale cultivation effort using various Fe(III) oxides and carbon substrates along a dilution gradient to enrich for microbial populations capable of reducing Fe oxides spanning a wide range of crystallinities and reduction potentials highlights the need for further targeted investigations into the composition and activity of speciation-directed metal-reducing populations within natural environments.
Abstract: Iron (Fe) oxides exist in a spectrum of structures in the environment, with ferrihydrite widely considered the most bioavailable phase. Yet, ferrihydrite is unstable and rapidly transforms to more crystalline Fe(III) oxides (e.g., goethite, hematite), which are poorly reduced by model dissimilatory Fe(III)-reducing microorganisms. This begs the question, what processes and microbial groups are responsible for reduction of crystalline Fe(III) oxides within sedimentary environments? Further, how do changes in Fe mineralogy shape oxide-hosted microbial populations? To address these questions, we conducted a large-scale cultivation effort using various Fe(III) oxides (ferrihydrite, goethite, hematite) and carbon substrates (glucose, lactate, acetate) along a dilution gradient to enrich for microbial populations capable of reducing Fe oxides spanning a wide range of crystallinities and reduction potentials. While carbon source was the most important variable shaping community composition within Fe(III)-reducing enrichments, both Fe oxide type and sediment dilution also had a substantial influence. For instance, with acetate as the carbon source, only ferrihydrite enrichments displayed a significant amount of Fe(III) reduction and the well known dissimilatory metal reducer Geobacter sp. was the dominant organism enriched. In contrast, when glucose and lactate were provided, all three Fe oxides were reduced and reduction coincided with the presence of fermentative (e.g. Enterobacter spp.) and sulfate-reducing bacteria (e.g. Desulfovibrio spp.). Thus, changes in Fe oxide structure and resource availability may shift Fe(III)-reducing communities between dominantly metal-respiring to fermenting and/or sulfate-reducing organisms which are capable of reducing more recalcitrant Fe phases. These findings highlight the need for further targeted investigations into the composition and activity of speciation-directed metal-reducing populations within natural environments.