Reduction of blue tungsten oxide

International Nuclear Information System (INIS)

Wilken, T.; Wert, C.; Woodhouse, J.; Morcom, W.

1975-01-01

A significant portion of commercial tungsten is produced by hydrogen reduction of oxides. Although several modes of reduction are possible, hydrogen reduction is used where high purity tungsten is required and where the addition of other elements or compounds is desired for modification of the metal, as is done for filaments in the lamp industry. Although several investigations of the reduction of oxides have been reported (1 to 5), few principles have been developed which can aid in assessment of current commercial practice. The reduction process was examined under conditions approximating commercial practice. The specific objectives were to determine the effects of dopants, of water vapor in the reducing atmosphere, and of reduction temperature upon: (1) the rate of the reaction by which blue tungsten oxide is reduced to tungsten metal, (2) the intermediate oxides associated with reduction, and (3) the morphology of the resulting tungsten powder

Impact of environmental chemistry on mycogenic Mn oxide minerals

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Santelli, C. M.; Farfan, G. A.; Post, A.; Post, J. E.

2012-12-01

Manganese (Mn) oxide minerals are ubiquitous in aquatic and terrestrial environments and their presence can have broad environmental consequences. In particular, Mn oxides scavenge nutrients and metals, degrade complex organics, and oxidize a variety of inorganic contaminants. The "reactivity" of Mn oxides, however, is highly dependent upon crystallite size, composition, and structure, which are largely determined by environmental factors such as solution chemistry. It is has been suggested that most Mn oxides in terrestrial and aquatic environments are formed by microbial activity; indeed, a diversity of Mn(II)-oxidizing bacteria and fungi have been isolated and their mineral byproducts are consistent with those observed in natural systems. Previous studies showed that Mn(II)-oxidizing Ascomycete fungi produce highly-disordered, nanocrystalline Mn oxides that are structurally similar to synthetic δ-MnO2 or natural vernadite. Unlike related studies with Mn-oxidizing bacteria, Mn oxides produced by these fungi did not "age" or transform to more crystalline mineral phases with time. We hypothesize that fungal growth conditions, in particular the low concentration of cations, are inhibiting secondary mineral formation. The overall goal of this research is to examine the structure and speciation of fungally-precipitated Mn oxides with respect to fungal species, time, and concentration of soluble Mn(II), Na, and Ca - three environmentally relevant cations that promote the transformation of δ-MnO2 to more crystalline mineral phases such as feitknechtite, birnessite, or ranciéite. For this study, we examined the Mn oxides formed by different species of Mn(II)-oxidizing fungi (Pyrenochaeta sp., Stagonospora sp., Plectosphaerella cucumerina., and Acremonium strictum). Isolates were grown for 8 or 16 days in a nutrient lean media consisting of yeast extract, trace elements and 0.2 mM MnCl2 supplemented with varying concentrations of Na, Ca, or Mn(II) compounds. The

A review of zinc oxide mineral beneficiation using flotation method.

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Ejtemaei, Majid; Gharabaghi, Mahdi; Irannajad, Mehdi

2014-04-01

In recent years, extraction of zinc from low-grade mining tailings of oxidized zinc has been a matter of discussion. This is a material which can be processed by flotation and acid-leaching methods. Owing to the similarities in the physicochemical and surface chemistry of the constituent minerals, separation of zinc oxide minerals from their gangues by flotation is an extremely complex process. It appears that selective leaching is a promising method for the beneficiation of this type of ore. However, with the high consumption of leaching acid, the treatment of low-grade oxidized zinc ores by hydrometallurgical methods is expensive and complex. Hence, it is best to pre-concentrate low-grade oxidized zinc by flotation and then to employ hydrometallurgical methods. This paper presents a critical review on the zinc oxide mineral flotation technique. In this paper, the various flotation methods of zinc oxide minerals which have been proposed in the literature have been detailed with the aim of identifying the important factors involved in the flotation process. The various aspects of recovery of zinc from these minerals are also dealt with here. The literature indicates that the collector type, sulfidizing agent, pH regulator, depressants and dispersants types, temperature, solid pulp concentration, and desliming are important parameters in the process. The range and optimum values of these parameters, as also the adsorption mechanism, together with the resultant flotation of the zinc oxide minerals reported in the literature are summarized and highlighted in the paper. This review presents a comprehensive scientific guide to the effectiveness of flotation strategy. Copyright © 2013 Elsevier B.V. All rights reserved.

Reductive mineralization of cellulose with vanadium, iron and tungsten chlorides and access to MxOy metal oxides and MxOy/C metal oxide/carbon composites.

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Henry, Aurélien; Hesemann, Peter; Alauzun, Johan G; Boury, Bruno

2017-10-15

M x O y and M x O y /C composites (M=V, Fe and W) were obtained by mineralization of cellulose with several metal chlorides. Cellulose was used both as a templating agent and as an oxygen and a carbon source. Soluble chloride molecules (VOCl 3 and WCl 6 ) and a poorly soluble ionic chloride compound (FeCl 3 ) were chosen as metal oxide precursors. In a first time, primary metal oxide/cellulose composites were obtained via a thermal treatment by reacting urea impregnated filter paper with the corresponding metal chlorides in an autoclave at 150°C after 3days. After either pyrolysis or calcination steps of these intermediate materials, interesting metal oxides with various morphologies were obtained (V 2 O 5, V 2 O 3 , Fe 3 O 4 , WO 3, H 0.23 WO 3 ), composites (V 2 O 3 /C) as well as carbides (hexagonal W 2 C and WC, Fe 3 C) This result highlight the reductive role that can play cellulose during the pyrolysis step that allows to tune the composition of M x O y /C composites. The materials were characterized by FTIR, Raman, TGA, XRD and SEM. This study highlights that cellulose can be used for a convenient preparation of a variety of highly demanded M x O y and M x O y /C composites with original shapes and morphologies. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfur isotope fractionation during heterogeneous oxidation of SO2 on mineral dust

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P. Hoppe

2012-06-01

Full Text Available Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34S/32S fractionation factor α34 for oxidation of SO2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ~60% of global dust emissions and loading, was used for the experiments. The fractionation factor for aqueous oxidation in dust leachate is αleachate = 0.9917±0.0046, which is in agreement with previous measurements of aqueous SO2 oxidation by iron solutions. This fractionation factor is representative of a radical chain reaction oxidation pathway initiated by transition metal ions. Oxidation on the dust surface at subsaturated relative humidity (RH had an overall fractionation factor of αhet = 1.0096±0.0036 and was found to be almost an order of magnitude faster when the dust was simultaneously exposed to ozone, light and RH of ~40%. However, the presence of ozone, light and humidity did not influence isotope fractionation during oxidation on dust surfaces at subsaturated relative humidity. All the investigated reactions showed mass-dependent fractionation of 33S relative to 34S. A positive matrix factorization model was used to investigate surface oxidation on the different components of dust. Ilmenite, rutile and iron oxide were found to be the most reactive components, accounting for 85% of sulfate production with a fractionation factor of α34 = 1.012±0.010. This overlaps within the analytical uncertainty with the fractionation of other major atmospheric oxidation pathways such as the oxidation of SO2 by H2O2 and O3 in the aqueous phase and OH in the gas phase. Clay minerals accounted for roughly 12% of the sulfate production, and oxidation on clay minerals

Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals

International Nuclear Information System (INIS)

Feng Xionghan; Zhai Limei; Tan Wenfeng; Liu Fan; He Jizheng

2007-01-01

Several Mn oxide minerals commonly occurring in soils were synthesized by modified or optimized methods. The morphologies, structures, compositions and surface properties of the synthesized Mn oxide minerals were characterized. Adsorption and redox reactions of heavy metals on these minerals in relation to the mineral structures and surface properties were also investigated. The synthesized birnessite, todorokite, cryptomelane, and hausmannite were single-phased minerals and had the typical morphologies from analyses of XRD and TEM/ED. The PZCs of the synthesized birnessite, todorokite and cryptomelane were 1.75, 3.50 and 2.10, respectively. The magnitude order of their surface variable negative charge was: birnessite ≥ cryptomelane > todorokite. The hausmannite had a much higher PZC than others with the least surface variable negative charge. Birnessite exhibited the largest adsorption capacity on heavy metals Pb 2+ , Cu 2+ , Co 2+ , Cd 2+ and Zn 2+ , while hausmannite the smallest one. Birnessite, cryptomelane and todorokite showed the greatest adsorption capacity on Pb 2+ among the tested heavy metals. Hydration tendency (pK 1 ) of the heavy metals and the surface variable charge of the Mn minerals had significant impacts on the adsorption. The ability in Cr(III) oxidation and concomitant release of Mn 2+ varied greatly depending on the structure, composition, surface properties and crystallinity of the minerals. The maximum amounts of Cr(III) oxidized by the Mn oxide minerals in order were (mmol/kg): birnessite (1330.0) > cryptomelane (422.6) > todorokite (59.7) > hausmannite (36.6). - The characteristics of heavy metal adsorption and Cr(III) oxidation on Mn oxide minerals are determined by their structure, composition, surface property and crystallinity

Glycine Polymerization on Oxide Minerals

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Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

2017-06-01

It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH3 + group of adsorbed Gly to the nucleophilic NH2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

Glycine Polymerization on Oxide Minerals.

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Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

2017-06-01

It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

Vegetation successfully prevents oxidization of sulfide minerals in mine tailings.

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Li, Yang; Sun, Qingye; Zhan, Jing; Yang, Yang; Wang, Dan

2016-07-15

The oxidization of metal sulfide in tailings causes acid mine drainage. However, it remains unclear whether vegetation prevents the oxidization of metal sulfides. The oxidization characteristics and microbial indices of the tailings in the presence of various plant species were investigated to explore the effects of vegetation on the oxidization of sulfide minerals in tailings. The pH, reducing sulfur, free iron oxides (Fed), chemical oxygen consumption (COC) and biological oxygen consumption (BOC) were measured. Key iron- and sulfur-oxidizing bacteria (Acidithiobacillus spp., Leptospirillum spp. and Thiobacillus spp.) were quantified using real-time PCR. The results indicate that vegetation growing on tailings can effectively prevent the oxidization of sulfide minerals in tailings. A higher pH and reducing-sulfur content and lower Fed were observed in the 0-30 cm depth interval in the presence of vegetation compared to bare tailings (BT). The COC gradually decreased with depth in all of the soil profiles; specifically, the COC rapidly decreased in the 10-20 cm interval in the presence of vegetation but gradually decreased in the BT profiles. Imperata cylindrica (IC) and Chrysopogon zizanoides (CZ) profiles contained the highest BOC in the 10-20 cm interval. The abundance of key iron- and sulfur-oxidizing bacteria in the vegetated tailings were significantly lower than in the BT; in particular, IC was associated with the lowest iron- and sulfur-oxidizing bacterial abundance. In conclusion, vegetation successfully prevented the oxidization of sulfide minerals in the tailings, and Imperata cylindrica is the most effective in reducing the number of iron- and sulfur-oxidizing bacteria and helped to prevent the oxidization of sulfide minerals in the long term. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

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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.

Sequential reductive and oxidative biodegradation of chloroethenes stimulated in a coupled bioelectro-process.

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Lohner, Svenja T; Becker, Dirk; Mangold, Klaus-Michael; Tiehm, Andreas

2011-08-01

This article for the first time demonstrates successful application of electrochemical processes to stimulate sequential reductive/oxidative microbial degradation of perchloroethene (PCE) in mineral medium and in contaminated groundwater. In a flow-through column system, hydrogen generation at the cathode supported reductive dechlorination of PCE to cis-dichloroethene (cDCE), vinyl chloride (VC), and ethene (ETH). Electrolytically generated oxygen at the anode allowed subsequent oxidative degradation of the lower chlorinated metabolites. Aerobic cometabolic degradation of cDCE proved to be the bottleneck for complete metabolite elimination. Total removal of chloroethenes was demonstrated for a PCE load of approximately 1.5 μmol/d. In mineral medium, long-term operation with stainless steel electrodes was demonstrated for more than 300 days. In contaminated groundwater, corrosion of the stainless steel anode occurred, whereas DSA (dimensionally stable anodes) proved to be stable. Precipitation of calcareous deposits was observed at the cathode, resulting in a higher voltage demand and reduced dechlorination activity. With DSA and groundwater from a contaminated site, complete degradation of chloroethenes in groundwater was obtained for two months thus demonstrating the feasibility of the sequential bioelectro-approach for field application.

Fungal oxidative dissolution of the Mn(II)-bearing mineral rhodochrosite and the role of metabolites in manganese oxide formation.

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Tang, Yuanzhi; Zeiner, Carolyn A; Santelli, Cara M; Hansel, Colleen M

2013-04-01

Microbially mediated oxidation of Mn(II) to Mn(III/IV) oxides influences the cycling of metals and remineralization of carbon. Despite the prevalence of Mn(II)-bearing minerals in nature, little is known regarding the ability of microbes to oxidize mineral-hosted Mn(II). Here, we explored oxidation of the Mn(II)-bearing mineral rhodochrosite (MnCO3 ) and characteristics of ensuing Mn oxides by six Mn(II)-oxidizing Ascomycete fungi. All fungal species substantially enhanced rhodochrosite dissolution and surface modification. Mineral-hosted Mn(II) was oxidized resulting in formation of Mn(III/IV) oxides that were all similar to δ-MnO2 but varied in morphology and distribution in relation to cellular structures and the MnCO3 surface. For four fungi, Mn(II) oxidation occurred along hyphae, likely mediated by cell wall-associated proteins. For two species, Mn(II) oxidation occurred via reaction with fungal-derived superoxide produced at hyphal tips. This pathway ultimately resulted in structurally unique Mn oxide clusters formed at substantial distances from any cellular structure. Taken together, findings for these two fungi strongly point to a role for fungal-derived organic molecules in Mn(III) complexation and Mn oxide templation. Overall, this study illustrates the importance of fungi in rhodochrosite dissolution, extends the relevance of biogenic superoxide-based Mn(II) oxidation and highlights the potential role of mycogenic exudates in directing mineral precipitation. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

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

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

2014-10-01

Ferrous iron has been known to function as an electron source for iron-oxidizing microorganisms in both anoxic and oxic environments. A diversity of bacteria has been known to oxidize both soluble and solid-phase Fe(II) forms coupled to the reduction of nitrate. Here, we show for the first time Fe(II) oxidation by Sphaerotilus natans strain DSM 6575(T) under mixotrophic condition. Sphaerotilus natans has been known to form a sheath structure enclosing long chains of rod-shaped cells, resulting in a thick biofilm formation under oxic conditions. Here, we also demonstrate that strain DSM 6575(T) grows mixotrophically with pyruvate, Fe(II) as electron donors and nitrate as an electron acceptor and single cells of strain DSM 6575(T) are dominant under anoxic conditions. Furthermore, strain DSM 6575(T) forms nanoball-shaped amorphous Fe(III) oxide minerals encrusting on the cell surfaces through the mixotrophic iron oxidation reaction under anoxic conditions. We propose that cell encrustation results from the indirect Fe(II) oxidation by biogenic nitrite during nitrate reduction and that causes the bacterial morphological change to individual rod-shaped single cells from filamentous sheath structures. This study extends the group of existing microorganisms capable of mixotrophic Fe(II) oxidation by a new strain, S. natans strain DSM 6575(T) , and could contribute to biogeochemical cycles of Fe and N in the environment. © 2014 The Authors. FEMS Microbiology Ecology published by John Wiley & Sons Ltd on behalf of Federation of European Microbiological Societies.

Impact of clay mineral on air oxidation of PAH-contaminated soils.

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Biache, Coralie; Kouadio, Olivier; Lorgeoux, Catherine; Faure, Pierre

2014-09-01

This work investigated the impact of a clay mineral (bentonite) on the air oxidation of the solvent extractable organic matters (EOMs) and the PAHs from contaminated soils. EOMs were isolated from two coking plant soils and mixed with silica sand or bentonite. These samples, as well as raw soils and bentonite/soil mixtures, were oxidized in air at 60 and 100 °C for 160 days. Mineralization was followed by measuring the CO2 produced over the experiments. EOM, polycyclic aromatic compound (PAC), including PAH, contents were also determined. Oxidation led to a decrease in EOM contents and PAH concentrations, these diminutions were enhanced by the presence of bentonite. Transfer of carbon from EOM to insoluble organic matter pointed out a condensation phenomenon leading to a stabilization of the contamination. Higher mineralization rates, observed during the oxidation of the soil/bentonite mixtures, seem to indicate that this clay mineral had a positive influence on the transformation of PAC into CO2.

Behavior of Colorado Plateau uranium minerals during oxidation

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Garrels, Robert Minard; Christ, C.L.

1956-01-01

Uranium occurs as U(VI) and U(IV) in minerals of the Colorado Plateau ores. The number of species containing U(VI) is large, but only two U(IV) minerals are known from the Plateau: uraninite, and oxide, and coffinite, a hydroxy-silicate. These oxidize to yield U(VI) before reacting significantly with other mineral constituents. Crystal-structure analysis has shown that U(VI) invariable occurs as uranyl ion, UO2+2. Uranyl ion may form complex carbonate or sulfate ions with resulting soluble compounds, but only in the absence of quinquevalent vanadium, arsenic, or phosphorous. In the presence of these elements in the +5 valence state, the uranyl ion is fixed in insoluble layer compounds formed by union of uranyl ion with orthovanadate, orthophosphate, or orthoarsenate. Under favorable conditions UO2+2 may react to form the relatively insoluble rutherfordine, UO2CO3, or hydrated uranyl hydroxides. These are rarely found on the Colorado Plateau as opposed to their excellent development in other uraniferous areas, a condition which is apparently related to the semiarid climate and low water table of the Plateau. Uranium may also be fixed as uranyl silicate, but little is known about minerals of this kind. In the present study emphasis has been placed on a detailing of the chemical and crystal structural changes which occur in the oxidation paragenetic sequence.

Reduction of iron-bearing lunar minerals for the production of oxygen

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Massieon, Charles; Cutler, Andrew; Shadman, Farhang

1992-01-01

The kinetics and mechanism of the reduction of simulants of the iron-bearing lunar minerals olivine ((Fe,Mg)2SiO4), pyroxene ((Fe,Mg,Ca)SiO3), and ilmenite (FeTiO3) are investigated, extending previous work with ilmenite. Fayalite is reduced by H2 at 1070 K to 1480 K. A layer of mixed silica glass and iron forms around an unreacted core. Reaction kinetics are influenced by permeation of hydrogen through this layer and a reaction step involving dissociated hydrogen. Reaction mechanisms are independent of Mg content. Augite, hypersthene, and hedenbergite are reduced in H2 at the same temperatures. The products are iron metal and lower iron silicates mixed throughout the mineral. Activation energy rises with calcium content. Ilmenite and fayalite are reduced with carbon deposited on partially reduced minerals via the CO disproportionation reaction. Reduction with carbon is rapid, showing the carbothermal reduction of lunar minerals is possible.

Direct Flotation of Niobium Oxide Minerals from Carbonatite Niobium Ores

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Ni, Xiao

Currently the recovery of niobium oxide minerals from carbonatite niobium ores relies on the use of non-selective cationic collectors. This leads to complicated process flowsheets involving multiple desliming and multiple reverse flotation stages, and low niobium recovery. In this research, anionic collectors that are capable of strong chemisorption on the niobium minerals were studied with the objective of directly floating the niobium oxide minerals from the carbonatite ores. In the flotation of both high purity minerals and Niobec ores, it was shown that the combination of hydroxamic acid and sodium metaphosphate was an effective reagent scheme for the direct flotation of niobium oxide from its ores. Batch flotation on the Niobec Mill Feed showed that over 95% of niobium oxide was recovered into a rougher concentrate that was less than 47% of the original feed mass. Preliminary cleaning tests showed that the reagent scheme could also be used to upgrade the rougher concentrate, although the depression of iron oxide minerals required further study. X-ray photoelectron spectroscopic (XPS) measurement results confirm that OHA (octyl hydroxamic acid) could chemisorb on pyrochlore surface while only physically adsorb on calcite, judging by the chemical shifts of electron binding energies in the elements in both OHA and the mineral surfaces. When hydroxamic acid was adsorbed on calcite surface, the binding energies of the N 1s electrons, at 400.3 eV, did not shift. However, after adsorption on pyrochlore, the N 1s binding energy peak split into two peaks, one at a binding energy of around 399 eV, representing chemically adsorbed OHA, the other at between 400 and 401 eV. The experimental data suggested a strong chemisorption of the OHA on pyrochlore surface in the form of a vertical head-on orientation of the OHA molecules so that the pyrochlore was strongly hydrophobized even at low OHA concentrations, followed by possibly randomly oriented physisorbed OHA molecules

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

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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

Science.gov (United States)

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

Flotation of zinc and lead oxide minerals from Olkusz region calamine ores

Directory of Open Access Journals (Sweden)

Cichy Krystian

2016-01-01

Full Text Available The paper presents chemical and mineralogical characteristics of calamine ore from the Pomorzany mine. A flowsheet for recovery of sulphide minerals of zinc and lead in the form of the Zn-Pb bulk concentrate was presented. In the following part, preparation of the feed for flotation of Zn-Pb oxide minerals and optimal conditions for separation from it iron sulphide minerals, represented by marcasite, were determined. In the final section the results of flotation of Zn-Pb oxide minerals with anionic collector AM2 belonging to the hydroxyamide group of collectors and a cationic collector in the form of a coconut amine, being a mixture of primary aliphatic amines, were presented. Basing on the obtained results, a technological flowsheet for the recovery of Zn-Pb sulphide and oxide minerals from the calamine ore of the Pomorzany mine was presented.

Effect of Ca-Fe oxides additives on NOx reduction in iron ore sintering

Institute of Scientific and Technical Information of China (English)

Zhi-yuan Yu; Xiao-hui Fan; Min Gan; Xu-ling Chen

2017-01-01

As the emission control regulations get stricter, the NOx reduction in the sintering process becomes an important environmental concern owing to its role in the formation of photochemical smog and acid rain. The NOx emissions from the sintering machine account for 48% of total amount from the iron and steel industry.Thus, it is essential to reduce NOx emissions from the sintering machine, for the achievement of clean production of sinter.Ca-Fe oxides, serving as the main binding phase in the sinter, are therefore used as additives into the sintering mixture to reduce NOx emissions.The results show that the NOx re-duction ratio achieves 27.76% with 8% Ca-Fe oxides additives since the Ca-Fe oxides can advance the ig-nition and inhibit the nitrogen oxidation compared with the conventional condition.Meanwhile, the exist-ence of Ca-Fe oxides was beneficial to the sinter quality since they were typical low melting point com-pounds.The optimal mass fraction of Ca-Fe oxides additives should be less than 8% since the permeability of sintering bed was significantly decreased with a further increase of the Ca-Fe oxides fines, inhibiting the mineralization reaction of sintering mixture.Additionally, the appropriate particle size can be obtained when mixing an equal amount of Ca-Fe oxides additives of -0.5 mm and 0.5-3.0 mm in size.

Effect of the Lithium Oxide Concentration on a Reduction of Lanthanide Oxides

International Nuclear Information System (INIS)

Choi, In-Kyu; Jeong, Myeong-Soo; Do, Jae-Bum; Seo, Chung-Seok

2007-01-01

The pyrochemical reduction process of spent oxide fuel is one of the options to handle spent PWR fuels in Korea. After spent oxide fuel is converted to a metallic form, fission products will be removed from the resultant uranium and higher actinide metals by an electrorefining process. The chemical behaviors of lanthanide oxides during the pyrochemical process has been extensively studied. It was also reported that about 30 to 50% of several lanthanide oxides were reduced to corresponding metals by an electrolytic reduction process having 1 wt% of a lithium oxide concentration. Korea Atomic Energy Research Institute (KAERI), however, has been used 3 wt% of lithium oxide to increase the applied current of the electrolytic reduction process. Though it was reported that U 3 O 8 was reduced to uranium metal having a high reduction yield at 3 wt% of the Li 2 O concentration, the effect of the lithium oxide concentration on the reduction of lanthanide oxides has not been clarified

Heterogeneous reactions of carbonyl sulfide on mineral oxides: mechanism and kinetics study

Directory of Open Access Journals (Sweden)

Y. Liu

2010-11-01

Full Text Available The heterogeneous reactions of carbonyl sulfide (OCS on the typical mineral oxides in the mineral dust particles were investigated using a Knudsen cell flow reactor and a diffuse reflectance UV-vis spectroscopy. The reaction pathway for OCS on mineral dust was identified based on the gaseous products and surface species. The hydrolysis of OCS and succeeding oxidation of intermediate products readily took place on α-Al₂O₃, MgO, and CaO. Reversible and irreversible adsorption of OCS were observed on α-Fe₂O₃ and ZnO, respectively, whereas no apparent uptake of OCS by SiO₂ and TiO₂ was observed. The reactivity of OCS on these oxides depends on both the basicity of oxides and the decomposition reactivity of oxides for H₂S. Based on the individual uptake coefficients and chemical composition of authentic mineral dust, the uptake coefficient (γ_BET of mineral dust was estimated to be in the range of 3.84×10⁻⁷–2.86×10⁻⁸. The global flux of OCS due to heterogeneous reactions and adsorption on mineral dust was estimated at 0.13–0.29 Tg yr⁻¹, which is comparable to the annual flux of OCS for its reaction with ·OH.

A New Direction for Biomining: Extraction of Metals by Reductive Dissolution of Oxidized Ores

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Kevin B. Hallberg

2013-01-01

Full Text Available Biomining, the biotechnology that uses microorganisms to extract metals from ores and concentrates, is currently used exclusively for processing reduced ores and mine wastes. Metals of economic value also occur extensively in oxidized ores, such as nickel laterites. While these are not amenable to oxidative dissolution, the ferric iron minerals they contain can, in theory, be disrupted by iron reduction, causing associated metals to be released. We have harnessed the ability of the facultatively anaerobic, acidophilic bacterium Acidithiobacillus ferroooxidans to couple the oxidation of elemental sulphur to the reduction of ferric iron in the goethite fraction of a limonitic nickel ore at 30 °C. Nickel and other metals (Co, Cr and Mn were effectively solubilised and maintained in solution due to the low pH (1.8 of the leach liquor. The results highlight the potential for the bioprocessing of oxidized, iron-rich ores using an approach that is energy-saving and environmentally-benign compared with metallurgical processes currently applied to the extraction of Ni from lateritic ores.

Molecular Underpinnings of Fe(III Oxide Reduction by Shewanella oneidensis MR-1

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Liang eShi

2012-02-01

Full Text Available In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III] (oxy(hydroxide minerals as the terminal electron acceptors for anaerobic respiration. At circumneutral pH and in the absence of strong complexing ligands, Fe(III oxides are relatively insoluble and thus are external to the bacterial cells. S. oneidensis MR-1 has evolved the machinery (i.e., metal-reducing or Mtr pathway for transferring electrons across the entire cell envelope to the surface of extracellular Fe(III oxides. The protein components identified to date for the Mtr pathway include CymA, MtrA, MtrB, MtrC and OmcA. CymA is an inner-membrane tetraheme c-type cytochrome (c-Cyt that is proposed to oxidize the quinol in the inner-membrane and transfers the released electrons to redox proteins in the periplasm. Although the periplasmic proteins receiving electrons from CymA during Fe(III oxidation have not been identified, they are believed to relay the electrons to MtrA. A decaheme c-Cyt, MtrA is thought to be embedded in the trans outer-membrane and porin-like protein MtrB. Together, MtrAB deliver the electrons across the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. Functioning as terminal reductases, the outer membrane and decaheme c-Cyts MtrC and OmcA can bind the surface of Fe(III oxides and transfer electrons directly to these minerals. To increase their reaction rates, MtrC and OmcA can use the flavins secreted by S. oneidensis MR-1 cells as diffusible co-factors for reduction of Fe(III oxides. MtrC and OmcA can also serve as the terminal reductases for soluble forms of Fe(III. Although our understanding of the Mtr pathway is still far from complete, it is the best characterized microbial pathway used for extracellular electron exchange. Characterizations of the Mtr pathway have made significant contributions to the molecular understanding of microbial reduction of Fe(III oxides.

The adsorption of chelating reagents on oxide minerals

International Nuclear Information System (INIS)

Bryson, M.A.W.

1984-06-01

This work constitutes a fundamental study of the interaction between chelating reagents and oxide minerals. The adsorption mechanisms have been elucidated for most of the systems generated by the oxides of copper(II) or iron(III) and chelating reagents octyl hydroxamate, N-phenylbenzohydroxamate, salicylaldoxime, 5-nitro-salicylaldoxime or 8-hydroxyquinoline. In order to better understand the adsorption process associated with copper(II) oxide, the oxide was recrystallized to produce a coarser material with a more uniform surface. This allowed the oxide surface to be viewed under the scanning electron microscope. A detailed investigation of the effect of the system variables; pH, conditioning period, concentration, temperature, surface area and dispersing reagent on the rate of precipitation of the copper chelate species of general form, Cu(chel) 2 , was made. In addition the chemical nature of the adsorbed species and the structural form of the precipitates were determined with the aid of infra-red spectroscopy and the scanning electron microscope. On the basis of these results a model has been formulated for the adsorption processes. The precipitation process was examined in more detail by the study of the adsorption of chelate on copper metal. Contact angle measurements of air bubbles on copper metal conditioned with chelate were related to the adsorption results in an attempt to isolate the optimum conditions for flotation of oxide minerals

Mineral transformations and magnetic properties: example of an uranium rich front of oxido-reduction

International Nuclear Information System (INIS)

Mergaux, O.; Samama, J.C.

1987-01-01

In sedimentary environments, the mineral associations and the associated magnetic properties may be ascribed to superimposed processes of sedimentation, diagenesis and epigenesis. In the case of uranium sandstone deposits, the epigenetic processes of oxido-reduction are responsible for both concentration in uranium and specific mineral transformations which are related to variations in the magnetic properties of the rocks. These variations are illustrated by the Treville deposit (Southwestern France), where uranium rich bodies have developed within the Tertiary sandstones. The unaltered sandstones are characterized by a low magnetic susceptibility (scarcity of ferrimagnetic species but abundance of paramagnetic species). The siderite rich facies forming part of the front does not display any significant change in the mean magnetic susceptibility whilst the uranium-pyrite facies which belongs to the same front indicates a much lower susceptibility. The mean susceptibility facies resulting from pyrite and siderite oxidation remains unchanged. The facies of alteration of the iron rich silicates is responsible for higher susceptibility. The comparison between measured susceptibility and computed susceptibility helps in interpreting the role of the various species in the overall susceptibility of the rocks. It may also help in restituting the mineral associations from magnetic and chemical logging

Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium.

Science.gov (United States)

Liu, D; Dong, H; Bishop, M E; Zhang, J; Wang, H; Xie, S; Wang, S; Huang, L; Eberl, D D

2012-03-01

Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate-reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu-2, mixed-layer illite-smectite RAr-1 and ISCz-1, and illite IMt-1) were exposed to D. vulgaris in a non-growth medium with and without anthraquinone-2,6-disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X-ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals. © 2011 Blackwell Publishing Ltd.

Kinetics and Products of Chromium(VI) Reduction by Iron(II/III)-Bearing Clay Minerals.

Science.gov (United States)

Joe-Wong, Claresta; Brown, Gordon E; Maher, Kate

2017-09-05

Hexavalent chromium is a water-soluble pollutant, the mobility of which can be controlled by reduction of Cr(VI) to less soluble, environmentally benign Cr(III). Iron(II/III)-bearing clay minerals are widespread potential reductants of Cr(VI), but the kinetics and pathways of Cr(VI) reduction by such clay minerals are poorly understood. We reacted aqueous Cr(VI) with two abiotically reduced clay minerals: an Fe-poor montmorillonite and an Fe-rich nontronite. The effects of ionic strength, pH, total Fe content, and the fraction of reduced structural Fe(II) [Fe(II)/Fe(total)] were examined. The last variable had the largest effect on Cr(VI) reduction kinetics: for both clay minerals, the rate constant of Cr(VI) reduction varies by more than 3 orders of magnitude with Fe(II)/Fe(total) and is described by a linear free energy relationship. Under all conditions examined, Cr and Fe K-edge X-ray absorption near-edge structure spectra show that the main Cr-bearing product is a Cr(III)-hydroxide and that Fe remains in the clay structure after reacting with Cr(VI). This study helps to quantify our understanding of the kinetics of Cr(VI) reduction by Fe(II/III)-bearing clay minerals and may improve predictions of Cr(VI) behavior in subsurface environments.

Reduction Behaviors of Carbon Composite Iron Oxide Briquette Under Oxidation Atmosphere

Energy Technology Data Exchange (ETDEWEB)

Lee, Ki-Woo; Kim, Kang-Min; Kwon, Jae-Hong; Han, Jeong-Whan [Inha University, Incheon (Korea, Republic of); Son, Sang-Han [POSCO, Pohang (Korea, Republic of)

2017-01-15

The carbon composite iron oxide briquette (CCB) is considered a potential solution to the upcoming use of low grade iron resources in the ironmaking process. CCB is able to reduce raw material cost by enabling the use of low grade powdered iron ores and coal. Additionally, the fast reduction of iron oxides by direct contact with coal can be utilized. In this study, the reduction behaviors of CCB were investigated in the temperature range of 200-1200 ℃ under oxidizing atmosphere. Briquettes were prepared by mixing iron ore and coal in a weight ratio of 8:2. Then reduction experiments were carried out in a mixed gas atmosphere of N{sub 2}, O{sub 2}, and CO{sub 2}. Compressive strength tests and quantitative analysis were performed by taking samples at each target temperature. In addition, the reduction degree depending on the reaction time was evaluated by off-gas analysis during the reduction test. It was found that the compressive strength and the metallization degree of the reduced briquettes increased with increases in the reaction temperature and holding time. However, it tended to decrease when the re-oxidation phenomenon was caused by injected oxygen. The degree of reduction reached a maximum value in 26 minutes. Therefore, the re-oxidation phenomenon becomes dominant after 26 minutes.

Green reduction of graphene oxide using alanine

International Nuclear Information System (INIS)

Wang, Jiabin; Salihi, Elif Caliskan; Šiller, Lidija

2017-01-01

There remains a real need for the easy, eco-friendly and scalable preparation method of graphene due to various potential applications. Chemical reduction is the most versatile method for the large scale production of graphene. Here we report the operating conditions for a one-step, economical and green synthesis method for the reduction of graphene oxide using a biomolecule (alanine). Graphene oxide was produced by the oxidation and exfoliation of natural graphite flake with strong oxidants using Hummers method (Hummers and Offeman, 1958), but the method was revised in our laboratory to set up a safe and environmentally friendly route. The reduction of graphene oxide was investigated using alanine at various operating conditions in order to set up optimum conditions (treatment time, temperature and concentration of the reagent). Samples have been characterized by using UV–Visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction analysis. - Highlights: • An environmentally friendly route was reported for the chemical reduction of graphene oxide (GO). • Alanine could reduce GO to rGO (reduced graphene oxide) without using any stabilizer or alcaline medium. • Characterization studies confirmed the successful deoxygenation of GO.

Green reduction of graphene oxide using alanine

Energy Technology Data Exchange (ETDEWEB)

Wang, Jiabin [Newcastle University, School of Chemical Engineering and Advanced Materials, Newcastle upon Tyne NE1 7RU (United Kingdom); Salihi, Elif Caliskan, E-mail: caliskanelif@gmail.com [Newcastle University, School of Chemical Engineering and Advanced Materials, Newcastle upon Tyne NE1 7RU (United Kingdom); Marmara University, Faculty of Pharmacy, Department of Basic Pharmaceutical Sciences, 34668 Istanbul (Turkey); Šiller, Lidija [Newcastle University, School of Chemical Engineering and Advanced Materials, Newcastle upon Tyne NE1 7RU (United Kingdom)

2017-03-01

There remains a real need for the easy, eco-friendly and scalable preparation method of graphene due to various potential applications. Chemical reduction is the most versatile method for the large scale production of graphene. Here we report the operating conditions for a one-step, economical and green synthesis method for the reduction of graphene oxide using a biomolecule (alanine). Graphene oxide was produced by the oxidation and exfoliation of natural graphite flake with strong oxidants using Hummers method (Hummers and Offeman, 1958), but the method was revised in our laboratory to set up a safe and environmentally friendly route. The reduction of graphene oxide was investigated using alanine at various operating conditions in order to set up optimum conditions (treatment time, temperature and concentration of the reagent). Samples have been characterized by using UV–Visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction analysis. - Highlights: • An environmentally friendly route was reported for the chemical reduction of graphene oxide (GO). • Alanine could reduce GO to rGO (reduced graphene oxide) without using any stabilizer or alcaline medium. • Characterization studies confirmed the successful deoxygenation of GO.

Global Emissions of Nitrous Oxide: Key Source Sectors, their Future Activities and Technical Opportunities for Emission Reduction

Science.gov (United States)

Winiwarter, W.; Höglund-Isaksson, L.; Klimont, Z.; Schöpp, W.; Amann, M.

2017-12-01

Nitrous oxide originates primarily from natural biogeochemical processes, but its atmospheric concentrations have been strongly affected by human activities. According to IPCC, it is the third largest contributor to the anthropogenic greenhouse gas emissions (after carbon dioxide and methane). Deep decarbonization scenarios, which are able to constrain global temperature increase within 1.5°C, require strategies to cut methane and nitrous oxide emissions on top of phasing out carbon dioxide emissions. Employing the Greenhouse gas and Air pollution INteractions and Synergies (GAINS) model, we have estimated global emissions of nitrous oxide until 2050. Using explicitly defined emission reduction technologies we demonstrate that, by 2030, about 26% ± 9% of the emissions can be avoided assuming full implementation of currently existing reduction technologies. Nearly a quarter of this mitigation can be achieved at marginal costs lower than 10 Euro/t CO2-eq with the chemical industry sector offering important reductions. Overall, the largest emitter of nitrous oxide, agriculture, also provides the largest emission abatement potentials. Emission reduction may be achieved by precision farming methods (variable rate technology) as well as by agrochemistry (nitrification inhibitors). Regionally, the largest emission reductions are achievable where intensive agriculture and industry are prevalent (production and application of mineral fertilizers): Centrally Planned Asia including China, North and Latin America, and South Asia including India. Further deep cuts in nitrous oxide emissions will require extending reduction efforts beyond strictly technological solutions, i.e., considering behavioral changes, including widespread adoption of "healthy diets" minimizing excess protein consumption.

Formation mechanism of uranium minerals at sandstone-type uranium deposits

International Nuclear Information System (INIS)

Li Shengfu; Zhang Yun

2004-01-01

By analyzing the behavior and existence form of uranium in different geochemical environments, existence form of uranium and uranium minerals species, this paper expounds the formation mechanism of main commercial uranium mineral--pitchblende: (1) uranium is a valence-changeable element. It is reactivated and migrates in oxidized environment, and is reduced and precipitated in reducing environment; (2) [UO 2 (CO 3 ) 3 ] 4- , [UO 2 (CO 3 ) 2 ] 2- coming from oxidized environment react with reductants such as organic matter, sulfide and low-valence iron at the redox front to form simple uranium oxide--pitchblende; (3)the adsorption of uranium by organic matter and clay minerals accelerates the reduction and the concentration of uranium. Therefore, it is considered, that the reduction of SO 4 2- by organic matter to form H 2 S, and the reduction of UO 2 2+ by H 2 S are the main reasons for the formation of pitchblende. This reaction is extensively and universally available in neutral and weakly alkaline carbonate solution. The existense of reductants such as H 2 S is the basic factor leading to the decrease of Eh in environments and the oversaturation of UO 2 2+ at the redox front in groundwater, thus accelerating the adsorption and the precipitation of uranium

Reduction and shaping of graphene-oxide by laser-printing for controlled bone tissue regeneration and bacterial killing

Science.gov (United States)

Palmieri, Valentina; Barba, Marta; Di Pietro, Lorena; Gentilini, Silvia; Chiara Braidotti, Maria; Ciancico, Carlotta; Bugli, Francesca; Ciasca, Gabriele; Larciprete, Rosanna; Lattanzi, Wanda; Sanguinetti, Maurizio; De Spirito, Marco; Conti, Claudio; Papi, Massimiliano

2018-01-01

Graphene and graphene oxide (GO) are capable of inducing stem cells differentiation into bone tissue with variable efficacy depending on reductive state of the material. Thus, modulation of osteogenic process and of bone mineral density distribution is theoretically possible by controlling the GO oxidative state. In this study, we laser-printed GO surfaces in order to obtain both a local photo-thermal GO reduction and the formation of nano-wrinkles along precise geometric pattern. Initially, after cells adhered on the surface, stem cells migrated and accumulated on the reduced and wrinkled surface. When the local density of the stem cells on the reduced stripes was high, cells started to proliferate and occupy the oxidized/flat area. The designed surfaces morphology guided stem cell orientation and the reduction accelerated differentiation. Furthermore the reduced sharp nano-wrinkles were able to enhance the GO antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA), a common cause of prosthetic joints infections. This strategy can offer a revolution in present and future trends of scaffolds design for regenerative medicine.

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

Science.gov (United States)

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.

Oxidative stress and repetitive element methylation changes in artisanal gold miners occupationally exposed to mercury

Directory of Open Access Journals (Sweden)

Diana M. Narváez

2017-09-01

Full Text Available Mercury (Hg exposure is a public health concern due to its persistence in the environment and its high toxicity. Such toxicity has been associated with the generation of oxidative stress in occupationally exposed subjects, such as artisanal gold miners. In this study, we characterize occupational exposure to Hg by measuring blood, urine and hair levels, and investigate oxidative stress and DNA methylation associated with gold mining. To do this, samples from 53 miners and 36 controls were assessed. We show higher levels of oxidative stress marker 8-OHdG in the miners. Differences in LINE1 and Alu(Yb8 DNA methylation between gold miners and control group are present in peripheral blood leukocytes. LINE1 methylation is positively correlated with 8-OHdG levels, while XRCC1 and LINE1 methylation are positively correlated with Hg levels. These results suggest an effect of Hg on oxidative stress and DNA methylation in gold miners that may have an impact on miners’ health.

Kinetics of the reduction of uranium oxide catalysts

International Nuclear Information System (INIS)

Heynen, H.W.G.; Camp-van Berkel, M.M.; Bann, H.S. van der

1977-01-01

The reduction of uranium oxide and uranium oxide on alumina catalysts by ethylbenzene and by hydrogen has been studied in a thermobalance. Ethylbenzene mole fractions between 0.0026 and 0.052 and hydrogen mole fractions between 0.1 and 0.6 were applied at temperatures of 425--530 0 C. During the reduction the uranium oxides are converted into UO 2 . The rate of reduction of pure uranium oxide appears to be constant in the composition region UO/sub 2.6/-UO/sub 2.25/. The extent of this region is independent of the concentration of the reducing agents and of the reaction temperature. The constant rate is explained in terms of a constant oxygen pressure which is in equilibrium with the two solid phases, U 3 O/sub 8-x/ and U 4 O 9 . The reduction rate is first order in hydrogen and zero order in ethylbenzene with activation energies of 120 and 190 kJ mol -1 , respectively. Oxygen diffusion through the lattice is probably not rate limiting. The reduction behavior of uranium oxide on alumina is different from that of pure uranium oxide; the rate of reduction continuously decreases with increasing degree of reduction. An explanation for this behavior has been given by visualizing this catalyst as a set of isolated uranium oxide crystallites with a relative wide variation of diameters, in an alumina matrix. At the beginning of the reduction, carbon dioxide and water are the only reaction products. Thereafter, benzene is found as well and, finally, at U/O ratios below 2.25, styrene also appears in the reactor outlet

Zeta potentials in the flotation of oxide and silicate minerals.

Science.gov (United States)

Fuerstenau, D W; Pradip

2005-06-30

Adsorption of collectors and modifying reagents in the flotation of oxide and silicate minerals is controlled by the electrical double layer at the mineral-water interface. In systems where the collector is physically adsorbed, flotation with anionic or cationic collectors depends on the mineral surface being charged oppositely. Adjusting the pH of the system can enhance or prevent the flotation of a mineral. Thus, the point of zero charge (PZC) of the mineral is the most important property of a mineral in such systems. The length of the hydrocarbon chain of the collector is important because of chain-chain association enhances the adsorption once the surfactant ions aggregate to form hemimicelles at the surface. Strongly chemisorbing collectors are able to induce flotation even when collector and the mineral surface are charged similarly, but raising the pH sufficiently above the PZC can repel chemisorbing collectors from the mineral surface. Zeta potentials can be used to delineate interfacial phenomena in these various systems.

Electrochemical reduction of actinides oxides in molten salts

International Nuclear Information System (INIS)

Claux, B.

2011-01-01

Reactive metals are currently produced from their oxide by multiple steps reduction techniques. A one step route from the oxide to the metal has been suggested for metallic titanium production by electrolysis in high temperature molten chloride salts. In the so-called FFC process, titanium oxide is electrochemically reduced at the cathode, generating O 2- ions, which are converted on a graphite anode into carbon oxide or dioxide. After this process, the spent salt can in principle be reused for several batches which is particularly attractive for a nuclear application in terms of waste minimization. In this work, the electrochemical reduction process of cerium oxide (IV) is studied in CaCl 2 and CaCl 2 -KCl melts to understand the oxide reduction mechanism. Cerium is used as a chemical analogue of actinides. Electrolysis on 10 grams of cerium oxide are made to find optimal conditions for the conversion of actinides oxides into metals. The scale-up to hundred grams of oxide is also discussed. (author) [fr

Oxidative Mineralization and Characterization of Polyvinyl Alcohol Solutions for Wastewater Treatment

Energy Technology Data Exchange (ETDEWEB)

Oji, L.N.

1999-08-31

The principal objectives of this study are to identify an appropriate polyvinyl alcohol (PVA) oxidative mineralization technique, perform compatibility and evaporation fate tests for neat and mineralized PVA, and determine potential for PVA chemical interferences which may affect ion exchange utilization for radioactive wastewater processing in the nuclear industry.

The redox properties of the natural iron-bearing clay mineral ferruginous smectite SWA-1: a combined electrochemical and spectroscopic study

International Nuclear Information System (INIS)

Gorski, Christopher A.; Voegelin, Andreas; Sander, Michael; Hofstetter, Thomas B.

2012-01-01

Document available in extended abstract form only. Iron-bearing clay minerals are ubiquitous in the environment and clay-mineral-based materials have been proposed to be part of backfill material in nuclear waste repositories. Laboratory and field studies have confirmed that structural iron (Fe) in clay minerals participates in redox reactions with organic pollutants, metals, and radionuclides, thus influencing their transport and reactivity. Knowledge of the redox properties of Fe-bearing clay minerals is therefore essential for understanding and predicting the fate, mobility, and bioavailability subsurface contaminants. A quantitative understanding of clay mineral redox behavior remains lacking, however, due to constraints in previous experimental approaches and the complex structural changes that accompany changes in the Fe oxidation state. This work provides a quantitative means for measuring the redox properties of Fe-bearing clay minerals, which can be applied to both field and laboratory studies tracking radionuclide-clay mineral redox reactions. Here we use mediated electrochemical reduction and oxidation to determine the electron accepting and donating capacities of several natural Fe-bearing clay minerals with different structural Fe content (2.3 to 21 wt-%) and varied redox histories. Results indicate that the fraction of redox-active Fe in clay minerals is mineral-dependent, and is linked to the thermodynamics of reduction and oxidation as well as to the ability of clay minerals to conduct electrons and facilitate structural re-arrangements required to maintain charge balance. The reduction potential (E H ) characteristics of a natural ferruginous smectite (SWa-1) were further characterized as a function of solution conditions and repeated Fe reduction and oxidation cycles. SWa-1 samples were analyzed with Moessbauer spectroscopy (MS) and X-ray absorption spectroscopy (XAS) to link observed redox potential behavior to structural properties and changes

Green reduction of graphene oxide using alanine.

Science.gov (United States)

Wang, Jiabin; Salihi, Elif Caliskan; Šiller, Lidija

2017-03-01

There remains a real need for the easy, eco-friendly and scalable preparation method of graphene due to various potential applications. Chemical reduction is the most versatile method for the large scale production of graphene. Here we report the operating conditions for a one-step, economical and green synthesis method for the reduction of graphene oxide using a biomolecule (alanine). Graphene oxide was produced by the oxidation and exfoliation of natural graphite flake with strong oxidants using Hummers method (Hummers and Offeman, 1958), but the method was revised in our laboratory to set up a safe and environmentally friendly route. The reduction of graphene oxide was investigated using alanine at various operating conditions in order to set up optimum conditions (treatment time, temperature and concentration of the reagent). Samples have been characterized by using UV-Visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction analysis. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Conductive iron oxide minerals accelerate syntrophic cooperation in methanogenic benzoate degradation

Energy Technology Data Exchange (ETDEWEB)

Zhuang, Li; Tang, Jia; Wang, Yueqiang; Hu, Min; Zhou, Shungui, E-mail: sgzhou@soil.gd.cn

2015-08-15

Highlights: • Paddy soil contaminated with benzoate incubated with hematite and magnetite. • Iron oxides addition enhanced methanogenic benzoate degradation by 25–53%. • The facilitated syntrophy might involve direct interspecies electron transfer. • Bacillaceae, Peptococcaceae, and Methanobacterium are potentially involved. - Abstract: Recent studies have suggested that conductive iron oxide minerals can facilitate syntrophic metabolism of the methanogenic degradation of organic matter, such as ethanol, propionate and butyrate, in natural and engineered microbial ecosystems. This enhanced syntrophy involves direct interspecies electron transfer (DIET) powered by microorganisms exchanging metabolic electrons through electrically conductive minerals. Here, we evaluated the possibility that conductive iron oxides (hematite and magnetite) can stimulate the methanogenic degradation of benzoate, which is a common intermediate in the anaerobic metabolism of aromatic compounds. The results showed that 89–94% of the electrons released from benzoate oxidation were recovered in CH{sub 4} production, and acetate was identified as the only carbon-bearing intermediate during benzoate degradation. Compared with the iron-free controls, the rates of methanogenic benzoate degradation were enhanced by 25% and 53% in the presence of hematite and magnetite, respectively. This stimulatory effect probably resulted from DIET-mediated methanogenesis in which electrons transfer between syntrophic partners via conductive iron minerals. Phylogenetic analyses revealed that Bacillaceae, Peptococcaceae, and Methanobacterium are potentially involved in the functioning of syntrophic DIET. Considering the ubiquitous presence of iron minerals within soils and sediments, the findings of this study will increase the current understanding of the natural biological attenuation of aromatic hydrocarbons in anaerobic environments.

Mineral sources and transport pathways for arsenic release in a coastal watershed, USA

Science.gov (United States)

Foley, Nora K.; Ayuso, Robert A.

2008-01-01

Metasedimentary bedrock of coastal Maine contains a diverse suite of As-bearing minerals that act as significant sources of elements found in ground and surface waters in the region. Arsenic sources in the Penobscot Formation include, in order of decreasing As content by weight: löllingite and realgar (c.70%), arsenopyrite, cobaltite, glaucodot, and gersdorffite (in the range of 34–45%), arsenian pyrite (Formation, the relative stability of primary As-bearing minerals follows a pattern where the most commonly observed highly altered minerals are pyrrhotite, realgar, niccolite, löllingite > glaucodot, arsenopyrite-cobaltian > arsenopyrite, cobaltite, gersdorffite, fine-grained pyrite, Ni-pyrite > coarse-grained pyrite. Reactions illustrate that oxidation of Fe-As disulphide group and As-sulphide minerals is the primary release process for As. Liberation of As by carbonation of realgar and orpiment in contact with high-pH groundwaters may contribute locally to elevated contents of As in groundwater, especially where As is decoupled from Fe. Released metals are sequestered in secondary minerals by sorption or by incorporation in crystal structures. Secondary minerals acting as intermediate As reservoirs include claudetite (c.75%), orpiment (61%), scorodite (c. 45%), secondary arsenopyrite (c. 46%), goethite (minerals. Reductive dissolution of Fe-oxide minerals may govern the ultimate release of iron and arsenic – especially As(V) – to groundwater; however, dissolution of claudetite (arsenic trioxide) may directly contribute As(III). Processes thought to explain the release of As from minerals in bedrock include oxidation of arsenian pyrite or arsenopyrite, or carbonation of As-sulphides, and most models based on these generally rely on discrete minerals or on a fairly limited series of minerals. In contrast, in the Penobscot Formation and other metasedimentary rocks of coastal Maine, oxidation of As-bearing Fe-cobalt-nickel-sulphide minerals, dissolution (by

Mechanisms of electrochemical reduction and oxidation of nitric oxide

NARCIS (Netherlands)

Vooys, de A.C.A.; Beltramo, G.L.; Riet, van B.; Veen, van J.A.R.; Koper, M.T.M.

2004-01-01

A summary is given of recent work on the reactivity of nitric oxide on various metal electrodes. The significant differences between the reactivity of adsorbed NO and NO in solution are pointed out, both for the reduction and the oxidation reaction(s). Whereas adsorbed NO can be reduced only to

Red Dawn: Characterizing Iron Oxide Minerals in Atmospheric Dust

Science.gov (United States)

Yauk, K.; Ottenfeld, C. F.; Reynolds, R. L.; Goldstein, H.; Cattle, S.; Berquo, T. S.; Moskowitz, B. M.

2012-12-01

Atmospheric dust is comprised of many components including small amounts of iron oxide minerals. Although the iron oxides make up a small weight percent of the bulk dust, they are important because of their roles in ocean fertilization, controls on climate, and as a potential health hazard to humans. Here we report on the iron oxide mineralogy in dust from a large dust storm, dubbed Red Dawn, which engulfed eastern Australia along a 3000 km front on 23 September 2009. Red Dawn originated from the lower Lake Eyre Basin of South Australia, western New South Wales (NSW) and southwestern Queensland and was the worst dust storm to have hit the city of Sydney in more than 60 years. Dust samples were collected from various locations across eastern Australia (Lake Cowal, Orange, Hornsby, Sydney) following the Red Dawn event. Our dust collection provides a good opportunity to study the physical and mineralogical properties of iron oxides from Red Dawn using a combination of reflectance spectroscopy, Mössbauer spectroscopy (MB), and magnetic measurements. Magnetization measurements from 20-400 K reveal that magnetite/maghemite, hematite and goethite are present in all samples with magnetite occurring in trace amounts (effects (d< 100 nm). Finally, we compared reflectance with a magnetic parameter (hard isothermal remanent magnetization, HIRM) for ferric oxide abundance to assess the degree to which ferric oxide in these samples might absorb solar radiation. In samples for which both parameters were obtained, HIRM and average reflectance over the visible wavelengths are correlated as a group (r2=0.24). These results indicate that the ferric oxide minerals in Red Dawn dust absorb solar radiation. Much of this ferric oxide occurs likely as grain coatings of nanohematite and nanogoethite, thereby providing high surface area to enhance absorption of solar radiation.

Development of reduction technology for oxide fuel. Behaviour of rare-earth in lithium reduction process

International Nuclear Information System (INIS)

Kato, Tetsuya; Usami, Tsuyoshi; Yuda, Ryoichi; Kurata, Masateru; Moriyama, Hirotake

2000-01-01

Solubility measurements of rare-earth oxides in molten LiCl-Li 2 O salt and reduction tests of UO 2 doped with rare-earth oxides were carried out to determine the behavior of rare-earths in lithium reduction process. The solubility of rare-earth oxides increases in the order of Gd 2 O concentration. In multi-element systems including 6 rare-earth oxides, the solubility of each element is smaller than that in the individual systems. In the reduction tests, more than 90% of UO 2 was reduced within 1 hour after starting reduction and about 7% of rare-earths eluded into the LiCl molten salt bath containing Li 2 O which is formed by the reduction of UO 2 . The rare-earth concentrations in the bath were evaluated using the solubility data, assuming that rare-earth oxides in multi-element systems form solid solution as the equilibrium solid phase and that the activity coefficients in the solid phase are independent of the compositions. The calculated concentrations are consistent with the experimental ones obtained in the reduction tests. (author)

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

Science.gov (United States)

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.

Neyshabour turquoise mine: the first Iron Oxide Cu-Au-U-LREE (IOCG mineralized system in Iran

Directory of Open Access Journals (Sweden)

Mohammad Hasan Karimpour

2011-11-01

Full Text Available Neyshabour turquoise mine is located in northwest of Neyshabour, southern Quchan volcanic belt. Eocene andesite and dacite forming as lava and pyroclastic rocks cover most of the area. Subvolcanic diorite to syenite porphyry (granitoids of magnetite series intruded the volcanic rocks. Both volcanic and subvolcanic rocks are highly altered. Four types of alteration are recognized including: silicification, argillic, calcification and propylitic. Silicification is dominant followed by argillic alteration. Mineralization is present as stockwork, disseminated and hydrothermal breccia. Hypogene minerals are pyrite, magnetite, specularite, chalcopyrite, and bornite. Secondary minerals are turquoise, chalcocite, covellite, and iron oxides. A broad zone of gossan has developed in the area. Oxidized zone has a thickness of about 80 m. Mineralized samples show high anomalies of Cu, Au, Zn, As, Mo, Co, U, LREE, Nb, and Th. Both aeromagnetic and radiometric (U and Th maps show very strong anomalies (10 × 5km within the mineralized area. Based on geology, alteration, mineralization, geochemistry, and geophysics, Neyshabour turquoise mine is a large Iron oxide Cu-Au-U-LREE (IOCG mineralized system. In comparison with other IOCG deposits, it has some similarities with Olympic Dam (Australia and Candelaria (Chile. In comparison with Qaleh Zari and Kuh Zar mines, Neyshabour turquoise mine is the first Iron oxide Cu-Au-U-LREE (IOCG mineralized system discovered in Iran.

Heteroaggregation of graphene oxide with minerals in aqueous phase.

Science.gov (United States)

Zhao, Jian; Liu, Feifei; Wang, Zhenyu; Cao, Xuesong; Xing, Baoshan

2015-03-03

Upon release into waters, sediments, and soils, graphene oxide (GO) may interact with fine mineral particles. We investigated the heteroaggregation of GO with different minerals, including montmorillonite, kaolinite, and goethite, in aqueous phase. GO significantly enhanced the dispersion of positively charged goethite (>50%) via heteroaggregation, while there was no interaction between GO and negatively charged montmorillonite or kaolinite. Electrostatic attraction was the dominant force in the GO-goethite heteroaggregation (pH 4.0-8.5), and the dissolved Fe ions (formation of multilayered GO-goethite complex with high configurational stability. These findings are useful for understanding the interaction of GO with mineral surfaces, and potential fate and toxicity of GO under natural conditions in aquatic environments, as well as in soils and sediments.

Fixation of Selenium by Clay Minerals and Iron Oxides

DEFF Research Database (Denmark)

Hamdy, A. A.; Nielsen, Gunnar Gissel

1977-01-01

In studying Se fixation, soil components capable of retaining Se were investigated. The importance of Fe hydrous oxides in the fixation of Se was established. The clay minerals common to soils, such as kaolinite, montmorillonite and vermiculite, all exhibited Se fixation, but greater fixation occ...

A microbial-mineralization-inspired approach for synthesis of manganese oxide nanostructures with controlled oxidation states and morphologies

Energy Technology Data Exchange (ETDEWEB)

Oba, Manabu; Oaki, Yuya; Imai, Hiroaki [Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan)

2010-12-21

Manganese oxide nanostructures are synthesized by a route inspired by microbial mineralization in nature. The combination of organic molecules, which include antioxidizing and chelating agents, facilitates the parallel control of oxidation states and morphologies in an aqueous solution at room temperature. Divalent manganese hydroxide (Mn(OH){sub 2}) is selectively obtained as a stable dried powder by using a combination of ascorbic acid as an antioxidizing agent and other organic molecules with the ability to chelate to manganese ions. The topotactic oxidation of the resultant Mn(OH){sub 2} leads to the selective formation of trivalent manganese oxyhydroxide ({beta}-MnOOH) and trivalent/tetravalent sodium manganese oxide (birnessite, Na{sub 0.55}Mn{sub 2}O{sub 4}.1.5H{sub 2}O). For microbial mineralization in nature, similar synthetic routes via intermediates have been proposed in earlier works. Therefore, these synthetic routes, which include in the present study the parallel control over oxidation states and morphologies of manganese oxides, can be regarded as new biomimetic routes for synthesis of transition metal oxide nanostructures. As a potential application, it is demonstrated that the resultant {beta}-MnOOH nanostructures perform as a cathode material for lithium ion batteries. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Decolorization and mineralization of Allura Red AC aqueous solutions by electrochemical advanced oxidation processes

International Nuclear Information System (INIS)

Thiam, Abdoulaye; Sirés, Ignasi; Garrido, José A.; Rodríguez, Rosa M.; Brillas, Enric

2015-01-01

Highlights: • Quicker degradation of Allura Red AC in the order EO-H 2 O 2 < EF < PEF with Pt or BDD anode. • Almost total mineralization achieved by the most powerful PEF process with BDD. • Similar decolorization and mineralization rate in SO 4 2− , ClO 4 − and NO 3 − media. • In Cl − medium, only slightly larger decolorization rate but strong inhibition of mineralization. • Identification of aromatic products, carboxylic acids and released NH 4 + , NO 3 − and SO 4 2− ions. - Abstract: The decolorization and mineralization of solutions containing 230 mg L −1 of the food azo dye Allura Red AC at pH 3.0 have been studied upon treatment by electrochemical oxidation with electrogenerated H 2 O 2 (EO-H 2 O 2 ), electro-Fenton (EF) and photoelectro-Fenton (PEF). Experiments were performed with a stirred tank reactor containing a boron-doped diamond (BDD) or Pt anode and an air-diffusion cathode to generate H 2 O 2 . The main oxidants were hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between H 2 O 2 and added Fe 2+ . The oxidation ability increased in the sequence EO-H 2 O 2 < EF < PEF and faster degradation was always obtained using BDD. PEF process with BDD yielded almost total mineralization following similar trends in SO 4 2− , ClO 4 − and NO 3 − media, whereas in Cl − medium, mineralization was inhibited by the formation of recalcitrant chloroderivatives. GC–MS analysis confirmed the cleavage of the −N=N− bond with formation of two main aromatics in SO 4 2− medium and three chloroaromatics in Cl − solutions. The effective oxidation of final oxalic and oxamic acids by BDD along with the photolysis of Fe(III)-oxalate species by UVA light accounted for the superiority of PEF with BDD. NH 4 + , NO 3 − and SO 4 2− ions were released during the mineralization

Minerals of oxidation zone of the Chokadambulaq iron deposit

International Nuclear Information System (INIS)

Safaraliev, N.S.

2008-01-01

The zone of oxidation of Chokadambulaq iron deposit has original mineral composition, which characterized specificity of their formation. Here is formed a secondary zone of enrichment marit ores, having practical meaning. In last is concentrated from 0.5 up to 1.0% from total quantities of reserves

The enhancing of Au-Ag-Te content in tellurium-bearing ore mineral by bio-oxidation-leaching

Science.gov (United States)

Kim, PyeongMan; Kim, HyunSoo; Myung, EunJi; Kim, YoonJung; Lee, YongBum; Park*, CheonYoung

2015-04-01

The purpose of this study is to enhance the content of valuable metals such as Au-Ag-Te in tellurium-bearing minerals by bio-oxidation-leaching. It was confirmed that pyrite, chalcopyrite, sphalerite and galena were produced together with tellurium-bearing minerals including hessite, sylvanite and tellurobismuthite from ore minerals and concentrates through microscopic observation and SEM/EDS analysis. In a bio-oxidation-leaching experiment, with regard to Au, Ag, Te, Cu and Fe, the changes in the amount of leaching and the content of leaching residues were compared and analyzed with each other depending on the adaptation of an indigenous microbe identified as Acidithiobacillus ferrooxidans. As a result of the experiment, the Au-Ag-Te content in tellurium-bearing ore mineral was enhanced in the order of physical oxidation leaching, physical/non-adaptive bio-oxidation-leaching and physical/adaptive biological leaching. It suggests that the bio-oxidation-leaching using microbes adapted in tellurium-bearing ore mineral can be used as a pre-treatment and a main process in a recovery process of valuable metals. "This research was supported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education(NRF-2013R1A1A2004898)"

Reduction of graphene oxide and its effect on square resistance of reduced graphene oxide films

Energy Technology Data Exchange (ETDEWEB)

Hou, Zhaoxia; Zhou, Yin; Li, Guang Bin; Wang, Shaohong; Wang, Mei Han; Hu, Xiaodan; Li, Siming [Liaoning Province Key Laboratory of New Functional Materials and Chemical Technology, School ofMechanical Engineering, Shenyang University, Shenyang (China)

2015-06-15

Graphite oxide was prepared via the modified Hummers’ method and graphene via chemical reduction. Deoxygenation efficiency of graphene oxide was compared among single reductants including sodium borohydride, hydrohalic acids, hydrazine hydrate, and vitamin C. Two-step reduction of graphene oxide was primarily studied. The reduced graphene oxide was characterized by XRD, TG, SEM, XPS, and Raman spectroscopy. Square resistance was measured as well. Results showed that films with single-step N2H4 reduction have the best transmittance and electrical conductivity with square resistance of ~5746 Ω/sq at 70% transmittance. This provided an experimental basis of using graphene for electronic device applications.

Formation conditions of uranium minerals in oxidation zone of uranium deposits

International Nuclear Information System (INIS)

Li Youzhu

2005-01-01

The paper concerns about the summary and classification of hydrothermal uranium deposit with oxidation zone. Based on the summary of observation results of forty uranium deposits located in CIS and Bulgaria which are of different sizes and industrial-genetic types, analysis on available published information concerning oxidation and uranium mineral enrichment in supergenic zone, oxidation zone classification of hydrothermal uranium had been put forward according to the general system of the exogenetic uranium concentration. (authors)

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.

Science.gov (United States)

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.

Sub-2 nm SnO2 nanocrystals: A reduction/oxidation chemical reaction synthesis and optical properties

International Nuclear Information System (INIS)

Zhang Hui; Du Ning; Chen Bindi; Cui Tianfeng; Yang Deren

2008-01-01

A simple reduction/oxidation chemical solution approach at room temperature has been developed to synthesize ultrafine SnO 2 nanocrystals, in which NaBH 4 is used as a reducing agent instead of mineralizers such as sodium hydroxide, ammonia, and alcohol. The morphology, structure, and optical property of the ultrafine SnO 2 nanocrystals have been characterized by high-resolution transmission electron microscopy (HRTEM), X-ray powder diffraction (XRD), differential scanning calorimetry and thermogravimetric analysis (DSC-TGA), X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectroscopy. It is indicated that the uniform tetragonal ultrafine SnO 2 nanocrystals with the size below 2 nm have been fabricated at room temperature. The band gap of the ultrafine SnO 2 nanocrystals is about 4.1 eV, exhibiting 0.5 eV blue shift from that of the bulk SnO 2 (3.6 eV). Furthermore, the mechanism for the reduction/oxidation chemical reaction synthesis of the ultrafine SnO 2 nanocrystals has been preliminary presented

Uranium fixation by mineralization at the redox front

International Nuclear Information System (INIS)

Isobe, Hiroshi

1998-01-01

The behavior of actinide elements including uranium in geomedia is controlled by redox conditions. Under the oxidized conditions, uranium forms uranyl ion (UO 2 2+ ) and its complexes, and dissolves in ground water. Under the reduced conditions, U(IV) has much lower solubility than uranyl ion. In the Koongarra uranium deposit, Australia, lead-bearing uraninite, uranyl lead oxide and uranyl silicate minerals occur in the unweathered, primary ore zone, and uranyl phosphate minerals occur in the weathered, secondary ore zone. Between unweathered and weathered zones, the transition zone exists as a redox front. In the transition zone, graphite and sulfide minerals react as reducing agents for species dissolved in ground water. By SEM, spherical grains of uraninite were observed in veins with graphite. Pyrite had coffinite rim with crystals of uraninite. Calculation based on the ground water chemistry and hydrology at Koongarra shows that the uranium in the transition zone may be fixed from the ground water. In the Koongarra transition zone, recent mineralization of uranium by reduction takes place. Mineralization is much stronger fixation mechanism than adsorption on clay minerals. Pyrite in the buffer materials of possible radioactive waste repositories can fix radionuclides in oxidized ground water by mineralization with reducing reactions. (author)

Pathways of organic carbon oxidation in three continental margin sediments

DEFF Research Database (Denmark)

Canfield, Donald Eugene; Jørgensen, Bo Barker; Fossing, Henrik

1993-01-01

We have combined several different methodologies to quantify rates of organic carbon mineralization by the various electron acceptors in sediments from the coast of Denmark and Norway. Rates of NH4+ and Sigma CO2 liberation sediment incubations were used with O2 penetration depths to conclude...... that O2 respiration accounted for only between 3.6-17.4% of the total organic carbon oxidation. Dentrification was limited to a narrow zone just below the depth of O2 penetration, and was not a major carbon oxidation pathway. The processes of Fe reduction, Mn reduction and sulfate reduction dominated...... organic carbon mineralization, but their relative significance varied depending on the sediment. Where high concentrations of Mn-oxide were found (3-4 wt% Mn), only Mn reduction occurred. With lower Mn oxide concentrations more typical of coastal sediments, Fe reduction and sulfate reduction were most...

Iron and manganese in oxide minerals and in glasses: preliminary consideration of Eh buffering potential at Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Caporuscio, F.A.; Vaniman, D.T.

1985-04-01

The tuffs of Yucca Mountain at the Nevada Test Site are currently under investigation as a possible deep burial site for high-level radioactive waste disposal. One of the main concerns is the effect of oxidizing groundwater on the transport of radionuclides. Rock components that may affect the oxygen content of groundwater include Fe-Ti oxides, Mn oxides, and glasses that contain ferrous iron. Some phenocryst Fe-Ti oxides at Yucca Mountain are in reduced states, whereas groundmass Fe-Ti oxides have been oxidized to hematite, rutile, and pseudobrookite (Fe 3+ -bearing phases) exclusively. Estimates of Fe 2+ -bearing oxides indicate that less than 0.33 vol% phenocrysts is available to act as solid buffering agents of Eh. Of this percentage, significant amounts of Fe-Ti oxides are isolated from effective interaction with groundwater because they occur in densely welded, devitrified tuffs that have low interstitial permeability. Manganese oxides occur primarily along fractures in the ash-flow tuffs. Because the Mn oxides are concentrated along the same pathways (fractures) where transport has occurred in the past, these small volume percentages could act as buffers. However, the oxidation states of actual Mn-oxide phases are high (Mn 4+ ), and these minerals have virtually no potential for reducing groundwater Eh. Manganese oxides may even act as oxidizing agents. However, regardless of their poor capabilities as reducing agents, the Mn oxides could be important as sorbents of heavy metals at Yucca Mountain. The lack of accessible, pristine Fe-Ti oxides and the generally high oxidation states of Mn oxides seem to rule out these oxides as Eh buffers of the Yucca Mountain groundwater system. Reduction of ferrous iron within glassy tuffs may have some effect on Eh, but further study is needed. At present it is prudent to assume that minerals and glasses have little or no capacity for reducing oxygen-rich groundwater at Yucca Mountain. 25 refs., 3 figs., 12 tabs

Photooxidation of chloride by oxide minerals: implications for perchlorate on Mars.

Science.gov (United States)

Schuttlefield, Jennifer D; Sambur, Justin B; Gelwicks, Melissa; Eggleston, Carrick M; Parkinson, B A

2011-11-09

We show that highly oxidizing valence band holes, produced by ultraviolet (UV) illumination of naturally occurring semiconducting minerals, are capable of oxidizing chloride ion to perchlorate in aqueous solutions at higher rates than other known natural perchlorate production processes. Our results support an alternative to atmospheric reactions leading to the formation of high concentrations of perchlorate on Mars.

Concentration of gold, sulphide minerals, and uranium oxide minerals by flotation from ores and metallurgical plant products

International Nuclear Information System (INIS)

Weston, D.

1976-01-01

A process is described for the concentration by flotation of gold, gold bearing minerals and uranium oxide minerals from ores and metallurgical plant products. A pulp of a ground ore is agitation conditioned in at least two agitation conditioning stages wherein in at least one stage the pH of the pulp is lowered with an acid agent to within the pH range of about 1.5 to 5.0, and wherein in at least one additional agitation conditioning stage the pH of the pulp is raised to within the pH range of about 6.0 to 11.0 and wherein in at least the last stage prior to flotation at least one collector selected from the group of sulfhydryl anionic collectors is present. Subsequently, the at least two stage agitation conditioned pulp is subjected to flotation to produce a flotation concentrate enriched in at least one of the mineral values from the group consisting of gold, gold bearing minerals and uranium minerals

Iron-titanium oxide minerals and magnetic susceptibility anomalies in the Mariano Lake-Lake Valley cores - Constraints on conditions of uranium mineralization in the Morrison Formation, San Juan Basin, New Mexico

International Nuclear Information System (INIS)

Reynolds, R.L.; Fishman, N.S.; Scott, J.H.; Hudson, M.R.

1986-01-01

Petrographic study of the Mariano Lake-Lake Valley cores reveals three distinct zones of postdepositional alteration of detrital Fe-Ti (iron-titanium) oxide minerals in the Westwater Canyon Member of the Upper Jurassic Morrisson Formation. In the uranium-bearing and adjacent portions of the Westwater Canyon, these detrital Fe-Ti oxide minerals have been thoroughly altered by leaching of iron. Stratigraphically lower parts of the Westwater Canyon and the underlying Recapture Member are characterized by preservation of Fe-Ti oxide grains, primarily magnetite and ilmenite, and of hematite, and by an absence or uranium concentrations. Partly destroyed Fe-Ti oxide minerals occupy an interval between the zones of destruction and preservation. Alteration patterns of the Fe-Ti oxide minerals are reflected in bore-hole magnetic susceptibility logs. Magnetic susceptibility response in the upper parts of the Westwater Canyon Member is flat and uniformly <500 μSI units, but at greater depths it fluctuates sharply, from <1,000 to nearly 8,000 μSI units. The boundary between uniformly low and high magnetic susceptibility response corresponds closely to the interval that divides the zone of completely altered from the zone of preserved detrital Fe-Ti oxide minerals. The alteration pattern suggests that solutions responsible for destruction of the Fe-ti oxide minerals originated in the overlying Brushy Basin Member of the Morrison Formation. Previous studies indicate that these solutions were rich in soluble organic matter and perhaps in uranium. Uranium precipitation may have been controlled by a vertically fluctuation interface between organic-rich solutions and geochemically different fluids in which the detrital Fe-Ti oxide minerals were preserved

2-22 Study of Oxidation/reduction Volatilization Technology

Institute of Scientific and Technical Information of China (English)

Tan; Cunmin[1; Cao; Shiwei[1; Tian; Yuan[1; Qin; Zhi[1

2015-01-01

As an advanced dry head-end processing of spent fuel reprocessing, the oxidation-reduction volatilization technology will use for pulverizing uranium oxide ceramic pellets, decladding, and removal of most of volatile and semi-volatile fission elements, 3H, 14C, Kr, Xe, I, Cs, Ru and Tc, from fuel prior to main treatment process. The AIROX and ORIOX process, including circulation of oxidation in oxygen atmosphere and reduction in hydrogen atmosphere, researched on international at present, is considered to be the first choice for head-end processing.

Large Scale Reduction of Graphite Oxide Project

Science.gov (United States)

Calle, Carlos; Mackey, Paul; Falker, John; Zeitlin, Nancy

2015-01-01

This project seeks to develop an optical method to reduce graphite oxide into graphene efficiently and in larger formats than currently available. Current reduction methods are expensive, time-consuming or restricted to small, limited formats. Graphene has potential uses in ultracapacitors, energy storage, solar cells, flexible and light-weight circuits, touch screens, and chemical sensors. In addition, graphite oxide is a sustainable material that can be produced from any form of carbon, making this method environmentally friendly and adaptable for in-situ reduction.

Physiochemical Influence of Soil Minerals on the Organic Reduction of Soil Chromium

International Nuclear Information System (INIS)

Njoku, P.C.; Nweze, C.A.

2009-01-01

The physiochemical influence of soil minerals (Bentonite, Kaolinite, Diatomite,Rutile and Ferrihydrite) on the organic reduction ofchromium (VI) has been investigated with Oxalic acid as the organic reductant. The effect of pH and particle sizes of the soil minerals were also investigated. Results showed that with 0.1mol/dm3 concentration of Oxalic acid, the concentration of chromium(VI) remaining was 0.28, 0.34,0.38, 0.46 and 0.52mg/kgfor Bentonite, Rutile, Diatomite, Kaolinite and Ferrihydrite respectively whereas at 0.5mol/dm3of oxalic acid, the concentration of chromium reduced to 0.20,0.26, 0.30, 0.38, and0.44mg/kg for Bentonite, Rutile, Diatomite, Kaolinite and Ferrihydrite. Increasedconcentration of oxalic acid increased the reduction of chromium(VI) to chromium(III). At pH 5.0, the concentration of chromium(VI)left was 0.28, 0.34, 0.38,0.46 and 0.52mg/kg forBentonite, Rutile, Diatomite, Kaolinite and Ferrihydrite while at pH 2.5, concentration was0.16, 0.22, 0.26, 0.34 and 0.43mg/kg respectively. At particle size of 47-42 microns, concentration of chromium(VI) was 0.28, 0.34,0.38, 0.46, 0.52mg/kg for the same order ofthe soil minerals. At micron sizes of33-29 and 28-25 ranges the concentration ofchromium(VI) left was 0.23, 0.29, 0.33,0.41 and 0.47mg/kg for both micron sizes and corresponding minerals as well. These results showed that above 33-29 micron sizes, the influence of particle size was negligible. (author)

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

Science.gov (United States)

Fox, P.M.; Davis, J.A.; Luther, G. W.

2009-01-01

The kinetics of iodide (I-) and molecular iodine (I2) oxidation by the manganese oxide mineral birnessite (??-MnO2) was investigated over the pH range 4.5-6.25. I- oxidation to iodate (IO3-) proceeded as a two-step reaction through an I2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I- from solution was first order with respect to I- concentration, pH, and birnessite concentration, such that -d[I-]/dt = k[I-][H+][MnO2], where k, the third order rate constant, is equal to 1.08 ?? 0.06 ?? 107 M-2 h-1. The data are consistent with the formation of an inner sphere I- surface complex as the first step of the reaction, and the adsorption of I- exhibited significant pH dependence. Both I2, and to a lesser extent, IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I2 and IO3-, as well as the biophilic nature of I2, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

A case of osteomalacia due to deranged mineral balance caused by saccharated ferric oxide and short-bowel syndrome

Science.gov (United States)

Nomoto, Hiroshi; Miyoshi, Hideaki; Nakamura, Akinobu; Nagai, So; Kitao, Naoyuki; Shimizu, Chikara; Atsumi, Tatsuya

2017-01-01

Abstract Rationale: Saccharated ferric oxide has been shown to lead to elevation of fibroblast growth factor 23, hypophosphatemia, and, consequently, osteomalacia. Moreover, mineral imbalance is often observed in patients with short-bowel syndrome to some degree. Patient concerns: A 62-year-old woman with short-bowel syndrome related with multiple resections of small intestines due to Crohn disease received regular intravenous administration of saccharated ferric oxide. Over the course of treatment, she was diagnosed with tetany, which was attributed to hypocalcemia. Additional assessments of the patient revealed not only hypocalcemia, but also hypophosphatemia, hypomagnesemia, osteomalacia, and a high concentration of fibroblast growth factor 23 (314 pg/mL). Diagnoses: We diagnosed her with mineral imbalance-induced osteomalacia due to saccharated ferric oxide and short-bowel syndrome. Interventions: Magnesium replacement therapy and discontinuation of saccharated ferric oxide alone. Outcomes: These treatments were able to normalize her serum mineral levels and increase her bone mineral density. Lessons: This case suggests that adequate evaluation of serum minerals, including phosphate and magnesium, during saccharated ferric oxide administration may be necessary, especially in patients with short-bowel syndrome. PMID:28953654

Oxygen Extraction from Minerals

Science.gov (United States)

Muscatello, Tony

2017-01-01

Oxygen, whether used as part of rocket bipropellant or for astronaut life support, is a key consumable for space exploration and commercialization. In Situ Resource Utilization (ISRU) has been proposed many times as a method for making space exploration more cost effective and sustainable. On planetary and asteroid surfaces the presence of minerals in the regolith that contain oxygen is very common, making them a potential oxygen resource. The majority of research and development for oxygen extraction from minerals has been for lunar regolith although this work would generally be applicable to regolith at other locations in space. This presentation will briefly survey the major methods investigated for oxygen extraction from regolith with a focus on the current status of those methods and possible future development pathways. The major oxygen production methods are (1) extraction from lunar ilmenite (FeTiO3) with either hydrogen or carbon monoxide, (2) carbothermal reduction of iron oxides and silicates with methane, and (3) molten regolith electrolysis (MRE) of silicates. Methods (1) and (2) have also been investigated in a two-step process using CO reduction and carbon deposition followed by carbothermal reduction. All three processes have byproducts that could also be used as resources. Hydrogen or carbon monoxide reduction produce iron metal in small amounts that could potentially be used as construction material. Carbothermal reduction also makes iron metal along with silicon metal and a glass with possible applications. MRE produces iron, silicon, aluminum, titanium, and glass, with higher silicon yields than carbothermal reduction. On Mars and possibly on some moons and asteroids, water is present in the form of mineral hydrates, hydroxyl (-OH) groups on minerals, andor water adsorbed on mineral surfaces. Heating of the minerals can liberate the water which can be electrolyzed to provide a source of oxygen as well. The chemistry of these processes, some key

Reduction of Graphene Oxide to Graphene by Using Gamma Irradiation

International Nuclear Information System (INIS)

Shamellia Sharin; Irman Abdul Rahman; Ainee Fatimah Ahmad

2015-01-01

This research aims to gauge the ability of gamma radiation to induce the reduction of graphene oxide to graphene. Graphene oxide powders were dispersed into a mixture of alcohol and deionized water, and the mixture was then irradiated with a "6"0Co source using a GammaCell 220 Excel irradiator at absorbed doses of 0, 5, 15, 20 and 35 kGy. According to characterization using Fourier Transformed Infrared Spectroscopy (FTIR), it can be seen that almost every oxygen-containing functional group has been removed after irradiation of the graphene oxide mixture. Reduction of graphene oxide was also proven from the characterization using UV-Vis Spectroscopy, in which the wavelength of graphene oxide at 237 nm was red-shifted to 277 nm after being irradiated and the peak at 292 nm, (indicating the carboxyl group) disappears in the UV-Vis spectrum of reduced graphene oxide. Morphology of graphene oxide also changed from a smooth and flat surface to crumpled. The ratio of carbon/ oxygen in the graphene oxide was lower than the carbon/ oxygen of reduced graphene oxide. At the end of the experiment, it can be deduced that graphene oxide underwent reduction, characterized before and after irradiation using Emission Scanned Electron Microscopy and Energy Dispersive X-ray, Fourier Transformed Infrared Spectroscopy and UV-Vis Spectroscopy. Therefore, we postulate that the irradiation technique that induces reduction, can be used to obtain reduced graphene oxide from graphene oxide. (author)

Graphene oxide reduction by microwave heating

International Nuclear Information System (INIS)

Longo, Angela; Carotenuto, Gianfranco

2016-01-01

The possibility to prepare thermal reduced graphene oxide (Tr-GO) colloidal suspensions by microwave heating of graphene oxide (GO) suspensions in N-methyl-2-pyrrolidone (NMP) has been investigated. According to transmission electron microscopy (TEM) and absorption and emission spectroscopy characterization, such a type of thermal reduction does not lead to graphene quantum dots formation because only mono-functional oxygen-containing groups are removed.

Graphene oxide reduction by microwave heating

Energy Technology Data Exchange (ETDEWEB)

Longo, Angela; Carotenuto, Gianfranco [Institute for Polymers, Composites, and Biomaterials, National Research Council, Piazzale Enrico Fermi 1, 80055 Portici (Italy)

2016-05-18

The possibility to prepare thermal reduced graphene oxide (Tr-GO) colloidal suspensions by microwave heating of graphene oxide (GO) suspensions in N-methyl-2-pyrrolidone (NMP) has been investigated. According to transmission electron microscopy (TEM) and absorption and emission spectroscopy characterization, such a type of thermal reduction does not lead to graphene quantum dots formation because only mono-functional oxygen-containing groups are removed.

Decolorization and mineralization of Allura Red AC aqueous solutions by electrochemical advanced oxidation processes

Energy Technology Data Exchange (ETDEWEB)

Thiam, Abdoulaye; Sirés, Ignasi; Garrido, José A.; Rodríguez, Rosa M.; Brillas, Enric, E-mail: brillas@ub.edu

2015-06-15

Highlights: • Quicker degradation of Allura Red AC in the order EO-H{sub 2}O{sub 2} < EF < PEF with Pt or BDD anode. • Almost total mineralization achieved by the most powerful PEF process with BDD. • Similar decolorization and mineralization rate in SO{sub 4}{sup 2−}, ClO{sub 4}{sup −} and NO{sub 3}{sup −} media. • In Cl{sup −} medium, only slightly larger decolorization rate but strong inhibition of mineralization. • Identification of aromatic products, carboxylic acids and released NH{sub 4}{sup +}, NO{sub 3}{sup −} and SO{sub 4}{sup 2−} ions. - Abstract: The decolorization and mineralization of solutions containing 230 mg L{sup −1} of the food azo dye Allura Red AC at pH 3.0 have been studied upon treatment by electrochemical oxidation with electrogenerated H{sub 2}O{sub 2} (EO-H{sub 2}O{sub 2}), electro-Fenton (EF) and photoelectro-Fenton (PEF). Experiments were performed with a stirred tank reactor containing a boron-doped diamond (BDD) or Pt anode and an air-diffusion cathode to generate H{sub 2}O{sub 2}. The main oxidants were hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between H{sub 2}O{sub 2} and added Fe{sup 2+}. The oxidation ability increased in the sequence EO-H{sub 2}O{sub 2} < EF < PEF and faster degradation was always obtained using BDD. PEF process with BDD yielded almost total mineralization following similar trends in SO{sub 4}{sup 2−}, ClO{sub 4}{sup −} and NO{sub 3}{sup −} media, whereas in Cl{sup −} medium, mineralization was inhibited by the formation of recalcitrant chloroderivatives. GC–MS analysis confirmed the cleavage of the −N=N− bond with formation of two main aromatics in SO{sub 4}{sup 2−} medium and three chloroaromatics in Cl{sup −} solutions. The effective oxidation of final oxalic and oxamic acids by BDD along with the photolysis of Fe(III)-oxalate species by UVA light accounted for the superiority of PEF with BDD. NH{sub 4

Clay mineral formation under oxidized conditions and implications for paleoenvironments and organic preservation on Mars.

Science.gov (United States)

Gainey, Seth R; Hausrath, Elisabeth M; Adcock, Christopher T; Tschauner, Oliver; Hurowitz, Joel A; Ehlmann, Bethany L; Xiao, Yuming; Bartlett, Courtney L

2017-11-01

Clay mineral-bearing locations have been targeted for martian exploration as potentially habitable environments and as possible repositories for the preservation of organic matter. Although organic matter has been detected at Gale Crater, Mars, its concentrations are lower than expected from meteoritic and indigenous igneous and hydrothermal reduced carbon. We conducted synthesis experiments motivated by the hypothesis that some clay mineral formation may have occurred under oxidized conditions conducive to the destruction of organics. Previous work has suggested that anoxic and/or reducing conditions are needed to synthesize the Fe-rich clay mineral nontronite at low temperatures. In contrast, our experiments demonstrated the rapid formation of Fe-rich clay minerals of variable crystallinity from aqueous Fe 3+ with small amounts of aqueous Mg 2+ . Our results suggest that Fe-rich clay minerals such as nontronite can form rapidly under oxidized conditions, which could help explain low concentrations of organics within some smectite-containing rocks or sediments on Mars.

Clay mineral formation under oxidized conditions and implications for paleoenvironments and organic preservation on Mars

Energy Technology Data Exchange (ETDEWEB)

Gainey, Seth R.; Hausrath, Elisabeth M.; Adcock, Christopher T.; Tschauner, Oliver; Hurowitz, Joel A.; Ehlmann, Bethany L.; Xiao, Yuming; Bartlett, Courtney L. (CIW); (UNLV); (CIT); (SBU)

2017-11-01

Clay mineral-bearing locations have been targeted for martian exploration as potentially habitable environments and as possible repositories for the preservation of organic matter. Although organic matter has been detected at Gale Crater, Mars, its concentrations are lower than expected from meteoritic and indigenous igneous and hydrothermal reduced carbon. We conducted synthesis experiments motivated by the hypothesis that some clay mineral formation may have occurred under oxidized conditions conducive to the destruction of organics. Previous work has suggested that anoxic and/or reducing conditions are needed to synthesize the Fe-rich clay mineral nontronite at low temperatures. In contrast, our experiments demonstrated the rapid formation of Fe-rich clay minerals of variable crystallinity from aqueous Fe3+ with small amounts of aqueous Mg2+. Our results suggest that Fe-rich clay minerals such as nontronite can form rapidly under oxidized conditions, which could help explain low concentrations of organics within some smectite-containing rocks or sediments on Mars.

Large Scale Reduction of Graphite Oxide

Data.gov (United States)

National Aeronautics and Space Administration — This project seeks to develop an optical method to reduce graphite oxide into graphene efficiently and in larger formats than currently available. Current reduction...

Electrochemical reduction of cerium oxides in molten salts

International Nuclear Information System (INIS)

Claux, B.; Serp, J.; Fouletier, J.

2011-01-01

This brief article describes a pyrochemical process that is used by CEA to turn actinide oxides into metal actinides. This process is applied to Cerium oxides (CeO 2 ) that simulate actinide oxides well chemically as cerium belongs to the lanthanide family. The process is in fact an electrolysis of cerium oxide in a bath of molten calcium chloride salt whose temperature is between 800 and 900 Celsius degrees. At those temperatures calcium chloride becomes a ionic liquid (Ca 2+ and Cl - ) that is a good electrical conductor and is particularly well-adapted as solvent to an electrolytic process. The electrolysis current allows the transformation of solvent Ca 2+ ions into metal calcium which, in turn, can reduce cerium oxide into metal cerium through chromatically. Experimental data shows the reduction of up to 90% of 10 g samples of CeO 2 in a 6 hour long electrolysis while the best reduction rate ever known was 80% so far. This result is all the more promising that cerium oxides are more difficult to reduce than actinide oxides from the thermodynamical perspective

Bioavailability of cadmium adsorbed on various oxides minerals to wetland plant species Phragmites australis

International Nuclear Information System (INIS)

Wang He; Jia Yongfeng; Wang Shaofeng; Zhu Huijie; Wu Xing

2009-01-01

The bioavailability of heavy metals strongly depends on their speciation in the environment. The effect of different chemical speciations of cadmium ions (i.e. adsorbed on different oxide minerals) on its bioavailability to wetland plant Phragmites australis was studied. Goethite, magnetite, gibbsite, alumina, and manganese oxide were chosen as representatives of metal (hydr)oxides commonly present in sediment. The cultivar system with Hoagland solution as nutrition supply, and single metal oxide with adsorbed Cd as contaminant was applied to study Cd accumulation by P. australis. The bioaccumulation degree in root after the 45-day treatment followed the order: Al(OH) 3 > Al 2 O 3 > Fe 3 O 4 > MnO 2 > FeOOH. The concentration of Cd in stem and leaf followed a similar order although it was considerably lower than that in root. Low-molecular-weight organic acids (LMWOAs), acetic acid, malic acid and citric acid were used to evaluate the desorbability of Cd from different oxides, which can be indicative of Cd-oxide bonding strength and Cd bioavailability. Desorption of Cd by acetic acid and malic acid followed the order: Al(OH) 3 > Fe 3 O 4 > Al 2 O 3 > FeOOH > MnO 2 , while by citric acid: Al(OH) 3 ≥ Al 2 O 3 > Fe 3 O 4 > FeOOH > MnO 2 . This was consistent with the Cd accumulation degree in the plant. Cd adsorbed on Al(OH) 3 was the most easily desorbable species and most bioavailable to P. australis among the oxide minerals, whereas MnO 2 adsorbed Cd was least desorbable by LMWOAs hence constituted the least bioavailable Cd species adsorbed on the oxide minerals.

A microbial-mineralization approach for syntheses of iron oxides with a high specific surface area.

Science.gov (United States)

Yagita, Naoki; Oaki, Yuya; Imai, Hiroaki

2013-04-02

Of minerals and microbes: A microbial-mineralization-inspired approach was used to facilitate the syntheses of iron oxides with a high specific surface area, such as 253 m(2)g(-1) for maghemite (γ-Fe(2)O(3)) and 148 m(2)g(-1) for hematite (α-Fe(2)O(3)). These iron oxides can be applied to electrode material of lithium-ion batteries, adsorbents, and catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced⁹⁹Tc retention in glass waste form using Tc(IV)-incorporated Fe minerals

OpenAIRE

Um, W; Luksic, SA; Wang, G; Saslow, S; Kim, DS; Schweiger, MJ; Soderquist, CZ; Bowden, ME; Lukens, WW; Kruger, AA

2017-01-01

© 2017 Elsevier B.V. Technetium ( 99 Tc) immobilization by doping into iron oxide mineral phases may alleviate the problems with Tc volatility during vitrification of nuclear waste. Because reduced Tc, Tc(IV), substitutes for Fe(III) in the crystal structure by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation of Fe oxide minerals, two Tc-incorporated Fe minerals (Tc-goethite and Tc-magnetite/maghemite) were prepared and tested for Tc retention in glass melt sample...

Self-propagating solar light reduction of graphite oxide in water

Energy Technology Data Exchange (ETDEWEB)

Todorova, N.; Giannakopoulou, T.; Boukos, N.; Vermisoglou, E. [Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, 153 41 Attikis (Greece); Lekakou, C. [Division of Mechanical, Medical, and Aerospace Engineering, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford (United Kingdom); Trapalis, C., E-mail: c.trapalis@inn.demokritos.gr [Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, 153 41 Attikis (Greece)

2017-01-01

Highlights: • Graphite oxide was partially reduced by solar light irradiation in water media. • No addition of catalysts nor reductive agent were used for the reduction. • Specific capacitance increased stepwise with increase of irradiation time. • Self-propagating reduction of graphene oxide by solar light is suggested. - Abstract: Graphite Oxide (GtO) is commonly used as an intermediate material for preparation of graphene in the form of reduced graphene oxide (rGO). Being a semiconductor with tunable band gap rGO is often coupled with various photocatalysts to enhance their visible light activity. The behavior of such rGO-based composites could be affected after prolonged exposure to solar light. In the present work, the alteration of the GtO properties under solar light irradiation is investigated. Water dispersions of GtO manufactured by oxidation of natural graphite via Hummers method were irradiated into solar light simulator for different periods of time without addition of catalysts or reductive agent. The FT-IR analysis of the treated dispersions revealed gradual reduction of the GtO with the increase of the irradiation time. The XRD, FT-IR and XPS analyses of the obtained solid materials confirmed the transition of GtO to rGO under solar light irradiation. The reduction of the GtO was also manifested by the CV measurements that revealed stepwise increase of the specific capacitance connected with the restoration of the sp{sup 2} domains. Photothermal self-propagating reduction of graphene oxide in aqueous media under solar light irradiation is suggested as a possible mechanism. The self-photoreduction of GtO utilizing solar light provides a green, sustainable route towards preparation of reduced graphene oxide. However, the instability of the GtO and partially reduced GO under irradiation should be considered when choosing the field of its application.

Iron oxide reduction in methane-rich deep Baltic Sea sediments

DEFF Research Database (Denmark)

Egger, Matthias; Hagens, Mathilde; Sapart, Celia J.

2017-01-01

/L transition. Our results reveal a complex interplay between production, oxidation and transport of methane showing that besides organoclastic Fe reduction, oxidation of downward migrating methane with Fe oxides may also explain the elevated concentrations of dissolved ferrous Fe in deep Baltic Sea sediments...... profiles and numerical modeling, we propose that a potential coupling between Fe oxide reduction and methane oxidation likely affects deep Fe cycling and related biogeochemical processes, such as burial of phosphorus, in systems subject to changes in organic matter loading or bottom water salinity....

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

Science.gov (United States)

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.

Mineral transformations during the dissolution of uranium ore minerals by dissimilatory metal-reducing bacteria

Science.gov (United States)

Glasauer, S.; Weidler, P.; Fakra, S.; Tyliszczak, T.; Shuh, D.

2011-12-01

Carnotite minerals [X2(UO2)2(VO4)2]; X = K, Ca, Ba, Mn, Na, Cu or Pb] form the major ore of uranium in the Colorado Plateau. These deposits are highly oxidized and contain U(VI) and V(IV). The biotransformation of U(VI) bound in carnotite by bacteria during dissimilatory metal reduction presents a complex puzzle in mineral chemistry. Both U(VI) and V(V) can be respired by metal reducing bacteria, and the mineral structure can change depending on the associated counterion. We incubated anaerobic cultures of S. putrefaciens CN32 with natural carnotite minerals from southeastern Utah in a nutrient-limited defined medium. Strain CN32 is a gram negative bacterium and a terrestrial isolate from New Mexico. The mineral and metal transformations were compared to a system that contained similar concentrations of soluble U(VI) and V(V). Electron (SEM, TEM) microscopies and x-ray spectromicroscopy (STXM) were used in conjunction with XRD to track mineral changes, and bacterial survival was monitored throughout the incubations. Slow rates of metal reduction over 10 months for the treatment with carnotite minerals revealed distinct biotic and abiotic processes, providing insight on mineral transformation and bacteria-metal interactions. The bacteria existed as small flocs or individual cells attached to the mineral phase, but did not adsorb soluble U or V, and accumulated very little of the biominerals. Reduction of mineral V(V) necessarily led to a dismantling of the carnotite structure. Bioreduction of V(V) by CN32 contributed small but profound changes to the mineral system, resulting in new minerals. Abiotic cation exchange within the carnotite group minerals induced the rearrangement of the mineral structures, leading to further mineral transformation. In contrast, bacteria survival was poor for treatments with soluble U(VI) and V(V), although both metals were reduced completely and formed solid UO2 and VO2; we also detected V(III). For these treatments, the bacteria

Mn(II,III) oxidation and MnO2 mineralization by an expressed bacterial multicopper oxidase

Science.gov (United States)

Butterfield, Cristina N.; Soldatova, Alexandra V.; Lee, Sung-Woo; Spiro, Thomas G.; Tebo, Bradley M.

2013-01-01

Reactive Mn(IV) oxide minerals are ubiquitous in the environment and control the bioavailability and distribution of many toxic and essential elements and organic compounds. Their formation is thought to be dependent on microbial enzymes, because spontaneous Mn(II) to Mn(IV) oxidation is slow. Several species of marine Bacillus spores oxidize Mn(II) on their exosporium, the outermost layer of the spore, encrusting them with Mn(IV) oxides. Molecular studies have identified the mnx (Mn oxidation) genes, including mnxG, encoding a putative multicopper oxidase (MCO), as responsible for this two-electron oxidation, a surprising finding because MCOs only catalyze single-electron transfer reactions. Characterization of the enzymatic mechanism has been hindered by the lack of purified protein. By purifying active protein from the mnxDEFG expression construct, we found that the resulting enzyme is a blue (absorption maximum 590 nm) complex containing MnxE, MnxF, and MnxG proteins. Further, by analyzing the Mn(II)- and (III)-oxidizing activity in the presence of a Mn(III) chelator, pyrophosphate, we found that the complex facilitates both electron transfers from Mn(II) to Mn(III) and from Mn(III) to Mn(IV). X-ray absorption spectroscopy of the Mn mineral product confirmed its similarity to Mn(IV) oxides generated by whole spores. Our results demonstrate that Mn oxidation from soluble Mn(II) to Mn(IV) oxides is a two-step reaction catalyzed by an MCO-containing complex. With the purification of active Mn oxidase, we will be able to uncover its mechanism, broadening our understanding of Mn mineral formation and the bioinorganic capabilities of MCOs. PMID:23818588

Graphene oxide/oxidized carbon nanofiber/mineralized hydroxyapatite based hybrid composite for biomedical applications

Science.gov (United States)

Murugan, N.; Sundaramurthy, Anandhakumar; Chen, Shen-Ming; Sundramoorthy, Ashok K.

2017-12-01

Hydroxyapatite (Ca10(PO4)6(OH)2, HAP), a multi-mineral substituted calcium phosphate is the main mineral component of tooth enamel and bone, has become an important biomaterial for biomedical applications. However, as-synthesized HAP has poor mechanical properties and inferior wear resistance, so it is not suitable to use in bone tissue engineering applications. We report the successful incorporation of oxidized carbon nanofibers (O-CNF) and graphene oxide (GO) into the mineralized hydroxyapatite (M-HAP) which showed excellent mechanical and biological properties. GO improved the high mechanical strength and corrosion protection of the substrate in simulated body fluid (SBF) solution and promoted the viability of osteoblasts MG63 cells. As-prepared M-HAP/O-CNF/GO composite showed materials characteristics that similar to natural bone (M-HAP) with high mechanical strength. The resultant M-HAP/O-CNF/GO composite was characterized out by x-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and Fourier-transform infrared spectroscopy (FT-IR), respectively. The mechanical strength of the material was determined by Vicker’s micro-hardness method and it was found that M-HAP/O-CNF/GO (468  ±  4 Hv) composite has superior mechanical properties than M-HAP (330  ±  3 Hv) and M-HAP/GO (425  ±  5 Hv) samples. In addition, antibacterial activity of the composite was studied against Staphylococcus aureus and Escherichia coli. Furthermore, the cell viability of the composite was observed in vitro against osteoblast cells. All these studies confirmed that the M-HAP/O-CNF/GO composite can be considered as potential candidate for dental and orthopedic applications.

International strategic minerals inventory summary report; rare-earth oxides

Science.gov (United States)

Jackson, W.D.; Christiansen, Grey

1993-01-01

Bastnaesite, monazite, and xenotime are currently the most important rare-earth minerals. Bastnaesite occurs as a primary mineral in carbonatites. Monazite and xenotime also can be found in primary deposits but are recovered principally from heavy-mineral placers that are mined for titanium or tin. Each of these minerals has a different composition of the 15 rare-earth elements. World resources of economically exploitable rare-earth oxides (REO) are estimated at 93.4 million metric tons in place, composed of 93 percent in primary deposits and 7 percent in placers. The average mineral composition is 83 percent bastnaesite, 13 percent monazite, and 4 percent of 10 other minerals. Annual global production is about 67,000 metric tons of which 41 percent is from placers and 59 percent is from primary deposits; mining methods consist of open pits (94 percent) and dredging (6 percent). This output could be doubled if the operations that do not currently recover rare earths would do so. Resources are more than sufficient to meet the demand for the predictable future. About 52 percent of the world's REO resources are located in China. Ranking of other countries is as follows: Namibia (22 percent), the United States (15 percent), Australia (6 percent), and India (3 percent); the remainder is in several other countries. Conversely, 38 percent of the production is in China, 33 percent in the United States, 12 percent in Australia, and 5 percent each in Malaysia and India. Several other countries, including Brazil, Canada, South Africa, Sri Lanka, and Thailand, make up the remainder. Markets for rare earths are mainly in the metallurgical, magnet, ceramic, electronic, chemical, and optical industries. Rare earths improve the physical and rolling properties of iron and steel and add corrosion resistance and strength to structural members at high temperatures. Samarium and neodymium are used in lightweight, powerful magnets for electric motors. Cerium and yttrium increase the

Reduction and Simultaneous Removal of ⁹⁹ Tc and Cr by Fe(OH) ₂ (s) Mineral Transformation

Energy Technology Data Exchange (ETDEWEB)

Saslow, Sarah A. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Um, Wooyong [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Pearce, Carolyn I. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Engelhard, Mark H. [Environmental; Bowden, Mark E. [Environmental; Lukens, Wayne [Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States; Leavy, Ian I. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Riley, Brian J. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Kim, Dong-Sang [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Schweiger, Michael J. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Kruger, Albert A. [United

2017-07-17

Technetium (Tc) remains a priority remediation concern due to persistent challenges, including rapid re-oxidation of immobilized Tc, and competing contaminants, e.g. Cr(VI), that inhibit targeted Tc reduction and incorporation into stable mineral phases. Here Fe(OH)₂(s) is investigated as a comprehensive solution for overcoming these challenges, by serving as both the reductant, (Fe(II)), and immobilization agent to form Tc-incorporated magnetite (Fe₃O₄). Trace metal analysis suggests removal of Tc(VII) and Cr(VI) from solution occurs simultaneously; however, complete removal and reduction of Cr(VI) is achieved earlier than the removal/reduction of co-mingled Tc(VII). Bulk oxidation state analysis of the magnetite solid phase by XANES confirms that the majority of Tc is Tc(IV), which is corroborated by XPS. Furthermore, EXAFS results show successful Tc(IV) incorporation into magnetite octahedral sites without additional substitution of Cr or Tc into neighboring Fe octahedral sites. XPS analysis of Cr confirms reduction to Cr(III) and the formation of a Cr-incorporated spinel, Cr2O₃, and Cr(OH)3 phases. Spinel (modeled as Fe₃O₄), goethite, and feroxyhyte are detected in all reacted solid phase samples analyzed by XRD, where Tc(IV) incorporation has little effect on the spinel lattice structure. In the presence of Cr(III) a spinel phase along the magnetite-chromite (Fe₃O₄-FeCr₂O₄) solid-solution line is formed.

Uranium reduction by carbon oxide during ore formation

International Nuclear Information System (INIS)

Matyash, I.V.; Gavrusevich, I.B.; Pasal'skaya, L.F.; Shcherba, D.I.

1981-01-01

Using the method of gas chromatography the gas content in Pre-Cambrian granitoils of various types and in natrometasomatites associted with them is studied. It is established that granites associated with ore-bearing albitites have sharply elevated amounts of CO as compared with granites, which do not include mineralization. Simultaneously in ore samples the absence or sharply low amounts of CO as compared with ore-free samples is observed, that is reverse dependence of CO and ore components. Carbon oxide is the reducing agent of uranium mineralization and alongside with other reducing agents can be a geochemical barrier in the process of ore formation [ru

Release of dissolved cadmium and sulfur nanoparticles from oxidizing sulfide minerals

Science.gov (United States)

Cadmium enrichment (relative to Fe and Zn) in paddy rice grain occurs during the pre-harvest drainage of flooded soil, which causes oxidative dissolution of sulfide minerals present in reduced soil. We investigated this process over a range of environmentally realistic Cdcontain...

Comparative study of synthesis and reduction methods for graphene oxide

KAUST Repository

Alazmi, Amira; Rasul, Shahid; Patole, Shashikant P.; Da Costa, Pedro M. F. J.

2016-01-01

Graphene oxide (GO) and reduced graphene oxide (rGO) have congregated much interest as promising active materials for a variety of applications such as electrodes for supercapacitors. Yet, partially given the absence of comparative studies in synthesis methodologies, a lack of understanding persists on how to best tailor these materials. In this work, the effect of using different graphene oxidation-reduction strategies in the structure and chemistry of rGOs is systematically discussed. Two of the most popular oxidation routes in the literature were used to obtain GO. Subsequently, two sets of rGO powders were synthesised employing three different reduction routes, totalling six separate products. It is shown that the extension of the structural rearrangement in rGOs is not just dependent on the reduction step but also on the approach followed for the initial graphite oxidation.

Comparative study of synthesis and reduction methods for graphene oxide

KAUST Repository

Alazmi, Amira

2016-05-14

Graphene oxide (GO) and reduced graphene oxide (rGO) have congregated much interest as promising active materials for a variety of applications such as electrodes for supercapacitors. Yet, partially given the absence of comparative studies in synthesis methodologies, a lack of understanding persists on how to best tailor these materials. In this work, the effect of using different graphene oxidation-reduction strategies in the structure and chemistry of rGOs is systematically discussed. Two of the most popular oxidation routes in the literature were used to obtain GO. Subsequently, two sets of rGO powders were synthesised employing three different reduction routes, totalling six separate products. It is shown that the extension of the structural rearrangement in rGOs is not just dependent on the reduction step but also on the approach followed for the initial graphite oxidation.

Bioavailability of cadmium adsorbed on various oxides minerals to wetland plant species Phragmites australis

Energy Technology Data Exchange (ETDEWEB)

Wang He, E-mail: he.wangworld@yahoo.com.cn [Key Laboratory of Terrestrial Ecological Process, Institute of Applied Ecology, Chinese Academy of Sciences, No. 72 Wenhua Road, Shenyang 110016 (China); Graduate School, Chinese Academy of Sciences, Beijing 100049 (China); Jia Yongfeng, E-mail: yongfeng.jia@iae.ac.cn [Key Laboratory of Terrestrial Ecological Process, Institute of Applied Ecology, Chinese Academy of Sciences, No. 72 Wenhua Road, Shenyang 110016 (China); Wang Shaofeng [Key Laboratory of Terrestrial Ecological Process, Institute of Applied Ecology, Chinese Academy of Sciences, No. 72 Wenhua Road, Shenyang 110016 (China); Zhu Huijie; Wu Xing [Key Laboratory of Terrestrial Ecological Process, Institute of Applied Ecology, Chinese Academy of Sciences, No. 72 Wenhua Road, Shenyang 110016 (China); Graduate School, Chinese Academy of Sciences, Beijing 100049 (China)

2009-08-15

The bioavailability of heavy metals strongly depends on their speciation in the environment. The effect of different chemical speciations of cadmium ions (i.e. adsorbed on different oxide minerals) on its bioavailability to wetland plant Phragmites australis was studied. Goethite, magnetite, gibbsite, alumina, and manganese oxide were chosen as representatives of metal (hydr)oxides commonly present in sediment. The cultivar system with Hoagland solution as nutrition supply, and single metal oxide with adsorbed Cd as contaminant was applied to study Cd accumulation by P. australis. The bioaccumulation degree in root after the 45-day treatment followed the order: Al(OH){sub 3} > Al{sub 2}O{sub 3} > Fe{sub 3}O{sub 4} > MnO{sub 2} > FeOOH. The concentration of Cd in stem and leaf followed a similar order although it was considerably lower than that in root. Low-molecular-weight organic acids (LMWOAs), acetic acid, malic acid and citric acid were used to evaluate the desorbability of Cd from different oxides, which can be indicative of Cd-oxide bonding strength and Cd bioavailability. Desorption of Cd by acetic acid and malic acid followed the order: Al(OH){sub 3} > Fe{sub 3}O{sub 4} > Al{sub 2}O{sub 3} > FeOOH > MnO{sub 2}, while by citric acid: Al(OH){sub 3} {>=} Al{sub 2}O{sub 3} > Fe{sub 3}O{sub 4} > FeOOH > MnO{sub 2}. This was consistent with the Cd accumulation degree in the plant. Cd adsorbed on Al(OH){sub 3} was the most easily desorbable species and most bioavailable to P. australis among the oxide minerals, whereas MnO{sub 2} adsorbed Cd was least desorbable by LMWOAs hence constituted the least bioavailable Cd species adsorbed on the oxide minerals.

Reduction of nitric oxide by arc vaporized carbons (AVC)

Energy Technology Data Exchange (ETDEWEB)

Tsang, S C; Chen, Y K; Green, M L.H. [The Catalysis Centre, Inorganic Chemistry Laboratory, University of Oxford, Oxford (United Kingdom)

1996-07-04

The reduction of nitric oxide by arc vaporized carbons (AVC) including the compound C{sub 6}0, fullerene soot and carbon nanotubes, giving dinitrogen and carbon oxides has been studied. It is found that the AVC carbons are more active towards oxidation by NO than by oxygen gas at low temperatures (300-400C). In contrast, conventional carbons such as graphite and microporous carbons are more readily oxidised by oxygen than by NO. The addition of copper salts and to a lesser extent, cobalt salts, to fullerene soot substantially promote NO reduction. The high intrinsic activity for NO reduction by AVC carbons compared to graphitic carbons is attributed to the presence of five membered carbon rings in the AVC carbons

In situ Reduction and Oxidation of Nickel from Solid Oxide Fuel Cells in a Transmission Electron Microscope

DEFF Research Database (Denmark)

Faes, Antonin; Jeangros, Quentin; Wagner, Jakob Birkedal

2009-01-01

Environmental transmission electron microscopy was used to characterize in situ the reduction and oxidation of nickel from a Ni/YSZ solid oxide fuel cell anode support between 300-500{degree sign}C. The reduction is done under low hydrogen pressure. The reduction initiates at the NiO/YSZ interface...

Simultaneous nitrate reduction and acetaminophen oxidation using the continuous-flow chemical-less VUV process as an integrated advanced oxidation and reduction process.

Science.gov (United States)

Moussavi, Gholamreza; Shekoohiyan, Sakine

2016-11-15

This work was aimed at investigating the performance of the continuous-flow VUV photoreactor as a novel chemical-less advanced process for simultaneously oxidizing acetaminophen (ACT) as a model of pharmaceuticals and reducing nitrate in a single reactor. Solution pH was an important parameter affecting the performance of VUV; the highest ACT oxidation and nitrate reduction attained at solution pH between 6 and 8. The ACT was oxidized mainly by HO while the aqueous electrons were the main working agents in the reduction of nitrate. The performance of VUV photoreactor improved with the increase of hydraulic retention time (HRT); the complete degradation of ACT and ∼99% reduction of nitrate with 100% N2 selectivity achieved at HRT of 80min. The VUV effluent concentrations of nitrite and ammonium at HRT of 80min were below the drinking water standards. The real water sample contaminated with the ACT and nitrate was efficiently treated in the VUV photoreactor. Therefore, the VUV photoreactor is a chemical-less advanced process in which both advanced oxidation and advanced reduction reactions are accomplished. This unique feature possesses VUV photoreactor as a promising method of treating water contaminated with both pharmaceutical and nitrate. Copyright © 2016 Elsevier B.V. All rights reserved.

Mineralization and biodegradability enhancement of Methyl Orange dye by an effective advanced oxidation process

International Nuclear Information System (INIS)

Paul Guin, Jhimli; Bhardwaj, Y.K.; Varshney, Lalit

2017-01-01

An effective process for the oxidation of Methyl Orange dye (MO) was determined by comparing the mineralization efficiency between two advanced oxidation processes (AOPs) viz., ozonolysis and gamma radiolysis in presence and absence of an added inorganic salt potassium persulfate (K_2S_2O_8). The effects of various operating parameters such as ozone flow rate and reaction temperature were optimized to achieve the best possible mineralization extent of MO by ozonolysis. The mineralization efficiency of MO was significantly enhanced during gamma radiolysis in presence of K_2S_2O_8 (γ+K_2S_2O_8) compared to in absence of K_2S_2O_8. The presence of methyl group at the amine of phenyl ring assisted the mineralization of dye during γ+K_2S_2O_8. The oxygen-equivalent chemical-oxidation capacities (OCC) of ozonolysis and γ+K_2S_2O_8 for 75% mineralization of the dye solution were calculated as 7.008 and 0.0336 kg equiv. O_2 m"−"3, respectively which signifies that γ+K_2S_2O_8 can be explored as an effective AOP. The non-biodegradable MO dye solution became biodegradable even after the dose of 0.5 kGy during γ+K_2S_2O_8 compared to 1 kGy in absence of K_2S_2O_8. The study concludes that a lower dose γ+K_2S_2O_8 could be one of the efficient pretreatment steps before undergoing biological degradation of dye solution. - Highlights: • Systematic investigation was performed for the treatment of Methyl Orange dye solution. • AOPs investigated were ozonolysis and gamma radiolysis. • The OCC and % mineralizations of the AOPs were compared. • Gamma radiolysis in presence of K_2S_2O_8 was found as most effective AOP.

Identification of Oxide Compound in Dolomite Mineral from Aceh Tamiang Region

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Nirmala Sari

2013-08-01

Full Text Available Indonesia has abundant mineral especially carbonate-based mineral, ike dolomite. Particularly in Aceh province's, the largest dolomite deposits is available in Aceh Tamiang district around 1.9 billion tons. Unfortunately, current use of dolomite in the industry and other applications is still limited. In this work we report the advanced preparation of dolomite using calcinations method. Whereas, with this method, the dolomite mineral can be processed into calcium and magnesium oxide which has a very wide field of application and higher values. To obtain optimal results, we also identify the effect of temperature on the formation of oxide compounds. Preliminary study using XRF founded that dolomite in village Selamat is known as the highest concentration of CaO (61.20% followed by MgO (25.28%. It is also showed that the main phase obtained by XRD is dolomite (CaMg(CO32. Furthermore, after the calcinations process at 700 °C, it was founded that the formation of dolomite were CaCO3 and MgO, whereas at temperatures of 900 °C mostly the CaCO3 has decomposed into CaO. SEM observations showed that dolomite has the composition of particles distributed homogeneously along the particle agglomerate when it calcinations.

Green reduction of graphene oxide by ascorbic acid

Science.gov (United States)

Khosroshahi, Zahra; Kharaziha, Mahshid; Karimzadeh, Fathallah; Allafchian, Alireza

2018-01-01

Graphene, a single layer of sp2-hybridized carbon atoms in a hexagonal (two-dimensional honey-comb) lattice, has attracted strong scientific and technological interest due to its novel and excellent optical, chemical, electrical, mechanical and thermal properties. The solution-processable chemical reduction of Graphene oxide (GO is considered as the most favorable method regarding mass production of graphene. Generally, the reduction of GO is carried out by chemical approaches using different reductants such as hydrazine and sodium borohydride. These components are corrosive, combustible and highly toxic which may be dangerous for personnel health and the environment. Hence, these reducing agents are not promising choice for reducing of graphene oxide (GO). As a consequence, it is necessary for further development and optimization of eco-friendly, natural reducing agent for clean and effective reduction of GO. Ascorbic acid, an eco-friendly and natural reducing agents, having a mild reductive ability and nontoxic property. So, the aim of this research was to green synthesis of GO with ascorbic acid. For this purpose, the required amount of NaOH and ascorbic acid were added to GO solution (0.5 mg/ml) and were heated at 95 °C for 1 hour. According to the X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and electrochemical results, GO were reduced with ascorbic acid like hydrazine with better electrochemical properties and ascorbic acid is an ideal substitute for hydrazine in the reduction of graphene oxide process.

Enhanced 99 Tc retention in glass waste form using Tc(IV)-incorporated Fe minerals

Energy Technology Data Exchange (ETDEWEB)

Um, Wooyong; Luksic, Steven A.; Wang, Guohui; Saslow, Sarah; Kim, Dong-Sang; Schweiger, Michael J.; Soderquist, Chuck Z.; Bowden, Mark E.; Lukens, Wayne W.; Kruger, Albert A.

2017-11-01

Technetium (99Tc) immobilization by doping into iron oxide mineral phases may alleviate the problems with Tc volatility during vitrification of nuclear waste. Reduced Tc, Tc(IV), substitutes for Fe(III) in the crystal structure by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation of Fe oxide minerals. Two Tc-incorporated Fe minerals (Tc-goethite and Tc-magnetite/maghemite) were prepared and tested for Tc retention in glass melt samples at temperatures between 600 – 1,000 oC. After being cooled, the solid glass specimens prepared at different temperatures were analyzed for Tc oxidation state using Tc K-edge XANES. In most samples, Tc was partially oxidized from Tc(IV) to Tc(VII) as the melt temperature increased. However, Tc retention in glass melt samples prepared using Tc-incorporated Fe minerals were moderately higher than in glass prepared using KTcO4 because of limited and delayed Tc volatilization.

Oxidative reduction of glove box wipers with a downdraft thermal oxidation system

International Nuclear Information System (INIS)

Phelps, M.R.; Wilcox, W.A.

1996-04-01

Wipers (rags) used for decontamination and glove box cleanup in the Plutonium Finishing Plant often become soaked with acid and plutonium-rich solutions. After use, these wipers are rinsed in a dilute NaOH solution and dried, but the formation of unstable nitrates and the hydrogen gas caused by hydrolysis are concerns that still must be addressed. This report gives the results of testing with a small downdraft thermal oxidation system that was constructed by Pacific Northwest National Laboratory to stabilize glove wiper waste, reduce the waste volume, and reclaim plutonium. Proof-of-principle testing was conducted with eight runs using various combinations of rag moisture and chemical pretreatment. All runs went to planned completion. Results of these tests indicate that the thermal oxidation system has the potential for providing significant reductions in waste volume. Weight reductions of 150:1 were easily obtainable during this project. Modifications could result in weight reductions of over 200:1, with possible volume reductions of 500:1

Crystal structure of the uranyl-oxide mineral rameauite

Energy Technology Data Exchange (ETDEWEB)

Plasil, Jakub [ASCR, Prague (Czech Republic). Inst. of Physics; Skoda, Radek [Masaryk Univ., Brno (Czech Republic). Dept. of Geological Sciences; Cejka, Jiri [National Museum, Prague (Czech Republic). Dept. of Mineralogy and Petrology; Bourgoin, Vincent; Boulliard, Jean-Claude [Pierre et Marie Curie Univ., Paris (France). Association Jean Wyart, Collection des Mineraux de Jussieu

2016-12-15

Rameauite is a rare supergene uranyl-oxide hydroxy-hydrate mineral that forms during hydration-oxidation weathering of uraninite. On the basis of single-crystal X-ray diffraction data collected on a microfocus source, rameauite is monoclinic, space group Cc, with a = 13.9458(19), b = 14.3105(19), c = 13.8959(18) Aa, β = 118.477(14) , V = 2437.7(6) Aa{sup 3} and Z = 4, with D{sub calc} = 5.467 g cm{sup -3}. The structure of rameauite (R = 0.060 for 1698 unique observed reflections) contains sheets of the β-U{sub 3}O{sub 8} topology, with both UO{sub 6} and UO{sub 7} bipyramids, which is similar to the sheets found in spriggite, ianthinite and wyartite. The sheets alternate with the interlayer, which contains K{sup +}, Ca{sup 2+} and H{sub 2}O molecules. Interstitial cations are linked into infinite chains that extend along [10-1]. Adjacent sheets are linked through K-O, Ca-O and H-bonds. The structural formula of rameauite is K{sub 2} Ca(H{sub 2}{sup [3]}O){sub 1}(H{sub 2}{sup [5]}O){sub 4}[(UO{sub 2}) {sub 6}O{sub 6}(OH){sub 4}](H{sub 2}{sup [4]}O){sub 1}. The empirical formula obtained from the average of eight electron-microprobe analyses is (on the basi s of 6 U p.f.u.) K{sub 1.87}(Ca{sub 1.10}Sr{sub 0.04}){sub Σ1.14}[(UO 2){sub 6}O{sub 6}(OH){sub 4.15}].6H{sub 2}O. The Raman spectrum is dominate d by U.O and O.H vibrations. A discussion of related uranyl-oxide minerals is given.

Comparative study of electrochemical oxidation of herbicide 2,4,5-T: Kinetics, parametric optimization and mineralization pathway

Directory of Open Access Journals (Sweden)

Hicham Zazou

2017-01-01

Full Text Available Oxidative degradation of herbicide 2,4,5-T was studied by electrochemical advanced oxidation processes anodic oxidation and electro-Fenton (EF using Pt/carbon felt and BDD/carbon felt cells. The effect of main operating parameters on oxidation of 2,4,5-T and mineralization of its aqueous solution were investigated. The rate constant for oxidation of 2,4,5-T by ·≡OH was determined as (3.7 ± 0.2 × 109 M−1 s−1 using competition kinetics method. The EF process with BDD anode was shown to be very efficient reaching 94% mineralization in 3 h treatment. Based on identified aromatic intermediates, short-chain carboxylic acids, released inorganic ions and total organic carbon removal measurements, a plausible oxidation pathway for mineralization of 2,4,5-T by hydroxyl radical was proposed. In addition, the evolution of solution toxicity during treatment was monitored by Microtox method showing the formation of toxic aromatic/cyclic intermediates. The results showed also that EF process was able to remove efficiently toxic intermediates and consequently solution toxicity.

Electrochemical reduction of nitroaromatic compounds by single sheet iron oxide coated electrodes

Energy Technology Data Exchange (ETDEWEB)

Huang, Li-Zhi, E-mail: lizhi@plen.ku.dk [Department of Plant and Environmental Sciences, University of Copenhagen, Thorvaldsensvej 40, DK–1871 Frederiksberg C (Denmark); Hansen, Hans Christian B. [Department of Plant and Environmental Sciences, University of Copenhagen, Thorvaldsensvej 40, DK–1871 Frederiksberg C (Denmark); Bjerrum, Morten Jannik [Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK–2100 København Ø (Denmark)

2016-04-05

Highlights: • Composite layers of single sheet iron oxides were coated on indium tin oxide electrodes. • Single sheet iron oxide is an electro-catalyst for reduction of nitroaromatic compounds in aqueous solution. • The reduction is well explained by a diffusion layer model. • The charge properties of the nitrophenols have an important influence on reduction. • Low-cost iron oxide based materials are promising electro-catalyst for water treatment. - Abstract: Nitroaromatic compounds are substantial hazard to the environment and to the supply of clean drinking water. We report here the successful reduction of nitroaromatic compounds by use of iron oxide coated electrodes, and demonstrate that single sheet iron oxides formed from layered iron(II)-iron(III) hydroxides have unusual electrocatalytic reactivity. Electrodes were produced by coating of single sheet iron oxides on indium tin oxide electrodes. A reduction current density of 10 to 30 μA cm{sup −2} was observed in stirred aqueous solution at pH 7 with concentrations of 25 to 400 μM of the nitroaromatic compound at a potential of −0.7 V vs. SHE. Fast mass transfer favors the initial reduction of the nitroaromatic compound which is well explained by a diffusion layer model. Reduction was found to comprise two consecutive reactions: a fast four-electron first-order reduction of the nitro-group to the hydroxylamine-intermediate (rate constant = 0.28 h{sup −1}) followed by a slower two-electron zero-order reduction resulting in the final amino product (rate constant = 6.9 μM h{sup −1}). The zero-order of the latter reduction was attributed to saturation of the electrode surface with hydroxylamine-intermediates which have a more negative half-wave potential than the parent compound. For reduction of nitroaromatic compounds, the SSI electrode is found superior to metal electrodes due to low cost and high stability, and superior to carbon-based electrodes in terms of high coulombic efficiency and

A case of osteomalacia due to deranged mineral balance caused by saccharated ferric oxide and short-bowel syndrome: A case report.

Science.gov (United States)

Nomoto, Hiroshi; Miyoshi, Hideaki; Nakamura, Akinobu; Nagai, So; Kitao, Naoyuki; Shimizu, Chikara; Atsumi, Tatsuya

2017-09-01

Saccharated ferric oxide has been shown to lead to elevation of fibroblast growth factor 23, hypophosphatemia, and, consequently, osteomalacia. Moreover, mineral imbalance is often observed in patients with short-bowel syndrome to some degree. A 62-year-old woman with short-bowel syndrome related with multiple resections of small intestines due to Crohn disease received regular intravenous administration of saccharated ferric oxide. Over the course of treatment, she was diagnosed with tetany, which was attributed to hypocalcemia. Additional assessments of the patient revealed not only hypocalcemia, but also hypophosphatemia, hypomagnesemia, osteomalacia, and a high concentration of fibroblast growth factor 23 (314 pg/mL). We diagnosed her with mineral imbalance-induced osteomalacia due to saccharated ferric oxide and short-bowel syndrome. Magnesium replacement therapy and discontinuation of saccharated ferric oxide alone. These treatments were able to normalize her serum mineral levels and increase her bone mineral density. This case suggests that adequate evaluation of serum minerals, including phosphate and magnesium, during saccharated ferric oxide administration may be necessary, especially in patients with short-bowel syndrome.

Methane oxidation in an intensively cropped tropical rice field soil under long-term application of organic and mineral fertilizers.

Science.gov (United States)

Nayak, D R; Babu, Y Jagadeesh; Datta, A; Adhya, T K

2007-01-01

Methane (CH4) oxidation is the only known biological sink process for mitigating atmospheric and terrestrial emissions of CH4, a major greenhouse gas. Methane oxidation in an alluvial soil planted to rice (Oryza sativa L.) under long-term application of organic (compost with a C/N ratio of 21.71), and mineral fertilizers was measured in a field-cum-laboratory incubation study. Oxidation rates were quantified in terms of decrease in the concentration of CH4 in the headspace of incubation vessels and expressed as half-life (t(1)2) values. Methane oxidation rates significantly differed among the treatments and growth stages of the rice crop. Methane oxidation rates were high at the maximum tillering and maturity stages, whereas they were low at grain-filling stage. Methane oxidation was low (t(1)2) = 15.76 d) when provided with low concentration of CH4. On the contrary, high concentration of CH4 resulted in faster oxidation (t(1)2) = 6.67 d), suggesting the predominance of "low affinity oxidation" in rice fields. Methane oxidation was stimulated following the application of mineral fertilizers or compost implicating nutrient limitation as one of the factors affecting the process. Combined application of compost and mineral fertilizer, however, inhibited CH4 oxidation probably due to N immobilization by the added compost. The positive effect of mineral fertilizer on CH4 oxidation rate was evident only at high CH4 concentration (t(1)2 = 4.80 d), while at low CH4 concentration their was considerable suppression (t(1) = 17.60 d). Further research may reveal that long-term application of fertilizers, organic or inorganic, may not inhibit CH4 oxidation.

Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

Science.gov (United States)

Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

2012-02-07

Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

Effects of sulfur dioxide and nitric oxide on mercury oxidation and reduction under homogeneous conditions

Energy Technology Data Exchange (ETDEWEB)

Yongxin Zhao; Michael D. Mann; Edwin S. Olson; John H. Pavlish; Grant E. Dunham [University of North Dakota, Grand Forks, ND (United States). Department of Chemical Engineering

2006-05-15

This paper is particularly related to elemental mercury (Hg{sup 0}) oxidation and divalent mercury (Hg{sup 2+} reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO{sub 2}). As a powerful oxidant and chlorinating reagent, Cl{sub 2} has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO{sub 2}, NO, as well as H{sub 2}O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO{sub 2} and NO on Hg{sup 0} oxidation and Hg{sup 2+} reduction with the intent of unraveling unrecognized interactions among Cl species, SO{sub 2}, and NO most importantly in the presence of H{sub 2}O. The experimental results demonstrated that SO{sub 2} and NO had pronounced inhibitory effects on Hg{sup 0} oxidation at high temperatures when H{sub 2}O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg{sup 2+} back into its elemental form. Data revealed that SO{sub 2} and NO were capable of promoting homogeneous reduction of Hg{sup 2+} to Hg{sup 0} with H{sub 2}O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H{sub 2}O was removed from the gas blend. 23 refs., 8 figs.

The Apparent Involvement of ANMEs in Mineral Dependent Methane Oxidation, as an Analog for Possible Martian Methanotrophy

Directory of Open Access Journals (Sweden)

Victoria J. Orphan

2011-11-01

Full Text Available On Earth, marine anaerobic methane oxidation (AOM can be driven by the microbial reduction of sulfate, iron, and manganese. Here, we have further characterized marine sediment incubations to determine if the mineral dependent methane oxidation involves similar microorganisms to those found for sulfate-dependent methane oxidation. Through FISH and FISH-SIMS analyses using 13C and 15N labeled substrates, we find that the most active cells during manganese dependent AOM are primarily mixed and mixed-cluster aggregates of archaea and bacteria. Overall, our control experiment using sulfate showed two active bacterial clusters, two active shell aggregates, one active mixed aggregate, and an active archaeal sarcina, the last of which appeared to take up methane in the absence of a closely-associated bacterial partner. A single example of a shell aggregate appeared to be active in the manganese incubation, along with three mixed aggregates and an archaeal sarcina. These results suggest that the microorganisms (e.g., ANME-2 found active in the manganese-dependent incubations are likely capable of sulfate-dependent AOM. Similar metabolic flexibility for Martian methanotrophs would mean that the same microbial groups could inhabit a diverse set of Martian mineralogical crustal environments. The recently discovered seasonal Martian plumes of methane outgassing could be coupled to the reduction of abundant surface sulfates and extensive metal oxides, providing a feasible metabolism for present and past Mars. In an optimistic scenario Martian methanotrophy consumes much of the periodic methane released supporting on the order of 10,000 microbial cells per cm2 of Martian surface. Alternatively, most of the methane released each year could be oxidized through an abiotic process requiring biological methane oxidation to be more limited. If under this scenario, 1% of this methane flux were oxidized by biology in surface soils or in subsurface aquifers (prior to

Study of film graphene/graphene oxide obtained by partial reduction chemical of oxide graphite

International Nuclear Information System (INIS)

Gascho, J.L.S.; Costa, S.F.; Hoepfner, J.C.; Pezzin, S.H.

2014-01-01

This study investigated the morphology of graphene/graphene oxide film obtained by partial chemical reduction of graphite oxide (OG) as well as its resistance to solvents. Films of graphene/graphene oxide are great candidates for replacement of indium oxide doped with tin (ITO) in photoelectric devices. The OG was obtained from natural graphite, by Hummer's method modified, and its reduction is made by using sodium borohydride. Infrared spectroscopy analysis of Fourier transform (FTIR), Xray diffraction (XRD) and scanning electron microscopy, high-resolution (SEM/FEG) for the characterization of graphene/graphene oxide film obtained were performed. This film proved to be resilient, not dispersing in any of the various tested solvents (such as ethanol, acetone and THF), even under tip sonication, this resistance being an important property for the applications. Furthermore, the film had a morphology similar to that obtained by other preparation methods.(author)

Modeling selenate adsorption behavior on oxides, clay minerals, and soils using the triple layer model

Science.gov (United States)

Selenate adsorption behavior was investigated on amorphous aluminum oxide, amorphous iron oxide, goethite, clay minerals: kaolinites, montmorillonites, illite, and 18 soil samples from Hawaii, and the Southwestern and the Midwestern regions of the US as a function of solution pH. Selenate adsorpti...

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

Science.gov (United States)

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.

In-Situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes

Science.gov (United States)

2010-12-28

DATES COVERED (From - To) 1/29/10-9/30/10 4. TITLE AND SUBTITLE In situ optical studies of oxidation/reduction kinetics on SOFC cermet anodes 5a...0572 In-situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes Department of Chemistry and Biochemistry Montana State University...of Research In-situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes Principal Investigator Robert Walker Organization

Characteristics of uranium mineralization and depositional system of host sediments, Bayantala basin, Inner Mongolia autonomous region

International Nuclear Information System (INIS)

Zhu Minqiang; Wu Rengui; Yu Dagan; Chen Anping; Shen Kefeng

2003-01-01

Based upon the research of basin fills at the Bayantala basin, the genetic facies of host sediments have been ascertained and the target beds and their range are delineated. The sand bodies of the Upper Member of Tengge'er Formation deposited in fan delta front is favorable to the formation of uranium mineralization of phreatic-interlayer oxidation. The Saihantala Fm deposited in fluvial system can be divided into Lower Member and Upper Member based on depositional microfacies and paleoclimate. The Lower Member of braided system is the most important target bed enriched in organic matter where basal-channel-type uranium mineralization occurs. Features of alteration and mineralization suggest that the early-stage and the late-stage uranium mineralization are related to phreatic oxidation and interlayer oxidation (roll-type) respectively. Meanwhile, the secondary reduction has superimposed over the earlier mineralization in the area caused by hydrocarbons raising along faults

[Small scale direct oxide reduction (DOR) experiments

International Nuclear Information System (INIS)

1987-01-01

Objectives were to provide process design information to the Plutonium Recovery Project and to produce DOR (direct oxide reduction) product which meets Foundry purity specifications and Oh-0 Foundry specifications

Mineral distribution in two southwest colombian coals using cyclone separation and oxidation at low temperature

International Nuclear Information System (INIS)

Rojas Andres F; Barraza, Juan M; Rojas, Andres F.

2010-01-01

It was studied the mineral distribution of two Colombian coals using a cyclone separation and oxidation at low temperature, OLT. The cyclone separation was carried out at two densities (1.3 and 1.4), three particle size (1000+ 600?m, 600+ 425?m and 425+ 250?m) and two processing stages. To determine the mineral matter, feed and under flow fractions from hydrocyclone were concentrated in mineral matter by OLT in a fluidized bed (T<300 celsius degrade). 18 minerals were identified by X Ray Diffraction, XRD. XRD results showed 13 minerals from Golondrinas and 15 minerals from Guachinte coal. It was found that kaolinite and quartz were the most abundant minerals in coal fractions from Golondrinas and Guachinte. Furthermore, it was found that mainly minerals kaolinite, quartz, dolomite, jarosite, gypsum and pyrite, exhibited affinity towards mineral matter, while siderite and valerite showed affinity towards organic matter.

Investigation of the Reduction of Graphene Oxide by Lithium Triethylborohydride

Directory of Open Access Journals (Sweden)

Guangyuan Xu

2016-01-01

Full Text Available The chemical reduction of a wet colloidal suspension of graphene oxide is a cost-effective and adaptable method for large scale production of “quasi” graphene for a wide variety of optoelectronic applications. In this study, modified Hummers’ procedure was used to synthesize high quality graphene oxide at 50°C. This modified protocol thus eliminates the potentially hazardous second high-temperature step in Hummers’ method for the production of GO. Furthermore, the reduction of graphene oxide by lithium triethylborohydride is demonstrated for the first time. According to FT-IR, UV-Vis, TGA, Raman, SEM/EDS, and AFM results, the reduced graphene oxide (LiEt3BH-RGO has properties comparable to other reduced graphene oxide products reported in the literature.

Thermodynamic analysis of reduction reactions of niobium oxides

International Nuclear Information System (INIS)

Takano, C.

1981-01-01

Reduction processes of niobium oxides by hydrogen, carbon and aluminium are analysed thermodinamically. It is shown that reduction by hydrogen is not technically feasible. High purity of raw materials is required. In the carbothermic process impurities which react to form high stability carbides should be avoided. (Author) [pt

Direct electrochemical reduction of solid uranium oxide in molten fluoride salts

Science.gov (United States)

Gibilaro, Mathieu; Cassayre, Laurent; Lemoine, Olivier; Massot, Laurent; Dugne, Olivier; Malmbeck, Rikard; Chamelot, Pierre

2011-07-01

The direct electrochemical reduction of UO 2 solid pellets was carried out in LiF-CaF 2 (+2 mass.% Li 2O) at 850 °C. An inert gold anode was used instead of the usual reactive sacrificial carbon anode. In this case, oxidation of oxide ions present in the melt yields O 2 gas evolution on the anode. Electrochemical characterisations of UO 2 pellets were performed by linear sweep voltammetry at 10 mV/s and reduction waves associated to oxide direct reduction were observed at a potential 150 mV more positive in comparison to the solvent reduction. Subsequent, galvanostatic electrolyses runs were carried out and products were characterised by SEM-EDX, EPMA/WDS, XRD and microhardness measurements. In one of the runs, uranium oxide was partially reduced and three phases were observed: nonreduced UO 2 in the centre, pure metallic uranium on the external layer and an intermediate phase representing the initial stage of reduction taking place at the grain boundaries. In another run, the UO 2 sample was fully reduced. Due to oxygen removal, the U matrix had a typical coral-like structure which is characteristic of the pattern observed after the electroreduction of solid oxides.

A device for reduction of metal oxides generated in electrokinetic separation equipment

International Nuclear Information System (INIS)

Kim, Gye-Nam; Kim, Seung-Soo; Kim, Il-Gook; Jeong, Jung-Whan; Choi, Jong-Won

2015-01-01

For a reduction of waste electrolyte volume and metal oxide volume, the reuse period of the waste electrolyte in the electrokinetic decontamination experiment and the method of a reduction of metal oxide volume in the cathode chamber were drawn out through several experiments with the manufactured 1.2 ton electrokinetic decontamination equipment. The optimum pH of electrolyte in cathode chamber for a reduction of volume of metal oxides was below 2.35. Indoor electrokinetic decontamination equipment for treatment of 1.2 tons of the contaminated soil per batch was manufactured to remove uranium from soil with high removal efficiency during a short time. For a reduction of waste electrolyte volume and metal oxide volume, the reuse period of waste electrolyte in the electrokinetic decontamination experiment and the method of a reduction of metal oxide volume in the cathode chamber were drawn out through several experiments with the manufactured electrokinetic equipment. Indoor electrokinetic decontamination equipment for treatment of 1.2 tons of the contaminated soil was manufactured to remove uranium from soil during a short time

A device for reduction of metal oxides generated in electrokinetic separation equipment

Energy Technology Data Exchange (ETDEWEB)

Kim, Gye-Nam; Kim, Seung-Soo; Kim, Il-Gook; Jeong, Jung-Whan; Choi, Jong-Won [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2015-10-15

For a reduction of waste electrolyte volume and metal oxide volume, the reuse period of the waste electrolyte in the electrokinetic decontamination experiment and the method of a reduction of metal oxide volume in the cathode chamber were drawn out through several experiments with the manufactured 1.2 ton electrokinetic decontamination equipment. The optimum pH of electrolyte in cathode chamber for a reduction of volume of metal oxides was below 2.35. Indoor electrokinetic decontamination equipment for treatment of 1.2 tons of the contaminated soil per batch was manufactured to remove uranium from soil with high removal efficiency during a short time. For a reduction of waste electrolyte volume and metal oxide volume, the reuse period of waste electrolyte in the electrokinetic decontamination experiment and the method of a reduction of metal oxide volume in the cathode chamber were drawn out through several experiments with the manufactured electrokinetic equipment. Indoor electrokinetic decontamination equipment for treatment of 1.2 tons of the contaminated soil was manufactured to remove uranium from soil during a short time.

Catalytic/non-catalytic combination process for nitrogen oxides reduction

International Nuclear Information System (INIS)

Luftglass, B.K.; Sun, W.H.; Hofmann, J.E.

1992-01-01

This patent describes a process for the reduction of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. It comprises introducing a nitrogenous treatment agent comprising urea, one or more of the hydrolysis products of urea, ammonia, compounds which produce ammonia as a by-product, ammonium salts of organic acids, 5- or 6-membered heterocyclic hydrocarbons having at least one cyclic nitrogen, hydroxy amino hydrocarbons, or mixtures thereof into the effluent at an effluent temperature between about 1200 degrees F and about 2100 degrees F; and contacting the treated effluent under conditions effective to reduce the nitrogen oxides in the effluent with a catalyst effective for the reduction of nitrogen oxides in the presence of ammonia

REPEATED REDUCTIVE AND OXIDATIVE TREATMENTS ON GRANULAR ACTIVATED CARBON

Science.gov (United States)

Fenton oxidation and Fenton oxidation preceded by reduction solutions were applied to granular activated carbon (GAC) to chemically regenerate the adsorbent. No adsorbate was present on the GAC so physicochemical effects from chemically aggressive regeneration of the carbon coul...

Pathogenic prion protein is degraded by a manganese oxide mineral found in soils

Science.gov (United States)

Russo, F.; Johnson, C.J.; McKenzie, D.; Aiken, Judd M.; Pedersen, J.A.

2009-01-01

Prions, the aetiological agents of transmissible spongiform encephalopathies, exhibit extreme resistance to degradation. Soil can retain prion infectivity in the environment for years. Reactive soil components may, however, contribute to the inactivation of prions in soil. Members of the birnessite family of manganese oxides (MnO2) rank among the strongest natural oxidants in soils. Here, we report the abiotic degradation of pathogenic prion protein (PrPTSE) by a synthetic analogue of naturally occurring birnessite minerals. Aqueous MnO2 suspensions degraded the PrPTSE as evidenced by decreased immunoreactivity and diminished ability to seed protein misfolding cyclic amplification reactions. Birnessite-mediated PrPTSE degradation increased as a solution's pH decreased, consistent with the pH-dependence of the redox potential of MnO2. Exposure to 5.6 mg MnO2 ml-1 (PrPTSE:MnO2=1 : 110) decreased PrPTSE levels by ???4 orders of magnitude. Manganese oxides may contribute to prion degradation in soil environments rich in these minerals. ?? 2009 SGM.

Degradation of the azo dye Acid Red 1 by anodic oxidation and indirect electrochemical processes based on Fenton's reaction chemistry. Relationship between decolorization, mineralization and products

International Nuclear Information System (INIS)

Florenza, Xavier; Solano, Aline Maria Sales; Centellas, Francesc; Martínez-Huitle, Carlos Alberto

2014-01-01

Highlights: • Degradation of Acid Red 1 by anodic oxidation, electro-Fenton and photoelectro-Fenton • Quicker and similar decolorization by electro-Fenton and photoelectro-Fenton due to oxidation with ● OH in the bulk • Almost total mineralization by photoelectro-Fenton with Pt or BDD due to fast photolysis of products by UVA light • Detection of 11 aromatic products, 15 hydroxylated compounds, 13 desulfonated derivatives and 7 carboxylic acids • Release of NH 4 + , NO 3 − and SO 4 2− ions, and generation of persistent N-products of low molecular mass - Abstract: Solutions of 236 mg dm −3 Acid Red 1 (AR1), an azo dye widely used in textile dying industries, at pH 3.0 have been comparatively treated by anodic oxidation with electrogenerated H 2 O 2 (AO-H 2 O 2 ), electro-Fenton (EF) and photoelectro-Fenton (PEF) at constant current density (j). Assays were performed with a stirred tank reactor equipped with a Pt or boron-doped diamond (BDD) anode and an air-diffusion cathode for H 2 O 2 generation from O 2 reduction. The main oxidizing agents were hydroxyl radicals produced at the anode from water oxidation in all methods and in the bulk from Fenton's reaction between generated H 2 O 2 and 0.5 mmol dm −3 Fe 2+ in EF and PEF. For each anode, higher oxidation power was found in the sequence AO-H 2 O 2 < EF < PEF. The oxidation ability of the BDD anode was always superior to that of Pt. Faster and similar decolorization efficiency was achieved in EF and PEF owing to the quicker destruction of aromatics with hydroxyl radicals produced in the bulk. The PEF process with BDD was the most potent method yielding almost total mineralization due to the additional rapid photolysis of recalcitrant intermediates like Fe(III)-carboxylate complexes under UVA irradiation. The increase in j always enhanced the decolorization and mineralization processes because of the greater production of hydroxyl radicals, but decreases the mineralization current efficiency

Solid-state Water-mediated Transport Reduction of Nanostructured Iron Oxides

International Nuclear Information System (INIS)

Smirnov, Vladimir M.; Povarov, Vladimir G.; Voronkov, Gennadii P.; Semenov, Valentin G.; Murin, Igor' V.; Gittsovich, Viktor N.; Sinel'nikov, Boris M.

2001-01-01

The Fe 2+ /Fe 3+ ratio in two-dimensional iron oxide nanosructures (nanolayers with a thickness of 0.3-1.5 nm on silica surface) may be precisely controlled using the transport reduction (TR) technique. The species ≡-O-Fe(OH) 2 and (≡Si-O-) 2 -FeOH forming the surface monolayer are not reduced at 400-600 deg. C because of their covalent bonding to the silica surface, as demonstrated by Moessbauer spectroscopy. Iron oxide microparticles (microstructures) obtained by the impregnation technique, being chemically unbound to silica, are subjected to reduction at T ≥ 500 deg. C with formation of metallic iron in the form of α-Fe. Transport reduction of supported nanostructures (consisting of 1 or 4 monolayers) at T ≥ 600 deg. C produces bulk iron(II) silicate and metallic iron phases. The structural-chemical transformations occurring in transport reduction of supported iron oxide nanolayers are proved to be governed by specific phase processes in the nanostructures themselves

Reduction-oxidation Enabled Glass-ceramics to Stainless Steel Bonding Part I: screening of doping oxidants

Energy Technology Data Exchange (ETDEWEB)

Dai, Steve Xunhu [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2015-09-01

Lithium silicate-based glass-ceramics with high coefficients of thermal expansion, designed to form matched hermetic seals in 304L stainless steel housing, show little evidence of interfacial chemical bonding, despite extensive inter-diffusion at the glass-ceramic-stainless steel (GC-SS) interface. A series of glass-ceramic compositions modified with a variety of oxidants, AgO, FeO, NiO, PbO, SnO, CuO, CoO, MoO₃ and WO₃, are examined for the feasibility of forming bonding oxides through reduction-oxidation (redox) at the GC-SS interface. The oxidants were selected according to their Gibbs free energy to allow for oxidation of Cr/Mn/Si from stainless steel, and yet to prevent a reduction of P2O5 in the glass-ceramic where the P₂O₅ is to form Li₃PO₄ nuclei for growth of high expansion crystalline SiO₂ phases. Other than the CuO and CoO modified glass-ceramics, bonding from interfacial redox reactions were not achieved in the modified glass-ceramics, either because of poor wetting on the stainless steel or a reduction of the oxidants at the surface of glass-ceramic specimens rather than the GC-SS interface.

Evolution of thermal stress and failure probability during reduction and re-oxidation of solid oxide fuel cell

Science.gov (United States)

Wang, Yu; Jiang, Wenchun; Luo, Yun; Zhang, Yucai; Tu, Shan-Tung

2017-12-01

The reduction and re-oxidation of anode have significant effects on the integrity of the solid oxide fuel cell (SOFC) sealed by the glass-ceramic (GC). The mechanical failure is mainly controlled by the stress distribution. Therefore, a three dimensional model of SOFC is established to investigate the stress evolution during the reduction and re-oxidation by finite element method (FEM) in this paper, and the failure probability is calculated using the Weibull method. The results demonstrate that the reduction of anode can decrease the thermal stresses and reduce the failure probability due to the volumetric contraction and porosity increasing. The re-oxidation can result in a remarkable increase of the thermal stresses, and the failure probabilities of anode, cathode, electrolyte and GC all increase to 1, which is mainly due to the large linear strain rather than the porosity decreasing. The cathode and electrolyte fail as soon as the linear strains are about 0.03% and 0.07%. Therefore, the re-oxidation should be controlled to ensure the integrity, and a lower re-oxidation temperature can decrease the stress and failure probability.

Catalytic activity of lanthanum oxide for the reduction of cyclohexanone

International Nuclear Information System (INIS)

Sugunan, S.; Sherly, K.B.

1994-01-01

Lanthanum oxides, La 2 O 3 has been found to be an effective catalyst for the liquid phase reduction of cyclohexanone. The catalytic activities of La 2 O 3 activated at 300, 500 and 800 degC and its mixed oxides with alumina for the reduction of cylcohexanone with 2-propanol have been determined and the data parallel that of the electron donating properties of the catalysts. The electron donating properties of the catalysts have been determined from the adsorption of electron acceptors of different electron affinities on the surface of these oxides. (author). 15 refs., 2 figs., 1 tab

Nitric oxide and nitrous oxide emissions from cattle-slurry and mineral fertiliser treated with nitrification inhibitor to an agricultural soil: A laboratory approach

Energy Technology Data Exchange (ETDEWEB)

Pereira, J.; Coutinho, J.; Fangueiro, D.; Trindade, H.

2015-07-01

The application of organic and mineral fertilisers to soil can result in increased gaseous emissions to the atmosphere such as nitric oxide (NO) and nitrous oxide (N2O) gases. The aim of this study was to evaluate under laboratory conditions the effects on mineral N dynamics and NO and N2O emissions of application to soil of cattle slurry derived liquid fraction (LF) obtained by screw press and mineral fertiliser (MF), both treated with or without the nitrification inhibitor 3,4-dimethylpyrazole phosphate (DMPP). An aerobic laboratory incubation was performed over 93 days with a Dystric Cambisol amended with mechanically separated LF or mineral fertiliser ammonium sulphate only or combined with DMPP. Two additional treatments were included: soil only and soil amended with DMPP. Nitrogen immobilisation was the dominant process with MF amendment, whereas N mineralisation has been observed with LF. The application of LF reduced significantly NO emissions by 80% relative to mineral but no differences were observed with N2O emissions. The addition of DMPP to MF induced a decrease of 18 and 29% in NO and N2O emissions whereas DMPP combined with LF reduced (numerically but not statistically) these emissions in 20 and 10%, respectively. Results obtained in our study suggest that N (NO + N2O) losses can be mitigated by adding DMPP to mineral fertilisers or replacing mineral fertiliser by LF. (Author)

Suspension Hydrogen Reduction of Iron Oxide Concentrates

Energy Technology Data Exchange (ETDEWEB)

H.Y. Sohn

2008-03-31

The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.

Charge state mapping of mixed valent iron and manganese mineral particles using Scanning Transmission X-ray Microscopy (STXM)

International Nuclear Information System (INIS)

Pecher, K.; Nealson, K.; Kneedler, E.; Rothe, J.; Meigs, G.; Warwick, T.; Tonner, B.

2000-01-01

The interfaces between solid mineral particles and water play a crucial role in partitioning and chemical transformation of many inorganic as well as organic pollutants in environmental systems. Among environmentally significant minerals, mixed-valent oxides and hydroxides of iron (e.g. magnetite, green rusts) and manganese (hausmanite, birnessite) have been recognized as particularly strong sorbents for metal ions. In addition, minerals containing Fe(II) have recently been proven to be powerful reductants for a wide range of pollutants. Chemical properties of these minerals strongly depend on the distribution and availability of reactive sites and little is known quantitatively about the nature of these sites. We have investigated the bulk distribution of charge states of manganese (Mn (II, III, IV)) and iron (Fe(II, III)) in single particles of natural manganese nodules and synthetic green rusts using Scanning Transmission X-ray SpectroMicroscopy (STXM). Pixel resolved spectra (XANES) extracted from stacks of images taken at different wave lengths across the metal absorption edge were fitted to total electron yield (TEY) spectra of single valent reference compounds. Two dimensional maps of bulk charge state distributions clearly reveal domains of different oxidation states within single particles of Mn-nodules and green rust precipitates. Changes of oxidation states of iron were followed as a result of reductive transformation of an environmental contaminant (CCl 4 ) using green rust as the only reductant

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

Science.gov (United States)

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.

Green reduction of graphene oxide via Lycium barbarum extract

Energy Technology Data Exchange (ETDEWEB)

Hou, Dandan, E-mail: houdandan114@163.com; Liu, Qinfu, E-mail: lqf@cumtb.edu.cn; Cheng, Hongfei, E-mail: h.cheng@cumtb.edu.cn; Zhang, Hao, E-mail: 1073261516@qq.com; Wang, Sen, E-mail: wscumtb@163.com

2017-02-15

The synthesis of graphene from graphene oxide (GO) usually involves toxic reducing agents that are harmful to human health and the environment. Here, we report a facile approach for effective reduction of GO, for the first time, using Lycium barbarum extract as a green and natural reducing agent. The morphology and de-oxidation efficiency of the reduced graphene were characterized and results showed that Lycium barbarum extract can effectively reduce GO into few layered graphene with a high carbon to oxygen ratio (6.5), comparable to that of GO reduced by hydrazine hydrate (6.6). The possible reduction mechanism of GO may be due to the active components existing in Lycium barbarum fruits, which have high binding affinity to the oxygen containing groups to form their corresponding oxides and other by-products. This method avoided the use of any nocuous chemicals, thus facilitating the mass production of graphene and graphene-based bio-materials. - Graphical abstract: Schematic illustration of the preparation of reduced graphene by Lycium barbarum extract. - Highlights: • The Lycium barbarum extract was used for the reduction of graphene oxide. • The obtained few layered graphene exhibited high carbon to oxygen ratio. • This approach can be applied in the preparation of graphene-based bio-materials.

Preparation of graphite derivatives by selective reduction of graphite oxide and isocyanate functionalization

Energy Technology Data Exchange (ETDEWEB)

Santha Kumar, Arunjunai Raja Shankar [Materials Science Centre, Indian Institute of Technology, Kharagpur, 721302, West Bengal (India); Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, 01069, Dresden (Germany); Piana, Francesco [Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, 01069, Dresden (Germany); Organic Chemistry of Polymers, Technische Universität Dresden, 01062, Dresden (Germany); Mičušík, Matej [Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 845 41, Bratislava (Slovakia); Pionteck, Jürgen, E-mail: pionteck@ipfdd.de [Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, 01069, Dresden (Germany); Banerjee, Susanta [Materials Science Centre, Indian Institute of Technology, Kharagpur, 721302, West Bengal (India); Voit, Brigitte [Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, 01069, Dresden (Germany); Organic Chemistry of Polymers, Technische Universität Dresden, 01062, Dresden (Germany)

2016-10-01

Heavily oxidized and ordered graphene nanoplatelets were produced from natural graphite by oxidation using a mixture of phosphoric acid, sulphuric acid, and potassium permanganate (Marcano's method). The atomic percentage of oxygen in the graphite oxide produced was more than 30% confirmed by XPS studies. The graphite oxide produced had intact basal planes and remains in a layered structure with interlayer distance of 0.8 nm, analyzed by WAXS. The graphite oxide was treated with 4,4′-methylenebis(phenyl isocyanate) (MDI) to produce grafted isocyanate functionalization. Introduction of these bulky functional groups widens the interlayer distance to 1.3 nm. In addition, two reduction methods, namely benzyl alcohol mediated reduction and thermal reduction were carried out on isocyanate modified and unmodified graphite oxides and compared to each other. The decrease in the oxygen content and the sp{sup 3} defect-repair were studied with XPS and RAMAN spectroscopy. Compared to the thermal reduction process, which is connected with large material loss, the benzyl alcohol mediated reduction process is highly effective in defect repair. This resulted in an increase of conductivity of at least 9 orders of magnitude compared to the graphite oxide. - Highlights: • Preparation of GO by Marcano's method results in defined interlayer spacing. • Treatment of GO with diisocyanate widens the interlayer spacing to 1.3 nm. • Chemical reduction of GO with benzyl alcohol is effective in defect repair. • Electrical conductivity increases by 9 orders of magnitude during chemical reduction. • The isocyanate functionalization is stable under chemical reducing conditions.

Electrochemical reduction of cerium oxide into metal

Energy Technology Data Exchange (ETDEWEB)

Claux, Benoit [CEA, Valduc, F-21120 Is-sur-Tille (France); Universite de Grenoble, LEPMI-ENSEEG, 1130 rue de la Piscine, BP75, F-38402 St Martin d' Heres Cedex (France); Serp, Jerome, E-mail: jerome.serp@cea.f [CEA, Valduc, F-21120 Is-sur-Tille (France); Fouletier, Jacques [Universite de Grenoble, LEPMI-ENSEEG, 1130 rue de la Piscine, BP75, F-38402 St Martin d' Heres Cedex (France)

2011-02-28

The Fray Farthing and Chen (FFC) and Ono and Suzuki (OS) processes were developed for the reduction of titanium oxide to titanium metal by electrolysis in high temperature molten alkali chloride salts. The possible transposition to CeO{sub 2} reduction is considered in this study. Present work clarifies, by electro-analytical techniques, the reduction pathway leading to the metal. The reduction of CeO{sub 2} into metal was feasible via an indirect mechanism. Electrolyses on 10 g of CeO{sub 2} were carried out to evaluate the electrochemical process efficiency. Ca metal is electrodeposited at the cathode from CaCl{sub 2}-KCl solvent and reacts chemically with ceria to form not only metallic cerium, but also cerium oxychloride.

Iron biomineralization by anaerobic neutrophilic iron-oxidizing bacteria

DEFF Research Database (Denmark)

Miot, Jennyfer; Benzerara, Karim; Morin, Guillaume

2009-01-01

Minerals formed by bio-oxidation of ferrous iron (Fe(II)) at neutral pH, their association with bacterial ultrastructures as well as their impact on the metabolism of iron-oxidizing bacteria remain poorly understood. Here, we investigated iron biomineralization by the anaerobic nitrate-dependent ......Minerals formed by bio-oxidation of ferrous iron (Fe(II)) at neutral pH, their association with bacterial ultrastructures as well as their impact on the metabolism of iron-oxidizing bacteria remain poorly understood. Here, we investigated iron biomineralization by the anaerobic nitrate...... precipitation in the periplasm (in a few tens of minutes), followed by the formation of surface-bound globules. Moreover, we frequently observed an asymmetric mineral thickening at the cell poles. In parallel, the evolution of iron oxidation was quantified by STXM: iron both contained in the bacteria...... and in the extracellular precipitates reached complete oxidation within 6 days. While a progressive oxidation of Fe in the bacteria and in the medium could be observed, spatial redox (oxido-reduction state) heterogeneities were detected at the cell poles and in the extracellular precipitates after 1 day. All...

Microbial interspecies electron transfer via electric currents through conductive minerals

Science.gov (United States)

Kato, Souichiro; Hashimoto, Kazuhito; Watanabe, Kazuya

2012-01-01

In anaerobic biota, reducing equivalents (electrons) are transferred between different species of microbes [interspecies electron transfer (IET)], establishing the basis of cooperative behaviors and community functions. IET mechanisms described so far are based on diffusion of redox chemical species and/or direct contact in cell aggregates. Here, we show another possibility that IET also occurs via electric currents through natural conductive minerals. Our investigation revealed that electrically conductive magnetite nanoparticles facilitated IET from Geobacter sulfurreducens to Thiobacillus denitrificans, accomplishing acetate oxidation coupled to nitrate reduction. This two-species cooperative catabolism also occurred, albeit one order of magnitude slower, in the presence of Fe ions that worked as diffusive redox species. Semiconductive and insulating iron-oxide nanoparticles did not accelerate the cooperative catabolism. Our results suggest that microbes use conductive mineral particles as conduits of electrons, resulting in efficient IET and cooperative catabolism. Furthermore, such natural mineral conduits are considered to provide ecological advantages for users, because their investments in IET can be reduced. Given that conductive minerals are ubiquitously and abundantly present in nature, electric interactions between microbes and conductive minerals may contribute greatly to the coupling of biogeochemical reactions. PMID:22665802

CuO reduction induced formation of CuO/Cu2O hybrid oxides

Science.gov (United States)

Yuan, Lu; Yin, Qiyue; Wang, Yiqian; Zhou, Guangwen

2013-12-01

Reduction of CuO nanowires results in the formation of a unique hierarchical hybrid nanostructure, in which the parent oxide phase (CuO) works as the skeleton while the lower oxide (Cu2O) resulting from the reduction reaction forms as partially embedded nanoparticles that decorate the skeleton of the parent oxide. Using in situ transmission electron microscopy observations of the reduction process of CuO nanowires, we demonstrate that the formation of such a hierarchical hybrid oxide structure is induced by topotactic nucleation and growth of Cu2O islands on the parent CuO nanowires.

Nitrous oxide reduction in nodules: denitrification or N2 fixation?

International Nuclear Information System (INIS)

Coyne, M.S.; Focht, D.D.

1987-01-01

Detached cowpea nodules that contained a nitrous oxide reductase-positive (Nor + ) rhizobium strain (8A55) and a nitrous oxide reductase-negative (Nor - ) rhizobium strain (32H1) were incubated with 1% 15 N 2 O (95 atom% 15 N) in the following three atmospheres: aerobic with C 2 H 2 (10%), aerobic without C 2 H 2 , and anaerobic (argon atmosphere) without C 2 H 2 . The greatest production of 15 N 2 occurred anaerobically with 8A55, yet very little was formed with 32H1. Although acetylene reduction activity was slightly higher with 32H1, about 10 times more 15 N 2 was produced aerobically by 8A55 than by 32H1 in the absence of acetylene. The major reductive pathway of N 2 O reduction by denitrifying rhizobium strain 8A55 is by nitrous oxide reductase rather than nitrogenase

Manganese-oxide minerals in fractures of the Crater Flat Tuff in drill core USW G-4, Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Carlos, B.A.; Bish, D.L.; Chipera, S.J.

1990-07-01

The Crater Flat Tuff is almost entirely below the water table in drill hole USW G-4 at Yucca Mountain, Nevada. Manganese-oxide minerals from the Crater Flat Tuff in USW G-4 were studied using optical, scanning electron microscopic, electron microprobe, and x-ray powder diffraction methods to determine their distribution, mineralogy, and chemistry. Manganese-oxide minerals coat fractures in all three members of the Crater Flat Tuff (Prow Pass, Bullfrog, and Tram), but they are most abundant in fractures in the densely welded devitrified intervals of these members. The coatings are mostly of the cryptomelane/hollandite mineral group, but the chemistry of these coatings varies considerably. Some of the chemical variations, particularly the presence of calcium, sodium, and strontium, can be explained by admixture with todorokite, seen in some x-ray powder diffraction patterns. Other chemical variations, particularly between Ba and Pb, demonstrate that considerable substitution of Pb for Ba occurs in hollandite. Manganese-oxide coatings are common in the 10-m interval that produced 75% of the water pumped from USW G-4 in a flow survey in 1983. Their presence in water-producing zones suggests that manganese oxides may exert a significant chemical effect on groundwater beneath Yucca Mountain. In particular, the ability of the manganese oxides found at Yucca Mountain to be easily reduced suggests that they may affect the redox conditions of the groundwater and may oxidize dissolved or suspended species. Although the Mn oxides at Yucca Mountain have low exchange capacities, these minerals may retard the migration of some radionuclides, particularly the actinides, through scavenging and coprecipitation. 23 refs., 21 figs., 2 tabs

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

Directory of Open Access Journals (Sweden)

Elizabeth D. Swanner

2015-10-01

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

A transmission electron microscopy analysis of secondary minerals formed in tungsten-mine tailings with an emphasis on arsenopyrite oxidation

International Nuclear Information System (INIS)

Petrunic, B.M.; Al, T.A.; Weaver, L.

2006-01-01

Grains of naturally oxidized arsenopyrite [FeAsS] collected from the oxidation zone in W-mine tailings were investigated, primarily using transmission electron microscopy. The grains are severely pitted and are surrounded by secondary minerals. The pitted nature of the grains is related to mechanisms governing the electrochemical oxidation of sulfide minerals, with prominent cusp-like features occurring at cathodic regions of the surface, and pits occurring at anodic regions. In general, the oxidation of arsenopyrite leads to the formation of an amorphous (or nanocrystalline) Fe-As-O-rich coating that contains small amounts of Si, Ca, Cu, Zn, Pb and Bi; nanoscale variation in the As, Pb, Bi and Zn contents of the coating was noted. Secondary Cu sulfides, thought to be chalcocite [Cu 2 S] and (or) djurleite [Cu 31 S 16 ], occur as a layer (generally 4 ] and an unidentified crystalline Bi-Pb-As-O mineral occur in voids within the coating, suggesting that these minerals precipitated from the local pore-water. Small and variable amounts of W, Ca, Bi, As and Zn are associated with the wulfenite, and Zn, Fe and Ca are associated with the Bi-Pb-As-O mineral. Some of the wulfenite is in contact with inclusions of molybdenite [MoS 2 ], suggesting that the oxidation of molybdenite in the presence of aqueous Pb(II) led to the formation of wulfenite. Mineralogical analyses at the nanoscale have improved the understanding of geochemical sources and sinks at this location. The results of this study indicate that the mineralogical controls on aqueous elemental concentrations at this tailings site are complex and are not predicted by thermodynamic calculations

Laser-Induced Reductive Sintering of Nickel Oxide Nanoparticles under Ambient Conditions

KAUST Repository

Paeng, Dongwoo; Lee, Daeho; Yeo, Junyeob; Yoo, Jae-Hyuck; Allen, Frances I.; Kim, Eunpa; So, Hongyun; Park, Hee K.; Minor, Andrew M.; Grigoropoulos, Costas P.

2015-01-01

© 2015 American Chemical Society. This work is concerned with the kinetics of laser-induced reductive sintering of nonstoichiometric crystalline nickel oxide (NiO) nanoparticles (NPs) under ambient conditions. The mechanism of photophysical reductive sintering upon irradiation using a 514.5 nm continuous-wave (CW) laser on NiO NP thin films has been studied through modulating the laser power density and illumination time. Protons produced due to high-temperature decomposition of the solvent present in the NiO NP ink, oxygen vacancies in the NiO NPs, and electronic excitation in the NiO NPs by laser irradiation all affect the early stage of the reductive sintering process. Once NiO NPs are reduced by laser irradiation to Ni, they begin to coalesce, forming a conducting material. In situ optical and electrical measurements during the reductive sintering process take advantage of the distinct differences between the oxide and the metallic phases to monitor the transient evolution of the process. We observe four regimes: oxidation, reduction, sintering, and reoxidation. A characteristic time scale is assigned to each regime.

Laser-Induced Reductive Sintering of Nickel Oxide Nanoparticles under Ambient Conditions

KAUST Repository

Paeng, Dongwoo

2015-03-19

© 2015 American Chemical Society. This work is concerned with the kinetics of laser-induced reductive sintering of nonstoichiometric crystalline nickel oxide (NiO) nanoparticles (NPs) under ambient conditions. The mechanism of photophysical reductive sintering upon irradiation using a 514.5 nm continuous-wave (CW) laser on NiO NP thin films has been studied through modulating the laser power density and illumination time. Protons produced due to high-temperature decomposition of the solvent present in the NiO NP ink, oxygen vacancies in the NiO NPs, and electronic excitation in the NiO NPs by laser irradiation all affect the early stage of the reductive sintering process. Once NiO NPs are reduced by laser irradiation to Ni, they begin to coalesce, forming a conducting material. In situ optical and electrical measurements during the reductive sintering process take advantage of the distinct differences between the oxide and the metallic phases to monitor the transient evolution of the process. We observe four regimes: oxidation, reduction, sintering, and reoxidation. A characteristic time scale is assigned to each regime.

Transformation of Leaf-like Zinc Dendrite in Oxidation and Reduction Cycle

International Nuclear Information System (INIS)

Nakata, Akiyoshi; Murayama, Haruno; Fukuda, Katsutoshi; Yamane, Tomokazu; Arai, Hajime; Hirai, Toshiro; Uchimoto, Yoshiharu; Yamaki, Jun-ichi; Ogumi, Zempachi

2015-01-01

Highlights: • Leaf-like zinc dendrites change to leaf-like residual oxides at high oxidation current density (10 mA cm −2 ) whereas it completely dissolves at low oxidation current density (1 mA cm −2 ). • Leaf-like residual oxide products is transformed to zinc deposits with particulate morphology, resulting in good rechargeability. • The residual zinc oxide provides sufficient zincate on its reduction, preventing the diffusion-limited condition that causes leaf-like dendrite formation. - Abstract: Zinc is a promising negative electrode material for aqueous battery systems whereas it shows insufficient rechargeability for use in secondary batteries. It has been reported that leaf-like dendrite deposits are often the origin of cell-failure, however, their nature and behavior on discharge (oxidation) - charge (reduction) cycling have been only poorly understood. Here we investigate the transformation of the leaf-like zinc dendrites using ex-situ scanning electron microscopy, X-ray computational tomography and in-situ X-ray diffraction. It is shown that the leaf-like zinc dendrites obtained under diffusion-limited conditions are nearly completely dissolved at a low oxidation current density of 1 mA cm −2 and cause re-evolution of the zinc dendrites. Oxidation at a high current density of 10 mA cm −2 leads to the formation of leaf-like zinc oxide residual products that result in particulate zinc deposits in the following reduction process, enabling good rechargeability. The reaction behavior of this oxide residue is detailed and discussed for the development of long-life zinc electrodes

Reduction Rates for Higher Americium Oxidation States in Nitric Acid

Energy Technology Data Exchange (ETDEWEB)

Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2015-09-30

The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

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

Science.gov (United States)

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

The Reduction of Cr(VI) to Cr(III) by Natural Fe-Bearing Minerals: A Synchrotron XAS Study

Science.gov (United States)

Xu, H.; Guo, X.; Ding, M.; Migdissov, A. A.; Boukhalfa, H.; Sun, C.; Roback, R. C.; Reimus, P. W.; Katzman, D.

2017-12-01

Cr(VI) in the form of CrO42- is a pollutant species in groundwater and soils that can pose health and environmental problems. Cr(VI) associated with use as a corrosion inhibitor at a power plant from 1956-1972 is present in a deep groundwater aquifer at Los Alamos National Laboratory. A potential remediation strategy for the Cr contamination is reduction of Cr(VI) to Cr(III) via the acceptance of electrons from naturally occurring or induced Fe(II) occurring in Fe-bearing minerals. In this work, using synchrotron-based X-ray techniques, we investigated the Cr reduction behavior by Fe-bearing minerals from outcrop and core samples representative of the contaminated portion of the aquifer. Samples were exposed to solutions with a range of known Cr (VI) concentrations. XANES and EXAFS spectra showed that all the Cr(VI) had been reduced to Cr(III), and micro XRF mapping revealed close correlation of Cr and Fe distribution, implying that Fe(II) in minerals reduced Cr(VI) in the solution. Similar behavior was observed from in-situ XANES measurements on Cr reduction and adsorption by mineral separates from the rock samples in Cr(VI)-bearing solutions. In addition, to obtain reference parameters for interpreting the data of natural samples, we collected Cr and Fe EXAFS spectra of Cr(III)-Fe(III) hydroxide solid solutions, which show progressive changes in the local structure around Cr and Fe over the whole series.

Biotechnological aspects of anaerobic oxidation of methane coupled to sulfate reduction

NARCIS (Netherlands)

Meulepas, R.J.W.

2009-01-01

Sulfate reduction (SR) can be used for the removal and recovery of metals and oxidized sulfur compounds from waste streams. Sulfate-reducing bacteria reduce oxidized sulfur compounds to sulfide. Subsequently, sulfide can precipitate dissolved metals or can be oxidized to elemental sulfur. Both metal

A transmission electron microscopy analysis of secondary minerals formed in tungsten-mine tailings with an emphasis on arsenopyrite oxidation

Energy Technology Data Exchange (ETDEWEB)

Petrunic, B.M. [Department of Geology, University of New Brunswick, Fredericton, NB, E3B 5A3 (Canada)]. E-mail: petrunic@gmail.com; Al, T.A. [Department of Geology, University of New Brunswick, Fredericton, NB, E3B 5A3 (Canada); Weaver, L. [Microscopy and Microanalysis Facility, University of New Brunswick, Fredericton, NB, E3B 5A3 (Canada)

2006-08-15

Grains of naturally oxidized arsenopyrite [FeAsS] collected from the oxidation zone in W-mine tailings were investigated, primarily using transmission electron microscopy. The grains are severely pitted and are surrounded by secondary minerals. The pitted nature of the grains is related to mechanisms governing the electrochemical oxidation of sulfide minerals, with prominent cusp-like features occurring at cathodic regions of the surface, and pits occurring at anodic regions. In general, the oxidation of arsenopyrite leads to the formation of an amorphous (or nanocrystalline) Fe-As-O-rich coating that contains small amounts of Si, Ca, Cu, Zn, Pb and Bi; nanoscale variation in the As, Pb, Bi and Zn contents of the coating was noted. Secondary Cu sulfides, thought to be chalcocite [Cu{sub 2}S] and (or) djurleite [Cu{sub 31}S{sub 16}], occur as a layer (generally <500 nm thick) along the arsenopyrite grain boundary, and also within the coating as aggregates, and as layers that parallel the grain boundary. Although the precipitation of secondary Cu minerals along the grain boundary is a nanoscale feature, the process of formation is thought to be analogous to the supergene enrichment that occurs in weathered sulfide deposits. As the oxidation of arsenopyrite proceeds, layers and clusters of secondary Cu sulfides become isolated in the Fe-As-O coating. Secondary wulfenite [PbMoO{sub 4}] and an unidentified crystalline Bi-Pb-As-O mineral occur in voids within the coating, suggesting that these minerals precipitated from the local pore-water. Small and variable amounts of W, Ca, Bi, As and Zn are associated with the wulfenite, and Zn, Fe and Ca are associated with the Bi-Pb-As-O mineral. Some of the wulfenite is in contact with inclusions of molybdenite [MoS{sub 2}], suggesting that the oxidation of molybdenite in the presence of aqueous Pb(II) led to the formation of wulfenite. Mineralogical analyses at the nanoscale have improved the understanding of geochemical sources

Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation.

Science.gov (United States)

Zeng, Zhirui; Tice, Michael M

2018-01-01

Some microbial carbonates are robust biosignatures due to their distinct morphologies and compositions. However, whether carbonates induced by microbial iron reduction have such features is unknown. Iron-reducing bacteria use various strategies to transfer electrons to iron oxide minerals (e.g., membrane-bound enzymes, soluble electron shuttles, nanowires, as well as different mechanisms for moving over or attaching to mineral surfaces). This diversity has the potential to create mineral biosignatures through manipulating the microenvironments in which carbonate precipitation occurs. We used Shewanella oneidensis MR-1, Geothrix fermentans, and Geobacter metallireducens GS-15, representing three different strategies, to reduce solid ferric hydroxide in order to evaluate their influence on carbonate and micropore formation (micro-size porosity in mineral rocks). Our results indicate that electron transfer strategies determined the morphology (rhombohedral, spherical, or long-chained) of precipitated calcium-rich siderite by controlling the level of carbonate saturation and the location of carbonate formation. Remarkably, electron transfer strategies also produced distinctive cell-shaped micropores in both carbonate and hydroxide minerals, thus producing suites of features that could potentially serve as biosignatures recording information about the sizes, shapes, and physiologies of iron-reducing organisms. Key Words: Microbial iron reduction-Micropore-Electron transfer strategies-Microbial carbonate. Astrobiology 18, 28-36.

Electrochemical reduction of nitrous oxide on La1-xSrxFeO3 perovskites

DEFF Research Database (Denmark)

Kammer Hansen, Kent

2010-01-01

The electrochemical reduction of nitrous oxide and oxygen has been studied on cone-shaped electrodes of La1-xSrxFeO3-delta perovskites in an all solid state cell, using cyclic voltammetry. It was shown that the activity of the La1-xSrxFeO3-delta perovskites for the electrochemical reduction...... of nitrous oxide mainly depends on the amount of Fe(III) and oxide ion vacancies. The activity of the La1-xSrxFeO3-delta perovskites towards the electrochemical reduction of nitrous oxide is much lower than the activity of the La1-xSrxFeO3-delta perovskites towards the electrochemical reduction of oxygen...

Technologies for the Reduction of Nitrogen Oxides Emissions

Directory of Open Access Journals (Sweden)

Paulica Arsenie

2015-06-01

Full Text Available When it comes to gas turbines, their main problem concerning pollutant emissions is represented by nitric oxides. Among other emissions, sulphur oxides being much reduced due to the use of liquid distilled and gas fuels with a low content of sulphur. Using water or steam injection became the favourite method during the '80s and especially the '90s since "dry" methods and catalytic reduction were both at the beginning of the development phase. Catalytic convertors have been used since the '80s and they are still used although the costs of renewing the catalyst are very high. In the last twenty years a gradual decrease has been registered on the limits of nitric oxides from 75 ppm to 25 ppm, and now the target is oriented towards the 9 ppm level. The evolution of burning technologies of combustion makes it possible to control the level of production of nitric oxides even from the source without being necessary to use "humid" methods. This, of course, opened the market for gas turbines because they can function even in areas with limited quality water reserves, such as maritime platforms and in the desert. In this paper, we are going to show that, although water injection is still used, "dry" control technologies of burning became favourite methods for the majority of users on the industrial power generators market. The great dependency between the creation of nitric oxides and the temperature reveals the effect of direct water or steam injection on reducing nitric oxides. Recent research showed that a reduction up to 85% of nitric oxides may be obtained by using the water or steam injection all together with the improvement of aerodynamic character of the burning room.

Au/iron oxide catalysts: temperature programmed reduction and X-ray diffraction characterization

International Nuclear Information System (INIS)

Neri, G.; Visco, A.M.; Galvagno, S.; Donato, A.; Panzalorto, M.

1999-01-01

Gold on iron oxides catalysts have been characterized by temperature programmed reduction (TPR) and X-ray diffraction spectroscopy (XRD). The influence of preparation method, gold loading and pretreatment conditions on the reducibility of iron oxides have been investigated. On the impregnated Au/iron oxide catalysts as well as on the support alone the partial reduction of Fe(III) oxy(hydroxides) to Fe 3 O 4 starts in the 550 and 700 K temperature range. On the coprecipitated samples, the temperature of formation of Fe 3 O 4 is strongly dependent on the presence of gold. The reduction temperature is lowered as the gold loading is increased. The reduction of Fe 3 O 4 to FeO occurs at about 900 K and is not dependent on the presence of gold and the preparation method. It is suggested that the effect of gold on the reducibility of the iron oxides is related to an increase of the structural defects and/or of the surface hydroxyl groups. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

Impact of natural organic matter coatings on the microbial reduction of iron oxides

Science.gov (United States)

Poggenburg, Christine; Mikutta, Robert; Schippers, Axel; Dohrmann, Reiner; Guggenberger, Georg

2018-03-01

Iron (Fe) oxyhydroxides are important constituents of the soil mineral phase known to stabilize organic matter (OM) under oxic conditions. In an anoxic milieu, however, these Fe-organic associations are exposed to microbial reduction, releasing OM into soil solution. At present, only few studies have addressed the influence of adsorbed natural OM (NOM) on the reductive dissolution of Fe oxyhydroxides. This study therefore examined the impact of both the composition and concentration of adsorbed NOM on microbial Fe reduction with regard to (i) electron shuttling, (ii) complexation of Fe(II,III), (iii) surface site coverage and/or pore blockage, and (iv) aggregation. Adsorption complexes with varying carbon loadings were synthesized using different Fe oxyhydroxides (ferrihydrite, lepidocrocite, goethite, hematite, magnetite) and NOM of different origin (extracellular polymeric substances from Bacillus subtilis, OM extracted from soil Oi and Oa horizons). The adsorption complexes were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), N2 gas adsorption, electrophoretic mobility and particle size measurements, and OM desorption. Incubation experiments under anaerobic conditions were conducted for 16 days comparing two different strains of dissimilatory Fe(III)-reducing bacteria (Shewanella putrefaciens, Geobacter metallireducens). Mineral transformation during reduction was assessed via XRD and FTIR. Microbial reduction of the pure Fe oxyhydroxides was controlled by the specific surface area (SSA) and solubility of the minerals. For Shewanella putrefaciens, the Fe reduction of adsorption complexes strongly correlated with the concentration of potentially usable electron-shuttling molecules for NOM concentrations <2 mg C L-1, whereas for Geobacter metallireducens, Fe reduction depended on the particle size and thus aggregation of the adsorption complexes. These diverging results suggest that

Volatile organic compounds and oxides of nitrogen. Further emission reductions

Energy Technology Data Exchange (ETDEWEB)

Froste, H [comp.

1997-12-31

This report presents the current status in relation to achievement of the Swedish Environmental target set by Parliament to reduce emission of volatile organic compounds by 50 per cent between 1988 and 2000. It also instructed the Agency to formulate proposed measures to achieve a 50 per cent reduction of emission of nitrogen oxides between 1985 and 2005. The report presents an overall account of emission trends for volatile organic compounds (from all sectors) and nitrogen oxides (from the industry sector) and steps proposed to achieve further emission reductions. 43 refs

Volatile organic compounds and oxides of nitrogen. Further emission reductions

Energy Technology Data Exchange (ETDEWEB)

Froste, H. [comp.

1996-12-31

This report presents the current status in relation to achievement of the Swedish Environmental target set by Parliament to reduce emission of volatile organic compounds by 50 per cent between 1988 and 2000. It also instructed the Agency to formulate proposed measures to achieve a 50 per cent reduction of emission of nitrogen oxides between 1985 and 2005. The report presents an overall account of emission trends for volatile organic compounds (from all sectors) and nitrogen oxides (from the industry sector) and steps proposed to achieve further emission reductions. 43 refs

Cuprous oxide nanoparticles dispersed on reduced graphene oxide as an efficient electrocatalyst for oxygen reduction reaction.

Science.gov (United States)

Yan, Xiao-Yan; Tong, Xi-Li; Zhang, Yue-Fei; Han, Xiao-Dong; Wang, Ying-Yong; Jin, Guo-Qiang; Qin, Yong; Guo, Xiang-Yun

2012-02-11

Cuprous oxide (Cu(2)O) nanoparticles dispersed on reduced graphene oxide (RGO) were prepared by reducing copper acetate supported on graphite oxide using diethylene glycol as both solvent and reducing agent. The Cu(2)O/RGO composite exhibits excellent catalytic activity and remarkable tolerance to methanol and CO in the oxygen reduction reaction. This journal is © The Royal Society of Chemistry 2012

Tuning the nonlinear optical absorption of reduced graphene oxide by chemical reduction.

Science.gov (United States)

Shi, Hongfei; Wang, Can; Sun, Zhipei; Zhou, Yueliang; Jin, Kuijuan; Redfern, Simon A T; Yang, Guozhen

2014-08-11

Reduced graphene oxides with varying degrees of reduction have been produced by hydrazine reduction of graphene oxide. The linear and nonlinear optical properties of both graphene oxide as well as the reduced graphene oxides have been measured by single beam Z-scan measurement in the picosecond region. The results reveal both saturable absorption and two-photon absorption, strongly dependent on the intensity of the pump pulse: saturable absorption occurs at lower pump pulse intensity (~1.5 GW/cm2 saturation intensity) whereas two-photon absorption dominates at higher intensities (≥5.7 GW/cm2). Intriguingly, we find that the two-photon absorption coefficient (from 1.5 cm/GW to 4.5cm/GW) and the saturation intensity (from 1 GW/cm2 to 2 GW/cm2) vary with chemical reduction, which is ascribed to the varying concentrations of sp2 domains and sp2 clusters in the reduced graphene oxides. Our results not only provide an insight into the evolution of the nonlinear optical coefficient in reduced graphene oxide, but also suggest that chemical engineering techniques may usefully be applied to tune the nonlinear optical properties of various nano-materials, including atomically thick graphene sheets.

The Dynamics of Nitrous Oxide Emission from the Use of Mineral Fertilizers in Russia

Directory of Open Access Journals (Sweden)

A AA. Romanovskaya

2001-01-01

Full Text Available The intensity of nitrous oxide (N2O emission was considered based on literature data on the single input of mineral N (nitrogen fertilizers into different agricultural soil types in Russia. Ambient environmental factors exert a combined effect on the process of gaseous nitrogen formation from fertilizers applied. To reduce the uncertainty of estimates as much as possible, only experimental results obtained under conditions similar to natural were selected for the assessments. Mineral nitric fertilizers were applied to soil at a rate of 40 to 75 kg/ha and the N2O emissions were measured for approximately 140 days. Daily average emission values varied from 0.08 to 0.45% of fertilizer nitrogen. Correspondingly, 1.26 and 2.38% of fertilizer nitrogen were emitted as N2O from chernozems and soddy podzols. In 1990, the use of fertilizers in Russian agricultural practices for 53 Gg N2O-N, which equates to approximately 6.1% of global nitrous oxide emissions from nitric fertilizers. Later, the emission dropped because of a decrease in the input of nitric fertilizers to agricultural crops, and in 1998, it constituted just 20.5% of the 1990 level. In the period from 2008 to 2012, the nitrous oxide emission is expected to vary from 0.5 to 65.0 Gg N2O-N due to possible changes in national agricultural development. In the most likely scenario, the use of mineral fertilizers in Russia will account for approximately 34 to 40 Gg N2O-N emissions annually from 2008�2012.

Photocatalytic mineralization of glyphosate in a small-scale plug flow simulation reactor by UV/TiO2.

Science.gov (United States)

Chen, Jian Q; Hu, Zhi J; Wang, Nan X

2012-01-01

The present work involves the photocatalytic mineralization of glyphosate on a plug flow reactor by UV/TiO(2). The effect of catalyst loading shows an optimal value (0.4 g L(-1)) which is necessary to mineralize glyphosate. The kinetic rate of glyphosate mineralization decreases with the increasing initial concentration of glyphosate, and the data can be described using the first-order model. An alkaline environment is conducive to glyphosate mineralization. The mineralization efficiency increases with elevated flow rate to 114 mL min(-1), which is followed by a decrease with a further increase in flow rate due to the reduction of the residence time. The presence of external oxidants (K(2)S(2)O(8), H(2)O(2) and KBrO(3)) and photosencitizer (humic acid) can significantly enhance glyphosate mineralization. Photocatalysis oxidation ability of the three studied oxidants decrease in the order of: S(2)O(8)(2-) > BrO(3)(-) > H(2)O(2). Finally, the Langmuir-Hinshelwood (L-H) model was used to rationalize the mechanisms of reactions occurring on TiO(2) surfaces and L-H model constants were also determined. Copyright © Taylor & Francis Group, LLC

The relations between hydrodynamic characteristics and interbedding oxidation zone type uranium mineralization

International Nuclear Information System (INIS)

Bai Jingping

2001-01-01

Infiltrating type hydrodynamic way controls the formation of interbedding oxidation zone type uranium deposit. The author analyzes hydrodynamic condition of Songliao basin and concludes that during evolution and development of Songliao basin, Water-bearing petrofabric of Mingshui Formation and above inherit completely infiltrating hydrodynamic way as they were deposited and that Sifangtai Formation inherit the way to some extent, that below Sifangtai Formation water bearing petrofabric were completely reformed in northern part of Songliao watershed. The contact line between infiltrating and out filtrating type hydrodynamic way, e.g. underground water dividing lines formed in different geological period, restricts development of interbedding oxidation zone in this period and controls uranium mineralization

Influence of Diatomite and Mineral Powder on Thermal Oxidative Ageing Properties of Asphalt

Directory of Open Access Journals (Sweden)

Yongchun Cheng

2015-01-01

Full Text Available Ageing of asphalt affects the performances of asphalt pavement significantly. Therefore, effects of diatomite and mineral powder on ageing properties of asphalt were investigated systematically in order to improve the antiageing property of mixture. Thin film oven test (TFOT was used to conduct the short term ageing in laboratory. Softening points, penetrations, force ductility, low temperature creep properties, and viscosities of asphalt mastics were tested before and after TFOT, respectively. Results indicated that percent retained penetration (PRP increased with the increasing of fillers. Increment of softening point (ΔT, ductility retention rate (DRR, deformation energy ageing index (JAI, and viscosity ageing index (VAI of asphalt mastics nonlinearly decreased with the increasing of fillers. Ageing of asphalt was reduced by diatomite and mineral powder. And the antiageing effect of diatomite was better than that of mineral powder as a result of its porous structure. It is suggested that the mineral powder could be reasonably replaced by diatomite in order to reduce thermal oxidative ageing of asphalt mixture. The optimal content of diatomite 12.8% is also suggested for engineering.

Carbon dioxide sequestration by mineral carbonation. Feasibility of enhanced natural weathering as a CO2 emission reduction technology

International Nuclear Information System (INIS)

Huijgen, W.J.J.

2007-01-01

A possible technology that can contribute to the reduction of carbon dioxide emissions is CO2 sequestration by mineral carbonation. The basic concept behind mineral CO2 sequestration is the mimicking of natural weathering processes in which calcium or magnesium containing minerals react with gaseous CO2 and form solid calcium or magnesium carbonates. Potential advantages of mineral CO2 sequestration compared to, e.g., geological CO2 storage include (1) the permanent and inherently safe sequestration of CO2, due to the thermodynamic stability of the carbonate product formed and (2) the vast potential sequestration capacity, because of the widespread and abundant occurrence of suitable feedstock. In addition, carbonation is an exothermic process, which potentially limits the overall energy consumption and costs of CO2 emission reduction. However, weathering processes are slow, with timescales at natural conditions of thousands to millions of years. For industrial implementation, a reduction of the reaction time to the order of minutes has to be achieved by developing alternative process routes. The aim of this thesis is an investigation of the technical, energetic, and economic feasibility of CO2 sequestration by mineral carbonation. In Chapter 1 the literature published on CO2 sequestration by mineral carbonation is reviewed. Among the potentially suitable mineral feedstock for mineral CO2 sequestration, Ca-silicates, more particularly wollastonite (CaSiO3), a mineral ore, and steel slag, an industrial alkaline solid residue, are selected for further research. Alkaline Ca-rich residues seem particularly promising, since these materials are inexpensive and available near large industrial point sources of CO2. In addition, residues tend to react relatively rapidly with CO2 due to their (geo)chemical instability. Various process routes have been proposed for mineral carbonation, which often include a pre-treatment of the solid feedstock (e.g., size reduction and

Progress in bioleaching: part B: applications of microbial processes by the minerals industries.

Science.gov (United States)

Brierley, Corale L; Brierley, James A

2013-09-01

This review presents developments and applications in bioleaching and mineral biooxidation since publication of a previous mini review in 2003 (Olson et al. Appl Microbiol Biotechnol 63:249-257, 2003). There have been discoveries of newly identified acidophilic microorganisms that have unique characteristics for effective bioleaching of sulfidic ores and concentrates. Progress has been made in understanding and developing bioleaching of copper from primary copper sulfide minerals, chalcopyrite, covellite, and enargite. These developments point to low oxidation-reduction potential in concert with thermophilic bacteria and archaea as a potential key to the leaching of these minerals. On the commercial front, heap bioleaching of nickel has been commissioned, and the mineral biooxidation pretreatment of sulfidic-refractory gold concentrates is increasingly used on a global scale to enhance precious metal recovery. New and larger stirred-tank reactors have been constructed since the 2003 review article. One biooxidation-heap process for pretreatment of sulfidic-refractory gold ores was also commercialized. A novel reductive approach to bioleaching nickel laterite minerals has been proposed.

C3 Epimerization of Glucose, via Regioselective Oxidation and Reduction

NARCIS (Netherlands)

Jumde, Varsha R.; Eisink, Niek N. H. M.; Witte, Martin D.; Minnaard, Adriaan J.

2016-01-01

Palladium-catalyzed oxidation can single out the secondary hydroxyl group at C3 in glucose, circumventing the more readily accessible hydroxyl at C6 and the more reactive anomeric hydroxyl. Oxidation followed by reduction results in either allose or allitol, each a rare sugar that is important in

Nitrous oxide production kinetics during nitrate reduction in river sediments.

Science.gov (United States)

Laverman, Anniet M; Garnier, Josette A; Mounier, Emmanuelle M; Roose-Amsaleg, Céline L

2010-03-01

A significant amount of nitrogen entering river basins is denitrified in riparian zones. The aim of this study was to evaluate the influence of nitrate and carbon concentrations on the kinetic parameters of nitrate reduction as well as nitrous oxide emissions in river sediments in a tributary of the Marne (the Seine basin, France). In order to determine these rates, we used flow-through reactors (FTRs) and slurry incubations; flow-through reactors allow determination of rates on intact sediment slices under controlled conditions compared to sediment homogenization in the often used slurry technique. Maximum nitrate reduction rates (R(m)) ranged between 3.0 and 7.1microg Ng(-1)h(-1), and affinity constant (K(m)) ranged from 7.4 to 30.7mg N-NO(3)(-)L(-1). These values were higher in slurry incubations with an R(m) of 37.9microg Ng(-1)h(-1) and a K(m) of 104mg N-NO(3)(-)L(-1). Nitrous oxide production rates did not follow Michaelis-Menten kinetics, and we deduced a rate constant with an average of 0.7 and 5.4ng Ng(-1)h(-1) for FTR and slurry experiments respectively. The addition of carbon (as acetate) showed that carbon was not limiting nitrate reduction rates in these sediments. Similar rates were obtained for FTR and slurries with carbon addition, confirming the hypothesis that homogenization increases rates due to release of and increasing access to carbon in slurries. Nitrous oxide production rates in FTR with carbon additions were low and represented less than 0.01% of the nitrate reduction rates and were even negligible in slurries. Maximum nitrate reduction rates revealed seasonality with high potential rates in fall and winter and low rates in late spring and summer. Under optimal conditions (anoxia, non-limiting nitrate and carbon), nitrous oxide emission rates were low, but significant (0.01% of the nitrate reduction rates). Copyright 2009 Elsevier Ltd. All rights reserved.

A Study on Electrochemical Reduction of Rare Earth Oxides in Molten LiCl-Li2O Salt

International Nuclear Information System (INIS)

Lee, Min Woo; Jeong, Sang Mun; Lee, See Hoon; Sohn, Jung Min

2016-01-01

In this study, the electrochemical reduction of RE 2 O 3 (RE = Nd or Ce) has been conducted via co-reduction NiO to increase the reduction degree of the rare earth oxides in molten molten LiCl containing 1wt% Li 2 O. The electrochemical reduction behavior of the mixed RE 2 O 3 -NiO oxide has been investigated and the reduction path of RE 2 O 3 has been proposed. An electorchemical spent fuel processing technology, pyroprocessing, has been developed for recycling of spent fuel to be applied to a sodium-cooled fast reactor. The spent fuel is reduced in the oxide reduction process. It is well known that the rare earth oxides are hardly reduced due to their electrochemical and thermodynamic stability. The rare earth oxides unreduced in the reduction process can cause problems via reaction with UCl 3 in the electrorefiner. To tackle those problems, the electrochemical reduction of rare earth oxide has been conducted via co-reduction of NiO in LiCl molten salt containing 1 wt% Li 2 O. The reduction of the oxide mixture starts from the reduction of NiO to Ni, followed by that of RE 2 O 3 on the produced Ni to form intermetallic RENi 5 . The mixed oxide pellets were successfully reduced to the RENi5 alloy by constant electrolysis at 3.0 V at 650 .deg. C. The crucial aspect to these results is that the thermodynamically stable rare-earth oxide, Nd 2 O 3 was successfully converted to the metal in the presence of NiO.

Microbiological oxidative dissolution of a complex mineral sample containing pyrite (FeS2), pyrrotite (Fe1-xS) and molybdenite (MoS2)

International Nuclear Information System (INIS)

Francisco Junior, Wilmo E.; Bevilaqua, Denise; Garcia Junior, Oswaldo

2007-01-01

This work aims to study the oxidation of a complex molybdenite mineral which contains pyrite and pyrrotite, by Acidithiobacillus ferroxidans. This study was performed by respirometric essays and bioleaching in shake flasks. Respirometric essays yielded the kinetics of mineral oxidation. The findings showed that sulfide oxidation followed classical Michaelis-Menten kinetics. Bioleaching in shake flasks allowed evaluation of chemical and mineralogical changes resulting from sulfide oxidation. The results demonstrated that pyrrotite and pyrite were completely oxidized in A. ferrooxidans cultures whereas molybdenite was not consumed. These data indicated that molybdenite was the most recalcitrant sulfide in the sample. (author)

Trace methane oxidation and the methane dependency of sulfate reduction in anaerobic granular sludge

KAUST Repository

Meulepas, Roel J.W.

2010-05-01

This study investigates the oxidation of labeled methane (CH4) and the CH4 dependence of sulfate reduction in three types of anaerobic granular sludge. In all samples, 13C-labeled CH4 was anaerobically oxidized to 13C-labeled CO2, while net endogenous CH4 production was observed. Labeled-CH4 oxidation rates followed CH4 production rates, and the presence of sulfate hampered both labeled-CH4 oxidation and methanogenesis. Labeled-CH4 oxidation was therefore linked to methanogenesis. This process is referred to as trace CH4 oxidation and has been demonstrated in methanogenic pure cultures. This study shows that the ratio between labeled-CH4 oxidation and methanogenesis is positively affected by the CH4 partial pressure and that this ratio is in methanogenic granular sludge more than 40 times higher than that in pure cultures of methanogens. The CH4 partial pressure also positively affected sulfate reduction and negatively affected methanogenesis: a repression of methanogenesis at elevated CH4 partial pressures confers an advantage to sulfate reducers that compete with methanogens for common substrates, formed from endogenous material. The oxidation of labeled CH 4 and the CH4 dependence of sulfate reduction are thus not necessarily evidence of anaerobic oxidation of CH4 coupled to sulfate reduction. © 2010 Federation of European Microbiological Societies.

Organic carbon and reducing conditions lead to cadmium immobilization by secondary Fe mineral formation in a pH-neutral soil.

Science.gov (United States)

Muehe, E Marie; Adaktylou, Irini J; Obst, Martin; Zeitvogel, Fabian; Behrens, Sebastian; Planer-Friedrich, Britta; Kraemer, Ute; Kappler, Andreas

2013-01-01

Cadmium (Cd) is of environmental relevance as it enters soils via Cd-containing phosphate fertilizers and endangers human health when taken up by crops. Cd is known to associate with Fe(III) (oxyhydr)oxides in pH-neutral to slightly acidic soils, though it is not well understood how the interrelation of Fe and Cd changes under Fe(III)-reducing conditions. Therefore, we investigated how the mobility of Cd changes when a Cd-bearing soil is faced with organic carbon input and reducing conditions. Using fatty acid profiles and quantitative PCR, we found that both fermenting and Fe(III)-reducing bacteria were stimulated by organic carbon-rich conditions, leading to significant Fe(III) reduction. The reduction of Fe(III) minerals was accompanied by increasing soil pH, increasing dissolved inorganic carbon, and decreasing Cd mobility. SEM-EDX mapping of soil particles showed that a minor fraction of Cd was transferred to Ca- and S-bearing minerals, probably carbonates and sulfides. Most of the Cd, however, correlated with a secondary iron mineral phase that was formed during microbial Fe(III) mineral reduction and contained mostly Fe, suggesting an iron oxide mineral such as magnetite (Fe3O4). Our data thus provide evidence that secondary Fe(II) and Fe(II)/Fe(III) mixed minerals could be a sink for Cd in soils under reducing conditions, thus decreasing the mobility of Cd in the soil.

Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments.

Science.gov (United States)

Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

2015-11-01

A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration--a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder.

Reduction of a thin chromium oxide film on Inconel surface upon treatment with hydrogen plasma

Energy Technology Data Exchange (ETDEWEB)

Vesel, Alenka, E-mail: alenka.vesel@guest.arnes.si [Jozef Stefan Institute, Jamova cesta 39, 1000 Ljubljana (Slovenia); Mozetic, Miran [Jozef Stefan Institute, Jamova cesta 39, 1000 Ljubljana (Slovenia); Balat-Pichelin, Marianne [PROMES-CNRS Laboratory, 7 Rue du four solaire, 66120 Font Romeu Odeillo (France)

2016-11-30

Highlights: • Oxidized Inconel alloy was exposed to hydrogen at temperatures up to 1500 K. • Oxide reduction in hydrogen plasma started at approximately 1300 K. • AES depth profiling revealed complete reduction of oxides in plasma. • Oxides were not reduced, if the sample was heated just in hydrogen atmosphere. • Surface of reduced Inconel preserved the same composition as the bulk material. - Abstract: Inconel samples with a surface oxide film composed of solely chromium oxide with a thickness of approximately 700 nm were exposed to low-pressure hydrogen plasma at elevated temperatures to determine the suitable parameters for reduction of the oxide film. The hydrogen pressure during treatment was set to 60 Pa. Plasma was created by a surfaguide microwave discharge in a quartz glass tube to allow for a high dissociation fraction of hydrogen molecules. Auger electron depth profiling (AES) was used to determine the decay of the oxygen in the surface film and X-ray diffraction (XRD) to measure structural modifications. During hydrogen plasma treatment, the oxidized Inconel samples were heated to elevated temperatures. The reduction of the oxide film started at temperatures of approximately 1300 K (considering the emissivity of 0.85) and the oxide was reduced in about 10 s of treatment as revealed by AES. The XRD showed sharper substrate peaks after the reduction. Samples treated in hydrogen atmosphere under the same conditions have not been reduced up to approximately 1500 K indicating usefulness of plasma treatment.

Kinetics of oxidation of H2 and reduction of H2O in Ni-YSZ based solid oxide cells

DEFF Research Database (Denmark)

Ebbesen, Sune Dalgaard; Mogensen, Mogens Bjerg

2012-01-01

Reduction of H2O and oxidation of H2 was studied in a Ni-YSZ electrode supported Solid Oxide Cells produced at DTU Energy conversion (former Risø DTU). Polarisation (i-V) and electrochemical impedance spectroscopic characterisation show that the kinetics for reduction of H 2O is slower compared...... to oxidation of H2. The kinetic differences cannot be explained by the reaction mechanisms which are similar in the two cases but are rather an effect of the thermodynamics. The preliminary analysis performed in this study show that the slow kinetic for reduction is partly related to the endothermic nature...... of the reaction, cooling the active electrode, thereby leading to slower kinetics at low current densities. Likewise, the increased kinetic for oxidation was found to be related to the exothermic nature of the reaction, heating the active electrode, and thereby leading to faster kinetics. At higher current...

Iron Oxide Minerals in Atmospheric Dust and Source Sediments-Studies of Types and Properties to Assess Environmental Effects

Science.gov (United States)

Reynolds, R. L.; Goldstein, H. L.; Moskowitz, B. M.; Till, J. L.; Flagg, C.; Kokaly, R. F.; Munson, S.; Landry, C.; Lawrence, C. R.; Hiza, M. M.; D'Odorico, P.; Painter, T. H.

2011-12-01

Ferric oxide minerals in atmospheric dust can influence atmospheric temperatures, accelerate melting of snow and ice, stimulate marine phytoplankton productivity, and impact human health. Such effects vary depending on iron mineral type, size, surface area, and solubility. Generally, the presence of ferric oxides in dust is seen in the red, orange, or yellow hues of plumes that originate in North Africa, central and southwest Asia, South America, western North America, and Australia. Despite their global importance, these minerals in source sediments, atmospheric dust, and downwind aeolian deposits remain poorly described with respect to specific mineralogy, particle size and surface area, or presence in far-traveled aerosol compounds. The types and properties of iron minerals in atmospheric dust can be better understood using techniques of rock magnetism (measurements at 5-300 K), Mössbauer and high-resolution visible and near-infrared reflectance spectroscopy; chemical reactivity of iron oxide phases; and electron microscopy for observing directly the ferric oxide coatings and particles. These studies can elucidate the diverse environmental effects of iron oxides in dust and can help to identify dust-source areas. Dust-source sediments from the North American Great Basin and Colorado Plateau deserts and the Kalahari Desert, southern Africa, were used to compare average reflectance values with a magnetic parameter (hard isothermal remanent magnetization, HIRM) for ferric oxide abundance. Lower reflectance values correspond strongly with higher HIRM values, indicating that ferric oxides (hematite or goethite, or both) contribute to absorption of solar radiation in these sediments. Dust deposited to snow cover of the San Juan Mountains (Colorado) and Wasatch Mountains (Utah) was used to characterize dust composition compared with properties of sediments exposed in source-areas identified from satellite retrievals. Results from multiple methods indicate that

Dual passivation of intrinsic defects at the compound semiconductor/oxide interface using an oxidant and a reductant.

Science.gov (United States)

Kent, Tyler; Chagarov, Evgeniy; Edmonds, Mary; Droopad, Ravi; Kummel, Andrew C

2015-05-26

Studies have shown that metal oxide semiconductor field-effect transistors fabricated utilizing compound semiconductors as the channel are limited in their electrical performance. This is attributed to imperfections at the semiconductor/oxide interface which cause electronic trap states, resulting in inefficient modulation of the Fermi level. The physical origin of these states is still debated mainly because of the difficulty in assigning a particular electronic state to a specific physical defect. To gain insight into the exact source of the electronic trap states, density functional theory was employed to model the intrinsic physical defects on the InGaAs (2 × 4) surface and to model the effective passivation of these defects by utilizing both an oxidant and a reductant to eliminate metallic bonds and dangling-bond-induced strain at the interface. Scanning tunneling microscopy and spectroscopy were employed to experimentally determine the physical and electronic defects and to verify the effectiveness of dual passivation with an oxidant and a reductant. While subsurface chemisorption of oxidants on compound semiconductor substrates can be detrimental, it has been shown theoretically and experimentally that oxidants are critical to removing metallic defects at oxide/compound semiconductor interfaces present in nanoscale channels, oxides, and other nanostructures.

Improvement in grade of minerals using simultaneous Bio-oxidation of invisible gold concentrate and deep-sea manganese crust

Science.gov (United States)

Myung, EunJi; Cho, Kang Hee; Kim, Hyun Soo; Park, Cheon Young

2016-04-01

Many sulfides of metal such as galena, sphalerite, chalcopyrite, and pyrite, are semiconductors. When two kinds of such minerals contact each other in an electrolyte, a galvanic couple, where the mineral of lower rest potential as anode, and that of higher rest potential as cathode forms. Manganese dioxide is also a semiconductor with much higher rest potential than all sulfides mentioned above, so that a galvanic couple in which both the minerals would dissolve simultaneously can form, when it contacts with any of the sulfides. The aim of this study was to investigate the improvement in grade of minerals using the simultaneous bio-oxidation of deep-sea manganese crust and invisible gold concentrate. The samples(deep-sea manganese crust and invisible gold concentrate) were characterized by chemical and XRD analysis. The primary components of the invisible gold concentrate was pyrite and quartz and the deep-sea manganese crust was amorphous material, as detected using XRD. The result of chemical analysis showed that Au, Ag, Te contents in the invisible gold concentrate 130.2, 954.1 and 1,043.6 mg/kg, respectively. and that Mn, Ni, Co contents in the deep-sea manganese crust 19,501.5, 151.9, 400.4 mg/kg, respectively. In order to increase the bacteria's tolerance of heavy metals, the bacteria using bio-oxidation experiments were repeatedly subcultured in an Cu adaptation-medium containing of 382.98 mg/l for 20 periods of 21 days. The improvement in grade of samples of in present adapted bacteria condition was greater than another conditions(control and in present non-adapted bacteria). The Au-Ag-Te contents in the invisible gold concentrate was enhanced in the order of physical oxidation, simultaneous/non-adaptive bio-oxidation, adaptive/bio-oxidation, simultaneous/adaptive bio-oxidation. If the bacteria is adapted to heavy metal ions and an optimization of conditions is found in future bio-oxidation-leaching processes. Acknowledgment : "This research was supported

The Upper Permian sandstones of Mountains Mecsek: form elements of uranium ore mineralization and facies relations Pt. 2

International Nuclear Information System (INIS)

Vincze, Janos; Somogyi, Janos

1984-01-01

The ore mineralization in the Upper Permian sandstones of Mountais Mecsek, Hungary, was brought about at the oxidation-reduction front between the grey and red sandstones; the predominant rock colour here is green. The sandstones of different colour are oxidation-reduction species. The formation is a megacycle containing in its core grey sandstones of reduced state with coalified plant remains and in its mantle oxidized red sandstones. Uranium accumulates mainly in the transitional green facies. Uranium content gets enriched to a commercial concentration only if the difference in potential of neighbouring beds is in the range of 400-480 mV. The relationship between organic matter and uranium content in the individual facies is shown. The principles of oxidation-reduction processes in the formation of boundary facies are discussed. (V.N.)

Direct chemical reduction of neptunium oxide to neptunium metal using calcium and calcium chloride

International Nuclear Information System (INIS)

Squires, Leah N.; Lessing, Paul

2016-01-01

A process of direct reduction of neptunium oxide to neptunium metal using calcium metal as the reducing agent is discussed. After reduction of the oxide to metal, the metal is separated by density from the other components of the reaction mixture and can be easily removed upon cooling. The direct reduction technique consistently produces high purity (98%–99% pure) neptunium metal.

Influence of tropical leaf litter on nitrogen mineralization and community structure of ammonia-oxidizing bacteria

Directory of Open Access Journals (Sweden)

Diallo, MD.

2015-01-01

Full Text Available Description of the subject. The present study concerns the relationships among leaf litter decomposition, substrate quality, ammonia-oxidizing bacteria (AOB community composition and nitrogen (N availability. Decomposition of organic matter affects the biogeochemical cycling of carbon (C and N. Since the composition of the soil microbial community can alter the physiological capacity of the community, it is timely to study the litter quality effect on N dynamic in ecosystems. Objectives. The aim of this study was to determine the influence of leaf litter decomposition on N mineralization. The specific objectives of this study were to evaluate the influence of the litter biochemistry of five plants species (Faidherbia albida A.Chev., Azadirachta indica A.Juss., Casuarina equisetifolia L., Andropogon gayanus Kunth and Eragrostis tremula Hochst. ex Steud. on N mineralization in a tropical ferrous soil (Lixisol, nitrification, and genetic diversity of ammonia-oxidizing bacteria. Denaturing gradient gel electrophoresis (DGGE of amplified fragments of genes coding for 16S rRNA was used to study the development of bacterial communities during decomposition of leaf litter in soils. Method. Community structure of AOB was determined at two time periods: day 0 and day 140. Ten strains were tested and each of these strains produced a single band. Thus, DGGE DNA band patterns were used to estimate bacterial diversity. Plant secondary compounds such as polyphenols are purported to influence nutrient cycling by affecting organic matter degradation, mineralization rates, N availability and humus formation. In a laboratory study, we investigated the influence of six phenolic acids (ferulic, gallic, vanillic, syringic, p-coumaric and p-HBA acids commonly found in the plant residues on N mineralization and NH4+ and NO3- production in soils. Results. The results showed that litter type did affect soil nitrification. Faidherbia albida litter was associated with

Advanced Chemical Reduction of Reduced Graphene Oxide and Its Photocatalytic Activity in Degrading Reactive Black 5

Directory of Open Access Journals (Sweden)

Christelle Pau Ping Wong

2015-10-01

Full Text Available Textile industries consume large volumes of water for dye processing, leading to undesirable toxic dyes in water bodies. Dyestuffs are harmful to human health and aquatic life, and such illnesses as cholera, dysentery, hepatitis A, and hinder the photosynthetic activity of aquatic plants. To overcome this environmental problem, the advanced oxidation process is a promising technique to mineralize a wide range of dyes in water systems. In this work, reduced graphene oxide (rGO was prepared via an advanced chemical reduction route, and its photocatalytic activity was tested by photodegrading Reactive Black 5 (RB5 dye in aqueous solution. rGO was synthesized by dispersing the graphite oxide into the water to form a graphene oxide (GO solution followed by the addition of hydrazine. Graphite oxide was prepared using a modified Hummers’ method by using potassium permanganate and concentrated sulphuric acid. The resulted rGO nanoparticles were characterized using ultraviolet-visible spectrophotometry (UV-Vis, X-ray powder diffraction (XRD, Raman, and Scanning Electron Microscopy (SEM to further investigate their chemical properties. A characteristic peak of rGO-48 h (275 cm−1 was observed in the UV spectrum. Further, the appearance of a broad peak (002, centred at 2θ = 24.1°, in XRD showing that graphene oxide was reduced to rGO. Based on our results, it was found that the resulted rGO-48 h nanoparticles achieved 49% photodecolorization of RB5 under UV irradiation at pH 3 in 60 min. This was attributed to the high and efficient electron transport behaviors of rGO between aromatic regions of rGO and RB5 molecules.

The flotation and adsorption of mixed collectors on oxide and silicate minerals.

Science.gov (United States)

Xu, Longhua; Tian, Jia; Wu, Houqin; Lu, Zhongyuan; Sun, Wei; Hu, Yuehua

2017-12-01

The analysis of flotation and adsorption of mixed collectors on oxide and silicate minerals is of great importance for both industrial applications and theoretical research. Over the past years, significant progress has been achieved in understanding the adsorption of single collectors in micelles as well as at interfaces. By contrast, the self-assembly of mixed collectors at liquid/air and solid/liquid interfaces remains a developing area as a result of the complexity of the mixed systems involved and the limited availability of suitable analytical techniques. In this work, we systematically review the processes involved in the adsorption of mixed collectors onto micelles and at interface by examining four specific points, namely, theoretical background, factors that affect adsorption, analytical techniques, and self-assembly of mixed surfactants at the mineral/liquid interface. In the first part, the theoretical background of collector mixtures is introduced, together with several core solution theories, which are classified according to their application in the analysis of physicochemical properties of mixed collector systems. In the second part, we discuss the factors that can influence adsorption, including factors related to the structure of collectors and environmental conditions. We summarize their influence on the adsorption of mixed systems, with the objective to provide guidance on the progress achieved in this field to date. Advances in measurement techniques can greatly promote our understanding of adsorption processes. In the third part, therefore, modern techniques such as optical reflectometry, neutron scattering, neutron reflectometry, thermogravimetric analysis, fluorescence spectroscopy, ultrafiltration, atomic force microscopy, analytical ultracentrifugation, X-ray photoelectron spectroscopy, Vibrational Sum Frequency Generation Spectroscopy and molecular dynamics simulations are introduced in virtue of their application. Finally, focusing on

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

Science.gov (United States)

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.

Method for Transformation of Weakly Magnetic Minerals (Hematite, Goethite into Strongly Magnetic Mineral (Magnetite to Improve the Efficiency of Technologies for Oxidized Iron Ores Benefication

Directory of Open Access Journals (Sweden)

Ponomarenko, O.

2015-03-01

Full Text Available A new method for relatively simple transformation of weakly magnetic minerals (goethite (α-FeOOH and hematite (α-Fe2O3 into strongly magnetic mineral (magnetite (Fe3O4 was developed. It was shown, that transformation of structure and magnetic characteristics of go ethite and hematite are realized in the presence of starch at relatively low temperatures (in the range of 300—600 °С. Obtained results open up new possibilities for development of effective technologies for oxidized iron ore beneficiation.

Nitric oxide reduction and oxidation on stepped Pt[n(111)x(111)] electrodes

NARCIS (Netherlands)

Beltramo, G.L.; Koper, M.T.M.

2003-01-01

The structure sensitivity of the reduction and oxidation of saturated and subsaturated NO adlayers has been studied on a series of stepped Pt[n(111)×(111)] electrodes by cyclic and stripping voltammetry experiments in sulfuric and perchloric acid solution. In agreement with earlier experimental

Development of metallic uranium recovery technology from uranium oxide by Li reduction and electrorefining

International Nuclear Information System (INIS)

Tokiwai, Moriyasu; Kawabe, Akihiro; Yuda, Ryouichi; Usami, Tsuyoshi; Fujita, Reiko; Nakamura, Hitoshi; Yahata, Hidetsugu

2002-01-01

The purpose of the study is to develop technology for pre-treatment of oxide fuel reprocessing through pyroprocess. In the pre-treatment process, it is necessary to reduce actinide oxide to metallic form. This paper outlines some experimental results of uranium oxide reduction and recovery of refined metallic uranium in electrorefining. Both uranium oxide granules and pellets were used for the experiments. Uranium oxide granules was completely reduced by lithium in several hours at 650degC. Reduced uranium pellets by about 70% provided a simulation of partial reduction for the process flow design. Almost all adherent residues of Li and Li 2 O were successfully washed out with fresh LiCl salt. During electrorefining, metallic uranium deposited on the iron cathode as expected. The recovery efficiencies of metallic uranium from reduced uranium oxide granules and from pellets were about 90% and 50%, respectively. The mass balance data provided the technical bases of Li reduction and refining process flow for design. (author)

Reduction of Ferrrihydrite and Akaganeite by Shewanella alga (PAH93)

Science.gov (United States)

Jung, M.; Kim, Y.; Lee, Y.; Kwon, K.; Roh, Y.

2009-12-01

Shewanella species are capable of oxidizing diverse organic acids coupled to reducing Fe(III) (oxy)hydroxides to crystalline Fe(II)-containing phases such as magnetite, siderite, and vivianite. The objective of this study was to examine reduction of ferrihydrite and akaganeite as the electron acceptors using various organic acids as the electron donors by Shewanella alga (PAH93) isolated from Yeosu, South Korea. Microbial reduction of akaganeite (40 mM) and ferrihydrite (40 mM) was examined using acetate (10 mM), glucose (10 mM), and lactate (10 mM) as electron donors at room temperature. Ferrozine method was used to analyze both water soluble and HCl soluble Fe(II) concentrations during the microbial Fe(III) reduction. XRD and TEM-EDX analyses were used to characterize biominerals formed by PAH93. PAH93 was completely reduced ferrihydrite to Fe(II), which transformed as siderite (FeCO3). PAH93 was oxidized acetate, glucose, and lactate coupled to reducing akaganeite to magnetite or green rust. Microbial reduction of ferrihydrite resulted in higher soluble Fe(II) concentration (446 - 498 mg/L) than the reduction of akaganeite (255 - 284 mg/L) within 6 days of incubation. For 21 days of incubation, souble Fe(II) concentration during akaganeite reduction (945 - 1316 mg/L) was higher than ferrihydrite reduction (120 - 738 mg/L). It may be attributed to the differences of crystallinity of the iron minerals used for microbial iron reduction. This study indicates types of the electron acceptors, ferrihydrite and akaganeite, affect Fe(II) reduction rate and types of the biotransformed minerals.

Simultaneous reduction and nitrogen functionalization of graphene oxide using lemon for metal-free oxygen reduction reaction

Science.gov (United States)

Begum, Halima; Ahmed, Mohammad Shamsuddin; Cho, Sung; Jeon, Seungwon

2017-12-01

Inspire by the vision of finding a simple and green method for simultaneous reduction and nitrogen (N)-functionalization of graphene oxide (GO), a N-rich reduced graphene oxide (rGO) has been synthesized through a facile and ecofriendly hydrothermal strategy while most of the existing methods are involving with multiple steps and highly toxic reducing agents that are harmful to human health and environment. In this paper, the simultaneous reduction and N-functionalization of GO using as available lemon juice (denoted as Lem-rGO) for metal-free electrocatalysis towards oxygen reduction reaction (ORR) is described. The proposed method is based on the reduction of GO using of the reducing and the N-precursor capability of ascorbic acid and citric acid as well as the nitrogenous compounds, respectively, that containing in lemon juice. The resultant Lem-rGO has higher reduction degree, higher specific surface area and better crystalline nature with N-incorporation than that of well investigated ascorbic acid and citric acid treated rGO. As a result, it shows better ORR electrocatalytic activity in respect to the improved onset potential, electron transfer rate and kinetics than those typical rGO catalysts. Moreover, it shows a significant tolerance to the anodic fuels and durability than the Pt/C during ORR.

In-situ sequential laser transfer and laser reduction of graphene oxide films

Science.gov (United States)

Papazoglou, S.; Petridis, C.; Kymakis, E.; Kennou, S.; Raptis, Y. S.; Chatzandroulis, S.; Zergioti, I.

2018-04-01

Achieving high quality transfer of graphene on selected substrates is a priority in device fabrication, especially where drop-on-demand applications are involved. In this work, we report an in-situ, fast, simple, and one step process that resulted in the reduction, transfer, and fabrication of reduced graphene oxide-based humidity sensors, using picosecond laser pulses. By tuning the laser illumination parameters, we managed to implement the sequential printing and reduction of graphene oxide flakes. The overall process lasted only a few seconds compared to a few hours that our group has previously published. DC current measurements, X-Ray Photoelectron Spectroscopy, X-Ray Diffraction, and Raman Spectroscopy were employed in order to assess the efficiency of our approach. To demonstrate the applicability and the potential of the technique, laser printed reduced graphene oxide humidity sensors with a limit of detection of 1700 ppm are presented. The results demonstrated in this work provide a selective, rapid, and low-cost approach for sequential transfer and photochemical reduction of graphene oxide micro-patterns onto various substrates for flexible electronics and sensor applications.

Low-temperature, mineral-catalyzed air oxidation: a possible new pathway for PAH stabilization in sediments and soils.

Science.gov (United States)

Ghislain, Thierry; Faure, Pierre; Biache, Coralie; Michels, Raymond

2010-11-15

Reactivity of polycyclic aromatic hydrocarbons (PAHs) in the subsurface is of importance to environmental assessment, as they constitute a highly toxic hazard. Understanding their reactivity in the long term in natural recovering systems is thus a key issue. This article describes an experimental investigation on the air oxidation of fluoranthene (a PAH abundant in natural systems polluted by industrial coal use) at 100°C on different mineral substrates commonly found in soils and sediments (quartz sand, limestone, and clay). Results demonstrate that fluoranthene is readily oxidized in the presence of limestone and clay, leading to the formation of high molecular weight compounds and a carbonaceous residue as end product especially for clay experiments. As demonstrated elsewhere, the experimental conditions used permitted the reproduction of the geochemical pathway of organic matter observed under natural conditions. It is therefore suggested that low-temperature, mineral-catalyzed air oxidation is a mechanism relevant to the stabilization of PAHs in sediments and soils.

Pyro-Electrochemical Reduction of a Mixture of Rare Earth Oxides and NiO in LiCl molten Salt

Energy Technology Data Exchange (ETDEWEB)

Lee, Min Woo; Jeong, Sang Mun [Department of Chemical Engineering, Chungbuk National University, Cheongju (Korea, Republic of)

2017-06-15

An electrochemical reduction of a mixture of NiO and rare earth oxides has been conducted to increase the reduction degree of rare earth oxides. Cyclic voltammetry (CV) measurement was carried out to determine the electrochemical reduction behavior of the mixed oxide in molten LiCl medium. Constant voltage electrolysis was performed with various supplied charges to understand the mechanism of electrochemical reduction of the mixed oxide as a working electrode. After completion of the electrochemical reduction, crystal structure of the reaction intermediates was characterized by using an X-ray diffraction method. The results clearly demonstrate that the rare earth oxide was converted to RE-Ni intermetallics via co-reduction with NiO.

Localized conductive patterning via focused electron beam reduction of graphene oxide

Energy Technology Data Exchange (ETDEWEB)

Kim, Songkil; Henry, Mathias [George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Kulkarni, Dhaval D.; Zackowski, Paul; Jang, Seung Soon; Tsukruk, Vladimir V. [School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Fedorov, Andrei G., E-mail: agf@gatech.edu [George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Parker H. Petit Institute for Bioengineering and Bioscience, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States)

2015-03-30

We report on a method for “direct-write” conductive patterning via reduction of graphene oxide (GO) sheets using focused electron beam induced deposition (FEBID) of carbon. FEBID treatment of the intrinsically dielectric graphene oxide between two metal terminals opens up the conduction channel, thus enabling a unique capability for nanoscale conductive domain patterning in GO. An increase in FEBID electron dose results in a significant increase of the domain electrical conductivity with improving linearity of drain-source current vs. voltage dependence, indicative of a change of graphene oxide electronic properties from insulating to semiconducting. Density functional theory calculations suggest a possible mechanism underlying this experimentally observed phenomenon, as localized reduction of graphene oxide layers via interactions with highly reactive intermediates of electron-beam-assisted dissociation of surface-adsorbed hydrocarbon molecules. These findings establish an unusual route for using FEBID as nanoscale lithography and patterning technique for engineering carbon-based nanomaterials and devices with locally tailored electronic properties.

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

Energy Technology Data Exchange (ETDEWEB)

Chan, Clara Sze-Yue [Univ. of Delaware, Newark, DE (United States)

2015-07-02

Fe oxidation and biomineral formation is important in aquifers because the highly-reactive oxides can control the mobility of nutrients (e.g. phosphate, C) and metals (e.g. arsenic, uranium). Mineral formation also has the potential to affect hydrology, depending on the volume and distribution in pore spaces. In this exploratory study, we sought to understand how microbial Fe-oxidizers and their biominerals affect, and are affected by groundwater flow. As part of work at the Rifle aquifer in Colorado, we initially hypothesized that Fe-oxidizers were contributing to aquifer clogging problems associated with enhanced bioremediation. To demonstrate the presence of Fe-oxidizers in the Rifle aquifer, we enriched FeOM from groundwater samples, and isolated two novel chemolithotrophic, microaerophilic Fe-oxidizing Betaproteobacteria, Hydrogenophaga sp. P101 and Curvibacter sp. CD03. To image cells and biominerals in the context of pores, we developed a “micro-aquifer,” a sand-filled flow-through culture chamber that allows for imaging of sediment pore space with multiphoton confocal microscopy. Fe oxide biofilms formed on sand grains, demonstrating that FeOM produce Fe oxide sand coatings. Fe coatings are common on aquifer sands, and tend to sequester contaminants; however, it has never previously been shown that microbes are responsible for their formation. In contrast to our original hypothesis, the biominerals did not clog the mini-aquifer. Instead, Fe biofilm distribution was dynamic: they grew as coatings, then periodically sloughed off sand grains, with some flocs later caught in pore throats. This has implications for physical hydrology, including pore scale architecture, and element transport. The sloughing of coatings likely prevents the biominerals from clogging wells and aquifers, at least initially. Although attached biomineral coatings sequester Fe-associated elements (e.g. P, As, C, U), when biominerals detach, these elements are transported as particles

Isothermal Oxidation of Magnetite to Hematite in Air and Cyclic Reduction/Oxidation Under Carbon Looping Combustion Conditions

Science.gov (United States)

Simmonds, Tegan; Hayes, Peter C.

2017-12-01

In the carbon looping combustion process the oxygen carrier is regenerated through oxidation in air; this process has been simulated by the oxidation of dense synthetic magnetite for selected temperatures and times. The oxidation of magnetite in air is shown to occur through the formation of dense hematite layers on the particle surface. This dense hematite forms through lath type shear transformations or solid-state diffusion through the product layer. Cyclic reduction in CO-CO2/oxidation in air of hematite single crystals has been carried out under controlled laboratory conditions at 1173 K (900 °C). It has been shown that the initial reduction step is critical to determining the product microstructure, which consists of gas pore dendrites in the magnetite matrix with blocky hematite formed on the pore surfaces. The progressive growth of the magnetite layer with the application of subsequent cycles appears to continue until no original hematite remains, after which physical disintegration of the particles takes place.

Carbon mineralization and pyrite oxidation in groundwater: Importance for silicate weathering in boreal forest soils and stream base-flow chemistry

International Nuclear Information System (INIS)

Klaminder, J.; Grip, H.; Moerth, C.-M.; Laudon, H.

2011-01-01

Research highlights: → Organic compounds is mineralized during later transport in deep groundwater aquifers. → Carbonic acid generated by this process stimulates dissolution of silicate minerals. → Protons derived from pyrite oxidation also affects weathering in deep groundwater. → The identified weathering mechanisms affect base-flow chemistry in boreal streams. - Abstract: What role does mineralized organic C and sulfide oxidation play in weathering of silicate minerals in deep groundwater aquifers? In this study, how H 2 CO 3 , produced as a result of mineralization of organic matter during groundwater transport, affects silicate weathering in the saturated zone of the mineral soil along a 70 m-long boreal hillslope is demonstrated. Stream water measurements of base cations and δ 18 O are included to determine the importance of the deep groundwater system for downstream surface water. The results suggest that H 2 CO 3 generated from organic compounds being mineralized during the lateral transport stimulates weathering at depths between 0.5 and 3 m in the soil. This finding is indicated by progressively increasing concentrations of base cations-, silica- and inorganic C (IC) in the groundwater along the hillslope that co-occur with decreasing organic C (OC) concentrations. Protons derived from sulfide oxidation appear to be an additional driver of the weathering process as indicated by a build-up of SO 4 2- in the groundwater during lateral transport and a δ 34 S per mille value of +0.26-3.76 per mille in the deep groundwater indicating S inputs from pyrite. The two identified active acids in the deep groundwater are likely to control the base-flow chemistry of streams draining larger catchments (>1 km 2 ) as evident by δ 18 O signatures and base cation concentrations that overlap with that of the groundwater.

Carbon mineralization and pyrite oxidation in groundwater: Importance for silicate weathering in boreal forest soils and stream base-flow chemistry

Energy Technology Data Exchange (ETDEWEB)

Klaminder, J., E-mail: jonatan.klaminder@emg.umu.se [Department of Forest Ecology and Management, SLU, SE-901 83 Umea (Sweden)] [Department of Ecology and Environmental Science, Umea University, SE-901 87 (Sweden); Grip, H. [Department of Forest Ecology and Management, SLU, SE-901 83 Umea (Sweden); Moerth, C.-M. [Department of Geological Sciences, Stockholm University, 106 91 Stockholm (Sweden); Laudon, H. [Department of Forest Ecology and Management, SLU, SE-901 83 Umea (Sweden)

2011-03-15

Research highlights: {yields} Organic compounds is mineralized during later transport in deep groundwater aquifers. {yields} Carbonic acid generated by this process stimulates dissolution of silicate minerals. {yields} Protons derived from pyrite oxidation also affects weathering in deep groundwater. {yields} The identified weathering mechanisms affect base-flow chemistry in boreal streams. - Abstract: What role does mineralized organic C and sulfide oxidation play in weathering of silicate minerals in deep groundwater aquifers? In this study, how H{sub 2}CO{sub 3}, produced as a result of mineralization of organic matter during groundwater transport, affects silicate weathering in the saturated zone of the mineral soil along a 70 m-long boreal hillslope is demonstrated. Stream water measurements of base cations and {delta}{sup 18}O are included to determine the importance of the deep groundwater system for downstream surface water. The results suggest that H{sub 2}CO{sub 3} generated from organic compounds being mineralized during the lateral transport stimulates weathering at depths between 0.5 and 3 m in the soil. This finding is indicated by progressively increasing concentrations of base cations-, silica- and inorganic C (IC) in the groundwater along the hillslope that co-occur with decreasing organic C (OC) concentrations. Protons derived from sulfide oxidation appear to be an additional driver of the weathering process as indicated by a build-up of SO{sub 4}{sup 2-} in the groundwater during lateral transport and a {delta}{sup 34}S per mille value of +0.26-3.76 per mille in the deep groundwater indicating S inputs from pyrite. The two identified active acids in the deep groundwater are likely to control the base-flow chemistry of streams draining larger catchments (>1 km{sup 2}) as evident by {delta}{sup 18}O signatures and base cation concentrations that overlap with that of the groundwater.

Effects of manganese oxide on arsenic reduction and leaching from contaminated floodplain soil

DEFF Research Database (Denmark)

Ehlert, Katrin; Mikutta, Christian; Kretzschmar, Ruben

2016-01-01

Reductive release of the potentially toxic metalloid As from Fe(III) (oxyhydr)oxides has been identified as an important process leading to elevated As porewater concentrations in soils and sediments. Despite the ubiquitous presence of Mn oxides in soils and their oxidizing power toward As.......7) on As speciation and release from an As-contaminated floodplain soil (214 mg As/kg) under anoxic conditions. Our results show that birnessite additions significantly decreased As leaching. The reduction of both As and Fe was delayed, and As(III) accumulated in birnessite-rich column parts, indicating...

A Study on Electrochemical Reduction of Rare Earth Oxides in Molten LiCl-Li{sub 2}O Salt

Energy Technology Data Exchange (ETDEWEB)

Lee, Min Woo; Jeong, Sang Mun; Lee, See Hoon [Chungbook National University, Chungju (Korea, Republic of); Sohn, Jung Min [Chonbuk National University, Jeonju (Korea, Republic of)

2016-05-15

In this study, the electrochemical reduction of RE{sub 2}O{sub 3} (RE = Nd or Ce) has been conducted via co-reduction NiO to increase the reduction degree of the rare earth oxides in molten molten LiCl containing 1wt% Li{sub 2}O. The electrochemical reduction behavior of the mixed RE{sub 2}O{sub 3}-NiO oxide has been investigated and the reduction path of RE{sub 2}O{sub 3} has been proposed. An electorchemical spent fuel processing technology, pyroprocessing, has been developed for recycling of spent fuel to be applied to a sodium-cooled fast reactor. The spent fuel is reduced in the oxide reduction process. It is well known that the rare earth oxides are hardly reduced due to their electrochemical and thermodynamic stability. The rare earth oxides unreduced in the reduction process can cause problems via reaction with UCl{sub 3} in the electrorefiner. To tackle those problems, the electrochemical reduction of rare earth oxide has been conducted via co-reduction of NiO in LiCl molten salt containing 1 wt% Li{sub 2}O. The reduction of the oxide mixture starts from the reduction of NiO to Ni, followed by that of RE{sub 2}O{sub 3} on the produced Ni to form intermetallic RENi{sub 5}. The mixed oxide pellets were successfully reduced to the RENi5 alloy by constant electrolysis at 3.0 V at 650 .deg. C. The crucial aspect to these results is that the thermodynamically stable rare-earth oxide, Nd{sub 2}O{sub 3} was successfully converted to the metal in the presence of NiO.

Molecular-Level Processes Governing the Interaction of Contaminants with Iron and Manganese Oxides - Final Report; FINAL

International Nuclear Information System (INIS)

Brown, G. E. Jr.; Chambers, S. A.

1999-01-01

Many of the inorganic and organic contaminants present in sediments at DOE sites can be altered or destroyed by reduction and oxidation (redox) reactions occurring at mineral surfaces. A fundamental understanding of such redox processes provided by molecular-level studies on structurally and compositionally well-defined mineral surfaces will lead to: (i) improved models of contaminant fate and transport in geochemical systems, and (ii) optimized manipulation of these processes for remediation purposes. To contribute to this understanding, we will study, both experimentally and theoretically, redox processes involving three important contaminants - chromate ion, carbon tetrachloride, and trichloroethene TCE, on the following iron and manganese oxides - hematite, magnetite, maghemite, and pyrolusite. These oxides and their hydroxylated analogs commonly occur as coatings on minerals or as interfaces in the subsurface environment. Single-crystal surfaces of these oxides will be synthesized in carefully controlled fashion by molecular beam epitaxy. These surfaces, as well as high surface are powdered samples of these oxides, will be used in spectroscopic and kinetic experiments in both aqueous and gas phases. Our goal is to identify products and to determine the kinetics and mechanisms of surface-catalyzed redox reaction of Cr(VI) and CR(III), and the reductive dechlorination of carbon tetrachloride and TCE. The combination of theory and experiment will provide the base information needed to scale from the molecular level to the microscopic grain level minerals

Thermodynamic analysis of the reduction process of Colombian lateritic nickel ore

International Nuclear Information System (INIS)

Diaz, S. C.; Garces, A.; Restrepo, O. J.; Lara, M. A.; Camporredondo, J. E.

2015-01-01

The Colombian nickeliferous laterites are minerals used for the nickel extraction by hydrometallurgical and pyrometallurgical processes. In this work the thermodynamic behaviour of three Colombian lateritic mineral samples are described, with contents of 1.42%, 1.78% y 2.04% of nickel, when they are subjected to the calcination and reduction processes. The mineral was characterized using X Rays Diffraction and X Rays Fluorescence, giving evidence of the presence of mineralogical species such as nepouite (Ni 3 Si 2 O 5 (OH) 4 ), goethite (Fe 2 O 3 .H 2 O), silica (SiO 2 ), antigorite (Mg 3 Si 2 O 5 (OH) 4 ) and fosferite (Mg 2 SiO 4 ). The thermodynamic analysis was conducted using the software HSC Chemistry for Windows 5.1 and was focused in the quantitative determination of the chemical evolution of the mixture of these minerals with variable quantities of coal, in function of temperature. The results produced by the program showed, in the equilibrium, the feasibility of complete reduction of the nickel, and additionally, a considerable high percentage of reduction of iron oxides (up to 99%) using ratio C/O .1 at temperatures close to 1100 degree centigrade. (Author)

Mode of distribution of uranium mineralization and sequence of the formation of minerals in albitites

International Nuclear Information System (INIS)

Grechishnikov, N.P.; Kramar, O.A.; Rapovich, F.I.

1985-01-01

On the basis of analysis and generalization of factural material data on the distribution nature of accessory uranium mineralization in albitites permitting to judge of the role and textural-structural peculiarities of enclosing rocks in mineralization localization are given. It is shown that the uranium mineral formation is closely related with the albitite formation and proceeded during two stages. A main mass of primary uranium minerals (brannerites and uraninites) in the form of impregnated mineralization was formed during the first uraninite-brannerite-albitite stage. Uranium oxides, silicates and titanates in the shape of veines formed. During the second coffinite-pitchblende-chloritic stage the formation of uranium oxides, silicates and titanates occured. Uranium mineralization in albitites developes in zones of cataclasm, small jointing, mylonitization localizing in fine-grained aggregates. A main mass of primary uranium minerals in albitites (brannerite, uraninite relates to neogenic during metasomatosis dark-coloured minerals (riebenite, aegirine, chlorite)

Nanoscale Phase Stability Reversal During the Nucleation and Growth of Titanium Oxide Minerals

Science.gov (United States)

Hummmer, D. R.; Heaney, P. J.; Kubicki, J. D.; Kent, P. R.; Post, J. E.

2008-12-01

Fine-grained titanium oxide minerals are important in soils, where they affect a variety of geochemical processes. They are also industrially important as catalysts, pigments, food additives, and dielectrics. Recent research has indicated an apparent reversal of thermodynamic stability between TiO2 phases at the nanoscale thought to be caused by an increased contribution of surface energy to the total free energy. Time-resolved X-ray diffraction (XRD) experiments in which titanium oxides crystallize from aqueous TiCl4 solutions confirm that anatase, a metastable phase, is always the first phase to nucleate under our range of initial conditions. Rutile peaks are observed only minutes after the first appearance of anatase, after which anatase abundance slowly decreases while rutile continues to form. Whole pattern refinement of diffraction data reveals that lattice constants of both phases increase throughout the crystallization process. In addition, transmission electron microscope (TEM) observations and kinetic modeling indicate that anatase does not undergo a solid-state transformation to the rutile structure as once thought. Instead, anatase appears to re-dissolve and then feed the growth of already nucleated rutile nanocrystals. Density functional theory (DFT) calculations were employed to model 1, 2, and 3 nm particles of both mineral phases. The total surface energies calculated from these models did yield lower values for anatase than for rutile by 8-13 kJ/mol depending on particle size, indicating that surface free energy is sufficient to account for stability reversal. However, these whole-particle surface energies were much higher than the sum of energies of each particle's constituent crystallographic surfaces. We attribute the excess energy to defects associated with the edges and corners of nanoparticles, which are not present on a 2-D periodic surface. This previously unreported edge and corner energy may play a dominant role in the stability reversal

Unusual nonlinear absorption response of graphene oxide in the presence of a reduction process

International Nuclear Information System (INIS)

Karimzadeh, Rouhollah; Arandian, Alireza

2015-01-01

The nonlinear absorption responses of graphene, graphene oxide and reduced graphene oxide are investigated using the Z-scan technique and laser beams at 405, 532 and 635 nm in a continuous wave regime. Results show that graphene, graphene oxide and reduced graphene oxide do not show any open Z-scan signals at wavelengths of 532 and 635 nm. At the same time, fresh graphene oxide suspension is found to exhibit a nonlinear absorption process in the case of a laser light at 405 nm. Moreover, it can be observed that the reduction of graphene oxide by 405 nm laser irradiation decreases its nonlinear absorption value significantly. These findings highlight the important role of the reduction process on the nonlinear absorption performance of graphene oxide. (letter)

Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at Uranium

OpenAIRE

Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; Mcinnes, Eric; Tuna, Floriana; Wooles, Ashley; Maron, Laurent; Liddle, Stephen

2017-01-01

Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here, we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido compl...

Effect of hydrogen peroxide and camellia sinensis extract on reduction of oxygen level in graphene oxide

Science.gov (United States)

Celina Selvakumari, J.; Dhanalakshmi, J.; Pathinettam Padiyan, D.

2016-10-01

The intention of this work is to reduce the oxygen level in graphene oxide. The reduction process was initiated while preparing graphene oxide using modified Hummer’s method. In this new method, increase in hydrogen peroxide concentration during the preparation process results in the oxygen content reduction. Adding green tea (camellia sinensis) extract with increased hydrogen peroxide results in further reduction of oxygen content and changed the graphene oxide to reduced graphene oxide. The structural and optical properties of the new found reduced graphene oxide was analysed using XRD, FTIR, TEM, Raman and UV-vis spectra. The overall observation reflects that the sp3 carbon network of graphene oxide changed into sp2 carbon lattice of graphene which is very handful in supercapacitor and biosensor fields.

Cell oxidation-reduction imbalance after modulated radiofrequency radiation.

Science.gov (United States)

Marjanovic, Ana Marija; Pavicic, Ivan; Trosic, Ivancica

2015-01-01

Aim of this study was to evaluate an influence of modulated radiofrequency field (RF) of 1800 MHz, strength of 30 V/m on oxidation-reduction processes within the cell. The assigned RF field was generated within Gigahertz Transversal Electromagnetic Mode cell equipped by signal generator, modulator, and amplifier. Cell line V79, was irradiated for 10, 30, and 60 min, specific absorption rate was calculated to be 1.6 W/kg. Cell metabolic activity and viability was determined by MTT assay. In order to define total protein content, colorimetric method was used. Concentration of oxidised proteins was evaluated by enzyme-linked immunosorbent assay. Reactive oxygen species (ROS) marked with fluorescent probe 2',7'-dichlorofluorescin diacetate were measured by means of plate reader device. In comparison with control cell samples, metabolic activity and total protein content in exposed cells did not differ significantly. Concentrations of carbonyl derivates, a product of protein oxidation, insignificantly but continuously increase with duration of exposure. In exposed samples, ROS level significantly (p < 0.05) increased after 10 min of exposure. Decrease in ROS level was observed after 30-min treatment indicating antioxidant defence mechanism activation. In conclusion, under the given laboratory conditions, modulated RF radiation might cause impairment in cell oxidation-reduction equilibrium within the growing cells.

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

International Nuclear Information System (INIS)

Maurice, P.

2004-01-01

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

Pathways of carbon oxidation in continental margin sediments off central Chile

DEFF Research Database (Denmark)

Thamdrup, B; Canfield, Donald Eugene

1996-01-01

Rates and oxidative pathways of organic carbon mineralization were determined in sediments at six stations on the shelf and slope off Concepcion Bay at 36.5 degrees S. The depth distribution of C oxidation rates was determined to 10 cm from accumulation of dissolved inorganic C in 1-5-d incubations...... the shelf was rich in NO3- and depleted of O2. Sediments at the four shelf stations were covered by mats of filamentous bacteria of the genera Thioploca and Beggiatoa. Carbon oxidation rates at these sites were extremely high near the sediment surface (>3 micromol cm-3 d-1) and decreased exponentially...... C oxidation between 0 and 10 cm. Carbon oxidation through Fe reduction contributed a further 12-29% of the depth-integrated rate, while the remainder of C oxidation was through SO4(2-) reduction. The depth distribution of Fe reduction agreed well with the distribution of poorly crystalline Fe oxides...

Nanoscale reduction of graphene oxide thin films and its characterization.

Science.gov (United States)

Lorenzoni, M; Giugni, A; Di Fabrizio, E; Pérez-Murano, Francesc; Mescola, A; Torre, B

2015-07-17

In this paper, we report on a method to reduce thin films of graphene oxide (GO) to a spatial resolution better than 100 nm over several tens of micrometers by means of an electrochemical scanning probe based lithography. In situ tip-current measurements show that an edged drop in electrical resistance characterizes the reduced areas, and that the reduction process is, to a good approximation, proportional to the applied bias between the onset voltage and the saturation thresholds. An atomic force microscope (AFM) quantifies the drop of the surface height for the reduced profile due to the loss of oxygen. Complementarily, lateral force microscopy reveals a homogeneous friction coefficient of the reduced regions that is remarkably lower than that of native graphene oxide, confirming a chemical change in the patterned region. Micro Raman spectroscopy, which provides access to insights into the chemical process, allows one to quantify the restoration and de-oxidation of the graphitic network driven by the electrochemical reduction and to determine characteristic length scales. It also confirms the homogeneity of the process over wide areas. The results shown were obtained from accurate analysis of the shift, intensity and width of Raman peaks for the main vibrational bands of GO and reduced graphene oxide (rGO) mapped over large areas. Concerning multilayered GO thin films obtained by drop-casting we have demonstrated an unprecedented lateral resolution in ambient conditions as well as an improved control, characterization and understanding of the reduction process occurring in GO randomly folded multilayers, useful for large-scale processing of graphene-based material.

Oxidation-reduction conditions of the plants with reference to their gas resistance

Energy Technology Data Exchange (ETDEWEB)

Krasinskii, N P

1944-01-01

The object of this work was to see if there is any relation between the oxidation-reduction conditions existing in a plant, and its ability to grow successfully in the cities where air contains H/sub 2/S. Oxidation-reduction potential, capacity for its water-soluble and insoluble matter to be oxidized with KMnO/sub 4/ before and after treatment with H/sub 2/S, and finally the effect of the age of the plant were determined for different spp. of several common families of plants. In the majority of the families it was found that in various spp. of the same family these characteristics vary within a narrow and different range. Oxidation with KMnO/sub 4/ of the water-insoluble matter was found to be the best criterion of the sensitivity of a plant to H/sub 2/S.

High-rate reduction of copper oxide using atmospheric-pressure inductively coupled plasma microjets

International Nuclear Information System (INIS)

Tajima, Satomi; Tsuchiya, Shouichi; Matsumori, Masashi; Nakatsuka, Shigeki; Ichiki, Takanori

2011-01-01

Reduction of copper oxide was performed using an atmospheric-pressure inductively coupled plasma (AP-ICP) microjet while varying the input power P between 15 and 50 W. Cuprous oxide (Cu 2 O) and cupric oxide (CuO) were formed on the sputtered Cu surface by thermal annealing. Dynamic behavior of the microplasma jet, optical emission from H atoms, the substrate temperature, chemical bonding states of the treated surface, and the thickness of the reduced Cu layer were measured to study the fundamental reduction process. Surface composition and the thickness of the reduced Cu layer changed significantly with P. Rapid reduction of CuO and Cu 2 O was achieved at a rate of 493 nm/min at P = 50 W since high-density H atoms were produced by the AP-ICP microjet.

High-rate reduction of copper oxide using atmospheric-pressure inductively coupled plasma microjets

Energy Technology Data Exchange (ETDEWEB)

Tajima, Satomi; Tsuchiya, Shouichi [Department of Bioengineering, Graduate School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, 113-8656 (Japan); Matsumori, Masashi; Nakatsuka, Shigeki [Panasonic Factory Solutions Co., Ltd., 2-7 Matsuba-cho, Kadoma-city, Osaka, 571-8502 (Japan); Ichiki, Takanori, E-mail: ichiki@sogo.t.u-tokyo.ac.jp [Department of Bioengineering, Graduate School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, 113-8656 (Japan); Institute of Engineering Innovation, Graduate School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo, 113-8656 (Japan)

2011-08-01

Reduction of copper oxide was performed using an atmospheric-pressure inductively coupled plasma (AP-ICP) microjet while varying the input power P between 15 and 50 W. Cuprous oxide (Cu{sub 2}O) and cupric oxide (CuO) were formed on the sputtered Cu surface by thermal annealing. Dynamic behavior of the microplasma jet, optical emission from H atoms, the substrate temperature, chemical bonding states of the treated surface, and the thickness of the reduced Cu layer were measured to study the fundamental reduction process. Surface composition and the thickness of the reduced Cu layer changed significantly with P. Rapid reduction of CuO and Cu{sub 2}O was achieved at a rate of 493 nm/min at P = 50 W since high-density H atoms were produced by the AP-ICP microjet.

Decomposition and Mineralization of Dimethyl Phthalate in an Aqueous Solution by Wet Oxidation

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Dar-Ren Ji

2015-01-01

Full Text Available Dimethyl phthalate (DMP was treated via wet oxygen oxidation process (WOP. The decomposition efficiency ηDMP of DMP and mineralization efficiency ηTOC of total organic carbons were measured to evaluate the effects of operation parameters on the performance of WOP. The results revealed that reaction temperature T is the most affecting factor, with a higher T offering higher ηDMP and ηTOC as expected. The ηDMP increases as rotating speed increases from 300 to 500 rpm with stirring enhancement of gas liquid mass transfer. However, it exhibits reduction effect at 700 rpm due to purging of dissolved oxygen by overstirring. Regarding the effects of pressure PT, a higher PT provides more oxygen for the forward reaction with DMP, while overhigh PT increases the absorption of gaseous products such as CO2 and decomposes short-chain hydrocarbon fragments back into the solution thus hindering the forward reaction. For the tested PT of 2.41 to 3.45 MPa, the results indicated that 2.41 MPa is appropriate. A longer reaction time of course gives better performance. At 500 rpm, 483 K, 2.41 MPa, and 180 min, the ηDMP and ηTOC are 93 and 36%, respectively.

A mineralogical investigation of the reduction of Mamatwan manganese ore with carbon

International Nuclear Information System (INIS)

Koursaris, A.; Kleyenstueber, A.S.E.; Finn, C.W.P.

1983-01-01

The paper describes two research programmes: small-scale experiments in which cubes (with sides of 20 mm) were heated with coke, coal, or graphite to temperatures of between 1 200 and 1 500 degrees Celsius for 1, 2 or 3 hours in an argon atmosphere; and large-scale experiments in which 4 kg charges of ore and coal, or of ore and coke, in stoichiometric proportions, were heated to temperatures between 1 300 and 1 600 degrees Celsius for up to four hours. The reacted charges were examined by microscopy, by X-ray diffraction analysis, and by X-ray microanalysis using an energy-dispersive system on a scanning electron microscope. It was found that the early stages of reduction involve complex mineralogical changes including the breakdown of braunite and gangue minerals, the reduction of the higher manganese oxides to manganous oxide and of hematite to metallic iron, and the formation of slag as a result of reaction between gangue and manganous oxides. Further reduction of the ore involves the carburisation of the metallic phase and the reduction of solid manganous oxide, or of manganous oxide dissolved in the slag, by solid carbon or carbon dissolved in the metal

Reduction of nitric oxide catalyzed by hydroxylamine oxidoreductase from an anammox bacterium.

Science.gov (United States)

Irisa, Tatsuya; Hira, Daisuke; Furukawa, Kenji; Fujii, Takao

2014-12-01

The hydroxylamine oxidoreductase (HAO) from the anammox bacterium, Candidatus Kuenenia stuttgartiensis has been reported to catalyze the oxidation of hydroxylamine (NH2OH) to nitric oxide (NO) by using bovine cytochrome c as an oxidant. In contrast, we investigated whether the HAO from anammox bacterium strain KSU-1 could catalyze the reduction of NO with reduced benzyl viologen (BVred) and the NO-releasing reagent, NOC 7. The reduction proceeded, resulting in the formation of NH2OH as a product. The oxidation rate of BVred was proportional to the concentration of BVred itself for a short period in each experiment, a situation that was termed quasi-steady state. The analyses of the states at various concentrations of HAO allowed us to determine the rate constant for the catalytic reaction, (2.85 ± 0.19) × 10(5) M(-1) s(-1), governing NO reduction by BVred and HAO, which was comparable to that reported for the HAO from the ammonium oxidizer, Nitrosomonas with reduced methyl viologen. These results suggest that the anammox HAO functions to adjust anammox by inter-conversion of NO and NH2OH depending on the redox potential of the physiological electron transfer protein in anammox bacteria. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Oxidation-reduction reactions. Overview and implications for repository studies

International Nuclear Information System (INIS)

Apted, Michael J.; Arthur, Randolph C.; Sasamoto, Hiroshi; Yui, Mikazu; Iwatsuki, Teruki

2001-02-01

The purpose of this report is to provide a survey and review on oxidation-reduction ('redox') reactions, with particular emphasis on implications for disposal of high-level waste (HLW) in deep geological formations. As an overview, the focus is on basic principles, problems, and proposed research related specifically to the assessment of redox for a HLW repository in Japan. For a more comprehensive treatment of redox and the myriad associated issues, the reader is directed to the cited textbooks used as primary references in this report. Low redox conditions in deep geological formations is a key assumption in the 'Second Progress Report on Research and Development for the Geological Disposal of HLW in Japan' (hereafter called H12'). The release behavior of multi-valent radioelements (e.g., Tc, Se, U, Pu, Np), as well as daughter radioelements of these radioelements, from a deep geological repository are sensitively related to redox conditions. Furthermore, the performance of certain barrier materials, such as overpack and buffer, may be impacted by redox conditions. Given this importance, this report summarizes some key topics for future technical studies supporting site characterization and repository performance as follows: To fully test the conceptual models for system Eh, it will be necessary to measure and evaluate trace element and isotopic information of both coexisting groundwater and reactive minerals of candidate rocks. Because of importance of volatile species (e.g., O 2 , H 2 etc.) in redox reactions, and given the high total pressure of a repository located 500 to 1000 meter deep, laboratory investigations of redox will necessarily require use of pressurized test devices that can fully simulate repository conditions. The stability (redox capacity) of the repository system with respect to potential changes in redox boundary condition induced by oxidizing waters intrusion should be established experimentally. An overall conceptual model that unifies

Descriptors and Thermodynamic Limitations of Electrocatalytic Carbon Dioxide Reduction on Rutile Oxide Surfaces

DEFF Research Database (Denmark)

Bhowmik, Arghya; Vegge, Tejs; Hansen, Heine Anton

2016-01-01

A detailed understanding of the electrochemical reduction of CO2 into liquid fuels on rutile metal oxide surfaces is developed by using DFT calculations. We consider oxide overlayer structures on RuO2(1 1 0) surfaces as model catalysts to elucidate the trends and limitations in the CO2 reduction...... and it defines the left leg of the activity volcano for CO2RR. HCOOH* is a key intermediate for products formed through further reduction, for example, methanediol, methanol, and methane. The surfaces that do not bind HCOOH* are selective towards formic acid (HCOOH) production, but hydrogen evolution limits...

Reduction of titanium dioxide and other metal oxides by electro-deoxidation

International Nuclear Information System (INIS)

Fray, Derek J.

2003-01-01

Titanium dioxide and other reactive metal compounds are reduced by more reactive metals to form pure metals. These, are expensive and time consuming processes which makes these metals very expensive. Many of these metals and alloys have excellent properties, high strength, low density and very good corrosion resistance, but their use is restricted by its high cost. Electro-deoxidation is a very simple technique where an oxide is made cathodic in a fused salt of an alkaline earth chloride. By applying a voltage, below the decomposition potential of the salt, it has been found that the cathodic reaction is the ionization of oxygen from the oxide to leave a pure metal, rather than the reduction of the ion alkaline earth ion element. Laboratory experiments have shown that this approach can be applied to the reduction of a large number of metal oxides. Another important observation is that when a mixture of oxides is used as the cathode, the product is an alloy of uniform composition. This is a considerable advantage for many alloys that are difficult to prepare using conventional technology. (Original)

Effects of iron-containing minerals on hydrothermal reactions of ketones

Science.gov (United States)

Yang, Ziming; Gould, Ian R.; Williams, Lynda B.; Hartnett, Hilairy E.; Shock, Everett L.

2018-02-01

Hydrothermal organic transformations occurring in geochemical processes are influenced by the surrounding environments including rocks and minerals. This work is focused on the effects of five common minerals on reactions of a model ketone substrate, dibenzylketone (DBK), in an experimental hydrothermal system. Ketones play a central role in many hydrothermal organic functional group transformations, such as those converting hydrocarbons to oxygenated compounds; however, how these minerals control the hydrothermal chemistry of ketones is poorly understood. Under the hydrothermal conditions of 300 °C and 70 MPa for up to 168 h, we observed that, while quartz (SiO2) and corundum (Al2O3) had no detectable effect on the hydrothermal reactions of DBK, iron-containing minerals, such as hematite (Fe2O3), magnetite (Fe3O4), and troilite (synthetic FeS), accelerated the reaction of DBK by up to an order of magnitude. We observed that fragmentation products, such as toluene and bibenzyl, dominated in the presence of hematite or magnetite, while use of troilite gave primarily the reduction products, e.g., 1, 3-diphenyl-propane and 1, 3-diphenyl-2-propanol. The roles of the three iron minerals in these transformations were further explored by (1) control experiments with various mineral surface areas, (2) measuring H2 in hydrothermal solutions, and (3) determining hydrogen balance among the organic products. These results suggest the reactions catalyzed by iron oxides (hematite and magnetite) are promoted mainly by the mineral surfaces, whereas the sulfide mineral (troilite) facilitated the reduction of ketone in the reaction solution. Therefore, this work not only provides a useful chemical approach to study and uncover complicated hydrothermal organic-mineral interactions, but also fosters a mechanistic understanding of ketone reactions in the deep carbon cycle.

Revisiting the effects of organic solvents on the thermal reduction of graphite oxide

International Nuclear Information System (INIS)

Barroso-Bujans, Fabienne; Fierro, José Luis G.; Alegría, Angel; Colmenero, Juan

2011-01-01

Highlights: ► Retention of organic solvent on graphite oxide interlayer space. ► Decreasing exfoliation temperature. ► Close link between structure and thermal behavior of solvent treated graphite oxide. ► Restacking inhibition of thermally reduced graphite oxide sheets. ► Changes in kinetic mechanisms of thermal reduction. - Abstract: Treatment of graphite oxide (GO) with organic solvents via sorption from either liquid or gas phase, and subsequent desorption, induces profound changes in the layered GO structure: loss of stacking order, retention of trace amounts of solvents and decreasing decomposition temperature. This study presents new evidences of the effect of organic solvents on the thermal reduction of GO by means of thermogravimetric analysis, X-ray diffraction and X-ray photoelectron spectroscopy. The results reveal a relative higher decrease of the oxygen amounts in solvent-treated GO as compared to untreated GO and the restacking inhibition of the thermally reduced GO sheets upon slow heating. The kinetic experiments evidence changes occurring in the reduction mechanisms of the solvent-treated GO, which support the close link between GO structure and thermal properties.

Use of ion conductors in the pyrochemical reduction of oxides

International Nuclear Information System (INIS)

Miller, W.E.; Tomczuk, Z.

1994-01-01

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO 2 oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a β-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca o used for reducing UO 2 and PuO 2 to U and Pu. 2 figures

Pathogenesis of Chronic Hyperglycemia: From Reductive Stress to Oxidative Stress

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Liang-Jun Yan

2014-01-01

Full Text Available Chronic overnutrition creates chronic hyperglycemia that can gradually induce insulin resistance and insulin secretion impairment. These disorders, if not intervened, will eventually be followed by appearance of frank diabetes. The mechanisms of this chronic pathogenic process are complex but have been suggested to involve production of reactive oxygen species (ROS and oxidative stress. In this review, I highlight evidence that reductive stress imposed by overflux of NADH through the mitochondrial electron transport chain is the source of oxidative stress, which is based on establishments that more NADH recycling by mitochondrial complex I leads to more electron leakage and thus more ROS production. The elevated levels of both NADH and ROS can inhibit and inactivate glyceraldehyde 3-phosphate dehydrogenase (GAPDH, respectively, resulting in blockage of the glycolytic pathway and accumulation of glycerol 3-phospate and its prior metabolites along the pathway. This accumulation then initiates all those alternative glucose metabolic pathways such as the polyol pathway and the advanced glycation pathways that otherwise are minor and insignificant under euglycemic conditions. Importantly, all these alternative pathways lead to ROS production, thus aggravating cellular oxidative stress. Therefore, reductive stress followed by oxidative stress comprises a major mechanism of hyperglycemia-induced metabolic syndrome.

Nanoscale reduction of graphene oxide thin films and its characterization

KAUST Repository

Lorenzoni, M.

2015-06-29

In this paper, we report on a method to reduce thin films of graphene oxide (GO) to a spatial resolution better than 100 nm over several tens of micrometers by means of an electrochemical scanning probe based lithography. In situ tip-current measurements show that an edged drop in electrical resistance characterizes the reduced areas, and that the reduction process is, to a good approximation, proportional to the applied bias between the onset voltage and the saturation thresholds. An atomic force microscope (AFM) quantifies the drop of the surface height for the reduced profile due to the loss of oxygen. Complementarily, lateral force microscopy reveals a homogeneous friction coefficient of the reduced regions that is remarkably lower than that of native graphene oxide, confirming a chemical change in the patterned region. Micro Raman spectroscopy, which provides access to insights into the chemical process, allows one to quantify the restoration and de-oxidation of the graphitic network driven by the electrochemical reduction and to determine characteristic length scales. It also confirms the homogeneity of the process over wide areas. The results shown were obtained from accurate analysis of the shift, intensity and width of Raman peaks for the main vibrational bands of GO and reduced graphene oxide (rGO) mapped over large areas. Concerning multilayered GO thin films obtained by drop-casting we have demonstrated an unprecedented lateral resolution in ambient conditions as well as an improved control, characterization and understanding of the reduction process occurring in GO randomly folded multilayers, useful for large-scale processing of graphene-based material. © 2015 IOP Publishing Ltd.

High Efficient Reduction of Graphene Oxide via Nascent Hydrogen at Room Temperature

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Qiqi Zhuo

2018-02-01

Full Text Available To develop a green and efficient method to synthesize graphene in relative milder conditions is prerequisite for graphene applications. A chemical reducing method has been developed to high efficiently reduce graphene oxide (GO using Fe2O3 and NH3BH3 as catalyst and reductants, respectively. During the process, environmental and strong reductive nascent hydrogen were generated surrounding the surface of GO sheets by catalyst hydrolysis reaction of NH3BH3 and were used for reduction of GO. The reduction process was studied by ultraviolet absorption spectroscopy, Raman spectroscopy, and Fourier transform infrared spectrum. The structure and morphology of the reduced GO were characterized with scanning electron microscopy and transmission electron microscopy. Compared to metal (Mg/Fe/Zn/Al particles and acid system which also use nascent hydrogen to reduce GO, this method exhibited higher reduction efficiency (43.6%. Also the reduction was carried out at room temperature condition, which is environmentally friendly. As a supercapacitor electrode, the reversible capacity of reduced graphene oxide was 113.8 F g−1 at 1 A g−1 and the capacitance retention still remained at 90% after 200 cycles. This approach provides a new method to reduce GO with high reduction efficiency by green reductant.

Clay minerals and metal oxides strongly influence the structure of alkane-degrading microbial communities during soil maturation.

Science.gov (United States)

Steinbach, Annelie; Schulz, Stefanie; Giebler, Julia; Schulz, Stephan; Pronk, Geertje J; Kögel-Knabner, Ingrid; Harms, Hauke; Wick, Lukas Y; Schloter, Michael

2015-07-01

Clay minerals, charcoal and metal oxides are essential parts of the soil matrix and strongly influence the formation of biogeochemical interfaces in soil. We investigated the role of these parental materials for the development of functional microbial guilds using the example of alkane-degrading bacteria harbouring the alkane monooxygenase gene (alkB) in artificial mixtures composed of different minerals and charcoal, sterile manure and a microbial inoculum extracted from an agricultural soil. We followed changes in abundance and community structure of alkane-degrading microbial communities after 3 and 12 months of soil maturation and in response to a subsequent 2-week plant litter addition. During maturation we observed an overall increasing divergence in community composition. The impact of metal oxides on alkane-degrading community structure increased during soil maturation, whereas the charcoal impact decreased from 3 to 12 months. Among the clay minerals illite influenced the community structure of alkB-harbouring bacteria significantly, but not montmorillonite. The litter application induced strong community shifts in soils, maturated for 12 months, towards functional guilds typical for younger maturation stages pointing to a resilience of the alkane-degradation function potentially fostered by an extant 'seed bank'.

Reduced graphene oxide supported gold nanoparticles for electrocatalytic reduction of carbon dioxide

Science.gov (United States)

Saquib, Mohammad; Halder, Aditi

2018-02-01

Electrochemical reduction of carbon dioxide is one of the methods which have the capability to recycle CO2 into valuable products for energy and industrial applications. This research article describes about a new electrocatalyst "reduced graphene oxide supported gold nanoparticles" for selective electrochemical conversion of carbon dioxide to carbon monoxide. The main aim for conversion of CO2 to CO lies in the fact that the latter is an important component of syn gas (a mixture of hydrogen and carbon monoxide), which is then converted into liquid fuel via well-known industrial process called Fischer-Tropsch process. In this work, we have synthesized different composites of the gold nanoparticles supported on defective reduced graphene oxide to evaluate the catalytic activity of reduced graphene oxide (RGO)-supported gold nanoparticles and the role of defective RGO support towards the electrochemical reduction of CO2. Electrochemical and impedance measurements demonstrate that higher concentration of gold nanoparticles on the graphene support led to remarkable decrease in the onset potential of 240 mV and increase in the current density for CO2 reduction. Lower impedance and Tafel slope values also clearly support our findings for the better performance of RGOAu than bare Au for CO2 reduction.

Lithium-Vanadium bronzes as model catalysts for the selective reduction of nitric oxide

NARCIS (Netherlands)

Bosch, H.; Bongers, Annemie; Enoch, Gert; Snel, Ruud; Ross, Julian R.H.

1989-01-01

The effect of alkali metals on the selective reduction of nitric oxide with ammonia has been studied on bulk iron oxide and bulk vanadium oxide. The influence of additions of LiOH, NaOH and KOH on the activity was screened by pulse experiments carried out in the absence of gaseous oxygen; FTIR

Fe2+ oxidation rate drastically affect the formation and phase of secondary iron hydroxysulfate mineral occurred in acid mine drainage

International Nuclear Information System (INIS)

Huang Shan; Zhou Lixiang

2012-01-01

During the processes of secondary iron hydroxysulfate mineral formation, Fe 2+ ion was oxidized by the following three methods: (1) biooxidation treatment by Acidithiobacillus ferrooxidans (A. ferrooxidans); (2) rapid abiotic oxidation of Fe 2+ with H 2 O 2 (rapid oxidation treatment); (3) slow abiotic oxidation of Fe 2+ with H 2 O 2 (slow oxidation treatment). X-ray diffraction (XRD) patterns, element composition, precipitate weight and total Fe removal efficiency were analyzed. The XRD patterns and element composition of precipitates synthesized through the biooxidation and the slow oxidation treatments well coincide with those of potassium jarosite, while precipitates formed at the initial stage of incubation in the rapid oxidation treatment showed a similar XRD pattern to schwertmannite. With the ongoing incubation, XRD patterns and element composition of the precipitates that occurred in the rapid oxidation treatment were gradually close to those in the biooxidation and the slow oxidation treatments. Due to the inhibition of A. ferrooxidans itself and its extracellular polymeric substances (EPS) in aggregation of precipitates, the amount of precipitates and soluble Fe removal efficiency were lower in the biooxidation treatment than in the slow oxidation treatment. Therefore, it is concluded that Fe 2+ oxidation rate can greatly affect the mineral phase of precipitates, and slow oxidation of Fe 2+ is helpful in improving jarosite formation. - Highlights: ► Slow oxidation of Fe 2+ is helpful in jarosite formation. ► The already-formed schwertmannite can be gradually transformed to jarosite. ► Precipitates formation can be inhibited probably by EPS from A. ferrooxidans.

Thermogravimetric study of reduction of oxides present in oxidized nickel-base alloy powders

Science.gov (United States)

Herbell, T. P.

1976-01-01

Carbon, hydrogen, and hydrogen plus carbon reduction of three oxidized nickel-base alloy powders (a solid solution strengthened alloy both with and without the gamma prime formers aluminum and titanium and the solid solution strengthened alloy NiCrAlY) were evaluated by thermogravimetry. Hydrogen and hydrogen plus carbon were completely effective in reducing an alloy containing chromium, columbium, tantalum, molybdenum, and tungsten. However, with aluminum and titanium present the reduction was limited to a weight loss of about 81 percent. Carbon alone was not effective in reducing any of the alloys, and none of the reducing conditions were effective for use with NiCrAlY.

Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation

Science.gov (United States)

Zeng, Zhirui; Tice, Michael M.

2018-01-01

Some microbial carbonates are robust biosignatures due to their distinct morphologies and compositions. However, whether carbonates induced by microbial iron reduction have such features is unknown. Iron-reducing bacteria use various strategies to transfer electrons to iron oxide minerals (e.g., membrane-bound enzymes, soluble electron shuttles, nanowires, as well as different mechanisms for moving over or attaching to mineral surfaces). This diversity has the potential to create mineral biosignatures through manipulating the microenvironments in which carbonate precipitation occurs. We used Shewanella oneidensis MR-1, Geothrix fermentans, and Geobacter metallireducens GS-15, representing three different strategies, to reduce solid ferric hydroxide in order to evaluate their influence on carbonate and micropore formation (micro-size porosity in mineral rocks). Our results indicate that electron transfer strategies determined the morphology (rhombohedral, spherical, or long-chained) of precipitated calcium-rich siderite by controlling the level of carbonate saturation and the location of carbonate formation. Remarkably, electron transfer strategies also produced distinctive cell-shaped micropores in both carbonate and hydroxide minerals, thus producing suites of features that could potentially serve as biosignatures recording information about the sizes, shapes, and physiologies of iron-reducing organisms.

Synthesis of reduced graphene oxide (rGO) via chemical reduction

International Nuclear Information System (INIS)

Thakur, Alpana; Rangra, V. S.; Kumar, Sunil

2015-01-01

Natural flake Graphite was used as the starting material for the graphene synthesis. In the first step flake graphite was treated with oxidizing agents under vigorous conditions to obtain graphite oxide. Layered graphite oxide decorated with oxygen has large inter-layer distance leading easy exfoliation into single sheets by ultrasonication giving graphene oxide. In the last step exfoliated graphene oxide sheets were reduced slowly with the help of reducing agent to obtain fine powder which is labeled as reduced graphene oxide (rGO). This rGO was further characterized by X-Ray Diffraction (XRD), Scanning Tunneling Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy techniques. XRD pattern shows peaks corresponding to (002) graphitic lattice planes indicating the formation of network of sp 2 like carbon structure. SEM images show the ultrathin, wrinkled, paper-like morphology of graphene sheets. IR study shows that the graphite has been oxidized to graphite oxide with the presence of various absorption bands confirming the presence of oxidizing groups. The FTIR spectrum of rGO shows no sharp peaks confirming the efficient reduction of rGO. The Raman spectrum shows disorder in the graphene sheets

Reduction of uranium and plutonium oxides by aluminum. Application to the recycling of plutonium

International Nuclear Information System (INIS)

Gallay, J.

1968-01-01

A process for treating plutonium oxide calcined at high temperatures (1000 to 2000 deg. C) with a view to recovering the metal consists in the reduction of this oxide dissolved in a mixture of aluminium, sodium and calcium fluorides by aluminium at about 1180 deg. C. The first part of the report presents the results of reduction tests carried out on the uranium oxides UO 2 and U 3 O 8 ; these are in agreement with the thermodynamic calculations of the exchange reaction at equilibrium. The second part describes the application of this method to plutonium oxides. The Pu-Al alloy obtained (60 per cent Pu) is then recycled in an aqueous medium. (author) [fr

Electrochemical processing of spent nuclear fuels: An overview of oxide reduction in pyroprocessing technology

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Eun-Young Choi

2015-12-01

Full Text Available The electrochemical reduction process has been used to reduce spent oxide fuel to a metallic form using pyroprocessing technology for a closed fuel cycle in combination with a metal-fuel fast reactor. In the electrochemical reduction process, oxides fuels are loaded at the cathode basket in molten Li2O–LiCl salt and electrochemically reduced to the metal form. Various approaches based on thermodynamic calculations and experimental studies have been used to understand the electrode reaction and efficiently treat spent fuels. The factors that affect the speed of the electrochemical reduction have been determined to optimize the process and scale-up the electrolysis cell. In addition, demonstrations of the integrated series of processes (electrorefining and salt distillation with the electrochemical reduction have been conducted to realize the oxide fuel cycle. This overview provides insight into the current status of and issues related to the electrochemical processing of spent nuclear fuels.

The effect of ammonia upon the electrocatalysis of hydrogen oxidation and oxygen reduction on polycrystalline platinum

DEFF Research Database (Denmark)

Verdaguer Casadevall, Arnau; Hernandez-Fernandez, Patricia; Stephens, Ifan E.L.

2012-01-01

The influence of ammonium ions on the catalysis of hydrogen oxidation and oxygen reduction is studied by means of rotating ring-disk electrode experiments on polycrystalline platinum in perchloric acid. While ammonium does not affect the hydrogen oxidation reaction, the oxygen reduction reaction...

Evidence for single metal two electron oxidative addition and reductive elimination at uranium.

Science.gov (United States)

Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; McInnes, Eric J L; Tuna, Floriana; Wooles, Ashley J; Maron, Laurent; Liddle, Stephen T

2017-12-01

Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction that satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests that nitrenes are not generated and thus a reductive elimination has occurred. Though not optimally balanced in this case, this work presents evidence that classical d-block redox chemistry can be performed reversibly by f-block metals, and that uranium can thus mimic elementary transition metal reactivity, which may lead to the discovery of new f-block catalysis.

In Situ Spectroscopic Analysis of the Carbothermal Reduction Process of Iron Oxides during Microwave Irradiation

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Jun Fukushima

2018-01-01

Full Text Available The effects of microwave plasma induction and reduction on the promotion of the carbothermal reduction of iron oxides (α-Fe2O3, γ-Fe2O3, and Fe3O4 are investigated using in situ emission spectroscopy measurements during 2.45 GHz microwave processing, and the plasma discharge (such as CN and N2 is measured during microwave E-field irradiation. It is shown that CN gas or excited CN molecules contribute to the iron oxide reduction reactions, as well as to the thermal reduction. On the other hand, no plasma is generated during microwave H-field irradiation, resulting in thermal reduction. Magnetite strongly interacts with the microwave H-field, and the reduction reaction is clearly promoted by microwave H-field irradiation, as well as thermal reduction reaction.

Are high rates of sulphate reduction associated with anaerobic oxidation of methane

Energy Technology Data Exchange (ETDEWEB)

Devol, A H; Ahmed, S I

1981-01-01

Classical models of sulphur diagenesis in marine sediments are based on the assumption that the rate of sulphate reduction is first order with respect to oxidizable particulate organic carbon (POC). This assumption requires that oxidizable POC, sulphate concentration and the sulphate reduction rate be highest at the top of the sulphate reduction zone and decrease exponentially with increasing sediment depth. However, to explain recent observations of concave upwards methane distributions, the anaerobic consumption of methane has been proposed. Furthermore, it has been proposed that this consumption takes place near the bottom of the sulphate reducing zone where sulphate concentrations are low. Thus, if sulphate reducing bacteria are associated with the anaerobic oxidation of methane, a peak in sulphate reduction rate might be expected in this deep consumption zone. The importance of the process in sedimentary sulphur diagenesis is indicated by calculations estimating that 30 to 75% of the downward sulphate flux at depth may be consumed by methane oxidation within this zone. We present here profiles of sulphate reduction rate in anoxic sediments that show distinct local maxima at the depth where the anaerobic oxidation of methane would be expected. Our measurements were made during July and August 1978 in Saanich Inlet, an anoxic fjord located on the south-east of Vancouver Island, British Columbia. The inlet has a shallow sill (approx 70 m) which restricts circulation of the deeper water (maximum depth 225 m) inside the basin to the extent that for about 8 months of the year the bottom waters contain hydrogen sulphide, the inlet is an ideal location for studying sedimentary sulphate reduction because reactions with oxygen and the effects of burrowing organisms can be neglected.

Dissimilatory oxidation and reduction of elemental sulfur in thermophilic archaea.

Science.gov (United States)

Kletzin, Arnulf; Urich, Tim; Müller, Fabian; Bandeiras, Tiago M; Gomes, Cláudio M

2004-02-01

The oxidation and reduction of elemental sulfur and reduced inorganic sulfur species are some of the most important energy-yielding reactions for microorganisms living in volcanic hot springs, solfataras, and submarine hydrothermal vents, including both heterotrophic, mixotrophic, and chemolithoautotrophic, carbon dioxide-fixing species. Elemental sulfur is the electron donor in aerobic archaea like Acidianus and Sulfolobus. It is oxidized via sulfite and thiosulfate in a pathway involving both soluble and membrane-bound enzymes. This pathway was recently found to be coupled to the aerobic respiratory chain, eliciting a link between sulfur oxidation and oxygen reduction at the level of the respiratory heme copper oxidase. In contrast, elemental sulfur is the electron acceptor in a short electron transport chain consisting of a membrane-bound hydrogenase and a sulfur reductase in (facultatively) anaerobic chemolithotrophic archaea Acidianus and Pyrodictium species. It is also the electron acceptor in organoheterotrophic anaerobic species like Pyrococcus and Thermococcus, however, an electron transport chain has not been described as yet. The current knowledge on the composition and properties of the aerobic and anaerobic pathways of dissimilatory elemental sulfur metabolism in thermophilic archaea is summarized in this contribution.

Generalized kinetic model of reduction of molecular oxidant by metal containing redox

International Nuclear Information System (INIS)

Kravchenko, T.A.

1986-01-01

Present work is devoted to kinetics of reduction of molecular oxidant by metal containing redox. Constructed generalized kinetic model of redox process in the system solid redox - reagent solution allows to perform the general theoretical approach to research and to obtain new results on kinetics and mechanism of interaction of redox with oxidants.

Preservation and concentration of uranium mineralization in the crust of weathering

International Nuclear Information System (INIS)

Ashikhmin, A.A.; Kuznetsov, S.V.; Shmarovich, E.M.

1983-01-01

Inprecision of the concept on indispensable evacuation of U from ores during formation of the crust of weathering of lateritic or kaolinitic profile due to the existence of oxidative situation in the crusts is established. At hydrothermal uranium deposit in Eocambrian sandy-shaly and Paleozoic volcanogenous-sedimentary rocks a high degree of mineralization preservation in lower and medium horizons of Mesozoic-Cenozoic hydro-micaceous-kaolinitic crust of weathering, characterized by reductive situation, presence of carbonaceous substance, pyrite and siderite, is established. Mineralization attained there black composition and was additionally enriched with uranium. A supposition is made that the case is specific for the development of lateritic and kaolinitic crust formation according to ore-bearing rocks, rich in reducing agents-carbonaceous substances, sulfides and minerals of protoxidic iron. The data obtained should be taken into account during prediction and prospecting activities

Effects of Muscle-Specific Oxidative Stress on Cytochrome c Release and Oxidation-Reduction Potential Properties.

Science.gov (United States)

Ke, Yiling; Mitacek, Rachel M; Abraham, Anupam; Mafi, Gretchen G; VanOverbeke, Deborah L; DeSilva, Udaya; Ramanathan, Ranjith

2017-09-06

Mitochondria play a significant role in beef color. However, the role of oxidative stress in cytochrome c release and mitochondrial degradation is not clear. The objective was to determine the effects of display time on cytochrome c content and oxidation-reduction potential (ORP) of beef longissimus lumborum (LL) and psoas major (PM) muscles. PM discolored by day 3 compared with LL. On day 0, mitochondrial content and mitochondrial oxygen consumption were greater in PM than LL. However, mitochondrial content and oxygen consumption were lower (P stress can affect cytochrome c release and ORP changes.

EMISSION REDUCTION FROM A DIESEL ENGINE FUELED BY CERIUM OXIDE NANO-ADDITIVES USING SCR WITH DIFFERENT METAL OXIDES COATED CATALYTIC CONVERTER

Directory of Open Access Journals (Sweden)

B. JOTHI THIRUMAL

2015-11-01

Full Text Available This paper reports the results of experimental investigations on the influence of the addition of cerium oxide in nanoparticle form on the major physiochemical properties and the performance of diesel. The fuel is modified by dispersing the catalytic nanoparticle by ultrasonic agitation. The physiochemical properties of sole diesel fuel and modified fuel are tested with ASTM standard procedures. The effects of the additive nanoparticles on the individual fuel properties, the engine performance, and emissions are studied, and the dosing level of the additive is optimized. Cerium oxide acts as an oxygen-donating catalyst and provides oxygen for the oxidation of CO during combustion. The active energy of cerium oxide acts to burn off carbon deposits within the engine cylinder at the wall temperature and prevents the deposition of non-polar compounds on the cylinder wall which results in reduction in HC emission by 56.5%. Furthermore, a low-cost metal oxide coated SCR (selective catalyst reduction, using urea as a reducing agent, along with different types of CC (catalytic converter, has been implemented in the exhaust pipe to reduce NOx. It was observed that a reduction in NOx emission is 50–60%. The tests revealed that cerium oxide nanoparticles can be used as an additive in diesel to improve complete combustion of the fuel and reduce the exhaust emissions significantly.

Redox properties of clay-rich sediments as assessed by mediated electrochemical analysis : Separating pyrite, siderite and structural Fe in clay minerals

NARCIS (Netherlands)

Hoving, Alwina L.; Sander, Michael; Bruggeman, Christophe; Behrends, Thilo

2017-01-01

Redox reactions with Fe-containing minerals in clay-rich sediments largely affect the speciation, mobility, and (bio-) availability of redox-sensitive contaminants. Here, we use mediated electrochemical oxidation (MEO) and reduction (MER), to quantify the electron accepting and donating capacities

OPAQUE MINERAL CONTENT OF DUTLUCA VOLCANICS (BURHANİYE - BALIKESİR: THE EFFECT OF HYDROTHERMAL ALTERATION ON THESE MINERALS

Directory of Open Access Journals (Sweden)

Şükrü KOÇ

2016-12-01

Full Text Available Dutluca volcanics, which are known as Hallaçlar Formation in regional scale in the study area (Kurshens- ky, 1976, are composed of hydrothermally altered andesite and basaltic andesite. In these rocks, sulfidic minerals such as pyrite, enargite and chalcosine, and oxide and hydroxide minerals such as magnetite, hematite and goethite were detected as opaque minerals. The presence of enargite in opaque mineral para- genesis, and the changes observed in structures and textures of opaque and silicate minerals indicate that examined volcanics have been altered by highly sulfidic hydrothermal solutions. During the hydrothermal alteration process, which indicates at least in two phases, a diffuse pyritization rich in H S in reducing conditions and enargite mineral, which is known as pathfinder minerals in such processes, formed in the first phase. Later on; the extensive martitization developed in oxidizing conditions.

Study on the influences of reduction temperature on nickel-yttria-stabilized zirconia solid oxide fuel cell anode using nickel oxide-film electrode

Science.gov (United States)

Jiao, Zhenjun; Ueno, Ai; Suzuki, Yuji; Shikazono, Naoki

2016-10-01

In this study, the reduction processes of nickel oxide at different temperatures were investigated using nickel-film anode to study the influences of reduction temperature on the initial performances and stability of nickel-yttria-stabilized zirconia anode. Compared to conventional nickel-yttria-stabilized zirconia composite cermet anode, nickel-film anode has the advantage of direct observation at nickel-yttria-stabilized zirconia interface. The microstructural changes were characterized by scanning electron microscopy. The reduction process of nickel oxide is considered to be determined by the competition between the mechanisms of volume reduction in nickel oxide-nickel reaction and nickel sintering. Electrochemical impedance spectroscopy was applied to analyze the time variation of the nickel-film anode electrochemical characteristics. The anode performances and microstructural changes before and after 100 hours discharging and open circuit operations were analyzed. The degradation of nickel-film anode is considered to be determined by the co-effect between the nickel sintering and the change of nickel-yttria-stabilized zirconia interface bonding condition.

Bacterial and iron oxide aggregates mediate secondary iron mineral formation: green rust versus magnetite.

Science.gov (United States)

Zegeye, A; Mustin, C; Jorand, F

2010-06-01

In the presence of methanoate as electron donor, Shewanella putrefaciens, a Gram-negative, facultative anaerobe, is able to transform lepidocrocite (gamma-FeOOH) to secondary Fe (II-III) minerals such as carbonated green rust (GR1) and magnetite. When bacterial cells were added to a gamma-FeOOH suspension, aggregates were produced consisting of both bacteria and gamma-FeOOH particles. Recently, we showed that the production of secondary minerals (GR1 vs. magnetite) was dependent on bacterial cell density and not only on iron reduction rates. Thus, gamma-FeOOH and S. putrefaciens aggregation pattern was suggested as the main mechanism driving mineralization. In this study, lepidocrocite bioreduction experiments, in the presence of anthraquinone disulfonate, were conducted by varying the [cell]/[lepidocrocite] ratio in order to determine whether different types of aggregate are formed, which may facilitate precipitation of GR1 as opposed to magnetite. Confocal laser scanning microscopy was used to analyze the relative cell surface area and lepidocrocite concentration within the aggregates and captured images were characterized by statistical methods for spatial data (i.e. variograms). These results suggest that the [cell]/[lepidocrocite] ratio influenced both the aggregate structure and the nature of the secondary iron mineral formed. Subsequently, a [cell]/[lepidocrocite] ratio above 1 x 10(7) cells mmol(-1) leads to densely packed aggregates and to the formation of GR1. Below this ratio, looser aggregates are formed and magnetite was systematically produced. The data presented in this study bring us closer to a more comprehensive understanding of the parameters governing the formation of minerals in dense bacterial suspensions and suggest that screening mineral-bacteria aggregate structure is critical to understanding (bio)mineralization pathways.

Study on emission characteristics and reduction strategy of nitrous oxide during wastewater treatment by different processes.

Science.gov (United States)

Sun, Shichang; Bao, Zhiyuan; Sun, Dezhi

2015-03-01

Given the inexorable increase in global wastewater treatment, increasing amounts of nitrous oxide are expected to be emitted from wastewater treatment plants and released to the atmosphere. It has become imperative to study the emission and control of nitrous oxide in the various wastewater treatment processes currently in use. In the present investigation, the emission characteristics and the factors affecting the release of nitrous oxide were studied via full- and pilot-scale experiments in anoxic-oxic, sequencing batch reactor and oxidation ditch processes. We propose an optimal treatment process and relative strategy for nitrous oxide reduction. Our results show that both the bio-nitrifying and bio-denitrifying treatment units in wastewater treatment plants are the predominant sites for nitrous oxide production in each process, while the aerated treatment units are the critical sources for nitrous oxide emission. Compared with the emission of nitrous oxide from the anoxic-oxic (1.37% of N-influent) and sequencing batch reactor (2.69% of N-influent) processes, much less nitrous oxide (0.25% of N-influent) is emitted from the oxidation ditch process, which we determined as the optimal wastewater treatment process for nitrous oxide reduction, given the current technologies. Nitrous oxide emissions differed with various operating parameters. Controlling the dissolved oxygen concentration at a proper level during nitrification and denitrification and enhancing the utilization rate of organic carbon in the influent for denitrification are the two critical methods for nitrous oxide reduction in the various processes considered.

Iron-Coupled Anaerobic Oxidation of Methane Performed by a Mixed Bacterial-Archaeal Community Based on Poorly Reactive Minerals.

Science.gov (United States)

Bar-Or, Itay; Elvert, Marcus; Eckert, Werner; Kushmaro, Ariel; Vigderovich, Hanni; Zhu, Qingzeng; Ben-Dov, Eitan; Sivan, Orit

2017-11-07

Anaerobic oxidation of methane (AOM) was shown to reduce methane emissions by over 50% in freshwater systems, its main natural contributor to the atmosphere. In these environments iron oxides can become main agents for AOM, but the underlying mechanism for this process has remained enigmatic. By conducting anoxic slurry incubations with lake sediments amended with 13 C-labeled methane and naturally abundant iron oxides the process was evidenced by significant 13 C-enrichment of the dissolved inorganic carbon pool and most pronounced when poorly reactive iron minerals such as magnetite and hematite were applied. Methane incorporation into biomass was apparent by strong uptake of 13 C into fatty acids indicative of methanotrophic bacteria, associated with increasing copy numbers of the functional methane monooxygenase pmoA gene. Archaea were not directly involved in full methane oxidation, but their crucial participation, likely being mediators in electron transfer, was indicated by specific inhibition of their activity that fully stopped iron-coupled AOM. By contrast, inhibition of sulfur cycling increased 13 C-methane turnover, pointing to sulfur species involvement in a competing process. Our findings suggest that the mechanism of iron-coupled AOM is accomplished by a complex microbe-mineral reaction network, being likely representative of many similar but hidden interactions sustaining life under highly reducing low energy conditions.

A new green approach for the reduction of graphene oxide ...

Indian Academy of Sciences (India)

2.2 Preparation of GO. GO was prepared by oxidizing the graphite powder in a mix- ... measured using a Diamond TG/DTA analyzer (Perkin Elmer. Instruments). ... domains during the reduction of GO.23 This change of ID/IG value is in good ...

Simultaneous iridium catalysed oxidation and enzymatic reduction employing orthogonal reagents

NARCIS (Netherlands)

Mutti, Francesco G.; Orthaber, Andreas; Schrittwieser, Joerg H.; Vries, Johannes G. de; Pietschnig, Rudolf; Kroutil, Wolfgang

2010-01-01

An iridium catalysed oxidation was coupled concurrently to an asymmetric biocatalytic reduction in one-pot; thus it was shown for the first time that iridium- and alcohol dehydrogenase-catalysed redox reactions are compatible. As a model system racemic chlorohydrins were transformed to

Direct printing and reduction of graphite oxide for flexible supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Jung, Hanyung [Department of Nano Science and Technology, Graduate School of Convergence Science and Technology, Seoul National University, Seoul (Korea, Republic of); Ve Cheah, Chang [Department of Mechanical and Aerospace Engineering, Seoul National University, Seoul (Korea, Republic of); Jeong, Namjo [Energy Materials and Convergence Research Department, Korea Institute of Energy Research, Daejeon (Korea, Republic of); Lee, Junghoon, E-mail: jleenano@snu.ac.kr [Department of Nano Science and Technology, Graduate School of Convergence Science and Technology, Seoul National University, Seoul (Korea, Republic of); Department of Mechanical and Aerospace Engineering, Seoul National University, Seoul (Korea, Republic of); Division of WCU Multiscale Mechanical Design, School of Mechanical and Aerospace Engineering, Seoul National University, Seoul (Korea, Republic of)

2014-08-04

We report direct printing and photo-thermal reduction of graphite oxide (GO) to obtain a highly porous pattern of interdigitated electrodes, leading to a supercapacitor on a flexible substrate. Key parameters optimized include the amount of GO delivered, the suitable photo-thermal energy level for effective flash reduction, and the substrate properties for appropriate adhesion after reduction. Tests with supercapacitors based on the printed-reduced GO showed performance comparable with commercial supercapacitors: the energy densities were 1.06 and 0.87 mWh/cm{sup 3} in ionic and organic electrolytes, respectively. The versatility in the architecture and choice of substrate makes this material promising for smart power applications.

Direct printing and reduction of graphite oxide for flexible supercapacitors

Science.gov (United States)

Jung, Hanyung; Ve Cheah, Chang; Jeong, Namjo; Lee, Junghoon

2014-08-01

We report direct printing and photo-thermal reduction of graphite oxide (GO) to obtain a highly porous pattern of interdigitated electrodes, leading to a supercapacitor on a flexible substrate. Key parameters optimized include the amount of GO delivered, the suitable photo-thermal energy level for effective flash reduction, and the substrate properties for appropriate adhesion after reduction. Tests with supercapacitors based on the printed-reduced GO showed performance comparable with commercial supercapacitors: the energy densities were 1.06 and 0.87 mWh/cm3 in ionic and organic electrolytes, respectively. The versatility in the architecture and choice of substrate makes this material promising for smart power applications.

Direct printing and reduction of graphite oxide for flexible supercapacitors

International Nuclear Information System (INIS)

Jung, Hanyung; Ve Cheah, Chang; Jeong, Namjo; Lee, Junghoon

2014-01-01

We report direct printing and photo-thermal reduction of graphite oxide (GO) to obtain a highly porous pattern of interdigitated electrodes, leading to a supercapacitor on a flexible substrate. Key parameters optimized include the amount of GO delivered, the suitable photo-thermal energy level for effective flash reduction, and the substrate properties for appropriate adhesion after reduction. Tests with supercapacitors based on the printed-reduced GO showed performance comparable with commercial supercapacitors: the energy densities were 1.06 and 0.87 mWh/cm 3 in ionic and organic electrolytes, respectively. The versatility in the architecture and choice of substrate makes this material promising for smart power applications

Lithotrophic iron-oxidizing bacteria produce organic stalks to control mineral growth: implications for biosignature formation

Energy Technology Data Exchange (ETDEWEB)

Chan, Clara S; Fakra, Sirine C; Emerson, David; Fleming, Emily J; Edwards, Katrina J

2011-07-01

Neutrophilic Fe-oxidizing bacteria (FeOB) are often identified by their distinctive morphologies, such as the extracellular twisted ribbon-like stalks formed by Gallionella ferruginea or Mariprofundus ferrooxydans. Similar filaments preserved in silica are often identified as FeOB fossils in rocks. Although it is assumed that twisted iron stalks are indicative of FeOB, the stalk's metabolic role has not been established. To this end, we studied the marine FeOB M. ferrooxydans by light, X-ray and electron microscopy. Using time-lapse light microscopy, we observed cells excreting stalks during growth (averaging 2.2 {micro}m h(-1)). Scanning transmission X-ray microscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy show that stalks are Fe(III)-rich, whereas cells are low in Fe. Transmission electron microscopy reveals that stalks are composed of several fibrils, which contain few-nanometer-sized iron oxyhydroxide crystals. Lepidocrocite crystals that nucleated on the fibril surface are much larger ({approx}100 nm), suggesting that mineral growth within fibrils is retarded, relative to sites surrounding fibrils. C and N 1s NEXAFS spectroscopy and fluorescence probing show that stalks primarily contain carboxyl-rich polysaccharides. On the basis of these results, we suggest a physiological model for Fe oxidation in which cells excrete oxidized Fe bound to organic polymers. These organic molecules retard mineral growth, preventing cell encrustation. This model describes an essential role for stalk formation in FeOB growth. We suggest that stalk-like morphologies observed in modern and ancient samples may be correlated confidently with the Fe-oxidizing metabolism as a robust biosignature.

Mineralization of herbicide 3,6-dichloro-2-methoxybenzoic acid in aqueous medium by anodic oxidation, electro-Fenton and photoelectro-Fenton

International Nuclear Information System (INIS)

Brillas, Enric; Banos, Miguel Angel; Garrido, Jose Antonio

2003-01-01

The mineralization of acidic aqueous solutions with 230 and 115 ppm of herbicide 3,6-dichloro-2-methoxybenzoic acid (dicamba) in 0.05 M Na 2 SO 4 of pH 3.0 has been studied by electro-Fenton and photoelectro-Fenton using a Pt anode and an O 2 -diffusion cathode, where oxidizing hydroxyl radicals are produced from Fenton's reaction between added Fe 2+ and H 2 O 2 generated by the cathode. While electro-Fenton only yields 60-70% mineralization, photoelectro-Fenton allows a fast and complete depollution of herbicide solutions, even at low currents, by the action of UV irradiation. In both treatments, the initial chlorine is rapidly released to the medium as chloride ion. Comparative electrolyses by anodic oxidation in the absence and presence of electrogenerated H 2 O 2 give very poor degradation. The dicamba decay follows a pseudo-first-order reaction, as determined by reverse-phase chromatography. Formic, maleic and oxalic acids have been detected in the electrolyzed solutions by ion-exclusion chromatography. In electro-Fenton, all formic acid is transformed into CO 2 , and maleic acid is completely converted into oxalic acid, remaining stable Fe 3+ -oxalato complexes in the solution. The fast mineralization of such complexes by UV light explains the highest oxidative ability of photoelectro-Fenton

XPS study of graphene oxide reduction induced by (100) and (111)-oriented Si substrates

Science.gov (United States)

Priante, F.; Salim, M.; Ottaviano, L.; Perrozzi, F.

2018-02-01

The reduction of graphene oxide (GO) has been extensively studied in literature in order to let GO partially recover the properties of graphene. Most of the techniques proposed to reduce GO are based on high temperature annealing or chemical reduction. A new procedure, based on the direct reduction of GO by etched Si substrate, was recently proposed in literature. In the present work, we accurately investigated the Si-GO interaction with x-ray photoelectron spectroscopy. In order to avoid external substrate oxidation factors we used EtOH as the GO solvent instead of water, and thermal annealing was carried out in UHV. We investigated the effect of Si(100), Si(111) and Au substrates on GO, to probe the role played by both the substrate composition and substrate orientation during the reduction process. A similar degree of GO reduction was observed for all samples but only after thermal annealing, ruling out the direct reduction effect of the substrate.

Effects of Low-temperature Pre-oxidation on the Titanomagnetite Ore Structure and Reduction Behaviors in a Fluidized Bed

Science.gov (United States)

Adetoro, Ajala Adewole; Sun, Haoyan; He, Shengyi; Zhu, Qingshan; Li, Hongzhong

2018-04-01

With respect to high efficient utilization of low-grade iron ore resource, the behavior of low-temperature "973 K to 1123 K (700 °C to 850 °C)" oxidation, on the phase transition of SA TTM ore (South African titanomagnetite), and its effect on subsequent reduction was investigated. The results showed that hematite and rutile are the oxidation product below 1048 K (775 °C), while pseudobrookite is the stable phase above 1073 K (800 °C). With the increase in temperature and oxidation time, there is a competitive relationship between the amount of hematite and pseudobrookite generated. The reduction efficiency of SA TTM was significantly improved by oxidation pretreatment, primarily due to the dissociation of titania-ferrous oxides to more easily reducible hematite. But the generation of pseudobrookite phase decreases the amount of free hematite available for reduction, which weakens the improvement effect of pre-oxidation. The equilibrium relationship between the metallization degree and the gas reduction potential for TTM ore with pre-oxidation treatment has been built. Finally, the reduction metallization degree for the first and second step can be improved averagely by 16.67 and 3.45 pct, respectively, for sample pre-oxidized at 1098 K (825 °C) for 15 and 90 minutes, while 26.96 and 7.4 pct, improvement is achieved for sample pre-oxidized at a lower temperature of 1048 K (775 °C) for 120 minutes.

The effect of preparation conditions and the ionizing radiation on the kinetics of cupric oxide reduction by hydrogen

International Nuclear Information System (INIS)

Pospisil, M.; Taras, P.

1977-01-01

Cupric oxide reduction in the temperature interval 170 to 350 degC was studied by thermogravimetry. The reduction kinetics can be quantitatively described by the modified Prout-Tompkinson equation, with the apparent activation energy varying within the limits (4.94 to 5.82)x10 4 J/mol. Irregularities observed during the reduction of the oxide of the oxalate origin are due to the high content of the metallic phase. The p-semiconducting nature of these oxides was proved for all samples. The effect of the pre-irradiation of samples with γ-rays (with an absorbed dose of (1.4 to 4.75)x10 6 J/kg) on the reduction kinetics depends on the origin of the cupric oxide. In contrast to NiO no correlation between the content of super-stoichiometric oxygen and the reduction kinetics was found. After irradiation with γ-rays or with fast neutrons at a dose of 79.8 J/kg the reduction rate increases and the activation energy decreases regardless of the oxide origin. At the same time the concentration of the ionic form of super-stoichiometric oxygen increases. (author)

ADVANCED OXIDATION PROCESSES FOR FOOD INDUSTRIAL WASTEWATER DECONTAMINATION

Directory of Open Access Journals (Sweden)

Dorota Krzemińska

2015-02-01

Full Text Available High organic matter content is a basic problem in food industry wastewaters. Typically, the amount and composition of the effluent varies considerably. In the article four groups of advanced processes and their combination of food industry wastewater treatment have been reviewed: electrochemical oxidation (EC, Fenton’s process, ozonation of water and photocatalytic processes. All advanced oxidation processes (AOP`s are characterized by a common chemical feature: the capability of exploiting high reactivity of HO• radicals in driving oxidation processes which are suitable for achieving decolonization and odour reduction, and the complete mineralization or increase of bioavailability of recalcitrant organic pollutants.

A study of integrated cathode assembly for electrolytic reduction of uranium oxide in LiCl-Li2O molten salt

International Nuclear Information System (INIS)

Park, Sung Bin; Seo, Jung Seok; Kang, Dae Seung; Kwon, Sun Kil; Park, Seong Won

2004-01-01

Interest of electrolytic reduction of uranium oxide is increasing in treatment of spent metal fuels. Argonne National Laboratory (ANL) has reported the experimental results of electrochemical reduction of uranium oxide fuel in bench-scale apparatus with cyclic voltammetry, and has designed high-capacity reduction (HCR) cells and conducted three kg-scale UO 2 reduction runs. From the cyclic voltammograms, the mechanism of electrolytic reduction of metal oxides is analyzed. The uranium oxide in LiCl-Li 2 O is converted to uranium metal according to the two mechanism; direct and indirect electrolytic reduction. In this study, cyclic voltammograms for LiCl-3wt% Li 2 O system and U 3 O 8 -LiCl-3wt% Li 2 O system using the 325-mesh stainless steel screen in cathode assembly have been obtained. Direct electrolytic reduction of uranium oxide in LiCl-3wt% Li 2 O molten salt has been conducted

An integrated technique using zero-valent iron and UV/H2O2 sequential process for complete decolorization and mineralization of C.I. Acid Black 24 wastewater

International Nuclear Information System (INIS)

Chang, M.-C.; Shu, H.-Y.; Yu, H.-H.

2006-01-01

The zero-valent iron (ZVI) reduction succeeds for decolorization, while UV/H 2 O 2 oxidation process results into mineralization, so that this study proposed an integrated technique by reduction coupling with oxidation process in order to acquire simultaneously complete both decolorization and mineralization of C.I. Acid Black 24. From the experimental data, the zero-valent iron addition alone can decolorize the dye wastewater yet it demanded longer time than ZVI coupled with UV/H 2 O 2 processes (Red-Ox). Moreover, it resulted into only about 30% removal of the total organic carbon (TOC), which was capable to be effectively mineralized by UV/H 2 O 2 process. The proposed sequential ZVI-UV/H 2 O 2 integration system cannot only effectively remove color and TOC in AB 24 wastewater simultaneously but also save irradiation power and time demand. Furthermore, the decolorization rate constants were about 3.77-4.0 times magnitude comparing with that by UV/H 2 O 2 process alone

Topotactic oxidative and reductive control of the structures and properties of layered manganese oxychalcogenides.

Science.gov (United States)

Hyett, Geoffrey; Barrier, Nicolas; Clarke, Simon J; Hadermann, Joke

2007-09-12

Topotactic modification, by both oxidation and reduction, of the composition, structures, and magnetic properties of the layered oxychalcogenides Sr4Mn3O7.5Cu2Ch2 (Ch=S, Se) is described. These Mn3+ compounds are composed of alternating perovskite-type strontium manganese oxide slabs separated by anti-fluorite-type copper chalcogenide layers and are intrinsically oxide deficient in the central layer of the perovskite slabs. The systems are unusual examples of perovskite-related compounds that may topotactically be both oxidized by fluorination and reduced by deintercalation of oxygen from the oxide-deficient part of the structure. The compounds exhibit antiferromagnetic ordering of the manganese magnetic moments in the outer layers of the perovskite slabs, while the other moments, in the central layers, exhibit spin-glass-like behavior. Fluorination has the effect of increasing the antiferromagnetic ordering temperature and the size of the ordered moment, whereas reduction destroys magnetic long-range order by introducing chemical disorder which leads to both further disorder and frustration of the magnetic interactions in the manganese oxide slab.

Dissimilatory reduction of nitrate and nitrite in the bovine rumen: nitrous oxide production and effect of acetylene.

Science.gov (United States)

Kaspar, H F; Tiedje, J M

1981-03-01

15N tracer methods and gas chromatography coupled to an electron capture detector were used to investigate dissimilatory reduction of nitrate and nitrite by the rumen microbiota of a fistulated cow. Ammonium was the only 15N-labeled end product of quantitative significance. Only traces of nitrous oxide were detected as a product of nitrate reduction; but in experiments with nitrite, up to 0.3% of the added nitrogen accumulated as nitrous oxide, but it was not further reduced. Furthermore, when 13NO3- was incubated with rumen microbiota virtually no [13N]N2 was produced. Acetylene partially inhibited the reduction of nitrite to ammonium as well as the formation of nitrous oxide. It is suggested that in the rumen ecosystem nitrous oxide is a byproduct of dissimilatory nitrite reduction to ammonium rather than a product of denitrification and that the latter process is absent from the rumen habitat.

Novel Insights Into Microbial Uranium Reduction and Immobilization

Science.gov (United States)

Loeffler, F. E.; Fletcher, K.; Thomas, S.; Kemner, K. M.; Boyanov, M.; Sanford, R.

2010-12-01

Many ferric iron- and manganese oxide-reducing bacteria affect the oxidation state and complexation of toxic radionuclides in subsurface environments. Relevant to uranium (U) speciation are bacteria that reduce predominantly water-soluble and mobile U(VI) to U(IV), which has reduced solubility and typically forms the uraninite (UO2) mineral. Gram-negative model organisms including Shewanella spp., Geobacter spp., and more recently Anaeromyxobacter spp. use U(VI) as growth-supporting electron acceptor; however, the biomass yields are lower than predicted based on the theoretical free energy changes associated with U(VI)-to-U(IV) reduction. Recent findings demonstrated that U(VI) reduction is not limited to Gram-negative bacteria, and members of the genus Desulfitobacterium, which are commonly found in soil and subsurface environments, share the ability to reduce U(VI). Interestingly, extended X-ray absorption fine structure (EXAFS) analysis demonstrated that the U(IV) produced in cultures of five Desulfitobacterium spp. was not UO2 but rather a phase or mineral composed of mononuclear U(IV) atoms. Since the properties of the reduced product influence U(IV) fate, knowledge of the diversity of U reduction mechanisms and the stability of the end products is desirable for controlling and predicting U fate. For example, UO2 is susceptible to reoxidation by oxidants, and oxic/anoxic interface processes are controlling the stability of the precipitated material. In other words, metal reducers that thrive at the oxic/anoxic interface are likely key players affecting long-term U fate. Anaeromyxobacter spp. are facultative microaerophiles and grow with oxygen as electron acceptor at partial pressures equal to or below 0.18 atm. Thus, Anaeromyxobacter are uniquely adapted to life at the oxic-anoxic interface where they consume oxygen and take advantage of oxidized metal species including U(VI) as electron acceptors. The application of 16S rRNA gene-targeted qPCR approaches

Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

Science.gov (United States)

Bulavchenko, O A; Vinokurov, Z S; Afonasenko, T N; Tsyrul'nikov, P G; Tsybulya, S V; Saraev, A A; Kaichev, V V

2015-09-21

A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-δ) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-δ proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-δ undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 → Mn3O4 → MnO.

Efficient reduction of graphene oxide film by low temperature heat treatment and its effect on electrical conductivity

Energy Technology Data Exchange (ETDEWEB)

Hu, Xuebing; Chen, Zheng [Jingdezhen Ceramic Institute, Jingdezhen (China). Key Lab. of Inorganic Membrane; Yu, Yun [Shanghai Institute of Ceramics, Shanghai (China). Key Lab. of Inorganic Coating Materials; Zhang, Xiaozhen; Wang, Yongqing; Zhou, Jianer [Jingdezhen Ceramic Institute, Jingdezhen (China). Dept. of Materials Engineering

2018-03-01

Graphene-based conductive films have already attracted great attention due to their unique and outstanding physical properties. In this work, in order to develop a novel, effective method to produce these films with good electrical conductivity, a simple and green method is reported to rapidly and effectively reduce graphene oxide film using a low temperature heat treatment. The reduction of graphene oxide film is verified by XRD, FT-IR and Raman spectroscopy. Compared with graphene oxide film, the obtained reduced graphene oxide film has better electrical conductivity and its sheet resistance decreases from 25.3 kΩ x sq{sup -1} to 3.3 kΩ x sq{sup -1} after the heat treatment from 160 to 230 C. The mechanism of thermal reduction of the graphene oxide film mainly results from the removal of the oxygen-containing functional groups and the structural changes. All these results indicate that the low temperature heat treatment is a suitable and effective method for the reduction of graphene oxide film.

New french uranium mineral species

International Nuclear Information System (INIS)

Branche, G.; Chervet, J.; Guillemin, C.

1952-01-01

In this work, the authors study the french new uranium minerals: parsonsite and renardite, hydrated phosphates of lead and uranium; kasolite: silicate hydrated of uranium and lead uranopilite: sulphate of uranium hydrated; bayleyite: carbonate of uranium and of hydrated magnesium; β uranolite: silicate of uranium and of calcium hydrated. For all these minerals, the authors give the crystallographic, optic characters, and the quantitative chemical analyses. On the other hand, the following species, very rare in the french lodgings, didn't permit to do quantitative analyses. These are: the lanthinite: hydrated uranate oxide; the α uranotile: silicate of uranium and of calcium hydrated; the bassetite: uranium phosphate and of hydrated iron; the hosphuranylite: hydrated uranium phosphate; the becquerelite: hydrated uranium oxide; the curite: oxide of uranium and lead hydrated. Finally, the authors present at the end of this survey a primary mineral: the brannerite, complex of uranium titanate. (author) [fr

Oxidative Addition and Reductive Elimination at Main-Group Element Centers.

Science.gov (United States)

Chu, Terry; Nikonov, Georgii I

2018-04-11

Oxidative addition and reductive elimination are key steps in a wide variety of catalytic reactions mediated by transition-metal complexes. Historically, this reactivity has been considered to be the exclusive domain of d-block elements. However, this paradigm has changed in recent years with the demonstration of transition-metal-like reactivity by main-group compounds. This Review highlights the substantial progress achieved in the past decade for the activation of robust single bonds by main-group compounds and the more recently realized activation of multiple bonds by these elements. We also discuss the significant discovery of reversible activation of single bonds and distinct examples of reductive elimination at main-group element centers. The review consists of three major parts, starting with oxidative addition of single bonds, proceeding to cleavage of multiple bonds, and culminated by the discussion of reversible bond activation and reductive elimination. Within each subsection, the discussion is arranged according to the type of bond being cleaved or formed and considers elements from the left to the right of each period and down each group of the periodic table. The majority of results discussed in this Review come from the past decade; however, earlier reports are also included to ensure completeness.

Investigations involving oxidation-reduction (REDOX) pretreatment in conjunction with biological remediation of contaminated soils

International Nuclear Information System (INIS)

Montemagno, C.D.; Peters, R.W.; Tyree, A.

1991-01-01

Oxidation-reduction (REDOX) reactions are among the most important reactions involved in the environmental engineering field. Oxidation is a reaction in which the oxidation state of the treated compound is increased, i.e., the material loses electrons. Reduction involves the addition of a chemical (reducing) agent which lowers the oxidation state of a substance, i.e., the material gains electrons. Both processes of oxidation and reduction occur together. All REDOX reactions are thermodynamically based. There are a number of oxidizing agents which have been reported in the technical literature for treatment of refractory organic compounds. Common oxidizing agents include: hydrogen peroxide, ozone, ultraviolet (UV) irradiation, and combinations thereof, such as UV/ozone and UV/peroxide. A gradient of REDOX reactions is possible, depending on such factors as the oxidation-reduction reaction conditions, the availability of electron donors and acceptors, and the nature of the organic compounds involved. A review of the technical literature revealed that the majority of the oxidation-reduction applications have been in the areas of wastewater treatment and groundwater remediation, with very little attention devoted to the potential of using REDOX technologies for remediation of hydrocarbon contaminated soils. In this particular study, feasibility studies were performed on gasoline- contaminated soil. These studies focused on three major phases: 1) containment of the contamination by addition of tailoring agents to the soil, 2) biological remediation either performed in situ or on-site (using a slurry reactor system), and 3) pretreatment of the contaminated soils using REDOX systems, prior to biological remediation. This particular paper focuses on the third phase of the project, aimed at ''softening'' the refractory organics resulting in the formation of organic compounds which are more amenable to biological degradation. This paper focuses its attention on the use of

Investigations involving oxidation-reduction (REDOX) pretreatment in conjunction with biological remediation of contaminated soils

Energy Technology Data Exchange (ETDEWEB)

Montemagno, C. D. [Argonne National Laboratory, Argonne, IL (United States); Peters, R. W.; Tyree, A.

1991-07-01

Oxidation-reduction (REDOX) reactions are among the most important reactions involved in the environmental engineering field. Oxidation is a reaction in which the oxidation state of the treated compound is increased, i.e., the material loses electrons. Reduction involves the addition of a chemical (reducing) agent which lowers the oxidation state of a substance, i.e., the material gains electrons. Both processes of oxidation and reduction occur together. All REDOX reactions are thermodynamically based. There are a number of oxidizing agents which have been reported in the technical literature for treatment of refractory organic compounds. Common oxidizing agents include: hydrogen peroxide, ozone, ultraviolet (UV) irradiation, and combinations thereof, such as UV/ozone and UV/peroxide. A gradient of REDOX reactions is possible, depending on such factors as the oxidation-reduction reaction conditions, the availability of electron donors and acceptors, and the nature of the organic compounds involved. A review of the technical literature revealed that the majority of the oxidation-reduction applications have been in the areas of wastewater treatment and groundwater remediation, with very little attention devoted to the potential of using REDOX technologies for remediation of hydrocarbon contaminated soils. In this particular study, feasibility studies were performed on gasoline- contaminated soil. These studies focused on three major phases: 1) containment of the contamination by addition of tailoring agents to the soil, 2) biological remediation either performed in situ or on-site (using a slurry reactor system), and 3) pretreatment of the contaminated soils using REDOX systems, prior to biological remediation. This particular paper focuses on the third phase of the project, aimed at ''softening'' the refractory organics resulting in the formation of organic compounds which are more amenable to biological degradation. This paper focuses its attention on the use of

Redox properties of structural Fe in clay minerals: 3. Relationships between smectite redox and structural properties.

Science.gov (United States)

Gorski, Christopher A; Klüpfel, Laura E; Voegelin, Andreas; Sander, Michael; Hofstetter, Thomas B

2013-01-01

Structural Fe in clay minerals is an important redox-active species in many pristine and contaminated environments as well as in engineered systems. Understanding the extent and kinetics of redox reactions involving Fe-bearing clay minerals has been challenging due to the inability to relate structural Fe(2+)/Fe(total) fractions to fundamental redox properties, such as reduction potentials (EH). Here, we overcame this challenge by using mediated electrochemical reduction (MER) and oxidation (MEO) to characterize the fraction of redox-active structural Fe (Fe(2+)/Fe(total)) in smectites over a wide range of applied EH-values (-0.6 V to +0.6 V). We examined Fe(2+)/Fe(total )- EH relationships of four natural Fe-bearing smectites (SWy-2, SWa-1, NAu-1, NAu-2) in their native, reduced, and reoxidized states and compared our measurements with spectroscopic observations and a suite of mineralogical properties. All smectites exhibited unique Fe(2+)/Fe(total) - EH relationships, were redox active over wide EH ranges, and underwent irreversible electron transfer induced structural changes that were observable with X-ray absorption spectroscopy. Variations among the smectite Fe(2+)/Fe(total) - EH relationships correlated well with both bulk and molecular-scale properties, including Fe(total) content, layer charge, and quadrupole splitting values, suggesting that multiple structural parameters determined the redox properties of smectites. The Fe(2+)/Fe(total) - EH relationships developed for these four commonly studied clay minerals may be applied to future studies interested in relating the extent of structural Fe reduction or oxidation to EH-values.

Discrete Event System Based Pyroprocessing Modeling and Simulation: Oxide Reduction

International Nuclear Information System (INIS)

Lee, H. J.; Ko, W. I.; Choi, S. Y.; Kim, S. K.; Hur, J. M.; Choi, E. Y.; Im, H. S.; Park, K. I.; Kim, I. T.

2014-01-01

Dynamic changes according to the batch operation cannot be predicted in an equilibrium material flow. This study began to build a dynamic material balance model based on the previously developed pyroprocessing flowsheet. As a mid- and long-term research, an integrated pyroprocessing simulator is being developed at the Korea Atomic Energy Research Institute (KAERI) to cope with a review on the technical feasibility, safeguards assessment, conceptual design of facility, and economic feasibility evaluation. The most fundamental thing in such a simulator development is to establish the dynamic material flow framework. This study focused on the operation modeling of pyroprocessing to implement a dynamic material flow. As a case study, oxide reduction was investigated in terms of a dynamic material flow. DES based modeling was applied to build a pyroprocessing operation model. A dynamic material flow as the basic framework for an integrated pyroprocessing was successfully implemented through ExtendSim's internal database and item blocks. Complex operation logic behavior was verified, for example, an oxide reduction process in terms of dynamic material flow. Compared to the equilibrium material flow, a model-based dynamic material flow provides such detailed information that a careful analysis of every batch is necessary to confirm the dynamic material balance results. With the default scenario of oxide reduction, the batch mass balance was verified in comparison with a one-year equilibrium mass balance. This study is still under progress with a mid-and long-term goal, the development of a multi-purpose pyroprocessing simulator that is able to cope with safeguards assessment, economic feasibility, technical evaluation, conceptual design, and support of licensing for a future pyroprocessing facility

Surface analytical techniques applied to minerals processing

International Nuclear Information System (INIS)

Smart, R.St.C.

1991-01-01

An understanding of the chemical and physical forms of the chemically altered layers on the surfaces of base metal sulphides, particularly in the form of hydroxides, oxyhydroxides and oxides, and the changes that occur in them during minerals processing lies at the core of a complete description of flotation chemistry. This paper reviews the application of a variety of surface-sensitive techniques and methodologies applied to the study of surface layers on single minerals, mixed minerals, synthetic ores and real ores. Evidence from combined XPS/SAM/SEM studies have provided images and analyses of three forms of oxide, oxyhydroxide and hydroxide products on the surfaces of single sulphide minerals, mineral mixtures and complex sulphide ores. 4 refs., 2 tabs., 4 figs

Enhanced Cr(VI) reduction and As(III) oxidation in ice phase: Important role of dissolved organic matter from biochar

Energy Technology Data Exchange (ETDEWEB)

Dong, Xiaoling [Department of Soil and Water Science, University of Florida, Gainesville, FL 32611 (United States); Ma, Lena Q., E-mail: lqma@ufl.edu [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Jiangsu 210046 (China); Department of Soil and Water Science, University of Florida, Gainesville, FL 32611 (United States); Gress, Julia; Harris, Willie [Department of Soil and Water Science, University of Florida, Gainesville, FL 32611 (United States); Li, Yuncong [Soil and Water Science Department, Tropical Research and Education Center, University of Florida, Homestead, FL 33031-3314 (United States)

2014-02-01

Graphical abstract: - Highlights: • Biochar-derived dissolved organic matter (DOM) effectively reduced Cr(VI) and oxidized As(III). • Cr(VI) and As(III) could serve as a redox couple. • Cr(VI) and As(III) redox conversion was more effective in the ice phase than aqueous phase. • FTIR and ESR showed that biochar DOM served as both electron donor and acceptor. - Abstract: This study evaluated the impact of DOM from two biochars (sugar beet tailing and Brazilian pepper) on Cr(VI) reduction and As(III) oxidation in both ice and aqueous phases with a soil DOM as control. Increasing DOM concentration from 3 to 300 mg C L{sup −1} enhanced Cr(VI) reduction from 20% to 100% and As(III) oxidation from 6.2% to 25%; however, Cr(VI) reduction decreased from 80–86% to negligible while As(III) oxidation increased from negligible to 18–19% with increasing pH from 2 to 10. Electron spin resonance study suggested semiquinone radicals in DOM were involved in As(III) oxidation while Fourier transform infrared analysis suggested that carboxylic groups in DOM participated in both Cr(VI) reduction and As(III) oxidation. During Cr(VI) reduction, part of DOM (∼10%) was oxidized to CO{sub 2}. The enhanced conversion of Cr(VI) and As(III) in the ice phase was due to the freeze concentration effect with elevated concentrations of electron donors and electron acceptors in the grain boundary. Though DOM enhanced both Cr(VI) reduction and As(III)oxidation, Cr(VI) reduction coupled with As(III) oxidation occurred in absence of DOM. The role of DOM, Cr(VI) and/or As(III) in Cr and As transformation may provide new insights into their speciation and toxicity in cold regions.

Stability of radioactive minerals in an oxidizing hydrogeological environment: new results from an alluvial placer deposit, Naegi district, central Japan

International Nuclear Information System (INIS)

Sasao, Eiji; Komuro, Kosei; Nakata, Masataka

2009-01-01

Study of the stability of radioactive minerals in a placer deposit in the Naegi District, southeastern Gifu Prefecture, Central Japan contributes to understanding the modes of nuclide migration under various hydrogeological environments in the tectonically active Japanese Island Arc system. The placer deposit is embedded in basal conglomerates of the lower-most alluvial sequences, exposed to a near-surface, oxidizing hydrogeological environment. The mineral samples, ranging in mesh size from 120 to 250, were identified after sieving and magnetic separation to be mainly cassiterite, thorite, monazite, and topaz, with subordinate amounts of zircon, fergusonite-(Y), xenotime and wolframite. Observations using optical and scanning microscopy indicated that many grains of zircon have well-preserved crystal faces. Most monazite and fergusonite-(Y) grains are partly abraded and corroded whereas thorite grains are highly abraded and corroded. This indicates that under an oxidizing hydrogeological environment, the mechanical durability and geological stability decrease from zircon to monazite/fergusonite-(Y) to thorite, which correlates well with the Mohs's hardness scale. Cut and polished thorite grains display a high degree of alteration. The altered portions have higher Th, Fe and Y contents, and lower U and Si contents in comparison with the unaltered portions, indicating leaching of U and Si. In the fergusonite-(Y) grains, the altered portions have higher Th, Nb and Ta contents, and lower U and Y contents in comparison with the unaltered portions, indicate leaching of U and Y. Thus it is determined that uranium is strongly leached in an oxidizing hydrogeological environment. The leaching behaviour is dependent on mineralogy and is consistent with thermodynamic estimates. The alteration rate of fergusonite-(Y) was calculated to range from 0.05 to 0.000025 μm/year based on the thickness of the external alteration film and the duration of exposure to the oxidizing

Application Of Bacterial Iron Reduction For The Removal Of Iron Impurities From Industrial Silica Sand And Kaolin

Science.gov (United States)

Zegeye, A.; Yahaya, S.; Fialips, C. I.; White, M.; Manning, D. A.; Gray, N.

2008-12-01

Biogeochemical evidence exists to support the potential importance of crystalline or amorphous Fe minerals as electron acceptor for Fe reducing bacteria in soils and subsurface sediments. This microbial metabolic activity can be exploited as alternative method in different industrial applications. For instance, the removal of ferric iron impurities from minerals for the glass and paper industries currently rely on physical and chemical treatments having substantial economical and environmental disadvantages. The ability to remove iron by other means, such as bacterial iron reduction, may reduce costs, allow lower grade material to be mined, and improve the efficiency of mineral processing. Kaolin clay and silica sand are used in a wide range of industrial applications, particularly in paper, ceramics and glass manufacturing. Depending on the geological conditions of deposition, they are often associated with iron (hydr)oxides that are either adsorbed to the mineral surfaces or admixed as separate iron bearing minerals. In this study, we have examined the Fe(III) removal efficiency from kaolin and silica sand by a series of iron- reducing bacteria from the Shewanella species (S. alga BrY, S. oneidensis MR-1, S. putrefaciens CN32 and S. putrefaciens ATCC 8071) in the presence of anthraquinone 2,6 disulfonate (AQDS). We have also investigated the effectiveness of a natural organic matter, extracted with the silica sand, as a substitute to AQDS for enhancing Fe(III) reduction kinetics. The microbial reduction of Fe(III) was achieved using batch cultures under non-growth conditions. The rate and the extent of Fe(III) reduction was monitored as a function of the initial Fe(III) content, Shewanella species and temperature. The bacterially- treated minerals were analyzed by transmission electron microscopy (TEM) and X-ray diffraction (XRD) to observe any textural and mineralogical transformation. The whiteness and ISO brightness of the kaolin was also measured by

The extraction of trace amounts of tantalum(V) from different mineral acid solutions by 4-(5-nonyl) pyridine oxide and trioctylamine oxide

International Nuclear Information System (INIS)

Ejaz, M.; Carswell, D.J.

1976-01-01

Data are presented on the distribution of trace amounts of tantalum(V) between different mineral acid solutions and 0.1M solutions of N-oxides of 4-(5-nonyl) pyridine and trioctylamine. The optimal acidity is 0.01-0.5M, depending on the nature of the acid. Common anions have little effect on extraction. Possible mechanism of extraction are suggested making use of slope analysis data. Separation factors for a number of metal ions with respect to tantalum are reported for the 0.1M 4-(5-nonyl)pyridine oxide - 1M sulphuric acid extraction system. Separation from uranium(VI), thorium(IV) and a number of fission products is suggested. The conclusions are unique as follows: Amine oxides are as unique as oxygen-donor extractants in their extraction of tantalum(V) from weakly acid solutions; tantalum is almost completely extracted from weakly nitric, hydrochloric and sulphuric acid solutions by both of the amine oxides; the extraction in low acidity solutions is independent of the nature of the anion of the acids present, indicating the ability of amine oxides to extract the product of hydrolysis of hydrolysable elements. In this respect amine oxides are much better than tributyl phosphate. (T.G.)

Technetium Reduction and Permanent Sequestration by Abiotic and Biotic Formation of Low-Solubility Sulfide Mineral Phases

Energy Technology Data Exchange (ETDEWEB)

Tratnyek, Paul G. [Oregon Health & Science Univ., Beaverton, OR (United States); Tebo, Bradley M. [Oregon Health & Science Univ., Beaverton, OR (United States); Fan, Dimin [Oregon Health & Science Univ., Beaverton, OR (United States); Anitori, Roberto [Oregon Health & Science Univ., Beaverton, OR (United States); Szecsody, Jim [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Jansik, Danielle [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2015-11-14

One way to minimize the mobility of the Tc^VII oxyanion pertechnetate (TcO₄^-) is to effect reduction under sulfidogenic conditions (generated abiotically by Fe₀ or biotically) to form TcS_x, which is significantly slower to oxidize than Tc^IVO₂. In sediment systems, TcS_x and other precipitates may oxidize more slowly due to oxygen diffusion limitations to these low permeability precipitate zones. In addition, the TcO₄^- reduction rate may be more rapid in the presence of sediment because of additional reductive surface phases. This project aims to provide a fundamental understanding of the feasibility of immobilization of TcO₄^- as TcS_x in the vadose zone or groundwater by application nano zero-valent iron (nZVI), and sulfide or sulfate. Biotic batch experiments have used the sulfate-reducing bacterium (SRB) Desulfotomaculum reducens. The iron sulfide mineral mackinawite was generated under these conditions, while vivianite was formed in nZVI only controls. The sulfide/bacteria-containing system consistently reduced aqueous pertechnetate rapidly (> 95% in the first hour), a rate similar to that for the sulfide-free, nZVI only system. Reduced Tc (aged for 3 months) generated in both SRB/nZVI systems was highly resistant to reoxidation. In reduced samples, Tc was found associated with solid phases containing Fe and S (D. reducens/nZVI) or Fe (nZVI only). Experiments using D. reducens without nZVI provided some additional insights. Firstly, stationary phase cultures were able to slowly reduce pertechnetate. Secondly, addition of pertechnetate at the beginning of cell growth (lag phase) resulted in a faster rate of Tc reduction, possibly indicating a direct (e.g. enzymatic) role for D. reducens in Tc reduction. Abiotic batch experiments were conducted with Na₂S as the sulfide source. Pertechnetate reduction was

Catalyst for reduction of nitrogen oxides

Science.gov (United States)

Ott, Kevin C.

2010-04-06

A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

Cd Mobility in Anoxic Fe-Mineral-Rich Environments - Potential Use of Fe(III)-Reducing Bacteria in Soil Remediation

Science.gov (United States)

Muehe, E. M.; Adaktylou, I. J.; Obst, M.; Schröder, C.; Behrens, S.; Hitchcock, A. P.; Tylsizczak, T.; Michel, F. M.; Krämer, U.; Kappler, A.

2014-12-01

Agricultural soils are increasingly burdened with heavy metals such as Cd from industrial sources and impure fertilizers. Metal contaminants enter the food chain via plant uptake from soil and negatively affect human and environmental health. New remediation approaches are needed to lower soil metal contents. To apply these remediation techniques successfully, it is necessary to understand how soil microbes and minerals interact with toxic metals. Here we show that microbial Fe(III) reduction initially mobilizes Cd before its immobilization under anoxic conditions. To study how microbial Fe(III) reduction influences Cd mobility, we isolated a new Cd-tolerant, Fe(III)-reducing Geobacter sp. from a heavily Cd-contaminated soil. In lab experiments, this Geobacter strain first mobilized Cd from Cd-loaded Fe(III) hydroxides followed by precipitation of Cd-bearing mineral phases. Using Mössbauer spectroscopy and scanning electron microscopy, the original and newly formed Cd-containing Fe(II) and Fe(III) mineral phases, including Cd-Fe-carbonates, Fe-phosphates and Fe-(oxyhydr)oxides, were identified and characterized. Using energy-dispersive X-ray spectroscopy and synchrotron-based scanning transmission X-ray microscopy, Cd was mapped in the Fe(II) mineral aggregates formed during microbial Fe(III) reduction. Microbial Fe(III) reduction mobilizes Cd prior to its precipitation in Cd-bearing mineral phases. The mobilized Cd could be taken up by phytoremediating plants, resulting in a net removal of Cd from contaminated sites. Alternatively, Cd precipitation could reduce Cd bioavailability in the environment, causing less toxic effects to crops and soil microbiota. However, the stability and thus bioavailability of these newly formed Fe-Cd mineral phases needs to be assessed thoroughly. Whether phytoremediation or immobilization of Cd in a mineral with reduced Cd bioavailability are feasible mechanisms to reduce toxic effects of Cd in the environment remains to be

Effect of Calcium Oxide on the Crushing Strength, Reduction, and Smelting Performance of High-Chromium Vanadium–Titanium Magnetite Pellets

Directory of Open Access Journals (Sweden)

Gongjin Cheng

2017-05-01

Full Text Available The effect of calcium oxide on the crushing strength, reduction, and smelting performance of high-chromium vanadium–titanium magnetite pellets (HCVTMP was studied in this work. The main characterization methods of an electronic universal testing machine (EUTM, X-ray fluorescent (XRF, inductively-coupled plasma-atomic emission spectroscopy (ICP-AES, X-ray diffraction (XRD, and scanning electron microscope-energy disperse spectroscopy (SEM-EDS were employed. The crushing strength was affected by the mineral phases generated during oxidative baking and the subsequently-formed pellet microstructures owing to CaO addition. The reduction and smelting properties of HCVTMP with different CaO additives were measured and characterized with different softening-melting-dripping indices. Although HCVTMP showed the highest crushing strength with CaO addition of ca. 2 wt %, more CaO addition may be needed to achieve high permeability of the furnace burdens and a good separation condition of the slag and melted iron. In the formation process of the slag and melted iron, it can be determined that CaO could have a relationship with the transformation behavior of Cr, V, and Ti to some extent, with respect to the predominant chemical composition analysis of ICP-AES and XRF. With the microscopic examination, the restraining formation of Ti(C,N and the promoting formation of CaTiO3 are in accordance with the improved melting-dripping indices, including the decrease of the maximum external static load and gas permeability, and the increase of the melting-dripping zone and dripping difficulty.

Synthesis of 3-substituted 4-piperidinones via a one-pot tandem oxidation-cyclization-oxidation process: stereodivergent reduction to 3,4-disubstituted piperidines.

Science.gov (United States)

Bahia, Perdip S; Snaith, John S

2004-04-30

A novel approach to 3-substituted 4-piperidinones is described. The one-pot tandem oxidation-cyclization-oxidation of unsaturated alcohols 1a-e by PCC or PCC and trifluoromethanesulfonic acid affords piperidinones 2a-e in good yield. Reduction of 2a-e by L-Selectride gives the corresponding cis 3,4-disubstituted piperidines with diastereomeric ratios of >99:1. By contrast, reduction of 2a-e by Al-isopropoxydiisobutylalane gives the trans products with diastereomeric ratios of up to 99:1.

Oxidation and reduction behaviors of a prototypic MgO-PuO{sub 2-x} inert matrix fuel

Energy Technology Data Exchange (ETDEWEB)

Miwa, Shuhei, E-mail: miwa.shuhei@jaea.go.jp; Osaka, Masahiko

2017-04-15

Oxidation and reduction behaviors of prototypic MgO-based inert matrix fuels (IMFs) containing PuO{sub 2-x} were experimentally investigated by means of thermogravimetry. The oxidation and reduction kinetics of the MgO-PuO{sub 2-x} specimen were determined. The oxidation and reduction rates of the MgO-PuO{sub 2-x} were found to be low compared with those of PuO{sub 2-x}. It is note that the changes in O/Pu ratios of MgO-PuO{sub 2-x} from stoichiometry were smaller than those of PuO{sub 2-x} at high oxygen partial pressure.

To the micro-climatic condition influence upon the environment pollution during exploitation of being oxidized mineral deposits

International Nuclear Information System (INIS)

Akhmedzhanov, T.K.; Al'mukhambetova, Sh.K.; Bajramov, I.M.

1998-01-01

Conducted researches showed dependence of environment pollution rate under exploration of being oxidized mineral deposits from number of meteorological futures of season changes. Zones of gases spreading in atmosphere from sources of pollution in dependence from micro-climatic conditions are estimated. Results can be used during preventive measures projecting for environment in deposits districts. (author)

Characterization of Cu/CeO2/Al2O3 catalysts by temperature programmed reduction and activity for CO oxidation

International Nuclear Information System (INIS)

Cataluna, Renato; Baibich, Ione M.; Dallago, R.M.; Picinini, C.; Martinez-Arias, A.; Soria, J.

2001-01-01

The kinetic parameters for the CO oxidation reaction using copper/alumina-modified ceria as catalysts were determined. The catalysts with different concentrations of the metals were prepared using impregnation methods. In addition, the reduction-oxidation behaviour of the catalysts were investigated by temperature-programmed reduction. The activity results show that the mechanism for CO oxidation is bifunctional: oxygen is activated on the anionic vacancies of ceria surface, while carbon monoxide is adsorbed preferentially on the higher oxidation copper site. Therefore, the reaction occurs on the interfacial active centers. Temperatures-programmed Reduction patterns show a higher dispersion when cerium oxide is present. (author)

Transition Metal Oxides for the Oxygen Reduction Reaction: Influence of the Oxidation States of the Metal and its Position on the Periodic Table.

Science.gov (United States)

Toh, Rou Jun; Sofer, Zdeněk; Pumera, Martin

2015-11-16

Electrocatalysts have been developed to meet the needs and requirements of renewable energy applications. Metal oxides have been well explored and are promising for this purpose, however, many reports focus on only one or a few metal oxides at once. Herein, thirty metal oxides, which were either commercially available or synthesized by a simple and scalable method, were screened for comparison with regards to their electrocatalytic activity towards the oxygen reduction reaction (ORR). We show that although manganese, iron, cobalt, and nickel oxides generally displayed the ability to enhance the kinetics of oxygen reduction under alkaline conditions compared with bare glassy carbon, there is no significant correlation between the position of a metal on the periodic table and the electrocatalytic performance of its respective metal oxides. Moreover, it was also observed that mixed valent (+2, +3) oxides performed the poorest, compared with their respective pure metal oxides. These findings may be of paramount importance in the field of renewable energy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trace methane oxidation and the methane dependency of sulfate reduction in anaerobic granular sludge

KAUST Repository

Meulepas, Roel J.W.; Jagersma, Christian G.; Zhang, Yu; Petrillo, Michele; Cai, Hengzhe; Buisman, Cees J.N.; Stams, Alfons J.M.; Lens, Piet N.L.

2010-01-01

This study investigates the oxidation of labeled methane (CH4) and the CH4 dependence of sulfate reduction in three types of anaerobic granular sludge. In all samples, 13C-labeled CH4 was anaerobically oxidized to 13C-labeled CO2, while net

Maxi- and mini-ferritins: minerals and protein nanocages.

Science.gov (United States)

Bevers, Loes E; Theil, Elizabeth C

2011-01-01

Ferritins synthesize ferric oxide biominerals and are central to all life for concentrating iron and protection against oxidative stress from the ferrous and oxidant chemistry. The ferritin protein nanocages and biomineral synthesis are discussed in terms of wide biological distribution of the maxi-ferritins (24 subunit ± heme) and mini-ferritins (Dps) (12 subunit), conservations of the iron/oxygen catalytic sites in the protein cages, mineral formation (step i. Fe(II) entry and binding, step ii. O(2) or H(2)O(2) binding and formation of transition intermediates, step iii. release of differric oxo mineral precursors from active sites, step iv. nucleation and mineralization) properties of the minerals, and protein control of mineral dissolution and release of Fe(II). Pores in ferritin protein cages control iron entry for mineralization and iron exit after mineral dissolution. The relationship between phosphate or the presence of catalytically inactive subunits (animal L subunits) and ferritin iron mineral disorder is developed based on new information about contributions of ferritin protein cage structure to nucleation in protein cage subunit channels that exit close enough to those of other subunits and exiting mineral nuclei to facilitate bulk mineral formation. How and where protons move in and out of the protein during mineral synthesis and dissolution, how ferritin cage assembly with 12 or 24 subunits is encoded in the widely divergent ferritin amino acid sequences, and what is the role of the protein in synthesis of the bulk mineral are all described as problems requiring new approaches in future investigations of ferritin biominerals.

Advanced Experimental Analysis of Controls on Microbial Fe(III) Oxide Reduction - Final Report - 09/16/1996 - 03/16/2001; FINAL

International Nuclear Information System (INIS)

Roden, Eric E.

2001-01-01

Considering the broad influence that microbial Fe(III) oxide reduction can have on subsurface metal/organic contaminant biogeochemistry, understanding the mechanisms that control this process is critical for predicting the behavior and fate of these contaminants in anaerobic subsurface environments. Knowledge of the factors that influence the rates of growth and activity of Fe(III) oxide-reducing bacteria is critical for predicting (i.e., modeling) the long-term influence of these organisms on the fate of contaminants in the subsurface, and for effectively utilizing Fe(III) oxide reduction and associated geochemical affects for the purpose of subsurface metal/organic contamination bioremediation. This research project will refine existing models for microbiological and geochemical controls on Fe(III) oxide reduction, using laboratory reactor systems that mimic, to varying degrees, the physical and chemical conditions of the subsurface. Novel experimental methods for studying the kinetics of microbial Fe(III) oxide reduction and measuring growth rates of Fe(III) oxide-reducing bacteria will be developed. These new methodologies will be directly applicable to studies on subsurface contaminant transformations directly coupled to or influenced by microbial Fe(III) oxide reduction

A genetic link between magnetite mineralization and diorite intrusion at the El Romeral iron oxide-apatite deposit, northern Chile

Science.gov (United States)

Rojas, Paula A.; Barra, Fernando; Reich, Martin; Deditius, Artur; Simon, Adam; Uribe, Francisco; Romero, Rurik; Rojo, Mario

2018-01-01

El Romeral is one of the largest iron oxide-apatite (IOA) deposits in the Coastal Cordillera of northern Chile. The Cerro Principal magnetite ore body at El Romeral comprises massive magnetite intergrown with actinolite, with minor apatite, scapolite, and sulfides (pyrite ± chalcopyrite). Several generations of magnetite were identified by using a combination of optical and electron microscopy techniques. The main mineralization event is represented by zoned magnetite grains with inclusion-rich cores and inclusion-poor rims, which form the massive magnetite ore body. This main magnetite stage was followed by two late hydrothermal events that are represented by magnetite veinlets that crosscut the massive ore body and by disseminated magnetite in the andesite host rock and in the Romeral diorite. The sulfur stable isotope signature of the late hydrothermal sulfides indicates a magmatic origin for sulfur (δ34S between - 0.8 and 2.9‰), in agreement with previous δ34S data reported for other Chilean IOA and iron oxide-copper-gold deposits. New 40Ar/39Ar dating of actinolite associated with the main magnetite ore stage yielded ages of ca. 128 Ma, concordant within error with a U-Pb zircon age for the Romeral diorite (129.0 ± 0.9 Ma; mean square weighted deviation = 1.9, n = 28). The late hydrothermal magnetite-biotite mineralization is constrained at ca. 118 Ma by 40Ar/39Ar dating of secondary biotite. This potassic alteration is about 10 Ma younger than the main mineralization episode, and it may be related to post-mineralization dikes that crosscut and remobilize Fe from the main magnetite ore body. These data reveal a clear genetic association between magnetite ore formation, sulfide mineralization, and the diorite intrusion at El Romeral (at 129 Ma), followed by a late and more restricted stage of hydrothermal alteration associated with the emplacement of post-ore dikes at ca. 118 Ma. Therefore, this new evidence supports a magmatic-hydrothermal model for the

Oxidation-reduction enzymes of myocardium under ionizing radiation effect

International Nuclear Information System (INIS)

Uteshev, A.B.

1988-01-01

Tissue respiration proceses under radiation effect were investigated which allowed one to reveal slight biochemical disturbances in a cell which make up the base of functional changes of different organs and tissues and to get to know the essence of tissue respiration processes. An attempt to explain significant value of oxidation enzyme system radiosensitivity in the course of cell respiration process altogether is made when studying the state of separate links of oxidation-reduction chain. It is shown that at early periods of radiation injury activity of catalase, dehydrogenases (isocitric, α-ketoglutaric, malic, succinic acids) is suppressed, concentration of a number of cytochromes is reduced and general ferrum content is increased which is connected with conformation changes of ultrastructure of mitochondrial membranes

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

Science.gov (United States)

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

Ferrihydrite-associated organic matter (OM stimulates reduction by Shewanella oneidensis MR-1 and a complex microbial consortia

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R. E. Cooper

2017-11-01

Full Text Available The formation of Fe(III oxides in natural environments occurs in the presence of natural organic matter (OM, resulting in the formation of OM–mineral complexes that form through adsorption or coprecipitation processes. Thus, microbial Fe(III reduction in natural environments most often occurs in the presence of OM–mineral complexes rather than pure Fe(III minerals. This study investigated to what extent does the content of adsorbed or coprecipitated OM on ferrihydrite influence the rate of Fe(III reduction by Shewanella oneidensis MR-1, a model Fe(III-reducing microorganism, in comparison to a microbial consortium extracted from the acidic, Fe-rich Schlöppnerbrunnen fen. We found that increased OM content led to increased rates of microbial Fe(III reduction by S. oneidensis MR-1 in contrast to earlier findings with the model organism Geobacter bremensis. Ferrihydrite–OM coprecipitates were reduced slightly faster than ferrihydrites with adsorbed OM. Surprisingly, the complex microbial consortia stimulated by a mixture of electrons donors (lactate, acetate, and glucose mimics S. oneidensis under the same experimental Fe(III-reducing conditions suggesting similar mechanisms of electron transfer whether or not the OM is adsorbed or coprecipitated to the mineral surfaces. We also followed potential shifts of the microbial community during the incubation via 16S rRNA gene sequence analyses to determine variations due to the presence of adsorbed or coprecipitated OM–ferrihydrite complexes in contrast to pure ferrihydrite. Community profile analyses showed no enrichment of typical model Fe(III-reducing bacteria, such as Shewanella or Geobacter sp., but an enrichment of fermenters (e.g., Enterobacteria during pure ferrihydrite incubations which are known to use Fe(III as an electron sink. Instead, OM–mineral complexes favored the enrichment of microbes including Desulfobacteria and Pelosinus sp., both of which can utilize lactate and

Ferrihydrite-associated organic matter (OM) stimulates reduction by Shewanella oneidensis MR-1 and a complex microbial consortia

Science.gov (United States)

Cooper, Rebecca Elizabeth; Eusterhues, Karin; Wegner, Carl-Eric; Totsche, Kai Uwe; Küsel, Kirsten

2017-11-01

The formation of Fe(III) oxides in natural environments occurs in the presence of natural organic matter (OM), resulting in the formation of OM-mineral complexes that form through adsorption or coprecipitation processes. Thus, microbial Fe(III) reduction in natural environments most often occurs in the presence of OM-mineral complexes rather than pure Fe(III) minerals. This study investigated to what extent does the content of adsorbed or coprecipitated OM on ferrihydrite influence the rate of Fe(III) reduction by Shewanella oneidensis MR-1, a model Fe(III)-reducing microorganism, in comparison to a microbial consortium extracted from the acidic, Fe-rich Schlöppnerbrunnen fen. We found that increased OM content led to increased rates of microbial Fe(III) reduction by S. oneidensis MR-1 in contrast to earlier findings with the model organism Geobacter bremensis. Ferrihydrite-OM coprecipitates were reduced slightly faster than ferrihydrites with adsorbed OM. Surprisingly, the complex microbial consortia stimulated by a mixture of electrons donors (lactate, acetate, and glucose) mimics S. oneidensis under the same experimental Fe(III)-reducing conditions suggesting similar mechanisms of electron transfer whether or not the OM is adsorbed or coprecipitated to the mineral surfaces. We also followed potential shifts of the microbial community during the incubation via 16S rRNA gene sequence analyses to determine variations due to the presence of adsorbed or coprecipitated OM-ferrihydrite complexes in contrast to pure ferrihydrite. Community profile analyses showed no enrichment of typical model Fe(III)-reducing bacteria, such as Shewanella or Geobacter sp., but an enrichment of fermenters (e.g., Enterobacteria) during pure ferrihydrite incubations which are known to use Fe(III) as an electron sink. Instead, OM-mineral complexes favored the enrichment of microbes including Desulfobacteria and Pelosinus sp., both of which can utilize lactate and acetate as an electron

Iron oxide minerals in dust-source sediments from the Bodélé Depression, Chad: Implications for radiative properties and Fe bioavailability of dust plumes from the Sahara

Science.gov (United States)

Moskowitz, Bruce M; Reynolds, Richard L.; Goldstein, Harland L.; Beroquo, Thelma; Kokaly, Raymond F.; Bristow, Charlie S

2016-01-01

Atmospheric mineral dust can influence climate and biogeochemical cycles. An important component of mineral dust is ferric oxide minerals (hematite and goethite) which have been shown to influence strongly the optical properties of dust plumes and thus affect the radiative forcing of global dust. Here we report on the iron mineralogy of dust-source samples from the Bodélé Depression (Chad, north-central Africa), which is estimated to be Earth’s most prolific dust producer and may be a key contributor to the global radiative budget of the atmosphere as well as to long-range nutrient transport to the Amazon Basin. By using a combination of magnetic property measurements, Mössbauer spectroscopy, reflectance spectroscopy, chemical analysis, and scanning electron microscopy, we document the abundance and relative amounts of goethite, hematite, and magnetite in dust-source samples from the Bodélé Depression. The partition between hematite and goethite is important to know to improve models for the radiative effects of ferric oxide minerals in mineral dust aerosols. The combination of methods shows (1) the dominance of goethite over hematite in the source sediments, (2) the abundance and occurrences of their nanosize components, and (3) the ubiquity of magnetite, albeit in small amounts. Dominant goethite and subordinate hematite together compose about 2% of yellow-reddish dust-source sediments from the Bodélé Depression and contribute strongly to diminution of reflectance in bulk samples. These observations imply that dust plumes from the Bodélé Depression that are derived from goethite-dominated sediments strongly absorb solar radiation. The presence of ubiquitous magnetite (0.002–0.57 wt%) is also noteworthy for its potentially higher solubility relative to ferric oxide and for its small sizes, including PM iron apportionment is estimated at about 33% in ferric oxide minerals, 1.4% in magnetite, and 65% in ferric silicates. Structural iron in clay

Formation of secondary minerals in a lysimeter approach - A mineral-microbe interaction

Science.gov (United States)

Schäffner, F.; Merten, D.; De Giudici, G.; Beyer, A.; Akob, D. M.; Ricci, P. C.; Küsel, K.; Büchel, G.

2012-04-01

Heavy metal contamination of large areas due to uranium mining operations poses a serious long-term environmental problem. In the Ronneburg district (eastern Thuringia, Germany), leaching of low grade uranium bearing ores (uranium content metals, especially Cd, Ni, Co, Cu and Zn due to a residual contamination even after remediation efforts. To reveal the processes of secondary mineral precipitation in the field a laboratory lysimeter approach was set up under in situ-like conditions. Homogenized soil from the field site and pure quartz sand were used as substrates. In general, in situ measurements of redox potentials in the substrates showed highly oxidizing conditions (200-750 mV). Water was supplied to the lysimeter from below via a mariottés bottle containing contaminated groundwater from the field. Evaporation processes were allowed, providing a continuous flow of water. This led to precipitation of epsomite and probably aplowite on the top layer of substrate, similar to what is observed in field investigations. After 4 weeks, the first iron and manganese bearing secondary minerals became visible. Soil water samples were used to monitor the behaviour of metals within the lysimeter. Saturation indices (SI) for different secondary minerals were calculated with PHREEQC. The SI of goethite showed oversaturation with respect to the soil solution. SEM-EDX analyses and IR spectroscopy confirmed the formation of goethite. Geochemical data revealed that goethite formation was mainly dominated by Eh/pH processes and that heavy metals, e.g. Zn and U, could be enriched in this phase. Although Eh/pH data does not support formation of manganese minerals, Mn(II)-oxidizing bacteria (MOB) could be isolated from field soil samples, supporting the fact that microorganisms may influence this natural attenuation process. Laser ablation ICP-MS data reveal accumulation of manganese in MOB biomass on Mn(II)-containing agar plates. Furthermore, it was possible to show the importance

Reduction of Tc(VII) and Np(V) in solution by ferrous iron. A laboratory study of homogeneous and heterogeneous redox processes

International Nuclear Information System (INIS)

Cui, D.; Eriksen, T.E.

1996-03-01

The redox chemistry of Technetium and Neptunium in deep groundwater systems has been studied under well controlled conditions in laboratory experiments. The measured redox potentials in anoxic deep groundwater systems are consistent with redox reactions between Fe(II) in solution and hydrous Fe(III)-oxide phases. The fracture filling material and groundwater in transmissive fractures in bedrock constitute two different compartments in the groundwater system and experiments were therefore carried out in homogeneous Fe(II) containing solutions and in heterogeneous mixtures of solution with Fe(II) containing solid mineral phases. Reduction of the strongly sorbing neptunyl cation (NpO 2 + ) and the slightly sorbing pertechnetate anion (TcO 4 - ) by Fe(II) in solution was found to proceed very slowly, if at all, in reaction vessels with hydrophobic inner surfaces. However, in the heterogeneous systems we observed surface mediated reduction to the slightly soluble ( -8 mol*dm -3 ) tetravalent (hydr)oxides TcO 2 *nH 2 O (=Tc(OH) 4 ) and NpO 2 *nH 2 O (=Np(OH) 4 ) by Fe(II) sorbed on quartz,precipitated Fe(OH) 2 (s), Fe(II)CO 3 (s) and Fe(II) bearing minerals such as magnetite, hornblende and Fe(II)-chlorite. It is concluded that surface mediated redox-reactions will be the most effective pathway for the reduction of Tc(VII) and Np(V) in deep groundwater systems. On exposure of the surface-precipitated tetravalent (hydr)oxides to air saturated groundwater solutions the oxidative dissolution was found to be a very slow process and high concentration of hydrogen peroxide was required for oxidative dissolution. The slow rate of oxidative dissolution is most probably due to kinetic suppression of the reactions between dissolved oxygen and the precipitated (hydr)oxides. The kinetic suppression is caused by competing redox reactions at the surface of the Fe(II)-bearing minerals which consumes the dissolved oxygen. 30 refs, 22 figs

Reduction of Tc(VII) and Np(V) in solution by ferrous iron. A laboratory study of homogeneous and heterogeneous redox processes

Energy Technology Data Exchange (ETDEWEB)

Cui, D.; Eriksen, T.E. [Royal Inst. of Tech., Stockholm (Sweden). Dept. of Chemistry

1996-03-01

The redox chemistry of Technetium and Neptunium in deep groundwater systems has been studied under well controlled conditions in laboratory experiments. The measured redox potentials in anoxic deep groundwater systems are consistent with redox reactions between Fe(II) in solution and hydrous Fe(III)-oxide phases. The fracture filling material and groundwater in transmissive fractures in bedrock constitute two different compartments in the groundwater system and experiments were therefore carried out in homogeneous Fe(II) containing solutions and in heterogeneous mixtures of solution with Fe(II) containing solid mineral phases. Reduction of the strongly sorbing neptunyl cation (NpO{sub 2}{sup +}) and the slightly sorbing pertechnetate anion (TcO{sub 4}{sup -}) by Fe(II) in solution was found to proceed very slowly, if at all, in reaction vessels with hydrophobic inner surfaces. However, in the heterogeneous systems we observed surface mediated reduction to the slightly soluble (<10{sub -8} mol*dm{sup -3}) tetravalent (hydr)oxides TcO{sub 2}*nH{sub 2}O (=Tc(OH){sub 4}) and NpO{sub 2}*nH{sub 2}O (=Np(OH){sub 4}) by Fe(II) sorbed on quartz,precipitated Fe(OH){sub 2}(s), Fe(II)CO{sub 3}(s) and Fe(II) bearing minerals such as magnetite, hornblende and Fe(II)-chlorite. It is concluded that surface mediated redox-reactions will be the most effective pathway for the reduction of Tc(VII) and Np(V) in deep groundwater systems. On exposure of the surface-precipitated tetravalent (hydr)oxides to air saturated groundwater solutions the oxidative dissolution was found to be a very slow process and high concentration of hydrogen peroxide was required for oxidative dissolution. The slow rate of oxidative dissolution is most probably due to kinetic suppression of the reactions between dissolved oxygen and the precipitated (hydr)oxides. The kinetic suppression is caused by competing redox reactions at the surface of the Fe(II)-bearing minerals which consumes the dissolved oxygen.

Predictors of bone mineral density reduction in adolescents with anorexia nervosa.

Science.gov (United States)

Castro, J; Lázaro, L; Pons, F; Halperin, I; Toro, J

2000-11-01

To determine which variables are associated with a significant reduction in bone mineral density (BMD) in adolescent anorexia nervosa and to establish guidelines for indication of bone densitometry. One hundred seventy patients (treated from 1997 until 1999), aged 10 to 17 years, with a DSM-IV diagnosis of anorexia nervosa were evaluated by dual-energy-x-ray absorptiometry in the lumbar spine (L2-L4) and the femoral neck. The results were compared with the normative data for BMD values by age and sex in Spanish adolescents. 44.1% of patients had osteopenia at the lumbar spine and 24.7% at the femoral neck. The following variables were related to osteopenia: more than 12 months since onset of the disorder (p anorexia nervosa patients with the characteristics outlined above are at high risk of reduced BMD, and densitometry is recommended to determine the degree of osteopenia.

Low Temperature Selective Catalytic Reduction of Nitrogen Oxides in Production of Nitric Acid by the Use of Liquid

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Kabljanac, Ž.

2011-11-01

Full Text Available This paper presents the application of low-temperature selective catalytic reduction of nitrous oxides in the tail gas of the dual-pressure process of nitric acid production. The process of selective catalytic reduction is carried out using the TiO2/WO3 heterogeneous catalyst applied on a ceramic honeycomb structure with a high geometric surface area per volume. The process design parameters for nitric acid production by the dual-pressure procedure in a capacity range from 75 to 100 % in comparison with designed capacity for one production line is shown in the Table 1. Shown is the effectiveness of selective catalytic reduction in the temperature range of the tail gas from 180 to 230 °C with direct application of liquid ammonia, without prior evaporation to gaseous state. The results of inlet and outlet concentrations of nitrous oxides in the tail gas of the nitric acid production process are shown in Figures 1 and 2. Figure 3 shows the temperature dependence of the selective catalytic reduction of nitrous oxides expressed as NO2in the tail gas of nitric acid production with the application of a constant mass flow of liquid ammonia of 13,0 kg h-1 and average inlet mass concentration of the nitrous oxides expressed as NO2of 800,0 mgm-3 during 100 % production capacity. The specially designed liquid-ammonia direct-dosing system along with the effective homogenization of the tail gas resulted in emission levels of nitrous oxides expressed as NO2 in tail gas ranging from 100,0 to 185,0 mg m-3. The applied low-temperature selective catalytic reduction of the nitrous oxides in the tail gases by direct use of liquid ammonia is shown in Figure 4. It is shown that low-temperature selective catalytic reduction with direct application of liquid ammonia opens a new opportunity in the reduction of nitrous oxide emissions during nitric acid production without the risk of dangerous ammonium nitrate occurring in the process of subsequent energy utilization of

Primary oxidation and reduction products in x-irradiated aspartic acid

International Nuclear Information System (INIS)

Adams, S.M.; Budzinski, E.E.; Box, H.C.

1976-01-01

The primary reduction products identified by ESR--ENDOR spectroscopy in single crystals of DL-aspartic acid hydrochloride irradiated at 4.2degreeK are anions formed by addition of an electron to the carbonyl oxygen atoms of the carboxylic acid groups. The main consequence of the oxidation process is to produce a hole centered mainly on atomic chlorine

Electron Transfer between Electrically Conductive Minerals and Quinones

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Olga Taran

2017-07-01

Full Text Available Long-distance electron transfer in marine environments couples physically separated redox half-reactions, impacting biogeochemical cycles of iron, sulfur and carbon. Bacterial bio-electrochemical systems that facilitate electron transfer via conductive filaments or across man-made electrodes are well-known, but the impact of abiotic currents across naturally occurring conductive and semiconductive minerals is poorly understood. In this paper I use cyclic voltammetry to explore electron transfer between electrodes made of common iron minerals (magnetite, hematite, pyrite, pyrrhotite, mackinawite, and greigite, and hydroquinones—a class of organic molecules found in carbon-rich sediments. Of all tested minerals, only pyrite and magnetite showed an increase in electric current in the presence of organic molecules, with pyrite showing excellent electrocatalytic performance. Pyrite electrodes performed better than commercially available glassy carbon electrodes and showed higher peak currents, lower overpotential values and a smaller separation between oxidation and reduction peaks for each tested quinone. Hydroquinone oxidation on pyrite surfaces was reversible, diffusion controlled, and stable over a large number of potential cycles. Given the ubiquity of both pyrite and quinones, abiotic electron transfer between minerals and organic molecules is likely widespread in Nature and may contribute to several different phenomena, including anaerobic respiration of a wide variety of microorganisms in temporally anoxic zones or in the proximity of hydrothermal vent chimneys, as well as quinone cycling and the propagation of anoxic zones in organic rich waters. Finally, interactions between pyrite and quinones make use of electrochemical gradients that have been suggested as an important source of energy for the origins of life on Earth. Ubiquinones and iron sulfide clusters are common redox cofactors found in electron transport chains across all domains

Electron Transfer Between Electrically Conductive Minerals and Quinones

Science.gov (United States)

Taran, Olga

2017-07-01

Long-distance electron transfer in marine environments couples physically separated redox half-reactions, impacting biogeochemical cycles of iron, sulfur and carbon. Bacterial bio-electrochemical systems that facilitate electron transfer via conductive filaments or across man-made electrodes are well known, but the impact of abiotic currents across naturally occurring conductive and semiconducitve minerals is poorly understood. In this paper I use cyclic voltammetry to explore electron transfer between electrodes made of common iron minerals (magnetite, hematite, pyrite, pyrrhotite, mackinawite and greigite), and hydroquinones - a class of organic molecules found in carbon-rich sediments. Of all tested minerals, only pyrite and magnetite showed an increase in electric current in the presence of organic molecules, with pyrite showing excellent electrocatalytic performance. Pyrite electrodes performed better than commercially available glassy carbon electrodes and showed higher peak currents, lower overpotential values and a smaller separation between oxidation and reduction peaks for each tested quinone. Hydroquinone oxidation on pyrite surfaces was reversible, diffusion controlled, and stable over a large number of potential cycles. Given the ubiquity of both pyrite and quinones, abiotic electron transfer between minerals and organic molecules is likely widespread in Nature and may contribute to several different phenomena, including anaerobic respiration of a wide variety of microorganisms in temporally anoxic zones or in the proximity of hydrothermal vent chimneys, as well as quinone cycling and the propagation of anoxic zones in organic rich waters. Finally, interactions between pyrite and quinones make use of electrochemical gradients that have been suggested as an important source of energy for the origins of life on Earth. Ubiquinones and iron sulfide clusters are common redox cofactors found in electron transport chains across all domains of life and

In situ reduction of as-prepared γ-Iron Oxide Nanoparticles

DEFF Research Database (Denmark)

Garbus, Pelle Gorm; Ahlburg, Jakob; Christensen, Mogens

-ray diffraction measurement. The as-prepared maghemite nanoparticles were synthesized by the continuous decomposition of solutes in supercritical hydrothermal flow synthesis [3, 4]. The reagent used was ferric ammonium citrate (C6H8O7•xFe(III)•yNH3) that under hydrothermal flow synthesis decomposes into the γ......-iron oxide Fe2O3. The reduction of maghemite to body centered cubic (BCC) iron does not go through a detectable intermediate state.1.Jensen, K.M., et al., Mechanisms for iron oxide formation under hydrothermal conditions: an in situ total scattering study. ACS nano, 2014. 8(10): p. 10704-10714.2.Andersen, H...

Degradation of azo dyes by sequential Fenton's oxidation and aerobic biological treatment

International Nuclear Information System (INIS)

Tantak, Nilesh P.; Chaudhari, Sanjeev

2006-01-01

A two stage sequential Fenton's oxidation followed by aerobic biological treatment train was used to achieve decolorization and to enhance mineralization of azo dyes, viz. Reactive Black 5 (RB5), Reactive Blue 13 (RB13), and Acid Orange 7 (AO7). In the first stage, Fenton's oxidation process was used while in the second stage aerobic sequential batch reactors (SBRs) were used as biological process. Study was done to evaluate effect of pH on Fenton's oxidation process. Results reveal that pH 3 was optimum pH for achieving decolorization and dearomatization of dyes by Fenton's process. Degradation of dye was assessed by COD reduction and reduction in aromatic amines (naphthalene chromophores) which was measured by reduction in absorbance at 200 nm. More than 95% of color was removed with Fenton's oxidation process in all dyes. In overall treatment train 81.95, 85.57, and 77.83% of COD reduction was achieved in RB5, RB13, and AO7 dyes, respectively. In the Fenton's oxidation process 56, 24.5, and 80% reduction in naphthalene group was observed in RB5, RB13, and AO7, respectively, which further increased to 81.34, 68.73, and 92% after aerobic treatment. Fenton's oxidation process followed by aerobic SBRs treatment sequence seems to be viable method for achieving significant degradation of azo dye

Determination of reduction yield of lithium metal reduction process

International Nuclear Information System (INIS)

Choi, In Kyu; Cho, Young Hwan; Kim, Taek Jin; Jee, Kwang Young

2004-01-01

Metal reduction of spent oxide fuel is the first step for the effective storage of spent fuel in Korea as well as transmutation purpose of long-lived radio-nuclides. During the reduction of uranium oxide by lithium metal to uranium metal, lithium oxide is stoichiometrically produced. By determining the concentration of lithium oxide in lithium chloride, we can estimate that how much uranium oxide is converted to uranium metal. Previous method to determine the lithium oxide concentration in lithium chloride is tedious and timing consuming. This paper describe the on-line monitoring method of lithium oxide during the reduction process

Reduction of antibiotic resistance genes in municipal wastewater effluent by advanced oxidation processes

International Nuclear Information System (INIS)

Zhang, Yingying; Zhuang, Yao; Geng, Jinju; Ren, Hongqiang; Xu, Ke; Ding, Lili

2016-01-01

This study investigated the reduction of antibiotic resistance genes (ARGs), intI1 and 16S rRNA genes, by advanced oxidation processes (AOPs), namely Fenton oxidation (Fe"2"+/H_2O_2) and UV/H_2O_2 process. The ARGs include sul1, tetX, and tetG from municipal wastewater effluent. The results indicated that the Fenton oxidation and UV/H_2O_2 process could reduce selected ARGs effectively. Oxidation by the Fenton process was slightly better than that of the UV/H_2O_2 method. Particularly, for the Fenton oxidation, under the optimal condition wherein Fe"2"+/H_2O_2 had a molar ratio of 0.1 and a H_2O_2 concentration of 0.01 mol L"−"1 with a pH of 3.0 and reaction time of 2 h, 2.58–3.79 logs of target genes were removed. Under the initial effluent pH condition (pH = 7.0), the removal was 2.26–3.35 logs. For the UV/H_2O_2 process, when the pH was 3.5 with a H_2O_2 concentration of 0.01 mol L"−"1 accompanied by 30 min of UV irradiation, all ARGs could achieve a reduction of 2.8–3.5 logs, and 1.55–2.32 logs at a pH of 7.0. The Fenton oxidation and UV/H_2O_2 process followed the first-order reaction kinetic model. The removal of target genes was affected by many parameters, including initial Fe"2"+/H_2O_2 molar ratios, H_2O_2 concentration, solution pH, and reaction time. Among these factors, reagent concentrations and pH values are the most important factors during AOPs. - Highlights: • AOPs including Fenton oxidation and UV/H_2O_2 process could reduce ARGs effectively. • Fenton oxidation is slightly more effective than UV/H_2O_2 process in ARG reduction. • Removal of ARGs by AOPs follows the first-order reaction kinetic model. • Selected ARGs and 16S rRNA genes exhibit similar change trends during AOPs.

Oxaloacetate-to-malate conversion by mineral photoelectrochemistry: implications for the viability of the reductive tricarboxylic acid cycle in prebiotic chemistry

Science.gov (United States)

Guzman, Marcelo I.; Martin, Scot T.

2008-10-01

The carboxylic acids produced by the reductive tricarboxylic acid (rTCA) cycle are possibly a biosynthetic core of initial life, although several steps such as the reductive kinetics of oxaloacetate (OAA) to malate (MA) are problematic by conventional chemical routes. In this context, we studied the kinetics of this reaction as promoted by ZnS mineral photoelectrochemistry. The quantum efficiency φMA of MA production from the photoelectrochemical reduction of OAA followed φMA=0.13 [OAA] (2.1×10-3+[OAA])-1 and was independent of temperature (5 to 50°C). To evaluate the importance of this forward rate under a prebiotic scenario, we also studied the temperature-dependent rate of the backward thermal decarboxylation of OAA to pyruvate (PA), which followed an Arrhenius behavior as log (k-2)=11.74 4956/T, where k-2 is in units of s-1. These measured rates were employed in conjunction with the indirectly estimated carboxylation rate of PA to OAA to assess the possible importance of mineral photoelectrochemistry in the conversion of OAA to MA under several scenarios of prebiotic conditions on early Earth. As an example, our analysis shows that there is 90% efficiency with a forward velocity of 3 yr/cycle for the OAA→MA step of the rTCA cycle at 280 K. Efficiency and velocity both decrease for increasing temperature. These results suggest high viability for mineral photoelectrochemistry as an enzyme-free engine to drive the rTCA cycle through the early aeons of early Earth, at least for the investigated OAA→MA step.

A study on the electrolytic reduction of uranium oxide in a LiCl-Li2O molten salt

International Nuclear Information System (INIS)

Su, J. S.; Hu, J. M.; Hong, S. S.; Jang, D. S.; Park, S. W.

2003-01-01

New electrolytic reduction technology was proposed that is based on the integration of metallization of uranium oxide and Li 2 O electrowinning. In this electrolytic reduction reaction, electrolytically reduced Li deposits on cathode and simultaneously reacts with uranium oxides to produce uranium metal showing more than 99% conversion. For the verification of process feasibility, the experiments to obtain basic data on the metallization of uranium oxide, investigation of reaction mechanism, the characteristics of closed recycle of Li 2 O and mass transfer were carried out. This evolutionary electrolytic reduction technology would give benefits over the conventional Li-reduction process improving economic viability such as: avoidance of handling of chemically active Li-LiCl molten salt, increase of metallization yield, and simplification of process

Biogeochemical Processes Controlling Microbial Reductive Precipitation of Radionuclides

International Nuclear Information System (INIS)

Fredrickson, James K.; Brooks, Scott C.

2004-01-01

This project is focused on elucidating the principal biogeochemical reactions that govern the concentrations, chemical speciation, and distribution of the redox sensitive contaminants uranium (U) and technetium (Tc) between the aqueous and solid phases. The research is designed to provide new insights into the under-explored areas of competing geochemical and microbiological oxidation-reduction reactions that govern the fate and transport of redox sensitive contaminants and to generate fundamental scientific understanding of the identity and stoichiometry of competing microbial reduction and geochemical oxidation reactions. These goals and objectives are met through a series of hypothesis-driven tasks that focus on (1) the use of well-characterized microorganisms and synthetic and natural mineral oxidants, (2) advanced spectroscopic and microscopic techniques to monitor redox transformations of U and Tc, and (3) the use of flow-through experiments to more closely approximate groundwater environments. The results are providing an improved understanding and predictive capability of the mechanisms that govern the redox dynamics of radionuclides in subsurface environments. For purposes of this poster, the results are divided into three sections: (1) influence of Ca on U(VI) bioreduction; (2) localization of biogenic UO 2 and TcO 2 ; and (3) reactivity of Mn(III/IV) oxides.

Solid-phase electrochemical reduction of graphene oxide films in alkaline solution

Science.gov (United States)

Basirun, Wan J.; Sookhakian, Mehran; Baradaran, Saeid; Mahmoudian, Mohammad R.; Ebadi, Mehdi

2013-09-01

Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO.

Thermogravimetric study of the reduction of oxides of nickel and chromium

Science.gov (United States)

Herbell, T. P.

1973-01-01

The effectiveness of hydrogen, carbon and hydrogen-carbon in reducing NiO, Cr2O3, mixed NiO-Cr2O3 and oxidized Ni-20Cr was evaluated by thermogravimetry. NiO was effectively reduced by all three atmospheres, Cr2O3 only by hydrogen-carbon, NiO-Cr2O3 by hydrogen and hydrogen-carbon and oxidized Ni-20Cr by hydrogen, hydrogen-carbon and partially by carbon alone. The results indicate that nickel and carbon promote the reduction of Cr2O3.

Removal of oxides from alkali metal melts by reductive titration to electrical resistance-change end points

Science.gov (United States)

Tsang, Floris Y.

1980-01-01

Alkali metal oxides dissolved in alkali metal melts are reduced with soluble metals which are converted to insoluble oxides. The end points of the reduction is detected as an increase in electrical resistance across an alkali metal ion-conductive membrane interposed between the oxide-containing melt and a material capable of accepting the alkali metal ions from the membrane when a difference in electrical potential, of the appropriate polarity, is established across it. The resistance increase results from blocking of the membrane face by ions of the excess reductant metal, to which the membrane is essentially non-conductive.

Oxidation and Reduction of Liquid SnPb (60/40) under Ambient and Vacuum Conditions

DEFF Research Database (Denmark)

Kuhmann, Jochen Friedrich; Maly, K.; Preuss, A.

1998-01-01

One of the most straightforward approaches to fluxless solder bonding is using vacuum conditions to prevent further oxidation and, where needed, to reduce solder oxides by the use of molecular hydrogen (H-2).(1-3) This study On oxidation and reduction of solder oxides on SnPb (60/40) is aimed...... to provide a better understanding for fluxless solder bonding applications under controlled atmospheric conditions; By means of scanning Auger spectroscopy it is shown, that growth of oxide films on metallic SnPb above the eutectic temperature can be significantly reduced by decreasing the O-2 partial...

The Simulation of an Oxidation-Reduction Titration Curve with Computer Algebra

Science.gov (United States)

Whiteley, Richard V., Jr.

2015-01-01

Although the simulation of an oxidation/reduction titration curve is an important exercise in an undergraduate course in quantitative analysis, that exercise is frequently simplified to accommodate computational limitations. With the use of readily available computer algebra systems, however, such curves for complicated systems can be generated…

A rapid in situ method for determining the ages of uranium oxide minerals: Evolution of the Cigar Lake deposit, Athabasca Basin

International Nuclear Information System (INIS)

Fayek, M.; Harrison, T.M.; Grove, M.; Coath, C.D.

2000-01-01

The authors present a rapid and accurate technique for making in situ U-Pb isotopic measurements of uranium oxide minerals that utilizes both electron and ion microprobes. U and Pb concentrations are determined using an electron microprobe, whereas the isotopic composition of Pb for the same area is measured using a high-resolution ion microprobe. The advantages of this approach are: mineral separation and chemical digestion are unnecessary; homogeneous uranium oxide standards, which are difficult to obtain, are not required; and precise and accurate U-Pb ages on ∼10 microm spots can be obtained in a matter of hours. The authors have applied their method to study the distribution of U-Pb ages in complexly intergrown uranium oxides from the unconformity-type Cigar Lake uranium deposit, Saskatchewan, Canada. In situ U-Pb results from early formed uraninite define a well-correlated array on concordia with upper and lower intercepts of 1,467 ± 63 Ma and 443 ± 96 Ma (±1σ), respectively. The 1,467 Ma age is interpreted as the minimum age of mineralization and is consistent with the age of clay-mineral alteration (approximately1477 Ma) and magnetization of diagenetic hematite (1,650 to 1,450 Ma) that is associated with these unconformity-type uranium deposits and early diagenesis of the Athabasca Basin sediments. In situ U-Pb isotopic analysis of uraninite and coffinite can document the Pb*/U heterogeneities that can occur on a scale of 15 to 30 microm, thus providing relatively accurate information regarding the timing of fluid interactions associated with the evolution of these deposits

Microbial Mineral Transformations at the Fe(II)/Fe(III) Redox Boundary for Solid Phase Capture of Strontium and Other Metal/Radionuclide Contaminants

International Nuclear Information System (INIS)

Ferris, F.G.; Roden, E.E.

2000-01-01

The migration of 90 Sr in groundwater is a significant environmental concern at former nuclear weapons production sites in the US and abroad. Although retardation of 90 Sr transport relative to mean groundwater velocity is known to occur in contaminated aquifers, Sr 2+ does not sorb as strongly to iron oxides and other mineral phases as do other metal-radionuclides contaminants. Thus, some potential exists for extensive 90 Sr migration from sources of contamination. Chemical or biological processes capable of retarding or immobilizing Sr 2+ in groundwater environments are of interest from the standpoint of understanding controls on subsurface Sr 2+ migration. In addition, it may be possible to exploit such processes for remediation of subsurface Sr contamination. In this study the authors examined the potential for the solid phase sorption and incorporation of Sr 2+ into carbonate minerals formed during microbial Fe(III) oxide reduction as a first step toward evaluating whether this process could be used to promote retardation of 90 Sr migrations in anaerobic subsurface environments. The demonstration of Sr 2+ capture in carbonate mineral phases formed during bacterial HFO reduction and urea hydrolysis suggests that microbial carbonate mineral formation could contribute to Sr 2+ retardation in groundwater environments. This process may also provide a mechanism for subsurface remediation of Sr 2+ and other divalent metal contaminants that form insoluble carbonate precipitates

Oxidation-reduction induced roughening of platinum (111) surface

International Nuclear Information System (INIS)

You, H.; Nagy, Z.

1993-06-01

Platinum (111) single crystal surface was roughened by repeated cycles of oxidation and reduction to study dynamic evolution of surface roughening. The interface roughens progressively upon repeated cycles. The measured width of the interface was fit to an assumed pow law, W ∼t β , with β = 0.38(1). The results are compared with a simulation based on a random growth model. The fraction of the singly stepped surface apparently saturates to 0. 25 monolayer, which explains the apparent saturation to a steady roughness observed in previous studies

Sorption of pesticides to aquifer minerals

DEFF Research Database (Denmark)

Clausen, Liselotte; Fabricius, Ida Lykke

2000-01-01

This paper summarizes results from a work were the sorption of five pesticides on seven minerals were studied in order to quantify the adsorption to different mineral surfaces. Investigated mineral phases are: quartz, calcite, kaolinite, a-alumina, and three iron oxides (2-line ferrihydrite......, goethite, lepidocrocite). Selected pesticides are: atrazine, isoproturon, mecoprop, 2,4-D, and bentazone. The results demonstrate that pesticides adsorb to pure mineral surfaces. However, the size of the adsorption depends on the type of pesticide and the type of mineral....

Surveying Clay Mineral Diversity in the Murray Formation, Gale Crater, Mars

Science.gov (United States)

Bristow, T.F.; Blake, D. F..; Vaniman, D. T.; Chipera, S. J.; Rampe, E. B.; Grotzinger, J. P.; McAdam, A. C.; Ming, D. W..; Morrison, S. M.; Yen, A. S.;

Electrodeposition of uranium metal by reduction of uranium oxides in molten Lif-KF=NaF-CaF 2-UF4

International Nuclear Information System (INIS)

Pao, D.S.; Burris, L.; Steunenberg, R.K.; Tomczuk, Z.

1990-01-01

Although electrolytic reduction of uranium oxides was shown to be feasible in the early 1960's it is recognized that considerable improvement in the electrolytic reduction technology must be achieved for practical applications. This exploratory work on electrolytic reduction of uranium oxide was undertaken to investigate potential improvements in the technology. The approach taken was to deposit solid uranium metal directly on a solid cathode at temperatures below the melting point of uranium (1132 degrees C). The lower temperature electrolytic reduction process has several advantages over the existing chemical reduction processes. It lessens materials problems and special heating and insulating requirements associated with high-temperature operations. It removes most impurities. It does not produce the large quantities of byproduct oxides wastes typical of chemical reduction processes

Study of the Electrolytic Reduction of Uranium Oxide in LiCl-Li2O Molten Salts with an Integrated Cathode Assembly

International Nuclear Information System (INIS)

Park, Sung Bin; Seo, Chung Seok; Kang, Dae Seung; Kwon, Seon Gil; Park, Seong Won

2005-01-01

The electrolytic reduction of uranium oxide in a LiCl-Li 2 O molten salt system has been studied in a 10 g U 3 O 3 /batch-scale experimental apparatus with an integrated cathode assembly at 650 .deg. C. The integrated cathode assembly consists of an electric conductor, the uranium oxide to be reduced and the membrane for loading the uranium oxide. From the cyclic voltammograms for the LiCl-3 wt% Li 3 O system and the U 3 O 3 -LiCl-3 wt% Li 2 O system according to the materials of the membrane in the cathode assembly, the mechanisms of the predominant reduction reactions in the electrolytic reactor cell were to be understood; direct and indirect electrolytic reduction of uranium oxide. Direct and indirect electrolytic reductions have been performed with the integrated cathode assembly. Using the 325-mesh stainless steel screen the uranium oxide failed to be reduced to uranium metal by a direct and indirect electrolytic reduction because of a low current efficiency and with the porous magnesia membrane the uranium oxide was reduced successfully to uranium metal by an indirect electrolytic reduction because of a high current efficiency.

Ice nucleation by surrogates for atmospheric mineral dust and mineral dust/sulfate particles at cirrus temperatures

Directory of Open Access Journals (Sweden)

C. M. Archuleta

2005-01-01

Full Text Available This study examines the potential role of some types of mineral dust and mineral dust with sulfuric acid coatings as heterogeneous ice nuclei at cirrus temperatures. Commercially-available nanoscale powder samples of aluminum oxide, alumina-silicate and iron oxide were used as surrogates for atmospheric mineral dust particles, with and without multilayer coverage of sulfuric acid. A sample of Asian dust aerosol particles was also studied. Measurements of ice nucleation were made using a continuous-flow ice-thermal diffusion chamber (CFDC operated to expose size-selected aerosol particles to temperatures between -45 and -60°C and a range of relative humidity above ice-saturated conditions. Pure metal oxide particles supported heterogeneous ice nucleation at lower relative humidities than those required to homogeneously freeze sulfuric acid solution particles at sizes larger than about 50 nm. The ice nucleation behavior of the same metal oxides coated with sulfuric acid indicate heterogeneous freezing at lower relative humidities than those calculated for homogeneous freezing of the diluted particle coatings. The effect of soluble coatings on the ice activation relative humidity varied with the respective uncoated core particle types, but for all types the heterogeneous freezing rates increased with particle size for the same thermodynamic conditions. For a selected size of 200 nm, the natural mineral dust particles were the most effective ice nuclei tested, supporting heterogeneous ice formation at an ice relative humidity of approximately 135%, irrespective of temperature. Modified homogeneous freezing parameterizations and theoretical formulations are shown to have application to the description of heterogeneous freezing of mineral dust-like particles with soluble coatings.

Interim glycol flowsheet reduction/oxidation (redox) model for the Defense Waste Processing Facility (DWPF)

Energy Technology Data Exchange (ETDEWEB)

Jantzen, C. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Williams, M. S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Zamecnik, J. R. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Missimer, D. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2016-03-08

Control of the REDuction/OXidation (REDOX) state of glasses containing high concentrations of transition metals, such as High Level Waste (HLW) glasses, is critical in order to eliminate processing difficulties caused by overly reduced or overly oxidized melts. Operation of a HLW melter at Fe⁺²/ΣFe ratios of between 0.09 and 0.33, a range which is not overly oxidizing or overly reducing, helps retain radionuclides in the melt, i.e. long-lived radioactive ⁹⁹Tc species in the less volatile reduced Tc⁴⁺ state, ¹⁰⁴Ru in the melt as reduced Ru⁺⁴ state as insoluble RuO₂, and hazardous volatile Cr⁶⁺ in the less soluble and less volatile Cr⁺³ state in the glass. The melter REDOX control balances the oxidants and reductants from the feed and from processing additives such as antifoam. Currently, the Defense Waste Processing Facility (DWPF) is running a formic acid-nitric acid (FN) flowsheet where formic acid is the main reductant and nitric acid is the main oxidant. During decomposition formate and formic acid releases H₂ gas which requires close control of the melter vapor space flammability. A switch to a nitric acid-glycolic acid (GN) flowsheet is desired as the glycolic acid flowsheet releases considerably less H₂ gas upon decomposition. This would greatly simplify DWPF processing. Development of an EE term for glycolic acid in the GN flowsheet is documented in this study.

Facile synthesis of reduced graphene oxide nanosheets by a sodium diphenylamine sulfonate reduction process and its electrochemical property

International Nuclear Information System (INIS)

Ji, Yunzhou; Liu, Qi; Cheng, Meiling; Lai, Lifang; Li, Zhanfeng; Peng, Yuxin; Yang, Yong

2013-01-01

We report a new method to convert graphene oxide (GO) to stable colloidal dispersion of reduced graphene oxide nanosheets (RGONS) using sodium diphenylamine sulfonate (SDAS) as a reductant, as well as itself and its redox product as the stabilizer. The as-prepared RGONS have been characterized by X-ray diffraction, Fourier transform infrared spectroscopy, UV–visible spectroscopy, thermo-gravimetric analysis, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, atomic force microscopy and Raman spectroscopy. The results indicate that the bulk of oxygen-containing functional groups from GO have been removed. Based on the cyclic voltammogram (CV) analyses, it is found that the RGONS-based material exhibits better electrochemical activity in sensing ascorbic acid than GO. The simple method provides a new efficient route for the synthesis of water-soluble RGONS on a large scale and novel composites. - Highlights: • We report a new environment-friendly reductant for the reduction of graphene oxide. • The reduction process needn't use other stabilizer except for using reductant. • The reduced graphene oxide nanosheet (RGONS) aqueous dispersion is stable. • The RGONS shows a high electrochemical activity in sensing ascorbic acid

Anaerobic oxidation of methane coupled to thiosulfate reduction in a biotrickling filter.

Science.gov (United States)

Cassarini, Chiara; Rene, Eldon R; Bhattarai, Susma; Esposito, Giovanni; Lens, Piet N L

2017-09-01

Microorganisms from an anaerobic methane oxidizing sediment were enriched with methane gas as the substrate in a biotrickling filter (BTF) using thiosulfate as electron acceptor for 213days. Thiosulfate disproportionation to sulfate and sulfide were the dominating sulfur conversion process in the BTF and the sulfide production rate was 0.5mmoll -1 day -1 . A specific group of sulfate reducing bacteria (SRB), belonging to the Desulforsarcina/Desulfococcus group, was enriched in the BTF. The BTF biomass showed maximum sulfate reduction rate (0.38mmoll -1 day -1 ) with methane as sole electron donor, measured in the absence of thiosulfate in the BTF. Therefore, a BTF fed with thiosulfate as electron acceptor can be used to enrich SRB of the DSS group and activate the inoculum for anaerobic oxidation of methane coupled to sulfate reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Results of Study of Sulfur Oxide Reduction During Combustion of Coal-Water Slurry Fuel Through use of Sulfur Capturing Agents

Directory of Open Access Journals (Sweden)

Murko Vasiliy I.

2016-01-01

Full Text Available It is shown that an effective way of burning high sulfur coal is to burn coal-water slurry fuel (CWF prepared on its basis containing a sulfur capture agent (SCA entered in the slurry at the stage of preparation. The technique of thermodynamic analysis of chemical reactions during CWF burning has been developed including burning in the presence of SCA. Using the developed calculation program, the optimal temperature conditions have been determined as required for the effective reduction of sulfur oxides in flue gases when using different types of SCA. According to the results of calculating the composition of CWF combustion products when entering various substances in the burner space as SCA it has been determined that magnesite, calcite, and dolomite are the most effective natural minerals. The analysis of calculated and experimental data proves the efficiency of SCA addition as well as validity of the obtained results.

Organic matter in uranium concentration during ancient bed oxidation of carboniferons sediments

International Nuclear Information System (INIS)

Kruglova, V.G.; Uspenskij, V.A.; Dement'ev, P.K.; Kochenov, A.V.

1984-01-01

Changes in the organic matter accompanying the process of epigenetic ore formation are studied using the example of a deposit localized in carboniferous molasse strata of the Cretaceous period. Peculiarities of the organic matter as the main mineralization agent are studied by a complex of physical and themical methods. A distinct relationship between the uranium concentration and the degree of organic matter oxigenation is a most characteristic feature of the ore localization, however, there is no direct correlation between the contents of uranium and organic matter in ores. Uranium minerallzation was accumulated during infiltration of acid uraniferous.waters into grey stratum in the process of the bed oxidation zone formation oxidizing. Brown coal matter possessing a maximum adsorbability, as compared to other sedimentary rocks, apprared to be the uranium precipitator. The adsorption was accompanie by the formation of proper uranium minerals (coffinite, pitchblende) due to uranium reduction by oxidizing organic matter. Thus, the oxidative epigenesis was an are-forming process with the uranium concentration on organic matter proportionally to oxidation of the latter

Reduction of Mn-oxides by ferrous iron in a flow system: column experiment and reactive transport modeling

DEFF Research Database (Denmark)

Postma, Diederik Jan; Appelo, C. A. J.

2000-01-01

Cl2 solution into the column, an ion distribution pattern was observed in the effluent that suggests the formation of separate reaction fronts for Mn(III)-oxide and Mn(IV)-oxide travelling at different velocities through the column. At the proximal reaction front, Fe21 reacts with MnO2 producing Fe......The reduction of Mn-oxide by Fe21 was studied in column experiments, using a column filled with natural Mn-oxide coated sand. Analysis of the Mn-oxide indicated the presence of both Mn(III) and Mn(IV) in the Mn-oxide. The initial exchange capacity of the column was determined by displacement...... of adsorbed Ca21 with Mg21. Subsequently a FeCl2 solution was injected into the column causing the reduction of the Mn-oxide and the precipitation of Fe(OH)3. Finally the exchange capacity of the column containing newly formed Fe(OH)3 was determined by injection of a KBr solution. During injection of the Fe...

Fe-Impregnated Mineral Colloids for Peroxide Activation: Effects of Mineral Substrate and Fe Precursor.

Science.gov (United States)

Li, Yue; Machala, Libor; Yan, Weile

2016-02-02

Heterogeneous iron species at the mineral/water interface are important catalysts for the generation of reactive oxygen species at circumneutral pH. One significant pathway leading to the formation of such species arises from deposition of dissolved iron onto mineral colloids due to changes in redox conditions. This study investigates the catalytic properties of Fe impregnated on silica, alumina, and titania nanoparticles (as prototypical mineral colloids). Fe impregnation was carried out by immersing the mineral nanoparticles in dilute Fe(II) or Fe(III) solutions at pH 6 and 3, respectively, in an aerobic environment. The uptake of iron per unit surface area follows the order of nTiO2 > nAl2O3 > nSiO2 for both types of Fe precursors. Impregnation of mineral particles in Fe(II) solutions results in predominantly Fe(III) species due to efficient surface-mediated oxidation. The catalytic activity of the impregnated solids to produce hydroxyl radical (·OH) from H2O2 decomposition was evaluated using benzoic acid as a probe compound under dark conditions. Invariably, the rates of benzoic acid oxidation with different Fe-laden particles increase with the surface density of Fe until a critical density above which the catalytic activity approaches a plateau, suggesting active Fe species are formed predominantly at low surface loadings. The critical surface density of Fe varies with the mineral substrate as well as the aqueous Fe precursor. Fe impregnated on TiO2 exhibits markedly higher activity than its Al2O3 and SiO2 counterparts. The speciation of interfacial Fe is analyzed with diffuse reflectance UV-vis analysis and interpretation of the data in the context of benzoic oxidation rates suggests that the surface activity of the solids for ·OH generation correlates strongly with the isolated (i.e., mononuclear) Fe species. Therefore, iron dispersed on mineral colloids is a significant form of reactive iron surfaces in the aquatic environment.

Production of SmCo5 alloy by calciothermic reduction of samarium oxide

International Nuclear Information System (INIS)

Krishnan, T.S.; Gupta, C.K.

1988-01-01

Among the established permanent magnets, SmCo 5 magnet occupies the foremost position as it offers a unique combination of high energy product, coercivity and curie temperature. The SmCo 5 magnets are thus extensively used for high field applications. These are also best suited for use in environments where high demagnetizing field and high temperature are operative. Also, for applications where high performance and miniaturization are the over-riding considerations, the choice again falls on SmCo 5 magnets. The main deterrent to the widespread use of SmCo 5 magnet is its high cost. Both samarium and cobalt metals are high priced, and the magnets prepared from their directly melted alloy are thus naturally very expensive. An alternate process involving calcium reduction of their oxide intermediates has, therefore, been studied and the alloy prepared by this process has been evaluated and found satisfactory for magnet production. The process essentially involves compaction of the charge mix containing samarium oxide, cobalt oxide (or metal) and calcium metal and reduction of the charge compact at 1000-1300 degrees C in hydrogen atmosphere, followed by water and acid leaching, drying and classification

Photoactivity of N-doped ZnO nanoparticles in oxidative and reductive reactions

Science.gov (United States)

Oliveira, Jéssica A.; Nogueira, André E.; Gonçalves, Maria C. P.; Paris, Elaine C.; Ribeiro, Caue; Poirier, Gael Y.; Giraldi, Tania R.

2018-03-01

N-doped ZnO is a prospective material for photocatalytic reactions. However, only oxidative paths are well investigated in the literature. This paper describes a comparative study about ZnO and ZnO:N potential for oxidative and reductive reactions, probed by rhodamine B dye photodegradation and CO2 photoreduction. The materials were prepared by the polymeric precursor method, using urea as a nitrogen source, and different heat treatments were used to observe their effects on surface decontamination, crystallinity, particle sizes and shapes, and photocatalytic performance. ZnO and ZnO:N presented a wurtzite crystalline structure and nanometric-scale particles. Samples submitted to higher temperatures showed lower specific surface areas, but higher crystallinity and lower contents of species adsorbed on their surfaces. On the other hand, the photocatalysts annealed in shorter times presented smaller crystallite sizes and lower crystallinity. These factors influenced the photoactivity in both conditions, i.e., oxidation and reduction reactions, under the ultraviolet and visible light, indicating that structural factors influenced the adequate charge separation and consequent photocatalytic activity since the as-synthesized samples were versatile photocatalysts in both redox reactions.

Topotactic reduction yielding black titanium oxide nanostructures as metallic electronic conductors.

Science.gov (United States)

Tominaka, Satoshi

2012-10-01

Detailed analyses of reduced, single crystal, rutile-type TiO(2) via high-resolution transmission electron microscopy (TEM) are reported which reveal that the reduction proceeds topotactically via interstitial diffusion of Ti ions at low temperature, around 350 °C. This important finding encouraged the production of various nanostructured reduced titanium oxides from TiO(2) precursors with morphology retention, and in the process, the synthesis of black titanium oxide nanorods using TiO(2) nanorods was demonstrated. Interestingly, as opposed to the semiconductive behavior of Ti(2)O(3) synthesized at high temperature, topotactically synthesized Ti(2)O(3) exhibits metallic electrical resistance, and the value at room temperature is quite low (topotactically synthesized Ti(2)O(3). This work shows that topotactically reduced titanium oxides can have fascinating properties as well as nanostructures.

Catalysed electrolytic metal oxide dissolution processes

International Nuclear Information System (INIS)

Machuron-Mandard, X.

1994-01-01

The hydrometallurgical processes designed for recovering valuable metals from mineral ores as well as industrial wastes usually require preliminary dissolution of inorganic compounds in aqueous media before extraction and purification steps. Unfortunately, most of the minerals concerned hardly or slowly dissolve in acidic or basic solutions. Metallic oxides, sulfides and silicates are among the materials most difficult to dissolve in aqueous solutions. They are also among the main minerals containing valuable metals. The redox properties of such materials sometimes permit to improve their dissolution by adding oxidizing or reducing species to the leaching solution, which leads to an increase in the dissolution rate. Moreover, limited amounts of redox promoters are required if the redox agent is regenerated continuously thanks to an electrochemical device. Nuclear applications of such concepts have been suggested since the dissolution of many actinide compounds (e.g., UO 2 , AmO 2 , PuC, PuN,...) is mainly based on redox reactions. In the 1980s, improvements of the plutonium dioxide dissolution process have been proposed on the basis of oxidation-reduction principles, which led a few years later to the design of industrial facilities (e.g., at Marcoule or at the french reprocessing plant of La Hague). General concepts and well-established results obtained in France at the Atomic Energy Commission (''Commissariat a l'Energie Atomique'') will be presented and will illustrate applications to industrial as well as analytical problems. (author)

Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

Energy Technology Data Exchange (ETDEWEB)

Taylor, S. D. [Pacific Northwest National Laboratory, Physical Sciences Division, P.O. Box; Becker, U. [The University of Michigan, Department of Earth; Rosso, K. M. [Pacific Northwest National Laboratory, Physical Sciences Division, P.O. Box

2017-09-06

This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed, such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis

Application of a chronoamperometric measurement to the on-line monitoring of a lithium metal reduction for uranium oxide

International Nuclear Information System (INIS)

Kim, Tack-Jin; Cho, Young-Hwan; Choi, In-Kyu; Kang, Jun-Gill; Song, Kyuseok; Jee, Kwang-Yong

2008-01-01

Both a potentiometric and a chronoamperometric electrochemical technique have been applied in an attempt to develop an efficient method for an on-line monitoring of a lithium metal reduction process of uranium oxides at a high-temperature in a molten salt medium. As a result of this study, it was concluded that the chronoamperometric method provided a simple and effective way for a direct on-line monitoring measurement of a lithium metal reduction process of uranium oxides at 650 o C by the measuring electrical currents dependency on a variation of the reduction time for the reaction. A potentiometric method, by adopting a homemade oxide ion selective electrode made of ZrO 2 stabilized by a Y 2 O 3 doping, however, was found to be inappropriate for an on-line monitoring of the reduction reaction of uranium oxide in the presence of lithium metal due to an abnormal behavior of the adopted electrodes. The observed experimental results were discussed in detail by comparing them with previously published experimental data

Heterogeneous reduction of nitric oxide on synthetic coal chars

Energy Technology Data Exchange (ETDEWEB)

C. Pevida; A. Arenillas; F. Rubiera; J.J. Pis [Instituto Nacional del Carbon (CSIC), Oviedo (Spain)

2005-12-01

Model compounds, with a controlled heteroatoms content and well-defined functionalities, were used to study the release of nitrogen compounds from char combustion. In the present work, the mechanisms involved in NO-char heterogeneous reduction were studied with a synthetic coal (SC) char as carbon source. Another synthetic char (SN) without any nitrogen in its composition was also employed in these studies. Temperature programmed reduction (TPR) tests with a gas mixture of 400 ppm NO in argon and with isotopically labelled nitric oxide, {sup 15}NO (500 ppm {sup 15}NO in argon), were carried out. The gases produced were quantitatively determined by means of MS and FTIR analysers. Under the conditions of this work the main products of the NO-C reaction were found to be N{sub 2} and CO{sub 2}. The main path of reaction involves the formation of surface nitrogen compounds that afterwards react with nitrogen from the reactive gas to form N{sub 2}. It was observed that fuel-N also participates in the overall heterogeneous reduction reaction, although to a lesser extent.

Recovery of iron oxide from coal fly ash

Science.gov (United States)

Dobbins, Michael S.; Murtha, Marlyn J.

1983-05-31

A high quality iron oxide concentrate, suitable as a feed for blast and electric reduction furnaces is recovered from pulverized coal fly ash. The magnetic portion of the fly ash is separated and treated with a hot strong alkali solution which dissolves most of the silica and alumina in the fly ash, leaving a solid residue and forming a precipitate which is an acid soluble salt of aluminosilicate hydrate. The residue and precipitate are then treated with a strong mineral acid to dissolve the precipitate leaving a solid residue containing at least 90 weight percent iron oxide.

Reduction of antibiotic resistance genes in municipal wastewater effluent by advanced oxidation processes

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yingying; Zhuang, Yao; Geng, Jinju, E-mail: jjgeng@nju.edu.cn; Ren, Hongqiang; Xu, Ke; Ding, Lili

2016-04-15

This study investigated the reduction of antibiotic resistance genes (ARGs), intI1 and 16S rRNA genes, by advanced oxidation processes (AOPs), namely Fenton oxidation (Fe{sup 2+}/H{sub 2}O{sub 2}) and UV/H{sub 2}O{sub 2} process. The ARGs include sul1, tetX, and tetG from municipal wastewater effluent. The results indicated that the Fenton oxidation and UV/H{sub 2}O{sub 2} process could reduce selected ARGs effectively. Oxidation by the Fenton process was slightly better than that of the UV/H{sub 2}O{sub 2} method. Particularly, for the Fenton oxidation, under the optimal condition wherein Fe{sup 2+}/H{sub 2}O{sub 2} had a molar ratio of 0.1 and a H{sub 2}O{sub 2} concentration of 0.01 mol L{sup −1} with a pH of 3.0 and reaction time of 2 h, 2.58–3.79 logs of target genes were removed. Under the initial effluent pH condition (pH = 7.0), the removal was 2.26–3.35 logs. For the UV/H{sub 2}O{sub 2} process, when the pH was 3.5 with a H{sub 2}O{sub 2} concentration of 0.01 mol L{sup −1} accompanied by 30 min of UV irradiation, all ARGs could achieve a reduction of 2.8–3.5 logs, and 1.55–2.32 logs at a pH of 7.0. The Fenton oxidation and UV/H{sub 2}O{sub 2} process followed the first-order reaction kinetic model. The removal of target genes was affected by many parameters, including initial Fe{sup 2+}/H{sub 2}O{sub 2} molar ratios, H{sub 2}O{sub 2} concentration, solution pH, and reaction time. Among these factors, reagent concentrations and pH values are the most important factors during AOPs. - Highlights: • AOPs including Fenton oxidation and UV/H{sub 2}O{sub 2} process could reduce ARGs effectively. • Fenton oxidation is slightly more effective than UV/H{sub 2}O{sub 2} process in ARG reduction. • Removal of ARGs by AOPs follows the first-order reaction kinetic model. • Selected ARGs and 16S rRNA genes exhibit similar change trends during AOPs.

Distribution of Clay Minerals in Light Coal Fractions and the Thermal Reaction Products of These Clay Minerals during Combustion in a Drop Tube Furnace

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Sida Tian

2016-06-01

Full Text Available To estimate the contribution of clay minerals in light coal fractions to ash deposition in furnaces, we investigated their distribution and thermal reaction products. The light fractions of two Chinese coals were prepared using a 1.5 g·cm−3 ZnCl2 solution as a density separation medium and were burned in a drop-tube furnace (DTF. The mineral matter in each of the light coal fractions was compared to that of the relevant raw coal. The DTF ash from light coal fractions was analysed using hydrochloric acid separation. The acid-soluble aluminium fractions of DTF ash samples were used to determine changes in the amorphous aluminosilicate products with increasing combustion temperature. The results show that the clay mineral contents in the mineral matter of both light coal fractions were higher than those in the respective raw coals. For the coal with a high ash melting point, clay minerals in the light coal fraction thermally transformed more dehydroxylation products compared with those in the raw coal, possibly contributing to solid-state reactions of ash particles. For the coal with a low ash melting point, clay minerals in the light coal fraction produced more easily-slagging material compared with those in the raw coal, playing an important role in the occurrence of slagging. Additionally, ferrous oxide often produces low-melting substances in coal ash. Due to the similarities of zinc oxide and ferrous oxide in silicate reactions, we also investigated the interactions of clay minerals in light coal fractions with zinc oxide introduced by a zinc chloride solution. The extraneous zinc oxide could react, to a small extent, with clay minerals in the coal during DTF combustion.

In situ oxidation and reduction of triangular nickel nanoplates via environmental transmission electron microscopy

KAUST Repository

LAGROW, A.P.

2017-08-29

Understanding the oxidation and reduction mechanisms of transition metals, such as nickel (Ni), is important for their use in industrial applications of catalysis. A powerful technique for investigating the redox reactive species is in situ environmental transmission electron microscopy (ETEM), where oxidation and reduction can be tracked in real time. One particular difficulty in understanding the underlying reactions is understanding the underlying morphology of the starting structure in a reaction, in particular the defects contained in the material, and the exposed surface facets. Here-in, we use a colloidal nanoparticle synthesis in a continuous flow reactor to form nanoplates of nickel coated with oleylamine as a capping agent. We utilise an in situ heating procedure at 300 °C in vacuum to remove the oleylamine ligands, and then oxidise the Ni nanoparticles at 25 °C with 2 Pa oxygen, and follow the nanoparticles initial oxidation. After that, the nanoparticles are oxidised at 200 and 300 °C, making the size of the oxide shell increase to ∼4 nm. The oxide shell could be reduced under 2 Pa hydrogen at 500 °C to its initial size of ∼1 nm. High temperature oxidation encouraged the nanoparticles to form pure NiO nanoparticles, which occurred via the Kirkendall effect leading to hollowing and void formation.

In situ oxidation and reduction of triangular nickel nanoplates via environmental transmission electron microscopy

KAUST Repository

LAGROW, A.P.; AlYami, Noktan; LLOYD, D.C.; Bakr, Osman; BOYES, E.D.; GAI, P.L.

2017-01-01

Understanding the oxidation and reduction mechanisms of transition metals, such as nickel (Ni), is important for their use in industrial applications of catalysis. A powerful technique for investigating the redox reactive species is in situ environmental transmission electron microscopy (ETEM), where oxidation and reduction can be tracked in real time. One particular difficulty in understanding the underlying reactions is understanding the underlying morphology of the starting structure in a reaction, in particular the defects contained in the material, and the exposed surface facets. Here-in, we use a colloidal nanoparticle synthesis in a continuous flow reactor to form nanoplates of nickel coated with oleylamine as a capping agent. We utilise an in situ heating procedure at 300 °C in vacuum to remove the oleylamine ligands, and then oxidise the Ni nanoparticles at 25 °C with 2 Pa oxygen, and follow the nanoparticles initial oxidation. After that, the nanoparticles are oxidised at 200 and 300 °C, making the size of the oxide shell increase to ∼4 nm. The oxide shell could be reduced under 2 Pa hydrogen at 500 °C to its initial size of ∼1 nm. High temperature oxidation encouraged the nanoparticles to form pure NiO nanoparticles, which occurred via the Kirkendall effect leading to hollowing and void formation.

Water-evaporation reduction by duplex films: application to the human tear film.

Science.gov (United States)

Cerretani, Colin F; Ho, Nghia H; Radke, C J

2013-09-01

Water-evaporation reduction by duplex-oil films is especially important to understand the physiology of the human tear film. Secreted lipids, called meibum, form a duplex film that coats the aqueous tear film and purportedly reduces tear evaporation. Lipid-layer deficiency is correlated with the occurrence of dry-eye disease; however, in-vitro experiments fail to show water-evaporation reduction by tear-lipid duplex films. We review the available literature on water-evaporation reduction by duplex-oil films and outline the theoretical underpinnings of spreading and evaporation kinetics that govern behavior of these systems. A dissolution-diffusion model unifies the data reported in the literature and identifies dewetting of duplex films into lenses as a key challenge to obtaining significant evaporation reduction. We develop an improved apparatus for measuring evaporation reduction by duplex-oil films including simultaneous assessment of film coverage, stability, and temperature, all under controlled external mass transfer. New data reported in this study fit into the larger body of work conducted on water-evaporation reduction by duplex-oil films. Duplex-oil films of oxidized mineral oil/mucin (MOx/BSM), human meibum (HM), and bovine meibum (BM) reduce water evaporation by a dissolution-diffusion mechanism, as confirmed by agreement between measurement and theory. The water permeability of oxidized-mineral-oil duplex films agrees with those reported in the literature, after correction for the presence of mucin. We find that duplex-oil films of bovine and human meibum at physiologic temperature reduce water evaporation only 6-8% for a 100-nm film thickness pertinent to the human tear film. Comparison to in-vivo human tear-evaporation measurements is inconclusive because evaporation from a clean-water surface is not measured and because the mass-transfer resistance is not characterized. Copyright © 2013 Elsevier B.V. All rights reserved.

Photochemical modelling of photo-oxidant levels over the Swiss plateau and emission reduction scenarios

International Nuclear Information System (INIS)

Rosselet, C.M.; Kerr, J.A.

1993-05-01

During summertime high pressure conditions, high photo-oxidant (O 3 , H 2 O 2 , PAN and others) levels are frequently observed in the planetary boundary layer in central Europe. It is well known that close to the earth's surface ozone is formed by complex reactions involving VOC, NO x , and sunlight. Substantial reductions of both precursors are needed to reduce photo-oxidant levels. In this context the reductions of the abundance of the precursors and the variation of their ratios is of great importance. Here we report model calculations from the Harwell Photochemical Trajectory Model of the levels of O 3 , H 2 O 2 and PAN along a trajectory over the Swiss Plateau from Lake Constance to Lake Geneva. These calculations are in satisfactory agreement with measurements made during the intensive observation period of the research program POLLUMET (Pollution and Meteorology in Switzerland). Sensitivity calculations of emission reduction scenarios indicate that on the Swiss Plateau the ozone production may be mainly NO x -limited; under conditions where the CO levels are closer to the upper limit within the range (120-600 ppbv). The calculated peak ozone level reduction caused by an exclusive NO x -emission reduction is about three times larger than that caused by an exclusive VOC reduction. The combined reduction of all precursor compounds is the most efficient strategy, although it is only marginally more efficient than the NO x -reduction scenario alone. (author) figs., tabs., 75 refs

Metal porphyrin intercalated reduced graphene oxide nanocomposite utilized for electrocatalytic oxygen reduction

Directory of Open Access Journals (Sweden)

Mingyan Wang

2017-07-01

Full Text Available In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin –MtTMPyP (Mt= Cobalt (II, Manganese (III, or Iron (III; TMPyP = 5, 10, 15, 20-tetrakis (N-methylpyridinium-4-yl porphyrin intercalated into the layer of graphene oxide (GO by the cooperative effects of electrostatic and π–π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2D MtTMPyP/rGOn were fabricated. The as-prepared 2D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction (ORR in an alkaline medium. The MtTMPyP/rGOn hybrids, especially CoTMPyP/rGO5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries. Keywords: Metal porphyrin, Reduced graphene oxide, Intercalation, Oxygen reduction reaction, Catalyst

Metallization of uranium oxide powders by lithium reduction

International Nuclear Information System (INIS)

Kim, I. S.; Seo, J. S.; Oh, S. C.; Hong, S. S.; Lee, W. K.

2002-01-01

Laboratory scale experiments on the reduction of uranium oxide powders into metal by lithium were performed in order to determine the equipment setup and optimum operation conditions. The method of filtration using the porous magnesia filter was introduced to recover uranium metal powders produced. Based on the laboratory scale experimental results, mock-up scale (20 kg U/batch) metallizer was designed and made. The applicability to the metallization process was estimated with respect to the thermal stability of the porous magnesia filter in the high temperature molten salt, the filtration of the fine uranium metal powders, and the operability of the equipment

A Study on the Electrolytic Reduction Mechanism of Uranium Oxide in a LiCl-Li2O Molten Salt

International Nuclear Information System (INIS)

Oh, Seung Chul; Hur, Jin Mok; Seo, Chung Seok; Park, Seong Won

2003-01-01

This study proposed a new electrolytic reduction technology that is based on the integration of simultaneous uranium oxide metallization and Li 2 O electrowinning. In this electrolytic reduction reaction, electrolytically reduced Li deposits on cathode and simultaneously reacts with uranium oxides to produce uranium metal showing more than 99% conversion. For the verification of process feasibility, the experiments to obtain basic data on the metallization of uranium oxide, investigation of reaction mechanism, the characteristics of closed recycle of Li 2 O and mass transfer were carried out. This evolutionary electrolytic reduction technology would give benefits over the conventional Li-reduction process improving economic viability such as: avoidance of handling of chemically active Li-LiCl molten salt increase of metallization yield, and simplification of process.

Nitrate reduction, nitrous oxide formation, and anaerobic ammonia oxidation to nitrite in the gut of soil-feeding termites (Cubitermes and Ophiotermes spp.)

KAUST Repository

Ngugi, David

2011-11-28

Soil-feeding termites play important roles in the dynamics of carbon and nitrogen in tropical soils. Through the mineralization of nitrogenous humus components, their intestinal tracts accumulate enormous amounts of ammonia, and nitrate and nitrite concentrations are several orders of magnitude above those in the ingested soil. Here, we studied the metabolism of nitrate in the different gut compartments of two Cubitermes and one Ophiotermes species using 15N isotope tracer analysis. Living termites emitted N 2 at rates ranging from 3.8 to 6.8nmolh -1 (g fresh wt.) -1. However, in homogenates of individual gut sections, denitrification was restricted to the posterior hindgut, whereas nitrate ammonification occurred in all gut compartments and was the prevailing process in the anterior gut. Potential rates of nitrate ammonification for the entire intestinal tract were tenfold higher than those of denitrification, implying that ammonification is the major sink for ingested nitrate in the intestinal tract of soil-feeding termites. Because nitrate is efficiently reduced already in the anterior gut, reductive processes in the posterior gut compartments must be fuelled by an endogenous source of oxidized nitrogen species. Quite unexpectedly, we observed an anaerobic oxidation of 15N-labelled ammonia to nitrite, especially in the P4 section, which is presumably driven by ferric iron; nitrification and anammox activities were not detected. Two of the termite species also emitted substantial amounts of N 2O, ranging from 0.4 to 3.9nmolh -1 (g fresh wt.) -1, providing direct evidence that soil-feeding termites are a hitherto unrecognized source of this greenhouse gas in tropical soils. © 2011 Society for Applied Microbiology and Blackwell Publishing Ltd.

Study on the oxidation and reduction of tungsten surface for sub-50 nm patterning process

Energy Technology Data Exchange (ETDEWEB)

Kim, Jong Kyu; Nam, Seok Woo; Cho, Sung Il; Jhon, Myung S.; Min, Kyung Suk; Kim, Chan Kyu; Jung, Ho Bum; Yeom, Geun Young [Memory Division Semiconductor Business, Samsung Electronics, San No. 16 Banwol-Ri, Taean-Eup, Hwasung-City, Gyeonggi-Do 449-711, South Korea and Department of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon, Gyeonggi-do 440-746 (Korea, Republic of); Memory Division Semiconductor Business, Samsung Electronics, San No. 16 Banwol-Ri, Taean-Eup, Hwasung-City, Gyeonggi-Do 449-711 (Korea, Republic of); Department of Chemical Engineering and Data Storage Systems Center, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213 (United States); Department of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon, Gyeonggi-do 440-746 (Korea, Republic of)

2012-11-15

The oxidation characteristics of tungsten line pattern during the carbon-based mask-layer removal process using oxygen plasmas have been investigated for sub-50 nm patterning processes, in addition to the reduction characteristics of the WO{sub x} layer formed on the tungsten line surface using hydrogen plasmas. The surface oxidation of tungsten lines during the mask layer removal process could be minimized by using low-temperature (300 K) plasma processing for the removal of the carbon-based material. Using this technique, the thickness of WO{sub x} on the tungsten line could be decreased to 25% compared to results from high-temperature processing. The WO{sub x} layer could also be completely removed at a low temperature of 300 K using a hydrogen plasma by supplying bias power to the tungsten substrate to provide a activation energy for the reduction. When this oxidation and reduction technique was applied to actual 40-nm-CD device processing, the complete removal of WO{sub x} formed on the sidewall of tungsten line could be observed.

Pilot-scale equipment development for lithium-based reduction of spent oxide fuel

International Nuclear Information System (INIS)

Herrmann, S. D.

1998-01-01

An integral function of the electrometallurgical conditioning of DOE spent nuclear fuel is the standardization of waste forms. Argonne National Laboratory (ANL) has developed and is presently demonstrating the electrometallurgical conditioning of sodium-bonded metal fuel from Experimental Breeder Reactor II, resulting in uranium, ceramic waste, and metal waste forms. Engineering studies are underway at ANL in support of pilot-scale equipment development, which would precondition irradiated oxide fuel and likewise demonstrate the application of electrometallurgical conditioning to such non-metallic fuels. This paper highlights the integration of proposed spent oxide fuel conditioning with existing electrometallurgical processes. Additionally, technical bases for engineering activities to support a scale up of an oxide reduction process are described

Standard test method for measurement of oxidation-reduction potential (ORP) of soil

CERN Document Server

American Society for Testing and Materials. Philadelphia

2009-01-01

1.1 This test method covers a procedure and related test equipment for measuring oxidation-reduction potential (ORP) of soil samples removed from the ground. 1.2 The procedure in Section 9 is appropriate for field and laboratory measurements. 1.3 Accurate measurement of oxidation-reduction potential aids in the analysis of soil corrosivity and its impact on buried metallic structure corrosion rates. 1.4 The values stated in inch-pound units are to be regarded as standard. The values given in parentheses are mathematical conversions to SI units that are provided for information only and are not considered standard. 1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

Minerals in thalassaemia major patients: An overview.

Science.gov (United States)

Ozturk, Zeynep; Genc, Gizem Esra; Gumuslu, Saadet

2017-05-01

Thalassaemia major (TM) is a hereditary blood disease characterised by reduced or absent production of beta globin chains. Erythrocyte transfusions are given to raise the haemoglobin level in patients with thalassaemia major. However, transfusions have been related to increased risk of iron overload and tissue damage related to excess iron. Both elevated oxidative stress due to iron overload and increased hemolysis lead to over utilisation of minerals required for antioxidant enzymes activities. Iron chelators have been used to prevent iron overload in thalassaemia major patients, but these chelators have the possibility of removing minerals from the body. Thalassaemia patients are more at risk for mineral deficiency because of increased oxidative stress and iron chelation therapies. Growth and maturational delay, cardiomyopathy, endocrinopathies and osteoporosis are the complications of thalassaemia. Minerals may play a particular role to prevent these complications. In the current review, we provide an overview of minerals including zinc (Zn), copper (Cu), selenium (Se), magnesium (Mg) and calcium (Ca) in thalassaemia major patients. We, also, underline that some complications of thalassaemia can be caused by an increased need for minerals or lack of the minerals. Copyright © 2017 Elsevier GmbH. All rights reserved.