Science.gov

Sample records for ablation fe oxidation

  1. Ablation of crystalline oxides by infrared femtosecond laser pulses

    SciTech Connect

    Watanabe, Fumiya; Cahill, David G.; Gundrum, Bryan; Averback, R. S.

    2006-10-15

    We use focused laser pulses with duration of 180 fs and wavelength of 800 nm to study the interactions of high power near-infrared light with the surfaces of single-crystal transparent oxides (sapphire, LaAlO{sub 3}, SrTiO{sub 3}, yttria-stabilized ZrO{sub 2}, and MgO); the morphologies of the ablation craters are studied by atomic force microscopy and scanning electron microscopy. With the exception of LaAlO{sub 3}, the high temperature annealing of these oxide crystals produces atomically flat starting surfaces that enable studies of the morphology of ablation craters with subnanometer precision. The threshold fluence for ablation is determined directly from atomic-force microscopy images and increases approximately linearly with the band gap of the oxide. For all oxides except sapphire, the depth of the ablation crater increases approximately as the square root of the difference between the peak laser fluence and the threshold fluence for ablation. Sapphire shows unique behavior: (i) at laser fluences within 1 J/cm{sup 2} of the threshold for ablation, the depth of the ablation crater increases gradually instead of abruptly with laser fluence, and (ii) the rms roughness of the ablation crater shows a pronounced minimum of <0.2 nm at a laser fluence of 1 J/cm{sup 2} above the threshold.

  2. Laser ablation synthesis of lanthanide oxide clusters: Mechanisms and chemistry

    SciTech Connect

    Gibson, J.K.

    1995-07-15

    Excimer laser ablation into vacuum of hydrated lanthanide oxalates has produced new lanthanide (Ln) oxide cluster ions which were identified by time-of-flight mass spectrometry. In addition to binary oxide clusters (Ln{sub {ital m}}O{sup +}{sub {ital n}}), mixed lanthanide oxide clusters [Ln{sub {ital m}1}Ln{sub {ital m}2}{sup {prime}}O{sup +}{sub {ital n}} with ({ital m}1+{ital m}2){le}9] were discerned for the following Ln-Ln{prime}: La-Tb, La-Ho, La-Lu, and Ho-Lu. The observed cluster ion stoichiometries, abundance distributions, and hydration systematics provide insights into cluster formation mechanisms and chemistries. Time-variable ion sampling revealed cluster enhancement in the tail of the ablation plume. The body of experimental results support cluster formation by aggregation of small ablated species. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  3. Optical and magnetic properties of Fe2O3 nanoparticles synthesized by laser ablation/fragmentation technique in different liquid media

    NASA Astrophysics Data System (ADS)

    Pandey, B. K.; Shahi, A. K.; Shah, Jyoti; Kotnala, R. K.; Gopal, Ram

    2014-01-01

    Iron oxide (Fe2O3) bulk powder have been ablated/fragmented in different liquid medium by Nd:YAG laser beam using 1064 nm wavelength. Sodium dodecyl sulfate (SDS), cetyltrimethyl ammonium bromide (CTAB) and double distilled water (DDW) are used as liquid medium. Crystalline size, lattice strain, phase and structure of ablated particles have been investigated using synchrotron X-ray diffraction. Optical band gap energy of as purchased Fe2O3 found 1.92 eV that increased to 2.03 eV after ablation in CTAB determined by UV-vis absorption spectroscopy. Magnetic properties have been analyzed by hysteresis loops using vibrating sample magnetometer (VSM). Crystalline sizes have been found in the range of 29.23-16.54 nm and coercivity tailored in the range of 206.91-298.36 Oe using laser ablation. Saturation magnetization and remanence have been found in the range of 0.013-3.41 emu/g and 0.0023-.0.51 emu/g respectively. Particle shape and size have been examined by scanning electron microscopy (SEM). CTAB (cationic) and SDS (anionic) surfactants are used as capping agent. CTAB produces phase transformation in ablated iron oxide (Fe2O3). Crystallinity and crystalline size of ablated particles in DDW increased due to presence of rich oxygen in it due to oxidation. Ablated Fe2O3 nanoparticles have been widely used experimentally for numerous in vivo applications such as MRI contrast enhancement agent, tissue repair, immunoassay, detoxification of biological fluids, hyperthermia, drug delivery and cell separation.

  4. Moessbauer Study of Electrodeposited Fe/Fe-Oxide Multilayers

    SciTech Connect

    Kuzmann, E.; Homonnay, Z.; Klencsar, Z.; Vertes, A.; Lakatos-Varsanyi, M.; Miko, A.; Varga, L.K.; Kalman, E.; Nagy, F.

    2005-04-26

    Iron has been deposited electrochemically by short current pulses in Na-saccharin containing FeII-chloride and sulphate solution electrolytes. Combined electrochemical techniques with initial pulse plating of iron nanolayer and its subsequent anodic oxidation under potential control have been used for production of Fe/Fe-oxide multilayers. 57Fe CEM spectra of pulse plated iron revealed the presence of a minor doublet attributed mainly to {gamma}-FeOOH in addition to the dominant sextet of {alpha}-iron. In the case of anodically oxidized pulse plated iron and of samples after repeated deposition of anodically oxidized pulse plated iron an additional minor doublet, assigned to ferrous chloride, also appears in the Moessbauer spectra. A significant change in the magnetic anisotropy of {alpha}-iron was observed with the anodic oxidation. The thickness of the layers were estimated from the CEM spectrum data by a modified computer program of the Liljequist method. The coercive field and the power loss versus frequency data showed that the pulse plated iron cores are good inductive elements up to several kHz frequencies.

  5. Synthesis of Titanium Oxide Nanoparticles by Ytterbium Fiber Laser Ablation

    NASA Astrophysics Data System (ADS)

    Boutinguiza, M.; del Val, J.; Riveiro, A.; Lusquiños, F.; Quintero, F.; Comesaña, R.; Pou, J.

    Nanosized titanium particles have recently received a special attention due to their applications in many different fields, such as catalysis, biomedical engineering, etc. Pulsed laser ablation in liquid media allows obtaining metallic and metallic oxide nanoparticles in colloids. This technique has been used in the present work to prepare titanium colloids from a solid piece immersed in liquid media. A monomode Ytterbium doped fiber laser has been focused onto the upper surface of the titanium target in de-ionized water or ethanol. Crystalline phases, morphology and optical properties of the obtained colloidal nanoparticles were characterized by XRD, HRTEM, and UV/VIS absorption spectroscopy. The produced titanium oxide crystalline nanoparticles show spherical shape and are polycrystalline, exhibiting anatase as well as rutile phases.

  6. Growth of metal oxide nanoparticles using pulsed laser ablation technique

    NASA Astrophysics Data System (ADS)

    Gondal, M. A.; Drmosh, Q. A.; Saleh, Tawfik A.; Yamani, Z. H.

    2011-02-01

    Nano particles exhibit physical and chemical properties distinctively different from that of bulk due to high number of surface atoms, surface energy and surface area to volume ratio. Laser is a unique source of radiation and has been applied in the synthesis of nano structured metal oxides. The pulsed laser ablation (PLA) technique in liquid medium has been proven an effective and simple technique for preparing nanoparticles of high purity. Pulsed laser deposition (PLD) is another way to fabricate nano structured single crystal thin films of metal oxides. PLA technique has been applied in our laboratory for the growth of metal oxides such as nano-ZnO, nano-ZnO2 nano- SnO2, nano-Bi2O3, nano-NiO and nano-MnO2. Different techniques such as AFM, UV, FT-IR, PL and XRD were applied to characterize these materials. We will present our latest development in the growth of nano metal oxides using PLA and PLD.

  7. On the plume splitting of pulsed laser ablated Fe and Al plasmas

    NASA Astrophysics Data System (ADS)

    Mahmood, S.; Rawat, R. S.; Darby, M. S. B.; Zakaullah, M.; Springham, S. V.; Tan, T. L.; Lee, P.

    2010-10-01

    A time resolved imaging study of pulsed laser ablated Fe and Al plasma plumes with specific interest in the splitting of plumes into the slow and fast moving components as they expand through the background argon gas at different pressures is reported. The material ablation was achieved using a Q-switched Nd:YAG (yttrium aluminum garnet) laser operating at 532 nm with a pulse duration of ˜8 ns full width at half maximum and a fluence of 30 Jcm-2 at the target surface. Typical time resolved images with low magnification show that the splitting occurs at moderate background gas pressures (0.5 and 1.0 mbar for Fe, and 0.2 mbar for Al plasma plumes). The plume splitting did not occur for higher background gas pressures.

  8. On the plume splitting of pulsed laser ablated Fe and Al plasmas

    SciTech Connect

    Mahmood, S.; Rawat, R. S.; Springham, S. V.; Tan, T. L.; Lee, P.; Darby, M. S. B.; Zakaullah, M.

    2010-10-15

    A time resolved imaging study of pulsed laser ablated Fe and Al plasma plumes with specific interest in the splitting of plumes into the slow and fast moving components as they expand through the background argon gas at different pressures is reported. The material ablation was achieved using a Q-switched Nd:YAG (yttrium aluminum garnet) laser operating at 532 nm with a pulse duration of {approx}8 ns full width at half maximum and a fluence of 30 Jcm{sup -2} at the target surface. Typical time resolved images with low magnification show that the splitting occurs at moderate background gas pressures (0.5 and 1.0 mbar for Fe, and 0.2 mbar for Al plasma plumes). The plume splitting did not occur for higher background gas pressures.

  9. Characteristics of Fe Ablation Trials Observed During the 1998 Leonid Meteor Shower

    NASA Technical Reports Server (NTRS)

    Chu, Xin-Zhao; Pan, Wei-Lin; Papen, George; Swenson, Gary; Gardner, Chester S.; Jenniskens, Peter; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Eighteen Fe ablation trails were observed during the 17/18 Nov 1998 Leonid meteor shower with an airborne Fe lidar aboard the National Simulation Facility/National Center for Atmospheric Research (NSF/NCAR) Electra aircraft over Okinawa. The average altitude of the 18 trails from the high velocity (72 km/s) Leonid meteors, 95.67 +/- 0.93 km, is approximately 6.7 km higher than previously observed for slower (approx. 30 km/s) sporadic meteors. This height difference is consistent with the assumption that meteors ablate when the kinetic energy imparted to the atmosphere reaches a critical threshold. The average age of the Fe trails, determined by a diffusion model, is 10.1 min. The youngest ages were observed below 92 km and above 98 km where chemistry and diffusion dominate, respectively. The average abundance of the trails is ten percent of the abundance of the background Fe layer. Observations suggest that the 1998 Leonid shower did not have a significant impact on the abundance of the background Fe layer.

  10. Guidelines for finding concretionary Mn-Fe oxides in streams

    USGS Publications Warehouse

    Nowlan, G.A.

    1982-01-01

    Concretionary Mn-Fe oxides in streams form at interfaces between oxidizing and reducing environments. A reducing environment produces waters high in dissolved Mn and Fe, and an oxidizing environment causes precipitation. Mineralogical, microprobe, and optical studies of concretionary Mn-Fe oxides may further our understanding of the role of Mn-Fe oxides in determining the trace-element geochemistry of stream sediments. ?? 1982.

  11. Gas Effect On Plasma Dynamics Of Laser Ablation Zinc Oxide

    NASA Astrophysics Data System (ADS)

    Abdelli-Messaci, S.; Kerdja, T.; Lafane, S.; Malek, S.

    2008-09-01

    In order to synthesis zinc oxide thin films and nanostructures, laser ablation of ZnO target into both vacuum and oxygen atmosphere was performed. The gas effect on the plume dynamics was studied for O2 pressures varied between 10-2 to 70 mbar. Plasma plume evolution was investigated by ICCD camera fast imaging. The plasma was created by a KrF excimer laser (λ = 248 nm, τ = 25 ns) at a fluence of 2 J/cm2. The light emitted by the plume was observed along the perpendicular to the ejection direction through a fast intensified charge-coupled device (ICCD). We have found that the plasma dynamics is very affected by the gas pressures. The photographs reveal the stratification of plasma into slow and fast components for 0.5 mbar O2 pressures and beyond. The photographs also show the apparition of hydrodynamic instabilities which are related to chemical reactions between the plasma and the surrounding gas for a certain range of pressures.

  12. Gas Effect On Plasma Dynamics Of Laser Ablation Zinc Oxide

    SciTech Connect

    Abdelli-Messaci, S.; Kerdja, T.; Lafane, S.; Malek, S.

    2008-09-23

    In order to synthesis zinc oxide thin films and nanostructures, laser ablation of ZnO target into both vacuum and oxygen atmosphere was performed. The gas effect on the plume dynamics was studied for O{sub 2} pressures varied between 10{sup -2} to 70 mbar. Plasma plume evolution was investigated by ICCD camera fast imaging. The plasma was created by a KrF excimer laser ({lambda} = 248 nm, {tau} = 25 ns) at a fluence of 2 J/cm{sup 2}. The light emitted by the plume was observed along the perpendicular to the ejection direction through a fast intensified charge-coupled device (ICCD). We have found that the plasma dynamics is very affected by the gas pressures. The photographs reveal the stratification of plasma into slow and fast components for 0.5 mbar O{sub 2} pressures and beyond. The photographs also show the apparition of hydrodynamic instabilities which are related to chemical reactions between the plasma and the surrounding gas for a certain range of pressures.

  13. Oxidation of Fe(II)-EDTA by nitrite and by two nitrate-reducing Fe(II)-oxidizing Acidovorax strains.

    PubMed

    Klueglein, N; Picardal, F; Zedda, M; Zwiener, C; Kappler, A

    2015-03-01

    The enzymatic oxidation of Fe(II) by nitrate-reducing bacteria was first suggested about two decades ago. It has since been found that most strains are mixotrophic and need an additional organic co-substrate for complete and prolonged Fe(II) oxidation. Research during the last few years has tried to determine to what extent the observed Fe(II) oxidation is driven enzymatically, or abiotically by nitrite produced during heterotrophic denitrification. A recent study reported that nitrite was not able to oxidize Fe(II)-EDTA abiotically, but the addition of the mixotrophic nitrate-reducing Fe(II)-oxidizer, Acidovorax sp. strain 2AN, led to Fe(II) oxidation (Chakraborty & Picardal, 2013). This, along with other results of that study, was used to argue that Fe(II) oxidation in strain 2AN was enzymatically catalyzed. However, the absence of abiotic Fe(II)-EDTA oxidation by nitrite reported in that study contrasts with previously published data. We have repeated the abiotic and biotic experiments and observed rapid abiotic oxidation of Fe(II)-EDTA by nitrite, resulting in the formation of Fe(III)-EDTA and the green Fe(II)-EDTA-NO complex. Additionally, we found that cultivating the Acidovorax strains BoFeN1 and 2AN with 10 mM nitrate, 5 mm acetate, and approximately 10 mM Fe(II)-EDTA resulted only in incomplete Fe(II)-EDTA oxidation of 47-71%. Cultures of strain BoFeN1 turned green (due to the presence of Fe(II)-EDTA-NO) and the green color persisted over the course of the experiments, whereas strain 2AN was able to further oxidize the Fe(II)-EDTA-NO complex. Our work shows that the two used Acidovorax strains behave very differently in their ability to deal with toxic effects of Fe-EDTA species and the further reduction of the Fe(II)-EDTA-NO nitrosyl complex. Although the enzymatic oxidation of Fe(II) cannot be ruled out, this study underlines the importance of nitrite in nitrate-reducing Fe(II)- and Fe(II)-EDTA-oxidizing cultures and demonstrates that Fe(II)-EDTA cannot

  14. Enhanced dechlorination of m-DCB using iron@graphite/palladium (Fe@C/Pd) nanoparticles produced by pulsed laser ablation in liquid.

    PubMed

    Yu, Yiseul; Jung, Hyeon Jin; Je, Mingyu; Choi, Hyun Chul; Choi, Myong Yong

    2016-07-01

    In this work, the zero valent Fe (ZVI) and graphite-encapsulated Fe (Fe@C) nanoparticles (NPs) were easily and selectively prepared by a pulsed laser ablation (PLA) method in an aqueous sodium borohydride solution and ascorbic acid dissolved in methanol, respectively. Here, the Fe@C NPs were uniquely synthesized by PLA in methanol, where the solvent is used as both a carbon source for the graphitic layers and solvent, which is very unique. Furthermore, Pd NPs were loaded onto the surface of the Fe@C NPs to prepare bimetallic (Fe@C/Pd) NPs for the enhancement of the degradation efficiency of m-dichlorobenzene (m-DCB). The morphology, crystallinity, and surface composition of the prepared NPs were carefully characterized by high-resolution transmission electron microscopy (HRTEM), energy dispersive x-ray spectrometer (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The degradation rate of m-DCB using single (Fe and Pd) or bimetallic (Fe/Pd and Fe@C/Pd) NPs were compared by using gas chromatography. Among these NPs produced in this work, the Fe@C/Pd NPs with 1.71 wt % of Pd showed an excellent dechlorination efficiency for m-DCB with 100% degradation within 75 min. The graphitic layer on the Fe NPs played as not only an oxidation resistant for the Fe NPs to surroundings, but also a supporter of the Pd NPs for the enhanced degradation efficiency of m-DCB. PMID:27129061

  15. Microbial Lithotrophic Oxidation of Structural Fe(II) in Biotite

    PubMed Central

    Xu, Huifang; Konishi, Hiromi; Kukkadapu, Ravi; Wu, Tao; Blöthe, Marco; Roden, Eric

    2012-01-01

    Microorganisms are known to participate in the weathering of primary phyllosilicate minerals through the production of organic ligands and acids and through the uptake of products of weathering. Here we show that the lithotrophic Fe(II)-oxidizing, nitrate-reducing enrichment culture described by Straub et al. (K. L. Straub, M. Benz, B. Schink, and F. Widdel, Appl. Environ. Microbiol. 62:1458–1460, 1996) can grow via oxidation of structural Fe(II) in biotite, a Fe(II)-rich trioctahedral mica found in granitic rocks. Oxidation of silt/clay-sized biotite particles was detected by a decrease in extractable Fe(II) content and simultaneous nitrate reduction. Mössbauer spectroscopy confirmed structural Fe(II) oxidation. Approximately 1.5 × 107 cells were produced per μmol of Fe(II) oxidized, in agreement with previous estimates of the growth yield of lithoautotrophic circumneutral-pH Fe(II)-oxidizing bacteria. Microbial oxidation of structural Fe(II) resulted in biotite alterations similar to those found in nature, including a decrease in the unit cell b dimension toward dioctahedral levels and Fe and K release. Structural Fe(II) oxidation may involve either direct enzymatic oxidation, followed by solid-state mineral transformation, or indirect oxidation as a result of the formation of aqueous Fe, followed by electron transfer from Fe(II) in the mineral to Fe(III) in solution. Although it is not possible to distinguish between these two mechanisms with available data, the complete absence of aqueous Fe in oxidation experiments favors the former alternative. The demonstration of microbial oxidation of structural Fe(II) suggests that microorganisms are directly responsible for the initial step in the weathering of biotite in granitic aquifers and the plant rhizosphere. PMID:22685132

  16. Destruction of monocrystalline silicon with nanosecond pulsed fiber laser accompanied by the oxidation of ablation microparticles

    NASA Astrophysics Data System (ADS)

    Veiko, V. P.; Skvortsov, A. M.; Huynh, C. T.; Petrov, A. A.

    2013-11-01

    In this work, we report an observation of process of local destruction monocrystalline silicon with a scanning beam irradiation of pulse ytterbium fiber laser with a wavelength λ= 1062 nm, accompanied by the oxidation of ablation microparticles. It is shown that depending on the power density of irradiation was observed a large scatter size of the microparticles. From a certain average power density is observed beginning oxidation particulate emitted from the surface of the irradiated area. By varying the parameters of the laser beam such as scanning speed, pulse repetition rate, overlap of laser spot, radiation dose can be achieved almost complete oxidation of all formed during the ablation of microparticles.

  17. Fractionation of Fe isotopes during Fe(II) oxidation by a marine photoferrotroph is controlled by the formation of organic Fe-complexes and colloidal Fe fractions

    NASA Astrophysics Data System (ADS)

    Swanner, Elizabeth D.; Wu, Wenfang; Schoenberg, Ronny; Byrne, James; Michel, F. Marc; Pan, Yongxin; Kappler, Andreas

    2015-09-01

    Much interest exists in finding mineralogical, organic, morphological, or isotopic biosignatures for Fe(II)-oxidizing bacteria (FeOB) that are retained in Fe-rich sediments, which could indicate the activity of these organisms in Fe-rich seawater, more common in the Precambrian Era. To date, the effort to establish a clear Fe isotopic signature in Fe minerals produced by Fe(II)-oxidizing metabolisms has been thwarted by the large kinetic fractionation incurred as freshly oxidized aqueous Fe(III) rapidly precipitates as Fe(III) (oxyhydr)oxide minerals at near neutral pH. The Fe(III) (oxyhydr)oxide minerals resulting from abiotic Fe(II) oxidation are isotopically heavy compared to the Fe(II) precursor and are not clearly distinguishable from minerals formed by FeOB isotopically. However, in marine hydrothermal systems and Fe(II)-rich springs the minerals formed are often isotopically lighter than expected considering the fraction of Fe(II) that has been oxidized and experimentally-determined fractionation factors. We measured the Fe isotopic composition of aqueous Fe (Feaq) and the final Fe mineral (Feppt) produced in batch experiment using the marine Fe(II)-oxidizing phototroph Rhodovulum iodosum. The δ56Feaq data are best described by a kinetic fractionation model, while the evolution of δ56Feppt appears to be controlled by a separate fractionation process. We propose that soluble Fe(III), and Fe(II) and Fe(III) extracted from the Feppt may act as intermediates between Fe(II) oxidation and Fe(III) precipitation. Based on 57Fe Mössbauer spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray total scattering, we suggests these Fe phases, collectively Fe(II/III)interm, may consist of organic-ligand bound, sorbed, and/or colloidal Fe(II) and Fe(III) mineral phases that are isotopically lighter than the final Fe(III) mineral product. Similar intermediate phases, formed in response to organic carbon produced by FeOB and inorganic

  18. Fe-Oxides in Water Remediation Technologies

    NASA Astrophysics Data System (ADS)

    Vaclavikova, M.; Stefusova, K.; Gallios, G. P.

    Water is essential for life, a strategic resource for every country and population. Its availability and sanitary safety is highly connected with the health and economic status of a population. The burden of disease due to polluted water is a major public health problem throughout the world. Many pollutants in water streams have been identified as toxic and harmful to the environment and human health, and among them arsenic, mercury and cadmium are considered those with the highest priority. Iron is the fourth most abundant element in the Earth's crust, and reactions involving iron play a major role in the environmental cycling of a range of important contaminants. Our earlier research has shown that Fe oxides/oxyhydroxides are particularly effective adsorbents of a range of contaminants (toxic metals), due to their high (reactive) specific surface area. It has been proven that Fe is particularly effective in As removal as a chemical bond is created on Fe surface and As is stabilised and can be safely deposited. Removal of contaminants from waste streams through precipitation with (hydrous) ferric oxides is an established methodology in a number of industrial processes (high density sludge systems for arsenic control in effluents from the mining industry, and in the treatment of textile dye effluent).

  19. Incorporation of oxidized uranium into Fe (hydr)oxides during Fe(II) catalyzed remineralization

    SciTech Connect

    Nico, Peter S.; Stewart, Brandy D.; Fendorf, Scott

    2009-07-01

    The form of solid phase U after Fe(II) induced anaerobic remineralization of ferrihydrite in the presence of aqueous and absorbed U(VI) was investigated under both abiotic batch and biotic flow conditions. Experiments were conducted with synthetic ground waters containing 0.168 mM U(VI), 3.8 mM carbonate, and 3.0 mM Ca{sup 2+}. In spite of the high solubility of U(VI) under these conditions, appreciable removal of U(VI) from solution was observed in both the abiotic and biotic systems. The majority of the removed U was determined to be substituted as oxidized U (U(VI) or U(V)) into the octahedral position of the goethite and magnetite formed during ferrihydrite remineralization. It is estimated that between 3% and 6% of octahedral Fe(III) centers in the new Fe minerals were occupied by U(VI). This site specific substitution is distinct from the non-specific U co-precipitation processes in which uranyl compounds, e.g. uranyl hydroxide or carbonate, are entrapped with newly formed Fe oxides. The prevalence of site specific U incorporation under both abiotic and biotic conditions and the fact that the produced solids were shown to be resistant to both extraction (30 mM KHCO{sub 3}) and oxidation (air for 5 days) suggest the potential importance of sequestration in Fe oxides as a stable and immobile form of U in the environment.

  20. Fe-Hydroxysulphates from Bacterial Fe2+ Oxidation

    NASA Astrophysics Data System (ADS)

    Eneroth, E.; Bender Koch, C.

    2004-12-01

    Precipitates formed due to Fe(II)-oxidation catalysed by Acidithiobacillus ferrooxidans between pH 1.6 and 3.2 have been studied by powder X-ray diffraction, infrared spectroscopy and Mössbauer spectroscopy. The precipitates consist of well crystalline, ammonium-containing jarosite at pH 1.6, and mixtures of jarosite and poorly crystalline schwertmannite at pH 2.5 and 3.2. At low temperatures (10 and 20 K) the components of the two phases overlap strongly. Jarosites ordered (c. 45 K - defect antiferromagnetic) at temperatures well below the ordering temperature for schwertmannite (c. 80 K at pH 3.2 and c. 70 K at pH 2.5). Thus thermoscans measured between 100 and 10 K facilitates characterization of these two minerals when occurring in mixtures.

  1. Influence of film thickness on laser ablation threshold of transparent conducting oxide thin-films

    NASA Astrophysics Data System (ADS)

    Rung, S.; Christiansen, A.; Hellmann, R.

    2014-06-01

    We report on a comprehensive study of the laser ablation threshold of transparent conductive oxide thin films. The ablation threshold is determined for both indium tin oxide and gallium zinc oxide as a function of film thickness and for different laser wavelengths. By using a pulsed diode pumped solid state laser at 1064 nm, 532 nm, 355 nm and 266 nm, respectively, the relationship between optical absorption length and film thickness is studied. We find that the ablation threshold decreases with increasing film thickness in a regime where the absorption length is larger than the film thickness. In turn, the ablation threshold increases in case the absorption length is smaller than the film thickness. In particular, we observe a minimum of the ablation threshold in a region where the film thickness is comparable to the absorption length. To the best of our knowledge, this behaviour previously predicted for thin metal films, has been unreported for all three regimes in case of transparent conductive oxides, yet. For industrial laser scribing processes, these results imply that the efficiency can be optimized by using a laser where the optical absorption length is close to the film thickness.

  2. Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals

    USGS Publications Warehouse

    Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

    2009-01-01

    Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.

  3. Microbial Lithotrophic Oxidation of Structural Fe(II) in Biotite

    SciTech Connect

    Shelobolina, Evgenya S.; Xu, Huifang; Konishi, Hiromi; Kukkadapu, Ravi K.; Wu, Tao; Blothe, Marco; Roden, Eric E.

    2012-06-08

    Microorganisms are known to participate in the weathering of primary phyllosilicate minerals through production of organic ligands and acids, and through uptake of products of weathering. Here we show that a lithotrophic Fe(II)-oxidizing, nitrate-reducing enrichment culture (Straub, 6 1996) can grow via oxidation of structural Fe(II) in biotite, a Fe(II)-rich trioctahedral mica found in granitic rocks. Oxidation of silt/clay sized biotite particles was detected by a decrease in extractable Fe(II) content and simultaneous nitrate reduction. Moessbauer spectroscopy confirmed structural Fe(II) oxidation. Approximately 107 cells were produced per {micro}mol Fe(II) oxidized, in agreement with previous estimates of the growth yield of lithoautotrophic circumneutral-pH Fe(II)-oxidizing bacteria. Microbial oxidation of structural Fe(II) resulted in biotite alterations similar to those found in nature, including decrease in unit cell b-dimension toward dioctahedral levels and iron and potassium release. The demonstration of microbial oxidation of structural Fe(II) suggests that microorganisms may be directly responsible for the initial step in the weathering of biotite in granitic aquifers and the plant rhizosphere.

  4. Endometrial ablation

    MedlinePlus

    Hysteroscopy-endometrial ablation; Laser thermal ablation; Endometrial ablation-radiofrequency; Endometrial ablation-thermal balloon ablation; Rollerball ablation; Hydrothermal ablation; Novasure ablation

  5. Martian Oxidant: May be Ferrate (Fe(VI))?

    NASA Technical Reports Server (NTRS)

    Tsapin, A.; Goldfeld, M.; McDonald, G.; Nealson, K.; Moskovitz, B.; Solheid, P.; Kemner, K.; Orlandini, K.

    1999-01-01

    Fe(VI) in the form of ferrate salts, with FeO(sub 4)(sup 2-) anion, was studied for its spectral and oxidative properties, with the question of whether it might be a suitable analog of the Mars soil oxidant, proposed as a result of the Viking missions of the early 1970s.

  6. Oxidation of silicon nanoparticles produced by nanosecond laser ablation in liquids

    NASA Astrophysics Data System (ADS)

    Vaccaro, L.; Camarda, P.; Messina, F.; Buscarino, G.; Agnello, S.; Gelardi, F. M.; Cannas, M.; Boscaino, R.

    2014-10-01

    We investigated nanoparticles produced by laser ablation of silicon in water by the fundamental harmonic (1064 nm) of a ns pulsed Nd:YAG. The silicon oxidation is evidenced by IR absorption features characteristic of amorphous SiO2 (silica). This oxide is highly defective and manifests a luminescence activity under UV excitation: two emission bands at 2.7 eV and 4.4 eV are associated with the twofold coordinated silicon, =SiO••.

  7. Iron and iron oxide nanoparticles obtained by ultra-short laser ablation in liquid

    NASA Astrophysics Data System (ADS)

    De Bonis, A.; Lovaglio, T.; Galasso, A.; Santagata, A.; Teghil, R.

    2015-10-01

    Laser ablation of an iron target in water and acetone has been carried out using a frequency doubled Nd:glass laser source (pulse duration of 250 fs and frequency repetition rate of 10 Hz). The observation of the nanostructures formed in the laser irradiated region of the metallic target and fast shadowgraphic analysis of the laser induced cavitation bubble have been performed in order to correlate the size distribution of the obtained nanoparticles to the dynamics of the ablation process. The composition, morphology and oxidation state of the synthesized nanoproducts have been investigated by XPS (X-ray Photoelectron Spectroscopy), TEM (Transmission Electron Microscopy) and microRaman spectroscopy. The experimental data support a relationship between the nanoparticles size distribution and the femtosecond laser ablation mechanism, while the chemical and structural characteristics of the nanoparticles can be tuned by varying the liquid medium.

  8. Self-limiting and complete oxidation of silicon nanostructures produced by laser ablation in water

    NASA Astrophysics Data System (ADS)

    Vaccaro, L.; Popescu, R.; Messina, F.; Camarda, P.; Schneider, R.; Gerthsen, D.; Gelardi, F. M.; Cannas, M.

    2016-07-01

    Oxidized Silicon nanomaterials produced by 1064 nm pulsed laser ablation in deionized water are investigated. High-resolution transmission electron microscopy coupled with energy dispersive X-ray spectroscopy allows to characterize the structural and chemical properties at a sub-nanometric scale. This analysis clarifies that laser ablation induces both self-limiting and complete oxidation processes which produce polycrystalline Si surrounded by a layer of SiO2 and amorphous fully oxidized SiO2, respectively. These nanostructures exhibit a composite luminescence spectrum which is investigated by time-resolved spectroscopy with a tunable laser excitation. The origin of the observed luminescence bands agrees with the two structural typologies: Si nanocrystals emit a μs-decaying red band; defects of SiO2 give rise to a ns-decaying UV band and two overlapping blue bands with lifetime in the ns and ms timescale.

  9. Ablation behavior of monolayer and multilayer Ir coatings under carburizing and oxidizing oxyacetylene flames

    NASA Astrophysics Data System (ADS)

    Wu, Wangping; Jiang, Jinjin; Chen, Zhaofeng

    2016-06-01

    Iridium is one of the most promising candidates for protective barrier of refractory materials to endure high service temperature. The multilayer iridium coating was produced by a double glow plasma process on the polished tungsten carbide substrates, compared with monolayer. The ablation behaviors of the monolayer on the unpolished and polished substrates were investigated under carburizing and oxidizing oxyacetylene flames, respectively, at the same time the multilayer coating ablated under oxidizing flames. Multilayer coating was a polycrystalline phase with the preferential (220) orientation. Monolayer on the unpolished substrate had fine coarse grains and some small microcracks were present. Multilayer consisted of columnar grains with some voids between the grains boundaries. The formation of a WIr phase in the as-deposited multilayer was attributed to high deposition temperature. The monolayer could endure high temperature up to 1800 °C in carburizing flame. The substrates could be protected more effectively by multilayer than monolayer at 2000- 2200 °C in oxidizing flame.

  10. Ligand-hole localization in oxides with unusual valence Fe

    PubMed Central

    Chen, Wei-Tin; Saito, Takashi; Hayashi, Naoaki; Takano, Mikio; Shimakawa, Yuichi

    2012-01-01

    Unusual high-valence states of iron are stabilized in a few oxides. A-site-ordered perovskite-structure oxides contain such iron cations and exhibit distinct electronic behaviors at low temperatures, e.g. charge disproportionation (4Fe4+ → 2Fe3+ + 2Fe5+) in CaCu3Fe4O12 and intersite charge transfer (3Cu2+ + 4Fe3.75+ → 3Cu3+ + 4Fe3+) in LaCu3Fe4O12. Here we report the synthesis of solid solutions of CaCu3Fe4O12 and LaCu3Fe4O12 and explain how the instabilities of their unusual valence states of iron are relieved. Although these behaviors look completely different from each other in simple ionic models, they can both be explained by the localization of ligand holes, which are produced by the strong hybridization of iron d and oxygen p orbitals in oxides. The localization behavior in the charge disproportionation of CaCu3Fe4O12 is regarded as charge ordering of the ligand holes, and that in the intersite charge transfer of LaCu3Fe4O12 is regarded as a Mott transition of the ligand holes. PMID:22690318

  11. Fe@Fe2O3 core-shell nanowires enhanced Fenton oxidation by accelerating the Fe(III)/Fe(II) cycles.

    PubMed

    Shi, Jingu; Ai, Zhihui; Zhang, Lizhi

    2014-08-01

    In this study we demonstrate Fe@Fe2O3 core-shell nanowires can improve Fenton oxidation efficiency by two times with rhodamine B as a model pollutant at pH > 4. Active species trapping experiments revealed that the rhodamine B oxidation enhancement was attributed to molecular oxygen activation induced by Fe@Fe2O3 core-shell nanowires. The molecular oxygen activation process could generate superoxide radicals to assist iron core for the reduction of ferric ions to accelerate the Fe(III)/Fe(II) cycles, which favored the H2O2 decomposition to produce more hydroxyl radicals for the rhodamine B oxidation. The combination of Fe@Fe2O3 core-shell nanowires and ferrous ions (Fe@Fe2O3/Fe(2+)) offered a superior Fenton catalyst to decompose H2O2 for producing OH. We employed benzoic acid as a probe reagent to check the generation of OH and found the OH generation rate of Fe@Fe2O3/Fe(2+) was 2-4 orders of magnitude larger than those of commonly used iron based Fenton catalysts and 38 times that of Fe(2+). The reusability and the stability of Fe@Fe2O3 core-shell nanowires were studied. Total organic carbon and ion chromatography analyses revealed the mineralization of rhodamine B and the releasing of nitrate ions. Gas chromatograph-mass spectrometry was used to investigate the degradation intermediates to propose the possible rhodamine B Fenton oxidation pathway in the presence of Fe@Fe2O3 nanowires. This study not only provides a new Fenton oxidation system for pollutant control, but also widen the application of molecular oxygen activation induced by nanoscale zero valent iron. PMID:24793112

  12. Synthesis and magnetic study of carbon coated iron oxide nanoparticles by laser ablation in solution

    NASA Astrophysics Data System (ADS)

    Prajapat, C. L.; Sharma, P.; Gonal, M. R.; Vatsa, R. K.; Singh, M. R.; Ravikumar, G.

    2016-05-01

    Magnetic Iron oxides nanoparticles (NPs) were prepared by Laser Ablation in Solution method. Formation and average size of iron oxide NPs (~8 nm) is confirmed by XRD pattern and magnetization studies. Detailed magnetic studies have been carried out using SQUID magnetometer. The saturation magnetization for the iron oxide NPs was found to be 60.07 emu/g. Below the blocking temperature of 150 K the hysteresis loop shows ferromagnetic nature, whereas it shows superparamagnetic behavior at 300 K, for the synthesized NPs.

  13. Preparation of iron oxide nanoparticles by laser ablation in DMF under effect of external magnetic field

    NASA Astrophysics Data System (ADS)

    Ismail, Raid A.; Sulaiman, Ghassan M.; Abdulrahman, Safa A.

    2016-05-01

    We have studied the effect of applying an external magnetic field on the characteristics of iron oxide (IO) nanoparticles (NPs) synthesized by pulsed laser ablation in dimethylformamide (DMF). The NPs synthesized with and without applying of magnetic field were characterized by Fourier transformation infrared spectroscopy (FT-IR), UV-Vis absorption, scanning electron microscope (SEM), atomic force microscope (AFM), and X-ray diffraction (XRD). SEM results confirmed that the particle size was decreased after applying magnetic field.

  14. Sustaining reactivity of Fe(0) for nitrate reduction via electron transfer between dissolved Fe(2+) and surface iron oxides.

    PubMed

    Han, Luchao; yang, Li; Wang, Haibo; Hu, Xuexiang; Chen, Zhan; Hu, Chun

    2016-05-01

    The mechanism of the effects of Fe(2+)(aq) on the reduction of NO3(-) by Fe(0) was investigated. The effects of initial pH on the rate of NO3(-) reduction and the Fe(0) surface characteristics revealed Fe(2+)(aq) and the characteristics of minerals on the surface of Fe(0) played an important role in NO3(-) reduction. Both NO3(-) reduction and the decrease of Fe(2+)(aq) exhibited similar kinetics and were promoted by each other. This promotion was associated with the types of the surface iron oxides of Fe(0). Additionally, further reduction of NO3(-) produced more surface iron oxides, supplying more active sites for Fe(2+)(aq), resulting in more electron transfer between Fe(2+) and surface iron oxides and a higher reaction rate. Using the isotope specificity of (57)Fe Mossbauer spectroscopy, it was verified that the Fe(2+)(aq) was continuously converted into Fe(3+) oxides on the surface of Fe(0) and then converted into Fe3O4 via electron transfer between Fe(2+) and the pre-existing surface Fe(3+) oxides. Electrochemistry measurements confirmed that the spontaneous electron transfer between the Fe(2+) and structural Fe(3+) species accelerated the interfacial electron transfer between the Fe species and NO3(-). This study provides a new insight into the interaction between Fe species and contaminants and interface electron transfer. PMID:26835898

  15. Synthesis of oxidation resistant lead nanoparticle films by modified pulsed laser ablation

    SciTech Connect

    Shin, Eunsung; Murray, P. Terrence; Subramanyam, Guru; Malik, Hans K.; Schwartz, Kenneth L.

    2012-07-30

    Thin layers of lead nanoparticles have been produced by a modified pulsed laser ablation (PLA) process in which smaller nanoparticles were swept out of the ablation chamber by a stream of flowing Ar. Large ({mu}m-sized) particles, which are usually deposited during the standard PLA process, were successfully eliminated from the deposit. The nanoparticles deposited on room temperature substrates were well distributed, and the most probable particle diameter was in the order of 30 nm. Since lead is highly reactive, the nanoparticles formed in Ar were quickly oxidized upon exposure to air. A small partial pressure of H{sub 2}S gas was subsequently added to the effluent, downstream from the ablation chamber, and this resulted in the formation of nanoparticle deposits that were surprisingly oxidation resistant. The properties of the nanoparticle films (as determined by transmission electron microscopy, scanning electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy, and conductivity measurements) are reported, and the mechanism of the oxidation retardation process is discussed.

  16. Synthesis of oxidation resistant lead nanoparticle films by modified pulsed laser ablation

    NASA Astrophysics Data System (ADS)

    Shin, Eunsung; Murray, P. Terrence; Subramanyam, Guru; Malik, Hans K.; Schwartz, Kenneth L.

    2012-07-01

    Thin layers of lead nanoparticles have been produced by a modified pulsed laser ablation (PLA) process in which smaller nanoparticles were swept out of the ablation chamber by a stream of flowing Ar. Large (μm-sized) particles, which are usually deposited during the standard PLA process, were successfully eliminated from the deposit. The nanoparticles deposited on room temperature substrates were well distributed, and the most probable particle diameter was in the order of 30 nm. Since lead is highly reactive, the nanoparticles formed in Ar were quickly oxidized upon exposure to air. A small partial pressure of H2S gas was subsequently added to the effluent, downstream from the ablation chamber, and this resulted in the formation of nanoparticle deposits that were surprisingly oxidation resistant. The properties of the nanoparticle films (as determined by transmission electron microscopy, scanning electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy, and conductivity measurements) are reported, and the mechanism of the oxidation retardation process is discussed.

  17. Electrochromism of dip-coated Fe-oxide, Fe/Ti-oxide and Fe/Si-oxide films prepared by the sol-gel route

    SciTech Connect

    Orel, B.; Macek, M.; Surca, A.

    1994-12-31

    Iron oxide films which were synthesized via the sol-gel route from the iron (III) chloride precursor exhibit electrochromism (T{sub b}-T{sub c} {approx_equal} 55% at 400 nm) in LiOH (0.01 M) electrolyte. The structure of the XRD amorphous films was identified with the help of near-normal reflection absorption (6{degree}) (IRRA) and near-grazing incidence angle (NGIA) FT-IR spectroscopy to correspond to the nano-crystalline {gamma}-Fe{sub 2}O{sub 3}. Ex-situ NGIA FT-IR spectra of bleached and re-colored films were measured and it was found that the Fe-oxide films irreversibly change to the new phase in which ``amorphous iron oxide`` is admixed with the characteristic LO mode at 545 cm{sup {minus}1}. Electrochemical stability of the Fe-oxide film was modified by admixing other non-absorbing Ti and Si-oxides. The structure of the mixed oxide films was identified from the corresponding IR spectra and was described as translatory disordered solid solution in which the phonon modes exhibit one mode (Fe/Ti-oxide) and two-mode (Fe/Si-oxide) behavior. Electrochemical investigations revealed that the films are able to uptake reversibly Li{sup +}, Na{sup +}, K{sup +} ions with Q/d values in the range 0.1--0.31 mQ/cm{sup 2}nm. The electrochromic properties of the films investigated were established from the measured in-situ UV-VIS spectroelectrochemical measurements which revealed that the electrochromic efficiencies ({Delta}OD/Q{sub (de)int}) are in the range of 6--14 cm{sup 2}/C. The nature of the electrochromic process is discussed and correlated to the absorption edges of the various iron oxygenated compounds.

  18. Comparative study of magnetite (Fe3O4) thin films grown by pulsed laser ablation and sputtering

    NASA Astrophysics Data System (ADS)

    Bohra, Murtaza; Varun Karthik Y., S.; Haveesh, G.; Tarun Y. S., N.; Prasad, D. V. B.; Chowdhury, D. Roy; Prasad, K. Eswar

    2016-05-01

    Comparative study of magnetite (Fe3O4) thin films grown by pulsed laser ablation (PLD) and radio frequency (RF)-sputtering of α-Fe2O3 target have been investigated. We have found strong correlation between RF power (P) of sputtering and substrate temperature (Ts) of PLD films on their structural and magnetic properties. Films grown at low P and Ts are dominated by antiferromagnetic α-Fe2O3 phase while ferrimagnetic Fe3O4 phase is dominant at high P and Ts Post-annealing in H2/H2O atmosphere at 450 °C, these films show single phase Fe3O4 but RF power and substrate temperature still play a significant role. With increasing P and Ts values, the orientation of Fe3O4 films change from (110) to (111) followed by complete randomizations. These (110) to (111) orientations affect magnetic properties differently above Verwey transition temperature of 120 K. The RF-power and substrate temperature have the same influence on the physical properties of Fe3O4 films, as both are related to thermal energy.

  19. Optical properties of petal-like aggregated nanocrystalline zinc oxide synthesized by laser ablation

    SciTech Connect

    Jafarkhani, P.; Chehrghani, A.; Torkamany, M.J.

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer Petal like ZnO nanocrystals are synthesized by high frequency laser ablation in water. Black-Right-Pointing-Pointer Optical band gap of ZnO nanocrystals was tunable by changing the laser pulse energy. Black-Right-Pointing-Pointer Nonlinear optical properties and limiting threshold were obtained by Z-scan technique. -- Abstract: The results of the investigations carried out on the third-order nonlinearity in zinc oxide (ZnO) nanocrystals (NCs) by Z-scan technique are included in this paper. ZnO NCs show negative nonlinearity and good nonlinear absorption behavior at 532 nm. The third-order optical susceptibility {chi}(3) increases with enlargement of NCs due to the size dependent enhancement of exciton oscillator strength. The synthesis of ZnO NCs was performed by laser ablation from a high-purity metallic target of Zn in distilled water medium. For the ablation process, a high frequency pulsed Nd:YAG laser was employed operating at 532 nm with 100 ns pulse duration. UV-vis absorption spectroscopy illustrated the enhancement of the size of ZnO NCs upon increasing the laser pulse energy applied in ablation process. Accordingly the corresponding optical band gap (E{sub g}) decrease by increasing the size of NCs. X-ray diffraction (XRD) associated with transmission electron microscopy (TEM) was utilized to characterize the crystalline phase and also for determining the ZnO NCs morphology.

  20. Effects of FeS on Chromium Oxidation Mediated by Manganese Oxidizers

    SciTech Connect

    Wu, Youxian; Deng, Baolin

    2004-03-31

    Reductive immobilization of Cr(VI) has been widely explored as a cost-effective approach for Cr-contaminated site remediation. The long-term stability of the immobilized Cr(III), however, is a concern. Cr(III) is known to be oxidized by Mn oxides chemically and Mn-oxides could be produced through microbially mediated Mn(II) oxidation. This study examined the effect of FeS on Cr(III) oxidation mediated by Pseudomonas putida. The results showed that commercial granular FeS did not affect Cr(III) oxidation in the culture of P. putida with Mn(II), but freshly precipitated FeS slurry inhibited Cr(III) oxidation. A 10 mg/l of FeS did not inhibit the microbial growth, but delayed the production of Mn oxides, thus postponing potential Cr(III) oxidation. In the presence of excessive FeS slurry, both Cr(VI) and Mn oxides were reduced rapidly. The reduced Cr(III) could not be re-oxidized as long as freshly formed FeS was present, even in the presence of the manganese oxidizers.

  1. Ferrates(FeVI, FeV, and FeIV) oxidation of iodide: Formation of triiodide.

    PubMed

    Kralchevska, Radina P; Sharma, Virender K; Machala, Libor; Zboril, Radek

    2016-02-01

    The presence of iodide (I(-)) in water during disinfection and oxidative treatment of water is a potential health concern because of the formation of iodinated disinfection by-products (DBPs), which may be more toxic than chlorinated DBPs. The kinetics of the oxidation of I(-) by a greener oxidant, ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) was determined as a function of pH. The second-order rate constants (k, M(-1) s(-1)) decreased from 3.9 × 10(4) M(-1) s(-1) at pH 5.0 to 1.2 × 10(1) M(-1) s(-1) at pH 10.3. The kinetics results could be described by the reactivity of monoprotonated species of Fe(VI) (HFe(VI)O4(-)) with I(-). In excess I(-) concentration, triiodide (I3(-)) was formed and the stoichiometry of ∼1:1 ([Fe(VI)]:[I3(-)]) was found in both acidic and basic pH. Ferrate(V) (Fe(V)O4(3-), Fe(V)) and ferrate(IV) (Fe(VI)O4(4-), Fe(IV)) also showed the formation of I3(-) in presence of excess I(-). A mechanism of the formation of I3(-) is proposed, which is consistent with the observed stoichiometry of 1:1. The oxidative treatment of I(-) in water will be rapid (t1/2 = 0.6 s at pH 7.0 using 10 mg L(-1) K2FeO4). The implications of the results and their comparison with the oxidation of I(-) by conventional disinfectants/oxidants in water treatment are briefly discussed. PMID:26461440

  2. Biostimulation of Iron Reduction and Subsequent Oxidation of Sediment Containing Fe-silicates and Fe-oxides: Effect of Redox Cycling on Fe(III) Bioreduction

    SciTech Connect

    Komlos, John; Kukkadapu, Ravi K.; Zachara, John M.; Jaffe, Peter R.

    2007-07-01

    Microbial reduction of iron has been shown to be important in the transformation and remediation of contaminated sediments. Re-oxidation of microbially reduced iron may occur in sediments that experience oxidation-reduction cycling and can thus impact the extent of contaminant remediation. The purpose of this research was to quantify iron oxidation in a flow-through column filled with biologically-reduced sediment and to compare the iron phases in the re-oxidized sediment to both the pristine and biologically-reduced sediment. The sediment contained both Fe(III)-oxides (primarily goethite) and silicate Fe (illite/vermiculite) and was biologically reduced in phosphate buffered (PB) medium during a 497 day column experiment with acetate supplied as the electron donor. Long-term iron reduction resulted in partial reduction of silicate Fe(III) without any goethite reduction, based on Mössbauer spectroscopy measurements. This reduced sediment was treated with an oxygenated PB solution in a flow-through column resulting in the oxidation of 38% of the biogenic Fe(II). Additional batch experiments showed that the Fe(III) in the oxidized sediment was more quickly reduced compared to the pristine sediment, indicating that oxidation of the sediment not only regenerated Fe(III) but also enhanced iron reduction compared to the pristine sediment. Oxidation-reduction cycling may be a viable method to extend iron-reducing conditions during in-situ bioremediation.

  3. Photoluminescent zinc oxide polymer nanocomposites fabricated using picosecond laser ablation in an organic solvent

    NASA Astrophysics Data System (ADS)

    Wagener, Philipp; Faramarzi, Shamsolzaman; Schwenke, Andreas; Rosenfeld, Rupert; Barcikowski, Stephan

    2011-06-01

    Nanocomposites made of ZnO nanoparticles dispersed in thermoplastic polyurethane were synthesized using picosecond laser ablation of zinc in a polymer-doped solution of tetrahydrofuran. The pre-added polymer stabilizes the ZnO nanoparticles in situ during laser ablation by forming a polymer shell around the nanoparticles. This close-contact polymer shell has a layer thickness up to 30 nm. Analysis of ZnO polyurethane nanocomposites using optical spectroscopy, high resolution transmission electron microscopy and X-ray diffraction revealed that oxidized and crystalline ZnO nanoparticles were produced. Those nanocomposites showed a green photoluminescence emission centred at 538 nm after excitation at 350 nm, which should be attributed to oxygen defects generated during the laser formation mechanism of the monocrystalline nanoparticles. Further, the influence of pulse energy and polymer concentration on the production rate, laser fluence and energy-specific mass productivity was investigated.

  4. Oxidation behavior of FeAl+Hf,Zr,B

    NASA Technical Reports Server (NTRS)

    Smialek, James L.; Doychak, Joseph

    1988-01-01

    The oxidation behavior of Fe-40Al-1Hf, Fe-40Al-1Hf-0.4B, and Fe-40Al-0.1Zr-0.4B (at. percent) alloys was characterized after 900, 1000, and 100 C exposures. Isothermal tests revealed parabolic kinetics after a period of transitional theta-alumina scale growth. The parabolic growth rates for the subsequent alpha-alumina scales were about five times higher than those for NiAl+0.1Zr alloys. The isothermally grown scales showed a propensity toward massive scale spallation due to both extensive rumpling from growth stresses and to an inner layer of HfO2. Cyclic oxidation for 200 1-hr cycles produced little degradation at 900 or 1000 C, but caused significant spallation at 1100 C in the form of small segments of the outer scale. The major difference in the cyclic oxidation of the three FeAl alloys was increased initial spallation for FeAl+Zr,B. Although these FeAl alloys showed many similarities to NiAl alloys, they were generally less oxidation resistant. It is believed that this resulted from nonoptimal levels of dopants and larger thermal expansion mismatch stresses.

  5. Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

    USGS Publications Warehouse

    Balci, N.; Bullen, T.D.; Witte-Lien, K.; Shanks, Wayne C.; Motelica, M.; Mandernack, K.W.

    2006-01-01

    Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42- and Cl- salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor ??Fe(III)aq-Fe(II)aq???1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (???1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (???1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9??? (??Fe(III)aq-Fe(II)aq ???1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments

  6. The Diverse Microbiology of Anaerobic Fe(II) Oxidation

    NASA Astrophysics Data System (ADS)

    Coates, J. D.; Weber, K. A.; Scherer, M.; Achenbach, L. A.

    2007-12-01

    Although anaerobic microbial oxidation of Fe(II) has been know for over a decade there is still a paucity of information available on this important metabolic process or the organisms involved. Recent studies have indicated that the metabolism is ubiquitous and a broad diversity of organisms are capable of oxidizing Fe(II) in the absence of oxygen. Our previous studies demonstrated the existence of geochemical conditions conducive to supporting the activity of nitrate-dependent Fe(II) oxidizing bacteria (NFoB) in sedimentary environments. As part of these studies we isolated and characterized several novel NFoBs. Three of these organisms, Diaphorobacter sp. strain TPSY, Ferrutens nitratireducens strain 2002 and Azospira suillum strain PS are currently undergoing whole genome shotgun sequencing in an effort to gain insight into the biochemistry and molecular biology of this geochemically important metabolism. These organisms represent diverse genera capable of anaerobically oxidizing Fe(II) using nitrate as the electron acceptor. Two of these organisms, strain 2002 and strain TPSY, are also capable of the anaerobic nitrate-dependent oxidation of U(IV) to U(VI). Diaphorobacter sp. strain TPSY was isolated from uranium and nitrate contaminated groundwater and is a member of the Comamonadaceae family in the beta subclass of the Proteobacteria, closely related to Diaphorobacter nitroreducens. It represents the first example of an anaerobic Fe(II)-oxidizer from the Comamonadaceae family and grows mixotrophically requiring an organic carbon source when growing with Fe(II) and nitrate as the electron donor and acceptor respectively. F. nitratireducens strain 2002 was isolated from aquatic sediment and is the type strain of a new genus, Ferrutens, in the beta class of the Proteobacteria. Its closest relative is Chromobacterium violaceum, a common soil bacterium. In contrast to C. violaceum, F. nitratireducens is non-fermentative and does not produce free cyanide (CN-) or

  7. Single-step synthesis of graphene quantum dots by femtosecond laser ablation of graphene oxide dispersions.

    PubMed

    Russo, Paola; Liang, Robert; Jabari, Elahe; Marzbanrad, Ehsan; Toyserkani, Ehsan; Zhou, Y Norman

    2016-04-21

    In the last few years, graphene quantum dots (GQDs) have attracted the attention of many research groups for their outstanding properties, which include low toxicity, chemical stability and photoluminescence. One of the challenges of GQD synthesis is finding a single-step, cheap and sustainable approach for synthesizing these promising nanomaterials. In this study, we demonstrate that femtosecond laser ablation of graphene oxide (GO) dispersions could be employed as a facile and environmentally friendly synthesis method for GQDs. With the proper control of laser ablation parameters, such as ablation time and laser power, it is possible to produce GQDs with average sizes of 2-5 nm, emitting a blue luminescence at 410 nm. We tested the feasibility of the synthesized GQDs as materials for electronic devices by aerosol-jet printing of an ink that is a mixture of water dispersion of laser synthesized GQDs and silver nanoparticle dispersion, which resulted in lower resistivity of the final printed patterns. Preliminary results showed that femtosecond laser synthesized GQDs can be mixed with silver nanoparticle dispersion to fabricate a hybrid material, which can be employed in printing electronic devices by either printing patterns that are more conductive and/or reducing costs of the ink by decreasing the concentration of silver nanoparticles (AgNPs) in the ink. PMID:27071944

  8. Synthesis of silver nanoparticles and antimony oxide nanocrystals by pulsed laser ablation in liquid media

    NASA Astrophysics Data System (ADS)

    Mendivil, M. I.; Krishnan, B.; Sanchez, F. A.; Martinez, S.; Aguilar-Martinez, J. A.; Castillo, G. A.; Garcia-Gutierrez, D. I.; Shaji, S.

    2013-03-01

    Pulsed laser ablation in liquid media (PLALM) is a prominent technique for the controlled fabrication of nanomaterials via rapid reactive quenching of ablated species at the interface between the plasma and liquid. Results on nanoparticles and nanocrystals formed by PLALM of silver (Ag) and antimony (Sb) solid targets in different liquid environments (Sodium Dodecyl Sulfate, distilled water) are presented. These experiments were done by irradiating solid targets of Ag and Sb with a nanosecond pulsed Nd:YAG laser output of wavelength 532 nm. Nanoparticles of silver and nanocrystals of antimony oxide (Sb2O3) obtained were characterized using UV-Vis spectrometry, Scanning Electron Microscopy (SEM), transmission electron microscopy (TEM), X-ray Energy Dispersion Analysis (EDAX) and X-ray diffractometry (XRD). The morphology of nanomaterials formed is studied as a function of surfactant environment. The silver nanoparticles obtained were spherical of size in the order of 10-35 nm in solution of SDS having different concentrations. In case of the Sb target, ablation was performed in two different molarities of SDS solution and distilled water. Nanocrystals of Sb2O3 in powder form having cubic and orthorhombic phases were formed in SDS solution and as fibers of nanocrystals of cubic Sb2O3 in distilled water.

  9. CO sub 2 -laser ablation of Bi-Sr-Ca-Cu oxide by millisecond pulse lengths

    SciTech Connect

    Meskoob, M.; Honda, T.; Safari, A.; Wachtman, J.B.; Danforth, S. ); Wilkens, B.J. )

    1990-03-15

    We have achieved ablation of Bi-Sr-Ca-Cu oxide from single targets of superconducting pellets by CO{sub 2}-laser pulses of l ms length to grow superconducting thin films. Upon annealing, the 6000-A thin films have a {ital T}{sub {ital c}} (onset) of 90 K and zero resistance at 78 K. X-ray diffraction patterns indicate the growth of single-phase thin films. This technique allows growth of uniform single-phase superconducting thin films of lateral area greater than 1 cm{sup 2}.

  10. Effect of phosphate and sulfate on Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide mineral recrystallization

    NASA Astrophysics Data System (ADS)

    Hinkle, Margaret A. G.; Catalano, Jeffrey G.

    2015-09-01

    Dissolved Fe(II) activates coupled oxidative growth and reductive dissolution of Fe(III) oxide minerals, causing recrystallization and the repartitioning of structurally-compatible trace metals. Phosphate and sulfate, two ligands common to natural aquatic systems, alter Fe(II) adsorption onto Fe(III) oxides and affect Fe(III) oxide dissolution and precipitation. However, the effect of these oxoanions on trace metal repartitioning during Fe(II)-catalyzed Fe(III) oxide recrystallization is unclear. The effects of phosphate and sulfate on Ni adsorption and Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide recrystallization were investigated as such repartitioning may be affected by both Fe(II)-oxoanion and metal-oxoanion interactions. In most systems examined, phosphate alters Ni repartitioning during Fe(II)-catalyzed recrystallization to a larger extent than sulfate. Phosphate substantially enhances Ni adsorption onto hematite but decreases (nearly inhibiting) Fe(II)-catalyzed Ni incorporation into and release from this mineral. In the goethite system, however, phosphate suppresses Ni release but enhances Ni incorporation in the presence of aqueous Fe(II). In contrast, sulfate has little effect on macroscopic Ni adsorption and release of Ni from Fe(III) oxides, but substantially enhances Ni incorporation into goethite. This demonstrates that phosphate and sulfate have unique, mineral-specific interactions with Ni during Fe(II)-catalyzed Fe(III) oxide recrystallization. This research suggests that micronutrient bioavailability at redox interfaces in hematite-dominated systems may be especially suppressed by phosphate, while both oxoanions likely have limited effects in goethite-rich soils or sediments. Phosphate may also exert a large control on contaminant fate at redox interfaces, increasing Ni retention on iron oxide surfaces. These results further indicate that trace metal retention by iron oxides during lithification and later repartitioning during

  11. Graphyne-supported single Fe atom catalysts for CO oxidation.

    PubMed

    Wu, Ping; Du, Pan; Zhang, Hui; Cai, Chenxin

    2015-01-14

    Single atom catalysts (SACs) are highly desirable for the effort to maximize the efficiency of metal atom use. However, the synthesis of SACs is a major challenge that largely depends on finding an appropriate supporting substrate to achieve a well-defined and highly dispersed single atom. This work demonstrates that, based on the density functional theory (DFT) calculation, graphyne is a good substrate for single Fe atom catalysts. The Fe atom can be tightly embedded in a graphyne sheet with a high binding energy of ∼4.99 eV and a high diffusion energy barrier of ∼1.0 eV. The graphyne-supported Fe (Fe-graphyne) SAC shows high catalytic activity towards CO oxidation, which is often regarded as a prototype reaction for designing atomic-scale catalysts. We studied the adsorption characteristics of CO and O2 on Fe-graphyne SACs, and simulated the reaction mechanism of CO oxidation involving Fe-graphyne. The simulation results indicate that O2 binding on Fe-graphyne is much stronger than that of CO, and the adsorbed O2 prior to occupy the Fe atoms as the co-existence of O2 and CO. The reaction of CO oxidation by adsorbed O2 on Fe-graphyne SACs favors to proceed via the Eley-Rideal (ER) mechanism with the energy barrier of as low as ∼0.21 eV in the rate-limiting step. Calculation of the electronic density of states (DOS) of each reaction step demonstrates that the strong interaction of the O2 and Fe adatom promotes the CO oxidation on Fe-graphyne SACs. The results presented here suggest that graphyne could provide a unique platform to synthesize SACs, and the Fe-graphyne SACs could find potential use in solving the growing environmental problems caused by CO emission from automobiles and industrial processes, in removing CO contamination from vehicle exhaust and in fuel cells. PMID:25429422

  12. Proteome of Geobacter sulfurreducens grown with Fe(III) oxide or Fe(III) citrate as the electron acceptor.

    SciTech Connect

    Ding, Y-H R.; Hixson, Kim K.; Aklujkar, Ma; Lipton, Mary S.; Smith, Richard D.; Lovley, Derek R.; Mester, Tunde

    2008-12-01

    e(III) oxides are the most abundant source of reducible Fe(III) by microorganisms in most soils and sediments, yet few studies on the physiology of Fe(III)-reducing microorganisms during growth on Fe(III) oxide have been conducted because of the technical difficulties in working with cell growth and harvest in the presence of Fe(III) oxides. Geobacter sulfurreducens is a representative of the Geobacter species that predominate in a variety of subsurface environments in which Fe(III) oxide is important. In order to better understand the physiology of Geobacter species during growth on Fe(III) oxide, the proteome of G. sulfurreducens grown on Fe(III) oxide was compared with the proteome of cells grown with soluble Fe(III) citrate. Two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) revealed 19 proteins that were more abundant during growth on Fe(III) oxide than on soluble Fe(III). These included proteins related to protein synthesis, electron transfer and energy production, oxidative stress, protein folding, outer membrane proteins, nitrogen metabolism and hypothetical proteins. Further analysis of the proteome with the accurate mass and time (AMT) tag method revealed additional proteins associated with growth on Fe(III) oxide. These included the outer-membrane c-type cytochrome, OmcS and OmcG, which genetic studies have suggested are required for Fe(III) oxide reduction. Furthermore, several other cytochromes, as yet unstudied, were detected to be significantly up regulated during growth on Fe(III) oxide and other proteins of unknown function were more abundant during growth on Fe(III) oxide than on soluble Fe(III). PilA, the structural protein for pili, which is required for Fe(III) oxide reduction, and other pilin-associated proteins were also more abundant during growth on Fe(III) oxide. Confirmation of the differential expression of proteins known to be important in Fe(III) oxide reduction was observed, and an additional number of previously

  13. Heterogeneous oxidation of Fe(II) on iron oxides in aqueous systems: Identification and controls of Fe(III) product formation

    NASA Astrophysics Data System (ADS)

    Larese-Casanova, Philip; Kappler, Andreas; Haderlein, Stefan B.

    2012-08-01

    The aqueous Fe(II)-oxide Fe(III) system is a reactant for many classes of redox sensitive compounds via an interfacial Fe(II) sorption and electron transfer process. The poorly soluble Fe(III) products formed as a result of contaminant reduction and Fe(II) oxidation on iron oxides may be capable of modifying iron oxide surfaces and affecting subsequent reduction rates of contaminants such as halogenated ethenes or nitroaromatic compounds. The scope of this study was to identify the secondary Fe(III) mineral phases formed after Fe(II) oxidation on common iron oxides during heterogeneous contaminant reduction by directly targeting the secondary minerals using Mössbauer-active isotopes. Fe(III) mineral characterization was performed using 57Fe-Mössbauer spectroscopy, μ-X-ray diffraction, and electron microscopy after oxidation of dissolved 57Fe(II) using nitrobenzenes as a model oxidant in pH-buffered suspensions of 56hematite, 56goethite, 56magnetite, and 56maghemite. Mössbauer spectra confirmed sorbed 57Fe(II) becomes oxidized by the parent 56Fe(III)-oxide sorbent and assimilated as the sorbent oxide prior to any nitrobenzene reduction, consistent with several reports in the literature. In addition to oxide sorbent growth, Fe(II) sorption and oxidation by nitrobenzene result also in the formation of secondary Fe(III) minerals. Goethite formed on three hematite morphologies (rhombohedra, needles, and hexagonal platelets), and acicular needle shapes typical of goethite appeared on the micron-sized hexagonal platelets, at times aligned in 60° orientations on (0 0 1) faces. The proportion of goethite formation on the three hematites was linked to number of surface sites. Only goethite was observed to form on a goethite sorbent. In contrast, lepidocrocite was observed to form on magnetite and maghemite sorbents (consistent with homogeneous Fe(II) oxidation by O2) and assumed spherulite morphologies. All secondary Fe(III) phases were confirmed within

  14. Pd2+ reduction and gasochromic properties of colloidal tungsten oxide nanoparticles synthesized by pulsed laser ablation

    NASA Astrophysics Data System (ADS)

    Tahmasebi Garavand, N.; Mahdavi, S. M.; Iraji zad, A.

    2012-08-01

    Tungsten oxide nanoparticles were fabricated by a pulsed laser ablation method in deionized water using the first harmonic of a Nd:YAG laser ( λ=1064 nm) at three different laser pulse energies (E1 =160, E2 =370 and E3 =500 mJ/pulse), respectively. The aim is to investigate the effect of laser pulse energy on the size distribution and gasochromic property of colloidal nanoparticles. The products were characterized by dynamic light scattering (DLS), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and UV-Vis spectroscopy. The results indicated that WO3 nanoparticles were formed. After ablation, a 0.2 g/l PdCl2 solution was added to activate the solution against hydrogen gas. In this process Pd2+ ions were reduced to deposit fine metallic Pd particles on the surface of tungsten oxide nanoparticles. The gasochromic response was measured by H2 and O2 gases bubbling into the produced colloidal Pd-WO3. The results indicate that the number of unreduced ions (Pd2+) decreases with increasing laser pulse energy; therefore, for colloidal nanoparticles synthesized at the highest laser pulse energy approximately all Pd2+ ions have been reduced. Hence, the gasochromic response for this sample is nearly reversible in all cycles, whereas those due to other samples are not reversible in the first cycle.

  15. Characterization of Tungsten Oxide Thin Films Produced by Spark Ablation for NO2 Gas Sensing.

    PubMed

    Isaac, Nishchay A; Valenti, Marco; Schmidt-Ott, Andreas; Biskos, George

    2016-02-17

    Tungsten oxides (WOx) thin films are currently used in electro-chromic devices, solar-cells and gas sensors as a result of their versatile and unique characteristics. In this study, we produce nanoparticulate WOx films by spark ablation and focused inertial deposition, and demonstrate their application for NO2 sensing. The primary particles in the as-deposited film samples are amorphous with sizes ranging from 10 to 15 nm. To crystallize the samples, the as-deposited films are annealed at 500 °C in air. This also caused the primary particles to grow to 30-50 nm by sintering. The morphologies and crystal structures of the resulting materials are studied using scanning and transmission electron microscopy and X-ray diffraction, whereas information on composition and oxidation states are determined by X-ray photoemission spectroscopy. The observed sensitivity of the resistance of the annealed films is ∼100 when exposed to 1 ppm of NO2 in air at 200 °C, which provides a considerable margin for employing them in gas sensors for measuring even lower concentrations. The films show a stable and repeatable response pattern. Considering the numerous advantages of spark ablation for fabricating nanoparticulate thin films, the results reported here provide a promising first step toward the production of high sensitivity and high accuracy sensors. PMID:26796099

  16. Bismuth Oxide Thin Films Deposited on Silicon Through Pulsed Laser Ablation, for Infrared Detectors

    NASA Astrophysics Data System (ADS)

    Condurache-Bota, Simona; Constantinescu, Catalin; Tigau, Nicolae; Praisler, Mirela

    2016-12-01

    Infrared detectors are used in many human activities, from industry to military, telecommunications, environmental studies and even medicine. Bismuth oxide thin films have proved their potential for optoelectronic applications, but their uses as infrared sensors have not been thoroughly studied so far. In this paper, pulsed laser ablation of pure bismuth targets within a controlled oxygen atmosphere is proposed for the deposition of bismuth oxide films on Si (100) substrates. Crystalline films were obtained, whose uniformity depends on the deposition conditions (number of laser pulses and the use of a radio-frequency (RF) discharge of the oxygen inside the deposition chamber). The optical analysis proved that the refractive index of the films is higher than 3 and that their optical bandgap is around 1eV, recommending them for infrared applications.

  17. Fe biomineralization mirrors individual metabolic activity in a nitrate-dependent Fe(II)-oxidizer

    PubMed Central

    Miot, Jennyfer; Remusat, Laurent; Duprat, Elodie; Gonzalez, Adriana; Pont, Sylvain; Poinsot, Mélanie

    2015-01-01

    Microbial biomineralization sometimes leads to periplasmic encrustation, which is predicted to enhance microorganism preservation in the fossil record. Mineral precipitation within the periplasm is, however, thought to induce death, as a result of permeability loss preventing nutrient and waste transit across the cell wall. This hypothesis had, however, never been investigated down to the single cell level. Here, we cultured the nitrate reducing Fe(II) oxidizing bacteria Acidovorax sp. strain BoFeN1 that have been previously shown to promote the precipitation of a diversity of Fe minerals (lepidocrocite, goethite, Fe phosphate) encrusting the periplasm. We investigated the connection of Fe biomineralization with carbon assimilation at the single cell level, using a combination of electron microscopy and Nano-Secondary Ion Mass Spectrometry. Our analyses revealed strong individual heterogeneities of Fe biomineralization. Noteworthy, a small proportion of cells remaining free of any precipitate persisted even at advanced stages of biomineralization. Using pulse chase experiments with 13C-acetate, we provide evidence of individual phenotypic heterogeneities of carbon assimilation, correlated with the level of Fe biomineralization. Whereas non- and moderately encrusted cells were able to assimilate acetate, higher levels of periplasmic encrustation prevented any carbon incorporation. Carbon assimilation only depended on the level of Fe encrustation and not on the nature of Fe minerals precipitated in the cell wall. Carbon assimilation decreased exponentially with increasing cell-associated Fe content. Persistence of a small proportion of non-mineralized and metabolically active cells might constitute a survival strategy in highly ferruginous environments. Eventually, our results suggest that periplasmic Fe biomineralization may provide a signature of individual metabolic status, which could be looked for in the fossil record and in modern environmental samples. PMID

  18. Room temperature ferromagnetism in liquid-phase pulsed laser ablation synthesized nanoparticles of nonmagnetic oxides

    NASA Astrophysics Data System (ADS)

    Singh, S. C.; Kotnala, R. K.; Gopal, R.

    2015-08-01

    Intrinsic Room Temperature Ferromagnetism (RTF) has been observed in undoped/uncapped zinc oxide and titanium dioxide spherical nanoparticles (NPs) obtained by a purely green approach of liquid phase pulsed laser ablation of corresponding metal targets in pure water. Saturation magnetization values observed for zinc oxide (average size, 9 ± 1.2 nm) and titanium dioxide (average size, 4.4 ± 0.3 nm) NPs are 62.37 and 42.17 memu/g, respectively, which are several orders of magnitude larger than those of previous reports. In contrast to the previous works, no postprocessing treatments or surface modification is required to induce ferromagnetism in the case of present communication. The most important result, related to the field of intrinsic ferromagnetism in nonmagnetic materials, is the observation of size dependent ferromagnetism. Degree of ferromagnetism in titanium dioxide increases with the increase in particle size, while it is reverse for zinc oxide. Surface and volume defects play significant roles for the origin of RTF in zinc oxide and titanium dioxide NPs, respectively. Single ionized oxygen and neutral zinc vacancies in zinc oxide and oxygen and neutral/ionized titanium vacancies in titanium dioxide are considered as predominant defect centres responsible for observed ferromagnetism. It is expected that origin of ferromagnetism is a consequence of exchange interactions between localized electron spin moments resulting from point defects.

  19. Room temperature ferromagnetism in liquid-phase pulsed laser ablation synthesized nanoparticles of nonmagnetic oxides

    SciTech Connect

    Singh, S. C. Gopal, R.; Kotnala, R. K.

    2015-08-14

    Intrinsic Room Temperature Ferromagnetism (RTF) has been observed in undoped/uncapped zinc oxide and titanium dioxide spherical nanoparticles (NPs) obtained by a purely green approach of liquid phase pulsed laser ablation of corresponding metal targets in pure water. Saturation magnetization values observed for zinc oxide (average size, 9 ± 1.2 nm) and titanium dioxide (average size, 4.4 ± 0.3 nm) NPs are 62.37 and 42.17 memu/g, respectively, which are several orders of magnitude larger than those of previous reports. In contrast to the previous works, no postprocessing treatments or surface modification is required to induce ferromagnetism in the case of present communication. The most important result, related to the field of intrinsic ferromagnetism in nonmagnetic materials, is the observation of size dependent ferromagnetism. Degree of ferromagnetism in titanium dioxide increases with the increase in particle size, while it is reverse for zinc oxide. Surface and volume defects play significant roles for the origin of RTF in zinc oxide and titanium dioxide NPs, respectively. Single ionized oxygen and neutral zinc vacancies in zinc oxide and oxygen and neutral/ionized titanium vacancies in titanium dioxide are considered as predominant defect centres responsible for observed ferromagnetism. It is expected that origin of ferromagnetism is a consequence of exchange interactions between localized electron spin moments resulting from point defects.

  20. Discovery of New Iron Oxide Fe7O9 and its Solid Solution, (Mg,Fe2+)3Fe3+4O9

    NASA Astrophysics Data System (ADS)

    Sinmyo, R.; Bykova, E.; Ovsyannikov, S. V.; McCammon, C. A.; Kupenko, I.; Ismailova, L.; Dubrovinsky, L. S.

    2015-12-01

    Iron oxides are fundamentally important compounds for Earth science. Particularly, the stability and properties of iron oxides are essential information to understand the structure and chemistry of the mantle. Here we report new high-pressure polymorphs of iron oxide Fe7O9 (Fe3+/Fe2+ = 4/3) and its Fe2+-Mg solid solution (Mg,Fe2+)3Fe3+4O9 that can be recovered at ambient conditions. We synthesized single crystals of the both compounds at about 24-26 GPa using a multi-anvil press. Single crystal X-ray diffraction (XRD) studies showed that the crystal structures of both Fe7O9 and (Mg,Fe2+)3Fe3+4O9 have monoclinic C2/m space groups, that differ from any other known lattices of iron oxides. Mössbauer spectra are in agreement with the crystal structure refined from single crystal XRD. This newly found Fe7O9 polymorph suggests that iron oxides may have more variable mixed valence state under high-pressure condition than previously thought. Based on analogy with Fe2+1+nFe3+2O4+n group, a Fe2+3±nFe3+4O9±n group might be also stable at certain high pressures and temperatures and oxygen fugacity.

  1. Immobilization of Radionuclides Through Anaerobic Bio-oxidation of Fe(ll)

    SciTech Connect

    Coates, John D.

    2006-06-01

    Anaerobic, Nitrate-Dependent Fe(II) Bio-Oxidation: A Column Study Report FY 2005/2006 Previous studies have demonstrated that nitrate-dependent bio-oxidation of Fe(II) by Azospira suillium strain PS results in the formation of crystalline mixed Fe(II)/Fe(III) mineral phases which results in the subsequent immobilization of heavy metals and radionuclides.

  2. Single-step synthesis of graphene quantum dots by femtosecond laser ablation of graphene oxide dispersions

    NASA Astrophysics Data System (ADS)

    Russo, Paola; Liang, Robert; Jabari, Elahe; Marzbanrad, Ehsan; Toyserkani, Ehsan; Zhou, Y. Norman

    2016-04-01

    In the last few years, graphene quantum dots (GQDs) have attracted the attention of many research groups for their outstanding properties, which include low toxicity, chemical stability and photoluminescence. One of the challenges of GQD synthesis is finding a single-step, cheap and sustainable approach for synthesizing these promising nanomaterials. In this study, we demonstrate that femtosecond laser ablation of graphene oxide (GO) dispersions could be employed as a facile and environmentally friendly synthesis method for GQDs. With the proper control of laser ablation parameters, such as ablation time and laser power, it is possible to produce GQDs with average sizes of 2-5 nm, emitting a blue luminescence at 410 nm. We tested the feasibility of the synthesized GQDs as materials for electronic devices by aerosol-jet printing of an ink that is a mixture of water dispersion of laser synthesized GQDs and silver nanoparticle dispersion, which resulted in lower resistivity of the final printed patterns. Preliminary results showed that femtosecond laser synthesized GQDs can be mixed with silver nanoparticle dispersion to fabricate a hybrid material, which can be employed in printing electronic devices by either printing patterns that are more conductive and/or reducing costs of the ink by decreasing the concentration of silver nanoparticles (AgNPs) in the ink.In the last few years, graphene quantum dots (GQDs) have attracted the attention of many research groups for their outstanding properties, which include low toxicity, chemical stability and photoluminescence. One of the challenges of GQD synthesis is finding a single-step, cheap and sustainable approach for synthesizing these promising nanomaterials. In this study, we demonstrate that femtosecond laser ablation of graphene oxide (GO) dispersions could be employed as a facile and environmentally friendly synthesis method for GQDs. With the proper control of laser ablation parameters, such as ablation time and

  3. Dynamic Fe-precipitate formation induced by Fe(II) oxidation in aerated phosphate-containing water

    NASA Astrophysics Data System (ADS)

    Voegelin, Andreas; Senn, Anna-Caterina; Kaegi, Ralf; Hug, Stephan J.; Mangold, Stefan

    2013-09-01

    We studied the effect of phosphate on the precipitation of Fe during the oxidation of 1 mM Fe(II) in aerated 8 mM NaHCO3-CO2 buffered aqueous solutions at near-neutral pH. The structure and morphology of the precipitates were analyzed by X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS) spectroscopy at the Fe K-edge, and transmission electron microscopy (TEM). Up to an initial dissolved P/Fe ratio of ˜0.55, most phosphate was incorporated into the fresh Fe(III)-precipitates. At dissolved P/Fe ratios from 0.55 to 1.91, the precipitate P/Fe ratios only exhibited a minor increase from 0.56 to 0.72. XRD patterns and Fe EXAFS spectra indicated a shift in precipitate type from mostly poorly-crystalline lepidocrocite in the absence of phosphate to amorphous Fe(III)-phosphate (mostly monomeric and oligomeric Fe(III) coordinated with phosphate) at dissolved P/Fe ratios >0.55. A time-resolved oxidation experiment at an initial dissolved P/Fe ratio of 0.29 revealed that amorphous Fe(III)-phosphate formed during Fe(II) oxidation until phosphate was nearly depleted from solution. During continuing Fe(II) oxidation, about half of the newly formed Fe(III) contributed to the polymerization of Fe-phosphate into phosphate-rich hydrous ferric oxide with a maximum P/Fe ratio of 0.25 (HFO-P; edge-sharing linkage of Fe(III) octahedra) and about half precipitated as poorly-crystalline lepidocrocite in the phosphate-depleted solution. At initial P/Fe ratios <0.2, initially formed Fe(III)-phosphate was fully transformed into HFO-P during continuing Fe(II) oxidation. The dynamic interactions between phosphate and Fe described in this study impact the structure of fresh Fe(III)-precipitates at redox transitions in environmental and technical systems. The modulating effects of other dissolved species such as silicate and Ca on Fe precipitate formation and implications for co-transformed trace elements require further study.

  4. Effect of Fe coating of nucleation sites on epitaxial growth of Fe oxide nanocrystals on Si substrates

    NASA Astrophysics Data System (ADS)

    Ishibe, Takafumi; Watanabe, Kentaro; Nakamura, Yoshiaki

    2016-08-01

    We studied the effect of Fe coating on the epitaxial growth of Fe3O4 nanocrystals (NCs) over Fe-coated Ge epitaxial nuclei on Si(111). To completely cover Ge nuclei with Fe, some amount of Fe (>8 monolayers) must be deposited. Such covering is a key to epitaxial growth because an Fe coating layer prevents the oxidation of Ge surfaces during Fe3O4 formation, resulting in the epitaxial growth of Fe3O4 on them. This study demonstrates that an appropriate Fe coating of nucleation sites leads to the epitaxial growth of Fe3O4 NCs on Si substrates, indicating the realization of environmentally friendly and low-cost Fe3O4 NCs as the resistance random access memory material.

  5. Oxidation of Fe-W Alloy Electrodeposits for Application to Anodes as Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Su, Changwei; Ye, Mengchao; Zhon, Linxing; Hou, Jianping; Li, Junmin; Guo, Junming

    2016-12-01

    A citrate-ammonia bath was selected to electrodeposit Fe-W alloys, which exhibit a crystalline structure even if the content of W in the Fe-W alloy is up to 37.8wt%. Those alloys could be oxidized partly at 700∘C. Resultant oxides were composed of Fe2O3, Fe3O4 and amorphous products. The composite oxides presented better electrochemical properties than those of the Fe2O3 and Fe3O4 composite formed by oxidation of Fe deposits. For instance, such an electrode demonstrates the reversible capacity of up to 2438.3mAhg-1 (in terms of incremental oxygen) after 100 charge-discharge cycles, while the electrodes of Fe2O3 and Fe3O4 composites formed by oxidation of Fe deposits were of only 667.5mAhg-1.

  6. Effect of oxidation on interlayer exchange coupling in Fe|MgO|Fe tunnel junctions

    NASA Astrophysics Data System (ADS)

    Yang, H.-X.; Chshiev, M.; Kalitsov, A.; Schuhl, A.; Butler, W. H.

    2010-03-01

    The interlayer exchange coupling (IEC) in MgO-based magnetic tunnel junctions (MTJ) is a subject of major interest for spintronics community [1,2]. Recent experiments demonstrated that oxydation conditions strongly affect the character of the IEC in Fe/MgO/Fe(001) MTJs [3]. In order to elucidate the effect of over- and under-oxidation on the nature of the IEC in Fe|MgO|Fe MTJs, we performed systematic studies of the influence of O impurities and vacancies on the IEC using ab-initio and tight-binding approaches. We found that the O vacancies cause strong AF IEC in agreement with previous studies [2-4]. Furthermore, an additional O atom at the Fe|MgO interface makes the IEC ferromagnetic in for 3ML and above MgO thicknesses in agreement with experiment [3]. We demonstrate also that the full structural relaxation of ideal Fe|MgO|Fe MTJs may lead to the antiferromagnetic IEC. Tight-binding calculations of the IEC in the framework of the Keldysh formalism were also performed. The results obtained support our first principles calculations. [1] J. Faure-Vincent et al, Phys. Rev. Lett. 89, 107206 (2002); [2] T. Katayama et al., Appl. Phys. Lett. 89, 112503 (2006); [3] Y.F. Chiang et al, Phys. Rev. B 79, 184410 (2009); [4] M.Y. Zhuravlev et al, Phys. Rev. Lett. 94, 026806 (2005).

  7. Electronic State of Fe in Double Perovskite Oxide Sr 2FeWO 6

    NASA Astrophysics Data System (ADS)

    Kawanaka, Hirofumi; Hase, Izumi; Toyama, Shunichiro; Nishihara, Yoshikazu

    1999-09-01

    The magnetic properties of double perovskite oxide Sr2FeWO6 have been reported. The magnetic susceptibility and Mössbauer effect of 57Fe show that this compound is an antiferromagnet with T N=37 K. The Mössbauer parameters below ˜20 K are the center shift of +1.2 mm/s relative to metallic iron, the quadrupole splitting of 1.9 mm/s and the hyperfine field of ˜110 kOe. The quadrupole splitting has a strong temperature dependence. From these data, we conclude that Fe in Sr2FeWO6 is in the Fe2+ high-spin state, while the hyperfine field seems to be quite small. The cell volume shows a large increase compared to other Sr2FeTO6 ( T= Mo, Re, etc.), which is in the Fe3+ high-spin state. These results suggest that these compounds have a strongly coupled charge and lattice systems.

  8. Iron isotope composition of particles produced by UV-femtosecond laser ablation of natural oxides, sulfides, and carbonates.

    PubMed

    d'Abzac, Francois-Xavier; Beard, Brian L; Czaja, Andrew D; Konishi, Hiromi; Schauer, James J; Johnson, Clark M

    2013-12-17

    The need for femtosecond laser ablation (fs-LA) systems coupled to MC-ICP-MS to accurately perform in situ stable isotope analyses remains an open question, because of the lack of knowledge concerning ablation-related isotopic fractionation in this regime. We report the first iron isotope analysis of size-resolved, laser-induced particles of natural magnetite, siderite, pyrrhotite, and pyrite, collected through cascade impaction, followed by analysis by solution nebulization MC-ICP-MS, as well as imaging using electron microscopy. Iron mass distributions are independent of mineralogy, and particle morphology includes both spheres and agglomerates for all ablated phases. X-ray spectroscopy shows elemental fractionation in siderite (C-rich agglomerates) and pyrrhotite/pyrite (S-rich spheres). We find an increase in (56)Fe/(54)Fe ratios of +2‰, +1.2‰, and +0.8‰ with increasing particle size for magnetite, siderite, and pyrrhotite, respectively. Fe isotope differences in size-sorted aerosols from pyrite ablation are not analytically resolvable. Experimental data are discussed using models of particles generation by Hergenröder and elemental/isotopic fractionation by Richter. We interpret the isotopic fractionation to be related to the iron condensation time scale, dependent on its saturation in the gas phase, as a function of mineral composition. Despite the isotopic variations across aerosol size fractions, total aerosol composition, as calculated from mass balance, confirms that fs-LA produces a stoichiometric sampling in terms of isotopic composition. Specifically, both elemental and isotopic fractionation are produced by particle generation processes and not by femtosecond laser-matter interactions. These results provide critical insights into the analytical requirements for laser-ablation-based stable isotope measurements of high-precision and accuracy in geological samples, including the importance of quantitative aerosol transport to the ICP. PMID

  9. Oxide Melt Solution Calorimetry of Fe2+ -bearing Oxides and Application to the Magnetite - Maghemite (Fe3O4-Fe8/3O4) system

    SciTech Connect

    Lilova, Kristina I.; Xu, Fen; Rosso, Kevin M.; Pearce, Carolyn I.; Kamali, Saeed; Navrotsky, Alexandra

    2012-01-01

    A consistent methodology for obtaining enthalpy of formation of Fe{sup 2+}-containing binary and multicomponent oxides using high temperature oxide melt solution calorimetry has been developed. The enthalpies of wuestite (FeO) and magnetite (Fe{sub 3}O{sub 4}) oxidation to hematite (Fe{sub 2}O{sub 3}) were measured using oxidative drop solution calorimetry in which the final product is dissolved ferric oxide. Two methods were applied: drop solution calorimetry at 1073 K in lead borate solvent and at 973 K in sodium molybdate, each under both oxygen flowing over and bubbling through the solvent, giving consistent results in agreement with literature values. The enthalpies of formation of all three iron oxides from the elements were obtained using a thermodynamic cycle involving the directly measured oxidative dissolution enthalpy of iron metal in sodium molybdate at 973 K and gave excellent consistency with literature data. The methodology was then applied to the magnetite - maghemite system. The enthalpy of mixing of the Fe{sub 3}O{sub 4}-Fe{sub 8/3}O{sub 4} spinel solid solution is exothermic and, 2 represented by a subregular (Margules) formalism, {Delta}H{sub mix} = x(1-x)(-63.36 {+-} 8.60(1-x) + 17.65 {+-} 6.40x) kJ/mol, where x is the mole fraction of magnetite. The entropies of mixing of the solid solution were calculated for different assumptions about the distribution of cations, charges, and vacancies in these defect spinels. The different models lead to only small differences in the entropy of mixing. Calculated free energies of mixing show no evidence for a solvus in the magnetite - maghemite system.

  10. A Structural Molar Volume Model for Oxide Melts Part III: Fe Oxide-Containing Melts

    NASA Astrophysics Data System (ADS)

    Thibodeau, Eric; Gheribi, Aimen E.; Jung, In-Ho

    2016-04-01

    As part III of this series, the model is extended to iron oxide-containing melts. All available experimental data in the FeO-Fe2O3-Na2O-K2O-MgO-CaO-MnO-Al2O3-SiO2 system were critically evaluated based on the experimental condition. The variations of FeO and Fe2O3 in the melts were taken into account by using FactSage to calculate the Fe2+/Fe3+ distribution. The molar volume model with unary and binary model parameters can be used to predict the molar volume of the molten oxide of the Li2O-Na2O-K2O-MgO-CaO-MnO-PbO-FeO-Fe2O3-Al2O3-SiO2 system in the entire range of compositions, temperatures, and oxygen partial pressures from Fe saturation to 1 atm pressure.

  11. Silicon oxide cluster formation and stability in the laser ablation of SiO targets.

    PubMed

    Jadraque, María; Santos, Magna; Díaz, Luís; Alvarez-Ruiz, Jesús; Martín, Margarita

    2009-10-15

    The formation mechanism and stability of silicon oxide clusters observed in the ablation of SiO targets at 266 nm were investigated by time-of-flight mass spectrometry, laser-induced fluorescence (LIF), and DFT calculations. Neutral and positively charged Si(n)(+/0) and Si(n)O(m)H(0,1)(+) clusters were identified in the plume, but neutral Si(n)O(m) could not be observed. The time distribution of SiO in the plume measured by postionization with an ArF laser (Delta lambda approximately 1 nm, tau approximately 14 ns) and mass spectrometric detection was compared with that obtained by LIF with narrowband dye laser selective excitation of one specific rovibronic transition in SiO. Postionization leads to a multicomponent distribution that extends up to times near 100 micros after ablation, whereas LIF measurements obtain time distributions shorter than 20 micros. DFT calculations of several Si(n)O(m)(0/+) were performed, showing that one photon absorption of the postionization laser makes available low-energy dissociation channels of the neutrals, whereas two photon absorption is required for ionization. DFT calculations were carried out for stoichiometric H-containing clusters Si(n)O(n)H(+) (n = 1-4). For n = 1,2, the optimized geometries involve bonding of hydrogen to one oxygen atom in the clusters; for n = 3 and 4, the structures containing H-Si bonds are more stable. PMID:19810756

  12. Features of the synthesis of nanocolloid oxides by laser ablation of bulk metal targets in solutions

    NASA Astrophysics Data System (ADS)

    Lapin, Ivan N.; Svetlichnyi, Valery A.

    2015-12-01

    Laser ablation of bulk targets in a fluid -- a promising new method for the synthesis of "pure" nanocolloids. Nanocrystalline materials produced by laser ablation are widely used in biology, medicine, and catalysis. High local temperature during ablation and large surface area of the particles promote chemical reactions and the formation of a complex composition of nanoparticles. In this paper the characteristics of the process of ablation and the obtaining of nanoparticles in a liquid by laser ablation of active materials (Zn, Ce, Ti, Si) were studied. Ways of increasing the productivity of laser ablation were discussed. Characterization of nanocolloids and nanocrystalline powders were performed.

  13. Superparamagnetic Fe3O4 particles formed by oxidation of pyrite heated in an anoxic atmosphere

    USGS Publications Warehouse

    Thorpe, A.N.; Senftle, F.E.; Talley, R.; Hetherington, S.; Dulong, F.

    1990-01-01

    As a follow-up to previous gas analysis experiments in which pyrite was heated to 681 K in an anoxic (oxygen starved) atmosphere, the first oxidation product, FeSO4, was studied as a bulk material. No decomposition of FeSO4 to Fe3O4 was observed in the temperature range studied. The lack of decomposition of bulk FeSO4 to Fe3O4 suggests that FeS2 oxidizes directly to Fe3O4, or that FeSO4, FeS2 and O2 react together to form Fe3O4. Magnetic susceptibility and magnetization measurements, along with magnetic hysteresis curves, show that small particles of Fe3O4 form on the pyrite surface, rather than a continuous layer of bulk Fe3O4. A working model describing the oxidation steps is presented. ?? 1990.

  14. On line diagnostics and characterization of thin films deposited by laser ablation of solid oxides precursors of superconductors

    NASA Astrophysics Data System (ADS)

    Giardini-Guidoni, A.; Desimoni, E.; Salvi, A. M.; Teghil, R.; Ambrico, M.; Morone, A.; Piccirillo, S.; Snels, M.

    This work presents the analysis of composite solid targets made by laser irradiation of mixtures of simple oxides and of superconducting YBCO and BISCO. The results are discussed in relation to previous studies on laser cluster ion formation of these materials and their chemical reactivity. The films of ablated materials have been analyzed by XPS and SEM.

  15. Fe /Fe oxide nanocomposite particles with large specific absorption rate for hyperthermia

    NASA Astrophysics Data System (ADS)

    Zeng, Q.; Baker, I.; Loudis, J. A.; Liao, Y.; Hoopes, P. J.; Weaver, J. B.

    2007-06-01

    Using a water-in-oil microemulsion with cetyl trimethyl ammonium bromide as the surfactant, iron was reduced to form a metallic core on which a passivating oxide shell was grown. Transmission electron microscopy, vibrating sample magnetometry, and heating measurements were used to characterize these monodispersed magnetic Fe /Fe3O4 composite nanoparticles with respect to the possible application for magnetic hyperthermia treatments of cancer. The aim is to utilize the fact that an iron core (high saturation magnetization) will give a greater heating effect than iron oxide, while the iron oxide coating will allow the nanoparticles to be observed using magnetic resonance imaging so that therapy can be effectively monitored and targeted. The largest specific absorption rate obtained was 345W/g under an alternating magnetic field of 150Oe at 250kHz.

  16. Oxidation states of Fe and Ti in blue sapphire

    NASA Astrophysics Data System (ADS)

    Wongrawang, P.; Monarumit, N.; Thammajak, N.; Wathanakul, P.; Wongkokua, W.

    2016-02-01

    X-ray absorption near-edge spectroscopy (XANES) can be used to study the oxidation state of a dilute system such as transition metal defects in solid-state samples. In blue sapphire, Fe and Ti are defects that cause the blue color. Inter-valence charge transfer (IVCT) between Fe2+ and Ti4+ has been proposed to describe the optical color’s origin. However, the existence of divalent iron cations has not been thoroughly investigated. Fluorescent XANES is therefore employed to study K-edge absorptions of Fe and Ti cations in various blue sapphire samples including natural, synthetic, diffused and heat-treated sapphires. All the samples showed an Fe absorption edge at 7124 eV, corresponding to the Fe3+ state; and Ti at 4984 eV, corresponding to Ti4+. From these results, we propose Fe3+-Ti4+ mixed acceptor states located at 1.75 eV and 2.14 eV above the valence band of corundum, that correspond to 710 nm and 580 nm bands of UV-vis absorption spectra, to describe the cause of the color of blue sapphire.

  17. Characterization of the physiology and cell-mineral interactions of the marine anoxygenic phototrophic Fe(II) oxidizer Rhodovulum iodosum--implications for Precambrian Fe(II) oxidation.

    PubMed

    Wu, Wenfang; Swanner, Elizabeth D; Hao, Likai; Zeitvogel, Fabian; Obst, Martin; Pan, Yongxin; Kappler, Andreas

    2014-06-01

    Anoxygenic phototrophic Fe(II)-oxidizing bacteria (photoferrotrophs) are suggested to have contributed to the deposition of banded iron formations (BIFs) from oxygen-poor seawater. However, most studies evaluating the contribution of photoferrotrophs to Precambrian Fe(II) oxidation have used freshwater and not marine strains. Therefore, we investigated the physiology and mineral products of Fe(II) oxidation by the marine photoferrotroph Rhodovulum iodosum. Poorly crystalline Fe(III) minerals formed initially and transformed to more crystalline goethite over time. During Fe(II) oxidation, cell surfaces were largely free of minerals. Instead, the minerals were co-localized with EPS suggesting that EPS plays a critical role in preventing cell encrustation, likely by binding Fe(III) and directing precipitation away from cell surfaces. Fe(II) oxidation rates increased with increasing initial Fe(II) concentration (0.43-4.07 mM) under a light intensity of 12 μmol quanta m(-2) s(-1). Rates also increased as light intensity increased (from 3 to 20 μmol quanta m(-2) s(-1)), while the addition of Si did not significantly change Fe(II) oxidation rates. These results elaborate on how the physical and chemical conditions present in the Precambrian ocean controlled the activity of marine photoferrotrophs and confirm the possibility that such microorganisms could have oxidized Fe(II), generating the primary Fe(III) minerals that were then deposited to some Precambrian BIFs. PMID:24606418

  18. Studies of aluminum oxide thin films deposited by laser ablation technique

    NASA Astrophysics Data System (ADS)

    Płóciennik, P.; Guichaoua, D.; Korcala, A.; Zawadzka, A.

    2016-06-01

    This paper presents the structural and optical investigations of the aluminum oxide nanocrystalline thin films. Investigated films were fabricated by laser ablation technique in high vacuum onto quartz substrates. The films were deposited at two different temperatures of the substrates equal to room temperature and 900 K. X-ray Diffraction spectra proved nanocrystalline character and the corundum phase of the film regardless on the substrate temperature during the deposition process. Values of the refractive indices, extinction and absorption coefficients were calculated by using Transmission and Reflection Spectroscopy in the UV-VIS-NIR range of the wavelength. Coupling Prism Method was used for films thickness estimations. Experimental measurements and theoretical calculations of the Third Harmonic Generation were also reported. Obtained results show that the lattice strain may affect obtained values of the third order nonlinear optical susceptibility.

  19. Effects of natural oxidation on the photoluminescence properties of Si nanocrystals prepared by pulsed laser ablation

    NASA Astrophysics Data System (ADS)

    Xu, Yanmei; Han, Yinghui

    2014-07-01

    In this work, Si nanocrystals (Si-NCs) have been prepared by pulsed laser ablation technique in dichloromethane, and the microstructure and photoluminescence (PL) properties of the Si-NCs before and after natural oxidation were investigated. Transmission electron microscopy and Raman results show that the average diameter of the Si-NCs is 2.42 nm in the dichloromethane solution. Blue-violet PL with a lifetime of 4.6 ns is observed at room temperature, and the PL peak shifts toward longer wavelength with the red shift of excitation wavelength. The PL excitation spectrum indicates that the bandgap of the Si-NCs in solution is 2.64 eV, which confirms that the blue-violet PL originates from interband transition of Si-NCs caused by quantum confinement effect. The PL peak red shifts to 607 nm after natural oxidation, and the peak lifetime of which is slow down to 13.1 μs. The fixed PL peak excited by different wavelengths and the slow PL decay time indicate that interface defects become the main PL mechanism after natural oxidation. The results will add new information for understanding the PL mechanism of Si-NCs in different environments.

  20. Effects of oxidizing medium on the composition, morphology and optical properties of copper oxide nanoparticles produced by pulsed laser ablation

    NASA Astrophysics Data System (ADS)

    Gondal, M. A.; Qahtan, Talal F.; Dastageer, M. A.; Saleh, Tawfik A.; Maganda, Yasin W.; Anjum, D. H.

    2013-12-01

    Pulsed laser ablation in liquid (PLAL) with 532 nm wavelength laser with 5 ns pulse duration is used to produce the nanostructure copper oxide and the effects of oxidizing media (deionized water and hydrogen peroxide) on the composition, morphology and optical properties of the product materials produced by PLAL were studied. XRD and TEM studies indicate that in the absence of hydrogen peroxide, the product material is in two phases (Cu/Cu2O) with the spherical nanoparticle structure, whereas in the presence of hydrogen peroxide in the liquid medium, the product material revealed other two phases (Cu/CuO) with nanorod-like structure. The optical studies revealed a considerable red shift (3.34-2.5 eV) in the band gap energy in the case of hydrogen peroxide in the liquid medium in PLAL synthesis compared to the one in the absence of it. Also the product material in the presence of hydrogen peroxide in the liquid medium showed a reduced photoluminescence intensity indicating the reduced electron-hole recombination rate. The red shift in the band gap energy and the reduced electron-hole recombination rate make the product material an ideal photocatalyst to harvest solar radiation for various applications. The most relevant signals on the FTIR spectrum for the samples are the absorption bands in the region between 450 and 700 cm-1 which are the characteristics bands of coppersbnd oxygen bonds. The reported laser ablation approach for the synthesis of Cu2O and CuO nanoparticles has the advantages of being clean method with controlled particle properties.

  1. Biological Fe oxidation controlled deposition of banded iron formation in the ca. 3770 Ma Isua Supracrustal Belt (West Greenland)

    NASA Astrophysics Data System (ADS)

    Czaja, Andrew D.; Johnson, Clark M.; Beard, Brian L.; Roden, Eric E.; Li, Weiqiang; Moorbath, Stephen

    2013-02-01

    The redox balance of the Archean atmosphere-ocean system is among the most significant uncertainties in our understanding of the earliest history of Earth's surface zone. Most workers agree that oxygen did not constitute a significant proportion of the atmosphere until after ca. 2.45 Ga, after the Great Oxidation Event, but there is less agreement on when O2 production began, and how this may have been consumed by reduced species such as Fe(II) in the oceans. The Fe redox cycle through time has been traced using banded iron formations (BIFs), and Fe isotopes are increasingly used to constrain the conditions of Earth's paleoenvironments, including the pathways of formation of BIFs. Iron isotope analyses of BIFs from the 3.7 to 3.8 Ga Isua Supracrustal Belt (ISB), obtained by micro-sampling of magnetite-rich layers and conventional analysis, as well as by in situ femtosecond laser ablation (fs-LA-ICP-MS), indicate a consistently narrow range of non-zero δ56Fe values. Analysis of magnetite by fs-LA-ICP-MS allows for precise and accurate micron-scale analyses without the problems of orientation effects that are associated with secondary ion mass spectrometry (SIMS) analyses. Magnetite δ56Fe values range from +0.4‰ to +1.1‰ among different bands, but within individual layers magnetite grains are mostly homogeneous. Although these BIFs have been metamorphosed to amphibolite-facies, the metamorphism can neither explain the range in Fe isotope compositions across bands, nor that between hand samples. The isotopic compositions therefore reflect “primary”, low-temperature sedimentary values. The positive δ56Fe values measured from the ISB magnetites are best explained by deposition of Fe(III)-oxides produced by partial oxidation of Fe(II)-rich ocean water. A dispersion/reaction model, which accounts for rates of hydrothermal Fe(II)aq input, rates of oxidation, and rates of Fe(OH)3 settling suggests exceptionally low O2 contents, <0.001% of modern O2 contents in

  2. Physiology, Fe(II) oxidation, and Fe mineral formation by a marine planktonic cyanobacterium grown under ferruginous conditions

    NASA Astrophysics Data System (ADS)

    Swanner, Elizabeth; Wu, Wenfang; Hao, Likai; Wuestner, Marina; Obst, Martin; Moran, Dawn; McIlvin, Matthew; Saito, Mak; Kappler, Andreas

    2015-10-01

    Evidence for Fe(II) oxidation and deposition of Fe(III)-bearing minerals from anoxic or redox-stratified Precambrian oceans has received support from decades of sedimentological and geochemical investigation of Banded Iron Formations (BIF). While the exact mechanisms of Fe(II) oxidation remains equivocal, reaction with O2 in the marine water column, produced by cyanobacteria or early oxygenic phototrophs, was likely. In order to understand the role of cyanobacteria in the deposition of Fe(III) minerals to BIF, we must first know how planktonic marine cyanobacteria respond to ferruginous (anoxic and Fe(II)-rich) waters in terms of growth, Fe uptake and homeostasis, and Fe mineral formation. We therefore grew the common marine cyanobacterium Synechococcus PCC 7002 in closed bottles that began anoxic, and contained Fe(II) concentrations that span the range of possible concentrations in Precambrian seawater. These results, along with cell suspension experiments, indicate that Fe(II) is likely oxidized by this strain via chemical oxidation with oxygen produced during photosynthesis, and not via any direct enzymatic or photosynthetic pathway. Imaging of the cell-mineral aggregates with scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM) are consistent with extracellular precipitation of Fe(III) (oxyhydr)oxide minerals, but that >10% of Fe(III) sorbs to cell surfaces rather than precipitating. Proteomic experiments support the role of reactive oxygen species (ROS) in Fe(II) toxicity to Synechococcus PCC 7002. The proteome expressed under low Fe conditions included multiple siderophore biosynthesis and siderophore and Fe transporter proteins, but most siderophores are not expressed during growth with Fe(II). These results provide a mechanistic and quantitative framework for evaluating the geochemical consequences of perhaps life’s greatest metabolic innovation, i.e. the evolution and activity of oxygenic photosynthesis, in ferruginous

  3. Advanced experimental analysis of controls on microbial Fe(III) oxide reduction. 1998 annual progress report

    SciTech Connect

    Roden, E.E.; Urrutia, M.M.

    1998-06-01

    'Understanding factors which control the long-term survival and activity of Fe(III)-reducing bacteria (FeRB) in subsurface sedimentary environments is important for predicting their ability to serve as agents for bioremediation of organic and inorganic contaminants. This project seeks to refine the authors quantitative understanding of microbiological and geochemical controls on bacterial Fe(III) oxide reduction and growth of FeRB, using laboratory reactor systems which mimic to varying degrees the physical and chemical conditions of subsurface sedimentary environments. Methods for studying microbial Fe(III) oxide reduction and FeRB growth in experimental systems which incorporate advective aqueous phase flux are being developed for this purpose. These methodologies, together with an accumulating database on the kinetics of Fe(III) reduction and bacterial growth with various synthetic and natural Fe(III) oxide minerals, will be applicable to experimental and modeling studies of subsurface contaminant transformations directly coupled to or influenced by bacterial Fe(III) oxide reduction and FeRB activity. This report summarizes research accomplished after approximately 1.5 yr of a 3-yr project. A central hypothesis of the research is that advective elimination of the primary end-product of Fe(III) oxide reduction, Fe(II), will enhance the rate and extent of microbial Fe(III) oxide reduction in open experimental systems. This hypothesis is based on previous studies in the laboratory which demonstrated that association of evolved Fe(II) with oxide and FeRB cell surfaces (via adsorption or surface precipitation) is a primary cause for cessation of Fe(III) oxide reduction activity in batch culture experiments. Semicontinuous culturing was adopted as a first approach to test this basic hypothesis. Synthetic goethite or natural Fe(III) oxide-rich subsoils were used as Fe(III) sources, with the Fe(III)-reducing bacterium Shewanella alga as the test organism.'

  4. Sulphur mustard degradation on zirconium doped Ti-Fe oxides.

    PubMed

    Štengla, Václav; Grygar, Tomáš Matys; Opluštil, František; Němec, Tomáš

    2011-09-15

    Zirconium doped mixed nanodispersive oxides of Ti and Fe were prepared by homogeneous hydrolysis of sulphate salts with urea in aqueous solutions. Synthesized nanodispersive metal oxide hydroxides were characterised as the Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared (IR) spectroscopy, scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX) microanalysis, and acid-base titration. These oxides were taken for an experimental evaluation of their reactivity with sulphur mustard (chemical warfare agent HD or bis(2-chloroethyl)sulphide). The presence of Zr(4+) dopant tends to increase both the surface area and the surface hydroxylation of the resulting doped oxides in such a manner that it can contribute to enabling the substrate adsorption at the oxide surface and thus accelerate the rate of degradation of warfare agents. The addition of Zr(4+) to the hydrolysis of ferric sulphate with urea shifts the reaction route and promotes formation of goethite at the expense of ferrihydrite. We discovered that Zr(4+) doped oxo-hydroxides of Ti and Fe exhibit a higher degradation activity towards sulphur mustard than any other yet reported reactive sorbents. The reaction rate constant of the slower parallel reaction of the most efficient reactive sorbents is increased with the increasing amount of surface base sites. PMID:21775058

  5. Artificial meteor ablation studies. [for identification of cosmic dust particles

    NASA Technical Reports Server (NTRS)

    Blanchard, M. B.

    1973-01-01

    Artificial meteor ablation was performed on natural minerals, composed predominately of magnetite and hematite, using an arc heated plasma stream of air. Analysis of the ablated debris indicated most was composed of two or more minerals. The more volatile elements were depleted and the relative abundance of Fe increased as a result of both volatile depletion and a reduction in its oxidation state. Hematite was converted to magnetite in the ablation zone, and quartz and apatite minerals were converted to an Fe-rich glass consisting of varying amounts of Si, P, Cl, and Ca, depending upon the accessory minerals available at the time of melting. Artificially created ablation products from iron oxides exhibited unique properties depending on the composition of the original material and the environmental conditions of formation. In addition to the accepted elemental criteria, these properties were morphologic characteristics, textural parameters, and the existence of metastable minerals.

  6. The role of biogenic Fe-Mn oxides formed in situ for arsenic oxidation and adsorption in aquatic ecosystems.

    PubMed

    Bai, Yaohui; Yang, Tingting; Liang, Jinsong; Qu, Jiuhui

    2016-07-01

    As(III&V), Mn(II), and Fe(II) may occur simultaneously in some groundwater and surface water. Studying their redox reactions and interactions is essential to unravel the biogeochemical cycles of these metal ions in aquatic ecosystems and to find effective methods to remove them simultaneously in drinking water treatment. Here, the formation of biogenic Fe-Mn oxides (BFMO, defined as a mixture of biogenic Mn oxide (BMO) and Fe oxide) as well as its oxidation and adsorption of As in a Fe(II)-Mn(II)-As(III&V)-Mn-oxidizing microbe (Pseudomonas sp. QJX-1) system were investigated. Batch experiments and structure characterization revealed that the BFMO was formed via a sequential precipitation of Fe oxide and BMO. The first formed Fe oxide was identified as FeOOH (lepidocrocite) and the latter formed BMO was identified as MnO2 (similar to hexagonal birnessite). In the BFMO mixture, the BMO part was mainly responsible for As(III) oxidation, and the Fe oxide part dominated As adsorption. Remarkably, the BMO could oxidize Fe(II) to form FeOOH, which may improve As adsorption. The optimum Mn(II)/Fe(II) ratio for As removal was approximately 1:3 (mol/mol). Taken together, in Fe(II)-Mn(II)-As(III&V)-Mn-oxidizing microbe ecosystems, the in situ formation of BFMO could eliminate or decrease Fe(II), Mn(II), and As(III&V) species simultaneously. Therefore, based on this study, new approaches may be developed for As removal from water containing high concentrations of Fe(II) and Mn(II). PMID:27088246

  7. Thermodynamics of Fe(II)Fe(III) oxide systems I. Hydrothermal Fe3O4

    USGS Publications Warehouse

    Bartel, J.J.; Westrum, E.F., Jr.; Haas, J.L., Jr.

    1976-01-01

    The heat capacity of a hydrothermally-prepared polycrystalline sample of Fe3O4 was measured from 53 to 350 K, primarily to study the thermophysics of the Verwey transitions. Although the bifurcation of the transition was confirmed, the sample was found to contain traces of manganese. The observed transition temperatures of 117.0 and 123.0 K are 3.7 and 4.2 K higher respectively than those found in pure Fe3O4. Ancillary analytical results are consistent and indicate a stoichiometry of Mn0.008Fe2.992O4 for this material. Characteristics in the transition region are ascribed to dopant effects. ?? 1976.

  8. Influence of Oxidation Behavior of Feedstock on Microstructure and Ablation Resistance of Plasma-Sprayed Zirconium Carbide Coating

    NASA Astrophysics Data System (ADS)

    Hu, Cui; Ge, Xuelian; Niu, Yaran; Li, Hong; Huang, Liping; Zheng, Xuebin; Sun, Jinliang

    2015-10-01

    Plasma spray is one of the suitable technologies to deposit carbide coatings with high melting point, such as ZrC. However, in the spray processes performed under atmosphere, oxidation of the carbide powder is inevitable. To investigate the influence of the oxidation behavior of feedstock on microstructure and ablation resistance of the deposited coating, ZrC coatings were prepared by atmospheric and vacuum plasma spray (APS and VPS) technologies, respectively. SiC-coated graphite was applied as the substrate. The obtained results showed that the oxidation of ZrC powder in APS process resulted in the formation of ZrO and Zr2O phases. Pores and cracks were more likely to be formed in the as-sprayed APS-ZrC coating. The VPS-ZrC coating without oxides possessed denser microstructure, higher thermal diffusivity, and lower coefficients of thermal expansion as compared with the APS-ZrC coating. A dense ZrO2 layer would be formed on the surface of the VPS-ZrC-coated sample during the ablation process and the substrate can be protected sufficiently after being ablated in high temperature plasma jet. However, the ZrO2 layer, formed by oxidation of the APS-ZrC coating having loose structure, was easy to be washed away by the shearing action of the plasma jet.

  9. Fe hydroxyphosphate precipitation and Fe(II) oxidation kinetics upon aeration of Fe(II) and phosphate-containing synthetic and natural solutions

    NASA Astrophysics Data System (ADS)

    van der Grift, B.; Behrends, T.; Osté, L. A.; Schot, P. P.; Wassen, M. J.; Griffioen, J.

    2016-08-01

    Exfiltration of anoxic Fe-rich groundwater into surface water and the concomitant oxidative precipitation of Fe are important processes controlling the transport of phosphate (PO4) from agricultural areas to aquatic systems. Here, we explored the relationship between solution composition, reaction kinetics, and the characteristics of the produced Fe hydroxyphosphate precipitates in a series of aeration experiments with anoxic synthetic water and natural groundwater. A pH stat device was used to maintain constant pH and to record the H+ production during Fe(II) oxidation in the aeration experiments in which the initial aqueous P/Fe ratios ((P/Fe)ini), oxygen concentration and pH were varied. In general, Fe(II) oxidation proceeded slower in the presence of PO4 but the decrease of the PO4 concentration during Fe(II) oxidation due to the formation of Fe hydroxyphosphates caused additional deceleration of the reaction rate. The progress of the reaction could be described using a pseudo-second-order rate law with first-order dependencies on PO4 and Fe(II) concentrations. After PO4 depletion, the Fe(II) oxidation rates increased again and the kinetics followed a pseudo-first-order rate law. The first-order rate constants after PO4 depletion, however, were lower compared to the Fe(II) oxidation in a PO4-free solution. Hence, the initially formed Fe hydroxyphosphates also affect the kinetics of continuing Fe(II) oxidation after PO4 depletion. Presence of aqueous PO4 during oxidation of Fe(II) led to the formation of Fe hydroxyphosphates. The P/Fe ratios of the precipitates ((P/Fe)ppt) and the recorded ratio of H+ production over decrease in dissolved Fe(II) did not change detectably throughout the reaction despite a changing P/Fe ratio in the solution. When (P/Fe)ini was 0.9, precipitates with a (P/Fe)ppt ratio of about 0.6 were formed. In experiments with (P/Fe)ini ratios below 0.6, the (P/Fe)ppt decreased with decreasing (P/Fe)ini and pH value. Aeration experiments with

  10. Operando Analysis of NiFe and Fe Oxyhydroxide Electrocatalysts for Water Oxidation: Detection of Fe⁴⁺ by Mössbauer Spectroscopy.

    PubMed

    Chen, Jamie Y C; Dang, Lianna; Liang, Hanfeng; Bi, Wenli; Gerken, James B; Jin, Song; Alp, E Ercan; Stahl, Shannon S

    2015-12-01

    Nickel-iron oxides/hydroxides are among the most active electrocatalysts for the oxygen evolution reaction. In an effort to gain insight into the role of Fe in these catalysts, we have performed operando Mössbauer spectroscopic studies of a 3:1 Ni:Fe layered hydroxide and a hydrous Fe oxide electrocatalyst. The catalysts were prepared by a hydrothermal precipitation method that enabled catalyst growth directly on carbon paper electrodes. Fe(4+) species were detected in the NiFe hydroxide catalyst during steady-state water oxidation, accounting for up to 21% of the total Fe. In contrast, no Fe(4+) was detected in the Fe oxide catalyst. The observed Fe(4+) species are not kinetically competent to serve as the active site in water oxidation; however, their presence has important implications for the role of Fe in NiFe oxide electrocatalysts. PMID:26601790

  11. Oxidation of Fe-Cr-Al and Fe-Cr-Al-Y Single Crystals

    NASA Astrophysics Data System (ADS)

    Grabke, H. J.; Siegers, M.; Tolpygo, V. K.

    1995-03-01

    Single crystal samples of the alloy Fe-20%Cr-5%Al with and without Y-doping were used to study the "reactive element" (RE) effect, which causes improved oxidation behaviour and formation of a protective Al2O3 layer on this alloy. The oxidation was followed by AES at 10-7 mbar O2 up to about 1000 °C. Most observations were peculiar for this low pO2 environment, but yttrium clearly favors the formation of Al-oxide and stabilizes it also under these conditions, probably by favoring its nucleation. The oxides formed are surface compounds of about monolayer thickness, not clearly related to bulk oxides. Furthermore, the morphologies of oxide scales were investigated by SEM, after oxidation at 1000°C for 100 h at 133 mbar O2. On Fe-Cr-Al the scale is strongly convoluted and tends to spalling, whereas the presence of Y leads to flat scales which are well adherent. This difference is explained by a change in growth mechanism. The tendency for separation of oxide and metal was highest for the samples with low energy metal surface, i.e. (100) and (110), the scale was better adherent on the (111) oriented surface and on the polycrystalline specimen, since in the latter cases the overall energy for scale/metal separation is higher. All observations, from the low and from the high pO2 experiments, are discussed in relation to the approximately ten mechanisms proposed in the literature for explanation of the RE effects.

  12. Scavenging of Cd through Fe/Mn oxides within natural surface coatings.

    PubMed

    Li, Yu; Huang, Guo-he; Zhang, Bai-yu; Guo, Shu-hai

    2006-01-01

    The dynamics of Cd scavenging from solutions by Fe/Mn oxides in natural surface coatings (NSCs) was investigated under laboratory conditions. Selective extraction methods were employed to estimate the contributions of Fe/Mn oxides, where hydroxylamine hydrochloride (0.01 mol/L NH2OH x HCl + 0.01 mol/L HNO3), sodium dithionite (0.4 mol/L Na2S2O4) and nitric acid (10% HNO3) were used as extraction reagents. The Cd scavenging was accomplished with developing periods of the NSCs (totally 21 data sets). The resulting process dynamics fitted well to the Elovich equation, demonstrating that the amount of Cd scavenged was proportional to the increments of Fe/Mn oxides that were accumulated in the NSCs. The amount of Cd bound to Fe oxides (M,,) and Mn oxides (MCdMn could be quantified by solving two equations based on the properties of two extraction reagents. The amount of Cd scavenged by Fe/Mn oxides could also be estimated using MCdFe and MCdMn, divided by the total amounts of Fe and Mn oxides in the NSCs, respectively. The results indicated that the Cd scavenging by Fe/Mn oxides was dominated by Fe oxides, with less roles attributed to Mn oxides. The estimated levels of Cd scavenging through Fe and Mn oxides agreed well with those predicted through additive-adsorption and linear-regression models. PMID:17294965

  13. Oxidation behavior of Fe-20Cr steels alloyed with titanium at 1073 K

    NASA Astrophysics Data System (ADS)

    Setiawan, Asep Ridwan; Artono, Tri Juni

    2016-02-01

    In this work, the oxidation behavior of Fe-20 wt%Cr steels alloyed with different titanium contents: 0, 0.5, and 1 wt% are studied as a function of time in air atmosphere. The samples were isothermally oxidized at 1073 K for 86.4, 172.8, and 345.6 ks in a muffle furnace. The mass of specimen were recorded before and after oxidation. After the oxidation, phases in the oxide were identified by X-ray diffraction (XRD). Optical microscopy observation on the chromium base alloys show that the microstructure consist only ferritic phases. The addition of titanium in the Fe-20Cr alloys does not alter the microstructure significantly. The oxidation behavior of Fe-20Cr, Fe-20Cr-0.5Ti and Fe-20Cr-1Ti were followed the classical parabolic relationship with time. XRD analysis indicated that the oxide scales developed on the Fe-20Cr alloys surface during oxidation tests consisted mainly of Cr2O3. On the other hand, the oxide scales developed on the surface of Fe-20Cr-0.5Ti and Fe-20Cr-1Ti alloys comprised of Cr2O3 and TiO2 oxide. The formation of TiO2 oxide in the Ti-containing alloys consequently increases the mass gain of the alloys during oxidation compared to that of Fe-20Cr alloys.

  14. Thermodynamic controls on the kinetics of microbial low-pH Fe(II) oxidation.

    PubMed

    Larson, Lance N; Sánchez-España, Javier; Kaley, Bradley; Sheng, Yizhi; Bibby, Kyle; Burgos, William D

    2014-08-19

    Acid mine drainage (AMD) is a major worldwide environmental threat to surface and groundwater quality. Microbial low-pH Fe(II) oxidation could be exploited for cost-effective AMD treatment; however, its use is limited because of uncertainties associated with its rate and ability to remove Fe from solution. We developed a thermodynamic-based framework to evaluate the kinetics of low-pH Fe(II) oxidation. We measured the kinetics of low-pH Fe(II) oxidation at five sites in the Appalachian Coal Basin in the US and three sites in the Iberian Pyrite Belt in Spain and found that the fastest rates of Fe(II) oxidation occurred at the sites with the lowest pH values. Thermodynamic calculations showed that the Gibbs free energy of Fe(II) oxidation (ΔG(oxidation)) was also most negative at the sites with the lowest pH values. We then conducted two series of microbial Fe(II) oxidation experiments in laboratory-scale chemostatic bioreactors operated through a series of pH values (2.1-4.2) and found the same relationships between Fe(II) oxidation kinetics, ΔG(oxidation), and pH. Conditions that favored the fastest rates of Fe(II) oxidation coincided with higher Fe(III) solubility. The solubility of Fe(III) minerals, thus plays an important role on Fe(II) oxidation kinetics. Methods to incorporate microbial low-pH Fe(II) oxidation into active and passive AMD treatment systems are discussed in the context of these findings. This study presents a simplified model that describes the relationship between free energy and microbial kinetics and should be broadly applicable to many biogeochemical systems. PMID:25072394

  15. Fe and Mo EXAFS of Azotobacter vinelandii nitrogenase inpartially oxidized and singly reduced forms

    SciTech Connect

    Christiansen, J.; Tittsworth, R.C.; Hales, B.J.; Cramer, S.P. |

    1995-10-11

    Fe and Mo K-edge EXAFS spectra of the nitrogenase Mo-Fe protein in the indigo disulfonate (IDS) oxidized form and under slow turnover conditions have been recorded. The EXAFS of the one-electron reduced form E{sub 1} was obtained as a difference spectrum between the slow turnover and resting (E{sub 0}) spectra. Average Fe-S, Fe-Fe, and Fe-Mo distances of 2.33, 2.60, and 2.66A, respectively, along with a second Fe-Fe distance at 3.72 A were found for E{sub 1}. The IDS-oxidized MoFe protein contain spartially oxidized `P-clusters`. For this sample, average Fe-S,Fe-Fe, and Fe-Mo interactions at 2.31, 2.65, and 2.71 A, respectively, were found along with the long Fe-Fe interaction at 3.74 A. Combination of the current results with previous data on resting and thionin-oxidized nitrogenase shows a general trend a significant number of the metal-metal distances tend to contract as the enzyme becomes more reduced. 52 refs., 6 figs., 2 tabs.

  16. Enhanced magnetic properties of Fe soft magnetic composites by surface oxidation

    NASA Astrophysics Data System (ADS)

    Zhao, Guoliang; Wu, Chen; Yan, Mi

    2016-02-01

    Fe soft magnetic composites (SMCs) with low core loss were fabricated via surface oxidation of the Fe powders by H2O and O2 at elevated temperatures. Surface oxidation prevents magnetic dilution due to the formation of the ferromagnetic iron oxide coating layer, giving rise to high magnetic flux density and effective permeability of the SMCs compared with those fabricated with traditional phosphate coating. Mechanism of the oxidation process has been investigated where Fe3O4 forms by reactions of Fe with H2O and O2. The Fe3O4 coating layer tends to convert into γ-Fe2O3 with increased oxidation temperature and time. By controlling composition of the coating layer, low core loss of 688.9 mW/cm3 (measured at 50 mT and 100 kHz) and higher effective permeability of 88.3 can be achieved for the Fe SMCs.

  17. Anaerobic Microbial-Mineral Processes with Fe(III) Oxides: Experimental Considerations and Approaches

    SciTech Connect

    Zachara, John M.; Fredrickson, Jim K.; Kukkadapu, Ravi K.; Gorby, Yuri A.

    2007-07-01

    The biogeochemical cycle of Fe is a one of the dominant redox cycles operative in surface waters and sediments, soils and vadose zones, and groundwater systems. In this cycle which is pronounced at oxic-anoxic boundaries, Fe compounds and microorganisms couple to mediate the oxidation of organic matter by molecular oxygen. The cycle includes: i.) the reductive dissolution of Fe(III) oxides by biogenic organic acids and organic matter oxidizing-metal reducing bacteria yielding Fe2+(aq) and ferrous containing minerals as products, and ii.) the oxidation of dissolved and solid-phase ferrous iron by molecular oxygen and microaerophilic Fe(II)-oxidizing bacteria with subsequent precipitation of poorly crystalline Fe(III) oxides (e.g., ferrihydrite). These Fe(III) oxides; that may recrystallize slowly with time to goethite, hematite, and lepidocrocite; represent a primary redox buffering agent (in terms of electron equivalents) in soils, sediments, and subsurface materials. Manganese (III/IV) oxides are also important in this regard. Because of the high surface area and surface chemical reactivity of Fe(III) oxides and Fe(II) containing mineral phases, the Fe biogeochemical cycle is closely linked to those of the trace metals, phosphorous, and various organic and inorganic anthropogenic contaminants.

  18. Origin of concretionary Mn-Fe-oxides in stream sediments of Maine, U.S.A.

    USGS Publications Warehouse

    Nowlan, G.A.; McHugh, J.B.; Hessin, T.D.

    1983-01-01

    Studies of stream and sediment-pore waters largely explain the genesis of concretionary Mn-Fe-oxides in Maine. Waters of two small streams near Jackman, Maine, were studied in terms of pH, Eh, dissolved oxygen, dissolved organic carbon, dissolved Mn, total dissolved Fe, and ferrous and ferric Fe. Pyrite Creek has profuse concretions and coatings of Mn-Fe-oxides, whereas West Pyrite Creek has only sparse Mn-Fe-oxide stains. Pyrite Creek drains boggy terrain and West Pyrite Creek drains well-drained terrain. In West Pyrite Creek, stream and subjacent pore waters have chemical characteristics that do not differ greatly. However, dissolved Mn, ferrous Fe, dissolved oxygen, and in situ Eh measurements show that a steep Eh gradient exists between stream and subjacent pore waters of Pyrite Creek. The steep Eh gradient is manifested by the common zonation of coatings and stains on rocks in stream sediment. The bottom zone has no deposition of oxides, the middle zone is red and consists mostly of Fe-oxides, and the upper zone is black or dark-brown and consists of Mn-oxides with varying amounts of Fe-oxides. The zonation agrees with theoretical predictions of oxide stability as one moves from a reducing to an oxidizing environment. At locations where concretionary Mn-Fe-oxides form, pore waters are depleted of oxygen because of abundant decaying organic material in the stream sediment. The pore waters are charged with dissolved Mn and Fe because mechanically deposited Mn-Fe-oxides are remobilized due to the low-Eh conditions. Groundwaters also contribute dissolved Mn and Fe. Stream waters, on the other hand, are oxygenated and the high-Eh conditions result in low concentrations of dissolved Mn and Fe in stream waters because of the insolubility of Mn-Fe-oxides in high-Eh environments. Therefore, concretionary Mn-Fe-oxides form at the interface between pore and stream waters because Mn- and Fe-rich pore waters, which are undersaturated with respect to Mn-Fe-oxides, mix with

  19. Ablation of the Locus Coeruleus Increases Oxidative Stress in Tg-2576 Transgenic but Not Wild-Type Mice

    PubMed Central

    Hurko, Orest; Boudonck, Kurt; Gonzales, Cathleen; Hughes, Zoe A.; Jacobsen, J. Steve; Reinhart, Peter H.; Crowther, Daniel

    2010-01-01

    Mice transgenic for production of excessive or mutant forms of beta-amyloid differ from patients with Alzheimer's disease in the degree of inflammation, oxidative damage, and alteration of intermediary metabolism, as well as the paucity or absence of neuronal atrophy and cognitive impairment. Previous observers have suggested that differences in inflammatory response reflect a discrepancy in the state of the locus coeruleus (LC), loss of which is an early change in Alzheimer's disease but which is preserved in the transgenic mice. In this paper, we extend these observations by examining the effects of the LC on markers of oxidative stress and intermediary metabolism. We compare four groups: wild-type or Tg2576 Aβ transgenic mice injected with DSP4 or vehicle. Of greatest interest were metabolites different between ablated and intact transgenics, but not between ablated and intact wild-type animals. The Tg2576_DSP4 mice were distinguished from the other three groups by oxidative stress and altered energy metabolism. These observations provide further support for the hypothesis that Tg2576 Aβ transgenic mice with this ablation may be a more congruent model of Alzheimer's disease than are transgenics with an intact LC. PMID:20981353

  20. Sphaerotilus natans encrusted with nanoball-shaped Fe(III) oxide minerals formed by nitrate-reducing mixotrophic Fe(II) oxidation.

    PubMed

    Park, Sunhwa; Kim, Dong-Hun; Lee, Ji-Hoon; Hur, Hor-Gil

    2014-10-01

    Ferrous iron has been known to function as an electron source for iron-oxidizing microorganisms in both anoxic and oxic environments. A diversity of bacteria has been known to oxidize both soluble and solid-phase Fe(II) forms coupled to the reduction of nitrate. Here, we show for the first time Fe(II) oxidation by Sphaerotilus natans strain DSM 6575(T) under mixotrophic condition. Sphaerotilus natans has been known to form a sheath structure enclosing long chains of rod-shaped cells, resulting in a thick biofilm formation under oxic conditions. Here, we also demonstrate that strain DSM 6575(T) grows mixotrophically with pyruvate, Fe(II) as electron donors and nitrate as an electron acceptor and single cells of strain DSM 6575(T) are dominant under anoxic conditions. Furthermore, strain DSM 6575(T) forms nanoball-shaped amorphous Fe(III) oxide minerals encrusting on the cell surfaces through the mixotrophic iron oxidation reaction under anoxic conditions. We propose that cell encrustation results from the indirect Fe(II) oxidation by biogenic nitrite during nitrate reduction and that causes the bacterial morphological change to individual rod-shaped single cells from filamentous sheath structures. This study extends the group of existing microorganisms capable of mixotrophic Fe(II) oxidation by a new strain, S. natans strain DSM 6575(T) , and could contribute to biogeochemical cycles of Fe and N in the environment. PMID:24965827

  1. Sphaerotilus natans encrusted with nanoball-shaped Fe(III) oxide minerals formed by nitrate-reducing mixotrophic Fe(II) oxidation

    PubMed Central

    Park, Sunhwa; Kim, Dong-Hun; Lee, Ji-Hoon; Hur, Hor-Gil

    2014-01-01

    Ferrous iron has been known to function as an electron source for iron-oxidizing microorganisms in both anoxic and oxic environments. A diversity of bacteria has been known to oxidize both soluble and solid-phase Fe(II) forms coupled to the reduction of nitrate. Here, we show for the first time Fe(II) oxidation by Sphaerotilus natans strain DSM 6575T under mixotrophic condition. Sphaerotilus natans has been known to form a sheath structure enclosing long chains of rod-shaped cells, resulting in a thick biofilm formation under oxic conditions. Here, we also demonstrate that strain DSM 6575T grows mixotrophically with pyruvate, Fe(II) as electron donors and nitrate as an electron acceptor and single cells of strain DSM 6575T are dominant under anoxic conditions. Furthermore, strain DSM 6575T forms nanoball-shaped amorphous Fe(III) oxide minerals encrusting on the cell surfaces through the mixotrophic iron oxidation reaction under anoxic conditions. We propose that cell encrustation results from the indirect Fe(II) oxidation by biogenic nitrite during nitrate reduction and that causes the bacterial morphological change to individual rod-shaped single cells from filamentous sheath structures. This study extends the group of existing microorganisms capable of mixotrophic Fe(II) oxidation by a new strain, S. natans strain DSM 6575T, and could contribute to biogeochemical cycles of Fe and N in the environment. PMID:24965827

  2. Anaerobic, Nitrate-Dependent Fe(II) Oxidation Under Advective Flow

    NASA Astrophysics Data System (ADS)

    Weber, K. A.; Coates, J. D.

    2005-12-01

    Microbially-catalyzed nitrate-dependent Fe(II) oxidation has been identified as a ubiquitous biogeochemical process contributing to anaerobic iron redox cycling in sedimentary environments. Most probable number enumeration revealed nitrate-dependent Fe(II) oxidizing microbial communities in groundwater and subsurface sediments in the order of 0 - 2.04 x 103 cells mL-1 and 2.39 x 102 - 1.17 x 103 cells (g wet sediment)-1, respectively. The efficacy of nitrate-dependent Fe(II) oxidation under advective flow was evaluated in a meso-scale column reactor packed with sterile low iron sand amended with subsurface sediments collected from the NABIR FRC background field site (10% mass/mass). Continuous flow of minimal medium mimicked the natural groundwater. Periodic FeCl2 and nitrate injections over a period of 49 days resulted in the retention of 95% of the iron (290 mmol). Extraction of solid-phase Fe revealed a net increase in Fe(III) of 160 mmol above background Fe(III) content indicating that 55% of the injected Fe(II) was oxidized. Differential solubility analysis of 0.5M HCl-extractable Fe and 3M HCl-extractable Fe indicated that the oxidation product was crystalline in nature as only 20% was soluble in 0.5M HCl. This formation of crystalline biogenic Fe(III) oxides is consistent with previous studies. Periodic injections of nitrate and acetate did not result in significant changes in Fe(II) or Fe(III) throughout a control column. Together these results demonstrate that native subsurface sediments harbor microbial communities capable of nitrate-dependent Fe(II) oxidation under advective flow. The biogenic formation of reactive Fe(III) oxide minerals capable of immobilizing heavy metals and radionuclides presents a plausible bioremediative strategy for contaminated subsurface environments.

  3. Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides

    USGS Publications Warehouse

    White, A.F.; Peterson, M.L.

    1996-01-01

    Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25??C. For an aqueous transition metal m, such reactions are 3[Fe2+Fe3+2]O4(magnetite) + 2/nmz ??? 4[Fe3+2]O3(maghemite) + Fe2+ + 2/nmz-n and 3[Fe2+Ti]O3(ilmenite) + 2/nmz ??? Fe3+2Ti3O9(pseudorutile) + Fe2+ + 2/nmz-n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] ??? [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 ?? 10-10 mol m-2 s-1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe2+ is oxidized homogeneously in solution to Fe3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental

  4. Molecular-level modes of As binding to Fe(III) (oxyhydr)oxides precipitated by the anaerobic nitrate-reducing Fe(II)-oxidizing Acidovorax sp. strain BoFeN1

    NASA Astrophysics Data System (ADS)

    Hohmann, Claudia; Morin, Guillaume; Ona-Nguema, Georges; Guigner, Jean-Michel; Brown, Gordon E.; Kappler, Andreas

    2011-09-01

    Sorption of contaminants such as arsenic (As) to natural Fe(III) (oxyhydr)oxides is very common and has been demonstrated to occur during abiotic and biotic Fe(II) oxidation. The molecular mechanism of adsorption- and co-precipitation of As has been studied extensively for synthetic Fe(III) (oxyhydr)oxide minerals but is less documented for biogenic ones. In the present study, we used Fe and As K-edge X-ray Absorption Near Edge Structure (XANES), extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, Mössbauer spectroscopy, XRD, and TEM in order to investigate the interactions of As(V) and As(III) with biogenic Fe(III) (oxyhydr)oxide minerals formed by the nitrate-reducing Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1. The present results show the As immobilization potential of strain BoFeN1 as well as the influence of As(III) and As(V) on biogenic Fe(III) (oxyhydr)oxide formation. In the absence of As, and at low As loading (As:Fe ≤ 0.008 mol/mol), goethite (Gt) formed exclusively. In contrast, at higher As/Fe ratios (As:Fe = 0.020-0.067), a ferrihydrite (Fh) phase also formed, and its relative amount systematically increased with increasing As:Fe ratio, this effect being stronger for As(V) than for As(III). Therefore, we conclude that the presence of As influences the type of biogenic Fe(III) (oxyhydr)oxide minerals formed during microbial Fe(II) oxidation. Arsenic-K-edge EXAFS analysis of biogenic As-Fe-mineral co-precipitates indicates that both As(V) and As(III) form inner-sphere surface complexes at the surface of the biogenic Fe(III) (oxyhydr)oxides. Differences observed between As-surface complexes in BoFeN1-produced Fe(III) (oxyhydr)oxide samples and in abiotic model compounds suggest that associated organic exopolymers in our biogenic samples may compete with As oxoanions for sorption on Fe(III) (oxyhydr)oxides surfaces. In addition HRTEM-EDXS analysis suggests that As(V) preferentially binds to poorly crystalline phases, such as

  5. Advanced experimental analysis of controls on microbial Fe(III) oxide reduction. First year progress report

    SciTech Connect

    Roden, E.E.; Urrutia, M.M.

    1997-07-01

    'The authors have made considerable progress toward a number of project objectives during the first several months of activity on the project. An exhaustive analysis was made of the growth rate and biomass yield (both derived from measurements of cell protein production) of two representative strains of Fe(III)-reducing bacteria (Shewanellaalga strain BrY and Geobactermetallireducens) growing with different forms of Fe(III) as an electron acceptor. These two fundamentally different types of Fe(III)-reducing bacteria (FeRB) showed comparable rates of Fe(III) reduction, cell growth, and biomass yield during reduction of soluble Fe(III)-citrate and solid-phase amorphous hydrous ferric oxide (HFO). Intrinsic growth rates of the two FeRB were strongly influenced by whether a soluble or a solid-phase source of Fe(III) was provided: growth rates on soluble Fe(III) were 10--20 times higher than those on solid-phase Fe(III) oxide. Intrinsic FeRB growth rates were comparable during reduction of HF0 and a synthetic crystalline Fe(III) oxide (goethite). A distinct lag phase for protein production was observed during the first several days of incubation in solid-phase Fe(III) oxide medium, even though Fe(III) reduction proceeded without any lag. No such lag between protein production and Fe(III) reduction was observed during growth with soluble Fe(III). This result suggested that protein synthesis coupled to solid-phase Fe(III) oxide reduction in batch culture requires an initial investment of energy (generated by Fe(III) reduction), which is probably needed for synthesis of materials (e.g. extracellular polysaccharides) required for attachment of the cells to oxide surfaces. This phenomenon may have important implications for modeling the growth of FeRB in subsurface sedimentary environments, where attachment and continued adhesion to solid-phase materials will be required for maintenance of Fe(III) reduction activity. Despite considerable differences in the rate and pattern

  6. The oxidation state of nanophase Fe particles in lunar soil: Implications for space weathering

    NASA Astrophysics Data System (ADS)

    Thompson, Michelle S.; Zega, Thomas J.; Becerra, Patricio; Keane, James T.; Byrne, Shane

    2016-05-01

    We report measurements of the oxidation state of Fe nanoparticles within lunar soils that experienced varied degrees of space weathering. We measured >100 particles from immature, submature, and mature lunar samples using electron energy-loss spectroscopy (EELS) coupled to an aberration-corrected transmission electron microscope. The EELS measurements show that the nanoparticles are composed of a mixture of Fe0, Fe2+, and Fe3+ oxidation states, and exhibit a trend of increasing oxidation state with higher maturity. We hypothesize that the oxidation is driven by the diffusion of O atoms to the surface of the Fe nanoparticles from the oxygen-rich matrix that surrounds them. The oxidation state of Fe in the nanoparticles has an effect on modeled reflectance properties of lunar soil. These results are relevant to remote sensing data for the Moon and to the remote determination of relative soil maturities for various regions of the lunar surface.

  7. The oxidation state of nanophase Fe particles in lunar soil: Implications for space weathering

    NASA Astrophysics Data System (ADS)

    Thompson, Michelle S.; Zega, Thomas J.; Becerra, Patricio; Keane, James T.; Byrne, Shane

    2016-06-01

    We report measurements of the oxidation state of Fe nanoparticles within lunar soils that experienced varied degrees of space weathering. We measured >100 particles from immature, submature, and mature lunar samples using electron energy-loss spectroscopy (EELS) coupled to an aberration-corrected transmission electron microscope. The EELS measurements show that the nanoparticles are composed of a mixture of Fe0, Fe2+, and Fe3+ oxidation states, and exhibit a trend of increasing oxidation state with higher maturity. We hypothesize that the oxidation is driven by the diffusion of O atoms to the surface of the Fe nanoparticles from the oxygen-rich matrix that surrounds them. The oxidation state of Fe in the nanoparticles has an effect on modeled reflectance properties of lunar soil. These results are relevant to remote sensing data for the Moon and to the remote determination of relative soil maturities for various regions of the lunar surface.

  8. Interaction of Fe(II) with phosphate and sulfate on iron oxide surfaces

    NASA Astrophysics Data System (ADS)

    Hinkle, Margaret A. G.; Wang, Zimeng; Giammar, Daniel E.; Catalano, Jeffrey G.

    2015-06-01

    Sulfate and phosphate, oxoanions common in natural systems, affect iron oxide growth and dissolution processes, the adsorption behavior of divalent cations, and iron oxide phase transformations. These oxoanions may thus influence Fe(II) adsorption behavior and subsequently alter the mechanisms and products of Fe(II)-catalyzed Fe(III) oxide recrystallization processes, such as trace metal repartitioning. In this study, the macroscopic and molecular-scale effects of the coadsorption of Fe(II) and sulfate or phosphate onto Fe(III) oxide surfaces were investigated. Macroscopic adsorption edges show that both sulfate and phosphate increase Fe(II) adsorption and that Fe(II) increases sulfate and phosphate adsorption. Attenuated total reflectance Fourier transform infrared spectroscopy shows that the cooperative adsorption behavior of oxoanions and aqueous Fe(II) likely results from a combination of ternary complexation and electrostatic interactions. Surface complexation modeling requires the inclusion of ternary complexes to simulate all conditions of the macroscopic data, further suggesting that these oxoanions and Fe(II) form ternary complexes on Fe(III) oxide surfaces. Despite clear evidence in previous research for Fe(II) oxidation upon adsorption on iron oxide surfaces, this work shows that Fe(II) also displays macroscopic and molecular-scale behaviors associated with divalent (i.e., non-oxidative) cation adsorption. Prior work has shown that metal release from iron oxides caused by ET-AE reactions is directly proportional to the macroscopically-determined Fe(II) surface coverage. Predicting the effects of sulfate and phosphate on processes controlled by ET-AE reactions at redox interfaces, such as mineral phase transformations and trace element repartitioning, may thus not require the explicit consideration of electron transfer processes.

  9. Multilayered metal oxide thin film gas sensors obtained by conventional and RF plasma-assisted laser ablation

    NASA Astrophysics Data System (ADS)

    Mitu, B.; Marotta, V.; Orlando, S.

    2006-04-01

    Multilayered thin films of In 2O 3 and SnO 2 have been deposited by conventional and RF plasma-assisted reactive pulsed laser ablation, with the aim to evaluate their behaviour as toxic gas sensors. The depositions have been carried out by a frequency doubled Nd-YAG laser ( λ = 532 nm, τ = 7 ns) on Si(1 0 0) substrates, in O 2 atmosphere. The thin films have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrical resistance measurements. A comparison of the electrical response of the simple (indium oxide, tin oxide) and multilayered oxides to toxic gas (nitric oxide, NO) has been performed. The influence on the structural and electrical properties of the deposition parameters, such as substrate temperature and RF power is reported.

  10. Adhesion of Escherichia coli to nano-Fe/Al oxides and its effect on the surface chemical properties of Fe/Al oxides.

    PubMed

    Liu, Zhao-Dong; Li, Jiu-Yu; Jiang, Jun; Hong, Zhi-Neng; Xu, Ren-Kou

    2013-10-01

    We investigated the adhesion of Escherichia coli to α-Fe2O3 and γ-Al2O3 and the effects of adhesion on the surface properties of the oxides in batch experiments, where we conducted potentiometric titration, zeta potential measurements, and FTIR spectroscopy. The adhesion isotherms fitted a Langmuir equation well. γ-Al2O3 had a higher adhesion capacity than α-Fe2O3 because of the higher positive charge on γ-Al2O3. The adhesion of E. coli to Fe/Al oxides decreased with increasing pH. Adhesion increased with increasing NaCl concentration, reaching its maximum at 0.05M for α-Fe2O3 and at 0.1M for γ-Al2O3, after which it decreased with further increases in NaCl concentration. Therefore, the electrostatic force plays an important role in the adhesion of E. coli to Fe/Al oxides. The zeta potential-pH curves of the binary-system fell between that for bacteria and those for Fe/Al oxides. Thus, overlapping of the diffuse layers of the electric double layers on the negatively-charged E. coli and positively-charged Fe/Al oxides reduced the effective surface charge density of the minerals and bacteria. E. coli adhesion decreased the point of zero salt effect and the isoelectric point of the Fe/Al oxides. The FTIR spectra indicated that non-electrostatic force also contributed to the interaction between E. coli and Fe/Al oxides, in addition to the electrostatic force between them. PMID:23732807

  11. Induction of Nitrate-Dependent Fe(II) Oxidation by Fe(II) in Dechloromonas sp. Strain UWNR4 and Acidovorax sp. Strain 2AN

    PubMed Central

    Chakraborty, Anirban

    2013-01-01

    We evaluated the inducibility of nitrate-dependent Fe(II)-EDTA oxidation (NDFO) in non-growth, chloramphenicol-amended, resting-cell suspensions of Dechloromonas sp. strain UWNR4 and Acidovorax sp. strain 2AN. Cells previously incubated with Fe(II)-EDTA oxidized ca. 6-fold more Fe(II)-EDTA than cells previously incubated with Fe(III)-EDTA. This is the first report of induction of NDFO by Fe(II). PMID:23144134

  12. Acid-tolerant microaerophilic Fe(II)-oxidizing bacteria promote Fe(III)-accumulation in a fen.

    PubMed

    Lüdecke, Claudia; Reiche, Marco; Eusterhues, Karin; Nietzsche, Sandor; Küsel, Kirsten

    2010-10-01

    The ecological importance of Fe(II)-oxidizing bacteria (FeOB) at circumneutral pH is often masked in the presence of O(2) where rapid chemical oxidation of Fe(II) predominates. This study addresses the abundance, diversity and activity of microaerophilic FeOB in an acidic fen (pH ∼ 5) located in northern Bavaria, Germany. Mean O(2) penetration depth reached 16 cm where the highest dissolved Fe(II) concentrations (up to 140 µM) were present in soil water. Acid-tolerant FeOB cultivated in gradient tubes were most abundant (10(6) cells g(-1) peat) at the 10-20 cm depth interval. A stable enrichment culture was active at up to 29% O(2) saturation and Fe(III) accumulated 1.6 times faster than in abiotic controls. An acid-tolerant, microaerophilic isolate (strain CL21) was obtained which was closely related to the neutrophilic, lithoautotrophic FeOB Sideroxydans lithotrophicus strain LD-1. CL21 oxidized Fe(II) between pH 4 and 6.0, and produced nanoscale-goethites with a clearly lower mean coherence length (7 nm) perpendicular to the (110) plane than those formed abiotically (10 nm). Our results suggest that an acid-tolerant population of FeOB is thriving at redox interfaces formed by diffusion-limited O(2) transport in acidic peatlands. Furthermore, this well-adapted population is successfully competing with chemical oxidation and thereby playing an important role in the microbial iron cycle. PMID:20545739

  13. Structure and high temperature oxidation of mechanical alloyed Fe-Al coating

    NASA Astrophysics Data System (ADS)

    Aryanto, Didik; Sudiro, Toto; Wismogroho, Agus S.

    2016-04-01

    The structure and high temperature oxidation resistance of Fe-Al coating on low carbon steel were investigated. The Fe-Al coating was deposited on the surface of low carbon steel using a mechanical alloying method. The coating was then annealed at 600°C for 2 hour in a vacuum of 5 Pa. The cyclic-oxidation tests of low carbon steel, Fe-Al coatings with and without annealing were performed at 600°C for up to 60h in air. The structure of oxidized samples was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy X-ray spectroscopy (EDS). The results show that the Fe-Al coatings exhibit high oxidation resistance compared to the uncoated steel. After 60 h exposure, the uncoated steel formed mainly Fe3O4 and Fe2O3 layers with the total thickness of around 75.93 µm. Fe-Al coating without annealing formed a thin oxide layer, probably (Fe,Al)2O3. Meanwhile, for annealed sample, EDX analysis observed the formation of two Fe-Al layers with difference in elements concentration. The obtained results suggest that the deposition of Fe-Al coating on low carbon steel can improve the oxidation resistance of low carbon steel.

  14. Growth of epitaxial films of iron oxide, nickel oxide, cobalt oxide, strontium hexagonal ferrite, and yttrium iron garnet by laser ablation (abstract)

    SciTech Connect

    Kennedy, R.J.

    1996-04-01

    Thin films of iron oxide, nickel oxide, cobalt oxide, strontium hexagonal ferrite, and yttrium iron garnet have been grown by laser ablation. With the exception of Co{sub 3}O{sub 4} deposited on LaAlO{sub 3}, the first three materials deposited on [100] LaAlO{sub 3}, SrTiO{sub 3}, and MgO result in high quality {ital c} axis [100] growth. Co{sub 3}O{sub 4} deposited on LaAlO{sub 3} produces highly oriented but random in-plane growth. Similar highly oriented but random in-plane growth occurs for all three materials deposited on glass. The same three materials deposited on cubic zirconia grow [111] oriented and twinned. Strontium hexagonal ferrite and yttrium iron garnet have been deposited on [111] large lattice constant garnet. Epitaxial [0001] films are obtained for the former while the latter gives [111]-oriented films. For yttrium iron garnet the closeness of lattice match to the substrate necessitates that the mosaicity (rocking curves) obtained from area maps be compared to the growth temperatures and pressures to determine the optimum growth conditions for epitaxiality. {copyright} {ital 1996 American Institute of Physics.}

  15. Neutrophilic Fe-Oxidizing Bacteria Are Abundant at the Loihi Seamount Hydrothermal Vents and Play a Major Role in Fe Oxide Deposition

    PubMed Central

    Emerson, David; Moyer, Craig L.

    2002-01-01

    A number of hydrothermal vent sites exist on the summit of the Loihi Seamount, a shield volcano that is part of the Hawaiian archipelago. The vents are 1,100 to 1,325 m below the surface and range in temperature from slightly above ambient (10°C) to high temperature (167°C). The vent fluid is characterized by high concentrations of CO2 (up to 17 mM) and Fe(II) (up to 268 μM), but there is a general paucity of H2S. Most of the vents are surrounded by microbial mats that have a gelatinous texture and are heavily encrusted with rust-colored Fe oxides. Visually, the Fe oxides appeared homogeneous. However, light microscopy revealed that the oxides had different morphologies, which fell into three classes: (i) sheaths, (ii) twisted or irregular filaments, and (iii) amorphous oxides. A morphological analysis of eight different samples indicated that the amorphous oxides were overall the most abundant; however, five sites had >50% sheaths and filamentous oxides. These latter morphologies are most likely the direct result of microbial deposition. Direct cell counts revealed that all of the oxides had abundant microbial populations associated with them, from 6.9 × 107 to 5.3 × 108 cells per ml of mat material. At most sites, end point dilution series for lithotrophic Fe oxidizers were successful out to dilutions of 10−6 and 10−7. A pure culture was obtained from a 10−7 dilution tube; this strain, JV-1, was an obligate, microaerophilic Fe oxidizer that grew at 25 to 30°C. A non-cultivation-based molecular approach with terminal-restriction fragment length polymorphism also indicated the common presence of Fe-oxidizing bacteria at Loihi. Together, these results indicate that Fe-oxidizing bacteria are common at the Loihi Seamount and probably play a major role in Fe oxidation. A review of the literature suggests that microbially mediated Fe oxidation at hydrothermal vents may be important globally. PMID:12039770

  16. Oxidation of Orange G by persulfate activated by Fe(II), Fe(III) and zero valent iron (ZVI).

    PubMed

    Rodriguez, S; Vasquez, L; Costa, D; Romero, A; Santos, A

    2014-04-01

    Persulfate (PS) was employed in the oxidation of Orange G (OG), an azo dye commonly found in textile wastewaters. Activation of PS was conducted with iron to generate sulfate free radicals (SO4(-)) with high redox potential capable to oxidize most of the organics in water. Identification of oxidation intermediates was carried out by analyzing at different times organic by-products generated from treatment of a concentrate dye solution (11.6 mM) with 153 mM of PS and 20 mM of Fe(II) at 20 °C. Intermediate reaction products (mainly phenol (PH) and benzoquinone (BQ), and in less extent aniline, phenolic compounds and naphthalene type compounds with quinone groups) were identified by GC/MS and HPLC, and an oxidation pathway was proposed for the oxidation of OG with iron activated PS. The effect of iron valence (0, II and III) in the oxidation of an aqueous solution of OG (containing 0.1 mM) was studied in a 0.5 L batch reactor at 20 °C. Initial activator and PS concentrations employed were both 1 mM. Complete pollutant removal was achieved within the first 30 min when iron II or III were employed as activators. Quinone intermediates generated during pollutant oxidation may act as electron shuttles, allowing the reduction of Fe(III) into Fe(II) in the redox cycling of iron. Therefore, activation of PS by Fe(III) allowed complete OG removal. When zero valent iron (ZVI) was employed (particle diameter size 0.74 mm) the limiting step in SO4(-) generation was the surface reaction between ZVI and the oxidant yielding a lower oxidation rate of the dye. An increase in the oxidant dosage (0.2 mM OG, 2 mM Fe(III) and 6 mM PS) allowed complete pollutant and ecotoxicity removal, as well as mineralization close to 75%. PMID:24439838

  17. Requirement for a microbial consortium to completely oxidize glucose in Fe(III)- reducing sediments

    USGS Publications Warehouse

    Lovley, D.R.; Phillips, E.J.P.

    1989-01-01

    In various sediments in which Fe(III) reduction was the terminal electron-accepting process, [14C]glucose was fermented to 14C-fatty acids in a manner similar to that observed in methanogenic sediments. These results are consistent with the hypothesis that, in Fe(III)-reducing sediments, fermentable substrates are oxidized to carbon dioxide by the combined activity of fermentative bacteria and fatty acid-oxidizing, Fe(III)-reducing bacteria.

  18. High-valent iron (Fe(VI), Fe(V), and Fe(IV)) species in water: characterization and oxidative transformation of estrogenic hormones.

    PubMed

    MachalováŠišková, Karolína; Jančula, Daniel; Drahoš, Bohuslav; Machala, Libor; Babica, Pavel; Alonso, Paula Godoy; Trávníček, Zdeněk; Tuček, Jiří; Maršálek, Blahoslav; Sharma, Virender K; Zbořil, Radek

    2016-07-28

    This paper presents solid state synthesis and characterization of tetra-oxy iron(iv) and iron(v) species in their salt forms (Na4FeO4-Fe(IV) and K3FeO4-Fe(V)). Stability of the synthesized salts, commonly called ferrates, in water was determined by applying the (57)Fe Mössbauer spectroscopy technique. Within 2 s in water, Fe(IV) converted into Fe(III) while Fe(V) transformed into Fe(VI) and Fe(III) at pH = 8.2. Comparatively, Fe(VI) (bought as K2FeO4) remained stable in aqueous solution during the short time period. The oxidative removal efficiency of the high-valent iron species was then tested against five environmentally important estrogenic hormones (estron (E1), 17-β-estradiol (E2), estriol (E3), 17-α-ethinylestradiol (EE2), and diethylstibestrol (DES)) in effluent water of a wastewater treatment plant. Three dosages of iron species (1, 10, and 100 mg L(-1)) were applied to the effluent water. An increase in the concentration of dosages enhanced the removal of estrogens. Both Fe(V) and Fe(VI) were effective in degrading estrogens, but Fe(IV) showed limited oxidation capacity to transform estrogens. The oxidized products of the estrogens were analyzed using Raman spectroscopy and high-performance liquid chromatography-mass spectrometry (HPLC-MS) techniques. Results demonstrated the transformation of estrogens into low molecular weight oxygenated compounds such as quinone-like and opened-aromatic ring species. A detailed study on E1 by using excess Fe(VI) showed the mineralization of the parent compound. The results demonstrate great potential of high-valent iron species in the degradation of endocrine disruptor chemicals like estrogens with several superior aspects including fast reactions, complete degradation and/or formation of benign organic species, and environmentally-acceptable iron oxide by-products. PMID:27344983

  19. Protection of Nitrate-Reducing Fe(II)-Oxidizing Bacteria from UV Radiation by Biogenic Fe(III) Minerals.

    PubMed

    Gauger, Tina; Konhauser, Kurt; Kappler, Andreas

    2016-04-01

    Due to the lack of an ozone layer in the Archean, ultraviolet radiation (UVR) reached early Earth's surface almost unattenuated; as a consequence, a terrestrial biosphere in the form of biological soil crusts would have been highly susceptible to lethal doses of irradiation. However, a self-produced external screen in the form of nanoparticular Fe(III) minerals could have effectively protected those early microorganisms. In this study, we use viability studies by quantifying colony-forming units (CFUs), as well as Fe(II) oxidation and nitrate reduction rates, to show that encrustation in biogenic and abiogenic Fe(III) minerals can protect a common soil bacteria such as the nitrate-reducing Fe(II)-oxidizing microorganisms Acidovorax sp. strain BoFeN1 and strain 2AN from harmful UVC radiation. Analysis of DNA damage by quantifying cyclobutane pyrimidine dimers (CPD) confirmed the protecting effect by Fe(III) minerals. This study suggests that Fe(II)-oxidizing microorganisms, as would have grown in association with mafic and ultramafic soils/outcrops, would have been able to produce their own UV screen, enabling them to live in terrestrial habitats on early Earth. PMID:27027418

  20. Constructing Hierarchical Interfaces: TiO2-Supported PtFe-FeO(x) Nanowires for Room Temperature CO Oxidation.

    PubMed

    Zhu, Huiyuan; Wu, Zili; Su, Dong; Veith, Gabriel M; Lu, Hanfeng; Zhang, Pengfei; Chai, Song-Hai; Dai, Sheng

    2015-08-19

    In this communication, we report a facile approach to constructing catalytic active hierarchical interfaces in one-dimensional (1D) nanostructure, exemplified by the synthesis of TiO2-supported PtFe-FeO(x) nanowires (NWs). The hierarchical interface, constituting atomic level interactions between PtFe and FeO(x) within each NW and the interactions between NWs and support (TiO2), enables CO oxidation with 100% conversion at room temperature. We identify the role of the two interfaces by probing the CO oxidation reaction with isotopic labeling experiments. Both the oxygen atoms (Os) in FeO(x) and TiO2 participate in the initial CO oxidation, facilitating the reaction through a redox pathway. Moreover, the intact 1D structure leads to the high stability of the catalyst. After 30 h in the reaction stream, the PtFe-FeO(x)/TiO2 catalyst exhibits no activity decay. Our results provide a general approach and new insights into the construction of hierarchical interfaces for advanced catalysis. PMID:26244820

  1. A kinetic model for bacterial Fe(III) oxide reduction in batch cultures

    NASA Astrophysics Data System (ADS)

    Hacherl, Eric L.; Kosson, David S.; Cowan, Robert M.

    2003-04-01

    A model has been developed describing the microbial reduction of solid-phase electron acceptors (Fe(III) oxides) as well as dissolved electron acceptors (chelated Fe(III) or organic electron shuttles) in Shewanella alga BrY. The model utilized a multiple-substrate, Monod kinetics formulation. The Monod description of solid Fe(III) reduction requires a normalization of surface Fe concentration to biomass concentration in order to describe the "bioavailable" Fe(III) concentration. The model also contains provisions for irreversible sorption of Fe(II) to Fe(III) oxide surfaces and for the precipitation of Fe(III) carbonates. The loss of bioavailable Fe(III) due to sorption of Fe(II) was found to be minor, even for highly sorptive amorphous Fe(III) oxyhydroxides. However, the final extent of microbial reduction is very sensitive to the rate of siderite precipitation, assuming that siderite precipitation could partially occlude Fe(III) surface sites. The use of a multisubstrate Monod kinetics model enabled an evaluation of the effects of electron shuttles on solid Fe(III) reduction. Because the electron shuttle is recycled, very small additions can greatly increase the overall rate of solid Fe(III) reduction.

  2. Bacterial nanometric amorphous Fe-based oxide: a potential lithium-ion battery anode material.

    PubMed

    Hashimoto, Hideki; Kobayashi, Genki; Sakuma, Ryo; Fujii, Tatsuo; Hayashi, Naoaki; Suzuki, Tomoko; Kanno, Ryoji; Takano, Mikio; Takada, Jun

    2014-04-23

    Amorphous Fe(3+)-based oxide nanoparticles produced by Leptothrix ochracea, aquatic bacteria living worldwide, show a potential as an Fe(3+)/Fe(0) conversion anode material for lithium-ion batteries. The presence of minor components, Si and P, in the original nanoparticles leads to a specific electrode architecture with Fe-based electrochemical centers embedded in a Si, P-based amorphous matrix. PMID:24689687

  3. Silver-silver oxide core-shell nanoparticles by femtosecond laser ablation: core and shell sizing by extinction spectroscopy

    NASA Astrophysics Data System (ADS)

    Schinca, D. C.; Scaffardi, L. B.; Videla, F. A.; Torchia, G. A.; Moreno, P.; Roso, L.

    2009-11-01

    The generation of small silver metal nanoparticles (Nps) by ultrashort pulsed laser ablation has been an active area of research in recent years due to their interest in several fields of applied research such as biotechnology and material research, in particular those with sizes smaller than 10 nm. In general, laser ablation tends to produce environmentally clean metal Nps compared with wet chemical methods. However, since silver may be oxidized in the presence of water or ethanol, core-shell silver-silver oxide (Ag-Ag2O) Nps can be formed, whose size and thickness must be determined and characterized for functionalization related to future applications. This work analyses the size characteristics of core-shell Ag-Ag2O colloid nanostructures (smaller than 10 nm) obtained by femtosecond laser ablation of solid silver targets in different liquid media (water or ethanol) through the study of their optical extinction spectra. A fit of full experimental spectrum using Mie theory allows the determination of core size and shell thickness distributions as a function of fluence. The red-shift of the plasmon peak wavelength with respect to the bare-core peak wavelength at 400 nm, produced by the oxide shell, may be easily measured even for very small thicknesses. It was found that the dominant Ag2O effective thickness is inversely proportional to the fluence, reaching a maximum of 0.2 nm for a fluence of 60 J cm-2 and a minimum of 0.04 nm for a fluence of 1000 J cm-2.

  4. Nd:YVO4 laser direct ablation of indium tin oxide films deposited on glass and polyethylene terephthalate substrates.

    PubMed

    Wang, Jian-Xun; Kwon, Sang Jik; Han, Jae-Hee; Cho, Eou Sik

    2013-09-01

    A Q-switched diode-pumped neodymium-doped yttrium vanadate (Nd:YVO4, lambda = 1064 nm) laser was applied to obtain the indium tin oxide (ITO) patterns on flexible polyethylene terephthalate (PET) substrate by a direct etching method. After the ITO films were deposited on a soda-lime glass and PET substrate, laser ablations were carried out on the ITO films for various conditions and the laser ablated results on the ITO films were investigated and analyzed considering the effects of substrates on the laser etching. The laser ablated widths on ITO deposited on glass were found to be much narrower than those on ITO deposited on PET substrate, especially, at a higher scanning speed of laser beam such as 1000 mm/s and 2000 mm/s. As the thermal conductivity of glass substrate is about 7.5 times higher than that of PET, more thermal energy would be spread and transferred to lateral direction in the ITO film in case of PET substrate. PMID:24205645

  5. Planar square spiral inductor generated through indium-tin oxide film removal by using UV laser ablation

    NASA Astrophysics Data System (ADS)

    Yang, Ching-Ching; Hung, Min-Wei; Tsai, Hsin-Yi; Chuang, Wen-Ning; Huang, Kuo-Cheng

    2016-04-01

    Induction efficiency is the evaluation index for measuring the induced voltage of a wireless-sensing module, and this index is affected by the electric properties, shape, number, and position of inductances. In this study, indium-tin oxide with a thickness of 30 nm was coated on a glass substrate to fabricate a planar square spiral inductor (PSSI), and patterns were then ablated using a UV laser with a wavelength of 355 nm. Single and array patterns with different dimensions were designed to investigate the variation of induction efficiency. The results indicated that the 3 × 3 PSSI array ablated at a frequency of 100 kHz and that a scanning speed of 1000 mm/s had the highest induction efficiency of 6.4 %, which was 2.4 % higher than that of PSSIs that ablated at other processing parameters. The induction efficiency could be enhanced, but the uniformity of sensing decreased as the array number decreased, and the highest induction efficiency of 10 % and highest variation of 7.2 % were caused by position deviation, which was obtained from a single pattern. In addition, the induction efficiency of 3.2 % was obtained from the 4 × 4 array pattern, and the variation caused by the position was controlled to less than 0.8 %. The results showed the specific relationship among the dimensions, number of patterns, and induction efficiency. The designed inductances can be applied to micro wireless-sensing modules in the future.

  6. Immobilization of Radionuclides and Heavy Metals through Anaerobic Bio-Oxidation of Fe(II)

    PubMed Central

    Lack, Joseph G.; Chaudhuri, Swades K.; Kelly, Shelly D.; Kemner, Kenneth M.; O'Connor, Susan M.; Coates, John D.

    2002-01-01

    Adsorption of heavy metals and radionuclides (HMR) onto iron and manganese oxides has long been recognized as an important reaction for the immobilization of these compounds. However, in environments containing elevated concentrations of these HMR the adsorptive capacity of the iron and manganese oxides may well be exceeded, and the HMR can migrate as soluble compounds in aqueous systems. Here we demonstrate the potential of a bioremediative strategy for HMR stabilization in reducing environments based on the recently described anaerobic nitrate-dependent Fe(II) oxidation by Dechlorosoma species. Bio-oxidation of 10 mM Fe(II) and precipitation of Fe(III) oxides by these organisms resulted in rapid adsorption and removal of 55 μM uranium and 81 μM cobalt from solution. The adsorptive capacity of the biogenic Fe(III) oxides was lower than that of abiotically produced Fe(III) oxides (100 μM for both metals), which may have been a result of steric hindrance by the microbial cells on the iron oxide surfaces. The binding capacity of the biogenic oxides for different heavy metals was indirectly correlated to the atomic radius of the bound element. X-ray absorption spectroscopy indicated that the uranium was bound to the biogenically produced Fe(III) oxides as U(VI) and that the U(VI) formed bidentate and tridentate inner-sphere complexes with the Fe(III) oxide surfaces. Dechlorosoma suillum oxidation was specific for Fe(II), and the organism did not enzymatically oxidize U(IV) or Co(II). Small amounts (less than 2.5 μM) of Cr(III) were reoxidized by D. suillum; however, this appeared to be inversely dependent on the initial concentration of the Cr(III). The results of this study demonstrate the potential of this novel approach for stabilization and immobilization of HMR in the environment. PMID:12039723

  7. Control of the permeability loss-peak frequency of Ni81Fe19 thin films through laser ablation of triangular and square cluster geometries

    NASA Technical Reports Server (NTRS)

    Grimes, C. A.; Lumpp, J. K.

    2000-01-01

    Laser ablation arrays of triangular and square shaped clusters, comprised of 23 micrometers diam circular holes, are defined upon 100 nm thick Ni81Fe19 films used to control the rf permeability spectra. Cluster-to-cluster spacing is varied from 200 to 600 micrometers. For each geometry it is found that the loss peak frequency and permeability magnitude shift lower, in a step-wise fashion, at a cluster-to-cluster spacing between 275 and 300 micrometers. The nonlinear shift in the behavior of the permeability spectra correlates with a dramatic increase in domain wall density. c2000 American Institute of Physics.

  8. Effect of dissolved organic matter on Fe(II) oxidation in natural and engineered waters.

    PubMed

    Lee, Ying Ping; Fujii, Manabu; Terao, Koumei; Kikuchi, Tetsuro; Yoshimura, Chihiro

    2016-10-15

    Fe(II) oxidation was investigated in samples from the Sagami River basin (Japan) with particular emphasis on the effect of dissolved organic matter (DOM) in an urban river system. Collected samples consisted of main stream and tributary waters impacted to a moderate and minor extent by anthropogenic activities, respectively, and treated effluents from adjacent municipal wastewater treatment plants (MWWTPs: as representative anthropogenic point source). Nanomolar Fe(II) oxidation was measured in air-saturated waters using luminol chemiluminescence in the dark at 25 °C. Second-order rate constant for Fe(II) oxidation (with respect to Fe(II) and O2 concentrations) showed spatial and temporal variation. Annual average of the rate constant was highest for MWWTP effluents, followed by reservoir and river waters, with tributary waters showing the lowest oxidation rate. Manipulation experiments indicated that, in addition to pH (7.8-8.4), DOM characteristics are important explanatory variable for the Fe(II) oxidation. For example, the addition of MWWTP-derived humic-type DOM to anthropogenically less-influenced tributary water resulted in substantial increase in the oxidation rate. Significant negative correlation observed between the specific UV absorbance (SUVA254) and Fe(II) oxidation rate constant (pH 8.0) suggests a potential effect of humic-type DOM with low SUVA254 (high aliphatic content) on Fe(II) oxidation in natural and engineered waters. PMID:27450354

  9. Oxidation Control of Atmospheric Plasma Sprayed FeAl Intermetallic Coatings Using Dry-Ice Blasting

    NASA Astrophysics Data System (ADS)

    Song, Bo; Dong, Shujuan; Coddet, Pierre; Hansz, Bernard; Grosdidier, Thierry; Liao, Hanlin; Coddet, Christian

    2013-03-01

    The performance of atmospheric plasma sprayed FeAl coatings has been remarkably limited because of oxidation and phase transformation during the high-temperature process of preparation. In the present work, FeAl intermetallic coatings were prepared by atmospheric plasma spraying combined with dry-ice blasting. The microstructure, oxidation, porosity, and surface roughness of FeAl intermetallic coatings were investigated. The results show that a denser FeAl coating with a lower content of oxide and lower degree of phase transformation can be achieved because of the cryogenic, the cleaning, and the mechanical effects of dry-ice blasting. The surface roughness value decreased, and the adhesive strength of FeAl coating increased after the application of dry-ice blasting during the atmospheric plasma spraying process. Moreover, the microhardness of the FeAl coating increased by 72%, due to the lower porosity and higher dislocation density.

  10. Ion irradiation of Fe-Fe oxide core-shell nanocluster films: Effect of interface on stability of magnetic properties

    SciTech Connect

    McCloy, John S.; Jiang, Weilin; Droubay, Timothy C.; Varga, Tamas; Kovarik, Libor; Sundararajan, Jennifer A.; Kaur, Maninder; Qiang, You; Burks, Edward C.; Liu, Kai

    2013-08-28

    A cluster deposition method was used to produce films of loosely aggregated nanoclusters (NCs) of Fe core-Fe{sub 3}O{sub 4} shell or fully oxidized Fe{sub 3}O{sub 4}. Films of these NC on Si(100) or MgO(100)/Fe{sub 3}O{sub 4}(100) were irradiated to 10{sup 16} Si{sup 2+}/cm{sup 2} near room temperature using an ion accelerator. Ion irradiation creates structural change in the NC film with corresponding chemical and magnetic changes which depend on the initial oxidation state of the cluster. Films were characterized using magnetometry (hysteresis, first order reversal curves), microscopy (transmission electron, helium ion), and x-ray diffraction. In all cases, the particle sizes increased due to ion irradiation, and when a core of Fe is present, irradiation reduces the oxide shells to lower valent Fe species. These results show that ion irradiated behavior of the NC films depends strongly on the initial nanostructure and chemistry, but in general saturation magnetization decreases slightly.

  11. High-Temperature Oxidation Behavior of Fe-Si-Ce Alloys

    NASA Astrophysics Data System (ADS)

    Su, Yong; Zhang, Shunke; Fu, Guangyan; Liu, Qun; Tang, Yuanze

    2016-02-01

    The oxidation behavior of Fe-Si-Ce alloys with different Ce content at 1,173 and 1,273 K has been studied by means of optical microscope (OM), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscope (SEM). Results show that the Ce addition refines the grain size of Fe-Si alloys, and correspondingly the grain size of the oxides decreases, which increases the grain boundary concentration and promotes the short-path diffusion of the alloying elements and oxygen. During oxidation, the positive effect of the grain refinement on the oxidation behavior of the alloy is more obvious than negative effect, so the Ce addition improves the oxidation resistances of the Fe-3Si alloys. Compared to Fe-3Si-0.5Ce alloy, Fe-3Si-5.0Ce alloy has the larger mass gain for the preferential oxidation of the excessive content of Ce exceeding its beneficial effects. The rare earth Ce changes the oxidation mechanism of Fe-Si alloys. Oxygen penetrates the oxide scales and reacts preferentially with Ce-rich phases, which results in the pinning effect and improves the adhesion of the oxide scales.

  12. Reduction and persulfate oxidation of nitro explosives in contaminated soils using Fe-bearing materials.

    PubMed

    Oh, Seok-Young; Yoon, Hyun-Su; Jeong, Tae-Yong; Kim, Sang Don; Kim, Dong-Wook

    2016-07-13

    The oxidative and reductive transformation of nitro explosives in contaminated soils with Fe-bearing materials and persulfate (S2O8(2-)) was examined via batch experiments. Zero-valent cast iron [Fe(0)], steel dust from a steel manufacturing plant, and FeS rapidly reduced 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in soil under anaerobic conditions as long as a sufficient amount of water was present. The Fe-bearing materials also effectively activated persulfate to enhance the oxidative transformation of TNT and RDX in soil-water systems. Kinetically, reductive and oxidative transformations removed more than 90% of the explosives from a soil-water system within 5 h under the given conditions. Pseudo-first-order rates in the range of 0.7-23.4 h(-1) were observed. By increasing the concentration of persulfate or Fe-bearing materials, the oxidative transformation could be promoted. Treated soils via redox reactions using the Fe-bearing materials did not show significant toxicity, except for the case of TNT-contaminated soils oxidized by FeS-assisted persulfate. Considering the kinetics of explosive degradation and the toxicity of treated wastewaters and soils, Fe(0) or steel dust-assisted persulfate oxidation may be a safe option as an ex situ remediation process for the treatment of explosive-contaminated soils. PMID:27327861

  13. Influence of Fe3O4/Fe-phthalocyanine decorated graphene oxide on the microwave absorbing performance

    NASA Astrophysics Data System (ADS)

    Li, Jingwei; Wei, Junji; Pu, Zejun; Xu, Mingzhen; Jia, Kun; Liu, Xiaobo

    2016-02-01

    Novel graphene oxide@Fe3O4/iron phthalocyanine (GO@Fe3O4/FePc) hybrid materials were prepared through a facile one-step solvothermal method with graphene oxide (GO) sheets as template in ethylene glycol. The morphology and structure of the hybrid materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectrophotometer (FTIR) and X-ray diffraction (XRD), respectively. The results indicated that the monodispersed Fe3O4/FePc hybrid microspheres were uniformly self-assembled along the surface of GO sheets through electrostatic attraction and the morphology can be tuned by controlling the amount of 4,4‧-bis(3,4-dicyanophenoxy)biphenyl (BPH). As the BPH content increases, magnetization measurement of the GO@Fe3O4/FePc hybrid materials showed that the coercivity increased, while saturation magnetizations decreased. Electromagnetic properties of the hybrid materials were measured in the range of 0.5-18.0 GHz. The microwave absorbing performance enhanced with the increase of BPH content and a maximum reflection loss of -27.92 dB was obtained at 10.8 GHz when the matching thickness was 2.5 mm. Therefore, the novel electromagnetic hybrid materials can be considered as potential materials in the microwave absorbing field.

  14. Microstructure and oxygen evolution of Fe-Ce mixed oxides by redox treatment

    NASA Astrophysics Data System (ADS)

    Li, Kongzhai; Haneda, Masaaki; Ning, Peihong; Wang, Hua; Ozawa, Masakuni

    2014-01-01

    The relationship between structure and reduction/redox properties of Fe-Ce mixed oxides with a Fe content of 5, 10, 20 or 30 mol%, prepared by a coprecipitation method, were investigated by XRD, Raman, TEM, TPR and TPO techniques. It is found that all the iron ions can be incorporated into the ceria lattice to form a solid solution for the FeCe 5 (Fe 5%) sample, but amorphous or crystal Fe2O3 particles were found to be present on the Fe-Ce oxide samples with higher the iron content. The reducibility of single solid solution was much better than the pure CeO2, and the appearance of dispersed Fe2O3 particles improved the surface reducibility of materials. The iron ions incorporated into the CeO2 lattice accelerated the oxygen release from bulk to surface, and surface Fe2O3 particles in close contact to CeO2 acted as a catalyst for the reaction between solid solution and hydrogen. The microstructure of exposed Fe2O3 with Ce-Fe-O solid solution allows the Fe-Ce mixed oxides to own good reducibility and high OSC, which also counteracts the deactivation of the reducibility resulting from the sintering of materials in the redox cycling.

  15. Relationship Between Iron Whisker Growth and Doping Amount of Oxide During Fe2O3 Reduction

    NASA Astrophysics Data System (ADS)

    Gong, Xuzhong; Zhao, Zhilong; Wang, Zhi; Zhang, Ben; Guo, Lei; Guo, Zhancheng

    2016-04-01

    Iron whisker growth during Fe2O3 doped with oxide reduced by CO was investigated by using in situ observation and scanning electron microscopy. The results indicated that the minimum doping amount (MDA) of various oxides, hindering the iron whisker growth, was different. The MDA of Al2O3, Li2O, Na2O, and K2O was 0.5, 0.4, 4, and 12 pct, respectively. From the reduction rate, it was found that Li2O, MgO, and Al2O3 had some suppressive effects on the Fe2O3 reduction process, thus, confining the growth of iron whisker. However, other oxides had some catalytic effects on the Fe2O3 reduction process (Fe2O3-Fe3O4-FeO-Fe), such as CaO, SrO, BaO, Na2O, and K2O. As long as their doping amount was enough, these oxides could inhibit the diffusion of the Fe atom. When the metal ionic radius in doped oxide was bigger than that of Fe3+, such as Ca2+, Sr2+, Ba2+, Na+, and K+, there were lots of spaces left in Fe2O3 doped with oxide after reduction, improving Fe atom diffusion. Consequently, their MDA was more than that of small radius to restrain the growth of iron whisker. Finally, the relationship between corresponding metal ionic radius, electron layer number, valence electron number, and MDA of oxide was expressed by using data fitting as follows: N_{{{{A}}y {{O}}x }} = 1.3 × 10^{ - 5} × {r_{{{{A}}^{x + } }}2 × √{n_{{{{A}}^{x + } }} } }/{f_{q }}

  16. Resonance Raman and magnetic resonance spectroscopic characterization of the Fe(I), Fe(II), Fe(III), and Fe(IV) oxidation states of Fe(2-TMPyP)[sup n+] (aq)

    SciTech Connect

    Rodgers, K.R.; Reed, R.A.; Spiro, T.G. ); Su, Y.O. )

    1992-06-24

    Four oxidation states of aqueous meso-5,10,15,20-tetrakis(2-N-methylpyridyl)porphinatoiron (Fe(2-TMPyP)(aq)) have been characterized at pH 9 and 12 via resonance Raman (RR), NMR, and ESR spectroscopic methods. These pH values were chosen because they are below and above the pK[sub a] values of the Fe(II) (11.2), Fe(III) (11.0), and Fe(IV) (10.0) complexes. The 2-TMPyP[sup 2+] ligand stabilizes four iron oxidation states, I-IV, in aqueous solution. ESR data of the highly reduced complex (g[perpendicular] = 2.32 and g[parallel] = 2.00) clearly demonstrate that Fe(II) reduction gives Fe(I) and not the porphyrin [pi]-anion radical at pH 9 and 12. This is the first Fe(I) complex to be observed in aqueous solution, and the potentials of the Fe(II/I) couples ([minus]0.740 V at pH 9 and [minus]0.763 V at pH 12) are among the most positive of any yet observed for a porphinato complex. The first observation of a Fe[sup II]-OH stretch in a model heme complex is reported and assigned to a band at 464 cm[sup [minus]1] on the basis of its 20-cm[sup [minus]1] downshift in H[sub 2][sup 18]O. The Fe(IV/III) potentials at pH 9 and 12 are among the least positive ever reported for porphyrin complexes. For solutions with pH [gt] pK[sub a[Fe(IV)

  17. Hydrophilic molybdenum oxide nanomaterials with controlled morphology and strong plasmonic absorption for photothermal ablation of cancer cells.

    PubMed

    Song, Guosheng; Shen, Jia; Jiang, Feiran; Hu, Ronggui; Li, Wenyao; An, Lei; Zou, Rujia; Chen, Zhigang; Qin, Zongyi; Hu, Junqing

    2014-03-26

    The molybdenum oxide nanosheets have shown strong localized surface plasmon resonance (LSPR) absorption in the near-infrared (NIR) region. However, the long alky chains of ligands made them hydrophobic and less biocompatible. To meet the requirements of molybdenum based nanomaterials for use as a future photothermal therapy, a simple hydrothermal route has been developed for hydrophilic molybdenum oxide nanospheres and nanoribbons using a molybdenum precursor and poly(ethylene glycol) (PEG). First, molybdenum oxide nanomaterials prepared in the presence of PEG exhibit strong localized surface plasmon resonance (LSPR) absorption in near-infrared (NIR) region, compared with that of no PEG. Second, elevation of synthetic temperature leads to a gradual transformation of molybdenum oxide nanospheres into nanoribbons, entailing the evolution of an intense LSPR absorption in the NIR region. Third, as-prepared molybdenum oxide nanomaterials coated with PEG possess a hydrophilic property and thus can be directly used for biological applications without additional post treatments. Moreover, molybdenum oxide nanoribbons as a model of photothermal materials can efficiently convert the 980 nm wavelength laser energy into heat energy, and this localized hyperthermia produces the effective thermal ablation of cancer cells, meaning a potential photothermal material. PMID:24564332

  18. Oxidation Resistant Ti-Al-Fe Diffusion Barrier for FeCrAlY Coatings on Titanium Aluminides

    NASA Technical Reports Server (NTRS)

    Brady, Michael P. (Inventor); Smialke, James L. (Inventor); Brindley, William J. (Inventor)

    1996-01-01

    A diffusion barrier to help protect titanium aluminide alloys, including the coated alloys of the TiAl gamma + Ti3Al (alpha2) class, from oxidative attack and interstitial embrittlement at temperatures up to at least 1000 C is disclosed. The coating may comprise FeCrAlX alloys. The diffusion barrier comprises titanium, aluminum, and iron in the following approximate atomic percent: Ti-(50-55)Al-(9-20)Fe. This alloy is also suitable as an oxidative or structural coating for such substrates.

  19. Zeta-Fe2O3--A new stable polymorph in iron(III) oxide family.

    PubMed

    Tuček, Jiří; Machala, Libor; Ono, Shigeaki; Namai, Asuka; Yoshikiyo, Marie; Imoto, Kenta; Tokoro, Hiroko; Ohkoshi, Shin-ichi; Zbořil, Radek

    2015-01-01

    Iron(III) oxide shows a polymorphism, characteristic of existence of phases with the same chemical composition but distinct crystal structures and, hence, physical properties. Four crystalline phases of iron(III) oxide have previously been identified: α-Fe2O3 (hematite), β-Fe2O3, γ-Fe2O3 (maghemite), and ε-Fe2O3. All four iron(III) oxide phases easily undergo various phase transformations in response to heating or pressure treatment, usually forming hexagonal α-Fe2O3, which is the most thermodynamically stable Fe2O3 polymorph under ambient conditions. Here, from synchrotron X-ray diffraction experiments, we report the formation of a new iron(III) oxide polymorph that we have termed ζ-Fe2O3 and which evolved during pressure treatment of cubic β-Fe2O3 (Ia3 space group) at pressures above 30 GPa. Importantly, ζ-Fe2O3 is maintained after pressure release and represents the first monoclinic Fe2O3 polymorph (I2/a space group) that is stable at atmospheric pressure and room temperature. ζ-Fe2O3 behaves as an antiferromagnet with a Néel transition temperature of ~69 K. The complex mechanism of pressure-induced transformation of β-Fe2O3, involving also the formation of Rh2O3-II-type Fe2O3 and post-perovskite-Fe2O3 structure, is suggested and discussed with respect to a bimodal size distribution of precursor nanoparticles. PMID:26469883

  20. Zeta-Fe2O3 - A new stable polymorph in iron(III) oxide family

    NASA Astrophysics Data System (ADS)

    Tuček, Jiří; Machala, Libor; Ono, Shigeaki; Namai, Asuka; Yoshikiyo, Marie; Imoto, Kenta; Tokoro, Hiroko; Ohkoshi, Shin-Ichi; Zbořil, Radek

    2015-10-01

    Iron(III) oxide shows a polymorphism, characteristic of existence of phases with the same chemical composition but distinct crystal structures and, hence, physical properties. Four crystalline phases of iron(III) oxide have previously been identified: α-Fe2O3 (hematite), β-Fe2O3, γ-Fe2O3 (maghemite), and ɛ-Fe2O3. All four iron(III) oxide phases easily undergo various phase transformations in response to heating or pressure treatment, usually forming hexagonal α-Fe2O3, which is the most thermodynamically stable Fe2O3 polymorph under ambient conditions. Here, from synchrotron X-ray diffraction experiments, we report the formation of a new iron(III) oxide polymorph that we have termed ζ-Fe2O3 and which evolved during pressure treatment of cubic β-Fe2O3 ( space group) at pressures above 30 GPa. Importantly, ζ-Fe2O3 is maintained after pressure release and represents the first monoclinic Fe2O3 polymorph (I2/a space group) that is stable at atmospheric pressure and room temperature. ζ-Fe2O3 behaves as an antiferromagnet with a Néel transition temperature of ~69 K. The complex mechanism of pressure-induced transformation of β-Fe2O3, involving also the formation of Rh2O3-II-type Fe2O3 and post-perovskite-Fe2O3 structure, is suggested and discussed with respect to a bimodal size distribution of precursor nanoparticles.

  1. The effect of Ti addition on oxidation behavior of FeAl intermetallic alloy

    SciTech Connect

    Li, D.; Lin, D.

    1997-12-31

    The influence of Ti addition on the high temperature oxidation behaviors of FeAl intermetallic alloys in air at 1,000 C and 1,100 C have been investigated. The oxidation kinetics of FeAl alloys were examined by the weight gain method and oxide products were examined by XRD, SEM, EDS and EPMA. The results showed that the oxidation kinetic curves of both Ti-doped and binary Fe-36.5Al alloys were described as different parabolas followed the formula: ({Delta}W/S){sup 2} = K{sub p}t. The parabolic rate constant, K{sub p} values are about 2.4 and 3.3 mg{sup 2}cm{sup {minus}4}h{sup {minus}1} for Fe-36.5Al alloy and about 1.3 and 2.0 mg{sup 2}cm{sup {minus}4}h{sup {minus}1} for Fe-36.5Al-2Ti alloy when oxidizing at 1,000 C and 1,100 C respectively. The difference between Fe-36.5Al and Fe-36.5Al-2Ti alloy is not only in the surface morphology but also in the phase components. In the surface there is only {alpha}-Al{sub 2}O{sub 3} oxide for the Fe-36.5Al alloy while there are {alpha}-Al{sub 2}O{sub 3} and TiO oxide for the Fe-36.5Al-2Ti alloy. The effects of Ti addition on the oxidation resistance of FeAl alloy were discussed based on the microstructural evidence.

  2. Oxidation mechanism of porous Zr₂Fe used as a hydrogen getter.

    PubMed

    Cohen, Dror; Nahmani, Moshe; Rafailov, Genadi; Attia, Smadar; Shamish, Zorik; Landau, Miron; Merchuk, Jose; Zeiri, Yehuda

    2016-01-01

    We determined the oxidation mechanism of porous ST-198, which mainly comprises Zr2Fe. Oxidation kinetics depended on temperature, oxygen partial pressure, and oxidation extent. The passivation role of oxidation in hydrogen scavenging is probably due to the development of a surface oxide, independent of oxygen concentration. Zr2Fe would be a superior hydrogen getter in oxygen-contaminated environments at high temperatures, as most oxygen will be consumed at the outer shell by mass transfer limitations, protecting the bulk of the getter for hydrogen scavenging. PMID:26408914

  3. Influence of Fe(2+)-catalysed iron oxide recrystallization on metal cycling.

    PubMed

    Latta, Drew E; Gorski, Christopher A; Scherer, Michelle M

    2012-12-01

    Recent work has indicated that iron (oxyhydr-)oxides are capable of structurally incorporating and releasing metals and nutrients as a result of Fe2+-induced iron oxide recrystallization. In the present paper, we briefly review the current literature examining the mechanisms by which iron oxides recrystallize and summarize how recrystallization affects metal incorporation and release. We also provide new experimental evidence for the Fe2+-induced release of structural manganese from manganese-doped goethite. Currently, the exact mechanism(s) for Fe2+-induced recrystallization remain elusive, although they are likely to be both oxide-and metal-dependent. We conclude by discussing some future research directions for Fe2+-catalysed iron oxide recrystallization. PMID:23176453

  4. Influence of Oxygen and Nitrate on Fe (Hydr)oxide Mineral Transformation and Soil Microbial Communities during Redox Cycling.

    PubMed

    Mejia, Jacqueline; Roden, Eric E; Ginder-Vogel, Matthew

    2016-04-01

    Oscillations between reducing and oxidizing conditions are observed at the interface of anaerobic/oxic and anaerobic/anoxic environments, and are often stimulated by an alternating flux of electron donors (e.g., organic carbon) and electron acceptors (e.g., O2 and NO3(-)). In iron (Fe) rich soils and sediments, these oscillations may stimulate the growth of both Fe-reducing bacteria (FeRB) and Fe-oxidizing bacteria (FeOB), and their metabolism may induce cycling between Fe(II) and Fe(III), promoting the transformation of Fe (hydr)oxide minerals. Here, we examine the mineralogical evolution of lepidocrocite and ferrihydrite, and the adaptation of a natural microbial community to alternating Fe-reducing (anaerobic with addition of glucose) and Fe-oxidizing (with addition of nitrate or air) conditions. The growth of FeRB (e.g., Geobacter) is stimulated under anaerobic conditions in the presence of glucose. However, the abundance of these organisms depends on the availability of Fe(III) (hydr)oxides. Redox cycling with nitrate results in decreased Fe(II) oxidation thereby decreasing the availability of Fe(III) for FeRB. Additionally, magnetite is detected as the main product of both lepidocrocite and ferrihydrite reduction. In contrast, introduction of air results in increased Fe(II) oxidation, increasing the availability of Fe(III) and the abundance of Geobacter. In the lepidocrocite reactors, Fe(II) oxidation by dissolved O2 promotes the formation of ferrihydrite and lepidocrocite, whereas in the ferrihydrite reactors we observe a decrease in magnetite stoichiometry (e.g., oxidation). Understanding Fe (hydr)oxide transformation under environmentally relevant redox cycling conditions provides insight into nutrient availability and transport, contaminant mobility, and microbial metabolism in soils and sediments. PMID:26949922

  5. Biomineralization by a Newly-Isolated Stalk-Forming Fe-oxidizing Bacterium: Towards Interpretation of Putative Fe Microfossils

    NASA Astrophysics Data System (ADS)

    Krepski, S. T.; Chan, C. S.

    2010-12-01

    Diverse aerobic, lithotrophic Fe-oxidizing bacteria (FeOB) produce distinctive extracellular Fe-rich filaments, which resemble putative Fe microfossils dating from recent to 1.7 Ga (Slack et al., 2007, EPSL: 243). The filament morphology, texture, and composition are promising biosignatures for these FeOB; however, somewhat similar morphologies have been shown to result from chemical precipitates. In order to accurately identify and interpret such biosignatures, morphology must described in detail and be linked to physiological function and growth conditions in extant organisms. Towards this goal, we aimed to isolate a novel, stalk-forming microaerophilic FeOB, since there exist few isolates. We successfully obtained a pure strain (named R-1) from a circumneutral, freshwater Fe seep in Christiana Creek, Newark, DE. This strain produces a twisted stalk, similar to Gallionella and Mariprofundus in morphology and in mineralogy. Our work shows that R-1 is a neutrophilic obligate FeOB, unable to oxidize other organic or inorganic substrates. It is a Beta-Proteobacterium in the Gallionellaceae family but is phylogenetically distinct from previously isolated Gallionella sp. and Sideroxydans sp. The closest cultured relative is S. lithotrophicus (97% similar) and the closest environmental clone is 98% similar. We have begun growing R-1 and the marine stalk-forming FeOB Mariprofundus ferrooxydans in microslide cultures, which allow direct microscope observation without disturbing growth. We are monitoring oxygen concentration gradients and FeOB response to oxygen levels. In order to link morphology to biological function and growth conditions, we will observe stalk formation under various conditions and document various morphological and textural parameter (e.g. branching and orientation) to establish criteria for biogenicity. No organisms are known to make stalks under anaerobic conditions, so if these structures are detected in the rock record, they could be used as

  6. Bacterial reductive dissolution of crystalline Fe(III) oxide in continuous-flow column reactors

    SciTech Connect

    Roden, E.E.; Urrutia, M.M.; Mann, C.J.

    2000-03-01

    Bacterial reductive dissolution of synthetic crystalline Fe(III) oxide-coated sand was studied in continuous-flow column reactors in comparison with parallel batch cultures. The cumulative amount of aqueous Fe(II) exported from the columns over a 6-month incubation period corresponded to (95.0 {+-} 3.7)% (n = 3) of their original Fe(III) content. Wet-chemical analysis revealed that only (6.5 {+-} 3.2)% of the initial Fe(III) content remained in the columns at the end of the experiment. The near-quantitative removal of Fe was visibly evidenced by extensive bleaching of color from the sand in the columns. In contrast to the column reactors, Fe(II) production quickly reached an asymptote in batch cultures, and only (13.0 {+-} 2.2)% (n = 3) of the Fe(III) oxide content was reduced. Sustained bacterial-cell growth occurred in the column reactors, leading to the production and export of a quantity of cells 100-fold greater than that added during inoculation. Indirect estimates of cell growth, based on the quantity of Fe(III) reduced, suggest that only an approximate doubling of initial cell abundance was likely to have occurred in the batch cultures. Their results indicate that removal of biogenic Fe(II) via aqueous-phase transport in the column reactors decreased the passivating influence of surface-bound Fe(II) on oxide reduction activity, thereby allowing a dramatic increase in the extent of Fe(III) oxide reduction and associated bacterial growth. These findings have important implications for understanding the fate of organic and inorganic contaminants whose geochemical behavior is linked to Fe(III) oxide reduction.

  7. Advanced Experiment Analysis of controls on Microbial FE(III) Oxide Reduction

    SciTech Connect

    Roden, Eric E.; Urrutia, Matilde M.

    1999-06-01

    Understanding factors which control the long-term survival and activity of Fe(III)-reducing bacteria (FeRB) in subsurface sedimentary environments is important for predicting the ability of these organisms to serve as agents for bioremediation of organic and inorganic contaminants. This project seeks to refine our quantitative understanding of microbiological and geochemical controls on bacterial Fe(III) oxide reduction and growth of FeRB, using laboratory reactor systems which mimic to varying degrees the physical and chemical conditions of subsurface sedimentary environments. Methods for studying microbial Fe(III) oxide reduction and FeRB growth in experimental systems which incorporate advective aqueous phase flux are being developed for this purpose. These methodologies, together with an accumulating database on the kinetics of Fe(III) reduction and bacterial growth with various synthetic and natural Fe(III) oxide minerals, will be applicable to experimental and modeling studies of subsurface contaminant transformations directly coupled to or influenced by bacterial Fe(III) oxide reduction activity.

  8. X-ray Diffraction of Permalloy Nanoparticles Fabricated by Laser Ablation in Water

    SciTech Connect

    Musaev, O.; Midgley, A; Muthu, D; Wrobel, J; Kruger, M

    2009-01-01

    Permalloy (NiFeMo) nanoparticles were fabricated by laser ablation of bulk material in water with a UV pulsed laser. Transmission electron microscope images showed that approximately spherical particles about 50 nm in diameter were formed in the ablation process. All diffraction peaks corresponding to the bulk material were present in the nanoparticles. In addition to these peaks several new peaks were observed in the nanoparticles, which were attributed to nickel oxide.

  9. The role of microaerophilic Fe-oxidizing micro-organisms in producing banded iron formations.

    PubMed

    Chan, C S; Emerson, D; Luther, G W

    2016-09-01

    Despite the historical and economic significance of banded iron formations (BIFs), we have yet to resolve the formation mechanisms. On modern Earth, neutrophilic microaerophilic Fe-oxidizing micro-organisms (FeOM) produce copious amounts of Fe oxyhydroxides, leading us to wonder whether similar organisms played a role in producing BIFs. To evaluate this, we review the current knowledge of modern microaerophilic FeOM in the context of BIF paleoenvironmental studies. In modern environments wherever Fe(II) and O2 co-exist, microaerophilic FeOM proliferate. These organisms grow in a variety of environments, including the marine water column redoxcline, which is where BIF precursor minerals likely formed. FeOM can grow across a range of O2 concentrations, measured as low as 2 μm to date, although lower concentrations have not been tested. While some extant FeOM can tolerate high O2 concentrations, many FeOM appear to prefer and thrive at low O2 concentrations (~3-25 μm). These are similar to the estimated dissolved O2 concentrations in the few hundred million years prior to the 'Great Oxidation Event' (GOE). We compare biotic and abiotic Fe oxidation kinetics in the presence of varying levels of O2 and show that microaerophilic FeOM contribute substantially to Fe oxidation, at rates fast enough to account for BIF deposition. Based on this synthesis, we propose that microaerophilic FeOM were capable of playing a significant role in depositing the largest, most well-known BIFs associated with the GOE, as well as afterward when global O2 levels increased. PMID:27392195

  10. Structural Fe(II) Oxidation in Biotite by an Ectomycorrhizal Fungi Drives Mechanical Forcing.

    PubMed

    Bonneville, Steeve; Bray, Andrew W; Benning, Liane G

    2016-06-01

    Microorganisms are essential agents of Earth's soil weathering engine who help transform primary rock-forming minerals into soils. Mycorrhizal fungi, with their vast filamentous networks in symbiosis with the roots of most plants can alter a large number of minerals via local acidification, targeted excretion of ligands, submicron-scale biomechanical forcing, and mobilization of Mg, Fe, Al, and K at the hypha-biotite interface. Here, we present experimental evidence that Paxillus involutus-a basidiomycete fungus-in ectomycorrhizal symbiosis with Scots pine (Pinus sylvestris), is able to oxidize a substantial amount of structural Fe(II) in biotite. Iron redox chemistry, quantified by X-ray absorption near edge spectra on 13 fungi-biotite sections along three distinct hypha colonizing the [001] basal plane of biotite, revealed variable but extensive Fe(II) oxidation up to ∼2 μm in depth and a Fe(III)/Fetotal ratio of up to ∼0.8. The growth of Fe(III) hydroxide implies a volumetric change and a strain within the biotite lattice potentially large enough to induce microcrack formation, which are abundant below the hypha-biotite interface. This Fe(II) oxidation also leads to the formation of a large pool of Fe(III) (i.e., structural Fe(III) and Fe(III) oxyhydroxides) within biotite that could participate in the Fe redox cycling in soils. PMID:27128742

  11. Influence of Oxygen Supply on Oxide Coarsening During the Internal Oxidation of Two-Phase Fe-Y Alloys

    NASA Astrophysics Data System (ADS)

    Kachur, Stephen J.; Webler, Bryan A.

    2016-05-01

    Fe-Y binary alloys underwent thermogravimetric analysis while exposed to low oxidant partial pressures using a mixture of 5 pct H2-95 pct Ar gas at two flow rates. The alloys experienced in situ internal oxidation of Y-rich intermetallic phases. Kinetics and microstructures were both affected by flowrate. Lower flow rates resulted in coarser oxides and decreased oxidation rates. Results show the possible impacts of rate-controlling processes in the gas phase on internal oxidation with dilute oxidants.

  12. Constructing hierarchical interfaces: TiO2-supported PtFe-FeOx nanowires for room temperature CO oxidation

    DOE PAGESBeta

    Zhu, Huiyuan; Wu, Zili; Dong, Su; Veith, Gabriel M.; Lu, Hanfeng; Zhang, Pengfei; Chai, Song -Hai; Dai, Sheng

    2015-08-05

    This is a report of a facile approach to constructing catalytic active hierarchical interfaces in one-dimensional (1D) nanostructure, exemplified by the synthesis of TiO2-supported PtFe–FeOx nanowires (NWs). The hierarchical interface, constituting atomic level interactions between PtFe and FeOx within each NW and the interactions between NWs and support (TiO2), enables CO oxidation with 100% conversion at room temperature. We identify the role of the two interfaces by probing the CO oxidation reaction with isotopic labeling experiments. Both the oxygen atoms (Os) in FeOx and TiO2 participate in the initial CO oxidation, facilitating the reaction through a redox pathway. Moreover, themore » intact 1D structure leads to the high stability of the catalyst. After 30 h in the reaction stream, the PtFe–FeOx/TiO2 catalyst exhibits no activity decay. These results provide a general approach and new insights into the construction of hierarchical interfaces for advanced catalysis.« less

  13. Mtr Extracellular Electron Transfer Pathways in Fe(III)-reducing or Fe(II)-oxidizing Bacteria: A Genomic Perspective

    SciTech Connect

    Shi, Liang; Rosso, Kevin M.; Zachara, John M.; Fredrickson, Jim K.

    2012-12-01

    Originally discovered in the dissimilatory metal-reducing bacterium Shewanella oneidensis MR-1 (MR-1), the Mtr (i.e., metal-reducing) pathway exists in all characterized strains of metal-reducing Shewanella. The protein components identified to date for the Mtr pathway of MR-1 include four multi-heme c-type cytochromes (c-Cyts), CymA, MtrA, MtrC and OmcA, and a porin-like, outer membrane protein MtrB. They are strategically positioned along the width of the MR-1 cell envelope to mediate electron transfer from the quinone/quinol pool in the inner-membrane to the Fe(III)-containing minerals external to the bacterial cells. A survey of microbial genomes revealed homologues of the Mtr pathway in other dissimilatory Fe(III)-reducing bacteria, including Aeromonas hydrophila, Ferrimonas balearica and Rhodoferax ferrireducens, and in the Fe(II)-oxidizing bacteria Dechloromonas aromatica RCB, Gallionella capsiferriformans ES-2 and Sideroxydans lithotrophicus ES-1. The widespread distribution of Mtr pathways in Fe(III)-reducing or Fe(II)-oxidizing bacteria emphasizes the importance of this type of extracellular electron transfer pathway in microbial redox transformation of Fe. Their distribution in these two different functional groups of bacteria also emphasizes the bi-directional nature of electron transfer reactions carried out by the Mtr pathways. The characteristics of the Mtr pathways may be shared by other pathways used by microorganisms for exchanging electrons with their extracellular environments.

  14. Oxide shell reduction and magnetic property changes in core-shell Fe nanoclusters under ion irradiation

    SciTech Connect

    Sundararajan, Jennifer A.; Kaur, Maninder; Qiang, You; Jiang, Weilin; McCloy, John S.

    2014-05-07

    Ion irradiation effects are studied on the Fe-based core-shell nanocluster (NC) films with core as Fe and shell as Fe{sub 3}O{sub 4}/Fe{sub 3}N. These NC films were deposited on Si substrates to thickness of ∼0.5 μm using a NC deposition system. The films were irradiated at room temperature with 5.5 MeV Si{sup 2+} ions to ion fluences of 10{sup 15} and 10{sup 16} ions/cm{sup 2}. It is found that the irradiation induces grain growth, Fe valence reduction in the shell, and crystallization or growth of Fe{sub 3}N. The film retained its Fe-core and its ferromagnetic properties after irradiation. The nature and mechanism of oxide shell reduction and composition dependence after irradiation were studied by synthesizing additional NC films of Fe{sub 3}O{sub 4} and FeO + Fe{sub 3}N and irradiating them under the same conditions. The presence of nanocrystalline Fe is found to be a major factor for the oxide shell reduction. The surface morphologies of these films show dramatic changes in the microstructures due to cluster growth and agglomeration as a result of ion irradiation.

  15. Inhibition of the Fe(III)-catalyzed dopamine oxidation by ATP and its relevance to oxidative stress in Parkinson's disease.

    PubMed

    Jiang, Dianlu; Shi, Shuyun; Zhang, Lin; Liu, Lin; Ding, Bingrong; Zhao, Bingqing; Yagnik, Gargey; Zhou, Feimeng

    2013-09-18

    Parkinson's disease (PD) is characterized by the progressive degeneration of dopaminergic cells, which implicates a role of dopamine (DA) in the etiology of PD. A possible DA degradation pathway is the Fe(III)-catalyzed oxidation of DA by oxygen, which produces neuronal toxins as side products. We investigated how ATP, an abundant and ubiquitous molecule in cellular milieu, affects the catalytic oxidation reaction of dopamine. For the first time, a unique, highly stable DA-Fe(III)-ATP ternary complex was formed and characterized in vitro. ATP as a ligand shifts the catecholate-Fe(III) ligand metal charge transfer (LMCT) band to a longer wavelength and the redox potentials of both DA and the Fe(III) center in the ternary complex. Remarkably, the additional ligation by ATP was found to significantly reverse the catalytic effect of the Fe(III) center on the DA oxidation. The reversal is attributed to the full occupation of the Fe(III) coordination sites by ATP and DA, which blocks O2 from accessing the Fe(III) center and its further reaction with DA. The biological relevance of this complex is strongly implicated by the identification of the ternary complex in the substantia nigra of rat brain and its attenuation of cytotoxicity of the Fe(III)-DA complex. Since ATP deficiency accompanies PD and neurotoxin 1-methyl-4-phenylpyridinium (MPP(+)) induced PD, deficiency of ATP and the resultant impairment toward the inhibition of the Fe(III)-catalyzed DA oxidation may contribute to the pathogenesis of PD. Our finding provides new insight into the pathways of DA oxidation and its relationship with synaptic activity. PMID:23823941

  16. Molecular orbital (SCF-X-α-SW) theory of Fe2+-Mn3+, Fe3+-Mn2+, and Fe3+-Mn3+ charge transfer and magnetic exchange in oxides and silicates

    USGS Publications Warehouse

    Sherman, David M.

    1990-01-01

    Metal-metal charge-transfer and magnetic exchange interactions have important effects on the optical spectra, crystal chemistry, and physics of minerals. Previous molecular orbital calculations have provided insight on the nature of Fe2+-Fe3+ and Fe2+-Ti4+ charge-transfer transitions in oxides and silicates. In this work, spin-unrestricted molecular orbital calculations on (FeMnO10) clusters are used to study the nature of magnetic exchange and electron delocalization (charge transfer) associated with Fe3+-Mn2+, Fe3+-Mn3+, and Fe2+-Mn3+ interactions in oxides and silicates. 

  17. Aluminum affects heterogeneous Fe(III) (Hydr)oxide nucleation, growth, and ostwald ripening.

    PubMed

    Hu, Yandi; Li, Qingyun; Lee, Byeongdu; Jun, Young-Shin

    2014-01-01

    Heterogeneous coprecipitation of iron and aluminum oxides is an important process for pollutant immobilization and removal in natural and engineered aqueous environments. Here, using a synchrotron-based small-angle X-ray scattering technique, we studied heterogeneous nucleation and growth of Fe(III) (hydr)oxide on quartz under conditions found in acid mine drainage (at pH = 3.7 ± 0.2, [Fe(3+)] = 10(-4) M) with different initial aqueous Al/Fe ratios (0:1, 1:1, and 5:1). Interestingly, although the atomic ratios of Al/Fe in the newly formed Fe(III) (hydr)oxide precipitates were less than 1%, the in situ particle size and volume evolutions of the precipitates on quartz were significantly influenced by aqueous Al/Fe ratios. At the end of the 3 h experiments, with aqueous Al/Fe ratios of 0:1, 1:1, and 5:1, the average radii of gyration of particles on quartz were 5.7 ± 0.3, 4.6 ± 0.1, and 3.7 ± 0.3 nm, respectively, and the ratio of total particle volumes on quartz was 1.7:3.4:1.0. The Fe(III) (hydr)oxide precipitates were poorly crystallized, and were positively charged in all solutions. In the presence of Al(3+), Al(3+) adsorption onto quartz changed the surface charge of quartz from negative to positive, which caused the slower heterogeneous growth of Fe(III) (hydr)oxide on quartz. Furthermore, Al affected the amount of water included in the Fe(III) (hydr)oxides, which can influence their adsorption capacity. This study yielded important information usable for pollutant removal not only in natural environments, but also in engineered water treatment processes. PMID:24289329

  18. Metastable alloy nanoparticles, metal-oxide nanocrescents and nanoshells generated by laser ablation in liquid solution: influence of the chemical environment on structure and composition.

    PubMed

    Scaramuzza, Stefano; Agnoli, Stefano; Amendola, Vincenzo

    2015-11-14

    Alloy nanoparticles are characterized by the combination of multiple interesting properties, which are attractive for technological and scientific purposes. A frontier topic of this field is nanoalloys with compositions not thermodynamically allowed at ordinary temperature and pressure (i.e. metastable), because they require out-of-equilibrium synthetic approaches. Recently, laser ablation synthesis in solution (LASiS) was successfully applied for the realization of metastable nanoalloys because of the fast kinetics of nanoparticle formation. However, the role played by the chemical environment on the final composition and structure of laser generated nanoalloys still has to be fully elucidated. Here, we investigated the influence of different synthetic conditions on the LASiS of metastable nanoalloys composed of Au and Fe, such as the use of water instead of ethanol, the bubbling of inert gases and the addition of a few vol% of H2O2 and H2O. The two elements showed different reactivity when LASiS was performed in water instead of ethanol, while minor effects were observed from bubbling pure gases such as N2, Ar and CO2 in the liquid solution. Moreover, the plasmonic response and the structure of the nanoalloys were sensibly modified by adding H2O2 to water. We also found that nanoparticle production is dramatically influenced just by adding 0.2% of H2O in ethanol. These results suggest that the formation of a cavitation bubble with long lifetime and large size during LASiS is useful for the preservation of the metastable alloy composition, whereas an oxidative environment hampers the formation of metastable alloy nanoparticles. Overall, by acting on the type of solvent and solutes, we were able to switch from a traditional synthetic approach for the composition of Au-Fe nanoalloys to one using a reactive environment, which gives unconventional structures such as metal@iron-oxide nanoshells and nanocrescents of oxide supported on metal nanospheres. These results

  19. Rapid anaerobic benzene oxidation with a variety of chelated Fe(III) forms

    USGS Publications Warehouse

    Lovley, D.R.; Woodward, J.C.; Chapelle, F.H.

    1996-01-01

    Fe(III) chelated to such compounds as EDTA, N-methyliminodiacetie acid, ethanol diglycine, humic acids, and phosphates stimulated benzene oxidation coupled to Fe(III) reduction in anaerobic sediments from a petroleum- contaminated aquifer as effectively as or more effectively than nitrilotriacetic acid did in a previously demonstrated stimulation experiment. These results indicate that many forms of chelated Fe(III) might be applicable to aquifer remediation.

  20. High longitudinal relaxivity of ultra-small gadolinium oxide prepared by microsecond laser ablation in diethylene glycol

    SciTech Connect

    Luo Ningqi; Xiao Jun; Hu Wenyong; Chen Dihu; Tian Xiumei; Yang Chuan; Li Li

    2013-04-28

    Ultra-small gadolinium oxide (Gd{sub 2}O{sub 3}) can be used as T{sub 1}-weighted Magnetic Resonance Imaging (MRI) contrast agent own to its high longitudinal relaxivity (r{sub 1}) and has attracted intensive attention in these years. In this paper, ultra-small Gd{sub 2}O{sub 3} nanoparticles of 3.8 nm in diameter have been successfully synthesized by a microsecond laser ablating a gadolinium (Gd) target in diethylene glycol (DEG). The growth inhibition effect induced by the large viscosity of DEG makes it possible to synthesize ultra-small Gd{sub 2}O{sub 3} by laser ablation in DEG. The r{sub 1} value and T{sub 1}-weighted MR images are measured by a 3.0 T MRI spectroscope. The results show these nanoparticles with a high r{sub 1} value of 9.76 s{sup -1} mM{sup -1} to be good MRI contrast agents. We propose an explanation for the high r{sub 1} value of ultra-small Gd{sub 2}O{sub 3} by considering the decreasing factor (surface to volume ratio of the nanoparticles, S/V) and the increasing factor (water hydration number of the Gd{sup 3+} on Gd{sub 2}O{sub 3} surface, q), which offer a new look into the relaxivity studies of MRI contrast agents. Our research provides a new approach to preparing ultra-small Gd{sub 2}O{sub 3} of high r{sub 1} value by laser ablation in DEG and develops the understanding of high relaxivity of ultra-small Gd{sub 2}O{sub 3} MRI contrast agents.

  1. Chemolithotrophic nitrate-dependent Fe(II)-oxidizing nature of actinobacterial subdivision lineage TM3

    PubMed Central

    Kanaparthi, Dheeraj; Pommerenke, Bianca; Casper, Peter; Dumont, Marc G

    2013-01-01

    Anaerobic nitrate-dependent Fe(II) oxidation is widespread in various environments and is known to be performed by both heterotrophic and autotrophic microorganisms. Although Fe(II) oxidation is predominantly biological under acidic conditions, to date most of the studies on nitrate-dependent Fe(II) oxidation were from environments of circumneutral pH. The present study was conducted in Lake Grosse Fuchskuhle, a moderately acidic ecosystem receiving humic acids from an adjacent bog, with the objective of identifying, characterizing and enumerating the microorganisms responsible for this process. The incubations of sediment under chemolithotrophic nitrate-dependent Fe(II)-oxidizing conditions have shown the enrichment of TM3 group of uncultured Actinobacteria. A time-course experiment done on these Actinobacteria showed a consumption of Fe(II) and nitrate in accordance with the expected stoichiometry (1:0.2) required for nitrate-dependent Fe(II) oxidation. Quantifications done by most probable number showed the presence of 1 × 104 autotrophic and 1 × 107 heterotrophic nitrate-dependent Fe(II) oxidizers per gram fresh weight of sediment. The analysis of microbial community by 16S rRNA gene amplicon pyrosequencing showed that these actinobacterial sequences correspond to ∼0.6% of bacterial 16S rRNA gene sequences. Stable isotope probing using 13CO2 was performed with the lake sediment and showed labeling of these Actinobacteria. This indicated that they might be important autotrophs in this environment. Although these Actinobacteria are not dominant members of the sediment microbial community, they could be of functional significance due to their contribution to the regeneration of Fe(III), which has a critical role as an electron acceptor for anaerobic microorganisms mineralizing sediment organic matter. To the best of our knowledge this is the first study to show the autotrophic nitrate-dependent Fe(II)-oxidizing nature of TM3 group of uncultured Actinobacteria

  2. The oxidation state of Fe in MORB glasses and the oxygen fugacity of the upper mantle

    NASA Astrophysics Data System (ADS)

    Cottrell, Elizabeth; Kelley, Katherine A.

    2011-05-01

    Micro-analytical determination of Fe3+/∑Fe ratios in mid-ocean ridge basalt (MORB) glasses using micro X-ray absorption near edge structure (μ-XANES) spectroscopy reveals a substantially more oxidized upper mantle than determined by previous studies. Here, we show that global MORBs yield average Fe3+/∑Fe ratios of 0.16 ± 0.01 (n = 103), which trace back to primary MORB melts equilibrated at the conditions of the quartz-fayalite-magnetite (QFM) buffer. Our results necessitate an upward revision of the Fe3+/∑Fe ratios of MORBs, mantle oxygen fugacity, and the ferric iron content of the mantle relative to previous wet chemical determinations. We show that only 0.01 (absolute, or < 10%) of the difference between Fe3+/∑Fe ratios determined by micro-colorimety and XANES can be attributed to the Mössbauer-based XANES calibration. The difference must instead derive from a bias between micro-colorimetry performed on experimental vs. natural basalts. Co-variations of Fe3+/∑Fe ratios in global MORB with indices of low-pressure fractional crystallization are consistent with Fe3+ behaving incompatibly in shallow MORB magma chambers. MORB Fe3+/∑Fe ratios do not, however, vary with indices of the extent of mantle melting (e.g., Na2O(8)) or water concentration. We offer two hypotheses to explain these observations: The bulk partition coefficient of Fe3+ may be higher during peridotite melting than previously thought, and may vary with temperature, or redox exchange between sulfide and sulfate species could buffer mantle melting at ~ QFM. Both explanations, in combination with the measured MORB Fe3+/∑Fe ratios, point to a fertile MORB source with greater than 0.3 wt.% Fe2O3.

  3. Physiology and Mechanism of Phototrophic Fe(II) Oxidation by Rhodopseudomonas palustris TIE-1

    NASA Astrophysics Data System (ADS)

    Jiao, Y.; Newman, D.

    2007-12-01

    Phototrophic Fe(II)-oxidizing bacteria use electrons from ferrous iron [Fe(II)] and energy from light to drive reductive CO2 fixation. This metabolism is thought to be ancient in origin, and plays an important role in environmental iron cycling. It has been implicated in the deposition of Banded Iron Formations, a class of ancient sedimentary iron deposits. Consistent with this hypothesis, we discovered that hydrogen gas, a thermodynamically favorable electron donor to Fe(II), in an Archean atmosphere would not have inhibited phototrophic Fe(II) oxidation. To understand this physiology and the connection to BIF formation at the molecular level, the mechanisms of phototrophic Fe(II) oxidation were examined in a model organism Rhodopseudomonas palustris TIE-1. Increased expression of a putative decaheme c-type cytochrome, encoded by pioA, was observed when cells were grown under Fe(II)-oxidizing conditions. Two genes located immediately downstream of pioA in the same operon, pioB and pioC, encode a putative outer membrane beta-barrel protein and a putative high potential iron-sulfur protein, respectively. Deletion studies demonstrated that all three genes are involved in phototrophic Fe(II) oxidation. This study provides our first insight into the molecular mechanisms of this metabolism, which will be further characterized by in vitro biochemical studies.

  4. Anomalous spin state of Fe in double perovskite oxide Sr 2FeWO 6

    NASA Astrophysics Data System (ADS)

    Kawanaka, H.; Hase, I.; Toyama, S.; Nishihara, Y.

    2000-07-01

    In the series of Sr 2FeTO 6 (T=4d or 5d), the valence of Fe is 3+ in most of the compounds. However, recently we have found that the Sr 2FeWO 6 has Fe 2+ state. Sr 2FeWO 6 is an insulator with an antiferromagnetic transition temperature of 37 K. From the Mössbauer experiment, below ∼20 K, a center shift of +1.2 mm/ s relative to metallic iron and a quadrupole splitting of 1.9 mm/ s are obtained. The quadrupole splitting has strong temperature dependence. The hyperfine field is ∼110 kOe which seems to be quite small. We concluded that the iron ground state of Sr 2FeWO 6 is Fe 2+ high-spin ( S=2) state.

  5. A redox hydrogel protects the O2 -sensitive [FeFe]-hydrogenase from Chlamydomonas reinhardtii from oxidative damage.

    PubMed

    Oughli, Alaa Alsheikh; Conzuelo, Felipe; Winkler, Martin; Happe, Thomas; Lubitz, Wolfgang; Schuhmann, Wolfgang; Rüdiger, Olaf; Plumeré, Nicolas

    2015-10-12

    The integration of sensitive catalysts in redox matrices opens up the possibility for their protection from deactivating molecules such as O2 . [FeFe]-hydrogenases are enzymes catalyzing H2 oxidation/production which are irreversibly deactivated by O2 . Therefore, their use under aerobic conditions has never been achieved. Integration of such hydrogenases in viologen-modified hydrogel films allows the enzyme to maintain catalytic current for H2 oxidation in the presence of O2 , demonstrating a protection mechanism independent of reactivation processes. Within the hydrogel, electrons from the hydrogenase-catalyzed H2 oxidation are shuttled to the hydrogel-solution interface for O2 reduction. Hence, the harmful O2 molecules do not reach the hydrogenase. We illustrate the potential applications of this protection concept with a biofuel cell under H2 /O2 mixed feed. PMID:26073322

  6. Study of high-temperature oxidation of ultrathin fe films on Pt(100) by using X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Nahm, T.-U.

    2016-05-01

    High-temperature oxidation of iron thin films deposited on Pt(100) surfaces was studied by using X-ray photoelectron spectroscopy (XPS). Upon an oxygen exposure of 300 Langmuir onto a 7.5- monolayer (ML) Fe film at 830 K, about 2 monolayers of the Fe film were oxidized as Fe3O4 while the remaining Fe atoms diffused into the substrate. For 1.25-, 2.5-, and 3.75-monolayer Fe films, only about a monolayer of the Fe film was oxidized as FeO, regardless of the number of Fe atoms. The oxide layers on the 7.5-monolayer Fe film were observed to be stable upon post-annealing at 1030 K.

  7. Oxide Shell Reduction and Magnetic Property Changes in Core-Shell Fe Nanoclusters under Ion Irradiation

    SciTech Connect

    Sundararajan, Jennifer A.; Kaur, Maninder; Jiang, Weilin; McCloy, John S.; Qiang, You

    2014-02-12

    Ion irradiation effects are studied on the Fe-based core-shell nanocluster (NC) films with core as Fe and shell as Fe3O4/FeO. These NC films were were deposited on Si substrates to thickness of ~0.5 micrometers using a NC deposition system. The films were irradiated at room temperature with 5.5 MeV Si2+ ions to ion fluences of 1015 and 1016 ions/cm2. It is found that the irradiation induces grain growth, Fe valence reduction in the shell, and crystallization of Fe3N. The nature and mechanism of oxide shell reduction and composition dependence after irradiation were studied by synthesizing additional NC films of Fe3O4 and FeO+Fe3N and irradiating them under the same conditions. The presence of nanocrystalline Fe is found to be a major factor for the oxide shell reduction. The surface morphologies of these films show dramatic changes in the microstructures due to cluster growth and agglomeration as a result of ion irradiation.

  8. Fe(3-x)Ti(x)O4 nanoparticles as tunable probes of microbial metal oxidation.

    PubMed

    Liu, Juan; Pearce, Carolyn I; Liu, Chongxuan; Wang, Zheming; Shi, Liang; Arenholz, Elke; Rosso, Kevin M

    2013-06-19

    Present and emerging biotechnological applications for iron (oxyhydr)oxide nanomaterials depend on their interaction with microorganisms, as do their toxicity, transport, and fate in biological and environmental systems. However, mass or electron transfer along key molecular pathways at microbe-nanomaterial interfaces is extremely difficult to quantify because of system complexity. Inspired by Fe(II)-oxidizing microbes widespread in nature, we isolate and characterize one such pathway by examining the oxidation of Fe(3-x)Ti(x)O4 (magnetite-titanomagnetite) nanoparticles by the bacterial electron transfer enzyme MtoA, a decaheme c-type cytochrome. Oxidation by MtoA was studied as a function of the thermodynamic driving force for electron transfer by controlling the Ti(IV) doping content (x), which tunes the solid-state Fe(II)/Fe(III) ratio built into the nanoparticles. A higher Fe(II)/Fe(III) ratio appears to systematically increase the electron transfer kinetics to the cytochrome. In situ X-ray diffraction indicated that, during oxidation, the spinel ferrite lattice remains intact while structural Fe(II) is progressively depleted. Surface and atomic site specific Fe L(2,3)-edge X-ray magnetic circular dichroism indicated that MtoA directly accesses magnetically ordered B-sublattice Fe(II) at the interface. This study provides the first quantitative insights into an isolated molecular pathway for biotransformation of iron (oxyhydr)oxide nanomaterials, and more generally, it also illustrates new techniques for probing these pathways in detail, featuring use of tailored nanoparticles, purified metalloenzyme, and synchrotron X-ray absorption spectroscopies. PMID:23672679

  9. Fe3-xTixO4 Nanoparticles as Tunable Probes of Microbial Metal Oxidation

    SciTech Connect

    Liu, Juan; Pearce, Carolyn I.; Liu, Chongxuan; Wang, Zheming; Shi, Liang; Arenholz, Elke; Rosso, Kevin M.

    2013-05-14

    Present and emerging biotechnological applications for iron (oxyhydr)oxide nanomaterials depend on their interaction with microorganisms, as do their toxicity, transport, and fate in biological and environmental systems. However, mass or electron transfer along key molecular pathways at microbe-nanomaterial interfaces is extremely difficult to quantify because of system complexity. Inspired by Fe(II)-oxidizing microbes widespread in nature, we isolate and characterize one such pathway by examining the oxidation of Fe3-xTixO4 (magnetite-titanomagnetite) nanoparticles by the bacterial electron transfer enzyme MtoA, a decaheme c-type cytochrome. Oxidation by MtoA was studied as a function of the thermodynamic driving force for electron transfer by controlling the Ti(IV) doping content (x), which tunes the solid-state Fe(II)/Fe(III) ratio built into the nanoparticles. A higher Fe(II)/Fe(III) ratio appears to proportionally increase the electron transfer kinetics to the cytochrome. In situ x-ray diffraction indicated that during oxidation the spinel ferrite lattice remains intact while structural Fe(II) is progressively depleted. Surface and atomic site specific Fe L2,3-edge x-ray magnetic circular dichroism indicated that MtoA directly accesses magnetically-ordered B-sublattice Fe(II) at the interface. This study provides first quantitative insights into an isolated molecular pathway for biotransformation of iron (oxyhydr)oxide nanomaterials. And, more generally, it also illustrates new techniques for probing these pathways in detail, featuring use of tailored nanoparticles, purified metalloenzyme, and synchrotron x-ray absorption spectroscopies.

  10. Pro-oxidant activity of aluminum: promoting the Fenton reaction by reducing Fe(III) to Fe(II).

    PubMed

    Ruipérez, F; Mujika, J I; Ugalde, J M; Exley, C; Lopez, X

    2012-12-01

    The possibility for an Al-superoxide complex to reduce Fe(III) to Fe(II), promoting oxidative damage through the Fenton reaction, is investigated using highly accurate ab initio methods and density functional theory in conjunction with solvation continuum methods to simulate bulk solvent effects. It is found that the redox reaction between Al-superoxide and Fe(III) to produce Fe(II) is exothermic. Moreover, the loss of an electron from the superoxide radical ion in the Al-superoxide complex leads to a spontaneous dissociation of molecular oxygen from aluminum, recovering therefore an Al(3+) hexahydrated complex. As demonstrated in previous studies, this complex is again prone to stabilize another superoxide molecule, suggesting a catalytic cycle that augments the concentration of Fe(II) in the presence of Al(III). Similar results are found for Al(OH)(2+) and Al(OH)(2)(+) hydrolytic species. Our work reinforces the idea that the presence of aluminum in biological systems could lead to an important pro-oxidant activity through a superoxide formation mechanism. PMID:23085591

  11. Structure and magnetic properties of the cubic oxide fluoride BaFeO{sub 2}F

    SciTech Connect

    Berry, Frank J.; Coomer, Fiona C.; Hancock, Cathryn; Helgason, Orn; Moore, Elaine A.; Slater, Peter R.; Wright, Adrian J.; Thomas, Michael F.

    2011-06-15

    Fluorination of the parent oxide, BaFeO{sub 3-{delta}}, with polyvinylidine fluoride gives rise to a cubic compound with a=4.0603(4) A at 298 K. {sup 57}Fe Moessbauer spectra confirmed that all the iron is present as Fe{sup 3+}. Neutron diffraction data showed complete occupancy of the anion sites, indicating a composition BaFeO{sub 2}F, with a large displacement of the iron off-site. The magnetic ordering temperature was determined as T{sub N}=645{+-}5 K. Neutron diffraction data at 4.2 K established G-type antiferromagnetism with a magnetic moment per Fe{sup 3+} ion of 3.95 {mu}{sub B}. However, magnetisation measurements indicated the presence of a weak ferromagnetic moment that is assigned to the canting of the antiferromagnetic structure. {sup 57}Fe Moessbauer spectra in the temperature range 10-300 K were fitted with a model of fluoride ion distribution that retains charge neutrality of the perovskite unit cell. - Graphical abstract: The cubic oxide fluoride of composition BaFeO{sub 2}F has been synthesised and characterised. Highlights: > Fluorination of BaFeO{sub 3-{delta}} with polyvinylidene fluoride gives a cubic oxide fluoride of composition BaFeO{sub 2}F. > BaFeO{sub 2}F adopts a canted antiferromagnetic structure and is different from the related phase of composition SrFeO{sub 2}F. > A model of fluoride ion distribution about iron in BaFeO{sub 2}F has been explored.

  12. Coexistence of Microaerophilic, Nitrate-Reducing, and Phototrophic Fe(II) Oxidizers and Fe(III) Reducers in Coastal Marine Sediment

    PubMed Central

    Laufer, Katja; Nordhoff, Mark; Røy, Hans; Schmidt, Caroline; Behrens, Sebastian; Jørgensen, Bo Barker

    2015-01-01

    Iron is abundant in sediments, where it can be biogeochemically cycled between its divalent and trivalent redox states. The neutrophilic microbiological Fe cycle involves Fe(III)-reducing and three different physiological groups of Fe(II)-oxidizing microorganisms, i.e., microaerophilic, anoxygenic phototrophic, and nitrate-reducing Fe(II) oxidizers. However, it is unknown whether all three groups coexist in one habitat and how they are spatially distributed in relation to gradients of O2, light, nitrate, and Fe(II). We examined two coastal marine sediments in Aarhus Bay, Denmark, by cultivation and most probable number (MPN) studies for Fe(II) oxidizers and Fe(III) reducers and by quantitative-PCR (qPCR) assays for microaerophilic Fe(II) oxidizers. Our results demonstrate the coexistence of all three metabolic types of Fe(II) oxidizers and Fe(III) reducers. In qPCR, microaerophilic Fe(II) oxidizers (Zetaproteobacteria) were present with up to 3.2 × 106 cells g dry sediment−1. In MPNs, nitrate-reducing Fe(II) oxidizers, anoxygenic phototrophic Fe(II) oxidizers, and Fe(III) reducers reached cell numbers of up to 3.5 × 104, 3.1 × 102, and 4.4 × 104 g dry sediment−1, respectively. O2 and light penetrated only a few millimeters, but the depth distribution of the different iron metabolizers did not correlate with the profile of O2, Fe(II), or light. Instead, abundances were homogeneous within the upper 3 cm of the sediment, probably due to wave-induced sediment reworking and bioturbation. In microaerophilic Fe(II)-oxidizing enrichment cultures, strains belonging to the Zetaproteobacteria were identified. Photoferrotrophic enrichments contained strains related to Chlorobium and Rhodobacter; the nitrate-reducing Fe(II) enrichments contained strains related to Hoeflea and Denitromonas. This study shows the coexistence of all three types of Fe(II) oxidizers in two near-shore marine environments and the potential for competition and interrelationships between them

  13. Coexistence of Microaerophilic, Nitrate-Reducing, and Phototrophic Fe(II) Oxidizers and Fe(III) Reducers in Coastal Marine Sediment.

    PubMed

    Laufer, Katja; Nordhoff, Mark; Røy, Hans; Schmidt, Caroline; Behrens, Sebastian; Jørgensen, Bo Barker; Kappler, Andreas

    2015-01-01

    Iron is abundant in sediments, where it can be biogeochemically cycled between its divalent and trivalent redox states. The neutrophilic microbiological Fe cycle involves Fe(III)-reducing and three different physiological groups of Fe(II)-oxidizing microorganisms, i.e., microaerophilic, anoxygenic phototrophic, and nitrate-reducing Fe(II) oxidizers. However, it is unknown whether all three groups coexist in one habitat and how they are spatially distributed in relation to gradients of O2, light, nitrate, and Fe(II). We examined two coastal marine sediments in Aarhus Bay, Denmark, by cultivation and most probable number (MPN) studies for Fe(II) oxidizers and Fe(III) reducers and by quantitative-PCR (qPCR) assays for microaerophilic Fe(II) oxidizers. Our results demonstrate the coexistence of all three metabolic types of Fe(II) oxidizers and Fe(III) reducers. In qPCR, microaerophilic Fe(II) oxidizers (Zetaproteobacteria) were present with up to 3.2 × 10(6) cells g dry sediment(-1). In MPNs, nitrate-reducing Fe(II) oxidizers, anoxygenic phototrophic Fe(II) oxidizers, and Fe(III) reducers reached cell numbers of up to 3.5 × 10(4), 3.1 × 10(2), and 4.4 × 10(4) g dry sediment(-1), respectively. O2 and light penetrated only a few millimeters, but the depth distribution of the different iron metabolizers did not correlate with the profile of O2, Fe(II), or light. Instead, abundances were homogeneous within the upper 3 cm of the sediment, probably due to wave-induced sediment reworking and bioturbation. In microaerophilic Fe(II)-oxidizing enrichment cultures, strains belonging to the Zetaproteobacteria were identified. Photoferrotrophic enrichments contained strains related to Chlorobium and Rhodobacter; the nitrate-reducing Fe(II) enrichments contained strains related to Hoeflea and Denitromonas. This study shows the coexistence of all three types of Fe(II) oxidizers in two near-shore marine environments and the potential for competition and interrelationships between

  14. Exchange bias in Ag/FeCo/Ag core/shell/shell nanoparticles due to partial oxidation of FeCo intermediate shell

    NASA Astrophysics Data System (ADS)

    Takahashi, Mari; Mohan, Priyank; Mott, Derrick M.; Maenosono, Shinya

    2016-03-01

    Recently we developed magnetic-plasmonic Ag/FeCo/Ag core/shell/shell nanoparticles for the purpose of biological applications. In these heterostructured nanoparticles, exchange bias is observed as a result of the formation of an interface between ferromagnetic FeCo and antiferromagnetic CoxFe1-xO due to the partial oxidation of the FeCo intermediate shell. In this study we thoroughly characterized the surface oxide layer of the FeCo shell by XPS, XRD and SQUID magnetometer.

  15. Dissolution of Fe(III)(hydr)oxides by an Aerobic Bacterium

    SciTech Connect

    Maurice, P.

    2004-12-13

    This project investigated the effects of an aerobic Pseudomonas mendocina bacterium on the dissolution of Fe(III)(hydr)oxides. The research is important because metals and radionuclides that adsorb to Fe(III)(hydr)oxides could potentially be remobilized by dissolving bacteria. We showed that P. mendocina is capable of dissolving Fe-bearing minerals by a variety of mechanisms, including production of siderophores, pH changes, and formation of reductants. The production of siderophores by P. mendocina was quantified under a variety of growth conditions. Finally, we demonstrated that microbial siderophores may adsorb to and enhance dissolution of clay minerals.

  16. Measurement of ablation threshold of oxide-film-coated aluminium nanoparticles irradiated by femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Chefonov, O. V.; Ovchinnikov, A. V.; Il'ina, I. V.; Agranat, M. B.

    2016-03-01

    We report the results of experiments on estimation of femtosecond laser threshold intensity at which nanoparticles are removed from the substrate surface. The studies are performed with nanoparticles obtained by femtosecond laser ablation of pure aluminium in distilled water. The attenuation (or extinction, i.e. absorption and scattering) spectra of nanoparticles are measured at room temperature in the UV and optical wavelength ranges. The size of nanoparticles is determined using atomic force microscopy. A new method of scanning photoluminescence is proposed to evaluate the threshold of nanoparticle removal from the surface of a glass substrate exposed to IR femtosecond laser pulses with intensities 1011 – 1013 W cm-2.

  17. Rate law of Fe(II) oxidation under low O2 conditions

    NASA Astrophysics Data System (ADS)

    Kanzaki, Yoshiki; Murakami, Takashi

    2013-12-01

    Despite intensive studies on Fe(II) oxidation kinetics, the oxidation rate law has not been established under low O2 conditions. The importance of Fe(II) oxidation under low O2 conditions has been recently recognized; for instance, the Fe(II)/Fe(III) compositions of paleosols, ancient soils formed by weathering, can produce a quantitative pattern of the atmospheric oxygen increase during the Paleoproterozoic. The effects of partial pressure of atmospheric oxygen (PO2) on the Fe(II) oxidation rate were investigated to establish the Fe(II) oxidation rate - PO2 relationships under low O2 conditions. All oxidation experiments were carried out in a glove box by introducing Ar gas at ∼10-5-∼10-4 atm of PO2, pH 7.57-8.09 and 22 °C. Luminol chemiluminescence was adopted to measure low Fe(II) concentrations (down to ∼2 nM). Combining previous data under higher PO2 conditions (10-3-0.2 atm) with the present data, the rate law for Fe(II) oxidation over a wide range of PO2 (10-5-0.2 atm) was found to be written as: d[Fe(II)]/dt=-k[Fe(II)][[]2 where the exponent of [O2], x, and the rate constant, k, change from x = 0.98 (±0.04) and log k = 15.46 (±0.06) at ∼6 × 10-3-0.2 atm of PO2 to x = 0.58 (±0.02) and log k = 13.41 (±0.03) at 10-5-∼6 × 10-3 atm of PO2. The most plausible mechanism that explains the change in x under low O2 conditions is that, instead of O2, oxygen-derived oxidants, H2O2 and to some extent, O2rad -, dominate the oxidation reactions at <∼10-3 atm of PO2. The rate law found in the present study requires us to reconsider distributions of Fe redox species at low PO2 in natural environments, especially in paleoweathering profiles, and may provide a deeper understanding of the evolution of atmospheric oxygen in the Precambrian.

  18. Vibration DOS of 57Fe and Zn doped rutile Sn(Sb) oxides

    NASA Astrophysics Data System (ADS)

    Nomura, Kiyoshi; Rykov, Alexandre; Németh, Zoltán; Yoda, Yoshitaka

    2012-03-01

    Sn oxides co-doped with Zn, Sb and 57Fe were prepared by sol-gel method, and especially the doping effect of non-magnetic Zn ions was studied. The bulk saturation magnetization is in accordance with the intensity of the magnetic component in Mössbauer spectra. The nuclear inelastic scattering (NIS) spectra of these compounds were measured in SPring 8. The vibration density of states (VDOS) of 57Fe doped Sn(Sb) oxides showed that the softening peaks around 15-20 meV appeared by doping less than 10% Zn ions. The clusters of non-magnetic ZnFe2O4 may be most probably formed under the limit of XRD detections. The results suggest that the strengthening of ferromagnetism, which appears in the dilute Zn doping, may occur due to the spin arrangement of dilute Fe3 + through magnetic defects rather than the formation of magnetic iron oxides.

  19. Formic acid electro-oxidation at PtAu alloyed nanoparticles synthesized by pulsed laser ablation in liquids

    NASA Astrophysics Data System (ADS)

    Oko, Daniel Nii; Zhang, Jianming; Garbarino, Sébastien; Chaker, Mohamed; Ma, Dongling; Tavares, Ana C.; Guay, Daniel

    2014-02-01

    A series of mono dispersed PtxAu100-x alloy nanoparticles (NPs), with x varying from 0 to 100, were prepared by pulsed laser ablation in liquids, using a series of targets that were made by mixing pure Pt and pure Au powders. The structures of PtxAu100-x alloy NPs were assessed by transmission electron microscopy and X-ray diffraction. A face-centered solid solution is obtained over the whole composition range, and the particle size increases from 2.5 to 5.3 nm as x is increased from 0 to 100. The electrocatalytic performances of the PtxAu100-x alloy NPs towards the formic acid oxidation were investigated by cyclic voltammetry and chronoamperometry. On as-prepared PtxAu100-x alloy NPs, oxidation of formic acid occurs through dehydrogenation, while dehydration is the privileged mechanism on as-prepared mixtures of Pt and Au NPs. However, after a series of CV in 0.5 M H2SO4, both types of catalysts are able to oxidize formic acid according to the dehydrogenation pathway. After 600 s of electrolysis, the mass activities of PtxAu100-x alloy NPs is a factor of two larger than that of mixtures of pure Pt and pure Au NPs with the same surface composition, although both types of catalysts display similar activity with respect to the total electrochemically active surface area.

  20. Resistance of Nanostructured Fe-Cr Alloys to Oxidative Degradation: Role of Zr and Cr Contents

    NASA Astrophysics Data System (ADS)

    Mahesh, B. V.; Singh Raman, R. K.; Koch, C. C.

    2015-04-01

    This article investigates the effect of grain size and Cr concentration on the oxidation resistance of nanocrystalline Fe-Cr alloys having varying Cr contents between 2 and 10 wt pct. The results have been compared with microcrystalline Fe-Cr alloys with 10 and 20 wt pct Cr. Pellets of nanocrystalline and microcrystalline Fe-Cr alloys were prepared by mechanical alloying followed by hot compaction and sintering, and then oxidized at 823 K (550 °C) for 150-hours. Oxidation kinetics was determined by measuring the weight gain during oxidation, and the post-oxidation characterization of the oxide scales was performed using secondary ion mass spectroscopy. The chromium content at the inner oxide scale of nanocrystalline Fe-Cr alloys (with >7 pct Cr) was found to be comparable with that of microcrystalline 20 pctCr alloy, which suggests that nanocrystalline grain size distribution can be exploited to develop highly oxidation resistant alloys with much lower amounts of expensive alloying element (Cr). A mechanistic understanding of the high temperature oxidation in nanostructured alloys has been presented and the critical amount of bulk Cr content required to form a protective chromia layer has been calculated. The paper also investigates the role of a reactive element Zr on the high temperature oxidation resistance of nanocrystalline Fe-Cr. The beneficial effect is more pronounced at low bulk Cr (2 to 4 pct) concentrations (compared to higher Cr (>7 pct) concentration), however, at low bulk Cr, insufficient Cr enrichment occurs to establish a protective chromium oxide layer.

  1. Na-ion Storage Performances of FeSex and Fe2O3 Hollow Nanoparticles-Decorated Reduced Graphene Oxide Balls prepared by Nanoscale Kirkendall Diffusion Process

    NASA Astrophysics Data System (ADS)

    Park, Gi Dae; Cho, Jung Sang; Lee, Jung-Kul; Kang, Yun Chan

    2016-02-01

    Uniquely structured FeSex-reduced graphene oxide (rGO) composite powders, in which hollow FeSex nanoparticles are uniformly distributed throughout the rGO matrix, were prepared by spray pyrolysis applying the nanoscale Kirkendall diffusion process. Iron oxide-rGO composite powders were transformed into FeSex-rGO composite powders by a two-step post-treatment process. Metallic Fe nanocrystals formed during the first-step post-treatment process were transformed into hollow FeSex nanoparticles during the selenization process. The FeSex-rGO composite powders had mixed crystal structures of FeSe and FeSe2 phases. A rGO content of 33% was estimated from the TG analysis of the FeSex-rGO composite powders. The FeSex-rGO composite powders had superior sodium-ion storage properties compared to those of the Fe2O3-rGO composite powders with similar morphological characteristics. The discharge capacities of the FeSex- and Fe2O3-rGO composite powders for the 200th cycle at a constant current density of 0.3 A g-1 were 434 and 174 mA h g-1, respectively. The FeSex-rGO composite powders had a high discharge capacity of 311 mA h g-1 for the 1000th cycle at a high current density of 1 A g-1.

  2. Complexity of High-Pressure Orthorhombic Iron Oxides, the Characterization of Fe5O6

    NASA Astrophysics Data System (ADS)

    Lavina, B.; Meng, Y.

    2014-12-01

    Occurring as accessory minerals in most rocks and forming large deposits of considerable economical importance, iron oxides have a major petrological importance. Their role as oxygen buffers, in differentiation processes and as magnetic phases summarize the critical importance of iron oxides in most petrological contexts, independently of their abundance.The discovery of a new compound in the Fe-O system, Fe4O5[1], reshaped our assumptions on the behavior of iron oxides in the Earth's deep interior, where phases of FeO and Fe3O4 were considered the sole plausible players. Further studies found that Fe4O5 is stable in a wide compositional range[2] and can accept a wide extent of isomorphic substitutions[3].We used laser heating synthesis in diamond anvil cell and microdiffraction mapping with high brilliance synchrotron x-ray[4] to explore the complexity of the Fe-O system at high pressure and temperature. We found coexistence of two to three oxides in most of the samples we investigated. By means of a careful exploration of diffraction effects in the reciprocal space, we singled-out the diffraction peaks of a few grains in multiphase diffraction patterns. These allowed a reliable characterization of yet a new iron oxide, Fe5O6. This compound, synthesized between 10 and 20 GPa, is also orthorhombic and can be described with the same building blocks of the other known orthorhombic iron oxides. A comparison of compressibility and lattice parameters of the latest iron oxides will be presented. [1] Lavina, B. et al. Discovery of the recoverable high-pressure iron oxide Fe4O5. Proc Natl Acad Sci U S A 108, 17281-5 (2011).[2] Woodland, A. B., Frost, D. J., Trots, D. M., Klimm, K. & Mezouar, M. In situ observation of the breakdown of magnetite (Fe3O4) to Fe4O5 and hematite at high pressures and temperatures. Am Mineral 97, 1808-1811 (2012).[3] Woodland, A. B. et al. Fe4O5 and its solid solutions in several simple systems. Cotrib Mineral Petrol 166, 1677-1686 (2013

  3. Highly-oriented Fe2O3/ZnFe2O4 nanocolumnar heterojunction with improved charge separation for photoelectrochemical water oxidation.

    PubMed

    Luo, Zhibin; Li, Chengcheng; Zhang, Dong; Wang, Tuo; Gong, Jinlong

    2016-07-12

    This paper describes the design and synthesis of a heterojunction photoanode composed of highly-oriented Fe2O3/ZnFe2O4 nanocolumnar arrays with a well-defined morphology by reactive ballistic deposition and atomic layer deposition. This specific structure enhances the charge separation at the Fe2O3/ZnFe2O4 interface, leading to an improved photoelectrochemical performance for water oxidation. PMID:26696447

  4. Fe-oxidizing microbes are hydrothermal vent ecosystem engineers at the Loihi Seamount (Invited)

    NASA Astrophysics Data System (ADS)

    Chan, C. S.; McAllister, S.; Leavitt, A.; Emerson, D.; Moyer, C. L.; Glazer, B. T.

    2013-12-01

    Microaerophilic Fe-oxidizing microorganisms (FeOM) colonize gradients of Fe(II) and oxygen, taking advantage of the available chemical energy. Vast communities of FeOM proliferate at deep sea hydrothermal vents, forming mineralized mats that range from centimeters to meters thick. Because these mats structure the environment for both FeOM and the entire microbial community, the Fe-oxidizers are acting as ecosystem engineers. What organisms are responsible for initiating these mats, and how does the physical structure and community composition develop as the mats mature? By connecting structure, function, and ecology, we can better interpret modern mat structures, as well as ancient fossilized mats. We have been studying Fe microbial mats at Loihi Seamount in Hawaii, a long-term study site that has become a model for Fe oxidation in marine hydrothermal systems. Recent improvements in ROV imaging systems allow us to see a great range of mat textures and colors, which may represent diverse habitats and/or different stages of mat development. With improved imaging and sampling techniques, we have been able to obtain discrete, intact samples of these delicate microbial mats. Previous bulk sampling methods showed that mats consist of a mixture of Fe-mineralized morphologies. Our analyses of intact mats show that mats are initiated by one type of structure-former (either a stalk-former like Mariprofundus ferrooxydans or a Zetaproteobacterial sheath-former). These microbes may be the vanguard organisms that stabilize chemical gradients in this dynamic environment, allowing colonization by other organisms (evidenced by branching tubes, fibrillar nests, and other morphologies). We will show evidence of the composition and development of these mats, and discuss parallels between these marine Fe mats and their freshwater counterparts, supporting the idea that FeOM engineer environments favorable for growth.

  5. Green synthesis of Fe0 and bimetallic Fe0 for oxidative catalysis and reduction applications

    EPA Science Inventory

    A single-step green approach to the synthesis of nanoscale zero valent iron (nZVI) and nanoscale bimetallic (Fe0/Pd) particles using tea (Camellia sinensis) polyphenols is described. The expedient reaction between polyphenols and ferric chloride (FeCl3) occurs within a minute at ...

  6. Sorption and catalytic oxidation of Fe(II) at the surface of calcite

    NASA Astrophysics Data System (ADS)

    Mettler, Suzanne; Wolthers, Mariëtte; Charlet, Laurent; Gunten, Urs von

    2009-04-01

    The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds-minutes) was followed by (b) a slower incorporation (hours-weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4 mol% Fe:Ca and a mixed carbonate layer thickness of 25 nm (after 168 h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA57 (1993), 3505; Pokrovsky et al., Langmuir16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO 3Fe + and >CO 3FeCO 3H 0. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15 h, the oxidation kinetics was comparable to a calcite-free system ( t1/2 = 145 ± 15 min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite ( t1/2 = 41 ± 1 min and t1/2 = 100 ± 15 min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO 3FeCO 3H 0, for which the species specific rate constant was estimated.

  7. Effects of Fe oxide on N transformations in subtropical acid soils

    PubMed Central

    Jiang, Xianjun; Xin, Xiaoping; Li, Shiwei; Zhou, Junchao; Zhu, Tongbin; Müller, Christopher; Cai, Zucong; Wright, Alan L.

    2015-01-01

    Subtropical ecosystems are often characterized by high N cycling rates, but net nitrification rates are often low in subtropical acid soils. NO3−-N immobilization into organic N may be a contributing factor to understand the observed low net nitrification rates in these acid soils. The effects of Fe oxide and organic matter on soil N transformations were evaluated using a 15N tracing study. Soil net nitrification was low for highly acidic yellow soil (Ferralsols), but gross ammonia oxidation was 7 times higher than net nitrification. In weakly acidic purple soil (Cambisols), net nitrification was 8 times higher than in Ferralsols. The addition of 5% Fe oxide to Cambisols, reduced the net nitrification rate to a negative rate, while NO3−-N immobilization rate increased 8 fold. NO3−-N immobilization was also observed in Ferralsols which contained high Fe oxides levels. A possible mechanism for these reactions could be stimulation of NO3−-N immobilization by Fe oxide which promoted the abiotic formation of nitrogenous polymers, suggesting that the absence of net nitrification in some highly acid soils may be due to high rates of NO3−-N immobilization caused by high Fe oxide content rather than a low pH. PMID:25722059

  8. Effects of Fe oxide on N transformations in subtropical acid soils.

    PubMed

    Jiang, Xianjun; Xin, Xiaoping; Li, Shiwei; Zhou, Junchao; Zhu, Tongbin; Müller, Christopher; Cai, Zucong; Wright, Alan L

    2015-01-01

    Subtropical ecosystems are often characterized by high N cycling rates, but net nitrification rates are often low in subtropical acid soils. NO3(-)-N immobilization into organic N may be a contributing factor to understand the observed low net nitrification rates in these acid soils. The effects of Fe oxide and organic matter on soil N transformations were evaluated using a (15)N tracing study. Soil net nitrification was low for highly acidic yellow soil (Ferralsols), but gross ammonia oxidation was 7 times higher than net nitrification. In weakly acidic purple soil (Cambisols), net nitrification was 8 times higher than in Ferralsols. The addition of 5% Fe oxide to Cambisols, reduced the net nitrification rate to a negative rate, while NO3(-)-N immobilization rate increased 8 fold. NO3(-)-N immobilization was also observed in Ferralsols which contained high Fe oxides levels. A possible mechanism for these reactions could be stimulation of NO3(-)-N immobilization by Fe oxide which promoted the abiotic formation of nitrogenous polymers, suggesting that the absence of net nitrification in some highly acid soils may be due to high rates of NO3(-)-N immobilization caused by high Fe oxide content rather than a low pH. PMID:25722059

  9. Discovery of Fe-Ce Oxide/BiVO4 Photoanodes through Combinatorial Exploration of Ni-Fe-Co-Ce Oxide Coatings.

    PubMed

    Shinde, Aniketa; Guevarra, Dan; Liu, Guiji; Sharp, Ian D; Toma, Francesca M; Gregoire, John M; Haber, Joel A

    2016-09-14

    An efficient photoanode is a prerequisite for a viable solar fuels technology. The challenges to realizing an efficient photoanode include the integration of a semiconductor light absorber and a metal oxide electrocatalyst to optimize corrosion protection, light trapping, hole transport, and photocarrier recombination sites. To efficiently explore metal oxide coatings, we employ a high-throughput methodology wherein a uniform BiVO4 film is coated with 858 unique metal oxide coatings covering a range of metal oxide loadings and the full (Ni-Fe-Co-Ce)Ox pseudoquaternary composition space. Photoelectrochemical characterization of the photoanodes reveals that specific combinations of metal oxide composition and loading provide up to a 13-fold increase in the maximum photoelectrochemical power generation for oxygen evolution in pH 13 electrolyte. Through mining of the high-throughput data we identify composition regions that form improved interfaces with BiVO4. Of particular note, integrated photoanodes with catalyst compositions in the range Fe(0.4-0.6)Ce(0.6-0.4)Ox exhibit high interface quality and excellent photoelectrochemical power conversion. Scaled-up inkjet-printed electrodes and photoanodic electrodeposition of this composition on BiVO4 confirms the discovery and the synthesis-independent interface improvement of (Fe-Ce)Ox coatings on BiVO4. PMID:27549019

  10. Synthesis and characterization of mixed Fe-Cr oxide pillared {alpha}-zirconium phosphate materials

    SciTech Connect

    Perez-Reina, F.J.; Olivera-Pastor, P.; Rodriguez-Castellon, E.; Jimenez-Lopez, A.

    1996-02-15

    Mixed Fe/Cr hydroxyacetate oligomers ranging in composition from 90/10 to 10/90 have been prepared by mixing Fe{sup 3+} and Cr{sup 3+} nitrate solutions and then adding n-propylammonium acetate up to an acetate/Cr{sup 3+} ratio of 2.8 and pH 4. The oligomers were intercalated into colloidal {alpha}-zirconium phosphate or precipitated with excess n-propylamine. The precipitates are all amorphous and show differential thermal behavior in comparison with the intercalates. Upon calcination in air, the precipitates become crystalline, showing the characteristic XRD peaks of mixed Fe/Cr oxides. These mixed oxides present unusually high BET surface areas (up to 276 m {sup 2}{center_dot}g{sup {minus}1}), especially those with low Fe/Cr ratios. The intercalates are poorly crystalline or amorphous at room temperature and upon calcination at 400{degrees}C in air or under N{sub 2}, which indicates that there is no oxide segregation from the interlayers. From these results it is suggested that mixed Fe/Cr oxides are cross-linked to the phosphate layer, forming a pillared structure. Significantly, the mixed oxides segregated from the phosphate surface at 1000{degrees}C present XRD patterns identical to the mixed oxides obtained from the precipitates with the same Fe/Cr ratios. The pillared materials show high BET surface areas, from 200 to 306 m{sup 2}/g, and narrow pore size distributions with pore radius ranging from 8.5 to 13.8 {Angstrom}. XPS analysis reveals a higher affinity of the phosphate surface for Cr{sup 3+} at high Fe/Cr ratios from 70/30 to 90/10. In these samples the partial oxidation of Cr(III) to Cr(VI) was observed in the XPS spectra, in spite of the materials being calcined under N{sub 2}.

  11. Interpreting nanoscale size-effects in aggregated Fe-oxide suspensions: Reaction of Fe(II) with Goethite

    NASA Astrophysics Data System (ADS)

    Cwiertny, David M.; Handler, Robert M.; Schaefer, Michael V.; Grassian, Vicki H.; Scherer, Michelle M.

    2008-03-01

    The Fe(II)/Fe(III) redox couple plays an important role in both the subsurface fate and transport of groundwater pollutants and the global cycling of carbon and nitrogen in iron-limited marine environments. Iron oxide particles involved in these redox processes exhibit broad size distributions, and the recent demonstrations of dramatic nanoscale size-effects with various metal oxides has compelled us, as well as many others, to consider whether the rate and extent of Fe(II)/Fe(III) cycling depends upon oxide particle size in natural systems. Here, we investigated the reaction of Fe(II) with three different goethite particle sizes in pH 7.5 suspensions. Acicular goethite rods with primary particle dimensions ranging from 7 by 80 nm to 25 by 670 nm were studied. Similar behavior with respect to Fe(II) sorption, electron transfer and nitrobenzene reduction was observed on a mass-normalized basis despite almost a threefold difference in goethite specific surface areas. Scanning electron microscopy (SEM) images, dynamic light scattering (DLS) and sedimentation measurements all indicated that, at pH 7.5, significant aggregation occurred with all three sizes of goethite particles. SEM images further revealed that nanoscale particles formed dense aggregates on the order of several microns in diameter. The clear formation of particle aggregates in solution raises questions regarding the use of primary particle surface area as a basis for assessing nanoscale size-effects in iron oxide suspensions at circum-neutral pH values. In our case, normalizing the Fe(II) sorption densities and rate constants for nitrobenzene reduction by BET surface area implies that goethite nanoparticles are less reactive than larger particles. We suspect, however, that aggregation is responsible for this observed size-dependence, and argue that BET values should not be used to assess differences in surface site density or intrinsic surface reactivity in aggregated particle suspensions. In order to

  12. Easy and quantitative access to Fe(II) and Fe(III) di(aryl)alkynylphosphine oxides featuring [Fe(dppe)Cp*] endgroups: terminal P=O functionality blocks the dimerisation of the Fe(III) derivatives.

    PubMed

    Tohmé, Ayham; Hagen, Charles T; Essafi, Stéphanie; Bondon, Arnaud; Roisnel, Thierry; Carmichael, Duncan; Paul, Frédéric

    2015-01-25

    A series of paramagnetic di(aryl)alkynylphosphine oxides [PF6] featuring an open-shell [Fe(κ(2)-dppe)(η(5)-C5Me5)](+) endgroup were obtained by oxidation of their neutral Fe(II) parents 3a-c, themselves obtained in a simple and nearly quantitative fashion from the corresponding Fe(II) metallophosphines 1a-c. The new organometallic radicals were characterised by NMR and ESR and were shown to be perfectly stable in solution, in contrast to species such as 1a-b[PF6] which readily dimerise. PMID:25483340

  13. Interfacial strain and defects in asymmetric Fe-Mn oxide hybrid nanoparticles.

    PubMed

    Mayence, Arnaud; Wéry, Madeleine; Tran, Dung Trung; Wetterskog, Erik; Svedlindh, Peter; Tai, Cheuk-Wai; Bergström, Lennart

    2016-08-01

    Asymmetric Fe-Mn oxide hybrid nanoparticles have been obtained by a seed-mediated thermal decomposition-based synthesis route. The use of benzyl ether as the solvent was found to promote the orientational growth of Mn1-xO onto the iron oxide nanocube seeds yielding mainly dimers and trimers whereas 1-octadecene yields large nanoparticles. HRTEM imaging and HAADF-STEM tomography performed on dimers show that the growth of Mn1-xO occurs preferentially along the edges of iron oxide nanocubes where both oxides share a common crystallographic orientation. Fourier filtering and geometric phase analysis of dimers reveal a lattice mismatch of 5% and a large interfacial strain together with a significant concentration of defects. The saturation magnetization is lower and the coercivity is higher for the Fe-Mn oxide hybrid nanoparticles compared to the iron oxide nanocube seeds. PMID:27385323

  14. Neodymium isotopic study of rare earth element sources and mobility in hydrothermal Fe oxide (Fe-P-REE) systems

    SciTech Connect

    Gleason, J.D.; Marikos, M.A.; Barton, M.D.; Johnson, D.A.

    2000-03-01

    Rare earth element (REE)-enriched, igneous-related hydrothermal Fe-oxide hosted (Fe-P-REE) systems from four areas in North America have been analyzed for their neodymium iosotopic composition to constrain REE sources and mobility in these systems. The Nd isotopic results evidence a common pattern of REE concentration from igneous sources despite large differences in age (Proterozoic to Tertiary), tectonic setting (subduction vs. intraplate), and magmatic style (mafic vs. felsic). In the Middle Proterozoic St. Francois Mountains terrane of southeastern Missouri, {epsilon}{sub Nd} for Fe-P-REE (apatite, monazite, xenotime) deposits ranges from +3.5 to +5.1, similar to associated felsic to intermediate igneous rocks of the same age ({epsilon}{sub Nd} = +2.6 to +6.2). At the mid-Jurassic Humboldt mafic complex in western Nevada, {epsilon}{sub Nd} for Fe-P-REE (apatite) mineralization varies between +1.1 and +2.4, similar to associated mafic igneous rocks ({minus}1.0 to +3.5). In the nearby Cortez Mountains in central Nevada, mid-Jurassic felsic volcanic and plutonic rocks ({epsilon}{sub Nd} = {minus}2.0 to {minus}4.4) are associated with Fe-P-REE (apatite-monazite) mineralization having similar {epsilon}{sub Nd}({minus}1.7 to {minus}2.4). At Cerro de Mercado, Durango, Mexico, all assemblages analyzed in this Tertiary rhyolite-hosted Fe oxide deposit have identical isotopic compositions with {epsilon}{sub Nd} = {minus}2.5. These data are consistent with coeval igneous host rocks being the primary source of REE in all four regions, and are inconsistent with a significant contribution of REE from other sources. Interpretations of the origin of these hydrothermal systems and their concomitant REE mobility must account for nonspecialized igneous sources and varied tectonic settings.

  15. Neodymium isotopic study of rare earth element sources and mobility in hydrothermal Fe-oxide (Fe-P-REE) systems

    NASA Astrophysics Data System (ADS)

    Gleason, James D.; Marikos, Mark A.; Barton, Mark D.; Johnson, David A.

    2000-03-01

    Rare earth element (REE)-enriched, igneous-related hydrothermal Fe-oxide hosted (Fe-P-REE) systems from four areas in North America have been analyzed for their neodymium isotopic composition to constrain REE sources and mobility in these systems. The Nd isotopic results evidence a common pattern of REE concentration from igneous sources despite large differences in age (Proterozoic to Tertiary), tectonic setting (subduction vs. intraplate), and magmatic style (mafic vs. felsic). In the Middle Proterozoic St. Francois Mountains terrane of southeastern Missouri, ɛ Nd for Fe-P-REE (apatite, monazite, xenotime) deposits ranges from +3.5 to +5.1, similar to associated felsic to intermediate igneous rocks of the same age (ɛ Nd = +2.6 to +6.2). At the mid-Jurassic Humboldt mafic complex in western Nevada, ɛ Nd for Fe-P-REE (apatite) mineralization varies between +1.1 and +2.4, similar to associated mafic igneous rocks (-1.0 to +3.5). In the nearby Cortez Mountains in central Nevada, mid-Jurassic felsic volcanic and plutonic rocks (ɛ Nd = -2.0 to -4.4) are associated with Fe-P-REE (apatite-monazite) mineralization having similar ɛ Nd (-1.7 to -2.4). At Cerro de Mercado, Durango, Mexico, all assemblages analyzed in this Tertiary rhyolite-hosted Fe oxide deposit have identical isotopic compositions with ɛ Nd = -2.5. These data are consistent with coeval igneous host rocks being the primary source of REE in all four regions, and are inconsistent with a significant contribution of REE from other sources. Interpretations of the origin of these hydrothermal systems and their concomitant REE mobility must account for nonspecialized igneous sources and varied tectonic settings.

  16. Oxidation State of Nakhlites as inferred from Fe-Ti oxide Equilibria and Augite/Melt Europium Partitioning

    NASA Technical Reports Server (NTRS)

    Makishima, J.; McKay, G.; Le, L.; Miyamoto, M.; Mikouchi, T.

    2007-01-01

    Recent studies have shown that Martian magmas had wide range of oxygen fugacities (fO2) and that this variation is correlated with the variation of La/Yb ratio and isotopic characteristics of the Martian basalts, shergottite meteorites. The origin of this correlation must have important information about mantle sources and Martian evolution. In order to understand this correlation, it is necessary to know accurate value of oxidation state of other Martian meteorite groups. Nakhlites, cumulate clinopyroxenites, are another major group of Martian meteorites and have distinctly different trace element and isotopic characteristics from shergottites. Thus, estimates of oxidation state of nakhlites will give us important insight into the mantle source in general. Several workers have estimated oxidation state of nakhlites by using Fe-Ti oxide equilibrium. However, Fe-Ti oxides may not record the oxidation state of the parent melt of the nakhlite because it is a late-stage mineral. Furthermore, there is no comprehensive study which analyzed all nakhlite samples at the same time. Therefore, in this study (1) we reduced the uncertainty of the estimate using the same electron microprobe and the same standards under the same condition for Fe-Ti oxide in 6 nakhlites and (2) we also performed crystallization experiments to measure partition coefficients of Eu into pyroxene in the nakhlite system in order to estimate fO2 when the pyroxene core formed (i.e. Eu oxybarometer [e.g. 2,6]).

  17. Iron atoms redistribution in oxide films of Zr-Fe, Zr-Fe-Cu alloys during corrosion in autoclave at 350°C

    NASA Astrophysics Data System (ADS)

    Filippov, V.; Bateev, A.

    2016-04-01

    The data on changes of iron atoms state in the oxide films of binary Zr-1.24 mas.%Fe and ternary Zr-1.39 mas.%Fe-0.60 mas.%Cu zirconium alloys are obtained. Alloys are subjected to corrosion tests under autoclave conditions at 350°C temperature in a steam-water environment under pressure p = 16.8 MPa. In initial specimens of the alloys the iron atoms are in the form of intermetallic compounds. In oxide films the decomposition of intermetallic compounds and formation of new compounds occurs with structural phase distortion. In the oxide films metallic the metallic iron particles α-Fe, iron oxide in the form of hematite α-Fe2O3, solid solutions of iron ions in ZrO2 are formed. The phase composition of the oxide films depends on the alloy composition and changes during the growth process of the oxide film.

  18. Potential Role of Nitrite for Abiotic Fe(II) Oxidation and Cell Encrustation during Nitrate Reduction by Denitrifying Bacteria

    PubMed Central

    Klueglein, Nicole; Zeitvogel, Fabian; Stierhof, York-Dieter; Floetenmeyer, Matthias; Konhauser, Kurt O.; Obst, Martin

    2014-01-01

    Microorganisms have been observed to oxidize Fe(II) at neutral pH under anoxic and microoxic conditions. While most of the mixotrophic nitrate-reducing Fe(II)-oxidizing bacteria become encrusted with Fe(III)-rich minerals, photoautotrophic and microaerophilic Fe(II) oxidizers avoid cell encrustation. The Fe(II) oxidation mechanisms and the reasons for encrustation remain largely unresolved. Here we used cultivation-based methods and electron microscopy to compare two previously described nitrate-reducing Fe(II) oxidizers ( Acidovorax sp. strain BoFeN1 and Pseudogulbenkiania sp. strain 2002) and two heterotrophic nitrate reducers (Paracoccus denitrificans ATCC 19367 and P. denitrificans Pd 1222). All four strains oxidized ∼8 mM Fe(II) within 5 days in the presence of 5 mM acetate and accumulated nitrite (maximum concentrations of 0.8 to 1.0 mM) in the culture media. Iron(III) minerals, mainly goethite, formed and precipitated extracellularly in close proximity to the cell surface. Interestingly, mineral formation was also observed within the periplasm and cytoplasm; intracellular mineralization is expected to be physiologically disadvantageous, yet acetate consumption continued to be observed even at an advanced stage of Fe(II) oxidation. Extracellular polymeric substances (EPS) were detected by lectin staining with fluorescence microscopy, particularly in the presence of Fe(II), suggesting that EPS production is a response to Fe(II) toxicity or a strategy to decrease encrustation. Based on the data presented here, we propose a nitrite-driven, indirect mechanism of cell encrustation whereby nitrite forms during heterotrophic denitrification and abiotically oxidizes Fe(II). This work adds to the known assemblage of Fe(II)-oxidizing bacteria in nature and complicates our ability to delineate microbial Fe(II) oxidation in ancient microbes preserved as fossils in the geological record. PMID:24271182

  19. Interfacial strain and defects in asymmetric Fe-Mn oxide hybrid nanoparticles

    NASA Astrophysics Data System (ADS)

    Mayence, Arnaud; Wéry, Madeleine; Tran, Dung Trung; Wetterskog, Erik; Svedlindh, Peter; Tai, Cheuk-Wai; Bergström, Lennart

    2016-07-01

    Asymmetric Fe-Mn oxide hybrid nanoparticles have been obtained by a seed-mediated thermal decomposition-based synthesis route. The use of benzyl ether as the solvent was found to promote the orientational growth of Mn1-xO onto the iron oxide nanocube seeds yielding mainly dimers and trimers whereas 1-octadecene yields large nanoparticles. HRTEM imaging and HAADF-STEM tomography performed on dimers show that the growth of Mn1-xO occurs preferentially along the edges of iron oxide nanocubes where both oxides share a common crystallographic orientation. Fourier filtering and geometric phase analysis of dimers reveal a lattice mismatch of 5% and a large interfacial strain together with a significant concentration of defects. The saturation magnetization is lower and the coercivity is higher for the Fe-Mn oxide hybrid nanoparticles compared to the iron oxide nanocube seeds.Asymmetric Fe-Mn oxide hybrid nanoparticles have been obtained by a seed-mediated thermal decomposition-based synthesis route. The use of benzyl ether as the solvent was found to promote the orientational growth of Mn1-xO onto the iron oxide nanocube seeds yielding mainly dimers and trimers whereas 1-octadecene yields large nanoparticles. HRTEM imaging and HAADF-STEM tomography performed on dimers show that the growth of Mn1-xO occurs preferentially along the edges of iron oxide nanocubes where both oxides share a common crystallographic orientation. Fourier filtering and geometric phase analysis of dimers reveal a lattice mismatch of 5% and a large interfacial strain together with a significant concentration of defects. The saturation magnetization is lower and the coercivity is higher for the Fe-Mn oxide hybrid nanoparticles compared to the iron oxide nanocube seeds. Electronic supplementary information (ESI) available: Materials characterization, powder X-ray diffraction, EFTEM images, EELS spectra, HAADF-STEM. See DOI: 10.1039/c6nr01373b

  20. Magnetic solid-phase extraction of protein by ionic liquid-coated Fe@graphene oxide.

    PubMed

    Wen, Qian; Wang, Yuzhi; Xu, Kaijia; Li, Na; Zhang, Hongmei; Yang, Qin; Zhou, Yigang

    2016-11-01

    Amino functional dicationic ionic liquid (AFDCIL) was prepared and then coated on the surface of magnetic graphene oxide (GO) as a new magnetic adsorbent (Fe@GO@AFDCIL) for the magnetic solid-phase extraction (MSPE) of protein. The Fe@GO@AFDCIL composite was characterized by vibrating sample magnetometer (VSM), X-ray diffraction (XRD), Fourier transform infrared spectrometry (FT-IR), thermal gravimetric analysis (TGA), field emission scanning electron microscopy (FESEM) and zeta-potential nanoparticles. The bovine hemoglobin (BHb) was used as the analyte, and the extraction performance of Fe@GO@AFDCIL was investigated in the MSPE procedure. The concentration of BHb in samples was determined by a UV-vis spectrophotometer. A comparative investigation of Fe@GO@AFDCIL composite and traditional IL-coated Fe@GO composites (Fe@GO@IL) exhibited the benefits of Fe@GO@AFDCIL. The adsorbed BHb could be eluted from the Fe@GO@AFDCIL by 4% sodium dodecyl sulfate (SDS) solution. The Fe@GO@AFDCIL exhibited favorable stability which could be reused at least 15 times. Under the optimized condition, the real samples were investigated, which demonstrated that the Fe@GO@AFDCIL was able to be applied in extracting bovine hemoglobin (BHb) from real biological samples. PMID:27591642

  1. Oxidation-Induced Surface Roughening of Aluminum Nanoparticles Formed in an Ablation Plume

    NASA Astrophysics Data System (ADS)

    Förster, Georg Daniel; Girault, Marie; Menneveux, Jérôme; Lavisse, Luc; Jouvard, Jean-Marie; Marco de Lucas, Maria del Carmen; Potin, Valérie; Ouf, François-Xavier; Kerkar, Moussa; Le Garrec, Jean-Luc; Carvou, Erwann; Carles, Sophie; Rabilloud, Franck; Calvo, Florent; Yu, Jin; Mitchell, James Brian

    2015-12-01

    Nanoparticles formed within an ablation plume produced by the impact of a nanosecond laser pulse on the surface of an aluminum target have been directly measured using small-angle x-ray scattering. The target was immersed in an oxygen-nitrogen gas mixture at atmospheric pressure with the O2/N2 ratio being precisely controlled. The results for an increasing oxygen content reveal remarkable effects on the morphology of the generated particles, which include a decrease in the particle volume but a marked increase in its surface ruggedness. Molecular dynamics simulations using a reactive potential and performed under similar conditions as the experiment reproduce the experimental trends and show in detail how the shape and surface structure of the nanoparticles evolve with increasing oxygen content. This good agreement between in situ observations in the plume and atomistic simulations emphasizes the key role of chemical reactivity together with thermodynamic conditions on the morphology of the particles thus produced.

  2. Biological reduction of nitric oxide in aqueous Fe(II)EDTA solutions.

    PubMed

    van der Maas, Peter; van de Sandt, Thomas; Klapwijk, Bram; Lens, Piet

    2003-01-01

    The reduction of nitric oxide (NO) in aqueous solutions of Fe(II)EDTA is one of the core processes in BioDeNOx, an integrated physicochemical and biological technique for NO(x)() removal from industrial flue gases. NO reduction in aqueous solutions of Fe(II)EDTA (20-25 mM, pH 7.2 +/- 0.2) was investigated in batch experiments at 55 degrees C. Reduction of NO to N(2) was found to be biologically catalyzed with nitrous oxide (N(2)O) as an intermediate. Various sludges from full-scale denitrifying and anaerobic reactors were capable to catalyze NO reduction under thermophilic conditions. The NO reduction rate was not affected by the presence of ethanol or acetate. EDTA-chelated Fe(II) was found to be a suitable electron donor for the biological reduction of nitric oxide to N(2), with the concomitant formation of Fe(III)EDTA. In the presence of ethanol, EDTA-chelated Fe(III) was reduced to Fe(II)EDTA. This study strongly indicates that redox cycling of FeEDTA plays an important role in the biological denitrification process within the BioDeNOx concept. PMID:12892497

  3. A hydrogen-oxidizing, Fe(III)-reducing microorganism from the Great Bay estuary, New Hampshire

    USGS Publications Warehouse

    Caccavo, F., Jr.; Blakemore, R.P.; Lovley, D.R.

    1992-01-01

    A dissimilatory Fe(III)- and Mn(IV)-reducing bacterium was isolated from bottom sediments of the Great Bay estuary, New Hampshire. The isolate was a facultatively anaerobic gram-negative rod which did not appear to fit into any previously described genus. It was temporarily designated strain BrY. BrY grew anaerobically in a defined medium with hydrogen or lactate as the electron donor and Fe(III) as the electron acceptor. BrY required citrate, fumarate, or malate as a carbon source for growth on H2 and Fe(III). With Fe(III) as the sole electron acceptor, BrY metabolized hydrogen to a minimum threshold at least 60-fold lower than the threshold reported for pure cultures of sulfate reducers. This finding supports the hypothesis that when Fe(III) is available, Fe(III) reducers can outcompete sulfate reducers for electron donors. Lactate was incompletely oxidized to acetate and carbon dioxide with Fe(III) as the electron acceptor. Lactate oxidation was also coupled to the reduction of Mn(IV), U(VI), fumarate, thiosulfate, or trimethylamine n-oxide under anaerobic conditions. BrY provides a model for how enzymatic metal reduction by respiratory metal-reducing microorganisms has the potential to contribute to the mobilization of iron and trace metals and to the immobilization of uranium in sediments of Great Bay Estuary.

  4. Bacterial Fe(II) oxidation distinguished by long-range correlation in redox potential

    NASA Astrophysics Data System (ADS)

    Enright, Allison M. L.; Ferris, F. Grant

    2016-05-01

    The kinetics of bacterial Fe(II) oxidation was investigated 297 m underground at the Äspö Hard Rock Laboratory (near Oskarshamn, Sweden) under steady state groundwater flow conditions in a flow-through cell containing well-developed flocculent mats of bacteriogenic iron oxides (BIOS). Pseudo first-order rate constants of 0.004 min-1 and 0.009 min-1 were obtained for chemical and bacterial Fe(II) oxidation, respectively, based on the 104 min retention time of groundwater in the flow cell, inlet Fe(II) concentration of 21.0 ± 0.5 µm, outlet Fe(II) concentration of 8.5 ± 0.7 µm, as well as constant pH = - log H+ of 7.42 ± 0.01, dissolved O2 concentration of 0.11 ± 0.01 mg/L, and groundwater temperature of 12.4 ± 0.1°C. Redox potential was lower at the BIOS-free inlet (-135.4 ± 1.16 mV) compared to inside BIOS within the flow cell (-112.6 ± 1.91 mV), consistent with the Nernst relationship and oxidation of Fe(II) to Fe(III). Further evaluation of the redox potential time series data using detrended fluctuation analysis (DFA) revealed power law scaling in the amplitude of fluctuations over increasing intervals of time with significantly different (p < 0.01) DFA α scaling exponents of 1.89 ± 0.03 for BIOS and 1.67 ± 0.06 at the inlet. These α values not only signal the presence of long-range correlation in the redox potential time series measurements but also distinguish between the slower rate of chemical Fe(II) oxidation at the inlet and faster rate accelerated by FeOB in BIOS.

  5. Effect of Dunaliella tertiolecta organic exudates on the Fe(II) oxidation kinetics in seawater.

    PubMed

    González, A G; Santana-Casiano, J M; González-Dávila, M; Pérez-Almeida, N; Suárez de Tangil, M

    2014-07-15

    The role played by the natural organic ligands excreted by the green algae Dunaliella tertiolecta on the Fe(II) oxidation rate constants was studied at different stages of growth. The concentration of dissolved organic carbon increased from 2.1 to 7.1 mg L(-1) over time of culture. The oxidation kinetics of Fe(II) was studied at nanomolar levels and under different physicochemical conditions of pH (7.2-8.2), temperature (5-35 °C), salinity (10-37), and dissolved organic carbon produced by cells (2.1-7.1 mg L(-1)). The experimental rate always decreased in the presence of organic exudates with respect to that in the control seawater. The Fe(II) oxidation rate constant was also studied in the context of Marcus theory, where ΔG° was 39.31-51.48 kJ mol(-1). A kinetic modeling approach was applied for computing the equilibrium and rate constants for Fe(II) and exudates present in solution, the Fe(II) speciation, and the contribution of each Fe(II) species to the overall oxidation rate constant. The best fit model took into account two acidity equilibrium constants for the Fe(II) complexing ligands with pKa,1=9.45 and pKa,2=4.9. The Fe(II) complexing constants were KFe(II)-LH=3×10(10) and KFe(II)-L=10(7), and the corresponding computed oxidation rates were 68±2 and 36±8 M(-1) min(-1), respectively. PMID:24941285

  6. New type of magnetic tunnel junction based on spin filtering through a reduced symmetry oxide: FeCo|Mg3B2O6|FeCo.

    PubMed

    Stewart, Derek A

    2010-01-01

    Magnetic tunnel junctions with high-tunneling magnetoresistance values such as Fe|MgO|Fe capitalize on spin filtering in the oxide region based on the band symmetry of incident electrons. However, these structures rely on magnetic leads and oxide regions of the same cubic symmetry class. A new magnetic tunnel junction (FeCo|Mg(3)B(2)O(6)|FeCo) is presented that uses a reduced symmetry oxide region (orthorhombic) to provide spin filtering between the two cubic magnetic leads. Complex band structure analysis of Mg(3)B(2)O(6) based on density functional calculations shows that significant spin filtering could occur in this system. This new type of magnetic tunnel junction may have been fabricated already and can explain recent experimental studies of rf-sputtered FeCoB|MgO|FeCoB junctions where there is significant B diffusion into the MgO region. PMID:20017563

  7. Oxidation of Sulfonamides in Aqueous Solution by UV-TiO2-Fe(VI)

    PubMed Central

    Ma, Yan; Zhang, Kejia; Li, Cong; Zhang, Tuqiao; Gao, Naiyun

    2015-01-01

    The photocatalytic degradation of sulfonamides in aqueous TiO2 suspension under UV irradiation has been investigated using potassium ferrate as electron acceptors. The results showed that the stability of Fe(VI) is dependent on pH significantly, and the stability reduces obviously in the presence of UV-TiO2. The experiments indicated that Fe(VI) could effectively scavenge the conduction band electrons from the surface of TiO2. The photocatalytic oxidation of sulfonamides with Fe(VI) was found to be much faster than that without Fe(VI). The SD, SM, and SMX concentration was greatly reduced by 89.2%, 83.4%, and 82.0%, respectively, after 10 min with UV-TiO2-Fe(VI), comparing to 65.2%, 66.0%, and 71.9%, respectively, with Fe(VI) only in the dark and 71.3%, 72.7%, and 76.0%, respectively, with UV-TiO2. The pH value of solution significantly influenced the sulfonamides degradation in UV-TiO2-Fe(VI) system. The degradation amount of sulfonamides after 10 min was a maximum at pH 7. The intermediate products of sulfonamides oxidation by UV-TiO2-Fe(VI) were analysed by LC-HESI-MS-MS and the results suggested that a majority of sulfonamides turned into large-molecule products without complete mineralization. PMID:26347888

  8. Oxidation of Sulfonamides in Aqueous Solution by UV-TiO2-Fe(VI).

    PubMed

    Ma, Yan; Zhang, Kejia; Li, Cong; Zhang, Tuqiao; Gao, Naiyun

    2015-01-01

    The photocatalytic degradation of sulfonamides in aqueous TiO2 suspension under UV irradiation has been investigated using potassium ferrate as electron acceptors. The results showed that the stability of Fe(VI) is dependent on pH significantly, and the stability reduces obviously in the presence of UV-TiO2. The experiments indicated that Fe(VI) could effectively scavenge the conduction band electrons from the surface of TiO2. The photocatalytic oxidation of sulfonamides with Fe(VI) was found to be much faster than that without Fe(VI). The SD, SM, and SMX concentration was greatly reduced by 89.2%, 83.4%, and 82.0%, respectively, after 10 min with UV-TiO2-Fe(VI), comparing to 65.2%, 66.0%, and 71.9%, respectively, with Fe(VI) only in the dark and 71.3%, 72.7%, and 76.0%, respectively, with UV-TiO2. The pH value of solution significantly influenced the sulfonamides degradation in UV-TiO2-Fe(VI) system. The degradation amount of sulfonamides after 10 min was a maximum at pH 7. The intermediate products of sulfonamides oxidation by UV-TiO2-Fe(VI) were analysed by LC-HESI-MS-MS and the results suggested that a majority of sulfonamides turned into large-molecule products without complete mineralization. PMID:26347888

  9. Phototrophic Fe(II)-oxidation in the chemocline of a ferruginous meromictic lake

    PubMed Central

    Walter, Xavier A.; Picazo, Antonio; Miracle, Maria R.; Vicente, Eduardo; Camacho, Antonio; Aragno, Michel; Zopfi, Jakob

    2014-01-01

    Precambrian Banded Iron Formation (BIF) deposition was conventionally attributed to the precipitation of iron-oxides resulting from the abiotic reaction of ferrous iron (Fe(II)) with photosynthetically produced oxygen. Earliest traces of oxygen date from 2.7 Ga, thus raising questions as to what may have caused BIF precipitation before oxygenic photosynthesis evolved. The discovery of anoxygenic phototrophic bacteria thriving through the oxidation of Fe(II) has provided support for a biological origin for some BIFs, but despite reports suggesting that anoxygenic phototrophs may oxidize Fe(II) in the environment, a model ecosystem of an ancient ocean where they are demonstrably active was lacking. Here we show that anoxygenic phototrophic bacteria contribute to Fe(II) oxidation in the water column of the ferruginous sulfate-poor, meromictic lake La Cruz (Spain). We observed in-situ photoferrotrophic activity through stimulation of phototrophic carbon uptake in the presence of Fe(II), and determined light-dependent Fe(II)-oxidation by the natural chemocline microbiota. Moreover, a photoferrotrophic bacterium most closely related to Chlorobium ferrooxidans was enriched from the ferruginous water column. Our study for the first time demonstrates a direct link between anoxygenic photoferrotrophy and the anoxic precipitation of Fe(III)-oxides in a ferruginous water column, providing a plausible mechanism for the bacterial origin of BIFs before the advent of free oxygen. However, photoferrotrophs represent only a minor fraction of the anoxygenic phototrophic community with the majority apparently thriving by sulfur cycling, despite the very low sulfur content in the ferruginous chemocline of Lake La Cruz. PMID:25538702

  10. Phototrophic Fe(II)-oxidation in the chemocline of a ferruginous meromictic lake.

    PubMed

    Walter, Xavier A; Picazo, Antonio; Miracle, Maria R; Vicente, Eduardo; Camacho, Antonio; Aragno, Michel; Zopfi, Jakob

    2014-01-01

    Precambrian Banded Iron Formation (BIF) deposition was conventionally attributed to the precipitation of iron-oxides resulting from the abiotic reaction of ferrous iron (Fe(II)) with photosynthetically produced oxygen. Earliest traces of oxygen date from 2.7 Ga, thus raising questions as to what may have caused BIF precipitation before oxygenic photosynthesis evolved. The discovery of anoxygenic phototrophic bacteria thriving through the oxidation of Fe(II) has provided support for a biological origin for some BIFs, but despite reports suggesting that anoxygenic phototrophs may oxidize Fe(II) in the environment, a model ecosystem of an ancient ocean where they are demonstrably active was lacking. Here we show that anoxygenic phototrophic bacteria contribute to Fe(II) oxidation in the water column of the ferruginous sulfate-poor, meromictic lake La Cruz (Spain). We observed in-situ photoferrotrophic activity through stimulation of phototrophic carbon uptake in the presence of Fe(II), and determined light-dependent Fe(II)-oxidation by the natural chemocline microbiota. Moreover, a photoferrotrophic bacterium most closely related to Chlorobium ferrooxidans was enriched from the ferruginous water column. Our study for the first time demonstrates a direct link between anoxygenic photoferrotrophy and the anoxic precipitation of Fe(III)-oxides in a ferruginous water column, providing a plausible mechanism for the bacterial origin of BIFs before the advent of free oxygen. However, photoferrotrophs represent only a minor fraction of the anoxygenic phototrophic community with the majority apparently thriving by sulfur cycling, despite the very low sulfur content in the ferruginous chemocline of Lake La Cruz. PMID:25538702

  11. Use of Walnut Shell Powder to Inhibit Expression of Fe(2+)-Oxidizing Genes of Acidithiobacillus Ferrooxidans.

    PubMed

    Li, Yuhui; Liu, Yehao; Tan, Huifang; Zhang, Yifeng; Yue, Mei

    2016-01-01

    Acidithiobacillus ferrooxidans is a Gram-negative bacterium that obtains energy by oxidizing Fe(2+) or reduced sulfur compounds. This bacterium contributes to the formation of acid mine drainage (AMD). This study determined whether walnut shell powder inhibits the growth of A. ferrooxidans. First, the effects of walnut shell powder on Fe(2+) oxidization and H⁺ production were evaluated. Second, the chemical constituents of walnut shell were isolated to determine the active ingredient(s). Third, the expression of Fe(2+)-oxidizing genes and rus operon genes was investigated using real-time polymerase chain reaction. Finally, growth curves were plotted, and a bioleaching experiment was performed to confirm the active ingredient(s) in walnut shells. The results indicated that both walnut shell powder and the phenolic fraction exert high inhibitory effects on Fe(2+) oxidation and H⁺ production by A. ferrooxidans cultured in standard 9K medium. The phenolic components exert their inhibitory effects by down-regulating the expression of Fe(2+)-oxidizing genes and rus operon genes, which significantly decreased the growth of A. ferrooxidans. This study revealed walnut shell powder to be a promising substance for controlling AMD. PMID:27144574

  12. Use of Walnut Shell Powder to Inhibit Expression of Fe2+-Oxidizing Genes of Acidithiobacillus Ferrooxidans

    PubMed Central

    Li, Yuhui; Liu, Yehao; Tan, Huifang; Zhang, Yifeng; Yue, Mei

    2016-01-01

    Acidithiobacillus ferrooxidans is a Gram-negative bacterium that obtains energy by oxidizing Fe2+ or reduced sulfur compounds. This bacterium contributes to the formation of acid mine drainage (AMD). This study determined whether walnut shell powder inhibits the growth of A. ferrooxidans. First, the effects of walnut shell powder on Fe2+ oxidization and H+ production were evaluated. Second, the chemical constituents of walnut shell were isolated to determine the active ingredient(s). Third, the expression of Fe2+-oxidizing genes and rus operon genes was investigated using real-time polymerase chain reaction. Finally, growth curves were plotted, and a bioleaching experiment was performed to confirm the active ingredient(s) in walnut shells. The results indicated that both walnut shell powder and the phenolic fraction exert high inhibitory effects on Fe2+ oxidation and H+ production by A. ferrooxidans cultured in standard 9K medium. The phenolic components exert their inhibitory effects by down-regulating the expression of Fe2+-oxidizing genes and rus operon genes, which significantly decreased the growth of A. ferrooxidans. This study revealed walnut shell powder to be a promising substance for controlling AMD. PMID:27144574

  13. Micro-structural, electrical and spectroscopic investigations of pulsed laser ablated palladium incorporated nanostructured tungsten oxide films.

    PubMed

    Lethy, K J; Beena, D; Pillai, V P Mahadevan; Suresh, K A

    2009-09-01

    Pure and Pd incorporated (0.5, 1 and 5 wt%) WO3 films are prepared on quartz substrates using pulsed laser ablation (PLD) technique in an oxygen ambient of 0.12 mbar, at a substrate temperature (Ts) of 873 K. Palladium incorporation effects on the microstructure, optical and electrical properties of tungsten oxide films are systematically investigated using techniques like X-ray diffraction (XRD), Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM), Energy dispersive X-ray spectroscopy (EDX), micro-Raman spectroscopy, UV-Vis absorption spectroscopy and temperature dependent electrical resistivity measurements. The micro-structural analysis by XRD and micro-Raman indicates that Pd addition can perturb the tungsten oxide lattice and suppress the grain growth. Optical band gap values of the films increases from 3.17 eV for pure WO3 to 3.29 eV for 5 wt% Pd incorporated WO3 films. All the films present high transparency in the visible spectral range. The electrical resistivity studies of the pure and Pd incorporated films done at room temperature and for the range of temperature; 170-450 K reveal that Pd addition can lower the resistivity of the WO3 thin films. Room temperature resistivity as well as activation energy of the film decreases exponentially with Pd incorporation concentration. Highly transparent, nanocrystalline and semiconducting WO3 films with low resistivity obtained by Pd incorporation can make WO3 suitable for microelectronics industry and for gas sensing applications. PMID:19928224

  14. Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(III)/Fe(II) cycle with hydroxylamine.

    PubMed

    Zou, Jing; Ma, Jun; Chen, Liwei; Li, Xuchun; Guan, Yinghong; Xie, Pengchao; Pan, Chao

    2013-10-15

    The reaction between ferrous iron (Fe(II)) with peroxymonosulfate (PMS) generates reactive oxidants capable of degrading refractory organic contaminants. However, the slow transformation from ferric iron (Fe(III)) back to Fe(II) limits its widespread application. Here, we added hydroxylamine (HA), a common reducing agent, into Fe(II)/PMS process to accelerate the transformation from Fe(III) to Fe(II). With benzoic acid (BA) as probe compound, the addition of HA into Fe(II)/PMS process accelerated the degradation of BA rapidly in the pH range of 2.0-6.0 by accelerating the key reactions, including the redox cycle of Fe(III)/Fe(II) and the generation of reactive oxidants. Both sulfate radicals and hydroxyl radicals were considered as the primary reactive oxidants for the degradation of BA in HA/Fe(II)/PMS process with the experiments of electron spin resonance and alcohols quenching. Moreover, HA was gradually degraded to N2, N2O, NO2 (−), and NO3 (−), while the environmentally friendly gas of N2 was considered as its major end product in the process. The present study might provide a promising idea based on Fe(II)/PMS process for the rapid degradation of refractory organic contaminants in water treatment. PMID:24033112

  15. Microbial Fe(III) oxide reduction potential in Chocolate Pots hot spring, Yellowstone National Park.

    PubMed

    Fortney, N W; He, S; Converse, B J; Beard, B L; Johnson, C M; Boyd, E S; Roden, E E

    2016-05-01

    Chocolate Pots hot springs (CP) is a unique, circumneutral pH, iron-rich, geothermal feature in Yellowstone National Park. Prior research at CP has focused on photosynthetically driven Fe(II) oxidation as a model for mineralization of microbial mats and deposition of Archean banded iron formations. However, geochemical and stable Fe isotopic data have suggested that dissimilatory microbial iron reduction (DIR) may be active within CP deposits. In this study, the potential for microbial reduction of native CP Fe(III) oxides was investigated, using a combination of cultivation dependent and independent approaches, to assess the potential involvement of DIR in Fe redox cycling and associated stable Fe isotope fractionation in the CP hot springs. Endogenous microbial communities were able to reduce native CP Fe(III) oxides, as documented by most probable number enumerations and enrichment culture studies. Enrichment cultures demonstrated sustained DIR driven by oxidation of acetate, lactate, and H2 . Inhibitor studies and molecular analyses indicate that sulfate reduction did not contribute to observed rates of DIR in the enrichment cultures through abiotic reaction pathways. Enrichment cultures produced isotopically light Fe(II) during DIR relative to the bulk solid-phase Fe(III) oxides. Pyrosequencing of 16S rRNA genes from enrichment cultures showed dominant sequences closely affiliated with Geobacter metallireducens, a mesophilic Fe(III) oxide reducer. Shotgun metagenomic analysis of enrichment cultures confirmed the presence of a dominant G. metallireducens-like population and other less dominant populations from the phylum Ignavibacteriae, which appear to be capable of DIR. Gene (protein) searches revealed the presence of heat-shock proteins that may be involved in increased thermotolerance in the organisms present in the enrichments as well as porin-cytochrome complexes previously shown to be involved in extracellular electron transport. This analysis offers

  16. Characterization of the Fe-Doped Mixed-Valent Tunnel Structure 2 Manganese Oxide KOMS-2

    SciTech Connect

    Hanson J. C.; Shen X.; Morey A.M.; Liu J.; Ding Y.; Cai J.; Durand J.; Wang Q.; Wen W.; Hines W.A.; Bai J.; Frenkel A.I.; Reiff W.; Aindow M.; Suib S.L.

    2011-11-10

    A sol-gel-assisted combustion method was used to prepare Fe-doped manganese oxide octahedral molecular sieve (Fe-KOMS-2) materials with the cryptomelane structure. Characterization of the nanopowder samples over a wide range of Fe-doping levels (0 {le} Fe/Mn {le} 1/2) was carried out using a variety of experimental techniques. For each sample, Cu K{alpha} XRD and ICP-AES were used to index the cryptomelane structure and determine the elemental composition, respectively. A combination of SEM and TEM images revealed that the morphology changes from nanoneedle to nanorod after Fe doping. Furthermore, TGA scans indicated that the thermal stability is also enhanced with the doping. Anomalous XRD demonstrated that the Fe ions replace the Mn ions in the cryptomelane structure, particularly in the (211) planes, and results in a lattice expansion along the c axis, parallel to the tunnels. Reasonable fits to EXAFS data were obtained using a model based on the cryptomelane structure. Moessbauer spectra for selected Fe-KOMS-2 samples indicated that the Fe is present as Fe{sup 3+} in an octahedral environment similar to Mn in the MnO{sub 6} building blocks of KOMS-2. Magnetization measurements detected a small amount of {gamma}-Fe{sub 2}O{sub 3} second phase (e.g., 0.6 wt % for the Fe/Mn = 1/10 sample), the vast majority of the Fe being in the structure as Fe{sup 3+} in the high-spin state.

  17. Structural and dielectric properties of laser ablated BaTiO3 films deposited over electrophoretically dispersed CoFe2O4 grains

    NASA Astrophysics Data System (ADS)

    Barbosa, J. G.; Gomes, I. T.; Pereira, M. R.; Moura, C.; Mendes, J. A.; Almeida, B. G.

    2014-10-01

    Thin film nanocomposites with mixed connectivity, composed by CoFe2O4 grains, deposited by electrophoresis on Si|Pt substrates, and subsequently covered by a laser ablation deposited BaTiO3 layer were prepared with different cobalt ferrite concentrations. Their structure presented a combination of BaTiO3, with its tetragonal and the orthorhombic phases coexisting at room temperature, and CoFe2O4 with the cubic spinel structure. The cobalt ferrite nanograins were under in-plane tensile stress, while the BaTiO3 phase was under in-plane compressive stress. The dielectric measurements showed that as the barium titanate grain size decreased, its ferroelectric Curie temperature shifted to lower temperatures relative to the bulk. This grain size dependent TC shift was associated and modeled by a core-shell structure of BaTiO3 grains in the films, with a tetragonal core and cubic shell. Additionally, a diffuse tetragonal-orthorhombic phase transition was observed and, in agreement with Raman spectroscopy results, associated to the coexistence of barium titanate orthorhombic and tetragonal phases in the room temperature region. This led to the formation of polar nanoclusters with random polarization orientations, which induced a frustrated phase transition between the tetragonal and orthorhombic phases of barium titanate in the films.

  18. The influence of magmatic differentiation on the oxidation state of Fe in a basaltic arc magma

    SciTech Connect

    Kelley, Katherine A.; Cottrell, Elizabeth

    2012-05-09

    Subduction zone basalts are more oxidized than basalts from other tectonic settings (e.g., higher Fe{sup 3+}/{Sigma}Fe), and this contrast may play a central role in the unique geochemical processes that generate arc and continental crust. The processes generating oxidized arc magmas, however, are poorly constrained, although they appear inherently linked to subduction. Near-surface differentiation processes unique to arc settings might drive oxidation of magmas that originate in equilibrium with a relatively reduced mantle source. Alternatively, arc magmas could record the oxidation conditions of a relatively oxidized mantle source. Here, we present new measurements of olivine-hosted melt inclusions from a single eruption of Agrigan volcano, Marianas, in order to test the influence of differentiation processes vs. source conditions on the Fe{sup 3+}/{Sigma}Fe ratio, a proxy for system oxygen fugacity (fO{sub 2}). We determined Fe{sup 3+}/{Sigma}Fe ratios in glass inclusions using {mu}-XANES and couple these data with major elements, dissolved volatiles, and trace elements. After correcting for post-entrapment crystallization, Fe{sup 3+}/{Sigma}Fe ratios in the Agrigan melt inclusions (0.219 to 0.282), and their modeled fO{sub 2}s ({Delta}QFM + 1.0 to + 1.8), are uniformly more oxidized than MORB, and preserve a portion of the evolution of this magma from 5.7 to 3.2 wt.% MgO. Fractionation of olivine {+-} clinopyroxene {+-} plagioclase should increase Fe{sup 3+}/{Sigma}Fe as MgO decreases in the melt, but the data show Fe{sup 3+}/{Sigma}Fe ratios decreasing as MgO decreases below 5 wt.% MgO. The major element trajectories, taken in combination with this strong reduction trend, are inconsistent with crystallization of common ferromagnesian phases found in the bulk Agrigan sample, including magnetite. Rather, decreasing Fe{sup 3+}/{Sigma}Fe ratios correlate with decreasing S concentrations, suggesting that electronic exchanges associated with SO{sub 2} degassing may

  19. 3D Visualization of the Iron Oxidation State in FeO/Fe3O4 Core-Shell Nanocubes from Electron Energy Loss Tomography.

    PubMed

    Torruella, Pau; Arenal, Raúl; de la Peña, Francisco; Saghi, Zineb; Yedra, Lluís; Eljarrat, Alberto; López-Conesa, Lluís; Estrader, Marta; López-Ortega, Alberto; Salazar-Alvarez, Germán; Nogués, Josep; Ducati, Caterina; Midgley, Paul A; Peiró, Francesca; Estradé, Sonia

    2016-08-10

    The physicochemical properties used in numerous advanced nanostructured devices are directly controlled by the oxidation states of their constituents. In this work we combine electron energy-loss spectroscopy, blind source separation, and computed tomography to reconstruct in three dimensions the distribution of Fe(2+) and Fe(3+) ions in a FeO/Fe3O4 core/shell cube-shaped nanoparticle with nanometric resolution. The results highlight the sharpness of the interface between both oxides and provide an average shell thickness, core volume, and average cube edge length measurements in agreement with the magnetic characterization of the sample. PMID:27383904

  20. Iron-Oxidizing Bacteria Are Associated with Ferric Hydroxide Precipitates (Fe-Plaque) on the Roots of Wetland Plants

    PubMed Central

    Emerson, David; Weiss, Johanna V.; Megonigal, J. Patrick

    1999-01-01

    The presence of Fe-oxidizing bacteria in the rhizosphere of four different species of wetland plants was investigated in a diverse wetland environment that had Fe(II) concentrations ranging from tens to hundreds of micromoles per liter and a pH range of 3.5 to 6.8. Enrichments for neutrophilic, putatively lithotrophic Fe-oxidizing bacteria were successful on roots from all four species; acidophilic Fe-oxidizing bacteria were enriched only on roots from plants whose root systems were exposed to soil solutions with a pH of <4. In Sagittaria australis there was a positive correlation (P < 0.01) between cell numbers and the total amount of Fe present; the same correlation was not found for Leersia oryzoides. These results present the first evidence for culturable Fe-oxidizing bacteria associated with Fe-plaque in the rhizosphere. PMID:10347074

  1. L10 ordering of FePtB layers by oxidation-induced stress of capping layer

    NASA Astrophysics Data System (ADS)

    Choi, Gyung-Min; Min, Byoung-Chul; Shin, Kyung-Ho

    2013-05-01

    We have studied the L10 ordering of FePtB layers assisted by the oxidation-induced stress of a capping layer. In the thermally oxidized Si substrate/MgO/CoFeB/FePtB/Ti structure, the oxidation of the Ti capping layer during post-deposition annealing exerts an in-plane tensile stress on the FePtB layer, which promotes L10 ordering of the FePtB layer. The diffusion of boron from the FePtB layer into the Ti layer also plays a crucial role in the L10 ordering. The CoFeB/FePtB composite layers can be used for the top electrode of perpendicular magnetic tunnel junctions.

  2. Discovery of Fe7O9: a new iron oxide with a complex monoclinic structure.

    PubMed

    Sinmyo, Ryosuke; Bykova, Elena; Ovsyannikov, Sergey V; McCammon, Catherine; Kupenko, Ilya; Ismailova, Leyla; Dubrovinsky, Leonid

    2016-01-01

    Iron oxides are fundamentally important compounds for basic and applied sciences as well as in numerous industrial applications. In this work we report the synthesis and investigation of a new binary iron oxide with the hitherto unknown stoichiometry of Fe7O9. This new oxide was synthesized at high-pressure high-temperature (HP-HT) conditions, and its black single crystals were successfully recovered at ambient conditions. By means of single crystal X-ray diffraction we determined that Fe7O9 adopts a monoclinic C2/m lattice with the most distorted crystal structure among the binary iron oxides known to date. The synthesis of Fe7O9 opens a new portal to exotic iron-rich (M,Fe)7O9 oxides with unusual stoichiometry and distorted crystal structures. Moreover, the crystal structure and phase relations of such new iron oxide groups may provide new insight into the cycling of volatiles in the Earth's interior. PMID:27605075

  3. Discovery of Fe7O9: a new iron oxide with a complex monoclinic structure

    PubMed Central

    Sinmyo, Ryosuke; Bykova, Elena; Ovsyannikov, Sergey V.; McCammon, Catherine; Kupenko, Ilya; Ismailova, Leyla; Dubrovinsky, Leonid

    2016-01-01

    Iron oxides are fundamentally important compounds for basic and applied sciences as well as in numerous industrial applications. In this work we report the synthesis and investigation of a new binary iron oxide with the hitherto unknown stoichiometry of Fe7O9. This new oxide was synthesized at high-pressure high-temperature (HP-HT) conditions, and its black single crystals were successfully recovered at ambient conditions. By means of single crystal X-ray diffraction we determined that Fe7O9 adopts a monoclinic C2/m lattice with the most distorted crystal structure among the binary iron oxides known to date. The synthesis of Fe7O9 opens a new portal to exotic iron-rich (M,Fe)7O9 oxides with unusual stoichiometry and distorted crystal structures. Moreover, the crystal structure and phase relations of such new iron oxide groups may provide new insight into the cycling of volatiles in the Earth’s interior. PMID:27605075

  4. Oxidation of synthesized sub-micron pyrite (FeS2) in seawater

    NASA Astrophysics Data System (ADS)

    Gartman, Amy; Luther, George W.

    2014-11-01

    Synthesized sub-micron pyrite was oxidized in 0.2 μm-filtered Sargasso seawater in order to investigate the rate of oxidation and reaction end-products. Over the initial phase of the reaction, the sub-micron pyrite behaved as a soluble entity as the initial rate of oxidation was determined to be first order with respect to both pyrite and oxygen concentration, where the rate is described as -dFeS2/dt = k[FeS2][O2] and k, the rate constant, is 7.60 × 10-5 + 6.29 × 10-5 μM-1 day-1 at 25 °C. Oxidation proceeds inward from an initial surface oxidation of the pyrite and the formation of an amorphous mixed valence Fe(II)/(III) oxide surrounding the remaining pyrite core. The oxidation rates obtained through this study are up to two orders of magnitude slower than reported in previous pyrite oxidation studies using ground rather than synthesized pyrite at similar pH values. These results may be applied anywhere seawater and sub-micron pyrite are found, including hydrothermal vents, salt marshes and marine sediments.

  5. Pyrite (FeS 2) oxidation: A sub-micron synchrotron investigation of the initial steps

    NASA Astrophysics Data System (ADS)

    Chandra, Anand P.; Gerson, Andrea R.

    2011-10-01

    Pyrite is an environmentally significant mineral being the major contributor to acid rock drainage. Synchrotron based SPEM (scanning photoelectron microscopy) and micro-XPS (X-ray photoelectron spectroscopy) have been used to characterise fresh and oxidised pyrite (FeS 2) with a view to understanding the initial oxidation steps that take place during natural weathering processes. Localised regions of the pyrite surface containing Fe species of reduced coordination have been found to play a critical role. Such sites not only initiate the oxidation process but also facilitate the formation of highly reactive hydroxyl radical species, which then lead the S oxidation process. Four different S species are found to be present on fresh fractured pyrite surfaces: S 22-(bulk) (4-fold coordination), S 22-(surface) (3-fold coordination), S 2- and S 0/S n2- (metal deficient sulfide and polysulfide respectively). These species were found to be heterogeneously distributed on the fractured pyrite surface. Both O 2 and H 2O gases are needed for effective oxidation of the pyrite surface. The process is initiated when O 2 dissociatively and H 2O molecularly adsorb onto the surface Fe sites where high dangling bond densities exist. H 2O may then dissociate to produce rad OH radicals. The adsorption of these species leads to the formation of Fe-oxy species prior to the formation of sulfoxy species. Evidence suggests that Fe-O bonds form prior to Fe-OH bonds. S oxidation occurs through interactions of rad OH radicals formed at the Fe sites, with formation of SO 42- occurring via S 2O 32-/SO 32- intermediates. The pyrite oxidation process is electrochemical in nature and was found to occur in patches, where site specific adsorption of O 2 and H 2O has occurred. Fe and S oxidation was found to occur within the same area of oxidation probably in atomic scale proximity. Furthermore, the O in SO 42- arises largely from H 2O; however, depending on the surface history, SO 42- formed early in

  6. Molecular Underpinnings of Fe(III) Oxide Reduction by Shewanella Oneidensis MR-1

    PubMed Central

    Shi, Liang; Rosso, Kevin M.; Clarke, Tomas A.; Richardson, David J.; Zachara, John M.; Fredrickson, James K.

    2012-01-01

    In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III)] (oxy)(hydr)oxide minerals as the terminal electron acceptors for anaerobic respiration. At circumneutral pH and in the absence of strong complexing ligands, Fe(III) oxides are relatively insoluble and thus are external to the bacterial cells. S. oneidensis MR-1 and related strains of metal-reducing Shewanella have evolved machinery (i.e., metal-reducing or Mtr pathway) for transferring electrons from the inner-membrane, through the periplasm and across the outer-membrane to the surface of extracellular Fe(III) oxides. The protein components identified to date for the Mtr pathway include CymA, MtrA, MtrB, MtrC, and OmcA. CymA is an inner-membrane tetraheme c-type cytochrome (c-Cyt) that belongs to the NapC/NrfH family of quinol dehydrogenases. It is proposed that CymA oxidizes the quinol in the inner-membrane and transfers the released electrons to MtrA either directly or indirectly through other periplasmic proteins. A decaheme c-Cyt, MtrA is thought to be embedded in the trans outer-membrane and porin-like protein MtrB. Together, MtrAB deliver the electrons through the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. MtrC and OmcA are the outer-membrane decaheme c-Cyts that are translocated across the outer-membrane by the bacterial type II secretion system. Functioning as terminal reductases, MtrC and OmcA can bind the surface of Fe(III) oxides and transfer electrons directly to these minerals via their solvent-exposed hemes. To increase their reaction rates, MtrC and OmcA can use the flavins secreted by S. oneidensis MR-1 cells as diffusible co-factors for reduction of Fe(III) oxides. Because of their extracellular location and broad redox potentials, MtrC and OmcA can also serve as the terminal reductases for soluble forms of Fe(III). In addition to Fe(III) oxides, Mtr pathway is also involved in reduction of

  7. Role of oxidants in enhancing dewaterability of anaerobically digested sludge through Fe (II) activated oxidation processes: hydrogen peroxide versus persulfate

    PubMed Central

    Song, Kang; Zhou, Xu; Liu, Yiqi; Gong, Yanyan; Zhou, Beibei; Wang, Dongbo; Wang, Qilin

    2016-01-01

    Improving dewaterability of sludge is important for the disposal of sludge in wastewater treatment plants (WWTPs). This study, for the first time, investigated the Fe(II) activated oxidization processes in improving anaerobically digested sludge (ADS) dewaterability. The combination of Fe(II) (0–100 mg/g total solids (TS)) and persulfate (0–1,000 mg/g TS) under neutral pH as well as the combination of Fe(II) (0–100 mg/g TS) and hydrogen peroxide (HP) (0–1,000 mg/g TS) under pH 3.0 were used to examine and compare their effect on the ADS dewaterability enhancement. The highest ADS dewaterability enhancement was attained at 25 mg Fe(II)/g TS and 50 mg HP/g TS, when the CST (CST: the capillary suction time, a sludge dewaterability indicator) was reduced by 95%. In contrast, the highest CST reduction in Fe(II)-persulfate conditioning was 90%, which was obtained at 50 mg Fe(II)/g TS and 250 mg persulfate/g TS. The results showed that Fe(II)-HP conditioning was comparable with Fe(II)-persulfate conditioning in terms of highest CST reduction. Economic analysis suggested that the Fe(II)-HP conditioning was more promising for improving ADS dewaterability compared with Fe(II)-persulfate conditioning, with the saving being up to $65,000 per year in a WWTP with a population equivalent of 100,000. PMID:27109500

  8. Role of oxidants in enhancing dewaterability of anaerobically digested sludge through Fe (II) activated oxidation processes: hydrogen peroxide versus persulfate.

    PubMed

    Song, Kang; Zhou, Xu; Liu, Yiqi; Gong, Yanyan; Zhou, Beibei; Wang, Dongbo; Wang, Qilin

    2016-01-01

    Improving dewaterability of sludge is important for the disposal of sludge in wastewater treatment plants (WWTPs). This study, for the first time, investigated the Fe(II) activated oxidization processes in improving anaerobically digested sludge (ADS) dewaterability. The combination of Fe(II) (0-100 mg/g total solids (TS)) and persulfate (0-1,000 mg/g TS) under neutral pH as well as the combination of Fe(II) (0-100 mg/g TS) and hydrogen peroxide (HP) (0-1,000 mg/g TS) under pH 3.0 were used to examine and compare their effect on the ADS dewaterability enhancement. The highest ADS dewaterability enhancement was attained at 25 mg Fe(II)/g TS and 50 mg HP/g TS, when the CST (CST: the capillary suction time, a sludge dewaterability indicator) was reduced by 95%. In contrast, the highest CST reduction in Fe(II)-persulfate conditioning was 90%, which was obtained at 50 mg Fe(II)/g TS and 250 mg persulfate/g TS. The results showed that Fe(II)-HP conditioning was comparable with Fe(II)-persulfate conditioning in terms of highest CST reduction. Economic analysis suggested that the Fe(II)-HP conditioning was more promising for improving ADS dewaterability compared with Fe(II)-persulfate conditioning, with the saving being up to $65,000 per year in a WWTP with a population equivalent of 100,000. PMID:27109500

  9. Tuning the Reactivity of Ultrathin Oxides: NO Adsorption on Monolayer FeO(111).

    PubMed

    Merte, Lindsay R; Heard, Christopher J; Zhang, Feng; Choi, Juhee; Shipilin, Mikhail; Gustafson, Johan; Weaver, Jason F; Grönbeck, Henrik; Lundgren, Edvin

    2016-08-01

    Ultrathin metal oxides exhibit unique chemical properties and show promise for applications in heterogeneous catalysis. Monolayer FeO films supported on metal surfaces show large differences in reactivity depending on the metal substrate, potentially enabling tuning of the catalytic properties of these materials. Nitric oxide (NO) adsorption is facile on silver-supported FeO, whereas a similar film grown on platinum is inert to NO under similar conditions. Ab initio calculations link this substrate-dependent behavior to steric hindrance caused by substrate-induced rumpling of the FeO surface, which is stronger for the platinum-supported film. Calculations show that the size of the activation barrier to adsorption caused by the rumpling is dictated by the strength of the metal-oxide interaction, offering a straightforward method for tailoring the adsorption properties of ultrathin films. PMID:27346455

  10. Discovery of the recoverable high-pressure iron oxide Fe4O5

    PubMed Central

    Lavina, Barbara; Dera, Przemyslaw; Kim, Eunja; Meng, Yue; Downs, Robert T.; Weck, Philippe F.; Sutton, Stephen R.; Zhao, Yusheng

    2011-01-01

    Phases of the iron–oxygen binary system are significant to most scientific disciplines, directly affecting planetary evolution, life, and technology. Iron oxides have unique electronic properties and strongly interact with the environment, particularly through redox reactions. The iron–oxygen phase diagram therefore has been among the most thoroughly investigated, yet it still holds striking findings. Here, we report the discovery of an iron oxide with formula Fe4O5, synthesized at high pressure and temperature. The previously undescribed phase, stable from 5 to at least 30 GPa, is recoverable to ambient conditions. First-principles calculations confirm that the iron oxide here described is energetically more stable than FeO + Fe3O4 at pressure greater than 10 GPa. The calculated lattice constants, equation of states, and atomic coordinates are in excellent agreement with experimental data, confirming the synthesis of Fe4O5. Given the conditions of stability and its composition, Fe4O5 is a plausible accessory mineral of the Earth’s upper mantle. The phase has strong ferrimagnetic character comparable to magnetite. The ability to synthesize the material at accessible conditions and recover it at ambient conditions, along with its physical properties, suggests a potential interest in Fe4O5 for technological applications. PMID:21969537

  11. Enhanced dewaterability of waste activated sludge by Fe(II)-activated peroxymonosulfate oxidation.

    PubMed

    Liu, Jun; Yang, Qi; Wang, Dongbo; Li, Xiaoming; Zhong, Yu; Li, Xin; Deng, Yongchao; Wang, Liqun; Yi, Kaixin; Zeng, Guangming

    2016-04-01

    The effect of Fe(II)-activated peroxymonosulfate (Fe(II)-PMS) oxidation on the waste activated sludge (WAS) dewatering and its mechanisms were investigated in this study. The capillary suction time (CST), specific resistance to filterability (SRF) of sludge and water content (WC) of dewatered sludge cake were chosen as the main parameters to evaluate the sludge dewaterability. Experimental results showed that Fe(II)-PMS effectively disintegrated sludge and improved sludge dewaterability. High CST and SRF reduction (90% and 97%) was achieved at the optimal conditions of PMS (HSO5(-)) 0.9mmol/gVSS, Fe(II) 0.81mmol/gVSS, and pH 6.8. Extracellular polymeric substances (EPS) and three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy before and after Fe(II)-PMS oxidation were determined to explain the enhanced dewatering mechanism. The release of EPS-bound water induced by the destruction of EPS was the primary reason for the improvement of sludge dewaterability during Fe(II)-PMS oxidation. PMID:26851897

  12. Oxygen sensitivity of zinc oxide nanoparticles produced via laser-ablated plasma in pressurized liquid

    NASA Astrophysics Data System (ADS)

    Goto, Taku; Shimizu, Yoshiki; Ito, Tsuyohito

    2015-09-01

    While traditional semiconductor oxygen sensor operate only with elevated temperature (= 700 K), the room-temperature operation of the ZnO oxygen sensors have been demonstrated with the help of UV light irradiation. Especially, ZnO nanotubes and nanoparticles have attracted much attentions as highly sensitive oxygen sensors and photodetectors. To the best of our knowledge, the reported works of gas sensors with ZnO nanostructures have been mostly intended for revealing effects of the morphology/shape and the size of the nanostructures. For further improvements of the ZnO-based gas sensors, it is probably required to understand effects of microscopic structures, such as densities of various defects. In this study, we synthesized the ZnO nanoparticles with various defects by means of laser-ablated plasma in pressurized water-ethanol mixture. The results indicate that the defects in ZnO affect oxygen sensitivity, and especially VO + defects seem to be mostly responsible for the resistance change of ZnO nanoparticles. We demonstrate that partial oxygen pressure can be measured with high sensitivity.

  13. Influence of recrystallization on phase separation kinetics of oxide dispersion strengthened Fe Cr Al alloy

    SciTech Connect

    Capdevila, C.; Miller, Michael K; Pimentel, G.; Chao, J.

    2012-01-01

    The effect of different starting microstructures on the kinetics of Fe-rich ({alpha}) and Cr-rich ({alpha}') phase separation during aging of Fe-Cr-Al oxide dispersion strengthened (ODS) alloys has been analyzed with a combination of atom probe tomography and thermoelectric power measurements. The results revealed that the high recrystallization temperature necessary to produce a coarse grained microstructure in Fe-base ODS alloys affects the randomness of Cr-atom distributions and defect density, which consequently affect the phase separation kinetics at low annealing temperatures.

  14. Cerebral bioimaging of Cu, Fe, Zn, and Mn in the MPTP mouse model of Parkinson's disease using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    PubMed

    Matusch, Andreas; Depboylu, Candan; Palm, Christoph; Wu, Bei; Höglinger, Günter U; Schäfer, Martin K-H; Becker, J Sabine

    2010-01-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been established as a powerful technique for the determination of metal and nonmetal distributions within biological systems with high sensitivity. An imaging LA-ICP-MS technique for Fe, Cu, Zn, and Mn was developed to produce large series of quantitative element maps in native brain sections of mice subchronically intoxicated with 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridin (MPTP) as a model of Parkinson's disease. Images were calibrated using matrix-matched laboratory standards. A software solution allowing a precise delineation of anatomical structures was implemented. Coronal brain sections were analyzed crossing the striatum and the substantia nigra, respectively. Animals sacrificed 2 h, 7 d, or 28 d after the last MPTP injection and controls were investigated. We observed significant decreases of Cu concentrations in the periventricular zone and the fascia dentata at 2 h and 7d and a recovery or overcompensation at 28 d, most pronounced in the rostral periventricular zone (+40%). In the cortex Cu decreased slightly to -10%. Fe increased in the interpeduncular nucleus (+40%) but not in the substantia nigra. This pattern is in line with a differential regulation of periventricular and parenchymal Cu, and with the histochemical localization of Fe, and congruent to regions of preferential MPTP binding described in the rodent brain. The LA-ICP-MS technique yielded valid and statistically robust results in the present study on 39 slices from 19 animals. Our findings underline the value of routine micro-local analytical techniques in the life sciences and affirm a role of Cu availability in Parkinson's disease. PMID:19892565

  15. Stability of uranium incorporated into Fe(hydr)oxides under fluctuating redox conditions

    SciTech Connect

    Stewart, B.D.; Nico, P.S.; Fendorf, S.

    2009-04-01

    Reaction pathways resulting in uranium bearing solids that are stable (i.e., having limited solubility) under both aerobic and anaerobic conditions will limit dissolved concentrations and migration of this toxin. Here we examine the sorption mechanism and propensity for release of uranium reacted with Fe (hydr)oxides under cyclic oxidizing and reducing conditions. Upon reaction of ferrihydrite with Fe(II) under conditions where aqueous Ca-UO{sub 2}-CO{sub 3} species predominate (3 mM Ca and 3.8 mM CO{sub 3}-total), dissolved uranium concentrations decrease from 0.16 mM to below detection limit (BDL) after 5 to 15 d, depending on the Fe(II) concentration. In systems undergoing 3 successive redox cycles (15 d of reduction followed by 5 d of oxidation) and a pulsed decrease to 0.15 mM CO{sub 3}-total, dissolved uranium concentrations varied depending on the Fe(II) concentration during the initial and subsequent reduction phases - U concentrations resulting during the oxic 'rebound' varied inversely with the Fe(II) concentration during the reduction cycle. Uranium removed from solution remains in the oxidized form and is found both adsorbed on and incorporated into the structure of newly formed goethite and magnetite. Our 15 results reveal that the fate of uranium is dependent on anaerobic/aerobic conditions, aqueous uranium speciation, and the fate of iron.

  16. Comparison study of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts for selective catalytic reduction of NO with NH3 at low temperature.

    PubMed

    Zhu, Lin; Zhong, Zhaoping; Yang, Han; Wang, Chunhua

    2016-09-15

    In this paper, a series of Cu-Fe-Ti and Co-Fe-Ti oxide catalysts were prepared by sol gel method. Cu-Fe-Ti and Co-Fe-Ti oxide catalysts showed the moderate catalytic activity for selective catalytic reduction (SCR) of NO with NH3 at low temperature. The catalysts with the molar ratio as 4:1:10 (M:Fe:Ti) were selected as the representatives for comparison of reaction properties and H2O resistance, which were denoted as Cu-Fe/TiO2 and Co-Fe/TiO2 respectively. The characterization results manifested Co-Fe/TiO2 owned more adsorption capacity of the reactants and Cu-Fe/TiO2 had better redox ability. The in situ DRIFTS experiments indicated that adsorbed NH3 species and nitrate species both exhibited reaction activity for Co-Fe/TiO2, while nitric oxide was only be reduced by adsorbed NH3 species through Eley-Rideal mechanism for Cu-Fe/TiO2 at 150°C. Co-Fe/TiO2 exhibited the better resistance to H2O and its temperature window shifted towards the higher temperature in presence of 10vol% H2O, while the SCR activity of Cu-Fe/TiO2 was inhibited significantly in the whole temperature range investigated. The suppression of adsorption and activation for NH3 and NOx might be the reasons for the reversible inactivation, which was confirmed by the inhibitation of catalytic activities for separation NH3 and NO oxidation under the wet condition. We speculated that different thermal stability of adsorbed species and redox capacity of catalysts leaded to the different SCR behavior in absence and presence of H2O. PMID:27280535

  17. The Oxidation State of Fe in MORB Glasses and the Oxygen Fugacity of the Upper Mantle

    SciTech Connect

    E Cottrell; K Kelley

    2011-12-31

    Micro-analytical determination of Fe{sup 3+}/{Sigma}Fe ratios in mid-ocean ridge basalt (MORB) glasses using micro X-ray absorption near edge structure ({mu}-XANES) spectroscopy reveals a substantially more oxidized upper mantle than determined by previous studies. Here, we show that global MORBs yield average Fe{sup 3+}/{Sigma}Fe ratios of 0.16 {+-} 0.01 (n = 103), which trace back to primary MORB melts equilibrated at the conditions of the quartz-fayalite-magnetite (QFM) buffer. Our results necessitate an upward revision of the Fe{sup 3+}/{Sigma}Fe ratios of MORBs, mantle oxygen fugacity, and the ferric iron content of the mantle relative to previous wet chemical determinations. We show that only 0.01 (absolute, or < 10%) of the difference between Fe{sup 3+}/{Sigma}Fe ratios determined by micro-colorimety and XANES can be attributed to the Moessbauer-based XANES calibration. The difference must instead derive from a bias between micro-colorimetry performed on experimental vs. natural basalts. Co-variations of Fe{sup 3+}/{Sigma}Fe ratios in global MORB with indices of low-pressure fractional crystallization are consistent with Fe{sup 3+} behaving incompatibly in shallow MORB magma chambers. MORB Fe{sup 3+}/{Sigma}Fe ratios do not, however, vary with indices of the extent of mantle melting (e.g., Na{sub 2}O(8)) or water concentration. We offer two hypotheses to explain these observations: The bulk partition coefficient of Fe{sup 3+} may be higher during peridotite melting than previously thought, and may vary with temperature, or redox exchange between sulfide and sulfate species could buffer mantle melting at {approx} QFM. Both explanations, in combination with the measured MORB Fe{sup 3+}/{Sigma}Fe ratios, point to a fertile MORB source with greater than 0.3 wt.% Fe{sub 2}O{sub 3}.

  18. Electronic spectra of Fe3+ oxides and oxide hydroxides in the near IR to near UV.

    USGS Publications Warehouse

    Sherman, David M.; Waite, T.D.

    1985-01-01

    Optical absorption and diffuse reflectance spectra of several Fe2O3 and FeOOH polymorphs (hematite, maghemite, goethite, lepidocrocite) in the near-IR to near-UV spectral regions (2000-200 nm) are presented. The spectra consist primarily of Fe3+ ligand field and ligand-to-metal charge-transfer transitions.-J.A.Z.

  19. Thin Oxides as a Cu Diffusion Barrier for NIF Be Ablator Capsules

    SciTech Connect

    Youngblood, Kelly P.; Huang, H.; Xu, H. W.; Hayes, J.; Moreno, K. A.; Wu, J. J.; Nikroo, A.; Alford, C. A.; Hamza, A. V.; Kucheyev, S. O.; Wang, Y. M.; Wu, K. J.

    2013-03-01

    The NIF point design uses a five-layer capsule to modify the X-ray absorption in order to achieve optimized shock timing. A stepped copper dopant design defines the layer structure. The production of the capsule involves pyrolysis to remove the inner plastic mandrel. Copper atoms diffuse radially and azimuthally throughout the capsule during pyrolysis. This diffusion significantly diminishes the capsule performance during implosion. Thermal and coated oxide barrier layers employed between layers mitigate the diffusion of copper during the mandrel removal process. The copper atoms do not diffuse through this barrier during pyrolysis. A capsule fabrication method that produces a capsule with a thin oxide layer will be discussed.

  20. Surface passivation limited UO2 oxidative dissolution in the presence of FeS.

    PubMed

    Bi, Yuqiang; Hayes, Kim F

    2014-11-18

    Iron sulfide minerals produced during in situ bioremediation of U can serve as an oxygen scavenger to retard uraninite (UO2) oxidation upon oxygen intrusion. Under persistent oxygen supply, however, iron sulfides become oxidized and depleted, giving rise to elevated dissolved oxygen (DO) levels and remobilization of U(IV). The present study investigated the mechanism that regulates UO2 oxidative dissolution rate in a flow-through system when oxygen breakthrough occurred as a function of mackinawite (FeS) and carbonate concentrations. The formation and evolution of surface layers on UO2 were characterized using XAS and XPS. During FeS inhibition period, the continuous supply of carbonate and calcium in the influent effectively complexed and removed oxidized U(VI) to preserve an intermediate U4O9 surface. When the FeS became depleted by oxidization, a transient, rapid dissolution of UO2 was observed along with DO breakthrough in the reactor. This rate was greater than during the preceding FeS inhibition period and control experiments in the absence of FeS. With increasing DO, the rate slowed and the rate-limiting step shifted from surface oxidation to U(VI) detachment as U(VI) passivation layers developed. In contrast, increasing the carbonate concentrations facilitated detachment of surface-associated U(VI) complexes and impeded the formation of U(VI) passivation layer. This study demonstrates the critical role of U(VI) surface layer formation versus U(VI) detachment in controlling UO2 oxidative dissolution rate during periods of variable oxygen presence under simulated groundwater conditions. PMID:25322064

  1. Temperature control of the growth of iron oxide nanoislands on Fe(001)

    NASA Astrophysics Data System (ADS)

    Kazu Yamada, Toyo; Sakaguchi, Yuki; Gerhard, Lukas; Wulfhekel, Wulf

    2016-08-01

    The control of atomically flat interfaces between iron (Fe) and insulating oxide films, such as the Fe/MgO(001) interface, is crucial for tunnel-magnetoresistance (TMR) devices. However, the realization of an ideal atomically flat and clean interface is rather difficult since iron easily binds to impurities such as oxygen. Atomic step defects and iron oxide at the interface could reduce TMR. In this study, the oxidization of an atomically flat and clean Fe(001)-whisker single crystal at different substrate and annealing temperatures was investigated with an ultrahigh-vacuum scanning tunneling microscope (STM). Annealing up to a temperature of 850 K was required to obtain ordered and atomically flat Fe(001)-p(1×1)O terraces after the oxidization with the coexistence of Fe–O nanoislands (∼1 nm in height, ∼50 nm in size). We found that the growth of such nanoislands, which enhances interface roughness, strongly depends on the substrate temperature (T S) during the oxidization. A T S lower than 300 K reduces the coverage by the nanoislands to less than 10%.

  2. Schwertmannite and Fe oxides formed by biological low-pH Fe(II) oxidation versus abiotic neutralization: Impact on trace metal sequestration

    NASA Astrophysics Data System (ADS)

    Burgos, William D.; Borch, Thomas; Troyer, Lyndsay D.; Luan, Fubo; Larson, Lance N.; Brown, Juliana F.; Lambson, Janna; Shimizu, Masayuki

    2012-01-01

    Three low-pH coal mine drainage (CMD) sites in central Pennsylvania were studied to determine similarities in sediment composition, mineralogy, and morphology. Water from one site was used in discontinuous titration/neutralization experiments to produce Fe(III) minerals by abiotic oxidative hydrolysis for comparison with the field precipitates that were produced by biological low-pH Fe(II) oxidation. Even though the hydrology and concentration of dissolved metals of the CMD varied considerably between the three field sites, the mineralogy of the three iron mounds was very similar. Schwertmannite was the predominant mineral precipitated at low-pH (2.5-4.0) along with lesser amounts of goethite. Trace metals such as Zn, Ni and Co were only detected at μmol/g concentrations in the field sediments, and no metals (other than Fe) were removed from the CMD at any of the field sites. Metal cations were not lost from solution in the field because of unfavorable electrostatic attraction to the iron mound minerals. Ferrihydrite was the predominant mineral formed by abiotic neutralization (pH 4.4-8.4, 4 d aging) with lesser amounts of schwertmannite and goethite. In contrast to low-pH precipitation, substantial metal removal occurred in the neutralized CMD. Al was likely removed as hydrobasaluminite and Al(OH) 3, and as a co-precipitate into schwertmannite or ferrihydrite. Zn, Ni and Co were likely removed via adsorption onto and co-precipitation into the freshly formed Fe and Al solids. Mn was likely removed by co-precipitation and, at the highest final pH values, as a Mn oxide. Biological low-pH Fe(II) oxidation can be cost-effectively used to pre-treat CMD and remove Fe and acidity prior to conventional neutralization techniques. A further benefit is that solids formed under these conditions may be of industrial value because they do not contain trace metal or metalloid contaminants.

  3. Synthesis of Zn–Fe layered double hydroxides via an oxidation process and structural analysis of products

    SciTech Connect

    Morimoto, Kazuya; Tamura, Kenji; Anraku, Sohtaro; Sato, Tsutomu; Suzuki, Masaya; Yamada, Hirohisa

    2015-08-15

    The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. The product derived from the synthesis employing Fe(II) was found to transition to a Zn–Fe(III) layered double hydroxides phase following oxidation process. In contrast, the product obtained with Fe(III) did not contain a layered double hydroxides phase, but rather consisted of simonkolleite and hydrous ferric oxide. It was determined that the valency of the Fe reagent used in the initial synthesis affected the generation of the layered double hydroxides phase. Fe(II) species have ionic radii and electronegativities similar to those of Zn, and therefore are more likely to form trioctahedral hydroxide layers with Zn species. - Graphical abstract: The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. - Highlights: • Iron valency affected the generation of Zn–Fe layered double hydroxides. • Zn–Fe layered double hydroxides were successfully synthesized using Fe(II). • Fe(II) species were likely to form trioctahedral hydroxide layers with Zn species.

  4. Effect Of Inorganic, Synthetic And Naturally Occurring Chelating Agents On Fe(II) Mediated Advanced Oxidation Of Chlorophenols

    EPA Science Inventory

    This study examines the feasibility and application of Advanced Oxidation Technologies (AOTs) for the treatment of chlorophenols that are included in US EPA priority pollutant list. A novel class of sulfate/hydroxyl radical-based homogeneous AOTs (Fe(II)/PS, Fe(II)/PMS, Fe(II)/H...

  5. Doped LaFeO3 as SOFC Catalysts: Control of Oxygen Mobility Oxidation Activity

    SciTech Connect

    N Lakshminarayanan; J Kuhn; S Rykov; J Millet; U Ozkan; T Rao; J Smedley; E Wang; E Muller; et al.

    2011-12-31

    The bulk structure and surface properties of Fe-based perovskite-type oxides with the formula La{sub 0.6}Sr{sub 0.4}Co{sub y}Fe{sub 1-y}O{sub 3-{delta}} for y = 0.1, 0.2, and 0.3 have been investigated. The properties were found to strongly depend upon Co content, temperature, and environment. The materials were selected due to their potential use as solid oxide fuel cell cathodes. The intermediate Co loading formed oxygen vacancies most easily and several other properties including oxidation activity and surface sites showed a similar non-linear trend. Trends are related to a possible transition in electronic structure. Activity for oxidation of methane, oxygen storage and chemical compatibility was shown to be superior to that of the La{sub 0.6}Sr{sub 0.4}MnO{sub 3}.

  6. The life cycle of iron Fe(III) oxide: impact of fungi and bacteria

    NASA Astrophysics Data System (ADS)

    Bonneville, Steeve

    2014-05-01

    Iron oxides are ubiquitous reactive constituents of soils, sediments and aquifers. They exhibit vast surface areas which bind a large array of trace metals, nutrients and organic molecules hence controlling their mobility/reactivity in the subsurface. In this context, understanding the "life cycle" of iron oxide in soils is paramount to many biogeochemical processes. Soils environments are notorious for their extreme heterogeneity and variability of chemical, physical conditions and biological agents at play. Here, we present studies investigating the role of two biological agents driving iron oxide dynamics in soils, root-associated fungi (mycorrhiza) and bacteria. Mycorrhiza filaments (hypha) grow preferentially around, and on the surface of nutrient-rich minerals, making mineral-fungi contact zones, hot-spots of chemical alteration in soils. However, because of the microscopic nature of hyphae (only ~ 5 µm wide for up to 1 mm long) and their tendency to strongly adhere to mineral surface, in situ observations of this interfacial micro-environment are scarce. In a microcosm, ectomycorrhiza (Paxillus involutus) was grown symbiotically with a pine tree (Pinus sylvestris) in the presence of freshly-cleaved biotite under humid, yet undersaturated, conditions typical of soils. Using spatially-resolved ion milling technique (FIB), transmission electron microscopy and spectroscopy (TEM/STEM-EDS), synchrotron based X-ray microscopy (STXM), we were able to quantify the speciation of Fe at the biotite-hypha interface. The results shows that substantial oxidation of biotite structural-Fe(II) into Fe(III) subdomains occurs at the contact zone between mycorrhiza and biotite. Once formed, iron(III) oxides can reductively dissolve under suboxic conditions via several abiotic and microbial pathways. In particular, they serve as terminal electron acceptors for the oxidation of organic matter by iron reducing bacteria. We aimed here to understand the role of Fe(III) mineral

  7. Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe5O6.

    PubMed

    Lavina, Barbara; Meng, Yue

    2015-06-01

    The iron-oxygen system is the most important reference of rocks' redox state. Even as minor components, iron oxides can play a critical role in redox equilibria, which affect the speciation of the fluid phases chemical differentiation, melting, and physical properties. Until our recent finding of Fe4O5, iron oxides were assumed to comprise only the polymorphs of FeO, Fe3O4, and Fe2O3. Combining synthesis at high pressure and temperature with microdiffraction mapping, we have identified yet another distinct iron oxide, Fe5O6. The new compound, which has an orthorhombic structure, was obtained in the pressure range from 10 to 20 GPa upon laser heating mixtures of iron and hematite at ~2000 K, and is recoverable to ambient conditions. The high-pressure orthorhombic iron oxides Fe5O6, Fe4O5, and h-Fe3O4 display similar iron coordination geometries and structural arrangements, and indeed exhibit coherent systematic behavior of crystallographic parameters and compressibility. Fe5O6, along with FeO and Fe4O5, is a candidate key minor phase of planetary interiors; as such, it is of major petrological and geochemical importance. We are revealing an unforeseen complexity in the Fe-O system with four different compounds-FeO, Fe5O6, Fe4O5, and h-Fe3O4-in a narrow compositional range (0.75 < Fe/O < 1.0). New, finely spaced oxygen buffers at conditions of the Earth's mantle can be defined. PMID:26601196

  8. Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe5O6

    PubMed Central

    Lavina, Barbara; Meng, Yue

    2015-01-01

    The iron-oxygen system is the most important reference of rocks’ redox state. Even as minor components, iron oxides can play a critical role in redox equilibria, which affect the speciation of the fluid phases chemical differentiation, melting, and physical properties. Until our recent finding of Fe4O5, iron oxides were assumed to comprise only the polymorphs of FeO, Fe3O4, and Fe2O3. Combining synthesis at high pressure and temperature with microdiffraction mapping, we have identified yet another distinct iron oxide, Fe5O6. The new compound, which has an orthorhombic structure, was obtained in the pressure range from 10 to 20 GPa upon laser heating mixtures of iron and hematite at ~2000 K, and is recoverable to ambient conditions. The high-pressure orthorhombic iron oxides Fe5O6, Fe4O5, and h-Fe3O4 display similar iron coordination geometries and structural arrangements, and indeed exhibit coherent systematic behavior of crystallographic parameters and compressibility. Fe5O6, along with FeO and Fe4O5, is a candidate key minor phase of planetary interiors; as such, it is of major petrological and geochemical importance. We are revealing an unforeseen complexity in the Fe-O system with four different compounds—FeO, Fe5O6, Fe4O5, and h-Fe3O4—in a narrow compositional range (0.75 < Fe/O < 1.0). New, finely spaced oxygen buffers at conditions of the Earth’s mantle can be defined. PMID:26601196

  9. Enhanced antibacterial activity of copper/copper oxide nanowires prepared by pulsed laser ablation in water medium

    NASA Astrophysics Data System (ADS)

    Swarnkar, R. K.; Pandey, J. K.; Soumya, K. K.; Dwivedi, P.; Sundaram, S.; Prasad, Sanjay; Gopal, R.

    2016-07-01

    Copper/copper oxide nanowires (NWs) are well known for its antibacterial activity against various pathogens. In the present study, we have shown the enhanced antibacterial activity of the NWs against gram-negative bacterial strains ( Escherichia coli, Pseudomonas aeruginosa and Salmonella typhi) and gram-positive bacterial strains ( Bacillus subtilis and Staphylococcus aureus). The increase in the activity is because of the shape and size of the colloidal NWs which were prepared at room temperature in a one-step process by pulsed laser ablation of copper metal target. The purity, shape and size of the colloidal NWs were well characterized by UV-visible absorption spectroscopy and transmission electron microscopy (TEM). The NWs were of diameters in the range of 15-30 nm and lengths ranging from 200 to 600 nm. The dose-dependent antibacterial activity of these NWs was found to be more effective against gram-negative bacteria compared to gram-positive bacteria. As gram-negative bacteria have thinner layer of cell wall made up of peptidoglycan possibly which makes them more susceptible to Cu/Cu2O NWs, Cu/Cu2O NWs can be a potent candidate to be used as bactericidal or as growth inhibitor.

  10. Kinetics and mechanism of the oxidation process of two-component Fe-Al alloys

    NASA Technical Reports Server (NTRS)

    Przewlocka, H.; Siedlecka, J.

    1982-01-01

    The oxidation process of two-component Fe-Al alloys containing up to 7.2% Al and from 18 to 30% Al was studied. Kinetic measurements were conducted using the isothermal gravimetric method in the range of 1073-1223 K and 1073-1373 K for 50 hours. The methods used in studies of the mechanism of oxidation included: X-ray microanalysis, X-ray structural analysis, metallographic analysis and marker tests.

  11. Draft Genome Sequence of a Potential Nitrate-Dependent Fe(II)-Oxidizing Bacterium, Aquabacterium parvum B6

    PubMed Central

    Zhang, Xiaoxin

    2016-01-01

    Aquabacterium parvum B6 is a potential nitrate-dependent Fe(II)-oxidizing bacterium. The genes related to its denitrifying mechanism and iron metabolisms were unknown. We present the draft genome of Aquabacterium parvum B6, which could provide further insight into the nitrate-dependent Fe(II)-oxidizing mechanism of strain B6. PMID:26823591

  12. Draft Genome Sequence of a Potential Nitrate-Dependent Fe(II)-Oxidizing Bacterium, Aquabacterium parvum B6.

    PubMed

    Zhang, Xiaoxin; Ma, Fang; Szewzyk, Ulrich

    2016-01-01

    Aquabacterium parvum B6 is a potential nitrate-dependent Fe(II)-oxidizing bacterium. The genes related to its denitrifying mechanism and iron metabolisms were unknown. We present the draft genome of Aquabacterium parvum B6, which could provide further insight into the nitrate-dependent Fe(II)-oxidizing mechanism of strain B6. PMID:26823591

  13. Coupled interactions between volatile activity and Fe oxidation state during arc crustal processes

    USGS Publications Warehouse

    Humphreys, Madeleine C.S.; Brooker, R; Fraser, D.C.; Burgisser, A; Mangan, Margaret T.; McCammon, C

    2015-01-01

    Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

  14. Facile One-pot Transformation of Iron Oxides from Fe2O3 Nanoparticles to Nanostructured Fe3O4@C Core-Shell Composites via Combustion Waves.

    PubMed

    Shin, Jungho; Lee, Kang Yeol; Yeo, Taehan; Choi, Wonjoon

    2016-01-01

    The development of a low-cost, fast, and large-scale process for the synthesis and manipulation of nanostructured metal oxides is essential for incorporating materials with diverse practical applications. Herein, we present a facile one-pot synthesis method using combustion waves that simultaneously achieves fast reduction and direct formation of carbon coating layers on metal oxide nanostructures. Hybrid composites of Fe2O3 nanoparticles and nitrocellulose on the cm scale were fabricated by a wet impregnation process. We demonstrated that self-propagating combustion waves along interfacial boundaries between the surface of the metal oxide and the chemical fuels enabled the release of oxygen from Fe2O3. This accelerated reaction directly transformed Fe2O3 into Fe3O4 nanostructures. The distinctive color change from reddish-brown Fe2O3 to dark-gray Fe3O4 confirmed the transition of oxidation states and the change in the fundamental properties of the material. Furthermore, it simultaneously formed carbon layers of 5-20 nm thickness coating the surfaces of the resulting Fe3O4 nanoparticles, which may aid in maintaining the nanostructures and improving the conductivity of the composites. This newly developed use of combustion waves in hybridized nanostructures may permit the precise manipulation of the chemical compositions of other metal oxide nanostructures, as well as the formation of organic/inorganic hybrid nanostructures. PMID:26902260

  15. Facile One-pot Transformation of Iron Oxides from Fe2O3 Nanoparticles to Nanostructured Fe3O4@C Core-Shell Composites via Combustion Waves

    PubMed Central

    Shin, Jungho; Lee, Kang Yeol; Yeo, Taehan; Choi, Wonjoon

    2016-01-01

    The development of a low-cost, fast, and large-scale process for the synthesis and manipulation of nanostructured metal oxides is essential for incorporating materials with diverse practical applications. Herein, we present a facile one-pot synthesis method using combustion waves that simultaneously achieves fast reduction and direct formation of carbon coating layers on metal oxide nanostructures. Hybrid composites of Fe2O3 nanoparticles and nitrocellulose on the cm scale were fabricated by a wet impregnation process. We demonstrated that self-propagating combustion waves along interfacial boundaries between the surface of the metal oxide and the chemical fuels enabled the release of oxygen from Fe2O3. This accelerated reaction directly transformed Fe2O3 into Fe3O4 nanostructures. The distinctive color change from reddish-brown Fe2O3 to dark-gray Fe3O4 confirmed the transition of oxidation states and the change in the fundamental properties of the material. Furthermore, it simultaneously formed carbon layers of 5–20 nm thickness coating the surfaces of the resulting Fe3O4 nanoparticles, which may aid in maintaining the nanostructures and improving the conductivity of the composites. This newly developed use of combustion waves in hybridized nanostructures may permit the precise manipulation of the chemical compositions of other metal oxide nanostructures, as well as the formation of organic/inorganic hybrid nanostructures. PMID:26902260

  16. Facile One-pot Transformation of Iron Oxides from Fe2O3 Nanoparticles to Nanostructured Fe3O4@C Core-Shell Composites via Combustion Waves

    NASA Astrophysics Data System (ADS)

    Shin, Jungho; Lee, Kang Yeol; Yeo, Taehan; Choi, Wonjoon

    2016-02-01

    The development of a low-cost, fast, and large-scale process for the synthesis and manipulation of nanostructured metal oxides is essential for incorporating materials with diverse practical applications. Herein, we present a facile one-pot synthesis method using combustion waves that simultaneously achieves fast reduction and direct formation of carbon coating layers on metal oxide nanostructures. Hybrid composites of Fe2O3 nanoparticles and nitrocellulose on the cm scale were fabricated by a wet impregnation process. We demonstrated that self-propagating combustion waves along interfacial boundaries between the surface of the metal oxide and the chemical fuels enabled the release of oxygen from Fe2O3. This accelerated reaction directly transformed Fe2O3 into Fe3O4 nanostructures. The distinctive color change from reddish-brown Fe2O3 to dark-gray Fe3O4 confirmed the transition of oxidation states and the change in the fundamental properties of the material. Furthermore, it simultaneously formed carbon layers of 5-20 nm thickness coating the surfaces of the resulting Fe3O4 nanoparticles, which may aid in maintaining the nanostructures and improving the conductivity of the composites. This newly developed use of combustion waves in hybridized nanostructures may permit the precise manipulation of the chemical compositions of other metal oxide nanostructures, as well as the formation of organic/inorganic hybrid nanostructures.

  17. Thin Oxides as a Cu Diffusion Barrier for NIF Be Ablator Capsules

    DOE PAGESBeta

    Youngblood, Kelly P.; Huang, H.; Xu, H. W.; Hayes, J.; Moreno, K. A.; Wu, J. J.; Nikroo, A.; Alford, C. A.; Hamza, A. V.; Kucheyev, S. O.; et al

    2013-03-01

    The NIF point design uses a five-layer capsule to modify the X-ray absorption in order to achieve optimized shock timing. A stepped copper dopant design defines the layer structure. The production of the capsule involves pyrolysis to remove the inner plastic mandrel. Copper atoms diffuse radially and azimuthally throughout the capsule during pyrolysis. This diffusion significantly diminishes the capsule performance during implosion. Thermal and coated oxide barrier layers employed between layers mitigate the diffusion of copper during the mandrel removal process. The copper atoms do not diffuse through this barrier during pyrolysis. A capsule fabrication method that produces a capsulemore » with a thin oxide layer will be discussed.« less

  18. Reductive Biotransformation of Fe in Shale-Limestone Saprolite Containing Fe(III) Oxides and Fe(II)/Fe(III) Phyllosilicates

    SciTech Connect

    Kukkadapu, Ravi K.; Zachara, John M.; Fredrickson, Jim K.; McKinley, James P.; Kennedy, David W.; Smith, Steven C.; Dong, Hailiang

    2006-07-15

    A <2.0-mm fraction of a mineralogically complex subsurface sediment containing goethite and Fe(II)/Fe(III) phyllosilicates was incubated with Shewanella putrefaciens (strain CN32) and lactate at circumneutral pH under anoxic conditions to investigate electron acceptor preference and the nature of the resulting biogenic Fe(II) fraction. Anthraquinone-2,6-disulfonate (AQDS), an electron shuttle, was included in select treatments to enhance bioreduction and subsequent biomineralization. The sediment was highly aggregated and contained two distinct clast populations: i) a highly weathered one with “sponge-like” internal porosity, large mineral crystallites, and Fe-containing micas, and ii) a dense, compact one with fine-textured Fe-containing illite and nano-sized goethite, as revealed by various forms of electron microscopic analyses. Approximately 10 to 15% of the Fe(III)TOT was bioreduced by CN32 over 60 d in media without AQDS, whereas 24% and 35% of the Fe(III)TOT was bioreduced by CN32 after 40 and 95 d in media with AQDS. Little or no Fe2+, Mn, Si, Al, and Mg were evident in aqueous filtrates after reductive incubation. Mössbauer measurements on the bioreduced sediments indicated that both goethite and phyllosilicate Fe(III) were partly reduced without bacterial preference. Goethite was more extensively reduced in the presence of AQDS whereas phyllosilicate Fe(III) reduction was not influenced by AQDS. Biogenic Fe(II) resulting from phyllosilicate Fe(III) reduction remained in a layer-silicate environment that displayed enhanced solubility in weak acid. The mineralogic nature of the goethite biotransformation product was not determined. Chemical and cryogenic Mössbauer measurements, however, indicated that the transformation product was not siderite, green rust, magnetite, Fe(OH)2, or Fe(II) adsorbed on phyllosilicate or bacterial surfaces. Several lines of evidence suggested that biogenic Fe(II) existed as surface associated phase on the residual goethite

  19. Characterization of Bimetallic Fe-Ru Oxide Nanoparticles Prepared by Liquid-Phase Plasma Method.

    PubMed

    Lee, Sung-Jin; Lee, Heon; Jeon, Ki-Joon; Park, Hyunwoong; Park, Young-Kwon; Jung, Sang-Chul

    2016-12-01

    The bimetallic Fe-Ru oxide nanoparticles were synthesized in the liquid-phase plasma (LPP) method which employed iron chloride and ruthenium chloride as precursors. The active species (OH·, Hα, Hβ, and O(I)) and the iron and ruthenium ions were observed in the plasma field created by the LPP process. The spherical-shaped bimetallic Fe-Ru oxide nanoparticles were synthesized by the LPP reaction, and the size of the particles was growing along with the progression of the LPP reaction. The synthesized bimetallic Fe-Ru oxide nanoparticles were comprised of Fe2O3, Fe3O4, RuO, and RuO2. Ruthenium had a higher reduction potential than iron and resulted in higher ruthenium composition in the synthesized bimetallic nanoparticles. The control of the molar ratio of the precursors in the reactant solution was found to be employed as a means to control the composition of the elements in bimetallic nanoparticles. PMID:27456502

  20. Characterization of Bimetallic Fe-Ru Oxide Nanoparticles Prepared by Liquid-Phase Plasma Method

    NASA Astrophysics Data System (ADS)

    Lee, Sung-Jin; Lee, Heon; Jeon, Ki-Joon; Park, Hyunwoong; Park, Young-Kwon; Jung, Sang-Chul

    2016-07-01

    The bimetallic Fe-Ru oxide nanoparticles were synthesized in the liquid-phase plasma (LPP) method which employed iron chloride and ruthenium chloride as precursors. The active species (OH·, Hα, Hβ, and OI) and the iron and ruthenium ions were observed in the plasma field created by the LPP process. The spherical-shaped bimetallic Fe-Ru oxide nanoparticles were synthesized by the LPP reaction, and the size of the particles was growing along with the progression of the LPP reaction. The synthesized bimetallic Fe-Ru oxide nanoparticles were comprised of Fe2O3, Fe3O4, RuO, and RuO2. Ruthenium had a higher reduction potential than iron and resulted in higher ruthenium composition in the synthesized bimetallic nanoparticles. The control of the molar ratio of the precursors in the reactant solution was found to be employed as a means to control the composition of the elements in bimetallic nanoparticles.

  1. Amphibolite-hosted Fe-Ti oxide mineralization of the Mitrashinci deposit, Eastern Macedonia

    NASA Astrophysics Data System (ADS)

    Spasovski, O.; Volkov, A. V.; Serafimovski, T.; Boev, B.

    2015-05-01

    The Mitrashinci deposit in Eastern Macedonia represents a unique type of metamorphosed Fe-Ti deposits. Fe-Ti oxide mineralization was identified in amphibolites from the metamorphic complex of the Serbo-Macedonian massif, which comprise two different stratigraphic horizons striking NW-SE. At Mitrashinci, Fe-Ti oxide mineralization is hosted by deeply buried amphibolites of the second stratigraphic horizon. Two types of amphibolites were recognized, almost barren garnet-biotite and mineralized garnet-cummingtonite. The mineralized zone (varying in thickness from 20 to 300 m) has been traced for 12 km within amphibolite host rocks. Several lens-like ore bodies hosted by garnet-cummingtonite amphibolites striking NW-SE have been intersected by mining operations at Kobilski Rid, Gromadna, Leskovica, Dolga Poljana, and Bliznakov Cukar. The contents of Fe and Ti vary greatly in the ores (13-23% and 4-9.1%, respectively). The ore bodies consist mainly of Fe-Ti oxides, such as magnetite, titanomagnetite, ilmenite, and hematite (martite), and minor pyrite, chalcopyrite, pyrrhotite, rutile, titanite, leucoxene, and goethite. The major ore minerals (ilmenite, titanomagnetite, and magnetite with a minor sulfide phase) were formed during the magmatic phase of ore deposition and were not considerably affected by subsequent polyphase metamorphism.

  2. Synthesis of Zn-Fe layered double hydroxides via an oxidation process and structural analysis of products

    NASA Astrophysics Data System (ADS)

    Morimoto, Kazuya; Tamura, Kenji; Anraku, Sohtaro; Sato, Tsutomu; Suzuki, Masaya; Yamada, Hirohisa

    2015-08-01

    The synthesis of Zn-Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. The product derived from the synthesis employing Fe(II) was found to transition to a Zn-Fe(III) layered double hydroxides phase following oxidation process. In contrast, the product obtained with Fe(III) did not contain a layered double hydroxides phase, but rather consisted of simonkolleite and hydrous ferric oxide. It was determined that the valency of the Fe reagent used in the initial synthesis affected the generation of the layered double hydroxides phase. Fe(II) species have ionic radii and electronegativities similar to those of Zn, and therefore are more likely to form trioctahedral hydroxide layers with Zn species.

  3. Mediated electron transfer between Fe(II) adsorbed onto hydrous ferric oxide and a working electrode.

    PubMed

    Klein, Annaleise R; Silvester, Ewen; Hogan, Conor F

    2014-09-16

    The redox properties of Fe(II) adsorbed onto mineral surfaces have been highly studied over recent years due to the wide range of environmental contaminants that react with this species via abiotic processes. In this work the reactivity of Fe(II) adsorbed onto hydrous ferric oxide (HFO) has been studied using ferrocene (bis-cyclopentadienyl iron(II); Fc) derivatives as electron shuttles in cyclic voltammetry (CV) experiments. The observed amplification of the ferrocene oxidation peak in CV is attributed to reaction between the electrochemically generated ferrocenium (Fc(+)) ion and adsorbed Fe(II) species in a catalytic process (EC' mechanism). pH dependence studies show that the reaction rate increases with Fe(II) adsorption and is maintained in the absence of aqueous Fe(2+), providing strong evidence that the electron transfer process involves the adsorbed species. The rate of reaction between Fc(+) and adsorbed Fe(II) increases with the redox potential of the ferrocene derivative, as expected, with bimolecular rate constants in the range 10(3)-10(5) M(-1) s(-1). The ferrocene-mediated electrochemical method described has considerable promise in the development of a technique for measuring electron-transfer rates in geochemical and environmental systems. PMID:25157830

  4. A NiFeCu alloy anode catalyst for direct-methane solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Zhu, Huaiyu; Yang, Guangming; Park, Hee Jung; Jung, Doh Won; Kwak, Chan; Shao, Zongping

    2014-07-01

    In this study, a new anode catalyst based on a NiFeCu alloy is investigated for use in direct-methane solid oxide fuel cells (SOFCs). The influence of the conductive copper introduced into the anode catalyst layer on the performance of the SOFCs is systematically studied. The catalytic activity for partial oxidation of methane and coking resistance tests are proposed with various anode catalyst layer materials prepared using different methods, including glycine nitrate process (GNP), physical mixing (PM) and impregnation (IMP). The surface conductivity tests indicate that the conductivities of the NiFe-ZrO2/Cu (PM) and NiFe-ZrO2/Cu (IMP) catalysts are considerably greater than that of NiFe-ZrO2/Cu (GNP), which is consistent with the SEM results. Among the three preparation methods, the cell containing the NiFe-ZrO2/Cu (IMP) catalyst layer performs best on CH4-O2 fuel, especially under reduced temperatures, because the coking resistance should be considered in real fuel cell conditions. The cell containing the NiFe-ZrO2/Cu (IMP) catalyst layer also delivers an excellent operational stability using CH4-O2 fuel for 100 h without any signs of decay. In summary, this work provides new alternative anode catalytic materials to accelerate the commercialization of SOFC technology.

  5. Mixed-valence iron minerals on Venus: Fe(2+)-Fe(3+) oxides and oxy-silicates formed by surface-atmosphere interactions

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.; Straub, Darcy W.

    1992-01-01

    Inferences from these investigations are that Fe(3+)-bearing minerals such as hematite magnesioferrite, acmite, and epidote are thermodynamically unstable, and that magnetite is the predominant mixed-valence iron oxide mineral on venus. Recently, the Fe(2+)-Fe(3+) silicate mineral laihunite was proposed to be a reaction product of olivine with the venusian atmosphere. This possibility is discussed further here. We suggest that other mixed-valence Fe(2+)-Fe(3+)-Oz-OH(-) silicates could also result from surface-atmosphere interactions on Venus. Topics discussed include the following: (1) conversion of hematite to magnetite; (2) stability of laihunite; (3) the possible existence of oxy-amphiboles and oxy-micas on Venus; and (4) other mixed-valence Fe(2+)-Fe(3+) silicates likely to exist on Venus.

  6. Nondestructive covalent functionalization of carbon nanotubes by selective oxidation of the original defects with K2FeO4

    NASA Astrophysics Data System (ADS)

    Zhang, Zhao-yang; Xu, Xue-cheng

    2015-08-01

    Chemical oxidation is still the major approach to the covalent functionalization of carbon nanotubes (CNTs). Theoretically, the defects on CNTs are more reactive than skeletal hexagons and should be preferentially oxidized, but conventional oxidation methods, e.g., HNO3/H2SO4 treatment, have poor reaction selectivity and inevitably consume the Cdbnd C bonds in the hexagonal lattices, leading to structural damage, π-electrons loss and weight decrease. In this work, we realized the nondestructive covalent functionalization of CNTs by selective oxidation of the defects. In our method, potassium ferrate K2FeVIO4 was employed as an oxidant for CNTs in H2SO4 medium. The CNT samples, before and after K2FeO4/H2SO4 treatment, were characterized with colloid dispersibility, IR, Raman spectroscopy, FESEM and XPS. The results indicated that (i) CNTs could be effectively oxidized by Fe (VI) under mild condition (60 °C, 3 h), and hydrophilic CNTs with abundant surface sbnd COOH groups were produced; and (ii) Fe (VI) oxidation of CNTs followed a defect-specific oxidation process, that is, only the sp3-hybridized carbon atoms on CNT surface were oxidized while the Cdbnd C bonds remained unaffected. This selective/nondestructive oxidation afforded oxidized CNTs in yields of above 100 wt%. This paper shows that K2FeO4/H2SO4 is an effective, nondestructive and green oxidation system for oxidative functionalization of CNTs and probably other carbon materials as well.

  7. ADVANCED EXPERIMENTAL ANALYSIS OF CONTROLS ON MICROBIAL FE(III) OXIDE REDUCTION

    EPA Science Inventory

    Fe(III) oxides are ubiquitous components of soils, sediments, and subsurface materials, and are one of the most important sorbents for heavy metals, radionuclides, organic contaminants and organic/metal co-contaminants in the subsurface. These compounds can serve as electron sink...

  8. FINAL REPORT. ADVANCED EXPERIMENTAL ANALYSIS OF CONTROLS ON MICROBIAL FE(III) OXIDE REDUCTION

    EPA Science Inventory

    The objectives of this research project were to refine existing models of microbiological and geochemical controls on Fe(III) oxide reduction, using laboratory reactor systems which mimic to varying degrees the physical and chemical conditions of the subsurface. Novel experimenta...

  9. OXIDATION OF ALCOHOLS OVER FE3+/MONTMORILLONITE-K10 USING HYDROGEN PEROXIDE

    EPA Science Inventory

    Oxidation of various primary and secondary alcohols is studied in liquid phase at atmospheric pressure over Fe3+/montmorillonite-K10 catalyst prepared by ion-exchange method at a pH of 4 in an environmentally friendly protocol using hydrogen peroxide. The catalyst and the method ...

  10. MegaOhm extraordinary Hall effect in oxidized CoFeB

    NASA Astrophysics Data System (ADS)

    Kopnov, G.; Gerber, A.

    2016-07-01

    We report on the development of controllably oxidized CoFeB ferromagnetic films demonstrating the extraordinary Hall effect (EHE) resistivity exceeding 1 Ω cm and magnetic field sensitivity up to 106 Ω/T. Such EHE resistivity is four orders of magnitude higher than that previously observed in ferromagnetic materials, while sensitivity is two orders larger than the best of semiconductors.

  11. Constraints on biotic and abiotic role in the formation of Fe-Si oxides from the PACMANUS hydrothermal field

    NASA Astrophysics Data System (ADS)

    Yang, Baoju; Zeng, Zhigang; Qi, Haiyan; Wang, Xiaoyuan; Ma, Yao; Rong, Kunbo

    2015-12-01

    Fe-Si oxide deposits were recovered from the PACMANUS (Papua New Guinea-Australia-Canada-Manus) hydrothermal field in Eastern Manus basin. Samples were loose and fragile. Optical and scanning electron microscopy showed that the samples had abundant rod-like or twisted filamentous and granular structures. Electron probe microanalysis revealed that these filaments and grains were mainly composed of Fe and Si. The presence of spherical grains on the surface of the filaments suggests the intergrowth of biotic and abiotic reactions. Biotic and abiotic kinetics competition always exists in the redox gradient. Based on the physico-chemical conditions of PACMANUS hydrothermal fluids, we calculated a strict abiotic oxidation rate of Fe2+ to Fe3+, which is approximately 0.0123 g/min. If the fluids had been erupting consistently and the concentration of Fe2+ was constant, 3.232 kg per year of Fe would be deposited in this vent. The amount of Fe oxides around the studied vent was larger than the amount determined by strict abiotic kinetic calculation. Bacteria may also play an important role in Fe oxidation. A mesh-like microenvironment constructed by biogenic filaments ensured adequate Fe2+ and low oxygen content for the growth of bacteria. Moreover, this structure promoted the deposition of abiotic Fe-Si oxides.

  12. Na-ion Storage Performances of FeSex and Fe2O3 Hollow Nanoparticles-Decorated Reduced Graphene Oxide Balls prepared by Nanoscale Kirkendall Diffusion Process

    PubMed Central

    Park, Gi Dae; Cho, Jung Sang; Lee, Jung-Kul; Kang, Yun Chan

    2016-01-01

    Uniquely structured FeSex-reduced graphene oxide (rGO) composite powders, in which hollow FeSex nanoparticles are uniformly distributed throughout the rGO matrix, were prepared by spray pyrolysis applying the nanoscale Kirkendall diffusion process. Iron oxide-rGO composite powders were transformed into FeSex-rGO composite powders by a two-step post-treatment process. Metallic Fe nanocrystals formed during the first-step post-treatment process were transformed into hollow FeSex nanoparticles during the selenization process. The FeSex-rGO composite powders had mixed crystal structures of FeSe and FeSe2 phases. A rGO content of 33% was estimated from the TG analysis of the FeSex-rGO composite powders. The FeSex-rGO composite powders had superior sodium-ion storage properties compared to those of the Fe2O3-rGO composite powders with similar morphological characteristics. The discharge capacities of the FeSex- and Fe2O3-rGO composite powders for the 200th cycle at a constant current density of 0.3 A g−1 were 434 and 174 mA h g−1, respectively. The FeSex-rGO composite powders had a high discharge capacity of 311 mA h g−1 for the 1000th cycle at a high current density of 1 A g−1. PMID:26928312

  13. Mechanism of inhibition of NiFe hydrogenase by nitric oxide.

    PubMed

    Ceccaldi, Pierre; Etienne, Emilien; Dementin, Sébastien; Guigliarelli, Bruno; Léger, Christophe; Burlat, Bénédicte

    2016-04-01

    Hydrogenases reversibly catalyze the oxidation of molecular hydrogen and are inhibited by several small molecules including O2, CO and NO. In the present work, we investigate the mechanism of inhibition by NO of the oxygen-sensitive NiFe hydrogenase from Desulfovibrio fructosovorans by coupling site-directed mutagenesis, protein film voltammetry (PFV) and EPR spectroscopy. We show that micromolar NO strongly inhibits NiFe hydrogenase and that the mechanism of inhibition is complex, with NO targeting several metallic sites in the protein. NO reacts readily at the NiFe active site according to a two-step mechanism. The first and faster step is the reversible binding of NO to the active site followed by a slower and irreversible transformation at the active site. NO also induces irreversible damage of the iron-sulfur centers chain. We give direct evidence of preferential nitrosylation of the medial [3Fe-4S] to form dinitrosyl-iron complexes. PMID:26827939

  14. Australasian microtektites from Antarctica: XAS determination of the Fe oxidation state

    NASA Astrophysics Data System (ADS)

    Giuli, Gabriele; Cicconi, Maria Rita; Eeckhout, Sigrid Griet; Pratesi, Giovanni; Paris, Eleonora; Folco, Luigi

    2014-04-01

    The Fe oxidation state and coordination number of 29 impact glass spherules recently recovered from the Transantarctic Mountains (Antarctica) have been determined by X-ray absorption near edge structure (XANES) spectroscopy. Based on geochemical, isotopic, and fission track data, these spherules are considered as microtektites from the Australasian tektite/microtektite strewn field. Their find location is the farthest so far discovered from the possible source crater region, and their alkali content is the lowest compared with other published data on Australasian microtektite glasses. The Fe3+/(Fe2++Fe3+) ratio, determined from the analysis of the pre-edge peak energy position and integrated intensity, is below 0.1 (±0.04) for all the samples, and is comparable to that of most tektites and microtektites from the Australasian strewn field. Also, the pre-edge peak integrated intensity, which is sensitive to the average Fe coordination geometry, is comparable to that of other Australasian microtektites reported in the literature. The agreement of the Fe oxidation state and coordination number, between the Transantarctic Mountain microtektites (TAM) and the Australasian tektites and microtektites, further confirms the impact origin of these glass spherules and provides an independent suggestion that they represent a major extension southeastward of the Australasian strewn field. The fact that similar redox conditions are observed in tektites and microtektites within the Australasian strewn field regardless of the distance from the source crater area (up to approximately 11000 km) could be an important constraint for better understanding the different processes affecting microtektite formation and transport. The fact that the Fe oxidation state of microtektites does not increase with distance, as in the case of North American microtektites, means that thermal and redox histories of Australasian and TAM microtektites could differ significantly from those of North

  15. Tumor Ablation and Nanotechnology

    PubMed Central

    Manthe, Rachel L.; Foy, Susan P.; Krishnamurthy, Nishanth; Sharma, Blanka; Labhasetwar, Vinod

    2010-01-01

    Next to surgical resection, tumor ablation is a commonly used intervention in the treatment of solid tumors. Tumor ablation methods include thermal therapies, photodynamic therapy, and reactive oxygen species (ROS) producing agents. Thermal therapies induce tumor cell death via thermal energy and include radiofrequency, microwave, high intensity focused ultrasound, and cryoablation. Photodynamic therapy and ROS producing agents cause increased oxidative stress in tumor cells leading to apoptosis. While these therapies are safe and viable alternatives when resection of malignancies is not feasible, they do have associated limitations that prevent their widespread use in clinical applications. To improve the efficacy of these treatments, nanoparticles are being studied in combination with nonsurgical ablation regimens. In addition to better thermal effect on tumor ablation, nanoparticles can deliver anticancer therapeutics that show synergistic anti-tumor effect in the presence of heat and can also be imaged to achieve precision in therapy. Understanding the molecular mechanism of nanoparticle-mediated tumor ablation could further help engineer nanoparticles of appropriate composition and properties to synergize the ablation effect. This review aims to explore the various types of nonsurgical tumor ablation methods currently used in cancer treatment and potential improvements by nanotechnology applications. PMID:20866097

  16. Carbohydrate oxidation coupled to Fe(III) reduction, a novel form of anaerobic metabolism.

    PubMed

    Coates, J D; Councell, T; Ellis, D J; Lovley, D R

    1998-12-01

    An isolate, designated GC-29, that could incompletely oxidize glucose to acetate and carbon dioxide with Fe(III) serving as the electron acceptor was recovered from freshwater sediments of the Potomac River, Maryland. This metabolism yielded energy to support cell growth. Strain GC-29 is a facultatively anaerobic, gram-negative motile rod which, in addition to glucose, also used sucrose, lactate, pyruvate, yeast extract, casamino acids or H2 as alternative electron donors for Fe(III) reduction. Stain GC-29 could reduce NO3(-), Mn(IV), U(VI), fumarate, malate, S2O3(2-), and colloidal S0 as well as the humics analog, 2,6-anthraquinone disulfonate. Analysis of the almost complete 16S rRNA sequence indicated that strain GC-29 belongs in the Shewanella genus in the epsilon subdivision of the Proteobacteria. The name Shewanella saccharophilia is proposed. Shewanella saccharophilia differs from previously described fermentative microorganisms that metabolize glucose with the reduction of Fe(III) because it transfers significantly more electron equivalents to Fe(III); acetate and carbon dioxide are the only products of glucose metabolism; energy is conserved from Fe(III) reduction; and glucose is not metabolized in the absence of Fe(III). The metabolism of organisms like S. saccharophilia may account for the fact that glucose is metabolized primarily to acetate and carbon dioxide in a variety of sediments in which Fe(III) reduction is the terminal electron accepting process. PMID:16887653

  17. Carbohydrate oxidation coupled to Fe(III) reduction, a novel form of anaerobic metabolism

    USGS Publications Warehouse

    Coates, J.D.; Councell, T.; Ellis, D.J.; Lovley, D.R.

    1998-01-01

    An isolate, designated GC-29, that could incompletely oxidize glucose to acetate and carbon dioxide with Fe(III) serving as the electron acceptor was recovered from freshwater sediments of the Potomac River, Maryland. This metabolism yielded energy to support cell growth. Strain GC-29 is a facultatively anaerobic, Gram-negative motile rod which, in addition to glucose, also used sucrose, lactate, pyruvate, yeast extract, casamino acids or H2 as alternative electron donors for Fe(III) reduction. Stain GC-29 could reduce NO-3, Mn(IV), U(VI), fumarate, malate, S2O32-, and colloidal S0 as well as the humics analog, 2,6-anthraquinone disulfonate. Analysis of the almost complete 16S rRNA sequence indicated that strain GC-29 belongs in the Shewanella genus in the epsilon subdivision of the Proteobacteria. The name Shewanella saccharophilia is proposed. Shewanella saccharophilia differs from previously described fermentative microorganisms that metabolize glucose with the reduction of Fe(III) because it transfers significantly more electron equivalents to Fe(III); acetate and carbon dioxide are the only products of glucose metabolism; energy is conserved from Fe(III) reduction; and glucose is not metabolized in the absence of Fe(III). The metabolism of organisms like S. saccharophilia may account for the fact that glucose is metabolized primarily to acetate and carbon dioxide in a variety of sediments in which Fe(III) reduction is the terminal electron accepting process.

  18. Ultrasound assisted ambient temperature synthesis of ternary oxide Ag MO 2 ( M=Fe, Ga)

    NASA Astrophysics Data System (ADS)

    Nagarajan, R.; Tomar, Nobel

    2009-06-01

    The application of ultrasound for the synthesis of ternary oxide Ag MO 2 ( M=Fe, Ga) was investigated. Crystalline α-AgFeO 2 was obtained from the alkaline solutions of silver and iron hydroxides by sonication for 40 minutes. α-AgFeO 2 was found to absorb optical radiation in the 300-600 nm range as shown by diffuse reflectance spectroscopy. The Raman spectrum of α-AgFeO 2 exhibited two bands at 345 and 638 cm -1. When β-NaFeO 2 was sonicated with aqueous silver nitrate solution for 60 minutes, β-AgFeO 2 possessing orthorhombic structure was obtained as the ion-exchanged product. The Raman spectrum of β-AgFeO 2 showed four strong bands at 295, 432, 630 and 690 cm -1. Sonication of β-NaGaO 2 with aqueous silver nitrate solution for 60 minutes resulted in olive green colored, α-AgGaO 2. The diffuse reflectance spectrum and the EDX analysis confirmed that the ion-exchange through sonication was complete. The Raman spectrum of α-AgGaO 2 had weak bands at 471 and 650 cm -1.

  19. Free energies of (Co, Fe, Ni, Zn)Fe2O4 spinels and oxides in water at high temperatures and pressure from density functional theory: results for stoichiometric NiO and NiFe2O4 surfaces

    NASA Astrophysics Data System (ADS)

    O'Brien, C. J.; Rák, Z.; Brenner, D. W.

    2013-11-01

    A set of effective chemical potentials (ECPs) are derived that connect energies of (Co, Fe, Ni, Zn)Fe2O4 spinels and oxides calculated at 0 K from density functional theory (DFT) to free energies in high temperature and pressure water. The ECPs are derived and validated by solving a system of linear equations that combine DFT and experimental free energies for NiO, ZnO, Fe2O3, Fe3O4, FeO(OH), CoFe2O4, ZnFe2O4, NiFe2O4 and H2O. To connect to solution phase chemistry, a set of ECPs are also derived for solvated Ni2+, Zn2+, Fe2+ and Fe3+ ions using an analogous set of linear equations and the solid ECPs. The ECPs are used to calculate free energies of low index stoichiometric surfaces of nickel oxide (NiO) and nickel ferrite (NiFe2O4) in water as a function of temperature from 300 to 600 K at a pressure of 155 bar. Surface denuding at high temperatures is predicted, the implications of which for the formation of oxide corrosion products on heat transfer surfaces in light-water nuclear reactors are discussed.

  20. Magnetic Fe3O4 nanoparticle catalyzed chemiluminescence for detection of nitric oxide in living cells.

    PubMed

    Wang, Huiliang; Li, Mei; Wang, Bing; Wang, Meng; Kurash, Ibrahim; Zhang, Xiangzhi; Feng, Weiyue

    2016-08-01

    Direct and real-time measurement of nitric oxide (NO) in biological media is very difficult due to its transient nature. Fe3O4 nanoparticles (nanoFe3O4) because of their unique catalytic activities have attracted much attention as catalysts in a variety of organic and inorganic reactions. In this work, we have developed a magnetic Fe3O4 nanoparticle-based rapid-capture system for real-time detection of cellular NO. The basic principle is that the nanoFe3O4 can catalyze the decomposition of H2O2 in the system to generate superoxide anion (O2 (·-)) and the O2 (·-) can serve as an effective NO(·) trapping agent yielding peroxynitrite oxide anion, ONOO(-). Then the concentration of NO in cells can be facilely determined via peroxynitrite-induced luminol chemiluminescence. The linear range of the method is from 10(-4) to 10(-8) mol/L, and the detection of limit (3σ, n = 11) is as low as 3.16 × 10(-9) mol/L. By using this method, the NO concentration in 0.1 and 0.5 mg/L LPS-stimulated BV2 cells was measured as 4.9 and 11.3 μM, respectively. Surface measurements by synchrotron X-ray photoelectron spectroscopy (SRXPS) and scanning transmission X-ray microscopy (STXM) demonstrate the catalytic mechanism of the nanoFe3O4-based system is that the significantly excess Fe(II) exists on the surface of nanoFe3O4 and mediates the rapid heterogeneous electron transfer, thus presenting a new Fe2O3 phase on the surface. PMID:27289465

  1. Aluminum Coprecipitates with Fe (hydr)oxides: Does Isomorphous Substitution of Al3plus for Fe3plus in Goethite Occur

    SciTech Connect

    E Bazilevskaya; D Archibald; M Aryanpour; J Kubicki; C Martinez

    2011-12-31

    Iron (hydr)oxides are common in natural environments and typically contain large amounts of impurities, presumably the result of coprecipitation processes. Coprecipitation of Al with Fe (hydr)oxides occurs, for example, during alternating reduction-oxidation cycles that promote dissolution of Fe from Fe-containing phases and its re-precipitation as Fe-Al (hydr)oxides. We used chemical and spectroscopic analyses to study the formation and transformation of Al coprecipitates with Fe (hydr)oxides. In addition, periodic density functional theory (DFT) computations were performed to assess the structural and energetic effects of isolated or clustered Al atoms at 8 and 25 mol% Al substitution in the goethite structure. Coprecipitates were synthesized by raising the pH of dilute homogeneous solutions containing a range of Fe and Al concentrations (100% Fe to 100% Al) to 5. The formation of ferrihydrite in initial suspensions with {<=}20 mol% Al, and of ferrihydrite and gibbsite in initial suspensions with {>=}25 mol% Al was confirmed by infrared spectroscopic and synchrotron-based X-ray diffraction analyses. While base titrations showed a buffer region that corresponded to the hydrolysis of Fe in initial solutions with {<=}25 mol% Al, all of the Al present in these solutions was retained by the solid phases at pH 5, thus indicating Al coprecipitation with the primary Fe hydroxide precipitate. In contrast, two buffer regions were observed in solutions with 30 mol% Al (at pH {approx}2.25 for Fe{sup 3+} and at pH {approx}4 for Al{sup 3+}), suggesting the formation of Fe and Al (hydr)oxides as two separate phases. The Al content of initial coprecipitates influenced the extent of ferrihydrite transformation and of its transformation products as indicated by the presence of goethite, hematite and/or ferrihydrite in aged suspensions. DFT experiments showed that: (i) optimized unit cell parameters for Al-substituted goethites (8 and 25 Mol% Al) in clustered arrangement (i.e., the

  2. Structural, optical and photocatalytic properties of Fe and (Co, Fe) co-doped copper oxide spin coated films.

    PubMed

    El Sayed, A M; Shaban, Mohamed

    2015-10-01

    Copper oxide films with composition Cu1-x-yFexCoyO (where x⩽0.06 and y⩽0.03 in a molar ratio) and thickness of about 2 μm were spin coated onto ultrasonically cleaned glass substrates. These films were annealed at 500 °C in the air. XRD results show that films are CuO of polycrystalline and monoclinic structures without the detection of any Fe or Co traces. The average crystallite size of pure CuO is 20.44 nm reduced to 18.72 nm after Fe doping, then increased to 26.82 nm due to the co-doping with Co atoms. The optical band gap blue-shifted from 2.15 eV to 2.3 eV followed by red-shift to 2.15 eV after the Co incorporation. The influence of Fe doping and Co co-doping on the optical constants of CuO films as well as the photocatalytic removal of methylene blue (MB) dye is reported. The correlations between the structural modifications and the resultant optical properties are discussed. The obtained results of the fabricated system are compared with those of similar materials. PMID:25985128

  3. Hydrogen production by partial oxidation of methanol over gold supported on Fe2O3.

    PubMed

    Roselin, L Selva; Liao, Li-Mei; Ou, You-Chen; Chang, Feg-Wen

    2014-09-01

    Partial oxidation of methanol (POM) to produce hydrogen was investigated over Au/Fe2O3 catalysts. The catalysts were prepared by inverse co-precipitation method. The influence of catalyst synthesis parameters such as precipitant, gold loading, calcination temperature and reaction parameter such as reaction temperature on POM reaction to produce hydrogen were investigated. The catalysts have been characterized by means of TGA, BET, XRD, TEM, SEM-EDS and XPS analyses. TGA and DTGA profiles clearly indicate that minimum decomposition temperature required to obtain Fe2O3 in Au/Fe2O3 catalysts is 660 K. SEM-EDS analysis confirms that Au and Fe in Au/Fe2O3 are homogeneously distributed over the agglomerate. A detailed microstuctural characterization of Au/Fe2O3 sample by XRD, TEM and XPS analyses has shown that nanometer sized gold particles with oxidized gold species is in predominant amount in the uncalcined catalysts sample. The mean particle size and metallic state of gold particles increase with increasing calcination temperature. A highly active Au/Fe2O3 catalyst is obtained by using Na2CO3 as precipitant with lower gold loading and calcination at 673 K. The catalytic behavior of the Au/Fe2O3 catalyst is related not only to the gold but also to the chemical state of the support. The effect of reaction temperature on the catalytic performance of the Au/Fe2O3 catalysts was studied in the temperature range of 423 to 523 K. Oxygen conversion was complete through out the examined temperature range. Methanol conversion increased with rise in temperature and attains 100% at 503 K; Hydrogen selectivity increased with rise in reaction temperature up to 523 K and then dropped off. The overall reactions involved are methanol combustion, partial oxidation, steam reforming and decomposition. CO produced by methanol decomposition and/or by reverse water gas shift is subsequently transformed into CO2 and H2 by the water gas shift and/or CO oxidation. PMID:25924393

  4. Fe-Ca-phosphate, Fe-silicate, and Mn-oxide minerals in concretions from the Monterey Formation

    USGS Publications Warehouse

    Medrano, M.D.; Piper, D.Z.

    1997-01-01

    Concentrically zoned phosphatic-enriched concretions were collected at three sites from the Monterey Formation. The following minerals were identified: vivianite, lipscombite, rockbridgeite, leucophosphite, mitridatite, carbonate fluorapatite, nontronite, todorokite, and barite. The mineralogy of the concretions was slightly different at each of the three collection sites. None of the concretions contains all of the minerals, but the spatial distribution of minerals in individual concretions, overlapping mineralogies between different concretions, and the geochemical properties of the separate minerals suggest a paragenesis represented by the above order. Eh increased from the precipitation of vivianite to that of rockbridgeite/lipscombite. The precipitation of leucophosphite, then mitridatite, carbonate fluorapatite and todorokite/Fe-oxide indicates increasing pH. Concretion growth culminated with the precipitation of todorokite, a Mn oxide, and minor amounts of barite along microfractures. Conspicuously absent are Fe-sulfide and Mn-phosphate minerals. The concretions are hosted by finely laminated diatomite. The laminations exhibit little to no deformation around the concretions, requiring that the concretions formed after compaction. We interpret this sediment feature and the paragenesis as recording the evolving pore-water chemistry as the formation was uplifted into the fresh-ground-water zone.

  5. Zirconium doped nano-dispersed oxides of Fe, Al and Zn for destruction of warfare agents

    SciTech Connect

    Stengl, Vaclav; Houskova, Vendula; Bakardjieva, Snejana; Murafa, Nataliya; Marikova, Monika; Oplustil, Frantisek; Nemec, Tomas

    2010-11-15

    Zirconium doped nano dispersive oxides of Fe, Al and Zn were prepared by a homogeneous hydrolysis of the respective sulfate salts with urea in aqueous solutions. Synthesized metal oxide hydroxides were characterized using Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX). These oxides were taken for an experimental evaluation of their reactivity with sulfur mustard (HD or bis(2-chloroethyl)sulfide), soman (GD or (3,3'-Dimethylbutan-2-yl)-methylphosphonofluoridate) and VX agent (S-[2-(diisopropylamino)ethyl]-O-ethyl-methylphosphonothionate). The presence of Zr{sup 4+} dopant can increase both the surface area and the surface hydroxylation of the resulting doped oxides, decreases their crystallites' sizes thereby it may contribute in enabling the substrate adsorption at the oxide surface thus it can accelerate the rate of degradation of warfare agents. Addition of Zr{sup 4+} converts the product of the reaction of ferric sulphate with urea from ferrihydrite to goethite. We found out that doped oxo-hydroxides Zr-FeO(OH) - being prepared by a homogeneous hydrolysis of ferric and zirconium oxo-sulfates mixture in aqueous solutions - exhibit a comparatively higher degradation activity towards chemical warfare agents (CWAs). Degradation of soman or VX agent on Zr-doped FeO(OH) containing ca. 8.3 wt.% of zirconium proceeded to completion within 30 min.

  6. Melt inclusions in Fe oxide and phosphate tephra of El Laco volcano, Chile

    NASA Astrophysics Data System (ADS)

    Mungall, J. E.; Naslund, H. R.

    2009-05-01

    The El Laco volcano of northern Chile is noted for its controversial iron ore deposits, which some researchers regard as examples of iron oxide lava flows but others regard as epithermal deposits replacing pre-existing silicate lava flows. Lava flows with textures and structures typical of ordinary silicate lavas are composed entirely of magnetite. Unconsolidated Fe oxide block and ash deposits show fine air-fall stratification and bomb sags. It has always been unclear how Fe-oxide melts could have formed by liquid immiscibility from intermediate silicate magmas. Some kind of fluxing component would seem to be required. We have examined blocks and ash from El Laco in polished grain mounts prepared without water to prevent loss of water-soluble minerals. The ash component of the tephra is composed of black magnetite and hematite crystals and polycrystalline aggregates ranging in size from several micrometres to several millimetres, commonly coated by soft dark olive green material with local orange and yellow crusts. Rare large euhedra of hematite up to one or two cm in size are also observed. Ash particle morphologies include euhedral Fe oxide crystals and crystal fragments as well as irregularly shaped polycrystalline Fe oxide aggregates. Most oxide crystals and aggregates display fenestral textures and locally highly convoluted margins. Scanning electron microscopy (SEM) suplemented by standardless semiquantitative energy dispersive X-ray spectrometry (EDS) of the grain mounts show that the re-entrant cavities are partially or completely filled by aggregates of Fe phosphate (probably beraunite or dufrenite), Fe-oxide, silica, and monazite. Some ash particles are wholly or partially composed of fine-grained aggregates of the same phosphate-rich material. Ovoid cavities within some of the oxide ash particles are wholly or partially occupied by the same polymineralic assemblage as the external cavities but also include domains interpreted to be finely crystallized

  7. Oxidation of Fe-C alloys in the temperature range 600-852/sup 0/C

    SciTech Connect

    Malik, A.U.; Whittle, D.P.

    1981-12-01

    The oxidation behavior of Fe-C alloys in the temperature range 600-850/sup 0/C has been studied. CO/sub 2/ evolved during oxidation was measured using an infrared gas analyzer. The presence of C lowers the oxidation rate relative to that of pure Fe and this has been related to the rejection of carbon at the alloy-scale interface causing poor contact between scale and alloy. As a result, the scale contains a higher proportion of magnetite, which reduces its overall growth rate. Very little carbon is lost to the atmosphere. The ease with which the rejected carbon is incorporated into the alloy depends on the alloy structure.

  8. Biomineralization of lepidocrocite and goethite by nitrate-reducing Fe(II)-oxidizing bacteria: Effect of pH, bicarbonate, phosphate, and humic acids

    NASA Astrophysics Data System (ADS)

    Larese-Casanova, Philip; Haderlein, Stefan B.; Kappler, Andreas

    2010-07-01

    Fe(III) solid phases are the products of Fe(II) oxidation by Fe(II)-oxidizing bacteria, but the Fe(III) phases reported to form within growth experiments are, at times, poorly crystalline and therefore difficult to identify, possibly due to the presence of ligands (e.g., phosphate, carbonate) that complex iron and disrupt iron (hydr)oxide precipitation. The scope of this study was to investigate the influences of geochemical solution conditions (pH, carbonate, phosphate, humic acids) on the Fe(II) oxidation rate and Fe(III) mineralogy. Fe(III) mineral characterization was performed using 57Fe-Mössbauer spectroscopy and μ-X-ray diffraction after oxidation of dissolved Fe(II) within Mops-buffered cell suspensions of Acidovorax sp. BoFeN1, a nitrate-reducing, Fe(II)-oxidizing bacterium. Lepidocrocite (γ-FeOOH) (90%), which also forms after chemical oxidation of Fe(II) by dissolved O 2, and goethite (α-FeOOH) (10%) were produced at pH 7.0 in the absence of any strongly complexing ligands. Higher solution pH, increasing concentrations of carbonate species, and increasing concentrations of humic acids promoted goethite formation and caused little or no changes in Fe(II) oxidation rates. Phosphate species resulted in Fe(III) solids unidentifiable to our methods and significantly slowed Fe(II) oxidation rates. Our results suggest that Fe(III) mineralogy formed by bacterial Fe(II) oxidation is strongly influenced by solution chemistry, and the geochemical conditions studied here suggest lepidocrocite and goethite may coexist in aquatic environments where nitrate-reducing, Fe(II)-oxidizing bacteria are active.

  9. Uranium Immobilization through Fe(II) bio-oxidation: A Column study

    SciTech Connect

    Coates, John D.

    2009-09-14

    Current research on the bioremediation of heavy metals and radionuclides is focused on the ability of reducing organisms to use these metals as alternative electron acceptors in the absence of oxygen and thus precipitate them out of solution. However, many aspects of this proposed scheme need to be resolved, not the least of which is the time frame of the treatment process. Once treatment is complete and the electron donor addition is halted, the system will ultimately revert back to an oxic state and potentially result in the abiotic reoxidation and remobilization of the immobilized metals. In addition, the possibility exists that the presence of more electropositive electron acceptors such as nitrate or oxygen will also stimulate the biological oxidation and remobilization of these contaminants. The selective nitrate-dependent biooxidation of added Fe(II) may offer an effective means of “capping off” and completing the attenuation of these contaminants in a reducing environment making the contaminants less accessible to abiotic and biotic reactions and allowing the system to naturally revert to an oxic state. Our previous DOE-NABIR funded studies demonstrated that radionuclides such as uranium and cobalt are rapidly removed from solution during the biogenic formation of Fe(III)-oxides. In the case of uranium, X-ray spectroscopy analysis indicated that the uranium was in the hexavalent form (normally soluble) and was bound to the precipitated Fe(III)-oxides thus demonstrating the bioremediative potential of this process. We also demonstrated that nitrate-dependent Fe(II)- oxidizing bacteria are prevalent in the sediment and groundwater samples collected from sites 1 and 2 and the background site of the NABIR FRC in Oakridge, TN. However, all of these studies were performed in batch experiments in the laboratory with pure cultures and although a significant amount was learned about the microbiology of nitrate-dependent bio-oxidation of Fe(II), the effects of

  10. Phase transition of Fe oxides under reducing condition and its relation with the As behavior

    NASA Astrophysics Data System (ADS)

    Choi, S. H.; Kim, S. H.; Jeong, G. Y.; Kim, K.

    2014-12-01

    Fe oxides are very common in the earth's crust and easily transform into other minerals such as magnetite and siderite under reducing conditions by microbial reactions. It is well known that As concentrations in groundwater is strongly regulated by adsorption onto Fe oxides. Even though some studies have suggested that the formation of siderite can also control the As concentration, direct evidences are not sufficient. In this study, we performed microbial incubation experiments to see the phase transition of As-rich Fe oxides under anoxic condition and to see how the water As concentrations are controlled accordingly. Three experiments were performed by changing organic carbon concentrations. Natural groundwaters and yeast extracts were used for the sources of microorganisms and organic carbon. Seven reactors were prepared for each experiment and opened one by one to observe the changes of the water chemistry and solid phases for 60 days. The formation of magnetite was observed at the early stage of each experiment. Siderite was formed at the later stage only when the dissolved organic carbon concentrations were high (donor/accepter molar ratio = 1.5). Goethite and hematite, instead of siderite, were formed from the experiment using low organic carbon concentration (donor/accepter molar ratio = 0.75). It is likely that dissolved ferrous ion adsorbs onto the Fe oxides and recrystallizes into hematite and goethite when the DOC concentration was low. As concentrations were generally very low in the water (normally 10 ug/L) and we could not find any relations with the Fe minerals formed by anoxic microbial reactions, maybe due to high Fe oxide/water ratio of our experiments. The sequential extraction analysis indicated that most of the As in solids are mostly associated with Fe-oxides and organic matters. The As bound to carbonates were very low even in the precipitates containing siderite due to low As concentrations in the water where the siderite formed. Further

  11. Metagenomic Analyses of the Autotrophic Fe(II)-Oxidizing, Nitrate-Reducing Enrichment Culture KS.

    PubMed

    He, Shaomei; Tominski, Claudia; Kappler, Andreas; Behrens, Sebastian; Roden, Eric E

    2016-05-01

    Nitrate-dependent ferrous iron [Fe(II)] oxidation (NDFO) is a well-recognized chemolithotrophic pathway in anoxic sediments. The neutrophilic chemolithoautotrophic enrichment culture KS originally obtained from a freshwater sediment (K. L. Straub, M. Benz, B. Schink, and F. Widdel, Appl Environ Microbiol 62:1458-1460, 1996) has been used as a model system to study NDFO. However, the primary Fe(II) oxidizer in this culture has not been isolated, despite extensive efforts to do so. Here, we present a metagenomic analysis of this enrichment culture in order to gain insight into electron transfer pathways and the roles of different bacteria in the culture. We obtained a near-complete genome of the primary Fe(II) oxidizer, a species in the familyGallionellaceae, and draft genomes from its flanking community members. A search of the putative extracellular electron transfer pathways in these genomes led to the identification of a homolog of the MtoAB complex [a porin-multiheme cytochromecsystem identified in neutrophilic microaerobic Fe(II)-oxidizingSideroxydans lithotrophicusES-1] in aGallionellaceaesp., and findings of other putative genes involving cytochromecand multicopper oxidases, such as Cyc2 and OmpB. Genome-enabled metabolic reconstruction revealed that thisGallionellaceaesp. lacks nitric oxide and nitrous oxide reductase genes and may partner with flanking populations capable of complete denitrification to avoid toxic metabolite accumulation, which may explain its resistance to growth in pure culture. This and other revealed interspecies interactions and metabolic interdependencies in nitrogen and carbon metabolisms may allow these organisms to cooperate effectively to achieve robust chemolithoautotrophic NDFO. Overall, the results significantly expand our knowledge of NDFO and suggest a range of genetic targets for further exploration. PMID:26896135

  12. Green and Tunable Decoration of Graphene with Spherical Nanoparticles Based on Laser Ablation in Water: A Case of Ag Nanoparticle/Graphene Oxide Sheet Composites.

    PubMed

    He, Hui; Wang, Haibo; Li, Kai; Zhu, Jun; Liu, Jianshuang; Meng, Xiangdong; Shen, Xiaoshuang; Zeng, Xianghua; Cai, Weiping

    2016-02-23

    A simple and green strategy is presented to decorate graphene with nanoparticles, based on laser ablation of targets in graphene auqeous solution. Ag and graphene oxide (GO) are chosen as model materials. The surface of GO sheets is strongly anchored with spherical Ag nanoparticles. The density and size of the Ag nanoparticles can be easily tuned by laser ablation conditions. Further, the GO sheets can be decorated with other nanoparticles from simple metals or semiconductors to multicomponent hybrids. Additionally, the Ag nanoparticle/GO sheet colloids can be utilized as blocks to build three-dimensional structures, such as sandwich membranes by evaporation-induced self-assembly. These graphene-based composite materials could be very useful in catalysis, sensors, and nanodevices. Particularly, the Ag nanoparticle/GO sheet sandwich composite membranes exhibit excellent surface-enhanced Raman scattering performance and possess the huge potential in trace-detecting persistent organic pollutants in the environment. PMID:26840791

  13. Reactive Transport Modeling of Microbe-mediated Fe (II) Oxidation for Enhanced Oil Recovery

    NASA Astrophysics Data System (ADS)

    Surasani, V.; Li, L.

    2011-12-01

    Microbially Enhanced Oil Recovery (MEOR) aims to improve the recovery of entrapped heavy oil in depleted reservoirs using microbe-based technology. Reservoir ecosystems often contain diverse microbial communities those can interact with subsurface fluids and minerals through a network of nutrients and energy fluxes. Microbe-mediated reactions products include gases, biosurfactants, biopolymers those can alter the properties of oil and interfacial interactions between oil, brine, and rocks. In addition, the produced biomass and mineral precipitates can change the reservoir permeability profile and increase sweeping efficiency. Under subsurface conditions, the injection of nitrate and Fe (II) as the electron acceptor and donor allows bacteria to grow. The reaction products include minerals such as Fe(OH)3 and nitrogen containing gases. These reaction products can have large impact on oil and reservoir properties and can enhance the recovery of trapped oil. This work aims to understand the Fe(II) oxidation by nitrate under conditions relevant to MEOR. Reactive transport modeling is used to simulate the fluid flow, transport, and reactions involved in this process. Here we developed a complex reactive network for microbial mediated nitrate-dependent Fe (II) oxidation that involves both thermodynamic controlled aqueous reactions and kinetic controlled Fe (II) mineral reaction. Reactive transport modeling is used to understand and quantify the coupling between flow, transport, and reaction processes. Our results identify key parameter controls those are important for the alteration of permeability profile under field conditions.

  14. In-situ determination of the oxidation state of iron in Fe-bearing silicate melts

    NASA Astrophysics Data System (ADS)

    Courtial, P.; Wilke, M.; Potuzak, M.; Dingwell, D. B.

    2005-12-01

    Terrestrial lavas commonly contain up to 10 wt% of iron. Furthermore, rocks returned from the Moon indicate lunar lava containing up to 25 wt% of iron and planetary scientists estimated that the martian mantle has about 18 wt% of iron. An experimental challenge in dealing with Fe-bearing silicate melts is that the oxidation state, controlling the proportions of ferric and ferrous iron, is a function of composition, oxygen fugacity and temperature and may vary significantly. Further complications concerning iron originate from its potential to be either four-, six- or even five-fold coordinated in both valence states. Therefore, the oxidation state of iron was determined in air for various Fe-bearing silicate melts. Investigated samples were Na-disilicate (NS), one atmosphere anorthite-diopside eutectic (AD) and haplogranitic (HPG8) melts containing up to 20, 20 and 10 wt% of iron, respectively. XANES spectra at the Fe K-edge were collected for all the melts at beamline A1, HASYLAB, Hamburg, using a Si(111) 4-crystal monochromator. Spectra were collected for temperatures up to 1573 K using a Pt-Rh loop as heating device. The Fe oxidation state was determined from the centroid position of the pre-edge feature using the calibration of Wilke et al. (2004). XANES results suggest that oxidation state of iron does not change within error for NS melts with addition of Fe, while AD and HPG8 melts become more oxidised with increasing iron content. Furthermore, NS melts are well more oxidised than AD and HPG8 melts that exhibit relatively similar oxidation states for identical iron contents. The oxidation state of iron for NS melts appears to be slightly temperature-dependent within the temperature range investigated (1073-1573 K). However, this trend is stronger for AD and HPG8 melts. Assuming that glass reflects a picture of the homogeneous equilibria of the melt, the present in-situ Fe-oxidation states determined for these melts were compared to those obtained on quenched

  15. Metal Oxide Thin Film Growth by Laser Ablation and Its Applications in High Surface Area Photoanodes

    NASA Astrophysics Data System (ADS)

    Ghosh, Rudresh

    Thin films are widely used in various applications, including but not limited to simple reflective coatings for mirrors, electrodes for lithium batteries, conducting substrates for electronic circuits, gas sensors and solar cells. As the scope of their applications has widened over the years so has the need to obtain different structural motifs for thin films. A large variety of fabrication techniques are commonly employed to obtain these structures. Pulsed laser deposition (PLD) can be used to obtain films varying from extremely compact and only a few angstroms thick to micron thick porous structures. In this dissertation I introduce a model for predicting different structures as a function of laser parameters and deposition environments in a pulsed laser deposition system. This is followed by a comparison of simulated and experimentally obtained structures. I then use this model to obtain tailored structures suited for individual applications. One of the unique structures obtained using the PLD consists of vertically-aligned structures with nanoparticles as their building blocks. I investigate the superiority of this unique structure over random nanoparticle networks as photoanodes for titanium dioxide (TiO 2)-based dye-sensitized solar cells (DSSC). UV-Vis studies show that there is a 1.4 x enhancement of surface area for PLD-TiO2 photoanodes compared to the best sol-gel films. PLD-TiO2 incident photon to current efficiency (IPCE) values are comparable to 3 x thicker sol-gel films and nearly 92% absorbed photon to current efficiency (APCE) values have been observed for optimized structures. I also examine the suitability of PLD-synthesized niobium oxide (Nb2O5) and tantalum-doped titanium oxide (Ta: TiO2) as photoanode materials. For optimized PLD-Nb2 O5 based DSSCs IPCE values up to 40%, APCE values around 90% and power conversion efficiency of 2.41% were obtained. DSSCs made of PLD-Ta:TiO2 show enhanced photocurrents as well photo efficiency over those based

  16. Study of the effect of plasma-striking atmosphere on Fe-oxidation in thermal dc arc-plasma processing

    SciTech Connect

    Banerjee, I.; Khollam, Y. B.; Mahapatra, S. K.; Das, A. K.; Bhoraskar, S. V.

    2010-11-15

    The effect of plasma-striking atmosphere: air and air+Ar-gas on the crystallization of Fe-oxide phases was studied using dc thermal arc-plasma processing route. The powders were characterized by x-ray diffraction, vibrating sample magnetometry, transmission electron microscopy, and Moessbauer spectroscopy techniques. At room temperature and O{sub 2} rich atmosphere, arc-evaporated Fe{sup 2+} ions oxidize into either {gamma}-Fe{sub 2}O{sub 3} or Fe{sub 3}O{sub 4} depending upon the combining ratio of Fe with molecular O{sub 2}. Fe/O ratio could be adjusted using proper flow rate of Ar gas to crystallize the pure {gamma}-Fe{sub 2}O{sub 3}.

  17. Effects of Nickel on the Oxide/Metal Interface Morphology and Oxidation Rate During High-Temperature Oxidation of Fe-Cu-Ni Alloys

    NASA Astrophysics Data System (ADS)

    Yin, Lan; Balaji, Sukumar; Sridhar, Seetharaman

    2010-06-01

    Steel produced in an electric arc furnace (EAF) contains a high amount of Cu that causes a surface-cracking phenomenon called surface hot shortness. Ni reduces the risk for surface hot shortness, and this work focuses on investigating the following two phenomena caused by Ni during oxidation at 1150 °C for Fe-Cu-Ni alloys: (1) the decrease in oxidation rate and (2) the formation of a wavy liquid-Cu/oxide and of liquid-Cu/γ-iron (γFe) interfaces, which promote Cu occlusion into the scale. Thermogravimetry, scanning electron microscopy, and transmission electron microscopy-energy dispersive spectroscopy techniques were applied. A numerical model also was developed to explain the experimental results. High Ni contents cause higher liquid-Cu/γFe interface nickel concentrations and more potential for an interface breakdown. The decrease in oxidation rate by adding nickel can be explained qualitatively by the decrease in Fe cation transport through the wüstite layer.

  18. Inactivation of Aeromonas hydrophila by Fe(II)-related-radical generation in oxidizing groundwaters.

    PubMed Central

    Kersters, I; Verstraete, W

    1996-01-01

    The survival of Aeromonas hydrophila AWWX1 in filter-sterilized phreatic groundwaters was studied by using viable counts. Aeromonas counts rapidly decreased 2 to 3 log units in oxidizing raw groundwaters from Snellegem and Beernem, Belgium (Snellegem-raw and Beernem-raw, respectively), containing high concentrations of Fe2+ (460 to 1,070 microM). The rapid decline in viable counts of Aeromonas cells in the oxidizing raw groundwater of Snellegem was prevented by the addition of an Fe2+ chelator (2,2'-dipyridyl) or compounds (i.e., ascorbic acid and catalase) that act on toxic oxygen species. The results suggest that free radicals, generated spontaneously in oxidizing Fe2+-containing groundwaters, caused the inactivation of A. hydrophila AWWX1. Evidence that free radicals are generated under the given conditions was provided by the observation that propylphosphonic acid, a compound which is very susceptible to radicals, was degraded upon addition to these waters. A. hydrophila PWBS, Pseudomonas fluorescens P17, Spirillum strain NOX, and heterotrophs showed decreases in culturability in filter-sterilized Snellegem-raw water similar to that shown by A. hydrophila AWWX1. These findings indicate that free radicals generated in Fe2+-containing groundwaters upon aeration are capable of inactivating various bacterial species. PMID:8795217

  19. Electrochemical synthesis of new magnetic mixed oxides of Sr and Fe: Composition, magnetic properties, and microstructure

    SciTech Connect

    Amigo, R.; Asenjo, J.; Krotenko, E.; Torres, F.; Tejada, J.; Brillas, E.

    2000-02-01

    An electrochemical method for the preparation of magnetic nanoparticles of new Sr-Fe oxides is presented in this work. It consists of the electrolysis of nitrate or chloride solutions with Sr{sup 2+} and Fe{sup 3+} salts using commercial Fe electrodes. Magnetic materials are collected as precipitates from nitrate media in the pH range 1-3 and from chloride media within the pH range 1--12. The presence of 100--300 ppm aniline in acidic nitrate media yields a decrease in energy cost and particle size. Inductively coupled plasma analysis of materials and energy-dispersive X-ray spectrometry of single particles confirm that they are composed of mixed oxides of Sr and Fe. All synthesized materials crystallize as inverse cubic spinels, usually with intermediate structures between magnetite and maghemite. They are formed by nanoparticles with average sizes from 2 nm to {approximately} 50 nm, as observed by scanning electron microscopy. The electrogenerated mixed oxides have higher saturation magnetization, but lower remanent magnetization and coercive field, than commercial strontium hexaferrite with micrometric particle size.

  20. Designing polar and magnetic oxides: Zn2FeTaO6--in search of multiferroics.

    PubMed

    Li, Man-Rong; Stephens, Peter W; Retuerto, Maria; Sarkar, Tapati; Grams, Christoph P; Hemberger, Joachim; Croft, Mark C; Walker, David; Greenblatt, Martha

    2014-06-18

    Polar oxides are technically of great interest but difficult to prepare. Our recent discoveries predicted that polar oxides can be synthesized in the corundum-derivative A2BB'O6 family with unusually small cations at the A-site and a d(0) electron configuration ion at B'-site. When magnetic transition-metal ions are incorporated more interesting polar magnetic oxides can form. In this work we experimentally verified this prediction and prepared LiNbO3 (LN)-type polar magnetic Zn2FeTaO6 via high pressure and temperature synthesis. The crystal structure analysis indicates highly distorted ZnO6 and (Fe/Ta)O6 octahedra, and an estimated spontaneous polarization (PS) of ∼50 μC/cm(2) along the c-axis was obtained from point charge model calculations. Zn2Fe(3+)Ta(5+)O6 has a lower magnetic transition temperature (TN ∼ 22 K) than the Mn2FeTaO6 analogue but is less conductive. The dielectric and polarization measurements indicate a potentially switchable component. PMID:24841411

  1. Comparative genomics of freshwater Fe-oxidizing bacteria: implications for physiology, ecology, and systematics

    PubMed Central

    Emerson, David; Field, Erin K.; Chertkov, Olga; Davenport, Karen W.; Goodwin, Lynne; Munk, Christine; Nolan, Matt; Woyke, Tanja

    2013-01-01

    The two microaerophilic, Fe-oxidizing bacteria (FeOB) Sideroxydans ES-1 and Gallionella ES-2 have single circular chromosomes of 3.00 and 3.16 Mb that encode 3049 and 3006 genes, respectively. Multi-locus sequence analysis (MLSA) confirmed the relationship of these two organisms to one another, and indicated they may form a novel order, the Gallionellalaes, within the Betaproteobacteria. Both are adapted for chemolithoautotropy, including pathways for CO2-fixation, and electron transport pathways adapted for growth at low O2-levels, an important adaptation for growing on Fe(II). Both genomes contain Mto-genes implicated in iron-oxidation, as well as other genes that could be involved in Fe-oxidation. Nearly 10% of their genomes are devoted to environmental sensing, signal transduction, and chemotaxis, consistent with their requirement for growing in narrow redox gradients of Fe(II) and O2. There are important differences as well. Sideroxydans ES-1 is more metabolically flexible, and can utilize reduced S-compounds, including thiosulfate, for lithotrophic growth. It has a suite of genes for nitrogen fixation. Gallionella ES-2 contains additional gene clusters for exopolysaccharide production, and has more capacity to resist heavy metals. Both strains contain genes for hemerythrins and globins, but ES-1 has an especially high numbers of these genes that may be involved in oxygen homeostasis, or storage. The two strains share homology with the marine FeOB Mariprofundus ferrooxydans PV-1 in CO2 fixation genes, and respiratory genes. In addition, ES-1 shares a suite of 20 potentially redox active genes with PV-1, as well as a large prophage. Combined these genetic, morphological, and physiological differences indicate that these are two novel species, Sideroxydans lithotrophicus ES-1T (ATCC 700298T; JCM 14762; DSMZ 22444; NCMA B100), and Gallionella capsiferriformans ES-2T (ATCC 700299T; JCM 14763; DSMZ 22445; NCMA B101). PMID:24062729

  2. Fe(VI) as a Possible Oxidant on the Martian Surface

    NASA Technical Reports Server (NTRS)

    Tsapin, A. I.; Goldfeld, M. G.; McDonald, G. D.; Nealson, K. H.

    1999-01-01

    The essential findings of the three biological experiments (Gas Exchange, Labeled Released, and Pyrolitic Release) aboard the Viking Mars landers were the discovery of the presence of one or more strong oxidants on the Martian surface. The Gas Exchange experiments showed that wetting Martian soil leads to the evolution of oxygen, while in the Labeled Release experiment addition of a nutrient solution containing C-14-labeled formate, glycine, lactate, alanine, and glycolic acid induced CO2 evolution. A general consensus was reached that all data taken together pointed to the presence on Martian surface of a strong oxidant, or most probably several different types of oxidants. Several candidates have been proposed as oxidants, including superoxides, hydrogen peroxide, and iron oxides (possibly gamma-Fe2O3). Additional information is contained in the original extended abstract.

  3. Structure of Oxide Nanoparticles in Fe-16Cr MA/ODS Ferritic Steel

    SciTech Connect

    Hsiung, L; Fluss, M; Kimura, A

    2010-04-06

    Oxide nanoparticles in Fe-16Cr ODS ferritic steel fabricated by mechanical alloying (MA) method have been examined using high-resolution transmission electron microscopy (HRTEM) techniques. A partial crystallization of oxide nanoparticles was frequently observed in as-fabricated ODS steel. The crystal structure of crystalline oxide particles is identified to be mainly Y{sub 4}Al{sub 2}O{sub 9} (YAM) with a monoclinic structure. Large nanoparticles with a diameter larger than 20 nm tend to be incoherent and have a nearly spherical shape, whereas small nanoparticles with a diameter smaller than 10 nm tend to be coherent or semi-coherent and have faceted boundaries. The oxide nanoparticles become fully crystallized after prolonged annealing at 900 C. These results lead us to propose a three-stage formation mechanism of oxide nanoparticles in MA/ODS steels.

  4. Preparation of a novel graphene oxide/Fe-Mn composite and its application for aqueous Hg(II) removal.

    PubMed

    Tang, Jingchun; Huang, Yao; Gong, Yanyan; Lyu, Honghong; Wang, Qilin; Ma, Jianli

    2016-10-01

    A novel graphene oxide/Fe-Mn (GO/Fe-Mn) composite was synthesized (molar ratio of Fe/Mn=3/1 and mass ratio of Fe/GO=1/7.5) and investigated for the sorption characteristics and mechanisms of aqueous mercury (Hg(2+)) as well as the biological effects to wheat and rice. Characterization tests showed that Fe-Mn oxides were impregnated onto GO sheets in an amorphous form through oxygen-containing functional groups (i.e., CO, epoxy COC, carboxyl OCO, and CO) and π-π interactions. GO/Fe-Mn possessed large surface area, surface enhanced Raman scattering with more sp(3) defects, and greater thermal stability than GO. XPS analysis revealed that Fe2O3, FeOOH, MnO2, MnOOH, and MnO were the dominant metal oxides in GO/Fe-Mn. Pseudo-second-order kinetic model and Sips isotherm model fitted well with the sorption kinetic and isotherm data. The maximum sorption capacity for mercury was 32.9mg/g. Ligand exchange and surface complexation were the dominant mechanisms for mercury removal. GO/Fe-Mn greatly reduced the bioavailability of mercury to wheat and rice, even promoted the seedling growth. This work suggests that GO/Fe-Mn can be used as an effective and environmental-friendly adsorbent in heavy metal remediation. PMID:27232726

  5. Fe(II)-mediated reduction and repartitioning of structurally incorporated Cu, Co, and Mn in iron oxides.

    PubMed

    Frierdich, Andrew J; Catalano, Jeffrey G

    2012-10-16

    The reduction of trace elements and contaminants by Fe(II) at Fe(III) oxide surfaces is well documented. However, the effect of aqueous Fe(II) on the fate of redox-active trace elements structurally incorporated into iron oxides is unknown. Here, we investigate the fate of redox-active elements during Fe(II)-activated recrystallization of Cu-, Co-, and Mn-substituted goethite and hematite. Enhanced release of Cu, Co, and Mn to solution occurs upon exposure of all materials to aqueous Fe(II) relative to reactions in Fe(II)-free fluids. The quantity of trace element release increases with pH when Fe(II) is present but decreases with increasing pH in the absence of Fe(II). Co and Mn release from goethite is predicted well using a second-order kinetic model, consistent with the release of redox-inactive elements such as Ni and Zn. However, Cu release and Co and Mn release from hematite require the sum of two rates to adequately model the kinetic data. Greater uptake of Fe(II) by Cu-, Co-, and Mn-substituted iron oxides relative to analogues containing only redox-inactive elements suggests that net Fe(II) oxidation occurs. Reduction of Cu, Co, and Mn in all materials following reaction with Fe(II) at pHs 7.0-7.5 is confirmed by X-ray absorption near-edge structure spectroscopy. This work shows that redox-sensitive elements structurally incorporated within iron oxides are reduced and repartitioned into fluids during Fe(II)-mediated recrystallization. Such abiotic reactions likely operate in tandem with partial microbial and abiotic iron reduction or during the migration of Fe(II)-containing fluids, mobilizing structurally bound contaminants and micronutrients in aquatic systems. PMID:22970760

  6. Zeta-Fe2O3 – A new stable polymorph in iron(III) oxide family

    PubMed Central

    Tuček, Jiří; Machala, Libor; Ono, Shigeaki; Namai, Asuka; Yoshikiyo, Marie; Imoto, Kenta; Tokoro, Hiroko; Ohkoshi, Shin-ichi; Zbořil, Radek

    2015-01-01

    Iron(III) oxide shows a polymorphism, characteristic of existence of phases with the same chemical composition but distinct crystal structures and, hence, physical properties. Four crystalline phases of iron(III) oxide have previously been identified: α-Fe2O3 (hematite), β-Fe2O3, γ-Fe2O3 (maghemite), and ε-Fe2O3. All four iron(III) oxide phases easily undergo various phase transformations in response to heating or pressure treatment, usually forming hexagonal α-Fe2O3, which is the most thermodynamically stable Fe2O3 polymorph under ambient conditions. Here, from synchrotron X-ray diffraction experiments, we report the formation of a new iron(III) oxide polymorph that we have termed ζ-Fe2O3 and which evolved during pressure treatment of cubic β-Fe2O3 ( space group) at pressures above 30 GPa. Importantly, ζ-Fe2O3 is maintained after pressure release and represents the first monoclinic Fe2O3 polymorph (I2/a space group) that is stable at atmospheric pressure and room temperature. ζ-Fe2O3 behaves as an antiferromagnet with a Néel transition temperature of ~69 K. The complex mechanism of pressure-induced transformation of β-Fe2O3, involving also the formation of Rh2O3-II-type Fe2O3 and post-perovskite-Fe2O3 structure, is suggested and discussed with respect to a bimodal size distribution of precursor nanoparticles. PMID:26469883

  7. Mechanosynthesis and magnetic properties of nanocrystalline LaFeO{sub 3} using different iron oxides

    SciTech Connect

    Cristobal, A.A. Botta, P.M.; Bercoff, P.G.; Porto Lopez, J.M.

    2009-05-06

    The synthesis of the orthoferrite LaFeO{sub 3} using high-energy ball-milling of La{sub 2}O{sub 3} and Fe{sub 3}O{sub 4} or {alpha}-Fe{sub 2}O{sub 3} oxides and subsequent thermal treatments of resulting powders was studied. The phase evolution during the mechanical treatment was analyzed by X-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM). Also, magnetic properties of the obtained materials were measured at room temperature by vibrating sample magnetometry (VSM). From 30 min of mechanochemical activation the gradual disappearance of reactants and the formation of LaFeO{sub 3} were observed. For both reactive mixtures the reaction was completed after 3 h of milling. Magnetic hysteresis loops of these mechanoactivated samples showed a significant ferromagnetic component in LaFeO{sub 3}. This behavior was interpreted on the basis of a spin-canting effect induced by the mechanochemical treatment. Thermal treatments allowed the relaxation of the distorted structure, resulting in the formation of the conventional antiferromagnetic LaFeO{sub 3} phase.

  8. Electronic Structure and Chemistry of Iron-Based Metal Oxide Nanostructured Materials: A NEXAFS Investigation of BiFeO3, Bi2Fe4O9, α-Fe2O3, γ-Fe2O3, and Fe/Fe3O4

    SciTech Connect

    Park,T.; Sambasivan, S.; Fischer, D.; Yoon, W.; Misewich, J.; Wong, S.

    2008-01-01

    We present a systematic and detailed near edge X-ray absorption fine structure (NEXAFS) experimental investigation of the electronic structure and chemistry of iron-based metal oxide nanostructured (FeMONS) materials including BiFeO3, Bi2Fe4O9, a-Fe2O3, ?-Fe2O3, and Fe/Fe3O4. Correlations of the electronic structure and structural chemistry of these intriguing nanomaterials are presented, ranging from the nano to the bulk scale. In this work, variations in the shape, position, and intensity of the O K-edge and Fe L-edge NEXAFS spectra have been analyzed in terms of electronic structure and surface chemistry of the FeMONS materials as compared with that of the bulk. We hypothesize that surface imperfection and surface strain anisotropies in nanoparticles induce distortion and site inequivalency of the oxygen Oh sites around the Fe ion located close to the surface, resulting in an increase in the degree of multiplicity as well as in nonstoichiometric effects in FeMONS materials.

  9. Transparent ferromagnetic and semiconducting behavior in Fe-Dy-Tb based amorphous oxide films

    PubMed Central

    Taz, H.; Sakthivel, T.; Yamoah, N. K.; Carr, C.; Kumar, D.; Seal, S.; Kalyanaraman, R.

    2016-01-01

    We report a class of amorphous thin film material comprising of transition (Fe) and Lanthanide metals (Dy and Tb) that show unique combination of functional properties. Films were deposited with different atomic weight ratio (R) of Fe to Lanthanide (Dy + Tb) using electron beam co-evaporation at room temperature. The films were found to be amorphous, with grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy studies indicating that the films were largely oxidized with a majority of the metal being in higher oxidation states. Films with R = 0.6 were semiconducting with visible light transmission due to a direct optical band-gap (2.49 eV), had low resistivity and sheet resistance (7.15 × 10−4 Ω-cm and ~200 Ω/sq respectively), and showed room temperature ferromagnetism. A metal to semiconductor transition with composition (for R < 11.9) also correlated well with the absence of any metallic Fe0 oxidation state in the R = 0.6 case as well as a significantly higher fraction of oxidized Dy. The combination of amorphous microstructure and room temperature electronic and magnetic properties could lead to the use of the material in multiple applications, including as a transparent conductor, active material in thin film transistors for display devices, and in spin-dependent electronics. PMID:27298196

  10. Transparent ferromagnetic and semiconducting behavior in Fe-Dy-Tb based amorphous oxide films

    NASA Astrophysics Data System (ADS)

    Taz, H.; Sakthivel, T.; Yamoah, N. K.; Carr, C.; Kumar, D.; Seal, S.; Kalyanaraman, R.

    2016-06-01

    We report a class of amorphous thin film material comprising of transition (Fe) and Lanthanide metals (Dy and Tb) that show unique combination of functional properties. Films were deposited with different atomic weight ratio (R) of Fe to Lanthanide (Dy + Tb) using electron beam co-evaporation at room temperature. The films were found to be amorphous, with grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy studies indicating that the films were largely oxidized with a majority of the metal being in higher oxidation states. Films with R = 0.6 were semiconducting with visible light transmission due to a direct optical band-gap (2.49 eV), had low resistivity and sheet resistance (7.15 × 10‑4 Ω-cm and ~200 Ω/sq respectively), and showed room temperature ferromagnetism. A metal to semiconductor transition with composition (for R < 11.9) also correlated well with the absence of any metallic Fe0 oxidation state in the R = 0.6 case as well as a significantly higher fraction of oxidized Dy. The combination of amorphous microstructure and room temperature electronic and magnetic properties could lead to the use of the material in multiple applications, including as a transparent conductor, active material in thin film transistors for display devices, and in spin-dependent electronics.

  11. Transparent ferromagnetic and semiconducting behavior in Fe-Dy-Tb based amorphous oxide films.

    PubMed

    Taz, H; Sakthivel, T; Yamoah, N K; Carr, C; Kumar, D; Seal, S; Kalyanaraman, R

    2016-01-01

    We report a class of amorphous thin film material comprising of transition (Fe) and Lanthanide metals (Dy and Tb) that show unique combination of functional properties. Films were deposited with different atomic weight ratio (R) of Fe to Lanthanide (Dy + Tb) using electron beam co-evaporation at room temperature. The films were found to be amorphous, with grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy studies indicating that the films were largely oxidized with a majority of the metal being in higher oxidation states. Films with R = 0.6 were semiconducting with visible light transmission due to a direct optical band-gap (2.49 eV), had low resistivity and sheet resistance (7.15 × 10(-4) Ω-cm and ~200 Ω/sq respectively), and showed room temperature ferromagnetism. A metal to semiconductor transition with composition (for R < 11.9) also correlated well with the absence of any metallic Fe(0) oxidation state in the R = 0.6 case as well as a significantly higher fraction of oxidized Dy. The combination of amorphous microstructure and room temperature electronic and magnetic properties could lead to the use of the material in multiple applications, including as a transparent conductor, active material in thin film transistors for display devices, and in spin-dependent electronics. PMID:27298196

  12. Preliminary study of heavy metal pollution from Fe-Al oxides in Peihuang Creek, North Taiwan

    NASA Astrophysics Data System (ADS)

    Lai, B.

    2012-12-01

    Tatun Volcano Group (TVG) is not active since late Pleistocene but the post-volcanic activities, such as hot spring and sulfur gas, still widespread around the volcano province. Peihuang Creek is the main watershed system in TVG. The creek water is characterized by higher temperature, low pH values (3.0-4.5) and high SO4 content (60-400 ppm) due to the mixing of hotspring. This would promote the geochemical interaction between water and andesitic rocks and results in waters with highly enriched iron, aluminum and silica. These elements prefer to form suspended colloidal particles in water and adsorb heavy metals. Once the pH of water increases under oxidation condition, the colloid would precipitate in the form of ochre colored powder on the riverbed. The previous study reports that the arsenic content can reach as high as hundreds ppm. It is very important to evaluate the desorption behavior of heavy metals, especially for the study area with highly developed agriculture. For the preliminary analysis, five samples of ochre colored powder were sampled along the creek. The results of XRF demonstrate that the powder is mainly composed of iron, aluminum and silica, which is Fe-Al hydroxide. The iron content of Fe-Al hydroxide decreases from 63% to 25% while the aluminum and silica contents gradually increase from 5% to 20% and from 9% to 30%, respectively. To evaluate the desorption of heavy metals, the sequential extraction procedure was conducted. In the first step for determining leachable metals, the Fe-Al oxides were extracted with deionized water in the room temperature for one week. All of the metals are in ppb level except copper. For determining reducible phase, Step 2 used reagent solution of 0.5 mol/L hydroxylamine hydrochloride, which was adjusted to pH=2 with ultrapure nitric acid, for one week. The extracted chromium, arsenic, lead and copper are in the dangerous level of tens to hundreds ppm. It is believed that only very small amounts of heavy metals

  13. Effects of temperature on rates and mineral products of microbial Fe(II) oxidation by Leptothrix cholodnii at microaerobic conditions

    NASA Astrophysics Data System (ADS)

    Vollrath, Susann; Behrends, Thilo; Koch, Christian Bender; Cappellen, Philippe Van

    2013-05-01

    Oxygen concentrations are important in constraining the geochemical niche of neutrophilic iron oxidizers. However, other factors like temperature may affect the competition between microbial and abiotic Fe(II) oxidation and may cause community changes. Here, rates and mineral products of Fe(II) oxidation (initial concentration 150 μmol Fe(II)/l) by the Fe(II) oxidizing bacterial strain Leptothrix cholodnii Appels were compared to those of abiotic oxidation in the temperature range 11-37 °C. Experiments were carried out in a batch reactor at 12-13 μmol O2/l (0.92-1% O2 saturation), pH 7 and, for the microbial experiments, a cell density of around 108 cells/ml. The iron precipitates formed at the different temperatures were characterized by SEM, XRD, FTIR and Mössbauer spectroscopy. Abiotic and microbial Fe(II) oxidation proceeded in two stages. During the initial stage, rates of microbial oxidation exhibited a temperature optimum curve. In contrast, the temperature dependency of abiotic Fe(II) oxidation rate followed the Arrhenius equation. As a consequence, microbial oxidation rates were about 10 times higher compared to the abiotic oxidation at 30 °C. During the second stage, microbial and abiotic rates and their temperature dependencies were similar. Independent of temperature or presence of bacteria, lepidocrocite and ferrihydrite were identified as reaction products, but the characteristics of the precipitates differed. At 37 °C, less lepidocrocite was precipitated in microbial and abiotic experiments due to high oxidation rates. Abiotic oxidation produced larger lepidocrocite crystals mixed with smaller, less crystalline oxides. Large crystals were absent in the microbial products, possibly due to growth inhibition of the minerals by EPS substances. Nevertheless, Mössbauer spectra revealed a better crystal structure of the smaller, microbial precipitates compared to the abiotically formed oxides.

  14. Mechanism of β-FeSi2 precipitates growth-and-dissolution and pyramidal defects' formation during oxidation of Fe-contaminated silicon wafers

    NASA Astrophysics Data System (ADS)

    De Luca, Anthony; Texier, Michaël; Portavoce, Alain; Burle, Nelly; Grosjean, Catherine; Morata, Stéphane; Michel, Fabrice

    2015-03-01

    Fe-implanted Si-wafers have been oxidized at 900 °C and 1100 °C in order to investigate the behaviour of Fe atoms at the growing SiO2/Si interface and the impact on the integrity of microelectronic devices of an involuntary Fe contamination before or during the oxidation process. As-implanted and oxidized wafers have been characterized using secondary ion mass spectroscopy, atom probe tomography, and high-resolution transmission electron microscopy. Experimental results were compared to calculated implantation profiles and simulated images. Successive steps of iron disilicide precipitation and oxidation were evidenced during the silicon oxidation process. The formation of characteristic pyramidal-shaped defects, at the SiO2/Si interface, was notably found to correlate with the presence of β-FeSi2 precipitates. Taking into account the competitive oxidation of these precipitates and of the surrounding silicon matrix, dynamic mechanisms are proposed to model the observed microstructural evolution of the SiO2/Si interface, during the growth of the silicon oxide layer.

  15. Mechanism of β-FeSi{sub 2} precipitates growth-and-dissolution and pyramidal defects' formation during oxidation of Fe-contaminated silicon wafers

    SciTech Connect

    De Luca, Anthony; Texier, Michaël Portavoce, Alain; Burle, Nelly; Grosjean, Catherine; Morata, Stéphane; Michel, Fabrice

    2015-03-21

    Fe-implanted Si-wafers have been oxidized at 900 °C and 1100 °C in order to investigate the behaviour of Fe atoms at the growing SiO{sub 2}/Si interface and the impact on the integrity of microelectronic devices of an involuntary Fe contamination before or during the oxidation process. As-implanted and oxidized wafers have been characterized using secondary ion mass spectroscopy, atom probe tomography, and high-resolution transmission electron microscopy. Experimental results were compared to calculated implantation profiles and simulated images. Successive steps of iron disilicide precipitation and oxidation were evidenced during the silicon oxidation process. The formation of characteristic pyramidal-shaped defects, at the SiO{sub 2}/Si interface, was notably found to correlate with the presence of β-FeSi{sub 2} precipitates. Taking into account the competitive oxidation of these precipitates and of the surrounding silicon matrix, dynamic mechanisms are proposed to model the observed microstructural evolution of the SiO{sub 2}/Si interface, during the growth of the silicon oxide layer.

  16. Towards a Predictive Thermodynamic Model of Oxidation States of Uranium Incorporated in Fe (hydr) oxides

    SciTech Connect

    Bagus, Paul S.

    2013-01-01

    The theoretical research in this project has been directed toward the interpretation of core-level spectroscopies for systems relevant to the project. For the initial efforts, the focus of our theoretical simulations has been the interpretation of laboratory and synchrotron X-Ray Photoemission Spectra, XPS. In more recent efforts, an increasing emphasis has been placed on developing transparent understandings of X-Ray Adsorption Spectra, XAS . For the XAS, the principal concern is for the near-edge features, either just below or just above, an ionization limit or edge, which are described as Near-Edge X-Ray Adsorption Fine Structure, NEXAFS. In particular, a priority has involved the analysis and interpretation of XPS and NEXAFS spectra, especially of Fe and U systems, as measured by our PNNL collaborators. The overall objective of our theoretical studies is to establish connections between features of the spectra and their origin in the electronic structure of the materials. The efforts for the analysis of XPS have been reviewed in a paper by the PI, C. J. Nelin, and E. S. Ilton from PNNL on “The interpretation of XPS spectra: Insights into materials properties”, Surf. Sci. Reports, 68, 273 (2013). Two materials properties of special interest have been the degree of ionicity and the character of the covalent bonding in a range of oxides formed with transition metal, lanthanide, and actinide cations. Since the systems treated have electrons in open shells, it has been necessary to determine the energetics and the character of the angular momentum coupling of the open shell electrons. In particular, we have established methods for the treatment of the “intermediate coupling” which arises when the system is between the limit of Russell-Saunders multiplets, and the limit of j-j coupling where the spin-orbit splittings of single electrons dominate. A recent paper by the PI, and M. J. Sassi, and K. M. Rosso, (both at PNNL) “Intermediate Coupling For Core

  17. Structure and contrast in scanning tunneling microscopy of oxides: FeO monolayer on Pt(111)

    SciTech Connect

    Galloway, H.C.; Sautet, P.; Salmeron, M.

    1996-10-01

    We applied electron-scattering quantum-chemistry theory to investigate the origin of contrast in scanning tunneling microscopy images of iron oxide grown on Pt(111). We show that (a) image contrast and surface topography are not directly related; (b) the maxima in the images occur over O positions for Pt tips and over Fe positions for O-terminated tips; (c) the short-range corrugation is always due to O {ital p}{sub {ital z}} orbitals, with a small but important contribution of Fe; and (d) the state that carriers most of the tunneling current is located near the Fermi level and is made mostly of O {ital p}{sub {ital z}} and Fe 3{ital d}{sub {ital z}2} orbitals. {copyright} {ital 1996 The American Physical Society.}

  18. CaFeAl mixed oxide derived heterogeneous catalysts for transesterification of soybean oil to biodiesel.

    PubMed

    Lu, Yongsheng; Zhang, Zaiwu; Xu, Yunfeng; Liu, Qiang; Qian, Guangren

    2015-08-01

    CaAl layered double oxides (LDO) were prepared by co-precipitation and calcined at 750°C, and then applied to biodiesel production by transesterification reaction between methanol and soybean oil. Compared with characteristics of CaFe/LDO and CaAl/LDO, CaFeAl/LDO had the best performance based on prominent catalytic activity and stability, and achieved over 90% biodiesel yield, which stayed stable (over 85%) even after 8 cycles of reaction. The optimal catalytic reaction condition was 12:1M-ratio of methanol/oil, reaction temperatures of 60°C, 270rpm stirring rate, 60min reaction time, and 6% weight-ratio of catalyst/oil. In addition, the CaFeAl/LDO catalyst is insoluble in both methanol and methyl esters and can be easily separated for further reaction, turning it into an excellent alternative for biodiesel synthesis. PMID:25740001

  19. Analysis of surface potential and magnetic properties of Fe3O4/graphene oxide nanocomposites

    NASA Astrophysics Data System (ADS)

    Mishra, Amodini; Mohanty, Tanuja

    2016-05-01

    Nanocomposite of magnetite/graphene oxide (Fe3O4/GO) has been synthesized by co-precipitation method. The phase formation of the magnetite nanoparticles (Fe3O4 NPs) was confirmed by X-ray diffraction (XRD) analysis. Effect of Fe3O4 NPs on the Raman spectra and on the surface potential of GO has been analyzed. Due to incorporation of NPs, change in the characteristic Raman peaks and also on the surface potential of GO is observed. Transmission electron microscopic (TEM) study has been carried out for surface morphology. Magnetic property measurement was carried out by using physical property measurement system (PPMS) at two different temperatures (30 K and 300K).

  20. One-pot synthesis of NiFe layered double hydroxide/reduced graphene oxide composite as an efficient electrocatalyst for electrochemical and photoelectrochemical water oxidation

    NASA Astrophysics Data System (ADS)

    Youn, Duck Hyun; Park, Yoon Bin; Kim, Jae Young; Magesh, Ganesan; Jang, Youn Jeong; Lee, Jae Sung

    2015-10-01

    As an efficient non-precious metal catalyst for oxygen evolution reaction (OER) in electrochemical and photoelectrochemical water splitting, NiFe layered double hydroxide (LDH)/reduced graphene oxide (NiFe/RGO) composite is synthesized by a simple solvothermal method in one-pot. NiFe LDHs are uniformly deposited on RGO layers of high electrical conductivity and large surface area. In electrochemical water splitting, NiFe/RGO shows superior OER performance compared to bare NiFe and reference IrO2 with a lower benchmark η10 value (required overpotential to drive 10 mA cm-2) of 0.245 V. Furthermore, NiFe/RGO substantially increases the performance of a hematite photoanode in photoelectrochemical water oxidation, demonstrating its potential as an OER co-catalyst for photoelectrodes.

  1. Ablative system

    NASA Technical Reports Server (NTRS)

    Gray, V. H. (Inventor)

    1973-01-01

    A carrier liquid containing ablative material bodies is connected to a plenum chamber wall with openings to a high temperature environment. The liquid and bodies pass through the openings of the wall to form a self replacing ablative surface. The wall is composed of honeycomb layers, spheres containing ablative whiskers or wads, and a hardening catalyst for the carrier liquid. The wall also has woven wicks of ablative material fibers that extend through the wall openings and into plenum chamber which contains the liquid.

  2. Biogeochemistry of Fe and Tc Reduction and Oxidation in FRC Sediment

    SciTech Connect

    John M. Zachara; James K. Fredrickson; Ravi K. Kukkadapu; Steven C. Smith; David W. Kennedy

    2004-03-17

    The objectives are: (1) To rigorously characterize the distribution of Fe(II) and Fe(III) in FRC sediment. (2) To identify changes to Fe(II)/Fe(III) distribution and concentration resulting from DIRB activity. (3) To determine the dependence of Tc(VII) reduction rate on biogenic Fe(II) and it's forms. (4) To establish tendency of Tc(IV) and biogenic Fe(II) to oxidize and their effects on Tc immobilization. The mineralogic and chemical properties of the pristine, bioreduced, and chemically extracted FRC sediments were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), X-ray microscopy (XRM, at the PNC-CAT beamline at APS), Moessbauer spectroscopy, and scanning and transmission electron microscopy with lattice fringe imaging. Chemical extraction included dithionite-citrate-bicarbonate (DCB), acid ammonium oxalate (AAO), and hydroxylamine hydrochloride (HAH). The FRC sediment was incubated under anoxic conditions with the facultative dissimilatory metal-reducing bacterium Shewanella putrefaciens, strain CN32 in defined aqueous solutions/media with bicarbonate and PIPES buffers for time periods exceeding 75 d. Lactate was used as the electron donor. Aqueous and sorbed Fe(II) (ferrozine assay and 0.5 N HCl extraction) and Mn(II) (ICP-MS and 10 mM CuSO{sub 4} extraction), and pH were monitored to define the reduction progress and extent. The bioreduced materials were characterized using the abovementioned techniques. Bioreduced (pasteurized) sediment or chemically extracted/reduced sediment spiked with Fe(II) was washed with a PIPES buffer/electrolyte solution, and spiked with NaTc(VII)O{sub 4} to yield a concentration of 20 {micro}M. The Tc(VII)-spiked samples were agitated and equilibrated at 25 C and sampled over time to assess the Tc(VII) reduction rate. Selected sediment samples containing 20 {micro}M of reduced Tc [Tc(IV)] were subjected to oxidation by: (1) successive headspace replacements of air, and (2) open system equilibration with air

  3. Microbial Fe(III) Oxide Reduction in Chocolate Pots Hot Springs, Yellowstone National Park

    NASA Astrophysics Data System (ADS)

    Fortney, N. W.; Roden, E. E.; Boyd, E. S.; Converse, B. J.

    2014-12-01

    Previous work on dissimilatory iron reduction (DIR) in Yellowstone National Park (YNP) has focused on high temperature, low pH environments where soluble Fe(III) is utilized as an electron acceptor for respiration. Much less attention has been paid to DIR in lower temperature, circumneutral pH environments, where solid phase Fe(III) oxides are the dominant forms of Fe(III). This study explored the potential for DIR in the warm (ca. 40-50°C), circumneutral pH Chocolate Pots hot springs (CP) in YNP. Most probable number (MPN) enumerations and enrichment culture studies confirmed the presence of endogenous microbial communities that reduced native CP Fe(III) oxides. Enrichment cultures demonstrated sustained DIR coupled to acetate and lactate oxidation through repeated transfers over ca. 450 days. Pyrosequencing of 16S rRNA genes indicated that the dominant organisms in the enrichments were closely affiliated with the well known Fe(III) reducer Geobacter metallireducens. Additional taxa included relatives of sulfate reducing bacterial genera Desulfohalobium and Thermodesulfovibrio; however, amendment of enrichments with molybdate, an inhibitor of sulfate reduction, suggested that sulfate reduction was not a primary metabolic pathway involved in DIR in the cultures. A metagenomic analysis of enrichment cultures is underway in anticipation of identifying genes involved in DIR in the less well-characterized dominant organisms. Current studies are aimed at interrogating the in situ microbial community at CP. Core samples were collected along the flow path (Fig. 1) and subdivided into 1 cm depth intervals for geochemical and microbiological analysis. The presence of significant quantities of Fe(II) in the solids indicated that DIR is active in situ. A parallel study investigated in vitro microbial DIR in sediments collected from three of the coring sites. DNA was extracted from samples from both studies for 16S rRNA gene and metagenomic sequencing in order to obtain a

  4. Biological Oxidation of Fe(II) in Reduced Nontronite Coupled with Nitrate Reduction by Pseudogulbenkiania sp. Strain 2002

    SciTech Connect

    Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.; Agrawal, A.; Liu, Deng; Zhang, Jing; Edelmann, Richard E.

    2013-10-15

    Nitrate contamination in soils, sediments, and water bodies is a significant issue. Although much is known about nitrate degradation in these environments, especially via microbial pathways, a complete understanding of all degradation processes, especially in clay mineral-rich soils, is still lacking. The objective of this study was to study the potential of removing nitrate contaminant using structural Fe(II) in clay mineral nontronite. Specifically, the coupled processes of microbial oxidation of Fe(II) in microbially reduced nontronite (NAu-2) and nitrate reduction by Pseudogulbenkiania species strain 2002 was investigated. Bio-oxidation experiments were conducted in bicarbonate-buffered medium under both growth and nongrowth conditions. The extents of Fe(II) oxidation and nitrate reduction were measured by wet chemical methods. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and 57Fe-Mössbauer spectroscopy were used to observe mineralogical changes associated with Fe(III) reduction and Fe(II) oxidation in nontronite. The bio-oxidation extent under growth and nongrowth conditions reached 93% and 57%, respectively. Over the same time period, nitrate was completely reduced under both conditions to nitrogen gas (N2), via an intermediate product nitrite. Magnetite was a mineral product of nitrate-dependent Fe(II) oxidation, as evidenced by XRD data and TEM diffraction patterns. The results of this study highlight the importance of iron-bearing clay minerals in the global nitrogen cycle with potential applications in nitrate removal in soils.

  5. MS title: Catalytic oxidation and removal of arsenite in the presence of Fe ions and zero-valent Al metals.

    PubMed

    Hsu, Liang-Ching; Chen, Kai-Yue; Chan, Ya-Ting; Deng, Youjun; Hwang, Che-En; Liu, Yu-Ting; Wang, Shan-Li; Kuan, Wen-Hui; Tzou, Yu-Min

    2016-11-01

    Arsenic immobilization in acid mine drainage (AMD) is required prior to its discharge to safeguard aquatic organisms. Zero-valent aluminum (ZVAl) such as aluminum beverage cans (AlBC) was used to induce the oxidation of As(III) to As(V) and enhance the subsequent As removal from an artificially prepared AMD. While indiscernible As(III) oxidation was found in aerated ZVAl systems, the addition of 0.10-0.55mM Fe(II) or Fe(III) into the AMD significantly promoted the As(V) production. Reactions between Fe(II) and H2O2, which was produced through an oxidative reaction of ZVAl with dissolved oxygen, generated OH radicals. Such OH radicals subsequently induced the As(III) oxidation. Over the course of the Fenton like reaction, ZVAl not only directly generated the H2O2, but indirectly enhanced the OH radical production by replenishing Fe(II). Arsenite oxidation in the aerated ZVAl/Fe and AlBC/Fe systems followed zero- and first-order kinetics. Differences in the kinetic reactions of ZVAl and AlBC with respect to As(III) oxidation were attributed to higher productive efficiency of the oxidant in the AlBC systems. After the completion of As(III) oxidation, As(V) could be removed simultaneously with Al(III) and Fe(III) by increasing solution's pH to 6 to produce Al/Fe hydroxides as As(V) scavengers or to form Al/Fe/As co-precipitates. PMID:27285595

  6. Secondary Fe- and Mn-Oxides Associated with Faults Near Moab, Utah: Records of Past Fluid Flow

    NASA Astrophysics Data System (ADS)

    Garcia, V. H.; Reiners, P. W.

    2015-12-01

    Secondary Fe- and Mn-oxides are locally common near faults and fractures, and as cements within sandstones of the Colorado Plateau, and provide evidence of past fluid-flow. Here we describe textural, mineralogic, and geochronologic observations from fault-zone Fe- and Mn-oxide mineralization in Flat Iron Mesa, near Moab, Utah. Several hypotheses have been proposed for their origin, including reactions associated with the mixing of deep reduced and near-surface oxygenated waters. We integrate field observations, detailed SEM and petrographic observations, geochemical models, (U-Th)/He and Ar/Ar dating, and other data to develop interpretations of the formation of these deposits. SEM imaging shows that sandstone matrix cement adjacent to the faults follows two precipitation sequences: Fe-oxide followed by barite and Fe-oxide followed by Mn-oxide. Dense oxide layers also accumulated in cm-scale fractures near faults, and show the following precipitation sequence: Fe-oxide, barite, Ba rich Mn-oxide, and pure Mn-oxide. The latter sequence is observed at larger scale across faults in one site in Flat Iron Mesa. Our new He dates for Mn-oxides are 1.7-2.9 Ma while Fe-oxide dates are 2.7-3.0 Ma. If these dates represent formation ages, they are consistent with the interpreted precipitation sequence but would require protracted mineralization over Ma-timescales. Alternatively, they may represent varying degrees of He retentivity in earlier formed deposits. Previous Ar/Ar dates have been interpreted as a 20-25 Ma formation age. Ongoing Ar/Ar and He diffusion studies will resolve this discordance. Assuming the previous Ar dates do not reflect contamination by detrital K-bearing phases and do reflect oxide formation, potential interpretations for the younger He ages include recent U-Th addition, recrystallization, later oxide growth, or large diffusive He loss at low temperatures.

  7. Influence of sediment components on the immobilization of Zn during microbial Fe-(hydr)oxide reduction.

    PubMed

    Coby, Aaron J; Picardal, Flynn W

    2006-06-15

    The fate of Zn and other sorbed heavy metals during microbial reduction of iron oxides is different when comparing synthetic Fe-(hydr)oxides and natural sediments undergoing a similar degree of iron reduction. Batch experiments with the iron-reducing organism Shewanella putrefaciens were conducted to examine the effects of an aqueous complexant (nitrilotriacetic acid or NTA), two solid-phase complexants (kaolinite and montmorillonite), an electron carrier (anthraquinone disulfonic acid or AQDS), and a humic acid on the speciation of Zn during microbial reduction of synthetic goethite. Compared to systems containing only goethite and Zn, microbial Fe(III) reduction in the presence of clay resulted in up to a 50% reduction in Zn immobilization (insoluble in a 2 h 0.5 M HCl extraction) without affecting Fe(II) production. NTA (3 mM) increased Fe(II) production 2-fold and resulted in recovery of nearly 75% of Zn in the aqueous fraction. AQDS (50 microM) resulted in a 12.5% decrease in Fe(II) production and a 44% reduction in Zn immobilization. Humic acid additions resulted in up to a 25% decrease in Fe(II) production and 51% decrease in Zn immobilization. The results suggest that all the components examined here as either complexing agents or electron shuttles reduce the degree of Zn immobilization by limiting the availability of Zn for incorporation into newly formed biogenic minerals. These results have implications for the remediation of heavy metals in a variety of natural sediments. PMID:16830547

  8. Tuning the superconductivity in single-layer FeSe/oxides by interface engineering

    NASA Astrophysics Data System (ADS)

    Peng, Rui

    2015-03-01

    The discovery of high Tc in single-layer FeSe films has enormous implications for both searching new high Tc superconductors and exploring the important factors for high temperature superconductivity. In this talk, I will show our recent angle-resolved photoemission studies on various FeSe-based heterostructures grown by molecular beam epitaxy. We systematically studied the electronic structures and superconducting properties of FeSe with varied strain, different interfacial oxide materials and different thicknesses, and uncover that electronic correlations and superconducting gap-closing temperatures are tuned by interfacial effects. We exclude the direct relation between superconductivity and tensile strain, or the energy of an interfacial phonon mode, and demonstrate the crucial and non-trivial role of FeSe/oxide interface on the high pairing temperature. By tuning the interface, superconducting pairing temperature reaches up to 75K in FeSe/Nb:BaTiO3/KTaO3 with the in-plane lattice of 3.99 Å, which sets a new superconducting-gap-closing temperature record for iron-based superconductors, and may paves the way to more cost-effective applications of ultra-thin superconductors. Besides, in extremely tensile-strained single-layer FeSe films, we found that the Fermi surfaces consist of two elliptical electron pockets at the zone corner, without detectable hybridization. The lifting of degeneracy is clearly observed for the first time for the iron-based superconductors with only electron Fermi surfaces. Intriguingly, the superconducting gap distribution is anisotropic but nodeless around the electron pockets, with minima at the crossings of the two pockets. Our results provide important experimental foundations for understanding the interfacial superconductivity and the pairing symmetry puzzle of iron-based superconductors, and also provide clues for further enhancing Tc through interface engineering.

  9. Molecular Underpinnings of Fe(III) Oxide Reduction by Shewanella oneidensis MR-1

    SciTech Connect

    Shi, Liang; Rosso, Kevin M.; Clarke, Thomas A.; Richardson, David J.; Zachara, John M.; Fredrickson, Jim K.

    2012-02-15

    In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III)] (oxy)(hydr)oxide minerals as the terminal electron acceptors for anaerobic respiration. At circumneutral pH and in the absence of strong complexing ligands, Fe(III) oxides are relatively insoluble and thus are external to the bacterial cells. S. oneidensis MR-1 and related strains of metal-reducing Shewanella have evolved the machinery (i.e., metal-reducing or Mtr pathway) for transferring electrons from the inner-membrane, through the periplasm and across the outer-membrane to the surface of extracellular Fe(III) oxides. The protein components identified to date for the Mtr pathway include CymA, MtrA, MtrB, MtrC and OmcA. CymA is an inner-membrane tetraheme c-type cytochrome (c-Cyt) that belongs to the NapC/NrfH family of quinol dehydrogenases. It is proposed that CymA oxidizes the quinol in the inner-membrane and transfers the released electrons to redox proteins in the periplasm. Although the periplasmic proteins receiving electrons from CymA during Fe(III) oxidation have not been identified, they are believed to relay the electrons in the periplasm to MtrA. A decaheme c-Cyt, MtrA is thought to be embedded in the trans outer-membrane and porin-like protein MtrB. Together, MtrAB deliver the electrons through the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. MtrC and OmcA are the outer-membrane decaheme c-Cyts that are translocated across the outer-membrane by the bacterial type II secretion system. Functioning as terminal reductases, MtrC and OmcA can bind the surface of Fe(III) oxides and transfer electrons directly to these minerals via their solvent-exposed hemes. To increase their reaction rates, MtrC and OmcA can use the flavins secreted by S. oneidensis MR-1 cells as diffusible co-factors for reduction of Fe(III) oxides. Because of their extracellular location and broad redox potentials, MtrC and OmcA can

  10. Electrochemical capacitance of iron oxide nanotube (Fe-NT): effect of annealing atmospheres

    NASA Astrophysics Data System (ADS)

    Sarma, Biplab; Jurovitzki, Abraham L.; Ray, Rupashree S.; Smith, York R.; Mohanty, Swomitra K.; Misra, Mano

    2015-07-01

    The effect of annealing atmosphere on the supercapacitance behavior of iron oxide nanotube (Fe-NT) electrodes has been explored and reported here. Iron oxide nanotubes were synthesized on a pure iron substrate through an electrochemical anodization process in an ethylene glycol solution containing 3% H2O and 0.5 wt.% NH4F. Subsequently, the annealing of the nanotubes was carried out at 500 °C for 2 h in various gas atmospheres such as air, oxygen (O2), nitrogen (N2), and argon (Ar). The morphology and crystal phases evolved after the annealing processes were examined via field emission scanning electron microscopy, x-ray diffraction, Raman spectroscopy, and x-ray photoelectron spectroscopy. The electrochemical capacitance properties of the annealed Fe-NT electrodes were evaluated by conducting cyclic voltammetry (CV), galvanostatic charge-discharge, and electrochemical impedance spectroscopy tests in the Li2SO4 electrolyte. Based on these experiments, it was found that the capacitance of the Fe-NT electrodes annealed in air and O2 atmospheres shows mixed behavior comprising both the electric double layer and pseudocapacitance. However, annealing in N2 and Ar environments resulted in well-defined redox peaks in the CV profiles of the Fe-NT electrodes, which are therefore attributed to the relatively higher pseudonature of the capacitance in these electrodes. Based on the galvanostatic charge-discharge studies, the specific capacitance achieved in the Fe-NT electrode after annealing in Ar was about 300 mF cm-2, which was about twice the value obtained for N2-annealed Fe-NTs and three times higher than those annealed in air and O2. The experiments also demonstrated excellent cycle stability for the Fe-NT electrodes with 83%-85% capacitance retention, even after many charge-discharge cycles, irrespective of the gas atmospheres used during annealing. The increase in the specific capacitance was discussed in terms of increased oxygen vacancies as a result of the

  11. JNK1 ablation in mice confers long-term metabolic protection from diet-induced obesity at the cost of moderate skin oxidative damage.

    PubMed

    Becattini, Barbara; Zani, Fabio; Breasson, Ludovic; Sardi, Claudia; D'Agostino, Vito Giuseppe; Choo, Min-Kyung; Provenzani, Alessandro; Park, Jin Mo; Solinas, Giovanni

    2016-09-01

    Obesity and insulin resistance are associated with oxidative stress, which may be implicated in the progression of obesity-related diseases. The kinase JNK1 has emerged as a promising drug target for the treatment of obesity and type 2 diabetes. JNK1 is also a key mediator of the oxidative stress response, which can promote cell death or survival, depending on the magnitude and context of its activation. In this article, we describe a study in which the long-term effects of JNK1 inactivation on glucose homeostasis and oxidative stress in obese mice were investigated for the first time. Mice lacking JNK1 (JNK1(-/-)) were fed an obesogenic high-fat diet (HFD) for a long period. JNK1(-/-) mice fed an HFD for the long term had reduced expression of antioxidant genes in their skin, more skin oxidative damage, and increased epidermal thickness and inflammation compared with the effects in control wild-type mice. However, we also observed that the protection from obesity, adipose tissue inflammation, steatosis, and insulin resistance, conferred by JNK1 ablation, was sustained over a long period and was paralleled by decreased oxidative damage in fat and liver. We conclude that compounds targeting JNK1 activity in brain and adipose tissue, which do not accumulate in the skin, may be safer and most effective.-Becattini, B., Zani, F., Breasson, L., Sardi, C., D'Agostino, V. G., Choo, M.-K., Provenzani, A., Park, J. M., Solinas, G. JNK1 ablation in mice confers long-term metabolic protection from diet-induced obesity at the cost of moderate skin oxidative damage. PMID:27230858

  12. Nanostructured Ternary FeCrAl Oxide Photocathodes for Water Photoelectrolysis.

    PubMed

    Kondofersky, Ilina; Müller, Alexander; Dunn, Halina K; Ivanova, Alesja; Štefanić, Goran; Ehrensperger, Martin; Scheu, Christina; Parkinson, Bruce A; Fattakhova-Rohlfing, Dina; Bein, Thomas

    2016-02-17

    A sol-gel method for the synthesis of semiconducting FeCrAl oxide photocathodes for solar-driven hydrogen production was developed and applied for the production of meso- and macroporous layers with the overall stoichiometry Fe0.84Cr1.0Al0.16O3. Using transmission electron microscopy and energy-dispersive X-ray spectroscopy, phase separation into Fe- and Cr-rich phases was observed for both morphologies. Compared to prior work and to the mesoporous layer, the macroporous FeCrAl oxide photocathode had a significantly enhanced photoelectrolysis performance, even at a very early onset potential of 1.1 V vs RHE. By optimizing the macroporous electrodes, the device reached current densities of up to 0.68 mA cm(-2) at 0.5 V vs RHE under AM 1.5 with an incident photon-to-current efficiency (IPCE) of 28% at 400 nm without the use of catalysts. Based on transient measurements, this performance increase could be attributed to an improved collection efficiency. At a potential of 0.75 V vs RHE, an electron transfer efficiency of 48.5% was determined. PMID:26743183

  13. Back transformation and oxidation of (Mg, Fe)2SiO4 spinels at high temperatures

    NASA Astrophysics Data System (ADS)

    Ming, L. C.; Kim, Y. H.; Manghnani, M. H.; Usha-Devi, S.; Ito, E.; Xie, H.-S.

    1991-10-01

    Based on the in situ and temperature-quench X-ray measurements, the back transformation in the (Mg, Fe)2SiO4-spinels has been characterized in terms of the transformation temperature ( T r ),mechanism and kinetics of the transformation, and of the end product(s), with specific emphasis on the effect of oxygen on this transformation. The in situ measurements were conducted to 900° C in vacuum (10-4 to 10-5 torr) and to 600° C in air using synchrotron radiation (SR) at Stanford Synchrotron Radiation Laboratory (SSRL). In the quench-type measurements, samples were heated in air to 1100° C, quenched and examined at ambient conditions using the conventional X-ray diffraction facilities. Important results are (1) in vacuum, all the spinels convert back into the olivine phase, with their T r decreasing with increasing iron content; (2) the spinel → olivine back transformation is a nucleation and growth type of transformation and can be described quantitatively using the Avrami equation; (3) in air, the (Mg, Fe)2SiO4-spinels with 0.2 mole fraction Fe or more are all oxidized, and the composition and phase of the end products depend upon the temperature and the starting composition; and (4) the oxidation of the iron-rich (Mg, Fe)2SiO4-spinels in air occurs at ˜350 400° C, which is significantly lower than its T r (˜ 300° C) in vacuum.

  14. Magnetic switching fluctuations from sidewall oxides in MgO/FeCoB magnetic tunnel junctions

    NASA Astrophysics Data System (ADS)

    Pomeroy, J. M.; Read, J. C.

    2011-08-01

    Sharp magnetic switching distributions with coupling to magnetic sidewall oxides in FeCoB/MgO magnetic tunnel junctions (MTJs) are revealed by magneto-resistance first order reversal curve (MR-FORC) measurements. Tunneling magneto-resistance (TMR) and FORC data in units of % TMR/mT2 are shown for two identical devices that differ only by the annealing. The annealed sample has much larger TMR and correspondingly higher switching density ρ. In both cases, the MR-FORC data exhibit a prominent "checkerboard" pattern that implies coupling to magnetic oxides on the MTJ sidewalls.

  15. Fe-Al-Pillared Clays: Catalysts for Wet Peroxide Oxidation of Phenol

    NASA Astrophysics Data System (ADS)

    Guélou, Erwan; Tatibouët, Jean-Michel; Barrault, Joël

    Catalytic phenol oxidation with hydrogen peroxide (CWPO) was performed over iron containing clays, pillared with Al or mixed Fe-Al complexes. This study deals with the better conditions for the oxidation reaction (temperature, pH, hydrogen peroxide concentration, atmosphere, etc.) in the presence of homogeneous or heterogeneous catalysts. The reaction was performed in a dynamic fixed-bed reactor, which gave the effect of the main experimental variables and an estimation of the kinetic parameters. The catalysts were characterized by classical techniques and by electron spin resonance (ESR). From ESR experiments the reaction mechanism involving hydroxyl radicals was also investigated.

  16. On the effect of the Fe(2+)/Fe(3+) redox couple on oxidation of carbon in hot H3PO4

    NASA Technical Reports Server (NTRS)

    Dhar, H. P.; Christner, L. G.; Kush, A. K.

    1986-01-01

    Oxidation studies of graphite:glassy carbon composites have been carried out at 1 and 4.7 atm. pressures in conc. H3PO4 in the presence and absence of iron ions. The concentration of the acid was varied over 85-100 wt pct, and of the iron ions over 30-300 ppm; the temperature varied over 190-210 C. Unlike the effect of Fe, which has been observed to increase the corrosion of carbon in sulphuric acid, the corrosion in phosphoric acid was observed to be slightly decreased or not at all affected. This result arises because of the catalytic reduction of the oxidized surface groups of carbon by Fe(2+) ions. The catalytic reduction is possible because under the experimental conditions the redox potential of the Fe(2+)/Fe(3+) couple is lower than the open-circuit voltage of carbon.

  17. Effect of MgO/Fe Interface Oxidation State on Electric-Field Modulation of Interfacial Magnetic Anisotropy

    NASA Astrophysics Data System (ADS)

    Guan, X. W.; Cheng, X. M.; Wang, S.; Huang, T.; Xue, K. H.; Miao, X. S.

    2016-06-01

    The impact of the MgO/Fe interface oxidation state on the electric-field-modified magnetic anisotropy in MgO/Fe has been revealed by density functional calculations. It is shown that the influence of the interface oxidation is strong enough to dominate the effect of the electric field on the magnetic anisotropy of MgO/Fe-based films. The magnetoelectric coefficients are calculated to be positive for the ideal and overoxidized MgO/Fe interface, but an abnormal negative value emerges in the underoxidized case. By analyzing the interface states based on density of states and band structures, we demonstrate that the considerably different electronic structures of the three oxidized MgO/Fe interfaces lead to the strong discrepancy in the electric-field modulation of the interfacial magnetic anisotropy. These results are of considerable interest in the area of electric-field-controlled magnetic anisotropy and switching.

  18. Effect of MgO/Fe Interface Oxidation State on Electric-Field Modulation of Interfacial Magnetic Anisotropy

    NASA Astrophysics Data System (ADS)

    Guan, X. W.; Cheng, X. M.; Wang, S.; Huang, T.; Xue, K. H.; Miao, X. S.

    2016-03-01

    The impact of the MgO/Fe interface oxidation state on the electric-field-modified magnetic anisotropy in MgO/Fe has been revealed by density functional calculations. It is shown that the influence of the interface oxidation is strong enough to dominate the effect of the electric field on the magnetic anisotropy of MgO/Fe-based films. The magnetoelectric coefficients are calculated to be positive for the ideal and overoxidized MgO/Fe interface, but an abnormal negative value emerges in the underoxidized case. By analyzing the interface states based on density of states and band structures, we demonstrate that the considerably different electronic structures of the three oxidized MgO/Fe interfaces lead to the strong discrepancy in the electric-field modulation of the interfacial magnetic anisotropy. These results are of considerable interest in the area of electric-field-controlled magnetic anisotropy and switching.

  19. Oxidative degradation of nalidixic acid by nano-magnetite via Fe2+/O2-mediated reactions.

    PubMed

    Ardo, Sandy G; Nélieu, Sylvie; Ona-Nguema, Georges; Delarue, Ghislaine; Brest, Jessica; Pironin, Elsa; Morin, Guillaume

    2015-04-01

    Organic pollution has become a critical issue worldwide due to the increasing input and persistence of organic compounds in the environment. Iron minerals are potentially able to degrade efficiently organic pollutants sorbed to their surfaces via oxidative or reductive transformation processes. Here, we explored the oxidative capacity of nano-magnetite (Fe3O4) having ∼ 12 nm particle size, to promote heterogeneous Fenton-like reactions for the removal of nalidixic acid (NAL), a recalcitrant quinolone antibacterial agent. Results show that NAL was adsorbed at the surface of magnetite and was efficiently degraded under oxic conditions. Nearly 60% of this organic contaminant was eliminated after 30 min exposure to air bubbling in solution in the presence of an excess of nano-magnetite. X-ray diffraction (XRD) and Fe K-edge X-ray absorption spectroscopy (XANES and EXAFS) showed a partial oxidation of magnetite to maghemite during the reaction, and four byproducts of NAL were identified by liquid chromatography-mass spectroscopy (UHPLC-MS/MS). We also provide evidence that hydroxyl radicals (HO(•)) were involved in the oxidative degradation of NAL, as indicated by the quenching of the degradation reaction in the presence of ethanol. This study points out the promising potentialities of mixed valence iron oxides for the treatment of soils and wastewater contaminated by organic pollutants. PMID:25756496

  20. Sodium-Ion Storage Properties of FeS-Reduced Graphene Oxide Composite Powder with a Crumpled Structure.

    PubMed

    Lee, Seung Yeon; Kang, Yun Chan

    2016-02-18

    The sodium-ion storage properties of FeS-reduced graphene oxide (rGO) and Fe3O4 -rGO composite powders with crumpled structures have been studied. The Fe3 O4 -rGO composite powder, prepared by one-pot spray pyrolysis, could be transformed to an FeS-rGO composite powder through a simple sulfidation treatment. The mean size of the Fe3O4 nanocrystals in the Fe3O4 -rGO composite powder was 4.4 nm. After sulfidation, FeS nanocrystals of size several hundred nanometers were confined within the crumpled structure of the rGO matrix. The initial discharge capacities of the FeS-rGO and Fe3O4 -rGO composite powders were 740 and 442 mA h g(-1), and their initial charge capacities were 530 and 165 mA h g(-1), respectively. The discharge capacities of the FeS-rGO and Fe3O4 -rGO composite powders at the 50th cycle were 547 and 150 mA h g(-1), respectively. The FeS-rGO composite powder showed superior sodium-ion storage performance compared to the Fe3O4 -rGO composite powder. PMID:26789137

  1. Immobilization of Radionuclides Through Anaerobic Bio-oxidation of Fe(ll)

    SciTech Connect

    Coates, John D.

    2005-06-01

    Over the last year we have focused our efforts on two independent aspects (a) further investigation of the microbiology and geochemistry of nitrate-dependent Fe(II) oxidation and (b) assembling the sequenced genome of Dechloromonas aromatica strain RCB. This work has been performed in a cooperative fashion amongst the independent labs of the three PI's with the UC Berkeley lab taking the lead under the guidance of J.D. Coates.

  2. Influence of organics and silica on Fe(II) oxidation rates and cell-mineral aggregate formation by the green-sulfur Fe(II)-oxidizing bacterium Chlorobium ferrooxidans KoFox - Implications for Fe(II) oxidation in ancient oceans

    NASA Astrophysics Data System (ADS)

    Gauger, Tina; Byrne, James M.; Konhauser, Kurt O.; Obst, Martin; Crowe, Sean; Kappler, Andreas

    2016-06-01

    Most studies on microbial phototrophic Fe(II) oxidation (photoferrotrophy) have focused on purple bacteria, but recent evidence points to the importance of green-sulfur bacteria (GSB). Their recovery from modern ferruginous environments suggests that these photoferrotrophs can offer insights into how their ancient counterparts grew in Archean oceans at the time of banded iron formation (BIF) deposition. It is unknown, however, how Fe(II) oxidation rates, cell-mineral aggregate formation, and Fe-mineralogy vary under environmental conditions reminiscent of the geological past. To address this, we studied the Fe(II)-oxidizer Chlorobium ferrooxidans KoFox, a GSB living in co-culture with the heterotrophic Geospirillum strain KoFum. We investigated the mineralogy of Fe(III) metabolic products at low/high light intensity, and in the presence of dissolved silica and/or fumarate. Silica and fumarate influenced the crystallinity and particle size of the produced Fe(III) minerals. The presence of silica also enhanced Fe(II) oxidation rates, especially at high light intensities, potentially by lowering Fe(II)-toxicity to the cells. Electron microscopic imaging showed no encrustation of either KoFox or KoFum cells with Fe(III)-minerals, though weak associations were observed suggesting co-sedimentation of Fe(III) with at least some biomass via these aggregates, which could support diagenetic Fe(III)-reduction. Given that GSB are presumably one of the most ancient photosynthetic organisms, and pre-date cyanobacteria, our findings, on the one hand, strengthen arguments for photoferrotrophic activity as a likely mechanism for BIF deposition on a predominantly anoxic early Earth, but, on the other hand, also suggest that preservation of remnants of Fe(II)-oxidizing GSB as microfossils in the rock record is unlikely.

  3. Development of FeCoB/Graphene Oxide based microwave absorbing materials for X-Band region

    NASA Astrophysics Data System (ADS)

    Das, Sukanta; Chandra Nayak, Ganesh; Sahu, S. K.; Oraon, Ramesh

    2015-06-01

    This work explored the microwave absorption capability of Graphene Oxide and Graphene Oxide coated with FeCoB for stealth technology. Epoxy based microwave absorbing materials were prepared with 30% loading of Graphene Oxide, FeCoB alloy and Graphene Oxide coated with FeCoB. Graphene Oxide and FeCoB were synthesized by Hummer's and Co-precipitation methods, respectively. The filler particles were characterized by FESEM, XRD and Vibrating Sample Magnetometer techniques. Permittivity, permeability and reflection loss values of the composite absorbers were measured with vector network analyzer which showed a reflection loss value of -7.86 dB, at 10.72 GHz, for single layered Graphene Oxide/Epoxy based microwave absorbers which can be correlated to the absorption of about 83.97% of the incident microwave energy. Reflection loss value of FeCoB/Epoxy based microwave absorber showed -13.30 dB at 11.67 GHz, which corresponded to maximum absorption of 93.8%. However, reflection loss values of Graphene Oxide coated with FeCoB/Epoxy based single-layer absorber increased to -22.24 dB at 12.4 GHz which corresponds to an absorption of 99% of the incident microwave energy.

  4. Selective Internal Oxidation as a Mechanism for Intergranular Stress Corrosion Cracking of Ni-Cr-Fe Alloys

    NASA Astrophysics Data System (ADS)

    Capell, Brent M.; Was, Gary S.

    2007-06-01

    The mechanism of selective internal oxidation (SIO) for intergranular stress corrosion cracking (IGSCC) of nickel-base alloys has been investigated through a series of experiments using high-purity alloys and a steam environment to control the formation of NiO on the surface. Five alloys (Ni-9Fe, Ni-5Cr, Ni-5Cr-9Fe, Ni-16Cr-9Fe, and Ni-30Cr-9Fe) were used to investigate oxidation and intergranular cracking behavior for hydrogen-to-water vapor partial pressure ratios (PPRs) between 0.001 and 0.9. The Ni-9Fe, Ni-5Cr, and Ni-5Cr-9Fe alloys formed a uniform Ni(OH)2 film at PPRs less than 0.09, and the higher chromium alloys formed chromium-rich oxide films over the entire PPR range studied. Corrosion coupon results show that grain boundary oxides extended for significant depths (>150 nm) below the sample surface for all but the highest Cr containing alloy. Constant extension rate tensile (CERT) test results showed that intergranular cracking varied with PPR and cracking was more pronounced at a PPR value where nonprotective Ni(OH)2 was able to form and a link between the nonprotective Ni(OH)2 film and the formation of grain boundary oxides is suggested. The observation of grain boundary oxides in stressed and unstressed samples as well as the influence of alloy content on IG cracking and oxidation support SIO as a mechanism for IGSCC.

  5. Evidence of a reduction reaction of oxidized iron/cobalt by boron atoms diffused toward naturally oxidized surface of CoFeB layer during annealing

    SciTech Connect

    Sato, Soshi Honjo, Hiroaki; Niwa, Masaaki; Ikeda, Shoji; Ohno, Hideo; Endoh, Tetsuo

    2015-04-06

    We have investigated the redox reaction on the surface of Ta/CoFeB/MgO/CoFeB magnetic tunnel junction stack samples after annealing at 300, 350, and 400 °C for 1 h using angle-resolved X-ray photoelectron spectroscopy for precise analysis of the chemical bonding states. At a capping tantalum layer thickness of 1 nm, both the capping tantalum layer and the surface of the underneath CoFeB layer in the as-deposited stack sample were naturally oxidized. By comparison of the Co 2p and Fe 2p spectra among the as-deposited and annealed samples, reduction of the naturally oxidized cobalt and iron atoms occurred on the surface of the CoFeB layer. The reduction reaction was more significant at higher annealing temperature. Oxidized cobalt and iron were reduced by boron atoms that diffused toward the surface of the top CoFeB layer. A single CoFeB layer was prepared on SiO{sub 2}, and a confirmatory evidence of the redox reaction with boron diffusion was obtained by angle-resolved X-ray photoelectron spectroscopy analysis of the naturally oxidized surface of the CoFeB single layer after annealing. The redox reaction is theoretically reasonable based on the Ellingham diagram.

  6. Dissolved and particulate Fe in a hydrothermal plume at 9{degree}45 minutes N, East Pacific Rise: Slow Fe (II) oxidation kinetics in Pacific plumes

    SciTech Connect

    Field, M.P.; Sherrell, R.M.

    2000-02-01

    Production of Fe(III) particles in hydrothermal plumes is of fundamental importance to the long-term effect of hydrothermal circulation on seawater composition. To elucidate the fundamental controls on Fe redox kinetics and solution/particle partitioning in neutrally buoyant plumes, the authors sampled near-field (<3 km) plume particles at 9{degree}45 minutes N on the East Pacific Rise in 1996, returning in 1997 to sample both particulate and dissolved phases (0.40 {micro}m filter). Concentrations of dissolved Fe varied from 320 to 20 nM in proximal (<0.3 km from vent site) to distal samples (1--3 km downfield), constituting {approximately}85--50% of total Fe, respectively. Based on vent fluid dilution factors calculated from dissolved Mn, a mass balance for vent fluid Fe at this site indicates that {approximately}65% of Fe is lost to particulate sulfide settling in the buoyant plume, and that particulate Fe in distal (1--3 km) samples is twice as concentrated as predicted from dilution of particles in proximal plume water. These observations are consistent with a calculated Fe(II) oxidation half-time of 3.3 h, long enough that Fe(III) colloid production and aggregation occurs primarily in the neutrally buoyant plume at relatively high dilutions, preventing generation of high particular Fe concentrations (11--56 nM observed). A general investigation of Fe(II) oxidation rates in plumes worldwide gives Fe(II) oxidation half-lives as short as 17 min at some Atlantic sites, and as long as 6 h at some Pacific sites. The calculations indicate that the distribution of Fe particles in plumes depends chiefly on inter-basin differences in ambient deep water chemistry (primarily pH and dissolved O{sub 2}) and on local currents driving plume dilution, and to a much lesser extent on variations in primary vent fluid composition. Long-term changes in thermohaline circulation or ocean biogeochemistry may therefore alter Fe dynamics and minor element fluxes associated with global

  7. Location of nanophase Fe-oxides in palagonitic soils: Implication for Martian pigments

    NASA Technical Reports Server (NTRS)

    Golden, D. C.; Morris, R. V.; Ming, D. W.; Lauer, H. V., Jr.

    1992-01-01

    Palagonitic materials from Mauna Kea, Hawaii, were identified as Mars analogs based on their spectral and magnetic properties. These materials probably resulted from hydrothermal alteration during eruption of the volcano and/or from weathering under ambient conditions. The reflectance spectra of the Mars surface obtained by Earth-based telescopes and the reflectance spectra of analogs obtained in the laboratory show features due to electronic transitions of Fe(III) in oxide particles that range in size from nanometer (nanophase) to micrometer sized or larger. The presence of Fe(III) suggests oxidizing conditions during the alteration process in Mars that may have occurred in the past or during a slow ongoing process. Two naturally altered basaltic samples from Hawaii (HWMK12 and HWMK13) and a laboratory-altered (PH-13-DCGT2) basaltic glass similar in elemental composition to the above two samples was examined. All three samples exhibited spectral characteristics similar to martian bright-region spectra. Chemical and mineralogical changes occurring at the surface of these basalts were studied in order to understand the basis for their Mars-like properties. The spectral properties of the three samples were examined after the removal of Fe oxides by chemical extractants.

  8. Extracellular Electron Transfer to Fe(III) Oxides by the Hyperthermophilic Archaeon Geoglobus ahangari via a Direct Contact Mechanism

    PubMed Central

    Manzella, Michael P.; Reguera, Gemma

    2013-01-01

    The microbial reduction of Fe(III) plays an important role in the geochemistry of hydrothermal systems, yet it is poorly understood at the mechanistic level. Here we show that the obligate Fe(III)-reducing archaeon Geoglobus ahangari uses a direct-contact mechanism for the reduction of Fe(III) oxides to magnetite at 85°C. Alleviating the need to directly contact the mineral with the addition of a chelator or the electron shuttle anthraquinone-2,6-disulfonate (AQDS) stimulated Fe(III) reduction. In contrast, entrapment of the oxides within alginate beads to prevent cell contact with the electron acceptor prevented Fe(III) reduction and cell growth unless AQDS was provided. Furthermore, filtered culture supernatant fluids had no effect on Fe(III) reduction, ruling out the secretion of an endogenous mediator too large to permeate the alginate beads. Consistent with a direct contact mechanism, electron micrographs showed cells in intimate association with the Fe(III) mineral particles, which once dissolved revealed abundant curled appendages. The cells also produced several heme-containing proteins. Some of them were detected among proteins sheared from the cell's outer surface and were required for the reduction of insoluble Fe(III) oxides but not for the reduction of the soluble electron acceptor Fe(III) citrate. The results thus support a mechanism in which the cells directly attach and transfer electrons to the Fe(III) oxides using redox-active proteins exposed on the cell surface. This strategy confers on G. ahangari a competitive advantage for accessing and reducing Fe(III) oxides under the extreme physical and chemical conditions of hot ecosystems. PMID:23728807

  9. Density functional theory study of nitrous oxide decomposition over Fe- and Co-ZSM-5

    SciTech Connect

    Ryder, Jason A.; Chakraborty, Arup K.; Bell, Alexis T.

    2001-12-19

    Iron- and cobalt-exchanged ZSM-5 are active catalysts for the dissociation of nitrous oxide. In this study, density functional theory was used to assess a possible reaction pathway for the catalytic dissociation of N2O. The active center was taken to be mononuclear [FeO]+ or [CoO]+, and the surrounding portion of the zeolite was represented by a 24-atom cluster. The first step of N2O decomposition involves the formation of [FeO2]+ or [CoO2]+ and the release of N2. The metal-oxo species produced in this step then reacts with N2O again, to release N2 and O2. The apparent activation energies for N2O dissociation in Fe-ZSM-5 and Co-ZSM-5 are 39.4 and 34.6 kcal/mol, respectively. The preexponential factor for the apparent first-order rate coefficient is estimated to be of the order 107 s-1 Pa-1. While the calculated activation energy for Fe-ZSM-5 is in good agreement with that measured experimentally, the value of the preexponential factor is an order of magnitude smaller than that observed . The calculated activation energy for Co-ZSM-5 is higher than that reported experimentally. However, consistent with experiment, the rate of N2O decomposition on Co-ZSM-5 is predicted to be significantly higher than that on Fe-ZSM-5.

  10. Monolayer-directed Assembly and Magnetic Properties of FePt Nanoparticles on Patterned Aluminum Oxide

    PubMed Central

    Yildirim, Oktay; Gang, Tian; Kinge, Sachin; Reinhoudt, David N.; Blank, Dave H.A.; van der Wiel, Wilfred G.; Rijnders, Guus; Huskens, Jurriaan

    2010-01-01

    FePt nanoparticles (NPs) were assembled on aluminum oxide substrates, and their ferromagnetic properties were studied before and after thermal annealing. For the first time, phosph(on)ates were used as an adsorbate to form self-assembled monolayers (SAMs) on alumina to direct the assembly of NPs onto the surface. The Al2O3 substrates were functionalized with aminobutylphosphonic acid (ABP) or phosphonoundecanoic acid (PNDA) SAMs or with poly(ethyleneimine) (PEI) as a reference. FePt NPs assembled on all of these monolayers, but much less on unmodified Al2O3, which shows that ligand exchange at the NPs is the most likely mechanism of attachment. Proper modification of the Al2O3 surface and controlling the immersion time of the modified Al2O3 substrates into the FePt NP solution resulted in FePt NPs assembly with controlled NP density. Alumina substrates were patterned by microcontact printing using aminobutylphosphonic acid as the ink, allowing local NP assembly. Thermal annealing under reducing conditions (96%N2/4%H2) led to a phase change of the FePt NPs from the disordered FCC phase to the ordered FCT phase. This resulted in ferromagnetic behavior at room temperature. Such a process can potentially be applied in the fabrication of spintronic devices. PMID:20480007

  11. [Nitric Oxide Removal with a Fe-TiO₂/PSF Hybrid Catalytic Membrane Bioreactor].

    PubMed

    Li, Bao-ren; Chen, Zhou-yang; Wang, Jian-bin; Zhang, Zai-li; Fan, Qing-juan; Wei, Zai-shan

    2016-03-15

    The Fe-doped titanium dioxide (Fe-TiO₂) was prepared by the sol-gel method and was loaded on polysulfone (PSF) hollow fiber membrane. A novel Fe-TiO₂/PSF hybrid catalytic membrane biofilm reactor (HCMBfR) was investigated for nitric oxide removal, to further improve the elimination capacity. HCMBfR exhibited a good stability in the 180-day operation period, the NO removal efficiency was up to 93.2% and the maximum elimination capacity reached 167.1 g · (m³ · h)⁻1. The additional use of the biofilm to wet Fe-TiO₂/PSF membrane catalysis reactor led to the enhancement of NO removal efficiency from 59. 5% to 66% . The NO removal efficiency in the intimate coupling of Fe-TiO₂/PSF hybrid catalytic membrane and biofilm reactor ( HCMBfR) increased from 1.4% to 13% as compared to that of the membrane biofilm reactor (MBfR) only. The optimal illumination intensity, gas residence time, pH and nC/nN were 670 lx, 9 a, 6.8-7.2 and 3.7, respectively. PMID:27337874

  12. Crystal and Electronic Study of Neodymium-Substituted CuFeO2 Oxide

    NASA Astrophysics Data System (ADS)

    Ozkendir, Osman Murat

    2016-06-01

    Neodymium-substituted CuFeO2 samples were investigated according to their crystal and electronic properties via the general formula Nd x Cu1- x FeO2. The crystal structure analysis results revealed polycrystalline formations in the sample and a change in crystalline sizes with the substituted heavy fermion "Nd." Increasing the Nd amount in the sample was determined to cause a disturbance on the Cu-Fe planes that supports the formation of crystal structures with low crystal symmetries such as monoclinic or triclinic geometries. To obtain the background mechanisms of the crystal properties, the X-ray absorption fine structure spectroscopy technique was used to study the electronic properties of the samples. Prominent changes in the crystal structures due to 4 f electrons' contributions from the substituted Nd atoms as the main "role player" in the phase transitions were determined. The Nd atoms were observed as the key element guiding the entire phenomenon as a result of their large size and narrow 4 f levels. Also, magnetic properties of the samples were tested at room temperature and without an applied magnetic field by X-ray magnetic circular dichroism study due to previous studies that reported the parent oxide CuFeO2 to have magnetic ordering at T N = 11 K (-262 °C). Except the sample for x = 1.0 (NdFeO3), no magnetic ordering was observed at room temperature; i.e., all of the samples showed paramagnetic behaviors.

  13. Oxidation of nitrogen oxide in hybrid plasma-catalytic reactors based on DBD and Fe2O3

    NASA Astrophysics Data System (ADS)

    Jõgi, Indrek; Erme, Kalev; Haljaste, Ants; Laan, Matti

    2013-02-01

    In the present study, Fe2O3 was used as catalyst for the removal of NO in a hybrid plasma- catalytic reactor. The catalyst was located either directly inside the hybrid plasma-catalytic reactor or in a separate catalytic reactor, which followed ozone producing and injecting plasma reactor. Ozone production in such a reactor was dependent on the state of the electrode surface. The fresh catalyst ensured an order of magnitude smaller ozone concentration in the outlet of the hybrid reactor. After a short treatment of the catalyst with NO2, its ability to destroy ozone diminished but was regained after heating of the reactor up to 100 °C. Similarly to earlier results obtained with TiO2, the removal of NO in the hybrid reactor with Fe2O3 was enhanced compared to that in an ordinary plasma reactor. In the ozone injection reactor, oxidation of NO to NO2 took place with considerably higher efficiency compared to the hybrid reactor. The use of catalyst in the ozonation stage further improved the oxidation of NO2 to N2O5. The time-dependence effects of NO removal during plasma and ozone oxidation were explained by reactions between NO2 adsorbed on surface, with surface-bound NO3 and gas phase NO as the reaction product. Contribution to the Topical Issue "13th International Symposium on High Pressure Low Temperature Plasma Chemistry (Hakone XIII)", Edited by Nicolas Gherardi, Henryca Danuta Stryczewska and Yvan Ségui.

  14. Effects of dissimilatory sulfate reduction on FeIII (hydr)oxide reduction and microbial community development

    NASA Astrophysics Data System (ADS)

    Kwon, Man Jae; Boyanov, Maxim I.; Antonopoulos, Dionysios A.; Brulc, Jennifer M.; Johnston, Eric R.; Skinner, Kelly A.; Kemner, Kenneth M.; O'Loughlin, Edward J.

    2014-03-01

    Although dissimilatory iron and sulfate reduction (DIR and DSR) profoundly affect the biogeochemical cycling of C, Fe, and S in subsurface systems, the dynamics of DIR and DSR in the presence of both FeIII (hydr)oxides and sulfate have not been well-studied with mixed microbial populations. This study examined the response of native microbial communities in subsurface sediment from the U.S. Department of Energy’s Integrated Field Research Challenge site in Rifle, CO to the availability of sulfate and specific FeIII (hydr)oxide minerals in experimental systems containing lactate as the electron donor, with ferrihydrite, goethite, or lepidocrocite and high (10.2 mM) or low (0.2 mM) sulfate as electron acceptors. We observed rapid fermentation of lactate to acetate and propionate. FeIII reduction was slow and limited in the presence of low-sulfate, but the extent of FeIII reduction increased more than 10 times with high-sulfate amendments. Furthermore, the extent of FeIII reduction was higher in ferrihydrite or lepidocrocite incubations than in goethite incubations. Propionate produced during fermentation of lactate was used as the electron donor for DSR. The concurrence of sulfate reduction and FeII production suggests that FeII production was driven primarily by reduction of FeIII by biogenic sulfide. X-ray absorption fine-structure analysis confirmed the formation of ferrous sulfide and the presence of O-coordinated ferrous species. 16S rRNA-based microbial community analysis revealed the development of distinct communities with different FeIII (hydr)oxides. These results highlight the highly coupled nature of C, Fe, and S biogeochemical cycles during DIR and DSR and provide new insight into the effects of electron donor utilization, sulfate concentration, and the presence of specific FeIII (hydr)oxide phases on microbial community development.

  15. Nitrous oxide decomposition over Fe-ZSM-5 in the presence of nitric oxide: a comprehensive DFT study.

    PubMed

    Heyden, Andreas; Hansen, Niels; Bell, Alexis T; Keil, Frerich J

    2006-08-31

    A number of experimental studies have shown recently that ppm-level additions of nitric oxide (NO) enhance the rate of nitrous oxide (N(2)O) decomposition catalyzed by Fe-ZSM-5 at low temperatures. In the present work, the NO-assisted N(2)O decomposition over mononuclear iron sites in Fe-ZSM-5 was studied on a molecular level using density functional theory (DFT) and transition-state theory. A reaction network consisting of over 100 elementary reactions was considered. The structure and energies of potential-energy minima were determined for all stable species, as were the structures and energies of all transition states. Reactions involving changes in spin potential-energy surfaces were also taken into account. In the absence of NO and at temperatures below 690 K, most active single iron sites (Z(-)[FeO](+)) are poisoned by small concentrations of water in the gas phase; however, in the presence of NO, these poisoned sites are converted into a novel active iron center (Z(-)[FeOH](+)). These latter sites are capable of promoting the dissociation of N(2)O into a surface oxygen atom and gas-phase N(2). The surface oxygen atom is removed by reaction with NO or nitrogen dioxide (NO(2)). N(2)O dissociation is the rate-limiting step in the reaction mechanism. At higher temperatures, water desorbs from inactive iron sites and the reaction mechanism for N(2)O decomposition becomes independent of NO, reverting to the reaction mechanism previously reported by Heyden et al. [J. Phys. Chem. B 2005, 109, 1857]. PMID:16928005

  16. Inventory of H2O in the ancient Martian regolith from Northwest Africa 7034: The important role of Fe oxides

    NASA Astrophysics Data System (ADS)

    Muttik, Nele; McCubbin, Francis M.; Keller, Lindsay P.; Santos, Alison R.; McCutcheon, Whitney A.; Provencio, Paula P.; Rahman, Zia; Shearer, Charles K.; Boyce, Jeremy W.; Agee, Carl B.

    2014-12-01

    Water-rich Martian regolith breccia Northwest Africa (NWA) 7034 was analyzed by Fourier transform infrared spectroscopy and transmission electron microscopy to determine the inventory and phase distribution of H2O (used herein to refer to both molecular H2O and OH- structural components in hydrous minerals). Hydrous Fe oxide phases (hydromaghemite and an unidentified nanocrystalline Fe-bearing oxide phase observed with hydromaghemite) and phyllosilicates (saponite) were identified as the primary mineralogic hosts for H2O with a minor contribution from Cl-rich apatite. Based on mass balance calculations and modal abundances of minerals constrained by powder X-ray diffraction and petrography, we can account for the entire 6000 ppm H2O measured in bulk rock analyses of NWA 7034. This H2O is distributed evenly between hydrous Fe-rich oxides and phyllosilicates, indicating that Fe oxides could be as important as phyllosilicates for H2O storage in Martian surface material.

  17. Superior anti-CO poisoning capability: Au-decorated PtFe nanocatalysts for high-performance methanol oxidation.

    PubMed

    Cai, Zhao; Lu, Zhiyi; Bi, Yongmin; Li, Yaping; Kuang, Yun; Sun, Xiaoming

    2016-03-11

    Herein we demonstrate a surface engineering strategy, namely, decorating Au on the surface of bimetallic PtFe nanocatalysts, to effectively decrease the adsorption energy of CO on the Pt center, which promotes the electrocatalytic activity towards methanol oxidation, far better than those of PtFe and commercial Pt/C catalysts. PMID:26833455

  18. Characterization of Fe(II) oxidizing bacterial activities and communities at two acidic Appalachian coalmine drainage-impacted sites

    SciTech Connect

    Senko, John M.; Wanjugi, Pauline; Lucas, Melanie; Bruns, Mary Ann; Burgos, William D.

    2008-06-12

    We characterized the microbiologically mediated oxidative precipitation of Fe(II) from coalminederived acidic mine drainage (AMD) along flow-paths at two sites in northern Pennsylvania. At the Gum Boot site, dissolved Fe(II) was efficiently removed from AMD whereas minimal Fe(II) removal occurred at the Fridays-2 site. Neither site received human intervention to treat the AMD. Culturable Fe(II) oxidizing bacteria were most abundant at sampling locations along the AMD flow path corresponding to greatest Fe(II) removal and where overlying water contained abundant dissolved O2. Rates of Fe(II) oxidation determined in laboratory-based sediment incubations were also greatest at these sampling locations. Ribosomal RNA intergenic spacer analysis and sequencing of partial 16S rRNA genes recovered from sediment bacterial communities revealed similarities among populations at points receiving regular inputs of Fe(II)-rich AMD and provided evidence for the presence of bacterial lineages capable of Fe(II) oxidation. A notable difference between bacterial communities at the two sites was the abundance of Chloroflexi-affiliated 16S rRNA gene sequences in clone libraries derived from the Gum Boot sediments. Our results suggest that inexpensive and reliable AMD treatment strategies can be implemented by mimicking the conditions present at the Gum Boot field site.

  19. Enhanced reduction of Fe(III) oxides and methyl orange by Klebsiella oxytoca in presence of anthraquinone-2-disulfonate.

    PubMed

    Yu, Lei; Wang, Shi; Tang, Qing-Wen; Cao, Ming-Yue; Li, Jia; Yuan, Kun; Wang, Ping; Li, Wen-Wei

    2016-05-01

    Klebsiella oxytoca GS-4-08 is capable of azo dye reduction, but its quinone respiration and Fe(III) reduction abilities have not been reported so far. In this study, the abilities of this strain were reported in detail for the first time. As the biotic reduction of Fe(III) plays an important role in the biogeochemical cycles, two amorphous Fe(III) oxides were tested as the sole electron acceptor during the anaerobic respiration of strain GS-4-08. For the reduction of goethite and hematite, the biogenic Fe(II) concentrations reached 0.06 and 0.15 mM, respectively. Humic acid analog anthraquinone-2-disulfonate (AQS) was found to serve as an electron shuttle to increase the reduction of both methyl orange (MO) and amorphous Fe(III) oxides, and improve the dye tolerance of the strain. However, the formation of Fe(II) was not accelerated by biologically reduced AQS (B-AH2QS) because of the high bioavailability of soluble Fe(III). For the K. oxytoca strain, high soluble Fe(III) concentrations (above 1 mM) limit its growth and decolorization ability, while lower soluble Fe(III) concentrations produce an electron competition with MO initially, and then stimulate the decolorization after the electron couples of Fe(III)/Fe(II) are formed. With the ability to respire both soluble Fe(III) and insoluble Fe(III) oxides, this formerly known azo-reducer may be used as a promising model organism for the study of the interaction of these potentially competing processes in contaminated environments. PMID:26762391

  20. Thermal decomposition of iron(VI) oxides, K{sub 2}FeO{sub 4} and BaFeO{sub 4}, in an inert atmosphere

    SciTech Connect

    Madarasz, Janos; Zboril, Radek; Homonnay, Zoltan . E-mail: vsharma@fit.edu; Pokol, Gyoergy

    2006-05-15

    The thermal decomposition of solid samples of iron(VI) oxides, K{sub 2}FeO{sub 4}.0.088 H{sub 2}O (1) and BaFeO{sub 4}.0.25H{sub 2}O (2) in inert atmosphere has been examined using simultaneous thermogravimetry and differential thermal analysis (TG/DTA), in combination with in situ analysis of the evolved gases by online coupled mass spectrometer (EGA-MS). The final decomposition products were characterized by {sup 57}Fe Moessbauer spectroscopy. Water molecules were released first, followed by a distinct decomposition step with endothermic DTA peak of 1 and 2 at 273 and 248 deg. C, respectively, corresponding to the evolution of molecular oxygen as confirmed by EGA-MS. The released amounts of O{sub 2} were determined as 0.42 and 0.52 mol pro formula of 1 and 2, respectively. The decomposition product of K{sub 2}FeO{sub 4} at 250 deg. C was determined as Fe(III) species in the form of KFeO{sub 2}. Formation of an amorphous mixture of superoxide, peroxide, and oxide of potassium may be other products of the thermal conversion of iron(VI) oxide 1 to account for less than expected released oxygen. The thermogravimetric and Moessbauer data suggest that barium iron perovskite with the intermediate valence state of iron (between III and IV) was the product of thermal decomposition of iron(VI) oxide 2.

  1. Thermal decomposition of iron(VI) oxides, K 2FeO 4 and BaFeO 4, in an inert atmosphere

    NASA Astrophysics Data System (ADS)

    Madarász, János; Zbořil, Radek; Homonnay, Zoltán; Sharma, Virender K.; Pokol, György

    2006-05-01

    The thermal decomposition of solid samples of iron(VI) oxides, K 2FeO 4·0.088 H 2O ( 1) and BaFeO 4·0.25H 2O ( 2) in inert atmosphere has been examined using simultaneous thermogravimetry and differential thermal analysis (TG/DTA), in combination with in situ analysis of the evolved gases by online coupled mass spectrometer (EGA-MS). The final decomposition products were characterized by 57Fe Mössbauer spectroscopy. Water molecules were released first, followed by a distinct decomposition step with endothermic DTA peak of 1 and 2 at 273 and 248 °C, respectively, corresponding to the evolution of molecular oxygen as confirmed by EGA-MS. The released amounts of O 2 were determined as 0.42 and 0.52 mol pro formula of 1 and 2, respectively. The decomposition product of K 2FeO 4 at 250 °C was determined as Fe(III) species in the form of KFeO 2. Formation of an amorphous mixture of superoxide, peroxide, and oxide of potassium may be other products of the thermal conversion of iron(VI) oxide 1 to account for less than expected released oxygen. The thermogravimetric and Mössbauer data suggest that barium iron perovskite with the intermediate valence state of iron (between III and IV) was the product of thermal decomposition of iron(VI) oxide 2.

  2. Controlled assembly of Fe3O4 magnetic nanoparticles on graphene oxide

    NASA Astrophysics Data System (ADS)

    Zhang, Yi; Chen, Biao; Zhang, Liming; Huang, Jie; Chen, Fenghua; Yang, Zupei; Yao, Jianlin; Zhang, Zhijun

    2011-04-01

    We describe a facile approach to controllable assembly of monodisperse Fe3O4nanoparticles (NPs) on chemically reduced graphene oxide (rGO). First, reduction and functionalization of GO by polyetheylenimine (PEI) were achieved simultaneously by simply heating the PEI and GO mixture at 60 °C for 12 h. The process is environmentally friendly and convenient compared with previously reported methods. Meso-2,3-dimercaptosuccinnic acid (DMSA)-modified Fe3O4 NPs were then conjugated to the PEI moiety which is located on the periphery of the GO sheets via formation of amide bonds between COOH groups of DMSA molecules bound on the surface of the Fe3O4 NPs and aminegroups of PEI. The magnetic GO composites were characterized by means of TEM, AFM, UV-vis, FTIR, Raman, TGA, and VSM measurements. Finally, preliminary results of using the Fe3O4-rGO composites for efficient removal of tetracycline, an antibiotic that is often found as a contaminant in the environment, are reported.We describe a facile approach to controllable assembly of monodisperse Fe3O4nanoparticles (NPs) on chemically reduced graphene oxide (rGO). First, reduction and functionalization of GO by polyetheylenimine (PEI) were achieved simultaneously by simply heating the PEI and GO mixture at 60 °C for 12 h. The process is environmentally friendly and convenient compared with previously reported methods. Meso-2,3-dimercaptosuccinnic acid (DMSA)-modified Fe3O4 NPs were then conjugated to the PEI moiety which is located on the periphery of the GO sheets via formation of amide bonds between COOH groups of DMSA molecules bound on the surface of the Fe3O4 NPs and aminegroups of PEI. The magnetic GO composites were characterized by means of TEM, AFM, UV-vis, FTIR, Raman, TGA, and VSM measurements. Finally, preliminary results of using the Fe3O4-rGO composites for efficient removal of tetracycline, an antibiotic that is often found as a contaminant in the environment, are reported. Electronic supplementary information

  3. The Oxidation State of Fe in Glasses from the Galapagos Archipelago: Variable Oxygen Fugacity as a Function of Mantle Source

    NASA Astrophysics Data System (ADS)

    Peterson, M. E.; Kelley, K. A.; Cottrell, E.; Saal, A. E.; Kurz, M. D.

    2015-12-01

    The oxidation state of the mantle plays an intrinsic role in the magmatic evolution of the Earth. Here we present new μ-XANES measurements of Fe3+/ΣFe ratios (a proxy for ƒO2) in a suite of submarine glasses from the Galapagos Archipelago. Using previously presented major, trace, and volatile elements and isotopic data for 4 groups of glass that come from distinct mantle sources (depleted upper mantle, 2 recycled, and a primitive mantle source) we show that Fe3+/ΣFe ratios vary both with the influence of shallow level processes and with variations in mantle source. Fe3+/ΣFe ratios increase with differentiation (i.e. decreasing MgO), but show a large variation at a given MgO. Progressive degassing of sulfur accompanies decreasing Fe3+/ΣFe ratios, while assimilation of hydrothermally altered crust (as indicated by increasing Sr/Sr*) is shown to increase Fe3+/ΣFe ratios. After taking these processes into account, there is still variability in the Fe3+/ΣFe ratios of the isotopically distinct sample suites studied, yielding a magmatic ƒO2 that ranges from ΔQFM = +0.16 to +0.74 (error < 0.5 log units) and showing that oxidation state varies as a function of mantle source composition in the Galapagos hotspot system. After correcting back to a common MgO content = 8.0 wt%, the trace element depleted group similar to MORB (ITD), and the group similar to Pinta (WD = high Th/La, Δ7/4, Δ8/4 ratios) show Fe3+/ΣFe ratios within the range of MORB (average ITD = 0.162 ± 0.003 and WD = 0.164 ± 0.006). Another trace element enriched group similar to Sierra Negra and Cerro Azul (ITE = enriched Sr and Pb isotopes) shows evidence of mixing between oxidized and reduced sources (ITE oxidized end-member = 0.177). This suggests that mantle sources in the Galapagos that are thought to contain recycled components (i.e., WD and ITE groups) have distinct oxidation states. The high 3He/4He Fernandina samples (HHe group) are shown to be the most oxidized (ave. 0.175 ± 0

  4. Mechanisms for Electron Transfer Through Pili to Fe(III) Oxide in Geobacter

    SciTech Connect

    Lovley, Derek R.

    2015-03-09

    The purpose of these studies was to aid the Department of Energy in its goal of understanding how microorganisms involved in the bioremediation of metals and radionuclides sustain their activity in the subsurface. This information is required in order to incorporate biological processes into decision making for environmental remediation and long-term stewardship of contaminated sites. The proposed research was designed to elucidate the mechanisms for electron transfer to Fe(III) oxides in Geobacter species because Geobacter species are abundant dissimilatory metal-reducing microorganisms in a diversity of sites in which uranium is undergoing natural attenuation via the reduction of soluble U(VI) to insoluble U(IV) or when this process is artificially stimulated with the addition of organic electron donors. This study investigated the novel, but highly controversial, concept that the final conduit for electron transfer to Fe(III) oxides are electrically conductive pili. The specific objectives were to: 1) further evaluate the conductivity along the pili of Geobacter sulfurreducens and related organisms; 2) determine the mechanisms for pili conductivity; and 3) investigate the role of pili in Fe(III) oxide reduction. The studies demonstrated that the pili of G. sulfurreducens are conductive along their length. Surprisingly, the pili possess a metallic-like conductivity similar to that observed in synthetic organic conducting polymers such as polyaniline. Detailed physical analysis of the pili, as well as studies in which the structure of the pili was genetically modified, demonstrated that the metallic-like conductivity of the pili could be attributed to overlapping pi-pi orbitals of aromatic amino acids. Other potential mechanisms for conductivity, such as electron hopping between cytochromes associated with the pili were definitively ruled out. Pili were also found to be essential for Fe(III) oxide reduction in G. metallireducens. Ecological studies demonstrated

  5. Effect of Oxidation on Creep Strength and Resistivity of Porous Fe-26Cr-1Mo

    NASA Astrophysics Data System (ADS)

    Scott, Justin A.; Dunand, David C.

    2014-12-01

    To investigate its application as a material for solid oxide fuel cell interconnects, oxidation rates of replicated E-Brite (Fe-26Cr-1Mo, wt pct) foams with 43 and 51 pct open porosity were measured in static laboratory air for up to 200 hours. Results correlate well with previously reported values for dense material when normalized by surface area. Area-specific resistance measurements, taken in the range of 823 K to 1073 K (550 °C to 800 °C) after 24 hours of oxidation at 1123 K (850 °C), yield activation energies in the range 69 to 82 kJ mol-1 for porous E-Brite that closely match dense E-Brite. Compressive creep properties, measured at 1073 K (800 °C) for pristine and oxidized porous E-Brite, show that pre-oxidation (10 hours at 1073 K (800 °C)) led to a ~100-fold decrease in creep rate. This is due to strengthening of the alloy foam by the formation of a continuous network of oxide, which coats the internal pore surface and reduces porosity by as much as 10 pct after 200 hours of oxidation at 1073 K (800 °C). Choking of the fenestrations between the pores, however, leads to an increase in closed porosity. Strengthening and pore filling effects should be taken into account in the design of the SOFC stack when using E-Brite as a porous interconnect material.

  6. Kinetics of oxidation of chlorobenzenes and phenyl-ureas by Fe(II)/H2O2 and Fe(III)/H2O2. Evidence of reduction and oxidation reactions of intermediates by Fe(II) or Fe(III).

    PubMed

    Gallard, H; De Laat, J

    2001-02-01

    The rates of degradation of 1,2,4-trichlorobenzene (TCB), 2,5-dichloronitrobenzene (DCNB), diuron and isoproturon by Fe(II)/H2O2 and Fe(III)/H2O2 have been investigated in dilute aqueous solution ([Organic compound]0 approximately 1 microM, at 25.0 +/- 0.2 degrees C and pH < or = 3). Using the relative rate method with atrazine as the reference compound, and the Fe(II)/H2O2 (with an excess of Fe(II)) and Fe(III)/H2O2 systems as sources of OH radicals, the rate constants for the reaction of OH* with TCB and DCNB were determined as (6.0 +/- 0.3)10(9) and (1.1 +/- 0.2)10(9) M(-1) s(-1). Relative rates of degradation of diuron and isoproturon by Fe(II)/H2O2 were about two times smaller in the absence of dissolved oxygen than in the presence of oxygen. These data indicate that radical intermediates are reduced back to the parent compound by Fe(II) in the absence of oxygen. Oxidation experiments with Fe(III)/H2O2 showed that the rate of decomposition of atrazine markedly increased in the presence of TCB and this increase has been attributed to a regeneration of Fe(II) by oxidation reactions of intermediates (radical species and dihydroxybenzenes) by Fe(III). PMID:11100792

  7. Size- and composition-dependent toxicity of synthetic and soil-derived Fe oxide colloids for the nematode Caenorhabditis elegans.

    PubMed

    Höss, Sebastian; Fritzsche, Andreas; Meyer, Carolin; Bosch, Julian; Meckenstock, Rainer U; Totsche, Kai Uwe

    2015-01-01

    Colloidal iron oxides (FeOx) are increasingly released to the environment due to their use in environmental remediation and biomedical applications, potentially harming living organisms. Size and composition could affect the bioavailability and toxicity of such colloids. Therefore, we investigated the toxicity of selected FeOx with variable aggregate size and variably composed FeOx-associated organic matter (OM) toward the nematode Caenorhabditis elegans. Ferrihydrite colloids containing citrate were taken up by C. elegans with the food and accumulated inside their body. The toxicity of ferrihydrite, goethite, and akaganeite was dependent on aggregate size and specific surface area, with EC50 values for reproduction ranging from 4 to 29 mg Fe L(-1). Experiments with mutant strains lacking mitochondrial superoxide dismutase (sod-2) showed oxidative stress for two FeOx and Fe(3+)-ions, however, revealed that it was not the predominant mechanism of toxicity. The OM composition determined the toxicity of mixed OM-FeOx phases on C. elegans. FeOx associated with humic acids or citrate were less toxic than OM-free FeOx. In contrast, soil-derived ferrihydrite, containing proteins and polysaccharides from mobile OM, was even more toxic than OM-free Fh of similar aggregate size. Consequently, the careful choice of the type of FeOx and the type of associated OM may help in reducing the ecological risks if actively applied to the subsurface. PMID:25438192

  8. The effects of Fe-oxidizing microorganisms on post-biostimulation permeability reduction and oxidative processes at the Rifle IFRC site

    SciTech Connect

    Chan, Clara Sze-Yue

    2015-07-02

    Fe oxidation and biomineral formation is important in aquifers because the highly-reactive oxides can control the mobility of nutrients (e.g. phosphate, C) and metals (e.g. arsenic, uranium). Mineral formation also has the potential to affect hydrology, depending on the volume and distribution in pore spaces. In this exploratory study, we sought to understand how microbial Fe-oxidizers and their biominerals affect, and are affected by groundwater flow. As part of work at the Rifle aquifer in Colorado, we initially hypothesized that Fe-oxidizers were contributing to aquifer clogging problems associated with enhanced bioremediation. To demonstrate the presence of Fe-oxidizers in the Rifle aquifer, we enriched FeOM from groundwater samples, and isolated two novel chemolithotrophic, microaerophilic Fe-oxidizing Betaproteobacteria, Hydrogenophaga sp. P101 and Curvibacter sp. CD03. To image cells and biominerals in the context of pores, we developed a “micro-aquifer,” a sand-filled flow-through culture chamber that allows for imaging of sediment pore space with multiphoton confocal microscopy. Fe oxide biofilms formed on sand grains, demonstrating that FeOM produce Fe oxide sand coatings. Fe coatings are common on aquifer sands, and tend to sequester contaminants; however, it has never previously been shown that microbes are responsible for their formation. In contrast to our original hypothesis, the biominerals did not clog the mini-aquifer. Instead, Fe biofilm distribution was dynamic: they grew as coatings, then periodically sloughed off sand grains, with some flocs later caught in pore throats. This has implications for physical hydrology, including pore scale architecture, and element transport. The sloughing of coatings likely prevents the biominerals from clogging wells and aquifers, at least initially. Although attached biomineral coatings sequester Fe-associated elements (e.g. P, As, C, U), when biominerals detach, these elements are transported as particles

  9. Performance of Al-Rich Oxidation Resistant Coatings For Fe-Base Alloys

    SciTech Connect

    Pint, Bruce A

    2010-01-01

    Aluminum-rich coatings made by chemical vapor deposition and pack cementation on ferritic (e.g. Fe-9Cr-1Mo) and austenitic (Type 304L) substrates are being evaluated at 650-800 C. For oxidation testing, a humid air environment was used to quantify coating performance, as uncoated substrates experience rapid oxidation at these temperatures. A main goal of this work is to demonstrate the potential benefits and problems with alumina-forming coatings. The higher exposure temperatures were selected to accelerate the degradation of the coating by interdiffusion with the substrate. A general conclusion of this testing was that coatings with less Al and a ferritic Fe(Al) structure could be more durable than higher Al content aluminide coatings which have a large thermal expansion mismatch with these substrates. A lifetime model has been developed using diffusion and oxidation observations to predict coating performance as a function of temperature and initial coating composition. To test and improve the model, additional experiments are now being conducted to determine the effect of substrate composition (e.g. Cr content using Fe-12Cr and Fe-9Cr-2W substrates) and exposure temperature on the critical Al content for coating failure. Because of the unexpectedly low level of Al measured at coating failure ({approx}3.5at.% at 700 C), exposures of specimens with thick ({approx}200 {mu}m) high Al content coatings were stopped after 10kh at 800 C and 20kh at 700 C because extremely long times to failure were predicted. Post-exposure Al concentration profiles for these specimens were measured using electron microprobe.

  10. Performance of Al-rich Oxidation Resistant Coatings for Fe-Base Alloys

    SciTech Connect

    Pint, Bruce A; Zhang, Ying

    2011-01-01

    Aluminum-rich coatings made by chemical vapor deposition and pack cementation on ferritic (e.g. Fe-9Cr-1Mo) and austenitic (Type 304L) substrates are being evaluated at 650-800 C. For oxidation testing, a humid air environment was used to quantify coating performance, as uncoated substrates experience rapid oxidation at these temperatures. A main goal of this work is to demonstrate the potential benefits and problems with alumina-forming coatings. The higher exposure temperatures were selected to accelerate the degradation of the coating by interdiffusion with the substrate. A general conclusion of this testing was that coatings with less Al and a ferritic Fe(Al) structure could be more durable than higher Al content aluminide coatings which have a large thermal expansion mismatch with these substrates. A lifetime model has been developed using diffusion and oxidation observations to predict coating performance as a function of temperature and initial coating composition. To test and improve the model, additional experiments are now being conducted to determine the effect of substrate composition (e.g. Cr content using Fe-12Cr and Fe-9Cr-2W substrates) and exposure temperature on the critical Al content for coating failure. Because of the unexpectedly low level of Al measured at coating failure ({approx}3.5 at.% at 700 C), exposures of specimens with thick ({approx}200 {micro}m) high Al content coatings were stopped after 10kh at 800 C and 20kh at 700 C because extremely long times to failure were predicted. Post-exposure Al concentration profiles for these specimens were measured using electron microprobe.

  11. Performance of Al-Rich Oxidation Resistant Coatings for Fe-Base Alloys

    SciTech Connect

    Pint, Bruce A; Zhang, Ying

    2009-01-01

    Aluminum-rich coatings made by chemical vapor deposition and pack cementation on ferritic (e.g. Fe-9Cr-1Mo) and austenitic (Type 304L) substrates are being evaluated at 650-800 C. For oxidation testing, a humid air environment was used to quantify coating performance, as uncoated substrates experience rapid oxidation at these temperatures. A main goal of this work is to demonstrate the potential benefits and problems with alumina-forming coatings. The higher exposure temperatures were selected to accelerate the degradation of the coating by interdiffusion with the substrate. A general conclusion of this testing was that coatings with less Al and a ferritic Fe(Al) structure could be more durable than higher Al content aluminide coatings which have a large thermal expansion mismatch with these substrates. A lifetime model has been developed using diffusion and oxidation observations to predict coating performance as a function of temperature and initial coating composition. To test and improve the model, additional experiments are now being conducted to determine the effect of substrate composition (e.g. Cr content using Fe-12Cr and Fe-9Cr-2W substrates) and exposure temperature on the critical Al content for coating failure. Because of the unexpectedly low level of Al measured at coating failure ({approx}3.5at.% at 700 C), exposures of specimens with thick ({approx}200 {micro}m) high Al content coatings were stopped after 10kh at 800 C and 20kh at 700 C because extremely long times to failure were predicted. Post-exposure Al concentration profiles for these specimens were measured using electron microprobe.

  12. Synthesis, structure and geometrically frustrated magnetism of the layered oxide-stannide compounds Fe(Fe3-xMnx)Si2Sn7O16.

    PubMed

    Allison, M C; Avdeev, M; Schmid, S; Liu, S; Söhnel, T; Ling, C D

    2016-06-21

    Fe4Si2Sn7O16 has a unique crystal structure that contains alternating layers of Fe(2+) ions octahedrally coordinated by O (oxide layer) and Sn (stannide layer), bridged by SiO4 tetrahedra. The formula can be written as FeFe3Si2Sn7O16 to emphasise the distinction between the layers. Here, we report the changes in structure and properties as iron is selectively replaced by manganese in the oxide layer. Solid-state synthesis was used to produce polycrystalline samples of Fe(Fe3-xMnx)Si2Sn7O16 for x≤ 2.55, the structures of which were characterised using high-resolution synchrotron X-ray and neutron powder diffraction. Single-crystal samples were also grown at x = 0.35, 0.95, 2.60 and characterised by single crystal X-ray diffraction. We show that manganese is doped exclusively into the oxide layer, and that this layer contains exclusively magnetically active high-spin M(2+) transition metal cations; while the stannide layer only accommodates non-magnetic low-spin Fe(2+). All samples show clear evidence of geometrically frustrated magnetism, which we associate with the fact that the topology of the high-spin M(2+) ions in the oxide layer describes a perfect kagomé lattice. Despite this frustration, the x = 0 and x = 2.55 samples undergo long-range antiferromagnetic ordering transitions at 3.0 K and 2.5 K, respectively. PMID:27225937

  13. Speciation and distribution of P associated with Fe and Al oxides in aggregate-sized fraction of an arable soil

    NASA Astrophysics Data System (ADS)

    Jiang, X.; Bol, R.; Willbold, S.; Vereecken, H.; Klumpp, E.

    2015-07-01

    To maximize crop productivity fertilizer P is generally applied to arable soils, a significant proportion of which becomes stabilized by mineral components and in part subsequently becomes unavailable to plants. However, little is known about the relative contributions of the different organic and inorganic P bound to Fe/Al oxides in the smaller soil particles. The alkaline (NaOH-Na2EDTA) extraction with solution 31P-nuclear magnetic resonance (31P-NMR) spectroscopy is considered as a reliable method for extracting and quantifying organic P and (some) inorganic P. However, any so-called residual P after the alkaline extraction has remained unidentified. Therefore, in the present study, the amorphous (a) and crystalline (c) Fe/Al oxide minerals and related P in soil aggregate-sized fractions (> 20, 2-20, 0.45-2 and < 0.45 μm) were specifically extracted by oxalate (a-Fe/Al oxides) and dithionite (DCB, both a- and c-Fe/Al oxides). These soil aggregate-sized fractions with and without the oxalate and DCB pre-treatments were then sequentially extracted by alkaline extraction prior to solution 31P-NMR spectroscopy. This was done to quantify the various chemical P forms which were associated with a- and c-Fe/Al oxides both in alkaline extraction and in the residual P of different soil aggregate-sized fractions. The results showed that overall P contents increased with decreasing size of the soil aggregate-sized fractions. However, the relative distribution and speciation of varying P forms were found to be independent of soil aggregate-size. The majority of alkaline extractable P was in the a-Fe/Al oxide fraction (42-47 % of total P), most of which was orthophosphate (36-41 % of total P). Furthermore, still significant amounts of particularly monoester P were bound to the oxides. Intriguingly, however, Fe/Al oxides were not the main bonding sites for pyrophosphate. Residual P contained similar amounts of total P associated with both a- (10-13 % of total P) and c-Fe

  14. Speciation and distribution of P associated with Fe and Al oxides in aggregate-sized fraction of an arable soil

    NASA Astrophysics Data System (ADS)

    Jiang, X.; Bol, R.; Willbold, S.; Vereecken, H.; Klumpp, E.

    2015-11-01

    To maximize crop productivity fertilizer P is generally applied to arable soils, a significant proportion of which becomes stabilized by mineral components and in part subsequently becomes unavailable to plants. However, little is known about the relative contributions of the different organic and inorganic P bound to Fe/Al oxides in the smaller soil particles. Alkaline (NaOH-Na2EDTA) extraction with solution 31P-nuclear magnetic resonance (31P-NMR) spectroscopy is considered a reliable method for extracting and quantifying organic P and (some) inorganic P. However, any so-called residual P after the alkaline extraction has remained unidentified. Therefore, in the present study, the amorphous (a) and crystalline (c) Fe/Al oxide minerals and related P in soil aggregate-sized fractions (> 20, 2-20, 0.45-2 and < 0.45 μm) were specifically extracted by oxalate (a-Fe/Al oxides) and dithionite-citrate-bicarbonate (DCB, both a- and c-Fe/Al oxides). These soil aggregate-sized fractions with and without the oxalate and DCB pre-treatments were then sequentially extracted by alkaline extraction prior to solution 31P-NMR spectroscopy. This was done to quantify the P associated with a- and c-Fe/Al oxides in both alkaline extraction and the residual P of different soil aggregate-sized fractions. The results showed that overall P contents increased with decreasing size of the soil aggregate-sized fractions. However, the relative distribution and speciation of varying P forms were found to be independent of soil aggregate-size. The majority of alkaline-extractable P was in the a-Fe/Al oxide fraction (42-47 % of total P), most of which was ortho-phosphate (36-41 % of total P). Furthermore, still significant amounts of particularly monoester P were bound to these oxides. Intriguingly, however, Fe/Al oxides were not the main bonding sites for pyrophosphate. Residual P contained similar amounts of total P associated with both a- (11-15 % of total P) and c-Fe oxides (7-13 % of total P

  15. Behavior of Ni, Zn and Cr during low temperature aqueous Fe oxidation processes on Mars

    NASA Astrophysics Data System (ADS)

    Zhao, Yu-Yan S.; McLennan, Scott M.

    2013-05-01

    The behavior of Ni(II), Zn(II) and Cr(III) during the melanterite (FeSO4·7H2O) to hematite (α-Fe2O3) oxidative transformations involving evolution pathways via jarosite ((H3O,K)Fe3(OH)6(SO4)2), schwertmannite (Fe8O8(OH)6(SO4)) and goethite (α-FeOOH) were investigated in an acidic saturated MgSO4 matrix. Results provide important clues about how elevated levels of trace elements are incorporated into the secondary Fe mineralogy assemblages found on Mars and the mechanism for formation of hematitic concretions at Meridiani Planum on Mars. Our results demonstrate that starting at the same concentrations in the initial solution, final amounts of Ni, Zn and Cr in hematite via different pathways are very different. In Path 1 (melanterite → jarosite → hematite), partitioning of Ni, Zn and Cr into jarosite and hematite (formed through dissolution of jarosite) is most likely in the order: Cr > Zn > Ni. In Path 2 (melanterite → schwertmannite → goethite → hematite), schwertmannite and goethite exhibited strong affinities for divalent Ni and Zn. During such a pathway, Ni should accumulate more than Zn by at least a factor of two, and partitioning of Ni, Zn and Cr to the hematite is most likely in the order: Cr > Ni > Zn. Therefore, our results suggest that the high Ni and moderate Zn distribution pattern observed in Meridiani hematitic spherule-bearing samples can be explained best by the schwertmannite-goethite to hematite pathway (Path 2), without need for an additional high Ni source in this region. Although the lack of goethite at Meridiani renders it uncertain if goethite ever served as a precursor to facilitate hematite formation, dehydration of nano-crystalline goethite is thermodynamically favored and cannot be ruled out. On the other hand, if hematitic concretions were formed by dissolution of jarosite (Path 1), then much higher initial Ni/Zn ratios than 1 in initial diagenetic fluids may be necessary to explain the elevated levels of Ni in the spherules

  16. Drop shaped zinc oxide quantum dots and their self-assembly into dendritic nanostructures: Liquid assisted pulsed laser ablation and characterizations

    NASA Astrophysics Data System (ADS)

    Singh, Subhash C.; Gopal, Ram

    2012-01-01

    Complex nanostructures and nano-assemblies have exhibited their potential application in the fabrication of future molecular machines and molecular devices. Liquid phase pulsed laser ablation is an easy, versatile, environmental friendly and rapidly growing method for the synthesis of nanostructured materials. Nanosecond pulsed laser ablation of zinc rod placed on the bottom of glass vessel containing methanol is used to produce colloidal solution of drop shaped zinc oxide quantum dots and their self-assembly into various dendritic nanostructures. UV-vis absorption, diffuse reflectance, transmission electron microscopy, and photoluminescence spectroscopy techniques are used for the optical, microscopic, structural and defect diagnosis of obtained colloidal quantum dots and their nano-assemblies. The average length, width and aspect ratio of drop shaped zinc oxide quantum dots are 6 ± 2.4 nm, 3.5 ± 1.4 nm and 1.69 ± 0.4 nm, respectively. Careful investigation of assemblies shows that most of them have linear growth, i.e. growth in longitudinal direction is higher as compared to the transverse direction with three types of classifications as (i) linear axis symmetrical branching, (ii) linear axis asymmetrical branching and (iii) curvilinear axis asymmetrical branching. Photoluminescence spectrum has emission peaks in UV, violet, blue and green spectral region corresponding to the excitonic and various defect related emissions.

  17. Evaluation of Fe(II) oxidation at an acid mine drainage site using laboratory-scale reactors

    NASA Astrophysics Data System (ADS)

    Brown, Juliana; Burgos, William

    2010-05-01

    Acid mine drainage (AMD) is a severe environmental threat to the Appalachian region of the Eastern United States. The Susquehanna and Potomac River basins of Pennsylvania drain to the Chesapeake Bay, which is heavily polluted by acidity and metals from AMD. This study attempted to unravel the complex relationships between AMD geochemistry, microbial communities, hydrodynamic conditions, and the mineral precipitates for low-pH Fe mounds formed downstream of deep mine discharges, such as Lower Red Eyes in Somerset County, PA, USA. This site is contaminated with high concentrations of Fe (550 mg/L), Mn (115 mg/L), and other trace metals. At the site 95% of dissolved Fe(II) and 56% of total dissolved Fe is removed without treatment, across the mound, but there is no change in the concentration of trace metals. Fe(III) oxides were collected across the Red Eyes Fe mound and precipitates were analyzed by X-ray diffraction, electron microscopy and elemental analysis. Schwertmannite was the dominant mineral phase with traces of goethite. The precipitates also contained minor amounts of Al2O3, MgO,and P2O5. Laboratory flow-through reactors were constructed to quantify Fe(II) oxidation and Fe removal over time at terrace and pool depositional facies. Conditions such as residence time, number of reactors in sequence and water column height were varied to determine optimal conditions for Fe removal. Reactors with sediments collected from an upstream terrace oxidized more than 50% of dissolved Fe(II) at a ten hour residence time, while upstream pool sediments only oxidized 40% of dissolved Fe(II). Downstream terrace and pool sediments were only capable of oxidizing 25% and 20% of Fe(II), respectively. Fe(II) oxidation rates measured in the reactors were determined to be between 3.99 x 10-8and 1.94 x 10-7mol L-1s-1. The sediments were not as efficient for total dissolved Fe removal and only 25% was removed under optimal conditions. The removal efficiency for all sediments

  18. Electrocatalytic oxidation behavior of NADH at Pt/Fe3O4/reduced-graphene oxide nanohybrids modified glassy carbon electrode and its determination.

    PubMed

    Roushani, Mahmoud; Hoseini, S Jafar; Azadpour, Mitra; Heidari, Vahid; Bahrami, Mehrangiz; Maddahfar, Mahnaz

    2016-10-01

    We have developed Pt/Fe3O4/reduced-graphene oxide nanohybrids modified glassy carbon (Pt/Fe3O4/RGO/GC) electrode as a novel system for the preparation of electrochemical sensing platform. Characterization of as-made composite was determined using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy (AFM) and energy-dispersive analysis of X-ray (EDAX) where the Pt, Fe, Si, O and C elements were observed. The Pt/Fe3O4/RGO/GC electrode was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Due to the synergistic effect between Pt, Fe3O4 and RGO, the nanohybrid exhibited excellent performance toward dihydronicotinamide adenine dinucleotide (NADH) oxidation in 0.1M phosphate buffer solution, pH7.0, with a low detection limit of 5nM. PMID:27287119

  19. Effects of oxidation of DyH3 in Nd-Fe-B sintered magnets

    NASA Astrophysics Data System (ADS)

    Yan, Gao-Lin; Fang, Zhi-Hao

    2015-10-01

    The effects of oxidation of DyH3 with respect to dysprosium addition to Nd-Fe-B sintered magnets are examined. Samples sintered with the addition of freshly milled dysprosium hydride, dysprosium hydride exposed to air at room temperature for 15 min and dysprosium hydride exposed to air at 100 °C for 3.5 hours are studied from the aspects of magnetic properties, microstructures, and their degradation, respectively. It is found that some oxidized dysprosium is distributed in the Nd-rich phase; hence, the decrease of remanence occurred. The degradation results indicate that pre-oxidised dysprosium can be a major factor in increasing the corrosion rate. The microstructures and corrosion acceleration test suggested that the oxidation is detrimental to remanence. Project supported by the National Natural Science Foundation of China (Grant Nos. 51172168 and 51072139) and the Science Funds from the Ministry of Science and Technology, China (Grant Nos. 2014DFB50130 and 2011CB612304).

  20. Combined magnetic and structural investigation of nano crystalline iron oxides: The interplay between crystal size and phase composition during FeS 2 oxidation

    NASA Astrophysics Data System (ADS)

    Eneroth, Erik

    2007-01-01

    The oxides that form during thermal oxidation of natural FeS 2 (pyrite and marcasite) consist of nanometer-sized crystals of α-Fe 2O 3 and γ-Fe 2O 3. This is shown with heating experiments that were made up to 650 °C, which resembles temperatures used in metallurgical processes. It is shown that magnetic measurements can play a key role in the investigation of this reaction, due to the unwanted blurring effects associated with finite crystal sizes if other methods are used. According to Mössbauer spectra combined with pXRD, many α-Fe 2O 3 crystals are in a stable magnetic state only due to the formation of bridging superexchange interactions in between them, but the γ-Fe 2O 3 experiences super-paramagnetic relaxation ceasing first at 20 K. Magnetisation measurements were used for two main purposes (1) determination of the amounts of γ-Fe 2O 3 in the products, and (2) for characterization of γ-Fe 2O 3 with respect to crystal size and possible magnetic surface effects such as spin-glass. It is proven that fine FeS 2 grains produce more γ-Fe 2O 3 than coarse. At 500 °C the fine FeS 2 grains oxidised into c. 30% γ-Fe 2O 3 and ca. 70% α-Fe 2O 3. At 525 °C, the γ-Fe 2O 3 amounts were also estimated in coarse oxidised FeS 2, and results were ca. 20% and 10% γ-Fe 2O 3 for the fine and coarse FeS 2 respectively. The γ-Fe 2O 3 crystal sizes were a function of both temperature and grain size, and it decreased with decreasing grain size, and upon rising the temperature from 450 to 550 °C. It is argued that the estimated errors during γ-Fe 2O 3 amount determination are due mainly to disordered magnetic sublattices at the crystal faces of γ-Fe 2O 3, giving an error of ca. 15% for those samples that have the smallest crystals.

  1. Controlled growth of LaFeO3 nanoparticles on reduced graphene oxide for highly efficient photocatalysis.

    PubMed

    Ren, Xiao; Yang, Haitao; Gen, Sai; Zhou, Jun; Yang, Tianzhong; Zhang, Xiangqun; Cheng, Zhaohua; Sun, Shouheng

    2016-01-14

    Using reduced graphene oxide (rGO) as a template and high temperature sol-gel chemistry, we have prepared LaFeO3 nanoparticles (NPs). The 15 nm LaFeO3 NPs have a bandgap of 1.86 eV and the LaFeO3-rGO can function as an efficient catalyst for degradation of methylene blue (MB) or Rhodamine B (RhB) under visible-light irradiation with the electron transfer from the dye to hole dominating the oxidation process. The reported synthesis offers a general approach to perovskite-type NPs for efficient photocatalytic applications. PMID:26658850

  2. Identification and Characterization of MtoA: A Decaheme c-Type Cytochrome of the Neutrophilic Fe(II)-Oxidizing Bacterium Sideroxydans lithotrophicus ES-1

    PubMed Central

    Liu, Juan; Wang, Zheming; Belchik, Sara M.; Edwards, Marcus J.; Liu, Chongxuan; Kennedy, David W.; Merkley, Eric D.; Lipton, Mary S.; Butt, Julea N.; Richardson, David J.; Zachara, John M.; Fredrickson, James K.; Rosso, Kevin M.; Shi, Liang

    2012-01-01

    The Gram-negative bacterium Sideroxydans lithotrophicus ES-1 (ES-1) grows on FeCO3 or FeS at oxic–anoxic interfaces at circumneutral pH, and the ES-1-mediated Fe(II) oxidation occurs extracellularly. However, the molecular mechanisms underlying ES-1’s ability to oxidize Fe(II) remain unknown. Survey of the ES-1 genome for candidate genes for microbial extracellular Fe(II) oxidation revealed that it contained a three-gene cluster encoding homologs of Shewanella oneidensis MR-1 (MR-1) MtrA, MtrB, and CymA that are involved in extracellular Fe(III) reduction. Homologs of MtrA and MtrB were also previously shown to be involved in extracellular Fe(II) oxidation by Rhodopseudomonas palustris TIE-1. To distinguish them from those found in MR-1, the identified homologs were named MtoAB and CymAES-1. Cloned mtoA partially complemented an MR-1 mutant without MtrA with regards to ferrihydrite reduction. Characterization of purified MtoA showed that it was a decaheme c-type cytochrome and oxidized soluble Fe(II). Oxidation of Fe(II) by MtoA was pH- and Fe(II)-complexing ligand-dependent. Under conditions tested, MtoA oxidized Fe(II) from pH 7 to pH 9 with the optimal rate at pH 9. MtoA oxidized Fe(II) complexed with different ligands at different rates. The reaction rates followed the order Fe(II)Cl2 >  Fe(II)–citrate > Fe(II)–NTA > Fe(II)–EDTA with the second-order rate constants ranging from 6.3 × 10−3 μM−1 s−1 for oxidation of Fe(II)Cl2 to 1.0 × 10−3 μM−1 s−1 for oxidation of Fe(II)–EDTA. Thermodynamic modeling showed that redox reaction rates for the different Fe(II)-complexes correlated with their respective estimated reaction-free energies. Collectively, these results demonstrate that MtoA is a functional Fe(II)-oxidizing protein that, by working in concert with MtoB and CymAES-1, may oxidize Fe(II) at the bacterial surface and transfer released electrons across the bacterial cell envelope to the quinone pool in the

  3. Oxidation of Refractory Benzothiazoles with PMS/CuFe2O4: Kinetics and Transformation Intermediates.

    PubMed

    Zhang, Tao; Chen, Yin; Leiknes, TorOve

    2016-06-01

    Benzothiazole (BTH) and its derivatives 2-(methylthio)bezothiazole (MTBT), 2-benzothiazolsulfonate (BTSA), and 2-hydroxybenzothiazole (OHBT) are refractory pollutants ubiquitously existing in urban runoff at relatively high concentrations. Here, we report their oxidation by CuFe2O4-activated peroxomonosulfate (PMS/CuFe2O4), focusing on kinetics and transformation intermediates. These benzothiazoles can be efficiently degraded by this oxidation process, which is confirmed to generate mainly sulfate radicals (with negligible hydroxyl-radical formation) under slightly acidic to neutral pH conditions. The molar exposure ratio of sulfate radical to residual PMS (i.e., Rct) for this process is a constant that is related to the reaction condition and can be easily determined. The reaction rate constants of these benzothiazoles toward sulfate radical are (3.3 ± 0.3) × 10(9), (1.4 ± 0.3) × 10(9), (1.5 ± 0.1) × 10(9), and (4.7 ± 0.5) × 10(9) M(-1) s(-1), respectively (pH 7 and 20 °C). On the basis of Rct and these rate constants, their degradation in the presence of organic matter can be well-predicted. A number of transformation products were detected and tentatively identified using triple-quadruple/linear ion trap MS/MS and high-resolution MS. It appears that sulfate radicals attack BTH, MTBT, and BTSA on their benzo ring via electron transfer, generating multiple hydroxylated intermediates that are reactive toward common oxidants. For OHBT oxidation, the thiazole ring is preferentially broken down. Due to competitions of the transformation intermediates, a minimum PMS/pollutant molar ratio of 10-20 is required for effective degradation. The flexible PMS/CuFe2O4 could be a useful process to remove the benzothiazoles from low dissolved organic carbon waters like urban runoff or polluted groundwater. PMID:27144396

  4. Inhibition of the Fe(III)-Catalyzed Dopamine Oxidation by ATP and Its Relevance to Oxidative Stress in Parkinson’s Disease

    PubMed Central

    2013-01-01

    Parkinson’s disease (PD) is characterized by the progressive degeneration of dopaminergic cells, which implicates a role of dopamine (DA) in the etiology of PD. A possible DA degradation pathway is the Fe(III)-catalyzed oxidation of DA by oxygen, which produces neuronal toxins as side products. We investigated how ATP, an abundant and ubiquitous molecule in cellular milieu, affects the catalytic oxidation reaction of dopamine. For the first time, a unique, highly stable DA–Fe(III)–ATP ternary complex was formed and characterized in vitro. ATP as a ligand shifts the catecholate–Fe(III) ligand metal charge transfer (LMCT) band to a longer wavelength and the redox potentials of both DA and the Fe(III) center in the ternary complex. Remarkably, the additional ligation by ATP was found to significantly reverse the catalytic effect of the Fe(III) center on the DA oxidation. The reversal is attributed to the full occupation of the Fe(III) coordination sites by ATP and DA, which blocks O2 from accessing the Fe(III) center and its further reaction with DA. The biological relevance of this complex is strongly implicated by the identification of the ternary complex in the substantia nigra of rat brain and its attenuation of cytotoxicity of the Fe(III)–DA complex. Since ATP deficiency accompanies PD and neurotoxin 1-methyl-4-phenylpyridinium (MPP+) induced PD, deficiency of ATP and the resultant impairment toward the inhibition of the Fe(III)-catalyzed DA oxidation may contribute to the pathogenesis of PD. Our finding provides new insight into the pathways of DA oxidation and its relationship with synaptic activity. PMID:23823941

  5. A Novel Lineage of Proteobacteria Involved in Formation of Marine Fe-Oxidizing Microbial Mat Communities

    PubMed Central

    Emerson, David; Rentz, Jeremy A.; Lilburn, Timothy G.; Davis, Richard E.; Chan, Clara; Moyer, Craig L.

    2007-01-01

    Background For decades it has been recognized that neutrophilic Fe-oxidizing bacteria (FeOB) are associated with hydrothermal venting of Fe(II)-rich fluids associated with seamounts in the world's oceans. The evidence was based almost entirely on the mineralogical remains of the microbes, which themselves had neither been brought into culture or been assigned to a specific phylogenetic clade. We have used both cultivation and cultivation-independent techniques to study Fe-rich microbial mats associated with hydrothermal venting at Loihi Seamount, a submarine volcano. Methodology/Principle Findings Using gradient enrichment techniques, two iron-oxidizing bacteria, strains PV-1 and JV-1, were isolated. Chemolithotrophic growth was observed under microaerobic conditions; Fe(II) and Fe0 were the only energy sources that supported growth. Both strains produced filamentous stalk-like structures composed of multiple nanometer sized fibrils of Fe-oxyhydroxide. These were consistent with mineralogical structures found in the iron mats. Phylogenetic analysis of the small subunit (SSU) rRNA gene demonstrated that strains PV-1 and JV-1 were identical and formed a monophyletic group deeply rooted within the Proteobacteria. The most similar sequence (85.3% similarity) from a cultivated isolate came from Methylophaga marina. Phylogenetic analysis of the RecA and GyrB protein sequences confirmed that these strains are distantly related to other members of the Proteobacteria. A cultivation-independent analysis of the SSU rRNA gene by terminal-restriction fragment (T-RF) profiling showed that this phylotype was most common in a variety of microbial mats collected at different times and locations at Loihi. Conclusions On the basis of phylogenetic and physiological data, it is proposed that isolate PV-1T ( = ATCC BAA-1019: JCM 14766) represents the type strain of a novel species in a new genus, Mariprofundus ferrooxydans gen. nov., sp. nov. Furthermore, the strain is the first

  6. Perpendicular magnetic anisotropy and magnetization dynamics in oxidized CoFeAl films.

    PubMed

    Wu, Di; Zhang, Zhe; Li, Le; Zhang, Zongzhi; Zhao, H B; Wang, J; Ma, B; Jin, Q Y

    2015-01-01

    Half-metallic Co-based full-Heusler alloys with perpendicular magnetic anisotropy (PMA), such as Co2FeAl in contact with MgO, are receiving increased attention recently due to its full spin polarization for high density memory applications. However, the PMA induced by MgO interface can only be realized for very thin magnetic layers (usually below 1.3 nm), which would have strong adverse effects on the material properties of spin polarization, Gilbert damping parameter, and magnetic stability. In order to solve this issue, we fabricated oxidized Co50Fe25Al25 (CFAO) films with proper thicknesses without employing the MgO layer. The samples show controllable PMA by tuning the oxygen pressure (PO2) and CFAO thickness (tCFAO), large perpendicular anisotropy field of ~8.0 kOe can be achieved at PO2 = 12% for the sample of tCFAO = 2.1 nm or at PO2 = 7% for tCFAO = 2.8 nm. The loss of PMA at thick tCFAO or high PO2 results mainly from the formation of large amount of CoFe oxides, which are superparamagnetic at room temperature but become hard magnetic at low temperatures. The magnetic CFAO films, with strong PMA in a relatively wide thickness range and small intrinsic damping parameter below 0.028, would find great applications in developing advanced spintronic devices. PMID:26190066

  7. Chemistry of arsenic removal during coagulation and Fe-Mn oxidation

    SciTech Connect

    Edwards, M. . Dept. of Civil Engineering)

    1994-09-01

    Arsenic removal during coagulation or Fe-Mn oxidation is examined to aid utilities that desire to improve arsenic removal. Fundamental mechanisms of arsenic removal are discussed, optimization strategies are forwarded, and some new insights are provided to guide future research. Specifically, As(III) removals by coagulation are primarily controlled by coagulant dose and relatively unaffected by solution pH, whereas the converse is true for As(V). When compared on the basis of moles iron or aluminum hydroxide solid formed during coagulation, iron and aluminum coagulants are of demonstrably equal effectiveness in removing As(V) at pH < 7.5. However, iron-based coagulants are advantageous if soluble metal residuals are problematic, if pH is > 7.5, or if the raw water contains As(III). Arsenic removal during Fe-Mn oxidation is controlled by the quantity of iron removed [Fe(OH)[sub 3] formed] and is relatively independent of the quantity of manganese removed (MnOOH formed). 63 refs.

  8. Oxide scales formed on Fe-Cr-Al-based model alloys exposed to oxygen containing molten lead

    NASA Astrophysics Data System (ADS)

    Weisenburger, A.; Jianu, A.; Doyle, S.; Bruns, M.; Fetzer, R.; Heinzel, A.; DelGiacco, M.; An, W.; Müller, G.

    2013-06-01

    Based on the state of the art oxide maps concerning oxidation behavior of Fe-Cr-Al model alloys at 800 and 1000 °C in oxygen atmosphere, ten compositions, belonging to this alloy system, were designed in order to tap the borders of the alumina stability domain, during their exposure to oxygen (10-6 wt.%) containing lead, at 400, 500 and 600 °C. Eight alloys, Fe-6Cr-6Al, Fe-8Cr-6Al, Fe-10Cr-5Al, Fe-14Cr-4Al, Fe-16Cr-4Al, Fe-6Cr-8Al, Fe-10Cr-7Al and Fe-12Cr-5Al, were found to be protected against corrosion in oxygen containing lead, either by a duplex layer (Fe3O4 + (Fe1-x-yCrxAly)3O4) or by (Fe1-x-yCrxAly)3O4, depending on the temperature at which they were exposed. Two alloys namely Fe-12Cr-7Al and Fe-16Cr-6Al were found to form transient aluminas, κ-Al2O3 (at 400 and 500 °C) and θ-Al2O3 (at 600 °C), as protective oxide scale against corrosion in oxygen containing lead. An oxide map illustrating the stability domain of alumina, grown on Fe-Cr-Al alloys when exposed to molten, oxygen containing lead, was drawn. The map includes also additional points, extracted from literature and corresponding to alumina forming alloys, when exposed to HLMs, which fit very well with our findings. Chromium and aluminium contents of 12.5-17 wt.% and 6-7.5 wt.%, respectively, are high enough to obtain thin, stable and protective alumina scales on Fe-Cr-Al-based alloys exposed to oxygen containing lead at 400, 500 and 600 °C. For the temperature range and exposure times used during the current evaluation, the growth rate of the alumina scale was low. No area with detached scale was observed and no trace of α-Al2O3 was detected.

  9. Effects of oxide precursors on superconducting properties of polycrystalline SmFeAsO1-xFx

    NASA Astrophysics Data System (ADS)

    Yuan, F. F.; Ding, Y.; Sun, Y.; Zhuang, J. C.; Zhou, W.; Li, G. Z.; Sumption, M.; Li, X. W.; Shi, Z. X.

    2013-12-01

    A series of polycrystalline SmFeAsO1-xFx samples were synthesized by one-step and two-step method at ambient pressure using different oxide precursors, namely As2O3, Fe2O3 and nano-Fe2O3 powder, as the source of element O. Results of X-ray diffraction and magnetic measurements manifest that starting oxides affected the phase formation and superconducting properties of SmFeAsO1-xFx. As2O3 as oxide precursor contributes to the fast formation of superconducting phase for a short period of sintering time. And samples prepared using As2O3 show higher superconducting transition temperature Tc and more stable fluorine doping level. Compared with Fe2O3, nano-Fe2O3 promotes fluorine doping into the O site. While using Fe2O3 leads to higher level of Fe and SmOF impurities. The critical current density Jcm were derived from magnetic hysteresis loops. Sample prepared using As2O3 shows higher Jcm in low temperature and high magnetic fields.

  10. Oxidation and electrical behavior of ferritic stainless steel interconnect with Fe-Co-Ni coating by electroplating

    NASA Astrophysics Data System (ADS)

    Geng, Shujiang; Qi, Shaojun; Xiang, Dong; Zhu, Shenglong; Wang, Fuhui

    2012-10-01

    Fe-Co-Ni coating is deposited on ferritic stainless steel using a cost-effective technique of electroplating for intermediate-temperature solid oxide fuel cell (SOFC) interconnects application. The steel with Fe-Co-Ni coating has been evaluated in air at 800 °C corresponding to the cathode environment of SOFC. The results indicate that the steel with Fe-Co-Ni coating experiences an initially large mass gain, and then the mass gain increases slightly after the first-week rapid oxidation stage. After thermal exposure in air at 800 °C, the Fe-Co-Ni coating has been converted into (Fe,Co,Ni)3O4 spinel layer underneath which a Cr2O3 layer is developed from the steel substrate. The outer layer of (Fe,Co,Ni)3O4 spinel has not only suppressed Cr migration outward but also reduced the growth rate of the inner layer of Cr2O3. The steel with Fe-Co-Ni coating exhibits a stable surface oxide scale area specific resistance (ASR) which is much lower than that of the bare steel. (Fe,Co,Ni)3O4 spinel is a promising protective coating for SOFC steel interconnect.

  11. Characterization of transparent superconductivity Fe-doped CuCrO2 delafossite oxide

    NASA Astrophysics Data System (ADS)

    Taddee, Chutirat; Kamwanna, Teerasak; Amornkitbamrung, Vittaya

    2016-09-01

    Delafossite CuCr1-xFexO2 (0.0 ≤ x ≤ 0.15) semiconductors were synthesized using a self-combustion urea nitrate process. The effects of Fe concentration on its microstructural, optical, magnetic, and electrical properties were investigated. X-ray diffraction (XRD) analysis results revealed the delafossite structure in all the samples. The lattice spacing of CuCr1-xFexO2 slightly increased with increasing substitution of Fe at the Cr sites. The optical properties measured at room temperature using UV-visible spectroscopy showed a weak absorbability in the visible light and near IR regions. The corresponding direct optical band gap was about 3.61 eV, exhibiting transparency in the visible region. The magnetic hysteresis loop measurements showed that the Fe-doped CuCrO2 samples exhibited ferromagnetic behavior at room temperature. This indicated that the substitution of Fe3+ for Cr3+ produced a mixed effect on the magnetic properties of CuCrO2 delafossite oxide. The temperature dependent resistivity measurements clearly revealed the presence of superconductivity in the CuCr1-xFexO2 with a superconducting transition up to 118 K.

  12. Adsorption mechanism of magnetically separable Fe3O4/graphene oxide hybrids

    NASA Astrophysics Data System (ADS)

    Ouyang, Ke; Zhu, Chuanhe; Zhao, Ya; Wang, Leichao; Xie, Shan; Wang, Qun

    2015-11-01

    A reclaimable Fe3O4/graphene oxide (GO) magnetic hybrid was successfully synthesized via a facile one-pot polyol approach and employed as a recyclable adsorbent for Bisphenol A (BPA) in aqueous solutions. The maximum adsorption capacity (qm) of the Fe3O4/GO hybrid for BPA was 72.80 mg/g at 273 K. The kinetics of the adsorption process and the adsorption isotherm data were fitted using the Freundlich equation and a pseudo-second-order kinetic model. The results of the thermodynamic parameters ΔH°, ΔS° and ΔG° showed that the adsorption process was exothermic and spontaneous. Furthermore, the reusability of the samples was investigated, and the results indicated that the samples exhibited high stability. The magnetic characterization demonstrated that hybrids were superparamagnetic and could be recovered conveniently by magnetic separation. The strong π-π interaction was determined to be the predominant driving force behind the adsorption of BPA onto the Fe3O4/GO hybrid. Therefore, the Fe3O4/GO hybrid could be regarded as a potential adsorbent for wastewater treatment and purification processes.

  13. Applicability of anaerobic nitrate-dependent Fe(II) oxidation to microbial enhanced oil recovery (MEOR).

    PubMed

    Zhu, Hongbo; Carlson, Han K; Coates, John D

    2013-08-01

    Microbial processes that produce solid-phase minerals could be judiciously applied to modify rock porosity with subsequent alteration and improvement of floodwater sweep in petroleum reservoirs. However, there has been little investigation of the application of this to enhanced oil recovery (EOR). Here, we investigate a unique approach of altering reservoir petrology through the biogenesis of authigenic rock minerals. This process is mediated by anaerobic chemolithotrophic nitrate-dependent Fe(II)-oxidizing microorganisms that precipitate iron minerals from the metabolism of soluble ferrous iron (Fe(2+)) coupled to the reduction of nitrate. This mineral biogenesis can result in pore restriction and reduced pore throat diameter. Advantageously and unlike biomass plugs, these biominerals are not susceptible to pressure or thermal degradation. Furthermore, they do not require continual substrate addition for maintenance. Our studies demonstrate that the biogenesis of insoluble iron minerals in packed-bed columns results in effective hydrology alteration and homogenization of heterogeneous flowpaths upon stimulated microbial Fe(2+) biooxidation. We also demonstrate almost 100% improvement in oil recovery from hydrocarbon-saturated packed-bed columns as a result of this metabolism. These studies represent a novel departure from traditional microbial EOR approaches and indicate the potential for nitrate-dependent Fe(2+) biooxidation to improve volumetric sweep efficiency and enhance both the quality and quantity of oil recovered. PMID:23799785

  14. Controlled assembly of Fe3O4 magnetic nanoparticles on graphene oxide.

    PubMed

    Zhang, Yi; Chen, Biao; Zhang, Liming; Huang, Jie; Chen, Fenghua; Yang, Zupei; Yao, Jianlin; Zhang, Zhijun

    2011-04-01

    We describe a facile approach to controllable assembly of monodisperse Fe(3)O(4) nanoparticles (NPs) on chemically reduced graphene oxide (rGO). First, reduction and functionalization of GO by polyetheylenimine (PEI) were achieved simultaneously by simply heating the PEI and GO mixture at 60 °C for 12 h. The process is environmentally friendly and convenient compared with previously reported methods. Meso-2,3-dimercaptosuccinnic acid (DMSA)-modified Fe(3)O(4) NPs were then conjugated to the PEI moiety which is located on the periphery of the GO sheets via formation of amide bonds between COOH groups of DMSA molecules bound on the surface of the Fe(3)O(4) NPs and amine groups of PEI. The magnetic GO composites were characterized by means of TEM, AFM, UV-vis, FTIR, Raman, TGA, and VSM measurements. Finally, preliminary results of using the Fe(3)O(4)-rGO composites for efficient removal of tetracycline, an antibiotic that is often found as a contaminant in the environment, are reported. PMID:21301708

  15. Constructing hierarchical interfaces: TiO2-supported PtFe-FeOx nanowires for room temperature CO oxidation

    SciTech Connect

    Zhu, Huiyuan; Wu, Zili; Dong, Su; Veith, Gabriel M.; Lu, Hanfeng; Zhang, Pengfei; Chai, Song -Hai; Dai, Sheng

    2015-08-05

    This is a report of a facile approach to constructing catalytic active hierarchical interfaces in one-dimensional (1D) nanostructure, exemplified by the synthesis of TiO2-supported PtFe–FeOx nanowires (NWs). The hierarchical interface, constituting atomic level interactions between PtFe and FeOx within each NW and the interactions between NWs and support (TiO2), enables CO oxidation with 100% conversion at room temperature. We identify the role of the two interfaces by probing the CO oxidation reaction with isotopic labeling experiments. Both the oxygen atoms (Os) in FeOx and TiO2 participate in the initial CO oxidation, facilitating the reaction through a redox pathway. Moreover, the intact 1D structure leads to the high stability of the catalyst. After 30 h in the reaction stream, the PtFe–FeOx/TiO2 catalyst exhibits no activity decay. These results provide a general approach and new insights into the construction of hierarchical interfaces for advanced catalysis.

  16. Identifying the redox activity of cation-disordered Li-Fe-V-Ti oxide cathodes for Li-ion batteries.

    PubMed

    Chen, Ruiyong; Witte, Ralf; Heinzmann, Ralf; Ren, Shuhua; Mangold, Stefan; Hahn, Horst; Hempelmann, Rolf; Ehrenberg, Helmut; Indris, Sylvio

    2016-03-01

    Cation-disordered oxides have recently shown promising properties on the way to explore high-performance intercalation cathode materials for rechargeable Li-ion batteries. Here, stoichiometric cation-disordered Li2FeVyTi1-yO4 (y = 0, 0.2, 0.5) nanoparticles are studied. The substitution of V for Ti in Li2FeVyTi1-yO4 increases the content of active transition metals (Fe and V) and accordingly the amount of Li(+) (about (1 + y)Li(+) capacity per formula unit) that can be reversibly intercalated. It is found that Fe(3+)/Fe(2+) and V(4+)/V(3+) redox couples contribute to the overall capacity performance, whereas Ti(4+) remains mainly inert. There is no evidence for the presence of Fe(4+) species after charging to 4.8 V, as confirmed from the ex situ(57)Fe Mössbauer spectroscopy and the Fe K-edge absorption spectra. The redox couple reactions for iron and vanadium are examined by performing in situ synchrotron X-ray absorption spectroscopy. During charging/discharging, the spectral evolution of the K-edges for Fe and V confirms the reversible Fe(3+)/Fe(2+) and V(4+)/V(3+) redox reactions during cycling between 1.5 and 4.8 V. PMID:26907961

  17. Oxidative catalytic evolution of redox- and spin-states of a Fe-phthalocyanine studied by EPR

    NASA Astrophysics Data System (ADS)

    Bletsa, Eleni; Solakidou, Maria; Louloudi, Maria; Deligiannakis, Yiannis

    2016-04-01

    The catalytic-oxidative evolution of the redox/spin states of a Fe-phthalocyanine (Fe-Pc) catalyst was studied by electron paramagnetic resonance spectroscopy. Under oxidative catalytic conditions, Fe-Pc may evolve via multiple redox/spin conformations. Axial ligation of imidazole, O2 or t-Bu-OOH as oxidant, results in a complex multipath redox/spin landscape that was determined in detail herein. The high-spin conformations of Fe-Pc/imidazole evolve more slowly than the low-spin conformations. Catalytically active vs. inactive conformations were distinguished. A unified physicochemical catalytic reaction mechanism is discussed herein based on the distinct role of the various structural, spin and redox forms.

  18. Microbial Oxidation of Fe2+ and Pyrite Exposed to Flux of Micromolar H2O2 in Acidic Media

    NASA Astrophysics Data System (ADS)

    Ma, Yingqun; Lin, Chuxia

    2013-06-01

    At an initial pH of 2, while abiotic oxidation of aqueous Fe2+ was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe2+ could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe2+ to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe2+-Fe3+ conversion rate in the solution (due to reduced microbial activity) weakened the Fe3+-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria.

  19. Microbial Oxidation of Fe2+ and Pyrite Exposed to Flux of Micromolar H2O2 in Acidic Media

    PubMed Central

    Ma, Yingqun; Lin, Chuxia

    2013-01-01

    At an initial pH of 2, while abiotic oxidation of aqueous Fe2+ was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe2+ could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe2+ to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe2+-Fe3+ conversion rate in the solution (due to reduced microbial activity) weakened the Fe3+-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria. PMID:23760258

  20. Mineralogy and geochemistry of Fe-Ti oxide and apatite (nelsonite) deposits and evaluation of the liquid immiscibility hypothesis.

    USGS Publications Warehouse

    Kolker, A.

    1982-01-01

    The modal mineralogy for 32 Fe-Ti oxides and apatites supports the 2:1 oxide:apatite ratio for these samples from New York, Quebec, Norway and Sweden. Accessory minerals include: biotite, clinoamphibole, spinel, zircon and sulphides, oxygen fugacities range from 10-11 to 10-20, and T 600o to 1000oC. - K.A.R.

  1. Coexistence of Fe(II)- and Mn(II)-oxidizing bacteria govern the formation of deep sea umber deposits

    NASA Astrophysics Data System (ADS)

    Peng, Xiaotong; Ta, Kaiwen; Chen, Shun; Zhang, Lijuan; Xu, Hengchao

    2015-11-01

    The genesis of umber deposits has remained controversial for several decades. Recently, microbial Fe(II) oxidation associated with low-temperature diffuse venting has been identified as a key process for the formation of umber deposits, but the exact biogeochemical mechanisms involved to the precipitation of Mn oxides in umber deposits still remain unknown. Here, we used nano secondary ion mass spectrometer, synchrotron-based X-ray absorption spectroscopy, electron microscopy, and molecular techniques to demonstrate the coexistence of two types of metal-oxidizing bacteria within deep-sea hydrothermal umber deposits at the South Mid-Atlantic Ridge, where we found unique spheroids composed of biogenic Fe oxyhydroxides and Mn oxides in the deposits. Our data show that Fe oxyhydroxides and Mn oxides are metabolic by-products of lithotrophic Fe(II)-oxidizing bacteria and heterotrophic Mn(II)-oxidizing bacteria, respectively. The hydrothermal vents fuel lithotrophic microorganisms, which constitute a trophic base that might support the activities of heterogenic Mn(II)-oxidizing bacteria. The biological origin of umber deposits shed light on the importance of geomicrobiological interaction in triggering the formation of metalliferous deposits, with important implications for the generation of submarine Mn deposits and crusts.

  2. Enhanced and Retarded SiO2 Growth on Thermally Oxidized Fe-Contaminated n-Type Si(001) Surfaces

    NASA Astrophysics Data System (ADS)

    Shimizu, Hirofumi; Hagiwara, Hiroyuki

    2013-04-01

    At the beginning of the oxidation of Fe-contaminated n-type Si(001) surfaces, Fe reacted with oxygen (O2) on the silicon (Si) substrate to form Fe2O3 and oxygen-induced point defects (emitted Si + vacancies). SiO2 growth was mainly enhanced by catalytic action of Fe. At 650 °C, SiO2 growth of the contaminated samples was faster than in reference samples rinsed in RCA solution during the first 60 min. However, it substantially slowed and became less than that of the reference samples. As the oxidation advanced, approximately half of the contaminated Fe atoms became concentrated close to the surface area of the SiO2 film layer. This Fe2O3-rich SiO2 layer acted as a diffusion barrier against oxygen species. The diffusion of oxygen atoms toward the SiO2/Si interface may have been reduced, and in turn, the emission of Si self-interstitials owing to oxidation-induced strain may have been decreased at the SiO2/Si interface, resulting in the retarded oxide growth. These results are evidence that emitted Si self-interstitials are oxidized not in the Fe2O3-rich SiO2 layer, but at the SiO2/Si interface in accordance with a previously proposed model. A possible mechanism based on the interfacial Si emission model is discussed. The activation energies for the oxide growth are found to be in accord with the enhanced and reduced growths of the Fe-contaminated samples.

  3. Facile and straightforward synthesis of superparamagnetic reduced graphene oxide-Fe3O4 hybrid composite by a solvothermal reaction.

    PubMed

    Liu, Yue-Wen; Guan, Meng-Xue; Feng, Lan; Deng, Shun-Liu; Bao, Jian-Feng; Xie, Su-Yuan; Chen, Zhong; Huang, Rong-Bin; Zheng, Lan-Sun

    2013-01-18

    A superparamagnetic reduced graphene oxide-Fe(3)O(4) hybrid composite (rGO-Fe(3)O(4)) was prepared via a facile and straightforward method through the solvothermal reaction of iron (III) acetylacetonate (Fe(acac)(3)) and graphene oxide (GO) in ethylenediamine (EDA) and water. By this method, chemical reduction of GO as well as the formation of Fe(3)O(4) nanoparticles (NPs) can be achieved in one step. The Fe(3)O(4) NPs are firmly deposited on the surfaces of rGO, avoiding their reassembly to graphite. The rGO sheets prevent the agglomeration of Fe(3)O(4) NPs and enable a uniform dispersion of these metal oxide particles. The size distribution and coverage density of Fe(3)O(4) NPs deposited on rGO can be controlled by varying the initial mass ratio of GO and iron precursor, Fe(acac)(3). With an initial mass ratio of GO and Fe(acac)(3) of 5:5, the surfaces of rGO sheets are densely covered by spherical Fe(3)O(4) NPs with an average size of 19.9 nm. The magnetic-functionalized rGO hybrid exhibits a good magnetic property and the specific saturation magnetization (M(s)) is 13.2 emu g(-1). The adsorption test of methylene blue from aqueous solution demonstrates the potential application of this rGO-Fe(3)O(4) hybrid composite in removing organic dyes from polluted water. PMID:23220906

  4. Mariprofundus ferrooxydans PV-1 the first genome of a marine Fe(II) oxidizing Zetaproteobacterium.

    PubMed

    Singer, Esther; Emerson, David; Webb, Eric A; Barco, Roman A; Kuenen, J Gijs; Nelson, William C; Chan, Clara S; Comolli, Luis R; Ferriera, Steve; Johnson, Justin; Heidelberg, John F; Edwards, Katrina J

    2011-01-01

    Mariprofundus ferrooxydans PV-1 has provided the first genome of the recently discovered Zetaproteobacteria subdivision. Genome analysis reveals a complete TCA cycle, the ability to fix CO(2), carbon-storage proteins and a sugar phosphotransferase system (PTS). The latter could facilitate the transport of carbohydrates across the cell membrane and possibly aid in stalk formation, a matrix composed of exopolymers and/or exopolysaccharides, which is used to store oxidized iron minerals outside the cell. Two-component signal transduction system genes, including histidine kinases, GGDEF domain genes, and response regulators containing CheY-like receivers, are abundant and widely distributed across the genome. Most of these are located in close proximity to genes required for cell division, phosphate uptake and transport, exopolymer and heavy metal secretion, flagellar biosynthesis and pilus assembly suggesting that these functions are highly regulated. Similar to many other motile, microaerophilic bacteria, genes encoding aerotaxis as well as antioxidant functionality (e.g., superoxide dismutases and peroxidases) are predicted to sense and respond to oxygen gradients, as would be required to maintain cellular redox balance in the specialized habitat where M. ferrooxydans resides. Comparative genomics with other Fe(II) oxidizing bacteria residing in freshwater and marine environments revealed similar content, synteny, and amino acid similarity of coding sequences potentially involved in Fe(II) oxidation, signal transduction and response regulation, oxygen sensation and detoxification, and heavy metal resistance. This study has provided novel insights into the molecular nature of Zetaproteobacteria. PMID:21966516

  5. Mariprofundus ferrooxydans PV-1 the First Genome of a Marine Fe(II) Oxidizing Zetaproteobacterium

    PubMed Central

    Singer, Esther; Emerson, David; Webb, Eric A.; Barco, Roman A.; Kuenen, J. Gijs; Nelson, William C.; Chan, Clara S.; Comolli, Luis R.; Ferriera, Steve; Johnson, Justin; Heidelberg, John F.; Edwards, Katrina J.

    2011-01-01

    Mariprofundus ferrooxydans PV-1 has provided the first genome of the recently discovered Zetaproteobacteria subdivision. Genome analysis reveals a complete TCA cycle, the ability to fix CO2, carbon-storage proteins and a sugar phosphotransferase system (PTS). The latter could facilitate the transport of carbohydrates across the cell membrane and possibly aid in stalk formation, a matrix composed of exopolymers and/or exopolysaccharides, which is used to store oxidized iron minerals outside the cell. Two-component signal transduction system genes, including histidine kinases, GGDEF domain genes, and response regulators containing CheY-like receivers, are abundant and widely distributed across the genome. Most of these are located in close proximity to genes required for cell division, phosphate uptake and transport, exopolymer and heavy metal secretion, flagellar biosynthesis and pilus assembly suggesting that these functions are highly regulated. Similar to many other motile, microaerophilic bacteria, genes encoding aerotaxis as well as antioxidant functionality (e.g., superoxide dismutases and peroxidases) are predicted to sense and respond to oxygen gradients, as would be required to maintain cellular redox balance in the specialized habitat where M. ferrooxydans resides. Comparative genomics with other Fe(II) oxidizing bacteria residing in freshwater and marine environments revealed similar content, synteny, and amino acid similarity of coding sequences potentially involved in Fe(II) oxidation, signal transduction and response regulation, oxygen sensation and detoxification, and heavy metal resistance. This study has provided novel insights into the molecular nature of Zetaproteobacteria. PMID:21966516

  6. Endometrial ablation

    MedlinePlus

    ... can be seen on the video screen. Small tools can be used through the scope to remove abnormal growths or tissue for examination. Ablation uses heat, cold, or electricity to destroy the lining of the womb. The ...

  7. Photoluminescence of Fe{sub 2}O{sub 3} nanoparticles prepared by laser oxidation of Fe catalysts in carbon nanotubes

    SciTech Connect

    Zhang Yong Liu Wenjin; Wu Chaofeng; Gong Tao; Wei Jinquan; Ma Mingxing; Wang Kunlin; Zhong Minlin; Wu Dehai

    2008-12-01

    Iron oxide nanoparticles have been produced on the top surface of aligned multi-walled carbon nanotubes by CO{sub 2} laser processing. They were characterized to be Fe{sub 2}O{sub 3} nanoparticles by X-ray photoelectron spectroscopy, X-ray diffraction and high resolution scanning electronic microscopy. Absorption bands in the visible region were found to be redshifted compared with the absorption of Fe{sub 2}O{sub 3} nanoparticles prepared by traditional chemical methods. Photoluminescence from these Fe{sub 2}O{sub 3} nanoparticles shows a broad emission band in the near infrared region for both excitations at 514 and 633 nm. Particle size is considered to be responsible for the unique optical properties of the Fe{sub 2}O{sub 3} nanoparticles.

  8. Loading the FeNiOOH cocatalyst on Pt-modified hematite nanostructures for efficient solar water oxidation.

    PubMed

    Deng, Jiujun; Lv, Xiaoxin; Zhang, Hui; Zhao, Binhua; Sun, Xuhui; Zhong, Jun

    2016-04-21

    A FeNiOOH-decorated hematite photoanode has been prepared using a facile electrodeposition method, with a significant cathodic shift of the onset potential (up to 190 mV) compared to the pristine sample. Synchrotron radiation based techniques have been used to identify the composition of the catalyst indicating the presence of FeOOH and NiOOH (FeNiOOH). The enhanced performance can be attributed to the better oxidation evolution reaction kinetics with the FeNiOOH cocatalyst. The FeNiOOH-decorated hematite is very stable for a long time. Moreover, the cocatalyst can be well coupled to the Pt-modified hematite photoanode achieving a high photocurrent of 2.21 mA cm(-2) at 1.23 V vs. RHE. The good catalytic properties and the facile preparation method suggest that the decoration of FeNiOOH is a favorable strategy to improve the performance of hematite. PMID:27029763

  9. [NiFe]Hydrogenase from Citrobacter sp. S-77 surpasses platinum as an electrode for H2 oxidation reaction.

    PubMed

    Matsumoto, Takahiro; Eguchi, Shigenobu; Nakai, Hidetaka; Hibino, Takashi; Yoon, Ki-Seok; Ogo, Seiji

    2014-08-18

    Reported herein is an electrode for dihydrogen (H2) oxidation, and it is based on [NiFe]Hydrogenase from Citrobacter sp. S-77 ([NiFe]S77). It has a 637 times higher mass activity than Pt (calculated based on 1 mg of [NiFe]S77 or Pt) at 50 mV in a hydrogen half-cell. The [NiFe]S77 electrode is also stable in air and, unlike Pt, can be recovered 100 % after poisoning by carbon monoxide. Following characterization of the [NiFe]S77 electrode, a fuel cell comprising a [NiFe]S77 anode and Pt cathode was constructed and shown to have a a higher power density than that achievable by Pt. PMID:24895095

  10. Ablation article and method

    NASA Technical Reports Server (NTRS)

    Erickson, W. D.; Sullivan, E. M. (Inventor)

    1973-01-01

    An ablation article, such as a conical heat shield, having an ablating surface is provided with at least one discrete area of at least one seed material, such as aluminum. When subjected to ablation conditions, the seed material is ablated. Radiation emanating from the ablated seed material is detected to analyze ablation effects without disturbing the ablation surface. By providing different seed materials having different radiation characteristics, the ablating effects on various areas of the ablating surface can be analyzed under any prevailing ablation conditions. The ablating article can be provided with means for detecting the radiation characteristics of the ablated seed material to provide a self-contained analysis unit.

  11. Nitric oxide reactivity of [2Fe-2S] clusters leading to H2S generation.

    PubMed

    Tran, Camly T; Williard, Paul G; Kim, Eunsuk

    2014-08-27

    The crosstalk between two biologically important signaling molecules, nitric oxide (NO) and hydrogen sulfide (H2S), proceeds via elusive mechanism(s). Herein we report the formation of H2S by the action of NO on synthetic [2Fe-2S] clusters when the reaction environment is capable of providing a formal H(•) (e(-)/H(+)). Nitrosylation of (NEt4)2[Fe2S2(SPh)4] (1) in the presence of PhSH or (t)Bu3PhOH results in the formation of (NEt4)[Fe(NO)2(SPh)2] (2) and H2S with the concomitant generation of PhSSPh or (t)Bu3PhO(•). The amount of H2S generated is dependent on the electronic environment of the [2Fe-2S] cluster as well as the type of H(•) donor. Employment of clusters with electron-donating groups or H(•) donors from thiols leads to a larger amount of H2S evolution. The 1/NO reaction in the presence of PhSH exhibits biphasic decay kinetics with no deuterium kinetic isotope effect upon PhSD substitution. However, the rates of decay increase significantly with the use of 4-MeO-PhSH or 4-Me-PhSH in place of PhSH. These results provide the first chemical evidence to suggest that [Fe-S] clusters are likely to be a site for the crosstalk between NO and H2S in biology. PMID:25113815

  12. Respective role of Fe and Mn oxide contents for arsenic sorption in iron and manganese binary oxide: an X-ray absorption spectroscopy investigation.

    PubMed

    Zhang, Gaosheng; Liu, Fudong; Liu, Huijuan; Qu, Jiuhui; Liu, Ruiping

    2014-09-01

    In our previous studies, a synthesized Fe-Mn binary oxide was found to be very effective for both As(V) and As(III) removal in aqueous phase, because As(III) could be easily oxidized to As(V). As(III) oxidation and As(V) sorption by the Fe-Mn binary oxide may also play an important role in the natural cycling of As, because of its common occurrence in the environment. In the present study, the respective role of Fe and Mn contents present in the Fe-Mn binary oxide on As(III) removal was investigated via a direct in situ determination of arsenic speciation using X-ray absorption spectroscopy. X-ray absorption near edge structure results indicate that Mn atoms exist in a mixed valence state of +3 and +4 and further confirm that MnOx (1.5 < x < 2) content is mainly responsible for oxidizing As(III) to As(V) through a two-step pathway [reduction of Mn(IV) to Mn(III) and subsequent Mn(III) to Mn(II)] and FeOOH content is dominant for adsorbing the formed As(V). No significant As(III) oxidation by pure FeOOH had been observed during its sorption, when the system was exposed to air. The extended X-ray absorption fine structure results reveal that the As surface complex on both the As(V)- and As(III)-treated sample surfaces is an inner-sphere bidentate binuclear corner-sharing complex with an As-M (M = Fe or Mn) interatomic distance of 3.22-3.24 Å. In addition, the MnOx and FeOOH contents exist only as a mixture, and no solid solution is formed. Because of its high effectiveness, low cost, and environmental friendliness, the Fe-Mn binary oxide would play a beneficial role as both an efficient oxidant of As(III) and a sorbent for As(V) in drinking water treatment and environmental remediation. PMID:25093452

  13. Enhanced magnetization in highly crystalline and atomically mixed bcc Fe-Co nanoalloys prepared by hydrogen reduction of oxide composites

    NASA Astrophysics Data System (ADS)

    Sharif, Md Jafar; Yamauchi, Miho; Toh, Shoichi; Matsumura, Syo; Noro, Shin-Ichiro; Kato, Kenichi; Takata, Masaki; Tsukuda, Tatsuya

    2013-01-01

    FexCo100-x nanoalloys (NAs) with 20 <= x <= 80 were prepared by hydrogen reduction of Fe-Co oxide nano-composites, which were composed of mixed phases (or domains) of Fe2O3 and CoO. In situ X-ray diffraction (XRD) measurements using synchrotron radiation clearly showed development of a solid-solution Fe-Co phase by hydrogen reduction from the oxide composites. High-resolution transmission electron microscopy (TEM), high-angle annular dark-field scanning TEM and powder XRD revealed that Fe-Co NAs form a single crystal structure and the two elements are mixed homogeneously. The saturation magnetization depends on the size and metal composition and shows the highest value (250 emu g-1) for the Fe70Co30 NA in the size range of 30-55 nm, which is comparable to that of the Fe70Co30 bulk alloy (245 emu g-1). This high magnetization is attributable to high crystallinity and homogeneous mixing of constituent atoms, which are attained by thermal treatment of oxide phases under a hydrogen atmosphere.FexCo100-x nanoalloys (NAs) with 20 <= x <= 80 were prepared by hydrogen reduction of Fe-Co oxide nano-composites, which were composed of mixed phases (or domains) of Fe2O3 and CoO. In situ X-ray diffraction (XRD) measurements using synchrotron radiation clearly showed development of a solid-solution Fe-Co phase by hydrogen reduction from the oxide composites. High-resolution transmission electron microscopy (TEM), high-angle annular dark-field scanning TEM and powder XRD revealed that Fe-Co NAs form a single crystal structure and the two elements are mixed homogeneously. The saturation magnetization depends on the size and metal composition and shows the highest value (250 emu g-1) for the Fe70Co30 NA in the size range of 30-55 nm, which is comparable to that of the Fe70Co30 bulk alloy (245 emu g-1). This high magnetization is attributable to high crystallinity and homogeneous mixing of constituent atoms, which are attained by thermal treatment of oxide phases under a hydrogen

  14. Biochemistry and Ecology of Novel Cytochromes Catalyzing Fe(II) Oxidation by an Acidophilic Microbial Community

    NASA Astrophysics Data System (ADS)

    Singer, S. W.; Jeans, C. J.; Thelen, M. P.; Verberkmoes, N. C.; Hettich, R. C.; Chan, C. S.; Banfield, J. F.

    2007-12-01

    An acidophilic microbial community found in the Richmond Mine at Iron Mountain, CA forms abundant biofilms in extremely acidic (pH<1) and toxic metal conditions. In this ecosystem, biological Fe(II) oxidation is critical to the metabolic functioning of the community, and in turn this process generates acid mine drainage, causing an environmental catastrophe. Two conspicuous novel proteins isolated from these biofilms were identified as gene products of Leptospirillum group II and were characterized as cytochromes with unique properties. Sulfuric acid extraction of biofilm samples liberated one of these proteins, a 16 kDa cytochrome with an unusual alpha-band absorption at 579 (Cyt579). Genomic sequencing of multiple biofilms indicated that several variants of Cyt579 were present in Leptospirillum strains. Intact protein MS analysis identified the dominant variants in each biofilm and documented multiple N-terminal cleavage sites for Cyt579. By combining biochemical, geochemical and microbiological data, we established that the sequence variation and N-terminal processing of Cyt579 are selected by ecological conditions. In addition to the soluble Cyt579, the second cytochrome appears as a much larger protein complex of ~210 kDa predominant in the biofilm membrane fraction, and has an alpha-band absorption at 572 nm. The 60 kDa cytochrome subunit, Cyt572, resides in the outer membrane of LeptoII, and readily oxidizes Fe(II) at low pH (0.95 - 3.0). Several genes encoding Cyt572 were localized within a recombination hotspot between two strains of LeptoII, causing a large range of variation in the sequences. Genomic sequencing and MS proteomic studies established that the variants were also selected by ecological conditions. A general mechanistic model for Fe(II) oxidation has been developed from these studies. Initial Fe(II) oxidation by Cyt572 occurs at the outer membrane. Cyt572 then transfers electrons to Cyt579, perhaps representing an initial step in energy flow

  15. Examination of carbon associated with metal-humus complexes, short-range-order Al and Fe oxides, and crystalline Al and Fe oxides: Differences in carbon abundance and mean residence time

    NASA Astrophysics Data System (ADS)

    Heckman, K. A.; Lawrence, C. R.

    2012-12-01

    Transport of SOM (soil organic matter) between soils and aquatic systems is regulated in part by sorption and desorption reactions happening at mineral surfaces, as well as precipitation and dissolution of metal-humus complexes. Fe and Al hydroxides play a particularly significant role in SOM stabilization in soils due to their ubiquitous distribution and their highly reactive surface properties. Fe and Al hydroxides exist in soils across a wide spectrum of crystallinity, ranging from dissolved Fe and Al cations which combine with organics to form metal-humus precipitates to the more crystalline end members, goethite and gibbsite, which sorb SOM through a variety of molecular interactions. Though the importance of these sorption and precipitation reactions has long been recognized, the distribution of SOM among Fe and Al hydroxides of differing crystallinity has not been well quantified, nor has the timescales over which these stabilization mechanisms operate. In an attempt to measure the distribution of organic C among i) Al- and Fe-humus complexes ii) short-range-order Al and Fe oxide surfaces and iii) crystalline Al and Fe oxide surfaces, a suite of selective dissolutions were applied to soils of four different geneses (a tropical forest andosol, a temperate basaltic mollisol, a grassland alfisol, and a northern pine spodosol. The traditional reactants used in selective dissolutions were replaced with carbon-free analogues so that the carbon released along with the Fe and Al at each stage of the selective dissolution process could be examined. Selective dissolutions were performed sequentially: Na-pyrophosphate (Al- and Fe-humus complexes) followed by hydroxyl-amine (short-range-order Al and Fe hydroxides) followed by dithionite/HCl (crystalline Al and Fe hydroxides). Carbon concentration, δ13C, and Δ14C were measured for the solutions yielded by each stage of the selective dissolution process. Δ14C were used to estimate a MRT (mean residence time) for SOM

  16. Controlled growth of LaFeO3 nanoparticles on reduced graphene oxide for highly efficient photocatalysis

    NASA Astrophysics Data System (ADS)

    Ren, Xiao; Yang, Haitao; Gen, Sai; Zhou, Jun; Yang, Tianzhong; Zhang, Xiangqun; Cheng, Zhaohua; Sun, Shouheng

    2015-12-01

    Using reduced graphene oxide (rGO) as a template and high temperature sol-gel chemistry, we have prepared LaFeO3 nanoparticles (NPs). The 15 nm LaFeO3 NPs have a bandgap of 1.86 eV and the LaFeO3-rGO can function as an efficient catalyst for degradation of methylene blue (MB) or Rhodamine B (RhB) under visible-light irradiation with the electron transfer from the dye to hole dominating the oxidation process. The reported synthesis offers a general approach to perovskite-type NPs for efficient photocatalytic applications.Using reduced graphene oxide (rGO) as a template and high temperature sol-gel chemistry, we have prepared LaFeO3 nanoparticles (NPs). The 15 nm LaFeO3 NPs have a bandgap of 1.86 eV and the LaFeO3-rGO can function as an efficient catalyst for degradation of methylene blue (MB) or Rhodamine B (RhB) under visible-light irradiation with the electron transfer from the dye to hole dominating the oxidation process. The reported synthesis offers a general approach to perovskite-type NPs for efficient photocatalytic applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06338h

  17. Structural and Electronic Effects on the Properties of Fe2(dobdc) upon Oxidation with N2O.

    PubMed

    Borycz, Joshua; Paier, Joachim; Verma, Pragya; Darago, Lucy E; Xiao, Dianne J; Truhlar, Donald G; Long, Jeffrey R; Gagliardi, Laura

    2016-05-16

    We report electronic, vibrational, and magnetic properties, together with their structural dependences, for the metal-organic framework Fe2(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and its derivatives, Fe2(O)2(dobdc) and Fe2(OH)2(dobdc)-species arising in the previously proposed mechanism for the oxidation of ethane to ethanol using N2O as an oxidant. Magnetic susceptibility measurements reported for Fe2(dobdc) in an earlier study and reported in the current study for Fe(II)0.26[Fe(III)(OH)]1.74(dobdc)(DMF)0.15(THF)0.22, which is more simply referred to as Fe2(OH)2(dobdc), were used to confirm the computational results. Theory was also compared to experiment for infrared spectra and powder X-ray diffraction structures. Structural and magnetic properties were computed by using Kohn-Sham density functional theory both with periodic boundary conditions and with cluster models. In addition, we studied the effects of different treatments of the exchange interactions on the magnetic coupling parameters by comparing several approaches to the exchange-correlation functional: generalized gradient approximation (GGA), GGA with empirical Coulomb and exchange integrals for 3d electrons (GGA+U), nonseparable gradient approximation (NGA) with empirical Coulomb and exchange integrals for 3d electrons (NGA+U), hybrid GGA, meta-GGA, and hybrid meta-GGA. We found the coupling between the metal centers along a chain to be ferromagnetic in the case of Fe2(dobdc) and antiferromagnetic in the cases of Fe2(O)2(dobdc) and Fe2(OH)2(dobdc). The shift in magnetic coupling behavior correlates with the changing electronic structure of the framework, which derives from both structural and electronic changes that occur upon metal oxidation and addition of the charge-balancing oxo and hydroxo ligands. PMID:27136308

  18. Isolation and Characterization of Novel Psychrophilic, Neutrophilic, Fe-Oxidizing, Chemolithoautotrophic α- and γ-Proteobacteria from the Deep Sea†

    PubMed Central

    Edwards, K. J.; Rogers, D. R.; Wirsen, C. O.; McCollom, T. M.

    2003-01-01

    We report the isolation and physiological characterization of novel, psychrophilic, iron-oxidizing bacteria (FeOB) from low-temperature weathering habitats in the vicinity of the Juan de Fuca deep-sea hydrothermal area. The FeOB were cultured from the surfaces of weathered rock and metalliferous sediments. They are capable of growth on a variety of natural and synthetic solid rock and mineral substrates, such as pyrite (FeS2), basalt glass (∼10 wt% FeO), and siderite (FeCO3), as their sole energy source, as well as numerous aqueous Fe substrates. Growth temperature characteristics correspond to the in situ environmental conditions of sample origin; the FeOB grow optimally at 3 to 10°C and at generation times ranging from 57 to 74 h. They are obligate chemolithoautotrophs and grow optimally under microaerobic conditions in the presence of an oxygen gradient or anaerobically in the presence of nitrate. None of the strains are capable of using any organic or alternate inorganic substrates tested. The bacteria are phylogenetically diverse and have no close Fe-oxidizing or autotrophic relatives represented in pure culture. One group of isolates are γ-Proteobacteria most closely related to the heterotrophic bacterium Marinobacter aquaeolei (87 to 94% sequence similarity). A second group of isolates are α-Proteobacteria most closely related to the deep-sea heterotrophic bacterium Hyphomonas jannaschiana (81 to 89% sequence similarity). This study provides further evidence for the evolutionarily widespread capacity for Fe oxidation among bacteria and suggests that FeOB may play an unrecognized geomicrobiological role in rock weathering in the deep sea. PMID:12732565

  19. Study of cluster anions generated by laser ablation of titanium oxides: a high resolution approach based on Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Barthen, Nicolas; Millon, Eric; Aubriet, Frédéric

    2011-03-01

    Laser ablation of titanium oxides at 355 nm and ion-molecule reactions between [(TiO(2))(x)](-•) cluster anions and H(2)O or O(2) were investigated by Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) with an external ion source. The detected anions correspond to [(TiO(2))(x)(H(2)O)(y)OH](-) and [(TiO(2))(x)(H(2)O)(y)O(2)](-•) oxy-hydroxide species with x=1 to 25 and y=1, 2, or 3 and were formed by a two step process: (1) laser ablation, which leads to the formation of [(TiO(2))(x)](-•) cluster anions as was previously reported, and (2) ion-molecule reactions during ion storage. Reactions of some [(TiO(2))(x)](-•) cluster anions with water and dioxygen conducted in the FTICR cell confirm this assessment. Tandem mass spectrometry experiments were also performed in sustained off-resonance irradiation collision-induced dissociation (SORI-CID) mode. Three fragmentation pathways were observed: (1) elimination of water molecules, (2) O(2) loss for radical anions, and (3) fission of the cluster. Density functional theory (DFT) calculations were performed to explain the experimental data. PMID:21472569

  20. Reduction Kinetics of Electric Arc Furnace Oxidizing Slag by Al-Fe Alloy

    NASA Astrophysics Data System (ADS)

    Lee, Jaehong; Oh, Joon Seok; Lee, Joonho

    2016-07-01

    Effects of temperature and slag basicity on the reduction rate of iron oxide in molten synthetic electric arc furnace oxidizing slag by Al-40 wt.%Fe alloy was investigated. An alloy sample was dropped into molten slag in an MgO crucible. When the initial slag temperature was 1723 K, there was no reduction. However, when the initial slag temperature was 1773 K and the slag basicity was 1.1, the reduction was initiated and the temperature of the slag rapidly increased. When the slag basicity was 1.1, increasing the initial slag temperature from 1773 K to 1823 K increases the reaction rate. As the slag basicity increased from 1.1 to 1.4 at 1773 K, the reaction rate increased. From SEM analysis, it was found that an Al2O3 or a spinel phase at the slag-metal interface inhibited the reaction at a lower temperature and a lower slag basicity.

  1. Preparation of iron oxide nanoparticles from FeCl3 solid powder using microemulsions

    NASA Astrophysics Data System (ADS)

    Nassar, Nashaat; Husein, Maen

    2006-05-01

    Nanoparticles of iron oxide were prepared by subjecting iron chloride powder to (w/o) microemulsions consisting of sodium bis(2-ethylhexyl) sulfosuccinate (AOT), isooctane and water. FeCl3 was first dissolved in the water pools of the microemulsion, and then reacted with NaOH added as an aqueous solution to form iron oxide. The amount of NaOH solution was limited so that single microemulsion phase is obtained. This technique serves as an in-situ nanoparticle preparation technique aimed at minimizing particle aggregation associated with particle transportation to required sites. In this study, the effects of AOT concentration and water to AOT mole ratio on the nanoparticle size were investigated. UV/Vis spectrophotometry and transmission electron microscopy (TEM) were used to measure the particle size distribution.

  2. Microdomain Formation, Oxidation, and Cation Ordering in LaCa2Fe3O8+y

    DOE PAGESBeta

    Price, Patrick M.; Browning, Nigel D.; Butt, Darryl P.

    2015-03-23

    The compound LaCa2Fe3O8+y, also known as the Grenier phase, is known to undergo an order-disorder transformation (ODT) at high temperatures. Oxidation has been observed when the compound is cooled in air after the ODT. In this study, we have synthesized the Grenier compound in air using traditional solid state reactions and investigated the structure and composition before and after the ODT. Thermal analysis showed that the material undergoes an order-disorder transformation in both oxygen and argon atmospheres with dynamic, temperature dependent, oxidation upon cooling. Results from scanning transmission electron microscopy (STEM) suggest that the Grenier phase has preferential segregation ofmore » Ca and La on the two crystallographic A-sites before the ODT, but a random distribution above the ODT temperature. Furthermore, STEM images suggest the possibility that oxygen excess may exist in La-rich regions within microdomains rather than at microdomain boundaries.« less

  3. Spin dependent transport in FeCo|MgBO|FeCo magnetic tunnel junctions: Can boron in the oxide region be a good thing?

    NASA Astrophysics Data System (ADS)

    Stewart, Derek

    2009-03-01

    Recent experimental studies on FeCoB/MgO/FeCoB tunnel junctions have shown that boron can diffuse into the oxide region during rf-sputtering and result in the formation of crystalline MgBO regions[1,2]. These tunnel junctions still provide high tunneling magnetoresistance values as well as very low RA products[3]. Using a plane wave-pseudopotential density functional approach, I have examined potential Mg(B) oxides such as Mg2B2O5 (both monoclinic and triclinic) as well at kotoite (Mg3B2O6). Total energy calculations indicate that these oxides should be more stable than the formation of separate regions of MgO and B2O3. Kotoite (Mg3B2O6) also has a boron concentration close to that found in the experimentally grown MgBO regions. In addition, kotoite provides a good lattice match with MgO and could act to template neighboring FeCo into crystalline bcc layers during annealing. This evidence suggests that kotoite is formed during the deposition process. I will also discuss the complex band structure of kotoite (Mg3B2O6) and examine how this will also affect spin dependent transport from the FeCo leads. [1] J. Y. Bae et al., J. Appl. Phys. 99 08T316 (2006) [2] J. C. Read et al., Appl. Phys. Lett. 90 132503 (2007) [3] J. C. Read personal communication

  4. Interaction between carbon oxides, hydrogen and Fe2O3 and A n + 1Fe n O3 n + 1 (A = Gd, Sr, n = 1, 2, …, ∞)

    NASA Astrophysics Data System (ADS)

    Sheshko, T. F.; Serov, Yu. M.; Kryuchkova, T. A.; Khairullina, I. A.; Chislova, I. V.; Zvereva, I. A.

    2016-06-01

    The interaction between carbon oxides and hydrogen and surfaces of iron(III) oxide and A n + 1Fe n O3 n + 1 (where A = Gd, Sr, and n = 1, 2, …, ∞ is the number of perovskite layers) complex oxides is studied for the first time by means of thermal programmed desorption. It is shown that carbon oxides are adsorbed in molecular form with the formation of carbonate-carboxylate complexes, and in dissociative form. The ratios of the adsorption forms of both oxides are determined by the structure of ferrites, the number of perovskite layers, and the valence state and coordinative saturation of iron. The presence of weakly and strongly bonded hydrogen forms is established, and it is suggested that hydrogen dissolves in the bulk of a perovskite.

  5. Immobilization of selenite in soil and groundwater using stabilized Fe-Mn binary oxide nanoparticles.

    PubMed

    Xie, Wenbo; Liang, Qiqi; Qian, Tianwei; Zhao, Dongye

    2015-03-01

    Stabilized Fe-Mn binary oxide nanoparticles were synthesized and tested for removal and in-situ immobilization of Se(IV) in groundwater and soil. A water-soluble starch or food-grade carboxymethyl cellulose (CMC) was used as a stabilizer to facilitate in-situ delivery of the particles into contaminated soil. While bare and stabilized nanoparticles showed rapid sorption kinetics, starch-stabilized Fe-Mn offered the greatest capacity for Se(IV). The Langmuir maximum capacity was determined to be 109 and 95 mg-Se/g-Fe for starch- and CMC-stabilized nanoparticles, respectively, and the high Se(IV) uptake was observed over the typical groundwater pH range of 5-8. Column breakthrough tests indicated that the stabilized nanoparticles were deliverable in a model sandy soil while non-stabilized particles were not. When a Se(IV)-spiked soil was treated in situ with the nanoparticles, >90% water leachable Se(IV) was transferred to the nanoparticle phase, and thereby immobilized as the particles were retained in the downstream soil matrix. The nanoparticle amendment reduced the TCLP (toxicity characteristic leaching procedure) leachability and the California WET (waste extraction test) leachability of Se(IV) by 76% and 71%, respectively. The technology holds the potential to fill a major technology gap in remediation of metals-contaminated soil and groundwater. PMID:25577492

  6. [Nitrate removal by a strain of nitrate-dependent Fe (II) -oxidizing bacteria].

    PubMed

    Wang, Hong-Yu; Yang, Kai; Zhang, Qian; Ji, Bin; Chen, Dan; Sun, Yu-Chong; Tian, Jun

    2014-04-01

    A nitrate-dependent Fe(II)-oxidizing bacterial strain, named W5, was isolated from the sediment of the East Lake in Wuhan. Strain W5 was studied for its characteristics of denitrification and nitrogen removal. According to its physiological and biochemical characteristics and the analysis of its 16S rRNA gene sequence, strain W5 was identified as Microbacterium sp. The optimal denitrification performance can be obtained under conditions of NO3(-) -N 40 mg x L(-1), Fe2+ 500 mg x L(-1) and pH 6.8-7.0. After one week of cultivation under optimal conditions, nitrate removal percentage reached 87.0%. During the process of the culture, the nitrite nitrogen concentration was no more than 0.31 mg x L(-1) and there was no ammonia nitrogen production. It was indicated that the nitrate was mostly converted into N2. The consumption rate of Fe2+ was 95.2%. PMID:24946599

  7. Nanowires, Capacitors, and Other Novel Outer-Surface Components Involved in Electron Transfer to Fe(III) Oxides in Geobacter Species

    SciTech Connect

    Lovley, Derek R.

    2005-06-01

    In the past year studies have primarily focused on elucidating the role of pili in electron transport to Fe(III) oxide in Geobacter sulfurreducens. As summarized in last year's report, it was previously found that pili are specifically expressed during growth on Fe(III) oxide and that Fe(III) oxide reduction is inhibited if the gene for the structural pilin protein is deleted. However, it was also found that a pilin-deficient mutant of G. sulfurreducens could attached to Fe(III) oxide as well as wild type.

  8. Heterotrophic Fe-Oxidizing Bacteria Associated With Basalt Surfaces Supporting Life On Vailulu'u Seamount, American Samoa

    NASA Astrophysics Data System (ADS)

    Haucke, L.; Templeton, A.; Bailey, B.; Tebo, B.; Staudigel, H.

    2005-12-01

    Fe, the fourth-most abundant element in the Earth's crust, is also one of the most biologically essential ones. The reduced form, Fe(II), is often considered to be biologically limiting as a result of its low solubility and rapid chemical oxidation to Fe(III)(hydr)oxides at circumneutral pH. The alteration of basaltic glass, enriched in Fe(II), however, provides an abundant supply of reduced iron and, thus, has a major influence on local ocean chemistry and Fe bioavailability. Despite the fact that chemical Fe(II) oxidation takes place very rapidly, we demonstrate that alteration processes of freshly formed basaltic glass can be crucially enhanced by microbial activity.Cultivation of bacteria from basalt surfaces collected from two active submarine volcanoes, Loihi (Hawaii) and Vailulu'u (American Samoa) show a large number of heterotrophic bacteria capable of oxidizing Fe(II) and that these bacteria. not only enhance basalt dissolution but also play a major role in precipitating large amounts of thick Fe(hydr)oxides mats on Vailulu'u Seamount, particularly in the vicinity of low temperature hydrothermal vents. These mats contain substantial quantities of organic carbon that may serve as food sources for some of the macrobiological life on Vailulu'u Seamount. This very prominently includes a substantial population of eels that is found in close spatial association with up to 1m thick Fe oxide/microbial mat at Nafanua volcano, a recent volcanic cone that grew from the crater floor of the seamount. Microbial community analysis on different substrates ranging from basalt surfaces to microbial mats were performed on specially designed culturing media for detection and isolation of heterotrophic bacteria capable of Fe(II)-oxidation. Clone libraries from microbial mats originating from an eel dominated area of Vailulu'u crater are being compared to libraries made from eel guts in order to provide information to what extent these mats are being used as a food source in

  9. Effect of ferric oxide on the high-temperature removal of hydrogen sulfide over ZnO-Fe{sub 2}O{sub 3} mixed metal oxide sorbent

    SciTech Connect

    Lee, Y.S.; Kim, H.T.; Yoo, K.O.

    1995-04-01

    The effect of ferric oxide on the removal of hydrogen sulfide over ZnO-Fe{sub 2}O{sub 3} mixed metal oxide sorbents and on the oxidative regeneration of sulfided sorbents was investigated. When ferric oxide was added to the zinc oxide, the reduction of ZnO was retarded by interaction of ZnO with ZnFe{sub 2}O{sub 4}. This interaction was confirmed by larger binding energies of Zn 2P{sub 3/2} and Zn 2P{sub 1/2}, identified by ESCA, of the ZnO-ZnFe{sub 2}O{sub 4} sorbent than those of ZnO. Zinc ferrite with a spinel structure yielded not only high H{sub 2}S removal capacity but also much SO{sub 2} generation. A linear increase of SO{sub 2} generation was confirmed up to 50 wt % Fe{sub 2}O{sub 3}. Resulting from the thermal decomposition of H{sub 2}S over metal sulfides, H{sub 2} generation increased with respect to Fe{sub 2}O{sub 3} according to a quadratic equation. Channeling, caused by sintering during sulfidation, made the flow path of the reactant change and thus pure ZnO sorbent and the sorbent containing 3 wt % Fe{sub 2}O did not sulfurate completely. Addition of Fe{sub 2}O{sub 3} prevented surface structural change like sintering of ZnO during sulfidation.

  10. [Enhanced electro-catalytic oxidation of dye wastewater with FePMo12 adopted catalyst].

    PubMed

    Wang, Li; Yue, Lin; Guo, Jian-Bo; Yang, Jing-Liang; Lian, Jing; Luo, Xiao; Wang, Kai-Hong

    2014-05-01

    Electrochemical oxidation degradation of azo dyes has become a widely used method in recent years. Iron phosphomolybdate (FePMo12) was synthesized with molybdophosphoric acid and ferric salt. Morphology and microstructure of catalyst were chararerized by IR spectrometry and X-ray diffraction. The heteropolyanion showed a Keggin structure. Electrochemical oxidation of acid red 3R was investigated in the presence of FePMo12 supported on modified 4A molecular sieve (4A) as packing materials in the reactor. The results showed that the optimal technological conditions for decolorization of acid red 3R simulated wastewater were as follows: active component load 3% , electrolytic voltage 22 V, initial pH 4, air-flow 0.08 m3 h- ', electrode span 3.0 cm. Under the opñrrizd conditions, the decolorization efficiency, COD and TOC removal efficiencies reached 75.3% , 65.4% and 46.0% after 90 min, respectively. With the addition of NaCI to the dyes solution during electrolysis, the decolorization efficiency increased, while the effect of Na2SO4 on the degradation was negative. The efficiency of degradation and mineralization of the acid red 3R were estimated based on the absorbance measurements by UV-vis. It shows that the conjugated structure of dye was destroyed primarily. PMID:25055676

  11. Denitrification and Nitrate-Dependent Fe(II) Oxidation in Various Pseudogulbenkiania Strains

    PubMed Central

    Ishii, Satoshi; Joikai, Kazuki; Otsuka, Shigeto; Senoo, Keishi; Okabe, Satoshi

    2016-01-01

    Pseudogulbenkiania is a relatively recently characterized genus within the order Neisseriales, class Betaproteobacteria. This genus contains several strains that are capable of anaerobic, nitrate-dependent Fe(II) oxidation (NDFO), a geochemically important reaction for nitrogen and iron cycles. In the present study, we examined denitrification functional gene diversities within this genus, and clarified whether other Pseudogulbenkiania sp. strains perform denitrification and NDFO. Seventy strains were analyzed, including two type strains, a well-characterized NDFO strain, and 67 denitrifying strains isolated from various rice paddy fields and rice-soybean rotation fields in Japan. We also attempted to identify the genes responsible for NDFO by mutagenesis. Our comprehensive analysis showed that all Pseudogulbenkiania strains tested performed denitrification and NDFO; however, we were unable to obtain NDFO-deficient denitrifying mutants in our mutagenesis experiment. This result suggests that Fe(II) oxidation in these strains is not enzymatic, but is caused by reactive N-species that are formed during nitrate reduction. Based on the results of the comparative genome analysis among Pseudogulbenkiania sp. strains, we identified low sequence similarity within the nos gene as well as different gene arrangements within the nos gene cluster, suggesting that nos genes were horizontally transferred. Since Pseudogulbenkiania sp. strains have been isolated from various locations around the world, their denitrification and NDFO abilities may contribute significantly to nitrogen and iron biogeochemical cycles. PMID:27431373

  12. Two-dimensional oxide topological insulator with iron-pnictide superconductor LiFeAs structure

    NASA Astrophysics Data System (ADS)

    Xu, Qiunan; Song, Zhida; Nie, Simin; Weng, Hongming; Fang, Zhong; Dai, Xi

    2015-11-01

    By using first-principles calculations, we propose that ZrSiO can be looked at as a three-dimensional (3D) oxide weak topological insulator (TI) and its single layer is a long-sought-after 2D oxide TI with a band gap up to 30 meV. Calculated phonon spectrum of the single layer ZrSiO indicates it is dynamically stable and the experimental achievements in growing oxides with atomic precision ensure that it can be readily synthesized. This will lead to novel devices based on TIs, the so-called "topotronic" devices, operating under room temperature and stable when exposed in the air. Thus a new field of "topotronics" will arise. Another intriguing thing is this oxide 2D TI has the similar crystal structure as the well-known iron-pnictide superconductor LiFeAs. This brings great promise in realizing the combination of superconductor and TI, paving the way to various extraordinary quantum phenomena, such as topological superconductor and Majorana modes. We further find that there are many other isostructural compounds hosting the similar electronic structure and forming a W H M family with W being Zr, Hf, or La, H being group IV or group V element, and M being group VI one.

  13. CoFe 2O 4 spinel protection coating thermally converted from the electroplated Co-Fe alloy for solid oxide fuel cell interconnect application

    NASA Astrophysics Data System (ADS)

    Bi, Z. H.; Zhu, J. H.; Batey, J. L.

    CoFe 2O 4 has been demonstrated as a potential spinel coating for protecting the Cr-containing ferritic interconnects. This spinel had an electrical conductivity of 0.85 S cm -1 at 800 °C in air and an average coefficient of thermal expansion (CTE) of 11.80 × 10 -6 K -1 from room temperature to 800 °C. A series of Co-Fe alloys were co-deposited onto the Crofer 22 APU ferritic steel via electroplating with an acidic chloride solution. After thermal oxidation in air at 800 °C, a CoFe 2O 4 spinel layer was attained from the plated Co 0.40Fe 0.60 film. Furthermore, a channeled Crofer 22 APU interconnect electrodeposited with a 40-μm Co 0.40Fe 0.60 alloy film as a protective coating was evaluated in a single-cell configuration. The presence of the dense, Cr-free CoFe 2O 4 spinel layer was effective in blocking the Cr migration/transport and thus contributed to the improvement in cell performance stability.

  14. Final Report: Molecular mechanisms and kinetics of microbial anaerobic nitrate-dependent U(IV) and Fe(II) oxidation

    SciTech Connect

    O'Day, Peggy A.; Asta, Maria P.; Kanematsu, Masakazu; Beller, Harry; Zhou, Peng; Steefel, Carl

    2015-02-27

    In this project, we combined molecular genetic, spectroscopic, and microscopic techniques with kinetic and reactive transport studies to describe and quantify biotic and abiotic mechanisms underlying anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation, which influences the long-term efficacy of in situ reductive immobilization of uranium at DOE sites. In these studies, Thiobacillus denitrificans, an autotrophic bacterium that catalyzes anaerobic U(IV) and Fe(II) oxidation, was used to examine coupled oxidation-reduction processes under either biotic (enzymatic) or abiotic conditions in batch and column experiments with biogenically produced UIVO2(s). Synthesis and quantitative analysis of coupled chemical and transport processes were done with the reactive transport modeling code Crunchflow. Research focused on identifying the primary redox proteins that catalyze metal oxidation, environmental factors that influence protein expression, and molecular-scale geochemical factors that control the rates of biotic and abiotic oxidation.

  15. Pyritic event beds and sulfidized Fe (oxyhydr)oxide aggregates in metalliferous black mudstones of the Paleoproterozoic Talvivaara formation, Finland

    NASA Astrophysics Data System (ADS)

    Virtasalo, Joonas J.; Laitala, Jaakko J.; Lahtinen, Raimo; Whitehouse, Martin J.

    2015-12-01

    The Paleoproterozoic, 2.0-1.9 Ga Talvivaara formation of Finland was deposited during the Shunga Event, a worldwide episode of enhanced accumulation of organic-rich sediments in the aftermath of the Lomagundi-Jatuli carbon isotope excursion. Sulfidic carbonaceous mudstones in the Talvivaara formation contain one of the largest known shale-hosted nickel deposits. In order to gain new insight into this Shungian sedimentary environment, sedimentological, petrographical and in situ S and Fe isotopic microanalyses were carried out on samples representing depositional and early-diagenetic conditions. The event-bedded lithology with tidal signatures in the organic-rich mudstones strongly indicates deposition from predominantly river-delivered mud on a highly-productive coastal area, below storm-wave base. The riverine supply of phosphorus, sulfate and iron supported high primary productivity and resulted in strong lateral and vertical chemical gradients in the nearshore waters with a shallow oxic surface layer underlain by euxinic water. The stratigraphic upper part of the Talvivaara formation contains banded intervals of thin alternating pyrite beds and carbonaceous mudstone beds. The pyrite beds were deposited by seaward excursions of the concentrated, acidic Fe-rich river plume subsequent to droughts or dry seasons, which led to intense pyrite precipitation upon mixing with euxinic waters. δ34S and δ56Fe values of the bedded pyrite (median δ34S = - 10.3 ‰ and δ56Fe = - 0.79 ‰) are consistent with the reaction of dissolved Fe(II) with H2S from bacterial sulfate reduction. Organic-rich clayey Fe-monosulfide-bearing granules were transported from the muddy estuary, and enclosed in Fe (oxyhydr)oxide aggregates that were forming by wave and current reworking in nearshore accumulations of river-delivered iron. The isotopic composition of these presently pyrrhotitic inclusions (median δ34S = - 3.3 ‰ and δ56Fe = - 1.6 ‰) indicates microbial iron reduction. The Fe

  16. Zinc oxide based diluted magnetic semiconductor nanoparticles: Synthesis by laser ablation in liquids, microstructural and optical properties

    NASA Astrophysics Data System (ADS)

    Savchuk, Andriy I.; Perrone, Alessio; Stolyarchuk, Ihor D.; Savchuk, Oleksandr A.; Makoviy, Vitaliy V.; Smolinsky, Mykhailo M.; Shporta, Oleksandra A.

    2013-12-01

    Nanoparticles of ZnO and ZnO doped with transition metals (Mn, Co) were synthesized by laser ablation in liquid medium. Scanning electron microscopy (SEM) showed formation of nanostructures with different shapes. Atomic force microscopy (AFM) gives information about surface morphology of the formed nanostructures. Absorption edge of ZnO, ZnO:Mn and ZnO:Co colloidal nanoparticles exhibits blue shift due to confinement effect. In photoluminescence spectra three peaks are attributed to the band-edge transitions and defect states. The Faraday rotation in ZnO:Mn nanoparticles gives evidence for paramagnetic behavior at room temperature.

  17. Perpendicular magnetic anisotropy and magnetization dynamics in oxidized CoFeAl films

    PubMed Central

    Wu, Di; Zhang, Zhe; Li, Le; Zhang, Zongzhi; Zhao, H. B.; Wang, J.; Ma, B.; Jin, Q. Y.

    2015-01-01

    Half-metallic Co-based full-Heusler alloys with perpendicular magnetic anisotropy (PMA), such as Co2FeAl in contact with MgO, are receiving increased attention recently due to its full spin polarization for high density memory applications. However, the PMA induced by MgO interface can only be realized for very thin magnetic layers (usually below 1.3 nm), which would have strong adverse effects on the material properties of spin polarization, Gilbert damping parameter, and magnetic stability. In order to solve this issue, we fabricated oxidized Co50Fe25Al25 (CFAO) films with proper thicknesses without employing the MgO layer. The samples show controllable PMA by tuning the oxygen pressure (PO2) and CFAO thickness (tCFAO), large perpendicular anisotropy field of ~8.0 kOe can be achieved at PO2 = 12% for the sample of tCFAO = 2.1 nm or at PO2 = 7% for tCFAO = 2.8 nm. The loss of PMA at thick tCFAO or high PO2 results mainly from the formation of large amount of CoFe oxides, which are superparamagnetic at room temperature but become hard magnetic at low temperatures. The magnetic CFAO films, with strong PMA in a relatively wide thickness range and small intrinsic damping parameter below 0.028, would find great applications in developing advanced spintronic devices. PMID:26190066

  18. Perpendicular magnetic anisotropy and magnetization dynamics in oxidized CoFeAl films

    NASA Astrophysics Data System (ADS)

    Wu, Di; Zhang, Zhe; Li, Le; Zhang, Zongzhi; Zhao, H. B.; Wang, J.; Ma, B.; Jin, Q. Y.

    2015-07-01

    Half-metallic Co-based full-Heusler alloys with perpendicular magnetic anisotropy (PMA), such as Co2FeAl in contact with MgO, are receiving increased attention recently due to its full spin polarization for high density memory applications. However, the PMA induced by MgO interface can only be realized for very thin magnetic layers (usually below 1.3 nm), which would have strong adverse effects on the material properties of spin polarization, Gilbert damping parameter, and magnetic stability. In order to solve this issue, we fabricated oxidized Co50Fe25Al25 (CFAO) films with proper thicknesses without employing the MgO layer. The samples show controllable PMA by tuning the oxygen pressure (PO2) and CFAO thickness (tCFAO), large perpendicular anisotropy field of ~8.0 kOe can be achieved at PO2 = 12% for the sample of tCFAO = 2.1 nm or at PO2 = 7% for tCFAO = 2.8 nm. The loss of PMA at thick tCFAO or high PO2 results mainly from the formation of large amount of CoFe oxides, which are superparamagnetic at room temperature but become hard magnetic at low temperatures. The magnetic CFAO films, with strong PMA in a relatively wide thickness range and small intrinsic damping parameter below 0.028, would find great applications in developing advanced spintronic devices.

  19. Strain-induced significant increase in metal-insulator transition temperature in oxygen-deficient Fe oxide epitaxial thin films

    NASA Astrophysics Data System (ADS)

    Hirai, Kei; Kan, Daisuke; Ichikawa, Noriya; Mibu, Ko; Yoda, Yoshitaka; Andreeva, Marina; Shimakawa, Yuichi

    2015-01-01

    Oxygen coordination of transition metals is a key for functional properties of transition-metal oxides, because hybridization of transition-metal d and oxygen p orbitals determines correlations between charges, spins and lattices. Strain often modifies the oxygen coordination environment and affects such correlations in the oxides, resulting in the emergence of unusual properties and, in some cases, fascinating behaviors. While these strain effects have been studied in many of the fully-oxygenated oxides, such as ABO3 perovskites, those in oxygen-deficient oxides consisting of various oxygen coordination environments like tetrahedra and pyramids as well as octahedra remain unexplored. Here we report on the discovery of a strain-induced significant increase, by 550 K, in the metal-insulator transition temperature of an oxygen-deficient Fe oxide epitaxial thin film. The observed transition at 620 K is ascribed to charge disproportionation of Fe3.66+ into Fe4+ and Fe3+, associated with oxygen-vacancy ordering. The significant increase in the metal-insulator transition temperature, from 70 K in the bulk material, demonstrates that epitaxial growth of oxygen-deficient oxides under substrate-induced strain is a promising route for exploring novel functionality.

  20. Strain-induced significant increase in metal-insulator transition temperature in oxygen-deficient Fe oxide epitaxial thin films

    PubMed Central

    Hirai, Kei; Kan, Daisuke; Ichikawa, Noriya; Mibu, Ko; Yoda, Yoshitaka; Andreeva, Marina; Shimakawa, Yuichi

    2015-01-01

    Oxygen coordination of transition metals is a key for functional properties of transition-metal oxides, because hybridization of transition-metal d and oxygen p orbitals determines correlations between charges, spins and lattices. Strain often modifies the oxygen coordination environment and affects such correlations in the oxides, resulting in the emergence of unusual properties and, in some cases, fascinating behaviors. While these strain effects have been studied in many of the fully-oxygenated oxides, such as ABO3 perovskites, those in oxygen-deficient oxides consisting of various oxygen coordination environments like tetrahedra and pyramids as well as octahedra remain unexplored. Here we report on the discovery of a strain-induced significant increase, by 550 K, in the metal-insulator transition temperature of an oxygen-deficient Fe oxide epitaxial thin film. The observed transition at 620 K is ascribed to charge disproportionation of Fe3.66+ into Fe4+ and Fe3+, associated with oxygen-vacancy ordering. The significant increase in the metal-insulator transition temperature, from 70 K in the bulk material, demonstrates that epitaxial growth of oxygen-deficient oxides under substrate-induced strain is a promising route for exploring novel functionality. PMID:25600001

  1. Order of Activity of Nitrogen, Iron Oxide, and FeNx Complexes towards Oxygen Reduction in Alkaline Medium.

    PubMed

    Zhu, Yansong; Zhang, Bingsen; Wang, Da-Wei; Su, Dang Sheng

    2015-12-01

    In alkaline medium, it seems that both metal-free and iron-containing carbon-based catalysts, such as nitrogen-doped nanocarbon materials, FeOx -doped carbon, and Fe/N/C catalysts, are active for the oxygen reduction reaction (ORR). However, the order of activity of these different active compositions has not been clearly determined. Herein, we synthesized nitrogen-doped carbon black (NCB), Fe3 O4 /CB, Fe3 O4 /NCB, and FeN4 /CB. Through the systematic study of the ORR catalytic activity of these four catalysts in alkaline solution, we confirmed the difference in the catalytic activity and catalytic mechanism for nitrogen, iron oxides, and Fe-N complexes, respectively. In metal-free NCB, nitrogen can improve the ORR catalytic activity with a four-electron pathway. Fe3 O4 /CB catalyst did not exhibit improved activity over that of NCB owing to the poor conductivity and spinel structure of Fe3 O4 . However, FeN4 coordination compounds as the active sites showed excellent ORR catalytic activity. PMID:26609795

  2. Role of "electron shuttles" in the bioreduction of Fe(III) oxides in humid forest tropical soils.

    NASA Astrophysics Data System (ADS)

    Peretyazhko, T.; Sposito, G.

    2004-12-01

    Dissimilatory iron-reducing bacteria (DIRB) can reduce Fe(III) oxides either by direct contact between the organisms and the oxide surface or by indirect mechanisms not involving contact. These latter mechanisms can include (i) "electron shuttling" or (ii) soluble Fe(III) complexation with subsequent reduction. In the presence of humic substances, indirect Fe(III) reduction occurs, particularly by mechanism (i). Important electron-accepting groups in humic substances include quinone moieties, complexed Fe(III) and conjugated aromatic moieties. A model compound frequently used to study mechanism (i) is anthraquinone-2,6-disulfonate (AQDS), which is believed to function as an "electron shuttle" in a manner similar to humic substances. We are currently investigating Fe(III) reduction in humid tropical forest soils as affected by "electron shuttles," using AQDS and humic substances in our experiments. The soil samples were collected at the bottom of a toposequence in the Luquillo Experimental Forest, Puerto Rico. Development of anaerobic conditions in these soils occurs due to high precipitation and runoff water inputs. Fourteen-day anoxic incubations of soil suspensions amended with AQDS showed enhanced production of both soluble and particulate forms of Fe(II) as compared to non-amended soil suspensions. Our data indicated clearly that DIRB in the soil could utilize added "electron shuttles" effectively to reduce Fe(III). To examine factors controlling Fe(III) reduction by humic acid (HA), three IHSS HA samples (soil, peat and Leonardite) were both abiotically reduced by H2 treatment and microbially reduced by incubation with a filtrate from a soil suspension, then titrated with three different oxidants (iodine, cyanoferrate, and ferric citrate) to provide chemical and biological estimates of electron-accepting capacity at pH 5 and 7. The results will be discussed in terms of the three oxidants used, the properties of the HA samples, pH, and the effects of chemical

  3. Sol-gel nanocasting synthesis of patterned hierarchical LaFeO3 fibers with enhanced catalytic CO oxidation activity.

    PubMed

    Li, Pengna; Hu, Xianluo; Zhang, Lei; Dai, Hongxing; Zhang, Lizhi

    2011-03-01

    Hierarchical LaFeO3 fibers were prepared by a sol-gel nanocasting method using a cotton cloth as the template. The resulting LaFeO3 fibers inherited the initial network morphology of the template very well and showed enhanced catalytic CO oxidation activity and satisfactory stability compared to the counterpart particles prepared by the conventional sol-gel method. PMID:21234504

  4. Role of a unique population of lithotrophic, Fe-oxidizing bacteria in forming microbial Fe-mats at the Loihi Seamount.

    NASA Astrophysics Data System (ADS)

    Emerson, D.; Rentz, J. A.; Moyer, C. L.

    2005-12-01

    The Loihi Seamount, located 30 km SE of the island of Hawai'i, is among the most active volcanos on Earth. The summit, at a depth of 1100m, includes a 250m deep caldera (Pele's Pit) formed by an eruption in 1996. The summit, and especially Pele's Pit, are the site of extensive low to intermediate temperature (10° to 65°C) hydrothermal venting, emanating both from diffuse fissures and orifices that have substantial flow rates. The vent fluid is characterized by a low sulfide content, high CO2 concentrations and Fe(II) amounts in the 10s to 100s of μM. Associated with all vents are extensive deposits of iron oxyhydroxides that typically have 107 to 108 bacterial cells/cc associated with them. The morphology of the Fe-oxides are indicative of biological origins. We have isolated microaerophilic, obligately lithotrophic Fe-oxidizing bacteria from Loihi and describe here `Mariprofundus ferroxydans' a unique bacterium that forms a filamentous iron oxide mineral. `M. ferroxydans' is the first cultured representative of a novel division of the Proteobacteria, known previously only from clones from different hydrothermal vent sites. Molecular evidence from Loihi mats based on clone libraries and terminal restriction length polymorphism (T-RFLP) analysis of 16S rRNA genes indicate that this lineage of Fe-oxidizing organisms are common inhabitants at Loihi. We speculate that this organism and its relatives form the basis of an active microbial mat community that owe their existence to the inherent gradients of Fe(II) and O2 that exist at the Loihi vents. In a geological context this is interesting because the Loihi summit and caldera are in an O2-minima zone; O2 concentrations in the bulk seawater are around 0.5 mg/l. In effect, Loihi could serve as a proxy for the late Archaean and early Proterozoic periods when the Earth's atmosphere went from reducing to oxidizing, and it is speculated that abundant Fe(II) in the Earth's oceans served as a major sink for O2 production

  5. Controlling phosphate releasing from poultry litter using stabilized Fe-Mn binary oxide nanoparticles.

    PubMed

    Xie, Wenbo; Zhao, Dongye

    2016-01-15

    Animal wastes contain high concentrations of phosphorus (P), most of which is lost into the environment due to uncontrolled release rates. Polysaccharide stabilized Fe-Mn binary oxide nanoparticles were prepared and tested for phosphate adsorption from water and for controlling leachability of P from poultry litter. A water soluble starch and carboxymethyl cellulose (CMC) were used as a stabilizer. Both the Freundlich and Langmuir models were able to adequately interpret the isotherm data. The Langmuir maximum capacity was determined at 252, 298 and 313 mg-P/g for bare, CMC- and starch-stabilized nanoparticles, respectively. The presence of the stabilizers not only enhanced the sorption capacity, but facilitated delivery and dispersion of the nanoparticles in poultry litter (PL) and in soil. High phosphate sorption capacity was observed over a broad pH range of 4-9. FTIR analyses indicated that inner sphere surface complexation (Fe-O-P) was the key mechanism for the enhanced uptake of P. When applied to poultry litter, the stabilized nanoparticles reduced water leachable phosphate by >86% at a dose of 0.2 g/L as Fe, and simultaneously, water leachable arsenic by >87-95%. Under conditions of simulated land application of PL, the nanoparticle amendment of PL reduced the water soluble P from 66% (for untreated PL) to 4.4%, and lowered the peak soluble P concentration from 300 to <20 mg/L. By transferring the peak soluble P to the nanoparticle-bound P, the nanoparticles not only greatly reduce the potential runoff loss of P from PL, but also provide a long-term slow-releasing nutrient source. Fortuitously, the nanoparticle treatment was able to immobilize arsenic from PL. With excellent adsorption capacity, easy deliverability, low cost and environmental innocuousness, the stabilized Fe-Mn nanoparticles appear promising for controlling P releases from poultry litter or other animal wastes and for phosphate recovery from water. PMID:26442720

  6. Fe(II) Oxidation Is an Innate Capability of Nitrate-Reducing Bacteria That Involves Abiotic and Biotic Reactions

    PubMed Central

    Carlson, Hans K.; Clark, Iain C.; Blazewicz, Steven J.; Iavarone, Anthony T.

    2013-01-01

    Phylogenetically diverse species of bacteria can catalyze the oxidation of ferrous iron [Fe(II)] coupled to nitrate (NO3−) reduction, often referred to as nitrate-dependent iron oxidation (NDFO). Very little is known about the biochemistry of NDFO, and though growth benefits have been observed, mineral encrustations and nitrite accumulation likely limit growth. Acidovorax ebreus, like other species in the Acidovorax genus, is proficient at catalyzing NDFO. Our results suggest that the induction of specific Fe(II) oxidoreductase proteins is not required for NDFO. No upregulated periplasmic or outer membrane redox-active proteins, like those involved in Fe(II) oxidation by acidophilic iron oxidizers or anaerobic photoferrotrophs, were observed in proteomic experiments. We demonstrate that while “abiotic” extracellular reactions between Fe(II) and biogenic NO2−/NO can be involved in NDFO, intracellular reactions between Fe(II) and periplasmic components are essential to initiate extensive NDFO. We present evidence that an organic cosubstrate inhibits NDFO, likely by keeping periplasmic enzymes in their reduced state, stimulating metal efflux pumping, or both, and that growth during NDFO relies on the capacity of a nitrate-reducing bacterium to overcome the toxicity of Fe(II) and reactive nitrogen species. On the basis of our data and evidence in the literature, we postulate that all respiratory nitrate-reducing bacteria are innately capable of catalyzing NDFO. Our findings have implications for a mechanistic understanding of NDFO, the biogeochemical controls on anaerobic Fe(II) oxidation, and the production of NO2−, NO, and N2O in the environment. PMID:23687275

  7. Fe/Ti co-pillared clay for enhanced arsenite removal and photo oxidation under UV irradiation

    NASA Astrophysics Data System (ADS)

    Li, Yuan; Cai, Xiaojiao; Guo, Jingwei; Zhou, Shimin; Na, Ping

    2015-01-01

    A series of iron and titanium co-pillared montmorillonites (Fe-Ti/MMT) were prepared using hydrolysis of inserted titanium and different iron content in montmorillonite (MMT). The Fe-Ti/MMT were characterized by X-ray fluorescence, N2 adsorption and desorption, X-ray diffraction, scanning electron microscopy (SEM) and transmission electron microscopy (TEM), confirming the effective insertion of Fe species and TiO2 in the MMT. The Fe-Ti/MMT was used to remove arsenite (As(III)) from aqueous solutions under different conditions. The result of As(III) adsorption under UV irradiation showed that the photo activity can be enhanced by incorporating Fe and Ti in MMT. Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis indicated that the hydroxyl groups bonded to metal oxide (M-OH) played an important role in the adsorption of As(III)

  8. Metagenomic insights into Fe(II)-oxidizing Zetaproteobacteria from a biomat at Loi'hi, Hawai'i

    NASA Astrophysics Data System (ADS)

    Singer, E.; Dhillon, A.; Barco, R. A.; Edwards, K. J.

    2011-12-01

    Zetaproteobacteria are among the most prevalent Fe(II)-oxidizing bacteria (FeOB) that proliferate at deep-sea hydrothermal vents, however, knowledge about the metabolic potential and diversity as well as environmental significance of this class is limited. Additionally, there are only four isolated Zetaproteobacteria to date, none of which represent any of the locally dominant or ubiquitous environmental operational taxonomic units (OTUs) (Mcallister et al., 2011). Understanding the physiology, ecology, and genetics of these FeOB is important for understanding the cycling of Fe and carbon at hydrothermal vents and potentially other marine sedimentary environments.We present the first 454 metagenomic dataset from a biomat isolated from the Lo'ihi Seamount, Hawai'i, dominated by Fe(II)-oxidizing Zetaproteobacteria. Zetaproteobacteria reads are dominated by a strain that is 99.5% identical to OTU1 (uncultured bacterial clone SPL_10), one of two ubiquitous Zetaproteobacteria clades in the Pacific Ocean (Mcallister et al., 2011). Metagenomic analysis revealed candidate genes required for Fe(II)-oxidation, which are homologous and similar in gene synteny to a gene cluster previously identified in the only sequenced Zetaproteobacteria genome from the isolate Mariprofundus ferrooxydans strain PV-1, as well as in the neutrophilic Fe(II) oxidizing organisms Sideroxydans lithotrophicus strain ES-1 and Gallionella ferruginea strain ES-2 (Singer et al., submitted). This gene cluster encodes for various electron transport proteins, including cytochromes and dehydrogenases, as well as a molydopterin oxidoreductase, which was previously extracted from an Fe(II)-oxidizing PV-1 at neutral pH and under microaerobic conditions. Based on comparative genomics and protein extraction results, we propose this gene cluster as a genetic biomarker for neutrophilic, microaerophilic FeOB. In addtion to genes required for iron metabolism, we also found genes required for trans-membrane iron

  9. Fabrication of Fe2O3 nanoflakes-based electrochemical solar cells prepared by facile thermal oxidation

    NASA Astrophysics Data System (ADS)

    Rashid, Norhana Mohamed; Kishi, Naoki; Soga, Tetsuo

    2016-06-01

    A Fe2O3 nanoflakes-based solar cell was successfully prepared by thermal oxidation of iron film on FTO glass. The short circuit current density (Jsc) of the cell increased with annealing time while the open circuit voltage was saturated after 1 h. This enhancement was caused by the increased surface area of the nanoflakes and improved electron transfer through the (110) crystal plane in the Fe2O3-based electrochemical solar cell. The overall photovoltaic performance significantly increased with ruthenium dye, which likely suppressed carrier recombination on the Fe2O3 surface.

  10. Structure and oxidation state of hematite surfaces reacted with aqueous Fe(II) at acidic and neutral pH

    NASA Astrophysics Data System (ADS)

    Catalano, Jeffrey G.; Fenter, Paul; Park, Changyong; Zhang, Zhan; Rosso, Kevin M.

    2010-03-01

    Structural changes and surface oxidation state were examined following the reaction of hematite (0 0 1), (0 1 2), and (1 1 0) with aqueous Fe(II). X-ray reflectivity measurements indicated that Fe(II) induces changes in the structure of all three surfaces under both acidic (pH 3) and neutral (pH 7) conditions. The structural changes were generally independent of pH although the extent of surface transformation varied slightly between acidic and neutral conditions; no systematic trends with pH were observed. Induced changes on the (1 1 0) and (0 1 2) surfaces include the addition or removal of partial surface layers consistent with either growth or dissolution. In contrast, a <1 nm thick, discontinuous film formed on the (0 0 1) surface that appears to be epitaxial yet is not a perfect extension of the underlying hematite lattice, being either structurally defective, compositionally distinct, or nanoscale in size and highly relaxed. Resonant anomalous X-ray reflectivity measurements determined that the surface concentration of Fe(II) present after reaction at pH 7 was below the detection limit of approximately 0.5-1 μmol/m 2 on all surfaces. These observations are consistent with Fe(II) oxidative adsorption, whereby adsorbed Fe(II) is oxidized by structural Fe(III) in the hematite lattice, with the extent of this reaction controlled by surface structure at the atomic scale. The observed surface transformations at pH 3 show that Fe(II) oxidatively adsorbs on hematite surfaces at pH values where little net adsorption occurs, based on historical macroscopic Fe(II) adsorption behavior on fine-grained hematite powders. This suggests that Fe(II) plays a catalytic role, in which an electron from an adsorbed Fe(II) migrates to and reduces a lattice Fe(III) cation elsewhere, which subsequently desorbs in a scenario with zero net reduction and zero net adsorption. Given the general pH-independence and substantial mass transfer involved, this electron and atom exchange

  11. Different enzymes are involved in anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation in Thiobacillus denitrificans

    NASA Astrophysics Data System (ADS)

    Zhou, P.; Beller, H. R.

    2011-12-01

    Thiobacillus denitrificans is a widespread, obligate chemolithoautotrophic bacterium that is capable of anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation. Both of these processes can mediate the mobility of uranium in contaminated aquifers and thereby influence the long-term efficacy of in situ reductive immobilization of uranium at DOE sites. T. denitrificans has been found at uranium-contaminated sites, including a contaminated aquifer at Oak Ridge National Laboratory. We previously reported that two membrane-associated, diheme, c-type cytochromes (a c4 cytochrome, Tbd_0187, and a c5 cytochrome, Tbd_0146) were involved in nitrate-dependent U(IV) oxidation in T. denitrificans. To date, these are the only genes identified to be involved in this process. In this poster, we report on work with T. denitrificans focused on determining whether the enzymes that were demonstrated to be involved in anaerobic, nitrate-dependent U(IV) oxidation are also involved in nitrate-dependent Fe(II) oxidation. Using a genetic system in T. denitrificans that enables us to create insertion mutants and complement them in trans, we constructed a series of insertion mutants. These included strains with mutations in the genes known to be associated with U(IV) oxidation (Tbd_0146 and Tbd_0187) as well as other genes encoding membrane-associated c-type cytochromes (a group of proteins that we hypothesize to be catalyzing Fe(II) oxidation). Anaerobic cell suspension assays were carried out to determine whether any of these mutants were defective in nitrate-dependent Fe(II) oxidation. We observed that the Tbd_0146 and Tbd_0187 mutants were not defective in nitrate-dependent Fe(II) oxidation, nor were any of the other c-type cytochrome mutants tested (including a Tbd_0146-Tbd_0187 double mutant). The finding that different enzymes are associated with nitrate-dependent Fe(II) and U(IV) oxidation has led us to pursue genome-wide studies in T. denitrificans to determine the genes associated

  12. Spinel type CoFe oxide porous nanosheets as magnetic adsorbents with fast removal ability and facile separation.

    PubMed

    Ge, X; Gu, C D; Wang, X L; Tu, J P

    2015-09-15

    Adsorption is often time consuming due to slow diffusion kinetic. Sizing he adsorbent down might help to accelerate adsorption. For CoFe spinel oxide, a magnetically separable adsorbent, the preparation of nanosheets faces many challenges including phase separation, grain growth and difficulty in preparing two-dimensional materials. In this work, we prepared porous CoFe oxide nanosheet with chemical formula of Co2.698Fe0.302O4 through topochemical transformation of a CoFe precursor, which has a layered double hydroxide (LDH) analogue structure and a large interlayer spacing. The LDH precursor was synthesized from a cheap deep eutectic solvent (DES) system. The calcined Co2.698Fe0.302O4 has small grain size (10-20nm), nanosheet morphology, and porous structure, which contribute to a large specific surface area of 79.5m(2)g(-1). The Co2.698Fe0.302O4 nanosheets show fast removal ability and good adsorption capacity for both organic waste (305mgg(-1) in 5min for Congo red) and toxic heavy metal ion (5.27mgg(-1) in 30min for Cr (VI)). Furthermore, the Co2.698Fe0.302O4 can be separated magnetically. Considering the precursor can be prepared through a fast, simple, surfactant-free and high-yield synthetic strategy, this work should have practical significance in fabricating adsorbents. PMID:26005799

  13. Abiotic process for Fe(II) oxidation and green rust mineralization driven by a heterotrophic nitrate reducing bacteria (Klebsiella mobilis).

    PubMed

    Etique, Marjorie; Jorand, Frédéric P A; Zegeye, Asfaw; Grégoire, Brian; Despas, Christelle; Ruby, Christian

    2014-04-01

    Green rusts (GRs) are mixed Fe(II)-Fe(III) hydroxides with a high reactivity toward organic and inorganic pollutants. GRs can be produced from ferric reducing or ferrous oxidizing bacterial activities. In this study, we investigated the capability of Klebsiella mobilis to produce iron minerals in the presence of nitrate and ferrous iron. This bacterium is well-known to reduce nitrate using an organic carbon source as electron donor but is unable to enzymatically oxidize Fe(II) species. During incubation, GR formation occurred as a secondary iron mineral precipitating on cell surfaces, resulting from Fe(II) oxidation by nitrite produced via bacterial respiration of nitrate. For the first time, we demonstrate GR formation by indirect microbial oxidation of Fe(II) (i.e., a combination of biotic/abiotic processes). These results therefore suggest that nitrate-reducing bacteria can potentially contribute to the formation of GR in natural environments. In addition, the chemical reduction of nitrite to ammonium by GR is observed, which gradually turns the GR into the end-product goethite. The nitrogen mass-balance clearly demonstrates that the total amount of ammonium produced corresponds to the quantity of bioreduced nitrate. These findings demonstrate how the activity of nitrate-reducing bacteria in ferrous environments may provide a direct link between the biogeochemical cycles of nitrogen and iron. PMID:24605878

  14. Combinatorial discovery through a distributed outreach program: investigation of the photoelectrolysis activity of p-type Fe, Cr, Al oxides.

    PubMed

    Rowley, John G; Do, Thanh D; Cleary, David A; Parkinson, B A

    2014-06-25

    We report the identification of a semiconducting p-type oxide containing iron, aluminum, and chromium (Fe2-x-yCrxAlyO3) with previously unreported photoelectrolysis activity that was discovered by an undergraduate scientist participating in the Solar Hydrogen Activity research Kit (SHArK) program. The SHArK program is a distributed combinatorial science outreach program designed to provide a simple and inexpensive way for high school and undergraduate students to participate in the search for metal oxide materials that are active for the photoelectrolysis of water. The identified Fe2-x-yCrxAlyO3 photoelectrolysis material possesses many properties that make it a promising candidate for further optimization for potential application in a photoelectrolysis device. In addition to being composed of earth abundant elements, the FeCrAl oxide material has a band gap of 1.8 eV. Current-potential measurements for Fe2-x-yCrxAlyO3 showed an open circuit photovoltage of nearly 1 V; however, the absorbed photon conversion efficiency for hydrogen evolution was low (2.4 × 10(-4) at 530 nm) albeit without any deposited hydrogen evolution catalyst. X-ray diffraction of the pyrolyzed polycrystalline thin Fe2-x-yCrxAlyO3 film on fluorine-doped tin oxide substrates shows a hexagonal phase (hematite structure) and scanning electron microscope images show morphology consisting of small crystallites. PMID:24670777

  15. Phonons and stability of infinite-layer iron oxides SrFeO2 and CaFeO2

    NASA Astrophysics Data System (ADS)

    Gupta, M. K.; Mittal, R.; Chaplot, S. L.; Tassel, Cédric; Kageyama, Hiroshi; Tomiyasu, K.; Taylor, Jon

    2016-09-01

    We present detailed ab-initio lattice dynamical analysis of the Fe-O infinite-layer compounds CaFeO2 and SrFeO2 in various magnetic configurations. These indicate strong spin-phonon coupling in SrFeO2 in contrast to that in case of CaFeO2. From our ab-initio calculations in SrFeO2 as a function of volume, we suggest that the distortion in SrFeO2 above 300 K is similar to that in CaFeO2 at ambient conditions. The distortion of the planer structure of CaFeO2 involves doubling of the planer unit cell that may be usually expected to be due to a soft phonon mode at the M-point (1/2 1/2 0). However, our ab-initio calculations show quite unusually that all the M-point (1/2 1/2 0) phonons are stable, but two stable M3+ and M2- modes anharmonically couple with an unstable Bu mode at the zone center and lead to the cell doubling and the distorted structure. Magnetic exchange interactions in both the compounds have been computed on the basis of the ideal planar structure (P4/mmm space group) and with increasing amplitude of the Bu phonon mode. These reveal that the magnetic exchange interactions reduce significantly with increasing distortion. We have extended the ab-initio phonon calculation to high pressures, which reveal that, above 20 GPa of pressure, the undistorted planer CaFeO2 becomes dynamically stable. We also report computed phonon spectra in SrFeO3 that has a cubic structure, which is useful to understand the role of the difference in geometry of oxygen atoms around the Fe atom with respect to planer SrFeO2. Finally, powder neutron inelastic scattering experiments on SrFeO2 have also been performed at temperatures from 5 K to 353 K in the antiferromagnetic phase. The 5-K data are compared to the ab-initio calculations.

  16. Observation of Oxide Formation for Molten Fe-Cr-C Alloy at a High Carbon Region by Oxygen Top Blowing

    NASA Astrophysics Data System (ADS)

    Mihara, Ryosuke; Gao, Xu; Kaneko, Shigeru; Kim, Sunjoong; Ueda, Shigeru; Shibata, Hiroyuki; Seok, Min Oh; Kitamura, Shin-ya

    2016-04-01

    The oxide formation behavior during decarburization by top blowing for molten Fe-Cr-C alloy was directly observed. For 11 mass pct Cr alloy at 1673 K to 1723 K (1400 °C to 1450 °C), as well as for 14 mass pct Cr alloy at 1623 K to 1673 K (1350 °C to 1400 °C), oxide particles always formed within several minutes after decarburization started. Also, unstable oxide film followed by stable oxide film formed after C content was decreased to certain levels. For 11 mass pct Cr alloy at 1773 K (1500 °C) and 14 mass pct Cr alloy at 1723 K (1450 °C), only the oxide particle and stable oxide film were observed. For 18 mass pct Cr-5 mass pct C alloy at 1723 K (1450 °C), stable oxide film formed twice. By comparing the critical C and Cr contents of alloy when oxides started to form with the equilibrium relation, the formation of the oxide particle and unstable oxide film was found to be under a nonequilibrium condition, whereas the stable oxide film that formed was near an equilibrium condition. For 11 and 14 mass pct Cr alloy, the decarburization rate stayed constant and was not affected by the formation of the oxide particle or unstable oxide film, but it started to decrease after the formation of the stable oxide film.

  17. Composition and structure of Fe(III)-precipitates formed by Fe(II) oxidation in water at near-neutral pH: Interdependent effects of phosphate, silicate and Ca

    NASA Astrophysics Data System (ADS)

    Senn, Anna-Caterina; Kaegi, Ralf; Hug, Stephan J.; Hering, Janet G.; Mangold, Stefan; Voegelin, Andreas

    2015-08-01

    We studied the interdependent effects of phosphate, silicate and Ca on the formation of Fe(III)-precipitate