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

Rear-side picosecond laser ablation of indium tin oxide micro-grooves

NASA Astrophysics Data System (ADS)

Liu, Peng; Wang, Wenjun; Mei, Xuesong; Liu, Bin; Zhao, Wanqin

2015-06-01

A comparative study of the fabrication of micro-grooves in indium tin oxide films by picosecond laser ablation for application in thin film solar cells is presented, evaluating the variation of different process parameters. Compared with traditional front-side ablation, rear-side ablation results in thinner grooves with varying laser power at a certain scan speed. In particular, and in contrast to front-side ablation, the width of the micro-grooves remains unchanged when the scan speed was changed. Thus, the micro-groove quality can be optimized by adjusting the scan speed while the groove width would not be affected. Furthermore, high-quality micro-grooves with ripple free surfaces and steep sidewalls could only be achieved when applying rear-side ablation. Finally, the formation mechanism of micro-cracks on the groove rims during rear-side ablation is analyzed and the cracks can be almost entirely eliminated by an optimization of the scan speed.

Effects of Pedogenic Fe Oxides on Soil Aggregate-Associated Carbon

NASA Astrophysics Data System (ADS)

Asefaw Berhe, A.; Jin, L.

2017-12-01

Carbon sequestration is intimately related to the soil structure, mainly soil aggregate dynamics. Carbon storage in soil aggregates has been recognized as an important carbon stabilization mechanism in soils. Organic matter and pedogenic Fe oxides are major binding agents that facilitate soil aggregate formation and stability. However, few studies have investigated how different forms of pedogenic Fe oxides can affect soil carbon distribution in different aggregate-size fractions. We investigated sequentially extracted pedogenic Fe oxides (in the order of organically complexed Fe extracted with sodium pyrophosphate, poorly-crystalline Fe oxides extracted with hydroxylamine hydrochloride, and crystalline Fe oxides extracted with dithionite hydrochloride) and determined the amount and nature of C in macroaggregates (2-0.25mm), microaggregates (0.25-0.053mm), and two silt and clay fractions (0.053-0.02mm, and <0.02mm) in Musick soil from Sierra Nevada mountain in California. We also determined how pedogenic Fe oxides affect soil carbon distribution along soil depth gradients. Findings of our study revealed that the proportion of organic matter complexed Fe decreased, but the proportion of crystalline Fe increased with increasing soil depths. Poorly crystalline Fe oxides (e.g. ferrihydrite) was identified as a major Fe oxide in surface soil, whereas crystalline Fe oxides (e.g. goethite) were found in deeper soil layers. These results suggest that high concentration of organic matter in surface soil suppressed Fe crystallization. Calcium cation was closely related to the pyrophosphate extractable Fe and C, which indicates that calcium may be a major cation that contribute to the organic matter complexed Fe and C pool. Increasing concentrations of extractable Fe and C with decreasing aggregate size fractions also suggests that Fe oxides play an important role in formation and stability of silt and clay fractions, and leading to further stabilization of carbon in soil

CoxFe1-x oxide coatings on metallic interconnects for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shen, Fengyu; Lu, Kathy

2016-10-01

In order to improve the performance of Cr-containing steel as an interconnect material for solid oxide fuel cells, CoFe alloy coatings with Co:Fe ratios of 9:1, 8:2, 7:3, 6:4, and 5:5 are deposited by electrodeposition and then oxidized to CoxFe1-x oxide coatings with a thickness of ∼6 μm as protective layers on the interconnect. The area specific resistance of the coated interconnect increases with the Fe content. Higher Co content oxide coatings are more effective in limiting the growth of the chromia scale while all coatings are effective in inhibiting Cr diffusion and evaporation. With the Co0.8Fe0.2 oxide coated interconnect, the electrochemical performance of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode is improved. Only 1.54 atomic percentage of Cr is detected on the surface of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode while no Cr is detected 0.66 μm or more into the cathode. CoxFe1-x oxide coatings are promising candidates for solid oxide fuel cell interconnects with the advantage of using existing cathode species for compatibility and performance enhancement.

Formation of iron (hydr)oxides during the abiotic oxidation of Fe(II) in the presence of arsenate.

PubMed

Song, Jia; Jia, Shao-Yi; Yu, Bo; Wu, Song-Hai; Han, Xu

2015-08-30

Abiotic oxidation of Fe(II) is a common pathway in the formation of Fe (hydr)oxides under natural conditions, however, little is known regarding the presence of arsenate on this process. In hence, the effect of arsenate on the precipitation of Fe (hydr)oxides during the oxidation of Fe(II) is investigated. Formation of arsenic-containing Fe (hydr)oxides is constrained by pH and molar ratios of As:Fe during the oxidation Fe(II). At pH 6.0, arsenate inhibits the formation of lepidocrocite and goethite, while favors the formation of ferric arsenate with the increasing As:Fe ratio. At pH 7.0, arsenate promotes the formation of hollow-structured Fe (hydr)oxides containing arsenate, as the As:Fe ratio reaches 0.07. Arsenate effectively inhibits the formation of magnetite at pH 8.0 even at As:Fe ratio of 0.01, while favors the formation of lepidocrocite and green rust, which can be latterly degenerated and replaced by ferric arsenate with the increasing As:Fe ratio. This study indicates that arsenate and low pH value favor the slow growth of dense-structured Fe (hydr)oxides like spherical ferric arsenate. With the rapid oxidation rate of Fe(II) at high pH, ferric (hydr)oxides prefer to precipitate in the formation of loose-structured Fe (hydr)oxides like lepidocrocite and green rust. Copyright © 2015 Elsevier B.V. All rights reserved.

Arsenate uptake and arsenite simultaneous sorption and oxidation by Fe-Mn binary oxides: influence of Mn/Fe ratio, pH, Ca2+, and humic acid.

PubMed

Zhang, Gaosheng; Liu, Huijuan; Qu, Jiuhui; Jefferson, William

2012-01-15

Arsenate retention, arsenite sorption and oxidation on the surfaces of Fe-Mn binary oxides may play an important role in the mobilization and transformation of arsenic, due to the common occurrence of these oxides in the environment. However, no sufficient information on the sorption behaviors of arsenic on Fe-Mn binary oxides is available. This study investigated the influences of Mn/Fe molar ratio, solution pH, coexisting calcium ions, and humic acids have on arsenic sorption by Fe-Mn binary oxides. To create Fe-Mn binary oxides, simultaneous oxidation and co-precipitation methods were employed. The Fe-Mn binary oxides exhibited a porous crystalline structure similar to 2-line ferrihydrite at Mn/Fe ratios 1:3 and below, whereas exhibited similar structures to δ-MnO(2) at higher ratios. The As(V) sorption maximum was observed at a Mn/Fe ratio of 1:6, but As(III) uptake maximum was at Mn/Fe ratio 1:3. However, As(III) adsorption capacity was much higher than that of As(V) at each Mn/Fe ratio. As(V) sorption was found to decrease with increasing pH, while As(III) sorption edge was different, depending on the content of MnO(2) in the binary oxides. The presence of Ca(2+) enhanced the As(V) uptake under alkaline pH, but did not significantly influence the As(III) sorption by 1:9 Fe-Mn binary oxide; whereas the presence of humic acid slightly reduced both As(V) and As(III) uptake. These results indicate that As(III) is more easily immobilized than As(V) in the environment, where Fe-Mn binary oxides are available as sorbents and they represent attractive adsorbents for both As(V) and As(III) removal from water and groundwater. Copyright © 2011 Elsevier Inc. All rights reserved.

Mechanisms for Fe(III) oxide reduction in sedimentary environments

USGS Publications Warehouse

Nevin, Kelly P.; Lovely, Derek R.

2002-01-01

Although it was previously considered that Fe(III)-reducing microorganisms must come into direct contact with Fe(III) oxides in order to reduce them, recent studies have suggested that electron-shuttling compounds and/or Fe(III) chelators, either naturally present or produced by the Fe(III)-reducing microorganisms themselves, may alleviate the need for the Fe(III) reducers to establish direct contact with Fe(III) oxides. Studies with Shewanella alga strain BrY and Fe(III) oxides sequestered within microporous beads demonstrated for the first time that this organism releases a compound(s) that permits electron transfer to Fe(III) oxides which the organism cannot directly contact. Furthermore, as much as 450 w M dissolved Fe(III) was detected in cultures of S. alga growing in Fe(III) oxide medium, suggesting that this organism releases compounds that can solublize Fe(III) from Fe(III) oxide. These results contrast with previous studies, which demonstrated that Geobacter metallireducens does not produce electron-shuttles or Fe(III) chelators. Some freshwater aquatic sediments and groundwaters contained compounds, which could act as electron shuttles by accepting electrons from G. metallireducens and then transferring the electrons to Fe(III). However, other samples lacked significant electron-shuttling capacity. Spectroscopic studies indicated that the electron-shuttling capacity of the waters was not only associated with the presence of humic substances, but water extracts of walnut, oak, and maple leaves contained electron-shuttling compounds did not appear to be humic substances. Porewater from a freshwater aquatic sediment and groundwater from a petroleum-contaminated aquifer contained dissolved Fe(III) (4-16 w M), suggesting that soluble Fe(III) may be available as an electron acceptor in some sedimentary environments. These results demonstrate that in order to accurately model the mechanisms for Fe(III) reduction in sedimentary environments it will be necessary

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.

Injectable PLGA/Fe3O4 implants carrying cisplatin for synergistic magnetic hyperthermal ablation of rabbit VX2 tumor.

PubMed

Yang, Yang; Wang, Fengjuan; Zheng, Kaiyuan; Deng, Liming; Yang, Lu; Zhang, Nan; Xu, Chunyan; Ran, Haitao; Wang, Zhaoxia; Wang, Zhigang; Zheng, Yuanyi

2017-01-01

Magnetic hyperthermia ablation has attracted wide attention in tumor therapy for its minimal invasion. Although the chemo-hyperthermal synergism has been proven to be effective in subcutaneously xenografted tumors of nude mice in our previous experiment, the occurrence of residual tumors due to incomplete ablation is more common in relatively larger and deeper-seated tumors in anti-tumor therapy. Thus, a larger tumor and larger animal model are needed for further study of the therapeutic efficacy. In this study, we tested the efficiency of this newly developed technique using a rabbit tumor model. Furthermore, we chose cisplatin (DDP), which has been confirmed with high efficiency in enhancing hyperthermia therapy as the chemotherapeutic drug for the synergistic magnetic hyperthermal ablation therapy of tumors. In vitro studies demonstrated that developed DDP-loaded magnetic implants (DDP/PLGA-Fe3O4) have great heating efficacy and the drug release can be significantly boosted by an external alternating magnetic field (AMF). In vivo studies showed that the phase-transitional DDP/PLGA-Fe3O4 materials that are ultrasound (US) and computerized tomography (CT) visible can be well confined in the tumor tissues after injection. When exposed to AMF, efficient hyperthermia was induced, which led to the cancer cells' coagulative necrosis and accelerating release of the drug to kill residual tumors. Furthermore, an activated anti-tumor immune system can promote apoptosis of tumor cells. In conclusion, the DDP/PLGA-Fe3O4 implants can be used efficiently for the combined chemotherapy and magnetic-hyperthermia ablation of rabbit tumors.

Magnetic effect on oxide-scale growth of Fe-5Cr alloy

NASA Astrophysics Data System (ADS)

Zhou, C. H.; Li, X. W.; Wang, S. H.; Ma, H. T.

2018-01-01

The oxidation behaviour of Fe-5Cr alloy was investigated at 650°C in the presence of magnetic field. Results indicated that the oxide scales were both consisted of an outer Fe-oxide scale and an inner mixed-oxide scale in the presence or absence of magnetic field. The oxide-scale growth of Fe-5Cr alloy, gained by measuring the oxide-scale thickness, was verified to follow parabolic lawyer. And the oxidation kinetics showed that the applied magnetic field retarded the oxide-scale growth of Fe-5Cr alloy.

Carbonate-mediated Fe(II) oxidation in the air-cathode fuel cell: a kinetic model in terms of Fe(II) speciation.

PubMed

Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi; Sun, Min; Jiang, Yuan

2013-06-06

Due to the high redox activity of Fe(II) and its abundance in natural waters, the electro-oxidation of Fe(II) can be found in many air-cathode fuel cell systems, such as acid mine drainage fuel cells and sediment microbial fuel cells. To deeply understand these iron-related systems, it is essential to elucidate the kinetics and mechanisms involved in the electro-oxidation of Fe(II). This work aims to develop a kinetic model that adequately describes the electro-oxidation process of Fe(II) in air-cathode fuel cells. The speciation of Fe(II) is incorporated into the model, and contributions of individual Fe(II) species to the overall Fe(II) oxidation rate are quantitatively evaluated. The results show that the kinetic model can accurately predict the electro-oxidation rate of Fe(II) in air-cathode fuel cells. FeCO3, Fe(OH)2, and Fe(CO3)2(2-) are the most important species determining the electro-oxidation kinetics of Fe(II). The Fe(II) oxidation rate is primarily controlled by the oxidation of FeCO3 species at low pH, whereas at high pH Fe(OH)2 and Fe(CO3)2(2-) are the dominant species. Solution pH, carbonate concentration, and solution salinity are able to influence the electro-oxidation kinetics of Fe(II) through changing both distribution and kinetic activity of Fe(II) species.

A novel Fe(II)-oxidizing Epsilonproteobacterium from a streambank aquifer

NASA Astrophysics Data System (ADS)

Chan, C. S.; McAllister, S.; Krepski, S.; Lin, C.; Lazareva, O.; Kan, J.

2013-12-01

Neutrophilic Fe(II)-oxidizing microorganisms (FeOM) play significant roles in elemental cycling in freshwater environments, forming biogenic Fe(III)-oxyhydroxides that sorb and sequester organics, phosphate, heavy metals, and other solutes. However, the extent of these microbes' diversity and influence are unknown, in part because we may only recognize a fraction of FeOM in environmental settings. Here we describe the first known Fe(II)-oxidizing Epsilonproteobacterium, Sulfuricurvum sp. strain EW, isolated from a biogeochemically dynamic streambank aquifer in southeastern Pennsylvania. This strain is related to the sulfur-oxidizer Sulfuricurvum kujiense (98.3% small subunit rRNA gene sequence identity). Strain EW is a facultative FeOM, capable of aerobically oxidizing reduced sulfur compounds, hydrogen, and a number of organic substrates. Pyrosequencing of the SSU rRNA gene (V1-V3 region) from porewater samples shows that Sulfuricurvum spp. is concentrated in an Fe- and organic-rich stratum within the streambank. Over the course of a year, the temporal patterns are similar to Gallionellaceae, a family with isolates that are almost exclusively FeOM. Correlation with geochemical parameters suggest that Sulfuricurvum presence is controlled by conditions favorable for Fe oxidation. These results significantly increase the known distribution, diversity, and physiology of FeOM, enabling further discoveries on the mechanisms and effects of microbial Fe oxidation. Although Epsilonproteobacteria have previously been associated with H2, S, and organic metabolisms, this discovery opens the door to understanding their roles in environmental Fe cycling.

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.

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. © 2010 Society for Applied Microbiology and Blackwell Publishing Ltd.

Modeling the Relationship Between Porosity and Permeability During Oxidation of Ablative Materials

NASA Technical Reports Server (NTRS)

Thornton, John M.; Panerai, Francesco; Ferguson, Joseph C.; Borner, Arnaud; Mansour, Nagi N.

2017-01-01

The ablative materials used in thermal protection systems (TPS) undergo oxidation during atmospheric entry which leads to an in-depth change in both permeability and porosity. These properties have a significant affect on heat transfer in a TPS during entry. X-ray micro-tomography has provided 3D images capturing the micro-structure of TPS materials. In this study, we use micro-tomography based simulations to create high-fidelity models relating permeability to porosity during oxidation of FiberForm, the carbon fiber preform of the Phenolic Impregnated Carbon Ablator (PICA) often used as a TPS material. The goal of this study is to inform full-scale models and reduce uncertainty in TPS modeling.

Specular spin-valve films with an FeCo nano-oxide layer by ion-assisted oxidation

NASA Astrophysics Data System (ADS)

Fukuzawa, Hideaki; Koi, Katsuhiko; Tomita, Hiroshi; Fuke, Hiromi Niu; Iwasaki, Hitoshi; Sahashi, Masashi

2002-05-01

We compared the specular spin-valve films with an Fe50Co50 nano-oxide layer (NOL) and a Co90Fe10 NOL in a pinned layer, prepared by natural oxidation (NO) and ion-assisted oxidation (IAO). For the IAO, an Ar-ion beam was used for the energy-assist effect during the oxidation, resulting in thermally stable NOL formation. With small oxygen exposures during the oxidation for the Fe50Co50 NOL by IAO, good ferromagnetic coupling through the NOL and high specularity at the NOL interface were concurrently obtained. Moreover, twisted coupling through the NOL was observed for the Fe50Co50 NOL by IAO for higher oxygen exposures. On the other hand, the NO did not cause large magnetoresistance (MR) enhancement for either the Co90Fe10 or Fe50Co50 NOLs, and the Co90Fe10 NOL by IAO caused weak magnetic coupling through the NOL, resulting in a small MR ratio. The Fe50Co50 NOL for small oxygen exposures is a good candidate for a final specular spin-valve film head for 100-Giga-bit per square inch recording.

Thermodynamic Characterization of Iron Oxide-Aqueous Fe(2+) Redox Couples.

PubMed

Gorski, Christopher A; Edwards, Rebecca; Sander, Michael; Hofstetter, Thomas B; Stewart, Sydney M

2016-08-16

Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe2+ and Fe3+ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe2+ associated with iron oxide surfaces (i.e., oxide-associated Fe2+) often reduces oxidized contaminants much faster than aqueous Fe2+ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides—hematite and goethite—and aqueous Fe2+ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (EH) values in solutions containing these oxides at different pH values and aqueous Fe2+ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (EH0) values of 768 ± 1 mV for the aqueous Fe2+–goethite redox couple and 769 ± 2 mV for the aqueous Fe2+–hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering EH values of aqueous Fe3+/Fe2+ redox couples.

Pulsed laser ablation of complex oxides: The role of congruent ablation and preferential scattering for the film stoichiometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wicklein, S.; Koehl, A.; Dittmann, R.

2012-09-24

By combining structural and chemical thin film analysis with detailed plume diagnostics and modeling of the laser plume dynamics, we are able to elucidate the different physical mechanisms determining the stoichiometry of the complex oxides model material SrTiO{sub 3} during pulsed laser deposition. Deviations between thin film and target stoichiometry are basically a result of two effects, namely, incongruent ablation and preferential scattering of lighter ablated species during their motion towards the substrate in the O{sub 2} background gas. On the one hand, a progressive preferential ablation of the Ti species with increasing laser fluence leads to a regime ofmore » Ti-rich thin film growth at larger fluences. On the other hand, in the low laser fluence regime, a more effective scattering of the lighter Ti plume species results in Sr rich films.« less

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.

In situ arsenic oxidation and sorption by a Fe-Mn binary oxide waste in soil.

PubMed

McCann, Clare M; Peacock, Caroline L; Hudson-Edwards, Karen A; Shrimpton, Thomas; Gray, Neil D; Johnson, Karen L

2018-01-15

The ability of a Fe-Mn binary oxide waste to adsorb arsenic (As) in a historically contaminated soil was investigated. Initial laboratory sorption experiments indicated that arsenite [As(III)] was oxidized to arsenate [As(V)] by the Mn oxide component, with concurrent As(V) sorption to the Fe oxide. The binary oxide waste had As(III) and As(V) adsorption capacities of 70mgg -1 and 32mgg -1 respectively. X-ray Absorption Near-Edge Structure and Extended X-ray Absorption Fine Structure at the As K-edge confirmed that all binary oxide waste surface complexes were As(V) sorbed by mononuclear bidentate corner-sharing, with 2 Fe at ∼3.27Ǻ. The ability of the waste to perform this coupled oxidation-sorption reaction in real soils was investigated with a 10% by weight addition of the waste to an industrially As contaminated soil. Electron probe microanalysis showed As accumulation onto the Fe oxide component of the binary oxide waste, which had no As innately. The bioaccessibility of As was also significantly reduced by 7.80% (p<0.01) with binary oxide waste addition. The results indicate that Fe-Mn binary oxide wastes could provide a potential in situ remediation strategy for As and Pb immobilization in contaminated soils. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

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

Mechanisms for chelator stimulation of microbial Fe(III) -oxide reduction

USGS Publications Warehouse

Lovley, D.R.; Woodward, J.C.

1996-01-01

The mechanisms by which nitrilotriacetic acid (NTA) stimulated Fe(III) reduction in sediments from a petroleum-contaminated aquifer were investigated in order to gain insight into how added Fe(III) chelators stimulate the activity of hydrocarbon-degrading, Fe(III)-reducing microorganisms in these sediments, and how naturally occurring Fe(III) chelators might promote Fe(III) reduction in aquatic sediments. NTA solubilized Fe(III) from the aquifer sediments. NTA stimulation of microbial Fe(III) reduction did not appear to be the result of making calcium, magnesium, potassium, or trace metals more available to the microorganisms. Stimulation of Fe(III) reduction could not be attributed to NTA serving as a source of carbon or fixed nitrogen for Fe(III)-reducing bacteria as NTA was not degraded in the sediments. Studies with the Fe(III)-reducing microorganism, Geobacter metallireducens, and pure Fe(III)-oxide forms, demonstrated that NTA stimulated the reduction of a variety of Fe(III) forms, including highly crystalline Fe(III)-oxides such as goethite and hematite. The results suggest that NTA solubilization of insoluble Fe(III)-oxide is an important mechanism for the stimulation of Fe(III) reduction by NTA in aquifer sediments.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aryanto, Didik, E-mail: Didik-phys@yahoo.co.id, E-mail: didi027@lipi.go.id; Sudiro, Toto; Wismogroho, Agus S.

2016-04-19

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 coatingsmore » exhibit high oxidation resistance compared to the uncoated steel. After 60 h exposure, the uncoated steel formed mainly Fe{sub 3}O{sub 4} and Fe{sub 2}O{sub 3} layers with the total thickness of around 75.93 µm. Fe-Al coating without annealing formed a thin oxide layer, probably (Fe,Al){sub 2}O{sub 3}. 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.« less

Analysis of long-term bacterial vs. chemical Fe(III) oxide reduction kinetics

NASA Astrophysics Data System (ADS)

Roden, Eric E.

2004-08-01

Data from studies of dissimilatory bacterial (10 8 cells mL -1 of Shewanella putrefaciens strain CN32, pH 6.8) and ascorbate (10 mM, pH 3.0) reduction of two synthetic Fe(III) oxide coated sands and three natural Fe(III) oxide-bearing subsurface materials (all at ca. 10 mmol Fe(III) L -1) were analyzed in relation to a generalized rate law for mineral dissolution (J t/m 0 = k'(m/m 0) γ, where J t is the rate of dissolution and/or reduction at time t, m 0 is the initial mass of oxide, and m/m 0 is the unreduced or undissolved mineral fraction) in order to evaluate changes in the apparent reactivity of Fe(III) oxides during long-term biological vs. chemical reduction. The natural Fe(III) oxide assemblages demonstrated larger changes in reactivity (higher γ values in the generalized rate law) compared to the synthetic oxides during long-term abiotic reductive dissolution. No such relationship was evident in the bacterial reduction experiments, in which temporal changes in the apparent reactivity of the natural and synthetic oxides were far greater (5-10 fold higher γ values) than in the abiotic reduction experiments. Kinetic and thermodynamic considerations indicated that neither the abundance of electron donor (lactate) nor the accumulation of aqueous end-products of oxide reduction (Fe(II), acetate, dissolved inorganic carbon) are likely to have posed significant limitations on the long-term kinetics of oxide reduction. Rather, accumulation of biogenic Fe(II) on residual oxide surfaces appeared to play a dominant role in governing the long-term kinetics of bacterial crystalline Fe(III) oxide reduction. The experimental findings together with numerical simulations support a conceptual model of bacterial Fe(III) oxide reduction kinetics that differs fundamentally from established models of abiotic Fe(III) oxide reductive dissolution, and indicate that information on Fe(III) oxide reactivity gained through abiotic reductive dissolution techniques cannot be used to

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.

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

Effects of tillage on the Fe oxides activation in soil

NASA Astrophysics Data System (ADS)

Chi, Guangyu; Chen, Xin; Shi, Yi; Wang, Jun; Zheng, Taihui

2009-07-01

Since mid-1950s, the wetland ecosystems in Sanjiang Plain of Northeast China have been experiencing greater changes in land use, which had negative effects on the soil environments. This study assessed the effects of soil tillage on the activation of soil Fe in the region. The test ecosystems included natural wetland, paddy field and upland field converted from wetland. Soil samples at the depths of 0-10 cm, 10-20 cm, 20-30 cm, 30-40 cm, 40-60 cm, 60-90 cm and 90-120 cm were collected from each of the ecosystems for the analysis of vertical distribution of soil pH, organic carbon, chelate Fe oxides and Fe(II). The results showed that the conversion of wetland into paddy field and upland field induced a decrease of organic carbon content in 0-10 cm soil layer by 61.8% (P <0.05) and 70.0% (P < 0.05), respectively. The correlations among iron forms and soil organic carbon showed that chelate Fe oxides and Fe(II) was correlated positively with soil organic carbon and chelate ratio had a more positive relationship with organic carbon than chelate Fe oxides and Fe(II). The results of chelate Fe oxides, Fe(II) and chelate ratio of Fe suggested that reclamation could prevent the Fe activation and organic matter is credited for having an important influence on the process of Fe activation.

Oxidative mutagenesis of doxorubicin-Fe(III) complex.

PubMed

Kostoryz, E L; Yourtee, D M

2001-02-20

Doxorubicin has a high affinity for inorganic iron, Fe(III), and has potential to form doxorubicin-Fe(III) complexes in biological systems. Indirect involvement of iron has been substantiated in the oxidative mutagenicity of doxorubicin. In this study, however, direct involvement of Fe(III) was evaluated in mutagenicity studies with the doxorubicin-Fe(III) complex. The Salmonella mutagenicity assay with strain TA102 was used with a pre-incubation step. The highest mutagenicity of doxorubicin-Fe(III) complex was observed at the dose of 2.5nmol/plate of the complex. The S9-mix decreased this highest mutagenicity but increased the number of revertants at a higher dose of 10nmol/plate of the complex. On the other hand, the mutagenicity of the doxorubicin-Fe(III) complex at the doses of 0.25, 0.5, 1 and 2nmol/plate was enhanced about twice by the addition of glutathione plus H(2)O(2). This enhanced mutagenicity as well as of the complex itself, the complex plus glutathione, and the complex plus H(2)O(2) were reduced by the addition of ADR-529, an Fe(III) chelator, and potassium iodide, a hydroxyl radical scavenger. These results indicate that doxorubicin-Fe(III) complex exert the mutagenicity through oxidative DNA damage and that Fe(III) is a required element in the mutagenesis of doxorubicin.

Fabrication of oxidation-resistant Ge colloidal nanoparticles by pulsed laser ablation in aqueous HCl

NASA Astrophysics Data System (ADS)

Hamanaka, Yasushi; Iwata, Masahiro; Katsuno, Junichi

2017-06-01

Spherical Ge nanoparticles with diameters of 20-80 nm were fabricated by laser ablation of a Ge single crystal in water and in aqueous HCl using sub-picosecond laser pulses (1040 nm, 700 fs, 100 kHz, and a pulse energy of 10 µJ). We found that the as-synthesized nanoparticles suffered rapid oxidization followed by dissolution when laser ablation was conducted in pure water. In contrast, oxidation of Ge nanoparticles produced in dilute HCl and stored intact was minimal, and colloidal dispersions of the Ge nanoparticles remained stable up to 7 days. It was elucidated that dangling bonds on the surfaces of the Ge nanoparticles were terminated by Cl, which inhibited oxidation, and that such hydrophilic surfaces might improve the dispersibility of nanoparticles in aqueous solvent.

Fe2O3/Reduced Graphene Oxide/Fe3O4 Composite in Situ Grown on Fe Foil for High-Performance Supercapacitors.

PubMed

Zhao, Chongjun; Shao, Xiaoxiao; Zhang, Yuxiao; Qian, Xiuzhen

2016-11-09

A Fe 2 O 3 /reduced graphene oxide (RGO)/Fe 3 O 4 nanocomposite in situ grown on Fe foil was synthesized via a simple one-step hydrothermal growth process, where the iron foil served as support, reductant of graphene oxide, Fe source of Fe 3 O 4 , and also the current collector of the electrode. When it directly acted as the electrode of a supercapacitor, as-synthesized Fe 2 O 3 /RGO/Fe 3 O 4 @Fe exhibited excellent electrochemical performance with a high capability of 337.5 mF/cm 2 at 20 mA/cm 2 and a superior cyclability with 2.3% capacity loss from the 600th to the 2000th cycle.

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.

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.

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.

Ferromagnetic phase in partially oxidized FeMn films

NASA Astrophysics Data System (ADS)

Svalov, A. V.; Savin, P. A.; Lepalovskij, V. N.; Vas'kovskiy, V. O.; Larrañaga, A.; Kurlyandskaya, G. V.

2018-04-01

The structure, magnetic and magnetoresistive properties of ferromagnetic phase in partially oxidized FeMn films was studied. The oxidation was performed by annealing of the samples under atmospheric pressure in a gas mixture (nitrogen with 0.5% oxygen) at the temperature of 300 °C. The resulting ferromagnetic phase was isotropic in the film plane. The value of the anisotropic magnetoresistance was similar to the value of the anisotropic magnetoresistance usually observed in films of pure iron. The oxidation of antiferromagnetic FeMn films resulted in the appearance of an exchange bias.

Water vapor effect on high-temperature oxidation behavior of Fe3Al intermetallics

PubMed Central

Chevalier, Sebastian; Juzon, Pitor; Przybylski, Kazimierz; Larpin, Jean-Pierre

2009-01-01

Fe3Al intermetallics (Fe3Al, Fe3Al-Zr, Fe3Al-Zr,Mo and Fe3Al-Zr, Mo, Nb) were oxidized at 950 °C in dry and humid (11 vol% water) synthetic air. Thermogravimetric measurements showed that the oxidation rates of the tested intermetallics were lower in humid air than in dry air (especially for Fe3Al-Zr, Mo and Fe3Al-Zr, Mo, Nb). The addition of small amounts of Zr, Mo or Nb improved the kinetics compared with that of the undoped Fe3Al. Fe3Al showed massive spallation, whereas Fe3Al-Zr, Fe3Al-Zr, Mo and Fe3Al-Zr, Mo, Nb produced a flat, adherent oxide layer. The rapid transformation of transient alumina into alpha alumina may explain the decrease in the oxidation rate in humid air. PMID:27877306

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

NASA Astrophysics Data System (ADS)

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.

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.

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

NASA Astrophysics Data System (ADS)

White, Art F.; Peterson, Maria L.

1996-10-01

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[FeFe23+]O+2/nm→4[Fe23+]O+Fe+2/nm and 3[FeTi]O+→Fe23+TiO+Fe+2/nm, 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 Fe 2+ (-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, Fe 2+ is oxidized homogeneously in solution to Fe 3+. 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 solution. In contrast, magnetite weathered under oxidizing vadose conditions show

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vaccaro, L.; Messina, F.; Camarda, P.

2016-07-14

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 SiO{sub 2} and amorphous fully oxidized SiO{sub 2}, 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 nanocrystalsmore » emit a μs-decaying red band; defects of SiO{sub 2} give rise to a ns-decaying UV band and two overlapping blue bands with lifetime in the ns and ms timescale.« less

Experimental and thermodynamic study of Co-Fe and Mn-Fe based mixed metal oxides for thermochemical energy storage application

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-06-01

Metal oxides are potential materials for thermochemical heat storage, and among them, cobalt oxide and manganese oxide are attracting attention. Furthermore, studies on mixed oxides are ongoing, as the synthesis of mixed oxides could be a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering, selected for thermochemical heat storage application. The addition of iron oxide is under investigation and the obtained results are presented. This work proposes a comparison of thermodynamic modelling with experimental data in order to identify the impact of iron oxide addition to cobalt oxide and manganese oxide. Fe addition decreased the redox activity and energy storage capacity of Co3O4, whereas the cycling stability of Mn2O3 was significantly improved with added Fe amounts above 20 mol% while the energy storage capacity was unchanged. The thermodynamic modelling method to predict the behavior of the Mn-Fe-O and Co-Fe-O systems was validated, and the possibility to identify other mixed oxides becomes conceivable, by enabling the selection of transition metals additives for metal oxides destined for thermochemical energy storage applications.

Ferrous Iron Oxidation under Varying pO2 Levels: The Effect of Fe(III)/Al(III) Oxide Minerals and Organic Matter.

PubMed

Chen, Chunmei; Thompson, Aaron

2018-01-16

Abiotic Fe(II) oxidation by O 2 commonly occurs in the presence of mineral sorbents and organic matter (OM) in soils and sediments; however, this tertiary system has rarely been studied. Therefore, we examined the impacts of mineral surfaces (goethite and γ-Al 2 O 3 ) and organic matter [Suwannee River fulvic acid (SRFA)] on Fe(II) oxidation rates and the resulting Fe(III) (oxyhydr)oxides under 21 and 1% pO 2 at pH 6. We tracked Fe dynamics by adding 57 Fe(II) to 56 Fe-labeled goethite and γ-Al 2 O 3 and characterized the resulting solids using 57 Fe Mössbauer spectroscopy. We found Fe(II) oxidation was slower at low pO 2 and resulted in higher-crystallinity Fe(III) phases. Relative to oxidation of Fe(II) (aq) alone, both goethite and γ-Al 2 O 3 surfaces increased Fe(II) oxidation rates regardless of pO 2 levels, with goethite being the stronger catalyst. Goethite surfaces promoted the formation of crystalline goethite, while γ-Al 2 O 3 favored nano/small particle or disordered goethite and some lepidocrocite; oxidation of Fe(II) aq alone favored lepidocrocite. SRFA reduced oxidation rates in all treatments except the mineral-free systems at 21% pO 2 , and SRFA decreased Fe(III) phase crystallinity, facilitating low-crystalline ferrihydrite in the absence of mineral sorbents, low-crystalline lepidocrocite in the presence of γ-Al 2 O 3 , but either crystalline goethite or ferrihydrite when goethite was present. This work highlights that the oxidation rate, the types of mineral surfaces, and OM control Fe(III) precipitate composition.

Thermodynamic Versus Surface Area Control of Microbial Fe(III) Oxide Reduction Kinetics

NASA Astrophysics Data System (ADS)

Roden, E. E.

2003-12-01

Recent experimental studies of synthetic and natural Fe(III) oxide reduction permit development of conceptual and quantitative models of enzymatic Fe(III) oxide reduction at circumneutral pH that can be compared to and contrasted with established models of abiotic mineral dissolution. The findings collectively support a model for controls on enzymatic reduction that differs fundamentally from those applied to abiotic reductive dissolution as a result of two basic phenomena: (1) the relatively minor influence of oxide mineralogical and thermodynamic properties on surface area-normalized rates of enzymatic reduction compared to abiotic reductive dissolution; and (2) the major limitation which sorption and/or surface precipitation of biogenic Fe(II) on residual oxide and Fe(III)-reducing bacterial cell surfaces poses to enzymatic electron transfer in the presence of excess electron donor. Parallel studies with two major Fe(III)-reducing bacteria genera (Shewanella and Geobacter) lead to common conclusions regarding the importance of these phenomena in regulating the rate and long-term extent of Fe(III) oxide reduction. Although the extent to which these phenomena can be traced to underlying kinetic vs. thermodynamic effects cannot be resolved with current information, models in which rates of enzymatic reduction are limited kinetically by the abundance of "available" oxide surface sites (as controlled by oxide surface area and the abundance of surface-bound Fe(II)) provide an adequate macroscopic description of controls on the initial rate and long-term extent of oxide reduction. In some instances, thermodynamic limitation posed by the accumulation of aqueous reaction end-products (i.e. Fe(II) and alkalinity) must also be invoked to explain observed long-term patterns of reduction. In addition, the abundance of Fe(III)-reducing microorganisms plays an important role in governing rates of reduction and needs to be considered in models of Fe(III) reduction in nonsteady

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

Evidence for the Existence of Autotrophic Nitrate-Reducing Fe(II)-Oxidizing Bacteria in Marine Coastal Sediment

PubMed Central

Laufer, Katja; Røy, Hans; Jørgensen, Bo Barker

2016-01-01

ABSTRACT Nitrate-reducing Fe(II)-oxidizing microorganisms were described for the first time ca. 20 years ago. Most pure cultures of nitrate-reducing Fe(II) oxidizers can oxidize Fe(II) only under mixotrophic conditions, i.e., when an organic cosubstrate is provided. A small number of nitrate-reducing Fe(II)-oxidizing cultures have been proposed to grow autotrophically, but unambiguous evidence for autotrophy has not always been provided. Thus, it is still unclear whether or to what extent Fe(II) oxidation coupled to nitrate reduction is an enzymatically catalyzed and energy-yielding autotrophic process or whether Fe(II) is abiotically oxidized by nitrite from heterotrophic nitrate reduction. The aim of the present study was to find evidence for the existence of autotrophic nitrate-reducing Fe(II) oxidizers in coastal marine sediments. Microcosm incubations showed that with increasing incubation times, the stoichiometric ratio of reduced nitrate/oxidized Fe(II) [NO3−reduced/Fe(II)oxidized] decreased, indicating a decreasing contribution of heterotrophic denitrification and/or an increasing contribution of autotrophic nitrate-reducing Fe(II) oxidation over time. After incubations of sediment slurries for >10 weeks, nitrate-reducing activity ceased, although nitrate was still present. This suggests that heterotrophic nitrate reduction had ceased due to the depletion of readily available organic carbon. However, after the addition of Fe(II) to these batch incubation mixtures, the nitrate-reducing activity resumed, and Fe(II) was oxidized, indicating the activity of autotrophic nitrate-reducing Fe(II) oxidizers. The concurrent reduction of 14C-labeled bicarbonate concentrations unambiguously proved that autotrophic C fixation occurred during Fe(II) oxidation and nitrate reduction. Our results clearly demonstrated that autotrophic nitrate-reducing Fe(II)-oxidizing bacteria were present in the investigated coastal marine sediments. IMPORTANCE Twenty years after the

Tuning the exchange bias in NiFe/Fe-oxide bilayers by way of different Fe-oxide based mixtures made with an ion-beam deposition technique.

PubMed

Lin, K W; Kol, P H; Guo, Z Y; Ouyang, H; van Lierop, J

2007-01-01

We have investigated the structural and magnetic properties of ion-beam deposited polycrystalline NiFe (25 nm)/Fe-oxide (35 nm) bilayers. A film prepared with an assist beam O2 to Ar gas ratio of 0% during deposition had a bottom layer that consisted of pure b.c.c. Fe (a = 2.87 A) whereas films prepared with 19%O2/Ar and 35%O2/Ar had either Fe3O4 (a = 8.47 angstroms) or alpha-Fe2O3 (a = 5.04 angstroms, c = 13.86 angstroms) bottom layers, respectively. Cross-sectional transmission electron microscopy revealed a smooth interface between the top nano-columnar NiFe and bottom nano-columnar Fe-oxide layer for all films. At room temperature, the observed coercivity (Hc approximately 25 Oe) for a film prepared with 19% O2/Ar indicates the existence of a magnetically hard ferrimagnetic Fe3O4 phase that is enhancing the plain NiFe (Hc approximately 2 Oe) by way of exchange coupling. A significant amount of exchange bias is observed below 50 K, and at 10 K the size of exchange bias hysteresis loops shift increases with increasing oxygen in the films. Furthermore, the strongest exchange coupling (H(ex) approximately 135 Oe at 10 K) is with alpha-Fe2O3 (35% O2/Ar) as the bottom film layer. This indicates that the pure antiferromagnetic phases work better than ferrimagnetic phases when in contact with ferromagnetic NiFe. H(ex) (T) is well described by an effective AF domain wall energy that creates an exchange field with a (1 - T/T(crit)) temperature dependence. Hc (T) exhibits three distinct regimes of constant temperature that may indicate the existence of different AF spin populations that couple to the FM layer at different temperatures.

Zinc oxide nanocolloids prepared by picosecond pulsed laser ablation in water at different temperatures

NASA Astrophysics Data System (ADS)

D'Urso, Luisa; Spadaro, Salvatore; Bonsignore, Martina; Santangelo, Saveria; Compagnini, Giuseppe; Neri, Fortunato; Fazio, Enza

2018-01-01

Zinc oxide with wide direct band gap and high exciton binding energy is one of the most promising materials for ultraviolet (UV) light-emitting devices. It further exhibits good performance in the degradation of non-biodegradable pollutants under UV irradiation. In this work, zinc oxide (ZnO) and zinc oxide/gold (ZnO/Au) nanocolloids are prepared by picosecond pulsed laser ablation (ps-PLA), using a Zn and Au metallic targets in water media at room temperature (RT) and 80°C. ZnO and Au nanoparticles (NPs) with size in the 10-50 nm range are obtained at RT, while ZnO nanorods (NRs) are formed when water is maintained at 80°C during the ps-PLA process. Au NPs, added to ZnO colloids after the ablation process, decorate ZnO NRs. The crystalline phase of all ZnO nanocolloids is wurtzite. Methylene blue dye is used to investigate the photo-catalytic activity of all the synthesised nanocolloids, under UV light irradiation.

THE EFFECT OF OXIDANTS ON THE PROPERTIES OF FE (III) PARTICLES AND SUSPENSIONS FORMED FROM THE OXIDATION OF FE (II)

EPA Science Inventory

Oxidation of Fe(II) to Fe(III) is an important reaction in drinking water treatment and distribution systems, and the ferric particles that form are a major source of consumer complaints of colored water. Ferrous iron is found naturally in many ground waters and can be released ...

The effects of Fe-oxidizing microorganisms on post-biostimulation permeability reduction and oxidative processes at the Rifle IFRC site

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 Riflemore » 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

Electrochemical characterization of Fe-air rechargeable oxide battery in planar solid oxide cell stacks

NASA Astrophysics Data System (ADS)

Fang, Qingping; Berger, Cornelius M.; Menzler, Norbert H.; Bram, Martin; Blum, Ludger

2016-12-01

Iron-air rechargeable oxide batteries (ROB) comprising solid oxide cells (SOC) as energy converters and Fe/metal-oxide redox couples were characterized using planar SOC stacks. The charge and discharge of the battery correspond to the operations in the electrolysis and fuel cell modes, respectively, but with a stagnant atmosphere consisting of hydrogen and steam. A novel method was employed to establish the stagnant atmosphere for battery testing during normal SOC operation without complicated modification to the test bench and stack/battery concept. Manipulation of the gas compositions during battery operation was not necessary, but the influence of the leakage current from the testing system had to be considered. Batteries incorporating Fe2O3/8YSZ, Fe2O3/CaO and Fe2O3/ZrO2 storage materials were characterized at 800 °C. A maximum charge capacity of 30.4 Ah per layer (with an 80 cm2 active cell area) with ∼0.5 mol Fe was reached with a current of 12 A. The charge capacity lost 11% after ∼130 ROB cycles due to the increased agglomeration of active materials and formation of a dense oxide layer on the surface. The round trip efficiencies of the tested batteries were ≤84% due to the large internal resistance. With state-of-the-art cells, the round trip efficiency can be further improved.

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.

A double Fe-Ti oxide and Fe-sulphide liquid immiscibility in the Itsindro Gabbro Complex, Madagascar

NASA Astrophysics Data System (ADS)

Augé, Thierry; Bailly, Laurent; Roig, Jean-Yves

2017-11-01

The petrology and mineralogy of the Itsindro complex in south-central Madagascar has been investigated through samples obtained from the 320.7 m-deep Lanjanina borehole. The section consists of a 254 m-thick pyroxenite unit with interbedded gabbro layers that overlies a gabbro unit and is itself overlain by a 19 m-thick granite unit. Most of the structures are sub-horizontal. A weak magmatic layering is locally observed but at the scale of the core, the intrusion does not appear to be a layered complex. Pyroxenite and gabbro show a systematic disseminated mineralization consisting of Fe-Ti-P oxides and Fe-(Cu-Ni) sulphides that takes the form of ilmenite-titanomagnetite ± apatite and pyrrhotite ± chalcopyrite ± pentlandite. In the upper zone, from 90 to 72 m, sub-massive centimetre-to decimetre-sized layers of oxides and sulphides comprise a total of 16 m of sub-massive sulphide (the main mineralized zone). In this mineralized zone the oxide/sulphide ratio is close to 1/1. The sulphide is strongly dominated by pyrrhotite, which may locally contain inclusions of molybdenite crystals with the Re sulphide rheniite (ReS2). Oxides are generally euhedral, included in or attached to the Fe-sulphide, and also locally form sub-massive centimetre-sized bands. Apatite as a cumulus phase is ubiquitous. Locally it may account for 30% of the ore-rich samples and some samples consist of apatite-Fe-Ti oxides-Fe-Cu-Ni sulphides with virtually no silicate. Apatite is the main REE carrier but the total REE content remains low (<90 ppm). Mineral compositions and whole rock geochemistry indicate that the rocks are highly differentiated, and in spite of a relatively limited thickness, the differentiation process is observed. Two zones can be distinguished: from the bottom to 162.8 m we see a decrease in the Mg number of olivine and pyroxene, and a drop in TiO2 and Al2O3 for the latter. A reverse trend is then observed within the pyroxenite unit from the 162.8 m level upwards. The

Fluorescent carbon and graphene oxide nanoparticles synthesized by the laser ablation in liquid

NASA Astrophysics Data System (ADS)

Małolepszy, A.; Błonski, S.; Chrzanowska-Giżyńska, J.; Wojasiński, M.; Płocinski, T.; Stobinski, L.; Szymanski, Z.

2018-04-01

The results of synthesis of the fluorescent carbon dots (CDots) from graphite target and reduced graphene oxide (rGO) nanoparticles performed by the nanosecond laser ablation in polyethylene glycol 200 (PEG200) are shown. Two-step laser irradiation (first graphite target, next achieved suspension) revealed a very effective production of CDots. However, the ablation in PEG appeared to be effective with 1064 nm laser pulse in contrast to the ablation with 355 nm laser pulse. In the case of rGO nanoparticles similar laser irradiation procedure was less efficient. In both cases, received nanoparticles exhibited strong, broadband photoluminescence with a maximum dependent on the excitation wavelength. The size distribution for obtained CDots was evaluated using the DLS technique and HRTEM images. The results from both methods show quite good agreement in nanoparticle size estimation although the DLS method slightly overestimates nanoparticle's diameter.

High-temperature oxidation of advanced FeCrNi alloy in steam environments

NASA Astrophysics Data System (ADS)

Elbakhshwan, Mohamed S.; Gill, Simerjeet K.; Rumaiz, Abdul K.; Bai, Jianming; Ghose, Sanjit; Rebak, Raul B.; Ecker, Lynne E.

2017-12-01

Alloys of iron-chromium-nickel are being explored as alternative cladding materials to improve safety margins under severe accident conditions. Our research focuses on non-destructively investigating the oxidation behavior of the FeCrNi alloy "Alloy 33" using synchrotron-based methods. The evolution and structure of oxide layer formed in steam environments were characterized using X-ray diffraction, hard X-ray photoelectron spectroscopy, X-ray fluorescence methods and scanning electron microscopy. Our results demonstrate that a compact and continuous oxide scale was formed consisting of two layers, chromium oxide and spinel phase (FeCr2O4) oxides, wherein the concentration of the FeCr2O4 phase decreased from the surface to the bulk-oxide interface.

CO oxidation and O2 removal on meteoric material in Venus' atmosphere

NASA Astrophysics Data System (ADS)

Frankland, Victoria L.; James, Alexander D.; Carrillo-Sánchez, Juan Diego; Nesvorný, David; Pokorný, Petr; Plane, John M. C.

2017-11-01

The heterogeneous oxidation of CO by O2 on olivine, Fe sulfate and Fe oxide particles was studied using a flow tube apparatus between 300 and 680 K. These particles were chosen as possible analogues of unablated cosmic dust and meteoric smoke in Venus' atmosphere. On olivine and Fe oxides, the rate of CO oxidation to CO2 only becomes significant above 450 K. For iron sulfates, CO2 production was not observed until these dust analogues had decomposed into iron oxides at ∼ 540 K. The CO oxidation rate increases significantly with a higher Fe content in the dust, implying that oxidation occurs through Fe active sites (no reaction was observed on Mg2SiO4). The oxidation kinetics can be explained by CO reacting with chemi-sorbed O2 through an Eley-Rideal mechanism, which is supported by electronic structure calculations. Uptake coefficients were measured from 450 to 680 K, yielding: log10(γ (CO on MgFeSiO4)) = (2.9 ± 0.1) × 10-3 T(K) - (8.2 ± 0.1); log10(γ (CO on Fe2SiO4)) = (2.3 ± 0.3) × 10-3 T(K) - (7.7 ± 0.2); log10(γ (CO on FeOOH/Fe2O3)) = (5.6 ± 0.8) × 10-3T(K) - (9.3 ± 0.4). A 1-D atmospheric model of Venus was then constructed to explore the role of heterogeneous oxidation. The cosmic dust input to Venus, mostly originating from Jupiter Family Comets, is around 32 tonnes per Earth day. A chemical ablation model was used to show that ∼34% of this incoming mass ablates, forming meteoric smoke particles which, together with unablated dust particles, provide a significant surface for the heterogeneous oxidation of CO to CO2 in Venus' troposphere. This process should cause almost complete removal of O2 below 40 km, but have a relatively small impact on the CO mixing ratio (since CO is in large excess over O2). Theoretical quantum calculations indicate that the gas-phase oxidation of CO by SO2 in the lower troposphere is not competitive with the heterogeneous oxidation of CO. Finally, the substantial number density of meteoric smoke particles predicted

Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

2018-04-01

Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy

Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

DOE PAGES

Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; ...

2017-05-19

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here in this work, we have measured themore » redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). Lastly, we present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.« less

Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here in this work, we have measured themore » redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). Lastly, we present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.« less

Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

NASA Astrophysics Data System (ADS)

Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; Till, Claire P.; Lee, Jong-Mi; Toner, Brandy M.; Marcus, Matthew A.

2017-08-01

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here we have measured the redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). We present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

E Bazilevskaya; D Archibald; M Aryanpour

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. Coprecipitatesmore » 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

An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.

PubMed

Gong, Ming; Li, Yanguang; Wang, Hailiang; Liang, Yongye; Wu, Justin Z; Zhou, Jigang; Wang, Jian; Regier, Tom; Wei, Fei; Dai, Hongjie

2013-06-12

Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.

Using metatranscriptomics to understand the roles of Fe(II)-oxidizing microbes in marine hydrothermal vents

NASA Astrophysics Data System (ADS)

Glazer, B. T.; Mcallister, S.; Polson, S. W.; Chan, C. S. Y.

2015-12-01

Fe(II)-oxidizing microbes (FeOM) are thought to be key players in marine Fe cycling, particularly at hydrothermal vents. However, we do not have tools to track their activity, largely because we do not know the genes involved in neutrophilic chemolithotrophic Fe oxidation. Researchers have used gene homology between FeOM isolates to suggest several genes that may be involved in Fe(II) oxidation, including the Fe oxidase cyc2 found in the Zetaproteobacteria type strain Mariprofundus ferrooxydans, as well as all other known neutrophilic microaerophilic FeOM. Although many Zetaproteobacteria are found within natural Fe mats, close relatives of Fe(II)-oxidizing isolates are rarely present. Therefore, one goal of this study was to determine the activity of putative Fe(II) oxidation genes in dominant OTUs found in natural environments. We collected Fe mats from hydrothermal vents at Loihi Seamount, Hawaii, preserving RNA in situ. By analyzing metatranscriptomes of different Fe mat niches, we were able to determine the OTUs involved and the gene expression patterns associated with Fe(II) oxidation in the marine environment. Analysis of metatranscriptomic data confirms that the Zetaproteobacteria express the various genes necessary to support the Fe mat community through chemoautotrophic growth. Globally ubiquitous and even some rare species of the Zetaproteobacteria were active, with different relative abundances depending on Fe mat niches defined by fluid flow and geochemistry. Initial results show that genes thought to be involved in the electron transport pathway from Fe(II) to O2, including cyc2, are some of the most highly expressed genes in marine Fe microbial mats. Species-specific variants of these genes suggest that many of the Zetaproteobacteria species, spanning the breadth of the diversity of the class, are expressing genes necessary for Fe(II) oxidation within natural Fe mat niches. Understanding the differential expression of these genes in different niches

Elemental Mercury Oxidation over Fe-Ti-Mn Spinel: Performance, Mechanism, and Reaction Kinetics.

PubMed

Xiong, Shangchao; Xiao, Xin; Huang, Nan; Dang, Hao; Liao, Yong; Zou, Sijie; Yang, Shijian

2017-01-03

The design of a high-performance catalyst for Hg 0 oxidation and predicting the extent of Hg 0 oxidation are both extremely limited due to the uncertainties of the reaction mechanism and the reaction kinetics. In this work, Fe-Ti-Mn spinel was developed as a high-performance catalyst for Hg 0 oxidation, and the reaction mechanism and the reaction kinetics of Hg 0 oxidation over Fe-Ti-Mn spinel were studied. The reaction orders of Hg 0 oxidation over Fe-Ti-Mn spinel with respect to gaseous Hg 0 concentration and gaseous HCl concentration were approximately 1 and 0, respectively. Therefore, Hg 0 oxidation over Fe-Ti-Mn spinel mainly followed the Eley-Rideal mechanism (i.e., the reaction of gaseous Hg 0 with adsorbed HCl), and the rate of Hg 0 oxidation mainly depended on Cl • concentration on the surface. As H 2 O, SO 2 , and NO not only inhibited Cl • formation on the surface but also interfered with the interface reaction between gaseous Hg 0 and Cl • on the surface, Hg 0 oxidation over Fe-Ti-Mn spinel was obviously inhibited in the presence of H 2 O, SO 2 , and NO. Furthermore, the extent of Hg 0 oxidation over Fe-Ti-Mn spinel can be predicted according to the kinetic parameter k E-R , and the predicted result was consistent with the experimental result.

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

Removal of thallium from aqueous solutions using Fe-Mn binary oxides.

PubMed

Li, Huosheng; Chen, Yongheng; Long, Jianyou; Li, Xiuwan; Jiang, Daqian; Zhang, Ping; Qi, Jianying; Huang, Xuexia; Liu, Juan; Xu, Ruibing; Gong, Jian

2017-09-15

In this study, Fe-Mn binary oxides, which harbor the strong oxidative power of manganese dioxide and the high adsorption capacity of iron oxides, were synthesized for Tl(I) removal using a concurrent chemical oxidation and precipitation method. The adsorption of Tl onto the Fe-Mn adsorbent was fast, effective, and selective, with equilibrium sorption reaching over 95% under a broad operating pH (3-12), and high ionic strength (0.1-0.5mol/L). The adsorption can be well fitted with both Langmuir and Freundlich isotherms, and the kinetics can be well described by the pseudo-second-order model. Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) spectra suggest that surface complexation, oxidation and precipitation were the main mechanisms for the removal of Tl. This study shows that the Fe-Mn binary oxides could be a promising adsorbent for Tl removal. Copyright © 2017 Elsevier B.V. All rights reserved.

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

High-temperature oxidation of advanced FeCrNi alloy in steam environments

DOE PAGES

Elbakhshwan, Mohamed S.; Gill, Simerjeet K.; Rumaiz, Abdul K.; ...

2017-07-04

Alloys of iron-chromium-nickel are being explored as alternative cladding materials to improve safety margins under severe accident conditions. Here, our research focuses on non-destructively investigating the oxidation behavior of the FeCrNi alloy “Alloy 33” using synchrotron-based methods. The evolution and structure of oxide layer formed in steam environments were characterized using X-ray diffraction, hard X-ray photoelectron spectroscopy, X-ray fluorescence methods and scanning electron microscopy. In conclusion, our results demonstrate that a compact and continuous oxide scale was formed consisting of two layers, chromium oxide and spinel phase (FeCr 2O 4) oxides, wherein the concentration of the FeCr 2O 4 phasemore » decreased from the surface to the bulk-oxide interface.« less

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

PubMed

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

2013-08-01

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 × 10(4) autotrophic and 1 × 10(7) 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 (13)CO2 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

Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

NASA Astrophysics Data System (ADS)

Ngwack, Bernd; Sigg, Laura

1997-03-01

The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

X-ray reflectivity of ruthenium nano-oxide layer in a CoFe-Ru-CoFe trilayer system

NASA Astrophysics Data System (ADS)

Asghari Zadeh, Saeid; Sutton, Mark; Altonian, Zaven; Mao, Ming; Lee, Chih-Ling

2006-03-01

A grazing incidence X-ray reflectivity technique is used to determine electron density profile(EDP) as a function of depth in CoFe-Ru-CoFe and CoFe-Ru nano oxide layer(NOL)-CoFe trilayers. Four trilayers with ruthenium thicknesses of 8,8.5 and 9 å.08cm and one with Ru8.5.05cmå.05cmNOL, prepared by a dc planetary sputtering system, were investigated. For all samples, EDP shows a central peak which is related to the Ru layer. Natural oxidation in all samples introduces a graded EDP of the top CoFe layer that decreases gradually to zero. The large surface resistivity of Ru8.5 å.05cm NOL compared to Ru 8.5å.08cm can be related to the remarkable difference between their EDP.

Fe(III) oxides accelerate microbial nitrate reduction and electricity generation by Klebsiella pneumoniae L17.

PubMed

Liu, Tongxu; Li, Xiaomin; Zhang, Wei; Hu, Min; Li, Fangbai

2014-06-01

Klebsiella pneumoniae L17 is a fermentative bacterium that can reduce iron oxide and generate electricity under anoxic conditions, as previously reported. This study reveals that K. pneumoniae L17 is also capable of dissimilatory nitrate reduction, producing NO2(-), NH4(+), NO and N2O under anoxic conditions. The presence of Fe(III) oxides (i.e., α-FeOOH, γ-FeOOH, α-Fe2O3 and γ-Fe2O3) significantly accelerates the reduction of nitrate and generation of electricity by K. pneumoniae L17, which is similar to a previous report regarding another fermentative bacterium, Bacillus. No significant nitrate reduction was observed upon treatment with Fe(2+) or α-FeOOH+Fe(2+), but a slight facilitation of nitrate reduction and electricity generation was observed upon treatment with L17+Fe(2+). This result suggests that aqueous Fe(II) or mineral-adsorbed Fe(II) cannot reduce nitrate abiotically but that L17 can catalyze the reduction of nitrate and generation of electricity in the presence of Fe(II) (which might exist as cell surface-bound Fe(II)). To rule out the potential effect of Fe(II) produced by L17 during microbial iron reduction, treatments with the addition of TiO2 or Al2O3 instead of Fe(III) oxides also exhibited accelerated microbial nitrate reduction and electricity generation, indicating that cell-mineral sorption did account for the acceleration effect. However, the acceleration caused by Fe(III) oxides is only partially attributed to the cell surface-bound Fe(II) and cell-mineral sorption but may be driven by the iron oxide conduction band-mediated electron transfer from L17 to nitrate or an electrode, as proposed previously. The current study extends the diversity of bacteria of which nitrate reduction and electricity generation can be facilitated by the presence of iron oxides and confirms the positive role of Fe(III) oxides on microbial nitrate reduction and electricity generation by particular fermentative bacteria in anoxic environments. Copyright �

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

Constructing hierarchical interfaces: TiO 2-supported PtFe-FeO x nanowires for room temperature CO oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Huiyuan; Wu, Zili; Dong, Su

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 TiO 2-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 (TiO 2), 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 TiO 2 participate in the initial CO oxidation, facilitating the reactionmore » 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. These results provide a general approach and new insights into the construction of hierarchical interfaces for advanced catalysis.« less

RGO modified Ni doped FeOOH for enhanced electrochemical and photoelectrochemical water oxidation

NASA Astrophysics Data System (ADS)

Zhang, Xiaofan; Zhang, Bingyan; Liu, Shuangshuang; Kang, Hongwei; Kong, Weiqian; Zhang, Shouren; Shen, Yan; Yang, Baocheng

2018-04-01

Ni,Fe-based (oxy)hydroxides have been one of the most active catalysts for the oxygen evolution reaction. In this article, reduced graphene oxide supported Ni doped FeOOH (RGO/Ni:FeOOH) was prepared for electrochemical and photoelectrochemical (PEC) water oxidation. The RGO/Ni:FeOOH exhibited a lower over-potential (260 mV at 10 mA cm-2) and smaller Tafel slope (32.3 mV dec-1) than that of the FeOOH and Ni:FeOOH. Such significant enhancement is attributed to Ni doping and RGO, which reduce the over-potential, improve the conductivity and enlarge surface areas. Besides, RGO/Ni:FeOOH decorated the TiO2 nanorods (NRs) was also fabricated for photoelectrochemical (PEC) water oxidation, which exhibited a higher photocurrent density and lower onset potential than that of TiO2 NRs the bare under illumination due to the synergistic effect of RGO and Ni:FeOOH. These results demonstrate the RGO/Ni:FeOOH has great promising as a co-catalyst to improve the PEC performance.

Synthesis of nanocrystalline α-Fe2O3 by using thermal oxidation of Fe Films

NASA Astrophysics Data System (ADS)

Fortas, G.; Saidoun, I.; Abboud, H.; Gabouze, N.; Haine, N.; Manseri, A.; Zergoug, M.; Menari, H.; Sam, S.; Cheraga, H.; Bozetine, I.

2018-03-01

α-Fe2O3 hematite films were prepared by thermal oxidation from Fe films electroplated on silicon. Electrodeposition of Fe thin films was carried out from a sulfate bath containing an ammonium chloride complexing agent. The electrochemical study was performed by cyclic voltammetry. The SEM analysis of the films obtained at a -1.3 V constant polarization shows dendritic grains in the form of islet. The DRX spectra exhibit characteristic iron peaks according to the face centered cubic (Fcc) structure. These samples were annealed. At a temperature of 650 ° C, a single iron oxide phase was well formed, with the hematite structure. The SEM photos show a well-assembled columnar structure with formation of nanowires at the surface of the deposit. The absorbance spectra reveal an absorption features in the ultraviolet range

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

2016-04-05

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.

High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-09-01

Metal oxides are potential materials for thermochemical heat storage via reversible endothermal/exothermal redox reactions, and among them, cobalt oxide and manganese oxide are attracting attention. The synthesis of mixed oxides is considered as a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering issues, and the materials potential for thermochemical heat storage application needs to be assessed. This work proposes a study combining thermodynamic calculations and experimental measurements by simultaneous thermogravimetric analysis and calorimetry, in order to identify the impact of iron oxide addition to Co and Mn-based oxides. Fe addition decreased the redox activity and energy storage capacity of Co3O4/CoO, whereas the reaction rate, reversibility and cycling stability of Mn2O3/Mn3O4 was significantly enhanced with added Fe amounts above 15 mol%, and the energy storage capacity was slightly improved. The formation of a reactive cubic spinel explained the improved re-oxidation yield of Mn-based oxides that could be cycled between bixbyite and cubic spinel phases, whereas a low reactive tetragonal spinel phase showing poor re-oxidation was formed below 15 mol% Fe. Thermodynamic equilibrium calculations predict accurately the behavior of both systems. The possibility to identify other suitable mixed oxides becomes conceivable, by enabling the selection of transition metal additives for tuning the redox properties of mixed metal oxides destined for thermochemical energy storage applications.

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.

Experimental determination of activities of FeO and Fe 2O 3 components in hydrous silicic melts under oxidizing conditions

NASA Astrophysics Data System (ADS)

Gaillard, Fabrice; Pichavant, Michel; Scaillet, Bruno

2003-11-01

The critical role of iron on crystal-silicate liquid relationships and melt differentiation is mainly controlled by the redox conditions prevailing in magmas, but the presently available database merely constrains the thermodynamic properties of iron-bearing components in strongly reduced and anhydrous molten silicate where iron is in the ferrous form. This paper provides new standard states for pure ferrous (FeOliq) and ferric (Fe2O3liq) molten iron oxides and extends the experimental database towards oxidizing and water-bearing domains. Iron-iridium, iron-platinum alloys, magnetite or hematite were equilibrated with synthetic silicic liquids at high temperature and high pressure under controlled oxygen fugacity (fO2) to determine activity-composition relationships for FeOliq and Fe2O3liq. Between 1000 and 1300°C, the fO2 ranges from that in air to 3-log units below that of the nickel-nickel oxide buffer (NNO). Experiments were performed on both anhydrous and hydrous melts containing up to 6-wt.% water. Incorporation of water under reducing conditions increases the activity coefficient of FeOliq but has an opposite effect on Fe2O3liq. As calcium is added to system, the effect of water becomes weaker and is inverted for Fe2O3liq. Under oxidizing conditions, water has a negligible effect on both activities of FeOliq and Fe2O3liq. In contrast, changes in redox conditions dominate the activity coefficients of both FeOliq and Fe2O3liq, which increase significantly with increasing fO2. The present results combined with the previous work provide a specific database on the energetics of iron in silicate melts that cover most of the condition prevailing in natural magmas.

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.

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.

A novel reduced symmetry oxide (Mg3B2O6) for magnetic tunnel junctions based on FeCo or Fe leads

NASA Astrophysics Data System (ADS)

Stewart, Derek

2010-03-01

Magnetic tunnel junctions with high TMR values, such as FeMgOFe, capitalize on spin filtering in the oxide due to the band symmetry of incident electrons. However, these structures rely on magnetic leads and oxide regions of the same cubic symmetry class. This raises the question of whether reducing the oxide symmetry can enhance spin filtering. A new magnetic tunnel junction (FeCoMg3B2O6FeCo) is presented that uses a reduced symmetry oxide region (orthorhombic) to filter spins between two cubic magnetic leads. Symmetry analysis of coupling between states in the cubic leads and the orthorhombic oxide indicates that majority carrier tunneling through the oxide should be favored over minority carriers. Complex band structure analysis of Mg3B2O6 shows that the relevant evanescent states in the band gap are due to boron p states and that there is sufficient difference in the decay rates of the imaginary bands for spin filtering to occur. Electronic transport calculations through a FeMg3B2O6Fe magnetic tunnel junction are also performed to address the possible influence of interface states. Some recent experimental studies of FeCoBMgOFeCoB junctions, with B diffusion into the MgO region, indicate that this new type of junction may have already been fabricated. The prospect of developing a general class of magnetic tunnel junctions based on reduced symmetry oxides is also examined.

Novel Fe-oxidizing Zetaproteobacteria floating in the Chesapeake: kinetics and genomic insights into microbial Fe cycling in a stratified marine water column

NASA Astrophysics Data System (ADS)

Chiu, B.; Field, E.; Kato, S.; Mcallister, S.; Luther, G. W., III; Chan, C. S. Y.

2016-12-01

Iron-oxidizing bacteria (FeOB) are potentially important drivers in iron redox cycling, with significant effects on other major elemental cycles (e.g. C, N, P, S, As), yet the biogeochemical impacts of these microbes have been difficult to quantify. FeOB have traditionally been studied in relatively few, Fe-rich environments (groundwater seeps and hydrothermal vents), but our recent studies show that they also occur in coastal marine environments. Here we report on two Zetaproteobacteria strains, CP-5 and CP-8, isolated from the Chesapeake Bay chemocline during seasonal stratification. They represent the first known planktonic chemolithotrophic FeOB and are unusual for living in very low (micromolar) Fe(II) conditions, intermediate (brackish) salinities, and pH values (7.3-7.4) at which abiotic Fe oxidation is typically rapid. However, kinetics experiments demonstrate that CP-8 accelerates iron oxidation, relative to killed controls, and allow us to quantify the effects of microbes on iron oxidation. Ongoing work is characterizing the O2 preferences of the CP strains, specifically the lower O2 limits of FeOB activity. We obtained complete, closed genomes of both CP-5 and CP-8 genomes (2.54 and 2.30 Mbp respectively) using the PacBio RSII sequencer. Our genomic analysis of the CP strains is focused on adaptations for growth in the Chesapeake Bay chemocline, including genes for energy metabolism, and C, N, and P cycling. Initial results indicate that both strains have putative iron oxidase Cyc2 as well as Rubisco which suggests that these microbes are using energy from Fe oxidation to fix carbon, despite the availability of organics from phototrophs living higher in the water column. Our work on these Chesapeake FeOB gives us insight into how chemolithotrophic FeOB can participate in Fe redox and nutrient cycling in a stratified marine water column.

Capabilities of laser ablation mass spectrometry in the differentiation of natural and artificial opal gemstones.

PubMed

Erel, Eric; Aubriet, Frédéric; Finqueneisel, Gisèle; Muller, Jean-François

2003-12-01

The potentialities of laser ablation coupled to ion cyclotron resonance Fourier transform mass spectrometry are evaluated to distinguish natural and artificial opals. The detection of specific species in both ion detection modes leads us to obtain relevant criteria of differentiation. In positive ions, species including hafnium and large amounts of zirconium atoms are found to be specific for artificial opal. In contrast, aluminum, titanium, iron, and rubidium are systematically detected in the study of natural opals. Moreover, some ions allow us to distinguish between natural opal from Australia and from Mexico. Australian gemstone includes specifically strontium, cesium, and barium. Moreover, it is also found that the yield of (H2O)0-1(SiO2)nX- (X- = O-, OH-, KO-, NaO-, SiO2-, AlO1-2-, FeO2-, ZrO2-, and ZrO3-) and (Al2O3)(SiO2)nAlO2- ions depends on the composition of the sample when opals are laser ablated. Ions, which include zirconium oxide species, are characteristics of artificial gem. In contrast, natural opals lead us, after laser ablation, to the production of ions including H2O, Al2O3 motifs and AlO-, KO-, NaO-, and FeO2- species.

Coupling catalytic hydrolysis and oxidation of HCN over HZSM-5 modified by metal (Fe,Cu) oxides

NASA Astrophysics Data System (ADS)

Hu, Yanan; Liu, Jiangping; Cheng, Jinhuan; Wang, Langlang; Tao, Lei; Wang, Qi; Wang, Xueqian; Ning, Ping

2018-01-01

In this work, a series of metal oxides (Fe,Cu) modified HZSM-5 catalysts were synthesized by incipient-wetness impregnation method and then characterized by XRD, N2 adsorption-desorption, H2-TPR, NH3-TPD, UV-vis, FT-IR and XPS measurements. The catalytic hydrolysis and oxidation behaviors toward HCN were investigated. The results indicated that the Fe-Cu/HZSM-5 catalysts exhibited more excellent performence on coupling catalytic hydrolysis and oxidation of HCN than HZSM-5, Fe/HZSM-5, Cu/HZSM-5, and both nearly 100% HCN conversion and 80% N2 selectivity were obtained at about 250 °C. The improved catalytic performance could be ascribed to the creation of highly dispersed iron and copper composites on the surface of the HZSM-5 support, the excellent redox and regulated acid properties of the active ingredients. Moreover, the highly N2 selectivity could be attributed to the good interaction between the Fe and Cu nanocomposites which was facilitated to the NH3-SCR (selective catalytic reduction of NO by NH3) reaction.

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. 

Antibacterial activity of trimetal (CuZnFe) oxide nanoparticles.

PubMed

Alzahrani, Khalid E; Niazy, Abdurahman A; Alswieleh, Abdullah M; Wahab, Rizwan; El-Toni, Ahmed M; Alghamdi, Hamdan S

2018-01-01

The increasing resistance of pathogenic bacteria to antibiotics is a challenging worldwide health problem that has led to the search for new and more efficient antibacterial agents. Nanotechnology has proven to be an effective tool for the fight against bacteria. In this paper, we present the synthesis and traits of trimetal (CuZnFe) oxide nanoparticles (NPs) using X-ray diffraction, high-resolution transmission electron microscopy, and energy dispersive x-ray spectroscopy. We evaluated the antibacterial activity of these NPs against gram-negative Escherichia coli and gram-positive Enterococcus faecalis and then compared it to that of their pure single-metal oxide components CuO and ZnO. Our study showed that the antibacterial activity of the trimetal oxide NPs was greater against E . coli than against E . faecalis . Overall, the antimicrobial effect of trimetal NPs is between those of pure ZnO and CuO nanoparticles, which may mean that their cytotoxicity is also between that of pure ZnO and CuO NPs, making them potential antibiotics. However, the cytotoxicity of trimetal NPs to mammalian cells needs to be verified. The combination of three metal oxide NPs (ZnO, CuO, and Fe 2 O 3 ) in one multimetal (CuZnFe) oxide NPs will enhance the therapeutic strategy against a wide range of microbial infections. Bacteria are unlikely to develop resistance against this new NP because bacteria must go through a series of mutations to become resistant to the trimetal oxide NP. Therefore, this NP can combat existing and emerging bacterial infections.

Laboratory simulations of atmospheric entry of micrometeoroids: ablation of magnesium

NASA Astrophysics Data System (ADS)

Bones, David; Gomez Martin, Juan Carlos; Diego Carrillo Sanchez, Juan; Dobson, Alexander; Plane, John

2017-04-01

We address the uncertainty in the cosmic dust input into the Earth's atmosphere by simulating the atmospheric entry of micrometeoroids in a custom built chamber, capable of heating particles to 3000 K in 2 s and able to precisely reproduce representative heating profiles. In lieu of interplanetary cosmic dust, we use a range of ground-up recovered meteorites and mineral analogues. We measure the ablation of two metals simultaneously with laser induced fluorescence (LIF). The resulting ablation profiles can be compared with the composition of the remaining, unablated particle, as determined from scanning electron microscopy-energy dispersive x-ray (SEM-EDX) analysis. Building on earlier studies of Na, Fe and Ca, here we present Mg profiles and compare them with results from our chemical ablation model (CABMOD). In general, Mg behaves as predicted, beginning to ablate steadily as one broad ablation peak once temperatures reach 2000 K. In contrast Fe, which should behave similarly to Mg, typically has two ablation peaks due to being present in two distinct phases.

Superparamagnetic PLGA-iron oxide microcapsules for dual-modality US/MR imaging and high intensity focused US breast cancer ablation.

PubMed

Sun, Yang; Zheng, Yuanyi; Ran, Haitao; Zhou, Yang; Shen, Hongxia; Chen, Yu; Chen, Hangrong; Krupka, Tianyi M; Li, Ao; Li, Pan; Wang, Zhibiao; Wang, Zhigang

2012-08-01

Organic/inorganic, hybrid, multifunctional, material-based platforms combine the merits of diverse functionalities of inorganic nanoparticles and the excellent biocompatibility of organic systems. In this work, superparamagnetic poly(lactic-co-glycolic acid) (PLGA) microcapsules (Fe(3)O(4)/PLGA) have been developed, as a proof-of-concept, for the application in ultrasound/magnetic resonance dual-modality biological imaging and enhancing the therapeutic efficiency of high intensity focused ultrasound (HIFU) breast cancer surgery in vitro and in vivo. Hydrophobic Fe(3)O(4) nanoparticles were successfully integrated into PLGA microcapsules by a typical double emulsion evaporation process. In this process, highly dispersed superparamagnetic Fe(3)O(4)/PLGA composite microcapsules with well-defined spherical morphology were obtained with an average diameter of 885.6 nm. The potential of these microcapsules as dual contrast agents for ultrasonography and magnetic resonance imaging were demonstrated in vitro and, also, preliminarily in vivo. Meanwhile, the prepared superparamagnetic composite microcapsules were administrated into rabbits bearing breast cancer model for the evaluation of the in vivo HIFU synergistic ablation efficiency caused by the introduction of such microcapsules. Our results showed that the employment of the composite microcapsules could efficiently enhance ultrasound imaging of cancer, and greatly enhance the HIFU ablation of breast cancer in rabbits. In addition, pathological examination was systematically performed to detect the structural changes of the target tissue caused by HIFU ablation. This finding demonstrated that successful introduction of these superparamagnetic microcapsules into HIFU cancer surgery provided an alternative strategy for the highly efficient imaging-guided non-invasive HIFU synergistic therapy of cancer. Copyright © 2012 Elsevier Ltd. All rights reserved.

Fe Oxides on Ag Surfaces: Structure and Reactivity

DOE PAGES

Shipilin, M.; Lundgren, E.; Gustafson, J.; ...

2016-09-09

One layer thick iron oxide films are attractive from both applied and fundamental science perspectives. The structural and chemical properties of these systems can be tuned by changing the substrate, making them promising materials for heterogeneous catalysis. In the present work, we investigate the structure of FeO(111) monolayer films grown on Ag(100) and Ag(111) substrates by means of microscopy and diffraction techniques and compare it with the structure of FeO(111) grown on other substrates reported in literature. We also study the NO adsorption properties of FeO(111)/Ag(100) and FeO(111)/Ag(111) systems utilizing different spectroscopic techniques. Finally, we discuss similarities and differences inmore » the data obtained from adsorption experiments and compare it with previous results for FeO(111)/Pt(111).« less

Fe Oxides on Ag Surfaces: Structure and Reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shipilin, M.; Lundgren, E.; Gustafson, J.

One layer thick iron oxide films are attractive from both applied and fundamental science perspectives. The structural and chemical properties of these systems can be tuned by changing the substrate, making them promising materials for heterogeneous catalysis. In the present work, we investigate the structure of FeO(111) monolayer films grown on Ag(100) and Ag(111) substrates by means of microscopy and diffraction techniques and compare it with the structure of FeO(111) grown on other substrates reported in literature. We also study the NO adsorption properties of FeO(111)/Ag(100) and FeO(111)/Ag(111) systems utilizing different spectroscopic techniques. Finally, we discuss similarities and differences inmore » the data obtained from adsorption experiments and compare it with previous results for FeO(111)/Pt(111).« less

Containerless solidification of BiFeO3 oxide under microgravity

NASA Astrophysics Data System (ADS)

Yu, Jianding; Arai, Yasutomo; Koshikawa, Naokiyo; Ishikawa, Takehito; Yoda, Shinichi

1999-07-01

Containerless solidification of BiFeO3 oxide has been carried out under microgravity with Electrostatic Levitation Furnace (ELF) aboard on the sounding rocket (TR-IA). It is a first containerless experiment using ELF under microgravity for studying the solidification of oxide insulator material. Spherical BiFeO3 sample with diameter of 5mm was heated by two lasers in oxygen and nitrogen mixing atmosphere, and the sample position by electrostatic force under pinpoint model and free drift model. In order to compare the solidification behavior in microgravity with on ground, solidification experiments of BiFeO3 in crucible and drop tube were carried out. In crucible experiment, it was very difficult to get single BiFeO3 phase, because segregation of Fe2O3 occured very fast and easily. In drop tube experiment, fine homogeneous BiFeO3 microstructure was obtained in a droplet about 300 μm. It implies that containerless processing can promote the phase selection in solidification. In microgravity experiment, because the heating temperature was lower than that of estimated, the sample was heated into Fe2O3+liquid phase region. Fe2O3 single crystal grew on the surface of the spherical sample, whose sample was clearly different from that observed in ground experiments.

Core-shell CoFe2O4@Co-Fe-Bi nanoarray: a surface-amorphization water oxidation catalyst operating at near-neutral pH.

PubMed

Ji, Xuqiang; Hao, Shuai; Qu, Fengli; Liu, Jingquan; Du, Gu; Asiri, Abdullah M; Chen, Liang; Sun, Xuping

2017-06-14

The exploration of high-performance and earth-abundant water oxidation catalysts operating under mild conditions is highly attractive and challenging. In this communication, core-shell CoFe 2 O 4 @Co-Fe-Bi nanoarray on carbon cloth (CoFe 2 O 4 @Co-Fe-Bi/CC) was successfully fabricated by in situ surface amorphization of CoFe 2 O 4 nanoarray on CC (CoFe 2 O 4 /CC). As a 3D water oxidation electrode, CoFe 2 O 4 @Co-Fe-Bi/CC shows outstanding activity with an overpotential of 460 mV to drive a geometrical catalytic current density of 10 mA cm -2 in 0.1 M potassium borate (pH 9.2). Notably, it also demonstrates superior long-term durability for at least 20 h with 96% Faradic efficiency. Density functional theory calculations indicate that the conversion from OOH* to O 2 is the rate-limiting step and the high water oxidation activity of CoFe 2 O 4 @Co-Fe-Bi/CC is associated with the lower free energy of 1.84 eV on a Co-Fe-Bi shell.

Magnetic properties of partially oxidized Fe films

NASA Astrophysics Data System (ADS)

Garcia, Miguel Angel; Lopez-Dominguez, Victor; Hernando, Antonio

Hybrid magnetic nanostructures exhibit appealing properties due to interface and proximity effects. A simple and interesting system of hybrid magnetic nanomaterials are partially oxidized ferromagnetic films. We have fabricated Fe films by thermal evaporation and performed a partial oxidation to magnetite (Fe3O4) by annealing in air at different times and temperatures. The magnetic properties of the films evolve from those of pure metallic iron to pure magnetite, showing intermediate states where the proximity effects control the magnetic behavior. At some stages, the magnetization curves obtained by SQUID and MOKE magnetometry exhibit important differences due to the dissimilar contribution of both phases to the magneto-optical response of the system This work has been supported by the Ministerio Español de Economia y Competitividad (MINECO) MAT2013-48009-C4-1. V.L.D and M.A.G. acknowledges financial support from BBVA foundation.

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.

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

Ruthenium nano-oxide layer in CoFe-Ru-CoFe trilayer system: An x-ray reflectivity study

NASA Astrophysics Data System (ADS)

Asgharizadeh, S.; Sutton, M.; Altounian, Z.; Mao, M.; Lee, C. L.

2008-05-01

A grazing incidence x-ray reflectivity technique is used to determine the electron density profile as a function of depth in CoFe-Ru-CoFe and CoFe-Ru nano-oxide layer (NOL)-CoFe trilayers. Four trilayers with ruthenium thicknesses of 8, 8.5, and 9Å and one with Ru 8.5Å NOL, prepared by a dc planetary sputtering system, were investigated. For all samples, the electron density profile (EDP) shows a central peak that is related to the Ru layer. Natural oxidation in all of the samples introduces a graded EDP of the top CoFe layers, which decreases gradually to zero. The large surface resistivity of Ru 8.5Å NOL as compared to Ru 8.5Å is related to the remarkable difference between their EDPs. EDP changes have also been investigated in Ru NOL trilayers after annealing at 280°C. The Ru phase in the EDP was observed to confirm the thermal stability of the spacer layer after annealing.

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.

Impact of solvent mixture on iron nanoparticles generated by laser ablation

NASA Astrophysics Data System (ADS)

Chakif, M.; Prymak, O.; Slota, M.; Heintze, E.; Gurevich, E. L.; Esen, C.; Bogani, L.; Epple, M.; Ostendorf, A.

2014-03-01

The present work reveals the structural and magnetic properties of iron oxide (FexOy) nanoparticles (NPs) prepared by femtosecond laser ablation. The FexOy-NPs were produced in solutions consisting of different ratios of water and acetone. Laser ablation in water yields agglomerates and that in acetone yields chain structures whereas that in water/acetone show a mixture of both. We observe significant fabrication dependent properties such as different crystallinities and magnetic behaviors. The structural characterization shows a change from iron (Fe) to a FexOy state of the NPs which depends on the solution composition. Furthermore, transmission electron microscopy measurements exhibit a broad particle size distribution in all samples but with significant differences in the mean sizes. Using magnetic measurements we show that nanoparticles fabricated in pure acetone have lower coercive fields which come along with a smaller mean particle size and therefore increasing superparamagnetic behavior.

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]).

Impact of Microcystis aeruginosa Exudate on the Formation and Reactivity of Iron Oxide Particles Following Fe(II) and Fe(III) Addition.

PubMed

Garg, Shikha; Wang, Kai; Waite, T David

2017-05-16

Impact of the organic exudate secreted by a toxic strain of Microcystis aeruginosa on the formation, aggregation, and reactivity of iron oxides that are formed on addition of Fe(II) and Fe(III) salts to a solution of the exudate is investigated in this study. The exudate has a stabilizing effect on the particles formed with decreased aggregation rate and increased critical coagulant concentration required for diffusion-limited aggregation to occur. These results suggest that the presence of algal exudates from Microcystis aeruginosa may significantly influence particle aggregation both in natural water bodies where Fe(II) oxidation results in oxide formation and in water treatment where Fe(III) salts are commonly added to aid particle growth and contaminant capture. The exudate also affects the reactivity of iron oxide particles formed with exudate coated particles undergoing faster dissolution than bare iron oxide particles. This has implications to iron availability, especially where algae procure iron via dissolution of iron oxide particles as a result of either reaction with reducing moieties, light-mediated ligand to metal charge transfer and/or reaction with siderophores. The increased reactivity of exudate coated particles is attributed, for the most part, to the smaller size of these particles, higher surface area and increased accessibility of surface sites.

Fe(II) oxidation during acid mine drainage neutralization in a pilot-scale Sequencing Batch Reactor.

PubMed

Zvimba, J N; Mathye, M; Vadapalli, V R K; Swanepoel, H; Bologo, L

2013-01-01

This study investigated Fe(II) oxidation during acid mine drainage (AMD) neutralization using CaCO3 in a pilot-scale Sequencing Batch Reactor (SBR) of hydraulic retention time (HRT) of 90 min and sludge retention time (SRT) of 360 min in the presence of air. The removal kinetics of Fe(II), of initial concentration 1,033 ± 0 mg/L, from AMD through oxidation to Fe(III) was observed to depend on both pH and suspended solids, resulting in Fe(II) levels of 679 ± 32, 242 ± 64, 46 ± 16 and 28 ± 0 mg/L recorded after cycles 1, 2, 3 and 4 respectively, with complete Fe(II) oxidation only achieved after complete neutralization of AMD. Generally, it takes 30 min to completely oxidize Fe(II) during cycle 4, suggesting that further optimization of SBR operation based on both pH and suspended solids manipulation can result in significant reduction of the number of cycles required to achieve acceptable Fe(II) oxidation for removal as ferric hydroxide. Overall, complete removal of Fe(II) during AMD neutralization is attractive as it promotes recovery of better quality waste gypsum, key to downstream gypsum beneficiation for recovery of valuables, thereby enabling some treatment-cost recovery and prevention of environmental pollution from dumping of sludge into landfills.

Linking Thermodynamics to Pollutant Reduction Kinetics by Fe2+ Bound to Iron Oxides.

PubMed

Stewart, Sydney M; Hofstetter, Thomas B; Joshi, Prachi; Gorski, Christopher A

2018-05-15

Numerous studies have reported that pollutant reduction rates by ferrous iron (Fe 2+ ) are substantially enhanced in the presence of an iron (oxyhydr)oxide mineral. Developing a thermodynamic framework to explain this phenomenon has been historically difficult due to challenges in quantifying reduction potential ( E H ) values for oxide-bound Fe 2+ species. Recently, our group demonstrated that E H values for hematite- and goethite-bound Fe 2+ can be accurately calculated using Gibbs free energy of formation values. Here, we tested if calculated E H values for oxide-bound Fe 2+ could be used to develop a free energy relationship capable of describing variations in reduction rate constants of substituted nitrobenzenes, a class of model pollutants that contain reducible aromatic nitro groups, using data collected here and compiled from the literature. All the data could be described by a single linear relationship between the logarithms of the surface-area-normalized rate constant ( k SA ) values and E H and pH values [log( k SA ) = - E H /0.059 V - pH + 3.42]. This framework provides mechanistic insights into how the thermodynamic favorability of electron transfer from oxide-bound Fe 2+ relates to redox reaction kinetics.

Nanostructured Mn-Fe Binary Mixed Oxide: Synthesis, Characterization and Evaluation for Arsenic Removal.

PubMed

Pillewan, Pradnya; Mukherjee, Shrabanti; Bansiwal, Amit; Rayalu, Sadhana

2014-07-01

Adsorption of arsenic on bimetallic Mn and Fe mixed oxide was carried out using both field as well as simulated water. The material was synthesized using hydrothermal method and characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Langmuir and Freundlich adsorption isotherms were computed using batch adsorption studies to determine the adsorption capacity of Mn-Fe binary mixed oxide for arsenic. Adsorption capacity for MFBMO obtained from Freundlich model was found to be 2.048 mg/g for simulated water and 1.084 mg/g for field water. Mn-Fe binary mixed oxide was found to be effective adsorbent for removal of arsenic from water.

Assembling tungsten oxide hydrate nanocrystal colloids formed by laser ablation in liquid into fast-response electrochromic films.

PubMed

Wang, Shalong; Dou, Kang; Zou, Yousheng; Dong, Yuhang; Li, Jubin; Ju, Dan; Zeng, Haibo

2017-03-01

High-performance electrochromic films based on tungsten oxide hydrate ([WO 2 (O 2 )H 2 O]·1.66H 2 O) colloidal nanocrystals with fast switching speed were fabricated by laser ablation in a mixture of water and hydrogen peroxide followed by electrophoretic methods. Through electrophoretic deposition, the nanoparticles in the colloids synthesized by laser ablation aggregated onto the FTO coated glass substrate forming a lager cell with a uniform size of around 200nm, which subsequently self-assembled into a porous tungsten oxide hydrate film. By optimizing the electrophoretic time (800s) and voltage (-0.5V), the mesh-like porous tungsten oxide hydrate film achieved a wide optical modulation of 32% at 632nm, fast coloration and bleaching response speed of 7.8 s and 1.7s respectively due to the synergetic effect of the unique atomic structure of [WO 2 (O 2 )H 2 O]·1.66H 2 O and porous structure with large surface area that facilitates the ion insertion/extraction. Thus the tungsten oxide hydrate can be a promising electrochromic material for practical applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Formation of the Fe,Mg-Silicates, Fe0, and Graphite (Diamond) Assemblage as a Result of Cohenite Oxidation under Lithospheric Mantle Conditions

NASA Astrophysics Data System (ADS)

Bataleva, Yu. V.; Palyanov, Yu. N.; Borzdov, Yu. M.; Zdrokov, E. V.; Novoselov, I. D.; Sobolev, N. V.

2018-03-01

Experimental studies in the Fe3C-SiO2-MgO system ( P = 6.3 GPa, T = 1100-1500°C, t = 20-40 h) have been carried out. It has been established that carbide-oxide interaction resulted in the formation of Fe-orthopyroxene, graphite, wustite, and cohenite (1100 and 1200°C), as well as a Fe-C-O melt (1300-1500°C). The main processes occurring in the system at 1100 and 1200°C are the oxidation of cohenite, the extraction of carbon from carbide, and the crystallization of metastable graphite, as well as the formation of ferrosilicates. At T ≥ 1300°C, graphite crystallization and diamond growth occur as a result of the redox interaction of a predominantly metallic melt (Fe-C-O) with oxides and silicates. The carbide-oxide interaction studied can be considered as the basis for modeling a number of carbon-producing processes in the lithospheric mantle at fO2 values near the iron-wustite buffer.

Oxidation of iopamidol with ferrate (Fe(VI)): Kinetics and formation of toxic iodinated disinfection by-products.

PubMed

Dong, Huiyu; Qiang, Zhimin; Liu, Shaogang; Li, Jin; Yu, Jianwei; Qu, Jiuhui

2018-03-01

Presence of iodinated X-ray contrast media (ICMs) in source water is of high concern, because of their potential to form highly toxic iodinated disinfection by-products (I-DBPs). This study investigated kinetics, mechanisms and products for oxidation of one ICMs, iopamidol (IPM) by ferrate (Fe(VI)). The obtained apparent second-order rate constants for oxidation of IPM by Fe(VI) ranged from 0.7 M -1  s -1 to 74.6 M -1  s -1  at pH 6.0-10.0, which were highly dependent on pH. It was found that the oxidation of IPM by Fe(VI) led to the formation of highly toxic I-DBPs. Iodoform (IF), iodoacetic acid and triiodoacetic acid formations were observed during the oxidation and IF dominated the formed I-DBPs. The formation of I-DBPs was also governed by pH and the maximum formation of I-DBPs occurred at pH 9.0. Transformation pathways of IPM by Fe(VI) oxidation were speculated to proceed through deiodination, amide hydrolysis and oxidation of amine reactions. The deiodination reaction during the oxidation of IPM by Fe(VI) contributed to the formation of I-DBPs. The formation of I-DBPs during the oxidation of IPM by Fe(VI) was significantly higher than those of iohexol, diatrizoate and iopromide, which was consistent with the lowest molecular orbital energy gap of IPM. Although Fe(VI) is considered as a green oxidant, the formation of highly toxic I-DBPs during the oxidation of IPM should receive great attention. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solid-State Reaction Between Fe-Al-Ca Alloy and Al2O3-CaO-FeO Oxide During Heat Treatment at 1473 K (1200 °C)

NASA Astrophysics Data System (ADS)

Liu, Chengsong; Yang, Shufeng; Li, Jingshe; Ni, Hongwei; Zhang, Xueliang

2017-04-01

The aim of this study was to control the physicochemical characteristics of inclusions in steel through appropriate heat treatment. Using a confocal scanning laser microscope (CSLM) and pipe furnace, the solid-state reactions between Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide during heat treatment at 1473 K (1200 °C) and the influence of these reactions on the compositions of and phases in the alloy and oxide were investigated by the diffusion couple method. Suitable pretreatment of the oxide using a CSLM and production of the diffusion couple of Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide gave good contact between the alloy and oxide. The diffusion couple was then sealed in a quartz tube with a piece of Ti foil to lower oxygen partial pressure and a block of Fe-Al-Ca alloy was introduced to conduct heat treatment experiments. Solid-state reactions between the alloy and oxide during heat treatment at 1473 K (1200 °C) were analyzed and discussed. A dynamic model to calculate the width of the particle precipitation zone based on the Wagner model of internal oxidation of metal was proposed. This model was helpful to understand the solid-state reaction mechanism between Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide.

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ57/54Fe Observations

PubMed Central

Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; Bach, Wolfgang; Edwards, Katrina J.

2016-01-01

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50′N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings

Iron transformation pathways and redox micro-environments in seafloor sulfide-mineral deposits: Spatially resolved Fe XAS and δ 57/54Fe observations

DOE PAGES

Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; ...

2016-05-10

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffractionmore » (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ 57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ(57/54)Fe Observations.

PubMed

Toner, Brandy M; Rouxel, Olivier J; Santelli, Cara M; Bach, Wolfgang; Edwards, Katrina J

2016-01-01

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ(57)Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings

Preparation and biodistribution of 59Fe-radiolabelled iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Pospisilova, Martina; Zapotocky, Vojtech; Nesporova, Kristina; Laznicek, Milan; Laznickova, Alice; Zidek, Ondrej; Cepa, Martin; Vagnerova, Hana; Velebny, Vladimir

2017-02-01

We report on the 59Fe radiolabelling of iron oxide nanoparticle cores through post-synthetic isotope exchange (59Fe-IONPex) and precursor labelling (59Fe-IONPpre). Scanning electron microscopy and dynamic light scattering measurements showed no impact of radiolabelling on nanoparticle size or morphology. While incorporation efficiencies of these methods are comparable—83 and 90% for precursor labelling and post-synthetic isotope exchange, respectively—59Fe-IONPpre exhibited much higher radiochemical stability in citrated human plasma. Quantitative ex vivo biodistribution study of 59Fe-IONPpre coated with triethylene glycol was performed in Wistar rats. Following the intravenous administration, high 59Fe concentration was observed in the lung and the organs of the reticuloendothelial system such as the liver, the spleen and the femur.

Synthesis of highly efficient α-Fe{sub 2}O{sub 3} catalysts for CO oxidation derived from MIL-100(Fe)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cui, Lifeng; Zhao, Di; Yang, Yang

Mesoporous hollow α-Fe{sub 2}O{sub 3} bricks were synthesized via a hydrothermal method to create a precursor MIL-100(Fe) and a subsequent calcination process was applied to prepare the Fe{sub 2}O{sub 3} phase. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results showed the morphology of hollow α-Fe{sub 2}O{sub 3} bricks which inherited from the MIL-100(Fe) template. The catalytic activities of hollow α-Fe{sub 2}O{sub 3} bricks for CO oxidation are studied in this work. Due to better low temperature reduction behavior, mesoporous hollow α-Fe{sub 2}O{sub 3} bricks obtained at calcination temperature of 430 °C displayed high catalytic activity and excellent stabilitymore » with a complete CO conversion temperature (T{sub 100}) of 255 °C. - Graphical abstract: Synthesis of highly efficient α-Fe{sub 2}O{sub 3} catalysts for CO oxidation derived from MIL-100(Fe). - Highlights: • α-Fe{sub 2}O{sub 3} is prepared by the thermolysis of a MIL-100(Fe) template. • The morphology of hollow α-Fe{sub 2}O{sub 3} bricks is inherited from MIL-100(Fe) template. • α-Fe{sub 2}O{sub 3} obtained at calcined temperature of 430 °C displays high activity • Enhanced activity is attributed to crystal plane and reduction behavior.« less

Complexation facilitated reduction of aromatic N-oxides by aqueous Fe(II)-tiron complex: reaction kinetics and mechanisms.

PubMed

Chen, Yiling; Zhang, Huichun

2013-10-01

Rapid reduction of carbadox (CDX), olaquindox and several other aromatic N-oxides were investigated in aqueous solution containing Fe(II) and tiron. Consistent with previous work, the 1:2 Fe(II)-tiron complex, FeL2(6-), is the dominant reactive species as its concentration linearly correlates with the observed rate constant kobs under various conditions. The N-oxides without any side chains were much less reactive, suggesting direct reduction of the N-oxides is slow. UV-vis spectra suggest FeL2(6-) likely forms 5- or 7-membered rings with CDX and olaquindox through the N and O atoms on the side chain. The formed inner-sphere complexes significantly facilitated electron transfer from FeL2(6-) to the N-oxides. Reduction products of the N-oxides were identified by HPLC/QToF-MS to be the deoxygenated analogs. QSAR analysis indicated neither the first electron transfer nor N-O bond cleavage is the rate-limiting step. Calculations of the atomic spin densities of the anionic N-oxides confirmed the extensive delocalization between the aromatic ring and the side chain, suggesting complex formation can significantly affect the reduction kinetics. Our results suggest the complexation facilitated N-oxide reduction by Fe(II)-tiron involves a free radical mechanism, and the subsequent deoxygenation might also benefit from the weak complexation of Fe(II) with the N-oxide O atom.

Oxidation and deprotonation of synthetic Fe{sup II}-Fe{sup III} (oxy)hydroxycarbonate Green Rust: An X-ray photoelectron study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mullet, M.; Guillemin, Y.; Ruby, C.

X-ray photoelectron spectroscopy (XPS) was used to investigate chemical bonding and distribution of iron and oxygen species at the surface of Green Rusts (GRs). GRs with variable composition, i.e. Fe{sup II}{sub 6(1-x)}Fe{sup III}{sub 6x}O{sub 12}H{sub 2(7-3x)} CO{sub 3}.3H{sub 2}O where the Fe{sup III} molar fraction of the positively charged hydroxide sheets, x=[Fe(III)]/[Fe(total)] belongs to [1/3, 1], were synthesised under an inert atmosphere. The broadened Fe(2p{sub 3/2}) spectra were fitted using Gupta and Sen multiplets peaks and additional satellite and surface features. The [Fe(III)]/[Fe(total)] surface atomic ratios closely agree with the x ratios expected from the bulk composition, which gives amore » high degree of confidence on the validity of the proposed fitting procedure. The valence band spectra are also reported and show dependencies on iron speciation. The O(1s) spectra revealed the presence of O{sup 2-}, OH{sup -} species and adsorbed water. The hydroxyl component decreases with increasing x values, i.e. with the amount of ferric iron, while the oxide component increases. This study provides direct spectroscopic evidence of the deprotonation of hydroxyl groups that occurs simultaneously with the oxidation of ferrous iron within the GR structure. - Graphical abstract: X-ray photoelectron spectroscopy (XPS) is used to investigate chemical bonding and distribution of iron and oxygen species at the surface of Green Rust (GR) compounds. First spectroscopic evidence of the deprotonation of hydroxyls groups occurring simultaneously to the oxidation of Fe(II) into Fe(III) species is provided.« less

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

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.

Laser ablation based fuel ignition

DOEpatents

Early, J.W.; Lester, C.S.

1998-06-23

There is provided a method of fuel/oxidizer ignition comprising: (a) application of laser light to a material surface which is absorptive to the laser radiation; (b) heating of the material surface with the laser light to produce a high temperature ablation plume which emanates from the heated surface as an intensely hot cloud of vaporized surface material; and (c) contacting the fuel/oxidizer mixture with the hot ablation cloud at or near the surface of the material in order to heat the fuel to a temperature sufficient to initiate fuel ignition. 3 figs.

Laser ablation based fuel ignition

DOEpatents

Early, James W.; Lester, Charles S.

1998-01-01

There is provided a method of fuel/oxidizer ignition comprising: (a) application of laser light to a material surface which is absorptive to the laser radiation; (b) heating of the material surface with the laser light to produce a high temperature ablation plume which emanates from the heated surface as an intensely hot cloud of vaporized surface material; and (c) contacting the fuel/oxidizer mixture with the hot ablation cloud at or near the surface of the material in order to heat the fuel to a temperature sufficient to initiate fuel ignition.

Room Temperature Ferromagnetism of Fe Doped Indium Tin Oxide Based on Dispersed Fe3O4 Nanoparticles

NASA Astrophysics Data System (ADS)

Okada, Koichi; Kohiki, Shigemi; Nishi, Sachio; Shimooka, Hirokazu; Deguchi, Hiroyuki; Mitome, Masanori; Bando, Yoshio; Shishido, Toetsu

2007-09-01

Transmission electron microscopy revealed that Fe3O4 nanoparticles with diameter of ≈200 nm dispersed in Fe doped indium tin oxide (Fe@ITO) powders exhibiting co-occurrence of room temperature ferromagnetism and superparamagnetism. Although we observed no X-ray diffraction peak from Fe related compounds for Fe0.19@ITO (ITO: In1.9Sn0.1O3) powders, the powders showed both hysteresis loop in field dependent magnetization at 300 K and divergence of zero-field-cooled magnetization from field-cooled magnetization. Scanning transmission electron microscopy with energy dispersive X-ray spectroscopy demonstrated that the nanoparticle with diameter of ≈200 nm consists of Fe and oxygen. Transmission electron diffraction revealed that crystal structure of the nanoparticle is inverse spinel type Fe3O4. The Fe3O4 crystalline phase by electron diffraction is consistent with the saturation magnetization of 1.3 μB/Fe and magnetic anomaly at ≈110 K observed for the powders.

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

Effect of orthophosphate on the oxidation products of Fe(II)-Fe(III) hydroxycarbonate: the transformation of green rust to ferrihydrite

NASA Astrophysics Data System (ADS)

Benali, Omar; Abdelmoula, Mustapha; Refait, Philippe; Génin, Jean-Marie Robert

2001-06-01

Hydroxycarbonate green rust GR(CO 32-) has been synthesized by oxidation of aqueous suspensions of Fe(OH) 2 by aeration at the air-liquid interface, in the presence of HCO 3- ions at pH 7.5 to 9. During the oxidation of GR(CO 32-), ferrihydrite formed first and then turned into goethite by dissolution and precipitation. The oxidation of GR(CO 32-) in the presence of orthophosphate ions, which were added as Na 2HPO 4 · 7H 2O salt, also involved the formation of ferrihydrite but not that of goethite, because the dissolution of ferrihydrite is inhibited by the adsorption of phosphate ions on its surface. The oxidation was slowed down because of the suppression of the catalytic effect of iron(III) hydroxide on the oxidation of Fe(II). In anoxic conditions without phosphate, a mixture of GR(CO 32-), goethite, and ferrihydrite was observed to transform spontaneously into a mixture of siderite and magnetite. It is thermodynamically consistent, which shows that GR(CO 32-) is metastable with respect to the two-phase system FeCO 3-Fe 3O 4. In the presence of phosphate, this transformation was inhibited and GR(CO 32-) did not transform in anoxic conditions. Anionic phosphate species dissolved in solution did not give rise to a corresponding GR, i.e., phosphate species did not substitute for carbonate inside the interlayers of the GR. Moreover, iron phosphates did not appear, neither during the oxidation of GR(CO 32-) in the presence of oxygen nor in anoxic conditions.

Cyclic Oxidation of FeCrAlY/Al2O3 Composites

NASA Technical Reports Server (NTRS)

Nesbitt, James A.; Draper, Susan L.; Barrett, Charles A.

1999-01-01

Three-ply FeCrAlY/Al2O3 composites and FeCrAlY matrix-only samples were cyclically oxidized at 1000 C and 1100 C for up to 1000 1-hr cycles. Fiber ends were exposed at the ends of the composite samples. Following cyclic oxidation, cracks running parallel to and perpendicular to the fibers were observed on the large surface of the composite. In addition, there was evidence of increased scale damage and spallation around the exposed fiber ends, particularly around the middle ply fibers. This damage was more pronounced at the higher temperature. The exposed fiber ends showed cracking between fibers in the outer plies, occasionally with Fe and Cr-rich oxides growing out of the cracks. Large gaps developed at the fiber/matrix interface around many of the fibers, especially those in the outer plies. Oxygen penetrated many of these gaps resulting in significant oxide formation at the fiber/matrix interface far within the composite sample. Around several fibers, the matrix was also internally oxidized showing Al2O3 precipitates in a radial band around the fibers. The results show that these composites have poor cyclic oxidation resistance due to the CTE mismatch and inadequate fiber/matrix bond strength at temperatures of 1000 C and above.

Ablation properties of carbon/carbon composites with tungsten carbide

NASA Astrophysics Data System (ADS)

Yin, Jian; Zhang, Hongbo; Xiong, Xiang; Huang, Baiyun; Zuo, Jinlv

2009-02-01

The ablation properties and morphologies of carbon/carbon (C/C) composites with tungsten carbide (WC) filaments were investigated by ablation test on an arc heater and scanning electron microscopy. And the results were compared with those without tungsten carbide (WC) filaments tested under the same conditions. It shows that there is a big difference between C/C composites with and without WC filaments on both macroscopic and microscopic ablation morphologies and the ablation rates of the former are higher than the latter. It is found that the ablation process of C/C composites with WC filaments includes oxidation of carbon fibers, carbon matrices and WC, melting of WC and WO 3, and denudation of WC, WO 3 and C/C composites. Oxidation and melting of WC leads to the formation of holes in z directional carbon fiber bundles, which increases the coarseness of the ablation surfaces of the composites, speeds up ablation and leads to the higher ablation rate. Moreover, it is further found that the molten WC and WO 3 cannot form a continuous film on the ablation surface to prevent further ablation of C/C composites.

Magnetoviscoelastic characteristics of superparamagnetic oxides (Fe, Ni) based ferrofluids

NASA Astrophysics Data System (ADS)

Katiyar, Ajay; Dhar, Purbarun; Nandi, Tandra; Das, Sarit K.

2017-08-01

Ferrofluids have been popular among the academic and scientific communities owing to their intelligent physical characteristics under external stimuli and are in fact among the first nanotechnology products to be employed in real world applications. However, studies on the magnetoviscoelastic behavior of concentrated ferrofluids, especially of superparamagnetic oxides of iron and nickel are rare. The present article comprises the formulation of magneto-colloids utilizing the three various metal oxides nanoparticles viz. Iron (II, III) oxide (Fe3O4), Iron (III) oxide (Fe2O3) and Nickel oxide (NiO) in oil. Iron (II, III) oxide based colloids demonstrate high magnetoviscous characteristics over the other oxides based colloids under external magnetic fields. The maximum magnitude of yield stress and viscosity is found to be 3.0 kPa and 2.9 kPa.s, respectively for iron (II, III) oxide based colloids at 2.6 vol% particle concentration and 1.2 T magnetic field. Experimental investigations reveal that the formulated magneto-nanocolloids are stable, even in high magnetic fields and almost reversible when exposed to rising and drop of magnetic fields of the same magnitude. Observations also reveal that the elastic behavior dominates over the viscous behavior with enhanced relaxation and creep characteristics under the magnetic field. The effect of temperature on viscosity and yield stress of magneto-nanocolloids under magnetic fields has also been discussed. Thus, the present findings have potential applications in various fields such as electromagnetic clutch and brakes of automotive, damping, sealing, optics, nanofinishing etc.

A method for determination of [Fe3+]/[Fe2+] ratio in superparamagnetic iron oxide

NASA Astrophysics Data System (ADS)

Jiang, Changzhao; Yang, Siyu; Gan, Neng; Pan, Hongchun; Liu, Hong

2017-10-01

Superparamagnetic iron oxide nanoparticles (SPION), as a kind of nanophase materials, are widely used in biomedical application, such as magnetic resonance imaging (MRI), drug delivery, and magnetic field assisted therapy. The magnetic property of SPION has close connection with its crystal structure, namely it is related to the ratio of Fe3+ and Fe2+ which form the SPION. So a simple way to determine the content of the Fe3+ and Fe2+ is important for researching the property of SPION. This review covers a method for determination of the Fe3+ and Fe2+ ratio in SPION by UV-vis spectrophotometry based the reaction of Fe2+ and 1,10-phenanthroline. The standard curve of Fe with R2 = 0.9999 is used for determination the content of Fe2+ and total iron with 2.5 mL 0.01% (w/v) SPION digested by HCl, pH = 4.30 HOAc-NaAc buffer 10 mL, 0.01% (w/v) 1,10-phenanthroline 5 mL and 10% (w/v) ascorbic acid 1 mL for total iron determine independently. But the presence of Fe3+ interfere with obtaining the actual value of Fe2+ (the error close to 9%). We designed a calibration curve to eliminate the error by devising a series of solution of different ratio of [Fe3+]/[Fe2+], and obtain the calibration curve. Through the calibration curve, the error between the measured value and the actual value can be reduced to 0.4%. The R2 of linearity of the method is 0.99441 and 0.99929 for Fe2+ and total iron respectively. The error of accuracy of recovery and precision of inter-day and intra-day are both lower than 2%, which can prove the reliability of the determination method.

Formation of silicon carbide by laser ablation in graphene oxide-N-methyl-2-pyrrolidone suspension on silicon surface

NASA Astrophysics Data System (ADS)

Jaleh, Babak; Ghasemi, Samaneh; Torkamany, Mohammad Javad; Salehzadeh, Sadegh; Maleki, Farahnaz

2018-01-01

Laser ablation of a silicon wafer in graphene oxide-N-methyl-2-pyrrolidone (GO-NMP) suspension was carried out with a pulsed Nd:YAG laser (pulse duration = 250 ns, wavelength = 1064 nm). The surface of silicon wafer before and after laser ablation was studied using optical microscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). The results showed that the ablation of silicon surface in liquid by pulsed laser was done by the process of melt expulsion under the influence of the confined plasma-induced pressure or shock wave trapped between the silicon wafer and the liquid. The X-ray diffraction‌ (XRD) pattern of Si wafer after laser ablation showed that 4H-SiC layer is formed on its surface. The formation of the above layer was also confirmed by Raman spectroscopy, and X-ray photoelectron spectroscopy‌ (XPS), as well as EDX was utilized. The reflectance of samples decreased with increasing pulse energy. Therefore, the morphological alteration and the formation of SiC layer at high energy increase absorption intensity in the UV‌-vis regions. Theoretical calculations confirm that the formation of silicon carbide from graphene oxide and silicon wafer is considerably endothermic. Development of new methods for increasing the reflectance without causing harmful effects is still an important issue for crystalline Si solar cells. By using the method described in this paper, the optical properties of solar cells can be improved.

Microbial mediated iron redox cycling in Fe (hydr)oxides for nitrite removal.

PubMed

Lu, Yongsheng; Xu, Lu; Shu, Weikang; Zhou, Jizhi; Chen, Xueping; Xu, Yunfeng; Qian, Guangren

2017-01-01

Nitrite, at an environmentally relevant concentration, was significantly reduced with iron (hydr)oxides mediated by Shewanella oneidensis MR-1. The average nitrite removal rates of 1.28±0.08 and 0.65±0.02(mgL -1 )h -1 were achieved with ferrihydrite and magnetite, respectively. The results showed that nitrite removal was able to undergo multiple redox cycles with iron (hydr)oxides mediated by Shewanella oneidensis MR-1. During the bioreduction of the following cycles, biogenic Fe(II) was subsequently chemically oxidized to Fe(III), which is associated with nitrite reduction. There was 11.18±1.26mgL -1 of NH 4 + -N generated in the process of redox cycling of ferrihydrite. Additionally, results obtained by using X-ray diffraction showed that ferrihydrite and magnetite remained mainly stable in the system. This study indicated that redox cycling of Fe in iron (hydr)oxides was a potential process associated with NO 2 - -N removal from solution, and reduced most nitrite abiotically to gaseous nitrogen species. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fe/Al synergy in Fe(2)O(3) nanoparticles supported on porous aluminosilicate materials: excelling activities in oxidation reactions.

PubMed

Mariana Balu, Alina; Pineda, Antonio; Yoshida, Kenta; Manuel Campelo, Juan; Gai, Pratibha L; Luque, Rafael; Angel Romero, Antonio

2010-11-07

A synergetic Fe-Al effect in Fe(2)O(3) nanoparticles supported on mesoporous aluminosilicates compared to pure siliceous silicates has been demonstrated, for the first time, by a remarkably superior catalytic activity of the former in the microwave-assisted selective oxidation of benzyl alcohol to benzaldehyde. This significant finding, that also deeply influences the acidity of the materials (increasing total and particularly Lewis acidity), can have important consequences in the improved efficiency of these systems in related oxidations as well as in acid catalysed processes.

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.

Ethylene Epoxidation with Nitrous Oxide over Fe-BTC Metal-Organic Frameworks: A DFT Study.

PubMed

Maihom, Thana; Choomwattana, Saowapak; Wannakao, Sippakorn; Probst, Michael; Limtrakul, Jumras

2016-11-04

The epoxidation of ethylene with N 2 O over the metal-organic framework Fe-BTC (BTC=1,3,5-benzentricarboxylate) is investigated by means of density functional calculations. Two reaction paths for the production of ethylene oxide or acetaldehyde are systematically considered in order to assess the efficiency of Fe-BTC for the selective formation of ethylene oxide. The reaction starts with the decomposition of N 2 O to form an active surface oxygen atom on the Fe site of Fe-BTC, which subsequently reacts with an ethylene molecule to form an ethyleneoxy intermediate. This intermediate can then be selectively transformed either by 1,2-hydride shift into the undesired product acetaldehyde or into the desired product ethylene oxide by way of ring closure of the intermediate. The production of ethylene oxide requires an activation energy of 5.1 kcal mol -1 , which is only about one-third of the activation energy of acetaldehyde formation (14.3 kcal mol -1 ). The predicted reaction rate constants for the formation of ethylene oxide in the relevant temperature range are approximately 2-4 orders of magnitude higher than those for acetaldehyde. Altogether, the results suggest that Fe-BTC is a good candidate catalyst for the epoxidation of ethylene by molecular N 2 O. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Organic Substances on the Efficiency of Fe(Ii) to Fe(Iii) Oxidation and Removal of Iron Compounds from Groundwater in the Sedimentation Process

NASA Astrophysics Data System (ADS)

Krupińska, Izabela

2017-09-01

One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3). The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D). It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot]), efficiency of Fe(II) to Fe(III) oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII) when used as an oxidizing agent. The application of potassium manganate (VII) for oxidation of Fe(II) ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.

Micro/nanostructured porous Fe-Ni binary oxide and its enhanced arsenic adsorption performances.

PubMed

Liu, Shengwen; Kang, Shenghong; Wang, Guozhong; Zhao, Huijun; Cai, Weiping

2015-11-15

A simple method is presented to synthesize micro/nano-structured Fe-Ni binary oxides based on co-precipitation and subsequent calcination. It has been found that the Fe-Ni binary oxides are composed of the porous microsized aggregates built with nanoparticles. When the atomic ratio of Fe to Ni is 2 to 1 the binary oxide is the micro-scaled aggregates consisting of the ultrafine NiFe2O4 nanoparticles with 3-6nm in size, and shows porous structure with pore diameter of 3nm and a specific surface area of 245m(2)g(-1). Such material is of abundant surface functional groups and has exhibited high adsorption performance to As(III) and As(V). The kinetic adsorption can be described by pseudo-second order model and the isothermal adsorption is subject to Langmuir model. The maximum adsorption capacity on such Fe-Ni porous binary oxide is up to 168.6mgg(-1) and 90.1mgg(-1) for As(III) and As(V), respectively, which are much higher than the arsenic adsorption capacity for most commercial adsorbents. Such enhanced adsorption ability for this material is mainly attributed to its porous structure and high specific surface area as well as the abundant surface functional groups. Further experiments have revealed that the influence of the anions such as sulfate, carbonate, and phosphate, which commonly co-exist in water, on the arsenic adsorption is insignificant, exhibiting strong adsorption selectivity to arsenic. This micro/nano-structured porous Fe-Ni binary oxide is hence of good practicability to be used as a highly efficient adsorbent for arsenic removal from the real arsenic-contaminated waters. Copyright © 2015 Elsevier Inc. All rights reserved.

Petrography and trace element signatures in silicates and Fe-Ti-oxides from the Lanjiahuoshan deposit, Panzhihua layered intrusion, Southwest China

NASA Astrophysics Data System (ADS)

Gao, Wenyuan; Ciobanu, Cristiana L.; Cook, Nigel J.; Huang, Fei; Meng, Lin; Gao, Shang

2017-12-01

Permian mafic-ultramafic layered intrusions in the central part of the Emeishan Large Igneous Province (ELIP), Southwestern China, host Fe-Ti-V-oxide ores that have features which distinguish them from other large layered intrusion-hosted deposits. The origin of these ores is highly debated. Careful petrographic examination, whole rock analysis, electron probe microanalysis, and measurement and mapping of trace element concentrations by laser ablation inductively coupled plasma mass spectrometry in all major and minor minerals (clinopyroxene, plagioclase, olivine, amphibole, titanomagnetite, ilmenite, pleonaste and pyrrhotite) has been undertaken on samples from the Lanjiahuoshan deposit, representing the Middle, Lower and Marginal Zone of the Panzhihua intrusion. Features are documented that impact on interpretation of intrusion petrology and with implications for genesis of the Fe-Ti-V-oxide ores. Firstly, there is evidence, as symplectites between clinopyroxene and plagioclase, for introduction of complex secondary melts. Secondly, reaction between a late hydrothermal fluid and clinopyroxene is recognized, which has led to formation of hydrated minerals (pargasite, phlogopite), as well as a potassium metasomatic event, postdating intrusion solidification, which led to formation of K-feldspar. Lastly, partitioning of trace elements between titanomagnetite and silicates needs to consider scavenging of metals by ilmenite (Mn, Sc, Zr, Nb, Sn, Hf and Ta) and sulfides, as well as the marked partitioning of Co, Ni, Zn, Ga, As and Sb into spinels exsolved from titanomagnetite. The role of these less abundant phases may have been understated in previous studies, highlighting the importance of petrographic examination of complex silicate-oxide-sulfide assemblages, as well as the need for a holistic approach to trace element analysis, acknowledging all minerals within the assemblage.

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

Ablation-resistant carbide Zr0.8Ti0.2C0.74B0.26 for oxidizing environments up to 3,000 °C

NASA Astrophysics Data System (ADS)

Zeng, Yi; Wang, Dini; Xiong, Xiang; Zhang, Xun; Withers, Philip J.; Sun, Wei; Smith, Matthew; Bai, Mingwen; Xiao, Ping

2017-06-01

Ultra-high temperature ceramics are desirable for applications in the hypersonic vehicle, rockets, re-entry spacecraft and defence sectors, but few materials can currently satisfy the associated high temperature ablation requirements. Here we design and fabricate a carbide (Zr0.8Ti0.2C0.74B0.26) coating by reactive melt infiltration and pack cementation onto a C/C composite. It displays superior ablation resistance at temperatures from 2,000-3,000 °C, compared to existing ultra-high temperature ceramics (for example, a rate of material loss over 12 times better than conventional zirconium carbide at 2,500 °C). The carbide is a substitutional solid solution of Zr-Ti containing carbon vacancies that are randomly occupied by boron atoms. The sealing ability of the ceramic's oxides, slow oxygen diffusion and a dense and gradient distribution of ceramic result in much slower loss of protective oxide layers formed during ablation than other ceramic systems, leading to the superior ablation resistance.

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.

Mössbauer study of oxide films of Fe-, Sn-, Cr- doped zirconium alloys during corrosion in autoclave

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Bateev, A. B.; Lauer, Yu. A.

2016-12-01

Mössbauer investigations were used to compare iron atom states in oxide films of binary Zr-Fe, ternary Zr-Fe-Cu and quaternary Zr-Fe-Cr-Sn alloys. Oxide films are received in an autoclave at a temperature of 350-360 °C and at pressure of 16.8 MPa. The corrosion process decomposes the intermetallic precipitates in alloys and forms metallic iron with inclusions of chromium atoms α-Fe(Cr), α-Fe(Cu), α-Fe 2O3 and Fe 3O4 compounds. Some iron ions are formed in divalent and in trivalent paramagnetic states. The additional doping influences on corrosion kinetics and concentration of iron compounds and phases formed in oxide films. It was shown the correlation between concentration of iron in different chemical states and corrosion resistance of alloys.

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.

Artificial meteor ablation studies: Olivine

NASA Technical Reports Server (NTRS)

Blanchard, M. B.; Cunningham, G. G.

1973-01-01

Artificial meteor ablation was performed on a Mg-rich olivine sample using an arc-heated plasma of ionized air. Experimental conditions simulated a meteor traveling about 12 km/sec at an altitude of 70 km. The mineral content of the original olivine sample was 98% olivine (including traces of olivine alteration products) and 2% chromite. Forsterite content of the original olivine was Fo-89. After ablation, the forsterite content had increased to Fo-94 in the recrystallized olivine. In addition, lamella-like intergrowths of magnetite were prevalent constituents. Wherever magnetite occurred, there was an increase in Mg and a corresponding decrease in Fe for the recrystallized olivine. The Allende fusion crust consisted of a recrystallized olivine, which was more Mg-rich and Fe-deficient than the original meteorite's olivine, and abundant magnetite grains. Although troilite and pentlandite were the common opaque mineral constituents in this meteorite, magnetite was the principal opaque mineral found in the fusion crust.

Oxidation behaviour of Fe-Ni alloy nanoparticles synthesized by thermal plasma route

NASA Astrophysics Data System (ADS)

Ghodke, Neha; Kamble, Shalaka; Raut, Suyog; Puranik, Shridhar; Bhoraskar, S. V.; Rayaprol, Sudhindra; Mathe, V. L.

2018-04-01

Here we report synthesis of Fe-Ni nanoparticles using thermal plasma route. In thermal plasma, gas phase nucleation and growth at sufficiently higher temperature is observed. The synthesized Fe-Ni nanoparticles are examined by X-ray Diffraction, Raman Spectroscopy, Vibrating Sample Magnetometer and Thermo gravimetric Analysis. Formation of 16-21 nm sized Fe-Ni nanoparticles having surface oxidation show maximum value of magnetization of ˜107 emu/g. The sample synthesized at relatively low power (4kW) show presence of carbonaceous species whereas the high power (6 kW) synthesis does not depicts carbonaceous species. The presence of carbonaceous species protects oxidation of the nanoparticles significantly as evidenced from TGA data.

Iron and Arsenic Speciation During As(III) Oxidation by Manganese Oxides in the Presence of Fe(II): Molecular-Level Characterization Using XAFS, Mössbauer, and TEM Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yun; Kukkadapu, Ravi K.; Livi, Kenneth J. T.

The redox state and speciation of metalloid arsenic (As) determine its toxicity and mobility. Knowledge of biogeochemical processes influencing the As redox state is therefore important to understand and predict its environmental behavior. Many previous studies examined As(III) oxidation by various Mn-oxides, but little is known the environmental influences (e.g. co-existing ions) on such process. In this study, we investigated the mechanisms of As(III) oxidation by a poorly crystalline hexagonal birnessite (δ-MnO2) in the presence of Fe(II) using X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy and transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDS). As K-edge X-ray absorption nearmore » edge spectroscopy (XANES) analysis revealed that, at low Fe(II) concentration (100 μM), As(V) was the predominant As species on the solid phase, while at higher Fe(II) concentration (200-1000 μM), both As(III) and As(V) were sorbed on the solid phase. As K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) analysis showed an increasing As-Mn/Fe distance over time, indicating As prefers to bind with the newly formed Fe(III)-(hydr)oxides. As adsorbed on Fe(III)-(hydr)oxides as a bidentate binuclear corner-sharing complex. Both Mössbauer and TEM-EDS investigations demonstrated that the oxidized Fe(III) products formed during Fe(II) oxidation by δ-MnO2 were predominantly ferrihydrite, goethite, and ferric arsenate like compounds. However, Fe EXAFS analysis also suggested the formation of a small amount of lepidocrocite. The Mn K-edge XANES data indicated that As(III) and Fe(II) oxidation occurs as a two electron transfer with δ-MnO2 and the observed Mn(III) is due to conproportionation of surface sorbed Mn(II) with Mn(IV) in δ-MnO2 structure. This study reveals that the mechanisms of As(III) oxidation by δ-MnO2 in the presence of Fe(II) are very complex, involving many simultaneous reactions, and the

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.

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.

Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe 5O 6

DOE PAGES

Lavina, Barbara; Meng, Yue

2015-06-26

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 Fe 4O 5, iron oxides were assumed to comprise only the polymorphs of FeO, Fe 3O 4, and Fe 2O 3. Combining synthesis at high pressure and temperature with micro- diffraction mapping, we have identified yet another distinct iron oxide, Fe 5O 6. The new compound, which has an orthorhombic structure, was obtained in themore » 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 Fe 5O 6, Fe 4O 5, and h-Fe 3O 4 display similar iron coordination geometries and structural arrangements, and indeed exhibit coherent systematic behavior of crystallographic parameters and compressibility. Fe 5O 6, along with FeO and Fe 4O 5, is a candidate key minor phase of planetary interiors; as such, it is of major petrological and geo- chemical importance. Here, we are revealing an unforeseen complexity in the Fe-O system with four different compounds—FeO, Fe 5O 6, Fe 4O 5, and h-Fe 3O 4—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.« less

The Cross-Sectional Investigation of Oxide Scale FeCr Alloys and Commercial Ferritic Steel Implanted with Lanthanum and Titanium Dopants after Oxidation Test at 900°C

NASA Astrophysics Data System (ADS)

Saryanto, Hendi; Sebayang, Darwin; Untoro, Pudji; Sujitno, Tjipto

2018-03-01

The cross-sectional examinations of oxide scales formed by oxidation on the surface of FeCr alloys and Ferritic Steel that implanted with lanthanum and titanium dopants were observed and investigated. Scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS) has been used to study the cross-sectional oxides produced by specimens after oxidation process. X-ray diffraction (XRD) analysis was used to strengthen the analysis of the oxide scale morphology, oxide phases and oxidation products. Cross-sectional observations show the effectiveness of La implantation for improving thinner and stronger scale/substrate interface during oxidation process. The result shows that the thickness of oxide scales formed on the surface of La implanted FeCr alloy and ferritic steel was found less than 3 μm and 300 μm, respectively. The oxide scale formed on the surface of La implanted specimens consisted roughly of Cr2O3 with a small amount of FeO mixture, which indicates that lanthanum implantation can improve the adherence, reduce the growth of the oxide scale as well as reduce the Cr evaporation. On the other side, the oxide scale formed on the surface of FeCr alloys and ferritic steel that implanted with titanium dopant was thicker, indicating that significant increase in oxidation mass gain. It can be noticed that titanium implantation ineffectively promotes Cr rich oxide. At the same time, the amount of Fe increased and diffused outwards, which caused the formation and rapid growth of FeO.

Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

NASA Astrophysics Data System (ADS)

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as

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.

Microwave absorbing performance enhancement of Fe75Si15Al10 composites by selective surface oxidation

NASA Astrophysics Data System (ADS)

Zhang, Nan; Wang, Xin; Liu, Tao; Xie, Jianliang; Deng, Longjiang

2017-09-01

An excessively large dielectric constant is a challenge to improve the performances of the Fe-based absorbing material. Here, we propose a selective surface oxidation method to reduce the permittivity without sacrificing the permeability, by annealing under 5%H2—95%N2 (H2/N2). It is found that a thin layer of aluminum and silicon oxides formed on the surface of Fe75Si15Al10 particles during annealing in the range of 500-780 °C under H2/N2, thereby leading to an obvious decrease of permittivity of the Fe75Si15Al10 composite. According to Gibbs free energy, aluminum and silicon oxides are formed and iron oxides are reduced during annealing under H2/N2 at above 500 °C. Interestingly, the XPS result shows that the atomic ratio of Fe decreases significantly on the particle surface, which infers that the reduced Fe atoms diffuse to the interior of the particles. The surface oxide layer can protect the inner part of the alloy from further oxidation, which contributes to a high permeability. Meanwhile, the XRD result shows the formation of DO3-type ordering, which leads to the promotion of permeability. The two reasons lead to the improvement of permeability of the Fe75Si15Al10 composite after annealing. The composite is confirmed to have high permeability and low permittivity, exhibiting better electromagnetic wave absorption properties.

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

Ordered Fe(II)Ti(IV)O3 Mixed Monolayer Oxide on Rutile TiO2(011).

PubMed

Halpegamage, Sandamali; Ding, Pan; Gong, Xue-Qing; Batzill, Matthias

2015-08-25

Oxide monolayers supported or intermixed with an oxide support are potential nanocatalysts whose properties are determined by the interplay with the support. For fundamental studies of monolayer oxides on metal oxide supports, well-defined systems are needed, but so far, the synthesis of monolayer oxides with long-range order on single-crystal oxide surfaces is rare. Here, we show by a combination of scanning tunneling microscopy, photoemission spectroscopy, and density functional theory (DFT)-based computational analysis that the rutile TiO2(011) surface supports the formation of an ordered mixed FeTiO3 monolayer. Deposition of iron in a slightly oxidizing atmosphere (10(-8) Torr O2) and annealing to 300 °C results in a well-ordered surface structure with Fe in a 2+ charge state and Ti in a 4+ charge states. Low-energy ion scattering suggests that the cation surface composition is close to half Fe and half Ti. This surface is stable in ultrahigh vacuum to annealing temperatures of 300 °C before the iron is reduced. DFT simulations confirm that a surface structure with coverage of 50% FeO units is stable and forms an ordered structure. Although distinct from known bulk phases of the iron-titanium oxide systems, the FeTiO3 monolayer exhibits some resemblance to the ilmenite structure, which may suggest that a variety of different mixed oxide phases (of systems that exist in a bulk ilmenite phase) may be synthesized in this way on the rutile TiO2(011) substrate.

Novel mesoporous FeAl bimetal oxides for As(III) removal: Performance and mechanism.

PubMed

Ding, Zecong; Fu, Fenglian; Cheng, Zihang; Lu, Jianwei; Tang, Bing

2017-02-01

In this study, novel mesoporous FeAl bimetal oxides were successfully synthesized, characterized, and employed for As(III) removal. Batch experiments were conducted to investigate the effects of Fe/Al molar ratio, dosage, and initial solution pH values on As(III) removal. The results showed that the FeAl bimetal oxide with Fe/Al molar ratio 4:1 (shorten as FeAl-4) can quickly remove As(III) from aqueous solution in a wide pH range. The FeAl-4 before and after reaction with As(III) was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED), Brunauer-Emmett-Teller (BET) surface area measurement, and X-ray photoelectron spectroscopy (XPS). The BET results showed that the original FeAl-4 with a high surface area of 223.9 m 2 /g was a mesoporous material. XPS analysis indicated that the surface of FeAl-4 possessed a high concentration of M-OH (where M represents Fe and Al), which was beneficial to the immobility of As(III). The excellent performance of FeAl-4 makes it a potentially attractive material for As(III) removal from aqueous solution. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Ablation-resistant carbide Zr0.8Ti0.2C0.74B0.26 for oxidizing environments up to 3,000 °C.

PubMed

Zeng, Yi; Wang, Dini; Xiong, Xiang; Zhang, Xun; Withers, Philip J; Sun, Wei; Smith, Matthew; Bai, Mingwen; Xiao, Ping

2017-06-14

Ultra-high temperature ceramics are desirable for applications in the hypersonic vehicle, rockets, re-entry spacecraft and defence sectors, but few materials can currently satisfy the associated high temperature ablation requirements. Here we design and fabricate a carbide (Zr 0.8 Ti 0.2 C 0.74 B 0.26 ) coating by reactive melt infiltration and pack cementation onto a C/C composite. It displays superior ablation resistance at temperatures from 2,000-3,000 °C, compared to existing ultra-high temperature ceramics (for example, a rate of material loss over 12 times better than conventional zirconium carbide at 2,500 °C). The carbide is a substitutional solid solution of Zr-Ti containing carbon vacancies that are randomly occupied by boron atoms. The sealing ability of the ceramic's oxides, slow oxygen diffusion and a dense and gradient distribution of ceramic result in much slower loss of protective oxide layers formed during ablation than other ceramic systems, leading to the superior ablation resistance.

Effect of SiC Content on the Ablation and Oxidation Behavior of ZrB₂-Based Ultra High Temperature Ceramic Composites.

PubMed

Hu, Ping; Gui, Kaixuan; Yang, Yang; Dong, Shun; Zhang, Xinghong

2013-04-29

The ablation and oxidation of ZrB₂-based ultra high temperature ceramic (UHTC) composites containing 10%, 15% and 30% v/v SiC were tested under different heat fluxes in a high frequency plasma wind tunnel. Performance was significantly affected by the surface temperature, which was strongly dependent on the composition. Composites containing 10% SiC showed the highest surface temperature (>2300 °C) and underwent a marked degradation under both conditions. In contrast, composites with 30% SiC exhibited the lowest surface temperature (<2000 °C) and demonstrated excellent ablation resistance. The surface temperature of UHTCs in aerothermal testing was closely associated with the dynamic evolution of the surface and bulk oxide properties, especially for the change in chemical composition on the exposed surface, which was strongly dependent on the material composition and testing parameters ( i.e. , heat flux, enthalpy, pressure and test time), and in turn affected its oxidation performance.

Evidence of a reduction reaction of oxidized iron/cobalt by boron atoms diffused toward naturally oxidized surface of CoFeB layer during annealing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sato, Soshi, E-mail: sato.soshi@cies.tohoku.ac.jp; Honjo, Hiroaki; Niwa, Masaaki

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.more » 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.« less

Biological Oxidation of Fe(II) in Reduced Nontronite Coupled with Nitrate Reduction by Pseudogulbenkiania sp. Strain 2002

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.

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. Themore » 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.« less

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

USGS Publications Warehouse

Caccavo, F.; 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.

Selective Internal Oxidation and Severe Plastic Deformation of Multiphase Fe-Y Alloys

NASA Astrophysics Data System (ADS)

Kachur, Stephen J.

Oxide dispersion strengthened (ODS) alloys are known for their desirable mechanical properties and unique microstructures. These alloys are characterized by an even dispersion of oxide phase throughout a metallic matrix, and exhibit high strength and enhanced creep properties at elevated temperatures. This makes them ideal candidate materials for use in many structural applications, such as coal-fired power plants or in next generation nuclear reactors. Currently most often produced by mechanical alloying, a powder metallurgy based process that utilizes high energy ball milling, these alloys are difficult and costly to produce. One proposed method for forming ODS alloys without high-energy ball milling is to internally oxidize a bulk alloy before subjecting it to severe plastic deformation to induce an even oxide distribution. This work examines such a processing scheme with a focus on the internal oxidation behavior. Internal oxidation has been shown to occur orders of magnitude faster than expected in multi-phase alloys where a highly reactive oxidizable solute has negligible solubility and diffusivity in other, more-noble, phases. Commonly referred to as in situ oxidation, this accelerated oxidation process has potential for use in a processing scheme for ODS alloys. While in situ oxidation has been observed in many different alloy systems, a comprehensive study of alloy composition and microstructure has not been performed to describe the unusual oxidation rates. This work used Fe-Y binary alloys as model system to study effects of composition and microstructure. These alloys have been shown to exhibit in situ oxidation, and additionally, Y is typically introduced during mechanical alloying to form Y-rich oxides in Fe-based ODS alloys. Alloys with Y content between 1.5 and 15 wt% were prepared using a laboratory scale arc-melting furnace. These alloys were two phase mixtures of Fe and Fe17Y2. First, samples were oxidized between 600 and 800 °C for 2 to 72

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.

Synthesis of α-Fe2O3 and Fe-Mn Oxide Foams with Highly Tunable Magnetic Properties by the Replication Method from Polyurethane Templates

PubMed Central

Feng, Yuping; Fornell, Jordina; Zhang, Huiyan; Solsona, Pau; Barό, Maria Dolors; Suriñach, Santiago; Sort, Jordi

2018-01-01

Open cell foams consisting of Fe and Fe-Mn oxides are prepared from metallic Fe and Mn powder precursors by the replication method using porous polyurethane (PU) templates. First, reticulated PU templates are coated by slurry impregnation. The templates are then thermally removed at 260 °C and the debinded powders are sintered at 1000 °C under N2 atmosphere. The morphology, structure, and magnetic properties are studied by scanning electron microscopy, X-ray diffraction and vibrating sample magnetometry, respectively. The obtained Fe and Fe-Mn oxide foams possess both high surface area and homogeneous open-cell structure. Hematite (α-Fe2O3) foams are obtained from the metallic iron slurry independently of the N2 flow. In contrast, the microstructure of the FeMn-based oxide foams can be tailored by adjusting the N2 flow. While the main phases for a N2 flow rate of 180 L/h are α-Fe2O3 and FeMnO3, the predominant phase for high N2 flow rates (e.g., 650 L/h) is Fe2MnO4. Accordingly, a linear magnetization versus field behavior is observed for the hematite foams, while clear hysteresis loops are obtained for the Fe2MnO4 foams. Actually, the saturation magnetization of the foams containing Mn increases from 5 emu/g to 52 emu/g when the N2 flow rate (i.e., the amount of Fe2MnO4) is increased. The obtained foams are appealing for a wide range of applications, such as electromagnetic absorbers, catalysts supports, thermal and acoustic insulation systems or wirelessly magnetically-guided porous objects in fluids. PMID:29439450

Characterization of Fe(II) oxidizing bacterial activities and communities at two acidic Appalachian coalmine drainage-impacted sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Senko, John M.; Wanjugi, Pauline; Lucas, Melanie

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 intergenicmore » 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.« less

Nitric oxide removal by combined urea and FeIIEDTA reaction systems.

PubMed

He, Feiqiang; Deng, Xianhe; Chen, Min

2017-02-01

(NH 2 ) 2 CO as well as Fe II EDTA is an absorbent for simultaneous desulfurization and denitrification. However, they have their own drawbacks, like the oxidation of Fe II EDTA and the low solubility of NO in urea solution. To overcome these defects, A mixed absorbent containing both (NH 2 ) 2 CO and Fe II EDTA was employed. The effects of various operating parameters (urea and Fe II EDTA concentration, temperature, inlet oxygen concentration, pH value) on NO removal were examined in the packed tower. The results indicated that the NO removal efficiency increased with the decrease of oxygen concentration as well as the increase of Fe II EDTA concentration. The NO removal efficiency had little change with a range of 25-45 °C, and sharply decreased at the temperature of above 55 °C. The NO removal efficiency initially increases up to the maximum value and then decreases with the increase of pH value as well as the raise of urea concentration. In addition, the synergistic mechanism of (NH 2 ) 2 CO and Fe II EDTA on NO removal was investigated. Results showed that urea could react with Fe II EDTA-NO to produce Fe II EDTA, N 2 , and CO 2 , and hinder oxidation of Fe II EDTA. Finally, to evaluate the effect of SO 3 2- on NO removal, a mixed absorbent containing Fe II EDTA, urea, and Na 2 SO 3 was employed to absorb NO. The mixed absorbent could maintain more than 78% for 80 min at 25 °C, pH = 7.0, (NH 2 ) 2 CO concentration of 5 wt%, Fe II EDTA concentration of 0.02 M, O 2 concentration of 7% (v/v), and Na 2 SO 3 concentration of 0.2 M. Copyright © 2016 Elsevier Ltd. All rights reserved.

Nonstoichiometric Titanium Oxides via Pulsed Laser Ablation in Water.

PubMed

Huang, Chang-Ning; Bow, Jong-Shing; Zheng, Yuyuan; Chen, Shuei-Yuan; Ho, Newjin; Shen, Pouyan

2010-04-13

Titanium oxide compounds TiO,Ti2O3, and TiO2 with a considerable extent of nonstoichiometry were fabricated by pulsed laser ablation in water and characterized by X-ray/electron diffraction, X-ray photoelectron spectroscopy and electron energy loss spectroscopy. The titanium oxides were found to occur as nanoparticle aggregates with a predominant 3+ charge and amorphous microtubes when fabricated under an average power density of ca. 1 × 108W/cm2 and 1011W/cm2, respectively followed by dwelling in water. The crystalline colloidal particles have a relatively high content of Ti2+ and hence a lower minimum band gap of 3.4 eV in comparison with 5.2 eV for the amorphous state. The protonation on both crystalline and amorphous phase caused defects, mainly titanium rather than oxygen vacancies and charge and/or volume-compensating defects. The hydrophilic nature and presumably varied extent of undercoordination at the free surface of the amorphous lamellae accounts for their rolling as tubes at water/air and water/glass interfaces. The nonstoichiometric titania thus fabricated have potential optoelectronic and catalytic applications in UV-visible range and shed light on the Ti charge and phase behavior of titania-water binary in natural shock occurrence.

Nonstoichiometric Titanium Oxides via Pulsed Laser Ablation in Water

PubMed Central

2010-01-01

Titanium oxide compounds TiO,Ti2O3, and TiO2 with a considerable extent of nonstoichiometry were fabricated by pulsed laser ablation in water and characterized by X-ray/electron diffraction, X-ray photoelectron spectroscopy and electron energy loss spectroscopy. The titanium oxides were found to occur as nanoparticle aggregates with a predominant 3+ charge and amorphous microtubes when fabricated under an average power density of ca. 1 × 108W/cm2 and 1011W/cm2, respectively followed by dwelling in water. The crystalline colloidal particles have a relatively high content of Ti2+ and hence a lower minimum band gap of 3.4 eV in comparison with 5.2 eV for the amorphous state. The protonation on both crystalline and amorphous phase caused defects, mainly titanium rather than oxygen vacancies and charge and/or volume-compensating defects. The hydrophilic nature and presumably varied extent of undercoordination at the free surface of the amorphous lamellae accounts for their rolling as tubes at water/air and water/glass interfaces. The nonstoichiometric titania thus fabricated have potential optoelectronic and catalytic applications in UV–visible range and shed light on the Ti charge and phase behavior of titania-water binary in natural shock occurrence. PMID:20672115

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.

Magnetic characteristics of ultrafine Fe particles reduced from uniform iron oxide particles

NASA Astrophysics Data System (ADS)

Bridger, K.; Watts, J.; Tadros, M.; Xiao, Gang; Liou, S. H.; Chien, C. L.

1987-04-01

Uniform, cubic 0.05-μm iron oxide particles were formed by forced hydrolysis of ferric perchlorate. These particles were reduced to α-Fe by heating in hydrogen at temperatures between 300 and 500 °C. The effect of reduction temperature and various prereduction treatments on the microstructure of the iron particles will be discussed. Complete reduction to α-Fe was established by 57Fe Mössbauer spectroscopy and x-ray diffraction. Magnetic measurements on epoxy and polyurethane films containing these particles with various mass fractions gave coercivities as high as 1000 Oe. The relationship between the magnetic measurements and the microstructure will be discussed. Na2SiO3 is found to be the best coating material for the process of reducing iron oxide particles to iron.

Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

PubMed

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides

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

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

Similarities and differences in ablative and non-ablative iron oxide nanoparticle hyperthermia cancer treatment

NASA Astrophysics Data System (ADS)

Petryk, Alicia A.; Misra, Adwiteeya; Kastner, Elliot J.; Mazur, Courtney M.; Petryk, James D.; Hoopes, P. Jack

2015-03-01

The use of hyperthermia to treat cancer is well studied and has utilized numerous delivery techniques, including microwaves, radio frequency, focused ultrasound, induction heating, infrared radiation, warmed perfusion liquids (combined with chemotherapy), and recently, metallic nanoparticles (NP) activated by near infrared radiation (NIR) and alternating magnetic field (AMF) based platforms. It has been demonstrated by many research groups that ablative temperatures and cytotoxicity can be produced with locally NP-based hyperthermia. Such ablative NP techniques have demonstrated the potential for success. Much attention has also been given to the fact that NP may be administered systemically, resulting in a broader cancer therapy approach, a lower level of tumor NP content and a different type of NP cancer therapy (most likely in the adjuvant setting). To use NP based hyperthermia successfully as a cancer treatment, the technique and its goal must be understood and utilized in the appropriate clinical context. The parameters include, but are not limited to, NP access to the tumor (large vs. small quantity), cancer cell-specific targeting, drug carrying capacity, potential as an ionizing radiation sensitizer, and the material properties (magnetic characteristics, size and charge). In addition to their potential for cytotoxicity, the material properties of the NP must also be optimized for imaging, detection and direction. In this paper we will discuss the differences between, and potential applications for, ablative and non-ablative magnetic nanoparticle hyperthermia.

Oxidative removal of Mn(II) from solution catalysed by the γ-FeOOH (lepidocrocite) surface

NASA Astrophysics Data System (ADS)

Sung, Windsor; Morgan, James J.

1981-12-01

A laboratory study was undertaken to ascertain the role of surface catalysis in Mn(II) oxidative removal. γ-FeOOH, a ferric oxyhydroxide formed by O2 oxidation of ferrous iron in solution, was studied in the following ways: surface charge characteristics by acid base titration, adsorption of Mn(II) and surface oxidation of Mn(II). A rate law was formulated to account for the effects of pH and the amount of surface on the surface oxidation rate of Mn(II). The presence of milli-molar levels of γ-FeOOH was shown to reduce significantly the half-life of Mn(II) in 0.7 M NaCl from hundreds of hours to hours. The numerical values of the surface rate constants for the γ-FeOOH and that reported for colloidal MnO2 are comparable in order of magnitude.

Analysis of ablation debris from natural and artificial iron meteorites

NASA Technical Reports Server (NTRS)

Blanchard, M. B.; Davis, A. S.

1977-01-01

Artificial ablation studies were performed on iron and nickel-iron samples using an arc-heated plasma of ionized air. Experiment conditions simulated a meteoroid traveling about 12 km/sec at an altitude of 70 km. The artificially produced fusion crusts and ablation debris show features very similar to natural fusion crusts of the iron meteorites Boguslavka, Norfork, and N'Kandhla and to magnetic spherules recovered from Mn nodules. X-ray diffraction, electron microprobe, optical, and scanning electron microscope analyses reveal that important mineralogical, elemental, and textural changes occur during ablation. Some metal is melted and ablated. The outer margin of the melted rind is oxidized and recrystallizes as a discontinuous crust of magnetite and wustite. Adjacent to the oxidized metallic ablation zone is an unoxidized metallic ablation zone in which structures such as Widmannstatten bands are obliterated as the metal is transformed to unequilibrated alpha 2 nickel-iron. Volatile elements are vaporized and less volatile elements undergo fractionation.

Kineococcus radiotolerans Dps forms a heteronuclear Mn-Fe ferroxidase center that may explain the Mn-dependent protection against oxidative stress.

PubMed

Ardini, Matteo; Fiorillo, Annarita; Fittipaldi, Maria; Stefanini, Simonetta; Gatteschi, Dante; Ilari, Andrea; Chiancone, Emilia

2013-06-01

The ferroxidase center of DNA-binding protein from starved cells (Dps) is a major player in the iron oxidation/detoxification process that leads to a decreased reactive oxygen species production. The possible Mn(II) participation in this process has been studied in Dps from Kineococcus radiotolerans, a radiation-resistant bacterium with a high cytosolic Mn/Fe ratio and a high capacity to survive ionizing and stress conditions. The X-ray structure of recombinant K. radiotolerans Dps loaded with Mn(II) has been solved at 2.0Å resolution. Mn(II) binding to K. radiotolerans Dps and its effect on Fe(II) oxidation have been characterized in spectroscopic measurements. In K. radiotolerans Dps, the Fe-Fe ferroxidase center can have a Mn-Fe composition. Mn(II) binds only at the high affinity, so-called A site, whereas Fe(II) binds also at the low affinity, so-called B site. The Mn-Fe and Fe-Fe centers behave distinctly upon iron oxidation by O2. A site-bound Mn(II) or Fe(II) plays a catalytic role, while B site-bound Fe(II) behaves like a substrate and can be replaced by another Fe(II) after oxidation. When H2O2 is the Fe(II) oxidant, single electrons are transferred to aromatic residues near the ferroxidase center and give rise to intra-protein radicals thereby limiting OH release in solution. The presence of the Mn-Fe center results in significant differences in the development of such intra-protein radicals. Mn(II) bound at the Dps ferroxidase center A site undergoes redox cycling provided the B site contains Fe. The results provide a likely molecular mechanism for the protective role of Mn(II) under oxidative stress conditions as it participates in redox cycling in the hetero-binuclear ferroxidase center. Copyright © 2013 Elsevier B.V. All rights reserved.

Effect of SiC Content on the Ablation and Oxidation Behavior of ZrB2-Based Ultra High Temperature Ceramic Composites

PubMed Central

Hu, Ping; Gui, Kaixuan; Yang, Yang; Dong, Shun; Zhang, Xinghong

2013-01-01

The ablation and oxidation of ZrB2-based ultra high temperature ceramic (UHTC) composites containing 10%, 15% and 30% v/v SiC were tested under different heat fluxes in a high frequency plasma wind tunnel. Performance was significantly affected by the surface temperature, which was strongly dependent on the composition. Composites containing 10% SiC showed the highest surface temperature (>2300 °C) and underwent a marked degradation under both conditions. In contrast, composites with 30% SiC exhibited the lowest surface temperature (<2000 °C) and demonstrated excellent ablation resistance. The surface temperature of UHTCs in aerothermal testing was closely associated with the dynamic evolution of the surface and bulk oxide properties, especially for the change in chemical composition on the exposed surface, which was strongly dependent on the material composition and testing parameters (i.e., heat flux, enthalpy, pressure and test time), and in turn affected its oxidation performance. PMID:28809239

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.

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

Streaming potential method for characterizing interaction of electrical double layers between rice roots and Fe/Al oxide-coated quartz in situ.

PubMed

Liu, Zhao-Dong; Wang, Hai-Cui; Li, Jiu-Yu; Xu, Ren-Kou

2017-10-01

The interaction between rice roots and Fe/Al oxide-coated quartz was investigated through zeta potential measurements and column leaching experiments in present study. The zeta potentials of rice roots, Fe/Al oxide-coated quartz, and the binary systems containing rice roots and Fe/Al oxide-coated quartz were measured by a specially constructed streaming potential apparatus. The interactions between rice roots and Fe/Al oxide-coated quartz particles were evaluated/deduced based on the differences of zeta potentials between the binary systems and the single system of rice roots. The zeta potentials of the binary systems moved in positive directions compared with that of rice roots, suggesting that there were overlapping of diffuse layers of electric double layers on positively charged Fe/Al oxide-coated quartz and negatively charged rice roots and neutralization of positive charge on Fe/Al oxide-coated quartz with negative charge on rice roots. The greater amount of positive charges on Al oxide led to the stronger interaction of Al oxide-coated quartz with rice roots and the more shift of zeta potential compared with Fe oxide. The overlapping of diffuse layers on Fe/Al oxide-coated quartz and rice roots was confirmed by column leaching experiments. The greater overlapping of diffuse layers on Al oxide and rice roots led to more simultaneous adsorptions of K + and NO 3 - and greater reduction in leachate electric conductivity when the column containing Al oxide-coated quartz and rice roots was leached with KNO 3 solution, compared with the columns containing rice roots and Fe oxide-coated quartz or quartz. When the KNO 3 solution was replaced with deionized water to flush the columns, more K + and NO 3 - were desorbed from the binary system containing Al oxide-coated quartz and rice roots than from other two binary systems, suggesting that the stronger electrostatic interaction between Al oxide and rice roots promoted the desorption of K + and NO 3 - from the binary

CO2-laser ablation of Bi-Sr-Ca-Cu oxide by millisecond pulse lengths

NASA Astrophysics Data System (ADS)

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

1990-03-01

We have achieved ablation of Bi-Sr-Ca-Cu oxide from single targets of superconducting pellets by CO2-laser pulses of l ms length to grow superconducting thin films. Upon annealing, the 6000-Å thin films have a Tc (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 cm2.

Ablation-resistant carbide Zr0.8Ti0.2C0.74B0.26 for oxidizing environments up to 3,000 °C

PubMed Central

Zeng, Yi; Wang, Dini; Xiong, Xiang; Zhang, Xun; Withers, Philip J.; Sun, Wei; Smith, Matthew; Bai, Mingwen; Xiao, Ping

2017-01-01

Ultra-high temperature ceramics are desirable for applications in the hypersonic vehicle, rockets, re-entry spacecraft and defence sectors, but few materials can currently satisfy the associated high temperature ablation requirements. Here we design and fabricate a carbide (Zr0.8Ti0.2C0.74B0.26) coating by reactive melt infiltration and pack cementation onto a C/C composite. It displays superior ablation resistance at temperatures from 2,000–3,000 °C, compared to existing ultra-high temperature ceramics (for example, a rate of material loss over 12 times better than conventional zirconium carbide at 2,500 °C). The carbide is a substitutional solid solution of Zr–Ti containing carbon vacancies that are randomly occupied by boron atoms. The sealing ability of the ceramic’s oxides, slow oxygen diffusion and a dense and gradient distribution of ceramic result in much slower loss of protective oxide layers formed during ablation than other ceramic systems, leading to the superior ablation resistance. PMID:28613275

Using Meteoric Ablation to Constrain Vertical Transport in the Upper Mesosphere

NASA Astrophysics Data System (ADS)

Plane, J. M. C.; Carrillo-Sánchez, J. D.; Nesvorny, D.; Pokorný, P.; Janches, D.

2016-12-01

Meteoric ablation injects a variety of metals into the upper mesosphere and lower thermosphere, giving rise to layers of metal atoms centered around 90 km. The Na, Fe, K and Ca atom densities are measured accurately using resonance lidars. Since the reaction kinetics of many of the chemical reactions which produce these layers have now been studied in the laboratory, chemistry modules for each of the metals have been developed with a reasonable degree of confidence. When these modules are put into a global high-top model such as NCAR's Whole Atmosphere Community Climate Model (WACCM), a major problem emerges: the injection flux of each of the metals, termed the Meteoric Input Function (MIF), has to be reduced substantially in order to model the observed metal atom densities. For instance, the Na and Fe MIFs need to be reduced by factors of 8 and 14, respectively, compared with the MIFs determined from the lidar-measured vertical fluxes of Na and Fe atoms. The accumulation of meteoric smoke particles in polar ice cores also indicates that the meteoric ablation flux is significantly larger that can be handled in models where vertical transport is solely due to eddy diffusional mixing. Here we derive new Na and Fe MIFs by determining the relative contributions of the known dust sources in the near-Earth environment: Jupiter Family Comets (JFCs), the main asteroid belt, Halley Type comets, and Oort Cloud comets. The mass/velocity/radiant distributions of these cosmic dust populations are Monte Carlo sampled and the elemental ablation rates calculated with the Leeds Chemical Ablation Model. The contribution of each dust source in the Earth's atmosphere is then determined by fitting the measured cosmic spherule accretion rate at the South Pole, and the measured vertical Na and Fe fluxes above 86 km. We conclude that JFCs contribute either 85% or 93% to the total incoming mass, depending on whether infra-red observations of the Zodiacal Dust Cloud by the IRAS or Planck

Metagenomic Analyses of the Autotrophic Fe(II)-Oxidizing, Nitrate-Reducing Enrichment Culture KS

PubMed Central

Tominski, Claudia; Kappler, Andreas; Behrens, Sebastian

2016-01-01

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 family Gallionellaceae, 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 cytochrome c system identified in neutrophilic microaerobic Fe(II)-oxidizing Sideroxydans lithotrophicus ES-1] in a Gallionellaceae sp., and findings of other putative genes involving cytochrome c and multicopper oxidases, such as Cyc2 and OmpB. Genome-enabled metabolic reconstruction revealed that this Gallionellaceae sp. 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

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

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.

Microbial oxidation of Fe²⁺ and pyrite exposed to flux of micromolar H₂O₂ in acidic media.

PubMed

Ma, Yingqun; Lin, Chuxia

2013-01-01

At an initial pH of 2, while abiotic oxidation of aqueous Fe(2+) was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe(2+) could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe(2+) to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe(2+)-Fe(3+) conversion rate in the solution (due to reduced microbial activity) weakened the Fe(3+)-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.

Potential function of added minerals as nucleation sites and effect of humic substances on mineral formation by the nitrate-reducing Fe(II)-oxidizer Acidovorax sp. BoFeN1.

PubMed

Dippon, Urs; Pantke, Claudia; Porsch, Katharina; Larese-Casanova, Phil; Kappler, Andreas

2012-06-19

The mobility of toxic metals and the transformation of organic pollutants in the environment are influenced and in many cases even controlled by iron minerals. Therefore knowing the factors influencing iron mineral formation and transformation by Fe(II)-oxidizing and Fe(III)-reducing bacteria is crucial for understanding the fate of contaminants and for the development of remediation technologies. In this study we followed mineral formation by the nitrate-reducing Fe(II)-oxidizing strain Acidovorax sp. BoFeN1 in the presence of the crystalline Fe(III) (oxyhydr)oxides goethite, magnetite and hematite added as potential nucleation sites. Mössbauer spectroscopy analysis of minerals precipitated by BoFeN1 in (57)Fe(II)-spiked microbial growth medium showed that goethite was formed in the absence of mineral additions as well as in the presence of goethite or hematite. The presence of magnetite minerals during Fe(II) oxidation induced the formation of magnetite in addition to goethite, while the addition of humic substances along with magnetite also led to goethite but no magnetite. This study showed that mineral formation not only depends on the aqueous geochemical conditions but can also be affected by the presence of mineral nucleation sites that initiate precipitation of the same underlying mineral phases.

Fe-Mn binary oxide incorporated into diatomite as an adsorbent for arsenite removal: preparation and evaluation.

PubMed

Chang, Fangfang; Qu, Jiuhui; Liu, Huijuan; Liu, Ruiping; Zhao, Xu

2009-10-15

Fe-Mn binary oxide incorporated into diatomite (FMBO-diatomite) was prepared by a simple coating method, and exhibited high oxidation and adsorption ability for arsenite [As(III)]. After being incorporated by Fe-Mn binary oxide, the surface area of diatomite increased 36%, and the pore volume increased five times. The pHzpc of FMBO-diatomite was determined to be 8.1. These characteristics are responsible for the increased As(III) adsorption efficiency. The adsorption equilibria of As(III) on FMBO-diatomite were described well by a Langmuir isotherm model due to the homogeneous distribution of Fe-Mn binary oxide on a diatomite surface. As(III) was oxidized into As(V), and then adsorbed by FMBO-diatomite. The oxidation and adsorption efficiencies for As(III) depended deeply on the pH of solution. When the pH was raised to 8.1, the As(III) adsorption efficiency of FMBO-diatomite was almost equal to the As(III) oxidation efficiency. Silicate and phosphate had negative effects on As(III) adsorption. Also the influence of silicate and phosphate with the pH variation was different.

Microplasma Jet Synthesis of Ni-Fe Oxide Films for Magnetic Exchange Bias and Electrocatalytic Studies

NASA Astrophysics Data System (ADS)

Pebley, Andrew Christian

Ni-Fe oxides have received significant interest from the scientific community because they have attractive magnetic and electrochemical properties for use in next generation data storage and energy conversion technologies. For example, the NiFe2O4/NiO nanogranular system exhibits the exchange bias effect, a magnetic phenomenon occurring at the interface of a ferro- or ferrimagnet (FM or FiM) and an antiferromagnet (AFM), where the AFM acts to increase the magnetic hardness of the corresponding FM or FiM. Additionally, doping of NiO with Fe has resulted in remarkably high catalytic activities for water splitting, a potential clean energy alternative to fossil fuels. A key challenge in implementing these Ni-Fe oxides for magnetic and electrocatalytic applications is the ability to control film morphology, crystallinity, composition, chemical phase, and doping during synthesis. Moreover, how these physiochemical properties effect magnetic and electrochemical behavior in the Ni-Fe oxide system is not fully understood. This dissertation focuses on the development and use of a novel synthesis technique, known as microplasma (MP) jet-based deposition, for the fabrication of biphasic NiFe2O4 (FiM)/NiO (AFM) and Fe-doped NiO nanostructured films for fundamental studies of exchange bias and electrocatalysis, respectively. The goal of this work was to understand how MP operation and deposition conditions (e.g., precursor composition, flux, substrate temperature, and post-deposition heat treatment) influence Ni-Fe oxide growth and film microstructure. Specifically, the role of composition, phase fraction, grain size, temperature, and interfacial density on exchange bias phenomena in NiFe 2O4/NiO nanogranular films was investigated. MP jets were also used to realize metastable Fe-doped NiO films with high surface area to assess how doping affects the electrochemical properties of NiO for the oxygen evolution reaction (OER). Biphasic NiFe2O4/NiO films of different composition

[Clinical effect of ultrasound-guided injection of biodegradable poly(lactic-co-glycolic acid)-Fe3O4 in situ implant for magnetic thermal ablation in treatment of nude mice with human liver cancer SMMC-7721 cells].

PubMed

Liang, B; Zuo, G Q; Zheng, Y Y; He, S; Zuo, D Y

2016-12-20

Objective: To prepare the Fe 3 O 4 -loaded biodegradable liquid-solid phase inversion poly(lactic-co-glycolic acid) (PLGA) in situ implant for ultrasound-guided injection into nude mouse tumor model, and to investigate its clinical effect in thermomagnetic treatment of nude mice with human liver cancer SMMC-7721 cells in an alternating magnetic field. Methods: An in situ implant containing 10% Fe 3 O 4 was prepared, and 50 μl Fe 3 O 4 -PLGA-NMP gel was injected into the subcutaneous tissue of Kunming mice. The degradation of this material was observed for 2 consecutive months, and the changes in body weight were recorded. HE staining and Prussian blue staining were performed for the heart, liver, spleen, lung, and kidney of Kunming mice. Fresh ex vivo bovine liver was taken and cut into cubes with a dimension of 2 cm×2 cm×2 cm and then 50 μl Fe 3 O 4 -PLGA-NMP gel was injected; after phase inversion, the cubes of ex vivo bovine liver were heated for 1, 2, 3, 4, and 5 minutes, respectively, and then cut open for observing the range of ablation; HE staining was also performed. Micro-CT scan was performed after ultrasound-guided injection of 50 μl Fe 3 O 4 -PLGA gel into the tumors of the nude mice, and then the nude mice were divided into treatment group and control group. The mice in the treatment group were given thermomagnetic treatment for 3 minutes, and tumor growth was observed daily. Results: The biodegradation of Fe 3 O 4 -PLGA-NMP implant showed that the subcutaneously injected material was gradually metabolized at 2 weeks after injection and that the nude mice were in good condition. The bovine liver ablation experiment showed that the range of ablation of 50 μl Fe 3 O 4 -PLGA implant reached 1.46 ± 0.11 cm. HE staining showed that part of bovine liver had coagulative necrosis. The phase inversion experiment of Fe 3 O 4 -PLGA gel showed quick liquid-solid phase inversion of the material after injection into the tumor, and the process of liquid

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.

Surface Electrochemical Modification of a Nickel Substrate to Prepare a NiFe-based Electrode for Water Oxidation.

PubMed

Guo, Dingyi; Qi, Jing; Zhang, Wei; Cao, Rui

2017-01-20

The slow kinetics of water oxidation greatly jeopardizes the efficiency of water electrolysis for H 2 production. Developing highly active water oxidation electrodes with affordable fabrication costs is thus of great importance. Herein, a Ni II Fe III surface species on Ni metal substrate was generated by electrochemical modification of Ni in a ferrous solution by a fast, simple, and cost-effective procedure. In the prepared Ni II Fe III catalyst film, Fe III was incorporated uniformly through controlled oxidation of Fe II cations on the electrode surface. The catalytically active Ni II originated from the Ni foam substrate, which ensured the close contact between the catalyst and the support toward improved charge-transfer efficiency. The as-prepared electrode exhibited high activity and long-term stability for electrocatalytic water oxidation. The overpotentials required to reach water oxidation current densities of 50, 100, and 500 mA cm -2 are 276, 290, and 329 mV, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

NiFe2O4 Spinel Protection Coating for High-Temperature Solid Oxide Fuel Cell Interconnect Application

NASA Astrophysics Data System (ADS)

Irankhah, Reza; Raissi, Babak; Maghsoudipour, Amir; Irankhah, Abdullah; Ghashghai, Sasan

2016-04-01

In the present study, Ni-Fe spinel powder was synthesized via a solid state reaction. In the next step, the electrophoretic deposition (EPD) method was used to apply the NiFe2O4 spinel, as an oxidation-resistant layer, on a commercially available stainless steel (SUS 430) in a potential range of 100 to 300 V. Microscopic studies of the deposited layers showed that crack-free NiFe2O4 films were obtained at 100 V. The coated and uncoated samples were then pre-sintered in air and 5% H2 bal Ar atmospheres at 900 °C for 3 h followed by cyclic oxidation at 800 °C for 500 h. The investigation of the oxidation resistance of the samples using Energy Dispersive Spectroscopy (EDS) revealed that the NiFe2O4 coating acted as an effective barrier against chromium migration into the coating. The oxidation resistance of 5% H2 bal Ar pre-sintered sample was enhanced with an oxidation rate constant ( K P) of 8.9 × 10-15 g2 cm-4 s-1.

Spectroscopic evidence for the role of a site of the di-iron catalytic center of ferritins in tuning the kinetics of Fe(ii) oxidation.

PubMed

Ebrahimi, Kourosh Honarmand; Bill, Eckhard; Hagedoorn, Peter-Leon; Hagen, Wilfred R

2016-11-15

Ferritin is a nanocage protein made of 24 subunits. Its major role is to manage intracellular concentrations of free Fe(ii) and Fe(iii) ions, which is pivotal for iron homeostasis across all domains of life. This function of the protein is regulated by a conserved di-iron catalytic center and has been the subject of extensive studies over the past 50 years. Yet, it has not been fully understood how Fe(ii) is oxidized in the di-iron catalytic center and it is not known why eukaryotic and microbial ferritins oxidize Fe(ii) with different kinetics. In an attempt to obtain a new insight into the mechanism of Fe(ii) oxidation and understand the origin of the observed differences in the catalysis of Fe(ii) oxidation among ferritins we studied and compared the mechanism of Fe(ii) oxidation in the eukaryotic human H-type ferritin (HuHF) and the archaeal ferritin from Pyrococcus furiosus (PfFtn). The results show that the spectroscopic characteristics of the intermediate of Fe(ii) oxidation and the Fe(iii)-products are the same in these two ferritins supporting the proposal of unity in the mechanism of Fe(ii) oxidation among eukaryotic and microbial ferritins. Moreover, we observed that a site in the di-iron catalytic center controls the distribution of Fe(ii) among subunits of HuHF and PfFtn differently. This observation explains the reported differences between HuHF and PfFtn in the kinetics of Fe(ii) oxidation and the amount of O 2 consumed per Fe(ii) oxidized. These results provide a fresh understanding of the mechanism of Fe(ii) oxidation by ferritins.

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.

Importance of allochthonous and autochthonous dissolved organic matter in Fe(II) oxidation: A case study in Shizugawa Bay watershed, Japan.

PubMed

Lee, Ying Ping; Fujii, Manabu; Kikuchi, Tetsuro; Natsuike, Masafumi; Ito, Hiroaki; Watanabe, Toru; Yoshimura, Chihiro

2017-08-01

Ferrous iron (Fe[II]) oxidation by dissolved oxygen was investigated in the Shizugawa Bay watershed with particular attention given to the effect of dissolved organic matter (DOM) properties on Fe(II) oxidation. To cover a wide spectrum of DOM composition, water samples were collected from various water sources including freshwater (e.g., river water and wastewater effluent) and coastal seawater. Measurement of nanomolar Fe(II) oxidation by using luminol chemiluminescence under dark, air-saturated conditions at 25 °C indicated that spatio-temporal variation of the second-order rate constant (6.7-74.5 M -1  s -1 ) was partially explained by the variation of the sample pH (7.5-8.6). However, at comparable pH values, the oxidation rates for freshwater were generally greater than those for coastal seawater. The substantial decline in oxidation rate constant after the removal of humic-type (allochthonous) DOM suggested that this hydrophobic DOM is a key factor that accelerates the Fe(II) oxidation in the freshwater samples. Observed lower oxidation rates for coastal seawater compared with freshwater and organic ligand-free seawater were likely associated with microbially derived autochthonous DOM, and the variation of Fe(II) oxidation at a fixed pH was best described by fluorescence index that represents the proportion of autochthonous and allochthonous DOM in natural waters. Consistently, Fe(II) oxidation was found to be slower in the presence of cellular exudates from phytoplankton. The present study highlighted the significant effect of DOM composition on the Fe(II) oxidation in inland and coastal waters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Demonstration and Analysis of Materials Processing by Ablation Plasma Ion Implantation (APII)

NASA Astrophysics Data System (ADS)

Qi, B.; Gilgenbach, R. M.; Lau, Y. Y.; Jones, M. C.; Lian, J.; Wang, L. M.; Doll, G. L.; Lazarides, A.

2001-10-01

Experiments have demonstrated laser-ablated Fe ion implantation into Si substrates. Baseline laser deposited films (0 kV) showed an amorphous Fe-Si film overlying the Si substrate with a top layer of nanocrystalline Fe. APII films exhibited an additional Fe ion-induced damage layer, extending 7.6 nm below the Si surface. The overlying Fe-Si layer and Fe top layer were amorphized by fast ions. Results were confirmed by XPS vs Ar ion etching time for depth profile of the deposited films. XPS showed primarily Fe (top layer), transitioning to roughly equal Fe/Si , then mostly Si with lower Fe (implanted region). These data clearly prove Fe ion implantation into Si, verifying the feasibility of APII as an ion acceleration and implantation process [1]. SRIM simulations predict about 20 percent deeper Fe ion penetration than data, due to:(a) Subsequent ions must pass through the Fe film deposited by earlier ions, and (b) the bias voltage has a slow rise and fall time. Theoretical research has developed the scaling laws for APII [2]. Recently, a model has successfully explained the shortening of the decay time in the high voltage pulse with the laser ablation plasma. This reduces the theoretical RC time constant, which agrees with the experimental data. * Research supported by National Science Foundation Grant CTS-9907106 [1] Appl. Phys. Lett. 78, 3785 (2001) [2] Appl. Phys. Lett. 78, 706 (2001)),

High-temperature steam oxidation and oxide crack effects of Zr-1Nb-1Sn-0.1Fe fuel cladding

NASA Astrophysics Data System (ADS)

Lee, Cheol Min; Mok, Yong-Kyoon; Sohn, Dong-Seong

2017-12-01

In this study, high-temperature steam oxidation experiments were performed at 1012-1207 °C on Zr-1Nb-1Sn-0.1Fe fuel cladding tubes to study their weight gains and microstructural characteristics. Many specimens were tested at each test temperature, and the results were reproducible and reliable. It is often debated whether the Zr-1Nb-1Sn-0.1Fe alloy follows the weight gain correlation developed by Cathcart and Pawel (C-P correlation) at around 1000 °C. According to our results, the C-P correlation overpredicts the weight gain at around 1000 °C, and this observation agrees well with the data reported by Westinghouse. In addition, the microstructures of the specimens were analyzed using scanning electron microscopy, and it was found that circumferential cracks are formed at the oxide-metal interface only at around 1000 °C. In previous studies, it has been postulated that cracks in the oxide promote the oxidation process, but it appears that the circumferential cracks at the oxide-metal interface decrease the oxidation rate before the breakaway oxidation occurs by disturbing the diffusion of oxygen. The oxidation rate reduction due to the circumferential cracks appears to be the reason for the overprediction of the C-P correlation at around 1000 °C.

Kinetic model to explain the effect of ocean warming and acidification on the Fe(II) oxidation rate in oligotrophic and eutrophic natural waters

NASA Astrophysics Data System (ADS)

González-Dávila, M.; Samperio-Ramos, G.; Santana-Casiano, J. M.; Gonzallez, A. G.; Pérez-Almeida, N.

2016-12-01

The speciation of inorganic Fe(II) as a function of the pH and temperature have been modeled in order to elucidate the inorganic Fe(II) redox behavior over a wide range of scenarios of acidification and global warming of the upper ocean, as well as, changes due to natural ambient fluctuations of pH and temperature. In addition, a kinetic modeling approach has been carried out to elucidate the fractional contribution of most kinetically active Fe(II) species to the overall oxidation rate to improve our future and present knowledge with respect to redox iron chemistry in the marine systems. The kinetic model considers the interactions of Fe(II) with the major ions in seawater, including phosphate and silicate and the competition with copper with the ROS. The model has been applied to the experimental results in order to describe the effect of temperature and pH in the speciation of Fe(II) and to compute the fractional contribution of each Fe(II)-specie to the overall oxidation rate. The oxidation rates (kapp) of nanomolar levels of Fe(II) have been studied in seawater enriched with nutrients (SWEN) in air saturated conditions. The nutrient effect (nitrate, phosphate and silicate), on the oxidation of Fe(II), has been evaluated as a function of pH (7.2-8.2), temperature (5-35 ºC) and salinity (10-37.09). The oxidation of Fe(II) was faster in the presence of nutrient with the change in the Fe(II) oxidation rates (Δlogkapp) more intensive at higher temperatures over the entire pH range studied. From the model it can be observed that the inorganic speciation of Fe(II) is controlled largely by pH, either in SW or in SWEN. A greater presence of Fe-nutrient reactive species (FeH3SiO4+ and FePO4-) in SWEN at higher temperatures explained the changes in the oxidation process. The individual oxidation rates by oxygen, for the Fe(II) most kinetically active species (Fe2+, FeOH+, Fe(OH)2, FeCO3(OH)-, FeCO3, Fe(CO3)22-, FeH3SiO3+, FePO4-), were fitted as a function of the

Enhanced Al and Zn removal from coal-mine drainage during rapid oxidation and precipitation of Fe oxides at near-neutral pH

USGS Publications Warehouse

Burrows, Jill E.; Cravotta, Charles A.; Peters, Stephen C.

2017-01-01

Net-alkaline, anoxic coal-mine drainage containing ∼20 mg/L FeII and ∼0.05 mg/L Al and Zn was subjected to parallel batch experiments: control, aeration (Aer 1 12.6 mL/s; Aer 2 16.8 mL/s; Aer 3 25.0 mL/s), and hydrogen peroxide (H2O2) to test the hypothesis that aeration increases pH, FeII oxidation, hydrous FeIII oxide (HFO) formation, and trace-metal removal through adsorption and coprecipitation with HFO. During 5.5-hr field experiments, pH increased from 6.4 to 6.7, 7.1, 7.6, and 8.1 for the control, Aer 1, Aer 2, and Aer 3, respectively, but decreased to 6.3 for the H2O2 treatment. Aeration accelerated removal of dissolved CO2, Fe, Al, and Zn. In Aer 3, dissolved Al was completely removed within 1 h, but increased to ∼20% of the initial concentration after 2.5 h when pH exceeded 7.5. H2O2 promoted rapid removal of all dissolved Fe and Al, and 13% of dissolved Zn.Kinetic modeling with PHREEQC simulated effects of aeration on pH, CO2, Fe, Zn, and Al. Aeration enhanced Zn adsorption by increasing pH and HFO formation while decreasing aqueous CO2 available to form ZnCO30 and Zn(CO3)22− at high pH. Al concentrations were inconsistent with solubility control by Al minerals or Al-containing HFO, but could be simulated by adsorption on HFO at pH < 7.5 and desorption at higher pH where Al(OH)4− was predominant. Thus, aeration or chemical oxidation with pH adjustment to ∼7.5 could be effective for treating high-Fe and moderate-Zn concentrations, whereas chemical oxidation without pH adjustment may be effective for treating high-Fe and moderate-Al concentrations.

Precious metal enrichment at low-redox in terrestrial native Fe-bearing basalts investigated using laser-ablation ICP-MS

NASA Astrophysics Data System (ADS)

Howarth, Geoffrey H.; Day, James M. D.; Pernet-Fisher, John F.; Goodrich, Cyrena A.; Pearson, D. Graham; Luo, Yan; Ryabov, Viktor V.; Taylor, Lawrence A.

2017-04-01

Primary native Fe is a rare crystallizing phase from terrestrial basaltic magmas, requiring highly reducing conditions (fO2 Fe alloy liquid. If this liquid also contains sufficient sulfur, it can undergo further division into conjugate Fe-C-rich and a Fe-S-rich immiscible melts that can effectively scavenge the highly siderophile elements (HSE: Re, Au, and the platinum group elements [PGE], Pd, Pt, Rh, Ru, Ir, Os), as well as Ni and Cu, to economic abundances. Three localities are known globally where native Fe bearing mafic rocks occur: (1) Paleocene basalts of Disko Island, West Greenland; (2) a Miocene lava of the Bühl basalts, Germany; and (3) mafic intrusions associated with the Late Permian Siberian flood basalts. In this contribution, we report major- and minor-element compositions and HSE concentrations for the main alloy phases (FeNi metal and cohenite) and sulfide, for all three known global occurrences of native Fe bearing basalt. Total HSE abundances in metal grains, obtained by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), are lowest in the Bühl basalt, (∼0.05 ppm), intermediate in the Disko Island basalts (4-8 ppm), and highest the Siberian Khungtukun and Dzhaltul intrusions (10-30 ppm). These differences demonstrate that, while native Fe formation is the result of carbonaceous crustal assimilation, HSE enrichment is not ubiquitous during this process. The Siberian occurrences are characterized by Pt PGE (PPGE: Pt, Pd) enrichment relative to the Ir PGE (IPGE: Rh, Ru, Ir, Os), consistent with models of early stage fractionation of olivine, chromite and metallic IPGE in staging magma reservoirs, prior to the addition of C-rich crustal materials in the shallow crust. Relative to Noril'sk Ni-Cu-PGE sulfide ores

Porous Ni-Fe alloys as anode support for intermediate temperature solid oxide fuel cells: I. Fabrication, redox and thermal behaviors

NASA Astrophysics Data System (ADS)

Wang, Xin; Li, Kai; Jia, Lichao; Zhang, Qian; Jiang, San Ping; Chi, Bo; Pu, Jian; Jian, Li; Yan, Dong

2015-03-01

Porous Ni-Fe anode supports for intermediate solid oxide fuel cells are prepared by reducing the sintered NiO-(0-50 wt. %) Fe2O3 composites in H2, their microstructure, redox and thermal expansion/cycling characteristics are systematically investigated. The sintered NiO-Fe2O3 composites are consisted of NiO and NiFe2O4, and are fully reducible to porous metallic Ni-Fe alloys in H2 at temperatures between 600 and 750 °C. The porous structure contains pores in bimodal distribution with larger pores between the sintered particles and smaller ones inside the particles. The oxidation resistance of the Ni-Fe alloy anode supports at 600 and 750 °C is increased by the addition of Fe, their oxidation kinetics obeys a multistage parabolic law in the form of (Percentageweightgain /Specificsurfacearea) 2 =kp · t , where kp is the rate constant and t the oxidation time. The dimension of the Ni-Fe anode supports is slightly changed without disintegrating their structure, and Fe addition is beneficial to the redox stability. The TEC of the Ni-Fe alloy anode supports decreases with the increase of Fe content. The anode supports containing Fe is less stable in dimension during thermal cycles due to the continuous sintering, but the dimension change after thermal cycles is within 1%.

The Reduction of Aqueous Metal Species on the Surfaces of Fe(II)-Containing Oxides: The Role of Surface Passivation

USGS Publications Warehouse

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

1998-01-01

The reduction of aqueous transition metal species at the surfaces of Fe(II)- containing oxides has important ramifications in predicting the transport behavior in ground water aquifers. Experimental studies using mineral suspensions and electrodes demonstrate that structural Fe(II) heterogeneously reduces aqueous ferric, cupric, vanadate and chromate ions on magnetite and ilmenite surfaces. The rates of metal reduction on natural oxides is strongly dependent on the extent of surface passivation and redox conditions in the weathering environment. Synchrotron studies show that surface oxidation of Fe(II)-containing oxide minerals decreases their capacity for Cr(VI) reduction at hazardous waste disposal sites.

Oxidation of tetracycline antibiotics induced by Fe(III) ions without light irradiation.

PubMed

Wang, Hui; Yao, Hong; Sun, Peizhe; Pei, Jin; Li, Desheng; Huang, Ching-Hua

2015-01-01

The presence of Fe(III) ions was found to induce degradation of three tetracycline antibiotics (TCs), tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC), in aqueous solutions without light. The presence of Fe(III) promoted the degradation of TCs in most experimental pH (5.0, 7.0 and 9.0) except at pH 9.0 for CTC. Degradation rate constants of TTC, OTC and CTC reached maximum ((6.2±0.5)×10(-3) h(-1), (10.6±0.1)×10(-3) h(-1) and (15.9±0.5)×10(-3) h(-1) at pH 7.0, 20 °C) when Fe(III):TC molar ratio was 1:1, 1:1 and 2:1, respectively. Such metal-to-ligand ratios agreed well with the most favorable complexation between Fe(III) and each TC. Compared to without metals, Fe(III) enhanced the degradation rate of TTC, OTC and CTC by up to 20.67, 7.07 and 2.30 times, respectively, in clean water matrix, and also promoted degradation of TCs in real surface water and wastewater matrices. The promoted degradation likely occurred via complexation of TCs and subsequent oxidation by Fe(III). Degradation results of CTC versus 4-epi-CTC suggested Fe(III) likely binds to TCs' C4 dimethylamino group. Toxicity of the complexes evaluated using Photobacterium phosphoreum T3 was increased after several hours of reaction, suggesting the transformation products may exert a stronger toxicity than parent TCs. This study identifies new oxidative transformation of TCs induced by Fe(III) ions without light irradiation, further supporting the important role of iron species in the environmental fate of TCs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Crystallographic studies of [NiFe]-hydrogenase mutants: towards consensus structures for the elusive unready oxidized states.

PubMed

Volbeda, Anne; Martin, Lydie; Barbier, Elodie; Gutiérrez-Sanz, Oscar; De Lacey, Antonio L; Liebgott, Pierre-Pol; Dementin, Sébastien; Rousset, Marc; Fontecilla-Camps, Juan C

2015-01-01

Catalytically inactive oxidized O2-sensitive [NiFe]-hydrogenases are characterized by a mixture of the paramagnetic Ni-A and Ni-B states. Upon O2 exposure, enzymes in a partially reduced state preferentially form the unready Ni-A state. Because partial O2 reduction should generate a peroxide intermediate, this species was previously assigned to the elongated Ni-Fe bridging electron density observed for preparations of [NiFe]-hydrogenases known to contain the Ni-A state. However, this proposition has been challenged based on the stability of this state to UV light exposure and the possibility of generating it anaerobically under either chemical or electrochemical oxidizing conditions. Consequently, we have considered alternative structures for the Ni-A species including oxidation of thiolate ligands to either sulfenate or sulfenic acid. Here, we report both new and revised [NiFe]-hydrogenases structures and conclude, taking into account corresponding characterizations by Fourier transform infrared spectroscopy (FTIR), that the Ni-A species contains oxidized cysteine and bridging hydroxide ligands instead of the peroxide ligand we proposed earlier. Our analysis was rendered difficult by the typical formation of mixtures of unready oxidized states that, furthermore, can be reduced by X-ray induced photoelectrons. The present study could be carried out thanks to the use of Desulfovibrio fructosovorans [NiFe]-hydrogenase mutants with special properties. In addition to the Ni-A state, crystallographic results are also reported for two diamagnetic unready states, allowing the proposal of a revised oxidized inactive Ni-SU model and a new structure characterized by a persulfide ion that is assigned to an Ni-'Sox' species.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 themore » 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.« less

Simultaneous NOx and Particulate Matter Removal from Diesel Exhaust by Hierarchical Fe-Doped Ce–Zr Oxide

PubMed Central

2017-01-01

Particulate matter and NOx emissions from diesel exhaust remains one of the most pressing environmental problems. We explore the use of hierarchically ordered mixed Fe–Ce–Zr oxides for the simultaneous capture and oxidation of soot and reduction of NOx by ammonia in a single step. The optimized material can effectively trap the model soot particles in its open macroporous structure and oxidize the soot below 400 °C while completely removing NO in the 285–420 °C range. Surface characterization and DFT calculations emphasize the defective nature of Fe-doped ceria. The isolated Fe ions and associated oxygen vacancies catalyze facile NO reduction to N2. A mechanism for the reduction of NO with NH3 on Fe-doped ceria is proposed involving adsorbed O2. Such adsorbed O2 species will also contribute to the oxidation of soot. PMID:28603656

Oxidative degradation stability and hydrogen sulfide removal performance of dual-ligand iron chelate of Fe-EDTA/CA.

PubMed

Miao, Xinmei; Ma, Yiwen; Chen, Zezhi; Gong, Huijuan

2017-09-05

Catalytic oxidation desulfurization using chelated iron catalyst is an effective method to remove H 2 S from various gas streams including biogas. However, the ligand of ethylenediaminetetraacetic acid (EDTA), which is usually adopted to prepare chelated iron catalyst, is liable to be oxidative degraded, and leads to the loss of desulfurization performance. In order to improve the degradation stability of the iron chelate, a series of iron chelates composed of two ligands including citric acid (CA) and EDTA were prepared and the oxidative degradation stability as well as desulfurization performance of these chelated iron catalysts were studied. Results show that the iron chelate of Fe-CA is more stable than Fe-EDTA, while for the desulfurization performance, the situation is converse. For the dual-ligand iron chelates of Fe-EDTA/CA, with the increase of mol ratio of CA to EDTA in the iron chelate solution, the oxidative degradation stability increased while the desulfurization performance decreased. The results of this work showed that Fe-EDTA/CA with a mol ratio of CA:EDTA = 1:1 presents a relative high oxidative degradation stability and an acceptable desulfurization performance with over 90% of H 2 S removal efficiency.

Petrogenesis and metallogenesis of the Wajilitag and Puchang Fe-Ti oxide-rich intrusive complexes, northwestern Tarim Large Igneous Province

NASA Astrophysics Data System (ADS)

Zhang, Dongyang; Zhang, Zhaochong; Huang, He; Cheng, Zhiguo; Charlier, Bernard

2018-04-01

The Wajilitag and Puchang intrusive complexes of the Tarim large igneous province (TLIP) are associated with significant resources of Fe-Ti oxide ores. These two mafic-ultramafic intrusions show differences in lithology and mineral chemistry. Clinopyroxenite and melagabbro are the dominant rock types in the Wajilitag complex, whereas the Puchang complex is generally gabbroic and anorthositic in composition with minor plagioclase-bearing clinopyroxenites in the marginal zone. Disseminated Fe-Ti oxide ores are found in the Wajilitag complex and closely associated with clinopyroxenites, whereas the Puchang complex hosts massive to disseminated Fe-Ti oxide ores mainly within its gabbroic rocks. The Wajilitag intrusive rocks are characterized by a restricted range of initial 87Sr/86Sr ratios (0.7038-0.7048) and positive εNd(t) (+0.04 - +3.01), indicating insignificant involvement of continental crustal contamination. The slightly higher initial 87Sr/86Sr ratios (0.7039-0.7059) and lower εNd(t) values (-1.05 - +2.35) of the Puchang intrusive rocks also suggest that the isotopic characteristics was controlled primarily by their mantle source, rather than by crustal contamination. Both complexes have Sr-Nd isotopic compositions close the neighboring kimberlitic rocks and their hosted mantle xenoliths in the TLIP. This indicates that the ferrobasaltic parental magmas were most probably originated from partial melting of a metasomatized subcontinental lithospheric mantle, modified recently with subduction-related materials by the impingement of the ascending mantle plume. The recycled subduction-related materials preserved in the lithospheric mantle could play a key role in the formation of the parental Fe-rich magmas in the context of an overall LIP system. The distinct variations in mineral assemblage for each complex and modeled results indicated that the Wajilitag and Puchang complexes experienced different crystallization path. Fe-Ti oxides in Wajilitag joined the

Evaluation of natural organic matter adsorption on Fe-Al binary oxide: Comparison with single metal oxides.

PubMed

Kim, Kyung-Jo; Jang, Am

2017-10-01

The adsorption characteristics of three types of standard natural organic matter (NOM) on iron-aluminum (Fe-Al) binary oxide (FAO) and heated aluminum oxide (HAO) under natural surface water condition were investigated using various adsorption isotherms and kinetic models. FAO was synthesized by Fe oxide and Al oxide, mixed using the sol-gel hydrothermal method, and aluminum sulfate was used to make HAO. The amount of adsorbed NOM was increased to 79.6 mg g -1 for humic acid (HA), 101.1 mg g -1 for sodium alginate (SA) in the FAO, but the maximum adsorption capacity of bovine serum albumin (BSA) (461.3 mg g -1 ) was identified on the HAO. The adsorption of HA, BSA, and SA dramatically increased (>70%) on FAO in 5 min and HA was significantly removed (90%) among the three NOM. Mutual interaction among the adsorbed NOM (BSA) occurred on the HAO surface during adsorption due to formation of monolayer by protein molecules at neutral pH. The pseudo second order clearly represented the adsorption kinetics for both adsorbents. The equilibrium isotherm data of FAO was better exhibited by the Langmuir isotherm model than by the Freundlich isotherm, but HAO was a slightly non-linear Langmuir type. Also, the free energy, enthalpy, and entropy of adsorption were determined from the thermodynamic experiments. Adsorption on FAO was spontaneous and an exothermic process. Fluorescence excitation-emission matrix (FEEM) spectra were used to elucidate the variation in organic components. The results obtained suggests that the significant changes in the surface property of the adsorbent (large surface area, increased crystalline intensity, and fine particle size) were effectively determined by the Fe-synthesized Al oxide mixed using the sol-gel hydrothermal method. The results also suggest that the changes enhanced the adsorption capacity, whereby three NOM were notably removed on FAO regardless of NOM characteristics (hydrophobic and hydrophilic). Copyright © 2017 Elsevier

An investigation of thin-film Ni-Fe oxide catalysts for the electrochemical evolution of oxygen.

PubMed

Louie, Mary W; Bell, Alexis T

2013-08-21

A detailed investigation has been carried out of the structure and electrochemical activity of electrodeposited Ni-Fe films for the oxygen evolution reaction (OER) in alkaline electrolytes. Ni-Fe films with a bulk and surface composition of 40% Fe exhibit OER activities that are roughly 2 orders of magnitude higher than that of a freshly deposited Ni film and about 3 orders of magnitude higher than that of an Fe film. The freshly deposited Ni film increases in activity by as much as 20-fold during exposure to the electrolyte (KOH); however, all films containing Fe are stable as deposited. The oxidation of Ni(OH)2 to NiOOH in Ni films occurs at potentials below the onset of the OER. Incorporation of Fe into the film increases the potential at which Ni(OH)2/NiOOH redox occurs and decreases the average oxidation state of Ni in NiOOH. The Tafel slope (40 mV dec(-1)) and reaction order in OH(-) (1) for the mixed Ni-Fe films (containing up to 95% Fe) are the same as those for aged Ni films. In situ Raman spectra acquired in 0.1 M KOH at OER potentials show two bands characteristic of NiOOH. The relative intensities of these bands vary with Fe content, indicating a change in the local environment of Ni-O. Similar changes in the relative intensities of the bands and an increase in OER activity are observed when pure Ni films are aged. These observations suggest that the OER is catalyzed by Ni in Ni-Fe films and that the presence of Fe alters the redox properties of Ni, causing a positive shift in the potential at which Ni(OH)2/NiOOH redox occurs, a decrease in the average oxidation state of the Ni sites, and a concurrent increase in the activity of Ni cations for the OER.

Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 (M = Mn, Fe).

PubMed

Laha, S; Natarajan, S; Gopalakrishnan, J; Morán, E; Sáez-Puche, R; Alario-Franco, M Á; Dos Santos-Garcia, A J; Pérez-Flores, J C; Kuhn, A; García-Alvarado, F

2015-02-07

We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R3[combining macron]m) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn(3+) and low spin configuration for Ru(4+) where the itinerant electrons occupy a π*-band. The onset of a net maximum in the χ vs. T plot at 9.5 K and the negative value of the Weiss constant (θ) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn(3+) and Ru(4+) are partially oxidized to Mn(4+) and Ru(5+) in the sloping region at low voltage, while in the long plateau, O(2-) is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to

Mechanisms for Electron Transfer Through Pili to Fe(III) Oxide in Geobacter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lovley, Derek R.

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) tomore » 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

Origin of Fe-Ti Oxide Mineralization in the Middle Paleoproterozoic Elet'ozero Syenite-Gabbro Intrusive Complex (Northern Karelia, Russia)

NASA Astrophysics Data System (ADS)

Sharkov, E. V.; Chistyakov, A. V.; Shchiptsov, V. V.; Bogina, M. M.; Frolov, P. V.

2018-03-01

Magmatic oxide mineralization widely developed in syenite-gabbro intrusive complexes is an important Fe and Ti resource. However, its origin is hotly debatable. Some researchers believe that the oxide ores were formed through precipitation of dense Ti-magnetite in an initial ferrogabbroic magma (Bai et al., 2012), whereas others consider them as a product of immiscible splitting of Fe-rich liquid during crystallization of Fe-Ti basaltic magma (Zhou et al., 2013). We consider this problem with a study of the Middle Paleoproterozoic (2086 ± 30 Ma) Elet'ozero Ti-bearing layered intrusive complex in northern Karelia (Baltic Shield). The first ore-bearing phase of the complex is mainly made up of diverse ferrogabbros, with subordinate clinopyroxenites and peridotites. Fe-Ti oxides (magnetite, Ti-magnetite, and ilmenite) usually account for 10-15 vol %, reaching 30-70% in ore varieties. The second intrusive phase is formed by alkaline and nepheline syenites. Petrographical, mineralogical, and geochemical data indicate that the first phase of the intrusion was derived from a moderately alkaline Fe-Ti basaltic melt, while the parental melt of the second phase was close in composition to alkaline trachyte. The orebodies comprise disseminated and massive ores. The disseminated Fe-Ti oxide ores make up lenses and layers conformable to general layering. Massive ores occur in subordinate amounts as layers and lenses, as well as cross-cutting veins. Elevated Nb and Ta contents in Fe-Ti oxides makes it possible to consider them complex ores. It is shown that the Fe-Ti oxide mineralization is related to the formation of a residual (Fe,Ti)-rich liquid, which lasted for the entire solidification history of the first intrusive phase. The liquid originated through multiple enrichment of Fe and Ti in the crystallization zone of the intrusion owing to the following processes: (1) precipitation of silicate minerals in the crystallization zone with a corresponding increase in the Fe and

[Reduction of nitrobenzene by iron oxides bound Fe(II) system at different pH values].

PubMed

Luan, Fu-Bo; Xie, Li; Li, Jun; Zhou, Qi

2009-07-15

Batch tests were conducted to investigate the reductive transformation of nitrobenzene by goethite, hematite, magnetite and steel converter slag bound Fe(II) system. And the reduction mechanism was explored at different pH values. Experimental results showed that hematite, magnetite and steel converter slag could adsorb Fe(II) on surfaces and form iron oxides bound Fe(II) system at pH from 6.5 to 7.0. The systems had strong reductive capacity and could reduce nitrobenzene to aniline. The reduction efficiency of nitrobenzene in surface bound Fe(II) system followed the sequence of magnetite, hematite and steel converter slag from high to low. The reduction efficiency of hematite and magnetite system increased with pH increasing. While it was almost pH independent in steel converter slag system. Although goethite adsorbed most of Fe(II) in solution, the adsorbed Fe(II) had no reductive activity for nitrobenzene. At pH 6.0, small amount of Fe(II) was adsorbed on magnetite and hematite and the systems did not show reductive activity for nitrobenzene. However, steel converter slag could adsorb Fe(II) at pH 6.0 and reduction efficiency almost equaled to the value at pH 7.0. When pH was above 7.5, dissolved Fe(II) could be converted to Fe(OH)2 and the newly formed Fe(OH)2 became the main redactor in the system. Under alkali condition, the presence of iron oxides inhibited the reduction capacity of system.

Oxide Morphology of a FeCrAl Alloy, Kanthal APMT, following Extended Aging at 300-600C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Nan; Parker, Stephen Scott; Wood, Elizabeth Sooby

Iron-chromium-aluminum (FeCrAl) alloys are of interest to the nuclear materials community due to their resistance to high temperature steam oxidation under accident conditions. The present work investigates oxide formation at temperatures relevant to light water reactor cladding operation following extended aging to assess growth kinetics, chemical composition, and microstructure of oxide formation on a commercial FeCrAl alloy, Fe-21wt.%Cr-5wt.%Al-3wt.%Mo (Kanthal APMT). Aging treatments were performed for 100-1000 hours in stagnant air at 300, 400, 500, and 600 °C, respectively. Oxide growth behavior under the investigated conditions follows a logarithmic time dependence. When the oxidization temperature is 400 °C or below, themore » oxide is amorphous. At 500 °C, isolated crystalline regions start to appear during short period aging time and expand with extended exposures. Crystalline α-Al2O3 oxide film develops at 600 °C and the correlated logarithmic rate constant decreases significantly, indicating enhanced oxidation resistance of the formed oxide film. In addition, Mo segregation at grain boundaries has been observed when the aging temperature exceeds 500 °C. The results of this study can be viewed as an upper bounding result for potential oxide coarsening during reactor operation.« less

Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction

DOE PAGES

Scofield, Megan E.; Koenigsmann, Christopher; Wang, Lei; ...

2014-11-25

In the search for alternatives to conventional Pt electrocatalysts, we have synthesized ultrathin, ternary PtRuFe nanowires (NW), possessing different chemical compositions in order to probe their CO tolerance as well as electrochemical activity as a function of composition for both (i) the methanol oxidation reaction (MOR) and (ii) the formic acid oxidation reaction (FAOR). As-prepared ‘multifunctional’ ternary NW catalysts exhibited both higher MOR and FAOR activity as compared with binary Pt₇Ru₃ NW, monometallic Pt NW, and commercial catalyst control samples. In terms of synthetic novelty, we utilized a sustainably mild, ambient wet-synthesis method never previously applied to the fabrication ofmore » crystalline, pure ternary systems in order to fabricate ultrathin, homogeneous alloy PtRuFe NWs with a range of controlled compositions. Thus, these NWs were subsequently characterized using a suite of techniques including XRD, TEM, SAED, and EDAX in order to verify not only the incorporation of Ru and Fe into the Pt lattice but also their chemical homogeneity, morphology, as well as physical structure and integrity. Lastly, these NWs were electrochemically tested in order to deduce the appropriateness of conventional explanations such as (i) the bi-functional mechanism as well as (ii) the ligand effect to account for our MOR and FAOR reaction data. Specifically, methanol oxidation appears to be predominantly influenced by the Ru content, whereas formic acid oxidation is primarily impacted by the corresponding Fe content within the ternary metal alloy catalyst itself.« less

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

Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

NASA Astrophysics Data System (ADS)

Eitel, Eryn M.; Taillefert, Martial

2017-10-01

Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

Heterojunction Fe2O3-SnO2 Nanostructured Photoanode for Efficient Photoelectrochemical Water Splitting

NASA Astrophysics Data System (ADS)

Han, Hyun Soo; Shin, Sun; Noh, Jun Hong; Cho, In Sun; Hong, Kug Sun

2014-04-01

Hierarchically organized nanostructures were fabricated by growing SnO2 nanoparticles on a fluorine-doped tin oxide/glass substrate via a laser ablation method. Cauliflower-like clusters consisting of agglomerated nanoparticles were deposited and aligned with respect to the substrate with a large internal surface area and open channels of pores. The morphological changes of SnO2 nanostructured films were investigated as a function of the oxygen working pressure in the range of 100-500 mTorr. A nanostructured scaffold prepared at an oxygen working pressure of 100 mTorr exhibited the best photoelectrochemical (PEC) performance. A Ti:Fe2O3-SnO2 nanostructured photoanode showed the photocurrent that was 34% larger than that of a Ti:Fe2O3 flat photoanode when the amount of Ti:Fe2O3 sensitizer was identical for the two photoanodes. The larger surface area and longer electron lifetime of the Ti:Fe2O3-SnO2 nanostructured photoanode explains its improved PEC performance.

Preparation and characterization of copper oxide nanoparticles decorated carbon nanoparticles using laser ablation in liquid

NASA Astrophysics Data System (ADS)

Khashan, K. S.; Jabir, M. S.; Abdulameer, F. A.

2018-05-01

Carbon nanoparticles CNPs ecorated by copper oxide nano-sized particles would be successfully equipped using technique named pulsed laser ablation in liquid. The XRD pattern proved the presence of phases assigned to carbon and different phases of copper oxide. The chemical structure of the as-prepared nanoparticles samples was decided by Energy Dispersive Spectrum (EDS) measurement. EDS analysis results show the contents of Carbon, Oxygen and Copper in the final product. These nanoparticles were spherical shaped with a size distribution 10 to 80 nm or carbon nanoparticles and 5 to 50 nm for carbon decorated copper oxide nanoparticles, according to Transmission Electron Microscopy (TEM) images and particle-size distribution histogram. It was found that after doping with copper oxide, nanoparticles become smaller and more regular in shape. Optical absorption spectra of prepared nanoparticles were measured using UV–VIS spectroscopy. The absorption spectrum of carbon nanoparticles without doping indicates absorption peak at about 228 nm. After doping with copper oxide, absorption shows appearance of new absorption peak at about (254-264) nm, which is referred to the movement of the charge between 2p and 4s band of Cu2+ ions.

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.

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.

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

Cu(II) removal by Anoxybacillus flavithermus-iron oxide composites during the addition of Fe(II)aq

NASA Astrophysics Data System (ADS)

Franzblau, Rachel E.; Daughney, Christopher J.; Swedlund, Peter J.; Weisener, Christopher G.; Moreau, Magali; Johannessen, Bernt; Harmer, Sarah L.

2016-01-01

There is currently poor understanding of metal removal by composites of bacteria and iron oxide minerals, even though they commonly co-occur and are among the most important sorbents in near-surface fluid-rock environments. This study evaluated Cu removal by composites of Anoxybacillus flavithermus and iron oxide over time during the addition, oxidation, and hydrolysis of Fe(II)aq and precipitation of the mineral, in comparison to Cu removal in the two single-sorbent end-member systems. In the absence of iron oxide, Cu removal by A. flavithermus was well described by a previously published surface complexation model, after inclusion of additional reactions describing aqueous complexation by exudate ligands released by the bacteria. In the absence of bacterial cells, Cu removal by iron oxide synthesized in the presence of the bacterial exudate ligands demonstrated the formation of ternary surface complexes. Removal of Cu by the A. flavithermus-iron oxide composites was ca. 20% greater than the prediction based on assumption of additivity in the two end-member systems. This non-additive behavior was attributed to (1) progressive physical blockage of bacterial surface sites by the iron oxide particles, (2) physical blockage of adsorption sites as a result of self-aggregation of the iron oxide particles, and (3) the reduction of Cu(II) to Cu(I) at the bacterial cell surface, as demonstrated by X-ray absorption spectroscopy. The extent of reduction of Cu(II) to Cu(I) was proportional to the concentration of solid phase Fe(II), suggesting that iron oxidation and copper reduction are linked. This study has shown that Cu removal by bacteria-iron oxide composites is greatly affected by redox processes such as Cu(II) reduction on the cell surface both by other bacterial surface ligands and the oxidation of sorbed Fe(II), as well as Fe(II) redox interactions, and aging effects of the mineral (i.e. surface site masking).

A photoelectrochemical (PEC) study on graphene oxide based hematite thin films heterojunction (R-GO/Fe2O3)

NASA Astrophysics Data System (ADS)

Sharma, Poonam; Zachariah, Michael; Ehrman, Sheryl; Shrivastava, Rohit; Dass, Sahab; Satsangi, Vibha; Michael Zachariah, Sheryl Ehrman Collaboration; Rohit Shrivastava, Sahab Dass Collaboration; Vibha R Satsangi, Poonam Sharma Team

2013-03-01

Graphene has an excellent electronic conductivity, a high theoretical surface area of 2630 m2/g and excellent mechanical properties and, thus, is a promising component for high-performance electrode materials. Following this, GO has been used to modify the PEC response of photoactive material hematite thin films in PEC cell. A reduced graphene oxide/iron oxide (R-GO/Fe2O3) thin film structure has been successfully prepared on ITO by directly growing iron oxide particles on the thermally reduced graphene oxide sheets prepared from suspension of exfoliated graphene oxide. R-GO/Fe2O3 thin films were tested in PEC cell and offered ten times higher photocurrent density than pristine Fe2O3 thin film sample. XRD, SEM, EDS, UV-Vis, Mott-Schottky and Raman studies were carried out to study spectro-electrochemical properties. Enhanced PEC performance of these photoelectrodes was attributed to its porous morphology, improved conductivity upon favorable carrier transfer across the oxides interface.

Efficiency of planetesimal ablation in giant planetary envelopes

NASA Astrophysics Data System (ADS)

Pinhas, Arazi; Madhusudhan, Nikku; Clarke, Cathie

2016-12-01

Observations of exoplanetary spectra are leading to unprecedented constraints on their atmospheric elemental abundances, particularly O/H, C/H, and C/O ratios. Recent studies suggest that elemental ratios could provide important constraints on formation and migration mechanisms of giant exoplanets. A fundamental assumption in such studies is that the chemical composition of the planetary envelope represents the sum-total of compositions of the accreted gas and solids during the formation history of the planet. We investigate the efficiency with which accreted planetesimals ablate in a giant planetary envelope thereby contributing to its composition rather than sinking to the core. From considerations of aerodynamic drag causing `frictional ablation' and the envelope temperature structure causing `thermal ablation', we compute mass ablations for impacting planetesimals of radii 30 m to 1 km for different compositions (ice to iron) and a wide range of velocities and impact angles, assuming spherical symmetry. Icy impactors are fully ablated in the outer envelope for a wide range of parameters. Even for Fe impactors substantial ablation occurs in the envelope for a wide range of sizes and velocities. For example, iron impactors of sizes below ˜0.5 km and velocities above ˜30 km s-1 are found to ablate by ˜60-80 per cent within the outer envelope at pressures below 103 bar due to frictional ablation alone. For deeper pressures (˜107 bar), substantial ablation happens over a wider range of parameters. Therefore, our exploratory study suggests that atmospheric abundances of volatile elements in giant planets reflect their accretion history during formation.

Oxide ion diffusion mechanism related to Co and Fe ions in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ using in-situ X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Itoh, Takanori; Imai, Hideto

2018-03-01

The time changes of the white line and pre-edge intensities of Co and Fe K-edge in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ (BSCF) were observed to estimate the oxide ion diffusion related to Co and Fe ions by using in - situ X-ray absorption spectroscopy (XAS) during oxidation. The 20 μm self-standing BSCF film was prepared for in - situ XAS measurements. The time changes of absorption were fitted to the exponential decay function with two terms. The longer relaxation time (τ), related to the oxide ion diffusion during the oxidation of BSCF, is dependent on temperature. The oxide ion diffusion coefficients (D) were calculated from the τ s estimated by in - situ XAS. The values of the activation energy (Ea) for D related to Co K-edge white line, Co pre-edge, and Fe pre-edge were 1.8-2.0 eV. The value of Ea for D related to Fe K-edge white line, however, was higher than other absorption values at approximately 2.3 eV. We discussed the oxide ion diffusion mechanism related to Co and Fe ions in BSCF using in - situ XAS.

Fe-Ti-Cr-Oxides in Martian Meteorite EETA79001 Studied by Point-counting Procedure Using Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Wang, Alian; Kuebler, Karla E.; Jolliff, Bradley L.; Haskin, Larry A.

2003-01-01

Fe-Ti-Cr-Oxide minerals contain much information about rock petrogenesis and alteration. Among the most important in the petrology of common intrusive and extrusive rocks are those of the FeO-TiO2-Cr2O3 compositional system chromite, ulv spinel-magnetite, and ilmenite-hematite. These minerals retain memories of oxygen fugacity. Their exsolution into companion mineral pairs give constraints on formation temperature and cooling rate. Laser Raman spectroscopy is anticipated to be a powerful technique for characterization of materials on the surface of Mars. A Mars Microbeam Raman Spectrometer (MMRS) is under development. It combines a micro sized laser beam and an automatic point-counting mechanism, and so can detect minor minerals or weak Raman-scattering phases such as Fe- Ti-Cr-oxides in mixtures (rocks & soils), and provide information on grain size and mineral mode. Most Fe-Ti-Cr-oxides produce weaker Raman signals than those from oxyanionic minerals, e.g. carbonates, sulfates, phosphates, and silicates, partly because most of them are intrinsically weaker Raman scatters, and partly because their dark colors limit the penetration depth of the excitation laser beam (visible wavelength) and of the Raman radiation produced. The purpose of this study is to show how well the Fe-Ti-Cr-oxides can be characterized by on-surface planetary exploration using Raman spectroscopy. We studied the basic Raman features of common examples of these minerals using well-characterized individual mineral grains. The knowledge gained was then used to study the Fe-Ti-Cr-oxides in Martian meteorite EETA79001, especially effects of compositional and structural variations on their Raman features.

Insights into Nitrate-Reducing Fe(II) Oxidation Mechanisms through Analysis of Cell-Mineral Associations, Cell Encrustation, and Mineralogy in the Chemolithoautotrophic Enrichment Culture KS.

PubMed

Nordhoff, M; Tominski, C; Halama, M; Byrne, J M; Obst, M; Kleindienst, S; Behrens, S; Kappler, A

2017-07-01

Most described nitrate-reducing Fe(II)-oxidizing bacteria (NRFeOB) are mixotrophic and depend on organic cosubstrates for growth. Encrustation of cells in Fe(III) minerals has been observed for mixotrophic NRFeOB but not for autotrophic phototrophic and microaerophilic Fe(II) oxidizers. So far, little is known about cell-mineral associations in the few existing autotrophic NRFeOB. Here, we investigate whether the designated autotrophic Fe(II)-oxidizing strain (closely related to Gallionella and Sideroxydans ) or the heterotrophic nitrate reducers that are present in the autotrophic nitrate-reducing Fe(II)-oxidizing enrichment culture KS form mineral crusts during Fe(II) oxidation under autotrophic and mixotrophic conditions. In the mixed culture, we found no significant encrustation of any of the cells both during autotrophic oxidation of 8 to 10 mM Fe(II) coupled to nitrate reduction and during cultivation under mixotrophic conditions with 8 to 10 mM Fe(II), 5 mM acetate, and 4 mM nitrate, where higher numbers of heterotrophic nitrate reducers were present. Two pure cultures of heterotrophic nitrate reducers ( Nocardioides and Rhodanobacter ) isolated from culture KS were analyzed under mixotrophic growth conditions. We found green rust formation, no cell encrustation, and only a few mineral particles on some cell surfaces with 5 mM Fe(II) and some encrustation with 10 mM Fe(II). Our findings suggest that enzymatic, autotrophic Fe(II) oxidation coupled to nitrate reduction forms poorly crystalline Fe(III) oxyhydroxides and proceeds without cellular encrustation while indirect Fe(II) oxidation via heterotrophic nitrate-reduction-derived nitrite can lead to green rust as an intermediate mineral and significant cell encrustation. The extent of encrustation caused by indirect Fe(II) oxidation by reactive nitrogen species depends on Fe(II) concentrations and is probably negligible under environmental conditions in most habitats. IMPORTANCE Most described nitrate

Insights into Nitrate-Reducing Fe(II) Oxidation Mechanisms through Analysis of Cell-Mineral Associations, Cell Encrustation, and Mineralogy in the Chemolithoautotrophic Enrichment Culture KS

PubMed Central

Nordhoff, M.; Tominski, C.; Halama, M.; Byrne, J. M.; Obst, M.; Behrens, S.

2017-01-01

ABSTRACT Most described nitrate-reducing Fe(II)-oxidizing bacteria (NRFeOB) are mixotrophic and depend on organic cosubstrates for growth. Encrustation of cells in Fe(III) minerals has been observed for mixotrophic NRFeOB but not for autotrophic phototrophic and microaerophilic Fe(II) oxidizers. So far, little is known about cell-mineral associations in the few existing autotrophic NRFeOB. Here, we investigate whether the designated autotrophic Fe(II)-oxidizing strain (closely related to Gallionella and Sideroxydans) or the heterotrophic nitrate reducers that are present in the autotrophic nitrate-reducing Fe(II)-oxidizing enrichment culture KS form mineral crusts during Fe(II) oxidation under autotrophic and mixotrophic conditions. In the mixed culture, we found no significant encrustation of any of the cells both during autotrophic oxidation of 8 to 10 mM Fe(II) coupled to nitrate reduction and during cultivation under mixotrophic conditions with 8 to 10 mM Fe(II), 5 mM acetate, and 4 mM nitrate, where higher numbers of heterotrophic nitrate reducers were present. Two pure cultures of heterotrophic nitrate reducers (Nocardioides and Rhodanobacter) isolated from culture KS were analyzed under mixotrophic growth conditions. We found green rust formation, no cell encrustation, and only a few mineral particles on some cell surfaces with 5 mM Fe(II) and some encrustation with 10 mM Fe(II). Our findings suggest that enzymatic, autotrophic Fe(II) oxidation coupled to nitrate reduction forms poorly crystalline Fe(III) oxyhydroxides and proceeds without cellular encrustation while indirect Fe(II) oxidation via heterotrophic nitrate-reduction-derived nitrite can lead to green rust as an intermediate mineral and significant cell encrustation. The extent of encrustation caused by indirect Fe(II) oxidation by reactive nitrogen species depends on Fe(II) concentrations and is probably negligible under environmental conditions in most habitats. IMPORTANCE Most described nitrate

Desorption of Furfural from Bimetallic Pt-Fe Oxides/Alumina Catalysts.

PubMed

Dimas-Rivera, Gloria Lourdes; de la Rosa, Javier Rivera; Lucio-Ortiz, Carlos J; De Los Reyes Heredia, José Antonio; González, Virgilio González; Hernández, Tomás

2014-01-20

In this work, the desorption of furfural, which is a competitive intermediate during the production of biofuel and valuable aromatic compounds, was studied using pure alumina, as well as alumina impregnated with iron and platinum oxides both individually and in combination, using thermogravimetric analysis (TGA). The bimetallic sample exhibited the lowest desorption percentage for furfural. High-resolution transmission electron microscopy (HRTEM) imaging revealed the intimate connection between the iron and platinum oxide species on the alumina support. The mechanism of furfural desorption from the Pt-Fe/Al₂O₃ 0.5%-0.5% sample was determined using physisorbed furfural instead of chemisorbed furfural; this mechanism involved the oxidation of the C=O group on furfural by the catalyst. The oxide nanoparticles on γ-Al₂O₃ support helped to stabilize the furfural molecule on the surface.

Phenol oxidation by a sequential CWPO-CWAO treatment with a Fe/AC catalyst.

PubMed

Quintanilla, A; Fraile, A F; Casas, J A; Rodríguez, J J

2007-07-31

Catalytic wet peroxide oxidation (CWPO) of phenol with a homemade Fe/activated carbon (Fe/AC) catalyst has been studied in a stainless steel fixed-bed reactor at different operating conditions (T=23-100 degrees C, P(T)=1-8atm, W=0-2.5g, and tau=20-320g(CAT)h/g(Phenol)). The results show that, thanks to the incorporation of Fe on the activated carbon, phenol conversion improved dramatically, reaching a 90% at 65 degrees C, 2atm, and 40g(CAT)h/g(Phenol). However, TOC conversion values remain fairly low, (around 5% at 40g(CAT)h/g(Phenol)), and no improvement was obtained with the inclusion of Fe. The presence of Fe seems to promote the nondesirable coupling reactions that take place in CWPO of phenol due to the condensation of the ring intermediates (the primary phenol oxidation products). These condensation products are quite refractory to CWPO at the conditions employed. Taking advantage of the high phenol conversions in CWPO and the high phenol mineralization in CWAO, along with the good stability of the Fe/AC catalyst, a CWPO-CWAO sequential treatment has been successfully performed by using a fixed-bed and trickle-bed reactor in series. A CWPO treatment at ambient conditions followed by a CWAO treatment at mild conditions (100 degrees C and 8atm) is presented as high efficiency process for the decontamination of phenolic wastewaters.

Water oxidation by size selected Co 27 clusters supported on Fe 2O 3

DOE PAGES

Pellin, Michael J.; Riha, Shannon C.; Tyo, Eric C.; ...

2016-09-22

The complexity of the water oxidation reaction makes understanding the role of individual catalytic sites critical to improving the process. Here, size-selected 27-atom cobalt clusters (Co 27) deposited on hematite (Fe 2O 3) anodes were tested for water oxidation activity. The uniformity of these anodes allows measurement of the activity of catalytic sites of well-defined nuclearity and known density. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) characterization of the anodes before and after electrochemical cycling demonstrates that these Co 27 clusters are stable to dissolution even in the harsh water oxidation electrochemical environment. They are also stable under illumination atmore » the equivalent of 0.4suns irradiation. The clusters show turnover rates for water oxidation that are comparable or higher than those reported for Pd- and Co-based materials or for hematite. The support for the Co 27 clusters is Fe 2O 3 grown by atomic layer deposition on a Si chip. We have chosen to deposit a Fe2O3 layer that is only a few unit cells thick (2nm), to remove complications related to exciton diffusion. We find that the electrocatalytic and the photoelectrocatalytic activity of the Co 27/Fe 2O 3 material is significantly improved when the samples are annealed (with the clusters already deposited). Lastly, given that the support is thin and that the cluster deposition density is equivalent to approximately 5% of an atomic monolayer, we suggest that annealing may significantly improve the exciton diffusion from the support to the catalytic moiety.« less

Effect of nano-oxide layers on giant magnetoresistance in pseudo-spin-valves using Co 2FeAl electrodes

NASA Astrophysics Data System (ADS)

Zhang, D. L.; Xu, X. G.; Wu, Y.; Miao, J.; Jiang, Y.

2011-03-01

We studied the pseudo-spin-valves (PSVs) with a structure of Ta/Co 2FeAl/NOL 1/Co 2FeAl/Cu/Co 2FeAl/NOL 2/Ta, where NOL represents the nano-oxide layer. Compared with the normal Co 2FeAl (CFA) PSV with a structure of Ta/Co 2FeAl/Cu/Co 2FeAl/Ta, which shows only a current-in-plane (CIP) giant magnetoresistance (GMR) of 0.03%, the CFA PSV with NOLs shows a large CIP-GMR of 5.84%. The enhanced GMR by the NOLs inserted in the CFA PSV is due to the large specular reflection caused by [(CoO)(Fe 2O 3)(Al 2O 3)] in NOL 1 and [(Fe 2O 3)(Al 2O 3)(Ta 2O 5)] in NOL 2. Another reason is that the roughness of the interface between Ta and CFA is improved by the oxidation procedure.

Dissociative Recombination of FeO(+) with Electrons: Implications for Plasma Layers in the Ionosphere.

PubMed

Bones, D L; Plane, J M C; Feng, W

2016-03-10

The dissociative recombination (DR) of FeO(+) ions with electrons has been studied in a flowing afterglow reactor. FeO(+) was generated by the pulsed laser ablation of a solid Fe target, and then entrained in an Ar(+) ion/electron plasma where the absolute electron density was measured using a Langmuir probe. A kinetic model describing gas-phase chemistry and diffusion to the reactor walls was fitted to the experimental data, yielding a DR rate coefficient at 298 K of k(FeO(+) + e(-)) = (5.5 ± 1.0) × 10(-7) cm(3) molecule(-1) s(-1), where the quoted uncertainty is at the 2σ level. Fe(+) ions in the lower thermosphere are oxidized by O3 to FeO(+), and this DR reaction is shown to provide a more important route for neutralizing Fe(+) below 110 km than the radiative/dielectronic recombination of Fe(+) with electrons. The experimental system was first validated by measuring two other DR reaction rate coefficients: k(O2(+) + e(-)) = (2.0 ± 0.4) × 10(-7) and k(N2O(+) + e(-)) = (3.3 ± 0.8) × 10(-7) cm(3) molecule(-1) s(-1), which are in good agreement with the recent literature.

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...

Enhanced magnetism of perovskite oxides, Sr(Sn,Fe)O3- δ , by substitution of nonmagnetic Ca and Ti ions

NASA Astrophysics Data System (ADS)

Nomura, Kiyoshi; Suzuki, Shigeyo; Mizunuma, Tomoya; Koike, Yuya; Okazawa, Atsushi

2017-11-01

Magnetic properties of perovskite oxides, SrSn1- x Fe x O3- δ ( x ≤ 0.15), substituted with nonmagnetic Ca and Ti ions were studied. XRD patterns showed the orthorhombic structure (close to tetragonal) of (Sr1- y Ca y )(Sn1- x Fe x )O3- δ and Sr(Sn1- x- y Fe x Ti y )O3- δ . The cell volumes decreased with the increase of Ca and Ti doping rates. Although Ti-substituted Sr(Sn, Fe)O3- δ showed small saturation magnetizations as compared with non-Ti substituted one, the magnetization increased a little with Ti doping rates up to 15%. On the other hand, all Ca-substituted Sr(Sn, Fe)O3- δ showed larger saturation magnetization than non-Ca substituted one. Two doublets of Fe3+ and a doublet of Fe4+ were observed in Mössbauer spectra of Ca-substituted Sr(Sn, Fe)O3- δ with weak ferromagnetism, and two sextets of high spin Fe3+ were additionally observed in Mössbauer spectra of Ca-doped Sr(Sn, Fe)O3- δ with relatively strong ferromagnetism. When Sr(Sn, Fe)O3- δ were further codoped with Ca and Ti ions, they showed the stable and enhanced ferromagnetic properties. It is considered that magnetic polarons among high spin Fe3+ species are overlapped by shrinking or deforming the crystal structure of perovskite oxides. That is the magnetism induced by a chemical pressure of perovskite oxides.

Fe (hydro) oxide controls Mo isotope fractionation during the weathering of granite

NASA Astrophysics Data System (ADS)

Wang, Zhibing; Ma, Jinlong; Li, Jie; Wei, Gangjian; Zeng, Ti; Li, Lei; Zhang, Le; Deng, Wenfeng; Xie, Luhua; Liu, Zhifeng

2018-04-01

Understanding the fractionation mechanisms of Mo isotopes and seeking the main hosts of light δ98/95Mo during chemical weathering of continental rocks is a prerequisite for constraining heavy δ98/95Mo input into rivers. This study investigates the Mo concentrations and δ98/95Mo values of bulk samples, chemical extractions, and clay fractions of weathering products in a granite weathering profile in Guangdong province, South China, as well as in surrounding stream water. Results from bulk samples show that the τ MoTiO2 values systematically decrease from 59.1% to -77.0%, and δ98/95Mo values systematically increase from -1.46‰ to -0.17‰, upwards in the profile (from 30 to 0 m depth). Atmospheric input has a limited effect on δ98/95Mo variations in the weathering profile. Adsorption and desorption processes of Fe (hydro) oxide are the dominant factors controlling the variations in δ98/95Mo, with light Mo isotopes preferentially adsorbed by Fe (hydro) oxide, and released during desorption process, whereas the incongruent dissolution of primary minerals has little effect. Organic materials and the clay fraction are not the main hosts of light δ98/95Mo, as indicated by the results of chemical extractions, which show that a large proportion (41.5-86.2%) of total Mo with light δ98/95Mo (-1.57‰ to -0.59‰) is associated with Fe (hydro) oxide. Moreover, a significant positive correlation exists between Mo concentrations and δ98/95Mo in the Fe (hydro) oxide extractions from bulk samples. Finally, δ98/95Mo in stream water indicates the release of heavier δ98/95Mo into river water during the chemical weathering of granite rock. The results advance our understanding the mechanisms of Mo isotope fractionation during chemical weathering and its isotopic mass balance in Earth's surface system.

High capacity of an Fe-air rechargeable battery using LaGaO3-based oxide ion conductor as an electrolyte.

PubMed

Inoishi, Atsushi; Ida, Shintaro; Uratani, Shouichi; Okano, Takayuki; Ishihara, Tatsumi

2012-10-05

Rapid growth and improved functions of mobile equipment present the need for an advanced rechargeable battery with extremely high capacity. In this study, we investigated the application of fuel cell technology to an Fe-air rechargeable battery. Because the redox potential of Fe is similar to that of H(2), the combination of H(2) formation by the oxidation of Fe with a fuel cell has led to a new type of metal-air rechargeable battery. By decreasing the operating temperature, a deep oxidation state of Fe can be achieved, resulting in enlarged capacity of the Fe-air battery. We found that the metal Fe is oxidized to Fe(3)O(4) by using H(2)/H(2)O as mediator. The observed discharge capacity is 817 mA h g(-1)-Fe, which is approximately 68% of the theoretical capacity of the formation of Fe(3)O(4), 1200 mA h g(-1)-Fe, at 10 mA cm(-2) and 873 K. Moreover, the cycle stability of this cell is examined. At 1073 K, the cell shows a discharge capacity of ca. 800 mA h g(-1)-Fe with reasonably high discharge capacity sustained over five cycles.

Catalytic Oxidation of Vanillyl Alcohol Using FeMCM-41 Nanoporous Tubular Reactor

NASA Astrophysics Data System (ADS)

Elamathi, P.; Kolli, Murali Krishna; Chandrasekar, G.

Iron containing nanoporous MCM-41 (FeMCM-41) with different Si/Fe ratios of 50, 100 and 150 was synthesized by hydrothermal synthesis process. The materials obtained from hydrothermal synthesis were characterized by various physico chemical techniques such as XRD, N2 adsorption, DR UV-vis, EPR and FTIR spectroscopy. XRD analyses of FeMCM-41 materials confirmed the presence of well-ordered crystalline structure. N2 isotherm of FeMCM-41 materials showed type IV adsorption isotherm. EPR and DR UV-vis analysis of FeMCM-41 samples indicates the presence of high tetrahedral coordination at the Si/Fe ratios of 100 and 150. The catalytic performance of FeMCM-41 nano tubular reactor was tested in the liquid phase oxidation of vanillyl alcohol into vanillin using H2O2 (50wt% in water). The reaction products were analyzed by gas chromatography in DB-5 capillary column with flame ionization detector. The products were confirmed by 1H NMR, 13C NMR and LC-Mass spectroscopy. The maximum conversion of vanillyl alcohol (85%) and selectivity towards vanillin (82%) were observed using the catalyst FeMCM-41(100) in 30min at 60∘C. The influence of reaction temperature, reaction time, reactants molar ratio, Si/Fe ratio and amount of catalyst were investigated.

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.

Microstructure and High Temperature Oxidation Property of Fe-Cr-B Based Metal/Ceramic Composite Manufactured by Powder Injection Molding Process

NASA Astrophysics Data System (ADS)

Joo, Yeun-Ah; Kim, Young-Kyun; Yoon, Tae-Sik; Lee, Kee-Ahn

2018-03-01

This study investigated the microstructure and high temperature oxidation property of Fe-Cr-B metal/ceramic composite manufactured using powder injection molding process. Observations of initial microstructure showed a unique structure where α-Fe and (Cr, Fe)2B form a continuous three-dimensional network. High temperature oxidation tests were performed at 900, 1000 and 1100 °C, for 24 h, and the oxidation weight gain according to each temperature condition was 0.13, 0.84 and 6.4 mg/cm2, respectively. The oxidation results according to time at 900 and 1000 °C conditions represented parabolic curves, and at 1100 °C condition formed a rectilinear curve. Observation and phase analysis results of the oxides identified Cr2O3 and SiO2 at 900 and 1000 °C. In addition to Cr2O3 and SiO2, CrBO3 and FeCr2O4 formed due to phase decomposition of boride were identified at 1100 °C. Based on the findings above, this study suggested the high temperature oxidation mechanism of Fe-Cr-B metal/ceramic composite manufactured using powder injection molding, and the possibility of its application as a high temperature component material was also discussed.

Experimental and Computational Evidence of Highly Active Fe Impurity Sites on the Surface of Oxidized Au for the Electrocatalytic Oxidation of Water in Basic Media

DOE PAGES

Klaus, Shannon; Trotochaud, Lena; Cheng, Mu-Jeng; ...

2015-10-22

Addition of Fe to Ni- and Co-based (oxy)hydroxides has been shown to enhance the activity of these materials for electrochemical oxygen evolution. Here we show that Fe cations bound to the surface of oxidized Au exhibit enhanced oxygen evolution reaction (OER) activity. We find that the OER activity increases with increasing surface concentration of Fe. Density functional theory analysis of the OER energetics reveals that oxygen evolution over Fe cations bound to a hydroxyl-terminated oxidized Au (Fe-Au 2O 3) occurs at an overpotential ~0.3V lower than over hydroxylated Au 2O 3 (0.82V). This finding agrees well with experimental observations andmore » is a consequence of the more optimal binding energetics of OER reaction intermediates at Fe cations bound to the surface of Au 2O 3. These findings suggest that the enhanced OER activity reported recently upon low-potential cycling of Au may be due to surface Fe impurities rather than to "superactive" Au(III) surfaquo species.« less

Humic substances and trace metals associated with Fe and Al oxides deposited in an acidic mountain stream

USGS Publications Warehouse

McKnight, Diane M.; Wershaw, R. L.; Bencala, K.E.; Zellweger, G.W.; Feder, G.L.

1992-01-01

Hydrous iron and aluminum oxides are deposited on the streambed in the confluence of the Snake River and Deer Creek, two streams in the Colorado Rocky Mountains. The Snake River is acidic and has high concentrations of dissolved Fe and Al. These metals precipitate at the confluence with the pristine, neutral pH, Deer Creek because of the greater pH (4.5-6.0) in the confluence. The composition of the deposited oxides changes consistently with distance downstream, with the most upstream oxide samples having the greatest Fe and organic carbon content. Fulvic acid accounts for most of the organic content of the oxides. Results indicate that streambed oxides in the confluence are not saturated with respect to their capacity to sorb dissolved humic substances from streamwater. The contents of several trace metals (Mn, Zn, Cu, Pb, Ni and Co) also decrease with distance downstream and are correlated with both the Fe and organic carbon contents. Strong metal-binding sites associated with the sorbed fulvic acid are more than sufficient to account for the trace metal content of the oxides. Complexation of trace metals by sorbed fulvic acid may explain the observed downstream decrease in trace metal content.

The Impact of Fe-Ti Oxide Concentration on the Structural Rigidity of the Lower Oceanic Crust, Atlantis Bank, Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Deans, J. R.; Winkler, D. A.

2017-12-01

Fe-Ti oxides are important components of oceanic core complexes (OCC) formed at slow-spreading ridges, since Fe-Ti oxide phases form throughout the crustal column and are weaker than silicate phases. This study investigated the predicted relationship between the presence and concentration of Fe-Ti oxides and the presence/intensity of crystal-plastic deformation in samples from Atlantis Bank, Southwest Indian Ridge (SWIR). Atlantis Bank is an OCC that formed through the exhumation of lower oceanic crust along a detachment shear zone/fault. OCCs form along slow-spreading ridges and are characterized by the complex interactions between magmatism and crustal extension, thus, making them more susceptible to crystal-plastic deformation at higher temperatures and for weaker phases like Fe-Ti oxides to preferentially partition strain. Atlantis Bank has been the focus of many scientific expeditions to various sites including; Ocean Drilling Program (ODP) Holes 735B and 1105A, and the International Oceanic Discovery Program (IODP) Hole U1473A. A total of 589 thin sections from all three holes were analyzed using the software package Fiji to calculate the Fe-Ti oxide concentration within the thin sections. The Fe-Ti oxide percentage was correlated with the crystal-plastic fabric (CPF) intensity, from 0-5 (no foliation - ultramylonite), for each thin section using the statistical software R. All three holes show a positive correlation between the abundance of Fe-Ti oxides and the CPF intensity. Specifically, 76.3% of samples with a concentration of 5% or more Fe-Ti oxides have a corresponding CPF intensity value of 2 or more (porphyroclastic foliation - ultramylonitic). The positive correlation may be explained by the Fe-Ti oxides preferentially partitioning strain, especially at temperatures below where dry plagioclase can recrystallize. This allows for a mechanism of continued slip along the shear zone or form new shear zones at amphibolite grade conditions while the lower

Desorption of Furfural from Bimetallic Pt-Fe Oxides/Alumina Catalysts

PubMed Central

Dimas-Rivera, Gloria Lourdes; de la Rosa, Javier Rivera; Lucio-Ortiz, Carlos J.; De los Reyes Heredia, José Antonio; González, Virgilio González; Hernández, Tomás

2014-01-01

In this work, the desorption of furfural, which is a competitive intermediate during the production of biofuel and valuable aromatic compounds, was studied using pure alumina, as well as alumina impregnated with iron and platinum oxides both individually and in combination, using thermogravimetric analysis (TGA). The bimetallic sample exhibited the lowest desorption percentage for furfural. High-resolution transmission electron microscopy (HRTEM) imaging revealed the intimate connection between the iron and platinum oxide species on the alumina support. The mechanism of furfural desorption from the Pt-Fe/Al2O3 0.5%-0.5% sample was determined using physisorbed furfural instead of chemisorbed furfural; this mechanism involved the oxidation of the C=O group on furfural by the catalyst. The oxide nanoparticles on γ-Al2O3 support helped to stabilize the furfural molecule on the surface. PMID:28788472

A simple route to improve rate performance of LiFePO4/reduced graphene oxide composite cathode by adding Mg2+ via mechanical mixing

NASA Astrophysics Data System (ADS)

Huang, Yuan; Liu, Hao; Gong, Li; Hou, Yanglong; Li, Quan

2017-04-01

Introducing Mg2+ to LiFePO4 and reduced graphene oxide composite via mechanical mixing and annealing leads to largely improved rate performance of the cathode (e.g. ∼78 mA h g-1 at 20 C for LiFePO4 and reduced graphene oxide composite with Mg2+ introduction vs. ∼37 mA h g-1 at 20 C for LiFePO4 and reduced graphene oxide composite). X-ray photoelectron spectroscopy unravels that the enhanced reduction of Fe2+ to Fe0 occurs in the simultaneous presence of Mg2+ and reduced graphene oxide, which is beneficial for the rate capability of cathode. The simple fabrication process provides a simple and effective means to improve the rate performance of the LiFePO4 and reduced graphene oxide composite cathode.

Development of accident tolerant FeCrAl-ODS steels utilizing Ce-oxide particles dispersion

NASA Astrophysics Data System (ADS)

Shibata, Hiroki; Ukai, Shigeharu; Oono, Naoko H.; Sakamoto, Kan; Hirai, Mutsumi

2018-04-01

FeCrAl-ODS ferritic steels with Ce-oxide dispersion instead of Y-oxide were produced for the accident tolerant fuel cladding of the light water reactor. Excess oxygen (Ex.O) was added to improve the mechanical property. The tensile strength at Ex.O = 0 is around 200 MPa at 700 °C, mainly owing to dispersed Ce2O3 particles in less than 10 nm size. The formation of the fine Ce2O3 particles is dominated by a coherent interface with ferritic matrix. With increasing Ex.O, an increased of number density of coarser Ce-Al type oxide particles over 10 nm size is responsible for the improvement of the tensile strength. Change of the type of oxide particle, CeO2, Ce2O3, CeAlO3, Al2O3, in FeCrAl-ODS steel was thermodynamically analyzed as a parameter of Ex.O.

Progressive Oxidation of Pyrite in Five Bituminous Coal Samples: An As XANES and 57Fe Mossbauer Spectroscopic Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kolker,A.; Huggins, F.

2007-01-01

Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period ofmore » 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32-1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26-0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O{sub 2} atmosphere; (3) room atmosphere (relative humidity {approx}20-60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and {sup 57}Fe Mossbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. {sup 57}Fe Mossbauer spectroscopy also shows a much greater proportion of Fe{sup 3+} forms (jarosite, Fe{sup 3+} sulfate, FeOOH) for samples stored under wet conditions, but much

Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lieberman, Craig M.; Barry, Matthew C.; Wei, Zheng

A series of mixed-valent, heterometallic (mixed-transition metal) diketonates that can be utilized as prospective volatile single-source precursors for the low-temperature preparation of M xM' 3–xO 4 spinel oxide materials is reported. Three iron–cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal–oxygen bonds with those in homometallic analogues, heterometallic compounds were formulated as [Fe III(acac) 3][Co II(hfac) 2] (1), [Co II(hfac) 2][Fe III(acac) 3][Co II(hfac) 2] (2), and [Fe II(hfac) 2][Fe III(acac) 3][Co II(hfac) 2]more » (3). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated CoII/FeII centers chelated by two hexafluoroacetylacetonate (hfac) ligands maintain bridging interactions with oxygen atoms of acetylacetonate (acac) groups that chelate the neighboring Fe III metal ion. Preliminary assignment of Fe and Co positions/oxidation states in 1–3 drawn from X-ray structural investigation was corroborated by a number of complementary techniques. Single-crystal resonant synchrotron diffraction and neutron diffraction experiments unambiguously confirmed the location of Fe and Co sites in the molecules of dinuclear (1) and trinuclear (2) complexes, respectively. Direct analysis in real time mass spectrometry revealed the presence of Fe III- and Co II-based fragments in the gas phase upon evaporation of precursors 1 and 2 as well as of Fe III, Fe II, and Co II species for complex 3. Theoretical investigation of two possible “valent isomers”, [Fe III(acac) 3][Co II(hfac) 2] (1) and [Co III(acac) 3][Fe II(hfac) 2] (1'), provided an additional support for the metal site/oxidation state assignment giving a preference of 6.48 kcal/mol for the experimentally observed molecule 1. Magnetic susceptibility measurements data are in agreement

Mechanism of selenite removal by a mixed adsorbent based on Fe-Mn hydrous oxides studied using X-ray absorption spectroscopy.

PubMed

Chubar, Natalia; Gerda, Vasyl; Szlachta, Małgorzata

2014-11-18

Selenium cycling in the environment is greatly controlled by various minerals, including Mn and Fe hydrous oxides. At the same time, such hydrous oxides are the main inorganic ion exchangers suitable (on the basis of their chemical nature) to sorb (toxic) anions, separating them from water solutions. The mechanism of selenite adsorption by the new mixed adsorbent composed of a few (amorphous and crystalline) phases [maghemite, MnCO3, and X-ray amorphous Fe(III) and Mn(III) hydrous oxides] was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy [supported by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data]. The complexity of the porous adsorbent, especially the presence of the amorphous phases of Fe(III) and Mn(III) hydrous oxides, is the main reason for its high selenite removal performance demonstrated by batch and column adsorption studies shown in the previous work. Selenite was bound to the material via inner-sphere complexation (via oxygen) to the adsorption sites of the amorphous Fe(III) and Mn(III) oxides. This anion was attracted via bidentate binuclear corner-sharing coordination between SeO3(2-) trigonal pyramids and both FeO6 and MnO6 octahedra; however, the adsorption sites of Fe(III) hydrous oxides played a leading role in selenite removal. The contribution of the adsorption sites of Mn(III) oxide increased as the pH decreased from 8 to 6. Because most minerals have a complex structure (they are seldom based on individual substances) of various crystallinity, this work is equally relevant to environmental science and environmental technology because it shows how various solid phases control cycling of chemical elements in the environment.

Microbial reduction of Fe(III) in acidic sediments: isolation of Acidiphilium cryptum JF-5 capable of coupling the reduction of Fe(III) to the oxidation of glucose.

PubMed

Küsel, K; Dorsch, T; Acker, G; Stackebrandt, E

1999-08-01

To evaluate the microbial populations involved in the reduction of Fe(III) in an acidic, iron-rich sediment, the anaerobic flow of supplemental carbon and reductant was evaluated in sediment microcosms at the in situ temperature of 12 degrees C. Supplemental glucose and cellobiose stimulated the formation of Fe(II); 42 and 21% of the reducing equivalents that were theoretically obtained from glucose and cellobiose, respectively, were recovered in Fe(II). Likewise, supplemental H(2) was consumed by acidic sediments and yielded additional amounts of Fe(II) in a ratio of approximately 1:2. In contrast, supplemental lactate did not stimulate the formation of Fe(II). Supplemental acetate was not consumed and inhibited the formation of Fe(II). Most-probable-number estimates demonstrated that glucose-utilizing acidophilic Fe(III)-reducing bacteria approximated to 1% of the total direct counts of 4', 6-diamidino-2-phenylindole-stained bacteria. From the highest growth-positive dilution of the most-probable-number series at pH 2. 3 supplemented with glucose, an isolate, JF-5, that could dissimilate Fe(III) was obtained. JF-5 was an acidophilic, gram-negative, facultative anaerobe that completely oxidized the following substrates via the dissimilation of Fe(III): glucose, fructose, xylose, ethanol, glycerol, malate, glutamate, fumarate, citrate, succinate, and H(2). Growth and the reduction of Fe(III) did not occur in the presence of acetate. Cells of JF-5 grown under Fe(III)-reducing conditions formed blebs, i.e., protrusions that were still in contact with the cytoplasmic membrane. Analysis of the 16S rRNA gene sequence of JF-5 demonstrated that it was closely related to an Australian isolate of Acidiphilium cryptum (99.6% sequence similarity), an organism not previously shown to couple the complete oxidation of sugars to the reduction of Fe(III). These collective results indicate that the in situ reduction of Fe(III) in acidic sediments can be mediated by heterotrophic

Design, properties, and weldability of advanced oxidation-resistant FeCrAl alloys

DOE PAGES

Gussev, M. N.; Field, K. G.; Yamamoto, Y.

2017-05-05

FeCrAl alloys are promising as corrosion- and oxidation-resistance materials for extreme high-temperature applications. However, further alloy design and improvement requires a delicate balance between workability, weldability, propensity for '-phase formation, among other factors. Here, a series of advanced oxidant resistant FeCrAl alloys were produced and investigated. Variants with Al (+2%), Nb (+1%), and TiC (0.1, 0.3, and 1%) additions over the reference alloy (Fe-13%Cr-5%Al) were characterized in detail before and after controlled laser beam welding using tensile tests with digital image correlation, SEM-EBSD analysis, and fractography. All investigated alloys demonstrated yield stress in the weldment over 500 MPa; no welding-inducedmore » cracking was observed. However, it was shown that the increase in the Al-content over 5% was detrimental leading to a brittle fracture mechanism and decreased ductility in the weldment. At the same time, Nb and TiC additions were beneficial for preventing grain growth and reducing local softening (yield stress reduction) in the heat-affected zone. The 1% TiC addition also effectively refined grain size in the weldment.« less

Design, properties, and weldability of advanced oxidation-resistant FeCrAl alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gussev, M. N.; Field, K. G.; Yamamoto, Y.

FeCrAl alloys are promising as corrosion- and oxidation-resistance materials for extreme high-temperature applications. However, further alloy design and improvement requires a delicate balance between workability, weldability, propensity for '-phase formation, among other factors. Here, a series of advanced oxidant resistant FeCrAl alloys were produced and investigated. Variants with Al (+2%), Nb (+1%), and TiC (0.1, 0.3, and 1%) additions over the reference alloy (Fe-13%Cr-5%Al) were characterized in detail before and after controlled laser beam welding using tensile tests with digital image correlation, SEM-EBSD analysis, and fractography. All investigated alloys demonstrated yield stress in the weldment over 500 MPa; no welding-inducedmore » cracking was observed. However, it was shown that the increase in the Al-content over 5% was detrimental leading to a brittle fracture mechanism and decreased ductility in the weldment. At the same time, Nb and TiC additions were beneficial for preventing grain growth and reducing local softening (yield stress reduction) in the heat-affected zone. The 1% TiC addition also effectively refined grain size in the weldment.« less

Partitioning of Cu between mafic minerals, Fe-Ti oxides and intermediate to felsic melts

NASA Astrophysics Data System (ADS)

Liu, Xingcheng; Xiong, Xiaolin; Audétat, Andreas; Li, Yuan

2015-02-01

This study used improved capsule technique i.e., Pt95Cu05 or Au95Cu05 alloy capsules as Cu sources to determine Cu partitioning between mafic minerals, Fe-Ti oxides and intermediate to felsic melts at 0.5-2.5 GPa, 950-1100 °C and various oxygen fugacities (fO2). In combination with the data from the mafic composition systems, the results demonstrate that Cu is generally highly incompatible in mafic minerals and moderately incompatible to compatible in Fe-Ti oxides. The general order of mineral/melt Cu partition coefficients (DCu) is garnet (0.01-0.06) ⩽ olivine (0.04-0.20) ≈ opx (0.04-0.24) ≈ amphibole (0.04-0.20) ⩽ cpx (0.04-0.45) ⩽ magnetite, titanomagnetite and Cr-spinel (0.18-1.83). The variations in DCu depend mainly on temperature, fO2 or mineral composition. In general, DCu for olivine (and perhaps opx) increases with decreasing temperature and increasing fO2. DCu increases for cpx with Na+ (pfu) in cpx, for magnetite and Cr-spinel with Fe3+ (pfu) in these phases and for titanomagnetite with Ti4+ (pfu) in this phase. The large number of DCu data (99 pairs) serves as a foundation for quantitatively understanding the behavior of Cu during magmatic processes. The generation of intermediate to felsic magmas via fractional crystallization or partial melting of mafic rocks (magmas) at deep levels of crust involves removal of or leaving assemblages of mafic minerals + Fe-Ti oxides ± sulfides. With our DCu data on mafic minerals and Fe-Ti oxides, DCubulk values around 0.2 were obtained for the sulfide-free assemblages. Cu will thus be concentrated efficiently in the derived melts during these two processes if sulfides are absent or negligible, explaining that high fO2 and sulfide-destabilization are favorable to formation of the porphyry Cu system.

Silicon doped hafnium oxide (HSO) and hafnium zirconium oxide (HZO) based FeFET: A material relation to device physics

NASA Astrophysics Data System (ADS)

Ali, T.; Polakowski, P.; Riedel, S.; Büttner, T.; Kämpfe, T.; Rudolph, M.; Pätzold, B.; Seidel, K.; Löhr, D.; Hoffmann, R.; Czernohorsky, M.; Kühnel, K.; Thrun, X.; Hanisch, N.; Steinke, P.; Calvo, J.; Müller, J.

2018-05-01

The recent discovery of ferroelectricity in thin film HfO2 materials renewed the interest in ferroelectric FET (FeFET) as an emerging nonvolatile memory providing a potential high speed and low power Flash alternative. Here, we report more insight into FeFET performance by integrating two types of ferroelectric (FE) materials and varying their properties. By varying the material type [HfO2 (HSO) versus hafnium zirconium oxide (HZO)], optimum content (Si doping/mixture ratio), and film thickness, a material relation to FeFET device physics is concluded. As for the material type, an improved FeFET performance is observed for HZO integration with memory window (MW) comparable to theoretical values. For different Si contents, the HSO based FeFET exhibited a MW trend with different stabilized phases. Similarly, the HZO FeFET shows MW dependence on the Hf:Zr mixture ratio. A maximized MW is obtained with cycle ratios of 16:1 (HfO2:Si) and 1:1 (Hf:Zr) as measured on HSO and HZO based FeFETs, respectively. The thickness variation shows a trend of increasing MW with the increased FE layer thickness confirming early theoretical predictions. The FeFET material aspects and stack physics are discussed with insight into the interplay factors, while optimum FE material parameters are outlined in relation to performance.

Unraveling the catalyzing behaviors of different iron species (Fe2+ vs. Fe0) in activating persulfate-based oxidation process with implications to waste activated sludge dewaterability.

PubMed

Zhen, Guangyin; Lu, Xueqin; Su, Lianghu; Kobayashi, Takuro; Kumar, Gopalakrishnan; Zhou, Tao; Xu, Kaiqin; Li, Yu-You; Zhu, Xuefeng; Zhao, Youcai

2018-05-01

Dewatering of waste activated sludge (WAS) is of major interest in its volume reduction, transportation and ultimate disposal. Persulfate-based oxidation process is a newly developed option for enhancing WAS dewaterability through the generation of powerful sulfate radicals (SO 4 - ·). However, the enhancement in WAS dewaterability by persulfate differs with the species of iron catalysts used. In this study, two types of iron catalysts (i.e. Fe 2+ vs. Fe 0 ) were employed to initiate the persulfate (S 2 O 8 2- ), and the catalyzing behaviors and the underlying principles in enhancing WAS dewaterability were investigated and compared. The Fe 2+ exhibited the high effectiveness in catalyzing the decomposition of persulfate to sulfate radicals (SO 4 - ·), inducing the greater improvement in WAS dewatering. The WAS dewaterability (indicated by dry solids content after filtration) increased with the added S 2 O 8 2- /Fe 2+ dosages, with the dry solids content reaching up to 5.1 ± 0.8 wt% at S 2 O 8 2- /Fe 2+ dosages of 1.2/1.5 mmol/g-VS after only 30 s' filtration, roughly 1.8-fold increase than raw WAS (1.8 ± 0.1 wt%). In contrast, the influence of the persulfate oxidation when activated with Fe 0 on WAS dewaterability was statistically insignificant. The WAS dewaterability remained nearly unchanged (i.e. dry solids content of 2.0 ± 0.0 wt%), irrespective of the employed S 2 O 8 2- /Fe 0 dosages. Further analysis demonstrated that the WAS dewaterability negatively corresponded to loosely bound extracellular polymeric substances (LB-EPS) and tightly bound EPS (TB-EPS). The abundant SO 4 - · from S 2 O 8 2- /Fe 2+ system could effectively disrupt the gel-like EPS matrix, break apart the cells and subsequently arouse the release of the water inside EPS and cells, facilitating water-solid separation. In the case of S 2 O 8 2- /Fe 0 , the dissolution of Fe 0 particles was the rate-limiting step, due to the formation of oxide iron layer near Fe 0

Fe-rich carbonate chimney in Okinawa Trough Implication for Fe-driven Microbial Anaerobic Oxidation of Methane (AMO)

NASA Astrophysics Data System (ADS)

Peng, X.; Guo, Z.

2016-12-01

Marine sediments associated with cold seeps at continental margins discharge substantial amounts of methane. Microbial anaerobic oxidation of methane (AMO) is a key biogeochemical process in these environments, which can trigger the formation of carbonate chimneys within sediments. The exact biogeochemical mechanism of how AMO control the formation of carbonate chimneys and influence their mineralogy and chemistry remains poorly constrained. Here, we use nano-scale secondary ion mass spectrometry to characterize the petrology and geochemistry of methane-derived Fe-rich carbonate chimneys formed between 5-7 Ma in the Northern Okinawa Trough. We find abundant framboid pyrites formed in the authigenic carbonates in the chimneys, indicating a non-Fe limitation sedimentary system. The δ13C values of carbonate (-18.9‰ to -45.9‰, PDB) show their probable origin from a mixing source of biogenic and thermogenic methane. The δ34S values range from -3.9 ± 0.5‰ to 23.2 ± 0.5‰ (VCDT), indicative of a strong exhaustion of sulfates in a local sulfate pool. We proposed that Fe-rich carbonate chimneys formed at the bottom of the sulfate-methane transition zone, beneath which Fe-driven AOM may happen and provide available ferrous for the extensive precipitation of pyrite in carbonate chimneys. The accumulation of reductive Fe in sediments via this process may widely occur in other analogous settings, with important application for Fe and S biogeochemical cycling within deep sediments at continental margins.

Non-Metallic Ti Oxides and MnS/FeS2 Complex Precipitation in Ti-Killed Steel

NASA Astrophysics Data System (ADS)

Chen, Jieyun; Zhao, Dan; Li, Huigai; Zheng, Shaobo

Titanium deoxidized experiments can be carried in vacuum induction furnace by adding Ti-Fe alloy in molten steel to simulate strip casting. Sub-rapid solidification samples were obtained in the method of suing copper mold. The morphology, the chemical composition and the structures of nanometer precipitations were carried out to investigate by transmission electron microscope (TEM) with Energy Dispersive X ray Spectrum (EDX) and by collecting diffraction patterns with carbon extraction specimens. It has been found that titanium oxides were TiO monoclinic, Ti4O7 anorthic and TiO2 orthogonal structure in one nanometer inclusion, as the composite oxide was precipitated MnS/FeS2 cubic structure during sub-rapid solidification. Thermodynamic calculation analysis showed that it was possible to precipitate different kinds of nonstoichiometric TiOx. The solid solution between MnS/FeS2 will precipitate on the surface of titanium oxides because of good coherency relationship.

[4Fe-4S]-cluster-depleted Azotobacter vinelandii ferredoxin I: a new 3Fe iron-sulfur protein.

PubMed Central

Stephens, P J; Morgan, T V; Devlin, F; Penner-Hahn, J E; Hodgson, K O; Scott, R A; Stout, C D; Burgess, B K

1985-01-01

Fe(CN)6(-3) oxidation of the aerobically isolated 7Fe Azotobacter vinelandii ferredoxin I, (7Fe)FdI, is a degradative reaction. Destruction of the [4Fe-4S] cluster occurs first, followed by destruction of the [3Fe-3S] cluster. At a Fe(CN)6(-3)/(7Fe)FdI concentration ratio of 20, the product is a mixture of apoprotein and protein containing only a [3Fe-3S] cluster, (3Fe)FdI. This protein mixture, after partial purification, has been characterized by absorption, CD, magnetic CD, and EPR and Fe x-ray absorption spectroscopies. EPR and magnetic CD spectra provide strong evidence that the [3Fe-3S] cluster in (3Fe)FdI is essentially identical in structure to that in (7Fe)FdI. Analysis of the extended x-ray absorption fine structure (EXAFS) of (3Fe)FdI finds Fe scattering at an average Fe...Fe distance of approximately equal to 2.7 A. The structure of the oxidized [3Fe-3S] cluster in solutions of oxidized (3Fe)FdI, and, by extension, of oxidized (7Fe)FdI, is thus different from that obtained by x-ray crystallography on oxidized (7Fe)FdI. Possible interpretations of this result are discussed. PMID:2994040

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.

Structural differences between the ready and unready oxidized states of [NiFe] hydrogenases.

PubMed

Volbeda, Anne; Martin, Lydie; Cavazza, Christine; Matho, Michaël; Faber, Bart W; Roseboom, Winfried; Albracht, Simon P J; Garcin, Elsa; Rousset, Marc; Fontecilla-Camps, Juan C

2005-05-01

[NiFe] hydrogenases catalyze the reversible heterolytic cleavage of molecular hydrogen. Several oxidized, inactive states of these enzymes are known that are distinguishable by their very different activation properties. So far, the structural basis for this difference has not been understood because of lack of relevant crystallographic data. Here, we present the crystal structure of the ready Ni-B state of Desulfovibrio fructosovorans [NiFe] hydrogenase and show it to have a putative mu-hydroxo Ni-Fe bridging ligand at the active site. On the other hand, a new, improved refinement procedure of the X-ray diffraction data obtained for putative unready Ni-A/Ni-SU states resulted in a more elongated electron density for the bridging ligand, suggesting that it is a diatomic species. The slow activation of the Ni-A state, compared with the rapid activation of the Ni-B state, is therefore proposed to result from the different chemical nature of the ligands in the two oxidized species. Our results along with very recent electrochemical studies suggest that the diatomic ligand could be hydro-peroxide.

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, S. C., E-mail: subhash.laserlab@gmail.com; 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, relatedmore » 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.« less

Fe-Ti oxide geothermometry: thermodynamic formulation and the estimation of intensive variables in silicic magmas

NASA Astrophysics Data System (ADS)

Ghiorso, Mark S.; Sack, O.

1991-10-01

A new thermodynamic formulation of the Fe-Ti oxide geothermometer/oxygen barometer is developed. The method is based upon recently calibrated models for spinel solid solutions in the quinary system (Fe2+, Mg)(Al,Fe3+,Cr)2O4-(Fe2+, Mg)2TiO4 by Sack and Ghiorso, and rhombohedral oxides in the quaternary system (Fe2+,Mg,Mn)TiO3-Fe2O3 (this paper). The formulation is internally consistent with thermodynamic models for (Fe2+,Mg)-olivine and -orthopyroxene solid solutions and end-member thermodynamic properties tabulated by Berman. The constituent expressions account for compositional and temperature dependent cation ordering and reproduce miscibility gap features in all of the component binaries. The calibration does not account for the excess Gibbs energy resulting from compositional and temperature dependent magnetic ordering in either phase. This limits application of the method to assemblages that equilibrated at temperatures above 600° C. Practical implementation of the proposed geothermometer/oxygen barometer requires minimal use of projection algorthms in accommodating compositions of naturally occurring phases. The new formulation is applied to the estimation of temperature and oxygen fugacity in a wide variety of intermediate to silicic volcanic rocks. In combination with previous work on olivine and orthopyroxene thermodynamics, equilibration pressures are computed for a subset of these volcanics that contain the assemblage quartz, oxides and either ferromagnesian silicate. The calculated log10 f O 2- T relations are reflected in coexisting ferromagnesian mineral assemblages. Volcanics with the lowest relative oxygen fugacity (Δlog10 f O 2) are characterized by the assemblage olivine-quartz, those with slightly higher Δ log10 f O 2 s, by the assemblage orthopyroxene-quartz. The sequence proceeds with the necessary phases biotite-feldspar, then hornblende-quartz-clinopyroxene, and finally at the highest Δ log10 f O 2 s, sphene

A model of early formation of uranium molecular oxides in laser-ablated plasmas

NASA Astrophysics Data System (ADS)

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.; Crowhurst, Jonathan C.; Rose, Timothy P.; Koroglu, Batikan; Radousky, Harry B.; Armstrong, Michael R.

2017-12-01

In this work, we present a newly constructed U x O y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. The global model is used to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.

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

Oxidation sulfidation resistance of Fe-Cr-Ni alloys

DOEpatents

Natesan, Ken; Baxter, David J.

1984-01-01

High temperature resistance of Fe-Cr-Ni alloy compositions to oxidative and/or sulfidative conditions is provided by the incorporation of about 1-8 wt. % of Zr or Nb and results in a two-phase composition having an alloy matrix as the first phase and a fine grained intermetallic composition as the second phase. The presence and location of the intermetallic composition between grains of the matrix provides mechanical strength, enhanced surface scale adhesion, and resistance to corrosive attack between grains of the alloy matrix at temperatures of 500.degree.-1000.degree. C.

Structured mesoporous Mn, Fe, and Co oxides: Synthesis, physicochemical, and catalytic properties

NASA Astrophysics Data System (ADS)

Maerle, A. A.; Karakulina, A. A.; Rodionova, L. I.; Moskovskaya, I. F.; Dobryakova, I. V.; Egorov, A. V.; Romanovskii, B. V.

2014-02-01

Structured mesoporous Mn, Fe, and Co oxides are synthesized using "soft" and "hard" templates; the resulting materials are characterized by XRD, SEM, TEM, BET, and TG. It is shown that in the first case, the oxides have high surface areas of up to 450 m2/g that are preserved after calcination of the material up to 300°C. Even though, the surface area of the oxides prepared by the "hard-template" method does not exceed 100 m2/g; it is, however, thermally stable up to 500°C. Catalytic activity of mesoporous oxides in methanol conversion was found to depend on both the nature of the transition metal and the type of template used in synthesis.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stengl, Vaclav, E-mail: stengl@uach.cz; Houskova, Vendula; Bakardjieva, Snejana

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 resultingmore » 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.« less

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

Ultra-small gadolinium oxide (Gd2O3) can be used as T1-weighted Magnetic Resonance Imaging (MRI) contrast agent own to its high longitudinal relaxivity (r1) and has attracted intensive attention in these years. In this paper, ultra-small Gd2O3 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 Gd2O3 by laser ablation in DEG. The r1 value and T1-weighted MR images are measured by a 3.0 T MRI spectroscope. The results show these nanoparticles with a high r1 value of 9.76 s-1 mM-1 to be good MRI contrast agents. We propose an explanation for the high r1 value of ultra-small Gd2O3 by considering the decreasing factor (surface to volume ratio of the nanoparticles, S/V) and the increasing factor (water hydration number of the Gd3+ on Gd2O3 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 Gd2O3 of high r1 value by laser ablation in DEG and develops the understanding of high relaxivity of ultra-small Gd2O3 MRI contrast agents.

Fe2P as a novel efficient catalyst promoter in Pd/C system for formic acid electro-oxidation in fuel cells reaction

NASA Astrophysics Data System (ADS)

Wang, Fulong; Xue, Huaiguo; Tian, Zhiqun; Xing, Wei; Feng, Ligang

2018-01-01

Developing catalyst promoter for Pd/C catalyst is significant for the catalytic ability improvement in energy transfer related electrochemical reactions. Herein, we demonstrate Fe2P as an efficient catalyst promoter in Pd/C catalyst system for formic acid electro-oxidation in fuel cells reactions. Adding Fe2P in the Pd/C catalyst system greatly increases the performances for formic acid oxidation by 3-4 times; the CO stripping technique displays two kinds of active sites formation in the Pd-Fe2P/C catalyst system coming from the interaction of Pd, Fe2P and Pd oxide species and both are more efficient for formic acid and CO-species electrooxidation. The smaller charge transfer resistance and Tafel slope for formic acid oxidation indicate the improvements in kinetics by Fe2P in the Pd-Fe2P/C system. The nanostructured hybrid units of Pd, Fe2P and carbon are evidently visible in the high resolution microscopy images and XPS technique confirmes the electronic effect in the catalyst system. The promotion effect of Fe2P in the catalyst system arising from the structure, composition and electronic effect changes is discussed with the help from multiple physical and electrochemical techniques. It is concluded that Fe2P as a significant catalyst promoter will have potential application in energy transfer related electrochemical reactions.

Synthesis and characterization of Fe-based metal and oxide based nanoparticles: discoveries and research highlights of potential applications in biology and medicine.

PubMed

Long, Nguyen Viet; Thi, Cao Minh; Yong, Yang; Cao, Yanqin; Wu, Haibo; Nogami, Masayuki

2014-01-01

In this review, we have presented the controlled synthesis of Fe-based metal and oxide nanoparticles with large size by chemical methods. The issues of the size, shape and morphology of Fe nanoparticles are discussed in the certain ranges of practical applications in biology and medicine. The homogeneous nanosystems of Fe-based metal and oxide nanoparticles with various sizes and shapes from the nano-to-micro ranges can be used in order to meet the demands of the treatments of dangerous tumors and cancers through magnetic hyperthermia and magnetic resonance imaging (MRI). In this context, the polyhedral Fe-based metal and oxide nanoparticles having large size in the ranges from 1000 nm to 5000 nm can be potentially used in magnetic hyperthermia and MRI in the innovative drug delivery, diagnosis, treatment, and therapy of tumor and cancer diseases because of their very high bio-adaptability. We have suggested that high stability and durability of Fe-based metal and oxide nanoparticles are very crucial to recent magnetic hyperthermia and MRI technology. The roles of various Fe-based nanostructures are focused in biomedical applications of tumors and cancers diagnostics, targeted drug delivery, and magnetic hyperthermia. Finally, Fe-based, α-, β- and γ-Fe2O3, and Fe3O4-based nanoparticles are shortly discussed in various potential applications in catalysis, biology, and medicine.

Lycopene, resveratrol, vitamin C and FeSO4 increase damage produced by pro-oxidant carcinogen 4-nitroquinoline-1-oxide in Drosophila melanogaster: Xenobiotic metabolism implications.

PubMed

Dueñas-García, I E; Heres-Pulido, M E; Arellano-Llamas, M R; De la Cruz-Núñez, J; Cisneros-Carrillo, V; Palacios-López, C S; Acosta-Anaya, L; Santos-Cruz, L F; Castañeda-Partida, L; Durán-Díaz, A

2017-05-01

4-nitroquinoline-1-oxide (4-NQO) is a pro-oxidant carcinogen bioactivated by xenobiotic metabolism (XM). We investigated if antioxidants lycopene [0.45, 0.9, 1.8 μM], resveratrol [11, 43, 172 μM], and vitamin C [5.6 mM] added or not with FeSO 4 [0.06 mM], modulate the genotoxicity of 4-NQO [2 mM] with the Drosophila wing spot test standard (ST) and high bioactivation (HB) crosses, with inducible and high levels of cytochromes P450, respectively. The genotoxicity of 4-NQO was higher when dissolved in an ethanol - acetone mixture. The antioxidants did not protect against 4-NQO in any of both crosses. In the ST cross, resveratrol [11 μM], vitamin C and FeSO 4 resulted in genotoxicity; the three antioxidants and FeSO 4 increased the damage of 4-NQO. In the HB cross, none of the antioxidants, neither FeSO 4 , were genotoxic. Only resveratrol [172 μM] + 4-NQO increased the genotoxic activity in both crosses. We concluded that the effects of the antioxidants, FeSO 4 and the modulation of 4-NQO were the result of the difference of Cyp450s levels, between the ST and HB crosses. We propose that the basal levels of the XM's enzymes in the ST cross interacted with a putative pro-oxidant activity of the compounds added to the pro-oxidant effects of 4-NQO. Copyright © 2017. Published by Elsevier Ltd.

CdS Nanoparticle-Modified α-Fe2O3/TiO2 Nanorod Array Photoanode for Efficient Photoelectrochemical Water Oxidation.

PubMed

Yin, Ruiyang; Liu, Mingyang; Tang, Rui; Yin, Longwei

2017-09-02

In this work, we demonstrate a facile successive ionic layer adsorption and reaction process accompanied by hydrothermal method to synthesize CdS nanoparticle-modified α-Fe 2 O 3 /TiO 2 nanorod array for efficient photoelectrochemical (PEC) water oxidation. By integrating CdS/α-Fe 2 O 3 /TiO 2 ternary system, light absorption ability of the photoanode can be effectively improved with an obviously broadened optical-response to visible light region, greatly facilitates the separation of photogenerated carriers, giving rise to the enhancement of PEC water oxidation performance. Importantly, for the designed abnormal type-II heterostructure between Fe 2 O 3 /TiO 2 , the conduction band position of Fe 2 O 3 is higher than that of TiO 2 , the photogenerated electrons from Fe 2 O 3 will rapidly recombine with the photogenerated holes from TiO 2 , thus leads to an efficient separation of photogenerated electrons from Fe 2 O 3 /holes from TiO 2 at the Fe 2 O 3 /TiO 2 interface, greatly improving the separation efficiency of photogenerated holes within Fe 2 O 3 and enhances the photogenerated electron injection efficiency in TiO 2 . Working as the photoanodes of PEC water oxidation, CdS/α-Fe 2 O 3 /TiO 2 heterostucture electrode exhibits improved photocurrent density of 0.62 mA cm - 2 at 1.23 V vs. reversible hydrogen electrode (RHE) in alkaline electrolyte, with an obviously negatively shifted onset potential of 80 mV. This work provides promising methods to enhance the PEC water oxidation performance of the TiO 2 -based heterostructure photoanodes.

3-D laser confocal microscopy study of the oxidation of NdFeB magnets in atmospheric conditions

NASA Astrophysics Data System (ADS)

Meakin, J. P.; Speight, J. D.; Sheridan, R. S.; Bradshaw, A.; Harris, I. R.; Williams, A. J.; Walton, A.

2016-08-01

Neodymium iron boron (NdFeB) magnets are used in a number of important applications, such as generators in gearless wind turbines, motors in electric vehicles and electronic goods (e.g.- computer hard disk drives, HDD). Hydrogen can be used as a processing gas to separate and recycle scrap sintered Nd-Fe-B magnets from end-of-life products to form a powder suitable for recycling. However, the magnets are likely to have been exposed to atmospheric conditions prior to processing, and any oxidation could lead to activation problems for the hydrogen decrepitation reaction. Many previous studies on the oxidation of NdFeB magnets have been performed at elevated temperatures; however, few studies have been formed under atmospheric conditions. In this paper a combination of 3-D laser confocal microscopy and Raman spectroscopy have been used to assess the composition, morphology and rate of oxidation/corrosion on scrap sintered NdFeB magnets. Confocal microscopy has been employed to measure the growth of surface reaction products at room temperature, immediately after exposure to air. The results showed that there was a significant height increase at the triple junctions of the Nd-rich grain boundaries. Using Raman spectroscopy, the product was shown to consist of Nd2O3 and formed only on the Nd-rich triple junctions. The diffusion coefficient of the triple junction reaction product growth at 20 °C was determined to be approximately 4 × 10-13 cm2/sec. This value is several orders of magnitude larger than values derived from the diffusion controlled oxide growth observations at elevated temperatures in the literature. This indicates that the growth of the room temperature oxidation products are likely defect enhanced processes at the NdFeB triple junctions.

Facile transformation of FeO/Fe3O4 core-shell nanocubes to Fe3O4 via magnetic stimulation

NASA Astrophysics Data System (ADS)

Lak, Aidin; Niculaes, Dina; Anyfantis, George C.; Bertoni, Giovanni; Barthel, Markus J.; Marras, Sergio; Cassani, Marco; Nitti, Simone; Athanassiou, Athanassia; Giannini, Cinzia; Pellegrino, Teresa

2016-09-01

Here, we propose the use of magnetic hyperthermia as a means to trigger the oxidation of Fe1-xO/Fe3-δO4 core-shell nanocubes to Fe3-δO4 phase. As a first relevant consequence, the specific absorption rate (SAR) of the initial core-shell nanocubes doubles after exposure to 25 cycles of alternating magnetic field stimulation. The improved SAR value was attributed to a gradual transformation of the Fe1-xO core to Fe3-δO4, as evidenced by structural analysis including high resolution electron microscopy and Rietveld analysis of X-ray diffraction patterns. The magnetically oxidized nanocubes, having large and coherent Fe3-δO4 domains, reveal high saturation magnetization and behave superparamagnetically at room temperature. In comparison, the treatment of the same starting core-shell nanocubes by commonly used thermal annealing process renders a transformation to γ-Fe2O3. In contrast to other thermal annealing processes, the method here presented has the advantage of promoting the oxidation at a macroscopic temperature below 37 °C. Using this soft oxidation process, we demonstrate that biotin-functionalized core-shell nanocubes can undergo a mild self-oxidation transformation without losing their functional molecular binding activity.

Correlation between the oxide impedance and corrosion behavior of Zr-Nb-Sn-Fe-Cu alloys

NASA Astrophysics Data System (ADS)

Park, Sang-Yoon; Lee, Myung-Ho; Jeong, Yong-Hwan; Jung, Youn-Ho

2004-12-01

The correlation between the oxide impedance and corrosion behavior of two series of Zr-Nb-Sn-Fe-Cu alloys was evaluated. Corrosion tests were performed in a 70 ppm LiOH aqueous solution at 360°C for 300 days. The results of the corrosion tests revealed that the corrosion behavior of the alloys depended on the Nb and Sn content. The impedance characteristics for the pre- and post-transition oxide layers formed on the surface of the alloys were investigated in sulfuric acid at room temperature. From the results, a pertinent equivalent circuit model was preferably established, explaining the properties of double oxide layers. The impedance of the oxide layers correlated with the corrosion behavior; better corrosion resistance always showed higher electric resistance for the inner layers. It is thus concluded that a pertinent equivalent circuit model would be useful for evaluating the long-term corrosion behavior of Zr-Nb-Sn-Fe-Cu alloys.

A Fe3O4/FeAl2O4 composite coating via plasma electrolytic oxidation on Q235 carbon steel for Fenton-like degradation of phenol.

PubMed

Wang, Jiankang; Yao, Zhongping; Yang, Min; Wang, Yajing; Xia, Qixing; Jiang, Zhaohua

2016-08-01

The Fe3O4/FeAl2O4 composite coatings were successfully fabricated on Q235 carbon steel by plasma electrolytic oxidation technique and used to degrade phenol by Fenton-like system. XRD, SEM, and XPS indicated that Fe3O4 and FeAl2O4 composite coating had a hierarchical porous structure. The effects of various parameters such as pH, phenol concentration, and H2O2 dosage on catalytic activity were investigated. The results indicated that with increasing of pH and phenol content, the phenol degradation efficiency was reduced significantly. However, the degradation rate was improved with the addition of H2O2, but dropped with further increasing of H2O2. Moreover, 100 % removal efficiency with 35 mg/L phenol was obtained within 60 min at 303 K and pH 4.0 with 6.0 mmol/L H2O2 on 6-cm(2) iron oxide coating. The degradation process consisted of induction period and rapid degradation period; both of them followed pseudo-first-order reaction. Hydroxyl radicals were the mainly oxidizing species during phenol degradation by using n-butanol as hydroxyl radical scavenger. Based on Fe leaching and the reaction kinetics, a possible phenol degradation mechanism was proposed. The catalyst exhibited excellent stability.

PHOTONICS AND NANOTECHNOLOGY Pulsed laser ablation of binary semiconductors: mechanisms of vaporisation and cluster formation

NASA Astrophysics Data System (ADS)

Bulgakov, A. V.; Evtushenko, A. B.; Shukhov, Yu G.; Ozerov, I.; Marin, W.

2010-12-01

Formation of small clusters during pulsed ablation of two binary semiconductors, zinc oxide and indium phosphide, in vacuum by UV, visible, and IR laser radiation is comparatively studied. The irradiation conditions favourable for generation of neutral and charged ZnnOm and InnPm clusters of different stoichiometry in the ablation products are found. The size and composition of the clusters, their expansion dynamics and reactivity are analysed by time-of-flight mass spectrometry. A particular attention is paid to the mechanisms of ZnO and InP ablation as a function of laser fluence, with the use of different ablation models. It is established that ZnO evapourates congruently in a wide range of irradiation conditions, while InP ablation leads to enrichment of the target surface with indium. It is shown that this radically different character of semiconductor ablation determines the composition of the nanostructures formed: zinc oxide clusters are mainly stoichiometric, whereas InnPm particles are significantly enriched with indium.

Oxidation behavior and area specific resistance of La, Cu and B alloyed Fe-22Cr ferritic steels for solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Swaminathan, Srinivasan; Ko, Yoon Seok; Lee, Young-Su; Kim, Dong-Ik

2017-11-01

Two Fe-22 wt% Cr ferritic stainless steels containing varying concentrations of La (0.14 or 0.52 wt%), Cu (0.17 or 1.74 wt%) and B (48 or 109 ppm) are investigated with respect to oxidation behavior and high temperature area specific resistance (ASR) of the surface oxide scales. To determine the oxidation resistance of developed steels, continuous isothermal oxidation is carried out at 800 °C in air, for 2000 h, and their thermally grown oxide scale is characterized using dynamic SIMS, SEM/EDX, XRD and GI-XRD techniques. To assess their electrical performance, the ASR measurement by four-point probe method is conducted at 800 °C in air, for 400 h. In higher La content steel, the La-oxides at the scale/alloy interface promotes the oxygen transport which resulted in sub-surface oxidation of Mn, Cr, Ti and Al. Moreover, the inward growth of oxides contributes to increase of Fe-Cr alloy protrusions within the scale, which reduced the ASR. In contrast, sub-surface oxidation is reduced in high Cu-alloyed steel by segregated Cu at the scale/alloy interface. Thus, addition of Cu is effective to oxidation resistance and also to better electrical performance. However, no obvious impact of B on the scale sequence and/or ASR is observed.

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.

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 ...

In situ growth of well-ordered NiFe-MOF-74 on Ni foam by Fe2+ induction as an efficient and stable electrocatalyst for water oxidation.

PubMed

Xing, Jiale; Guo, Kailu; Zou, Zehua; Cai, Minmin; Du, Jing; Xu, Cailing

2018-06-06

Well-ordered NiFe-MOF-74 is in situ grown on Ni foam by the induction of Fe2+ and directly used as an OER electrocatalyst. Benefited from the intrinsic open porous structure of MOF-74, the in situ formed MOF arrays and the synergistic effect of Ni and Fe, outstanding water oxidation activity is obtained in alkaline electrolytes with an overpotential of 223 mV at 10 mA cm-2.

Facile synthesis of magnetic ZnFe2O4-reduced graphene oxide hybrid and its photo-Fenton-like behavior under visible iradiation.

PubMed

Yao, Yunjin; Qin, Jiacheng; Cai, Yunmu; Wei, Fengyu; Lu, Fang; Wang, Shaobin

2014-06-01

A magnetic ZnFe2O4-reduced graphene oxide (rGO) hybrid was successfully developed as a heterogeneous catalyst for photo-Fenton-like decolorization of various dyes using peroxymonosulfate (PMS) as an oxidant under visible light irradiation. Through an in situ chemical deposition and reduction, ZnFe2O4 nanoparticles (NPs) with an average size of 23.7 nm were anchored uniformly on rGO sheets to form a ZnFe2O4-rGO hybrid. The catalytic activities in oxidative decomposition of organic dyes were evaluated. The reaction kinetics, effect of ion species and strength, catalytic stability, degradation mechanism, as well as the roles of ZnFe2O4 and graphene were also studied. ZnFe2O4-rGO showed to be a promising photocatalyst with magnetism for the oxidative degradation of aqueous organic pollutants and simple separation. The combination of ZnFe2O4 NPs with graphene sheets leads to a much higher catalytic activity than pure ZnFe2O4. Graphene acted as not only a support and stabilizer for ZnFe2O4 to prevent them from aggregation, largely improving the charge separation in the hybrid material, but also a catalyst for activating PMS to produce sulfate radicals at the same time. The ZnFe2O4-rGO hybrid exhibited stable performance without losing activity after five successive runs.

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

2015-01-06

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.

Fe-Ti-oxide textures and microstructures in shear zones from oceanic gabbros at Atlantis Bank, Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Till, Jessica; Morales, Luiz F. G.; Rybacki, Erik

2016-04-01

Ocean drilling expeditions at several oceanic core complexes formed at slow- and ultra-slow-spreading ridges have recovered cores containing numerous zones of oxide-rich gabbros containing ilmenite and magnetite. In these cores, high modal concentrations of Fe-Ti-oxides are systematically associated with high-temperature plastic deformation features in silicates. We present observations of Fe-Ti-oxide mineral structures and textural characteristics from a series of oxide-rich shear zones from Atlantis Bank (ODP Site 735B) on the Southwest Indian Ridge aimed at determining how oxide mineral abundances relate to strain localization. Fe-Ti-oxide minerals in undeformed oxide gabbros and in highly deformed samples from natural shear zones generally have morphologies characteristic of crystallized melt, including highly cuspate grains and low dihedral angles. Anisotropy of magnetic susceptibility in oxide-rich shear zones is very strong, with fabrics mainly characterized by strong magnetic foliations parallel to the macroscopic foliation. Crystallographic preferred orientations (CPO) in magnetite are generally weak, with occasionally well-defined textures. Ilmenite typically displays well-developed CPOs, however, the melt-like ilmenite grain shapes indicate that at least part of the crystallographic texture results from oriented ilmenite growth during post-deformation crystallization. The oxides are hypothesized to have initially been present as isolated pockets of trapped melt (intercumulus liquid) in a load-bearing silicate framework. Progressive plastic deformation of silicate phases at high-temperature mainly produced two features: (i) elongated melt pockets, which crystallized to form strings of opaque minerals and (ii), interconnected networks of melt regions. The latter lead to intense strain localization of the rock, which appears as oxide-rich mylonites in the samples. In some samples, abundant low-angle grain boundaries in both magnetite and ilmenite suggest

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. © FASEB.

[FeFe]- and [NiFe]-hydrogenase diversity, mechanism, and maturation.

PubMed

Peters, John W; Schut, Gerrit J; Boyd, Eric S; Mulder, David W; Shepard, Eric M; Broderick, Joan B; King, Paul W; Adams, Michael W W

2015-06-01

The [FeFe]- and [NiFe]-hydrogenases catalyze the formal interconversion between hydrogen and protons and electrons, possess characteristic non-protein ligands at their catalytic sites and thus share common mechanistic features. Despite the similarities between these two types of hydrogenases, they clearly have distinct evolutionary origins and likely emerged from different selective pressures. [FeFe]-hydrogenases are widely distributed in fermentative anaerobic microorganisms and likely evolved under selective pressure to couple hydrogen production to the recycling of electron carriers that accumulate during anaerobic metabolism. In contrast, many [NiFe]-hydrogenases catalyze hydrogen oxidation as part of energy metabolism and were likely key enzymes in early life and arguably represent the predecessors of modern respiratory metabolism. Although the reversible combination of protons and electrons to generate hydrogen gas is the simplest of chemical reactions, the [FeFe]- and [NiFe]-hydrogenases have distinct mechanisms and differ in the fundamental chemistry associated with proton transfer and control of electron flow that also help to define catalytic bias. A unifying feature of these enzymes is that hydrogen activation itself has been restricted to one solution involving diatomic ligands (carbon monoxide and cyanide) bound to an Fe ion. On the other hand, and quite remarkably, the biosynthetic mechanisms to produce these ligands are exclusive to each type of enzyme. Furthermore, these mechanisms represent two independent solutions to the formation of complex bioinorganic active sites for catalyzing the simplest of chemical reactions, reversible hydrogen oxidation. As such, the [FeFe]- and [NiFe]-hydrogenases are arguably the most profound case of convergent evolution. This article is part of a Special Issue entitled: Fe/S proteins: Analysis, structure, function, biogenesis and diseases. Copyright © 2014 Elsevier B.V. All rights reserved.

A model of early formation of uranium molecular oxides in laser-ablated plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.

Here, in this work, we present a newly constructed U xO y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. Finally, the global model is usedmore » to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.« less

A model of early formation of uranium molecular oxides in laser-ablated plasmas

DOE PAGES

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.; ...

2017-10-12

Here, in this work, we present a newly constructed U xO y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. Finally, the global model is usedmore » to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.« less

Biodegradation of organic matter and anodic microbial communities analysis in sediment microbial fuel cells with/without Fe(III) oxide addition.

PubMed

Xu, Xun; Zhao, Qingliang; Wu, Mingsong; Ding, Jing; Zhang, Weixian

2017-02-01

To enhance the biodegradation of organic matter in sediment microbial fuel cell (SMFC), Fe(III) oxide, as an alternative electron acceptor, was added into the sediment. Results showed that the SMFC with Fe(III) oxide addition obtained higher removal efficiencies for organics than the SMFC without Fe(III) oxide addition and open circuit bioreactor, and produced a maximum power density (P max ) of 87.85mW/m 2 with a corresponding maximum voltage (V max ) of 0.664V. The alteration of UV-254 and specific ultraviolet absorbance (SUVA) also demonstrated the organic matter in sediments can be effectively removed. High-throughput sequencing of anodic microbial communities indicated that bacteria from the genus Geobacter were predominantly detected (21.23%) in the biofilm formed on the anode of SMFCs, while Pseudomonas was the most predominant genus (18.12%) in the presence of Fe(III) oxide. Additionally, compared with the open circuit bioreactor, more electrogenic bacteria attached to the biofilm of anode in SMFCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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.

Final Report: Molecular mechanisms and kinetics of microbial anaerobic nitrate-dependent U(IV) and Fe(II) oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

O'Day, Peggy A.; Asta, Maria P.; Kanematsu, Masakazu

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 reactivemore » 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.« less

Triple-mixture of Zn, Mn, and Fe increases bioaccumulation and causes oxidative stress in freshwater neotropical fish.

PubMed

de Oliveira, Luciana Fernandes; Santos, Caroline; Risso, Wagner Ezequiel; Dos Reis Martinez, Claudia Bueno

2018-06-01

Metal bioaccumulation and oxidative stress biomarkers were determined in Prochilodus lineatus to understand the effects of short-term exposure to a triple-mixture of Zn, Mn, and Fe. Three independent tests were carried out, in which fish were exposed to 3 concentrations of Zn (0.18, 1.0, and 5.0 mg L -1 ), Mn (0.1, 0.5, and 5.0 mg L -1 ), and in the mix test to Fe (5.0 mg L -1 ) and a mixture of Zn (1.0 mg L -1 ) + Mn (0.5 mg L -1 ), with and without Fe. After exposure for 96 h, tissues were removed for metal bioaccumulation analysis and oxidative stress biomarkers were determined in liver, along with DNA damage in blood cells. Our results revealed that Zn and Mn were bioaccumulated in fish tissues after exposure to 5.0 mg L -1 , whereas Fe only bioaccumulated in muscle and gills after mixture exposure. Results indicated that 1 metal interfered with the other's bioaccumulation. In P. lineatus, 5 mg L -1 of both Mn and Fe were toxic, because damage was observed (lipid peroxidation [LPO] in liver and DNA damage in blood cells), whereas Zn induced liver responses (metallothionein [MT] and reduced glutathione [GSH] increases) to prevent damage. In terms of bioaccumulation and alterations of oxidative stress biomarkers, we showed that Zn, Mn, and Fe triple-mixture enhances individual metal toxicity in Neotropical fish P. lineatus. Environ Toxicol Chem 2018;37:1749-1756. © 2018 SETAC. © 2018 SETAC.

Fabrication, characterization, and photocatalytic property of α-Fe2O3/graphene oxide composite

NASA Astrophysics Data System (ADS)

Li, Hong; Zhao, Qidong; Li, Xinyong; Zhu, Zhengru; Tade, Moses; Liu, Shaomin

2013-06-01

Spindle-shaped microstructure of α-Fe2O3 was successfully synthesized by a simple hydrothermal method. The α-Fe2O3/graphene oxide (GO) composites was prepared using a modified Hummers' strategy. The properties of the samples were systematically investigated by X-ray powder diffraction (XRD), UV-Vis diffuse reflectance spectrophotometer, transmission electron microscope, atomic force microscope, X-ray photoelectron spectroscopy, and Raman spectroscopy (Raman) techniques. GO nanosheets act as supporting materials for anchoring the α-Fe2O3 particles. The average crystallite sizes of the α-Fe2O3 and α-Fe2O3/GO samples are ca. 27 and 24 nm, respectively. The possible growth of α-Fe2O3 onto GO layers led to a higher absorbance capacity for visible light by α-Fe2O3/GO than α-Fe2O3 composite. The photocatalytic degradation of toluene over the α-Fe2O3 and α-Fe2O3/GO samples under xenon-lamp irradiation was comparatively studied by in situ FTIR technique. The results indicate that the α-Fe2O3/GO sample synthesized exhibited a higher capacity for the degradation of toluene. The composite of α-Fe2O3/GO could be promisingly applied in photo-driven air purification.

Capacity and recycling of polyoxometalate applied in As(III) oxidation by Fe(II)-Amended zero-valent aluminum.

PubMed

Hsu, Liang-Ching; Cho, Yen-Lin; Liu, Yu-Ting; Tzou, Yu-Min; Teah, Heng Yi

2018-06-01

Arsenic remediation is often initiated by oxidizing As(III) to As(V) to alleviate its toxicity and mobility. Due to the easy availability, zero-valent Al (ZVAl) like Al can was considered as potential alternatives to facilitate As(III) oxidation. This study determined the capability and recycling of polyoxometalate (POM) to catalyze As(III) oxidation in Fe(II)-amended ZVAl systems. POM acquired electrons from ZVAl more effectively at pH 1 than at pH 2. While 76% of the reduced POM [POM(e - )] reacted with O 2(g) to generate H 2 O 2 at pH 1, only 60% of POM(e - ) was used to produce H 2 O 2 at pH 2. The remaining POM(e - ) was oxidized by the generated H 2 O 2 . Such additional consumption of POM(e - ) and H 2 O 2 led to the incomplete As(III) oxidation in the system without residual ZVAl and emphasized the need for a continuous electron supply from ZVAl to compensate the depletion of POM(e - ). After the hydrolyzation at pH 6.0, the XANES data evidenced that not only As(V) but WO 4 released from the POM retained on surfaces of Al/Fe hydroxides. The competition for sorption sites on Al/Fe hydroxides between As(V) and WO 4 led to the incomplete As removal. Despite the loss of WO 4 , the POM re-polymerized at pH 1 still showed the comparable capability to catalyze As(III) oxidation with original POM. This study revealed electron transfer pathways from ZVAl to As(III) as catalyzed by POM and evidenced the effective POM recycling after As removal, which lowers the cost of POM application and turns the ZVAl/Fe(II)/POM/O 2 system into a practical strategy for As remediation. Copyright © 2018 Elsevier Ltd. All rights reserved.

A kinetic study of the reactions FeO+ + O, Fe+.N2 + O, Fe+.O2 + O and FeO+ + CO: implications for sporadic E layers in the upper atmosphere.

PubMed

Woodcock, K R S; Vondrak, T; Meech, S R; Plane, J M C

2006-04-21

These gas-phase reactions were studied by pulsed laser ablation of an iron target to produce Fe(+) in a fast flow tube, with detection of the ions by quadrupole mass spectrometry. Fe(+).N(2) and Fe(+).O(2) were produced by injecting N(2) and O(2), respectively, into the flow tube. FeO(+) was produced from Fe(+) by addition of N(2)O, or by ligand-switching from Fe(+).N(2) following the addition of atomic O. The following rate coefficients were measured: k(FeO(+) + O --> Fe(+) + O(2), 186-294 K) = (3.2 +/- 1.5) x 10(-11); k(Fe(+).N(2) + O --> FeO(+)+ N(2), 294 K) = (4.6 +/- 2.5) x 10(-10); k(Fe(+).O(2) + O --> FeO(+) + O(2), 294 K) = (6.3 +/- 2.7) x 10(-11); and k(FeO(+) + CO --> Fe(+) + CO(2), 294 K) = (1.59 +/- 0.34) x 10(-10) cm(3) molecule(-1) s(-1), where the quoted uncertainties are a combination of the 1sigma standard errors in the kinetic data and the systematic experimental errors. The surprisingly slow reaction between FeO(+) and O is examined using ab initio quantum calculations of the relevant potential energy surfaces. The importance of this reaction for controlling the lifetime of sporadic E layers is then demonstrated using a model of the upper mesosphere and lower thermosphere.

Sc-substituted La0.6Sr0.4FeO3-δ mixed conducting oxides as promising electrodes for symmetrical solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Liu, Xuejiao; Han, Da; Zhou, Yucun; Meng, Xie; Wu, Hao; Li, Junliang; Zeng, Fanrong; Zhan, Zhongliang

2014-01-01

The main barrier to symmetrical solid oxide fuel cells (SOFCs), where the same catalytic materials are used simultaneously as the anodes and the cathodes, is to identify a redox-stable catalyst that exhibits superior catalytic activities for both fuel oxidation and oxygen reduction reactions. Here we report a Sc-substituted La0.6Sr0.4FeO3-δ oxide, La0.6Sr0.4Fe0.9Sc0.1O3-δ, that shows great promise as a new symmetrical electrode material with good structural stability and reasonable conductivities in air and hydrogen. We further demonstrate that nano-scale La0.6Sr0.4Fe0.9Sc0.1O3-δ catalysts impregnated into the porous La0.9Sr0.1Ga0.8Mg0.2O3-δ backbones exhibit good catalytic activities for oxygen reduction and hydrogen oxidation reactions and thereby yield low polarization resistances, e.g., 0.015 Ω cm2 in air and 0.29 Ω cm2 in hydrogen with appropriate current collection at 800 °C. Thin La0.9Sr0.1Ga0.8Mg0.2O3-δ electrolyte fuel cells with such symmetrical La0.6Sr0.4Fe0.9Sc0.1O3-δ catalysts showed maximum power densities of 0.56 and 0.32 W cm-2 when operating on 97% H2-3% H2O at 800 and 700 °C, respectively.

Spectral reflectance properties (0.4-2.5 um) of secondary Fe-oxide, Fe-hydroxide, and Fe-sulfate-hydrate minerals associated with sulfide-bearing mine waste

USGS Publications Warehouse

Crowley, J.K.; Williams, D.E.; Hammarstrom1, J.M.; Piatak, N.; Mars, J.C.; Chou, I-Ming

2006-01-01

Fifteen Fe-oxide, Fe-hydroxide, and Fe-sulphate-hydrate mineral species commonly associated with sulphide bearing mine wastes were characterized by using X-ray powder diffraction and scanning electron microscope methods. Diffuse reflectance spectra of the samples show diagnostic absorption features related to electronic processes involving ferric and/or ferrous iron, and to vibrational processes involving water and hydroxyl ions. Such spectral features enable field and remote sensing based studies of the mineral distributions. Because secondary minerals are sensitive indicators of pH, Eh, relative humidity, and other environmental conditions, spectral mapping of these minerals promises to have important applications to mine waste remediation studies. This report releases digital (ascii) spectra (spectral_data_files.zip) of the fifteen mineral samples to facilitate usage of the data with spectral libraries and spectral analysis software. The spectral data are provided in a two-column format listing wavelength (in micrometers) and reflectance, respectively.

Ferric iron amendment increases Fe(III)-reducing microbial diversity and carbon oxidation in on-site wastewater systems.

PubMed

Azam, Hossain M; Finneran, Kevin T

2013-01-01

Onsite wastewater systems, or septic tanks, serve approximately 25% of the United States population; they are therefore a critical component of the total carbon balance for natural water bodies. Septic tanks operate under strictly anaerobic conditions, and fermentation is the dominant process driving carbon transformation. Nitrate, Fe(III), and sulfate reduction may be operating to a limited extent in any given septic tank. Electron acceptor amendments will increase carbon oxidation, but nitrate is toxic and sulfate generates corrosive sulfides, which may damage septic system infrastructure. Fe(III) reducing microorganisms transform all major classes of organic carbon that are dominant in septic wastewater: low molecular weight organic acids, carbohydrate monomers and polymers, and lipids. Fe(III) is not toxic, and the reduction product Fe(II) is minimally disruptive if the starting Fe(III) is added at 50-150 mg L(-1). We used (14)C radiolabeled acetate, lactate, propionate, butyrate, glucose, starch, and oleic acid to demonstrate that short and long-term carbon oxidation is increased when different forms of Fe(III) are amended to septic wastewater. The rates of carbon mineralization to (14)CO(2) increased 2-5 times (relative to unamended systems) in the presence of Fe(III). The extent of mineralization reached 90% for some carbon compounds when Fe(III) was present, compared to levels of 50-60% in the absence of Fe(III). (14)CH(4) was not generated when Fe(III) was added, demonstrating that this strategy can limit methane emissions from septic systems. Amplified 16S rDNA restriction analysis indicated that unique Fe(III)-reducing microbial communities increased significantly in Fe(III)-amended incubations, with Fe(III)-reducers becoming the dominant microbial community in several incubations. The form of Fe(III) added had a significant impact on the rate and extent of mineralization; ferrihydrite and lepidocrocite were favored as solid phase Fe(III) and chelated Fe

Antioxidant properties of xanthones from Calophyllum brasiliense: prevention of oxidative damage induced by FeSO₄.

PubMed

Blanco-Ayala, Tonali; Lugo-Huitrón, Rafael; Serrano-López, Elizabeth M; Reyes-Chilpa, Ricardo; Rangel-López, Edgar; Pineda, Benjamín; Medina-Campos, Omar Noel; Sánchez-Chapul, Laura; Pinzón, Enrique; Cristina, Trejo-Solis; Silva-Adaya, Daniela; Pedraza-Chaverrí, José; Ríos, Camilo; de la Cruz, Verónica Pérez; Torres-Ramos, Mónica

2013-10-11

Reactive oxygen species (ROS) are important mediators in a number of degenerative diseases. Oxidative stress refers to the imbalance between the production of ROS and the ability to scavenge these species through endogenous antioxidant systems. Since antioxidants can inhibit oxidative processes, it becomes relevant to describe natural compounds with antioxidant properties which may be designed as therapies to decrease oxidative damage and stimulate endogenous cytoprotective systems. The present study tested the protective effect of two xanthones isolated from the heartwood of Calophyllum brasilienses against FeSO₄-induced toxicity. Through combinatory chemistry assays, we evaluated the superoxide (O₂·⁻), hydroxyl radical (OH·), hydrogen peroxide (H₂O₂) and peroxynitrite (ONO⁻) scavenging capacity of jacareubin (xanthone III) and 2-(3,3-dimethylallyl)-1,3,5,6-tetrahydroxyxanthone (xanthone V). The effect of these xanthones on murine DNA and bovine serum albumin degradation induced by an OH· generator system was also evaluated. Additionally, we investigated the effect of these xanthones on ROS production, lipid peroxidation and glutathione reductase (GR) activity in FeSO₄-exposed brain, liver and lung rat homogenates. Xanthone V exhibited a better scavenging capacity for O₂·⁻, ONOO⁻ and OH· than xanthone III, although both xanthones were unable to trap H₂O₂. Additionally, xanthones III and V prevented the albumin and DNA degradation induced by the OH· generator system. Lipid peroxidation and ROS production evoked by FeSO₄ were decreased by both xanthones in all tissues tested. Xanthones III and V also prevented the GR activity depletion induced by pro-oxidant activity only in the brain. Altogether, the collected evidence suggests that xanthones can play a role as potential agents to attenuate the oxidative damage produced by different pro-oxidants.

Oxidation Studies of SiAlON/MgAlON Ceramics with Fe2O3 and CaO Impurities, Part I: Kinetics

NASA Astrophysics Data System (ADS)

Li, Peng; Zhang, Mei; Teng, Lidong; Seetharaman, Seshadri

2013-02-01

T he oxidation behaviors of composites SiAlON/MgAlON phases (β-SiAlON, 15R-SiAlON and MgAlON) synthesized from the residue during the leaching treatment of salt cake and corresponding synthetic samples were investigated in air by thermogravimetric measurements. Combined kinetics, viz. linear law + arctan law + parabolic law, are used to describe the kinetics of oxidation in isothermal mode. The oxidation studies reveal the effects of impurities, namely, Fe2O3 and CaO, present in the salt cake residue. The addition of Fe2O3 results in a lower activation energy and more aggressive oxidation. The addition of CaO caused the shrinkage during the synthesis and liquid formation during the oxidation above 1673 K (1400 °C). The impurities of CaO and Fe2O3 in the leaching residue can result in an aggressive oxidation at low temperature and a protective oxidation at temperatures above the eutectic point.

Interaction mechanisms between α-Fe2O3, γ-Fe2O3 and Fe3O4 nanoparticles and Citrus maxima seedlings.

PubMed

Li, Junli; Hu, Jing; Xiao, Lian; Wang, Yunqiang; Wang, Xilong

2018-06-01

The interactions between α-Fe 2 O 3 , γ-Fe 2 O 3 , and Fe 3 O 4 nanoparticles (NPs) and Citrus maxima seedlings were examined so as to better understand possible particle applications as an Fe source for crop plants. NPs toxicity to the exposed plant was investigated as well. The α- and γ-Fe 2 O 3 NPs were accumulated by plant root cells through diapirism and endocytosis, respectively, but translocation to the shoots was negligible. Analysis of malondialdehyde (MDA), soluble protein content, and antioxidant enzyme activity revealed that Fe deficiency induced strong oxidative stress in Citrus maxima seedlings, which followed an order of Fe deficiency>Fe 3+ >α-Fe 2 O 3 , γ-Fe 2 O 3 NPs>Fe 3 O 4 NPs. However, the chlorophyll leaf content of plants exposed to α-Fe 2 O 3 , γ-Fe 2 O 3 , Fe 3 O 4 NPs and Fe 3+ were significantly reduced by 31.1%, 14.8%, 18.8% and 22.0%, respectively, relative to the control. Furthermore, RT-PCR analysis revealed no up-regulation of AHA and Nramp3 genes in Citrus maxima roots; however, the relative FRO2 gene expression upon exposure to iron oxide NPs was 1.4-2.8-fold higher than the control. Ferric reductase activity was consistently enhanced upon iron oxide NPs exposure. These findings advance understanding of the interaction mechanisms between metal oxide NPs and plants, and provide important knowledge need for the possible application of these materials in agriculture. Copyright © 2017 Elsevier B.V. All rights reserved.