High speed chalcogenide glass electrochemical metallization cells with various active metals.

PubMed

Hughes, Mark A; Burgess, Alexander; Hinder, Steven; Gholizadeh, A Baset; Craig, Christopher; Hewak, Daniel W

2018-08-03

We fabricated electrochemical metallization cells using a GaLaSO solid electrolyte, an InSnO inactive electrode and active electrodes consisting of various metals (Cu, Ag, Fe, Cu, Mo, Al). Devices with Ag and Cu active metals showed consistent and repeatable resistive switching behaviour, and had a retention of 3 and >43 days, respectively; both had switching speeds of <5 ns. Devices with Cr and Fe active metals displayed incomplete or intermittent resistive switching, and devices with Mo and Al active electrodes displayed no resistive switching ability. Deeper penetration of the active metal into the GaLaSO layer resulted in greater resistive switching ability of the cell. The off-state resistivity was greater for more reactive active metals which may be due to a thicker intermediate layer.

The Role of Anionogenic Elements (As, Sb, Mo, Se, S, P, N, Cl, F, C) In The Formation of Technogenic Geochemical Anomalies

NASA Astrophysics Data System (ADS)

Abrosimova, Natalya; Bortnikova, Svetlana

2017-12-01

The study was conducted on the example of sulphide-containing mine tailings with a varying amount of sulphide and arsenide minerals, from three distinct tailings dumps situated in Russia: Karabash Mine Site, South Ural; Komsomolsk tailings impoundment, Kemerovo region; Khovu-Aksy mine site, Tuva Republic. The aim of the study was to compare the mobility of anionogenic elements (As, Sb, Mo, Se, S, P, N, Cl, F, C) and their role in migration, precipitation, and concentration of metals during the water-tailings interaction depending on the physicochemical parameters (pH, Eh) of the medium and the mineral composition of the waste material. Using slightly acidic leaching experiments the quantitative estimation of mobile forms of elements is given. Based on the compositions of the obtained water leaching solutions, aqueous speciation of chemical elements and saturation index of key minerals in the experimental solutions were calculated. The results of calculating forms of chemical elements made it possible to construct series of mobility of metals and metalloids in solutions with different physicochemical parameters. In the alkaline conditions, Sb>As>Cd>Cu>Zn>Fe>Pb, when the medium is acidified, the series changes, As>Cd>Cu>Zn>Pb>Sb>Fe in weakly alkaline conditions, Sb>Mn>As>Zn>Fe however, when the medium is acidified, the series changes to Cd>Mn>Pb>Cu>Zn>Sb>Ni>Fe>As under acidic conditions Cd>Cu>Zn>Pb>Mn>Fe>Se>Mo>Sb>As>Ni. The mineral composition of the tailings was investigated, which will allow to determine the sources of toxic elements and to understand the processes of secondary mineral formation in technogenic objects. Arsenopyrite and pyrite predominate in the heavy fraction of the Komsomolsk tailings impoundment, arsenopyrite grains are often corroded, Sb contained in Sb oxide and Sb sulfide. The pyrite and barite are determined in the solid matter of the Karabash Mine Site and chalcopyrite, sphalerite, tennantite Cu3AsS3, and tetrahedrite (Cu,Fe)12Sb4S13 are determined in the form of inclusions in grains of pyrite.

The Effect of Ion Irradiation on Nanocrystallization and Surface Relief of a Ribbon from Fe72.5Cu1Nb2Mo1.5Si14B9 Alloy

NASA Astrophysics Data System (ADS)

Romanov, I. Yu.; Gushchina, N. V.; Ovchinnikov, V. V.; Makhinko, F. F.; Stepanov, A. V.; Medvedev, A. I.; Starodubtsev, Yu. N.; Belozerov, V. Ya.; Loginov, B. A.

2018-02-01

Using the methods of X-ray diffraction and atomic force microscopy, the process of crystallization of an amorphous Fe72.5Cu1Nb2Mo1.5Si14B9 alloy irradiated with accelerated Ar+ ions is investigated. It is found out that an irradiation by the Ar+ ions with the energy 30 keV at the ion current density 300 μA/cm2 (fluence 3.75·1015 cm-2, irradiation time 2 s, ion-beam short-duration heating up to 350°C, which is 150°C lower than the thermal crystallization threshold) results in a complete crystallization of this amorphous alloy (throughout the bulk of a 25 μm ribbon) followed by precipitation of solid solution crystals of α-Fe(Si), close in its composition to Fe80Si20, stable phase of Fe3Si, and metastable hexagonal phases. By the methods of atomic force and scanning tunneling microscopy it is shown that nanocrystallization caused by ion irradiation is accompanied by surface relief changes both on the irradiated and unirradiated sides of the Fe72.5Cu1Nb2Mo1.5Si14B9 alloy ribbon at the depth exceeding by a factor of 103 that of the physical ion penetration for this material. The data obtained, taking into account a significant temperature decrease and multiple acceleration of the crystallization process, serve an evidence of the radiation-dynamic influence of accelerated ions on the metastable amorphous medium.

Specific heat and related thermophysical properties of liquid Fe-Cu-Mo alloy

NASA Astrophysics Data System (ADS)

Wang, Haipeng; Luo, Bingchi; Chang, Jian; Wei, Bingbo

2007-08-01

The specific heat and related thermophysical properties of liquid Fe77.5Cu13Mo9.5 monotectic alloy were investigated by an electromagnetic levitation drop calorimeter over a wide temperature range from 1482 to 1818 K. A maximum undercooling of 221 K (0.13 T m) was achieved and the specific heat was determined as 44.71 J·mol-1·K-1. The excess specific heat, enthalpy change, entropy change and Gibbs free energy difference of this alloy were calculated on the basis of experimental results. It was found that the calculated results by traditional estimating methods can only describe the solidification process under low undercooling conditions. Only the experimental results can reflect the reality under high undercooling conditions. Meanwhile, the thermal diffusivity, thermal conductivity, and sound speed were derived from the present experimental results. Furthermore, the solidified microstructural morphology was examined, which consists of (Fe) and (Cu) phases. The calculated interface energy was applied to exploring the correlation between competitive nucleation and solidification microstructure within monotectic alloy.

Geochemical element mobility during the hydrothermal alteration in the Tepeoba porphyry Cu-Mo-Au deposits at Balikesir, NW Turkey

NASA Astrophysics Data System (ADS)

Abdelnasser, Amr; Kiran Yildirim, Demet; Doner, Zeynep; Kumral, Mustafa

2016-04-01

The Tepeoba porphyry Cu-Mo-Au deposit represents one of the important copper source and mineral deposits in the Anatolian tectonic belt at Balikesir province, NW Turkey. It considered as a vein-type deposit locally associated with intense hydrothermal alteration within the brecciation, quartz stockwork veining, and brittle fracture zones in the main host rock that represented by hornfels, as well as generally related to the shallow intermediate to silicic intrusive Eybek pluton. Based on the field and geologic relationships and types of ore mineral assemblages and the accompanied alteration types, there are two mineralization zones; hypogene (primary) and oxidation/supergene zones are observed associated with three alteration zones; potassic, phyllic, and propylitic zones related to this porphyry deposit. The phyllic and propylitic alterations locally surrounded the potassic alteration. The ore minerals related to the hypogene zone represented by mostly chalcopyrite, Molybdenite, and pyrite with subordinate amount of marcasite, enargite, and gold. On the other hand they include mainly cuprite with chalcopyrite, pyrite and gold as well as hematite and goethite at the oxidation/supergene zone. This study deals with the quantitative calculations of the mass/volume changes (gains and losses) of the major and trace elements during the different episodes of alteration in this porphyry deposit. These mass balance data reveal that the potassic alteration zone that the main Cu- and Mo-enriched zone, has enrichment of K, Si, Fe, and Mg, and depletion of Na referring to replacement of plagioclase and amphibole by K-feldspar, sericite and biotite. While the propylitic alteration that is the main Mo- and Au-enriched zone is accompanied with K and Na depletion with enrichment of Si, Fe, Mg, and Ca forming chlorite, epidote, carbonate and pyrite. On the other hand the phyllic alteration that occurred in the outer part around the potassic alteration, characterized by less amount of Cu and Mo mineralization having addition of Si and K with removal of Fe, Mg, Ca, and Na. Keywords: Mass balance calculation; Tepeoba porphyry Cu-Mo-Au deposits; Balikesir; Turkey

Investigation of the synthesis, activation, and isosteric heats of CO2 adsorption of the isostructural series of metal-organic frameworks M3(BTC)2 (M = Cr, Fe, Ni, Cu, Mo, Ru).

PubMed

Wade, Casey R; Dincă, Mircea

2012-07-14

The synthesis, activation, and heats of CO(2) adsorption for the known members of the M(3)(BTC)(2) (HKUST-1) isostructural series (M = Cr, Fe, Ni, Zn, Ni, Cu, Mo) were investigated to gain insight into the impact of CO(2)-metal interactions for CO(2) storage/separation applications. With the use of modified syntheses and activation procedures, improved BET surface areas were obtained for M = Ni, Mo, and Ru. The zero-coverage isosteric heats of CO(2) adsorption were measured for the Cu, Cr, Ni, Mo, and Ru analogues and gave values consistent with those reported for MOFs containing coordinatively unsaturated metal sites, but lower than for amine functionalized materials. Notably, the Ni and Ru congeners exhibited the highest CO(2) affinities in the studied series. These behaviors were attributed to the presence of residual guest molecules in the case of Ni(3)(BTC)(2)(Me(2)NH)(2)(H(2)O) and the increased charge of the dimetal secondary building unit in [Ru(3)(BTC)(2)][BTC](0.5).

AFLOWLIB.ORG: a Distributed Materials Properties Repository from High-throughput Ab initio Calculations

DTIC Science & Technology

2011-11-15

uncle) fcc (uncle) hcp (uncle) phase-diagram Ag Al Al Au Au Bi Bi Ca Ca Cd Cd Ce Ce Co Co Cr Cr Cu Cu Fe Fe Ga Ga Gd Gd Ge Ge Hf...Hf Hg Hg In In Ir Ir La La Li Li Mg Mg Mn Mn Mo Mo Na Na Nb Nb Ni Ni Os Os Pb Pb Pd Pd Pt Pt Rb Rb Re Re Rh Rh Ru Ru Sb Sb Sc...2 S. Curtarolo, A. N. Kolmogorov, and F. H. Cocks, High-throughput ab initio analysis of the Bi-In, Bi- Mg , Bi-Sb, In- Mg , In-Sb, and Mg -Sb systems

Trace Metal Requirements for Microbial Enzymes Involved in the Production and Consumption of Methane and Nitrous Oxide

PubMed Central

Glass, Jennifer B.; Orphan, Victoria J.

2011-01-01

Fluxes of greenhouse gases to the atmosphere are heavily influenced by microbiological activity. Microbial enzymes involved in the production and consumption of greenhouse gases often contain metal cofactors. While extensive research has examined the influence of Fe bioavailability on microbial CO2 cycling, fewer studies have explored metal requirements for microbial production and consumption of the second- and third-most abundant greenhouse gases, methane (CH4), and nitrous oxide (N2O). Here we review the current state of biochemical, physiological, and environmental research on transition metal requirements for microbial CH4 and N2O cycling. Methanogenic archaea require large amounts of Fe, Ni, and Co (and some Mo/W and Zn). Low bioavailability of Fe, Ni, and Co limits methanogenesis in pure and mixed cultures and environmental studies. Anaerobic methane oxidation by anaerobic methanotrophic archaea (ANME) likely occurs via reverse methanogenesis since ANME possess most of the enzymes in the methanogenic pathway. Aerobic CH4 oxidation uses Cu or Fe for the first step depending on Cu availability, and additional Fe, Cu, and Mo for later steps. N2O production via classical anaerobic denitrification is primarily Fe-based, whereas aerobic pathways (nitrifier denitrification and archaeal ammonia oxidation) require Cu in addition to, or possibly in place of, Fe. Genes encoding the Cu-containing N2O reductase, the only known enzyme capable of microbial N2O conversion to N2, have only been found in classical denitrifiers. Accumulation of N2O due to low Cu has been observed in pure cultures and a lake ecosystem, but not in marine systems. Future research is needed on metalloenzymes involved in the production of N2O by enrichment cultures of ammonia oxidizing archaea, biological mechanisms for scavenging scarce metals, and possible links between metal bioavailability and greenhouse gas fluxes in anaerobic environments where metals may be limiting due to sulfide-metal scavenging. PMID:22363333

Mechanically strong nanocrystalline Fe-Si-B-P-Cu soft magnetic powder cores utilizing magnetic metallic glass as a binder

NASA Astrophysics Data System (ADS)

Luan, Jian; Sharma, Parmanand; Yodoshi, Noriharu; Zhang, Yan; Makino, Akihiro

2016-05-01

We report on the fabrication and properties of soft magnetic powder cores with superior mechanical strength as well as low core loss (W). Development of such cores is important for applications in automobiles/devices operating in motion. High saturation magnetic flux density (Bs) Fe-Si-B-P-Cu powder was sintered with Fe55C10B5P10Ni15Mo5 metallic glass (MG) powder in its supercooled liquid state by spark plasma sintering. The sintered cores are made from the nanocrystalline powder particles of Fe-Si-B-P-Cu alloy, which are separated through a magnetic Fe55C10B5P10Ni15Mo5 MG alloy. Low W of ˜ 2.2 W/kg (at 1T and 50 Hz), and high fracture strength (yielding stress ˜500 MPa), which is an order of magnitude higher than the conventional powder cores, were obtained. Stronger metal-metal bonding and magnetic nature of MG binder (which is very different than the conventional polymer based binders) are responsible for the superior mechanical and magnetic properties. The MG binder not only helps in improving the mechanical properties but it also enhances the overall Bs of the core.

The effect of copper doping on martensite shear stress in porous TiNi(Mo,Fe,Cu) alloys

NASA Astrophysics Data System (ADS)

Khodorenko, V. N.; Kaftaranova, M. I.; Gunther, V. E.

2015-03-01

The properties of alloys based on porous nickel-titanium (TiNi) with copper additives have been studied. It is established that the copper doping of porous TiNi(Mo,Fe,Cu) alloys fabricated by the method of self-propagating high-temperature synthesis leads to a significant decrease in the martensite shear stress (below 30 MPa). Low values of the martensite shear stress (σmin) in copper-doped TiNi-based alloys allows medical implants of complex shapes to be manufactured for various purposes, including oral surgery. The optimum concentration of copper additives (within 3-6 at %) has been determined that ensures high performance characteristics of TiNi-based porous alloys for medical implants.

Diffuse-flow hydrothermal field in an oceanic fracture zone setting, Northeast Pacific: Deposit composition

USGS Publications Warehouse

Hein, J.R.; Koski, R.A.; Embley, R.W.; Reid, J.; Chang, S.-W.

1999-01-01

This is the first reported occurrence of an active hydrothermal field in an oceanic fracture zone setting. The hydrothermal field occurs in a pull-apart basin within the Blanco Fracture Zone (BFZ), which has four distinct mineral deposit types: (1) barite mounds and chimneys, (2) barite stockwork breccia, (3) silica-barite beds, and (4) silica, barite, and Fe-Mn oxyhydroxide in sediments. All deposit types contain minor amounts of sulfides. In barite stockwork, silica-barite beds, and mineralized sediment, Ba, Ph, Ag, S, Au, Zn, Cu, Hg, TI, As, Mo, Sb, U, Cd, and Cu are enriched relative to unmineralized rocks and sediments of the BFZ. Fe and Mn are not enriched in the barite stockwork or silica-barite beds, but along with P, Co, and Mg are enriched in the mineralized sediments. Silver contents in deposits of the hydrothermal field range up to 86 ppm, gold to 0.7 ppm, zinc to 3.2%, copper to 0.8%, and barium to 22%. Mineralization occurred by diffuse, low to intermediate temperature (mostly <250??C) discharge of hydrothermal fluids through pillow lavas and ponds of mixed volcaniclastic and biosiliceous sediments. Bacterial mats were mineralized by silica, barite, and minor Fe hydroxides, or less commonly, by Mn oxyhydroxides. Pervasive mineralization of bacterial mats resulted in formation of silica-barite beds. Silica precipitated from hydrothermal fluids by conductive cooling and mixing with seawater. Sulfate, U, and rare earth elements (REEs) in barite were derived from seawater, whereas the REE content of hydrothermal silica deposits and mineralized sediments is associated with the aluminosilicate detrital fraction. Fe-, Zn-, Cu-, Pb-, and Hg-sulfide minerals, Ba in barite, and Eu in all mineralized deposits were derived from hydrothermal fluids. Manganese oxides and associated elements (Co, Sb, Mo, W, Cl, and Cu) and Fe oxides and associated elements (Be, B, P, and Mo) precipitated as the result of mixing of hydrothermal fluids with seawater. ?? 2001 Canadian Institute of Mining, Metallurgy and Petroleum. All rights reserved.

Effects of dietary zinc, iron, and copper in layer feed on distribution of these elements in eggs, liver, excreta, soil, and herbage.

PubMed

Skrivan, M; Skrivanová, V; Marounek, M

2005-10-01

An experiment was conducted to evaluate the effect of dietary content and combinations of Zn, Fe, and Cu on deposition of these elements in egg components, liver, and excreta. Excreta were applied as a manure to a lawn, and 3 mo later soil and herbage samples were taken and analyzed. The experiment comprised 144 hens in 8 groups. The basal diet contained Zn, Fe, and Cu at 63.4, 92.8, and 9.0 mg/kg, respectively. It was supplemented with 1, 2, or 3 trace elements (inorganic forms) at 80 mg of Zn/kg, 120 mg of Fe/kg, and 25 mg of Cu/kg. Recovery of Zn, Fe, and Cu in eggs of hens fed the basal diet was 10.7, 9.8, and 4.4% of the alimentary intake, respectively. A Zn-Cu antagonism was observed; deposition of Zn in the yolk was significantly decreased by Cu addition and vice versa (P < 0.01). Supplementation of the basal diet with Fe increased Fe concentration in egg yolk and white by 6.3 and 2.2%, respectively. The combination of Fe with Zn and Cu, however, increased Fe concentration in the yolk and white by 36.7 and 34.9%, respectively (P < 0.01). The enrichment of eggs with the other elements was marginal (Cu) or absent (Zn). Effects of Zn, Fe, and Cu of the basal diet on liver concentrations of these elements were relatively small, and no antagonism between Zn and Cu was apparent. Supplementation of the basal diet with the combination of Zn and Fe, however, significantly decreased hepatic concentration of Cu. On the other hand, Cu supplementation significantly increased Fe concentration in livers of hens fed the Fe-supplemented diet (P < 0.01). Concentrations of Zn, Fe, and Cu in excreta were related to their dietary content. High concentrations of Zn, Fe, and Cu in excreta corresponded with limited deposition of the 3 elements in eggs and liver. Concentrations of Zn, Fe, and Cu in herbage correlated significantly with the supply of these elements by hen excreta into soil. The Zn supplied by hen excreta was more stable than Fe and Cu; thus Zn could accumulate in the soil.

Phase-transformation in iron oxide and formation of Cu/γ-Fe2O3 nanocomposite using radio-frequency sputtering with metal chips on an α-Fe2O3 target

NASA Astrophysics Data System (ADS)

Abe, Seishi; Watanabe, Masato

2017-07-01

A simple technique that uses radio-frequency sputtering with a functional element on a hematite (α-Fe2O3) target is presented for the production of maghemite (γ-Fe2O3) thin films. These films are prepared on water-cooled glass substrates in an Ar atmosphere. Investigations are done with Ti, Si, Al, Cu, Mo, and Zn, with γ-Fe2O3 being obtained only in the presence of Cu, indicating that phase transition occurs only for this metal. Mössbauer spectra and magnetization analysis reveal that the quality of the obtained γ-Fe2O3 films is higher than that of the film produced using Mg, which was reported in our previous work. High-angle annular dark-field scanning tunneling electron microscopy and electron energy-loss spectroscopy reveal that the added Cu remains in a metallic state (without oxidization), forming a Cu/γ-Fe2O3 phase-mixture in the as-deposited film. The Cu/γ-Fe2O3 composite film exhibits negative magnetoresistance (MR), with a MR ratio of approximately 0.6% at room temperature in an applied field of 10 kOe, and a negative Faraday rotation of -5708 deg cm-1 at 830 nm.

Distribution of heavy metals in road dust along an urban-rural gradient in Massachusetts

NASA Astrophysics Data System (ADS)

Apeagyei, Eric; Bank, Michael S.; Spengler, John D.

2011-04-01

Human exposures to particulate matter emitted from on-road motor vehicles include complex mixtures of metals from tires, brakes, parts wear and resuspended road dust. The aim of this study was to assess road dust for metals associated with motor vehicle traffic, particularly those metals coming from brake and tire wears. We hypothesized that the road dust would show significant difference in both composition and concentration by traffic type, road class and by location. X-ray fluorescence (XRF) analyses of 115 parked car tires showed Zn and Ca were likely associated with tire wear dust. XRF results of three used brake pads indicated high concentrations of Fe, Ti, Cu, Ba, Mo and Zr. To assess heavy metal exposures associated with tires and brake wear adjacent to roads of varying traffic and functional classes, 85 samples of road dust were collected from road surfaces adjacent to the curb and analyzed by XRF. Median concentrations for Fe, Ca and K were greater than Ti (1619 ppm), with concentration ratios of Fe: Ca: K: Ti [16:5:3:1]. Cumulative frequency distribution graphs showed distribution of Fe, Ba, Cu, and Mo were similar regardless of road traffic rating. However, Zn, Ti, and Zr varied significantly ( p < 0.05) with traffic ratings of roadways (heavy > moderate > low traffic). Fe, Ba, Cu, and Mo also had similar distributions regardless of road class while composition of Zn, Ti, and Zr varied significantly across road class ( p < 0.05) (Major roads > Minor roads > highway). In comparing urban road dust to rural road dust, we observed Fe, Ca, K, and Ti were significantly greater in urban road dust ( p < 0.05). In urban road dust the Fe: Ca: K: Ti relationship with median Ti of 2216 ppm was 12: 6: 3.5: 1. These results indicate that roadway dust may be important sources of metals for runoff water and localized resuspended particulate matter.

Electronic structure calculations on multiply charged anions containing M bond S bonds (M = Cr, Mo, W) and their heterobimetallic cluster complexes

NASA Astrophysics Data System (ADS)

Gili, Pedro; Tsipis, Athanassios C.

Molecular and electronic structures of multiply charged mononuclear [CrS4]2-/3-, [MoOxS4-x]2-/3- (x = 0-4) and [WS4]2-/3- anionic species, and their heterobimetallic dinuclear and trinuclear clusters formulated as [MoOS3(CuCl)]2-, [WOS3(CuCl)]2-, [MoS4{Cu(CN)}]2-, [(CN)Cu(?-CrS4)Cu(CN)]2-, [(CN)Cu(?-MoS4)Cu(CN)]2-, [ClCu(?-MoS4)CuCl]2-, [Cl2Fe(?-MoS4)CuCl2]2-, and [(CN)Cu(?-WS4)Cu(CN)]2- have been investigated using electronic structure calculation (HF, MP4SDQ and DFT) methods. For the discrete mononuclear anions HF/lanl2dz(M)?6-31+G*(S,O) method provided the best description of their molecular structures, while for the heterobimetallic dinuclear and trinuclear clusters the B3LYP/lanl2dz(M)?6-31+G* method gave equilibrium geometries closely resembling the experimental ones. Electronic and spectroscopic (IR, UV-Vis) properties of the thiometalates are discussed in relation to their structures, while the bonding mechanism was analyzed in the framework of the natural bond orbital (NBO) approach. The nature of the highest occupied molecular orbitals (HOMOs) of all thiometalates indicated their ability to act as ligands coordinated with metal centers and forming clusters of higher nuclearity. The lowest-lying vertical one-electron detachment processes from the ground state of the [CrS4]2/3-, [MoOxS4-x]2/3- (x = 0-4) and [WS4]2/3- anions have been calculated using the outer valence Green's function (OVGF) method. Interestingly, in the heterobimetallic dinuclear and trinuclear clusters intemetallic M?M? interactions exist corresponding to d10 ? d0 dative bonding. Finally, the complete energetic and geometric profile of the successive acid-catalyzed formation reactions:and the reverse hydrolysis reactions have been delineated and details of the mechanism have been furnished.

[Analysis of mineral elements in different organs at different harvesting times of Schizonepeta tenuifolia on ICP-AES].

PubMed

Shan, Ming-Qiu; Yu, Sheng; Yu, Li-Xia; Ding, An-Wei

2014-02-01

To study the main storage organ of each mineral element in Schizonepeta tenuifolia, and explain its reasonable harvesting time and medicinal parts in view of mineral elements. The mineral elements of Schizonepeta tenuifolia in different organs at different harvesting times were determined by ICP-AES technique. The mineral elements, K, Ca, Na, P, Mg, Mn, Zn, Cu, Fe, Mo, were determined in the study. The results showed that at different harvesting times, (1) the contents of K, P, Cu in fringe and the contents of Mg, Ca, Na, Fe, Mn, Zn in leaf were highest among different organs. (2) among the macroelements, the contents of K and Ca were highest while the content of Na was lowest; among the microelements, the content of Fe was highest while the content of Mo was lowest. (3) in item, the proportion of K:P was highest while the proportion of Zn: Cu was lowest; in fringe, the proportions of Ca:Mg and Fe:Mn were lowest. (4) within the harvest period, variations of the mineral elements were not obvious. In the stem of Schizonepeta tenuifolia, the contents of every mineral elements were lower than other organs, including leaves and spikes. Considering the mineral elements, the correlations of harvesting time and content change were not remarkable.

New detections of arsenic, selenium, and other heavy elements in two metal-poor stars

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

Roederer, Ian U.; Schatz, Hendrik; Beers, Timothy C.

2014-08-10

We use the Space Telescope Imaging Spectrograph on board the Hubble Space Telescope to obtain new high-quality spectra covering the 1900 ≤λ ≤ 2360 Å wavelength range for two metal-poor stars, HD 108317 and HD 128279. We derive abundances of Cu II, Zn II, As I, Se I, Mo II, and Cd II, which have not been detected previously in either star. Abundances derived for Ge I, Te I, Os II, and Pt I confirm those derived from lines at longer wavelengths. We also derive upper limits from the non-detection of W II, Hg II, Pb II, and Bi I.more » The mean [As/Fe] ratio derived from these two stars and five others in the literature is unchanged over the metallicity range –2.8 < [Fe/H] <–0.6, ([As/Fe]) = +0.28 ± 0.14 (σ = 0.36 dex). The mean [Se/Fe] ratio derived from these two stars and six others in the literature is also constant, ([Se/Fe]) = +0.16 ± 0.09 (σ = 0.26 dex). The As and Se abundances are enhanced relative to a simple extrapolation of the iron-peak abundances to higher masses, suggesting that this mass region (75 ≤A ≤ 82) may be the point at which a different nucleosynthetic mechanism begins to dominate the quasi-equilibrium α-rich freezeout of the iron peak. ([Cu II/Cu I]) = +0.56 ± 0.23 in HD 108317 and HD 128279, and we infer that lines of Cu I may not be formed in local thermodynamic equilibrium in these stars. The [Zn/Fe], [Mo/Fe], [Cd/Fe], and [Os/Fe] ratios are also derived from neutral and ionized species, and each ratio pair agrees within the mutual uncertainties, which range from 0.15 to 0.52 dex.« less

Micronutrients (B, Co, Cu, Fe, Mn, Mo, and Zn) content in made tea (Camellia sinensis L.) and tea infusion with health prospect: A critical review.

PubMed

Karak, Tanmoy; Kutu, Funso Raphael; Nath, Jyoti Rani; Sonar, Indira; Paul, Ranjit Kumar; Boruah, Romesh Kumar; Sanyal, Sandip; Sabhapondit, Santanu; Dutta, Amrit Kumar

2017-09-22

Tea (Camellia sinensis L.) is a perennial acidophilic crop, and known to be a nonalcoholic stimulating beverage that is most widely consumed after water. The aim of this review paper is to provide a detailed documentation of selected micronutrient contents, viz. boron (B), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), and zinc (Zn) in made tea and tea infusion. Available data from the literature were used to calculate human health aspect associated with the consumption of tea infusion. A wide range of micronutrients reported in both made tea and tea infusion could be the major sources of micronutrients for human. The content of B, Co, Cu, Fe, Mn, Mo, and Zn in made tea are ranged from 3.04 to 58.44 μg g -1 , below detectable limit (BDL) to 122.4 μg g -1 , BDL to 602 μg g -1 , 0.275 to 13,040 μg g -1 , 0.004 to 15,866 μg g -1 , 0.04 to 570.80 μg g -1 and 0.01 to 1120 μg g -1 , respectively. Only 3.2 μg L -1 to 7.25 mg L -1 , 0.01 μg L -1 to 7 mg L -1 , 3.80 μg L -1 to 6.13 mg L -1 , 135.59 μg L -1 -11.05 mg L -1 , 0.05 μg L -1 to 1980.34 mg L -1 , 0.012 to 3.78 μg L -1 , and 1.12 μg L -1 to 2.32 μg L -1 of B, Co, Cu, Fe, Mn, Mo, and Zn, respectively, are found in tea infusion which are lower than the prescribed limit of micronutrients in drinking water by World Health Organization. Furthermore, micronutrient contents in tea infusion depend on infusion procedure as well as on the instrument used for analysis. The proportion of micronutrients found in different tea types are 1.0-88.9% for B, 10-60% for Co, 2.0-97.8% for Cu, 67.8-89.9% for Fe, 71.0-87.4% for Mn, 13.3-34% for Mo, and 34.9-83% for Zn. From the results, it can also be concluded that consumption of three cups of tea infusion per day does not have any adverse effect on human health with respect to the referred micronutrients rather got beneficial effects to human.

A comparison of the bonding in organoiron clusters

NASA Astrophysics Data System (ADS)

Buhl, Margaret L.; Long, Gary J.

1994-12-01

The Mössbauer effect hyperfine parameters and the results of the Fenske-Hall molecular orbit (mo) calculations have been used to study the electronic properties of trinuclear iron, tetranuclear iron butterfly, Fe-Co, and Fe-Cu carbonyl clusters. The more negative Fe charge and the larger Fe 4s population in an Fe(CO)4 fragment as compared with that in an Fe(CO)3 or an Fe(CO)2 fragment is a result of the CO ligands rather than the near-neighbor metals. The clusters which contain heterometals have more negative isomer shifts. The isomer shift correlated well with the sum of the Fe 4s orbital population and the Zeff these electrons experience. The mo wave functions and the atomic charges generally give a larger calculated Δ E Q than is observed, indicating the need to include Sternheimer factors in the calculation. The valence contribution dominates the EFG.

The occurrence and distribution of trace metals in the Mississippi River and its tributaries

USGS Publications Warehouse

Taylor, Howard E.; Garbarino, J.R.; Brinton, T.I.

1990-01-01

Quantitative and semiquantitative analyses of dissolved trace metals are reported for designated sampling sites on the Mississippi River and its main tributaries utilizing depth-integrated and width-integrated sampling technology to collect statistically representative samples. Data are reported for three sampling periods, including: July-August 1987, November-December 1987, and May-June 1988. Concentrations of Al, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Pb, Sr, Tl, U, V, and Zn are reported quantitatively, with the remainder of the stable metals in the periodic table reported semiquantitatively. Correlations between As and V, Ba and U, Cu and Zn, Li and Ba, and Li and U are significant at the 99% confidence level for each of the sampling trips. Comparison of the results of this study for selected metals with other published data show generally good agreement for Cr, Cu, Fe, and Zn, moderate agreement for Mo, and poor agreement for Cd and V.

Sugar beet factory lime affects the mobilization of Cd, Co, Cr, Cu, Mo, Ni, Pb, and Zn under dynamic redox conditions in a contaminated floodplain soil.

PubMed

Shaheen, Sabry M; Rinklebe, Jörg

2017-01-15

The impact of sugar beet factory lime (SBFL) on the release dynamics and mobilization of toxic metals (TMs) under dynamic redox conditions in floodplain soils has not been studied up to date. Therefore, the aim of this study was to verify the scientific hypothesis that SBFL is able to immobilize Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, and Zn under different redox potentials (E H ) in a contaminated floodplain soil. For this purpose, the non-treated contaminated soil (CS) and the same soil treated with SBFL (CS+SBFL) were flooded in the laboratory using a highly sophisticated automated biogeochemical microcosm apparatus. The experiment was conducted stepwise from reducing (-13 mV) to oxidizing (+519 mV) soil conditions. Soil pH decreased under oxic conditions in CS (from 6.9 to 4.0) and in CS+SBFL (from 7.5 to 4.4). The mobilization of Cu, Cr, Pb, and Fe were lower in CS+SBFL than in CS under both reducing/neutral and oxic/acidic conditions. Those results demonstrate that SBFL is able to decrease concentrations of these elements under a wide range of redox and pH conditions. The mobilization of Cd, Co, Mn, Mo, Ni, and Zn were higher in CS+SBFL than in CS under reducing/neutral conditions; however, these concentrations showed an opposite behavior under oxic/acidic conditions and were lower in CS+SBFL than in CS. We conclude that SBFL immobilized Cu, Cr, Pb, and Fe under dynamic redox conditions and immobilized Cd, Co, Mn, Mo, Ni, and Zn under oxic acidic conditions; however, the latter elements were mobilized under reducing neutral conditions in the studied soil. Therefore, the addition of SBFL to acid floodplain soils contaminated with TMs might be an important alternative for ameliorating these soils with view to a sustainable management of these soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Detection of Labile Low-Molecular-Mass Transition Metal Complexes in Mitochondria

PubMed Central

McCormick, Sean P.; Moore, Michael J.; Lindahl, Paul A.

2015-01-01

Liquid chromatography was used with an on-line inductively coupled plasma mass spectrometer to detect low-molecular-mass (LMM) transition metal complexes in mitochondria isolated from fermenting yeast cells, human Jurkat cells, and mouse brain and liver. These complexes constituted 20 – 40% of total mitochondrial Mn, Fe, Zn, and Cu ions. The major LMM Mn complex in yeast mitochondria had a mass of ca. 1100 Da and a concentration of ~ 2 μM. Mammalian mitochondria contained a second Mn species with a mass of ca. 2000 Da at a comparable concentration. The major Fe complex in mitochondria isolated from exponentially growing yeast cells had a mass of ca. 580 Da; the concentration of Fe580 in mitochondria was ca. 100 μM. When mitochondria were isolated from fermenting cells in post-exponential phase, the mass of the dominant LMM Fe complex was ca. 1100 Da. Upon incubation, the intensity of Fe1100 declined and Fe580 increased, suggesting that the two are interrelated. Mammalian mitochondria contained Fe580 and 2 other Fe species (Fe2000 and Fe1100) at concentrations of ca. 50 μM each. The dominant LMM Zn species in mitochondria had a mass of ca. 1200 Da and a concentration of ca. 110 μM. Mammalian mitochondria contained a second major LMM Zn species at 1500 Da. The dominant LMM Cu species in yeast mitochondria had a mass of ca. 5000 Da and a concentration in yeast mitochondria of ca. 16 μM; Cu5000 was not observed in mammalian mitochondria. The dominant Co species in mitochondria, Co1200, had a concentration of 20 nM and was probably a cobalamin. Mammalian but not yeast mitochondria contained a LMM Mo species, Mo730, at ca. 1 μM concentration. Increasing Mn, Fe, Cu, and Zn concentrations 10 fold in the medium increased the concentration of the same element in the corresponding isolated mitochondria. Treatment with metal chelators confirmed that these LMM species were labile. The dominant S species at 1100 Da was not free GSH or GSSG. PMID:26018429

Radical scavenging propensity of Cu2 +, Fe3 + complexes of flavonoids and in-vivo radical scavenging by Fe3 +-primuletin

NASA Astrophysics Data System (ADS)

Jabeen, Erum; Janjua, Naveed Kausar; Ahmed, Safeer; Murtaza, Iram; Ali, Tahir; Hameed, Shahid

2017-01-01

Cu2 + and Fe3 + complexes of three flavonoids (morin or mo, quercetin or quer and primuletin or prim) were synthesized with the objective of improving antioxidant capacities of flavonoids. The radical scavenging activities of pure flavonoids and their metal complexes were assayed to monitor their tendencies towards sequestering of radicals at physiological conditions. The scavenger potencies of metal-flavonoid complexes were significantly higher than those of the parent flavonoids. Further, influence of the solvent polarity on the radical capturing by flavonoids and their metal complexes was in favor for the polar solvent. Fe3 +-prim displayed its radical scavenging ability via up gradation of CAT and SOD activities in in-vivo antioxidant assays.

Impact of saline aquifer water on surface and shallow pit corrosion of martensitic stainless steels during exposure to CO2 environment (CCS)

NASA Astrophysics Data System (ADS)

Pfennig, Anja; Kranzmann, Axel

2018-05-01

Pipe steels suitable for carbon capture and storage technology (CCS) require resistance against the corrosive environment of a potential CCS-site, e.g. heat, pressure, salinity of the aquifer, CO2-partial pressure. Samples of different mild and high alloyed stainless injection-pipe steels partially heat treated: 42CrMo4, X20Cr13, X46Cr13, X35CrMo4 as well as X5CrNiCuNb16-4 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in a CO2-saturated synthetic aquifer environment similar to possible geological on-shore CCS-sites in the northern German Basin. Main corrosion products are FeCO3 and FeOOH. Corrosion rates obtained at 100 bar are generally much lower than those measured at ambient pressure. Highest surface corrosion rates are 0.8 mm/year for 42CrMo4 and lowest 0.01 mm/year for X5CrNiCuNb16-4 in the vapour phase at ambient pressure. At 100 bar the highest corrosion rates are 0.01 mm/year for 42CrMo4, X20Cr13 (liquid phase), X46Cr13 and less than 0.01 mm/year for X35CrMo4 and X5CrNiCuNb16-4 after 8000 h of exposure with no regard to atmosphere. Martensitic microstructure offers good corrosion resistance.

Hot gas, regenerative, supported H.sub.2 S sorbents

NASA Technical Reports Server (NTRS)

Voecks, Gerald E. (Inventor); Sharma, Pramod K. (Inventor)

1993-01-01

Efficient, regenerable sorbents for removal of H.sub.2 S from moderately high temperature (usually 200.degree. C.-550.degree.C.) gas streams comprise a porous, high surface area aluminosilicate support, suitably a zeolite, and most preferably a sodium deficient zeolite containing 1 to 20 weight percent of binary metal oxides. The binary oxides are a mixture of a Group VB or VIB metal oxide with a Group IB, IIB or VIII metal oxide such as V-Zn-O, V-Cu-O, Cu-Mo-O, Zn-Mo-O or Fe-Mo-O contained in the support. The sorbent effectively removes H.sub.2 S from the host gas stream in high efficiency and can be repetitively regenerated at least 10 times without loss of activity.

Structure and magnetic properties of Fe12X clusters

NASA Astrophysics Data System (ADS)

Gutsev, G. L.; Johnson, L. E.; Belay, K. G.; Weatherford, C. A.; Gutsev, L. G.; Ramachandran, B. R.

2014-02-01

The electronic and geometrical structures of a Fe12X family of binary clusters Fe12Al, Fe12Sc, Fe12Ti, Fe12V, Fe12Cr, Fe12Mn, Fe12Co, Fe12Ni, Fe12Cu, Fe12Zn, Fe12Y, Fe12Zr, Fe12Nb, Fe12Mo, Fe12Tc, Fe12Ru, Fe12Rh, Fe12Pd, Fe12Ag, Fe12Cd, and Fe12Gd are studied using density functional theory within generalized gradient approximation. It is found that the geometrical structures corresponding to the lowest total energy states found for the Fe12X clusters possess icosahedral shape with the substituent atom occupying the central or a surface site. The only exception presents Fe12Nb where a squeezed cage structure is the energetically most favorable. The substitution of an atom in the Fe13 cluster results in the decrease of its total spin magnetic moment of 44 μB, except for Fe12Mn and Fe12Gd. The Fe12X clusters are more stable than the parent Fe13 cluster when X = Al, Sc, Ti, V, Co, Y, Zr, Nb, Mo, Tc, Ru, and Rh.

Mineral deficiency status of ranging zebu (Bos indicus) cattle around the Gilgel Gibe catchment, Ethiopia.

PubMed

Dermauw, Veronique; Yisehak, Kechero; Belay, Duguma; Van Hecke, Thomas; Du Laing, Gijs; Duchateau, Luc; Janssens, Geert P J

2013-06-01

Mineral deficiencies in cattle, widespread in East Africa, impair optimal health and production and consequently place a great burden on the farmers' income. Therefore, detection of shortages and imbalances of specific minerals is essential. Our objective was to evaluate the mineral status of grazing cattle around the Gilgel Gibe catchment in Ethiopia and associated factors. In study I, individual animal plasma and herd faecal Ca, P, Mg, Na, K, S, Fe, Zn, Mn and Cu concentrations were determined in adult zebu cattle (Bos indicus; n=90) grazing at three altitudes around the catchment, whilst recording body condition score and sex. In study II, liver samples of adult male zebu cattle (n=53) were analysed for Cu, Zn, Fe, Se and Mo concentrations and inspected for parasitic infections. Plasma and liver analyses revealed a Cu deficiency problem in the area, since 68 and 47 % of cattle, respectively, were Cu deprived according to diagnostic criteria for Bos taurus cattle. High hepatic Mo concentrations in 17 % of cases might reflect excessive dietary Mo intake. Liver Se and plasma Na concentrations were too low in 92 and 80 % of cattle. Plasma Mn concentrations were largely below the detection limit. Plasma Cu as well as Ca concentrations were lower in the lowest altitude compared to the highest altitude group (P<0.05), whereas lean to medium cattle had lower plasma Cu concentrations (P<0.05). No differences in hepatic mineral concentrations were detected between cattle with different types of parasitic infection. In conclusion, bovine mineral deficiencies were present in the Gilgel Gibe area and were associated with grazing altitude and body condition score.

Aegle marmelos Mediated Green Synthesis of Different Nanostructured Metal Hexacyanoferrates: Activity against Photodegradation of Harmful Organic Dyes

PubMed Central

Jassal, Vidhisha; Kaith, B. S.

2016-01-01

Prussian blue analogue potassium metal hexacyanoferrate (KMHCF) nanoparticles Fe4[Fe(CN)6]3 (FeHCF), K2Cu3[Fe(CN)6]2 (KCuHCF), K2Ni[Fe(CN)6]·3H2O (KNiHCF), and K2Co[Fe(CN)6] (KCoHCF) have been synthesized using plant based biosurfactant Aegle marmelos (Bael) and water as a green solvent. It must be emphasized here that no harmful reagent or solvent was used throughout the study. Plant extracts are easily biodegradable and therefore do not cause any harm to the environment. Hence, the proposed method of synthesis of various KMHCF nanoparticles followed a green path. The synthesized nanoparticles were characterized by powder X-ray diffraction (PXRD), Field-Emission Scanning Electron Microscopy (FE-SEM), Transmission Electron Microscopy (TEM), and Fourier Transform Infrared Spectroscopy (FT-IR). MHCF nanoparticles were used for the photocatalytic degradation of toxic dyes like Malachite Green (MG), Eriochrome Black T (EBT), Methyl Orange (MO), and Methylene Blue (MB). Under optimized reaction conditions, maximum photocatalytic degradation was achieved in case of KCuHCF nanoparticles mediated degradation process (MG: 96.06%, EBT: 83.03%, MB: 94.72%, and MO: 63.71%) followed by KNiHCF (MG: 95%, EBT: 80.32%, MB: 91.35%, and MO: 59.42%), KCoHCF (MG: 91.45%, EBT: 78.84%, MB: 89.28%, and MO: 58.20%). PMID:27034896

[Contents of nutrient elements in NH4(+)-N fertilizer and urea].

PubMed

Wang, Zheng-Rui; Qu, Gui-Qin; Rui, Yu-Kui; Shen, Jian-Bo; Zhang, Fu-Suo

2009-03-01

Fertilizer contains not only one compound or one element, so it is important to determine the contents of other elements necessitous and beneficial to plant. All the other nutrient elements for plant, including necessitous elements and beneficial elements in ammonia nitrogen fertilizer ((NH4)2SO4) and CO(NH2)2, were analyzed by method of ICP-MS. The results showed that ammonia nitrogen fertilizer ((NH4)2SO4) and CO(NH2)2 both contain many necessitous elements, Mg, P, K, Ca, Mn, Fe, Ni, Cu, Zn and Mo, thereinto the contents of Mg, P, K, Ca, Mn and Fe were on microg x g(-1) the level, and Ni, Cu, Zn and Mo were on the ng x g(-1) level; compared with CO(NH2)2, ammonia nitrogen fertilizer ((NH4)2SO4) contains more necessitous elements and beneficial elements except Mo and Si. All the above elements could influence the results of nitrogen fertilizer efficiency experiments, so pure fertilizer should be used in the future nitrogen fertilizer efficiency experiments and the comparative experiments of different form nitrogen fertilizer.

Structure and Electrochemistry of Copper Fluoride Nanocomposites Utilizing Mixed Conducting Matrices

DTIC Science & Technology

2007-01-01

similar to the conversion reaction of the metal fluoride. Attractive materials such as V2O5 , MoS2, and MoO3-δ can be utilized. Examples of metal...fluorides enabled by these MCM matrices are nanocomposites of FeF3 ( V2O5 ),2 BiF3 (MoS2),15 and as discussed herein, CuF2 (MoO3). In all cases, the...filled dry box using Whatman GF/D glass fiber separators saturated with 1M LiPF6 in 1:1 vol/vol ethylene carbonate:dimethyl carbonate elec- trolyte

Volatilization, transport and sublimation of metallic and non-metallic elements in high temperature gases at Merapi Volcano, Indonesia

USGS Publications Warehouse

Symonds, R.B.; Rose, William I.; Reed, M.H.; Lichte, F.E.; Finnegan, David L.

1987-01-01

Condensates, silica tube sublimates and incrustations were sampled from 500-800??C fumaroles and lava samples were collected at Merapi Volcano, Indonesia in Jan.-Feb., 1984. With respect to the magma, Merapi gases are enriched by factors greater than 105 in Se, Re, Bi and Cd; 104-105 in Au, Br, In, Pb and W; 103-104 in Mo, Cl, Cs, S, Sn and Ag; 102-103 in As, Zn, F and Rb; and 1-102 in Cu, K, Na, Sb, Ni, Ga, V, Fe, Mn and Li. The fumaroles are transporting more than 106 grams/day ( g d) of S, Cl and F; 104-106 g/d of Al, Br, Zn, Fe, K and Mg; 103-104 g d of Pb, As, Mo, Mn, V, W and Sr; and less than 103 g d of Ni, Cu, Cr, Ga, Sb, Bi, Cd, Li, Co and U. With decreasing temperature (800-500??C) there were five sublimate zones found in silica tubes: 1) cristobalite and magnetite (first deposition of Si, Fe and Al); 2) K-Ca sulfate, acmite, halite, sylvite and pyrite (maximum deposition of Cl, Na, K, Si, S, Fe, Mo, Br, Al, Rb, Cs, Mn, W, P, Ca, Re, Ag, Au and Co); 3) aphthitalite (K-Na sulfate), sphalerite, galena and Cs-K. sulfate (maximum deposition of Zn, Bi, Cd, Se and In; higher deposition of Pb and Sn); 4) Pb-K chloride and Na-K-Fe sulfate (maximum deposition of Pb, Sn and Cu); and 5) Zn, Cu and K-Pb sulfates (maximum deposition of Pb, Sn, Ti, As and Sb). The incrustations surrounding the fumaroles are also chemically zoned. Bi, Cd, Pb, W, Mo, Zn, Cu, K, Na, V, Fe and Mn are concentrated most in or very close to the vent as expected with cooling, atmospheric contamination and dispersion. The highly volatile elements Br, Cl, As and Sb are transported primarily away from high temperature vents. Ba, Si, P, Al, Ca and Cr are derived from wall rock reactions. Incomplete degassing of shallow magma at 915??C is the origin of most of the elements in the Merapi volcanic gas, although it is partly contaminated by particles or wall rock reactions. The metals are transported predominantly as chloride species. As the gas cools in the fumarolic environment, it becomes saturated with sublimate phases that fractionate from the gas in the order of their equilibrium saturation temperatures. Devolatilization of a cooling batholith could transport enough acids and metals to a hydrothermal system to play a significant role in forming an ore deposit. However, sublimation from a high temperature, high velocity carrier gas is not efficient enough to form a large ore deposit. Re, Se, Cd and Bi could be used as supporting evidence for magmatic fluid transport in an ore deposit. ?? 1987.

Trace elements distribution in hawksbill turtle (Eretmochelys imbricata) and green turtle (Chelonia mydas) tissues on the northern coast of Bahia, Brazil.

PubMed

de Macêdo, Gustavo R; Tarantino, Taiana B; Barbosa, Isa S; Pires, Thaís T; Rostan, Gonzalo; Goldberg, Daphne W; Pinto, Luis Fernando B; Korn, Maria Graças A; Franke, Carlos Roberto

2015-05-15

Concentrations of elements (As, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, Sb, Se, Sr, V, Zn) were determined in liver, kidneys and bones of Eretmochelys imbricata and Chelonia mydas specimens found stranded along the northern coast of Bahia, Brazil. Results showed that the concentrations of Cd, Cu, Ni and Zn in the liver and kidneys of juvenile C. mydas were the highest found in Brazil. We also observed a significant difference (p<0.05) on the bioaccumulation of trace elements between the two species: Al, Co, Mo, Na and Se in the liver; Al, Cr, Cu, K, Mo, Ni, Pb, Sr and V in the kidneys; and Al, Ba, Ca, Cd, Mn, Ni, Pb, Se, Sr and V in the bones. This study represents the first report on the distribution and concentration of trace elements in E. imbricata in the Brazilian coast. Copyright © 2015 Elsevier Ltd. All rights reserved.

The El Teniente porphyry Cu-Mo deposit from a hydrothermal rutile perspective

NASA Astrophysics Data System (ADS)

Rabbia, Osvaldo M.; Hernández, Laura B.; French, David H.; King, Robert W.; Ayers, John C.

2009-11-01

Mineralogical, textural, and chemical analyses (EPMA and PIXE) of hydrothermal rutile in the El Teniente porphyry Cu-Mo deposit help to better constrain ore formation processes. Rutile formed from igneous Ti-rich phases (sphene, biotite, Ti-magnetite, and ilmenite) by re-equilibration and/or breakdown under hydrothermal conditions at temperatures ranging between 400°C and 700°C. Most rutile nucleate and grow at the original textural position of its Ti-rich igneous parent mineral phase. The distribution of Mo content in rutile indicates that low-temperature (˜400-550°C), Mo-poor rutile (5.4 ± 1.1 ppm) is dominantly in the Mo-rich mafic wallrocks (high-grade ore), while high-temperature (˜550-700°C), Mo-rich rutile (186 ± 20 ppm) is found in the Mo-poor felsic porphyries (low-grade ore). Rutile from late dacite ring dikes is a notable exception to this distribution pattern. The Sb content in rutile from the high-temperature potassic core of the deposit to its low-temperature propylitic fringe remains relatively constant (35 ± 3 ppm). Temperature and Mo content of the hydrothermal fluids in addition to Mo/Ti ratio, modal abundance and stability of Ti-rich parental phases are key factors constraining Mo content and provenance in high-temperature (≥550°C) rutile. The initial Mo content of parent mineral phases is controlled by melt composition and oxygen fugacity as well as timing and efficiency of fluid-melt separation. Enhanced reduction of SO2-rich fluids and sulfide deposition in the Fe-rich mafic wallrocks influences the low-temperature (≤550°C) rutile chemistry. The data are consistent with a model of fluid circulation of hot (>550°C), oxidized (ƒO2 ≥ NNO + 1.3), SO2-rich and Mo-bearing fluids, likely exsolved from deeper crystallizing parts of the porphyry system and fluxed through the upper dacite porphyries and related structures, with metal deposition dominantly in the Fe-rich mafic wallrocks.

Determination of the Extent of Trace Metals Pollution in Soils, Sediments and Human Hair at e-Waste Recycling Site in Ghana.

PubMed

Tokumaru, Takashi; Ozaki, Hirokazu; Onwona-Agyeman, Siaw; Ofosu-Anim, John; Watanabe, Izumi

2017-10-01

The concentrations of trace elements (Mg, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, In, Sn, Sb, Cs, Ba, Tl, Pb, and Bi) in soils, sediment, human hair, and foodstuff collected around the electronic waste (e-waste) recycling sites in Accra, Ghana were detected using inductively coupled plasma-mass spectrometry (ICP-MS). High levels of Cu, Zn, Mo, Cd, In, Sn, Sb, and Pb were observed in soils collected from the e-waste recycling sites. Four sequential extraction procedures were used to evaluate the mobility and bioavailability of metals (Cu, Zn, Cd, Sb, and Pb). Especially, the results showed that Cd and Zn in soils were mostly recovered in exchangeable fraction (respectively 58.9 and 62.8%). Sediment collected from around the site had enrichment of Zn, Sn, Sb, Mo, In, Pb, and Bi. The concentrations of Cu, Mo, Cd, Sb, and Pb in human hair were significantly higher than those collected from the control site (p < 0.01). Additionally, hierarchical cluster analysis reviewed that these elements were derived from e-waste activities. The results of Pb isotopic ratios in the samples indicate that Pb in human hair possibly originated from contaminated soils, fish, and foodstuff.

Bioavailability of Lead in Small Arms Range Soils

DTIC Science & Technology

2007-09-01

minerals, and may also exist inside particles of inert matrix such as rock or slag of variable size, shape, and association; these chemical and...Abbreviations: Fe=iron, Pb=lead, Cu=copper, Ti=titanium, Zn= zinc , Sb=antimony, Rb=rubidium, Zr=zirconium, As=arsenic. Values are mean of three...20 30 40 50 60 70 80 FeOOH Cerussite Organic Phosphate PbMO PbAsO MnOOH Anglesite PbOOH PbCl4 Slag FeSO4 PbO Frequency of Occurrence Relative Pb

The role of carbon dioxide in the transport and fractionation of metals by geological fluids

NASA Astrophysics Data System (ADS)

Kokh, Maria A.; Akinfiev, Nikolay N.; Pokrovski, Gleb S.; Salvi, Stefano; Guillaume, Damien

2017-01-01

Although carbon dioxide is one of the major components of crustal fluids responsible for ore deposit formation, its effect on transport and precipitation of metals remains unknown, due to a lack of direct experimental data and physical-chemical models for CO2-rich fluids. To fill this gap, we combined laboratory experiments and thermodynamic modeling to systematically quantify the role played by CO2 for the solubility of economically important metals such as Fe, Cu, Zn, Au, Mo, Pt, Sn under hydrothermal conditions. Solubility measurements of common ore minerals of these metals (FeS2, CuFeS2, ZnS, Au, MoS2, PtS, SnO2) were performed, using a flexible-cell reactor equipped with a rapid sampling device, in a single-phase fluid (CO2-H2O-KCl) at 350-450 °C and 600-750 bar, buffered with iron sulfide and oxide and alkali-aluminosilicate mineral assemblages. In addition, another type of experiments was conducted to measure gold solubility in more sulfur-rich supercritical CO2-H2O-S-NaOH fluids at 450 °C and 700 bar using a batch reactor that allows fluid quenching. Our results show that the solubilities of Si, Au, Mo, Pt and Cu either decrease (within <1 log unit) or remain constant upon CO2 increase, whereas those of Fe, Zn and Sn increase significantly (>1 log unit) with CO2 contents in the fluid increasing from 0 to 50 wt%. These data were interpreted using a simple model that does not require any new adjustable parameters, and is based on the dielectric constant of the H2O-CO2 solvent and on the Born solvation parameter for the dominant metal-bearing species in an aqueous fluid. Our predictions using this model suggest that in a supercritical CO2-H2O-S-salt fluid typical of metamorphic Au deposits, in equilibrium with pyrite and chalcopyrite, the Cu/Fe ratio decreases by up to 2 orders of magnitude with an increase of CO2 content from 0 to 70 wt%. This effect is due to the decrease of the fluid dielectric constant in the presence of CO2, which favors the stability of neutral species (FeCl20) compared to charged ones (CuCl2-). Our results explain the Fe enrichment and Cu depletion in metamorphic gold deposits formed by CO2-rich fluids. The transport of gold is unfavorable in the presence of CO2 only in S-rich (>0.5 wt% S) fluids in which Au forms the negatively charged Au(HS)2- and Au(HS)S3- complexes. By contrast, it is only weakly affected in S-poor (<0.1 wt% S) acidic-to-neutral fluids in which the uncharged Au(HS)0 complex predominates. Thus, even at very high CO2 contents (>50 wt% CO2), the capacity of such fluids to transport gold (up to 100s ppb Au) remains comparable to that of aqueous fluids. These findings are in agreement with analyses of natural fluid inclusions in metamorphic deposits. In more saline oxidizing and S-rich fluids such as those in magmatic porphyry Cu-Au deposits, the Fe, Cu, and Au solubilities in the presence of CO2 decrease by ∼1 order of magnitude with CO2 increasing to 20-30 wt%, following the decrease in the stability of their dominant charged species (FeCl42-, CuCl2-, Au(HS)2- and Au(HS)S3-), but stay almost constant at higher CO2 contents (30-70 wt%) as controlled by the neutral species (FeCl20, Cu(HS)0 and Au(HS)0). Such solubility trends suggest a new potential trigger of ore precipitation in porphyry systems by CO2 pulses from the magmatic chamber, which may operate along with commonly admitted depositional mechanisms such as cooling, vapor-brine immiscibility, and water-rock interaction. The direct effect of CO2 on the mobility of Pt and Mo, metals that likely form hydrogen sulfide and oxy-hydroxide complexes, respectively, is expected to be weak in most settings. Among the studied elements, Sn is the only one whose solubility may be favored at high CO2 content (>20 wt%) due to carbonate complexing. This study demonstrates, for the first time, that, contrary to common belief, the presence of CO2 in a supercritical fluid may lead to enhanced mobility or, on contrary, to massive precipitation of some metals, depending on salinity and sulfur content, and, more generally, to significant fractionations between different metals.

Copper-Deficiency in Brassica napus Induces Copper Remobilization, Molybdenum Accumulation and Modification of the Expression of Chloroplastic Proteins

PubMed Central

Billard, Vincent; Ourry, Alain; Maillard, Anne; Garnica, Maria; Coquet, Laurent; Jouenne, Thierry; Cruz, Florence; Garcia-Mina, José-Maria; Yvin, Jean-Claude; Etienne, Philippe

2014-01-01

During the last 40 years, crop breeding has strongly increased yields but has had adverse effects on the content of micronutrients, such as Fe, Mg, Zn and Cu, in edible products despite their sufficient supply in most soils. This suggests that micronutrient remobilization to edible tissues has been negatively selected. As a consequence, the aim of this work was to quantify the remobilization of Cu in leaves of Brassica napus L. during Cu deficiency and to identify the main metabolic processes that were affected so that improvements can be achieved in the future. While Cu deficiency reduced oilseed rape growth by less than 19% compared to control plants, Cu content in old leaves decreased by 61.4%, thus demonstrating a remobilization process between leaves. Cu deficiency also triggered an increase in Cu transporter expression in roots (COPT2) and leaves (HMA1), and more surprisingly, the induction of the MOT1 gene encoding a molybdenum transporter associated with a strong increase in molybdenum (Mo) uptake. Proteomic analysis of leaves revealed 33 proteins differentially regulated by Cu deficiency, among which more than half were located in chloroplasts. Eleven differentially expressed proteins are known to require Cu for their synthesis and/or activity. Enzymes that were located directly upstream or downstream of Cu-dependent enzymes were also differentially expressed. The overall results are then discussed in relation to remobilization of Cu, the interaction between Mo and Cu that occurs through the synthesis pathway of Mo cofactor, and finally their putative regulation within the Calvin cycle and the chloroplastic electron transport chain. PMID:25333918

KMg0.09Fe1.91(PO4)2

PubMed Central

Yatskin, Michael M.; Zatovsky, Igor V.; Baumer, Vyacheslav N.; Ogorodnyk, Ivan V.; Slobodyanik, Nikolay S.

2012-01-01

KMg0.09Fe1.91(PO4)2, potassium [iron(II)/magnesium] iron(III) bis(orthophosphate), is a solid solution derived from compounds with general formula KM IIFe(PO4)2 (M II = Fe, Cu), in which the Mg atoms substitute Fe atoms only in the octa­hedrally surrounded sites. The framework of the structure is built up from [FeO5] trigonal bipyramids and [MO6] (M = (Fe, Mg) octa­hedra sharing corners and edges and connected by two types of bridging PO4 tetra­hedra. The K+ cations are nine-coordinated and are situated in channels running along [101]. PMID:22719280

Added dietary sulfur and molybdenum has a greater influence on hepatic copper concentration, intake, and performance in Holstein-Friesian dairy cows offered a grass silage-rather than corn silage-based diet.

PubMed

Sinclair, L A; Johnson, D; Wilson, S; Mackenzie, A M

2017-06-01

To test the hypothesis that the metabolism of Cu in dairy cows is affected by basal forage and added S and Mo, 56 dairy cows that were 35 (standard error ± 2.2) days postcalving and yielding 38.9 kg of milk/d (standard error ± 0.91) were offered 1 of 4 diets in a 2 × 2 factorial design for a 14-wk period. The 4 diets contained approximately 20 mg of Cu/kg of dry matter (DM), and had a corn silage-to-grass silage ratio of 0.75:0.25 (C) or 0.25:0.75 (G) and were either unsupplemented (-) or supplemented (+) with an additional 2 g of S/kg of DM and 6.5 mg of Mo/kg of DM. We found an interaction between forage source and added S and Mo on DM intake, with cows offered G+ having a 2.1 kg of DM lower intake than those offered G-, but no effect on the corn silage-based diets. Mean milk yield was 38.9 kg/d and we observed an interaction between basal forage and added S and Mo, with yield being decreased in cows offered G+ but increased on C+. No effect of dietary treatment on milk composition or live weight was noted, but body condition was lower in cows fed added S and Mo irrespective of forage source. We found an interaction between forage source and added S and Mo on milk somatic cell count, which was higher in cows offered G+ compared with G-, but not in cows fed the corn silage-based diets, although all values were low (mean values of 1.72, 1.50, 1.39, and 1.67 log 10 /mL for C-, C+, G-, and G+, respectively). Mean plasma Cu, Fe, and Mn concentrations were 13.8, 41.3, and 0.25 µmol/L, respectively, and were not affected by dietary treatment, whereas plasma Mo was 0.2 µmol/L higher in cows receiving added S and Mo. The addition of dietary S and Mo decreased liver Cu balance over the study period in cows fed either basal forage, but the decrease was considerably greater in cows receiving the grass silage-based diet. Similarly, hepatic Fe decreased more in cows receiving G than C when S and Mo were included in the diet. We concluded that added S and Mo reduces hepatic Cu reserves irrespective of basal forage source, but this decrease is considerably more pronounced in cows receiving grass silage- than corn silage-based rations and is associated with a decrease in intake and milk performance and an increase in milk somatic cell count. Copyright © 2017 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Too much is bad--an appraisal of phytotoxicity of elevated plant-beneficial heavy metal ions.

PubMed

Anjum, Naser A; Singh, Harminder P; Khan, M Iqbal R; Masood, Asim; Per, Tasir S; Negi, Asha; Batish, Daizy R; Khan, Nafees A; Duarte, Armando C; Pereira, Eduarda; Ahmad, Iqbal

2015-03-01

Heavy metal ions such as cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), and zinc (Zn) are considered essential/beneficial for optimal plant growth, development, and productivity. However, these ions readily impact functions of many enzymes and proteins, halt metabolism, and exhibit phytotoxicity at supra-optimum supply. Nevertheless, the concentrations of these heavy metal ions are increasing in agricultural soils worldwide via both natural and anthropogenic sources that need immediate attention. Considering recent breakthroughs on Co, Cu, Fe, Mn, Mo, Ni, and Zn in soil-plant system, the present paper: (a) overviews the status in soils and their uptake, transport, and significance in plants; (b) critically discusses their elevated level-mediated toxicity to both plant growth/development and cell/genome; (c) briefly cross talks on the significance of potential interactions between previous plant-beneficial heavy metal ions in plants; and (d) highlights so far unexplored aspects in the current context.

Street dust from a heavily-populated and industrialized city: Evaluation of spatial distribution, origins, pollution, ecological risks and human health repercussions.

PubMed

Urrutia-Goyes, R; Hernandez, N; Carrillo-Gamboa, O; Nigam, K D P; Ornelas-Soto, N

2018-09-15

Emissions from vehicles include particles from tire and brake wearing that can settle down and join industrial discharges into street dust. Metals present in street dust may create ecological and health threats and their analysis is of great environmental relevance. The city of Monterrey, Mexico is an industrial pillar of the country and shows an increasing fleet during the last years, which has yielded higher traffic and emissions. This study analyzes 44 street dust samples taken across the city for total element concentrations by using X-ray fluorescence. Associations and indicators are calculated to define possible origins, levels of pollution, natural or anthropogenic sources, and ecological and human health risks. High concentrations of As, Ba, Cu, Fe, Mo, Ni, Pb, Ti, and Zn were found. Main sources of metals were defined as: tire wearing for Zn and Fe; brake wearing for Ba, Cu, Fe, Pb and Zr; additional industrial sources for Mo, Ni, Pb, and Ti; and other natural sources for As. Ecological risk was found to be moderate across the city and risk due to Pb concentrations was established for children. Copyright © 2018 Elsevier Inc. All rights reserved.

Solubility of copper in a sulfur-free mafic melt

NASA Astrophysics Data System (ADS)

Ripley, Edward M.; Brophy, James G.

1995-12-01

The solubility of Cu in S-free mafic melts has been measured at a series of ƒ O2 values and temperatures of 1245 and 1300°C. At constant temperature Cu solubility increases from 0.04 wt% at log ƒ O2 = -11.9 to 1.10 wt% at log ƒ O 2 = -7.4 . Copper solubilities were in excess of 8 wt% in two runs controlled at very high ƒ O2 conditions of 10 -1.4 and 10 -22 Partitioning of Cu between metal and glass shows a strong ƒ O2 dependence, with D Cumet/gl ranging from 90 at log ƒ O2 = -7.4 to 2190 at log ƒ O2 = -11.9 . Slopes of Cu solubility and DCumet/gl vs. log ƒ O2 suggest that Cu dissolves predominantly in the +1 valence state. Copper solubility decreases with increasing temperature at constant ƒ O2, similar to experimental results for Ni, Co, and Mo (Dingwell et al., 1994; Holzheid et al., 1994). The data are consistent with Cu dissolution as an oxide (represented by CuO 0.5) and suggest that changes in ƒ O2 ( Fe2+/Fe3+ variations and Cu 1+ complexation with Fe 3+) may have large effects on the distribution of Cu between silicate and sulfide magmas. Results also suggest that the extraction of oxide-bonded Cu in mafic magmas by externally derived S may be an important mechanism in the generation of Cu-rich sulfide ores.

Concretionary manganese-iron oxides in streams and their usefulness as a sample medium for geochemical prospecting

USGS Publications Warehouse

Nowlan, G.A.

1976-01-01

Correlation studies of 400 samples of sieved stream sediments and 325 samples of fluvial, concretionary Mn-Fe oxides from Maine resulted in the separation of elements into the following categories: (1) elements not scavenged by Mn-Fe oxides - B, Cr, K, Mg, Rb, Sc, Ti, V, and Zr; (2) elements probably not scavenged by Mn-Fe oxides - Ag, Be, Ca, Ga, La, Sb, and Y; (3) elements scavenged weakly by Mn-Fe oxides - Cu, Mo, Pb, and Sr; (4) elements scavenged strongly by Mn oxides - Ba, Cd, Co, Ni, Tl, and Zn; and (5) elements scavenged strongly by Fe oxides - As and In. Studies of the scavenged elements showed that the deviation from the mean is characteristically greater in oxide samples as compared to sieved sediments from the same locality. However, a significant increase in contrast between anomalous and background localities, when oxides are the sample medium, more than offsets the disadvantage of data scatter. The use of oxides as a sampling medium clearly and significantly accentuates anomalous localities. In general, non-ratioed data on oxides give very nearly the same results as data consisting of scavenged elements ratioed to Mn and Fe. However, ratioed data expand the geographic area of specific anomalies. Cd and Zn consistently show strong correlations with concretionary Mn-Fe oxides, but their concentrations in the oxides do not generally show as much contrast between anomalous and background localities as do Cu, Mo, and Pb. These latter elements are strongly scavenged where rocks are mineralized. ?? 1976.

Structure and magnetism in Co/X, Fe/Si, and Fe/(FeSi) multilayers

NASA Astrophysics Data System (ADS)

Franklin, Michael Ray

Previous studies have shown that magnetic behavior in multilayers formed by repeating a bilayer unit comprised of a ferromagnetic layer and a non-magnetic spacer layer can be affected by small structural differences. For example, a macroscopic property such as giant magnetoresistance (GMR) is believed to depend significantly upon interfacial roughness. In this study, several complimentary structural probes were used to carefully characterize the structure of several sputtered multilayer systems-Co/Ag, Co/Cu, Co/Mo, Fe/Si, and Fe//[FeSi/]. X-ray diffraction (XRD) studies were used to examine the long-range structural order of the multilayers perpendicular to the plane of the layers. Transmission electron diffraction (TED) studies were used to probe the long-range order parallel to the layer plane. X-ray Absorption Fine Structure (XAFS) studies were used to determine the average local structural environment of the ferromagnetic atoms. For the Co/X systems, a simple correlation between crystal structure and saturation magnetization is discovered for the Co/Mo system. For the Fe/X systems, direct evidence of an Fe-silicide is found for the /[FeSi/] spacer layer but not for the Si spacer layer. Additionally, differences were observed in the magnetic behavior between the Fe in the nominally pure Fe layer and the Fe contained in the /[FeSi/] spacer layers.

Analysis of Mineral Elements, Metabolism, and Inflammation Indexes in the Plasma of Dairy Cows Suffering from Different Degrees of Lameness.

PubMed

Sun, Dongbo; Li, Chunqiu; Gu, Cheng; Chen, Jianfei; Qu, Yongli; Wang, Xinyu; Gao, Jing; Wei, Shan; Wang, Jianfa; Wu, Rui; Guo, Donghua

2015-12-01

In the plasma of dairy cows with 1-5 points of lameness, the mineral elements [calcium (Ca), iron (Fe), copper (Cu), zinc (Zn), iodine (I), selenium (Se), molybdenum (Mo), and chromium (Cr)], the energy metabolic indicators [triglyceride (TG), glucose (Glu), total cholesterol (CHO), nonesterified fatty acids (NEFA), β-hydroxybutyrate (BHBA), lactate (LA), and blood urea nitrogen (BUN)], and inflammatory indexes [bovine haptoglobin (BoHp), histamine (HIS), and immunoglobulin G (IgG)] were measured, respectively. Furthermore, the correlations of the measured indicators with the degrees of lameness were analyzed. The results showed that in the plasma of dairy cows with 2/3-5 points of lameness, for the mineral elements' levels, Ca, Cu, I, Se, and Fe significantly decreased, Cr significantly increased, and Mo showed a decreasing trend; for levels of the energy metabolism indicators, NEFA and BHBA significantly decreased, BUN and LA significantly increased, and Glu, CHO, and TG showed an increasing trend; for inflammation indexes, the concentrations of HIS, BoHp, and IgG all significantly increased; and further analysis indicated that the Mo, Fe, NEFA, BUN, BHBA, IgG, Ca, and Se had a significant correlation with the degrees of lameness. Resulting data revealed the changes of mineral elements, metabolism, and inflammation indexes in the plasma of dairy cows suffering from different degrees of lameness, which will provided basic knowledge for in-depth understanding of lameness in dairy cows.

For cermet inert anode containing oxide and metal phases useful for the electrolytic production of metals

DOEpatents

Ray, Siba P.; Liu, Xinghua; Weirauch, Douglas A.

2002-01-01

A cermet inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode comprises a ceramic phase including an oxide of Ni, Fe and M, where M is at least one metal selected from Zn, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mo, Hf and rare earths, preferably Zn and/or Co. Preferred ceramic compositions comprise Fe.sub.2 O.sub.3, NiO and ZnO or CoO. The cermet inert anode also comprises a metal phase such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. A preferred metal phase comprises Cu and Ag. The cermet inert anodes may be used in electrolytic reduction cells for the production of commercial purity aluminum as well as other metals.

Catalyst for selective NO.sub.x reduction using hydrocarbons

DOEpatents

Marshall, Christopher L [Naperville, IL; Neylon, Michael K [Naperville, IL

2007-05-22

A two phase catalyst is disclosed with one or more transition metals such as Cu, Co, Fe, Ag and Mo supported on a molecular sieve having a pore size not greater than 8 .ANG. along with a stabilizing oxide of one or more of the oxides of Zr, Mo, V, Nb or the rare earths coating the molecular sieve. A method of preparing the two phase catalyst and using same to remediate NO.sub.x in combustion gases is also described.

Distribution of potentially toxic elements (PTEs) in tailings, soils, and plants around Gol-E-Gohar iron mine, a case study in Iran

PubMed Central

Soltani, Naghmeh; Keshavarzi, Behnam; Moore, Farid; Sorooshian, Armin; Ahmadi, Mohamad Reza

2017-01-01

This study investigated the concentration of potentially toxic elements (PTEs) including Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, V, and Zn in 102 soils (in the Near and Far areas of the mine), 7 tailings, and 60 plant samples (shoots and roots of Artemisia sieberi and Zygophylum species) collected at the Gol-E-Gohar iron ore mine in Iran. The elemental concentrations in tailings and soil samples (in Near and Far areas) varied between 7.4 and 35.8 mg kg−1 for As (with a mean of 25.39 mg kg−1 for tailings), 7.9 and 261.5 mg kg−1 (mean 189.83 mg kg−1 for tailings) for Co, 17.7 and 885.03 mg kg−1 (mean 472.77 mg kg−1 for tailings) for Cu, 12,500 and 400,000 mg kg−1 (mean 120,642.86 mg kg−1 for tailings) for Fe, and 28.1 and 278.1 mg kg−1 (mean 150.29 mg kg−1 for tailings) for Ni. A number of physicochemical parameters and pollution index for soils were determined around the mine. Sequential extractions of tailings and soil samples indicated that Fe, Cr, and Co were the least mobile and that Mn, Zn, Cu, and As were potentially available for plants uptake. Similar to soil, the concentration of Al, As, Co, Cr, Cu, Fe, Mn, Mo, Ni, and Zn in plant samples decreased with the distance from the mining/processing areas. Data on plants showed that metal concentrations in shoots usually exceeded those in roots and varied significantly between the two investigated species (Artemisia sieberi > Zygophylum). All the reported results suggest that the soil and plants near the iron ore mine are contaminated with PTEs and that they can be potentially dispersed in the environment via aerosol transport and deposition. PMID:28620857

Synthesis and structural characterisation of iron(II) and copper(II) diphosphates containing flattened metal oxotetrahedra

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

Keates, Adam C.; Wang, Qianlong; Weller, Mark T., E-mail: m.t.weller@bath.ac.uk

2014-02-15

Single crystal and bulk polycrystalline forms of K{sub 2}MP{sub 2}O{sub 7} (M=Fe(II), Cu(II)) have been synthesised and their structures determined from single crystal X-ray diffraction data. Both compounds crystallize in the tetragonal system, space group P-42{sub 1}m. Their structures are formed from infinite sheets of linked oxopolyhedra of the stoichiometry [MP{sub 2}O{sub 7}]{sup 2−} with potassium cations situated between the layers. The MO{sub 4} tetrahedra share oxygen atoms with [P{sub 2}O{sub 7}]{sup 4−} diphosphate groups and the potassium ions have KO{sub 8} square prismatic geometry. In both compounds the M(II) centre has an unusual strongly flattened, tetrahedral coordination to oxygen,more » as a result of the Jahn–Teller (JT) effect for the high spin d{sup 6} Fe(II) and p-orbital mixing or a second order JT effect for d{sup 9} Cu(II) centres in four fold coordination. The uncommon transition metal ion environments found in these materials are reflected in their optical absorption spectra and magnetism data. - Graphical abstract: The structures of the tetragonal polymorphs of K{sub 2}MP{sub 2}O{sub 7}, M=Cu(II), Fe(II), consist of infinite sheets of stoichiometry [MP{sub 2}O{sub 7}]{sup 2−}, formed from linked pyrophosphate groups and MO{sub 4} tetrahedra, separated by potassium ions. In both compounds the unusual tetrahedral coordination of the M(II) centre is strongly flattened as a result of Jahn–Teller (JT) effects for high spin, d{sup 6} Fe(II) and p-orbital mixing and second-order JT effects for d{sup 9} Cu(II). Display Omitted - Highlights: • Tetrahedral copper and iron(II) coordinated by oxygen. • New layered phosphate structure. • Jahn–Teller and d{sup 10} distorted coordinations.« less

Source apportionment and health risk assessment of potentially toxic elements in road dust from urban industrial areas of Ahvaz megacity, Iran.

PubMed

Najmeddin, Ali; Keshavarzi, Behnam; Moore, Farid; Lahijanzadeh, Ahmadreza

2017-10-28

This study investigates the occurrence and spatial distribution of potentially toxic elements (PTEs) (Hg, Cd, Cu, Mo, Pb, Zn, Ni, Co, Cr, Al, Fe, Mn, V and Sb) in 67 road dust samples collected from urban industrial areas in Ahvaz megacity, southwest of Iran. Geochemical methods, multivariate statistics, geostatistics and health risk assessment model were adopted to study the spatial pollution pattern and to identify the priority pollutants, regions of concern and sources of the studied PTEs. Also, receptor positive matrix factorization model was employed to assess pollution sources. Compared to the local background, the median enrichment factor values revealed the following order: Sb > Pb > Hg > Zn > Cu > V > Fe > Mo > Cd > Mn > Cr ≈ Co ≈ Al ≈ Ni. Statistical results show that a significant difference exists between concentrations of Mo, Cu, Pb, Zn, Fe, Sb, V and Hg in different regions (univariate analysis, Kruskal-Wallis test p < 0.05), indicating the existence of highly contaminated spots. Integrated source identification coupled with positive matrix factorization model revealed that traffic-related emissions (43.5%) and steel industries (26.4%) were first two sources of PTEs in road dust, followed by natural sources (22.6%) and pipe and oil processing companies (7.5%). The arithmetic mean of pollution load index (PLI) values for high traffic sector (1.92) is greater than industrial (1.80) and residential areas (1.25). Also, the results show that ecological risk values for Hg and Pb in 41.8 and 9% of total dust samples are higher than 80, indicating their considerable or higher potential ecological risk. The health risk assessment model showed that ingestion of dust particles contributed more than 83% of the overall non-carcinogenic risk. For both residential and industrial scenarios, Hg and Pb had the highest risk values, whereas Mo has the lowest value.

Enrichment, spatial distribution of potential ecological and human health risk assessment via toxic metals in soil and surface water ingestion in the vicinity of Sewakht mines, district Chitral, Northern Pakistan.

PubMed

Rehman, Inayat Ur; Ishaq, Muhammad; Ali, Liaqat; Khan, Sardar; Ahmad, Imtiaz; Din, Imran Ud; Ullah, Hameed

2018-06-15

This study focuses on enrichment, spatial distribution, potential ecological risk index (PERI) and human health risk of various toxic metals taken via soil and surface water in the vicinity of Sewakht mines, Pakistan. The samples of soils (n = 54) of different fields and surface water (n = 38) were analyzed for toxic metals including cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), manganese (Mn), lead (Pb), nickel (Ni), zinc (Zn) and molybdenum (Mo). Soil pollution level was evaluated using pollution indices including geo-accumulation index (Igeo), contamination factor (CF), degree of contamination (CD), enrichment factor (EF) and PERI. CF showed moderate contamination of soil with Cd, Co, Fe and Mo, while Igeo values indicated moderate accumulation of Cu. For Cd, EF> 1.5 was found in agricultural soils of the study area. PERI findings presented a very high ecological risk (PERI > 380) at two sites (4%), considerable ecological risk at four sites (7.4%). Non-carcinogenic risk from exposure to Fe in soil was higher than limit (HI > 1) for both children and adults. Moreover, carcinogenic risk postured by soil contaminants i.e. Cd, Cr, Co and Ni in children was higher than their limits (except Pb), while in adults only Co posed higher risk of cancer than the limit (10 -4 ) through soil exposure. Non-carcinogenic risks in children due to Cd, Co, Mo via surface water intake were higher than their safe limits (HQ > 1), while in adults the risk order was Cr > Cd > Cu > Pb > Co > Mo. Moreover, carcinogenic risk exposure due to Co > Cd > Cr > Ni from surface water (except Pb) was higher than the tolerable limit (1 × 10 -4 ) both for children and adults. However, Pb concentrations in both soil and surface water exposure were not likely to cause cancer risk in the local population. Copyright © 2018 Elsevier Inc. All rights reserved.

Review of NMR studies of nanoscale molecular magnets composed of geometrically frustrated antiferromagnetic triangles

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

Furukawa, Yuji

This paper presents a comprehensive review of nuclear magnetic resonance (NMR) studies performed on three nanoscale molecular magnets with different novel configurations of geometrically frustrated antiferromagnetic (AFM) triangles: (1) the isolated single AFM triangle K 6[V 15As 6O 42(H 2O)]·8H 2O (in short V15), (2) the spin ball [Mo 72Fe 30O 252(Mo 2O 7(H 2O)) 2(Mo 2O 8H 2(H 2O)) (CH 3COO) 12(H 2O) 91]·150H 2O (in short Fe30 spin ball), and (3) the twisted triangular spin tube [(CuCl 2tachH) 3Cl]Cl 2 (in short Cu3 spin tube). In V15t, from 51V NMR spectra, the local spin configurations were directly determinedmore » in both the nonfrustrated total spin S T = 3/2 state at higher magnetic fields (H ge; 2.7 T) and the two nearly degenerate S T = 1/2 ground states at lower magnetic fields (H ≤ 2.7 T). The dynamical magnetic properties of V15 were investigated by proton spin-lattice relaxation rate (1/T 1) measurements. In the S T = 3/2 state, 1/T 1 shows thermally activated behaviour as a function of temperature. On the other hand, the temperature independent behaviour of 1/T 1 at very low temperatures is observed in the frustrated S T = 1/2 ground state. Possible origins for the peculiar behaviour of 1/T 1 will be discussed in terms of magnetic fluctuations due to spin frustrations. In Fe30, static and dynamical properties of Fe 3+ (s = 5/2) have been investigated by proton NMR spectra and 1/T 1 measurements. From the temperature dependence of 1/T 1, the fluctuation frequency of the Fe 3+ spins is found to decrease with decreasing temperature, indicating spin freezing at low temperatures. The spin freezing is also evidenced by the observation of a sudden broadening of 1H NMR spectra below 0.6 K. Finally, 1H NMR data in Cu3 will be described. An observation of magnetic broadening of 1H NMR spectra at low temperatures below 1 K directly revealed a gapless ground state. The 1/T 1 measurements revealed a usual slow spin dynamics in the Cu3 spin tube.« less

Review of NMR studies of nanoscale molecular magnets composed of geometrically frustrated antiferromagnetic triangles

DOE PAGES

Furukawa, Yuji

2016-10-01

This paper presents a comprehensive review of nuclear magnetic resonance (NMR) studies performed on three nanoscale molecular magnets with different novel configurations of geometrically frustrated antiferromagnetic (AFM) triangles: (1) the isolated single AFM triangle K 6[V 15As 6O 42(H 2O)]·8H 2O (in short V15), (2) the spin ball [Mo 72Fe 30O 252(Mo 2O 7(H 2O)) 2(Mo 2O 8H 2(H 2O)) (CH 3COO) 12(H 2O) 91]·150H 2O (in short Fe30 spin ball), and (3) the twisted triangular spin tube [(CuCl 2tachH) 3Cl]Cl 2 (in short Cu3 spin tube). In V15t, from 51V NMR spectra, the local spin configurations were directly determinedmore » in both the nonfrustrated total spin S T = 3/2 state at higher magnetic fields (H ge; 2.7 T) and the two nearly degenerate S T = 1/2 ground states at lower magnetic fields (H ≤ 2.7 T). The dynamical magnetic properties of V15 were investigated by proton spin-lattice relaxation rate (1/T 1) measurements. In the S T = 3/2 state, 1/T 1 shows thermally activated behaviour as a function of temperature. On the other hand, the temperature independent behaviour of 1/T 1 at very low temperatures is observed in the frustrated S T = 1/2 ground state. Possible origins for the peculiar behaviour of 1/T 1 will be discussed in terms of magnetic fluctuations due to spin frustrations. In Fe30, static and dynamical properties of Fe 3+ (s = 5/2) have been investigated by proton NMR spectra and 1/T 1 measurements. From the temperature dependence of 1/T 1, the fluctuation frequency of the Fe 3+ spins is found to decrease with decreasing temperature, indicating spin freezing at low temperatures. The spin freezing is also evidenced by the observation of a sudden broadening of 1H NMR spectra below 0.6 K. Finally, 1H NMR data in Cu3 will be described. An observation of magnetic broadening of 1H NMR spectra at low temperatures below 1 K directly revealed a gapless ground state. The 1/T 1 measurements revealed a usual slow spin dynamics in the Cu3 spin tube.« less

Biogeochemical characteristics of Rosa canina grown in hydrothermally contaminated soils of the Gümüşhane Province, Northeast Turkey.

PubMed

Vural, Alaaddin

2015-08-01

Kırkpavli alteration area (Gümüşhane, Northeast Turkey) is contaminated by heavy metals such as Cd, Pb, As, Cu and Zn. The quantity of accumulation of heavy metal trace elements and macroelements in 32 leaves of Rosa canina of the Kırkpavli alteration area has been studied within the scope of geochemical studies. Element contents of samples were assessed using various parameters including descriptive statistics, factor analysis, correlation coefficients and bioaccumulation factor. Concentrations were detected in the acceptable range for Mo, Cu, Pb, Ni, As, Cd, Sb, P, Ti, Na, Se and Sn. Concentrations of Co, Mn, Ba and Hg were detected close to the acceptable values, whereas Zn, Fe, Sr, V, Ca, Cr, Mg, B, Al, K, W, Sc, Cs and Rb concentrations were detected above the acceptable values. Principal component analysis was used to identify the elements that have a close relationship with each other and/or similar origins. It has been concluded that Zn, Cu, As and Mo content of the plant were related to hydrothermal alteration process and they behaved together, whereas Mn and Fe were especially products of weathering conditions, also behaved together. In terms of macroelements, Ca, Mg and Na had similar behaviour, while P and K had the same correlation.

Effects of substitution of Mo for Nb on less-common properties of Finemet alloys

NASA Astrophysics Data System (ADS)

Butvin, P.; Butvinová, B.; Silveyra, J. M.; Chromčíková, M.; Janičkovič, D.; Sitek, J.; Švec, P.; Vlasák, G.

2010-10-01

Particular properties of Fe-Nb/Mo-Cu-B-Si rapidly quenched ribbons were examined. Apart from minor variation, no significant difference due to the Mo for Nb substitution was observed in alloy density and its annealing-induced changes. The same holds for the anisotropic thermal expansion of as-cast ribbon when annealed and for induced anisotropy when annealed under stress. The Mo-substituted ribbons show only slightly higher crystallinity and lower coercivity if annealed in inert gas ambience than in vacuum. Some diversity in surface to interior heterogeneity of the differently annealed ribbons can still be distinguished. Preserving a minor percentage of Nb together with Mo does not seem substantiated to obtain favorable soft magnetic properties of ribbons annealed in inert gas.

The characteristics of hot swaged NiAl intermetallic compounds with ternary additions consolidated by HIP techniques

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

Ishiyama, S.; Eto, M.; Mishima, Y.

Stoichiometric and non-stoichiometric NiAl intermetallics with ternary additives, such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or Mo/e, W, Mn, Fe, Cu and B, fabricated with the combination of Hot Isostatic Pressing (HIP) and hot swaging techniques have been investigated. The mechanical properties of hot swaged NiAl with various ternary additives, consolidated by ion beam casting or HIP techniques, have been tested at temperatures ranging from R.T. to 1,000 C. It is found that significant tensile elongation at room temperature can be achieved by hot swaged as-HIP`ed NiAl compounds with Mo or Mo/Re additives, whereas cast and hotmore » swaged compounds with Mo addition resulted in some elongation above 400 C.« less

Sex, age, and tissue specific accumulation of eight metals, arsenic, and selenium in the European hedgehog (Erinaceus europaeus).

PubMed

Rautio, Anni; Kunnasranta, Mervi; Valtonen, Anu; Ikonen, Mirva; Hyvärinen, Heikki; Holopainen, Ismo J; Kukkonen, Jussi V K

2010-11-01

Many insectivores have been shown to be sensitive to heavy metals and therefore suitable for biomonitoring purposes. In Finland, the hibernation period of the European hedgehog (Erinaceus europaeus) is long, and during hibernation the stress caused by environmental toxins may be crucial. Concentrations of cadmium (Cd), copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), molybdenum (Mo), nickel (Ni), lead (Pb), arsenic (As), and selenium (Se) were measured in a population of hedgehogs in the town of Joensuu in eastern Finland during the summers of 2004 and 2005. The analyzed tissues were kidney, liver, hair, and spine. The sampled hedgehogs (n = 65) were mainly road-killed animals. As expected, the concentrations of heavy metals were low because the hedgehogs were living in a comparatively unpolluted area. Significant increases with age were found in Cd concentrations (kidney, liver, and spine) and some essential elements (Se in spine, kidney, and liver; Mo in kidney and liver; Cu in spine; Fe in liver; and Mn in spine). Age accumulation and correlations between Se and Cd and between Mo and Cd may indicate the protective roles of Se and Mo against Cd toxicity in hedgehogs, in which Cd is already at comparatively low concentrations. Sex had no significant effect on concentrations of the elements studied. In conclusion, age is an important parameter to be taken into account when studying heavy-metal concentrations in hedgehogs and other insectivores.

Effect of accelerated carbonation and zero valent iron on metal leaching from bottom ash.

PubMed

Nilsson, M; Andreas, L; Lagerkvist, A

2016-05-01

About 85% of the ashes produced in Sweden originated from the incineration of municipal solid waste and biofuel. The rest comes from the thermal treatment of recycled wood, peat, charcoal and others. About 68% of all ashes annually produced in Sweden are used for constructions on landfills, mainly slopes, roads and embankments, and only 3% for construction of roads and working surfaces outside the landfills (SCB, 2013). Since waste bottom ash (BA) often has similar properties to crushed bedrock or gravel, it could be used for road constructions to a larger extent. However, the leaching of e.g. Cr, Cu, Mo, Pb and Zn can cause a threat to the surrounding environment if the material is used as it is. Carbonation is a commonly used pre-treatment method, yet it is not always sufficient. As leaching from aged ash is often controlled by adsorption to iron oxides, increasing the number of Fe oxide sorption sites can be a way to control the leaching of several critical elements. The importance of iron oxides as sorption sites for metals is known from both mineralogical studies of bottom ash and from the remediation of contaminated soil, where iron is used as an amendment. In this study, zero valent iron (Fe(0)) was added prior to accelerated carbonation in order to increase the number of adsorption sites for metals and thereby reduce leaching. Batch, column and pHstat leaching tests were performed and the leaching behaviour was evaluated with multivariate data analysis. It showed that leaching changed distinctly after the tested treatments, in particular after the combined treatment. Especially, the leaching of Cr and Cu clearly decreased as a result of accelerated carbonation. The combination of accelerated carbonation with Fe(0) addition reduced the leaching of Cr and Cu even further and reduced also the leaching of Mo, Zn, Pb and Cd compared to untreated BA. Compared with only accelerated carbonation, the Fe(0) addition significantly reduced the leaching of Cr, Cu and Mo. The effects of Fe(0) addition can be related to binding of the studied elements to newly formed iron oxides. The effects of Fe(0) addition were often more distinct at pH values between 7 and 9, which indicates that a single treatment with only Fe addition would be less effective and a combined treatment is recommended. The pHstat results showed that accelerated carbonation in combination with Fe(0)(0) addition widens the pH range for low solubility of about one unit for several of the studied elements. This indicates that pre-treating the bottom ash with a combination of accelerated carbonation and Fe(0) addition makes the leaching properties of the ash less sensitive to pH changes that may occur during reuse. All in all, the addition of Fe(0) in combination with carbonation could be an effective pre-treatment method for decreasing the mobility of potentially harmful components in bottom ash. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Coupled modeling of the competitive gettering of transition metals and impact on performance of lifetime sensitive devices

NASA Astrophysics Data System (ADS)

Yazdani, Armin; Chen, Renyu; Dunham, Scott T.

2017-03-01

This work models competitive gettering of metals (Cu, Ni, Fe, Mo, and W) by boron, phosphorus, and dislocation loops, and connects those results directly to device performance. Density functional theory calculations were first performed to determine the binding energies of metals to the gettering sites, and based on that, continuum models were developed to model the redistribution and trapping of the metals. Our models found that Fe is most strongly trapped by the dislocation loops while Cu and Ni are most strongly trapped by the P4V clusters formed in high phosphorus concentrations. In addition, it is found that none of the mentioned gettering sites are effective in gettering Mo and W. The calculated metal redistribution along with the associated capture cross sections and trap energy levels are passed to device simulation via the recombination models to calculate carrier lifetime and the resulting device performance. Thereby, a comprehensive and predictive TCAD framework is developed to optimize the processing conditions to maximize performance of lifetime sensitive devices.

Anode materials for lithium ion batteries

DOEpatents

Abouimrane, Ali; Amine, Khalil

2017-04-11

An electrochemical device includes a composite material of general Formula (1-x)J-(x)Q wherein: J is a metal carbon alloy of formula Sn.sub.zSi.sub.z'Met.sub.wMet'.sub.w'C.sub.t; Q is a metal oxide of formula A.sub..gamma.M.sub..alpha.M'.sub..alpha.'O.sub..beta.; and wherein: A is Li, Na, or K; M and M' are individually Ge, Mo, Al, Ga, As, Sb, Te, Ti, Ta, Zr, Ca, Mg, Sr, Ba, Li, Na, K, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Rt, Ru or Cd; Met and Met' are individually Ge, Mo, Al, Ga, As, Sb, Te, Ti, Ta, Zr, Ca, Mg, Sr, Ba, Li, Na, K, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Rt, Ru or Cd; 0

Density functional study on redox energetics of LaMO{sub 3−δ} (M=Sc–Cu) perovskite-type oxides

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

Pishahang, Mehdi, E-mail: Mehdi.Pishahang@sintef.no; Erik Mohn, Chris; Stølen, Svein

2016-01-15

This study evaluates the redox energetics of LaMO{sub 3−δ} (M=Sc–Cu) perovskite-type oxides via generalized gradient approximation (GGA) to DFT. Two different approaches to redox energetics of oxygen deficient perovskites of strongly non-stoichiometric (δ=0.5) and dilute defect limits (δ→0) are studied. In the first approach the enthalpies of oxidation are calculated using the stoichiometric end-compounds of LaMO{sub 3} and LaMO{sub 2.5}. The most common structures for the reduced lanthanides and strontides similar to the ones experimentally reported for SrMnO{sub 2.5}, SrFeO{sub 2.5}, and LaNiO{sub 2.5} are considered. The second approach to the oxidation enthalpies termed (δ→0) follow the trend observed experimentally.more » This approach represents the experimental conditions of the measured oxygen enthalpies, and is hampered less by the artificial features due to spurious self-interaction errors in GGA.« less

Effects of Different Levels of Molybdenum on Rumen Microbiota and Trace Elements Changes in Tissues from Goats.

PubMed

Zhou, Sihui; Zhang, Caiying; Xiao, Qingyang; Zhuang, Yu; Gu, Xiaolong; Yang, Fan; Xing, Chenghong; Hu, Guoliang; Cao, Huabin

2016-11-01

Molybdenum (Mo) is an essential trace element for animals and human beings. However, the negative effects on rumen function and distribution of trace elements in tissues induced by excessive Mo have not been well understood. Therefore, the purpose of present study was to investigate the impact of Mo on rumen microbiota, distribution of trace elements in various organs, and hematological parameters of goats. A total of 36 goats were randomly distributed into three groups with equal number and low-Mo and high-Mo groups were orally administered ammonium molybdate at 15 and 45 mg · Mo · kg -1  · BW respectively, while the control group received corresponding quantitative deionized water. The results showed that the total number of ciliate and protozoa protein concentration decreased significantly (P < 0.01) on days 25 and 50. Concentrations of ammonia nitrogen and bacterial protein were significantly higher (P < 0.05) in low-Mo group, while they were lower (P < 0.05) in high-Mo group than the control group on days 25 and 50. In addition, Mo accumulated in serum and all detected tissues. Copper (Cu) and zinc (Zn) contents significantly decreased (P < 0.05) in hair and serum on days 25 and 50, while Cu contents increased (P < 0.05) and the change of Zn contents were not obvious (P > 0.05) in other tissues on days 25 and 50. Besides, there was no obvious variation in iron (Fe) contents during whole experiment period (P > 0.05). Furthermore, excessive Mo content had no significant effect on red blood cell (RBC) counts and hemoglobin (HGB) concentration (P > 0.05) on days 25 and 50, while white blood cell (WBC) counts increased significantly (P < 0.05) on day 50. These results indicated that excessive Mo content could impact the balance of ruminal microorganisms and interfere with the absorption and distribution of Mo and Cu mainly.

Mechanical Properties of Nb25Mo25Ta25W25 and V20Nb20Mo20Ta20W20 Refractory High Entropy Alloys (Postprint)

DTIC Science & Technology

2011-05-01

Mn, Fe, Co, Ni and Cu. Since metallic alloys for high temperature load bearing structures and thermal protection systems remain in high demand for aer...condition. These results indicate that the BCC crystal structure formed in both alloys during solidification is stable upon heating at least up to 1400 C... solidification (Fig. 5b). Higher magnification images reveal a dendritic structure in both alloys (Fig. 5c and d). Uneven Z contrast inside the grains indicates

Metal concentrations in the tissues of the hydrothermal vent mussel Bathymodiolus: reflection of different metal sources.

PubMed

Koschinsky, Andrea; Kausch, Matteo; Borowski, Christian

2014-04-01

Hydrothermal vent mussels of the genus Bathymodiolus are ideally positioned for the use of recording hydrothermal fluxes at the hydrothermal vent sites they inhabit. Barium, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Pb, Sr, and U concentrations in tissue sections of Bathymodiolus mussels from several hydrothermal fields between 15°N and 9°S at the Mid-Atlantic Ridge were determined and compared to the surrounding fluids and solid substrates in the habitats. Elements generally enriched in hydrothermal fluids, such as Fe, Cu, Zn, Pb and Cd, were significantly enriched in the gills and digestive glands of the hydrothermal mussels. The rather small variability of Zn (and Mn) and positive correlation with K and earth alkaline metals may indicate a biological regulation of accumulation. Enrichments of Mo and U in many tissue samples indicate that particulate matter such as hydrothermal mineral particles from the plumes can play a more important role as a metal source than dissolved metals. Highest enrichments of Cu in mussels from the Golden Valley site indicate a relation to the ≥400 °C hot heavy-metal rich fluids emanating in the vicinity. In contrast, mussels from the low-temperature Lilliput field are affected by the Fe oxyhydroxide sediment of their habitat. In a comparison of two different sites within the Logatchev field metal distributions in the tissues reflected small-scale local variations in the metal content of the fluids and the particulate material. Copyright © 2014 Elsevier Ltd. All rights reserved.

Broiler litter as a micronutrient source for cotton: concentrations in plant parts.

PubMed

Tewolde, H; Sistani, K R; Rowe, D E

2005-01-01

Analytically, poultry litter contains nearly all essential micronutrients but the extent of phytoavailability of these nutrients and whether cotton (Gossypium hirsutum L.) and other crop plants can receive adequate amounts of these nutrients from litter is not fully known. The objective of this research was to determine whether cotton receives sufficient amounts of Fe, Cu, Mn, and Zn from litter and estimate the efficiency of cotton in extracting these metal nutrients from litter in the absence of any other source of the micronutrients. The greenhouse research used plastic pots filled with approximately 11 kg of a 2:1 (v/v) sand to vermiculite growing mix. Cotton (cv. Stoneville 474) was grown in the pots fertilized with broiler litter at rates of 30, 60, 90, or 120 g pot(-1) in a factorial combination with four supplemental nutrient solution (NS) treatments. The nutrient solutions consisted of full Hoagland's nutrient solution (NS-full); a solution of the macronutrients N, P, K, Ca, and Mg (NS-macro); a solution of the micronutrients Fe, Zn, Mn, Cu, B, and Mo (NS-micro); and water (NS-none). Based on tissue nutrient analysis, a one-time broiler litter application supplied adequate amounts of Fe, Cu, and Mn to bring the concentration of these nutrients in upper leaves within published sufficiency ranges. Zinc, with <17 mg kg(-1) concentration in the upper leaves, was the only micronutrient below the established sufficiency range regardless of the rate of applied litter. Cotton extracted Fe and Mn more efficiently than Cu or Zn, removing as much as 8.8% of Fe and 7.2% of Mn supplied by 30 g litter pot(-1). In contrast, the extraction efficiency was 1.7% for Cu and 1.9% for Zn. Roots accumulated 58% of the total absorbed Fe and 64% of Cu, and leaves accumulated 32% of the Fe and only 13% of the Cu supplied by litter. In contrast, only 16% of the total absorbed Mn and 23% of Zn accumulated in roots while leaves accumulated 64% of the total Mn and 37% of Zn. These results demonstrate that broiler litter is a valuable source of the metal nutrients supplying Fe, Cu, and Mn in full and Zn in part, but a very large fraction of the litter-supplied metal nutrients remained in the growing mix.

The impact of highly concentrated Mo and Cu dietary supplements, fed as a bolus, on the efficacy of chelated versus inorganic Cu in cattle on a low-Cu diet.

PubMed

Grace, N D; West, D M; Smith, S L; Knowles, S O

2013-11-01

To compare the efficacy of chelated versus inorganic forms of dietary Cu supplements, fed as a bolus, when challenged by a daily bolus of dietary Mo in cattle on a low-Cu diet. Forty non-lactating, Friesian dairy cows of adequate Cu status were assigned to four groups and fed a basal diet of baled silage containing 5.3 mg Cu and 0.4 mg Mo/kg DM. The experimental design was a factorial of two chemical forms of supplemental Cu and two levels of Mo intake, provided as pelleted grain supplements made from crushed barley/molasses plus Cu and Mo. The supplements contained 140 mg Cu/kg as Cu sulphate pentahydrate (CS), 140 mg Cu/kg as Cu glycinate (CG), CS plus 38 mg Mo/kg as sodium molybdate (CS+Mo), or CG plus 38 mg Mo/kg (CG+Mo). Commencing on Day 0, supplements were fed once daily (offered 1-1.2 kg/cow) and were completely consumed within 5-10 minutes, which constitutes a bolus type of administration. Liver samples were collected by biopsy at Days -24, 13, 41 or 47, and 69 for Cu determinations. The diets fed to the Cu+Mo groups were roughly equivalent to 25 mg Cu and 5.7 mg Mo/kg DM. Mean initial concentration of Cu in liver for all groups was 516 (SE 54) μmol Cu/kg fresh tissue. In cows supplemented with CS and CG, the final (Day 69) concentrations increased (p<0.01) to 939 (SE 166) and 853 (SE 163) μmol Cu/kg, respectively. These values were not different (p=0.72). For groups CS+Mo and CG+Mo, the final concentrations of 535 (SE 122) and 453 (SE 102) μmol Cu/kg were not different from initial values or from each other (p>0.25). The rate of accumulation of Cu in liver following bolus Cu and Mo intake was highly variable but was not affected by initial concentration of Cu in liver (p>0.9) or by the form of Cu (p>0.6). Mean rates of accumulation of Cu in liver were 4.0 (SD 3.8) and 0.65 (SD 2.0) μmol Cu/kg fresh tissue/day for the Cu-only treatments and the Cu+Mo treatments, respectively. When fed together as a bolus, high Mo intake negated the effect of supplemental Cu but it did not reduce liver Cu stores. There was no difference in the reaction of dietary Mo with chelated Cu (as glycinate) versus inorganic Cu (as sulphate) dietary supplements.

Assessment of metal contamination in coastal sediments of Al-Khobar area, Arabian Gulf, Saudi Arabia

NASA Astrophysics Data System (ADS)

Alharbi, Talal; El-Sorogy, Abdelbaset

2017-05-01

An assessment of marine pollution due to heavy metals was made to coastal sediments collected from Al-Khobar coastline, in the Arabian Gulf, Saudi Arabia by analyzing of Al, V, Cr, Mn, Cu, Zn, Cd, Pb, Hg, Mo, Sr, Se, As, Fe, Co and Ni using Inductively Coupled Plasma-Mass Spectrometer (ICP-MS). The results indicated that the distribution of most metals was largely controlled by inputs of terrigenous material and most strongly associated with distribution of Al in sediments. In general Sr, Cr, Zn, Cu, V, Hg, Mo and Se show severe enrichment factors. Average values of Cu and Hg highly exceed the ERL and the Canadian ISQG values. Average Ni was higher than the ERL and the ERM values. The severe enrichment of some metals in the studied sediment could be partially attributed to anthropogenic activities, notably oil spills from exploration, transportation and from saline water desalination plants in Al-Khobar coast, and other industrial activities in the region.

Soil quality assessment using GIS-based chemometric approach and pollution indices: Nakhlak mining district, Central Iran.

PubMed

Moore, Farid; Sheykhi, Vahideh; Salari, Mohammad; Bagheri, Adel

2016-04-01

This paper is a comprehensive assessment of the quality of soil in the Nakhlak mining district in Central Iran with special reference to potentially toxic metals. In this regard, an integrated approach involving geostatistical, correlation matrix, pollution indices, and chemical fractionation measurement is used to evaluate selected potentially toxic metals in soil samples. The fractionation of metals indicated a relatively high variability. Some metals (Mo, Ag, and Pb) showed important enrichment in the bioavailable fractions (i.e., exchangeable and carbonate), whereas the residual fraction mostly comprised Sb and Cr. The Cd, Zn, Co, Ni, Mo, Cu, and As were retained in Fe-Mn oxide and oxidizable fractions, suggesting that they may be released to the environment by changes in physicochemical conditions. The spatial variability patterns of 11 soil heavy metals (Ag, As, Cd, Co, Cr, Cu, Mo, Ni, Pb, Sb, and Zn) were identified and mapped. The results demonstrated that Ag, As, Cd, Mo, Cu, Pb, Sb, and Zn pollution are associated with mineralized veins and mining operations in this area. Further environmental monitoring and remedial actions are required for management of soil heavy metals in the study area. The present study not only enhanced our knowledge regarding soil pollution in the study area but also introduced a better technique to analyze pollution indices by multivariate geostatistical methods.

Estimation of dietary intake and target hazard quotients for metals by consumption of wines from the Canary Islands.

PubMed

Gutiérrez, Angel J; Rubio, Carmen; Moreno, Isabel M; González, A Gustavo; Gonzalez-Weller, Dailos; Bencharki, Naouel; Hardisson, Arturo; Revert, Consuelo

2017-10-01

This paper describes the impact of mineral content on wines and assesses the potential health risk from consuming these wines from Canary Islands. The metal content (B, Ca, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Zn) of red wines belonging to different regions in the Canary Islands was determined by ICP-OES. The studied wine regions were Valle de la Orotava, Tacoronte-Acentejo, Ycoden-Daute-Isora, Abona and Valle de Güimar in Tenerife Island and only one in La Gomera and La Palma Islands. According to the content found, elements could be classified in two categories: the main group including Ca, K, Mg, Na, and the ''minor'' set consisting of B, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, Pb and Zn. Once calculated the metal intake through red wines consumption, we can conclude that Canarian drinkers are not exposed to unsafe levels of the metals studied, actually, the safety intake limits (daily) ranges between 0.9% in Zn and 2% in Cu, for normal drinkers. And also it has been demonstrated the good quality of Canarian red wines and there is no reason for health concern through the THQ calculation being the highest values determined in La Gomera wines. Copyright © 2017 Elsevier Ltd. All rights reserved.

Trace element accumulation in bivalve mussels Anodonta woodiana from Taihu Lake, China.

PubMed

Liu, Hongbo; Yang, Jian; Gan, Juli

2010-11-01

Data are presented for 13 trace metals (Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, and Pb) in 38 bivalve mussels Anodonta woodiana from four separate sites (Huzhou, Dapu, Sansandao, and Manshan) around the Taihu Lake of China. All elemental concentrations generally ranked in decreasing order, Mn > Fe > Zn > As ≈ Cu ≈ Cd ≈ Se > Pb > Mo ≈ Ag, except that Cr, Co, and Ni were not detected. Anodonta woodiana was able to bioaccumulate essential Mn and toxic Cd to the extremely high level of 19,240 and 53 mg/kg dry weight, respectively. Geographical differences in the concentrations of trace elements were usually significant between sampling sites except for As and Pb, and the mussels from Sanshandao site had mostly accumulated or were contaminated with essential and toxic elements. The residue level of Cd in A. woodiana from the Sanshandao and Manshan sites appeared to be even higher than those of the essential elements Cu and Se, and exceeded the corresponding maximum residue limits of China. The present study provides the most recent information on trace element bioaccumulation or contamination in Taihu Lake and, further, suggests that A. woodiana can be used as a suitable bioindicator for inland water environmental monitoring.

Complex, Precision Cast Columbium Alloy Gas Turbine Engine Nozzles Coated to Resist Oxidation.

DTIC Science & Technology

1980-04-01

Microstructures of Sprayed Specimens 64 Table 19 NS-4 Coated C129Y Alloy Specimens Weight Bisque Weight Sintered Weight Silicided Weight Pre-Oxidized...choice of another alloy , while perhaps assisting in the foundry process , would not have yielded a mechanical property data base with advantage over...Mo 250 ppm max; Fe 30 ppm max; Al , Ca, C, Si, Cr, Ni, Cu , Mn, Mg and Sn 10 ppm max each). Molybdenum វim powder (02 2000 ppm max; W 250 ppm max; Fe

Adsorptive Separation of Methanol-Acetone on Isostructural Series of Metal-Organic Frameworks M-BTC (M = Ti, Fe, Cu, Co, Ru, Mo): A Computational Study of Adsorption Mechanisms and Metal-Substitution Impacts.

PubMed

Wu, Ying; Chen, Huiyong; Xiao, Jing; Liu, Defei; Liu, Zewei; Qian, Yu; Xi, Hongxia

2015-12-09

The adsorptive separation properties of M-BTC isostructural series (M = Ti, Fe, Cu, Co, Ru, Mo) for methanol-acetone mixtures were investigated by using various computational procedures of grand canonical Monte Carlo simulations (GCMC), density functional theory (DFT), and ideal adsorbed solution theory (IAST), following with comprehensive understanding of adsorbate-metal interactions on the adsorptive separation behaviors. The obtained results showed that the single component adsorptions were driven by adsorbate-framework interactions at low pressures and by framework structures at high pressures, among which the mass effects, electrostatics, and geometric accessibility of the metal sites also played roles. In the case of methanol-acetone separation, the selectivity of methanol on M-BTCs decreased with rising pressures due to the pressure-dependent separation mechanisms: the cooperative effects between methanol and acetone hindered the separation at low pressures, whereas the competitive effects of acetone further resulted in the lower selectivity at high pressures. Among these M-BTCs, Ti and Fe analogues exhibited the highest thermodynamic methanol/acetone selectivity, making them promising for adsorptive methanol/acetone separation processes. The investigation provides mechanistic insights on how the nature of metal centers affects the adsorption properties of MOFs, and will further promote the rational design of new MOF materials for effective gas mixture separation.

Adsorption Mechanism of 4-Amino-5-mercapto-1,2,4-triazole as Flotation Reagent on Chalcopyrite.

PubMed

Yin, Zhigang; Hu, Yuehua; Sun, Wei; Zhang, Chenyang; He, Jianyong; Xu, Zhijie; Zou, Jingxiang; Guan, Changping; Zhang, Chenhu; Guan, Qingjun; Lin, Shangyong; Khoso, Sultan Ahmed

2018-04-03

A novel compound 4-amino-5-mercapto-1,2,4-triazole was first synthesized, and its selective adsorption mechanism on the surface of chalcopyrite was comprehensively investigated using UV-vis spectra, zeta-potential, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy measurements (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and first principles calculations. The experimental and computational results consistently demonstrated that AMT would chemisorb onto the chalcopyrite surface by the formation of a five-membered chelate ring. The first principles periodic calculations further indicated that AMT would prefer to adsorb onto Cu rather than Fe due to the more negative adsorption energy of AMT on Cu in the chalcopyrite (001) surface, which was further confirmed by the coordination reaction energies of AMT-Cu and AMT-Fe based on the simplified cluster models at a higher accuracy level (UB3LYP/Def2-TZVP). The bench-scale results indicated that the selective index improved significantly when using AMT as a chalcopyrite depressant in Cu-Mo flotation separation.

Using elemental profiles and stable isotopes to trace the origin of green coffee beans on the global market.

PubMed

Santato, Alessandro; Bertoldi, Daniela; Perini, Matteo; Camin, Federica; Larcher, Roberto

2012-09-01

A broad elemental profile incorporating 54 elements (Li, Be, B, Na, Mg, Al, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Mo, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Tm, Yb, Re, Ir, Pt, Au, Hg, Tl, Pb, Bi and U) in combination with δ(2) H, δ(13) C, δ(15) N and δ(18) O was used to characterise the composition of 62 green arabica (Coffea arabica) and robusta (Coffea canephora) coffee beans grown in South and Central America, Africa and Asia, the four most internationally renowned areas of production. The δ(2) H, Mg, Fe, Co and Ni content made it possible to correctly assign 95% of green coffee beans to the appropriate variety. Canonical discriminant analysis, performed using δ(13) C, δ(15) N, δ(18) O, Li, Mg, P, K, Mn, Co, Cu, Se, Y, Mo, Cd, La and Ce correctly traced the origin of 98% of coffee beans. Copyright © 2012 John Wiley & Sons, Ltd.

Toxic and essential elements in five tree nuts from Hangzhou market, China.

PubMed

Ni, Zhanglin; Tang, Fubin; Yu, Qing; Liu, Yihua

2016-12-01

In this study, a total of 35 tree nut samples of walnut, pecan, pine seed, hickory nut and torreya were obtained from 5 farm product markets in Hangzhou, China, and investigated for essential (Cr, Mn, Fe, Mo, Cu, Zn, Se and Sr) and toxic (Al, As, Cd and Pb) elements by inductively coupled plasma-mass spectroscopy. Mean elemental concentrations of different tree nuts were in the following ranges: Cr 0.26-0.78 mg kg -1 , Mn 42.1-174 mg kg -1 , Fe 33.7-43.9 mg kg -1 , Mo 0.11-0.48 mg kg -1 , Cu 10.3-17.6 mg kg -1 , Zn 21.6-56.1 mg kg -1 , Se 0.015-0.051 mg kg -1 , Al 1.44-37.6 mg kg -1 , As 0.0062-0.047 mg kg -1 , Cd 0.016-0.18 mg kg -1 and Pb 0.0069-0.029 mg kg -1 . The estimated provisional tolerable daily intake of Al, As, Cd and Pb was much lower than the provisional tolerable daily intake.

Deficiency of macro- and micronutrients induced by Lentinula edodes.

PubMed

Grotto, D; Gerenutti, M; Souza, V C O; Barbosa, F

2015-01-01

Mushroom Lentinula edodes has been widely studied therapeutically. However, there is no data regarding its daily intake level safety. Since L. edodes has many active compounds known to bind to metals, we evaluated macro and micronutrients in liver and kidney of healthy rats after subchronic exposure to L. edodes . Rats were divided into four groups, receiving water and L. edodes at 100, 400 and 800 mg/kg/day. The treatment lasted 30 days. Essential elements (Zn, Cu, Mg, Fe, Mn, Se, Co, Mo, and Li) were analyzed in an inductively coupled plasma mass spectrometer. Our results demonstrated a significant decrease in Cu, Fe, Mn and Co levels in liver of rats receiving L. edodes at the highest doses. In kidney, Mn, Mo and Li concentrations significantly dropped in the groups exposed to the highest doses. In this way, an important point is revealed concerning the food safety from L. edodes , once its chronic and high consumption could contribute to macro and micronutrients deficiency. Additionally, we speculate that the daily use of L. edodes could be unsuccessful for patients in mineral therapy besides being able to be unsafe for individuals with some propensity to mineral deficiency.

Geochemistry and economic potential of massive sulfide deposits from the eastern Pacific Ocean

USGS Publications Warehouse

Bischoff, James L.; Rosenbauer, R.J.; Aruscavage, P. J.; Baedecker, P.A.; Crock, J.G.

1983-01-01

Bulk chemical analyses are performed for major and minor elements using a variety of techniques on a suite of 9 samples of sea floor massive sulfide deposits from 21?N EPR, Juan de Fuca Ridge and Galapagos Rift. Results indicate that deposits at 21?N and Juan de Fuca are very similar despite a geographic separation of 2300 km and are composed primarily of Zn, Fe, and S, with important minor concentrations of Ag, As, Cd and Ge. The Galapagos Rift massive sulfide is primarily Fe, Cu and S and with important minor contents of only Co and Mo. Au is low, ranging from below detection up to 0.17 ppm. Pt group metals are very low, and average about 0.001 ppm. Consideration of enrichment factors and relative metal abundance suggests that MORB is a sufficient source for all the metals enriched in the sea floor deposits. The economically important metals for the 21?N and Juan de Fuca deposits are primarily Zn and Ag, (97%) with potential by-products of Cu, Cd and possibly, Ge. For the Galapagos Rift, the primary value is with Cu (86%) with potential by-products of Co and Mo. The Galapagos Rift deposit is similar to, but contains about twice the Cu content, of typical ore from the Skouriotisa mine of the Troodos complex of Cyprus. The grade of the 21?N/Juan de Fuca deposits is 4 times greater than that of the Galapagos Rift and about twice that of prime deep-sea manganese nodules.

Distribution of potentially toxic elements (PTEs) in tailings, soils, and plants around Gol-E-Gohar iron mine, a case study in Iran.

PubMed

Soltani, Naghmeh; Keshavarzi, Behnam; Moore, Farid; Sorooshian, Armin; Ahmadi, Mohamad Reza

2017-08-01

This study investigated the concentration of potentially toxic elements (PTEs) including Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, V, and Zn in 102 soils (in the Near and Far areas of the mine), 7 tailings, and 60 plant samples (shoots and roots of Artemisia sieberi and Zygophylum species) collected at the Gol-E-Gohar iron ore mine in Iran. The elemental concentrations in tailings and soil samples (in Near and Far areas) varied between 7.4 and 35.8 mg kg -1 for As (with a mean of 25.39 mg kg -1 for tailings), 7.9 and 261.5 mg kg -1 (mean 189.83 mg kg -1 for tailings) for Co, 17.7 and 885.03 mg kg -1 (mean 472.77 mg kg -1 for tailings) for Cu, 12,500 and 400,000 mg kg -1 (mean 120,642.86 mg kg -1 for tailings) for Fe, and 28.1 and 278.1 mg kg -1 (mean 150.29 mg kg -1 for tailings) for Ni. A number of physicochemical parameters and pollution index for soils were determined around the mine. Sequential extractions of tailings and soil samples indicated that Fe, Cr, and Co were the least mobile and that Mn, Zn, Cu, and As were potentially available for plants uptake. Similar to soil, the concentration of Al, As, Co, Cr, Cu, Fe, Mn, Mo, Ni, and Zn in plant samples decreased with the distance from the mining/processing areas. Data on plants showed that metal concentrations in shoots usually exceeded those in roots and varied significantly between the two investigated species (Artemisia sieberi > Zygophylum). All the reported results suggest that the soil and plants near the iron ore mine are contaminated with PTEs and that they can be potentially dispersed in the environment via aerosol transport and deposition.

Manganese containing layer for magnetic recording media

DOEpatents

Lambeth, David N.; Lee, Li-Lien; Laughlin, David E.

1999-01-01

The present invention provides for a magnetic recording media incorporating Mn-containing layers between a substrate and a magnetic layer to provide media having increased coercivity and lower noise. The Mn-containing layer can be incorporated in a rotating, translating or stationary recording media to operate in conjunction with magnetic transducing heads for recording and reading of magnetic data, as well as other applications. The magnetic recording medium of the invention preferably includes a Co or Co alloy film magnetic layer, and Mn-containing layer, preferably comprised of VMn, TiMn, MnZn, CrMnMo, CrMnW, CrMnV, and CrMnTi, and most preferably a CrMn alloy, disposed between the substrate and the magnetic layer to promote an epitaxial crystalline structure in the magnetic layer. The medium can further include seed layers, preferably polycrystalline MgO for longitudinal media, underlayers, and intermediate layers. Underlayers and intermediate layers are comprised of materials having either an A2 structure or a B2-ordered crystalline structure disposed between the seed layer and the magnetic layer. Materials having an A2 structure are preferably Cr or Cr alloys, such as CrV, CrMo, CrW and CrTi. Materials having a B2-ordered structure having a lattice constant that is substantially comparable to that of Cr, such as those preferably selected from the group consisting of NiAl, AILCo, FeAl, FeTi, CoFe, CoTi, CoHf, CoZr, NiTi, CuBe, CuZn, A-LMn, AlRe, AgMg, and Al.sub.2 FeMn.sub.2, and is most preferably FeAl or NiAl.

Background concentrations and reference values for heavy metals in soils of Cuba.

PubMed

Alfaro, Mirelys Rodríguez; Montero, Alfredo; Ugarte, Olegario Muñiz; do Nascimento, Clístenes Williams Araújo; de Aguiar Accioly, Adriana Maria; Biondi, Caroline Miranda; da Silva, Ygor Jacques Agra Bezerra

2015-01-01

The potential threat of heavy metals to human health has led to many studies on permissible levels of these elements in soils. The objective of this study was to establish quality reference values (QRVs) for Cd, Pb, Zn, Cu, Ni, Cr, Fe, Mn, As, Hg, V, Ba, Sb, Ag, Co, and Mo in soils of Cuba. Geochemical associations between trace elements and Fe were also studied, aiming to provide an index for establishing background concentrations of metals in soils. Surface samples of 33 soil profiles from areas of native forest or minimal anthropic influence were collected. Samples were digested (USEPA method 3051A), and the metals were determined by ICP-OES. The natural concentrations of metals in soils of Cuba followed the order Fe > Mn > Ni > Cr > Ba > V > Zn > Cu > Pb > Co > As > Sb > Ag > Cd > Mo > Hg. The QRVs found for Cuban soils were as follows (mg kg(-1)): Ag (1), Ba (111), Cd (0.6), Co (25), Cr (153), Cu (83), Fe (54,055), Mn (1947), Ni (170), Pb (50), Sb (6), V (137), Zn (86), Mo (0.1), As (19), and Hg (0.1). The average natural levels of heavy metals are above the global average, especially for Ni and Cr. The chemical fractionation of soil samples presenting anomalous concentrations of metals showed that Cu, Ni, Cr, Sb, and As have low bioavailability. This suggests that the risk of contamination of agricultural products via plant uptake is low. However, the final decision on the establishment of soil QRVs in Cuba depends on political, economic, and social issues and in-depth risk analyses considering all routes of exposure to these elements.

Comparative study of the mechanical and tribological properties of a Hadfield and a Fermanal steel

NASA Astrophysics Data System (ADS)

Astudillo A., P. C.; Soriano G., A. F.; Barona Osorio, G. M.; Sánchez Sthepa, H.; Ramos, J.; Durán, J. F.; Pérez Alcázar, G. A.

2017-11-01

In this study, Fe-12.50Mn-1.10C-1.70Cr-0.40Mo-0.40Si-0.50(max)P-0.50(max)S (Hadfield alloy) and Fe-28.4Mn-0.86C-1.63Al-0.42Cu-1.80Mo-1.59Si-0.60W (Fermanal alloy) (Wt. %) in the aged condition were compared in terms of its tribological and microstructural properties. The x-ray diffraction (XRD) patterns were refined with the lines of the austenitic γ-phase, Chromium Iron Carbide (Cr2Fe14C), Iron Carbide (Fe2C), and Iron Oxide (Fe0.974O (II)) for the Hadfield alloy, and the lines of the austenitic γ-phase, martensite (M), Mn1.1Al0.9 phase and iron carbide (Fe7C3) for the Fermanal alloy. Mössbauer spectra were fit with two sites for the Hadfield alloy, which displayed as a broad singlet because of the austenitic disordered phase, and had a magnetic hyperfine field distribution, which corresponds to the Cr2Fe14C ferromagnetic carbides found by XRD. There were two paramagnetic sites, a singlet, which corresponds to the austenite disordered phase, and a doublet, which can be attributed to the Fe7C3 carbide. The obtained Rockwell C hardness for aged Hadfield and Fermanal alloys were 43.786 and 50.018 HRc, respectively.

Spin pumping in ion-beam sputtered C o2FeAl /Mo bilayers: Interfacial Gilbert damping

NASA Astrophysics Data System (ADS)

Husain, Sajid; Kumar, Ankit; Barwal, Vineet; Behera, Nilamani; Akansel, Serkan; Svedlindh, Peter; Chaudhary, Sujeet

2018-02-01

The spin-pumping mechanism and associated interfacial Gilbert damping are demonstrated in ion-beam sputtered C o2FeAl (CFA)/Mo bilayer thin films employing ferromagnetic resonance spectroscopy. The dependence of the net spin-current transportation on Mo layer thickness, 0 to 10 nm, and the enhancement of the net effective Gilbert damping are reported. The experimental data have been analyzed using spin-pumping theory in terms of spin current pumped through the ferromagnet/nonmagnetic metal interface to deduce the real spin-mixing conductance and the spin-diffusion length, which are estimated to be 1.56 (±0.30 ) ×1019m-2 and 2.61 (±0.15 )nm , respectively. The damping constant is found to be 8.8 (±0.2 ) ×10-3 in the Mo(3.5 nm)-capped CFA(8 nm) sample corresponding to an ˜69 % enhancement of the original Gilbert damping 5.2 (±0.6 ) ×10-3 in the Al-capped CFA thin film. This is further confirmed by inserting the Cu dusting layer which reduces the spin transport across the CFA/Mo interface. The Mo layer thickness-dependent net spin-current density is found to lie in the range of 1 -4 MA m-2 , which also provides additional quantitative evidence of spin pumping in this bilayer thin-film system.

Phosphorus vacancy cluster model for phosphorus diffusion gettering of metals in Si

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

Chen, Renyu; Trzynadlowski, Bart; Dunham, Scott T.

2014-02-07

In this work, we develop models for the gettering of metals in silicon by high phosphorus concentration. We first performed ab initio calculations to determine favorable configurations of complexes involving phosphorus and transition metals (Fe, Cu, Cr, Ni, Ti, Mo, and W). Our ab initio calculations found that the P{sub 4}V cluster, a vacancy surrounded by 4 nearest-neighbor phosphorus atoms, which is the most favorable inactive P species in heavily doped Si, strongly binds metals such as Cu, Cr, Ni, and Fe. Based on the calculated binding energies, we build continuum models to describe the P deactivation and Fe getteringmore » processes with model parameters calibrated against experimental data. In contrast to previous models assuming metal-P{sub 1}V or metal-P{sub 2}V as the gettered species, the binding of metals to P{sub 4}V satisfactorily explains the experimentally observed strong gettering behavior at high phosphorus concentrations.« less

Element migration of pyrites during ductile deformation of the Yuleken porphyry Cu deposit (NW-China)

USGS Publications Warehouse

Hong, Tao; Xu, Xing-Wang; Gao, Jun; Peters, Stephen; Li, Jilei; Cao, Mingjian; Xiang, Peng; Wu, Chu; You, Jun

2017-01-01

The strongly deformed Yuleken porphyry Cu deposit (YPCD) occurs in the Kalaxiangar porphyry Cu belt (KPCB), which occupies the central area of the Central Asian Orogenic Belt (CAOB) between the Sawu’er island arc and the Altay Terrane in northern Xinjiang. The YPCD is one of several typical subduction-related deposits in the KPCB, which has undergone syn-collisional and post-collisional metallogenic overprinting. The YPCD is characterized by three pyrite-forming stages, namely a hydrothermal stage A (Py I), a syn-ductile deformation stage B (Py II) characterized by Cu-Au enrichment, and a fracture-filling stage C (Py III). In this study, we conducted systematic petrographic and geochemical studies of pyrites and coexist biotite, which formed during different stages, in order to constrain the physicochemical conditions of the ore formation. Euhedral, fragmented Py I has low Pb and high Te and Se concentration and Ni contents are low with Co/Ni ratios mostly between 1 and 10 (average 9.00). Py I is further characterized by enrichments of Bi, As, Ni, Cu, Te and Se in the core relative to the rim domains. Anhedral round Py II has moderate Co and Ni contents with high Co/Ni ratios >10 (average 95.2), and average contents of 46.5 ppm Pb and 5.80 ppm Te. Py II is further characterized by decreasing Bi, Cu, Pb, Zn, Ag, Te, Mo, Sb and Au contents from the rim to the core domains. Annealed Py III has the lowest Co content of all pyrite types with Co/Ni ratios mostly <0.1 (average 1.33). Furthermore, Py III has average contents of 3.31 ppm Pb, 1.33 ppm Te and 94.6 ppm Se. In addition, Fe does not correlate with Cu and S in the Py I and Py III, while Py II displays a negative correlation between Fe and Cu as well as a positive correlation between Fe and S. Therefore, pyrites which formed during different tectonic regimes also have different chemical compositions. Biotite geothermometer and oxygen fugacity estimates display increasing temperatures and oxygen fugacities from stage A to stage B, while temperature and oxygen fugacities decrease from stage B to stage C. The Co/Ni ratio of pyrite depends discriminates between the different mineralizing stages in the Yuleken porphyry copper deposit: Py II, associated with the deformation stage B and Cu-enrichment, shows higher Co/Ni ratios and enrichments of Pb, Zn, Mo, Te and Sb than the pyrites formed during the other two stages. The Co/Ni ratio of pyrite can not only apply to discriminate the submarine exhalative, magmatic or sedimentary origins for ore deposits but also can distinguish different ore-forming stages in a single porphyry Cu deposit. Thus, Co/Ni ratio of pyrites may act as an important exploration tool to distinguish pyrites from Cu-rich versus barren area. Furthermore, the distribution of Cu, Mo, Pb, Au, Bi, Sb and Zn in the variably deformed pyrite is proportional to the extent of deformation of the pyrites, indicating in accordance with variable physicochemical conditions different element migration behavior during the different stages of deformation and, thus, mineralisation.

Visible light responsive Cu2MoS4 nanosheets incorporated reduced graphene oxide for efficient degradation of organic pollutant

NASA Astrophysics Data System (ADS)

Rameshbabu, R.; Vinoth, R.; Navaneethan, M.; Harish, S.; Hayakawa, Y.; Neppolian, B.

2017-10-01

Visible light active copper molybdenum sulfide (Cu2MoS4) nanosheets were successfully anchored on reduced graphene oxide (rGO) using facile hydrothermal method. During the hydrothermal reaction, reduction of graphene oxide into rGO and the formation of Cu2MoS4 nanosheets were successfully obtained. The charge transfer interaction between the rGO sheets and Cu2MoS4 nanosheets extended the absorption to visible region in comparison with bare Cu2MoS4 nanosheets i.e without rGO sheets. Furthermore, the notable photoluminescence quenching observed for Cu2MoS4/rGO nanocomposite revealed the effective role of rGO towards the significant inhibition of electron-hole pair recombination. The photocatalytic efficiencies of bare Cu2MoS4 and Cu2MoS4/rGO nanocomposite was evaluated for the degradation of methyl orange dye under visible irradiation (λ > 420 nm). A maximum photodegradation efficiency of 99% was achieved for Cu2MoS4/rGO nanocomposite, while only 64% photodegradation was noted for bare Cu2MoS4. The enhanced optical absorption in visible region, high surface area, and low charge carrier recombination in the presence of rGO sheets were the main reasons for the enhancement in photodegardation of MO dye. In addition, the resultant Cu2MoS4/rGO nanocomposite was found to be reusable for five successive cycles without significant loss in its photocatalytic performance.

Double-perovskites A 2FeMoO 6- δ (A = Ca, Sr, Ba) as anodes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Zhang, Leilei; Zhou, Qingjun; He, Qiang; He, Tianmin

Double-perovskites A 2FeMoO 6- δ (A = Ca, Sr, Ba) have been investigated as potential anode materials for solid oxide fuel cells (SOFCs). At room temperature, A 2FeMoO 6- δ compounds crystallize in monoclinic, tetragonal, and cubic structures for A = Ca, Sr, and Ba, respectively. A weak peak observed at around 880 cm -1 in the Raman spectra can be attributed to traces of AMoO 4. XPS has confirmed the coexistence of Fe 2+-Mo 6+ and Fe 3+-Mo 5+ electronic configurations. Moreover, a systematic shift from Fe 2+/3+-Mo 6+/5+ to Fe 2+-Mo 6+ configuration is seen with increasing A-site cation size. A 2FeMoO 6- δ samples display distinct electrical properties in H 2, which can be attributed to different degrees of degeneracy of the Fe 2+-Mo 6+ and Fe 3+-Mo 5+ configurations. Ca 2FeMoO 6- δ is unstable in a nitrogen atmosphere, while Sr 2FeMoO 6- δ and Ba 2FeMoO 6- δ are stable up to 1200 °C. The thermal expansion coefficients of Sr 2FeMoO 6- δ and Ba 2FeMoO 6- δ are very close to that of La 0.9Sr 0.1Ga 0.8Mg 0.2O 3- δ (LSGM). The performances of cells with 300 μm thick LSGM electrolyte, double-perovskite SmBaCo 2O 5+ x cathodes, and A 2FeMoO 6- δ anodes follow the sequence Ca 2FeMoO 6- δ < Ba 2FeMoO 6- δ < Sr 2FeMoO 6- δ. The maximum power densities of a cell with an Sr 2FeMoO 6- δ anode reach 831 mW cm -2 in dry H 2 and 735 mW cm -2 in commercial city gas at 850 °C, respectively.

Determination of Heavy Metals in Almonds and Mistletoe as a Parasite Growing on the Almond Tree Using ICP-OES or ICP-MS.

PubMed

Kamar, Veysi; Dağalp, Rukiye; Taştekin, Mustafa

2017-12-28

In this study, the elements of Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Ni, Sr, Pb, Ti, and Zn were determined in the leaves, fruits, and branches of mistletoe, (Viscum albüm L.), used as a medicinal plant, and in the leaves, branches and barks of almond tree which mistletoe grows on. The aim of the study is to investigate whether the mistletoe are more absorbent than the almond tree in terms of the heavy metal contents and the determination of the amount of the elements penetrated into the mistletoe from the almond tree. ICP-MS (inductively coupled plasma-mass spectrometry) was used for the analysis of As, Cd, Mo, and Pb, whereas ICP-OES (inductively coupled plasma optical emission spectrometry) was used for the other elements. The results obtained were statistically evaluated at 95% confidence level. Within the results obtained in this study, it was determined whether there is a significant difference between metal elements in almond tree and mistletoe, or not. As a result, it was observed that there were higher contents of B, Ba, K, Mg, and Zn in the mistletoe than in the almond tree. K was found much higher than other elements in the mistletoe. On the other hand, Al, As, Ca, Cd, Cr, Cu, Fe, Mo, Ni, Sr, Pb, and Ti contents were determined to be more in almond tree than mistletoe.

Marine ferromanganese deposits as a source of rare metals for high- and green-tech applications: Comparison with land-based deposits

NASA Astrophysics Data System (ADS)

Hein, J. R.; Conrad, T. A.; Koschinsky, A.

2011-12-01

Marine ferromanganese (Fe-Mn) crusts are strongly enriched relative to the lithosphere in many rare and strategic metals, including Te, Co, Mo, Bi, Pt, W, Zr, Nb, Y, and rare-earth elements (REE). Fe-Mn nodules are strongly enriched in Ni, Cu, Co, Mo, Zr, Li, and REY. Relative to Fe-Mn crusts, nodules are more enriched in Ni, Cu, and Li, with subequal amounts of Mo. The metals are sorbed from seawater onto the Fe and Mn phases, and also from sediment pore waters for nodules. An electrochemical model describes a first-order process for acquisition of metals from seawater, with positively charged ions sorbed onto the negative charged surface of MnO2 and negatively charged and neutral ions in seawater sorbed on the slightly positive charged FeO(OH) surface. Second-order processes include surface oxidation (e.g., Co, Pt, Te, Ce, Tl), substitution, and precipitation of discrete phases. The metals most enriched in these marine deposits are essential for a wide variety of high- and green-tech applications. Over the past few years, the global market for many of them has been supplied from one or two major sources. Because of increased competition for resources from rapidly expanding economies (i.e. China, India, Brazil), supplies may not meet demands. Deep-ocean deposits may offer a partial solution to these projected shortages, but marine deposits have not been compared in terms of grade and tonnage with land-based deposits. Here we compare data for the Clarion-Clipperton Fe-Mn Nodule Zone (CCZ) in the NE Pacific and the central Pacific Fe-Mn crust zone (PCZ) with the global land-based reserves. Nodules in the CCZ have 1.1 times more Mn, 1.4 times more Te, 1.85 times more Ni, 3.2 times more Co, and 4 times more Y than the entire global land-based reserves for those metals. Metals in CCZ nodules as a percent of the total global land-based reserves are Cu 22%, Mo 63%, W 21%, Li 19%, Nb 13%, and REE 11%. Fe-Mn crusts in the PCZ have 3.8 times more Co, 3.5 times more Y, and an incredible 9 times more Te than the entire land-based reserves. Metals in PCZ crusts as a percent of the total global land-based reserves are Bi 47%, REO 13%, Nb 13%, and W 11%. CCZ nodules and PCZ crusts are compared with the two largest existing land-based REE mines, Mountain Pass (MP) in USA and Bayan Obo (Obo) in China. The land-based deposits are higher grade but lower tonnage (MP 0.3x108 tons at 7.5% total REEs as oxides (TREO); Obo, 0.5x108 tons at 6% TREO), compared to the CCZ (211x108 tons at 0.10% TREO) and PCZ (75.3x108 tons at 0.3% TREO). These grades and tonnages correspond to tons of TREO of 4.7x107 Obo, 2.6x106 MP; 2.1x107 CCZ, and 2.1x107 PCZ. Both land-based deposits have <1% heavy REE, whereas the CCZ has 10% HREE and the PCZ, 6.3% HREE, typical of crusts elsewhere in the global ocean. An important environmental issue is high Th contents in the land-based deposits (100s of ppm); in contrast to low Th in marine deposits (mean 14 ppm CCZ; 11 ppm PCZ). Rare metals in the marine deposits would likely be recovered as byproducts of Ni, Cu, and Co mining, with the possible exception of Te.

International Assessment of Carbon Nanotube Manufacturing and Applications

DTIC Science & Technology

2007-06-01

oriented and long SWNT arrays obtained by the “fast-heating” growth process (Huang et al . 2004); the Fe/Mo catalyst nanoparticles are deposited ...and Cu layers for top-layer electrical contact. More recent work has been with gas-phase- deposited Ni and Co nanoparticles as catalysts (Sato et al ...22 3.6 Microstructure of MWCNT materials produced by a continuous process at Nano Carbon technologies

Environmental exposures of trace elements assessed using keratinized matrices from patients with chronic kidney diseases of uncertain etiology (CKDu) in Sri Lanka.

PubMed

Diyabalanage, Saranga; Fonseka, Sanjeewani; Dasanayake, D M S N B; Chandrajith, Rohana

2017-01-01

An alarming increase in chronic kidney disease with unknown etiology (CKDu) has recently been reported in several provinces in Sri Lanka and chronic exposures to toxic trace elements were blamed for the etiology of this disease. Keratinized matrices such as hair and nails were investigated to determine the possible link between CKDu and toxic element exposures. Elements Li, B, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, Ba, Hg and Pb of hair and nails of patients and age that matched healthy controls were determined with Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The results showed that trace element contents in the hair of patients varies in the order of Zn>Fe>Al>Mn>Cu>Ba>Sr>Ni>Pb>Cr>B>Hg>Se>Mo>Co>As>Li>Cd while Fe>Al>Zn>Ni>Cu>Mn>Cr>Ba>Sr>B>Pb>Se>Mo>Co>Hg>Li>As>Cd in nail samples. The hair As levels of 0.007-0.165μgg -1 were found in CKDu subjects. However, no significant difference was observed between cases and controls. The total Se content in hair of CKDu subjects ranged from 0.043 to 0.513μgg -1 while it was varied from 0.031 to 1.15μgg -1 in controls. Selenium in nail samples varied from 0.037μgg -1 to 4.10μgg -1 in CKDu subjects and from 0.042μgg -1 to 2.19μgg -1 in controls. This study implies that substantial proportions of Sri Lankan population are Se deficient irrespective of gender, age and occupational exposure. Although some cutaneous manifestations were observed in patient subjects, chemical analyses of hair and nails indicated that patients were not exposed to toxic levels of arsenic or the other studied toxic elements. Therefore the early suggested causative factors such as exposure to environmental As and Cd, can be ruled out. Copyright © 2016 Elsevier GmbH. All rights reserved.

Power-Generation Characteristics After Vibration and Thermal Stresses of Thermoelectric Unicouples with CoSb3/Ti/Mo(Cu) Interfaces

NASA Astrophysics Data System (ADS)

Bae, Kwang Ho; Choi, Soon-Mok; Kim, Kyung-Hun; Choi, Hyoung-Seuk; Seo, Won-Seon; Kim, Il-Ho; Lee, Soonil; Hwang, Hae Jin

2015-06-01

Reliability tests for thermoelectric unicouples were carried out to investigate the adhesion properties of CoSb3/Ti/Mo(Cu) interfaces. The n-type In0.25 Co3.95Ni0.05Sb12 and p-type In0.25Co3FeSb12 bulks were prepared for fabricating a thermoelectric unicouple (one p- n couple) by an induction melting and a spark plasma sintering process. Mo-Cu alloy was selected as an electrode for the unicouples due to its high melting temperature and proper work function value. Many thermoelectric unicouples with the CoSb3/Ti/Mo(Cu) interfaces were fabricated with the proper brazing materials by means of a repeated firing process. Reliability of the unicouples with the interfaces was evaluated by a vibration test and a thermal cycling test. After the thermal cycling and vibration tests, the power-generation characteristics of the unicouples were compared with the unicouples before the tests. Even after the vibration test, electrical power with a power density of 0.5 W/cm2 was generated. The Ti-interlayer is considered as a possible candidate for making a reliable unicouple with high adhesion strength. With the thermal cycling test, the resistance of the unicouple increased and the electrical power from the unicouple decreased. A failure mode by the thermal cycling test was ascribed to a complex effect of micro-cracks originated from the thermal stress and oxidation problem of the thermoelectric materials; that is, a thick oxide layer more than 300 μm was detected after a high-temperature durability test of n-type In0.25Co3.95Ni0.05Sb12 material at 773 K in air for 7 days.

Nutritional significance of the Cu:Mo interrelationship to ruminants and non-ruminants

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

Suttle, N.F.

1973-01-01

Mo has been shown to interfere with the Cu metabolism of several species but the interrelationship is thought to be of practical significance only to ruminants when herbage Mo concentrations exceed 5 ppM. Evidence has been obtained that Mo interferes with Cu metabolism in both ruminants and non-ruminants at concentrations below 5 ppM and within a range encountered in foods for human consumption. Groups of hypocupraemic ewes were repleted with a semi-purified diet containing 8 mgCu/kg and one of four levels of dietary Mo, 0.5, 2.5, 4.5 and 8.5 mg/kg. Rate of recovery in plasma Cu was used as amore » measure of the efficiency of Cu utilization and successive increments in dietary Mo were found to decrease that efficiency by 40, 80 and 40%, respectively. The results suggest that differences of 1 mg/kg in dietary Mo are of biological significance to ruminants. When groups of Cu-depleted guinea pigs were subjected to repletion with diets containing 8 mg Cu/kg and 0.6, 4.1, 26 or 104 mg Mo/kg the lowest increment in Mo, 3.5 mg/kg, decreased the response in liver Cu as much as the highest, 75 mg/kg, a reduction fo 23% being recorded. The industrial uses of Mo make it a potential contaminant of man's environment and Mo concentrations > 4 mg/kg have been reported in vegetables and meats. The possibility that the Cu:Mo interrelationship influences Cu metabolism in man should therefore be re-examined. 20 references, 3 tables.« less

Season and location effects on serum and liver mineral concentrations of Senepol cattle on St Croix, Virgin Islands.

PubMed

Wildeus, S; McDowell, L R; Fugle, J R

1992-11-01

Serum and liver concentrations of selected macro- and trace minerals were determined in Senepol cattle at 8 sites (4 each in a high and low rainfall region) during the dry and wet season on St Croix. At each site an average of 15 mature, lactating cows, grazing native grass/legume pastures without supplementation were blood sampled each season. Liver samples were collected (n = 51) at slaughter from mature animals originating from the same sites. A preliminary analysis indicated no differences in serum mineral concentrations between mature lactating cows and growing heifers. There were differences between sites for serum magnesium (Mg) (P < 0.001), copper (Cu) (P < 0.05) selenium (Se) (P < 0.001) and zinc (Zn) (P < 0.01) in the dry season, and for Cu (P < 0.01), iron (Fe) (P < 0.001) and Zn (P < 0.01) in the wet season. Higher (P < 0.001) serum concentrations of Mg, Cu, Fe and Zn were observed in the dry season, while Se was higher (P < 0.01) in the wet season. Liver concentrations of Cu and Fe were lower (P < 0.01) and liver molybdenum (Mo) (P < 0.001) and Se (P < 0.05) higher during the dry season. The seasonal differences in serum Cu, Se and Zn concentrations have not been observed in other studies in the Central American region. More than 50% of serum samples were deficient in phosphorus (P) regardless of season, and in Cu and Zn during the wet season. Mineral supplementation should be considered.

Irradiation-induced microchemical changes in highly irradiated 316 stainless steel

NASA Astrophysics Data System (ADS)

Fujii, K.; Fukuya, K.

2016-02-01

Cold-worked 316 stainless steel specimens irradiated to 74 dpa in a pressurized water reactor (PWR) were analyzed by atom probe tomography (APT) to extend knowledge of solute clusters and segregation at higher doses. The analyses confirmed that those clusters mainly enriched in Ni-Si or Ni-Si-Mn were formed at high number density. The clusters were divided into three types based on their size and Mn content; small Ni-Si clusters (3-4 nm in diameter), and large Ni-Si and Ni-Si-Mn clusters (8-10 nm in diameter). The total cluster number density was 7.7 × 1023 m-3. The fraction of large clusters was almost 1/10 of the total density. The average composition (in at%) for small clusters was: Fe, 54; Cr, 12; Mn, 1; Ni, 22; Si, 11; Mo, 1, and for large clusters it was: Fe, 44; Cr, 9; Mn, 2; Ni, 29; Si, 14; Mo,1. It was likely that some of the Ni-Si clusters correspond to γ‧ phase precipitates while the Ni-Si-Mn clusters were precursors of G phase precipitates. The APT analyses at grain boundaries confirmed enrichment of Ni, Si, P and Cu and depletion of Fe, Cr, Mo and Mn. The segregation behavior was consistent with previous knowledge of radiation induced segregation.

In vitro cytotoxicity evaluation of elemental ions released from different prosthodontic materials.

PubMed

Elshahawy, Waleed M; Watanabe, Ikuya; Kramer, Phillip

2009-12-01

This study investigated the cytotoxicity of elemental ions contained in four fixed prosthodontic materials (gold, nickel-chromium, stainless-steel alloys and CAD-CAM ceramics). According to the determination of elements released from prosthodontic materials by using inductively coupled plasma mass spectroscopy, similar amounts of elements Pd, Ag, Zn, Cu, Ni, Cr, Mo, Be, Fe, Al, and K were prepared as salt solutions. Wells with a tenfold higher concentration of the tested elements were used as positive controls, while a well without any tested element was used as a negative control. These salt solutions were tested for cytotoxicity by culturing mouse L-929 fibroblasts in the salt solutions for a 7-day period of incubation. Then, the percentage of viable cells for each element was measured using trypan blue exclusion assay. The data (n=5) were statistically analyzed by ANOVA/Tukey test (p<0.05). The results showed a statistically significant difference for the cytotoxic effect of the tested elements salt solutions. For the released element concentrations the lowest percentage of viable cells (mean+/-SD) was evident with Zn, Cu or Ni indicating that they are the highly toxic elements. Be and Ag were found to be intermediate in cytotoxic effect. Fe, Cr, Mo, Al, Pd or K were found to be the least cytotoxic elements. Zn and Cu released from gold alloys, and Ni released from nickel-chromium alloys, which are commonly used as fixed prosthodontic restorations, show evidence of a high cytotoxic effect on fibroblast cell cultures.

Utilization of macrominerals and trace elements in pregnant heifers with distinct feed efficiencies.

PubMed

Dias, R S; Montanholi, Y R; Lopez, S; Smith, B; Miller, S P; France, J

2016-07-01

The objective of the study was to evaluate utilization of dietary minerals and trace elements in pregnant heifers with distinct residual feed intakes (RFI). Feed intake, body weight (BW), and body composition traits were recorded in 36 crossbred heifers over a period of 37 wk, starting shortly after weaning at 8.3 (0.10; standard deviation) mo of age with an average BW of 276 (7.8) kg. Both BW and body composition were monitored regularly throughout the study, whereas individual feed intake was assessed during the last 84 d of the trial. Data recorded were used to calculate RFI for each heifer. Heifers were ranked based on RFI and assigned to high (n=14) or low (n=10) RFI groups. After the RFI study, 24 selected heifers [age 18.2 (0.14) mo; 87.5 (4.74) d in gestation; 497 (8.5) kg of BW] were used in an indirect digestibility trial (lignin as internal marker). Heifers were fed a ration containing corn silage, haylage, and a mineral premix in which Ca, P, K, Na, Mg, S, Cu, Fe, Mn, Mo, Se, Zn, and Co were provided in the diet according to National Research Council requirements of pregnant replacement heifers. The digestibility trial lasted 1 wk, during which samples of feces were gathered twice daily, and blood and liver biopsy samples were collected on the last day. We noted no significant differences between low- and high-RFI heifers in dry matter digestibility. Apparent absorption of Cu, Zn, and Mn was increased in heifers with low RFI, and apparent absorption of Co tended to be greater for these animals. Concentrations of macrominerals and trace elements in serum of pregnant heifers were similar for both groups except for Se, which was increased in the serum of low-RFI heifers. Liver concentrations of Cu, Fe, Mn, Mo, Se, and Zn did not differ between low- and high-RFI heifers. In conclusion, whereas improved absorption of some trace elements (Cu, Zn, Mn, and Co) and increased Se serum concentration appear to be associated with superior feed efficiency in pregnant heifers, further studies are needed to investigate the causality of such relationships. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Phase relations in the system CuMoS

USGS Publications Warehouse

Dawei, H.; Chang, L.L.Y.; Knowles, C.R.

1990-01-01

Phase relations in the system CuMoS were studied in the temperature range 500-1000 ??C by using the conventional sealed, evacuated glass capsule technique. Reflected-light microscopy, X-ray powder diffraction and electron microprobe analysis were used for phase characterization. The chevrel-type phase, CuxMo3S4, is stable above 600??C, and forms equilibrium assemblages with the cubic Cu2S solid solution, copper, molybdenum, Mo2S3 and MoS2. Its solid solution ranges from Cu1.50-2.00Mo3S4 at 700??C to Cu1.22-2.00Mo3S4 at 1000 ??C. ?? 1990.

Synthesis and characterization of sulfur-voided cubanes. Structural analogues for the MoFe(3)S(3) subunit in the nitrogenase cofactor.

PubMed

Coucouvanis, Dimitri; Han, Jaehong; Moon, Namdoo

2002-01-16

A new class of Mo/Fe/S clusters with the MoFe(3)S(3) core has been synthesized in attempts to model the FeMo-cofactor in nitrogenase. These clusters are obtained in reactions of the (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et (I), (n)Pr (II)] clusters with CO. The new clusters include those preliminarily reported: (Cl(4)-cat)MoFe(3)S(3)(PEt(3))(2)(CO)(6) (III), (Cl(4)-cat)(O)MoFe(3)S(3)(PEt(3))(3)(CO)(5) (IV), (Cl(4)-cat)(Pyr)MoFe(3)S(3)(PEt(3))(2)(CO)(6) (VI), and (Cl(4)-cat)(Pyr)MoFe(3)S(3)(P(n)Pr(3))(3)(CO)(4) (VIII). In addition the new (Cl(4)-cat)(O)MoFe(3)S(3)(P(n)Pr(3))(3)(CO)(5) cluster (IVa), the (Cl(4)-cat)(O)MoFe(3)S(3)(PEt(3))(2)(CO)(6)cluster (V), the (Cl(4)-cat)(O)MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (Va), the (Cl(4)-cat)(Pyr)MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (VIa), and the (Cl(4)-cat)(P(n)Pr(3))MoFe(3)S(3)(P(n)Pr(3))(2)(CO)(6) cluster (VII) also are reported. Clusters III-VIII have been structurally and spectroscopically characterized. EPR, zero-field (57)Fe-Mössbauer spectroscopic characterizations, and magnetic susceptibility measurements have been used for a tentative assignment of the electronic and oxidation states of the MoFe(3)S(3) sulfur-voided cuboidal clusters. A structural comparison of the clusters with the MoFe(3)S(3) subunit of the FeMo-cofactor has led to the suggestion that the storage of reducing equivalents into M-M bonds, and their use in the reduction of substrates, may occur with the FeMo-cofactor, which also appears to have M-M bonding. On the basis of this argument, a possible N(2)-binding and reduction mechanism on the FeMoco-cofactor is proposed.

Role of Phragmites australis (common reed) for heavy metals phytoremediation of estuarine sediments.

PubMed

Cicero-Fernández, Diego; Peña-Fernández, Manuel; Expósito-Camargo, Jose A; Antizar-Ladislao, Blanca

2016-01-01

The ability of Phragmites australis to take up heavy metals (Co, Ni, Mo, Cd, Pb, Cr, Cu, Fe, Mn, Zn, and Hg) and other trace elements (As, Se, Ba), from estuarine sediments was investigated using a pilot plant experimental approach. Bioaccumulation (BCF) and translocation factors (TF) were calculated in vegetative and senescence periods for two populations of P. australis, from contaminated (MIC) and non-contaminated (GAL) estuarine sediments, respectively, both growing in estuarine contaminated sediment (RIA) from ría del Carmen y Boo, Santander Bay, Spain. The highest BCF values were obtained for Ni (0.43), Ba (0.43) Mo (0.36), Cr (0.35), and Cd (0.31) for plants collected from site GAL following the senescence period. The highest BCF values recorded for plants collected from MIC following the senescence period were for Mo (0.22) and Cu (0.22). Following senescence, plants collected from GAL and MIC presented TF>1 for Ni, Mo, Se, and Zn, and in addition plants collected from MIC presented TF>1 for Ba, Cr, and Mn. A substantial increase of Micedo's rhizosphere, six times higher than Galizano's rhizosphere, suggested adaptation to contaminated sediment. The evaluated communities of P. australis demonstrated their suitability for phytoremediation of heavy metals contaminated estuarine sediments.

Geologic cross sections showing the concentrations of As, Cd, Co, Cu, Cr, Fe, Mo, Ni, Pb, and Zn in acid-insoluble residues of Paleozoic rocks within the Doniphan/Eleven Point Ranger District of the Mark Twain National Forest, Missouri, USA

USGS Publications Warehouse

Lee, Lopaka; Goldhaber, Martin B.

2002-01-01

This report is a product of a U.S. Geological Survey investigation that is focused on characterizing the potential environmental impacts of lead-zinc mining within the Doniphan/Eleven Point ranger district of the Mark Twain national forest. The elemental concentrations of iron (Fe), arsenic (As), cadmium (Cd), cobalt (Co), copper (Cu), chromium (Cr), nickel (Ni), lead (Pb), and zinc (Zn) in acidinsoluble residues are shown for boreholes along two geologic cross sections within Doniphan/Elevan Point ranger district (Figure 1). The purpose of this report is to characterize, in a general sense, the distribution of economically and environmentally important elements within the rocks and aquifers of the Doniphan/Eleven Point ranger district

Metal pollution in Al-Khobar seawater, Arabian Gulf, Saudi Arabia.

PubMed

Alharbi, Talal; Alfaifi, Hussain; El-Sorogy, Abdelbaset

2017-06-15

In order to assess heavy metals pollution along the Al-Khobar coastline, 30 seawater samples and 15 sediment ones were collected for Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, Hg and Pb analysis by Inductively Coupled Plasma-Mass Spectrometer (ICP-MS). The analysis indicated a southward decreasing pattern in most heavy metal concentrations and the average values of Zn, Fe, Mn, Cu, As and Cr were higher than the ones reported from some worldwide seas and gulfs. Most of the highest levels were recorded within the bays and were related with in situ under sediments especially that composed of clays and very fine sands, and in localities characterized with anthropogenic activities like landfilling, desalination plants, fishing boats, oil spills and solid rubbish. The results of the present study provide useful background for further marine investigation and management in the Arabian Gulf region. Copyright © 2017 Elsevier Ltd. All rights reserved.

Construction of a novel Mo/Cu/S cluster with a closed double-cubane-like polyhedron and a chain polymer of W/Cu/S clusters.

PubMed

Li, Zhihua; Du, Shaowu; Wu, Xintao

2004-08-09

Reaction of [MoOS(3)](2)(-) and [WS(4)](2)(-) with Cudtp (dtp = diethyl dithiophosphate) gave rise to the clusters [Bu(4)N](2)[(MoOS(3))(4)Cu(12)(dtp)(6)], 1, and [Et(4)N][(WS(4)Cu(4))(dtp)(3)], 2, respectively. In cluster 1, the dtp- ligands act as both monodentate and bidentate ligands that bridge between Cu atoms and link together a closed double-cubane-like [Mo(2)O(2)S(6)Cu(6)](2+) core and two incomplete cubane-like [MoOS(3)Cu(3)]+ units. In cluster 2, the [WS(4)Cu(4)](2+) fragments were connected via bidentate and doubly bridging dtp- bridges to give a chain polymeric anion. Cluster 1 is the first example of a Mo/Cu/S cluster that contains a closed double-cubane-like structure. Compound 2 is also rare and the first W/Cu/S polymer with dtp- linkages.

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

PubMed Central

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

2009-01-01

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

Regional geochemical studies in the Patagonia Mountains, Santa Cruz County, Arizona

USGS Publications Warehouse

Chaffee, M.A.; Hill, R.H.; Sutley, S.J.; Watterson, J.R.

1981-01-01

The Patagonia Mountains in southern Arizona contain the deeply buried porphyry copper system at Red Mountain as well as a number of other base- and precious-metal mines and prospects. The range contains complex Basin and Range geology with units ranging in age from Precambrian to Holocene. Rock types present include igneous intrusive and extrusive units as well as sedimentary and metamorphic units, most of which have been tectonically disturbed. A total of 264 stream-sediment samples were collected and analyzed for 32 elements. Geochemical maps for Sb, Ag, Pb, Te, B, Mn, Au, Zn, Cu (total), Cu (cold-extractable), and Mo, as well as for Cu (cold-extractable)/Cu (total) and Fe/Mn, are presented. Anomaly patterns for these elements generally occur over the Red Mountain deposit and (or) along a north-northwest trend parallel to the major Harshaw Creek Fault. Much of the entire area sampled contains widespread anomalies for Pb, Te, and Cu; the other elements are only locally anomalous. Various plots of ratios of Cu (cold-extractable) to Cu (total) did not produce any new information not readily apparent on either one of the two copper maps. A plot of ratios of Fe to Mn delineated many areas of pyrite mineralization. Several of these areas may represent the pyritic halos around deeply buried porphyry copper systems. The best ore guide for the Red Mountain porphyry system is the coincidence of positive anomalies of Mo, Pb, and Te and a negative anomaly of Mn. Other areas with anomalies of the same suite of elements are present within the Patagonia Mountains. It is concluded that geochemical sampling, even in a highly contaminated area, can be useful in delineating major geologic features, such as porphyry copper belts and major faults. Multielement geochemical surveys on a regional scale can effectively locate large, deeply buried, zoned mineral systems such as that at Red Mountain. Plots of element ratios, where adequately understood, can provide geochemical information not readily discernible from plots of single elements alone. ?? 1981.

Major and trace elements in organically or conventionally produced milk.

PubMed

Hermansen, John E; Badsberg, Jens H; Kristensen, Troels; Gundersen, Vagn

2005-08-01

A total of 480 samples of milk from 10 organically and 10 conventionally producing dairy farms in Denmark and covering 8 sampling periods over 1 year (triplicate samplings) were analysed for 45 trace elements and 6 major elements by high-resolution inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectrometry. Sampling, sample preparation, and analysis of the samples were performed under carefully controlled contamination-free conditions. The dairy cattle breeds were Danish-Holstein or Jersey. Sources of variance were quantified, and differences between production systems and breeds were tested. The major source of variation for most elements was week of sampling. Concentrations of Al, Cu, Fe, Mo, Rb, Se, and Zn were within published ranges. Concentrations of As, Cd, Cr, Mn and Pb were lower, and concentrations of Co and Sr were higher than published ranges. Compared with Holsteins, Jerseys produced milk with higher concentrations of Ba, Ca, Cu, Fe, Mg, Mn, Mo, P, Rh, and Zn and with a lower concentration of Bi. The organically produced milk, compared with conventionally produced milk, contained a significantly higher concentration of Mo (48 v. 37 ng/g) and a lower concentration of Ba (43 v. 62 ng/g), Eu (4 v. 7 ng/g), Mn (16 v. 20 ng/g) and Zn (4400 v. 5150 ng/g respectively). The investigation yielded typical concentrations for the following trace elements in milk, for which no or very few data are available: Ba, Bi, Ce, Cs, Eu, Ga, Gd, In, La, Nb, Nd, Pd, Pr, Rh, Sb, Sm, Tb, Te, Th, Ti, Tl, U, V, Y, and Zr.

The metal content of molybdenum-mineralizing fluids

NASA Astrophysics Data System (ADS)

Lerchbaumer, L.; Audétat, A.

2012-04-01

Molybdenum can be found in porphyry-type systems as well as in hydrothermal veins and breccias associated with granite systems. Up to now our knowledge on the metal content of fluids forming molybdenum ore deposits has been very limited. The only data available so far are from the porphyry Mo deposit at Questa, New Mexico, and from the Cave Peak porphyry Mo-Nb deposit in Texas. We have studied early, intermediate-density fluid inclusions in quartz crystals from miarolitic cavities in the Drammen and Glitrevann granites (Norway) and the Treasure Mountain Dome (Colorado/USA) to obtain more information about the bulk composition of magmatic-hydrothermal fluids exsolved from these plutons. The Treasure Mountain Dome contains weak Mo mineralization and is an apophysis of the Alma Batholith that produced also the famous Climax and Henderson porphyry Mo deposits; the Glitrevann granite hosts a sub-economic Mo stockwork, and the Drammen Granite contains numerous vein-type Mo mineralizations. As a preliminary result, based on analyses of fluid inclusions using optical microscopy, microthermometry, Raman spectroscopy, and LA-ICP-MS we conclude that the primordial fluid of the Drammen granite was of high acidity and carried certain amounts of metals at conditions of 650°C and 1.3-1.5 kbar. The total elemental budget is: 3 wt% Na, 1.8 wt% K, 0.5 wt% S, 0.4 wt% Fe, 0.3 wt% Cu, 0.2 wt% Mn, 40 ppm Mo, 800 ppm Zn, 600 ppm Rb, 300 ppm Cs, 180 ppm Pb, 150 ppm As, 40 ppm W, 15 ppm Bi, and minor amounts of Ag, Sn, and Ce. Striking is the fact, that all the metal concentrations show little variability except the one of Cu. In view of recent studies (Lerchbaumer & Audétat, 2011) showing that the Cu-values in quartz-hosted fluid inclusions are not always representative of the primary fluid and in fact can be too high, we want to check if this could be the case for the Cu-values measured in the samples from Norway and Colorado. The alteration of the original Cu-concentrations stems from post-entrapment diffusion of Cu+ through the host quartz into the fluid inclusions. The trigger for this process is the changing pH of the outer fluid due to rock-buffered cooling: As this fluid gets more and more basic, the increasing concentration gradient promotes the loss of H+ from existing fluid inclusions and the corresponding uptake of Cu+. In order to experimentally reconstruct this process we will put a well characterized trail of fluid inclusions from the Drammen granite into a gold capsule together with its original, acidic fluid (known from analyses mentioned above) and subject it to its forming conditions in rapid quench autoclaves. In the case of fluid inclusions with a diffusively altered elemental composition, the pH-difference between the fluid inclusions and the outer fluid would reverse the diffusion process and would lead to quite diminished concentrations of Cu after the run. Such a result would finally indicate that these Mo-mineralizing fluids hardly transported any Cu. Lerchbaumer L. & Audétat A. (2011): Preferential partitioning of copper into the vapor phase: An artifact? Mineralogical Magazine 75 (3), 1302.

Sonocatalytic performance of magnetically separable CuS/CoFe2O4 nanohybrid for efficient degradation of organic dyes.

PubMed

Siadatnasab, Firouzeh; Farhadi, Saeed; Khataee, Alireza

2018-06-01

The sonocatalytic activity of the magnetic CuS/CoFe 2 O 4 (CuS/CFO) nanohybrid was studied through the H 2 O 2 -assisted system for degradation of water soluble organic pollutants such as methylene blue (MB), rhodamine B (RhB) and methyl orange (MO). The CuS/CFO nanohybrid was fabricated at 200 °C by hydrothermal method. X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) equipped with energy dispersive X-ray microanalysis (EDX), Fourier-transform infrared spectroscopy (FT-IR), UV-Vis spectroscopy, magnetic measurements, and Brunauere-Emmette-Teller (BET) were employed for the characterizing the structure and morphology of the so-synthesized nanohybrid. Compared with sonolysis/H 2 O 2 , the higher degradation of MB (25 mg/L) was achieved via sonocatalytic process. The degradation efficiency of sonolysis/H 2 O 2 , sonocatalysis using CuS/H 2 O 2 , CFO/H 2 O 2 and CuS/CFO/H 2 O 2 systems was 6%, 62%, 23% and 100% within reaction time of 30 min for MB, respectively. The integration of H 2 O 2 and catalyst dosage intensified the sonocatalytic degradation of MB. On the other hand, adding a hydroxyl radical (OH) scavenger (tert-butyl alcohol) and a hole scavenger (disodium ethylenediaminetetraacetate) decreased the degradation efficiency from 100% to 35% and 72% within 30 min, indicating the OH radicals as prominent oxidizing agent of this process. Furthermore, the magnetic property of the sample helped for easier separation of the nanohybrid, made it recyclable with a negligible decline in the performance even after four consecutive runs. Copyright © 2018 Elsevier B.V. All rights reserved.

Biogeochemistry of Metals in Periodic Cicada

NASA Astrophysics Data System (ADS)

Robinson, G. R.; Sibrell, P. L.; Boughton, C. J.; Yang, L. H.; Hancock, T. C.

2005-05-01

Metal concentrations were measured in three species of 17-year periodic cicadas (Magicicada spp.) to determine the bioavailability of metals from both uncontaminated and lead-arsenate-pesticide contaminated soils and evaluate whether these metal concentrations might threaten wildlife. Collections were made in Clarke and Frederick Counties, Virginia and Berkeley and Jefferson Counties, West Virginia during Brood X emergence in May and June 2004. Periodic cicadas emerge synchronously at high density after 13 or 17 years of underground development, feeding on xylem fluids, and molt into their adult form leaving a keratin exoskeleton shell. They are an important food source for birds and animals during emergence events, and influence nutrient cycles in woodland settings. Soil concentrations at the collection sites vary over one order of magnitude for Co, Cu, Fe, Hg, Mn, Mo, Se, and Zn and over two orders of magnitude for As, Au, and Pb. The concentration levels of metals in adult periodic cicadas do not pose a dietary threat to birds and other wildlife that preferentially feed upon cicadas during emergence events. The adult cicadas contain concentrations of metals similar to, or less than, other invertebrates, such as earthworms. Average adult cicada body concentrations for As, Cu, Hg, Pb, and Zn are 3, 64, 0.015, 0.4, and 160 mg/Kg (dry weight), respectively. Much of the cicada nymph body load of metals is partitioned into the molt exoskeleton. Elements, such as Al, Fe, and Pb, are strongly enriched in the exoskeleton relative to the adult body; Cu and Zn are enriched in bodies. Concentrations of Fe, Co, and Pb, when normalized to inert soil constituents such as aluminum and cerium, are similar between the molt exoskeleton and their host soil, implying that passive assimilation through prolonged soil contact (adhesion or adsorption) may control these metal concentrations. Normalized concentrations of bioessential elements, such as S, P, K, Ca, Mn, Cu, Zn, and Mo, and chalcophile (sulfur-loving) elements, such as As, Se, and Au, show strong enrichment in cicada tissues relative to soil, implying selective absorption by xylem fluids and/or cicada nymph during development. Chalcophile elements, such as As and heavy metals, accumulate in keratin-rich tissues and may bind to sulfhydryl groups. Metal concentrations in exoskeleton show a positive correlation with soil metal concentrations. Metal concentrations in adult bodies do not correlate with soil chemistry, but bioessential elements S, Mn, Fe, and Zn show differences by sex and Cu and Zn by species.

Low-cost Fe--Ni--Cr alloys for high temperature valve applications

DOEpatents

Muralidharan, Govindarajan

2017-03-28

An Fe--Ni--Cr alloy is composed essentially of, in terms of weight percent: 1 to 3.5 Al, up to 2 Co, 15 to 19.5 Cr, up to 2 Cu, 23 to 40 Fe, up to 0.3 Hf, up to 4 Mn, 0.15 to 2 Mo, up to 0.15 Si, up to 1.05 Ta, 2.8 to 4.3 Ti, up to 0.5 W, up to 0.06 Zr, 0.02 to 0.15 C, 0.0001 to 0.007 N, balance Ni, wherein, in terms of atomic percent: 6.5.ltoreq.Al+Ti+Zr+Hf+Ta.ltoreq.10, 0.33.ltoreq.Al/(Al+Ti+Zr+Hf+Ta).ltoreq.0.065, 4.ltoreq.(Fe+Cr)/(Al+Ti+Zr+Hf+Ta).ltoreq.10, the alloy being essentially free of Nb and V.

Socio-demographic, lifestyle, and dietary determinants of essential and possibly-essential trace element levels in adipose tissue from an adult cohort.

PubMed

Rodríguez-Pérez, Celia; Vrhovnik, Petra; González-Alzaga, Beatriz; Fernández, Mariana F; Martin-Olmedo, Piedad; Olea, Nicolás; Fiket, Željka; Kniewald, Goran; Arrebola, Juan P

2018-05-01

There is increasing evidence linking levels of trace elements (TEs) in adipose tissue with certain chronic conditions (e.g., diabetes or obesity). The objectives of this study were to assess concentrations of a selection of nine essential and possibly-essential TEs in adipose tissue samples from an adult cohort and to explore their socio-demographic, dietary, and lifestyle determinants. Adipose tissue samples were intraoperatively collected from 226 volunteers recruited in two public hospitals from Granada province. Trace elements (Co, Cr, Cu, Fe, Mn, Mo, Se, V, and Zn) were analyzed in adipose tissue by high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS). Data were collected on socio-demographic characteristics, lifestyle, diet, and health status by face-to-face interview. Predictors of TE concentrations were assessed by using multivariable linear and logistic regression. All TEs were detected in all samples with the exception of Se (53.50%). Iron, zinc, and copper showed the highest concentrations (42.60 mg/kg, 9.80 mg/kg, and 0.68 mg/kg, respectively). Diet was the main predictor of Cr, Fe, Mo, and Se concentrations. Body mass index was negatively associated with all TEs (β coefficients = -0.018 to -0.593, p = 0.001-0.090) except for Mn and V. Age showed a borderline-significant positive correlation with Cu (β = 0.004, p = 0.089). Residence in a rural or semi-rural area was associated with increased Co, Cr, Fe, Mo, Mn, V and Zn concentrations and with β coefficients ranging from 0.196 to 0.544 (p < 0.05). Furthermore, individuals with higher educational level showed increased Cr, Co, Fe and V concentrations (β coefficients = 0.276-0.368, p = 0.022-0.071). This is the first report on the distribution of these TEs in adipose tissue and on their determinants in a human cohort and might serve as an initial step in the elucidation of their clinical relevance. Copyright © 2017 Elsevier Ltd. All rights reserved.

Orientation dependence of grain-boundary energy in metals in the view of a pseudoheterophase dislocation core model

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

Missol, W.

A new dislocation model for symmetric tilt grain boundaries was developed as a basis for deriving the quantitative dependence of grain-boundary energy upon misorientation angle in the form of an expression similar to that given by Read and Shockley (Phys. Rev. 78: 275(1950)). The range of applicability of this equation was extended to over 20 degrees. A comparison of theory and experiment was made for Bi, Ag, Cu, and Fe--Si 3 percent in the teen-degree range of misorientation angles and for Au, ..cap alpha..-Fe, Mo, and W in the high-angle range.

VTVH-MCD study of the Delta nifB Delta nifZ MoFe protein from Azotobacter vinelandii.

PubMed

Cotton, Marcia S; Rupnik, Kresimir; Broach, Robyn B; Hu, Yilin; Fay, Aaron W; Ribbe, Markus W; Hales, Brian J

2009-04-08

NifZ is a member of a series of proteins associated with the maturation of the nitrogenase MoFe protein. An MCD spectroscopic study was undertaken on the Delta nifB Delta nifZ MoFe protein generated in the absence of both NifZ and NifB (deletion of NifB generates an apo-MoFe protein lacking the FeMo cofactor). Results presented here show that, in the absence of NifZ, only one of the two P-clusters of the MoFe protein is matured to the ultimate [8Fe-7S] structure. The other P-cluster site in the protein contains a [4Fe-4S] cluster pair, representing a P-cluster precursor that is electronically identical to the analogous clusters observed in the Delta nifH MoFe protein. These results suggest that the MoFe protein is synthesized in a stepwise fashion where NifZ is specifically required for the formation of the second P-cluster.

Ecological geochemical assessment and source identification of trace elements in atmospheric deposition of an emerging industrial area: Beibu Gulf economic zone.

PubMed

Zhong, Cong; Yang, Zhongfang; Jiang, Wei; Hu, Baoqing; Hou, Qingye; Yu, Tao; Li, Jie

2016-12-15

Industrialization and urbanization have led to a deterioration in air quality and provoked some serious environmental concerns. Fifty-four samples of atmospheric deposition were collected from an emerging industrial area and analyzed to determine the concentrations of 11 trace elements (As, Cd, Cu, Fe, Hg, Mn, Mo, Pb, Se, S and Zn). Multivariate geostatistical analyses were conducted to determine the spatial distribution, possible sources and enrichment degrees of trace elements in atmospheric deposition. Results indicate that As, Fe and Mo mainly originated from soil, their natural parent materials, while the remaining trace elements were strongly influenced by anthropogenic or natural activities, such as coal combustion in coal-fired power plants (Pb, Se and S), manganese ore (Mn, Cd and Hg) and metal smelting (Cu and Zn). The results of ecological geochemical assessment indicate that Cd, Pb and Zn are the elements of priority concern, followed by Mn and Cu, and other heavy metals, which represent little threat to local environment. It was determine that the resuspension of soil particles impacted the behavior of heavy metals by 55.3%; the impact of the coal-fired power plants was 18.9%; and the contribution of the local manganese industry was 9.6%. The comparison of consequences from various statistical methods (principal component analysis (PCA), cluster analysis (CA), enrichment factor (EF) and absolute principle component score (APCS)-multiple linear regression (MLR)) confirmed the credibility of this research. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of compost fertilization in organic farming on micronutrients and heavy metals in soil and crops

NASA Astrophysics Data System (ADS)

Erhart, Eva; Sager, Manfred; Bonell, Marion; Fuchs, Katrin; Haas, Dieter; Ableidinger, Christoph; Hartl, Wilfried

2015-04-01

For organic stockless and vegetable farms using biowaste compost is a way to sustain soil humus content. At the same time compost use in agriculture closes local nutrient cycles. Besides organic matter and main nutrients, biowaste compost also imports micronutrients and heavy metals in amounts determined by the compost input material. The aim of this work was to assess total and plant-available contents of micronutrients B, Ca, Cu, Fe, Mn, Mo, Ni, Zn, beneficial elements Co and Se and heavy metals Cd, Cr and Pb in the soil and in crops after 20 years of fertilization with compost produced from source-separated organic waste. Topsoil and wheat grain samples were collected from the long-term field experiment 'STIKO' situated near Vienna on a Molli-gleyic Fluvisol. Between 1992 and 2012 the organic treatments C1, C2 and C3 had received 5, 10 and 14 t ha-1 yr-1 (wet wt.) biowaste compost on average. They were compared with the unfertilized organic control treatment and with three mineral fertilization treatments, which had received 20, 32 and 44 kg N ha-1 yr 1, respectively, plus 40 kg P and 68 kg K ha-1 yr-1 on average. Total soil element contents of B, Cd, Cr, Co, Cu, Fe, Mn, Mo, Ni, Pb, Se and Zn were measured in aqua regia digestion. Immediately water-soluble elements were analysed in soil saturation extract, elements in exchangeable form in LiCl extract following Husz (2001), and long-term available elements in 0.5 N HCl extract. Wheat grains were dehulled, milled and subjected to microwave digestion with HNO3 and H2O2. Wheat was analyzed for Cd and Pb with ICP-MS. All other elements in wheat and all soil extracts were analyzed using ICP-AES. Total soil concentrations of micronutrients, heavy metals and beneficial elements were in the range of usual soil contents and lower than the Austrian background values for arable land with comparable pH and carbonate concentration (Schwarz and Freudenschuss, 2004) in all treatments (all mg kg-1: B 14-19, Fe 16000-18000, Mn 397-445, Mo 0.7-1.0, Cu 15-17, Ni 21-22, Zn 45-52, Cr 26-28, Pb 13-17, Co 7.5-8.4). Total soil concentrations of Cd (0.37-0.46 mg kg-1) were the same as the background values. No significant differences were found between the treatments and the unfertilized control. Similarly, the plant available LiCl-fraction and the long-term available HCl-fraction did not show significant differences between the treatments. In the soil saturation extracts, Cu content was 18-22 µg kg-1, B 172-187 µg kg-1, Fe 62-113 µg kg-1 and Ca 62-71 mg kg-1, all in the usual range of soil saturation extracts of agricultural fields without significant differences between treatments. The other elements were below the limit of determination. In the wheat, contents of micronutrients, heavy metals and beneficial elements were in the same range as in other Austrian wheat samples (Spiegel and Sager, 2008) with the exception of Ca. Element contents were (all in mg kg-1): B 0.5-0.6, Ca 387-464, Cd 0.023-0.028, Co 0.006, Cr 0.10-0.17, Cu 4.7-5.3, Fe 36-50, Mn 30-33, Mo 0.31-0.35, Ni 0.11-0.15, Se 0.15-0.27 and Zn 28-31. Pb was below the limit of determination in the wheat grains. No significant differences were detected between the treatments. After 20 years of compost fertilization with high quality biowaste compost at the above rates no increase in micronutrients and heavy metals was detected in total soil contents and in plant-available fractions nor in wheat grains.

Submicron-scale mineralogy of lithotypes and the implications for trace element associations: Blue Gem coal, Knox County, Kentucky

DOE PAGES

Hower, James C.; Berti, Debora; Hochella, Michael F.; ...

2018-04-16

Transmission electron microscopy accompanied by energy-dispersive spectroscopy and selected area electron diffraction of density-gradient separates from two lithotypes of the low-ash, low-sulfur Blue Gem coal, eastern Kentucky, revealed an array of previously unrecognized (in this coal, and arguable in most others) sub-micron minerals, some <10 nm in size. The first sample representing the 1.22–1.24 specific gravity fraction of the middle bench contains a mineral identified as a La-, Ce-, Nd-bearing monazite; other minerals with CrFe, CuFeS, FeZn-S, and Pb; and areas, probably comprising agglomerates of several grains, if not several minerals, with concentrations of Mg, Ca, Ti, Fe, Zn, Zr,more » and Mo. The second sample representing the 1.30–1.31 specific gravity fraction of the basal lithotype has aggregates of particles enriched in Mg, Ca, Ti, and Fe. Individual grains not specifically quantified include CrNiMnCuFeS, AgS, and CuS. Detailed investigation of one area (most of the variation within a <4 μm 2 region) demonstrates the presence of greenockite (CdS); minute phases containing NiCoGe and AgCdBi, the latter with a more evident S association than the former; metallic Bi; nisnite (Ni 3Sn); silver cadmium; manganosite (MnO); and siderite. Some minerals, such as the monazite, are most likely of detrital or tuffaceous origin. Many of the other assemblages could be of hydrothermal origin, a hypothesis supported by known regional geochemical and coal rank trends, but not previously demonstrated in mineral assemblages at the 10's of nm scale in this region.« less

Submicron-scale mineralogy of lithotypes and the implications for trace element associations: Blue Gem coal, Knox County, Kentucky

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

Hower, James C.; Berti, Debora; Hochella, Michael F.

Transmission electron microscopy accompanied by energy-dispersive spectroscopy and selected area electron diffraction of density-gradient separates from two lithotypes of the low-ash, low-sulfur Blue Gem coal, eastern Kentucky, revealed an array of previously unrecognized (in this coal, and arguable in most others) sub-micron minerals, some <10 nm in size. The first sample representing the 1.22–1.24 specific gravity fraction of the middle bench contains a mineral identified as a La-, Ce-, Nd-bearing monazite; other minerals with CrFe, CuFeS, FeZn-S, and Pb; and areas, probably comprising agglomerates of several grains, if not several minerals, with concentrations of Mg, Ca, Ti, Fe, Zn, Zr,more » and Mo. The second sample representing the 1.30–1.31 specific gravity fraction of the basal lithotype has aggregates of particles enriched in Mg, Ca, Ti, and Fe. Individual grains not specifically quantified include CrNiMnCuFeS, AgS, and CuS. Detailed investigation of one area (most of the variation within a <4 μm 2 region) demonstrates the presence of greenockite (CdS); minute phases containing NiCoGe and AgCdBi, the latter with a more evident S association than the former; metallic Bi; nisnite (Ni 3Sn); silver cadmium; manganosite (MnO); and siderite. Some minerals, such as the monazite, are most likely of detrital or tuffaceous origin. Many of the other assemblages could be of hydrothermal origin, a hypothesis supported by known regional geochemical and coal rank trends, but not previously demonstrated in mineral assemblages at the 10's of nm scale in this region.« less

Reduction-oxidation Enabled Glass-ceramics to Stainless Steel Bonding Part II interfacial bonding analysis

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

Dai, Steve Xunhu

2015-09-01

Among glass-ceramic compositions modified with a variety of oxidants (AgO, FeO, NiO, PbO, SnO, CuO, CoO, MoO 3 and WO 3) only CuO and CoO doped glass-ceramics showed existence of bonding oxides through reduction-oxidation (redox) at the GC-SS interface. The CuO-modified glass-ceramics demonstrate the formation of a continuous layer of strong bonding Cr 2O 3 at the interface in low partial oxygen (PO 2) atmosphere. However, in a local reducing atmosphere, the CuO is preferentially reduced at the surface of glass-ceramic rather than the GC-SS interface for redox. The CoO-modified glass-ceramics demonstrate improved GC-SS bonding. But the low mobility ofmore » Co ++ ions in the GC limited the amount of CoO that can diffuse to and participate in redox at the interface.« less

Metal concentration in the tourist beaches of South Durban: An industrial hub of South Africa.

PubMed

Vetrimurugan, E; Shruti, V C; Jonathan, M P; Roy, Priyadarsi D; Kunene, N W; Villegas, Lorena Elizabeth Campos

2017-04-15

South Durban basin of South Africa has witnessed tremendous urban, industrial expansion and mass tourism impacts exerting significant pressure over marine environments. 43 sediment samples from 7 different beaches (Bluff beach; Ansteys beach; Brighton beach; Cutting beach; Isipingo beach; Tiger Rocks beach; Amanzimtoti beach) were analyzed for acid leachable metals (ALMs) Fe, Mg, Mn, Cr, Cu, Mo, Ni, Co, Pb, Cd, Zn and Hg. The metal concentrations found in all the beaches were higher than the background reference values (avg. in μgg -1 ) for Cr (223-352), Cu (27.67-42.10), Mo (3.11-4.70), Ni (93-118), Co (45.52-52.44), Zn (31.26-57.01) and Hg (1.13-2.36) suggesting the influence of industrial effluents and harbor activities in this region. Calculated geochemical indexes revealed that extreme contamination of Cr and Hg in all the beach sediments and high Cr and Ni levels poses adverse biological effects. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interface characterization of Cu-Mo coating deposited on Ti-Al alloys by arc spraying

NASA Astrophysics Data System (ADS)

Bai, Shengqiang; Li, Fei; Wu, Ting; Yin, Xianglin; Shi, Xun; Chen, Lidong

2015-03-01

Cu-Mo pseudobinary alloys are promising candidates as electrode materials in CoSb3-based skutterudite thermoelectric (TE) devices for TE power generation. In this study, Cu-Mo coatings were deposited onto Ti-Al substrates by applying a dual-wire electric arc spraying coating technique. The microstructure of the surfaces, cross sections and coating interfaces were analyzed by scanning electron microscopy (SEM) and energy dispersion spectrometry (EDS). Cu-Mo coatings showed a typical banded splat with compact microstructures, and have no coarse pores nor micro-cracks. The thermal shock resistance of the Cu-Mo coating was also investigated to show good combinations with Ti-Al substrates. After 50 thermal shock cycles, there were no cracks observed at the interface. In contrast, the test of the thermal shock resistance of the Cu coating on the Ti-Al substrate was also investigated. Due to a large difference in the thermal expansion coefficients between Cu and Ti-Al alloys, the Cu coating flaked from the Ti-Al substrate completely after 10 thermal shock cycles. The contact resistivity of the Ti-Al/Cu-Mo interface was about 1.6 μΩṡcm2 and this value was unchanged after 50 thermal shock cycles, indicating the low electric resistance and high thermal stability of the Cu-Mo/Ti-Al interface.

Mossbauer and XRD characterization of the phase transformations in a Fe-Mn-Al-C-Mo-Si-Cu as cast alloy during tribology test

NASA Astrophysics Data System (ADS)

Ramos, J.; Piamba, J. F.; Sánchez, H.; Alcazar, G. A. Pérez

2015-06-01

In present study Fe-29.0Mn-6Al-0.9C-1.8Mo-1.6Si-0.4Cu (%w) alloy was obtained after melted in an induction furnace, and then molded as an ingot. From the as cast ingot it were cut samples for the different characterization measurements. The microstructure of the as-cast sample is of dendritic type and its XRD pattern was refined with the lines of the austenite, with a big volumetric fraction, and the lines of the martensite, with small volumetric fraction. The Mössbauer spectrum of the sample was fitted with a broad singlet which corresponds to disordered austenite. After the tribology test, its XRD pattern was refined with the lines of two austenite phases, one similar to the previous one and other with bigger lattice parameter. The total volumetric fraction of the austenite is smaller than that obtained for sample without wear. It was added the lines of the martensite phase with bigger volumetric fraction than that of the previous sample. The Mössbauer spectrum of the weared sample was fitted with two paramagnetic sites which correspond to the two Fe austenite phases and a hyperfine magnetic field distribution which is associated to the disordered original martensite and the new one which appears in the surface as a consequence of the wear process. These results show that during wear process the original austenite phase is transformed in martensite and in a new austenite phase. The increases of the martensitic phase improves mechanical properties and wear behavior.

The effect of pasteurization on trace elements in donor breast milk.

PubMed

Mohd-Taufek, N; Cartwright, D; Davies, M; Hewavitharana, A K; Koorts, P; McConachy, H; Shaw, P N; Sumner, R; Whitfield, K

2016-10-01

Premature infants often receive pasteurized donor human milk when mothers are unable to provide their own milk. This study aims to establish the effect of the pasteurization process on a range of trace elements in donor milk. Breast milk was collected from 16 mothers donating to the milk bank at the Royal Brisbane and Women's Hospital. Samples were divided into pre- and post-pasteurization aliquots and were Holder pasteurized. Inductively coupled plasma mass spectrometry was used to analyze the trace elements zinc (Zn), copper (Cu), selenium (Se), manganese (Mn), iodine (I), iron (Fe), molybdenum (Mo) and bromine (Br). Differences in trace elements pre- and post-pasteurization were analyzed. No significant differences were found between the trace elements tested pre- and post-pasteurization, except for Fe (P<0.05). The median (interquartile range, 25 to 75%; μg l(-1)) of trace elements for pre- and post- pasteurization aliquots were-Zn: 1639 (888-4508), 1743 (878-4143), Cu: 360 (258-571), 367 (253-531), Se: 12.34 (11.73-17.60), 12.62 (11.94-16.64), Mn: (1.48 (1.01-1.75), 1.49 (1.11-1.75), I (153 (94-189), 158 (93-183), Fe (211 (171-277), 194 (153-253), Mo (1.46 (0.37-2.99), 1.42 (0.29-3.73) and Br (1066 (834-1443), 989 (902-1396). Pasteurization had minimal effect on several trace elements in donor breast milk but high levels of inter-donor variability of trace elements were observed. The observed decrease in the iron content of pasteurized donor milk is, however, unlikely to be clinically relevant.

Transport and attenuation of metal(loid)s in mine tailings amended with organic carbon: Column experiments

NASA Astrophysics Data System (ADS)

Lindsay, Matthew B. J.; Blowes, David W.; Ptacek, Carol J.; Condon, Peter D.

2011-07-01

A laboratory-scale column experiment was conducted to evaluate the effect of organic carbon amendments on the mobility of As, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Tl and Zn in mine tailings. Three columns were packed with sulfide- and carbonate-rich tailings, which were amended with a 1:1 (vol.) mixture of peat and spent brewing grain at proportions of 0, 2 and 5 vol. %. A simulated input solution characterized by circumneutral pH and elevated concentrations of SO 4 and S 2O 3 was passed through the columns for 540 days. The input solution contained low concentrations of metal(loid)s during the initial 300 days and elevated concentrations thereafter. Decreases in mass transport of S 2O 3 were observed in all columns; with increased attenuation observed at 5 vol. % organic carbon content. Removal of Mn, Ni, Cu, Sb and Mo was observed in all columns during the initial 300 days. However, during this time, mobilization of Fe, As, Zn and Pb was observed, with the greatest increases in concentration observed at the higher organic carbon content. During the final 240 days, S 2O 3 removal was enhanced in columns containing organic carbon, and Fe, Mn, Ni, Tl, As and Sb removal also was observed. This study demonstrates the influence of organic carbon amendments on metal(loid) mobility in mine tailings. Decreases in mass discharge of metal(loid)s may be achieved using this technique; however, site-specific geochemical conditions must be considered before field-scale implementation.

Trace elements in winter snow of the Dolomites (Italy): a statistical study of natural and anthropogenic contributions.

PubMed

Gabrielli, P; Cozzi, G; Torcini, S; Cescon, P; Barbante, C

2008-08-01

Knowledge of the occurrence of trace elements deposited in fresh alpine snow is very limited. Although current sources of major ionic inorganic species have been well established, this is not the case for many trace elements. This manuscript attempts to reconstruct the origin of Ag, Ba, Bi, Cd, Co, Cr, Cu, Fe, Mo, Mn, Pb, Sb, Ti, U, V and Zn in winter surface snow, extensively collected in the Dolomites region (Eastern Alps, Italy). Sampling of surface snow was conducted weekly during the winter 1998 at 21 sites at altitudes ranging from approximately 1000 to approximately 3000 m. This led to a remarkable dataset of trace element concentrations in surface snow from low latitudes. Here we show a preliminary statistical investigation conducted on the 366 samples collected. It was found that V, Sb, Zn, Cd, Mo and Pb have a predominantly anthropogenic origin, linked to the road traffic in the alpine valleys and the nearby heavily industrialised area of the Po Valley. In addition, the occasionally strong Fe and Cr input may reflect the mechanical abrasion of ferrous components of the vehicles. However, much of the Fe along with Mn, U and Ti originates primarily from the geological background of the Dolomites. A marine contribution was found to be negligible for all the trace elements. The origin of other trace elements is less clear: Ag can be possibly attributed to a predominantly anthropogenic origin while Cr, Co, Cu and Ba are usually from crustal rocks but different than the Dolomites.

Development and characterization of (Ti, Mo)C carbides reinforced Fe-based surface composite coating produced by laser cladding

NASA Astrophysics Data System (ADS)

Wang, Xinhong; Zhang, Min; Qu, Shiyao

2010-09-01

In this study, in situ multiple carbides reinforced Fe-based surface composite coatings were fabricated successfully by laser cladding a precursor mixture of graphite, ferrotitanium (Fe-Ti) and ferromolybdenum (Fe-Mo) powders. The results showed that (Ti, Mo)C particles with flower-like and cuboidal shapes were in situ formed during the solidification and most shapes of (Ti, Mo)C particles were diversiform according to different contents of Fe-Mo powder in the Fe-Ti-Mo-C system. The growth morphology of the reinforcing (Ti, Mo)C carbide has typically faceted features, indicating that the lateral growth mechanism is still predominant growth mode under rapid solidification conditions. Increasing the amount of Fe-Mo in the reactants led to a decrease of carbide size and an increase of volume fraction of carbides. The coatings had good cracking resistance when the amounts of Fe-Mo were controlled within a range of 15 wt%.

Molybdenum L-Edge XAS Spectra of MoFe Nitrogenase

PubMed Central

Bjornsson, Ragnar; Delgado-Jaime, Mario U; Lima, Frederico A; Sippel, Daniel; Schlesier, Julia; Weyhermüller, Thomas; Einsle, Oliver; Neese, Frank; DeBeer, Serena

2015-01-01

A molybdenum L-edge X-ray absorption spectroscopy (XAS) study is presented for native and oxidized MoFe protein of nitrogenase as well as Mo-Fe model compounds. Recently collected data on MoFe protein (in oxidized and reduced forms) is compared to previously published Mo XAS data on the isolated FeMo cofactor in NMF solution and put in context of the recent Mo K-edge XAS study, which showed a MoIII assignment for the molybdenum atom in FeMoco. The L3-edge data are interpreted within a simple ligand-field model, from which a time-dependent density functional theory (TDDFT) approach is proposed as a way to provide further insights into the analysis of the molybdenum L3-edges. The calculated results reproduce well the relative spectral trends that are observed experimentally. Ultimately, these results give further support for the MoIII assignment in protein-bound FeMoco, as well as isolated FeMoco. PMID:26213424

Investigation of amorphous RuMoC alloy films as a seedless diffusion barrier for Cu/ p-SiOC:H ultralow- k dielectric integration

NASA Astrophysics Data System (ADS)

Jiao, Guohua; Liu, Bo; Li, Qiran

2015-08-01

Ultrathin RuMoC amorphous films prepared by magnetron co-sputtering with Ru and MoC targets in a sandwiched scheme Si/ p-SiOC:H/RuMoC/Cu were investigated as barrier in copper metallization. The evolution of final microstructure of RuMoC alloy films show sensitive correlation with the content of doped Mo and C elements and can be easily controlled by adjusting the sputtering power of the MoC target. There was no signal of interdiffusion between the Cu and SiOC:H layer in the sample of Cu/RuMoC/ p-SiOC:H/Si, even annealing up to 500 °C. Very weak signal of oxygen have been confirmed in the RuMoC barrier layer both as-deposited and after being annealed, and a good performance on preventing oxygen diffusion has been proved. Leakage current and resistivity evaluations also reveal the excellent thermal reliability of this Si/ p-SiOC:H/RuMoC/Cu film stack at the temperatures up to 500 °C, indicating its potential application in the advanced barrierless Cu metallization.

A study of the formation, purification and application as a SWNT growth catalyst of the nanocluster [HxPMo12O40[subset]H4Mo72Fe30(O2CMe)15O254(H2O)98].

PubMed

Anderson, Robin E; Colorado, Ramon; Crouse, Christopher; Ogrin, Douglas; Maruyama, Benji; Pender, Mark J; Edwards, Christopher L; Whitsitt, Elizabeth; Moore, Valerie C; Koveal, Dorothy; Lupu, Corina; Stewart, Michael P; Smalley, Richard E; Tour, James M; Barron, Andrew R

2006-07-07

The synthetic conditions for the isolation of the iron-molybdenum nanocluster FeMoC [HxPMo12O40 [subset]H4Mo72Fe30(O2CMe)15O254(H2O)98], along with its application as a catalyst precursor for VLS growth of SWNTs have been studied. As-prepared FeMoC is contaminated with the Keplerate cage [H4Mo72Fe30(O2CMe)15O254(H2O)98] without the Keggin [HxPMo12O40]n- template, however, isolation of pure FeMoC may be accomplished by Soxhlet extraction with EtOH. The resulting EtOH solvate is consistent with the replacement of the water ligands coordinated to Fe being substituted by EtOH. FeMoC-EtOH has been characterized by IR, UV-vis spectroscopy, MS, XPS and 31P NMR. The solid-state 31P NMR spectrum for FeMoC-EtOH (delta-5.3 ppm) suggests little effect of the paramagnetic Fe3+ centers in the Keplerate cage on the Keggin ion's phosphorous. The high chemical shift anisotropy, and calculated T1 (35 ms) and T2 (8 ms) values are consistent with a weak magnetic interaction between the Keggin ion's phosphorus symmetrically located within the Keplerate cage. Increasing the FeCl2 concentration and decreasing the pH of the reaction mixture optimizes the yield of FeMoC. The solubility and stability of FeMoC in H2O and MeOH-H2O is investigated. The TGA of FeMoC-EtOH under air, Ar and H2 (in combination with XPS) shows that upon thermolysis the resulting Fe : Mo ratio is highly dependent on the reaction atmosphere: thermolysis in air results in significant loss of volatile molybdenum components. Pure FeMoC-EtOH is found to be essentially inactive as a pre-catalyst for the VLS growth of single-walled carbon nanotubes (SWNTs) irrespective of the substrate or reaction conditions. However, reaction of FeMoC with pyrazine (pyz) results in the formation of aggregates that are found to be active catalysts for the growth of SWNTs. Activation of FeMoC may also be accomplished by the addition of excess iron. The observation of prior work's reported growth of SWNTs from FeMoC is discussed with respect to these results.

The effect of FeF2 on the magneto-optic response in FeF2/Fe/FeF2 sandwiches

NASA Astrophysics Data System (ADS)

Pištora, J.; Lesňák, M.; Lišková, E.; Višňovský, Š.; Harward, I.; Maslankiewicz, P.; Balin, K.; Celinski, Z.; Mistrík, J.; Yamaguchi, T.; Lopusnik, R.; Vlček, J.

2010-04-01

The room temperature optical constants n and k of MBE grown FeF2 films are reported. Because of poor chemical stability, FeF2 had to be coated with a protective Au layer. Reflection spectral ellipsometry in the photon energy range between 1.3 and 5.2 eV was performed on structures with a typical profile Au(0.5 nm)/FeF2(120 nm)/Au(30 nm)/Ag(20 nm)/Fe(0.6 nm) grown on GaAs(0 0 1) substrate. The spectra of n and k in FeF2 were subsequently employed in the design of FeF2/Fe/FeF2 sandwiches considered as magneto-optic (MO) sensors for weak microwave currents. Their MO response was evaluated using reflection MO (Kerr) spectroscopy at polar magnetization. The present results may be of interest in MO studies of magnetic nanostructures with Fe/FeF2/Fe, including MO magnetometry and MO magnetic domain imaging.

Recycling 100Mo for direct production of 99mTc on medical cyclotrons

NASA Astrophysics Data System (ADS)

Kumlin, Joel O.; Zeisler, Stefan K.; Hanemaayer, Victoire; Schaffer, Paul

2018-05-01

A scalable recycling technique for the recovery of 100Mo from previously irradiated and chemically processed targets is described. A combined process for both Cu and Ta supported targets and the respective `waste' solutions has been developed. This process involves selectively dissolving Cu target backings from undissolved portions of 100Mo pellets; precipitating Cu(OH)2 at pH 9; electrochemical removal of Cu traces; precipitating (NH4)2MoO4 at pH 2.5-3; thermally decomposing (NH4)2MoO4; and H2 reduction of MoO3 to Mo metal. Radionuclidic decontamination by a factor of 100 is observed, while overall 100Mo recovery from initial target plating to recycled Mo metal of 96% is achieved.

Magnetic {Mo72Fe30}-embedded hybrid nanocapsules.

PubMed

Cui, Jiwei; Fan, Dawei; Hao, Jingcheng

2009-02-15

Magnetic nanocapsules were constructed by fabricating nanometer scaled C(60)-like "Keplerate" type {Mo(72)Fe(30)} with molecular formula [Mo(72)(VI)Fe(30)(III)O(252)(CH(3)COO)(12){Mo(2)O(7)(H(2)O)}(2){H(2)Mo(2)O(8)(H(2)O)}(H(2)O)(91)] x ca.150 H(2)O into nanocapsule shells using the LbL technique. The morphology of the obtained hybrid nanocapsules was examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Shell thickness of the {Mo(72)Fe(30)}-embedded nanocapsules can be tailored at the nanometer level more precisely than other nanoparticle-embedded capsules due to the homogeneous diameter and surface charges of {Mo(72)Fe(30)}. Interestingly, the {Mo(72)Fe(30)}-embedded nanocapsules could be separated and aligned under a circumstance of magnetic field, though {Mo(72)Fe(30)} is a paramagnetic molecule. This is the first time to fabricate hybrid magnetic materials containing {Mo(72)Fe(30)} using LbL technique. The obtained nanocapsules can be a good candidate for bioseparation as well as targeted delivery.

A novel copper(II) coordination at His186 in full-length murine prion protein

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

Watanabe, Yasuko; Hiraoka, Wakako; Igarashi, Manabu

2010-04-09

To explore Cu(II) ion coordination by His{sup 186} in the C-terminal domain of full-length prion protein (moPrP), we utilized the magnetic dipolar interaction between a paramagnetic metal, Cu(II) ion, and a spin probe introduced in the neighborhood of the postulated binding site by the spin labeling technique (SDSL technique). Six moPrP mutants, moPrP(D143C), moPrP(Y148C), moPrP(E151C), moPrP(Y156C), moPrP(T189C), and moPrP(Y156C,H186A), were reacted with a methane thiosulfonate spin probe and a nitroxide residue (R1) was created in the binding site of each one. Line broadening of the ESR spectra was induced in the presence of Cu(II) ions in moPrP(Y148R1), moPrP(Y151R1), moPrP(Y156R1), andmore » moPrP(T189R1) but not moPrP(D143R1). This line broadening indicated the presence of electron-electron dipolar interaction between Cu(II) and the nitroxide spin probe, suggesting that each interspin distance was within 20 A. The interspin distance ranges between Cu(II) and the spin probes of moPrP(Y148R1), moPrP(Y151R1), moPrP(Y156R1), and moPrP(T189R1) were estimated to be 12.1 A, 18.1 A, 10.7 A, and 8.4 A, respectively. In moPrP(Y156R1,H186A), line broadening between Cu(II) and the spin probe was not observed. These results suggest that a novel Cu(II) binding site is involved in His186 in the Helix2 region of the C-terminal domain of moPrP{sup C}.« less

Electronic structures and nonlinear optical properties of trinuclear transition metal clusters M-(mu-S)-M' (M = Mo, W; M' = Cu, Ag, Au).

PubMed

Chen, Xihua; Wu, Kechen; Snijders, Jaap G; Lin, Chensheng

2003-01-27

A series of trinuclear metal clusters MS4(M'PPh3)2(M'PPh3) (M = Mo, W; M' = Cu, Ag, Au) have been studied using the density functional theory (DFT) method. The static polarizabilities and hyperpolarizabilities of the model clusters have been calculated using the finite-field (F-F) method. The model clusters, divided into two groups, are alike in the structure of two fragments of rhombic units M-(mu-S)2-M' (M = Mo, W; M' = Cu, Ag, Au), perpendicular to each other, which are joined by sharing the bridge metal M. It is the charge transfer from one of these moieties to the other in these characteristic sulfido-transitional metal cores that is responsible for the polarizabilities and hyperpolarizabilities. This kind of electronic delocalization, different from that of the planar pi-system, is interesting and warrants further investigation. The structural effects on properties are important. In these models, considerable third-order nonlinearities are exhibited. The element substitution effect of Mo and W is weak, while that of Cu and Ag is relatively substantial. An overall order is gamma xxxx(Mo-Ag) > gamma xxxx(W-Ag) > gamma xxxx(Mo-Au) > gamma xxxx(W-Au) > gamma xxxx (Mo-Cu) > gamma xxxx(W-Cu) and gamma av(Mo-Ag) approximately gamma av(W-Ag) > gamma av(Mo-Au) approximately gamma av(W-Au) approximately gamma av (Mo-Cu) approximately gamma av(W-Cu).

Laser surface processing on sintered PM alloys

NASA Astrophysics Data System (ADS)

Reiter, Wilfred; Daurelio, Giuseppe; Ludovico, Antonio D.

1997-08-01

Usually the P.M. alloys are heat treated like case hardening, gas nitriding or plasma nitriding for a better wear resistance of the product surface. There is an additional method for gaining better tribological properties and this is the surface hardening (or remelting or alloying) of the P.M. alloy by laser treatment on a localized part of the product without heating the whole sample. This work gives a cured experimentation about the proper sintering powder alloys for laser surface processing from the point of view of wear, fatigue life and surface quality. As concerns the materials three different basic alloy groups with graduated carbon contents were prepared. Regarding these sintered powder alloys one group holds Fe, Mo and C and other group holds Fe, Ni, Mo and C and the last one holds Fe, Ni, Cu, Mo and C contents. Obviously each group has a different surface hardness, different porosity distribution, different density and diverse metallurgical structures (pearlite or ferrite-pearlite, etc.). ON the sample surfaces a colloidal graphite coating, in different thicknesses, has been sprayed to increase laser energy surface absorption. On some other samples a Mo coating, in different thicknesses, has been produced (on the bulk alloy) by diverse deposition techniques (D.C. Sputtering, P.V.D. and Flame Spraying). Only a few samples have a Mo coating and also an absorber coating, that is a bulk material- Mo and a colloidal graphite coating. All these sintered alloys have been tested by laser technology; so that, many laser working parameters (covering gas, work-speed, focussed and defocussed spot, rastered and integrated beam spots, square and rectangular beam shapes and so on) have been experimented for two different processes at constant laser power and at constant surface temperature (by using a temperature surface sensor and a closed controlled link). For all experiments a transverse fast axial flow CO2 2.5 kW c.w. laser source has been employed.

Trace elements concentration and distributions in coal and coal mining wastes and their environmental and health impacts in Shaanxi, China.

PubMed

Hussain, Rahib; Luo, Kunli; Chao, Zhao; Xiaofeng, Zhao

2018-05-07

This study probe the probable impacts of coal mining pollution and its impacts on human's health and environment. A total of 144 samples including coal and coal wastes, soil, plants, foods, and water were collected from the Hancheng county and countryside of Shaanxi, China. All the samples were analyzed for trace elements using ICP-MS, OES, and AFS. Results showed that the concentration of Se, As, Cr, Cu, Pb, Cd, Co, Ni, Mo, U, Th (mgKg -1 ), Fe, Mn, Al, Ti (%) etc., in coal and coal wastes were 7.5, 12.1, 275, 55, 54.2, 0.8, 14.8, 94.5, 8.9, 4.9, 17.2, 3.5, 0.02, 19, 0.7, respectively. While in soil 0.6, 12, 194, 27.5, 7.4, 0.6, 11.3, 83.4, 0.7, 1.7, 9.9, 3.1, 0.04, 10.5, and 0.4 for the above elements, respectively. In Hancheng foods, the average concentration of Se-0.09, As-0.15, Cr-1.8, Cu-3.2, Pb-0.4, Cd-0.02, Co-0.09, Ni-0.4, Mo-0.64, U-0.01, Th-0.03, Fe-129, Mn-15.6, Al-234, and Ti-5.2 in mgKg -1 , respectively, which are comparably higher than the countryside. The elemental concentration in groundwater of both areas was below the WHO-2004 standard. In Hancheng, the average daily intake (mgKg -1 bw/d) of Se 0.004-0.0038, As 0.004-0.13, Cr 0.055-0.06, Cd 0.001-0.004, Ni 0.018-13.91, Pb 0.05-0.001 adult-children, respectively. The toxic trace elements such as Cr, Cu, Mn, Pb, Ti, Cd, Co, Th, Fe, Al, and Mo caused non-carcinogenic risk with high morbidity in children than adults. By assessing environmental risks, coal and coal wastes caused high risk, food and plants faced moderate to high risk, while mountain and agriculture soil are prone to low to considerable risk. The pollution in Hancheng County is extreme as compared to the countryside. The study concluded that the contamination is geogenic in both the areas but coal mining enhance the metals contamination and has extensive impacts on the living community and environment of Hancheng areas.

Mineralogical and geochemical characterization of weathering profiles developed on mylonites in the Fodjomekwet-Fotouni section of the Cameroon Shear Zone (CSZ), West Cameroon

NASA Astrophysics Data System (ADS)

Tematio, P.; Tchaptchet, W. T.; Nguetnkam, J. P.; Mbog, M. B.; Yongue Fouateu, R.

2017-07-01

The mineralogical and geochemical investigation of mylonitic weathering profiles in Fodjomekwet-Fotouni was done to better trace the occurrence of minerals and chemical elements in this area. Four representative soil profiles were identified in two geomorphological units (upland and lowland) differentiating three weathering products (organo-mineral, mineral and weathered materials). Weathering of these mylonites led to some minerals association such as vermiculite, kaolinite, goethite, smectite, halloysite, phlogopite and gibbsite. The minerals in a decreasing order of abundance are: quartz (24.2%-54.8%); kaolinite (8.4%-36.0%); phlogopite (5.5%-21.9%); goethite (7.8%-16.1%); vermiculite (6.7%-15.7%); smectite (10.2%-11.9%); gibbsite (9.0%-11.8%) and halloysite (5.6%-11.5%) respectively. Patterns of chemical elements allow highlighting three behaviors (enriched elements, depleted elements and elements with complex behavior), depending on the landscape position of the profiles. In the upland weathering products, K, Cr and REEs are enriched; Ca, Mg, Na, Mn, Rb, S and Sr are depleted while Si, Al, Fe, Ti, Ba, Co, Cu, Ga, Mo, Nb, Ni, Pb, Sc, V, Y, Zn and Zr portray a complex behavior. Contrarily, the lowland weathering profiles enriched elements are Fe, Ti, Co, Cr, Cu, V, Zr, Pr, Sm, Tb, Dy, Er and Yb; while depleted elements are Ca, Mg, K, Na, Mn, Ba, Ga, S, Sr, Y, Zn, La, Ce and Nd; and Si, Al, Mo, Nb, Ni, Pb, Rb, Sc evidenced complex behaviors. In all the studied weathering products, the REEs fractionation was also noticeable with a landscape-position dependency, showing light REEs (LREEs) enrichment in the upland areas and heavy REEs (HREEs) in lowland areas. SiO2, Al2O3 and Fe2O3 are positively correlated with most of the traces and REEs (Co, Cu, Nb, Ni, Mo, Pb, Sc, V, Zn, Zr, La, Ce, Sm, Tb, Dy, Er, Yb), pointing to the fact that they may be incorporated into newly formed clay minerals and oxides. Ba, Cr, Ga, Rb, S, Sr, Y, Pr and Nd behave like alkalis and alkaline earths, and are thus highly mobile during weathering.

Influences of Different Components on Agglomeration Behavior of MoS2 During Oxidation Roasting Process in Air

NASA Astrophysics Data System (ADS)

Wang, Lu; Zhang, Guo-Hua; Wang, Jing-Song; Chou, Kuo-Chih

2016-08-01

An agglomeration of the furnace charge always takes place during the oxidation roasting process of molybdenite concentrate (with the main component of MoS2) in multiple hearth furnaces, which greatly affects the production process and furnace service life. In the present work, a preliminary study about the influence of various components on the agglomeration phenomenon of pure MoS2 have been carried out. The results show that reaction temperature, impurity content, and air flow rate have significant effects on the agglomeration extent. Meanwhile, the impurity type added into the pure MoS2 plays a crucial role. It was found that CaO and MgO have a stronger sulfur-fixing effect and that the desulphurization of the roasted product was uncompleted. It was also concluded that the agglomeration is due to the formation of low-melting-point eutectics, including that between MoO3 and impurities and that between MoO3 and Mo4O11. It is suggested that decreasing the impurities contents, especially K, Cu, Pb, and Fe, is an effective method for reducing the extent of agglomeration.

A two-dimensional organic–inorganic hybrid compound, poly[(ethylenediamine)tri-μ-oxido-oxidocopper(II)molybdenum(VI)

PubMed Central

Gun, Ozgul; VanDerveer, Don; Emirdag-Eanes, Mehtap

2008-01-01

A new organic–inorganic two-dimensional hybrid compound, [CuMoO4(C2H8N2)], has been hydro­thermally synthesized at 443 K. The unit cell contains layers composed of CuN2O4 octa­hedra and MoO4 tetra­hedra. Corner-sharing MoO4 and CuN2O4 polyhedra form CuMoO4 bimetallic sites that are joined together through O atoms, forming an edge-sharing Cu2Mo2O4 chain along the c axis. The one-dimensional chains are further linked through bridging O atoms that join the Cu and Mo atoms into respective chains along the b axis, thus establishing layers in the bc plane. The ethyl­enediamine ligand is coordinated to the Cu atom through its two N atoms and is oriented perpendicularly to the two-dimensional –Cu—O—Mo– layers. The average distance between adjacent layers, as calculated by consideration of the closest and furthest distances between two layers, is 8.7 Å. The oxidation states of the Mo and Cu atoms of VI and II, respectively, were confirmed by bond-valence sum calculations. PMID:21200997

Metal isotope coded profiling of organic ligands by mass spectrometry in aquatic environments

NASA Astrophysics Data System (ADS)

Wichard, Thomas; Deicke, Michael; Frieder Mohr, Jan; Klein, Martin

2017-04-01

Metal isotope coded profiling (MICP) introduces a universal discovery platform for metal chelating natural products that act as metallophores, ion buffers or sequestering agents. The detection of cation and oxoanion complexing ligands is facilitated by the identification of unique isotopic signatures created by the application of isotopically pure metals. We present a targeted analysis of low-molecular-weight organic ligands based on fast UHPLC-ESI-MS measurements. Replacement of, for example, natural iron or molybdenum with isotopically pure 54Fe/58Fe (ratio 1:1) or 95Mo/98Mo (ratio 1:1) causes easily detectable unique isotopic signatures in the mass spectra of potential metal-complexing ligands. This can be achieved under laboratory conditions not only in growth media, but also by spiking directly aqueous samples or solid-phase extracts. Importantly, as the relative affinity of the metallophores for e.g., Mo or Fe is dependent on the pH, all experiments needs to be conducted under pH-controlled conditions. The improved ionization efficiency of some metal complexes helps to enhance the signal-to-noise ratio compared to the free ligand at the same chromatographic conditions. The methodology does not necessarily depend on HR-ESI-MS measurements (e.g., Q-Exactive Orbitrap) and can be applied to any mass spectrometer. With MICP, two birds can be killed with one stone: (i) the identification of metallophores (e.g., siderophores, molybdophores) for metal uptake by any organism and (ii) organic ligands which solely work as metal buffer in dissolved organic matter (DOM). We currently address following two main research lines: First, DOM has often been used as a proxy for bio-productivity in terms of a carbon source; however, the specific impact of DOM as a "metal buffer" for biological processes is still under-investigated. Upon the administration of individual isotopes or isotopic pairs, for example, 54Fe/58Fe, 63Cu/65Cu, 66Zn/68Zn, or 95Mo/98Mo and subsequent measurements by mass spectrometry, organic ligands can be identified that contribute potentially to the regulation of bioavailability and toxicity of metals in the water column. Secondly, metal acquisition by ligand exchange processes is vital for macroalgae-bacteria interactions. Both alga and bacteria contribute to the "soup of organic ligands" which potentially increases the bioavailability of metals due to various ligand exchanges with DOM. In particular, we will outline the analytical process resulting in the identification of ligands in the chemosphere of the marine macroalga Ulva (Chlorophyta) and its associated bacteria. In summary, the identification of metal organic ligands in natural samples will pave the way for understanding the organic ligand-mediated metal acquisition shuttled from DOM to alga. (References: Wichard T. (2016) Front. Mar. Sci. 3:131; Deicke M., Mohr J.M., Wichard T. (2014) Analyst, 139, 6096-6099)

MoS2 Nanosheet-Modified CuInS2 Photocatalyst for Visible-Light-Driven Hydrogen Production from Water.

PubMed

Yuan, Yong-Jun; Chen, Da-Qin; Huang, Yan-Wei; Yu, Zhen-Tao; Zhong, Jia-Song; Chen, Ting-Ting; Tu, Wen-Guang; Guan, Zhong-Jie; Cao, Da-Peng; Zou, Zhi-Gang

2016-05-10

Exploiting photocatalysts respond to visible light is of huge challenge for photocatalytic H2 production. Here, we synthesize a new composite material consisting of few-layer MoS2 nanosheets grown on CuInS2 surface as an efficient photocatalyst for solar H2 generation. The photocatalytic results demonstrate that the 3 wt % MoS2 /CuInS2 photocatalyst exhibits the highest H2 generation rate of 316 μmol h(-1)  g(-1) under visible light irradiation, which is almost 28 times higher than that of CuInS2 . Importantly, the MoS2 /CuInS2 photocatalyst shows a much higher photocatalytic activity than that of Pt-loaded CuInS2 photocatalyst. The enhanced photocatalytic activities of MoS2 /CuInS2 photocatalysts can be attributed to the improved charge separation at the interface of MoS2 and CuInS2, which is demonstrated by the significant enhancement of photocurrent responses in MoS2 /CuInS2 photoelectrodes. This work presents a noble-metal-free photocatalyst that responds to visible light for solar H2 generation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molybdenum toxicity and hypocuprosis in ruminants: a review

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

Ward, G.M.

1978-01-01

Elevated Mo intakes depress Cu availability and may produce a physiological Cu deficiency in ruminants. Total sulfur or sulfate in the ration generally potentiates the effect of Mo. The ratio of Cu to Mo in feed is important regardless of the absolute amount of each. For this reason, and because of the importance of the S content of the diet, it is impossible to define safe dietary limits for Cu and Mo. Physiological Cu deficiencies are produced by four classes of feeds: (1) high Mo, generally above 100 ppM, (2) low Cu:Mo ratio, 2:1 or less, (3) Cu deficiency, belowmore » 5 ppM, and (4) high protein, 20 to 30% protein in fresh forage. The latter situation probably results from higher levels of sulfide produced from sulfur amino acids during rumen fermentation. Copper sulfide is largely unabsorbed. Future instances of hypocuprosis in the US are most likely to occur from marginal copper deficiencies in forages.« less

Rapid Photodegradation of Methyl Orange (MO) Assisted with Cu(II) and Tartaric Acid

PubMed Central

Guo, Jing; Chen, Xue; Shi, Ying; Lan, Yeqing; Qin, Chao

2015-01-01

Cu(II) and organic carboxylic acids, existing extensively in soil and aquatic environments, can form complexes that may play an important role in the photodegradation of organic contaminants. In this paper, the catalytic role of Cu(II) in the removal of methyl orange (MO) in the presence of tartaric acid with light was investigated through batch experiments. The results demonstrate that the introduction of Cu(II) could markedly enhance the photodegradation of MO. In addition, high initial concentrations of Cu(II) and tartaric acid benefited the decomposition of MO. The most rapid removal of MO assisted by Cu(II) was achieved at pH 3. The formation of Cu(II)-tartaric acid complexes was assumed to be the key factor, generating hydroxyl radicals (•OH) and other oxidizing free radicals under irradiation through a ligand-to-metal charge-transfer pathway that was responsible for the efficient degradation of MO. Some intermediates in the reaction system were also detected to support this reaction mechanism. PMID:26241043

Phase stability of Keplerate-type polyoxomolybdates controlled by added cationic surfactant.

PubMed

Fan, Dawei; Hao, Jingcheng

2009-05-15

Phase stability of two nanometer-scale Keplerate-type polyoxomolybdates, (NH(4))(42)[Mo(VI)(72)Mo(V)(60)O(372)(CH(3)COO)(30)(H(2)O)(72)]300H(2)O10CH(3)COONH(4) ({Mo(132)}) and Mo(VI)(72)Fe(III)(30)O(252)L(102)ca. 180H(2)O with L=H(2)O/CH(3)COO(-)/Mo(2)O(n-)(8/9) ({Mo(72)Fe(30)}), can be easily achieved by controlling the concentration of a cationic surfactant, tetradecyltrimethylammonium bromide (TTABr), in aqueous solution. Precipitates and floccules were observed when the stoichiometric ratios of rTTA+/{Mo132} and rTTA+/{Mo72Fe30} were 40:1 and 90:1, respectively, which were determined by zeta potential measurements. The surface charge properties and structure morphologies of {Mo(132)} and {Mo(72)Fe(30)} induced by controlling cationic TTABr in aqueous solution were determined by zeta potential measurements and transmission electron microscopy (TEM) observations. {Mo(132)} and {Mo(72)Fe(30)} can self-assemble into supramolecular "Blackberry" structures and exist at compositions less than the stoichiometric ratios of rTTA+/{Mo132} and rTTA+/{Mo72Fe30} in aqueous solution. Above the 1:1 stoichiometric ratio of TTABr/{Mo(132)} or TTABr/{Mo(72)Fe(30)}, the precipitates and floccules dissolve. Dynamic laser light scattering (DLS) measurements clearly demonstrated that the R(h) values have essentially no angular dependence at excess amounts of TTABr, suggesting the presence of spherically symmetric aggregates of {Mo(132)} and {Mo(72)Fe(30)}. Bilayer-like structures in aqueous solution were also demonstrated by TEM images. The interesting phase transition observed in our model systems of {Mo(132)} and {Mo(72)Fe(30)} macroanions with high chemical stability, similar shape, and masses could provide models for the understanding of more complex polyelectrolyte solutions and self-assembled soft magnetic materials and in bioapplications for highly selective adsorbents of proteins with different molecular sizes and charges.

Electrical Conductivity of Dense Al, Ti, Fe, Ni, Cu, Mo, Ta, and W Plasmas

DTIC Science & Technology

2011-06-01

for all but tantalum and titanium shows a minimum at approximately 0.01 times solid density, followed by an increase as the density decreases further...internal energy and specific volume. Conductivity is observed to fall as the plasma expands for fixed internal energy, and for all but tantalum and...plasmas formed from elemental metal wires heated rapidly in a water bath by the electric current from discharge of a charged capacitor . Electrical

Detergentless ultrasound-assisted extraction of trace elements from edible oils using lipase as an extractant.

PubMed

Kara, Derya; Fisher, Andrew; Hill, Steve

2015-11-01

A new method for the extraction and preconcentration of trace elements (Al, Ba, Cd, Cu, Fe, Mn, Mo, Ni, Ti, V and Zn) from edible oils by producing detergentless micro-emulsions via an ultrasound-assisted extraction using a water phase containing Lipase at pH 3 as an extractant was developed. The trace elements in the water phase post-extraction were determined against matrix matched standards using ICP-MS. In the first step of the work, the parameters that affect extraction, such as pH, the volume of 1% lipase in the water phase and the ultrasonic and centrifugation times were optimized. Under the optimal conditions, the detection limits (µg kg(-1)) were 0.46, 0.03, 0.007, 0.028, 0.67, 0.038, 0.022, 0.14, 0.17, 0.05 and 0.07 for Al, Ba, Cd, Cu, Fe, Mn, Mo, Ni, Ti, V and Zn respectively for edible oils (3 Sb/m). A certified reference material (EnviroMAT HU-1 Used oil) was analysed to check the accuracy of the developed method. Results obtained were in agreement with certified values with a t-test showing that no significant differences at the 95% confidence levels were found. The proposed method was applied to different edible oils such as sunflower oil, rapeseed oil, olive oil and salmon oil. Copyright © 2015 Elsevier B.V. All rights reserved.

Rational synthesis of high nuclearity Mo/Fe/S clusters: the reductive coupling approach in the convenient synthesis of (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et, (n)Pr, (n)Bu] and the new [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl]-1/2(Fe(PEt(3))(2)(MeCN)(4)) and (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) clusters.

PubMed

Han, J; Koutmos, M; Ahmad, S A; Coucouvanis, D

2001-11-05

A general method for the synthesis of high nuclearity Mo/Fe/S clusters is presented and involves the reductive coupling of the (Et(4)N)(2)[(Cl(4)-cat)MoOFeS(2)Cl(2)] (I) and (Et(4)N)(2)[Fe(2)S(2)Cl(4)] (II) clusters. The reaction of I and II with Fe(PR(3))(2)Cl(2) or sodium salts of noncoordinating anions such as NaPF(6) or NaBPh(4) in the presence of PR(3) (R = Et, (n)Pr, or (n)Bu) affords (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et (IIIa), (n)Pr (IIIb), (n)Bu (IIIc)], Fe(6)S(6)(PEt(3))(4)Cl(2) (IV) and (PF(6))[Fe(6)S(8)(P(n)Pr(3))(6)] (V) as byproducts. The isolation of (Et(4)N)[Fe(PEt(3))Cl(3)] (VI), NaCl, and SPEt(3) supports a reductive coupling mechanism. Cluster IV and V also have been synthesized by the reductive self-coupling of compound II. The reductive coupling reaction between I and II by PEt(3) and NaPF(6) in a 1:1 ratio produces the (Et(4)N)(2)[(Cl(4)-cat)Mo(L)Fe(3)S(4)Cl(3)] clusters [L = MeCN (VIIa), THF (VIIb)]. The hitherto unknown [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl](+) cluster (VIII) has been isolated as the 2:1 salt of the (Fe(PEt(3))(2)(MeCN)(4))(2+) cation after the reductive self-coupling reaction of I in the presence of Fe(PEt(3))(2)Cl(2). Cluster VIII crystallizes in the monoclinic space group P2(1)/c with a = 11.098(3) A, b = 22.827(6) A, c = 25.855(6) A, beta = 91.680(4) degrees, and Z = 4. The formal oxidation states of metal atoms in VIII have been assigned as Mo(III), Mo(IV), Fe(II), and Fe(III) on the basis of zero-field Mössbauer spectra. The Fe(PEt(3))(2)(MeCN)(4) cation of VIII is also synthesized independently, isolated as the BPh(4)(-) salt (IX), and has been structurally characterized. The reductive coupling of compound I also affords in low yield the new (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) cluster (X) as a byproduct. Cluster X crystallizes in the monoclinic space group P2(1)/n with a = 14.811(3) A, b = 22.188(4) A, c = 21.864(4) A, beta = 100.124(3) degrees, and Z = 4 and the structure shows very short Mo-Fe, Fe-Fe, Mo-S, Fe-S bonds. The oxidation states of the metal atoms in this neutral cluster (X) have been assigned as Mo(IV)Mo(III)Fe(II)Fe(II)Fe(III) based on zero-field Mössbauer and magnetic measurement. All Fe atoms are high spin and two of the three Fe-Fe distances are found at 2.4683(9) A and 2.4721(9) A.

Superconducting transition temperature in the Y(1-x)M(x)Ba2Cu3O(y) system

NASA Astrophysics Data System (ADS)

Suzuki, Takeyuki; Yamazaki, Tsutomu; Sekine, Ryuuta; Koukitsu, Akinori; Seki, Hisashi

1989-04-01

Experimental results are presented for the inclusion of compositional additives, M, to the sintered high-temperature superconductor Y(1-x)M(x)Ba2Cu3O(y); M can be the oxides of Mg, Ce, Gd, Yb, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and Te, as well as Li, Na, K, Ca, Sr, and La carbonates. Temperature dependence of the electrical resistance was measured down to about 80 K. Attention is given to the influence of ionic radius and the valence of the M species.

Low-cost, high-strength Fe--Ni--Cr alloys for high temperature exhaust valve application

DOEpatents

Muralidharan, Govindarajan

2017-09-05

An Fe--Ni--Cr alloy is composed essentially of, in terms of wt. %: 2.4 to 3.7 Al, up to 1.05 Co, 14.8 to 15.9 Cr, 25 to 36 Fe, up to 1.2 Hf, up to 4 Mn, up to 0.6 Mo, up to 2.2 Nb, up to 1.05 Ta, 1.9 to 3.6 Ti, up to 0.08 W, up to 0.03 Zr, 0.18 to 0.27 C, up to 0.0015 N, balance Ni, wherein, in terms of atomic percent: 8.5.ltoreq.Al+Ti+Zr+Hf+Ta.ltoreq.11.5, 0.53.ltoreq.Al/(Al+Ti+Zr+Hf+Ta).ltoreq.0.65, and 0.16.ltoreq.Cr/(Fe+Ni+Cr+Mn).ltoreq.0.21, the alloy being essentially free of Cu, Si, and V.

Partitioning of Mo, P and other siderophile elements (Cu, Ga, Sn, Ni, Co, Cr, Mn, V, and W) between metal and silicate melt as a function of temperature and silicate melt composition

NASA Astrophysics Data System (ADS)

Righter, K.; Pando, K. M.; Danielson, L.; Lee, Cin-Ty

2010-03-01

Metal-silicate partition coefficients can provide information about the earliest differentiation histories of terrestrial planets and asteroids. Systematic studies of the effects of key parameters such as temperature and melt composition are lacking for many elements. In particular, data for Mo is scarce, but given its refractory nature, is of great value in interpreting metal-silicate equilibrium. Two series of experiments have been carried out to study Mo and P partitioning between Fe metallic liquid and basaltic to peridotitic silicate melt, at 1 GPa and temperatures between 1500 and 1900 °C. Because the silicate melt utilized was natural basalt, there are also measurable quantities of 9 other siderophile elements (Ni, Co, W, Sn, Cu, Mn, V, Cr, Ga and Zn). The Ni and Co data can be used to assess consistency with previous studies. In addition, the new data also allow a first systematic look at the temperature dependence of Cu, Ga, Sn, Cr, Mn V and W for basaltic to peridotitic melts. Many elements exhibit an increase in siderophile behavior at higher temperature, contrary to popular belief, but consistent with predictions from thermodynamics. Using these new data we examine DMomet/sil and DPmet/sil in detail and show that increasing temperature causes a decrease in the former and an increase in the latter, whereas both increase with MgO content of the silicate melt. The depletions of Mo and P in the mantle of the Earth can be explained by metal-silicate equilibrium at magma ocean conditions — both elements are satisfied at PT conditions of an intermediate depth magma ocean for the Earth 22.5 GPa and 2400 °C.

Indented Cu2MoS4 nanosheets with enhanced electrocatalytic and photocatalytic activities realized through edge engineering.

PubMed

Chen, Bang-Bao; Ma, De-Kun; Ke, Qing-Ping; Chen, Wei; Huang, Shao-Ming

2016-03-07

Edges often play a role as active centers for catalytic reactions in some nanomaterials. Therefore it is highly desirable to enhance catalytic activity of a material through modulating the microstructure of the edges. However, the study associated with edge engineering is less investigated and still at its preliminary stage. Here we report that Cu2MoS4 nanosheets with indented edges can be fabricated through a simple chemical etching route at room temperature, using Cu2MoS4 nanosheets with flat ones as sacrifice templates. Taking the electrocatalytic hydrogen evolution reaction (HER), photocatalytic degradation of rhodamine B (RhB) and conversion of benzyl alcohol as examples, the catalytic activity of Cu2MoS4 indented nanosheets (INSs) obtained through edge engineering was comparatively studied with those of Cu2MoS4 flat nanosheets (FNSs) without any modification. The photocatalytic tests revealed that the catalytic active sites of Cu2MoS4 nanosheets were associated with their edges rather than basal planes. Cu2MoS4 INSs were endowed with larger electrochemically active surface area (ECSA), more active edges and better hydrophilicity through the edge engineering. As a result, the as-fabricated Cu2MoS4 INSs exhibited an excellent HER activity with a small Tafel slope of 77 mV dec(-1), which is among the best records for Cu2MoS4 catalysts. The present work demonstrated the validity of adjusting catalytic activity of the material through edge engineering and provided a new strategy for designing and developing highly efficient catalysts.

Calcined Mg-Fe layered double hydroxide as an absorber for the removal of methyl orange

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

Peng, Chao; State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070; Dai, Jing

2015-05-15

In this work, methyl orange (MO) was effectively removed from aqueous solution with the calcined product of hydrothermal synthesized Mg/Fe layered double hydroxide (Mg/Fe-LDH). The structure, composition, morphology and textural properties of the Mg/Fe-LDH before and after adsorption were characterized by X-ray diffraction, Fourier transformation infrared spectroscopy, transmission electron microscopy, nitrogen adsorption apparatus and X-ray photoelectron spectroscopy. It was confirmed that MO had been absorbed by calcined Mg/Fe-LDH which had strong interactions with MO. The adsorption of MO onto the Mg/Fe-LDH was systematically investigated by batch tests. The adsorption capacity of the Mg/Fe-LDH toward MO was found to be 194.9more » mg • g{sup −1}. Adsorption kinetics and isotherm studies revealed that the adsorption of MO onto Mg/Fe-LDH was a spontaneous and endothermic process. These results indicate that Mg/Fe-LDH is a promising material for the removal of MO.« less

Screened hybrid functional applied to 3d0→3d8 transition-metal perovskites LaMO3 (M = Sc-Cu): Influence of the exchange mixing parameter on the structural, electronic, and magnetic properties

NASA Astrophysics Data System (ADS)

He, Jiangang; Franchini, Cesare

2012-12-01

We assess the performance of the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid density functional scheme applied to the perovskite family LaMO3 (M = Sc-Cu) and discuss the role of the mixing parameter α [which determines the fraction of exact Hartree-Fock exchange included in the density functional theory (DFT) exchange-correlation functional] on the structural, electronic, and magnetic properties. The physical complexity of this class of compounds, manifested by the largely varying electronic characters (band/Mott-Hubbard/charge-transfer insulators and metals), magnetic orderings, structural distortions (cooperative Jahn-Teller-type instabilities), as well as by the strong competition between localization/delocalization effects associated with the gradual filling of the t2g and eg orbitals, symbolize a critical and challenging case for theory. Our results indicate that HSE is able to provide a consistent picture of the complex physical scenario encountered across the LaMO3 series and significantly improve the standard DFT description. The only exceptions are the correlated paramagnetic metals LaNiO3 and LaCuO3, which are found to be treated better within DFT. By fitting the ground-state properties with respect to α, we have constructed a set of “optimum” values of α from LaScO3 to LaCuO3: it is found that the optimum mixing parameter decreases with increasing filling of the d manifold (LaScO3: 0.25; LaTiO3 and LaVO3: 0.10-0.15; LaCrO3, LaMnO3, and LaFeO3: 0.15; LaCoO3: 0.05; LaNiO3 and LaCuO3: 0). This trend can be nicely correlated with the modulation of the screening and dielectric properties across the LaMO3 series, thus providing a physical justification to the empirical fitting procedure. Finally, we show that by using this set of optimum mixing parameter, HSE predict dielectric constants in very good agreement with the experimental ones.

Molybdenite Mineral Evolution: A Study Of Trace Elements Through Time

NASA Astrophysics Data System (ADS)

McMillan, M. M.; Downs, R. T.; Stein, H. J.; Zimmerman, A.; Beitscher, B. A.; Sverjensky, D. A.; Papineau, D.; Armstrong, J. T.; Hazen, R. M.

2010-12-01

Mineral evolution explores changes through time in Earth’s near-surface mineralogy, including diversity of species, relative abundances of species, and compositional ranges of major, minor and trace elements. Such studies elucidate the co-evolution of the geosphere and biosphere. Accordingly, we investigated trace and minor elements in molybdenite (MoS2) with known ages from 3 billion years to recent. Molybdenite, the commonest mineral of Mo, may prove to be a useful case study as a consequence of its presence in Earth’s early history, the effects of oxidation on Mo mobility, and the possible role of Mo mineral coevolution with biology via its role in the nitrogen fixation enzyme nitrogenase. We employed ICPMS, SEM and electron microprobe analyses to detect trace and minor elements. We detected significant amounts of Mn and Cu (~100 ppm) and greater amounts of Fe, W, and Re (to ~4000 ppm). Molybdenites commonly contain micro inclusions, resulting in local concentrations in otherwise homogeneous samples. Inhomogeneities in Fe, Zn and Sn concentrations, for example, point to the presence of pyrite, sphalerite and cassiterite inclusions, respectively. Analyses examined as a function of time reveal that samples containing significant concentrations (>200 ppm, compared to average values < 100 ppm) of W and Re formed primarily within the last billion years. These trends may reflect changes in the mobility of W and Re in oxic hydrothermal fluids at shallow crustal conditions following the Great Oxidation Event.

Positron Annihilation Spectroscopy Characterization of Nanostructural Features in Reactor Steels

NASA Astrophysics Data System (ADS)

Glade, Stephen; Wirth, Brian; Asoka-Kumar, Palakkal; Sterne, Philip; Alinger, Matthew; Odette, George

2004-03-01

Irradiation embrittlement in nuclear reactor pressure vessel steels results from the formation of a high number density of nanometer sized copper rich precipitates and sub-nanometer defect-solute clusters. We present results of study to characterize the size and compositions of simple binary and ternary Fe-Cu-Mn model alloys and more representative Fe-Cu-Mn-Ni-Si-Mo-C reactor pressure vessel steels using positron annihilation spectroscopy (PAS). Using a recently developed spin-polarized PAS technique, we have also measured the magnetic properties of the nanometer-sized copper rich precipitates. Mn retards the precipitation kinetics and inhibits large vacancy cluster formation, suggesting a strong Mn-vacancy interaction which reduces radiation enhanced diffusion. The spin-polarized PAS measurements reveal the non-magnetic nature of the copper precipitates, discounting the notion that the precipitates contain significant quantities of Fe and providing an upper limit of at most a few percent Fe in the precipitates. PAS results on oxide dispersion-strengthened steel for use in fusion reactors will also be presented. Part of this work was performed under the auspices of the US Department of Energy by the University of California, Lawrence Livermore National Laboratory, under contract No. W-7405-ENG-48 with partial support provided from Basic Energy Sciences, Division of Materials Science.

NifX and NifEN exchange NifB cofactor and the VK-cluster, a newly isolated intermediate of the iron-molybdenum cofactor biosynthetic pathway.

PubMed

Hernandez, Jose A; Igarashi, Robert Y; Soboh, Basem; Curatti, Leonardo; Dean, Dennis R; Ludden, Paul W; Rubio, Luis M

2007-01-01

The iron-molybdenum cofactor of nitrogenase (FeMo-co) is synthesized in a multistep process catalysed by several Nif proteins and is finally inserted into a pre-synthesized apo-dinitrogenase to generate mature dinitrogenase protein. The NifEN complex serves as scaffold for some steps of this synthesis, while NifX belongs to a family of small proteins that bind either FeMo-co precursors or FeMo-co during cofactor synthesis. In this work, the binding of FeMo-co precursors and their transfer between purified Azotobacter vinelandii NifX and NifEN proteins was studied to shed light on the role of NifX on FeMo-co synthesis. Purified NifX binds NifB cofactor (NifB-co), a precursor to FeMo-co, with high affinity and is able to transfer it to the NifEN complex. In addition, NifEN and NifX exchange another [Fe-S] cluster that serves as a FeMo-co precursor, and we have designated it as the VK-cluster. In contrast to NifB-co, the VK-cluster is electronic paramagnetic resonance (EPR)-active in the reduced and the oxidized states. The NifX/VK-cluster complex is unable to support in vitro FeMo-co synthesis in the absence of NifEN because further processing of the VK-cluster into FeMo-co requires the simultaneous activities of NifEN and NifH. Our in vitro studies suggest that the role of NifX in vivo is to serve as transient reservoir of FeMo-co precursors and thus help control their flux during FeMo-co synthesis.

High-pressure behavior of cuprospinel CuFe 2O 4: Influence of the Jahn-Teller effect on the spinel structure

DOE PAGES

Kyono, Atsushi; Gramsch, Stephen A.; Nakamoto, Yuki; ...

2015-08-14

The Jahn-Teller-effect at Cu 2+ in cuprospinel CuFe 2O 4 was investigated using high-pressure, single crystal synchrotron x-ray diffraction (XRD) techniques at beamline BL10A at the Photon Factory, KEK, Japan. Six data sets were collected in the pressure range from ambient to 5.9 GPa at room temperature. Structural refinements based on the data were performed at 0.0, 1.8, 2.7, and 4.6 GPa. The unit cell volume of cuprospinel decreases continuously from 590.8 (6) Å 3 to 579.5 (8) Å 3 up to 3.8 GPa. Leastsquares fitting to a third-order Birch-Murnaghan equation of state yields zero-pressure volume V 0 = 590.7more » (1) Å 3 and bulk modulus K 0 = 188.1 (4.4) GPa with K’ fixed at 4.0. The crystal chemical composition determined by electron-probe analysis and x-ray site-occupancy refinement is represented as [Cu 0.526Fe 0.474] [6][Cu 0.074Fe 1.926]O 4. Most of the Cu 2+ are preferentially distributed onto the tetrahedral (T) site of the spinel structure. At 4.6 GPa, a cubic-tetragonal phase transition is indicated by a splitting of the a axis of the cubic structure into a smaller a axis and a longer c axis, with unit cell parameters a = 5.882 (1) Å and c = 8.337 (1) Å. The tetragonal crystal structure with space group I4 1/amd was refined to R1 = 0.0182 and wR2 = 0.0134 using observed 35 x-ray reflections. At the T site, the tetrahedral O-T-O bond angles along the c-axis direction of the unit cell decreases slightly from 109.47 ° to 108.7 (4) °, which generates a stretched tetrahedral geometry along the c-axis. The cubic-totetragonal transition induced by the Jahn-Teller effect at Cu 2+ is attributable to the angular distortion at the tetrahedral site. At the octahedral (M) site, on the other hand, the two M-O bonds parallel to the caxis are shortened with respect to the four M-O bonds parallel to the ab-plane, which are lengthened as a result of the phase transition, leading to a compressed octahedral geometry along the c-axis. With the competing distortions between the stretched tetrahedron and the compressed octahedron along the c-axis, the a unit cell parameter is shortened with respect to the c unit cell parameter, giving a c/a ratio slightly greater than unity as referred to cubic lattice (c/a = 1.002). The c/a value increases to 1.007 with pressure, suggesting a further evolution of the stretched tetrahedron and the compressed octahedron. The variation of c/a ratio of the cuprospinel is similar to that observed in the tetragonally distorted cuprospinel with Cu 2+ fully occupying the octahedral site of the structure.« less

Nanoamorphous carbon-based photonic crystal infrared emitters

DOEpatents

Norwood, Robert A [Tucson, AZ; Skotheim, Terje [Tucson, AZ

2011-12-13

Provided is a tunable radiation emitting structure comprising: a nanoamorphous carbon structure having a plurality of relief features provided in a periodic spatial configuration, wherein the relief features are separated from each other by adjacent recessed features, and wherein the nanoamorphous carbon comprises a total of from 0 to 60 atomic percent of one or more dopants of the dopant group consisting of: transition metals, lanthanoids, electro-conductive carbides, silicides and nitrides. In one embodiment, a dopant is selected from the group consisting of: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La and other lanthanides, Hf, Ta, W, Rh, Os, Ir, Pt, Au, and Hg. In one embodiment, a dopant is selected from the group consisting of: electro-conductive carbides (like Mo.sub.2C), silicides (like MoSi.sub.2) and nitrides (like TiN).

An amorphous FeMoS4 nanorod array toward efficient hydrogen evolution electrocatalysis under neutral conditions.

PubMed

Ren, Xiang; Wang, Weiyi; Ge, Ruixiang; Hao, Shuai; Qu, Fengli; Du, Gu; Asiri, Abdullah M; Wei, Qin; Chen, Liang; Sun, Xuping

2017-08-08

It is highly attractive to develop efficient hydrogen-evolving electrocatalysts under neutral conditions. In this communication, we report an amorphous FeMoS 4 nanorod array on carbon cloth (FeMoS 4 NRA/CC) prepared by hydrothermal treatment of an FeOOH nanorod array on carbon cloth (FeOOH NRA/CC) in (NH 4 ) 2 MoS 4 solution. As a 3D electrode for hydrogen evolution electrocatalysis, this FeMoS 4 NRA/CC demonstrates superior catalytic activity and strong long-term electrochemical durability in 1.0 M phosphate buffered saline (pH: 7). It needs an overpotential of 204 mV to drive a geometrical current density of 10 mA cm -2 , which is 450 mV less than that for FeOOH NRA/CC. Density functional theory calculations suggest that FeMoS 4 has a more favourable hydrogen adsorption free energy than FeOOH.

Molecular adsorption properties of CO and H2O on Au-, Cu-, and AuxCuy-doped MoS2 monolayer

NASA Astrophysics Data System (ADS)

Kadioglu, Yelda; Gökoğlu, Gökhan; Üzengi Aktürk, Olcay

2017-12-01

In this study, we investigate the adsorption properties of Au, Cu, and AuxCuy nanoclusters on MoS2 sheet and the interactions of the adsorbed systems with CO and H2O molecules by using first principles calculations. Results indicate that Au, Cu, or AuxCuy strongly binds to MoS2 monolayer resulting in enhanced chemical activity and sensitivity toward CO and H2O molecules compared to bare MoS2 monolayer. Although both CO and H2O molecules bind weakly to pristine MoS2 monolayer, CO strongly binds to MoS2 sheet in the presence of Au, Cu atoms or AuxCuy clusters. Semiconductor MoS2 monolayer turns into metal upon Au or Cu adsorption. AuxCuy nanocluster adsorption decreases the band gap of MoS2 monolayer acting as a n-type dopant. AuxCuy-doped MoS2 systems have improved adsorption properties for CO and H2O molecules, so the conclusions provided in this study can be useful as a guide for next generation device modeling.

Partitioning of V, Mn, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb, and Bi between sulfide phases and hydrous basanite melt at upper mantle conditions

NASA Astrophysics Data System (ADS)

Li, Yuan; Audétat, Andreas

2012-11-01

The partitioning of 15 major to trace metals between monosulfide solid solution (MSS), sulfide liquid (SL) and mafic silicate melt (SM) was determined in piston-cylinder experiments performed at 1175-1300 °C, 1.5-3.0 GPa and oxygen fugacities ranging from 3.1 log units below to 1.0 log units above the quartz-fayalite-magnetite fO2 buffer, which conditions are representative of partial melting in the upper mantle in different tectonic settings. The silicate melt was produced by partial melting of a natural, amphibole-rich mantle source rock, resulting in hydrous (˜5 wt% H2O) basanitic melts similar to low-degree partial melts of metasomatized mantle, whereas the major element composition of the starting sulfide (˜52 wt% Fe; 39 wt% S; 7 wt% Ni; 2 wt% Cu) was similar to the average composition of sulfides in this environment. SL/SM partition coefficients are high (≥100) for Au, Ni, Cu, Ag, Bi, intermediate (1-100) for Co, Pb, Sn, Sb (±As, Mo), and low (≤1) for the remaining elements. MSS/SM partition coefficients are generally lower than SL/SM partition coefficients and are high (≥100) for Ni, Cu, Au, intermediate (1-100) for Co, Ag (±Bi, Mo), and low (≤1) for the remaining elements. Most sulfide-silicate melt partition coefficients vary as a function of fO2, with Mo, Bi, As (±W) varying by a factor >10 over the investigated fO2 range, Sb, Ag, Sn (±V) varying by a factor of 3-10, and Pb, Cu, Ni, Co, Au, Zn, Mn varying by a factor of 3-10. The partitioning data were used to model the behavior of Cu, Au, Ag, and Bi during partial melting of upper mantle and during fractional crystallization of primitive MORB and arc magmas. Sulfide phase relationships and comparison of the modeling results with reported Cu, Au, Ag, and Bi concentrations from MORB and arc magmas suggest that: (i) MSS is the dominant sulfide in the source region of arc magmas, and thus that Au/Cu ratios in the silicate melt and residual sulfides may decrease with increasing degree of partial melting, (ii) both MSS and sulfide liquid are precipitated during fractional crystallization of MORB, and (iii) fractional crystallization of arc magmas is strongly dominated by MSS.

Evaluation of metal content in perch of the Ob River basin

NASA Astrophysics Data System (ADS)

Osipova, N. A.; Stepanova, K. D.; Matveenko, I. A.

2015-11-01

The geochemical features of river perch in the River Ob basin have been studied (the upper and middle reaches of the Ob River and the lower reach of the Tom River). The contents of Ag, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sn, W, Zn, Hg in perch's soft tissue are defined by the methods of ICP AES and stripping voltammetry, that of mercury in bones - by the atomic absorption method using mercury analyzer PA-915+. The distribution series of metal absolute concentrations in perch's soft tissue from the Ob River basin are plotted: Fe > Zn > Cu > Mn, typical for uncontaminated or slightly metal contaminated water bodies. In soft tissue of the studied samples the metal content does not exceed the permissible values. The mercury content in bones of studied samples is in the range 0,036-0,556 mg/kg. The mercury concentration is higher in bones in comparison with soft tissue in all samples.

Assessment of heavy metal contamination in intertidal gastropod and bivalve shells from central Arabian Gulf coastline, Saudi Arabia

NASA Astrophysics Data System (ADS)

El-Sorogy, Abdelbaset S.; Youssef, Mohamed

2015-11-01

In order to assess pollutants and impact of environmental changes along the Saudi Arabian Gulf coast, forty specimens of gastropod and bivalve shells belonging to Diodora funiculata, Lunella coronata, Cerithium caeruleum, Barbatia parva, Pinctada margaritifera, Amiantis umbonella, Acrosterigma assimile and Asaphis violascens from five localities are selected for Fe, Cu, Pb, Mn, Cd, Se, As, Co, B, Cr, Hg, Mo analysis. The analysis indicated that heavy metal values (except Fe) were less than those recorded in molluscan shells from Gulf of Oman, Red Sea and Indian Ocean. D. funiculate, L. coronata, B. parva and P. margaritifera are good accumulators of Cu, As, Cr. The other species gave a nearly constant concentration in all the studied areas. Al Jubail coast recorded the highest heavy metal concentrations (except Mn at Ras Al-Ghar and Se at Al Jubail industrial city). Heavy metal contamination is mostly attributed to anthropogenic sources, especially effluents from petrochemical industries, sewage and desalination plants.

Multiple diffraction in an icosahedral Al-Cu-Fe quasicrystal

NASA Astrophysics Data System (ADS)

Fan, C. Z.; Weber, Th.; Deloudi, S.; Steurer, W.

2011-07-01

In order to reveal its influence on quasicrystal structure analysis, multiple diffraction (MD) effects in an icosahedral Al-Cu-Fe quasicrystal have been investigated in-house on an Oxford Diffraction four-circle diffractometer equipped with an Onyx™ CCD area detector and MoKα radiation. For that purpose, an automated approach for Renninger scans (ψ-scans) has been developed. Two weak reflections were chosen as the main reflections (called P) in the present measurements. As is well known for periodic crystals, it is also observed for this quasicrystal that the intensity of the main reflection may significantly increase if the simultaneous (H) and the coupling (P-H) reflections are both strong, while there is no obvious MD effect if one of them is weak. The occurrence of MD events during ψ-scans has been studied based on an ideal structure model and the kinematical MD theory. The reliability of the approach is revealed by the good agreement between simulation and experiment. It shows that the multiple diffraction effect is quite significant.

Electrochemical hydrogen storage alloys and batteries fabricated from Mg containing base alloys

DOEpatents

Ovshinsky, Stanford R.; Fetcenko, Michael A.

1996-01-01

An electrochemical hydrogen storage material comprising: (Base Alloy).sub.a M.sub.b where, Base Alloy is an alloy of Mg and Ni in a ratio of from about 1:2 to about 2:1, preferably 1:1; M represents at least one modifier element chosen from the group consisting of Co, Mn, Al, Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb, La, Mm, and Ca; b is greater than 0.5, preferably 2.5, atomic percent and less than 30 atomic percent; and a+b=100 atomic percent. Preferably, the at least one modifier is chosen from the group consisting of Co, Mn, Al, Fe, and Cu and the total mass of the at least one modifier element is less than 25 atomic percent of the final composition. Most preferably, the total mass of said at least one modifier element is less than 20 atomic percent of the final composition.

Transcriptomic and physiological characterization of the fefe mutant of melon (Cucumis melo) reveals new aspects of iron–copper crosstalk

PubMed Central

Waters, Brian M.; McInturf, Samuel A.; Amundsen, Keenan

2014-01-01

Summary Iron (Fe) and copper (Cu) homeostasis are tightly linked across biology. In previous work, Fe deficiency interacted with Cu regulated genes and stimulated Cu accumulation. The C940-fe (fefe) Fe uptake mutant of melon (Cucumis melo) was characterized, and the fefe mutant was used to test whether Cu deficiency could stimulate Fe uptake. Wild type and fefe mutant transcriptomes were determined by RNA-seq under Fe and Cu deficiency. FeFe regulated genes included core Fe uptake, metal homeostasis, and transcription factor genes. Numerous genes were regulated by both Fe and Cu. The fefe mutant was rescued by high Fe or by Cu deficiency, which stimulated ferric-chelate reductase activity, FRO2 expression, and Fe accumulation. Accumulation of Fe in Cu deficient plants was independent of the normal Fe uptake system. One of the four FRO genes in the melon and cucumber (Cucumis sativus) genomes was Fe regulated, and one was Cu regulated. Simultaneous Fe and Cu deficiency synergistically upregulated Fe uptake gene expression. Overlap in Fe and Cu deficiency transcriptomes highlights the importance of Fe– Cu crosstalk in metal homeostasis. The fefe gene is not orthologous to FIT, thus identification of this gene will provide clues to help understand regulation of Fe uptake in plants. PMID:24975482

Effects of alloying elements (Mn, Co, Al, W, Sn, B, C and S) on biodegradability and in vitro biocompatibility of pure iron.

PubMed

Liu, B; Zheng, Y F

2011-03-01

Pure iron was determined to be a valid candidate material for biodegradable metallic stents in recent animal tests; however, a much faster degradation rate in physiological environments was desired. C, Mn, Si, P, S, B, Cr, Ni, Pb, Mo, Al, Ti, Cu, Co, V and W are common alloying elements in industrial steels, with Cr, Ni, Mo, Cu, Ti, V and Si being acknowledged as beneficial in enhancing the corrosion resistance of iron. The purpose of the present work (using Fe-X binary alloy models) is to explore the effect of the remaining alloying elements (Mn, Co, Al, W, B, C and S) and one detrimental impurity element Sn on the biodegradability and biocompatibility of pure iron by scanning electron microscopy, X-ray diffraction, metallographic observation, tensile testing, microhardness testing, electrochemical testing, static (for 6 months) and dynamic (for 1 month with various dissolved oxygen concentrations) immersion testing, cytotoxicity testing, hemolysis and platelet adhesion testing. The results showed that the addition of all alloying elements except for Sn improved the mechanical properties of iron after rolling. Localized corrosion of Fe-X binary alloys was observed in both static and dynamic immersion tests. Except for the Fe-Mn alloy, which showed a significant decrease in corrosion rate, the other Fe-X binary alloy corrosion rates were close to that of pure iron. It was found that compared with pure iron all Fe-X binary alloys decreased the viability of the L929 cell line, none of experimental alloying elements significantly reduced the viability of vascular smooth muscle cells and all the elements except for Mn increased the viability of the ECV304 cell line. The hemolysis percentage of all Fe-X binary alloy models were less than 5%, and no sign of thrombogenicity was observed. In vitro corrosion and the biological behavior of these Fe-X binary alloys are discussed and a corresponding mechanism of corrosion of Fe-X binary alloys in Hank's solution proposed. As a concluding remark, Co, W, C and S are recommended as alloying elements for biodegradable iron-based biomaterials. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

MoS{sub 2} nanosheet functionalized with Cu nanoparticles and its application for glucose detection

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

Huang, Jingwei; Dong, Zhengping; Gansu Provincial Engineering Laboratory for Chemical Catalysis, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000

Graphical abstract: - Highlights: • First report on decorating MoS{sub 2} nanosheet with Cu nanoparticles by chemical reduction. • Cu nanoparticles were uniformly decorated on MoS{sub 2} nanosheet. • Glucose biosensor based on copper nanoparticles-MoS{sub 2} nanosheet hybrid is fabricated. • The biosensor exhibits high sensitivity. - Abstract: For the first time, Cu nanoparticles were evenly decorated on MoS{sub 2} nanosheet by chemical reduction. The as-prepared Cu-MoS{sub 2} hybrid was characterized by atomic force microscope (AFM), Raman spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and then used to fabricate a non-enzymatic glucose sensor. The performance of our sensor wasmore » investigated by cyclic voltammetry and amperometric measurement in alkaline media. Electrochemical tests showed that Cu-MoS{sub 2} hybrid exhibited synergistic electrocatalytic activity on the oxidation of glucose with a high sensitivity of 1055 μA mM{sup −1} cm{sup −2} and a linear range up to 4 mM.« less

The oxidation state, and sulfur and Cu contents of arc magmas: implications for metallogeny

NASA Astrophysics Data System (ADS)

Richards, Jeremy P.

2015-09-01

Global data for measured Fe2O3/FeO ratios and Cu contents in unaltered volcanic and intrusive arc rocks indicate that, on average, they are slightly more oxidized than other magmas derived from depleted upper mantle (such as MORB), but contain similar Cu contents across their compositional ranges. Although Cu scatters to elevated values in some intermediate composition samples, the bulk of the data show a steady but gentle trend to lower concentrations with differentiation, reaching modal values of 50-100 ppm in andesitic rocks. These data suggest that Cu is mildly compatible during partial melting and fractionation processes, likely reflecting minor degrees of sulfide saturation throughout the magmatic cycle. However, the volume of sulfides must be small such that significant proportions of the metal content remain in the magma during fractionation to intermediate compositions. Previous studies have shown that andesitic magmas containing 50 ppm Cu can readily form large porphyry-type Cu deposits upon emplacement in the upper crust. A review of the literature suggests that the elevated oxidation state in the asthenospheric mantle wedge source of arc magmas (ΔFMQ ≈ + 1 ± 1) derives from the subduction of seawater-altered and oxidized oceanic crust, and is transmitted into the mantle wedge via prograde metamorphic dehydration fluids carrying sulfate and other oxidizing components. Progressive hydration and oxidation of the mantle wedge may take up to 10 m.y. to reach a steady state from the onset of subduction, explaining the rarity of porphyry deposits in primitive island arcs, and the late formation of porphyries in continental arc magmatic cycles. Magmas generated from this metasomatized and moderately oxidized mantle source will be hydrous basalts containing high concentrations of sulfur, mainly dissolved as sulfate or sulfite. Some condensed sulfides (melt or minerals) may be present due to the high overall fS2, despite the moderately high oxidation state. These sulfides may retain some highly siderophile elements in the source, but are unlikely to be sufficiently voluminous to significantly affect the budget of more modestly sulfide-compatible and more abundant elements such as Cu and Mo. These primary magmas can therefore be considered to be largely Cu-Mo-undepleted, although highly siderophile elements such as Au and platinum group elements (PGE) may be depleted unless no sulfides remain in the source. The latter condition seems unlikely during active subduction because of the continuous flux of fresh sulfur from the slab, but may occur during post-subduction re-melting (leading to potentially Au-rich post-subduction porphyry and alkalic-type epithermal systems). Lower crustal differentiation of main-stage arc magmas results in some loss of Cu to residual or cumulate sulfides, but again the amount appears to be minor, and does not drastically reduce the Cu content of derivative intermediate-composition melts. Fractionation and devolatilization affect the oxidation state of the magma in competing ways, but, while crystallization and segregation of Fe3 +-rich magnetite can cause reduction in reduced to moderately oxidized evolved magmas, this effect appears to be outweighed by the oxidative effects of degassing reduced or weakly oxidized gaseous species such as H2, H2S, and SIVO2, and preferential solvation and removal of Fe2 + in saline hydrothermal fluids. Consequently, most arc magmatic suites show slight increases in oxidation state during differentiation, reaching typical values of ΔFMQ = + 1 to + 2. This oxidation state is significant, because it corresponds to the transition from dissolved sulfide to sulfate dominance in magmas. It has been shown that Cu and Au solubilities in silicate magma increase up to this level (ΔFMQ ≈ + 1), but while Cu solubility continues to increase at higher oxidation states, Au shows a precipitous drop as sulfide, which solvates Au in the melt, is converted to sulfate. This may explain the somewhat restricted distribution of Au-rich porphyry Cu deposits, but the general association of porphyry Cu deposits with relatively oxidized magmas. Exsolution of a saline, high temperature aqueous fluid enables metals to partition from the magma into a highly mobile volatile phase. Sulfur also partitions strongly into this fluid phase, predominantly as SO2 at ΔFMQ = + 1 to + 2. However, as the fluid cools below 400 °C, SIVO2 disproportionates to form reduced H2S- II and oxidized H2SVIO4. The H2S bonds with metals in solution to precipitate as Cu- and Mo-sulfides, while the H2SO4 (and HCl) generates progressively acidic wallrock alteration (phyllic, argillic, advanced argillic). Gold may precipitate with early Cu/Mo-sulfides, but some may also stay in solution as bisulfide complexes, eventually reaching the epithermal environment. Thus, three components, [S], [H2O], and fO2 work together throughout subduction and arc magmatic processes to transport chalcophile and siderophile metals from the mantle into the upper crust, where they may be concentrated by hydrothermal processes to form ore deposits. These processes are far from 100% efficient, and metals (especially highly siderophile elements such as Au and PGE) may be left behind at various stages of the passage of arc magmas through the lithosphere, where they may form potentially metalliferous source rocks for partial melts and subsequent magmatic-hydrothermal ore deposits generated during later tectonomagmatic events.

A Comparative Study of Hydrodeoxygenation of Furfural Over Fe/Pt(111) and Fe/Mo 2C Surfaces

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

Wan, Weiming; Jiang, Zhifeng; Chen, Jingguang G.

It is desirable to convert biomass-derived furfural to 2-methylfuran through the hydrodeoxygenation (HDO) reaction using an inexpensive catalyst with high stability. In this work, Mo 2C was used as an alternative substrate to replace precious Pt to support monolayer Fe for the HDO reaction of furfural. The HDO activity and stability of Fe/Pt(111) and Fe/Mo 2C/Mo(110) surfaces were compared. Density functional theory calculations and vibrational spectroscopy results indicated that both surfaces bonded to furfural with similar adsorption geometries and should be active toward the furfural HDO reaction. Temperature programmed desorption experiments confirmed a similar HDO activity between the two surfaces,more » with Fe/Mo 2C/Mo(110) being more thermally stable than Fe/Pt(111). As a result, the combined theoretical and experimental results demonstrated that Fe/Mo 2C should be a promising non-precious metal catalyst for the HDO reaction of furfural to produce 2-methylfuran.« less

A Comparative Study of Hydrodeoxygenation of Furfural Over Fe/Pt(111) and Fe/Mo 2C Surfaces

DOE PAGES

Wan, Weiming; Jiang, Zhifeng; Chen, Jingguang G.

2018-01-19

It is desirable to convert biomass-derived furfural to 2-methylfuran through the hydrodeoxygenation (HDO) reaction using an inexpensive catalyst with high stability. In this work, Mo 2C was used as an alternative substrate to replace precious Pt to support monolayer Fe for the HDO reaction of furfural. The HDO activity and stability of Fe/Pt(111) and Fe/Mo 2C/Mo(110) surfaces were compared. Density functional theory calculations and vibrational spectroscopy results indicated that both surfaces bonded to furfural with similar adsorption geometries and should be active toward the furfural HDO reaction. Temperature programmed desorption experiments confirmed a similar HDO activity between the two surfaces,more » with Fe/Mo 2C/Mo(110) being more thermally stable than Fe/Pt(111). As a result, the combined theoretical and experimental results demonstrated that Fe/Mo 2C should be a promising non-precious metal catalyst for the HDO reaction of furfural to produce 2-methylfuran.« less

Diamond and Unusual Minerals Discovered from the Chromitite in Polar Ural: A First Report

NASA Astrophysics Data System (ADS)

Yang, J.; Bai, W.; Fang, Q.; Meng, F.; Chen, S.; Zhang, Z.

2007-12-01

Ultrahigh pressure (UHP) minerals, such as diamond, coesite, and pseudomorphs of octahedral olivine, and as well as about 80 other mineral species have been recovered from podiform chromitites of the Luobusa ophiolite, southern Tibet, and a new mineral, Luobusaite (Fe0.82Si2), has been approved recently by CNMMN. The UHP minerals from Luobusa are controversial because they have not found in situ and because ophiolites are currently believed to form at shallow levels above oceanic spreading centers. More detailed study and experimental work are needed to understand the origin and significance of these unusual minerals and investigations of other ophiolites are needed to determine if such minerals occur elsewhere. For this purpose, we collected about 1500 kg of chromitite from two orebodies in an ultramafic body in the Polar Urals. Thus far, more than 60 different mineral species have been separated from these ores. The most exciting discovery is the common occurrence of diamond, a typical UHP mineral in the Luobusa chromitites. Diamonds from Ural chromitite are clear, colorless, well-developed crystals with octahedral morphology, generally 0.2-0.3 mm in size. Attached with the diamonds and perhaps also occurring as inclusions within them are many minerals as chromite, MnNiCrFe alloy, native Si and Ta, corundum, zircon, feldspar, garnet, moissanite, confirming their natural origin and suggesting a long residence time in the mantle. Other mineral group include: (1) native elements: Cr, W, Ni, Co, Si, Al and Ta; (2) carbides: SiC and WC; (3) alloys: Cr-Fe, Si-Al-Fe, Ni-Cu, Ag-Au, Ag-Sn, Fe-Si, Fe-P, and Ag-Zn-Sn; (4) oxides: NiCrFe, PbSn, REE, rutile and Si- bearing rutile, ilmenite, corundum, chromite, MgO, and SnO2; (5) silicates: kyanite, pseudomorphs of octahedral olivine, zircon, garnet, feldspar, and quartz,; (6) sulfides of Fe, Ni, Cu, Mo, Pb, Ab, AsFe, FeNi, CuZn, and CoFeNi; and (7) iron groups: native Fe, FeO, and Fe2O3. These minerals are very similar in composition and structure to those reported from the Luobusa chromitites. For examples, some spherules of native iron contain spherical inclusions of FeO, exactly like comparable grains in the Luobusa sample.

Adsorption of gas molecules on Cu impurities embedded monolayer MoS2: A first- principles study

NASA Astrophysics Data System (ADS)

Zhao, B.; Li, C. Y.; Liu, L. L.; Zhou, B.; Zhang, Q. K.; Chen, Z. Q.; Tang, Z.

2016-09-01

Adsorption of small gas molecules (O2, NO, NO2 and NH3) on transition-metal Cu atom embedded monolayer MoS2 was investigated by first-principles calculations based on the density-functional theory (DFT). The embedded Cu atom is strongly constrained on the sulfur vacancy of monolayer MoS2 with a high diffusion barrier. The stable adsorption geometry, charge transfer and electronic structures of these gas molecules on monolayer MoS2 embedded with transition-metal Cu atom are discussed in detail. It is found that the monolayer MoS2 with embedded Cu atom can effectively capture these gas molecules with high adsorption energy. The NH3 molecule acts as electron donor after adsorption, which is different from the other gas molecules (O2, NO, and NO2). The results suggest that MoS2-Cu system may be promising for future applications in gas molecules sensing and catalysis, which is similar to those of the transition-metal embedded graphene.

Antisite-disorder, magnetic and thermoelectric properties of Mo-rich Sr2Fe1-yMo1+yO6 (0 ≤y≤ 0.2) double perovskites.

PubMed

Popuri, Srinivasa R; Redpath, Debbie; Chan, Gavin; Smith, Ronald I; Cespedes, Oscar; Bos, Jan-Willem G

2015-06-21

Structure analysis using X-ray and neutron powder diffraction and elemental mapping has been used to demonstrate that nominal A-site deficient Sr(2-x)FeMoO(6-δ) (0 ≤x≤ 0.5) compositions form as Mo-rich Sr(2)Fe(1-y)Mo(1+y)O(6) (0 ≤y≤ 0.2) perovskites at high temperatures and under reducing atmospheres. These materials show a gradual transition from the Fe and Mo rock salt ordered double perovskite structure to a B-site disordered arrangement. Analysis of the fractions of B-O-B' linkages revealed a gradual increase in the number of Mo-O-Mo linkages at the expense of the ferrimagnetic (FIM) Fe-O-Mo linkages that dominate the y = 0 material. All samples contain about 10-15% antiferromagnetic (AF) Fe-O-Fe linkages, independent of the degree of B-site ordering. The magnetic susceptibility of the y = 0.2 sample is characteristic of a small domain ferrimagnet (T(c)∼ 250 K), while room temperature neutron powder diffraction demonstrated the presence of G-type AF ordering linked to the Fe-O-Fe linkages (m(Fe) = 1.25(7)μ(B)). The high temperature thermoelectric properties are characteristic of a metal with a linear temperature dependence of the Seebeck coefficient, S (for all y) and electrical resistivity ρ (y≥ 0.1). The largest thermoelectric power factor S(2)/ρ = 0.12 mW m(-1) K(-1) is observed for Sr(2)FeMoO(6) at 1000 K.

Method for fabricating uranium foils and uranium alloy foils

DOEpatents

Hofman, Gerard L [Downers Grove, IL; Meyer, Mitchell K [Idaho Falls, ID; Knighton, Gaven C [Moore, ID; Clark, Curtis R [Idaho Falls, ID

2006-09-05

A method of producing thin foils of uranium or an alloy. The uranium or alloy is cast as a plate or sheet having a thickness less than about 5 mm and thereafter cold rolled in one or more passes at substantially ambient temperatures until the uranium or alloy thereof is in the shape of a foil having a thickness less than about 1.0 mm. The uranium alloy includes one or more of Zr, Nb, Mo, Cr, Fe, Si, Ni, Cu or Al.

Electrochemistry of cations in diopsidic melt - Determining diffusion rates and redox potentials from voltammetric curves

NASA Technical Reports Server (NTRS)

Colson, Russell O.; Haskin, Larry A.; Crane, Daniel

1990-01-01

Results are presented on determinations of reduction potentials and their temperature dependence of selected ions in diopsidic melt, by using linear sweep voltammetry. Diffusion coefficients were measured for cations of Eu, Mn, Cr, and In. Enthalpies and entropies of reduction were determined for the cations V(V), Cr(3+), Mn(2+), Mn(3+), Fe(2+), Cu(2+), Mo(VI), Sn(IV), and Eu(3+). Reduction potentials were used to study the structural state of cations in the melt.

Micro-PIXE analysis of silicate reference standards

USGS Publications Warehouse

Czamanske, G.K.; Sisson, T.W.; Campbell, J.L.; Teesdale, W.J.

1993-01-01

The accuracy and precision of the University of Guelph proton microprobe have been evaluated through trace-element analysis of well-characterized silicate glasses and minerals, including BHVO-1 glass, Kakanui augite and hornblende, and ten other natural samples of volcanic glass, amphibole, pyroxene, and garnet. Using the 2.39 wt% Mo in a NIST steel as the standard, excellent precision and agreement between reported and analyzed abundances were obtained for Fe, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, and Nb. -from Authors

Double perovskite Sr2FeMoO6-xNx (x=0.3, 1.0) oxynitrides with anionic ordering

NASA Astrophysics Data System (ADS)

Retuerto, M.; de la Calle, C.; Martínez-Lope, M. J.; Porcher, F.; Krezhov, K.; Menéndez, N.; Alonso, J. A.

2012-01-01

Two new oxynitride double perovskites of composition Sr2FeMoO6-xNx (x=0.3, 1.0) have been synthesized by annealing precursor powders obtained by citrate techniques in flowing ammonia at 750 °C and 650 °C, respectively. The polycrystalline samples have been characterized by chemical analysis, x-ray and neutron diffraction (NPD), Mössbauer spectroscopy and magnetic measurements. They exhibit a tetragonal structure with a=5.5959(1) Å, c=7.9024(2) Å, V=247.46(2) Å3 for Sr2FeMoO5.7N0.3; and a=5.6202(2) Å, c=7.9102(4) Å, V=249.85(2) Å3 for Sr2FeMoO5N; space group I4/m, Z=2. The nitridation process seems to extraordinarily improve the long-range Fe/Mo ordering, achieving 95% at moderate temperatures of 750 °C. The analysis of high resolution NPD data, based on the contrast existing between the scattering lengths of O and N, shows that both atoms are located at (O,N)2 anion substructure corresponding to the basal ab plane of the perovskite structure, whereas the O1 site is fully occupied by oxygen atoms. The evolution of the and distances suggests a shift towards a configuration close to Fe4+(3d4, S=2):Mo5+(4d1, S=1/2). The magnetic susceptibility shows a ferrimagnetic transition with a reduced saturation magnetization compared to Sr2FeMoO6, due to the different nature of the magnetic double exchange interactions through Fe-N-Mo-N-Fe paths in contrast to the stronger Fe-O-Mo-O-Fe interactions. Also, the effect observed by low-temperature NPD seems to reduce the ordered Fe moments and enhance the Mo moments, in agreement with the evolution of the oxidation states, thus decreasing the saturation magnetization.

High temperature regenerative H.sub.2 S sorbents

NASA Technical Reports Server (NTRS)

Flytani-Stephanopoulos, Maria (Inventor); Gavalas, George R. (Inventor); Tamhankar, Satish S. (Inventor)

1988-01-01

Efficient, regenerable sorbents for removal of H.sub.2 S from high temperature gas streams comprise porous, high surface area particles. A first class of sorbents comprise a thin film of binary oxides that form a eutectic at the temperature of the gas stream coated onto a porous, high surface area refractory support. The binary oxides are a mixture of a Group VB or VIB metal oxide with a Group IB, IIB or VIII metal oxide such as a film of V-Zn-O, V-Cu-O, Cu-Mo-O, Zn-Mo-O or Fe-Mo-O coated on an alumina support. A second class of sorbents consist of particles of unsupported mixed oxides in the form of highly dispersed solid solutions of solid compounds characterized by small crystallite size, high porosity and relatively high surface area. The mixed oxide sorbents contain one Group IB, IIB or VIIB metal oxide such as copper, zinc or manganese and one or more oxides of Groups IIIA, VIB or VII such as aluminum, iron or molybdenum. The presence of iron or aluminum maintains the Group IB, IIB or VIIB metal in its oxidized state. Presence of molybdenum results in eutectic formation at sulfidation temperature and improves the efficiency of the sorbent.

Treatment of reverse osmosis (RO) concentrate by the combined Fe/Cu/air and Fenton process (1stFe/Cu/air-Fenton-2ndFe/Cu/air).

PubMed

Ren, Yi; Yuan, Yue; Lai, Bo; Zhou, Yuexi; Wang, Juling

2016-01-25

To decompose or transform the toxic and refractory reverse osmosis (RO) concentrate and improve the biodegradability, 1stFe/Cu/air-Fenton-2ndFe/Cu/air were developed to treat RO concentrate obtained from an amino acid production plant in northern China. First, their operating conditions were optimized thoroughly. Furthermore, 5 control experiments were setup to confirm the superiority of 1stFe/Cu/air-Fenton-2ndFe/Cu/air and synergistic reaction between Fe/Cu/air and Fenton. The results suggest that the developed method could obtain high COD removal (65.1%) and BOD5/COD ratio (0.26) due to the synergistic reaction between Fe/Cu/air and Fenton. Under the optimal conditions, the influent and effluent of 1stFe/Cu/air-Fenton-2ndFe/Cu/air and 5 control experiments were analyzed by using UV, FTIR, EEM and LC, which confirm the superiority of 1stFe/Cu/air-Fenton-2ndFe/Cu/air. Therefore, the developed method in this study is a promising process for treatment of RO concentrate. Copyright © 2015 Elsevier B.V. All rights reserved.

Molybdenum isotopes in modern marine hydrothermal Fe/Mn deposits: Implications for Archean and Paleoproterozoic Mo cycles

NASA Astrophysics Data System (ADS)

Goto, K. T.; Hein, J. R.; Shimoda, G.; Aoki, S.; Ishikawa, A.; Suzuki, K.; Gordon, G. W.; Anbar, A. D.

2016-12-01

Molybdenum isotope (δ98/95Mo) variations recorded in Archean and Paleoproterozoic Fe/Mn-rich sediments have been used to constrain ocean redox conditions at the time of deposition (Canfield et al., 2013 PNAS; Planavsky et al., 2014 Nat. Geo.; Kurzweil et al., 2015 GCA). However, except for hydrogenous Fe-Mn crusts (Siebert et al., 2003), δ98/95Mo variation of modern Fe and Mn oxide deposits has been poorly investigated. Marine hydrothermal systems are thought to be the major source of Fe and Mn in Archean and Paleoproterozoic Fe- and Mn-rich sediments. Hence, to accurately interpret Mo isotope data of those ancient sedimentary rocks, it is important to evaluate the possible influence of hydrothermally derived Mo on δ98/95Mo of modern Fe- and Mn-rich sediments. In this study, we analyzed Mo isotopic compositions of one hydrothermal Fe oxide and 15 Mn oxides from five different hydrothermal systems in the modern ocean. The Fe oxide is composed mainly of goethite, and has a δ98/95Mo of 0.7‰, which is 1.4‰ lighter than that of present-day seawater. The observed offset is similar to isotope fractionation observed during adsorption experiments of Mo on goethite (Δ98/95Mogoethite-solution = -1.4 ± 0.5%; Goldberg et al., 2009 GCA). The 15 hydrothermal Mn oxides show large variations in δ98/95Mo ranging from -1.7 to 0.5‰. However, most of the values are similar to those of modern hydrogenous Fe-Mn crusts (Siebert et al., 2003 EPSL), and fall within the range of estimated δ98/95Mo of Mn oxides precipitated from present-day seawater using the isotope offset reported from adsorption experiments (Δ98/95Mo = -2.7 ± 0.3‰; Wasylenki et al., 2008 GCA). These findings indicate that seawater is the dominant source of Mo for modern hydrothermal Fe and Mn deposits. However, the observed large variation indicates that the contribution Mo from local hydrothermal systems is not negligible. The oceanic Mo inventory during the Archean and Paleoproterozoic is thought to be much smaller than that of present-day (Scott et al., 2008 Nature). Hence, δ98/95Mo of Archean and Paleoproterozoic Fe- and Mn-rich sediments could be strongly influenced by hydrothermally derived Mo, which may contrast to modern hydrothermal deposits. Possible Archean and Paleoproterozoic Mo cycles constrained by these data will also be discussed.

Effects of molybdenum and cadmium on the oxidative damage and kidney apoptosis in Duck.

PubMed

Shi, Lele; Cao, Huabin; Luo, Junrong; Liu, Ping; Wang, Tiancheng; Hu, Guoliang; Zhang, Caiying

2017-11-01

Molybdenum (Mo) is an essential element for human beings and animals; however, high dietary intake of Mo can lead to adverse reactions. Cadmium (Cd) is one of the major transitional metals which has toxic effects in animals. To investigate the co-induced toxic effects of Mo and Cd on oxidative damage and kidney apoptosis in duck, 120 ducks were randomly divided into control group and 5 treatment groups which were treated with a commercial diet containing different dosages of Mo and Cd. Kidney samples were collected on the 60th and 120th days to determine the mRNA expression levels of ceruloplasmin (CP), metallothionein (MT), Bak-1, and Caspase-3 by quantitative RT-PCR. Additionally, we also determined the antioxidant activity indexes and contents of Mo, Cd, copper (Cu), iron (Fe), zinc (Zn), and selenium (Se) in serum. Meanwhile, ultrastructural changes of the kidney were observed. The results showed that glutathione reductase (GR) activity and CP level in serum were decreased in combination groups. In addition, the antioxidant indexes were decreased in co-treated groups compared with single treated groups. The mRNA expression levels of Bak-1 and Caspase-3 increased in co-treated groups. The mRNA expression level of CP in high-dose combination group was downregulated, while the mRNA expression of MT was upregulated except for low-dose Mo group. Additionally, in the later period the content of Cu in serum decreased in joint groups while the contents of Mo and Cd increased. In addition, ultrastructural changes showed mitochondrial crest fracture, swelling, deformed nuclei, and karyopyknosis in co-treated groups. Taken together, it was suggested that dietary Mo and Cd might lead to oxidative stress, kidney apoptosis and disturb homeostasis of trace elements in duck, and it showed a possible synergistic relationship between the two elements. Copyright © 2017 Elsevier Inc. All rights reserved.

Fate of a giant {Mo72Fe30}-type polyoxometalate cluster in an aqueous solution at higher temperature: understanding related Keplerate chemistry, from molecule to material.

PubMed

Mekala, Raju; Supriya, Sabbani; Das, Samar K

2013-09-03

When the giant icosahedral {Mo72Fe30} cluster containing compound [Mo72Fe30O252(CH3COO)12{Mo2O7(H2O)}2{H2Mo2O8(H2O)}(H2O)91]·150H2O (1) is refluxed in water for 36 h, it results in the formation of nanoiron molybdate, Fe2(MoO4)3, in the form of a yellow precipitate; this simple approach not only generates nanoferric molybdate at a moderate temperature but also helps to understand the stability of {Mo72Fe30} in terms of the linker-pentagon complementary relationship.

Optimal copper supply is required for normal plant iron deficiency responses

PubMed Central

Waters, Brian M; Armbrust, Laura C

2013-01-01

Iron (Fe) and copper (Cu) homeostasis are tightly linked across biology. Understanding crosstalk between Fe and Cu nutrition could lead to strategies for improved growth on soils with low or excess metals, with implications for agriculture and phytoremediation. Here, we show that Cu and Fe nutrition interact to increase or decrease Fe and/or Cu accumulation in leaves and Fe uptake processes. Leaf Cu concentration increased under low Fe supply, while high Cu lowered leaf Fe concentration. Ferric reductase activity, an indicator of Fe demand, was inhibited at insufficient or high Cu supply. Surprisingly, plants grown without Fe were more susceptible to Cu toxicity. PMID:24084753

Optimal copper supply is required for normal plant iron deficiency responses.

PubMed

Waters, Brian M; Armbrust, Laura C

2013-01-01

Iron (Fe) and copper (Cu) homeostasis are tightly linked across biology. Understanding crosstalk between Fe and Cu nutrition could lead to strategies for improved growth on soils with low or excess metals, with implications for agriculture and phytoremediation. Here, we show that Cu and Fe nutrition interact to increase or decrease Fe and/or Cu accumulation in leaves and Fe uptake processes. Leaf Cu concentration increased under low Fe supply, while high Cu lowered leaf Fe concentration. Ferric reductase activity, an indicator of Fe demand, was inhibited at insufficient or high Cu supply. Surprisingly, plants grown without Fe were more susceptible to Cu toxicity.

Chelating resin immobilizing carboxymethylated polyethyleneimine for selective solid-phase extraction of trace elements: Effect of the molecular weight of polyethyleneimine and its carboxymethylation rate.

PubMed

Kagaya, Shigehiro; Kajiwara, Takehiro; Gemmei-Ide, Makoto; Kamichatani, Waka; Inoue, Yoshinori

2016-01-15

The effect of the molecular weight of polyethyleneimine (PEI), defined as a compound having two or more ethyleneamine units, and of its carboxymethylation rate (CM/N), represented by the ratio of ion-exchange capacity to the amount of N on the resin, on the selective solid-phase extraction ability of the chelating resin immobilizing carboxymethylated (CM) PEI was investigated. The chelating resins (24 types) were prepared by immobilization of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, PEI300 (MW=ca. 300), and PEI600 (MW=ca. 600) on methacrylate resins, followed by carboxymethylation with various amounts of sodium monochloroacetate. When resins with approximately the same CM/N ratio (0.242-0.271) were used, the recovery of Cd, Co, Cu, Fe, Ni, Pb, Ti, Zn, and alkaline earth elements increased with increasing the molecular weight of PEIs under acidic and weakly acidic conditions; however, the extraction behavior of Mo and V was only slightly affected. This was probably due to the increase in N content of the resin, resulting in an increase in carboxylic acid groups; the difference in the molecular weight of PEIs immobilized on the resin exerts an insignificant influence on the selective extraction ability. The CM/N ratio considerably affected the extraction behavior for various elements. Under acidic and neutral conditions, the recovery of Cd, Co, Cu, Fe, Ni, Pb, Ti, and Zn increased with increasing CM/N values. However, under these conditions, the recovery of alkaline earth elements was considerably low when a resin with low CM/N ratio was used. This is presumably attributed to the different stability constants of the complexes of these elements with aminocarboxylic acids and amines, and to the electrostatic repulsion between the elements and the protonated amino groups in the CM-PEI. The recovery of Mo and V decreased or varied with increasing CM/N values, suggesting that the extraction of these elements occurred mainly by the anion-exchange reaction. For the separation and preconcentration of trace elements in samples containing large amounts of alkali and alkaline earth elements, the CM-PEI600 resin with CM/N=0.131 (Cu(II) extraction capacity, 0.37mmol g(-)(1)) was found to be the most suitable because it scarcely extracts alkali and alkaline earth elements under acidic and neutral conditions. This resin proved to be convenient for separating and preconcentrating Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in the certified reference materials (EnviroMAT EU-L-1 wastewater and ES-L-1 ground water) and commercially available table salt. Copyright © 2015 Elsevier B.V. All rights reserved.

The late Variscan ferroan granite magmatism of southern Sardinia: inferences from Mo metallogenesis

NASA Astrophysics Data System (ADS)

Naitza, Stefano; Conte, Aida Maria; Cuccuru, Stefano; Fadda, Sandro; Fiori, Maddalena; Oggiano, Giacomo; Secchi, Francesco

2017-04-01

Metallogeny is a powerful tool to investigate crustal evolution; a good example is offered by the Variscan basement of Sardinia and its Mo deposits. Mo ores are poorly represented in Variscan metallogenic provinces of Europe: however, in Sardinia, numerous small Mo deposits, often associated to Sn, W and F ores, are present, invariably related to an early Permian intrusive peak bracketed at about 290 Ma (Fadda et al., 2015; Naitza et al., 2017). In Sardinia, two main magmatic peaks have been schematized at pre-300 and 290 Ma. In southern Sardinia, the 290 magmatic peak is made up of several intrusive F-bearing rock-suites (Conte et al., 2016), belonging to ilmenite series, showing a slight peraluminous character and mostly classifiable as ferroan granites (sensu Frost and Frost, 2011). Mo-bearing granites form a distinct suite of relatively small plutons, emplaced at very shallow depth (about 1kb) in an exhumed Variscan low-grade basement. Peculiar characters of Mo-bearing granites are the occurrence of greisenized microgranite and granophyre cupolas, with fayalite-bearing pegmatites, and ilmenite, xenotime-(Y), monazite, fluorite, and local topaz as accessory phases. Recently, Conte et al. (2016) interpreted these granites as originated by partial melting of low crustal felsic metaigneous photoliths enriched in granophiles (Mo, Sn, W). Mo ores occur as: a) endo- and exo- quartz-muscovite greisens with molybdenite±Fe-Cu sulphides, and b) quartz-molybdenite±wolframite±Fe-Cu-Zn sulphides±fluorite±topaz hydrothermal veins and stockworks, hosted in granites or in country rocks. Redox state of magmas exerts a strong control on Mo metallogeny, as in Mo districts worldwide ores are usually hosted by high-fO2 magnetite series intrusions (Ishihara, 1981). The close field association of Sardinian Mo mineralization with ferroan, low-fO2 ilmenite-series granites may be explained in terms of Mo-enriched crustal sources of magmas, and very efficient geochemical concentration processes. Mo concentration occurred during latest intrusive phases in granitic cupolas, as local subsolidus reactions. They involve: 1) leaching of Mo5+ and Mo6+ from their primary hosts (e.g., biotites) by Cl- and F-rich fluids under decreasing pH and increasing fH2O and fO2, and 2) transport of Mo cations towards intrusive contacts, where they quickly reacted with Sulphur from country rocks to be reduced as MoS2. Overall, the late Variscan Mo metallogenic peak in Sardinia is a single event located in a short timespan at around 290 Ma. In the early Permian extensional setting of Corsica-Sardinia batholith, a distinct HT/LP event related to melting of mantle lithosphere (Rossi et al., 2015), triggered partial melting of Mo-bearing deep crustal sources, producing the F-bearing ferroan magmas. The singular concentration of Mo-bearing granites could indicate a peculiar compositional character of the Sardinian lower crust. References: Conte A.M. et al. (2016). Proc. 2nd European Mineralogical Conference, Rimini, Italy, 154. Fadda et al. (2015). Proc. 13th Biennial SGA Meeting, Nancy, France, Vol. 2, 721-724. Frost, C. D. and Frost R. B. (2011). J. Petrol. 52, 39-53. Ishihara S. (1981). Econ. Geol., 75th Anniversary Volume, 458-484. Naitza S. et al. (2017). Ore Geol. Rev. 80, 1259-1278. Rossi et al. (2015). Bull. Soc. Géol. France 186, 171-192.

Structure and electronic properties of Cu nanoclusters supported on Mo 2C(001) and MoC(001) surfaces

DOE PAGES

Posada-Pérez, Sergio; Viñes, Francesc; Rodríguez, José A.; ...

2015-09-15

In this study, the atomic structure and electronic properties of Cu n nanoclusters (n = 4, 6, 7, and 10) supported on cubic nonpolar δ-MoC(001) and orthorhombic C- or Mo-terminated polar β-Mo 2C(001) surfaces have been investigated by means of periodic density functional theory based calculations. The electronic properties have been analyzed by means of the density of states, Bader charges, and electron localization function plots. The Cu nanoparticles supported on β-Mo 2C(001), either Mo- or C-terminated, tend to present a two-dimensional structure whereas a three-dimensional geometry is preferred when supported on δ-MoC(001), indicating that the Mo:C ratio and themore » surface polarity play a key role determining the structure of supported clusters. Nevertheless, calculations also reveal important differences between the C- and Mo-terminated β-Mo 2C(001) supports to the point that supported Cu particles exhibit different charge states, which opens a way to control the reactivity of these potential catalysts.« less

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

Danyal, Karamatullah; Rasmussen, Andrew J.; Keable, Stephen M.

The reduction of substrates catalyzed by nitrogenase normally requires nucleotide-dependent Fe protein delivery of electrons to the MoFe protein, which contains the active site FeMo-cofactor. Here, it is reported that independent substitution of three amino acids (ß-98Tyr→His, α-64Tyr→His, and ß-99Phe→His) located between the P cluster and FeMo-cofactor within the MoFe protein endows it with the ability to reduce protons to H2, azide to ammonia, and hydrazine to ammonia without the need for Fe protein or ATP. Instead, electrons can be provided by the low potential reductant polyaminocarboxylate ligated Eu(II) (Em -1.1 to -0.84 V vs NHE). The crystal structure ofmore » the ß-98Tyr→His variant MoFe protein was determined, revealing only small changes near the amino acid substitution that affect the solvent structure and immediate vicinity between the P cluster and the FeMo-cofactor, with no global conformational changes observed. Computational normal mode analysis on the nitrogenase complex reveal coupling in the motions of the Fe protein and the region of the MoFe protein with these three amino acids, which suggests a possible mechanism for how Fe protein might communicate deep within the MoFe protein subtle changes that profoundly affect intramolecular electron transfer and substrate reduction. This work was supported by a grant from the National Science Foundation (MCB-1330807) to JWP and LCS. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-SC0010687 and DE-SC0010834 to LCS and DRD) and the Division of Chemical Sciences, Geosciences, and Bio-Sciences (SR). The coordinates for the ß-98His MoFe protein were deposited with the Protein Data Bank (PDB 4XPI).« less

Phase Evolution and Properties of Al2CrFeNiMo x High-Entropy Alloys Coatings by Laser Cladding

NASA Astrophysics Data System (ADS)

Wu, Wei; Jiang, Li; Jiang, Hui; Pan, Xuemin; Cao, Zhiqiang; Deng, Dewei; Wang, Tongmin; Li, Tingju

2015-10-01

A series of Al2CrFeNiMo x ( x = 0 to 2.0 at.%) high-entropy alloys coatings was synthesized on stainless steel by laser cladding. The effect of Mo content on the microstructures and mechanical properties of Al2CrFeNiMo x coatings was studied. The results show that the laser clad layer consists of the cladding zone, bonding zone, and heat-affected zone. The Al2CrFeNiMo x coatings are composed of two simple body-center cubic phases and the cladding zone is mainly composed of equiaxed grains. When the content of Mo reaches 2 at.%, a eutectic structure is found in the interdendritic regions. The surface microhardness of the Al2CrFeNiMo2 coating is 678 HV, which is about three times higher than that of the substrate (243 HV). Compared with stainless steel, the wear resistance of the coatings has been improved greatly. The wear mass loss of the Al2CrFeNiMo alloy is 9.8 mg, which is much less than that of the substrate (18.9 mg) and its wear scar width is the lowest among the Al2CrFeNiMo x coatings, indicating that the wear resistance of the Al2CrFeNiMo is the best.

Investigation on microstructure and mechanical properties of Mo2FeB2 based cermets with and without PVA

NASA Astrophysics Data System (ADS)

Shen, Yupeng; Huang, Zhifu; Jian, Yongxin; Yang, Ming; Li, Kemin

2018-03-01

Mo2FeB2 based cermets with and without PVA have been investigated by x-ray diffractometry (XRD), x-ray photoelectron spectroscope (XPS) and scanning electron microscopy (SEM). The density and transverse rupture strength (TRS) of green compact, relative density, hardness (HRA), fracture toughness (KIC) and TRS of Mo2FeB2 based cermets were also measured. The results indicate that, compared with the Mo2FeB2 based cermets without PVA, the density of green compact with PVA can be improved slightly at the same pressure. However, the much higher TRS is obtained for the green compact without PVA. Meanwhile, Mo2FeB2 particles exhibit the finer and less congruity feature for Mo2FeB2 based cermets without PVA. In addition, the higher relative density, hardness, fracture toughness and TRS can be acquired for the cermets without PVA. Obviously, considering the mechanical properties and preparation period of Mo2FeB2 based cermets, no adding PVA is the optimized process of powder molding in the manufacture of Mo2FeB2 based cermets.

In vitro synthesis of the iron–molybdenum cofactor of nitrogenase from iron, sulfur, molybdenum, and homocitrate using purified proteins

PubMed Central

Curatti, Leonardo; Hernandez, Jose A.; Igarashi, Robert Y.; Soboh, Basem; Zhao, Dehua; Rubio, Luis M.

2007-01-01

Biological nitrogen fixation, the conversion of atmospheric N2 to NH3, is an essential process in the global biogeochemical cycle of nitrogen that supports life on Earth. Most of the biological nitrogen fixation is catalyzed by the molybdenum nitrogenase, which contains at its active site one of the most complex metal cofactors known to date, the iron–molybdenum cofactor (FeMo-co). FeMo-co is composed of 7Fe, 9S, Mo, R-homocitrate, and one unidentified light atom. Here we demonstrate the complete in vitro synthesis of FeMo-co from Fe2+, S2−, MoO42−, and R-homocitrate using only purified Nif proteins. This synthesis provides direct biochemical support to the current model of FeMo-co biosynthesis. A minimal in vitro system, containing NifB, NifEN, and NifH proteins, together with Fe2+, S2−, MoO42−, R-homocitrate, S-adenosyl methionine, and Mg-ATP, is sufficient for the synthesis of FeMo-co and the activation of apo-dinitrogenase under anaerobic-reducing conditions. This in vitro system also provides a biochemical approach to further study the function of accessory proteins involved in nitrogenase maturation (as shown here for NifX and NafY). The significance of these findings in the understanding of the complete FeMo-co biosynthetic pathway and in the study of other complex Fe-S cluster biosyntheses is discussed. PMID:17978192

Investigation of electronic structure of tri- and tetranuclear molybdenum clusters by X-ray photoelectron and emission spectroscopies and quantum chemical methods

NASA Astrophysics Data System (ADS)

Kryuchkova, Natalya A.; Syrokvashin, Mikhail M.; Gushchin, Artem L.; Korotaev, Evgeniy V.; Kalinkin, Alexander V.; Laricheva, Yuliya A.; Sokolov, Maxim N.

2018-02-01

Charge state studies of compounds [Mo3S4(tu)8(H2O)]Cl4·4H2O (1), [Mo3S4Cl3(dbbpy)3]Cl·5H2O (2), [Mo3S4(CuCl)Cl3(dbbpy)3][CuCl2] (3), containing {Mo3S4}4+ and {Mo3CuS4}5+ cluster cores bearing terminal thiourea (tu) or 4,4‧-di-tert-butyl-2,2‧-bipyridine (dbbpy) ligands, have been performed by X-ray photoelectron and X-ray emission spectroscopies combined with quantum chemical calculations. The best agreement between theory and experiments has been obtained using the B3LYP method. According to the experimental and calculated data, the Mo atoms are in the oxidation state 4+ for all compounds. The energies and shapes of the Cu2p lines indicate formal oxidation states of Cu as 1+. The coordination of Cu(I) to the cluster {Mo3S4} in 3 does not lead to significant changes in the charge state of the molybdenum atoms and the {Mo3S4} unit can be considered as a tridentate metallothia crown ether.

Energy for the interface system of (Nb, Mo)C/γ-Fe

NASA Astrophysics Data System (ADS)

Zhou, Yanyuan; Wang, Zhenqiang; Zhao, Jiaying; Leng, Zhe; Niu, Zhongyi; Guo, Chunhuan; Zhang, Zhengyan; Yang, Zhigang; Yao, Chunfa; Jiang, Fengchun

2017-08-01

The interfacial energies of MC/γ-Fe and formation energies of MC carbides have been investigated using first-principles calculations based on density functional theory (DFT). Results show that the replacement of Nb by Mo in the NbC lattice is unfavorable with respect to the formation energy. However, it reduces the lattice parameter of MC and decreases the σ_{{chemical}} (interfacial chemical energy) of MC/γ-Fe, thus favoring the formation of complex (Nb, Mo)C carbide. The substitution of Nb by Mo at the interface of MC/γ-Fe system promotes the hybridizations of Mo-1NNFe and C-1NNFe (or 2NNFe) (the first or second nearest neighboring Fe atoms), which leads to a decrease in σ_{{chemical}}. The influence of bond energy is estimated using the discrete lattice plane/nearest neighbor broken bond (DLP/NNBB) model. It is found that the reduced σ_{{chemical}} is attributed to the much smaller value of e_{{{{Fe-C}}}} - e_{{{{Mo-C}}}} (the difference between Fe-C and Mo-C interactions) compared to e_{{{{Fe-C}}}} - e_{{{{Nb-C}}}} (the difference between Fe-C and Nb-C interactions). The results obtained from the analysis of the precipitates in Nb- and Nb-Mo-bearing steels are in a good agreement with the calculations.

Comparing electrochemical performance of transition metal silicate cathodes and chevrel phase Mo6S8 in the analogous rechargeable Mg-ion battery system

NASA Astrophysics Data System (ADS)

Chen, Xinzhi; Bleken, Francesca L.; Løvvik, Ole Martin; Vullum-Bruer, Fride

2016-07-01

Polyanion based silicate materials, MgMSiO4 (M = Fe, Mn, Co), previously reported to be promising cathode materials for Mg-ion batteries, have been re-examined. Both the sol-gel and molten salt methods are employed to synthesize MgMSiO4 composites. Mo6S8 is synthesized by a molten salt method combined with Cu leaching and investigated in the equivalent electrochemical system as a bench mark. Electrochemical measurements for Mo6S8 performed using the 2nd generation electrolyte show similar results to those reported in literature. Electrochemical performance of the silicate materials on the other hand, do not show the promising results previously reported. A thorough study of these published results are presented here, and compared to the current experimental data on the same material system. It appears that there are certain inconsistencies in the published results which cannot be explained. To further corroborate the present experimental results, atomic-scale calculations from first principles are performed, demonstrating that diffusion barriers are very high for Mg diffusion in MgMSiO4. In conclusion, MgMSiO4 (M = Fe, Mn, Co) olivine materials do not seem to be such good candidates for cathode materials in Mg-ion batteries as previously reported.

Trace elements and radon in groundwater across the United States, 1992-2003

USGS Publications Warehouse

Ayotte, Joseph D.; Gronberg, Jo Ann M.; Apodaca, Lori E.

2011-01-01

Trace-element concentrations in groundwater were evaluated for samples collected between 1992 and 2003 from aquifers across the United States as part of the U.S. Geological Survey National Water-Quality Assessment Program. This study describes the first comprehensive analysis of those data by assessing occurrence (concentrations above analytical reporting levels) and by comparing concentrations to human-health benchmarks (HHBs). Data from 5,183 monitoring and drinking-water wells representing more than 40 principal and other aquifers in humid and dry regions and in various land-use settings were used in the analysis. Trace elements measured include aluminum (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), boron (B), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), lithium (Li), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silver (Ag), strontium (Sr), thallium (Tl), uranium (U), vanadium (V), and zinc (Zn). Radon (Rn) gas also was measured and is included in the data analysis. Climate influenced the occurrence and distribution of trace elements in groundwater whereby more trace elements occurred and were found at greater concentrations in wells in drier regions of the United States than in humid regions. In particular, the concentrations of As, Ba, B, Cr, Cu, Mo, Ni, Se, Sr, U, V, and Zn were greater in the drier regions, where processes such as chemical evolution, ion complexation, evaporative concentration, and redox (oxidation-reduction) controls act to varying degrees to mobilize these elements. Al, Co, Fe, Pb, and Mn concentrations in groundwater were greater in humid regions of the United States than in dry regions, partly in response to lower groundwater pH and (or) more frequent anoxic conditions. In groundwater from humid regions, concentrations of Cu, Pb, Rn, and Zn were significantly greater in drinking-water wells than in monitoring wells. Samples from drinking-water wells in dry regions had greater concentrations of As, Ba, Pb, Li, Sr, V, and Zn, than samples from monitoring wells. In humid regions, however, concentrations of most trace elements were greater in monitoring wells than in drinking-water wells; the exceptions were Cu, Pb, Zn, and Rn. Cu, Pb, and Zn are common trace elements in pumps and pipes used in the construction of drinking-water wells, and contamination from these sources may have contributed to their concentrations. Al, Sb, Ba, B, Cr, Co, Fe, Mn, Mo, Ni, Se, Sr, and U concentrations were all greater in monitoring wells than in drinking-water wells in humid regions. Groundwater from wells in agricultural settings had greater concentrations of As, Mo, and U than groundwater from wells in urban settings, possibly owing to greater pH in the agricultural wells. Significantly greater concentrations of B, Cr, Se, Ag, Sr, and V also were found in agricultural wells in dry regions. Groundwater from dry-region urban wells had greater concentrations of Co, Fe, Pb, Li, Mn, and specific conductance than groundwater from agricultural wells. The geologic composition of aquifers and aquifer geochemistry are among the major factors affecting trace-element occurrence. Trace-element concentrations in groundwater were characterized in aquifers from eight major groups based on geologic material, including (1) unconsolidated sand and gravel; (2) glacial unconsolidated sand and gravel; (3) semiconsolidated sand; (4) sandstone; (5) sandstone and carbonate rock; (6) carbonate rock; (7) basaltic and other volcanic rock; and (8) crystalline rock. The majority of groundwater samples and the largest percentages of exceedences of HHBs were in the glacial and nonglacial unconsolidated sand and gravel aquifers; in these aquifers, As, Mn, and U are the most common trace elements exceeding HHBs. Overall, 19 percent of wells (962 of 5,097) exceeded an HHB for at least one trace element. The trace elements with HHBs included in this summary were Sb, As, Ba, Be, B, Cd, Cr,

Geochemistry of ferromanganese nodule-sediment pairs from Central Indian Ocean Basin

NASA Astrophysics Data System (ADS)

Pattan, J. N.; Parthiban, G.

2011-01-01

Fourteen ferromanganese nodule-sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule-sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo - (307, 273), Ni - (71, 125), Mn - (64, 87), Cu - (43, 80), Co - (23, 75), Pb - (15, 24), Zn - (9, 11) and V - (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation ( r ⩾ 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.

Site specific ligand substitution in cubane-type Mo3FeS(4)(4+) clusters: kinetics and mechanism of reaction and isolation of mixed ligand Cl/SPh complexes.

PubMed

Algarra, Andrés G; Basallote, Manuel G; Fernandez-Trujillo, M J; Llusar, Rosa; Pino-Chamorro, Jose A; Sorribes, Ivan; Vicent, Cristian

2010-04-21

The synthesis, crystal structure and solution characterization of the cubane-type [Mo(3)(FeCl)S(4)(dmpe)(3)Cl(3)] (1) (dmpe = 1,2-bis(dimethylphophane-ethane)) cluster are reported and the ligand substitution processes of chloride by thiophenolate investigated. The kinetics and the intimate mechanism of these substitutions reveal that compound 1 undergoes a number of Fe and Mo site specific ligand substitution reactions in acetonitrile solutions. In particular, PhS(-) coordination at the tetrahedral Fe site proceeds in a single resolved kinetic step whereas such substitutions at the Mo sites proceed more slowly. The effect of the presence of acids in the reaction media is also investigated and reveals that an acid excess hinders substitution reactions both at the Fe and Mo sites; however, an acid-promoted solvolysis of the Fe-Cl bonds is observed. Electrospray ionization (ESI) and tandem (ESI-MS/MS) mass spectrometry allow the identification of all the reaction intermediates proposed on the basis of stopped-flow measurements. The distinctive site specific reactivity made it possible to isolate two new clusters of the Mo(3)FeS(4)(4+) family featuring mixed chlorine/thiophenolate ligands, namely Mo(3)S(4)(FeSPh)(dmpe)(3)Cl(3) (2) and [Mo(3)S(4)(FeSPh)(dmpe)(3)(SPh)(3)] (3). A detailed computational study has also been carried out to understand the details of the mechanism of substitution at the M-Cl (M = Mo and Fe) bonds as well as the solvolysis at the Fe-Cl sites, with particular emphasis on the role of acids on the substitution process. The results of the calculations are in agreement with the experimental observations, thus justifying the non-existence of an accelerating effect of acids on the thiophenolate substitution reaction, which differs from previous proposals for the Fe(4)S(4) and MoFe(3)S(4) clusters and some related compounds.

[Dietary reference intakes of trace elements for Japanese and problems in clinical fields].

PubMed

Inoue, Yoshifumi

2016-07-01

In the dietary reference intakes, EAR(estimated average requirement), RDA(recommended dietary allowance), AL(adequate intake), DG(tentative dietary goal for preventing life style related diseases) and UL(tolerable upper intake level) of eight types of trace elements (iron: Fe, zinc: Zn, copper: Cu, manganese: Mn, iodine: I, selenium: Se, chromium: Cr, molybdenum: Mo) have been set. However, in the meals of hospitals, only iron of which has been taken into account. The content of these trace elements in the enteral nutrient released after 2000 was determined by considering the content of dietary reference intakes of trace elements for Japanese and considered so not fall into deficiency. However, enteral nutrient must be used considering the content of Zn, Cu and the Zn/Cu ratio, the selenium content, and the route of administration, in order to avoid falling into deficiency.

Regulation of brain copper homeostasis by the brain barrier systems: Effects of Fe-overload and Fe-deficiency

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

Monnot, Andrew D.; Behl, Mamta; Ho, Sanna

2011-11-15

Maintaining brain Cu homeostasis is vital for normal brain function. The role of systemic Fe deficiency (FeD) or overload (FeO) due to metabolic diseases or environmental insults in Cu homeostasis in the cerebrospinal fluid (CSF) and brain tissues remains unknown. This study was designed to investigate how blood-brain barrier (BBB) and blood-SCF barrier (BCB) regulated Cu transport and how FeO or FeD altered brain Cu homeostasis. Rats received an Fe-enriched or Fe-depleted diet for 4 weeks. FeD and FeO treatment resulted in a significant increase (+ 55%) and decrease (- 56%) in CSF Cu levels (p < 0.05), respectively; however,more » neither treatment had any effect on CSF Fe levels. The FeD, but not FeO, led to significant increases in Cu levels in brain parenchyma and the choroid plexus. In situ brain perfusion studies demonstrated that the rate of Cu transport into the brain parenchyma was significantly faster in FeD rats (+ 92%) and significantly slower (- 53%) in FeO rats than in controls. In vitro two chamber Transwell transepithelial transport studies using primary choroidal epithelial cells revealed a predominant efflux of Cu from the CSF to blood compartment by the BCB. Further ventriculo-cisternal perfusion studies showed that Cu clearance by the choroid plexus in FeD animals was significantly greater than control (p < 0.05). Taken together, our results demonstrate that both the BBB and BCB contribute to maintain a stable Cu homeostasis in the brain and CSF. Cu appears to enter the brain primarily via the BBB and is subsequently removed from the CSF by the BCB. FeD has a more profound effect on brain Cu levels than FeO. FeD increases Cu transport at the brain barriers and prompts Cu overload in the CNS. The BCB plays a key role in removing the excess Cu from the CSF.« less

Effect of different levels of copper and molybdenum supplements on serum lipid profiles and antioxidant status in cashmere goats.

PubMed

Zhang, Wei; Zhang, Yu; Zhang, Shi W; Song, Xian Z; Jia, Zhi H; Wang, Run L

2012-09-01

An experiment was conducted to investigate on the effects of different levels of copper (Cu: 0, 19, and 38 mg/kg) and molybdenum (Mo: 0 and 5 mg/kg) supplements and the interaction of these two factors on serum lipid profiles and antioxidant status in cashmere goats during the cashmere fiber growing period. Thirty-six Liaoning cashmere goats (approximately 1.5 years of age; 27.53±1.38 kg of body weight) were assigned to one of six treatments in a completely randomized design involving a 2×3 factorial arrangement. Goats were housed in individual pens and fed with Chinese wild rye- and alfalfa hay-based diet containing 4.72 mg Cu/kg, 0.16 mg Mo/kg, and 0.21 % S for 84 days. Blood samples were collected on day 84. The triglyceride concentration did not differ among treatments (P>0.05). Supplemental Cu, regardless of Mo level, decreased (P<0.05) the concentrations of serum total cholesterol and low density lipoprotein cholesterol, and increased (P<0.05) the concentration of serum high density lipoprotein cholesterol, but there were no differences (P>0.05) in these values between Cu-supplemented groups. Supplemental Cu increased (P<0.05) the activities of serum ceruloplasmin (Cp), Cu-zinc superoxide dismutase (SOD), and glutathione peroxidase (GSH-Px), and decreased (P<0.05) the malondialdehyde content. The serum GSH-Px activity was also increased (P<0.05) by Mo supplementation. There was a tendency of the interaction effects of Cu and Mo on the activities of Cp (P=0.094), SOD (P=0.057), and GSH-Px (P=0.062), and goats fed with 19 mg Cu/kg in the absence of Mo tended to show the highest serum SOD activity, while goats fed with 38 mg Cu/kg with 5 mg Mo/kg tended to show the highest values of serum Cp and GSH-Px. Addition of Cu, Mo, or their interaction had no influence (P>0.05) on the activities of serum glutamate oxaloacetate transaminase, glutamate pyruvate transaminase, and lactate dehydrogenase, and the concentrations of serum glucose and total protein. In conclusion, addition of 19 mg Cu/kg in the absence of Mo (the total dietary Cu level of 23.72 mg/kg) was recommended for altering the fat metabolism and obtaining the optimal antioxidant activity of cashmere goats, while 38 mg Cu/kg should be supplemented when 5 mg Mo/kg was added in the basal diet (the total dietary level of 42.72 mg Cu/kg, 5.16 mg Mo/kg, and 0.21 % S) during the cashmere growing period.

Enhanced reactivity of microscale Fe/Cu bimetallic particles (mFe/Cu) with persulfate (PS) for p-nitrophenol (PNP) removal in aqueous solution.

PubMed

Ji, Qingqing; Li, Jun; Xiong, Zhaokun; Lai, Bo

2017-04-01

In this study, batch experiments were conducted to examine the enhanced reactivity of microscale Fe/Cu bimetallic particles (mFe/Cu) with persulfate (PS) for p-nitrophenol (PNP) removal in aqueous solution. The key operating parameters (i.e., theoretical Cu mass loadings (TML Cu ), mFe/Cu dosage, PS dose, initial pH and temperature) were optimized by the batch experiments, respectively. The experimental data were followed well the pseudo-first-order kinetic model. Result reveals that refractory PNP (500 mg L -1 ) was effectively degraded by mFe/Cu-PS system with removal of 98.4% and k obs of 1.91 min -1 after only 3 min treatment under the optimal operating conditions. Moreover, compared with control experiments (i.e., mFe/Cu, microscale Fe 0 with PS (mFe 0 -PS), and PS alone), mFe/Cu-PS system exerted better performance for PNP removal due to the strong synergistic effect between PS and mFe/Cu. According to the analysis results of degradation kinetics of PNP, COD (chemical oxygen demand) removal, UV-vis absorption spectra and the intermediates formed, the results reveal that the PNP removal by mFe/Cu-PS system was mainly attributed to reduction accompanied slight oxidation. And based on the analysis of surface characteristics of mFe/Cu particles, it is further demonstrated that PS could enhance the reactivity of mFe/Cu through rapid corrosion of iron surface and decrease of surface passivation of mFe/Cu surface when the low molar ratio of PS to mFe/Cu (i.e., 1:43) was used in this study. These results also illustrates mFe/Cu-PS can be as a high efficient pretreatment technology for the removal of toxic refractory PNP from wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Facile preparation of magnetic mesoporous Fe3O4/C/Cu composites as high performance Fenton-like catalysts

NASA Astrophysics Data System (ADS)

Li, Keyan; Zhao, Yongqin; Janik, Michael J.; Song, Chunshan; Guo, Xinwen

2017-02-01

Fe-Cu composites with different compositions and morphologies were synthesized by a hydrothermal method combined with precursor thermal transformation. γ-Fe2O3/CuO and α-Fe2O3/CuO were obtained by calcining the Fe and Cu tartrates under air atmosphere at 350 °C and 500 °C, respectively, while Fe3O4/C/Cu was obtained by calcining the tartrate precursor under N2 atmosphere at 500 °C. The Fe3O4/C/Cu composite possessed mesoporous structure and large surface area up to 133 m2 g-1. The Fenton catalytic performance of Fe3O4/C/Cu composite was closely related to the Fe/Cu molar ratio, and only proper amounts of Fe and Cu exhibited a synergistic enhancement in Fenton catalytic activity. Cu inclusion reduced Fe3+ to Fe2+, which accelerated the Fe3+/Fe2+ cycles and favored H2O2 decomposition to produce more hydroxyl radicals for methylene blue (MB) oxidation. Due to the photo-reduction of Fe3+ and Cu2+, the Fenton catalytic performance was greatly improved when amending with visible light irradiation in the Fe3O4/C/Cu-H2O2 system, and MB (100 mg L-1) was nearly removed within 60 min. The Fe3O4/C/Cu composite showed good recyclability and could be conveniently separated by an applied magnetic field. Compared with conventional methods for mesoporous composite construction, the thermolysis method using mixed metal tartrates as precursors has the advantages of easy preparation and low cost. This strategy provides a facile, cheap and green method for the synthesis of mesoporous composites as excellent Fenton-like catalysts, without any additional reductants or organic surfactants.

Ionomic profiling of Nicotiana langsdorffii wild-type and mutant genotypes exposed to abiotic stresses.

PubMed

Ardini, Francisco; Soggia, Francesco; Abelmoschi, Maria Luisa; Magi, Emanuele; Grotti, Marco

2013-01-01

To provide a new insight into the response of plants to abiotic stresses, the ionomic profiles of Nicotiana langsdorffii specimens have been determined before and after exposure to toxic metals (chromium) or drought conditions. The plants were genetically transformed with the rat glucocorticoid receptor (GR) or the gene for Agrobacterium rhizogenes rolC, because these modifications are known to produce an imbalance in phytohormone equilibria and a significant change in the defence response of the plant. Elemental profiles were obtained by developing and applying analytical procedures based on inductively coupled plasma atomic emission and mass spectrometry (ICP-AES/MS). In particular, the removal of isobaric interferences affecting the determination of Cr and V by ICP-MS was accomplished by use of a dynamic reaction cell, after optimization of the relevant conditions. The combined use of ICP atomic emission and mass spectrometry enabled the determination of 29 major and trace elements (Ba, Bi, Ca, Cd, Co, Cr, Cu, Eu, Fe, Ga, K, Li, Mg, Mn, Mo, Na, P, Pb, Pt, Rb, S, Sb, Sn, Sr, Te, V, W, Y, and Zn) in different parts of the plants (roots, stems, and leaves), with high accuracy and precision. Multivariate data processing and study of element distribution patterns provided new information about the ionomic response of the target organism to chemical treatment or water stress. Genetic modification mainly affected the distribution of Bi, Cr, Mo, Na, and S, indicating that these elements were involved in biochemical processes controlled by the GR or rolC genes. Chemical stress strongly affected accumulation of several elements (Ba, Ca, Fe, Ga, K, Li, Mn, Mo, Na, P, Pb, Rb, S, Sn, Te, V, and Zn) in different ways; for Ca, Fe, K, Mn, Na, and P the effect was quite similar to that observed in other studies after treatment with other transition elements, for example Cu and Cd. The effect of water deficit was less evident, mainly consisting in a decrease of Ba, Cr, Na, and Sr in roots.

Extraction of heavy metals characteristics of the 2011 Tohoku tsunami deposits using multiple classification analysis.

PubMed

Nakamura, Kengo; Kuwatani, Tatsu; Kawabe, Yoshishige; Komai, Takeshi

2016-02-01

Tsunami deposits accumulated on the Tohoku coastal area in Japan due to the impact of the Tohoku-oki earthquake. In the study reported in this paper, we applied principal component analysis (PCA) and cluster analysis (CA) to determine the concentrations of heavy metals in tsunami deposits that had been diluted with water or digested using 1 M HCl. The results suggest that the environmental risk is relatively low, evidenced by the following geometric mean concentrations: Pb, 16 mg kg(-1) and 0.003 ml L(-1); As, 1.8 mg kg(-1) and 0.004 ml L(-1); and Cd, 0.17 mg kg(-1) and 0.0001 ml L(-1). CA was performed after outliers were excluded using PCA. The analysis grouped the concentrations of heavy metals for leaching in water and acid. For the acid case, the first cluster contained Ni, Fe, Cd, Cu, Al, Cr, Zn, and Mn; while the second contained Pb, Sb, As, and Mo. For water, the first cluster contained Ni, Fe, Al, and Cr; and the second cluster contained Mo, Sb, As, Cu, Zn, Pb, and Mn. Statistical analysis revealed that the typical toxic elements, As, Pb, and Cd have steady correlations for acid leaching but are relatively sparse for water leaching. Pb and As from the tsunami deposits seemed to reveal a kind of redox elution mechanism using 1 M HCl. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Characteristics of trace metals in traffic-derived particles in Hsuehshan Tunnel, Taiwan: size distribution, potential source, and fingerprinting metal ratio

NASA Astrophysics Data System (ADS)

Lin, Y.-C.; Tsai, C.-J.; Wu, Y.-C.; Zhang, R.; Chi, K.-H.; Huang, Y.-T.; Lin, S.-H.; Hsu, S.-C.

2015-04-01

Traffic emissions are a significant source of airborne particulate matter (PM) in ambient environments. These emissions contain an abundance of toxic metals and thus pose adverse effects on human health. Size-fractionated aerosol samples were collected from May to September 2013 by using micro-orifice uniform deposited impactors (MOUDIs). Sample collection was conducted simultaneously at the inlet and outlet sites of Hsuehshan Tunnel in northern Taiwan, which is the second-longest freeway tunnel (12.9 km) in Asia. This endeavor aims to characterize the chemical constituents and size distributions, as well as fingerprinting ratios of particulate metals emitted by vehicle fleets. A total of 36 metals in size-resolved aerosols were determined through inductively coupled plasma mass spectrometry. Three major groups - namely, tailpipe emissions (Zn, Pb, and V in fine mode), wear debris (Cu, Cd, Fe, Ga, Mn, Mo, Sb, and Sn), and resuspended dust (Ca, Mg, K, and Rb) - of airborne PM metals were categorized on the basis of the results of enrichment factor, correlation matrix, and principal component analysis. Size distributions of wear-originated metals resembled the pattern of crustal elements, which were predominated by super-micron particulates (PM1-10). By contrast, tailpipe exhaust elements such as Zn, Pb, and V were distributed mainly in submicron particles. By employing Cu as a tracer of wear abrasion, several inter-metal ratios - including Fe / Cu (14), Ba / Cu (1.05), Sb / Cu (0.16), Sn / Cu (0.10), and Ga / Cu (0.03) - served as fingerprints for wear debris. However, the data set collected in this work is useful for further studies on traffic emission inventory and human health effects of traffic-related PM.

Characteristics of trace metals in traffic-derived particles in Hsuehshan Tunnel, Taiwan: size distribution, fingerprinting metal ratio, and emission factor

NASA Astrophysics Data System (ADS)

Lin, Y.-C.; Tsai, C.-J.; Wu, Y.-C.; Zhang, R.; Chi, K.-H.; Huang, Y.-T.; Lin, S.-H.; Hsu, S.-C.

2014-05-01

Traffic emissions are a significant source of airborne particulate matter (PM) in ambient environments. These emissions contain high abundance of toxic metals and thus pose adverse effects on human health. Size-fractionated aerosol samples were collected from May to September 2013 by using micro-orifice uniform deposited impactor (MOUDI). Sample collection was conducted simultaneously at the inlet and outlet sites of Hsuehshan Tunnel in northern Taiwan, which is the second longest freeway tunnel (12.9 km) in Asia. Such endeavor aims to characterize the chemical constituents, size distributions, and fingerprinting ratios, as well as the emission factors of particulate metals emitted by vehicle fleets. A total of 36 metals in size-resolved aerosols were determined through inductively coupled plasma mass spectrometry. Three major groups, namely, tailpipe emissions (Zn, Pb, and V), wear debris (Cu, Cd, Fe, Ga, Mn, Mo, Sb, and Sn), and resuspended dust (Ca, Mg, K, and Rb), of airborne PM metals were categorized on the basis of the results of enrichment factor, correlation matrix, and principal component analysis. Size distributions of wear-originated metals resembled the pattern of crustal elements, which were predominated by super-micron particulates (PM1-10). By contrast, tailpipe exhaust elements such as Zn, Pb, and V were distributed mainly in submicron particles. By employing Cu as a tracer of wear abrasion, several inter-metal ratios, including Fe/Cu (14), Ba/Cu (1.05), Sb/Cu (0.16), Sn/Cu (0.10), and Ga/Cu (0.03), served as fingerprints for wear debris. Emission factor of PM10 mass was estimated to be 7.7 mg vkm-1. The metal emissions were mostly predominated in super-micron particles (PM1-10). Finally, factors that possibly affect particulate metal emissions inside Hsuehshan Tunnel are discussed.

Two new hybrid molybdenum arsenate derivative constructed from [As2Mo6O26]6- building: Synthesis, structural characterization and photocatalysis property

NASA Astrophysics Data System (ADS)

Zhang, Xiao; Luo, Xuan; Duan, Yuanling; Huang, Yanping; Zhang, Nanxi; Zhao, Liyan; Wu, Jie

2017-08-01

Two new inorganic-organic hybrid materials [Cu(enMe)2]2{(As2Mo6O26) [Cu(enMe)2]}·4H2O (1) and [As2Mo6(OH)2O24][Cu(H2O)2(phen)]2 (2) (enMe = 1,2'-propanediamine, phen = 1,10'-phenanthroline) based on [As2Mo6O26]6- building blocks, denoted as [As2Mo6], have been obtained by hydrothermal methods. 1 shows a 1-D straight chain structure constructed form [As2Mo6] building blocks and [Cu(enMe)2] complexes, and then extended to 3-D supramolecular network by lattice water via hydrogen bonds interactions. 2 exhibits a new 1-D covalent ribbon with large rectangular grids formed from [As2Mo6] building blocks connected by [Cu(H2O)2(phen)] complexes, then extended into 3-D supramolecular network via hydrogen bonds and π···π interactions. In additional, the photocatalytic activity for methylene blue degradation under visible-light irradiation of 2 was investigated.

Negative cooperativity in the nitrogenase Fe protein electron delivery cycle

DOE PAGES

Danyal, Karamatullah; Shaw, Sudipta; Page, Taylor R.; ...

2016-10-04

Mo-dependent nitrogenase catalyzes the biological reduction of atmospheric dinitrogen (N2) to two ammonia (NH3) molecules, through the action of two component proteins, the MoFe protein and the Fe protein. The catalytic MoFe protein is a symmetric dimer of αβ units, each of which contains one active site FeMo-co (FeMo-co; [7Fe-9S-Mo-C-homocitrate]) and an electron-carrier P cluster. Each half of the nitrogenase ternary complex, in which one Fe protein with two bound ATP molecules has bound to each MoFe protein αβ unit, undergoes an electron transfer (ET) cycle with ET from a Fe protein [4Fe-4S] cluster into its αβ unit followed bymore » the hydrolysis of the two ATP to two ADP and two Pi. The prevailing model holds that each αβ unit of the MoFe protein functions independently. We now report that the ET cycle exhibits negative cooperativity, with ET and ATP hydrolysis in one half of the ternary nitrogenase complex suppressing these processes in the other half. The observed ET, ATP hydrolysis, and Pi release behavior is captured in a global fit to a two-branch negative-cooperativity kinetic model. A possible mechanism for communication between the two halves of MoFe protein is suggested by normal mode analysis showing correlated and anti-correlated motions between the two nitrogenase αβ halves. EPR spectra furthermore show small differences between those of resting-state and singly-reduced MoFe protein that can be attributed to an intra-complex allosteric perturbation of the resting-state FeMo-co in one αβ unit by reduction of FeMo-co in the other. This work is supported as a part of the Biological and Electron Transfer and Catalysis (EFRC) program, an Energy Frontiers Research Center funded by the US Department of Energy (DOE), Office of Science (DE-SC0012518) to LCS, by National Institutes of Health (NIH) grants HL 63203 and GM 111097to BMH, and R15GM110671 to EA, and by the Division of Chemical Sciences, Geosciences, and Bio-Sciences, DOE to SR. The protein production, ATP hydrolysis, and stopped flow electron transfer studies were supported by the EFRC program, phosphate release and pulse chase by the NIH, calculations by the DOE, and rapid freeze quench and data fitting by the NIH.« less

Negative cooperativity in the nitrogenase Fe protein electron delivery cycle

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

Danyal, Karamatullah; Shaw, Sudipta; Page, Taylor R.

Mo-dependent nitrogenase catalyzes the biological reduction of atmospheric dinitrogen (N 2) to two ammonia (NH 3) molecules, through the action of two component proteins, the MoFe protein and the Fe protein. The catalytic MoFe protein is a symmetric dimer of αβ units, each of which contains one active site FeMo-co (FeMo-co; [7Fe-9S-Mo-C-homocitrate]) and an electron-carrier P cluster. Each half of the nitrogenase ternary complex, in which one Fe protein with two bound ATP molecules has bound to each MoFe protein αβ unit, undergoes an electron transfer (ET) cycle with ET from a Fe protein [4Fe-4S] cluster into its αβ unitmore » followed by the hydrolysis of the two ATP to two ADP and two Pi. The prevailing model holds that each αβ unit of the MoFe protein functions independently. We now report that the ET cycle exhibits negative cooperativity, with ET and ATP hydrolysis in one half of the ternary nitrogenase complex suppressing these processes in the other half. The observed ET, ATP hydrolysis, and Pi release behavior is captured in a global fit to a two-branch negative-cooperativity kinetic model. A possible mechanism for communication between the two halves of MoFe protein is suggested by normal mode analysis showing correlated and anti-correlated motions between the two nitrogenase αβ halves. EPR spectra furthermore show small differences between those of resting-state and singly-reduced MoFe protein that can be attributed to an intra-complex allosteric perturbation of the resting-state FeMo-co in one αβ unit by reduction of FeMo-co in the other. This work is supported as a part of the Biological and Electron Transfer and Catalysis (EFRC) program, an Energy Frontiers Research Center funded by the US Department of Energy (DOE), Office of Science (DE-SC0012518) to LCS, by National Institutes of Health (NIH) grants HL 63203 and GM 111097to BMH, and R15GM110671 to EA, and by the Division of Chemical Sciences, Geosciences, and Bio-Sciences, DOE to SR. The protein production, ATP hydrolysis, and stopped flow electron transfer studies were supported by the EFRC program, phosphate release and pulse chase by the NIH, calculations by the DOE, and rapid freeze quench and data fitting by the NIH.« less

Bulk amorphous steels based on Fe alloys

DOEpatents

Lu, ZhaoPing; Liu, Chain T.

2006-05-30

A bulk amorphous alloy has the approximate composition: Fe.sub.(100-a-b-c-d-e)Y.sub.aMn.sub.bT.sub.cM.sub.dX.sub.e wherein: T includes at least one of the group consisting of: Ni, Cu, Cr and Co; M includes at least one of the group consisting of W, Mo, Nb, Ta, Al and Ti; X includes at least one of the group consisting of Co, Ni and Cr; a is an atomic percentage, and a<5; b is an atomic percentage, and b.ltoreq.25; c is an atomic percentage, and c.ltoreq.25; d is an atomic percentage, and d.ltoreq.25; and e is an atomic percentage, and 5.ltoreq.e.ltoreq.30.

Chemically stable ceramic-metal composite membrane for hydrogen separation

DOEpatents

Chen, Fanglin; Fang, Shumin; Brinkman, Kyle S.

2017-06-27

A hydrogen permeation membrane is provided that can include a metal and a ceramic material mixed together. The metal can be Ni, Zr, Nb, Ta, Y, Pd, Fe, Cr, Co, V, or combinations thereof, and the ceramic material can have the formula: BaZr.sub.1-x-yY.sub.xT.sub.yO.sub.3-.delta. where 0.ltoreq.x.ltoreq.0.5, 0.ltoreq.y.ltoreq.0.5, (x+y)>0; 0.ltoreq..delta..ltoreq.0.5, and T is Sc, Ti, Nb, Ta, Mo, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Sn, or combinations thereof. A method of forming such a membrane is also provided. A method is also provided for extracting hydrogen from a feed stream.

Potential health risk assessment of potato (Solanum tuberosum L.) grown on metal contaminated soils in the central zone of Punjab, Pakistan.

PubMed

Khan, Zafar Iqbal; Ahmad, Kafeel; Yasmeen, Sumaira; Akram, Nudrat Aisha; Ashraf, Muhammad; Mehmood, Naunain

2017-01-01

Metal buildup was estimated in potato (Solanum tuberosum L.), grown in central Punjab, Pakistan. This crop was irrigated with multiple water sources like ground, sewage and canal water. Concentrations of different metals like zinc (Zn), arsenic (As), lead (Pb), iron (Fe), nickel (Ni), molybdenum (Mo), copper (Cu), and selenium (Se) were assessed in the potato crop irrigated with different types of waters. Sewage water treated crop and soil had higher metal concentrations than those treated with other two treatments. All metals had positive and significant correlation except for Mo which was non-significantly correlated between the vegetable and soil. Highest daily intake was observed for Fe (0.267), whereas the lowest was seen for Se (0.003). The enrichment factor and health index varied between 0.135-15.08 and 0.285-83.77, respectively. This study concludes that vegetables cultivated on soil treated with sewage water is a potent threat for human health as the metals manifest toxicity after entering the food chain. Copyright © 2016 Elsevier Ltd. All rights reserved.

Turnover-Dependent Inactivation of the Nitrogenase MoFe-Protein at High pH

PubMed Central

2013-01-01

Proton uptake accompanies the reduction of all known substrates by nitrogenase. As a consequence, a higher pH should limit the availability of protons as a substrate essential for turnover, thereby increasing the proportion of more highly reduced forms of the enzyme for further study. The utility of the high-pH approach would appear to be problematic in view of the observation reported by Pham and Burgess [(1993) Biochemistry 32, 13725–13731] that the MoFe-protein undergoes irreversible protein denaturation above pH 8.65. In contrast, we found by both enzyme activity and crystallographic analyses that the MoFe-protein is stable when incubated at pH 9.5. We did observe, however, that at higher pHs and under turnover conditions, the MoFe-protein is slowly inactivated. While a normal, albeit low, level of substrate reduction occurs under these conditions, the MoFe-protein undergoes a complex transformation; initially, the enzyme is reversibly inhibited for substrate reduction at pH 9.5, yet in a second, slower process, the MoFe-protein becomes irreversibly inactivated as measured by substrate reduction activity at the optimal pH of 7.8. The final inactivated MoFe-protein has an increased hydrodynamic radius compared to that of the native MoFe-protein, yet it has a full complement of iron and molybdenum. Significantly, the modified MoFe-protein retains the ability to specifically interact with its nitrogenase partner, the Fe-protein, as judged by the support of ATP hydrolysis and by formation of a tight complex with the Fe-protein in the presence of ATP and aluminum fluoride. The turnover-dependent inactivation coupled to conformational change suggests a mechanism-based transformation that may provide a new probe of nitrogenase catalysis. PMID:24392967

Turnover-dependent inactivation of the nitrogenase MoFe-protein at high pH.

PubMed

Yang, Kun-Yun; Haynes, Chad A; Spatzal, Thomas; Rees, Douglas C; Howard, James B

2014-01-21

Proton uptake accompanies the reduction of all known substrates by nitrogenase. As a consequence, a higher pH should limit the availability of protons as a substrate essential for turnover, thereby increasing the proportion of more highly reduced forms of the enzyme for further study. The utility of the high-pH approach would appear to be problematic in view of the observation reported by Pham and Burgess [(1993) Biochemistry 32, 13725-13731] that the MoFe-protein undergoes irreversible protein denaturation above pH 8.65. In contrast, we found by both enzyme activity and crystallographic analyses that the MoFe-protein is stable when incubated at pH 9.5. We did observe, however, that at higher pHs and under turnover conditions, the MoFe-protein is slowly inactivated. While a normal, albeit low, level of substrate reduction occurs under these conditions, the MoFe-protein undergoes a complex transformation; initially, the enzyme is reversibly inhibited for substrate reduction at pH 9.5, yet in a second, slower process, the MoFe-protein becomes irreversibly inactivated as measured by substrate reduction activity at the optimal pH of 7.8. The final inactivated MoFe-protein has an increased hydrodynamic radius compared to that of the native MoFe-protein, yet it has a full complement of iron and molybdenum. Significantly, the modified MoFe-protein retains the ability to specifically interact with its nitrogenase partner, the Fe-protein, as judged by the support of ATP hydrolysis and by formation of a tight complex with the Fe-protein in the presence of ATP and aluminum fluoride. The turnover-dependent inactivation coupled to conformational change suggests a mechanism-based transformation that may provide a new probe of nitrogenase catalysis.

Fabrication of MgFe2O4/MoS2 Heterostructure Nanowires for Photoelectrochemical Catalysis.

PubMed

Fan, Weiqiang; Li, Meng; Bai, Hongye; Xu, Dongbo; Chen, Chao; Li, Chunfa; Ge, Yilin; Shi, Weidong

2016-02-16

A novel one-dimensional MgFe2O4/MoS2 heterostructure has been successfully designed and fabricated. The bare MgFe2O4 was obtained as uniform nanowires through electrospinning, and MoS2 thin film appeared on the surface of MgFe2O4 after further chemical vapor deposition. The structure of the MgFe2O4/MoS2 heterostructure was systematic investigated by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectrometry (XPS), and Raman spectra. According to electrochemical impedance spectroscopy (EIS) results, the MgFe2O4/MoS2 heterostructure showed a lower charge-transfer resistance compared with bare MgFe2O4, which indicated that the MoS2 played an important role in the enhancement of electron/hole mobility. MgFe2O4/MoS2 heterostructure can efficiently degrade tetracycline (TC), since the superoxide free-radical can be produced by sample under illumination due to the active species trapping and electron spin resonance (ESR) measurement, and the optimal photoelectrochemical degradation rate of TC can be achieved up to 92% (radiation intensity: 47 mW/cm(2), 2 h). Taking account of its unique semiconductor band gap structure, MgFe2O4/MoS2 can also be used as an photoelectrochemical anode for hydrogen production by water splitting, and the hydrogen production rate of MgFe2O4/MoS2 was 5.8 mmol/h·m(2) (radiation intensity: 47 mW/cm(2)), which is about 1.7 times that of MgFe2O4.

Mineral sulphide-lime reactions and effect of CaO/C mole ratio during carbothermic reduction of complex mineral sulphides

NASA Astrophysics Data System (ADS)

Hara, Yotamu Stephen Rainford

2014-01-01

Mineral sulphide (MS)-lime (CaO) ion exchange reactions (MS + CaO = MO + CaS) and the effect of CaO/C mole ratio during carbothermic reduction (MS + CaO + C = M + CaS + CO(g)) were investigated for complex froth flotation mineral sulphide concentrates. Phases in the partially and fully reacted samples were characterised by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The primary phases during mineral sulphide-lime ion exchange reactions are Fe3O4, CaSO4 Cu2S, and CaS. A complex liquid phase of Ca2CuFeO3S forms during mineral sulphide-lime exchange reactions above 1173 K. The formation mechanisms of Ca2CuFeO3S liquid phase are determined by characterising the partially reacted samples. The reduction rate and extent of mineral sulphides in the presence of CaO and C increase with the increase in CaO/C ratio. The metallic phases are surrounded by the CaS rich phase at CaO/C > 1, but the metallic phases and CaS are found as separate phases at CaO/C < 1. Experimental results show that the stoichiometric ratio of carbon should be slightly higher than that of CaO. The reactions between CaO and gangue minerals (SiO2 and Al2O3) are only observed at CaO/C > 1 and the reacted samples are excessively sintered.

Concentrations and health risk assessment of trace elements in animal-derived food in southern China.

PubMed

Wu, Yaketon; Zhang, Huimin; Liu, Guihua; Zhang, Jianqing; Wang, Jizhong; Yu, Yingxin; Lu, Shaoyou

2016-02-01

This study aimed to investigate the levels of trace elements in animal-derived food in Shenzhen, Southern China. The concentrations of 14 trace elements (Cd, Hg, Pb, As, Cr, Cu, Fe, Zn, Mn, Mo, Ni, Co, Se and Ti) in a total of 220 meat samples, collected from the local markets of Shenzhen were determined. Cu, Fe and Zn were the major elements, with concentrations approximately 2-3 orders of magnitude higher than those of other elements. However, the daily intakes of Cu, Fe and Zn merely via the consumption of the meat products were lower than the recommended nutrient intake values provided by the 2013 Chinese Dietary Guide. Among the non-essential trace elements, Cd was accumulated in animal viscera, and the concentration ratios of chicken gizzard/chicken, chicken liver/chicken, pig kidney/pork and pig liver/pork were 41.6, 55.2, 863 and 177, respectively. In addition, high concentrations of As were found in aquatic products, especially in marine fish. The concentration of As in marine fish was slightly higher than the limits recommended by China, USA and Croatia. The health risk assessment of trace elements through the consumption of meat products by adult residents in Shenzhen was evaluated by using the target hazard quotient (THQ) method. The total THQ was greater than 1, implying a potential health risk. Approximately 66% of total THQ values, mainly from As, were from the consumption of aquatic products. Copyright © 2015 Elsevier Ltd. All rights reserved.

Three 3D hybrid networks based on octamolybdates and different Cu{sup I}/Cu{sup II}-bis(triazole) motifs

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

Zhang, Chun-Jing; Pang, Hai-Jun; Tang, Qun

2010-12-15

Three 3D compounds based on octamolybdate clusters and various Cu{sup I}/Cu{sup II}-bis(triazole) motifs, [Cu{sup I}{sub 2}btb][{beta}-Mo{sub 8}O{sub 26}]{sub 0.5} (1), [Cu{sup I}{sub 2}btpe][{beta}-Mo{sub 8}O{sub 26}]{sub 0.5} (2), and [Cu{sup II}(btpe){sub 2}][{beta}-Mo{sub 8}O{sub 26}]{sub 0.5} (3) [btb=1,4-bis(1,2,4-triazol-1-yl)butane, btpe=1,5-bis(1,2,4-triazol-1-yl)pentane], were isolated via tuning flexible ligand spacer length and metal coordination preferences. In 1, the copper(I)-btb motif is a one-dimensional (1D) chain which is further linked by hexadentate {beta}-[Mo{sub 8}O{sub 26}]{sup 4-} clusters via coordinating to Cu{sup I} cations giving a 3D structure. In 2, the copper(I)-btpe motif exhibits a 'stairs'-like [Cu{sup I}{sub 2}btpe]{sup 2+} sheet, and the tetradentate {beta}-[Mo{sub 8}O{sub 26}]{sup 4-}more » clusters interact with two neighboring [Cu{sup I}{sub 2}btpe]{sup 2+} sheets constructing a 3D framework. In 3, the copper(II)-btpe motif possesses a novel (2D{yields}3D) interdigitated structure, which is further connected by the tetradentate {beta}-[Mo{sub 8}O{sub 26}]{sup 4-} clusters forming a 3D framework. The thermal stability and luminescent properties of 1-3 are investigated in the solid state. -- Graphical abstract: Three 3D compounds based on {beta}-[Mo{sub 8}O{sub 26}]{sup 4-} clusters with different Cu{sup I}/Cu{sup II}-bis(triazole) motifs were synthesized by regularly tuning flexible ligand spacer length and metal coordination preferences. Display Omitted« less

Facile synthesis of CuFe2O4-Fe2O3 composite for high-performance supercapacitor electrode applications

NASA Astrophysics Data System (ADS)

Khan, Rashid; Habib, Muhammad; Gondal, Mohammed A.; Khalil, Adnan; Rehman, Zia Ur; Muhammad, Zahir; Haleem, Yasir A.; Wang, Changda; Wu, Chuan Qiang; Song, Li

2017-10-01

We report the synthesis of CuFe2O4-Fe2O3 composite material for efficient and highly stable supercapacitor electrode by using eco-friendly low-temperature co-precipitation method. The CuFe2O4-Fe2O3 composite demonstrated the highest specific capacitance of 638.24 F g-1 and excellent stability up to 2000 charge/discharge cycles. The achieved capacitance value is 16 times higher than that of pure CuFe2O4. The results revealed the extraordinary performance of CuFe2O4-Fe2O3 composite as supercapacitor electrode with excellent retention in comparison to CuFe2O4. The enhanced electrochemical activity of CuFe2O4-Fe2O3 composite is attributed to the synergistic effect which is responsible for redox coupling between Cu2+ and Fe3+ that has never been achieved by single component before.

Metal ions potentiate microglia responsiveness to endotoxin.

PubMed

Rachmawati, Dessy; Peferoen, Laura A N; Vogel, Daphne Y S; Alsalem, Inás W A; Amor, Sandra; Bontkes, Hetty J; von Blomberg, B Mary E; Scheper, Rik J; van Hoogstraten, Ingrid M W

2016-02-15

Oral metal exposure has been associated with diverse adverse reactions, including neurotoxicity. We showed previously that dentally applied metals activate dendritic cells (MoDC) via TLR4 (Ni, Co, Pd) and TLR3 (Au). It is still unknown whether the low levels of dental metals reaching the brain can trigger local innate cells or prime them to become more responsive. Here we tested whether dentally applied metals (Cr, Fe, Co, Ni, Cu, Zn, Au, Hg) activate primary human microglia in vitro and, as a model, monocytic THP-1-cells, in high non-toxic as well as near-physiological concentrations. In addition the effects of 'near-physiological' metal exposure on endotoxin (LPS) responsiveness of these cells were evaluated. IL-8 and IL-6 production after 24h was used as read out. In high, non-toxic concentrations all transition metals except Cr induced IL-8 and IL-6 production in microglia, with Ni and Co providing the strongest stimulation. When using near-physiological doses (up to 10× the normal plasma concentration), only Zn and Cu induced significant IL-8 production. Of note, the latter metals also markedly potentiated LPS responsiveness of microglia and THP-1 cells. In conclusion, transition metals activate microglia similar to MoDCs. In near-physiological concentrations Zn and Cu are the most effective mediators of innate immune activation. A clear synergism between innate responses to Zn/Cu and LPS was observed, shedding new light on the possible relation between oral metal exposure and neurotoxicity. Copyright © 2015. Published by Elsevier B.V.

Self-assembled monolayer and multilayer films of the nanocluster [HxPMo12O40 subsetH4Mo72Fe30(O2CMe)15O254(H2O)68] on gold.

PubMed

Colorado, Ramon; Crouse, Christopher A; Zeigler, Christopher N; Barron, Andrew R

2008-08-19

Films of the molybdenum-iron nanocluster [H x PMo 12O 40 subsetH 4Mo 72Fe 30(O 2CMe) 15O 254(H2O) 68] (FeMoC) were generated on gold via the self-assembly technique using two divergent routes. The first route entails the self-assembly of unfunctionalized FeMoC onto a preprepared carboxyl-terminated SAM on gold. The second route involves the preparation of thiol-terminated functionalized FeMoC clusters, which are then allowed to self-assemble onto bare gold surfaces. Monolayer films of FeMoC clusters are attained via both routes, with the second route requiring shorter immersion times (2 days) than the first route (6 days). Multilayer films of FeMoC are formed via the second route for immersion times longer than 2 days. Characterization of these films using optical ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy confirm the self-assembly of the clusters on the surfaces.

Metal trafficking for nitrogen fixation: NifQ donates molybdenum to NifEN/NifH for the biosynthesis of the nitrogenase FeMo-cofactor

PubMed Central

Hernandez, Jose A.; Curatti, Leonardo; Aznar, Constantino P.; Perova, Zinaida; Britt, R. David; Rubio, Luis M.

2008-01-01

The molybdenum nitrogenase, present in a diverse group of bacteria and archea, is the major contributor to biological nitrogen fixation. The nitrogenase active site contains an iron–molybdenum cofactor (FeMo-co) composed of 7Fe, 9S, 1Mo, one unidentified light atom, and homocitrate. The nifQ gene was known to be involved in the incorporation of molybdenum into nitrogenase. Here we show direct biochemical evidence for the role of NifQ in FeMo-co biosynthesis. As-isolated NifQ was found to carry a molybdenum–iron–sulfur cluster that serves as a specific molybdenum donor for FeMo-co biosynthesis. Purified NifQ supported in vitro FeMo-co synthesis in the absence of an additional molybdenum source. The mobilization of molybdenum from NifQ required the simultaneous participation of NifH and NifEN in the in vitro FeMo-co synthesis assay, suggesting that NifQ would be the physiological molybdenum donor to a hypothetical NifEN/NifH complex. PMID:18697927

Geochemical features of sulfides from the Deyin-1 hydrothermal field at the southern Mid-Atlantic Ridge near 15°S

NASA Astrophysics Data System (ADS)

Wang, Shujie; Li, Huaiming; Zhai, Shikui; Yu, Zenghui; Cai, Zongwei

2017-12-01

In this study, geochemical compositions of elements in sulfide samples collected from the Deyin-1 hydrothermal field near the 15°S southern Mid-Atlantic Ridge (SMAR) were analyzed by the X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS) to examine the enrichment regulations of ore-forming elements and hydrothermal mineralization. These sulfide precipitates can be classified macroscopically into three types: Fe-rich sulfide, Fe-Cu-rich sulfide and Fe-Zn-rich sulfide, and are characterized by the enrichment of base metal elements along with a sequence of Fe>Zn>Cu. Compared with sulfides from other hydrothermal fields on MAR, Zn concentrations of sulfides in the research area are significantly high, while Cu concentrations are relatively low. For all major, trace or rare-earth elements (REE), their concentrations and related characteristic parameters exhibit significant variations (up to one or two orders of magnitude), which indicates the sulfides from different hydrothermal vents or even a same station were formed at different stages of hydrothermal mineralization, and suggests the variations of chemical compositions of the hydrothermal fluid with respect to time. The hydrothermal temperatures of sulfides precipitation decreased gradually from station TVG10 (st.TVG10) to st.TVG12, and to st.TVG11, indicating that the precipitation of hydrothermal sulfides is subjected to conditions changed from high temperature to low temperature, and that the hydrothermal activity of study area was at the late stage of a general trend of evolution from strong to weak. The abnormally low concentrations of REE in sulfides and their similar chondrite-normalized REE patterns show that REEs in all sulfides were derived from a same source, but underwent different processes of migration or enrichment, or sulfides were formed at different stages of hydrothermal mineralization. The sulfides collected from the active hydrothermal vent were mainly attributed to precipitating directly from the hydrothermal fluid, while those collected from the extinct hydrothermal chimney might have already been altered by the seawater. Generally, ore-forming elements in the sulfides can be divided into three groups: Fe-based element group, Cu-based element group and Zn-based element group. The first group includes Fe, Mn, Cr, Mo, Sn, Rb and bio-enriching elements, such as P and Si, reflecting the similar characteristics to Fe in the study area. And the second group contains Cu, W, Co, Se, Te and Bi, suggesting the similar behavior with Cu. Moreover, the third group includes Zn, Hf, Hg, Cd, Ta, Ga, Pb, As, Ag, Ni and Sb, which indicates the geochemical characteristics of most dispersed trace elements controlled by Zn-bearing minerals to some extent.

The important role of polyvinylpyrrolidone and Cu on enhancing dechlorination of 2,4-dichlorophenol by Cu/Fe nanoparticles: Performance and mechanism study

NASA Astrophysics Data System (ADS)

Fang, Liping; Xu, Cuihong; Zhang, Wenbin; Huang, Li-Zhi

2018-03-01

The important role of polyvinylpyrrolidone (PVP) and Cu on the reductive dechlorination of 2,4-dichlorophenol (2,4-DCP) by Cu/Fe bimetal nanoparticles has been investigated. The synthesized PVP coated Cu/Fe bimetal nanoparticles with different Cu/Fe ratios were systematically characterized by FTIR, XRD, TEM and magnetic hysteresis loops. The Cu/Fe ratio and the PVP loading were optimized for dechlorination performance, and the optimum ratio of PVP to Cu/Fe was found to be 0.35 and the content of Cu in Cu/Fe nanoparticles was 41%. The presence of PVP as a dispersant/stabilizer results in a highly-dispersed Cu/Fe NPs and increase the reactivity of Cu/Fe NPs for 2,4-DCP removal. The dechlorination rate was enhanced at lower pH and higher temperature conditions. The presence of humic acid, PO43-, NO3-, SO42- leads to a slightly decreased removal efficiency of 2,4-DCP. The magnetic property of PVP-Cu/Fe nanoparticles allows rapid magnetic separation of the catalysts after reaction. A galvanic corrosion model was proposed where iron corrodes and transfers electrons to Cu-rich catalytic regions of the nanoparticles, and finally accelerating the reduction efficiency of 2,4-DCP.

High light harvesting efficiency CuInS2 quantum dots/TiO2/MoS2 photocatalysts for enhanced visible light photocatalytic H2 production.

PubMed

Yuan, Yong-Jun; Fang, Gaoliang; Chen, Daqin; Huang, Yanwei; Yang, Ling-Xia; Cao, Da-Peng; Wang, Jingjing; Yu, Zhen-Tao; Zou, Zhi-Gang

2018-04-24

Expanding the photoresponse range of TiO2-based photocatalysts is of great interest for photocatalytic H2 production. Herein, noble-metal-free CuInS2 quantum dots were employed as a novel inorganic dye to expand the visible light absorption of TiO2/MoS2 for solar H2 generation. The as-prepared CuInS2/TiO2/MoS2 photocatalysts exhibit broad absorption from the ultraviolet to near-infrared region. Under visible light irradiation (λ > 420 nm), the CuInS2/TiO2/MoS2 photocatalyst with 0.6 mmol g-1 CuInS2 and 0.5 wt% MoS2 showed the highest H2 evolution rate with a value of 1034 μmol h-1 g-1. Moreover, a considerable H2 evolution rate of 141 μmol h-1 g-1 was obtained under the irradiation of the optimized CuInS2/TiO2/MoS2 photocatalyst with >500 nm light. The reaction mechanism of the CuInS2/TiO2/MoS2 photocatalyst for photocatalytic H2 evolution was investigated in detail by photoluminescence decay study, and the results showed that the photoexcited electrons of CuInS2 can be transferred efficiently through TiO2 to MoS2 and then react with the absorbed protons to generate H2. The reported sensitization strategy tremendously improves the visible light absorption capacity and the photocatalytic performance of TiO2-based photocatalysts.

Evaluation of Complexation Ability Using a Sensor Electrode Chip Equipped with a Wireless Screening System

PubMed Central

Isoda, Takaaki; Urushibara, Ikuko; Sato, Hikaru; Yamauchi, Noriyoshi

2012-01-01

We fabricated an electrode chip with a structure coated by an insulation layer that contains dispersed SiO2 adsorbent particles modified by an amino-group on a source-drain electrode. Voltage changes caused by chelate molecule adsorption onto electrode surfaces and by specific cation interactions were investigated. The detection of specific cations without the presence of chelate molecules on the free electrode was also examined. By comparing both sets of results the complexation ability of the studied chelate molecules onto the electrode was evaluated. Five pairs of source-drain electrodes(×8 arrays) were fabricated on a glass substrate of 20 × 30mm in size. The individual Au/Cr (1.0/0.1μm thickness) electrodes had widths of 50 μm and an inter-electrode interval of 100μm.The fabricated source-drain electrodes were further coated with an insulation layer comprising a porous SiO2 particle modified amino-group to adsorb the chelate molecules. The electrode chip was equipped with a handy-type sensor signal analyzer that was mounted on an amplifier circuit using a Miniship™ or a system in a packaged LSI device. For electrode surfaces containing different adsorbed chelate molecules an increase in the sensor voltage depended on a combination of host-guest reactions and generally decreased in the following order:5,10,15,20-tetrakis(N-methylpyridinium-4-yl)-21H,23H-porphine, tetrakis(p-toluenesulfonate) (TMPyP)as a Cu2+chelator and Cu2+>2-nitroso-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol(nitroso-PSAP) as an Fe2+chelator and Fe2+>4,7-diphenyl-1,10-phenanthrolinedisulfonic acid, disodium salt (BPDSA) as an Fe2+chelatorand Fe2+>3-[3-(2,4-dimethylphenylcarbamoyl)-2-hydroxynaphthalene-1-yl-azo]-4-hydroxybenzenesulfonic acid, sodium salt (XB-1) as a Mg2+chelator and Mg2+>2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolinedisulfonic acid, disodium salt (BCIDSA) as a Cu2+chelator and Cu2+, respectively. In contrast, for the electrode surfaces with adsorbed O,O′-bis(2-aminoethyl)ethyleneglycol-N,N,N′,N′-tetraacetic acid (GEDTA) or O,O′-bis(2-aminophenyl)ethyleneglycol-N,N,N′,N′-tetraacetic acid, tetrapotassium salt, hydrate (BAPTA) as a Ca2+chelator no increase in the detection voltage was found for all the electrode tests conducted in the presence of Ca2+.To determine the differences in electrode detection, molecular orbital (MO) calculations of the chelate molecules and surface molecular modeling of the adsorbents were carried out. In accordance with frontier orbital theory, the lowest unoccupied MO (LUMO) of the chelate molecules can accept two lone pair electrons at the highest occupied MO (HOMO) of the amino group on the model surface structure of the SiO2 particle. As a result, a good correlation was obtained between the LUMO-HOMO difference and the ion response of all the electrodes tested. Based on the results obtained, the order of adsorbed chelate molecules on adsorption particles reflects the different metal ion detection abilities of the electrode chips. PMID:22969407

The conversion of CO 2 to methanol on orthorhombic β-Mo 2C and Cu/β-Mo 2C catalysts: Mechanism for admetal induced change in the selectivity and activity

DOE PAGES

Posada-Pérez, Sergio; Ramírez, Pedro J.; Gutiérrez, Ramón A.; ...

2016-02-01

Here, the conversion of CO 2 into methanol catalyzed by β-Mo 2C and Cu/β-Mo 2C surfaces has been investigated by means of a combined experimental and theoretical study. Experiments have shown the direct activation and dissociation of the CO 2 molecule on bare β-Mo 2C, whereas on Cu/β-Mo 2C, CO 2 must be assisted by hydrogen for its conversion. Methane and CO are the main products on the clean surface and methanol production is lower. However, the deposition of Cu clusters avoids methane formation and increases methanol production even above that corresponding to a model of the technical catalyst. DFTmore » calculations on surface models of both possible C- and Mo-terminations corroborate the experimental observations. Calculations for the clean Mo-terminated surface reveal the existence of two possible routes for methane production (C + 4H → CH 4; CH 3O + 3H → CH 4 + H 2O) which are competitive with methanol synthesis, displaying slightly lower energy barriers. On the other hand, a model for Cu deposited clusters on the Mo-terminated surface points towards a new route for methanol and CO production avoiding methane formation. The new route is a direct consequence of the generation of a Mo 2C–Cu interface. The present experimental and theoretical results entail the interesting catalytic properties of Mo 2C as an active support of metallic nanoparticles, and also illustrate how the deposition of a metal can drastically change the activity and selectivity of a carbide substrate for CO 2 hydrogenation.« less

β-Li0.37Na0.63Fe(MoO4)2

PubMed Central

Souilem, Amira; Zid, Mohamed Faouzi; Driss, Ahmed

2014-01-01

The title compound, lithium/sodium iron(III) bis­[ortho­molyb­date(VI)], was obtained by a solid-state reaction. The main structure units are an FeO6 octa­hedron, a distorted MoO6 octa­hedron and an MoO4 tetra­hedron sharing corners. The crystal structure is composed of infinite double MoFeO11 chains along the b-axis direction linked by corner-sharing to MoO4 tetra­hedra so as to form Fe2Mo3O19 ribbons. The cohesion between ribbons via mixed Mo—O—Fe bridges leads to layers arranged parallel to the bc plane. Adjacent layers are linked by corners shared between MoO4 tetra­hedra of one layer and FeO6 octa­hedra of the other layer. The Na+ and Li+ ions partially occupy the same general position, with a site-occupancy ratio of 0.631 (9):0.369 (1). A comparison is made with AFe(MoO4)2 (A = Li, Na, K and Cs) structures. PMID:24764805

Five inorganic–organic hybrids based on Keggin polyanion [SiMo{sub 12}O{sub 40}]{sup 4−}: From 0D to 2D network

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

Yu, Xiao-Yang, E-mail: yangyangyu0103@sohu.com; Jilin Institute of Chemical Technology, Jilin City, Jilin 132022; Cui, Xiao-Bing

2014-01-15

Five new inorganic–organic hybrids based on 4,4′-bipyridine and Keggin-type polyoxometalate [SiMo{sub 12}O{sub 40}]{sup 4−}, (SiMo{sub 12}O{sub 40})(H{sub 2}bipy){sub 2}·2H{sub 2}O (1), [Cu(Hbipy){sub 4}(HSiMo{sub 12}O{sub 40})(SiMo{sub 12}O{sub 40})](H{sub 2}bipy){sub 0.5}·7H{sub 2}O (2), [Cu{sub 2}(Hbipy){sub 6}(bipy)(SiMo{sub 12}O{sub 40}){sub 3}](Hbipy){sub 2}·6H{sub 2}O (3), [Cu(bipy){sub 2}(SiMo{sub 12}O{sub 40})](H{sub 2}bipy)·2H{sub 2}O (4) and [Cu{sub 2}(bipy){sub 4}(H{sub 2}O){sub 4}](SiMo{sub 12}O{sub 40})·13H{sub 2}O (5) (bipy=4,4′-bipyridine), have been hydrothermally synthesized. 1 consists of H{sub 2}bipy{sup 2+} and [SiMo{sub 12}O{sub 40}]{sup 4−} units. In 2, two [SiMo{sub 12}O{sub 40}]{sup 4−} are bridged by [Cu(Hbipy){sub 4}]{sup 6+} to form a [Cu(Hbipy){sub 4}(SiMo{sub 12}O{sub 40}){sub 2}]{sup 2−} dimmer. In 3, [SiMo{submore » 12}O{sub 40}]{sup 4−} polyanions acting as bidentated bridging ligands and monodentated auxiliary ligands connect [Cu{sub 2}(Hbipy){sub 6}(bipy)]{sup 8+} units into a 1D zigzag chain. In 4, [SiMo{sub 12}O{sub 40}]{sup 4−} polyanions bridge neighboring 1D [Cu(bipy){sub 2}]{sup 2+} double chains into a 2D extended layer. In 5, [SiMo{sub 12}O{sub 40}]{sup 4−} polyanions acting as templates site alternately upon the grids from both sides of the square grid [Cu{sub 2}(bipy){sub 4}(H{sub 2}O){sub 4}]{sup 4+} layer. In addition, the electrochemical behaviors of 1, 3 and 4 and the photocatalysis property of 1 have been investigated. - Graphical abstract: Five new compounds based on [SiMo{sub 12}O{sub 40}]{sup 4−} have been successfully generated. [SiMo{sub 12}O{sub 40}]{sup 4−} anions play different roles in the structures of the five compounds. Display Omitted - Highlights: • Five new compounds based on [SiMo{sub 12}O{sub 40}]{sup 4−} have been generated. • [SiMo{sub 12}O{sub 40}]{sup 4−} anions play different roles in the five structures. • The electrochemical behaviors of 1, 3 and 4 have been investigated. • The photocatalysis property of 1 has been investigated.« less

Comparative study on the reactivity of Fe/Cu bimetallic particles and zero valent iron (ZVI) under different conditions of N2, air or without aeration.

PubMed

Xiong, Zhaokun; Lai, Bo; Yang, Ping; Zhou, Yuexi; Wang, Juling; Fang, Shuping

2015-10-30

In order to further compare the degradation capacity of Fe(0) and Fe/Cu bimetallic system under different aeration conditions, the mineralization of PNP under different aeration conditions has been investigated thoroughly. The results show that the removal of PNP by Fe(0) or Fe/Cu system followed the pseudo-first-order reaction kinetics. Under the optimal conditions, the COD removal efficiencies obtained through Fe(0) or Fe/Cu system under different aeration conditions followed the trend that Fe/Cu (air)>Fe/Cu (N2: 0-30 min, air: 30-120 min)>control-Fe (air)>Fe/Cu (without aeration)>Fe/Cu (N2)>control-Fe (N2). It revealed that dissolved oxygen (DO) could improve the mineralization of PNP, and Cu could enhance the reactivity of Fe(0). In addition, the degradation of PNP was further analyzed by using UV-vis, FTIR and GC/MS, and the results suggest that Fe/Cu bimetallic system with air aeration could completely break the benzene ring and NO2 structure of PNP and could generate the nontoxic and biodegradable intermediate products. Meanwhile, most of these intermediate products were further mineralized into CO2 and H2O, which brought about a high COD removal efficiency (83.8%). Therefore, Fe/Cu bimetallic system with air aeration would be a promising process for toxic refractory industry wastewater. Copyright © 2015 Elsevier B.V. All rights reserved.

New series of triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) with framework structures and mobile silver ion sublattices

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

Kotova, Irina Yu.; Buryat State University, Smolin St. 24a, Ulan-Ude 670000, Buryat Republic; Solodovnikov, Sergey F.

Triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) of the NaMg{sub 3}In(MoO{sub 4}){sub 5} type were synthesized and single crystals of AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) were grown. In their structures, the MoO{sub 4} tetrahedra, pairs and trimers of edge-shared (Mg, R)O{sub 6} octahedra are connected by common vertices to form a 3D framework. Large framework cavities involve Ag{sup +} cations disordered on three nearby positions with CN=3+1 or 4+1. Alternating (Mg, R)O{sub 6} octahedra and MoO{sub 4} tetrahedra in the framework form quadrangular windows penetrable for Ag{sup +} at elevated temperatures.more » Above 653–673 K, the newly obtained molybdates demonstrate abrupt reduction of the activation energy to 0.4–0.6 eV. At 773 K, AgMg{sub 3}Al(MoO{sub 4}){sub 5} shows electric conductivity 2.5·10{sup −2} S/cm and E{sub a}=0.39 eV compatible with characteristics of the best ionic conductors of the NASICON type. - Graphical abstract: Triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) of the NaMg{sub 3}In(MoO{sub 4}){sub 5} type were synthesized, AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) were structurally characterized, ion-conductive properties of AgMg{sub 3}Al(MoO{sub 4}){sub 5} were measured. Display Omitted - Highlights: • Triple molybdates AgA{sub 3}R(MoO{sub 4}){sub 5} (A=Mg, R=Cr, Fe; A=Mn, R=Al, Cr, Fe, Sc, In) of the NaMg{sub 3}In(MoO{sub 4}){sub 5} type were synthesized. • Single crystals of AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) were grown and their crystal structures were determined. • Disordering Ag{sup +} ions and penetrable framework structures of AgMg{sub 3}R(MoO{sub 4}){sub 5} (R=Cr, Fe) suggest 2D-character of silver-ion mobility. • Measured ion-conductive properties of AgMg{sub 3}Al(MoO{sub 4}){sub 5} are compatible with characteristics of the best ionic conductors of the NASICON type.« less

Single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers: Reactant- and stoichiometry-dependent syntheses, effective photocatalytic properties

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

Zhang, Jinfang, E-mail: zjf260@jiangnan.edu.cn; Wang, Chao; Wang, Yinlin

2015-11-15

The systematic study on the reaction variables affecting single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers (CPs) is firstly demonstrated. Five anionic single cyanide-bridged Mo(W)/S/Cu cluster-based CPs {[Pr_4N][WS_4Cu_3(CN)_2]}{sub n} (1), {[Pr_4N][WS_4Cu_4(CN)_3]}{sub n} (2), {[Pr_4N][WOS_3Cu_3(CN)_2]}{sub n} (3), {[Bu_4N][WOS_3Cu_3(CN)_2]}{sub n} (4) and {[Bu_4N][MoOS_3Cu_3(CN)_2]}{sub n} (5) were prepared by varying the molar ratios of the starting materials, and the specific cations, cluster building blocks and central metal atoms in the cluster building blocks. 1 possesses an anionic 3D diamondoid framework constructed from 4-connected T-shaped clusters [WS{sub 4}Cu{sub 3}]{sup +} and single CN{sup −} bridges. 2 is fabricated from 6-connected planar ‘open’ clusters [WS{sub 4}Cu{sub 4}]{supmore » 2+} and single CN{sup −} bridges, forming an anionic 3D architecture with an “ACS” topology. 3 and 4 exhibit novel anionic 2-D double-layer networks, both constructed from nest-shaped clusters [WOS{sub 3}Cu{sub 3}]{sup +} linked by single CN{sup −} bridges, but containing the different cations [Pr{sub 4}N]{sup +} and [Bu{sub 4}N]{sup +}, respectively. 5 is constructed from nest-shaped clusters [MoOS{sub 3}Cu{sub 3}]{sup +} and single CN{sup −} bridges, with an anionic 3D diamondoid framework. The anionic frameworks of 1-5, all sustained by single CN{sup −} bridges, are non-interpenetrating and exhibit huge potential void volumes. Employing differing molar ratios of the reactants and varying the cluster building blocks resulted in differing single cyanide-bridged Mo(W)/S/Cu cluster-based CPs, while replacing the cation ([Pr{sub 4}N]{sup +} vs. [Bu{sub 4}N]{sup +}) was found to have negligible impact on the nature of the architecture. Unexpectedly, replacement of the central metal atom (W vs. Mo) in the cluster building blocks had a pronounced effect on the framework. Furthermore, the photocatalytic activities of heterothiometallic cluster-based CPs were firstly explored by monitoring the photodegradation of methylene blue (MB) under visible light irradiation, which reveals that 2 exhibits effective photocatalytic properties. - Highlights: • Reaction variables affecting Mo(W)/S/Cu cluster-based CPs is firstly explored. • Replacing central metal atom had a pronounced effect on W/S/Cu cluster-based CPs. • Photocatalytic activities of Mo(W)/S/Cu cluster-based CPs are firstly investigated.« less

Comparative studies on the room-temperature ferrielectric and ferrimagnetic Ni3TeO6-type A2FeMoO6 compounds (A = Sc, Lu)

PubMed Central

Song, Guang; Zhang, Weiyi

2016-01-01

First-principles calculations have been carried out to study the structural, electric, and magnetic properties of Ni3TeO6-type A2FeMoO6 compounds (A = Sc, Lu). Their electric and magnetic properties behave like room-temperature ferrielectric and ferrimagnetic insulators where polarization comes from the un-cancelled antiparallel dipoles of (A(1), Fe3+) and (A(2), Mo3+) ion groups, and magnetization from un-cancelled antiparallel moments of Fe3+ and Mo3+ ions. The net polarization increases with A’s ionic radius and is 7.1 and 8.7 μCcm−2 for Sc2FeMoO6 and Lu2FeMoO6, respectively. The net magnetic moment is 2 μB per formula unit. The magnetic transition temperature is estimated well above room-temperature due to the strong antiferromagnetic superexchange coupling among Fe3+ and Mo3+ spins. The estimated paraelectric to ferrielectric transition temperature is also well above room-temperature. Moreover, strong magnetoelectric coupling is also anticipated because the magnetic ions are involved both in polarization and magnetization. The fully relaxed Ni3TeO6-type A2FeMoO6 structures are free from soft-phonon modes and correspond to stable structures. As a result, Ni3TeO6-type A2FeMoO6 compounds are possible candidates for room-temperature multiferroics with large magnetization and polarization. PMID:26831406

Copper(II) sorption onto goethite, hematite and lepidocrocite: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2004-06-01

We measured the adsorption of Cu(II) onto goethite (α-FeOOH), hematite (α-Fe 2O 3) and lepidocrocite (γ-FeOOH) from pH 2-7. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 complexes. These form inner-sphere complexes with the iron (hydr)oxide surfaces by corner-sharing with two or three edge-sharing Fe(O,OH) 6 polyhedra. Our interpretation of the EXAFS data is supported by ab initio (density functional theory) geometries of analogue Fe 2(OH) 2(H 2O) 8Cu(OH) 4and Fe 3(OH) 4(H 2O) 10Cu 2(OH) 6 clusters. We find no evidence for surface complexes resulting from either monodentate corner-sharing or bidentate edge-sharing between (CuO 4H n) n-6 and Fe(O,OH) 6 polyhedra. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed even though we are supersaturated with respect to CuO and Cu(OH) 2. Having identified the bidentate (FeOH) 2Cu(OH) 20 and tridentate (Fe 3O(OH) 2)Cu 2(OH) 30 surface complexes, we are able to fit the experimental copper(II) adsorption data to the reactions 3( FeOH)+2 Cu2++3 H2O=( Fe3O( OH) 2) Cu2( OH) 30+4 H+ and 2( FeOH)+ Cu2++2 H2O=( FeOH) 2Cu( OH) 20+2 H+. The two stability constants are similar for the three iron (hydr)oxide phases investigated.

The mechanism of Klebsiella pneumoniae nitrogenase action. Pre-steady-state kinetics of H2 formation.

PubMed Central

Lowe, D J; Thorneley, R N

1984-01-01

A comprehensive model for the mechanism of nitrogenase action is used to simulate pre-steady-state kinetic data for H2 evolution in the presence and in the absence of N2, obtained by using a rapid-quench technique with nitrogenase from Klebsiella pneumoniae. These simulations use independently determined rate constants that define the model in terms of the following partial reactions: component protein association and dissociation, electron transfer from Fe protein to MoFe protein coupled to the hydrolysis of MgATP, reduction of oxidized Fe protein by Na2S2O4, reversible N2 binding by H2 displacement and H2 evolution. Two rate-limiting dissociations of oxidized Fe protein from reduced MoFe protein precede H2 evolution, which occurs from the free MoFe protein. Thus Fe protein suppresses H2 evolution by binding to the MoFe protein. This is a necessary condition for efficient N2 binding to reduced MoFe protein. PMID:6395861

Solid-phase synthesis of Cu2MoS4 nanoparticles for degradation of methyl blue under a halogen-tungsten lamp

NASA Astrophysics Data System (ADS)

Li, Shi-na; Ma, Rui-xin; Wang, Cheng-yan

2018-03-01

The Cu2MoS4 nanoparticles were prepared using a relatively simple and convenient solid-phase process, which was applied for the first time. The crystalline structure, morphology, and optical properties of Cu2MoS4 nanoparticles were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and UV-vis spectrophotometry. Cu2MoS4 nanoparticles having a band gap of 1.66 eV exhibits good photocatalytic activity in the degradation of methylene blue, which indicates that this simple process may be critical to facilitate the cheap production of photocatalysts.

Fractionation of Cu and Mo isotopes caused by vapor-liquid partitioning, evidence from the Dahutang W-Cu-Mo ore field

NASA Astrophysics Data System (ADS)

Yao, Junming; Mathur, Ryan; Sun, Weidong; Song, Weile; Chen, Huayong; Mutti, Laurence; Xiang, Xinkui; Luo, Xiaohong

2016-05-01

The study presents δ65Cu and δ97Mo isotope values from cogenetic chalcopyrite and molybdenite found in veins and breccias of the Dahutang W-Cu-Mo ore field in China. The samples span a 3-4 km range. Both isotopes show a significant degree of fractionation. Cu isotope values in the chalcopyrite range from -0.31‰ to +1.48‰, and Mo isotope values in the molybdenite range from -0.03‰ to +1.06‰. For the cogenetic sulfide veined samples, a negative slope relationship exists between δ65Cu and δ97Mo values, which suggest a similar fluid history. Rayleigh distillation models the vein samples' change in isotope values. The breccia samples do not fall on the trend, thus indicating a different source mineralization event. Measured fluid inclusion and δD and δ18O data from cogenetic quartz indicate changes in temperature, and mixing of fluids do not appear to cause the isotopic shifts measure. Related equilibrium processes associated with the partitioning of metal between the vapor-fluid in the hydrothermal system could be the probable cause for the relationship seen between the two isotope systems.

Synthesis of MoS2-reduced graphene oxide/Fe3O4 nanocomposite for enhanced electromagnetic interference shielding effectiveness

NASA Astrophysics Data System (ADS)

Prasad, Jagdees; Singh, Ashwani Kumar; Shah, Jyoti; Kotnala, R. K.; Singh, Kedar

2018-05-01

This article presents a facile two step hydrothermal process for the synthesis of MoS2-reduced graphene oxide/Fe3O4 (MoS2-rGO/Fe3O4) nanocomposite and its application as an excellent electromagnetic interference shielding material. Characterization tools like; scanning electron microscope, transmission electron microscope, x-ray diffraction, and Raman spectroscopy were used to confirm the formation of nanocomposite and found that spherical Fe3O4 nanoparticles are well dispersed over MoS2-rGO composite with average particle size ∼25–30 nm was confirmed by TEM. Structural characterization done by XRD was found inconsistent with the known lattice parameter of MoS2 nanosheet, reduced graphene oxide and Fe3O4 nanoparticles. Electromagnetic shielding effectiveness of MoS2-rGO/Fe3O4 nanocomposite was evaluated and found to be an excellent EMI shielding material in X-band range (8.0–12.0 GHz). MoS2-rGO composite shows poor shielding capacity (SET ∼ 3.81 dB) in entire range as compared to MoS2-rGO/Fe3O4 nanocomposite (SET ∼ 8.27 dB). It is due to interfacial polarization in the presence of EM field. The result indicates that MoS2-rGO/Fe3O4 nanocomposite provide a new stage for the next generation in high-performance EM wave absorption and EMI shielding effectiveness.

Grain Boundary Character Distributions In Isostructural Materials

NASA Astrophysics Data System (ADS)

Ratanaphan, Sutatch

Anisotropic grain boundary character distributions (GBCDs), which influence macroscopic materials properties, are thought to be controlled by the grain boundary energy anisotropy. Structurally, grain boundary could be viewed as two free surfaces joined together. Grain boundary energy could be simply defined by the total excess energy for creating two free surfaces minus the energy gained when new bonds are formed between these surfaces. This implies that different crystal structure should have different GBEDs and GBCDs. It was recently discovered that grain boundary energy distributions (GBED) in isostructural materials, a class of materials that share the same crystal structure, are directly related to one another. This suggests that GBCDs in isostructural materials might also be related in a similar way. To test this hypothesis, electron backscatter diffraction (EBSD) was used to map grain orientations in Ag, Au, Cu, Fe, and Mo. The GBCDs were determined from the stereological interpretation of EBSD maps containing on the order of 100,000 grains. It was found that the GBCDs of face-centered cubic (FCC) metals are statistically correlated, while the GBCDs of body-centered cubic (BCC) Fe and Mo are not correlated to the GBCD of FCC metals. The degree of the correlations among the FCC metals is weaker if there are significant differences in grain shape or texture. For example, Ag has the weakest correlation to the other FCC materials and also has quantitatively different grain shapes and texture. The relationship between the populations and energies of grain boundaries was also studied. By comparing the GBCDs of Al, Au, Cu, and Ni to the energies of 388 grain boundaries previously calculated by the Embedded Atom Method (EAM), we observed a moderately inverse correlation between the relative areas of grain boundaries and their energies. Interestingly, there are strong inverse correlations between the energies and populations of the most common grain boundaries (Sigma3, Sigma9, and Sigma27). Because the enhancement of twin related boundaries due to the prevalence Sigma3 boundaries results in a decrease in the grain boundary populations for the other boundary types, this inverse correlation is influenced by the crystallographic constraints at triple junctions. In other words, having an anisotropic misorientation distribution with strong maxima for certain boundaries biases the inverse correlation between grain boundary population and energy for other boundaries and causes different slopes at each misorientation. Interestingly, the inverse correlation at each misorientation is consistent with the Boltzmann distribution. Based on our results, it is possible to predict the GBCDs and GBEDs in isostructural polycrystalline materials by using a single GBCD and GBED. This principle is demonstrated by predicting the GBCD and GBED of Actinium (Ac). To investigate the GBED in the isostructural BCC metals, the energies of 408 grain boundaries in Fe and Mo were computed using atomistic simulations based on the embedded-atom method (EAM) potential. We found that the calculated boundary energies in Fe and Mo were strongly correlated and scaled with the ratio of the cohesive energy divided by the square of the lattice constant (Ecoh/a02). We would expect that the GBCD of Fe and Mo might be correlated in a similar manner to that of FCC metals. To test this hypothesis, we compared the GBCDs of Fe and Mo. We found that the GBCDs of Fe and Mo are moderately and strongly correlated when all boundary types and only Sigma3 boundaries were considered, respectively. In this thesis, the results demonstrated that the GBCDs of isostructural materials are correlated with one another and the magnitudes of correlation coefficients varied. Reduced correlations were observed when there were differences in the microstructure and crystallographic texture. The inverse relationship between grain boundary population and energy is more strongly correlated at each misorientation than over the entire five macroscopic parameters of grain boundary, especially when there is significant misorientation texture. This relationship leads to GBCDs of isostructural materials that are also more strongly correlated at each misorientation than over the entire grain boundary space.

The coordination chemistry of the neutral tris-2-pyridyl silicon ligand [PhSi(6-Me-2-py)3].

PubMed

Plajer, Alex J; Colebatch, Annie L; Enders, Markus; García-Romero, Álvaro; Bond, Andrew D; García-Rodríguez, Raúl; Wright, Dominic S

2018-05-22

Difficulties in the preparation of neutral ligands of the type [RSi(2-py)3] (where 2-py is an unfunctionalised 2-pyridyl ring unit) have thwarted efforts to expand the coordination chemistry of ligands of this type. However, simply switching the pyridyl substituents to 6-methyl-pyridyl groups (6-Me-2-py) in the current paper has allowed smooth, high-yielding access to the [PhSi(6-Me-2-py)3] ligand (1), and the first exploration of its coordination chemistry with transition metals. The synthesis, single-crystal X-ray structures and solution dynamics of the new complexes [{PhSi(6-Me-2-py)3}CuCH3CN][PF6], [{PhSi(6-Me-2-py)3}CuCH3CN][CuCl2], [{PhSi(6-Me-2-py)3}FeCl2], [{PhSi(6-Me-2-py)3}Mo(CO)3] and [{PhSi(6-Me-2-py)3}CoCl2] are reported. The paramagnetic Fe2+ and Co2+ complexes show strongly shifted NMR resonances for the coordinated pyridyl units due to large Fermi-contact shifts. However, magnetic anisotropy also leads to considerable pseudo-contact shifts so that both contributions have to be included in the paramagnetic NMR analysis.

The Content of the 14 Metals in Cancellous and Cortical Bone of the Hip Joint Affected by Osteoarthritis

PubMed Central

Zioła-Frankowska, Anetta; Kubaszewski, Łukasz; Dąbrowski, Mikołaj; Kowalski, Artur; Rogala, Piotr; Strzyżewski, Wojciech; Łabędź, Wojciech; Kanicky, Viktor

2015-01-01

The aim of the study was to determine the content of particular elements Ca, Mg, P, Na, K, Zn, Cu, Fe, Mo, Cr, Ni, Ba, Sr, and Pb in the proximal femur bone tissue (cancellous and cortical bone) of 96 patients undergoing total hip replacement for osteoarthritis using ICP-AES and FAAS analytical techniques. The interdependencies among these elements and their correlations depended on factors including age, gender, place of residence, tobacco consumption, alcohol consumption, exposure to environmental pollution, physical activity, and type of degenerative change which were examined by statistical and chemometric methods. The factors that exerted the greatest influence on the elements in the femoral head and neck were tobacco smoking (higher Cr and Ni content in smokers), alcohol consumption (higher concentrations of Ni, Cu in people who consume alcohol), and gender (higher Cu, Zn, and Ni concentrations in men). The factors influencing Pb accumulation in bone tissue were tobacco, alcohol, gender, and age. In primary and secondary osteoarthritis of the hip, the content and interactions of elements are different (mainly those of Fe and Pb). There were no significant differences in the concentrations of elements in the femoral head and neck that could be attributed to residence or physical activity. PMID:26357659

Intense molybdenum accumulation in sediments underneath a nitrogenous water column and implications for the reconstruction of paleo-redox conditions based on molybdenum isotopes

NASA Astrophysics Data System (ADS)

Scholz, Florian; Siebert, Christopher; Dale, Andrew W.; Frank, Martin

2017-09-01

The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 μg g-1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery caused the 'anomalously' high interglacial Mo accumulation rates in the paleo-record. Our findings suggest that Fe- and nitrate-dependent Mo shuttling under nitrogenous conditions needs to be considered a possible reason for sedimentary Mo enrichments during past periods of widespread anoxia in the open ocean.

The interaction between dietary Fe, Cu and stress in Cu-67 retention and serum ceruloplasmin (Cp) activity in rats

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

Pellett, L.; Kattelmann, K.; Zinn, K.

1991-03-15

The objectives of the study were to determine the effects of dietary Fe and stress on Cu-67 retention and serum Cp activity in the rat. A 2 {times} 2 {times} 2 factorial arrangement of treatments was utilized. Male Sprague Dawley weanling rats were fed AIN-76 diets ad lib containing 0.8 ppm Cu (CuD) or 5.7 ppm Cu (CuA) with 22.5 ppm Fe (FeA) or 280 ppm Fe (FeE). After 19 days, one-half of the animals of each treatment were stressed by an intramuscular injection of 0.1 ml turpentine/100 gm body weight. Forty-eight hours later, animals were gavaged with Cu-67 andmore » counted over a 7 day period in a whole body high resolution gamma counter. Cu-67 retention was 20% higher in CuD rats compared to CuA rats. There were no significant effects caused by Fe or stress or the interaction between these variables on Cu-67 retention. In rats fed FeE-CuA diets, serum Cp activity was significantly depressed compared to rats fed FeA-CuA diets. These reductions in the acute phase protein Cp, were 85% and 70% in nonstressed and stressed rats, respectively. The results of this study suggest that the negative interaction effects of excess Fe on Cu utilization does not occur at the site of Cu absorption, but within the body and specifically in the liver.« less

Comparison of the early stages of condensation of Cu and Ag on Mo/100/ with Cu and Ag on W/100/

NASA Technical Reports Server (NTRS)

Soria, F.; Poppa, H.

1980-01-01

The adsorption and condensation of Cu and Ag, up to several monolayers in thickness, onto Mo(100) has been observed at pressures below 2 times 10 to the -10th torr in a study that used combined LEED, Auger, TDS (Thermal Desorption Spectroscopy), and work function measurements in a single experimental setup. The results show that Cu behaves similarly on Mo(100) and W(100) substrates, while some differences are found for Ag adsorption.

Fe and Cu isotope mass balances in the human body

NASA Astrophysics Data System (ADS)

Balter, V.; Albarede, F.; Jaouen, K.

2011-12-01

The ranges of the Fe and Cu isotope compositions in the human body are large, i.e. ~3% and ~2%, respectively. Both isotopic fractionations appear to be mainly controlled by redox conditions. The Fe and Cu isotope compositions of the tissues analyzed so far plot on a mixing hyperbolae between a reduced and an oxidized metals pools. The reduced metals pool is composed by erythrocytes, where Fe is bounded to hemoglobin as Fe(II) and Cu to superoxide-dismutase as Cu(I). The oxidized metals pool is composed by hepatocytes, where Fe and Cu are stored as Fe(III) ferritin and as Cu(II) ceruloplasmine, respectively. The position of each biological component in the δ56Fe-δ65Cu diagram therefore reflects the oxidation state of Fe and Cu of the predominant metal carrier protein and allows to quantify Fe and Cu fluxes between organs using mass balance calculations. For instance, serum and clot Fe and Cu isotope compositions show that current biological models of erythropoiesis violates mass conservation requirements, and suggest hidden Fe and Cu pathways during red blood cells synthesis. The results also show that a coupled Fe-Cu strong gender isotopic effect is observed in various organs. The isotopic difference between men and women is unlikely to be due to differential dietary uptake or endometrium loss, but rather reflects the effect of menstrual losses and a correlative solicitation of hepatic stores. We speculate that thorough studies of the metabolism of stable isotopes in normal conditions is a prerequisite for the understanding of the pathological dysregulations.

Standard Gibbs energy of formation of Mo 3Te 4 by emf measurements

NASA Astrophysics Data System (ADS)

Mallika, C.; Sreedharan, O. M.

1990-03-01

The emf of the galvanic cells Pt, Mo, MoO 2¦8 YSZ¦'FeO', Fe, Pt (I) and Pt, Fe,'FeO' ¦8 YSZ¦MoO 2, Mo 3Te 4, MoTe 2(α), C, Pt (II) were measured over the temperature ranges 837 to 1151 K and 775 to 1196 K, respectively, using 8 mass% yttria-stabilized zirconia (8 YSZ) as the solid electrolyte. From the emf values, the partial molar Gibbs energy of solution of molybdenum in Mo 3Te 4/MoTe 2(α), Δ ḠMo was found to be Δ ḠMo ± 1.19 ( kJ/mol) = -025.08 + 0.00420T(K) . Using the literature data for the Gibbs energy of formation of MoTe 2(α). the expression ΔG° f( Mo3Te4, s) ± 5.97 (kj/mol) = -253.58 + 0.09214 T( K) was derived for the range 775 to 1196 K. A third-law analysis yielded a value of -209 ± 10 kJ/mol for ΔH° f.298o of Mo 3Te 4(s).

Extraction of valuable metals by microwave discharge in crude oil

NASA Astrophysics Data System (ADS)

Lebedev, Yu A.; Averin, K. A.

2018-05-01

Microwave discharges in liquids are a new direction in the physics and chemistry of low temperature plasma. The article describes the results of experiments on the separation of metals from oil when a microwave discharge is created at atmospheric pressure in its volume. It is shown for the first time that the content of metals Al, Co, Cu, Fe, Mo, Ni, V, and Zn in a tree-like structure deposited on the microwave antenna is up to 10 times higher than their content in the initial substance.

Thermal Conductivity of Metals and Alloys at Low Temperatures. A Review of the Literature

DTIC Science & Technology

1954-09-01

between OnF and Ag , Ni. anda .. er.ta.. ducovruml s f (96) .. J m Sa . Oye-rveehg odciiy.. W.1 Powe28). sample .. &...... - .3a. IM. C.. Dp..... .Je...R. KikuchiBERYLIUM (932). Cominrl See figure 2, under "Metallic Elements".. E.J. Lewi 6.0 Ag ............. k= 1.16at27WC...9 Al 2 Zn, 0.1 .71 1.32 ........................ Aged . Mo. U ~5.Cu, 0.5 Si, 0.8 Fe, 0.5 Mn, 1.23 ......................... Quenched. MIA.B

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

Murgia, Fabrizio; Antitomaso, Philippe; Stievano, Lorenzo

The ternary Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} was successfully synthetized using a simple and cost-effective solid-state microwave-assisted reaction. While solid-state routes require days of high-temperature treatment under inert atmosphere, highly pure and crystalline Cu{sub 2}Mo{sub 6}S{sub 8} could be obtained in only 400 s from this precursor, the Chevrel binary phase Mo{sub 6}S{sub 8} was then obtained by copper removal through acidic leaching, and was evaluated as a positive electrode material for Mg-battery. The electrochemical performance in half-cell configuration shows reversible capacity exceeding 80 mAh/g, which is comparable to previous works carried out with materials synthesized by conventional high-temperaturemore » solid-state routes. - Graphical abstract: Ultrafast micro-wave synthesis of Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} towards Mo{sub 6}S{sub 8} as positive electrode of Mg-battery. - Highlights: • Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} is synthesized by fast microwave-assisted solid-state reaction. • Highly-pure and well-crystalline Cu{sub 2}Mo{sub 6}S{sub 8} is obtained. • Mo{sub 6}S{sub 8} obtained from leaching is tested as a positive electrode for Mg batteries.« less

COMPARATIVE ASSESSMENT OF THE COMPOSITION AND CHARGE STATE OF NITROGENASE FeMo-COFACTOR

PubMed Central

Harris, Travis V.; Szilagyi, Robert K.

2011-01-01

A significant limitation in our understanding of the molecular mechanism of biological nitrogen fixation is the uncertain composition of the FeMo-cofactor (FeMo-co) of nitrogenase. In this study we present a systematic, density functional theory-based evaluation of spin coupling schemes, iron oxidation states, ligand protonation states, and interstitial ligand composition using a wide range of experimental criteria. The employed functionals and basis sets were validated with molecular orbital information from X-ray absorption spectroscopic data of relevant iron-sulfur clusters. Independently from the employed level of theory, the electronic structure with the greatest number of antiferromagnetic interactions corresponds to the lowest energy state for a given charge and oxidation state distribution of the iron ions. The relative spin state energies of resting and oxidized FeMo-co already allowed the exclusion of certain iron oxidation state distributions and interstitial ligand compositions. Geometry optimized FeMo-co structures of several models further eliminated additional states and compositions, while reduction potentials indicated a strong preference for the most likely charge state of FeMo-co. Mössbauer and ENDOR parameter calculations were found to be remarkably dependent on the employed training set, density functional and basis set. Overall, we found that a more oxidized [MoIV-2FeII-5FeIII-9S2−-C4−] composition with a hydroxyl-protonated homocitrate ligand satisfies all of the available experimental criteria, and is thus favored over the currently preferred composition of [MoIV-4FeII-3FeIII-9S2−-N3−] from the literature. PMID:21545160

Effects of Pd substitution on the thermoelectric and electronic properties of delafossite Cu{sub 1−x}Pd{sub x}FeO{sub 2} (x=0.01, 0.03 and 0.05)

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

Ruttanapun, Chesta, E-mail: chesta.ruttanapun@gmail.com

Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} (x=0.01, 0.03 and 005) delafossite was prepared by solid state reactions and was calcined/sintered at 1050 °C. The effect of Pd{sup 2+} substitution for the Cu{sup 1+} sites on the thermoelectric and electronic properties of Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} were investigated. The crystal structure, oxygen decomposition, thermoelectric and electronic properties were characterized by X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy (XPS), Seebeck coefficient, electrical conductivity and thermal conductivity measurements. The characterization showed that Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} formed a hexagonal delafossite structure with R3−m symmetry. The existence of Pd{sup 2+}, Cu{sup 1+}, Cu{sup 2+}, Fe{sup 3+},more » Fe{sup 4+} and O was revealed from the XPS results. Confirmation of Pd{sup 2+} substitution for the Cu{sup 1+} sites occurred by increasing the c-axis in the lattice parameter with a Pd content. The O content intercalated at the center of the triangular Cu acted as a support to produce Cu{sup 2+} ions and was reduced with an increasing Pd content. The mixed valencies of Cu{sup 1+}/Cu{sup 2+} and Cu{sup 1+}/Pd{sup 2+} in the Cu layer changed the electrical conductivity and the Fe{sup 3+}/Fe{sup 4+} mixed valencies in the FeO{sub 6} layer caused the Seebeck coefficient to increase. Both the electrical conductivity and Seebeck coefficient for Pd contents of x=0.01 and 0.03 were higher than that of non-doped CuFeO{sub 2}. The low thermal conductivity of Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} resulted from the substitution of Pd, which has a large atomic mass, into structure. The Jonker plot indicated that the electronic properties displayed a degenerate density of states and that Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} was a semiconductor. A high ZT value of 0.055 was obtained for a Pd content of 0.03 at 950 K. The Pd{sup 2+} substitution for the Cu{sup 1+} sites influenced the thermoelectric and electronic properties of the delafossite Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} samples. - Graphical abstract: Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} (x=0.01, 0.03 and 005) delafossite was prepared by solid state reactions. The characterization showed that Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} formed a hexagonal delafossite structure with R3−m symmetry. The existence of Pd{sup 2+}, Cu{sup 1+}, Cu{sup 2+}, Fe{sup 3+}, Fe{sup 4+} and O was revealed from the XPS results. The O content intercalated at the center of the triangular Cu acted as a support to produce Cu{sup 2+} ions and was reduced with an increasing Pd content. The mixed valencies of Cu{sup 1+}/Cu{sup 2+} and Cu{sup 1+}/Pd{sup 2+} in the Cu layer changed the electrical conductivity and the Fe{sup 3+}/Fe{sup 4+} mixed valencies in the FeO{sub 6} layer caused the Seebeck coefficient to increase. Both the electrical conductivity and Seebeck coefficient for Pd contents of x=0.01 and 0.03 were higher than that of non-doped CuFeO{sub 2}. The low thermal conductivity of Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} resulted from the substitution of Pd, which has a large atomic mass, into structure. A high ZT value of 0.055 was obtained for a Pd content of 0.03 at 950 K. The Pd{sup 2+} substitution for the Cu{sup 1+} sites influenced the thermoelectric and electronic properties of the delafossite Cu{sub (1−x)}Pd{sub (x)}FeO{sub 2} samples. - Highlights: • New compound of Cu{sub 1−x}Pd{sub x}FeO{sub 2} (x=0.01, 0.03 and 0.05) forms phase of delafossite. • The compound displays p-type thermoelectric materials. • The Pd-substituted for Cu{sup 1+} sites forms Pd{sup 2+}. • Mixed valencies of Cu{sup +}/Cu{sup 2+}, Cu{sup +}/Pd{sup 2+} and Fe{sup 3+}/Fe{sup 4+} appear in the compound. • Large atomic mass of Pd-substituted causes low thermal conductivity.« less

Elemental analysis of different varieties of rice samples using XRF technique

NASA Astrophysics Data System (ADS)

Kaur, Jaspreet; Kumar, Anil

2016-05-01

Rice is most consumed staple food in the world providing over 21% of the calorie intake of world's population having high yielding capacity. Elements detected in rice are Al, As, Br, Cd, Cl, Co, Cs, Cu, Fe, Hg, K, Mg, Mn, Mo, Rb, Se and Zn by using Instrumental Neutron Activation with k0 standardization (R. Jayasekera etal,2004). Some of these trace elements are C, H, O, N, S, Ca, P, K, Na, Cl, Mn, Ti, Mg, Cu, Fe, Ni, Si and Zn are essential for growth of human physique The deficiency or excess of these elements in food is known to cause a variety of malnutrition or health disorders in the world. Every year, various varieties of rice are launched by Punjab Agriculture University, Ludhiana. The main purpose of which is to increases the yield to attain the maximum profit. But this leads to changing the elemental concentration in them, which may affect the human health according to variation in the nutrition values. The main objective is to study the presence of elemental concentration in various varieties of rice using EDXRF technique.

Evaluation of metal ion absorptive characteristics of three types of plastic sample bags used for pecipitation sampling

USGS Publications Warehouse

Good, A.B.; Schroder, L.J.

1984-01-01

Simulated precipitation samples containing 16 metal ions were prepared at 4 pH values. Absorptive characteristics of polypropylene, polyethylene, and polyester/polyolefin sacks were evaluated at pH 3.5, 4.0, 4.5, and 5.0. Simulated precipitation was in contact with the sacks for 17 days, and subsamples were removed for chemical analysis at 3, 7, 10, 14, and 17 days after initial contact. All three types of plastic sacks absorbed Fe throughout the entire pH range. Polypropylene and polyethylene absorbed Pb throughout the entire pH range; polyester/polyolefin sacks absorbed Pb at pH 4.0 or greater. All plastic sacks also absorbed Cu, Mo, and V at pH 4.5 and 5.0. Leaching the plastic sacks with 0.7 percent HNO3 did not result in 100 percent of Cu, Fe, Pb, and V. These sacks would be suitable collection vessels for Ba, Be, Ca, Cd, Co, Li, Mg, Mn, Na Sr and Zn in precipitation through the pH range of 3.5 to 5.0.

Research progress in photolectric materials of CuFeS2

NASA Astrophysics Data System (ADS)

Jing, Mingxing; Li, Jing; Liu, Kegao

2018-03-01

CuFeS2 as a photoelectric material, there are many advantages, such as high optical absorption coefficient, direct gap semiconductor, thermal stability, no photo-recession effect and so on. Because of its low price, abundant reserves and non-toxic, CuFeS2 has attracted extensive attention of scientists.Preparation method of thin film solar cells are included that Electrodeposition, sputtering, thermal evaporation, thermal spraying method, co-reduction method.In this paper, the development of CuFeS2 thin films prepared by co-reduction method and co-reduction method is introduced.In this paper, the structure and development of solar cells, advantages of CuFeS2 as solar cell material, the structure and photoelectric properties and magnetic properties of CuFeS2, preparation process analysis of CuFeS2 thin film, research and development of CuFeS2 in solar cells is included herein. Finally, the development trend of CuFeS2 optoelectronic materials is analyzed and further research directions are proposed.

Elemental composition of current automotive braking materials and derived air emission factors

NASA Astrophysics Data System (ADS)

Hulskotte, J. H. J.; Roskam, G. D.; Denier van der Gon, H. A. C.

2014-12-01

Wear-related PM emissions are an important constituent of total PM emissions from road transport. Due to ongoing (further) exhaust emission reduction wear emissions may become the dominant PM source from road transport in the near future. The chemical composition of the wear emissions is crucial information to assess the potential health relevance of these PM emissions. Here we provide an elemental composition profile of brake wear emissions as used in the Netherlands in 2012. In total, 65 spent brake pads and 15 brake discs were collected in car maintenance shops from in-use personal cars vehicles and analyzed with XRF for their metal composition (Fe, Cu, Zn, Sn, Al, Si, Zr, Ti, Sb, Cr, Mo, Mn, V, Ni, Bi, W, P, Pb and Co). Since car, engine and safety regulations are not nationally determined but controlled by European legislation the resulting profiles will be representative for the European personal car fleet. The brake pads contained Fe and Cu as the dominant metals but their ratio varied considerably, other relatively important metals were Sn, Zn and Sb. Overall a rather robust picture emerged with Fe, Cu, Zn and Sn together making up about 80-90% of the metals present in brake pads. Because the XRF did not give information on the contents of other material such as carbon, oxygen and sulphur, a representative selection of 9 brake pads was further analyzed by ICP-MS and a carbon and sulphur analyzer. The brake pads contained about 50% of non-metal material (26% C, 3% S and the remainder mostly oxygen and some magnesium). Based on our measurements, the average brake pad profile contained 20% Fe, 10% Cu, 4% Zn and 3% Sn as the dominant metals. The brake discs consisted almost entirely of metal with iron being the dominant metal (>95%) and only traces of other metals (<1% for individual metals). Non-metal components in the discs were 2-3% Silicon and, according to literature, ∼3% carbon. The robust ratio between Fe and Cu as found on kerbsides has been used to estimate the contribution of brake pads and brake discs to total brake wear. Based on this approach our hypothesis is that 70% of the brake wear originates from the discs and only 30% from the brake pads.

Spatial Variations and Sources of Trace Elements in Recent Snow from Glaciers at the Tibetan Plateau

NASA Astrophysics Data System (ADS)

Huang, J.; Li, Y.; Li, Z.; Cozzi, G.; Turetta, C.; Barbante, C.; Xiong, L.

2017-12-01

Various trace element (TEs) could be long-range transported through the atmosphere and deposited onto the snow surface. Recently, with the development of economy of China and the surrounding countries, TEs such as Pb, Cd, Mo and Sb in several glaciers from the Tibetan Plateau (TP) have been gradually affected by anthropogenic activities. This study presents the acid leached concentrations of TEs (e.g., Al, As, Ba, Co, Cr, Cs, Cu, Fe, Li, Mn, Mo, Pb, Rb, Sb, Sr, Ti, Tl, U, V) and dust content sampled from Qiumianleike (QMLK), Meikuang (MK), Yuzhufeng (YZF), Xiaodongkemadi (XDKMD), Gurenhekou (GRHK) glaciers on the TP from April to May of 2013. The different concentrations of TEs in the surface snow and snow pit samples over the five glaciers show that TEs were influenced both by surrounding environment of glaciers and seasonal variations of atmospheric impurity loading. Comparison of TEs concentrations with data of other sites, elevated concentrations of As, Cu, Mo, Pb and Sb were observed in glaciers of TP, showing significant atmospheric TEs pollution. Enrichment factor(EF) analysis indicates that Rb, V, U, Cr, Ba, Cs, Li, As, Co, Mn, Tl, Sr and Cu mainly originated from crustal dust, while anthropogenic inputs such as nonferrous metals melting, coal combustion and traffic emission made an important contribution to the Mo, Pb and Sb. Evidences from air mass back trajectories show the air masses arrived at QMLK mostly came from the Taklimakan desert, the TEs from the Taklimakan desert and the western TP could be transported to the MK and YZF glaciers . The air masses derived from the western TP and the southwestern TP affected the environment of the XDKMD and GRHK glaciers. Futhermore, the air masses passed through some big cities with developed industry and large population such as Urumqi, Bishkek, Dushanbe and some countries such as Pakistan and India could also bring pollutants to the studied glaciers.

Stabilization of Reduced Molybdenum-Iron-Sulfur Single and Double Cubane Clusters by Cyanide Ligation

PubMed Central

Pesavento, Russell P.; Berlinguette, Curtis P.; Holm, R. H.

2008-01-01

Recent work has shown that cyanide ligation increases the redox potentials of Fe4S4 clusters, enabling the isolation of [Fe4S4(CN)4]4−, the first synthetic Fe4S4 cluster obtained in the all-ferrous oxidation state (Scott, T. A.; Berlinguette, C. P.; Holm, R. H.; Zhou, H.-C., Proc. Natl. Acad. Sci. USA 2005, 102, 9741). The generality of reduced cluster stabilization has been examined with MoFe3S4 clusters. Reaction of single cubane [(Tp)MoFe3S4(PEt3)3]1+ and edge-bridged double cubane [(Tp)2Mo2Fe6S8(PEt3)4] with cyanide in acetonitrile affords [(Tp)MoFe3S4(CN)3]2− (2) and [(Tp)2Mo2Fe6S8(CN)4]4− (5), respectively. Reduction of 2 with KC14H10 yields [(Tp)MoFe3S4(CN)3]3− (3). Clusters were isolated in ca. 70–90% yields as Et4N+ or Bu4N+ salts; Clusters 3 and 5 contain all-ferrous cores; 3 is the first [MoFe3S4]1+ cluster isolated in substance. The structures of 2 and 3 are very similar; the volume of the reduced cluster core is slightly larger (2.5%), a usual effect upon reduction of cubane-type Fe4S4 and MFe3S4 clusters. Redox potentials and 57Fe isomer shifts of [(Tp)MoFe3S4L3]2−,3 and [(Tp)2Mo2Fe6S8L4]4−,3− clusters with L = CN, PhS, halide, and PEt3 are compared. Clusters with π-donor ligands (L = halide, PhS) exhibit larger isomer shifts and lower (more negative) redox potentials while π-acceptor ligands (L = CN, PEt3) induce smaller isomer shifts and higher (less negative) redox potentials. When potentials of 3/2 and [(Tp)MoFe3S4(SPh)3]3−/2− are compared, cyanide stabilizes 3 by 270 mV vs. the reduced thiolate cluster, commensurate with the 310 mV stabilization of [Fe4S4(CN)4]4− vs. [Fe4S4(SPh)4]4− where four ligands differ. These results demonstrate the efficacy of cyanide stabilization of lower cluster oxidation states. (Tp = hydrotris(pyrazolyl)borate(1−)). PMID:17279830

Stabilization of reduced molybdenum-iron-sulfur single- and double-cubane clusters by cyanide ligation.

PubMed

Pesavento, Russell P; Berlinguette, Curtis P; Holm, R H

2007-01-22

Recent work has shown that cyanide ligation increases the redox potentials of Fe(4)S(4) clusters, enabling the isolation of [Fe(4)S(4)(CN)4]4-, the first synthetic Fe(4)S(4) cluster obtained in the all-ferrous oxidation state (Scott, T. A.; Berlinguette, C. P.; Holm, R. H.; Zhou, H.-C. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 9741). The generality of reduced cluster stabilization has been examined with MoFe(3)S(4) clusters. Reaction of single-cubane [(Tp)MoFe(3)S(4)(PEt(3))3]1+ and edge-bridged double-cubane [(Tp)2Mo(2)Fe(6)S(8)(PEt(3))4] with cyanide in acetonitrile affords [(Tp)MoFe(3)S(4)(CN)3]2- (2) and [(Tp)2Mo(2)Fe(6)S(8)(CN)4]4- (5), respectively. Reduction of 2 with KC(14)H(10) yields [(Tp)MoFe(3)S(4)(CN)3]3- (3). Clusters were isolated in approximately 70-90% yields as Et(4)N+ or Bu(4)N+ salts; clusters 3 and 5 contain all-ferrous cores, and 3 is the first [MoFe(3)S(4)]1+ cluster isolated in substance. The structures of 2 and 3 are very similar; the volume of the reduced cluster core is slightly larger (2.5%), a usual effect upon reduction of cubane-type Fe(4)S(4) and MFe(3)S(4) clusters. Redox potentials and 57Fe isomer shifts of [(Tp)MoFe(3)S(4)L3]2-,3- and [(Tp)2Mo(2)Fe(6)S(8)L(4)]4-,3- clusters with L = CN-, PhS-, halide, and PEt3 are compared. Clusters with pi-donor ligands (L = halide, PhS) exhibit larger isomer shifts and lower (more negative) redox potentials, while pi-acceptor ligands (L = CN, PEt3) induce smaller isomer shifts and higher (less-negative) redox potentials. When the potentials of 3/2 and [(Tp)MoFe(3)S(4)(SPh)3]3-/2- are compared, cyanide stabilizes 3 by 270 mV versus the reduced thiolate cluster, commensurate with the 310 mV stabilization of [Fe(4)S(4)(CN)4]4- versus [Fe(4)S(4)(SPh)4]4- where four ligands differ. These results demonstrate the efficacy of cyanide stabilization of lower cluster oxidation states. (Tp = hydrotris(pyrazolyl)borate(1-)).

Influence of nonmagnetic Al ions on magnetoresistance of double-perovskite Sr2Fe1-xAlxMoO6 (0<=x<=0.30)

NASA Astrophysics Data System (ADS)

Sui, Yu; Wang, Xianjie; Cheng, Jinguang; Liu, Zhiguo; Miao, Jipeng; Huang, Xiqiang; Lu, Zhe; Qian, Zhengnan; Su, Wenhui; Tang, Jinke; Ong, C. K.

2005-09-01

The structural, magnetic, and magnetoresistance properties of the double-perovskite series Sr2Fe1-xAlxMoO6 (0<=x<=0.30) were systematically investigated in order to clarify the influence of nonmagnetic Al ions on the magnetoresistance. The structural refinements of these samples show that the degree of cationic order increases gradually from 88.5% for x=0 to 92% for x=0.30 without any change in the crystal structure. The magnetization measurements reveal that the substitution of nonmagnetic Al ion for Fe ion enhances the magnetic moment per Fe ion significantly. In addition, the magnetic-field dependence of magnetization and magnetoresistance of these Sr2Fe1-xAlxMoO6 samples were all fitted excellently by taking into account the contributions from ferromagnetic-coupled Fe-O-Mo region and nonferromagnetic-coupled regions. The fitting results indicate that the low-field magnetoresistance can be greatly enhanced due to the separation of the cationic-ordered Fe-O-Mo regions by the paramagnetic Mo-O-Al-O-Mo chains introduced through Al doping. Furthermore, doping nonmagnetic Al ions also suppress the formation of antiferromagnetic Fe-O-Fe antiphase boundaries, and then lead to the improvement of cation ordering and the reduction of magnetoresistance under high field.

Synthèse et étude structrale de lyonsite-type (Na0,4,Li0,6)(Fe,Li2)(MoO4)3

PubMed Central

Souilem, Amira; Zid, Mohamed Faouzi; Driss, Ahmed

2015-01-01

The new compound (Na0.4,Li0.6)(Fe,Li2)(MoO4)3 was synthesized by cooling from the melt. Its anionic framework is built up from two distinct MO6 octa­hedra, each containing disordered Li+ and Fe3+ ions in 0.6:0.4 and 0.7:0.3 ratios, and two MoO4 tetra­hedra, which link by vertex-sharing of their O atoms. These tetra­meric units are further linked by sharing edges between octa­hedra and by formation of M—O—Mo (M = Fe/Li) bridges, forming ribbons propagating in the [100] direction. The ribbons are cross-linked in both the b- and c-axis directions, giving rise to a three-dimensional framework having [100] tunnels in which the monovalent Na+/Li+ cations (0.4:0.6 ratio) lie. Bond-valence calculations are consistent with the disorder model for the cations. The structure of the title compound, which is isotypic with Li3Fe(MoO4)3 and Li3Ga(MoO4)3, is compared briefly with those of LiFeMo2O8 and Li1.6Mn2.2(MoO4)3. PMID:26090130

Origin, speciation, and fluxes of trace-element gases at Augustine volcano, Alaska: Insights into magma degassing and fumarolic processes

NASA Astrophysics Data System (ADS)

Symonds, Robert B.; Reed, Mark H.; Rose, William I.

1992-02-01

Thermochemical modeling predicts that trace elements in the Augustine gas are transported from near-surface magma as simple chloride (NaCl, KCl, FeCl 2, ZnCl 2, PbCl 2, CuCl, SbCl 3, LiCl, MnCl 2, NiCl 2, BiCl, SrCl 2), oxychloride (MoO 2Cl 2), sulfide (AsS), and elemental (Cd) gas species. However, Si, Ca, Al, Mg, Ti, V, and Cr are actually more concentrated in solids, beta-quartz (SiO 2), wollastonite (CaSiO 3), anorthite (CaAl 2Si 2O 8), diopside (CaMgSi 2O 6), sphene (CaTiSiO 5), V 2O 3(c), and Cr 2O 3(c), respectively, than in their most abundant gaseous species, SiF 4, CaCl 2, AlF 2O, MgCl 2 TiCl 4, VOCl 3, and CrO 2Cl 2. These computed solids are not degassing products, but reflect contaminants in our gas condensates or possible problems with our modeling due to "missing" gas species in the thermochemical data base. Using the calculated distribution of gas species and the COSPEC SO 2 fluxes, we have estimated the emission rates for many species (e.g., COS, NaCl, KCl, HBr, AsS, CuCl). Such forecasts could be useful to evaluate the effects of these trace species on atmospheric chemistry. Because of the high volatility of metal chlorides (e.g., FeCl 2, NaCl, KCl, MnCl 2, CuCl), the extremely HCl-rich Augustine volcanic gases are favorable for transporting metals from magma. Thermochemical modeling shows that equilibrium degassing of magma near 870°C can account for the concentrations of Fe, Na, K, Mn, Cu, Ni and part of the Mg in the gases escaping from the dome fumaroles on the 1986 lava dome. These calculations also explain why gases escaping from the lower temperature but highly oxidized moat vents on the 1976 lava dome should transport less Fe, Na, K, Mn and Ni, but more Cu; oxidation may also account for the larger concentrations of Zn and Mo in the moat gases. Nonvolatile elements (e.g., Al, Ca, Ti, Si) in the gas condensates came from eroded rock particles that dissolved in our samples or, for Si, from contamination from the silica sampling tube. Only a very small amount of rock contamination occurred (water/rock ratios between 10 4 and 10 6). Erosion is more prevalent in the pyroclastic flow fumaroles than in the summit vents, reflecting physical differences in the fumarole walls: ash vs. lava. Trace element contents of volcanic gases show enormous variability because of differences in the intensive parameters of degassing magma and variable amounts of wall rock erosion in volcanic fumaroles.

Trace elements levels in centenarian 'dodgers'.

PubMed

Alis, Rafael; Santos-Lozano, Alejandro; Sanchis-Gomar, Fabian; Pareja-Galeano, Helios; Fiuza-Luces, Carmen; Garatachea, Nuria; Lucia, Alejandro; Emanuele, Enzo

2016-05-01

Trace element bioavailability can play a role in several metabolic and physiological pathways known to be altered during the aging process. We aimed to explore the association of trace elements with increased lifespan by analyzing the circulating levels of seven trace elements (Cr, Cu, Fe, Mn, Mo, Se and Zn) in a cohort of healthy centenarians or 'dodgers' (≥100 years, free of major age-related diseases) in comparison with sex-matched younger elderly controls. Centenarians showed significant lower Cu (783.7 (76.7, 1608.9) vs 962.5 (676.3, 2064.4)μg/mL, P<0.001), but higher Fe (1.3 (0.4, 4.7) vs 1.1 (0.5, 8.4)μg/mL, P=0.003) and Se (85.7 (43.0, 256.7) vs 77.8 (24.3, 143.8)ng/mL, P=0.002) values compared with elderly controls. The logistic regression analysis identified the combination of Cu and Se as significant predictor variables associated with successful aging (P=0.001), while receiver operating characteristic (ROC) analysis confirmed that Cu and Se (either alone or in combination) were independent variables associated with healthy aging. An 'improved' trace element profile (reduced Cu and elevated Se, which are involved in key physiological processes) could play a role in the resistance to disease showed by centenarian 'dodgers', and, therefore, at least partly, be involved in the healthy aging phenotype shown by these subjects. These results should be confirmed in larger cohorts of other geographic/ethnic origin and the potential cause-effect association tested in mechanistic experimental settings. Copyright © 2016 Elsevier GmbH. All rights reserved.

Substrate channel in nitrogenase revealed by a molecular dynamics approach.

PubMed

Smith, Dayle; Danyal, Karamatullah; Raugei, Simone; Seefeldt, Lance C

2014-04-15

Mo-dependent nitrogenase catalyzes the biological reduction of N2 to two NH3 molecules at FeMo-cofactor buried deep inside the MoFe protein. Access of substrates, such as N2, to the active site is likely restricted by the surrounding protein, requiring substrate channels that lead from the surface to the active site. Earlier studies on crystallographic structures of the MoFe protein have suggested three putative substrate channels. Here, we have utilized submicrosecond atomistic molecular dynamics simulations to allow the nitrogenase MoFe protein to explore its conformational space in an aqueous solution at physiological ionic strength, revealing a putative substrate channel. The viability of this observed channel was tested by examining the free energy of passage of N2 from the surface through the channel to FeMo-cofactor, resulting in the discovery of a very low energy barrier. These studies point to a viable substrate channel in nitrogenase that appears during thermal motions of the protein in an aqueous environment and that approaches a face of FeMo-cofactor earlier implicated in substrate binding.

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

Smith, Dayle; Danyal, Karamatullah; Raugei, Simone

Mo-dependent nitrogenase catalyzes the biological reduction of N 2 to 2NH 3 at the FeMo-cofactor buried deep inside the MoFe protein. Access of substrates, such as N 2, to the active site is likely restricted by the surrounding protein, requiring substrate channels that lead from the surface to the active site. Earlier studies on crystallographic structures of the MoFe protein have suggested three putative substrate channels. Here, we have utilized sub-microsecond atomistic molecular dynamics simulations to allow the nitrogenase MoFe protein to explore its conformational space in an aqueous solution at physiological ionic strength, revealing a putative substrate channel notmore » previously reported. The viability of the proposed channel was tested by examining the free energy of passage of N 2 from the surface through the channel to FeMo-cofactor, with discovery of a very low energy barrier. These studies point to a viable substrate channel in nitrogenase that appears during thermal motions of the protein in an aqueous environment that approaches a face of FeMo-cofactor earlier implicated in substrate binding.« less

Structural Stabilities of β-Ti Alloys Studied Using a New Mo Equivalent Derived from [ β/( α + β)] Phase-Boundary Slopes

NASA Astrophysics Data System (ADS)

Wang, Qing; Dong, Chuang; Liaw, Peter K.

2015-08-01

Structural stabilities of β-Ti alloys are generally investigated by an empirical Mo equivalent, which quantifies the stability contribution of each alloying element, M, in comparison to that of the major β-Ti stabilizer, Mo. In the present work, a new Mo equivalent (Moeq)Q is proposed, which uses the slopes of the boundary lines between the β and ( α + β) phase zones in binary Ti-M phase diagrams. This (Moeq)Q reflects a simple fact that the β-Ti stability is enhanced, when the β phase zone is enlarged by a β-Ti stabilizer. It is expressed as (Moeq)Q = 1.0 Mo + 0.74 V + 1.01 W + 0.23 Nb + 0.30 Ta + 1.23 Fe + 1.10 Cr + 1.09 Cu + 1.67 Ni + 1.81 Co + 1.42 Mn + 0.38 Sn + 0.34 Zr + 0.99 Si - 0.57 Al (at. pct), where the equivalent coefficient of each element is the slope ratio of the [ β/( α + β)] boundary line of the binary Ti-M phase diagram to that of the Ti-Mo. This (Moeq)Q is shown to reliably characterize the critical stability limit of multi-component β-Ti alloys with low Young's moduli, where the critical lower limit for β stabilization is (Moeq)Q = 6.25 at. pct or 11.8 wt pct Mo.

Hepatic minerals of white-tailed and mule deer in the southern Black Hills, South Dakota

USGS Publications Warehouse

Zimmerman, T.J.; Jenks, J.A.; Leslie, David M.; Neiger, R.D.

2008-01-01

Because there is a paucity of information on the mineral requirements of free-ranging deer, data are needed from clinically healthy deer to provide a basis for the diagnosis of mineral deficiencies. To our knowledge, no reports are available on baseline hepatic mineral concentrations from sympatric white-tailed deer (Odocoileus virginianus) and mule deer (Odocoileus hemionus) using different habitats in the Northern Great Plains. We assessed variation in hepatic minerals of female white-tailed deer (n=42) and mule deer (n=41). Deer were collected in February and August 2002 and 2003 from study areas in Custer and Pennington Counties, South Dakota, in and adjacent to a wildfire burn. Hepatic samples were tested for levels (parts per million; ppm) of aluminum (Al), antimony (Sb), arsenic (As), barium (Ba), boron (B), cadmium (Cd), calcium (Ca), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), magnesium (Mg), manganese (Mn), mercury (Hg), molybdenum (Mo), nickel (Ni), phosphorus (P), potassium (K), selenium (Se), sodium (Na), sulfur (S), thalium (T1), and zinc (Zn). We predicted that variability in element concentrations would occur between burned and unburned habitat due to changes in plant communities and thereby forage availability. We determined that Zn, Cu, and Ba values differed (P???0.05) between habitats. Because of the nutritional demands of gestation and lactation, we hypothesized that elemental concentrations would vary depending on reproductive status; Cd, Cu, Ca, P, Mn, Mo, Na, and Zn values differed (P???0.05) by reproductive status. We also hypothesized that, due to variation in feeding strategies and morphology between deer species, hepatic elemental concentrations would reflect dietary differences; Ca, Cu, K, Co, Mo, Se, and Zn differed (P???0.05) between species. Further research is needed to determine causes of variation in hepatic mineral levels due to habitat, reproductive status, and species. ?? Wildlife Disease Association 2008.

Far-infrared study of the mechanochemically synthesized Cu2FeSnS4 (stannite) nanocrystals

NASA Astrophysics Data System (ADS)

Trajic, J.; Romcevic, M.; Paunovic, N.; Curcic, M.; Balaz, P.; Romcevic, N.

2018-05-01

The analysis of the optical properties of mechanochemically synthesized stannite Cu2FeSnS4 nanocrystals has been performed using far-infrared spectroscopy. The Cu2FeSnS4 stannite nanocrystals were synthesized mechanochemically from elemental precursors Cu, Fe, Sn, and S. Milling time was 45, 60, 90 and 120 min. Reflectivity spectra were analyzed using the classical form of the dielectric function, which includes the phonon and the free carrier contribution. The influence of milling time on synthesis of stannite Cu2FeSnS4 is observed. Among the modes that are characteristic for the stannite Cu2FeSnS4, we registered the modes of binary phases of FeS and SnS. The total disappearance of the binary phases of FeS and SnS and forming pure Cu2FeSnS4 is observed when the milling time is 120 min. Effective permittivity of Cu2FeSnS4 and binary phases of FeS and SnS were modeled by Maxwell - Garnet approximation.

Multivariate characterization of elements accumulated in King Bolete Boletus edulis mushroom at lowland and high mountain regions.

PubMed

Falandysz, J; Kunito, T; Kubota, R; Bielawski, L; Frankowska, A; Falandysz, Justyna J; Tanabe, S

2008-12-01

Based on ICP-MS, ICP-OES, HG-AAS, CV-AAS and elementary instrumental analysis of King Bolete collected from four sites of different soil bedrock geochemistry considered could be as mushroom abundant in certain elements. King's Bolete fruiting bodies are very rich in K (> 20 mg/g dry weight), rich in Ca, Mg, Na, Rb and Zn (> 100 microg/g dw), and relatively also rich in Ag, Cd, Cs, Cu, Fe, Mn and Se (> 10 microg/g dw). The caps of King Bolete when compared to stipes around two-to three-fold more abundant are in Ag, Cd, Cs, Cu, Hg, K, Mg, Mo, N, Rb, Se and Zn. King Bolete collected at the lowland and mountain sites showed Ag, Ba, Co, Cr, Hg, K, Mg, Mn, Mo and Na in caps in comparable concentrations, and specimens from the mountain areas accumulated more Cd and Sb. Elements such as Al, Pb and Rb occurred at relatively elevated concentration in King Bolete picked up at the metal ores-rich region of the Sudety Mountains. Because of high bioconcentration potential King Bolete at the background sites accumulate in fruiting bodies great concentrations of problematic elements such as Cd, Pb and Hg, i.e. up to nearly 20, 3 and 5 microg/g dw, on the average, respectively. The interdependence among determined mineral elements examined were using the principal components analysis (PCA) method. The PCA explained 56% of the total variance. The metals tend to cluster together (Ba, Cd, Cs, Cr, Ga, Rb, Se, Sr and V; K and Mg; Cu and Mo). The results provided useful environmental and nutritional background level information on 26 minerals as the composition of King Bolete from the sites of different bedrock soil geochemistry.

Plankton copper requirements and uptake in the subarctic Northeast Pacific Ocean

NASA Astrophysics Data System (ADS)

Semeniuk, David M.; Cullen, Jay T.; Johnson, W. Keith; Gagnon, Katie; Ruth, Thomas J.; Maldonado, Maria T.

2009-07-01

We undertook the first measurements of metabolic Cu requirements (net Cu:C assimilation ratios) and steady-state Cu uptake rates (ρCu ss) of natural plankton assemblages in the northeast subarctic Pacific using the short-lived radioisotope 67Cu. Size-fractionated net Cu:C assimilation ratios varied ˜3 fold (1.35-4.21 μmol Cu mol C -1) among the stations along Line P, from high Fe coastal waters to the Fe-limited open ocean. The variability in Cu:C was comparable to biogenic Fe:C ratios in this region. As previously observed for Fe uptake, the bacterial size class accounted for half of the total particulate ρCu ss. Interestingly, carbon biomass-normalized rates of Fe uptake from the siderophore desferrioxamine B (DFB) (ρFe DFB; a physiological proxy for Fe-limitation) by the >20 μm size class were positively correlated with the intracellular net Cu:C assimilation ratios in this size class, suggesting that intracellular Cu requirements for large phytoplankton respond to increased Fe-limitation. At Fe-limited Ocean Station Papa (OSP), we performed short-term Cu uptake (ρCu L) assays to determine the relative bioavailability of Cu bound to natural and synthetic ligands. Like the volumetric ρCu ss measured along Line P, the bacterial size class was responsible for at least 50% of the total ρCu L. Uptake rates of Cu from the various organic complexes suggest that Cu uptake was controlled by the oxidation state of the metal and by the metal:ligand concentration ratio, rather than the concentration of inorganic species of Cu in solution. Collectively, these data suggest that Cu likely plays an important role in the physiology of natural plankton communities beyond the toxicological effects studied previously.

Impact of an iron mine and a nickel smelter at the Norwegian/Russian border close to the Barents Sea on surface soil magnetic susceptibility and content of potentially toxic elements.

PubMed

Magiera, Tadeusz; Zawadzki, Jarosław; Szuszkiewicz, Marcin; Fabijańczyk, Piotr; Steinnes, Eiliv; Fabian, Karl; Miszczak, Ewa

2018-03-01

An important problem in soil magnetometry is unraveling the soil contamination signal in areas with multiple emitters. Here, geophysical and geochemical measurements were performed at four sites on a north - south transect along the Pasvik River in the Barents Region (northern Norway). These sites are influenced by depositions from the Bjørnevatn iron mine and a Ni-Cu smelter in Nikel, Russia. To relate the degree and type of pollution from these sources to the corresponding magnetic signal, the topsoil concentrations of 12 Potentially Toxic Elements (PTEs) (As, Cd, Co, Cr, Cu, Fe, Mo, Ni, Pb, Se, Ti, Zn), were determined, magnetic hysteresis parameters and thermomagnetic properties were measured. In situ magnetic low-field susceptibility decreases from north to south with increasing distance from the iron mine. Relatively large magnetic multidomain grains of magnetite and/or titanomagnetite are responsible for the strong magnetic signal from the topsoil close to Bjørnevatn. These particles are related to increased enrichment factors of As, Mo and Cu, yielding high positive correlation coefficients with susceptibility values. At a site furthest away from the iron mine and located 7 km from the Ni-Cu smelter magnetic susceptibility values are much lower but significant positive correlations on the level of p < .1 with 8 PTEs (Ni, Cu, Co, Se, As, Zn, Cd, Cr) have been observed. The magnetic signal in this area is due to fine-grained primary sulphides and secondary fine-grained magnetite and/or maghemite. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hierarchical assembly of urchin-like alpha-iron oxide hollow microspheres and molybdenum disulphide nanosheets for ethanol gas sensing.

PubMed

Zhang, Dongzhi; Fan, Xin; Yang, Aijun; Zong, Xiaoqi

2018-08-01

In this paper, we fabricated a high-performance ethanol sensor using layer-by-layer self-assembled urchin-like alpha-iron oxide (α-Fe 2 O 3 ) hollow microspheres/molybdenum disulphide (MoS 2 ) nanosheets heterostructure as sensitive materials. The nanostructural, morphological, and compositional properties of the as-prepared α-Fe 2 O 3 /MoS 2 heterostructure were characterized by X-ray diffraction (XRD), energy dispersive spectrometer (EDS), scanning electron microscopy (SEM), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS), which confirmed its successful preparation and rationality. The α-Fe 2 O 3 /MoS 2 nanocomposite sensor shows good selectivity, excellent reproducibility, fast response/recovery time and low detection limit towards ethanol gas at room temperature, which is superior to the single component of α-Fe 2 O 3 hollow microspheres and MoS 2 nanosheets. Furthermore, the response of the α-Fe 2 O 3 /MoS 2 nanocomposite sensor as a function of ethanol gas concentration was also demonstrated. The enhanced ethanol sensing properties of the α-Fe 2 O 3 /MoS 2 nanocomposite sensor were ascribed to the synergistic effect and heterojunction between the urchin-Like α-Fe 2 O 3 hollow microspheres and MoS 2 nanosheets. This work verifies that the hierarchical α-Fe 2 O 3 /MoS 2 nanoheterostructure is a potential candidate for fabricating room-temperature ethanol gas sensor. Copyright © 2018 Elsevier Inc. All rights reserved.

Photosynthetic Pigments in Hypogymnia Physodes with Different Metal Contents

NASA Astrophysics Data System (ADS)

Meysurova, A. F.; Notov, A. A.; Pungin, A. V.

2018-01-01

Chlorophyll a and b contents in Hypogymnia physodes specimens collected from various economic areas and natural complexes of Tver Region were found to differ substantially using a spectrophotometric method, showing that the lichen photosynthetic system is highly adaptable. The chlorophyll b content was linked primarily to adaptation to specific environmental features in various plant communities. The chlorophyll a content changed to provide the necessary compensatory responses under technogenic stress. A total of 15 metals (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Ti, V, and Zn) were detected in H. physodes samples using inductively coupled plasma atomicemission spectroscopy (ICP AES). The most widespread of them were Fe, Al, and Ti. Significant correlations among the concentrations of these metals and the chlorophyll a content were revealed.

Formation of cation-anion complexes in the photochemical reaction of molybdenocene dihydrode with iron pentacarbonyl. Crystal structures of (Cp/sub 2/Mo(CO)H)/sup +/(Fe/sub 3/(CO)/sub 11/H)/sup -/ and (Cp/sub 2/Mo(CO)H)/sup +/(CoMo(CO)/sub 3/)/sup -/ (triclinic modification) (in Russian)

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

Antsyshkina, A.S.; Dikareva, L.M.; Porai-Koshits, M.A.

1985-11-01

The reaction of Cp/sub 2/MoH/sub 2/ with Fe(CO)/sub 5/ in boiling benzene under UV irradiation gives the ionic complexes (Cp/sub 2/Mo(CO)H)/sup +/(Fe/sub 3/(CO)/sub 11/H)/sup -/ (I) and (Cp/sub 2/Mo(CO)H)/sup +/(CpMo(CO)/sub 3/)/sup -/ (II), whose structures were established by x-ray diffraction analysis (Syntex P2/sub 1/ automatic diffractometer, lambda Mo K/sub ..cap alpha../, graphite monochromator, theta/2theta scan technique, full-matrix least-squares method, isotropic variant for I on the basis of 2112 reflections to % = 0.11 and anisotropic variant for II on the basis of 3770 values of hkl to R = 0.052). In complexes I and II the (CpMo(CO)H)/sup +/ fragment ismore » a tapered sandwich with an eclipsed conformation of the rings. In complex I the angle between the rings is 33.9/sup 0/, the mean Mo-C(C/sub 5/H/sub 5/) distance is 2.28(3) A, the mean Mo-C(CO) distance is 2.03(3) A, and the mean Mo-H distance is 1.78(10) A. The corresponding parameters in complex II are: 32.4/sup 0/, 2.296(7), 2.020(6), and 1.87(7) A. The anion in complex I is based on a triangular cluster of Fe atoms, in which one Fe-Fe distance is significantly shorter (2.488(5) A) than the other two (2.702(5) and 2.697(5) A). The Fe atoms forming the short bond are joined additionally by hydride (Fe-H = 2.14 A) and carbonyl (Fe-C = 1.90(3) and 1.93(3) A) Bridges. The remaining groups are terminal. A probable scheme for the process of the formation of complexes I and II has been discussed.« less

Excellent photocatalytic hydrogen production over CdS nanorods via using noble metal-free copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts

NASA Astrophysics Data System (ADS)

Hong, Sangyeob; Kumar, D. Praveen; Reddy, D. Amaranatha; Choi, Jiha; Kim, Tae Kyu

2017-02-01

Charge carrier recombination and durability issues are major problems in photocatalytic hydrogen (H2) evolution processes. Thus, there is a very important necessitate to extend an efficient photocatalyst to control charge-carrier dynamics in the photocatalytic system. We have developed copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts with CdS nanorods for controlling charge carriers without recombination for use in photocatalytic H2 evolution under simulated solar light irradiation. Effective control and utilization of charge carriers are possible by loading Cu2MoS4 nanosheets onto the CdS nanorods. The loading compensates for the restrictions of CdS, and stimulated synergistic effects, such as efficient photoexcited charge separation, lead to an improvement in photostability because of the layered structure of the Cu2MoS4nanosheets. These layered Cu2MoS4 nanosheets have emerged as novel and active replacements for precious noble metal co-catalysts in photocatalytic H2 production by water splitting. We have obtained superior H2 production rates by using Cu2MoS4 loaded CdS nanorods. The physicochemical properties of the composites are analyzed by diverse characterization techniques.

Chemical characterization of gas- and oil-bearing shales by instrumental neutron activation analysis

USGS Publications Warehouse

Frost, J.K.; Koszykowski, R.F.; Klemm, R.C.

1982-01-01

The concentration of As, Ba, Ca, Co, Cr, Cs, Dy, Eu, Fe, Ga, Hf, K, La, Lu, Mn, Mo, Na, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, U, Yb, and Zn were determined by instrumental neutron activation analysis in block shale samples of the New Albany Group (Devonian-Mississippian) in the in the Illinois Basin. Uranium content of the samples was as high as 75 ppm and interfered in the determination of samarium, molybdenum, barium and cerium. In the determination of selenium a correction was made for interference from tantalum. U, As, Co, Mo, Ni and Sb as well as Cu, V and pyritic sulphur which were determined by other methods, were found to correlate positively with the organic carbon content of the samples. ?? 1982 Akade??miai Kiado??.

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

Sharp, D.J.; Panitz, J.K.G.; Mattox, D.M.

The erosion of materials by low energy ions is of concern in fusion reactors since high Z impurities in the plasma cause radiation cooling. Ion bombardment of the fusion reactor chamber walls arises from ions of fuel (D, T) material, gaseous impurities (O, C), and impurities from eroded components (Fe, Co, Ni, C, Mo, etc.) being accelerated across the wall sheath potential (0.1 to 1 keV). A Kaufman type ion source has been characterized for use with hydrogen, and subsequently used to determine the relative erosion rates of bulk Mo, C, Cu, coating of TiB/sub 2/, B/sub 4/C, Be, VBe/submore » 12/ and other materials. Ions of hydrogen (Z=1), argon (Z=18), and xenon (Z=54) at acceleration potentials of 250, 500, and 1000 V have been used to determine erosion yields.« less

Variation in the mineral element concentration of Moringa oleifera Lam. and M. stenopetala (Bak. f.) Cuf.: Role in human nutrition.

PubMed

Kumssa, Diriba B; Joy, Edward Jm; Young, Scott D; Odee, David W; Ander, E Louise; Broadley, Martin R

2017-01-01

Moringa oleifera (MO) and M. stenopetala (MS) (family Moringaceae; order Brassicales) are multipurpose tree/shrub species. They thrive under marginal environmental conditions and produce nutritious edible parts. The aim of this study was to determine the mineral composition of different parts of MO and MS growing in their natural environments and their potential role in alleviating human mineral micronutrient deficiencies (MND) in sub-Saharan Africa. Edible parts of MO (n = 146) and MS (n = 50), co-occurring cereals/vegetables and soils (n = 95) underneath their canopy were sampled from localities in southern Ethiopia and Kenya. The concentrations of seven mineral elements, namely, calcium (Ca), copper (Cu), iodine (I), iron (Fe), magnesium (Mg), selenium (Se), and zinc (Zn) in edible parts and soils were determined using inductively coupled plasma-mass spectrometry. In Ethiopian crops, MS leaves contained the highest median concentrations of all elements except Cu and Zn, which were greater in Enset (a.k.a., false banana). In Kenya, Mo flowers and MS leaves had the highest median Se concentration of 1.56 mg kg-1 and 3.96 mg kg-1, respectively. The median concentration of Se in MS leaves was 7-fold, 10-fold, 23-fold, 117-fold and 147-fold more than that in brassica leaves, amaranth leaves, baobab fruits, sorghum grain and maize grain, respectively. The median Se concentration was 78-fold and 98-fold greater in MO seeds than in sorghum and maize grain, respectively. There was a strong relationship between soil total Se and potassium dihydrogen phosphate (KH2PO4)-extractable Se, and Se concentration in the leaves of MO and MS. This study confirms previous studies that Moringa is a good source of several of the measured mineral nutrients, and it includes the first wide assessment of Se and I concentrations in edible parts of MO and MS grown in various localities. Increasing the consumption of MO and MS, especially the leaves as a fresh vegetable or in powdered form, could reduce the prevalence of MNDs, most notably Se deficiency.

Variation in the mineral element concentration of Moringa oleifera Lam. and M. stenopetala (Bak. f.) Cuf.: Role in human nutrition

PubMed Central

Kumssa, Diriba B; Joy, Edward JM; Young, Scott D; Odee, David W; Ander, E Louise

2017-01-01

Background Moringa oleifera (MO) and M. stenopetala (MS) (family Moringaceae; order Brassicales) are multipurpose tree/shrub species. They thrive under marginal environmental conditions and produce nutritious edible parts. The aim of this study was to determine the mineral composition of different parts of MO and MS growing in their natural environments and their potential role in alleviating human mineral micronutrient deficiencies (MND) in sub-Saharan Africa. Methods Edible parts of MO (n = 146) and MS (n = 50), co-occurring cereals/vegetables and soils (n = 95) underneath their canopy were sampled from localities in southern Ethiopia and Kenya. The concentrations of seven mineral elements, namely, calcium (Ca), copper (Cu), iodine (I), iron (Fe), magnesium (Mg), selenium (Se), and zinc (Zn) in edible parts and soils were determined using inductively coupled plasma-mass spectrometry. Results In Ethiopian crops, MS leaves contained the highest median concentrations of all elements except Cu and Zn, which were greater in Enset (a.k.a., false banana). In Kenya, Mo flowers and MS leaves had the highest median Se concentration of 1.56 mg kg-1 and 3.96 mg kg-1, respectively. The median concentration of Se in MS leaves was 7-fold, 10-fold, 23-fold, 117-fold and 147-fold more than that in brassica leaves, amaranth leaves, baobab fruits, sorghum grain and maize grain, respectively. The median Se concentration was 78-fold and 98-fold greater in MO seeds than in sorghum and maize grain, respectively. There was a strong relationship between soil total Se and potassium dihydrogen phosphate (KH2PO4)-extractable Se, and Se concentration in the leaves of MO and MS. Conclusion This study confirms previous studies that Moringa is a good source of several of the measured mineral nutrients, and it includes the first wide assessment of Se and I concentrations in edible parts of MO and MS grown in various localities. Increasing the consumption of MO and MS, especially the leaves as a fresh vegetable or in powdered form, could reduce the prevalence of MNDs, most notably Se deficiency. PMID:28388674

Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence

USGS Publications Warehouse

Helz, G.R.; Miller, C.V.; Charnock, J.M.; Mosselmans, J.F.W.; Pattrick, R.A.D.; Garner, C.D.; Vaughan, D.J.

1996-01-01

Molybdenum K-edge EXAFS (extended X-ray absorption fine structure) spectra yield new structural information about the chemical environment of Mo in high-Mo black shales and sediments. Two spectral types are found. The less common one, associated with Mo ores developed in shale in China, is that of a MoS2 phase, possibly X-ray amorphous jordisite. The other, associated with Cretaceous deep sea sediments and with other black shales, is characterized by short Mo-O distances (1.69-1.71 A??), by Mo-S distances of 2.30-2.38 A??, and in some cases by second shell Mo and Fe interactions, which suggests that some Mo resides in transition metal-rich phases. EXAFS spectra of synthetic amorphous materials, prepared by scavenging Mo from HS solutions with Fe(II), FeOOH, and humic acid, suggest that the second spectral type arises from Mo present chiefly in two forms. One is a compact, Mo-Fe-S "cubane" type compound with Mo-S distances of ???2.36 A?? and Mo-Fe distances of ???2.66 A??, while the other is probably an organic form containing some Mo-O double bonds (???1.69 A??). Laboratory products, that were prepared by scavenging dissolved Mo from sulfidic solutions with humic acid, yield spectra quite similar to the second spectral type observed in shales and sediments, including unexpected indications of Mo-Fe interactions. Molybdenum L-edge spectra indicate that the mean oxidation state in the sediments and shales lies between IV and VI. This work demonstrates the merit of EXAFS for obtaining structural information on natural materials containing X-ray amorphous components which defeat conventional mineralogical characterization. The implications of these findings regarding Mo scavenging from sulfidic natural waters are considered. We introduce the concept of a geochemical switch, in which HS- transforms the marine behavior of Mo from that of a conservative element to that of a particle reactive element. The action point of the HS- switch is calculated to be, aHS- = 10-3.6 - 10-4.3. When aHS- approaches the action point, Mo becomes reactive to particles containing transition metals (e.g., Fe). We conjecture that thiols, including humic-bound thiol groups, also switch Mo behavior. In contrast to previous ideas, our model for Mo scavenging deemphasizes the role of reduction from Mo(VI) to Mo(V) as the initial step in scavenging; instead, we emphasize the ease with which Mo forms covalent bonds to transition metals and organic molecules via S bridges.

Trace elements in farmed fish (Cyprinus carpio, Ctenopharyngodon idella and Oncorhynchus mykiss) from Beijing: implication from feed.

PubMed

Jiang, Haifeng; Qin, Dongli; Mou, Zhenbo; Zhao, Jiwei; Tang, Shizhan; Wu, Song; Gao, Lei

2016-06-01

Concentrations of 30 trace elements, Li, V, Cr, Mn, Fe, Ni, Cu, Mo, Zn, Se, Sr, Co, Al, Ti, As, Cs, Sc, Te, Ba, Ga, Pb, Sn, Cd, Sb, Ag, Tm, TI, Be, Hg and U in major cultured freshwater fish species (common carp-Cyprinus carpio, grass carp-Ctenopharyngodon idella and rainbow trout-Oncorhynchus mykiss) with the corresponding feed from 23 fish farms in Beijing, China, were investigated. The results revealed that Fe, Zn, Cu, Mn, Sr, Se were the major accumulated essential elements and Al, Ti were the major accumulated non-essential elements, while Mo, Co, Ga, Sn, Cd, Sb, Ag, Tm, U, TI, Be, Te, Pb and Hg were hardly detectable. Contents of investigated trace elements were close to or much lower than those in fish from other areas in China. Correlation analysis suggested that the elemental concentrations in those fish species were relatively constant and did not vary much with the fish feed. In comparison with the limits for aquafeeds and fish established by Chinese legislation, Cd in 37.5% of rainbow trout feeds and As in 20% of rainbow trout samples exceeded the maximum limit, assuming that inorganic As accounts for 10% of total As. Further health risk assessment showed that fish consumption would not pose risks to consumers as far as non-essential element contaminants are concerned. However, the carcinogenic risk of As in rainbow trout for the inhabitants in Beijing exceeded the acceptable level of 10(-)(4), to which more attention should be paid.

Reviews and new metallogenic models of mineral deposits in South China: An introduction

NASA Astrophysics Data System (ADS)

Hu, Rui-Zhong; Chen, Wei Terry; Xu, De-Ru; Zhou, Mei-Fu

2017-04-01

In South China, the Yangtze and Cathaysia blocks were welded together along the Jiangnan Fold Belt during Neoproterozoic time (∼830 Ma). Large-scale mineralization in these two blocks occurred from Proterozoic to Cenozoic, making the region one of the most important polymetallic metallogenic provinces in the world. Of particular importance are world-class deposits of iron-oxide copper gold (IOCG), sediment-hosted Mn-P-Al-(Ni, Mo, PGE), syenite-carbonatite-related REE, felsic intrusion-related Sn-W-Mo-Cu-Fe-Pb-Zn, mafic intrusion-related V-Ti-Fe and Cu-Ni-PGE and low-temperature hydrothermal Pb, Zn, Au, and Sb (Fig. 1). In addition, the Ta-Nb, Hg, As, Tl and U deposits in South China are among the world largest of these kinds. Because of these deposits, South China has been a focus of researches for many years. Publications before 2005 were mostly restricted in Chinese. In the past decade, some case studies on some world-class deposits in South China are available in international journals. These recent studies have advanced our understanding of their mode of formation. However, some important issues regarding the timing, tectonic setting and mechanisms of metal concentration still remain poorly understood. This special issue brings together some of the latest information on these topics, including major review papers on specific types of mineralization and several papers dealing with some specific deposits in the region. We anticipate that this issue will generate more interests in the studies of mineral deposits in South China. In this introduction, we outline the tectonic framework and associated deposits.

Levels of some microelements and essential heavy metals in herbal teas in Serbia.

PubMed

Mihaljev, Zeljko; Zivkov-Balos, Milica; Cupić, Zeljko; Jaksić, Sandra

2014-01-01

Levels of Fe, Mn, Cu, Zn, Mo, Co, Ni, Se, Sn and Al were determined in 14 medicinal plants from Serbia, which are widely used in phytopharmacy as herbal teas. The following plants were investigated: yarrow (Achillea millefolium L.), basil (Ocimum hasilicum L.), St. John's wort (Hypericum perforatum L.), peppermint (Mentha x piperita L.), field horsetail (Equisetum arvense L.), stinging nettle (Urtica dioica L.), thyme (Thymus serpyllum L.), maize silk (Zea mays L. - Maydis stigma), hibiscus (Hibiscus sabdariffa L.), marshmallow (Althaea officinalis L.), chamomile (Matricaria chamomilla L.), rosehip/dog rose (Rosa canina L.), winter savory (Satureja montana L.) and spearmint (Mentha spicata L.). A total of 16 samples of different parts of medicinal plants (root, leaf, flower, herba) were examined, whereby 13 samples were delivered in original package and three samples were loose leaf herbs. Samples were prepared using the microwave digestion technique, and measurements were performed applying the atomic absorption spectrometry and mass spectrometry with inductively coupled plasma. Contents of microelements in the examined samples were in the range: Mn (23.86 - 453.71 mg/kg); Fe (61.87 - 673.0 mg/kg); Cu (6.68 - 24.46 mg/kg); Zn (16.11 - 113.81 mg/kg); Mo (0.576 - 4.265 mg/kg); Co (0.039 - 0.532 mg/kg); Se (0.036 - 0.146 mg/kg); Ni (0.738 - 6.034 mg/kg); Al (154.0 - 3015.0 mg/kg) and Sn (2.68 - 10.22 mg/kg). According to determined amounts of microelements, the investigated samples of herbal teas are considered safe for human consumption.

Structures, thermal expansion properties and phase transitions of Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} (0.0 {le} x {le} 2.0).

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

Cheng, Y. Z.; Wu, M. M.; Peng, J.

2007-05-03

Structures, thermal expansion properties and phase transitions of Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} (0.0 {le} x {le} 2.0) have been investigated by X-ray diffraction and differential thermal analysis. The partial substitution of Er{sup 3+} for Fe{sup 3+} induces pronounced decreases in the phase transition temperature from monoclinic to orthorhombic structure. Rietveld analysis of the XRD data shows that both the monoclinic and orthorhombic Fe{sub 2}(MoO{sub 4}){sub 3}, as well as the orthorhombic Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} (x {le} 0.8) have positive thermal expansion coefficients. However, the linear thermal expansion coefficients of Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} (x = 0.6-2.0)more » decrease with increasing content of Er{sup 3+} and for x {ge} 1.0, compounds Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} show negative thermal expansion properties. Attempts for making zero thermal expansion coefficient materials result in that very low negative thermal expansion coefficient of -0.60 x 10{sup -6} C in Er{sub 1.0}Fe{sub 1.0}(MoO{sub 4}){sub 3} is observed in the temperature range of 180-400 C, and zero thermal expansion is observed in Er{sub 0.8}Fe{sub 1.2}(MoO{sub 4}){sub 3} in the temperature range of 350-450 C. In addition, anisotropic thermal expansions are found for all the orthorhombic Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} compounds, with negative thermal expansion coefficients along the a axes.« less

Photochemical synthesis of the Fe0/C3N4/MoS2 heterostructure as a highly active and reusable photocatalyst

NASA Astrophysics Data System (ADS)

Wang, Xiu; Zhou, Zhiming; Liang, Zhiyu; Zhuang, Zanyong; Yu, Yan

2017-11-01

The Fe0/C3N4/MoS2 heterostructure was fabricated through photochemical synthesis that was free of NaBH4. Specifically, the g-C3N4/MoS2 (GCNM) composite was used as the substrate. Visible light excited the electrons from the valence band of the GCNM in the substrate, and the excited electrons reduced the Fe2+ ions in the solution nearby GCNM to Fe0 and then created the Fe0/C3N4/MoS2 heterostructure. Small Fe0 (<9 nm) dots well dispersed on the GCNM surface were obtained, because the diffusion of the Fe ions in the solution and the diffusion of the electrons on the GCNM substrate restricted the growth of Fe0 nanoparticles. The smaller size of Fe0 provided a larger number of active metal centers and improved the carrier separation efficiency. As a result, the Fe0/C3N4/MoS2 heterostructure exhibited superior catalytic properties in the redox reactions of rhodamine B, Cr(VI), Pb(II), and Cd(II). It could also be readily recycled without severe loss of catalytic performance.

Meta-omic signatures of microbial metal and nitrogen cycling in marine oxygen minimum zones

PubMed Central

Glass, Jennifer B.; Kretz, Cecilia B.; Ganesh, Sangita; Ranjan, Piyush; Seston, Sherry L.; Buck, Kristen N.; Landing, William M.; Morton, Peter L.; Moffett, James W.; Giovannoni, Stephen J.; Vergin, Kevin L.; Stewart, Frank J.

2015-01-01

Iron (Fe) and copper (Cu) are essential cofactors for microbial metalloenzymes, but little is known about the metalloenyzme inventory of anaerobic marine microbial communities despite their importance to the nitrogen cycle. We compared dissolved O2, NO3−, NO2−, Fe and Cu concentrations with nucleic acid sequences encoding Fe and Cu-binding proteins in 21 metagenomes and 9 metatranscriptomes from Eastern Tropical North and South Pacific oxygen minimum zones and 7 metagenomes from the Bermuda Atlantic Time-series Station. Dissolved Fe concentrations increased sharply at upper oxic-anoxic transition zones, with the highest Fe:Cu molar ratio (1.8) occurring at the anoxic core of the Eastern Tropical North Pacific oxygen minimum zone and matching the predicted maximum ratio based on data from diverse ocean sites. The relative abundance of genes encoding Fe-binding proteins was negatively correlated with O2, driven by significant increases in genes encoding Fe-proteins involved in dissimilatory nitrogen metabolisms under anoxia. Transcripts encoding cytochrome c oxidase, the Fe- and Cu-containing terminal reductase in aerobic respiration, were positively correlated with O2 content. A comparison of the taxonomy of genes encoding Fe- and Cu-binding vs. bulk proteins in OMZs revealed that Planctomycetes represented a higher percentage of Fe genes while Thaumarchaeota represented a higher percentage of Cu genes, particularly at oxyclines. These results are broadly consistent with higher relative abundance of genes encoding Fe-proteins in the genome of a marine planctomycete vs. higher relative abundance of genes encoding Cu-proteins in the genome of a marine thaumarchaeote. These findings highlight the importance of metalloenzymes for microbial processes in oxygen minimum zones and suggest preferential Cu use in oxic habitats with Cu > Fe vs. preferential Fe use in anoxic niches with Fe > Cu. PMID:26441925

Meta-omic signatures of microbial metal and nitrogen cycling in marine oxygen minimum zones.

PubMed

Glass, Jennifer B; Kretz, Cecilia B; Ganesh, Sangita; Ranjan, Piyush; Seston, Sherry L; Buck, Kristen N; Landing, William M; Morton, Peter L; Moffett, James W; Giovannoni, Stephen J; Vergin, Kevin L; Stewart, Frank J

2015-01-01

Iron (Fe) and copper (Cu) are essential cofactors for microbial metalloenzymes, but little is known about the metalloenyzme inventory of anaerobic marine microbial communities despite their importance to the nitrogen cycle. We compared dissolved O2, NO[Formula: see text], NO[Formula: see text], Fe and Cu concentrations with nucleic acid sequences encoding Fe and Cu-binding proteins in 21 metagenomes and 9 metatranscriptomes from Eastern Tropical North and South Pacific oxygen minimum zones and 7 metagenomes from the Bermuda Atlantic Time-series Station. Dissolved Fe concentrations increased sharply at upper oxic-anoxic transition zones, with the highest Fe:Cu molar ratio (1.8) occurring at the anoxic core of the Eastern Tropical North Pacific oxygen minimum zone and matching the predicted maximum ratio based on data from diverse ocean sites. The relative abundance of genes encoding Fe-binding proteins was negatively correlated with O2, driven by significant increases in genes encoding Fe-proteins involved in dissimilatory nitrogen metabolisms under anoxia. Transcripts encoding cytochrome c oxidase, the Fe- and Cu-containing terminal reductase in aerobic respiration, were positively correlated with O2 content. A comparison of the taxonomy of genes encoding Fe- and Cu-binding vs. bulk proteins in OMZs revealed that Planctomycetes represented a higher percentage of Fe genes while Thaumarchaeota represented a higher percentage of Cu genes, particularly at oxyclines. These results are broadly consistent with higher relative abundance of genes encoding Fe-proteins in the genome of a marine planctomycete vs. higher relative abundance of genes encoding Cu-proteins in the genome of a marine thaumarchaeote. These findings highlight the importance of metalloenzymes for microbial processes in oxygen minimum zones and suggest preferential Cu use in oxic habitats with Cu > Fe vs. preferential Fe use in anoxic niches with Fe > Cu.

Copper nanoparticle interspersed MoS2 nanoflowers with enhanced efficiency for CO2 electrochemical reduction to fuel.

PubMed

Shi, Guodong; Yu, Luo; Ba, Xin; Zhang, Xiaoshu; Zhou, Jianqing; Yu, Ying

2017-08-15

Electrocatalytic conversion of carbon dioxide (CO 2 ) has been considered as an ideal method to simultaneously solve the energy crisis and environmental issue around the world. In this work, ultrasmall Cu nanoparticle interspersed flower-like MoS 2 was successfully fabricated via a facile microwave hydrothermal method. The designed optimal hierarchical Cu/MoS 2 composite not only exhibited remarkably enhanced electronic conductivity and specific surface area but also possessed improved CO 2 adsorption capacity, resulting in a significant increase in overall faradaic efficiency and a 7-fold augmentation of the faradaic efficiency of CH 4 in comparison with bare MoS 2 . In addition, the Cu/MoS 2 composite had superior stability with high efficiency retained for 48 h in the electrochemical process. It is anticipated that the designed Cu/MoS 2 composite electrocatalyst may provide new insights for transition metal sulfides and non-noble particles applied to CO 2 reduction.

Heterometal cubane-type MFe(3)S(4) clusters (M = Mo, V) trigonally symmetrized with hydrotris(pyrazolyl)borate(1-) and tris(pyrazolyl)methanesulfonate(1-) capping ligands.

PubMed

Fomitchev, Dmitry V; McLauchlan, Craig C; Holm, R H

2002-02-25

A series of heterometal cubane-type clusters containing [VFe(3)S(4)](2+) and [MoFe(3)S(4)](3+,2+) cores has been prepared. Ligand substitution of [(DMF)(3)VFe(3)S(4)Cl(3)](-) affords [(Tpms)VFe(3)S(4)L(3)](2)(-) (L = Cl(-) (8), EtS(-) (9), p-MeC(6)H(4)S(-), p-MeC(6)H(4)O(-)). A new procedure for the preparation of molybdenum single cubanes is introduced by the reaction of recently reported [(Tp)MoS(S(4))](-) with FeCl(2)/NaSEt to afford [(Tp)MoFe(3)S(4)Cl(3)](-) (1, 75% yield). This procedure is more efficient that the existing multistep synthesis of single cubanes, which generally affords clusters of mirror symmetry. Also prepared were [(Tp)MoFe(3)S(4)L(3)](-) (L = EtS(-) (2), p-MeC(6)H(4)S(-)). Reduction of 1 with borohydride gives [(Tp)MoFe(3)S(4)Cl(3)](2-) (5, 67%). Owing to the nature of the heterometal ligand, all clusters have idealized trigonal symmetry, reflected in their (1)H NMR spectra. Trigonal structures are demonstrated by crystallography of (Bu(4)N)[1,2], (Bu(4)N)(2)[5] x MeCN, and (Me(4)N)(2)[8,9]. The availability of 1 and 5 allows the first comparison of structures and (57)Fe isomer shifts of [MoFe(3)S(4)](3+,2+) in a constant ligand environment. Small increases in most bond distances indicate that an antibonding electron is added in the reduction of 1. Collective synthetic and electrochemical results from this and other studies demonstrate the existence of the series of oxidation states [VFe(3)S(4)](3+,2+,1+) and [MoFe(3)S(4)](4+,3+,2+) whose relative stabilities within a given series are strongly ligand dependent. Isomer shifts indicate that the reduction of 1 largely affects the Fe(3) subcluster and are consistent with the formal descriptions [MoFe(3+)(2)Fe(2+)S(4)](3+) (1) and [MoFe(3+)Fe(2+)(2)S(4)](2+) (5). Reaction of 1 with excess Li(2)S in acetonitrile affords the double cubane [[(Tp)MoFe(3)S(4)Cl(2)](2)(mu(2)(-)S)](2)(-), whose sulfide-bridged structure is supported by two sequential reductions separated by 290 mV, in analogy with previously reported double cubanes of higher charge. Trigonally symmetric single cubanes eliminate isomers in the formation of double cubanes and other cluster structures, and may be of considerable value in the preparation of new types of M-Fe-S clusters. (Tpms = tris(pyrazolyl)methanesulfonate(1-); Tp = hydrotris(pyrazolyl)borate(1-).)

Total reflection X-ray fluorescence spectrometric determination of elements in water hyacinth from the Lerma River

NASA Astrophysics Data System (ADS)

Tejeda, S.; Zarazúa, G.; Ávila-Pérez, P.; Carapia-Morales, L.; Martínez, T.

2010-06-01

The Lerma River is one of the most polluted body water in Mexico. For this reason, only the highly resistant organisms such as water hyacinth are able to reproduce in this river. The aim of this work was to evaluate the concentration of K, S, Fe, Ca, Mn, Ti, Zn, Sr, Rb, Cu, Cr, Ni, Pb and Br in roots of water hyacinth ( Eichhornia crassipes) from the Lerma River. The samples were collected from five sites in the river and analyzed in triplicate using a TXRF Spectrometer 'TX-2000 Ital Structures' with a Si(Li) detector and a resolution of 140 eV (FWHM) at Mn Kα. A Mo tube (40 kV, 30 mA) with 17.4 KeV excitation energy was used for a counting time of 500 s. Results show that the average metal concentration in the water hyacinth roots decrease in the following order: K (9698.2 µg/g) > S (7593.3 µg/g) > Fe (4406.6 µg/g) > Ca (2601.8 µg/g) > Mn (604.2 µg/g) > Ti (230.7 µg/g) > Zn (51.65 µg/g) > Sr (43.55 µg/g) > Rb (18.61 µg/g) > Cu (12.78 µg/g) > Cr (6.45 µg/g) > Ni (4.68 µg/g) > Pb (4.32 µg/g) > Br (4.31 µg/g) and the bioconcentration factors in the water hyacinth decrease in the sequence: Ti > Fe > Mn > Cu > Ni > Zn > S > Pb > Rb > K > Cr > Sr > Br > Ca. The concentrations in roots of water hyacinth reflect the high pollution level of the river.

Micronutrient mineral and folate content of Australian and imported dried fruit products.

PubMed

Bennett, Louise E; Singh, Davinder P; Clingeleffer, Peter R

2011-01-01

A selection of Australian and imported fresh and dried fruit products, including sultanas, Sunmuscats, Carina currants, Zante currants, apricots, and prunes, were analyzed for selected minerals (Ca, Mg, Na, S, B, Al, Fe, Mn, Cu, Zn, Mo, and Se), folate and vitamin C, and the capacity of dried fruits for dietary provision of these micronutrients evaluated. Micro-nutrients were concentrated by a factor of 3-5 in dried fruits compared with their fresh fruit counterparts and were consequently present in nutritionally significant levels, in contrast to fresh fruit. Australian dried sultanas, Carina currant, Zante currant, apricots, and prunes contained Cu, Fe, K, and Mn at levels of >20% of daily Required Dietary Intake (RDI, taken as the average for adult men and women as nominated by the Australian National Health and Medical Research Council) and Sunmuscats contained Cu, Fe, and K at >20% of RDI. All dried fruits studied contained boron in the range of 1.5 to 5.4 mg per 100 g; however, the RDI for boron has not been defined by the NHMRC at the present time. All sultanas and currants studied contained folate at levels of 10-20% of RDI per 100 g. Experimental drying methods significantly affected folate levels with higher folate content in non-ground versus ground-based drying methods. Of the micro-nutrients supplying >20% of RDI, folate represents a particular nutrient for which the mean daily intake of adult Australians is typically inadequate. This study shows that dried fruit consumption, in contrast with fresh fruit, can provide significant proportions of daily requirements of several micronutrients, particularly folate.

CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane.

PubMed

Khadka, Nimesh; Dean, Dennis R; Smith, Dayle; Hoffman, Brian M; Raugei, Simone; Seefeldt, Lance C

2016-09-06

The reduction of N2 to NH3 by Mo-dependent nitrogenase at its active-site metal cluster FeMo-cofactor utilizes reductive elimination of Fe-bound hydrides with obligatory loss of H2 to activate the enzyme for binding/reduction of N2. Earlier work showed that wild-type nitrogenase and a nitrogenase with amino acid substitutions in the MoFe protein near FeMo-cofactor can catalytically reduce CO2 by two or eight electrons/protons to carbon monoxide (CO) and methane (CH4) at low rates. Here, it is demonstrated that nitrogenase preferentially reduces CO2 by two electrons/protons to formate (HCOO(-)) at rates >10 times higher than rates of CO2 reduction to CO and CH4. Quantum mechanical calculations on the doubly reduced FeMo-cofactor with a Fe-bound hydride and S-bound proton (E2(2H) state) favor a direct reaction of CO2 with the hydride ("direct hydride transfer" reaction pathway), with facile hydride transfer to CO2 yielding formate. In contrast, a significant barrier is observed for reaction of Fe-bound CO2 with the hydride ("associative" reaction pathway), which leads to CO and CH4. Remarkably, in the direct hydride transfer pathway, the Fe-H behaves as a hydridic hydrogen, whereas in the associative pathway it acts as a protic hydrogen. MoFe proteins with amino acid substitutions near FeMo-cofactor (α-70(Val→Ala), α-195(His→Gln)) are found to significantly alter the distribution of products between formate and CO/CH4.

Oxidative degradation of the antibiotic oxytetracycline by Cu@Fe3O4 core-shell nanoparticles.

PubMed

Pham, Van Luan; Kim, Do-Gun; Ko, Seok-Oh

2018-08-01

A core-shell nanostructure composed of zero-valent Cu (core) and Fe 3 O 4 (shell) (Cu@Fe 3 O 4 ) was prepared by a simple reduction method and was evaluated for the degradation of oxytetracycline (OTC), an antibiotic. The Cu core and the Fe 3 O 4 shell were verified by X-ray diffractometry (XRD) and transmission electron microscopy. The optimal molar ratio of [Cu]/[Fe] (1/1) in Cu@Fe 3 O 4 created an outstanding synergic effect, leading to >99% OTC degradation as well as H 2 O 2 decomposition within 10min at the reaction conditions of 1g/L Cu@Fe 3 O 4 , 20mg/L OTC, 20mM H 2 O 2 , and pH3.0 (and even at pH9.0). The OTC degradation rate by Cu@Fe 3 O 4 was higher than obtained using single nanoparticle of Cu or Fe 3 O 4 . The results of the study using radical scavengers showed that OH is the major reactive oxygen species contributing to the OTC degradation. Finally, good stability, reusability, and magnetic separation were obtained with approximately 97% OTC degradation and no notable change in XRD patterns after the Cu@Fe 3 O 4 catalyst was reused five times. These results demonstrate that Cu@Fe 3 O 4 is a novel prospective candidate for the pharmaceutical and personal care products degradation in the aqueous phase. Copyright © 2018 Elsevier B.V. All rights reserved.

Coping with Iron Limitation: A Metabolomic Study of Synechocystis sp. PCC 6803.

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

Rivas-Ubach, Albert; Poret-Peterson, A. T.; Penuel

2018-02-28

Iron (Fe) is a key element for all living systems, especially for photosynthetic organisms because of its important role in the photosynthetic electron transport chain. Fe limitation in cyanobacteria leads to several physiological and morphological changes. However, the overall metabolic responses to Fe limitation are still poorly understood. In this study, we integrated elemental, stoichiometric, macromolecular, and metabolomic data to shed light on the responses of Synechocystis sp. PCC 6803, a non-N2-fixing freshwater cyanobacterium, to Fe limitation. Compared to Synechocystis growing at nutrient replete conditions, Fe-limited cultures had lower growth rates and amounts of chlorophyll a, RNA, RNA:DNA, C, N,more » and P and higher ratios of Protein:RNA, C:N, C:P and N:P, in accordance with the growth rate hypothesis which predicts faster growing organisms will have decreased biomass RNA contents and C:P and N:P ratios. Fe-limited Synechocystis had lower amounts Fe, Mn and Mo, and higher amount of Cu. Several changes in amino acids of cultures growing under Fe limitation suggest nitrogen limitation. Additionally, we found substantial increases in stress-related metabolites in Fe-limited cyanobacteria such antioxidants. This study represents an advance in understanding the stoichiometric, macromolecular and metabolic strategies that cyanobacteria use to cope with Fe limitation. This information, moreover, may further understanding of changes in cyanobacterial functions under scenarios of Fe limitation in aquatic ecosystems.« less

High spin polarization and the origin of unique ferromagnetic ground state in CuFeSb

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

Sirohi, Anshu; Saha, Preetha; Gayen, Sirshendu

CuFeSb is isostructural to the ferro-pnictide and chalcogenide superconductors and it is one of the few materials in the family that are known to stabilize in a ferromagnetic ground state. Majority of the members of this family are either superconductors or antiferromagnets. Therefore, CuFeSb may be used as an ideal source of spin polarized current in spin-transport devices involving pnictide and the chalcogenide superconductors. However, for that the Fermi surface of CuFeSb needs to be sufficiently spin polarized. In this paper we report direct measurement of transport spin polarization in CuFeSb by spin-resolved Andreev reflection spectroscopy. From a number ofmore » measurements using multiple superconducting tips we found that the intrinsic transport spin polarization in CuFeSb is high (∼47%). In order to understand the unique ground state of CuFeSb and the origin of large spin polarization at the Fermi level, we have evaluated the spin-polarized band structure of CuFeSb through first principles calculations. Apart from supporting the observed 47% transport spin polarization, such calculations also indicate that the Sb-Fe-Sb angles and the height of Sb from the Fe plane are strikingly different for CuFeSb than the equivalent parameters in other members of the same family thereby explaining the origin of the unique ground state of CuFeSb.« less

Facile one-pot synthesis of cellulose nanocrystal-supported hollow CuFe2O4 nanoparticles as efficient catalyst for 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Zhang, Sufeng; Zhao, Dongyan; Hou, Chen; Liang, Chen; Li, Hao

2018-06-01

A facile and efficient one-pot method for the synthesis of well-dispersed hollow CuFe2O4 nanoparticles (H-CuFe2O4 NPs) in the presence of cellulose nanocrystals (CNC) as the support was described. Based on the one-pot solvothermal condition control, magnetic H-CuFe2O4 NPs were in-situ grown on the CNC surface uniformly. TEM images indicated good dispersity of H-CuFe2O4 NPs with uniform size of 300 nm. The catalytic activity of H-CuFe2O4/CNC was tested in the catalytic reduction of 4-nitrophenol (4-NP) in aqueous solution. Compared with most CNC-based ferrite catalysts, H-CuFe2O4/CNC catalyst exhibited an excellent catalytic activity toward the reduction of 4-NP. The catalytic performance of H-CuFe2O4/CNC catalyst was remarkably enhanced with the rate constant of 3.24 s-1 g-1, which was higher than H-CuFe2O4 NPs (0.50 s-1 g-1). The high catalytic activity was attributed to the introduction of CNC and the special hollow mesostructure of H-CuFe2O4 NPs. In addition, the H-CuFe2O4/CNC catalyst promised good conversion efficiency without significant decrease even after 10 cycles, confirming relatively high stability. Because of its environmental sustainability and magnetic separability, H-CuFe2O4/CNC catalyst was shown to indicate that the ferrite nanoparticles supported on CNC were acted as a promising catalyst and exhibited potential applications in numerous ferrite based catalytic reactions.

Sorption Mechanisms of Cesium on Cu II2Fe II(CN) 6and Cu II3[Fe III(CN) 6] 2Hexacyanoferrates and Their Relation to the Crystalline Structure

NASA Astrophysics Data System (ADS)

Ayrault, S.; Jimenez, B.; Garnier, E.; Fedoroff, M.; Jones, D. J.; Loos-Neskovic, C.

1998-12-01

CuII2FeII(CN)6·xH2O and CuII3[FeIII(CN)6]2·xH2O can be prepared with reproducible chemical compositions and structures after careful washing. They have cubicFmoverline3mstructures with iron vacancies. In CuII2FeII(CN)6, copper occupies two different sites: Cu1 in position 4blinked to Fe through the CN groups, and Cu2 not linked to the CN groups and partially occupying the interstitial 24epositions. The second type of site is not present in CuII3[FeIII(CN)6]2. Sorption kinetics and isotherms were determined for cesium on both hexacyanoferrates by batch experiments. On CuII3[FeIII(CN)6]2, the maximum uptake is only 0.073 Cs/Fe (at./at.). On CuII2FeII(CN)6, the uptake reaches 1.5 Cs/Fe. The sorption kinetics include at least two steps: at1/2variation until approximately 72 h and then a slow evolution studied up to 6 months. The sorption mechanism is complex. The main process seems to be diffusion of ion pairs, followed by a reorganization of the solid, resulting in one or more new solid phases. The presence of the Cu2 site seems to play a favorable role in the sorption. Owing to its good midterm stability and the first rapid step of exchange, CuII2FeII(CN)6·xH2O seems to be one of the most promising compounds for the recovery of cesium from nuclear liquid wastes.

High strength-high conductivity Cu--Fe composites produced by powder compaction/mechanical reduction

DOEpatents

Verhoeven, John D.; Spitzig, William A.; Gibson, Edwin D.; Anderson, Iver E.

1991-08-27

A particulate mixture of Cu and Fe is compacted and mechanically reduced to form an "in-situ" Cu-Fe composite having high strength and high conductivity. Compaction and mechanical reduction of the particulate mixture are carried out at a temperature and time at temperature selected to avoid dissolution of Fe into the Cu matrix particulates to a harmful extent that substantially degrades the conductivity of the Cu-Fe composite.

Experimental investigation of inhomogeneities, nanoscopic phase separation, and magnetism in arc melted Fe-Cu metals with equal atomic ratio of the constituents

NASA Astrophysics Data System (ADS)

Hassnain Jaffari, G.; Aftab, M.; Anjum, D. H.; Cha, Dongkyu; Poirier, Gerald; Ismat Shah, S.

2015-12-01

Composition gradient and phase separation at the nanoscale have been investigated for arc-melted and solidified with equiatomic Fe-Cu. Diffraction studies revealed that Fe and Cu exhibited phase separation with no trace of any mixing. Microscopy studies revealed that immiscible Fe-Cu form dense bulk nanocomposite. The spatial distribution of Fe and Cu showed existence of two distinct regions, i.e., Fe-rich and Cu-rich regions. Fe-rich regions have Cu precipitates of various sizes and different shapes, with Fe forming meshes or channels greater than 100 nm in size. On the other hand, the matrix of Cu-rich regions formed strips with fine strands of nanosized Fe. Macromagnetic response of the system showed ferromagnetic behavior with a magnetic moment being equal to about 2.13 μB/ Fe atom and a bulk like negligible value of coercivity over the temperature range of 5-300 K. Anisotropy constant has been calculated from various laws of approach to saturation, and its value is extracted to be equal to 1350 J/m3. Inhomogeneous strain within the Cu and Fe crystallites has been calculated for the (unannealed) sample solidified after arc-melting. Annealed sample also exhibited local inhomogeneity with removal of inhomogeneous strain and no appreciable change in magnetic character. However, for the annealed sample phase separated Fe exhibited homogenous strain.

Coercivity Recovery Effect of Sm-Fe-Cu-Al Alloy on Sm2Fe17N3 Magnet

NASA Astrophysics Data System (ADS)

Otogawa, Kohei; Asahi, Toru; Jinno, Miho; Yamaguchi, Wataru; Takagi, Kenta; Kwon, Hansang

2018-03-01

The potential of a Sm-Fe-Cu-Al binder for improvement of the magnetic properties of Sm2Fe17N3 was examined. Transmission electron microscope (TEM) observation of a Sm-Fe-Cu-Al alloy-bonded Sm2Fe17N3 magnet which showed high coercivity revealed that the Sm-Fe-Cu-Al alloy had an effect of removing the surface oxide layer of the Sm2 Fe17N3 grains. However, the Sm-Fe-Cu-Al binder was contaminated by carbon and nitrogen, which originated from the organic solvent used as the milling medium during pulverization. To prevent carbon and nitrogen contamination, the Sm-Fe- Cu-Al alloy was added directly on the surface of the Sm2Fe17N3 grains by sputtering. Comparing the recovered coercivity per unit amount of the added binder the uncontaminated binder-coated sample had a higher coercivity recovery effect than the milled binder-added sample. These results suggested that sufficient addition of the contamination-free Sm-Fe-Cu-Al binder has the possibility to reduce the amount of binder necessary to produce a high coercive Sm2Fe17N3 magnet.

Aluminum alloy anode materials for Li-ion batteries

NASA Astrophysics Data System (ADS)

Sun, Z. H.; Chen, Z. F.; Fu, Q. W.; Jiang, X. Y.

2017-03-01

Aluminum has larger theoretical capacity of 2235 mAh/g than that of graphite (372 mAh/g), but it has big disadvantages including shorter cycle life and higher irreversible capacity loss. Improving cycle performance can be obtained via alloying of aluminum. In this paper, two ternary aluminum alloy, Al7Cu2Fe and Al73Cu5Fe22 were prepared. The main phase of Al7Cu2Fe alloy was Al7Cu2Fe. The heat treatment increased the proportion of Al7Cu2Fe. The main phase of Al73Cu5Fe22 alloy was Al60Cu30Fe10. The heat treatment reduced the proportion of Al60Cu30Fe10. For two alloys, the heat treatment could increase discharge capacity compared with cast alloy. The discharge capacity was improved by 50%. The content of aluminum in alloys has little effect on improving cycle performance, and it has obvious influence on the phase structure of alloy with heat treatment.

Ultrasmall Fe2O3 nanoparticles/MoS2 nanosheets composite as high-performance anode material for lithium ion batteries.

PubMed

Qu, Bin; Sun, Yue; Liu, Lianlian; Li, Chunyan; Yu, Changjian; Zhang, Xitian; Chen, Yujin

2017-02-20

Coupling ultrasmall Fe 2 O 3 particles (~4.0 nm) with the MoS 2 nanosheets is achieved by a facile method for high-performance anode material for Li-ion battery. MoS 2 nanosheets in the composite can serve as scaffolds, efficiently buffering the large volume change of Fe 2 O 3 during charge/discharge process, whereas the ultrasmall Fe 2 O 3 nanoparticles mainly provide the specific capacity. Due to bigger surface area and larger pore volume as well as strong coupling between Fe 2 O 3 particles and MoS 2 nanosheets, the composite exhibits superior electrochemical properties to MoS 2 , Fe 2 O 3 and the physical mixture Fe 2 O 3 +MoS 2 . Typically, after 140 cycles the reversible capacity of the composite does not decay, but increases from 829 mA h g -1 to 864 mA h g -1 at a high current density of 2 A g -1 . Thus, the present facile strategy could open a way for development of cost-efficient anode material with high-performance for large-scale energy conversion and storage systems.

Major and trace elements in Boletus aereus and Clitopilus prunulus growing on volcanic and sedimentary soils of Sicily (Italy).

PubMed

Alaimo, M G; Dongarrà, G; La Rosa, A; Tamburo, E; Vasquez, G; Varrica, D

2018-08-15

The aim of this study was to determine and compare the content of 28 elements (Ag, Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Rb, Sb, Se, Sr, Tl, U, V and Zn) in fruiting bodies of Boletus aereus Bull. and Clitopilus prunulus P. Kumm collected from eleven unpolluted sites of Sicily (Italy) and, also to relate the abundance of chemical elements in soil with their concentration in mushrooms. Median concentrations of the most abundant elements in Boletus aereus ranged from 31,290 μg/g (K) to 107 μg/g (Zn) in caps and from 24,009 μg/g (K) to 57 μg/g (Zn) in stalks with the following abundance order: K > Na > Ca > Mg > Fe > Al > Rb > Zn. The same elements, in the whole fruiting body of Clitopilus prunulus samples, varied in the range 54,073-92 μg/g following the abundance order: K > Na > Mg > Ca > Fe > Al > Rb > Zn. Metal contents in Boletus aereus and in the whole fruiting body of Clitopilus prunulus, collected from the same sampling sites, showed statistically significant differences for most elements. In particular, Clitopilus prunulus contained around two to four times more Co, Cr, Fe, Mg, Mo, Pb, U and V than caps and stalks of Boletus aereus species which, in turn, was from two to four times more enriched in Cu, Se and Tl. Thus, the elemental content of Boletus aereus and Clitopilus prunulus appeared to be species-dependent. The distribution of chemical elements in Boletus aereus was not uniform throughout the whole fruiting body as most elements were significantly bioconcentrated in caps. Furthermore, the fruit bodies of Boletus aereus from the volcanic soil differed both in major and minor elements concentrations from those collected from sedimentary soils. Cadmium and lead concentrations were below the threshold limits for wild mushrooms proposed by EU Directives (2008 and 2015). The elemental content was not significantly influenced by soil pH. Copyright © 2018 Elsevier Inc. All rights reserved.

Activity and Stability of Dispersed Multi Metallic Pt-based Catalysts for CO Tolerance in Proton Exchange Membrane Fuel Cell Anodes.

PubMed

Hassan, Ayaz; Ticianelli, Edson A

2018-01-01

Studies aiming at improving the activity and stability of dispersed W and Mo containing Pt catalysts for the CO tolerance in proton exchange membrane fuel cell (PEMFC) anodes are revised for the following catalyst systems: (1) a carbon supported PtMo electrocatalyst submitted to heat treatments; (2) Pt and PtMo nanoparticles deposited on carbon-supported molybdenum carbides (Mo2C/C); (3) ternary and quaternary materials formed by PtMoFe/C, PtMoRu/C and PtMoRuFe/C and; (4) Pt nanoparticles supported on tungsten carbide/carbon catalysts and its parallel evaluation with carbon supported PtW catalyst. The heat-treated (600 oC) Pt-Mo/C catalyst showed higher hydrogen oxidation activity in the absence and in the presence of CO and better stability, compared to all other Mo-containing catalysts. PtMoRuFe, PtMoFe, PtMoRu supported on carbon and Pt supported on Mo2C/C exhibited similar CO tolerances but better stability, as compared to as-prepared PtMo supported on carbon. Among the tungsten-based catalysts, tungsten carbide supported Pt catalyst showed reasonable performance and reliable stability in comparison to simple carbon supported PtW catalyst, though an uneven level of catalytic activity towards H2 oxidation in presence of CO is observed for the former as compared to Mo containing catalyst. However, a small dissolution of Mo, Ru, Fe and W from the anodes and their migration toward cathodes during the cell operation is observed. These results indicate that the fuel cell performance and stability has been improved but not yet totally resolved.

Rapid removal of ultra-high-concentration p-nitrophenol in aqueous solution by microwave-enhanced Fe/Cu bimetallic particle (MW-Fe/Cu) system.

PubMed

Ren, Yi; Zhou, Jinfan; Pan, Zhicheng; Lai, Bo; Yuan, Donghai

2017-10-10

Ultra-high-concentration PNP-contained wastewaters are produced sometimes due to the wide application of this nitrophenolic compound in the chemical industry. However, there is a lack of appropriate technologies to rapidly pretreat the ultra-high-concentration wastewater. Therefore, a new microwave-enhanced Fe/Cu bimetallic particles (MW-Fe/Cu) system was developed to rapidly remove ultra-high-concentration PNP. First, the priority of the determinative parameters was obtained by orthogonal experiment. Based on this result, the effects of initial pH, microwave power, Fe/Cu dosage and initial PNP concentration on PNP removal were optimized thoroughly. Under the optimal conditions (i.e. initial pH = 1.0, MW power = 385 W, Fe/Cu dosage = 30 g/L and initial PNP concentration = 4000 mg/L), four control treatment systems (i.e. MW-Fe 0 , heating-Fe/Cu, MW alone and Fe/Cu alone system) were set up to compare with the MW-Fe/Cu system. The results suggest that high PNP removal (more than 99% with 2.5 min, k 1 /k 2  = 1.18/6.91 min -1 ) and COD removal (26.6% with 5 min treatment) could be obtained by the MW-Fe/Cu system, which were much superior to those obtained using the MW-Fe 0 (k 1 /k 2  = 0.62/2.21 min -1 ) and the heating-Fe/Cu system (k 1 /k 2  = 0.53/1.52 min -1 ). Finally, the determination of the intermediates of PNP degradation by HPLC indicated that the MW assistance process did not change the degradation pathway of PNP. This concludes that the new MW-Fe/Cu system was the promising technology for pretreatment of wastewater containing ultra-high-concentration toxic and refractory pollutants at a fairly short treatment time.

Ligand-hole localization in oxides with unusual valence Fe

PubMed Central

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

2012-01-01

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

Enhancement of photodetection characteristics of MoS2 field effect transistors using surface treatment with copper phthalocyanine.

PubMed

Pak, Jinsu; Jang, Jingon; Cho, Kyungjune; Kim, Tae-Young; Kim, Jae-Keun; Song, Younggul; Hong, Woong-Ki; Min, Misook; Lee, Hyoyoung; Lee, Takhee

2015-11-28

Recently, two-dimensional materials such as molybdenum disulfide (MoS2) have been extensively studied as channel materials for field effect transistors (FETs) because MoS2 has outstanding electrical properties such as a low subthreshold swing value, a high on/off ratio, and good carrier mobility. In this study, we characterized the electrical and photo-responsive properties of MoS2 FET when stacking a p-type organic copper phthalocyanine (CuPc) layer on the MoS2 surface. We observed that the threshold voltage of MoS2 FET could be controlled by stacking the CuPc layers due to a charge transfer phenomenon at the interface. Particularly, we demonstrated that CuPc/MoS2 hybrid devices exhibited high performance as a photodetector compared with the pristine MoS2 FETs, caused by more electron-hole pairs separation at the p-n interface. Furthermore, we found the optimized CuPc thickness (∼2 nm) on the MoS2 surface for the best performance as a photodetector with a photoresponsivity of ∼1.98 A W(-1), a detectivity of ∼6.11 × 10(10) Jones, and an external quantum efficiency of ∼12.57%. Our study suggests that the MoS2 vertical hybrid structure with organic material can be promising as efficient photodetecting devices and optoelectronic circuits.

The Unique Biogeochemical Signature of the Marine Diazotroph Trichodesmium

PubMed Central

Nuester, Jochen; Vogt, Stefan; Newville, Matthew; Kustka, Adam B.; Twining, Benjamin S.

2012-01-01

The elemental composition of phytoplankton can depart from canonical Redfield values under conditions of nutrient limitation or production (e.g., N fixation). Similarly, the trace metal metallome of phytoplankton may be expected to vary as a function of both ambient nutrient concentrations and the biochemical processes of the cell. Diazotrophs such as the colonial cyanobacteria Trichodesmium are likely to have unique metal signatures due to their cell physiology. We present metal (Fe, V, Zn, Ni, Mo, Mn, Cu, Cd) quotas for Trichodesmium collected from the Sargasso Sea which highlight the unique metallome of this organism. The element concentrations of bulk colonies and trichomes sections were analyzed by ICP-MS and synchrotron x-ray fluorescence, respectively. The cells were characterized by low P contents but enrichment in V, Fe, Mo, Ni, and Zn in comparison to other phytoplankton. Vanadium was the most abundant metal in Trichodesmium, and the V quota was up to fourfold higher than the corresponding Fe quota. The stoichiometry of 600C:101N:1P (mol mol−1) reflects P-limiting conditions. Iron and V were enriched in contiguous cells of 10 and 50% of Trichodesmium trichomes, respectively. The distribution of Ni differed from other elements, with the highest concentration in the transverse walls between attached cells. We hypothesize that the enrichments of V, Fe, Mo, and Ni are linked to the biochemical requirements for N fixation either directly through enrichment in the N-fixing enzyme nitrogenase or indirectly by the expression of enzymes responsible for the removal of reactive oxygen species. Unintentional uptake of V via P pathways may also be occurring. Overall, the cellular content of trace metals and macronutrients differs significantly from the (extended) Redfield ratio. The Trichodesmium metallome is an example of how physiology and environmental conditions can cause significant deviations from the idealized stoichiometry. PMID:22557997

The Azotobacter vinelandii NifEN complex contains two identical [4Fe-4S] clusters.

PubMed

Goodwin, P J; Agar, J N; Roll, J T; Roberts, G P; Johnson, M K; Dean, D R

1998-07-21

The nifE and nifN gene products from Azotobacter vinelandii form an alpha2beta2 tetramer (NifEN complex) that is required for the biosynthesis of the nitrogenase FeMo cofactor. In the current model for NifEN complex organization and function, the complex is structurally analogous to the nitrogenase MoFe protein and provides an assembly site for a portion of FeMo cofactor biosynthesis. In this work, gene fusion and immobilized metal-affinity chromatography strategies were used to elevate the in vivo production of the NifEN complex and to facilitate its rapid and efficient purification. The NifEN complex produced and purified in this way exhibits an FeMo cofactor biosynthetic activity similar to that previously described for the NifEN complex purified by traditional chromatography methods. UV-visible, EPR, variable-temperature magnetic circular dichroism, and resonance Raman spectroscopies were used to show that the NifEN complex contains two identical [4Fe-4S]2+ clusters. These clusters have a predominantly S = 1/2 ground state in the reduced form, exhibit a reduction potential of -350 mV, and are likely to be coordinated entirely by cysteinyl residues on the basis of spectroscopic properties and sequence comparisons. A model is proposed where each NifEN complex [4Fe-4S] cluster is bridged between a NifE-NifN subunit interface at a position analogous to that occupied by the P clusters in the nitrogenase MoFe protein. In contrast to the MoFe protein P clusters, the NifEN complex [4Fe-4S] clusters are proposed to be asymmetrically coordinated to the NifEN complex where NifE cysteines-37, -62, and -124 and NifN cysteine-44 are the coordinating ligands. On the basis of a homology model of the three-dimensional structure of the NifEN complex, the [4Fe-4S] cluster sites are likely to be remote from the proposed FeMo cofactor assembly site and are unlikely to become incorporated into the FeMo cofactor during its assembly.

Iron Sulfide Attenuates the Methanogenic Toxicity of Elemental Copper and Zinc Oxide Nanoparticles and their Soluble Metal Ion Analogs

PubMed Central

Gonzalez-Estrella, Jorge; Gallagher, Sara; Sierra-Alvarez, Reyes; Field, Jim A.

2016-01-01

Elemental copper (Cu0) and zinc oxide (ZnO) nanoparticle (NP) toxicity to methanogens has been attributed to the release of soluble metal ions. Iron sulfide (FeS) partially controls the soluble concentration of heavy metals and their toxicity in aquatic environments. Heavy metals displace the Fe from FeS forming poorly soluble metal sulfides in the FeS matrix. Therefore, FeS may be expected to attenuate the NP toxicity. This work assessed FeS as an attenuator of the methanogenic toxicity of Cu0 and ZnO NPs and their soluble salt analogs. The toxicity attenuation capacity of fine (25–75 µm) and coarse (500 to 1200 µm) preparations of FeS (FeS-f and FeS-c respectively) was tested in the presence of highly inhibitory concentrations of CuCl2, ZnCl2 Cu0 and ZnO NPs. FeS-f attenuated methanogenic toxicity better than FeS-c. The results revealed that 2.5× less FeS-f than FeS-c was required to recover the methanogenic activity to 50% (activity normalized to uninhibited controls). The results also indicated that a molar FeS-f/Cu0 NP, FeS-f/ZnO NP, FeS-f/ZnCl2, and FeS-f/CuCl2 ratio of 2.14, 2.14, 4.28, and 8.56 respectively, was necessary to recover the methanogenic activity to >75%. Displacement experiments demonstrated that CuCl2 and ZnCl2 partially displaced Fe from FeS. As a whole, the results indicate that not all the sulfide in FeS was readily available to react with the soluble Cu and Zn ions which may explain the need for a large stoichiometric excesses of FeS to highly attenuate Cu and Zn toxicity. Overall, this study provides evidence that FeS attenuates the toxicity caused by Cu0 and ZnO NPs and their soluble ion analogs to methanogens. PMID:26803736

High strength-high conductivity Cu-Fe composites produced by powder compaction/mechanical reduction

DOEpatents

Verhoeven, J.D.; Spitzig, W.A.; Gibson, E.D.; Anderson, I.E.

1991-08-27

A particulate mixture of Cu and Fe is compacted and mechanically reduced to form an ''in-situ'' Cu-Fe composite having high strength and high conductivity. Compaction and mechanical reduction of the particulate mixture are carried out at a temperature and time at temperature selected to avoid dissolution of Fe into the Cu matrix particulates to a harmful extent that substantially degrades the conductivity of the Cu-Fe composite. 5 figures.

Nitrate removal by Fe0/Pd/Cu nano-composite in groundwater.

PubMed

Liu, Hongyuan; Guo, Min; Zhang, Yan

2014-01-01

Nitrate pollution in groundwater shows a great threat to the safety of drinking water. Chemical reduction by zero-valent iron is being considered as a promising technique for nitrate removal from contaminated groundwater. In this paper, Fe0/Pd/Cu nano-composites were prepared by the liquid-phase reduction method, and batch experiments of nitrate reduction by the prepared Fe0/Pd/Cu nano-composites under various operating conditions were carried out. It has been found that nano-Fe0/Pd/Cu composites processed dual functions: catalytic reduction and chemical reduction. The introduction of Pd and Cu not only improved nitrate removal rate, but also reduced the generation of ammonia. Nitrate removal rate was affected by the amount of Fe0/Pd/Cu, initial nitrate concentration, solution pH, dissolved oxygen (DO), reaction temperature, the presence of anions, and organic pollutant. Moreover, nitrate reduction by Fe0/Pd/Cu composites followed the pseudo-first-order reaction kinetics. The removal rate of nitrate and total nitrogen were about 85% and 40.8%, respectively, under the reaction condition of Fe-6.0%Pd-3.0%Cu amount of 0.25 g/L, pH value of 7.1, DO of 0.42 mg/L, and initial nitrate concentration of 100 mg/L. Compared with the previous studies with Fe0 alone or Fe-Cu, nano-Fe-6%Pd-3%Cu composites showed a better selectivity to N2.

Seebeck Coefficient of Cation-Substituted Disulfides CuCr1-x Fe x S2 and Cu1-x Fe x CrS2

NASA Astrophysics Data System (ADS)

Korotaev, Evgeniy V.; Syrokvashin, Mikhail M.; Filatova, Irina Yu.; Pelmenev, Konstantin G.; Zvereva, Valentina V.; Peregudova, Natalya N.

2018-03-01

The effect of cation substitution on the Seebeck coefficient of CuCr1-x Fe x S2 (x = 0 to 0.30) and Cu1-x Fe x CrS2 (x = 0 to 0.03) in the temperature range of 100 K to 450 K has been investigated. Increasing iron concentration led to a metal-insulator transition which suppressed the thermoelectric power. However, for low iron concentration (x < 0.03), the Seebeck coefficient of CuCr1-x Fe x S2 and Cu1-x Fe x CrS2 exceeded the values for the undoped copper-chromium disulfide matrix CuCrS2 at temperature below 300 K.

Thermal stability of intermetallic phases in Fe-rich Fe-Cr-Ni-Mo alloys

DOE PAGES

Yang, Ying; Tan, Lizhen; Busby, Jeremy T.

2015-06-12

Understanding the stability of precipitate phases in the Fe-rich Fe-Cr-Ni-Mo alloys is critical to the alloy design and application of Mo-containing Austenitic steels. Coupled with thermodynamic modeling, stability of the chi and Laves phases in two Fe-Cr-Ni-Mo alloys were investigated at 1000, 850 and 700 °C for different annealing time. The morphologies, compositions and crystal structures of the matrix and precipitate phases were carefully examined by Scanning Electron Microscopy, Electron Probe Microanalysis, X-ray diffraction and Transmission Electron Microscopy. The two key findings resulted from this work. One is that the chi phase is stable at high temperature and transformed intomore » the Laves phase at low temperature. The other is that both the chi and Laves phases have large solubilites of Cr, Mo and Ni, among which the Mo solubility has a major role on the relative stability of the precipitate phases. The developed thermodynamic models were then applied to evaluating the Mo effect on the stability of precipitate phases in AISI 316 and NF709 alloys.« less

Fabrication and electrocatalytic properties of chitosan and keplerate-type polyoxometalate {Mo72Fe30} hybrid films.

PubMed

Fan, Dawei; Hao, Jingcheng

2009-05-28

Hybrid films composed of chitosan and Keplerate-type polyoxometalate, {Mo72Fe30} (Mo72VIFe30IIIO252L102.ca.180H2O, L=H2O/CH3COO-/Mo2O8/9n-), were fabricated on quartz, silicon, and ITO substrates by layer-by-layer (LbL) method. The LbL films were characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and cyclic voltammetry (CV). UV-vis spectra show that the absorbance values at characteristic wavelengths of the multilayer films increase almost linearly with the number of chitosan/{Mo72Fe30} bilayers. XPS spectra confirm the incorporation of chitosan and {Mo72Fe30} into the films. The electrocatalytic reduction of ClO3-, BrO3-, and IO3- by chitosan/{Mo72Fe30} hybrid films in an acidic aqueous solution shows an electrocatalytic reduction activity of IO3->BrO3->ClO3-. In particular, the modified electrodes exhibited high electrocatalytic activity for reduction of IO3-.

Coercivity enhancement of Nd-Fe-B hot-deformed magnets by the eutectic grain boundary diffusion process using Nd-Ga-Cu and Nd-Fe-Ga-Cu alloys

NASA Astrophysics Data System (ADS)

Liu, Lihua; Sepehri-Amin, H.; Sasaki, T. T.; Ohkubo, T.; Yano, M.; Sakuma, N.; Kato, A.; Shoji, T.; Hono, K.

2018-05-01

Nd80Ga15Cu5 and Nd62Fe14Ga20Cu4 alloys were used as diffusion sources for the eutectic grain boundary diffusion process, applying to 4 mm-thick Nd-Fe-B hot-deformed magnets. Both samples showed nearly same coercivity of 2.2 T, while the sample processed with Nd62Fe14Ga20Cu4 showed smaller remanence deterioration from 1.50 T to 1.30 T, in contrast to that of the sample processed with Nd80Ga15Cu5 to 1.08 T. Mr/Ms of the initial sample and the samples processed with Nd62Fe14Ga20Cu4 and Nd80Ga15Cu5 were 0.946, 0.934 and 0.917, respectively, suggesting that the sample processed with Nd62Fe14Ga20Cu4 retains stronger c-axis texture after the diffusion process. Nd-rich phases with Ia3 ¯ and fcc structures were observed in the sample processed with Nd80Ga15Cu5, while the Nd-rich phases with the Ia3 ¯ and hcp structures were found in the sample processed with Nd62Fe14Ga20Cu4, all of which are the phases commonly observed in Nd-Fe-B sintered magnets.

Mechanism insight of pollutant degradation and bromate inhibition by Fe-Cu-MCM-41 catalyzed ozonation.

PubMed

Chen, Weirui; Li, Xukai; Tang, Yiming; Zhou, Jialu; Wu, Dan; Wu, Yin; Li, Laisheng

2018-03-15

A flexible catalyst, Fe-Cu-MCM-41, was employed to enhance diclofenac (DCF) mineralization and inhibit bromate formation in catalytic ozonation process. Greater TOC removal was achieved in Fe-Cu-MCM-41/O 3 process (78%) than those in Fe-MCM-41/O 3 (65%), Cu-MCM-41/O 3 (73%) and sole ozonation (42%). But it was interesting that both Cu-MCM-41/O 3 and Fe-MCM-41/O 3 achieved 93% bromate inhibition efficiency, only 71% inhibition efficiency was observed in Fe-Cu-MCM-41/O 3 . Influence of pH, TBA/NaHSO 3 and detection of by-products were conducted to explore the mechanism. By Pyridine adsorption-IR and XPS, a relationship was found among activity of catalysts, Lewis acid sites and electron transfer effect between Fe (II/III) and Cu (I/II). Fe-Cu-MCM-41 promoted ozone decomposition to generate OH, which accounted for enhanced DCF mineralization. The consumption of aqueous O 3 also suppressed the oxidative of Br - and HBrO/Br - . More HBrO/BrO - accumulated in catalytic ozonation process and less bromate generated. Bromate formation in Fe-Cu-MCM-41/O 3 process was sensitive with pH value, the acidic condition was not favor for bromate formation. Both DCF mineralization and bromate inhibition were influenced by surface reaction. Moreover, Fe-Cu-MCM-41 showed excellent catalytic performance in suppressing the accumulation of carboxylic acid, especially for oxalic acid. Nearly no oxalic acid was detected during Fe-Cu-MCM-41/O 3 process. Copyright © 2017 Elsevier B.V. All rights reserved.

Exploring the mechanism and kinetics of Fe-Cu-Ag trimetallic particles for p-nitrophenol reduction.

PubMed

Yuan, Yue; Yuan, Donghai; Zhang, Yunhong; Lai, Bo

2017-11-01

Preparation conditions of Fe-Cu-Ag trimetallic particles were optimized by single-factor and response surface methodology (RSM) batch experiments to obtain high-reactive Fe 0 -based materials for p-nitrophenol (PNP) removal. Under the optimal conditions (i.e., Fe 0 dosage of 34.86 g L -1 , theoretical Cu mass loading of 81.87 mg Cu/g Fe, theoretical Ag mass loading of 1.15 mg Ag/g Fe, and preparation temperature of 52.1 °C), the actual rate constant (k obs ) of PNP reduction in 5 min was 1.64 min -1 , which shows a good agreement between the model prediction (1.85 min -1 ) of RSM and the experimental data. Furthermore, the high reactivity of Fe 0 -based trimetals was mainly attributed to the plating order of transition metals (i.e., Ag and Cu). Furthermore, we propose a new theory that the pyramid trimetallic structure of Fe-Cu-Ag could improve the electron transport and create active sites with high electron density at the surface (Ag layer) that could enhance the generation of surface-bonded atomic hydrogen ([H] abs ) or the direct reduction of pollutant. Moreover, Fe-Cu-Ag trimetallic particles were characterized by SEM, EDS, and XPS, which also could confirm the proposed theory. In addition, the leached Cu 2+ (<10 μg L -1 ) and Ag + (below detection limits) in Fe-Cu-Ag system could be neglected completely, which suggests that Fe-Cu-Ag is reliable, safe, and environment friendly. Therefore, Fe-Cu-Ag trimetallic system would be promising for the removal of pollutants from industrial wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nanocomposite Nd-Y-Fe-B-Mo bulk magnets prepared by injection casting technique

NASA Astrophysics Data System (ADS)

Tao, Shan; Ahmad, Zubair; Zhang, Pengyue; Yan, Mi; Zheng, Xiaomei

2017-09-01

The phase composition, magnetic and microstructural properties of Nd2Fe14B/(α-Fe, Fe3B) nanocomposite magnets produced by injection casting technique have been studied. Magnetic hysteresis loop of the Nd7Y6Fe61B22Mo4 permanent magnet demonstrates the coercivity as high as 1289 kA/m. Electron microscopy elucidates a microstructure composed of magnetically soft α-Fe, Fe3B and hard Nd2Fe14B/Y2Fe14B nanograins (20-50 nm) separated by ultra-thin grain boundary layer. The Henkel plot curve of the Nd7Y6Fe61B22Mo4 magnet yields the existence of exchange coupling interactions between soft and hard phases. Macroscopically large size sheet magnet is obtained due to high glass forming ability of the Nd7Y6Fe61B22Mo4 alloy derived from large atomic radius mismatch and negative enthalpy of alloy constituent elements. The high coercivity of the magnet is attributed to the magnetically hard phase increment, nucleation of reverse domains and the presence of thin grain boundary phase. Good magnetic properties such as remanence of 0.51 T, coercivity of 1289 kA/m and maximum energy product of 46.2 kJ/m3 are obtained in directly casted Nd7Y6Fe61B22Mo4 sheet magnets.

The Synthesis and Characterization of Aromatic Hybrid Anderson–Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions

PubMed Central

Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette

2015-01-01

Four aromatic hybrid Anderson polyoxomolybdates with Fe3+ or Mn3+ as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, 1H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3[FeMo6O18{(OCH2)3CNHCOC6H5}2]⋅3.5 ACN (TBA-FeMo6-bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRIS–R=(HOCH2)3C–R)), (TBA)3[FeMo6O18{(OCH2)3CNHCOC8H7}2]⋅2.5 ACN (TBA-FeMo6-cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3[MnMo6O18{(OCH2)3CNHCOC6H5}2]⋅3.5 ACN (TBA-MnMo6-bzn), and (TBA)3[MnMo6O18{(OCH2)3CNHCOC8H7}2]⋅2.5 ACN (TBA-MnMo6-cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mm) sodium salts Na3[FeMo6O18{(OCH2)3CNHCOC6H5}2] (Na-FeMo6-bzn), Na3[FeMo6O18{(OCH2)3CNHCOC8H7}2] (Na-FeMo6-cin), Na3[MnMo6O18{(OCH2)3CNHCOC6H5}2] (Na-MnMo6-bzn), and Na3[MnMo6O18{(OCH2)3CNHCOC8H7}2] (Na-MnMo6-cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate–polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern–Volmer analysis, which suggested the formation of a 1:1 POM–protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic interactions with polar amino acid side chains from, for example, subdomain IB. PMID:26527418

Perpendicular magnetic anisotropy in Mo/Co2FeAl0.5Si0.5/MgO/Mo multilayers with optimal Mo buffer layer thickness

NASA Astrophysics Data System (ADS)

Saravanan, L.; Raja, M. Manivel; Prabhu, D.; Pandiyarasan, V.; Ikeda, H.; Therese, H. A.

2018-05-01

Perpendicular Magnetic Anisotropy (PMA) was realized in as-deposited Mo(10)/Co2FeAl0.5Si0.5(CFAS)(3)/MgO(0.5)/Mo multilayer stacks with large perpendicular magnetic anisotropy energy (Keff). PMA of this multilayer is found to be strongly dependent on the thickness of the individual CFAS (tCFAS), Mo (tMo) and MgO (tMgO) layers and annealing temperatures. The interactions at the Mo/CFAS/MgO interfaces are critical to induce PMA and are tuned by the interfacial oxidation. The major contribution to PMA is due to iron oxide at the CFAS/MgO interface. X-ray diffraction (XRD) and infrared spectroscopic (FT-IR) studies further ascertain this. However, an adequate oxidation of MgO and the formation of (0 2 4) and (0 1 8) planes of α-Fe2O3 at the optimal Mo buffer layer thickness is mainly inducing PMA in Mo/CFAS/MgO/Mo stack. Microstructural changes in the films are observed by atomic force microscopy (AFM). X-ray photoelectron spectroscopy (XPS) demonstrates the oxidation of CFAS/MgO interface and the formation of Fe-O bonds confirming that the real origin of PMA in Mo/CFAS/MgO is due to hybridization of Fe (3dz2) and O (2pz) orbitals and the resulted spin-orbit interaction at their interface. The half-metallic nature CFAS with Mo layer exhibiting PMA can be a potential candidate as p-MTJs electrodes for the new generation spintronic devices.

(1)H NMR and GC-MS Based Metabolomics Reveal Defense and Detoxification Mechanism of Cucumber Plant under Nano-Cu Stress.

PubMed

Zhao, Lijuan; Huang, Yuxiong; Hu, Jerry; Zhou, Hongjun; Adeleye, Adeyemi S; Keller, Arturo A

2016-02-16

Because copper nanoparticles are being increasingly used in agriculture as pesticides, it is important to assess their potential implications for agriculture. Concerns have been raised about the bioaccumulation of nano-Cu and their toxicity to crop plants. Here, the response of cucumber plants in hydroponic culture at early development stages to two concentrations of nano-Cu (10 and 20 mg/L) was evaluated by proton nuclear magnetic resonance spectroscopy ((1)H NMR) and gas chromatography-mass spectrometry (GC-MS) based metabolomics. Changes in mineral nutrient metabolism induced by nano-Cu were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Results showed that nano-Cu at both concentrations interferes with the uptake of a number of micro- and macro-nutrients, such as Na, P, S, Mo, Zn, and Fe. Metabolomics data revealed that nano-Cu at both levels triggered significant metabolic changes in cucumber leaves and root exudates. The root exudate metabolic changes revealed an active defense mechanism against nano-Cu stress: up-regulation of amino acids to sequester/exclude Cu/nano-Cu; down-regulation of citric acid to reduce the mobilization of Cu ions; ascorbic acid up-regulation to combat reactive oxygen species; and up-regulation of phenolic compounds to improve antioxidant system. Thus, we demonstrate that nontargeted (1)H NMR and GC-MS based metabolomics can successfully identify physiological responses induced by nanoparticles. Root exudates metabolomics revealed important detoxification mechanisms.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Site Preference of Ternary Alloying Additions to AuTi

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Mosca, Hugo O.; Noebe, Ronald D.

2006-01-01

Atomistic modeling of the site substitution behavior of several alloying additions, namely. Na, Mg, Al, Si. Sc, V, Cr, Mn. Fe, Co, Ni, Cu, Zn, Y, Zr. Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, and Pt in B2 TiAu is reported. The 30 elements can be grouped according to their absolute preference for a specific site, regardless of concentration, or preference for available sites in the deficient sublattice. Results of large scale simulations are also presented, distinguishing between additions that remain in solution from those that precipitate a second phase.

Exothermic Surface Reactions in Alumina-Aluminum Shell-Core Nanoparticles with Iodine Oxide Decomposition Fragments

DTIC Science & Technology

2014-02-22

substantially high heat of combustion 6.22 kJ/g in comparison to other thermite reactions such as Al/CuO (4.09 kJ/g), Al/MoO3 (4.72 kJ/g), and Al/Fe2O3 (3.97 kJ...oxide shell growth on nano aluminum thermite propagation rates. Combust Flame 159:3448 3453 Granier JJ, Pantoya ML (2004) Laser ignition of...nanocomposite thermites . Combust Flame 138:373 383 2310 Page 8 of 9 J Nanopart Res (2014) 16:2310 1 3 Hlavacek V, Pranda P, Prandova K (2005) Reactivity, stored

``Loose spins'' in Fe/Cu/Fe(001) structures

NASA Astrophysics Data System (ADS)

Heinrich, B.; Celinski, Z.; Liao, L. X.; From, M.; Cochran, J. F.

1994-05-01

Slonczewski recently proposed a model for the exchange coupling between ferromagnetic layers separated by a nonferromagnetic spacer based on the concept of ``loose spins.'' ``Loose spins'' contribute to the total exchange energy. We have studied the role of ``loose spins'' in bcc Fe/Cu/Fe(001) structures. bcc Fe/Cu/Fe(001) trilayers deposited at room temperature were investigated extensively in our previous studies. In our ``loose spin'' studies, the Fe was added inside the Cu interlayer. Several structures were atomically engineered in order to test the behavior of ``loose spins:'' One additional atomic layer of an (Fe+Cu) alloy were located in appropriate positions in a Cu spacer. The bilinear and biquadratic exchange coupling in the above structures was quantitatively studied with FMR in the temperature range 77-370 K and with MOKE at RT.

Rapid synthesis of Fe-doped CuO-Ce0.8Zr0.2O2 catalysts for CO preferential oxidation in H2-rich streams: Effect of iron source and the ratio of Fe/Cu

NASA Astrophysics Data System (ADS)

Wang, Jing; Han, Caiyun; Gao, Xiaoya; Lu, Jichang; Wan, Gengpin; He, Dedong; Chen, Ran; Chen, Kezhen; He, Sufang; Luo, Yongming

2017-03-01

A facile route (urea grind combustion method) is described for the rapid synthesis of Fe-doped Cu-Ce-Zr catalysts within 30 min through simple grinding and combustion. The effects of iron source and Fe/Cu mass ratio on the performances of the catalysts for CO preferential oxidation (CO-PROX) are evaluated. The influences of H2O, CO2, and their mixture on the activity as well as stability of the catalysts are also investigated. The samples are characterized by XRD, N2 adsorption-desorption, H2-TPR, TEM, Raman and XPS. Fe(NO3)3 is found to be superior to FeCl3 and Fe2(SO4)3 as the iron source for Fe-CuCZ catalyst. Among the different synthesized catalysts, 1/10Fe(N)-CuCZ is found to be the most active catalyst, indicating that the optimal Fe/Cu mass ratio is 1/10. The influences of H2O, CO2, and H2O + CO2 on the catalytic performance of 1/10Fe(N)-CuCZ are in the order of CO2 < CO2 + H2O < H2O. 1/10Fe(N)-CuCZ exhibits excellent stability during a 228 h time-on-stream test. 1/10Fe(N)-CuCZ shows the highest catalytic activity and excellent stability even in the presence of H2O and CO2. The excellent catalytic performance can be attributed to the synergy between the highly dispersed copper species and ceria, as well as the formation of more oxygen vacancies and reduced copper species.

Laser Additive Manufacturing of Magnetic Materials

NASA Astrophysics Data System (ADS)

Mikler, C. V.; Chaudhary, V.; Borkar, T.; Soni, V.; Jaeger, D.; Chen, X.; Contieri, R.; Ramanujan, R. V.; Banerjee, R.

2017-03-01

While laser additive manufacturing is becoming increasingly important in the context of next-generation manufacturing technologies, most current research efforts focus on optimizing process parameters for the processing of mature alloys for structural applications (primarily stainless steels, titanium base, and nickel base alloys) from pre-alloyed powder feedstocks to achieve properties superior to conventionally processed counterparts. However, laser additive manufacturing or processing can also be applied to functional materials. This article focuses on the use of directed energy deposition-based additive manufacturing technologies, such as the laser engineered net shaping (LENS™) process, to deposit magnetic alloys. Three case studies are presented: Fe-30 at.%Ni, permalloys of the type Ni-Fe-V and Ni-Fe-Mo, and Fe-Si-B-Cu-Nb (derived from Finemet) alloys. All these alloys have been processed from a blend of elemental powders used as the feedstock, and their resultant microstructures, phase formation, and magnetic properties are discussed in this paper. Although these alloys were produced from a blend of elemental powders, they exhibited relatively uniform microstructures and comparable magnetic properties to those of their conventionally processed counterparts.

What do the trace metal contents of urine and toenail samples from Qatar׳s farm workers bioindicate?

PubMed

Kuiper, Nora; Rowell, Candace; Nriagu, Jerome; Shomar, Basem

2014-05-01

Qatar׳s farm workers provide a unique population for exposure study: they are young, healthy males. This study combined trace element profiles in urine and toenail with survey information from 239 farm workers to assess the extent to which the biomarkers provide complementary exposure information. Urinary Mo levels (average=114 µg/L) were elevated; average urinary values (µg/L) for all other elements were: V (1.02), Cr (0.55), Mn (2.15), Fe (34.1), Co (0.47), Ni (2.95), Cu (15.0), As (47.8), Se (25.7), Cd (1.09), Ba (22.5), Pb (2.50) and U (0.15). Average toenail concentrations (mg/kg) were: Mn (2.48), Cu (4.43), As (0.26), Se (0.58), Mo (0.07), Cd (0.03), Ba (1.00), Pb (0.51) and U (0.02). No significant association was found between corresponding elements in urine and toenails. Elemental profiles suggest groundwater (with the exception of Mo) and soil-dust-crop exposure pathways cannot account for elemental variations. The main factors moderating trace element contents are related to depuration processes involving participants׳ trace element body burden prior to work in Qatar, and interactions of trace element metabolic cycles which over-ride the exposure footprint. Toenail and urine need to be carefully validated before reliable use as biomarkers of exposure in general populations for most elements in the study. Copyright © 2014 Elsevier Inc. All rights reserved.

Effects of chronic copper exposure during early life in rhesus monkeys.

PubMed

Araya, Magdalena; Kelleher, Shannon L; Arredondo, Miguel A; Sierralta, Walter; Vial, María Teresa; Uauy, Ricardo; Lönnerdal, Bo

2005-05-01

Whether infants regulate copper absorption and the potential effects of excess copper in early life remain poorly defined. The objective of the study was to assess copper retention, liver copper content, and liver function in infant rhesus monkeys fed infant formula containing 6.6 mg Cu/L. From birth to 5 mo of age, infant rhesus monkeys were fed formula that was supplemented with copper (0.6 mg Cu/L; n = 5) or not supplemented (n = 4). In all animals, weight and crown-rump length (by anthropometry), hemoglobin, hematocrit, plasma ceruloplasmin activity, and zinc and copper concentrations were measured monthly (birth to 6 mo) and at 8 and 12 mo. When the animals were 1, 5, and 8 mo old, liver copper and metallothionein concentrations, liver histology (by light and electron microscopy), and the number of Kupffer cells were assessed, and 67Cu retention was measured. Liver function was assessed by measurement of plasma alanine aminotransferase, aspartate aminotransferase, gamma-glutamyl transferase, and alkaline phosphatase activities and protein, albumin, bilirubin, and blood urea nitrogen concentrations. 67Cu retention was 19.2% and 10.9% after 1 and 5 mo of copper treatment, respectively, compared with approximately 75% in controls at age 2 mo. At age 8 mo, 67Cu retention was 22.9% in copper-treated animals and 31.5% in controls. Liver histology remained normal by light microscopy, with mild ultrastructural signs of cell damage at 5 mo. Liver copper concentration was 4711, 1139, and 498 microg/g dry tissue at 1, 5, and 8 mo, respectively, in copper-treated animals and 250 microg/g at 2 mo in controls. Measurements could not be completed in all animals. No clinical evidence of copper toxicity was observed. Copper absorption was down-regulated; increases in liver copper content at ages 1 and 5 mo did not result in histologic damage. Ultrastructural changes at age 5 mo could signal early cellular damage.

Photoemission and Auger-electron spectroscopic study of the Chevrel-phase compound FexMo6S8

NASA Astrophysics Data System (ADS)

Fujimori, A.; Sekita, M.; Wada, H.

1986-05-01

The electronic structure of the Chevrel-phase compound FexMo6S8 has been studied by photoemission and Auger-electron spectroscopy. Core-level shifts suggest a large charge transfer from the Fe atoms to the Mo6S8 clusters and a small Mo-to-S charge transfer within the cluster. Line-shape asymmetry in the core levels indicates that the density of states (DOS) at the Fermi level has a finite S 3p component as well as the dominant Mo 3d character. Satellite structure and exchange splitting in the Fe core levels point to weak Fe 3d-S 3p hybridization in spite of the short Fe-S distances comparable to that in FeS. The x-ray and ultraviolet valence-band photoemission spectra and the Mo 4d partial DOS obtained by deconvoluting the Mo M4,5VV Auger spectrum are compared with existing band-structure calculations, and the Mo 4d-S 3p bonding character, the structure of the Mo 4d-derived conduction band etc., are discussed. In particular, it is shown that the conduction-band structure is sensitive to the noncubic distortion of the crystal through changes in the intercluster Mo 4d-S 3p hybridization. A pronounced final-state effect is found in the Mo M4,5N2,3V Auger spectrum and is attributed to strong 4p-4d intershell coupling.

Note: Resonance magnetoelectric interactions in laminate of FeCuNbSiB and multilayer piezoelectric stack for magnetic sensor

NASA Astrophysics Data System (ADS)

Li, Jianqiang; Lu, Caijiang; Xu, Changbao; Zhong, Ming

2015-09-01

This paper develops a simple miniature magnetoelectric (ME) laminate FeCuNbSiB/PZT-stack made up of magnetostrictive Fe73.5Cu1Nb3Si13.5B9 (FeCuNbSiB) foils and piezoelectric Pb(Zr, Ti)O3 (PZT) multilayer stack vibrator. Resonant ME interactions of FeCuNbSiB/PZT-stack with different layers of FeCuNbSiB foil (L) are investigated in detail. The experimental results show that the ME voltage coefficient reaches maximum value of 141.5 (V/cm Oe) for FeCuNbSiB/PZT-stack with L = 6. The AC-magnetic sensitivities can reach 524.29 mV/Oe and 1.8 mV/Oe under resonance 91.6 kHz and off-resonance 1 kHz, respectively. The FeCuNbSiB/PZT-stack can distinguish small dc-magnetic field of ˜9 nT. The results indicate that the proposed ME composites are very promising for the cheap room-temperature magnetic field sensing technology.

Internal friction peaks observed in explosively deformed polycrystalline Mo, Nb, and Cu

NASA Technical Reports Server (NTRS)

Rieu, G. E.; Grimes, H. H.; Romain, J. P.; Defouquet, J.

1974-01-01

Explosive deformation (50 kbar range) induced, in Cu, Mo and Nb, internal friction peaks identical to those observed after large normal deformation. The variation of the peaks with pressure for Mo and Nb lead to an explanation of these processes in terms of double kink generation in screw and edge dislocations.

Adsorption of Heavy Metals in Industrial Wastewater by Magnetic Nano-particles

NASA Astrophysics Data System (ADS)

Tu, Y.; You, C.

2010-12-01

Industrial wastewater containing heavy metals is of great concern because of their toxic impact to living species and environments. Removal of metal ions from industrial effluent using nano-particles is an area of extensive research. This study collected wastewaters and effluents from 11 industrial companies in tanning, electronic plating, printed circuit board manufacturing, semi-conductor, and metal surface treatment industry and studied in detailed the major and trace element compositions to develop potential fingerprinting technique for pollutant source identification. The results showed that electronic plating and metal surface treatment industry produce high Fe, Mn, Cr, Zn, Ni and Mo wastewater. The tanning industry and the printed circuit board manufacturing industry released wastewater with high Fe and Cr, Cu and Ni, respectively. For semi-conductor industry, significant dissolved In was detected in wastewater. The absorption experiments to remove heavy metals in waters were conducted using Fe3O4 nano-particles. Under optimal conditions, more than 99 % dissolved metals were removed in a few minutes.

Effects of metal ions on biomass and 5-aminolevulinic acid production in Rhodopseudomonas palustris wastewater treatment.

PubMed

Liu, Shuli; Zhang, Guangming; Li, Jianzheng; Li, Xiangkun; Zhang, Jie

2016-01-01

This work investigated the effects of eight metal ions on Rhodopseudomonas palustris growth and 5-aminolevulinic acid (ALA) yield in wastewater treatment. Results show that metal ions (Mg(2+) of 15 mmol/L, Fe(2+) of 400 μmol/L, Co(2+) of 4 μmol/L, Ni(2+) of 8 μmol/L and Zn(2+) of 4 μmol/L) could effectively improve the chemical oxygen demand (COD) removal, Rp. palustris biomass and ALA yield. The highest ALA yield of 13.1 mg/g-biomass was achieved with Fe(2+) of 400 μmol/L. ALA yields were differentially increased under different metal ions in the following order: Fe(2+) group > Mg(2+) group > Co(2+) group = Ni(2+) group > Zn(2+) group = Mo(2+) group > control. Cu(2+) and Mn(2+) inhibited Rp. palustris growth and ALA production. Mechanism analysis revealed that metal ions changed ALA yields by influencing the activities of ALA synthetase and ALA dehydratase.

Mechanism of Mo-Dependent Nitrogenase

PubMed Central

Seefeldt, Lance C.; Hoffman, Brian M.; Dean, Dennis R.

2010-01-01

Nitrogen-fixing bacteria catalyze the reduction of dinitrogen (N2) to two ammonia molecules (NH3), the major contribution of fixed nitrogen into the biogeochemical nitrogen cycle. The most widely studied nitrogenase is the Mo-dependent enzyme. The reduction of N2 by this enzyme involves the transient interaction of two component proteins, designated the Fe protein and the MoFe protein, and minimally requires sixteen MgATP, eight protons, and eight electrons. The current state of knowledge on how these proteins and small molecules together effect the reduction of N2 to ammonia is reviewed. Included is a summary of the roles of the Fe protein and MgATP hydrolysis, information on the roles of the two metal clusters contained in the MoFe protein in catalysis, insights gained from recent success in trapping substrates and inhibitors at the active site metal cluster FeMo-cofactor, and finally, considerations of the mechanism of N2 reduction catalyzed by nitrogenase. PMID:19489731

Enhancement of spin-Seebeck effect by inserting ultra-thin Fe{sub 70}Cu{sub 30} interlayer

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

Kikuchi, D., E-mail: d.kikuchi@imr.tohoku.ac.jp; WPI Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577; Spin Quantum Rectification Project, ERATO, Japan Science and Technology Agency, Sendai 980-8577

2015-02-23

We report the longitudinal spin-Seebeck effects (LSSEs) for Pt/Fe{sub 70}Cu{sub 30}/BiY{sub 2}Fe{sub 5}O{sub 12} (BiYIG) and Pt/BiYIG devices. The LSSE voltage was found to be enhanced by inserting an ultra-thin Fe{sub 70}Cu{sub 30} interlayer. This enhancement decays sharply with increasing the Fe{sub 70}Cu{sub 30} thickness, suggesting that it is not due to bulk phenomena, such as a superposition of conventional thermoelectric effects, but due to interface effects related to the Fe{sub 70}Cu{sub 30} interlayer. Combined with control experiments using Pt/Fe{sub 70}Cu{sub 30} devices, we conclude that the enhancement of the LSSE voltage in the Pt/Fe{sub 70}Cu{sub 30}/BiYIG devices is attributedmore » to the improvement of the spin-mixing conductance at the Pt/BiYIG interfaces.« less

Multi-phase back contacts for CIS solar cells

DOEpatents

Rockett, A.A.; Yang, L.C.

1995-12-19

Multi-phase, single layer, non-interdiffusing M-Mo back contact metallized films, where M is selected from Cu, Ga, or mixtures thereof, for CIS cells are deposited by a sputtering process on suitable substrates, preferably glass or alumina, to prevent delamination of the CIS from the back contact layer. Typical CIS compositions include CuXSe{sub 2} where X is In or/and Ga. The multi-phase mixture is deposited on the substrate in a manner to provide a columnar microstructure, with micro-vein Cu or/and Ga regions which partially or fully vertically penetrate the entire back contact layer. The CIS semiconductor layer is then deposited by hybrid sputtering and evaporation process. The Cu/Ga-Mo deposition is controlled to produce the single layer two-phase columnar morphology with controllable Cu or Ga vein size less than about 0.01 microns in width. During the subsequent deposition of the CIS layer, the columnar Cu/Ga regions within the molybdenum of the Cu/Ga-Mo back layer tend to partially leach out, and are replaced by columns of CIS. Narrower Cu and/or Ga regions, and those with fewer inner connections between regions, leach out more slowly during the subsequent CIS deposition. This gives a good mechanical and electrical interlock of the CIS layer into the Cu/Ga-Mo back layer. Solar cells employing In-rich CIS semiconductors bonded to the multi-phase columnar microstructure back layer of this invention exhibit vastly improved photo-electrical conversion on the order of 17% greater than Mo alone, improved uniformity of output across the face of the cell, and greater Fill Factor. 15 figs.

Multi-phase back contacts for CIS solar cells

DOEpatents

Rockett, Angus A.; Yang, Li-Chung

1995-01-01

Multi-phase, single layer, non-interdiffusing M-Mo back contact metallized films, where M is selected from Cu, Ga, or mixtures thereof, for CIS cells are deposited by a sputtering process on suitable substrates, preferably glass or alumina, to prevent delamination of the CIS from the back contact layer. Typical CIS compositions include CuXSe.sub.2 where X is In or/and Ga. The multi-phase mixture is deposited on the substrate in a manner to provide a columnar microstructure, with micro-vein Cu or/and Ga regions which partially or fully vertically penetrate the entire back contact layer. The CIS semiconductor layer is then deposited by hybrid sputtering and evaporation process. The Cu/Ga-Mo deposition is controlled to produce the single layer two-phase columnar morphology with controllable Cu or Ga vein size less than about 0.01 microns in width. During the subsequent deposition of the CIS layer, the columnar Cu/Ga regions within the molybdenum of the Cu/Ga-Mo back layer tend to partially leach out, and are replaced by columns of CIS. Narrower Cu and/or Ga regions, and those with fewer inner connections between regions, leach out more slowly during the subsequent CIS deposition. This gives a good mechanical and electrical interlock of the CIS layer into the Cu/Ga-Mo back layer. Solar cells employing In-rich CIS semiconductors bonded to the multi-phase columnar microstructure back layer of this invention exhibit vastly improved photo-electrical conversion on the order of 17% greater than Mo alone, improved uniformity of output across the face of the cell, and greater Fill Factor.

Characterization of iron, manganese, and copper synthetic hydroxyapatites by electron paramagnetic resonance spectroscopy

NASA Technical Reports Server (NTRS)

Sutter, B.; Wasowicz, T.; Howard, T.; Hossner, L. R.; Ming, D. W.

2002-01-01

The incorporation of micronutrients (e.g., Fe, Mn, Cu) into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in NASA's Advanced Life Support (ALS) program for long-duration space missions. Separate Fe3+ (Fe-SHA), Mn2+ (Mn-SHA), and Cu2+ (Cu-SHA) containing SHA materials were synthesized by a precipitation method. Electron paramagnetic resonance (EPR) spectroscopy was used to determine the location of Fe3+, Mn2+, and Cu2+ ions in the SHA structure and to identify other Fe(3+)-, Mn(2+)-, and Cu(2+)-containing phases that formed during precipitation. The EPR parameters for Fe3+ (g=4.20 and 8.93) and for Mn2+ (g=2.01, A=9.4 mT, D=39.0 mT and E=10.5 mT) indicated that Fe3+ and Mn2+ possessed rhombic ion crystal fields within the SHA structure. The Cu2+ EPR parameters (g(z)=2.488, A(z)=5.2 mT) indicated that Cu2+ was coordinated to more than six oxygens. The rhombic environments of Fe3+ and Mn2+ along with the unique Cu2+ environment suggested that these metals substituted for the 7 or 9 coordinate Ca2+ in SHA. The EPR analyses also detected poorly crystalline metal oxyhydroxides or metal-phosphates associated with SHA. The Fe-, Mn-, and Cu-SHA materials are potential slow release sources of Fe, Mn, and Cu for ALS and terrestrial cropping systems.

Coagulation-flocculation as pre-treatment for micro-scale Fe/Cu/O3 process (CF-mFe/Cu/O3) treatment of the coating wastewater from automobile manufacturing.

PubMed

Xiong, Zhaokun; Cao, Jinyan; Yang, Dan; Lai, Bo; Yang, Ping

2017-01-01

A coagulation-flocculation as pre-treatment combined with mFe/Cu/O 3 (CF-mFe/Cu/O 3 ) process was developed to degrade the pollutants in automobile coating wastewater (ACW). In coagulation-flocculation (CF) process, high turbidity removal efficiency (97.1%) and low COD removal efficiency (10.5%) were obtained under the optimal conditions using Al 2 (SO 4 ) 3 ·18H 2 O and CaO. The effluent of CF process (ECF) was further disposed by mFe/Cu/O 3 process, and its key operating parameters were optimized by batch experiments. Optimally, COD removal efficiency of ECF obtained by the mFe/Cu/O 3 process (i.e., 87.6% after 30 min treatment) was much higher than those of mFe/Cu alone (8.3%), ozone alone (46.6%), and mFe/Cu/air (6.1%), which confirms the superiority of the mFe/Cu/O 3 process. In addition, the analysis results of UV-vis, excitation-emission matrix (EEM) fluorescence spectra and GC/MS further confirm that the phenol pollutants of ECF had been effectively decomposed or transformed after CF-mFe/Cu/O 3 process treatment. Meanwhile, B/C ratio of ACW increased from 0.19 to 0.56, which suggests the biodegradability was improved significantly. Finally, the operating cost of CF-mFe/Cu/O 3 process was about 1.83 USD t -1 for ACW treatment. Therefore, the combined process is a promising treatment technology for the coating wastewater from automobile manufacturing. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis of mesoporous triple-metal nanosorbent from layered double hydroxide as an efficient new sorbent for removal of dye from water and wastewater.

PubMed

Kostić, Miloš; Radović, Miljana; Velinov, Nena; Najdanović, Slobodan; Bojić, Danijela; Hurt, Andrew; Bojić, Aleksandar

2018-09-15

In this study, co-precipitation synthesis of the mesoporous triple-metal nanosorbent from Fe, Cu, Ni layered double hydroxide (FeCuNi-LDH), on the basis of the data obtained from the TG analysis was carried out. The FTIR spectroscopy and XRD results confirm the formation of CuO, NiO and Fe 2 O 3 nanoparticles, while the EDX analysis does not show significant variations on the surface in elemental composition. BET analysis shows that FeCuNi-280 (FeCuNi-LDH calcinated at 280 °C) with mesoporous structure, has larger surface area compared to FeCuNi-LDH and FeCuNi-550 (FeCuNi-LDH calcinated at 550 °C). The value of pH PZC of FeCuNi-280 is found to be 8.66. Obtained FeCuNi-280 material showed the ability for efficient removal of dye Reactive Blue 19 (RB19) from water, with a very high sorption capacity of 480.79 mg/g at optimal conditions: the sorbent dose of 0.6 g/dm 3 , stirring speed of 280 rpm and pH 2. The kinetics results of the sorption process were well fitted by pseudo-second order and Chrastil model, and the sorption isotherm was well described by Sips, Langmuir and Brouers-Sotolongo model. FeCuNi-280 was easily regenerated with aqueous solution of NaOH, and reutilization was successfully done in five sorption cycles. The present study show that easy-to-prepare, relatively inexpensive nanosorbent FeCuNi-280 is among the best sorbents for the removal of RB19 dye from water solution and wastewater from textile industry in wide range of pH. Copyright © 2018 Elsevier Inc. All rights reserved.

The role of copper and oxalate in the redox cycling of iron in atmospheric waters

NASA Astrophysics Data System (ADS)

Sedlak, David L.; Hoigné, Jürg

During daytime, the redox cycling of dissolved iron compounds in atmospheric waters, and the related in-cloud transformations of photooxidants, are affected by reactions of Fe and Cu with hydroperoxy (HO 2) and superoxide (O 2-) radicals and the photoreduction of Fe(III)-oxalato complexes. We have investigated several of the important chemical reactions in this redox cycle, through laboratory simulation of the system, using γ-radiation to produce HO 2/O 2-. At concentrations comparable to those measured in atmospheric waters, the redox cycling of Fe was dramatically affected by the presence of oxalate and trace concentrations of Cu. At concentrations more than a hundred times lower than Fe, Cu consumed most of the HO 2/O 2-, and cycled between the Cu(II) and Cu(I) forms. Cu + reacted with FeOH 2+ to produce Fe(II) and Cu(II), with a second order rate constant of approximately 3 × 10 7 M -1s -1. The presence of oxalate resulted in the formation of Fe(III)-oxalato complexes that were essentially unreactive with HO 2/O 2-. Only at high oxalate concentrations was the Fe(II)C 2O 4 complex also formed, and it reacted relatively rapidly with hydrogen peroxide ( k = (3.1 ± 0.6) × 10 4 M -1s -1). Simulations incorporating measurements for other redox mechanisms, including oxidation by ozone, indicate that, during daytime, Fe should be found mostly in the ferrous oxidation state, and that reactions of FeOH 2+ with Cu(I) and HO 2/O 2-, and to a lesser degree, the photolysis of Fe(III)-oxalato complexes, are important mechanisms of Fe reduction in atmospheric waters. The catalytic effect of Cu(II)/Cu(I) and Fe(III)/Fe(II) should also significantly increase the sink function of the atmospheric liquid phase for HO 2 present in a cloud. A simple kinetic model for the reactions of Fe, Cu and HO 2/O 2-, accurately predicted the changes in Fe oxidation states that occurred when authentic fogwater samples were exposed to HO 2/O 2-.

Isotopic Evidence of Unaccounted for Fe and Cu Erythropoietic Pathways

NASA Astrophysics Data System (ADS)

Albarede, F.; Telouk, P.; Lamboux, A.; Jaouen, K.; Balter, V.

2011-12-01

Despite its potential importance for understanding perturbations in the Fe-Cu homeostatic pathways, the natural isotopic variability of these metals in the human body remains unexplored. We measured the Fe, Cu, and Zn isotope compositions of total blood, serum, and red blood cells of ~50 young blood donors by multiple-collector ICP-MS after separation and purification by anion exchange chromatography. Zn is on average 0.2 permil heavier in erythrocytes (δ 66Zn=0.44±0.33 permil) with respect to serum but shows much less overall isotopic variability than Fe and Cu, which indicates that isotope fractionation depends more on redox conditions than on ligand coordination. On average, Fe in erythrocytes (δ 56Fe=-2.59±0.47 permil) is isotopically light by 1-2 permil with respect to serum, whereas Cu in erythrocytes (δ 65Cu=0.56±0.50 permil) is 0.8 percent heavier. Fe and Cu isotope compositions clearly separate erythrocytes of men and women. Fe and Cu from B-type men erythrocytes are visibly more fractionated than all the other blood types. Isotope compositions provide an original method for evaluating metal mass balance and homeostasis. Natural isotope variability shows that the current models of Fe and Cu erythropoiesis, which assume that erythropoiesis is restricted to bone marrow, violate mass balance requirements. It unveils unsuspected major pathways for Fe, with erythropoietic production of isotopically heavy ferritin and hemosiderin, and for Cu, with isotopically light Cu being largely channeled into blood and lymphatic circulation rather than into superoxide dismutase-laden erythrocytes. Iron isotopes provide an intrinsic measuring rod of the erythropoietic yield, while Cu isotopes seem to gauge the relative activity of erythropoiesis and lymphatics.

Fabrication of mesoporous iron (Fe) doped copper sulfide (CuS) nanocomposite in the presence of a cationic surfactant via mild hydrothermal method for supercapacitors

NASA Astrophysics Data System (ADS)

Brown, J. William; Ramesh, P. S.; Geetha, D.

2018-02-01

We report fabrication of mesoporous Fe doped CuS nanocomposites with uniform mesoporous spherical structures via a mild hydrothermal method employing copper nitrate trihydrate (Cu (NO3).3H2O), Thiourea (Tu,Sc(NH2)2 and Iron tri nitrate (Fe(No3)3) as initial materials with cationic surfactant cetyltrimethylamoniame bromide (CTAB) as stabilizer/size controller and Ethylene glycol as solvent at 130 °C temperature. The products were characterized by XRD, SEM/EDX, TEM, FTIR and UV analysis. X-ray diffraction (XRD) spectra confirmed the Fe doped CuS nanocomposites which are crystalline in nature. EDX and XRD pattern confirmed that the product is hexagonal CuS phase. Fe doped spherical structure of CuS with grain size of 21 nm was confirmed by XRD pattern. Fe doping was identified by energy dispersive spectrometry (EDS). The Fourier-transform infrared (FTIR) spectroscopy results revealed the occurrence of active functional groups required for the reduction of copper ions. Studies showed that after a definite time relining on the chosen copper source, the obtained Fe-CuS nanocomposite shows a tendency towards self-assembly and creating mesoporous like nano and submicro structures by TEM/SAED. The achievable mechanism of producing this nanocomposite was primarily discussed. The electrochemical study confirms the pseudocapacitive nature of the CuS and Fe-CuS electrodes. The CuS and Fe-CuS electrode shows a specific capacitance of about 328.26 and 516.39 Fg-1 at a scan rate of 5 mVs-1. As the electrode in a supercapacitor, the mesoporous nanostructured Fe-CuS shows excellent capacitance characteristics.

Synergetic effect of alkaline earth metal oxides and iron oxides on the degradation of hexachlorobenzene and its degradation pathway.

PubMed

Su, Guijin; Liu, Yexuan; Huang, Linyan; Shi, Yali; Zhang, Aiqian; Zhang, Lixia; Liu, Wenbin; Gao, Lirong; Zheng, Minghui

2013-01-01

The degradation of hexachlorobenzene (HCB) was carried out over physical mixtures of a series of alkaline earth metal oxides (MO: M=Mg, Ca, Sr, Ba) and iron oxides with different crystal types (Fe(x)O(y):Fe(2)O(3) or Fe(3)O(4)) at 300°C. These physical mixtures all showed a synergetic effect toward the degradation of HCB. A range of degradation products were identified by various methods, including tri- to penta-chlorobenzenes by gas chromatography/mass spectrometry (GC-MS), tri- to penta-chlorophenols, tetrachlorocatechol (TCC) and tetrachlorohydroquinone (TCHQ) by GC-MS after derivatization, and formic and acetic acids by ion chromatography. Two degradation pathways, hydrodechlorination and oxidative degradation, appear to occur competitively. However, more sequential chlorinated benzene and phenol congeners were formed over mixed MO/Fe(3)O(4) than over mixed MO/Fe(2)O(3) under the same conditions. The oxidative reaction dominated over mixed MO/Fe(2)O(3) and was promoted as the major reaction by the synergetic effect, while both the oxidative and hydrodechlorination reactions were important over mixed MO/Fe(3)O(4), and both pathways are remarkably promoted by the synergetic effect. The enhanced hydrodechlorination may be attributed to free electrons generated by the transformation of Fe(3)O(4) into Fe(2)O(3), and hydrogen provided by water adsorbed on the MO. Copyright © 2012 Elsevier Ltd. All rights reserved.

Local structure study of (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} thin films using x-ray absorption spectroscopy

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

Ren, Yuan; Xing, Yaya; Ma, Guanxiong

2015-07-15

The (In{sub 0.95−x}Fe{sub x}Cu{sub 0.05}){sub 2}O{sub 3} (x = 0.06, 0.08, 0.15, and 0.20) films prepared by RF-magnetron sputtering were investigated by the combination of x-ray absorption spectroscopy (XAS) at Fe, Cu, and O K-edge. Although the Fe and O K-edge XAS spectra show that the Fe atoms substitute for the In sites of In{sub 2}O{sub 3} lattice for all the films, the Cu K-edge XAS spectra reveal that the codoped Cu atoms are separated to form the Cu metal clusters. After being annealed in air, the Fe atoms are still substitutionally incorporated into the In{sub 2}O{sub 3} lattice, while the Cumore » atoms form the CuO secondary phases. With the increase of Fe concentration, the bond length R{sub Fe-O} shortens and the Debye–Waller factor σ{sup 2}{sub Fe-O} increases in the first coordination shell of Fe, which are attributed to the relaxation of oxygen environment around the substitutional Fe ions. The forming of Cu relating secondary phases in the films is due to high ionization energy of Cu atoms, leading that the Cu atoms are energetically much harder to be oxidized to substitute for the In sites of In{sub 2}O{sub 3} lattice than Fe atoms. These results provide new experimental guidance in the preparation of the codoped In{sub 2}O{sub 3} based dilute magnetic oxides.« less

Conditions and mechanisms for the formation of nano-sized Delafossite (CuFeO{sub 2}) at temperatures ≤90 °C in aqueous solution

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

John, Melanie, E-mail: melanie.john@min.uni-muenchen.de; Heuss-Aßbichler, Soraya; Ullrich, Aladin

In this study, we present the mechanism of CuFeO{sub 2} formation in aqueous solution at low temperatures ≤90 °C, using sulfate salts as reactants. Furthermore, we demonstrate the influence of experimental conditions (alkalization, reaction and ageing temperature and time) on the synthesized nanoparticles. In all cases, GR–SO{sub 4}, a Fe(II–III) layered double hydroxysulphate (Fe{sup 2+}{sub 4}Fe{sup 3+}{sub 2}(OH){sub 12}·SO{sub 4}) and Cu{sub 2}O precipitate first. During further OH{sup −} supply GR–SO{sub 4} oxidizes and forms Fe{sub 10}O{sub 14}(OH){sub 2}, Cu{sub 2}O and CuFeO{sub 2} crystals. Due to the high pH further CuFeO{sub 2} crystals grow at the cost of themore » unstable intermediate products. The reaction rate increases with increasing ageing temperature, reaction pH and, in particular, NaOH concentrations in the solution. As a result, highly crystalline CuFeO{sub 2} (3R and 2H polytypes) nanoparticles showing hexagonal morphology can be synthesized at 70 °C within 10 h or at 50 °C within 1 week. The formation of 2H polytype is favored by additional OH{sup −} supply during the pH-stat time and rather low temperatures. - Highlights: • We solve the formation mechanism of pure CuFeO{sub 2} using sulfates as reactants. • CuFeO{sub 2} nanoparticles crystallize on cost of green rust, Fe{sub 10}O{sub 14}(OH){sub 2} and Cu{sub 2}O. • The reaction rate increases with increasing temperature and OH- concentration. • CuFeO{sub 2} nanoparticles form at 50 °C within one week and at 70 °C within 10 h. • 2H-polytype of CuFeO{sub 2} is favored by additional NaOH supply during pH-stat-time.« less

Chemical characteristics and source of size-fractionated atmospheric particle in haze episode in Beijing

NASA Astrophysics Data System (ADS)

Tan, Jihua; Duan, Jingchun; Zhen, Naijia; He, Kebin; Hao, Jiming

2016-01-01

The abundance, behavior, and source of chemical species in size-fractionated atmospheric particle were studied with a 13-stage low pressure impactor (ELPI) during high polluted winter episode in Beijing. Thirty three elements (Al, Ca, Fe, K, Mg, Na, Si, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Sr, Zr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Hg, Tl, and Pb) and eight water soluble ions (Cl-, NO3-, SO42 -, NH4+, Na+, K+, Ca2 +, and Mg2 +) were determined by ICP/MS and IC, respectively. The size distribution of TC (OC + EC) was reconstructed. Averagely, 51.5 ± 5.3% and 74.1 ± 3.7% of the total aerosol mass was distributed in the sub-micron (PM1) and fine particle (PM2.5), respectively. A significant shift to larger fractions during heavy pollution episode was observed for aerosol mass, NH4+, SO42 -, NO3-, K, Fe, Cu, Zn, Cd, and Pb. The mass size distributions of NH4+, SO42 -, NO3-, and K were dominated by accumulation mode. Size distributions of elements were classified into four main types: (I) elements were enriched within the accumulation mode (< 1 μm, Ge, Se, Ag, Sn, Sb, Cs, Hg, Ti, and Pb); (II) those mass (K, Cr, Mn, Cu, Zn, As, Mo, and Cd) was resided mainly within the accumulation mode, ranged from 1 to 2 μm; (III) Na, V, Co, Ni, and Ga were distributed among fine, intermediate, and coarse modes; and (IV) those which were mainly found within particles larger than 2.7 μm (Al, Mg, Si, Ca, Sc, Tl, Fe, Sr, Zr, and Ba). [H+]cor showed an accumulation mode at 600-700 nm and the role of Ca2 + should be fully considered in the estimation of acidity. The acidity in accumulation mode particles suggested that generally gaseous NH3 was not enough to neutralize sulfate completely. PMF method was applied for source apportionment of elements combined with water soluble ions. Dust, vehicle, aged coal combustion, and sea salt were identified, and the size resolved source apportionments were discussed. Aged coal combustion was the important source of fine particles and dust contributed most to coarse particle.

Elemental analysis of different varieties of rice samples using XRF technique

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

Kaur, Jaspreet, E-mail: gillpreet05051812@gmail.com; Kumar, Anil, E-mail: gilljaspreet06@gmail.com

Rice is most consumed staple food in the world providing over 21% of the calorie intake of world’s population having high yielding capacity. Elements detected in rice are Al, As, Br, Cd, Cl, Co, Cs, Cu, Fe, Hg, K, Mg, Mn, Mo, Rb, Se and Zn by using Instrumental Neutron Activation with k0 standardization (R. Jayasekera etal,2004). Some of these trace elements are C, H, O, N, S, Ca, P, K, Na, Cl, Mn, Ti, Mg, Cu, Fe, Ni, Si and Zn are essential for growth of human physique The deficiency or excess of these elements in food is knownmore » to cause a variety of malnutrition or health disorders in the world. Every year, various varieties of rice are launched by Punjab Agriculture University, Ludhiana. The main purpose of which is to increases the yield to attain the maximum profit. But this leads to changing the elemental concentration in them, which may affect the human health according to variation in the nutrition values. The main objective is to study the presence of elemental concentration in various varieties of rice using EDXRF technique.« less

Structural characterization of the P1+ intermediate state of the P-cluster of nitrogenase.

PubMed

Keable, Stephen M; Zadvornyy, Oleg A; Johnson, Lewis E; Ginovska, Bojana; Rasmussen, Andrew J; Danyal, Karamatullah; Eilers, Brian J; Prussia, Gregory A; LeVan, Axl X; Raugei, Simone; Seefeldt, Lance C; Peters, John W

2018-05-02

Nitrogenase is the enzyme that reduces atmospheric dinitrogen (N 2 ) to ammonia (NH 3 ) in biological systems. It catalyzes a series of single-electron transfers from the donor iron protein (Fe protein) to the molybdenum-iron protein (MoFe protein) that contains the iron-molybdenum cofactor (FeMo-co) sites where N 2 is reduced to NH 3 The [8Fe-7S] P-cluster in the MoFe protein functions in nitrogenase catalysis as an intermediate electron carrier between the external electron donor, the Fe protein, and the FeMo-co sites of the MoFe protein. Previous work has revealed that the P-cluster undergoes redox dependent structural changes and that the transition from the all-ferrous resting (P N ) state to the two electron oxidized P 2+ state is accompanied by protein serince hydroxyl and backbone amide ligation to Fe. In this work, the MoFe protein was poised at defined potentials with redox mediators in an electrochemical cell, and the three distinct structural states of the P-cluster (P 2+ , P 1+ , and P N ) were characterized by X-ray crystallography and confirmed by computational analysis. These analyses revealed that the three oxidation states differ in coordination implicating that the P 1+ state retains the serine hydroxyl coordination but lacks the backbone amide coordination observed in the P 2+ states. These results provide a complete picture of the redox-dependent ligand rearrangements of the three P-cluster redox states. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

Improved photoswitching response times of MoS2 field-effect transistors by stacking p-type copper phthalocyanine layer

NASA Astrophysics Data System (ADS)

Pak, Jinsu; Min, Misook; Cho, Kyungjune; Lien, Der-Hsien; Ahn, Geun Ho; Jang, Jingon; Yoo, Daekyoung; Chung, Seungjun; Javey, Ali; Lee, Takhee

2016-10-01

Photoswitching response times (rise and decay times) of a vertical organic and inorganic heterostructure with p-type copper phthalocyanine (CuPc) and n-type molybdenum disulfide (MoS2) semiconductors are investigated. By stacking a CuPc layer on MoS2 field effect transistors, better photodetection capability and fast photoswitching rise and decay phenomena are observed. Specifically, with a 2 nm-thick CuPc layer on the MoS2 channel, the photoswitching decay time decreases from 3.57 s to 0.18 s. The p-type CuPc layer, as a passivation layer, prevents the absorption of oxygen on the surface of the MoS2 channel layer, which results in a shortened photoswitching decay time because adsorbed oxygen destroys the balanced ratio of electrons and holes, leading to the interruption of recombination processes. The suggested heterostructure may deliver enhanced photodetection abilities and photoswitching characteristics for realizing ultra-thin and sensitive photodetectors.

Tribological characterisation of Zr-based bulk metallic glass in simulated physiological media

NASA Astrophysics Data System (ADS)

Chen, Q.; Chan, K. C.; Liu, L.

2011-10-01

Due to their excellent wear resistant properties and high strength, as well as a low Young's modulus, Zr-based bulk metallic glasses (BMGs) are potentially suitable biomaterials for low-friction arthroplasty. The wear characteristics of the Zr60.14Cu22.31Fe4.85Al9.7Ag3 bulk amorphous alloy against ultra-high-molecular-weight polyethylene (UHMWPE) compared to a CoCrMo/UHMWPE combination were investigated in two different wear screening test devices, reciprocating and unidirectional. Hank's solution and sterile calf bovine serum were selected as the lubricant fluid media. It was found that different fluid media had insignificant effect on polyethylene wear against BMG counterfaces. The wear behaviour obtained on both test devices demonstrated that Zr-based BMG achieved UHMWPE counterface wear rates superior to conventional cast CoCrMo alloy, where the wear rate of UHMWPE is decreased by over 20 times. The tribological performance of these joints is superior to that of conventional metal-on-polymer designs. Contact angle measurements suggested that the advantage of BMG over a CoCrMo alloy counterface is attributed to its highly hydrophilic surfaces.

A Hybrid Mineral Battery: Energy Storage and Dissolution Behavior of CuFeS2 in a Fixed Bed Flow Cell.

PubMed

Deen, Kashif Mairaj; Asselin, Edouard

2018-05-09

The development of a hybrid system capable of storing energy and the additional benefit of Cu extraction is discussed in this work. A fixed bed flow cell (FBFC) was used in which a composite negative electrode containing CuFeS 2 (80 wt %) and carbon black (20 wt %) in graphite felt was separated from a positive (graphite felt) electrode by a proton-exchange membrane. The anolyte (0.2 m H 2 SO 4 ) and catholyte (0.5 m Fe 2+ in 0.2 m H 2 SO 4 with or without 0.1 m Cu 2+ ) were circulated in the cell. The electrochemical activity of the Fe 2+ /Fe 3+ redox couple over graphite felt significantly improved after the addition of Cu 2+ in the catholyte. Ultimately, in the CuFeS 2 ∥Fe 2+ /Cu 2+ (CFeCu) FBFC system, the specific capacity increased continuously to 26.4 mAh g -1 in 500 galvanostatic charge-discharge (GCD) cycles, compared to the CuFeS 2 ∥Fe 2+ (CFe) system (13.9 mAh g -1 ). Interestingly, the specific discharge energy gradually increased to 3.6 Wh kg -1 in 500 GCD cycles for the CFeCu system compared to 3.29 Wh kg -1 for the CFe system in 150 cycles. In addition to energy storage, 10.75 % Cu was also extracted from the mineral, which is an important feature of the CFeCu system as it would allow Cu extraction and recovery through hydrometallurgical methods. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of spin entropy and lattice strain from mixed-trivalent Fe3+/Cr3+ on the electronic, thermoelectric and optical properties of delafossite CuFe1-x Cr x O2 (x  =  0.25, 0.5, 0.75)

NASA Astrophysics Data System (ADS)

Ruttanapun, Chesta; Maensiri, Santi

2015-12-01

Mixed-trivalent Fe3+/Cr3+ content CuFe1-x Cr x O2 (x  =  0.25, 0.5, and 0.75) compounds were synthesized to investigate the effects of spin entropy, and lattice strain on their electronic, thermoelectric and optical properties. The XPS results showed the existence of mixed Cu1+/Cu2+, Fe3+/Fe4+ and Cr2+/Cr3+ ion states in the structures. The mixed Fe3+/Cr3+ions caused a strong correlation to occur between the spin and the orbitals of the carriers in the octahedral layer of the sample, affecting the carrier degeneracy Seebeck coefficient behaviour, and the Cu2+ and Fe4+ ions caused an effect of enhancing the electric conductivity. These effects meant that CuFe0.75Cr0.25O2 had the highest electrical conductivity, an enhanced Seebeck coefficient compared to that of CuFeO2-based compounds, and the highest thermopower value. The lowest thermal conductivity was that of CuFe0.5Cr0.5O2, which was a result of the mismatched atomic radii of the mixed trivalent Fe3+(0.645 Å)/Cr3+(0.615 Å), which caused the lattice strain to occur in the structure and thus affected the point defect scattering of the phonon thermal conductivity. The lowest total thermal conductivity was that of CuFe0.5Cr0.5O2, because it had the maximum lattice strain. Overall, the effect of the mixed trivalent elements caused CuFe0.75Cr0.25O2 to have the highest value of the dimensionless figure of merit ZT, with a value that was four times that of CuFeO2-based compounds and six times that of CuCrO2-based compounds. With regard to optical properties, the lattice strain causes the indirect optical gap to increase with increasing x content, but has no effect on the direct optical gap. These results verified that the mixed-trivalent Fe3+/Cr3+ content of CuFe1-x Cr x O2 (x  =  0.25, 0.5, and 0.75) affected the electronic, thermoelectric and optical properties of the structure by causing spin entropy and lattice strain to occur.

Discrimination between mineralized and unmineralized alteration zones using primary geochemical haloes in the Darreh-Zar porphyry copper deposit in Kerman, southeastern Iran

NASA Astrophysics Data System (ADS)

Parsapoor, A.; Khalili, M.; Maghami, M.

2017-08-01

Primary geochemical haloes were studied at the Darreh-Zar porphyry Cu-deposit, southern Iran. In terms of geochemical signatures, high K2O/Na2O enrichment, HREEs and HFSE's depletion in the potassic alteration, high (La/Sm)cn, (La/Yb)cn and (Gd/Yb)cn ratios in mineralized sericitic and potassic zones and notable depletion in the REEs content in argillic alteration is recognized. Further, Mg, Li, Sc, P enrichment and W depletion can serve to separate potassic alteration from the other altered zones, while (Eu/Eu*)cn and (Ce/Ce*)cn don't show pronounced changes in different alteration zones. The coupled positive Tl, Se, S, Rb, Co, Cs, Mo, K and negative Te, Ta, Ti, Sr, Rb, As, Bi, Ga, Hf, In, Mn, Zn and Zr anomalies can be adequately used in discriminating between the mineralized zones (potassic, chlorite-sericite and sericite alterations) and the barren (propylitic zone). The behavior of the trace elements on isocon diagrams reveal that HFSEs are depleted in mineralized altered zones and display variations in the amounts in the barren facies. Zonality index in the axial direction from drill holes 146 to 124 estimates the zonality sequence as Pb-Zn-Ag-Cu-Pb-Zn in the surface horizons. The calculated zonality in five drill holes and six levels indicates that the level of 550 m at the DH 117 in the central part of the area has the highest value (0.76) for Cu. The zonality sequence from the surface to the depth is variable and can be demonstrated as follow: DH 146: Pb-Zn-Cu-Mo-Ag; DH 137: Zn-Cu-Mo-Pb-Ag; DH 117: Ag-Zn-Pb-Mo-Cu; DH: 121: Cu-Mo-Zn-Ag-Pb; DH 136: Pb-Ag-Zn-Cu-Mo; DH 124: Zn-Mo-Cu-Pb-Ag. Available data of the enrichment factors shows different enrichment for copper and molybdenum (i.e. EF > 10), selenium and silver (i.e. EF > 5), tin and LREEs (i.e. 1 < EF < 5).

[Catalytic combustion of soot on combined oxide catalysts].

PubMed

He, Xu-wen; Yu, Jun-jie; Kang, Shou-fang; Hao, Zheng-ping; Hu, Chun

2005-01-01

Combined oxide catalysts are prepared for catalytic combustion of soot and regeneration from diesel emissions. Thermo-gravimetric analysis(TGA) and temperature programmed oxidation(TPO)are used to evaluate the activity of catalysts under the influence of composition,atomic ration, H2O, calcinations temperature and mass ration between catalysts and soot. Results show that Cu-Mo-O had high activity among double metal oxide catalysts. Among multicomponent metal oxide catalysts, Cu-K-Mo-O had high activity when atomic ratio Cu: K: Mo = 1:1:2 and mass ration between catalysts and soot equals 5: 1. Under this condition, soot ignition temperature of Cu-K-Mo-O catalyst was 327 degrees C. H2O addition and calcinations temperature had little influence on it,which is one kind of compatible catalyst for soot control and catalytic regeneration from diesel emissions.

Beneficial Role of Copper in the Enhancement of Durability of Ordered Intermetallic PtFeCu Catalyst for Electrocatalytic Oxygen Reduction.

PubMed

Arumugam, Balamurugan; Tamaki, Takanori; Yamaguchi, Takeo

2015-08-05

Design of Pt alloy catalysts with enhanced activity and durability is a key challenge for polymer electrolyte membrane fuel cells. In the present work, we compare the durability of the ordered intermetallic face-centered tetragonal (fct) PtFeCu catalyst for the oxygen reduction reaction (ORR) relative to its counterpart bimetallic catalysts, i.e., the ordered intermetallic fct-PtFe catalyst and the commercial catalyst from Tanaka Kikinzoku Kogyo, TKK-PtC. Although both fct catalysts initially exhibited an ordered structure and mass activity approximately 2.5 times higher than that of TKK-Pt/C, the presence of Cu at the ordered intermetallic fct-PtFeCu catalyst led to a significant enhancement in durability compared to that of the ordered intermetallic fct-PtFe catalyst. The ordered intermetallic fct-PtFeCu catalyst retained more than 70% of its mass activity and electrochemically active surface area (ECSA) over 10 000 durability cycles carried out at 60 °C. In contrast, the ordered intermetallic fct-PtFe catalyst maintained only about 40% of its activity. The temperature of the durability experiment is also shown to be important: the catalyst was more severely degraded at 60 °C than at room temperature. To obtain insight into the observed enhancement in durability of fct-PtFeCu catalyst, a postmortem analysis of the ordered intermetallic fct-PtFeCu catalyst was carried out using scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDX) line scan. The STEM-EDX line scans of the ordered intermetallic fct-PtFeCu catalyst over 10 000 durability cycles showed a smaller degree of Fe and Cu dissolution from the catalyst. Conversely, large dissolution of Fe was identified in the ordered intermetallic fct-PtFe catalyst, indicating a lesser retention of Fe that causes the destruction of ordered structure and gives rise to poor durability. The enhancement in the durability of the ordered intermetallic fct-PtFeCu catalyst is ascribed to the synergistic effects of Cu presence and the ordered structure of catalyst.

Influences on Distribution of Solute Atoms in Cu-8Fe Alloy Solidification Process Under Rotating Magnetic Field

NASA Astrophysics Data System (ADS)

Zou, Jin; Zhai, Qi-Jie; Liu, Fang-Yu; Liu, Ke-Ming; Lu, De-Ping

2018-05-01

A rotating magnetic field (RMF) was applied in the solidification process of Cu-8Fe alloy. Focus on the mechanism of RMF on the solid solution Fe(Cu) atoms in Cu-8Fe alloy, the influences of RMF on solidification structure, solute distribution, and material properties were discussed. Results show that the solidification behavior of Cu-Fe alloy have influenced through the change of temperature and solute fields in the presence of an applied RMF. The Fe dendrites were refined and transformed to rosettes or spherical grains under forced convection. The solute distribution in Cu-rich phase and Fe-rich phase were changed because of the variation of the supercooling degree and the solidification rate. Further, the variation in solute distribution was impacted the strengthening mechanism and conductive mechanism of the material.

Strain induced enhancement of magnetization in Ba{sub 2}FeMoO{sub 6} based heterostructure with (Ba{sub x}Sr{sub 1-x})TiO{sub 3}

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

Kim, Kyeong-Won; Norton, David P.; Ghosh, Siddhartha, E-mail: ghoshsid@gmail.com

2016-05-14

High quality epitaxial Ba{sub 2}FeMoO{sub 6} thin films and Ba{sub 2}FeMoO{sub 6}–(Ba{sub x}Sr{sub 1−x})TiO{sub 3} bi-layer (BL) and superlattice (SL) structures were grown via pulsed laser deposition under low oxygen pressure, and their structural, magnetic, and magneto-transport properties were examined. Superlattice and bi-layer structures were confirmed by X-ray diffraction patterns. Low temperature magnetic measurement shows that the saturation magnetization (M{sub S}) is significantly higher for SLs and almost similar or lower for BLs, when compared to phase pure Ba{sub 2}FeMoO{sub 6} thin films. The variation of the coercive field (H{sub C}) follows exact opposite trend, where BL samples have highermore » H{sub C} and SL samples have lower H{sub C} than pure Ba{sub 2}FeMoO{sub 6} thin films. Also, a significant decrease of the Curie temperature is found in both BL and SL structures compared to pure Ba{sub 2}FeMoO{sub 6} thin films. Negative magneto-resistance is seen in all the BL and SL structures as well as in pure Ba{sub 2}FeMoO{sub 6} thin films. In contrast to the magnetic properties, the magneto-transport properties do not show much variation with induced strain.« less

Comparison of four USEPA digestion methods for trace metal analysis using certified and Florida soils

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

Chen, M.; Ma, L.Q.

1998-11-01

It is critical to compare existing sample digestion methods for evaluating soil contamination and remediation. USEPA Methods 3050, 3051, 3051a, and 3052 were used to digest standard reference materials and representative Florida surface soils. Fifteen trace metals (Ag, As, Ba, Be, Cd, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, and Za), and six macro elements (Al, Ca, Fe, K, Mg, and P) were analyzed. Precise analysis was achieved for all elements except for Cd, Mo, Se, and Sb in NIST SRMs 2704 and 2709 by USEPA Methods 3050 and 3051, and for all elements except for As, Mo,more » Sb, and Se in NIST SRM 2711 by USEPA Method 3052. No significant differences were observed for the three NIST SRMs between the microwave-assisted USEPA Methods 3051 and 3051A and the conventional USEPA Method 3050 Methods 3051 and 3051a and the conventional USEPA Method 3050 except for Hg, Sb, and Se. USEPA Method 3051a provided comparable values for NIST SRMs certified using USEPA Method 3050. However, for method correlation coefficients and elemental recoveries in 40 Florida surface soils, USEPA Method 3051a was an overall better alternative for Method 3050 than was Method 3051. Among the four digestion methods, the microwave-assisted USEPA Method 3052 achieved satisfactory recoveries for all elements except As and Mg using NIST SRM 2711. This total-total digestion method provided greater recoveries for 12 elements Ag, Be, Cr, Fe, K, Mn, Mo, Ni, Pb, Sb, Se, and Zn, but lower recoveries for Mg in Florida soils than did the total-recoverable digestion methods.« less

Temporal evolution of mineralization events in the Bohemian Massif inferred from the Re-Os geochronology of molybdenite

NASA Astrophysics Data System (ADS)

Ackerman, Lukáš; Haluzová, Eva; Creaser, Robert A.; Pašava, Jan; Veselovský, František; Breiter, Karel; Erban, Vojtěch; Drábek, Milan

2017-06-01

Molybdenite is a common mineral accompanying Sn-W, Au, and base metal mineralizations located in different geotectonic units of the Bohemian Massif, but it is also widespread in granitoids and/or related quartz veins/pegmatites forming disseminated Mo mineralization. Thirty Re-Os ages were obtained for molybdenite samples from the Bohemian Massif to provide constraints on the timing and duration of mineralization event(s) within the framework of previously published geochronological data for the host and/or associated rocks. The obtained data for Sn-W-(Li) deposits in the Erzgebirge metallogenetic province indicate the predominance of one and/or multiple short-time mineralization events taking place between ˜319 and 323 Ma, with the exception of the Krupka deposit associated with the Altenberg-Teplice caldera where the data may suggest prolonged activity until ˜315 Ma. The ages of the Pb-Zn-(Au-Mo) Hůrky u Rakovníka and Fe-Cu-As Obří důl mineralizations from the exocontacts of the Čistá pluton and Krkonoše-Jizera Plutonic Complex, respectively, provide evidence for synchronous emplacement of the ore and the associated granitic rocks. In contrast, the Padrť Fe-As-Mo mineralization postdates the age of the associated Padrť granite. Disseminated Mo mineralization in Cadomian and Variscan granitoids and/or related to quartz veins/pegmatites provides Re-Os ages that overlap with the previously published geochronological data for the host rocks, suggesting coeval evolution. Molybdenite samples from the Sázava suite granites of the Central Bohemian Plutonic Complex (CBPC) have resolvable younger ages than their host granites, but similar to the age of spatially related Au mineralization which is associated with the latest evolution of the CBPC.

New insights into the Mo/Cu(In,Ga)Se2 interface in thin film solar cells: Formation and properties of the MoSe2 interfacial layer.

PubMed

Klinkert, T; Theys, B; Patriarche, G; Jubault, M; Donsanti, F; Guillemoles, J-F; Lincot, D

2016-10-21

Being at the origin of an ohmic contact, the MoSe 2 interfacial layer at the Mo/Cu(In,Ga)Se 2 interface in CIGS (Cu(In,Ga)Se 2 and related compounds) based solar cells has allowed for very high light-to-electricity conversion efficiencies up to 22.3%. This article gives new insights into the formation and the structural properties of this interfacial layer. Different selenization-steps of a Mo covered glass substrate prior to the CIGS deposition by co-evaporation led to MoSe 2 interfacial layers with varying thickness and orientation, as observed by x-ray diffraction and atomic resolution transmission electron microscopy. A novel model based on the anisotropy of the Se diffusion coefficient in MoSe 2 is proposed to explain the results. While the series resistance of finished CIGS solar cells is found to correlate with the MoSe 2 orientation, the adhesion forces between the CIGS absorber layer and the Mo substrate stay constant. Their counter-intuitive non-correlation with the configuration of the MoSe 2 interfacial layer is discussed and related to work from the literature.

AsMo7O27-bridged dinuclear sandwich-type heteropolymolybdates of Cr(III) and Fe(III): magnetism of [MM'(AsMo7O27)2]12- with MM' = FeFe, CrFe, and CrCr.

PubMed

Xu, Haisheng; Li, Lili; Liu, Bin; Xue, Ganglin; Hu, Huaiming; Fu, Feng; Wang, Jiwu

2009-11-02

Two new dinuclear sandwich-type heteropolymolybdates based on the mulitidendate inorganic fragment [AsMo(7)O(27)] and Cr(III) and Fe(III) ions, namely, the homometallic sandwich polyoxometalate (POM) (NH(4))(12)[Fe(2)(AsMo(7)O(27))(2)] x 12 H(2)O (1) and the first example of the "symmetrical" heterometallic Cr(III)-Fe(III) sandwich POM, (NH(4))(12)[FeCr(AsMo(7)O(27))(2)] x 13 H(2)O (2), were simultaneously synthesized in high yield. Their magnetic properties are thoroughly investigated together with the homometallic sandwich POM (NH(4))(12)[Cr(2)(AsMo(7)O(27))(2)] x 11 H(2)O (3). The chi(M)T values for compounds 1-3 at 300 K correspond well to the calculated spin-only values for Fe(III) (S = 5/2) and Cr(III) (S = 3/2) with g(Fe) = g(Cr) = 2. Upon cooling, the chi(M)T values decline monotonously and reach 0.14, 1.00, and 0.11 cm(3) K mol(-1) at 2.0 K for 1, 2, and 3, respectively, indicating a significant antiferromagnetic exchange between the magnetic centers with J = -2.09, -4.09, and -6.26 cm(-1), respectively, for 1, 2, and 3. The magnetic results clearly establish that compound 2 is formed by bimetallic Cr(III)-Fe(III) units and not by a mixture of the two antiferromagnetically coupled homometallic species. Their thermal properties are also characterized.

Preparation of Mo-Re-C samples containing Mo{sub 7}Re{sub 13}C with the β-Mn-type structure by solid state reaction of planetary-ball-milled powder mixtures of Mo, Re and C, and their crystal structures and superconductivity

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

Oh-ishi, Katsuyoshi, E-mail: oh-ishi@kc.chuo-u.ac.jp; Nagumo, Kenta; Tateishi, Kazuya

Mo-Re-C compounds containing Mo{sub 7}Re{sub 13}C with the β-Mn structure were synthesized with high-melting-temperature metals Mo, Re, and C powders using a conventional solid state method with a planetary ball milling machine instead of the arc melting method. Use of the ball milling machine was necessary to obtain Mo{sub 7}Re{sub 13}C with the β-Mn structure using the solid state method. Almost single-phase Mo{sub 7}Re{sub 13}C with a trace of impurity were obtained using the synthesis method. By XRF and lattice parameter measurements on the samples, Fe element existed in the compound synthesized using the planetary ball milling machine with amore » pot and balls made of steel, though Fe element was not detected in the compound synthesized using a pot and balls made of tungsten carbide. The former compound containg the Fe atom did not show superconductivity but the latter compound without the Fe atom showed superconductivity at 6.1 K. - Graphical abstract: Temperature dependence of the magnetic susceptibility measured under 10 Oe for the superconducting PBM-T samples without Fe element and non-superconducting PBM-S with Fe element. The inset is the enlarged view of the data for the PBM-S sample.« less

The Synthesis and Characterization of Aromatic Hybrid Anderson-Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions.

PubMed

Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette

2015-12-01

Four aromatic hybrid Anderson polyoxomolybdates with Fe(3+) or Mn(3+) as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, (1) H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-FeMo6 -bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRISR=(HOCH2 )3 CR)), (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-FeMo6 -cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-MnMo6 -bzn), and (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-MnMo6 -cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mM) sodium salts Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-FeMo6 -bzn), Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-FeMo6 -cin), Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-MnMo6 -bzn), and Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-MnMo6 -cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern-Volmer analysis, which suggested the formation of a 1:1 POM-protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic interactions with polar amino acid side chains from, for example, subdomain IB. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Improvement of pentathiophene/fullerene planar heterojunction photovoltaic cells by improving the organic films morphology through the anode buffer bilayer

NASA Astrophysics Data System (ADS)

El Jouad, Zouhair; Cattin, Linda; Martinez, Francisco; Neculqueo, Gloria; Louarn, Guy; Addou, Mohammed; Predeep, Padmanabhan; Manuvel, Jayan; Bernède, Jean-Christian

2016-05-01

Organic photovoltaic cells (OPVCs) are based on a heterojunction electron donor (ED)/electron acceptor (EA). In the present work, the electron donor which is also the absorber of light is pentathiophene. The typical cells were ITO/HTL/pentathiophene/fullerene/Alq3/Al with HTL (hole transport layer) = MoO3, CuI, MoO3/CuI. After optimisation of the pentathiophene thickness, 70 nm, the highest efficiency, 0.81%, is obtained with the bilayer MoO3/CuI as HTL. In order to understand these results the pentathiophene films deposited onto the different HTLs were characterized by scanning electron microscopy, atomic force microscopy, X-rays diffraction, optical absorption and electrical characterization. It is shown that CuI improves the conductivity of the pentathiophene layer through the modification of the film structure, while MoO3 decreases the leakage current. Using the bilayer MoO3/CuI allows cumulating the advantages of each layer. Contribution to the topical issue "Materials for Energy Harvesting, Conversion and Storage (ICOME 2015) - Elected submissions", edited by Jean-Michel Nunzi, Rachid Bennacer and Mohammed El Ganaoui

Studies of Positrons Trapped at Quantum-Dot Like Particles Embedded in Metal Surfaces

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Nadesalingam, M. P.; Weiss, A. H.

2009-03-01

Experimental studies of the positron annihilation induced Auger electron (PAES) spectra from the Fe-Cu alloy surfaces with quantum-dot like Cu nanoparticles embedded in Fe show that the PAES signal from Cu increase rapidly as the concentration of Cu is enhanced by vacuum annealing. These measurements indicate that almost 75% of positrons that annihilate with core electrons due so with Cu even though the surface concentration of Cu as measured by EAES is only 6%. This result suggests that positrons become localized at sites at the surface containing high concentration of Cu atoms before annihilation. These experimental results are investigated theoretically by performing calculations of the "image-potential" positron surface states and annihilation characteristics of the surface trapped positrons with relevant Fe and Cu core-level electrons for the clean Fe(100) and Cu(100) surfaces and for the Fe(100) surface with quantum-dot like Cu nanoparticles embedded in the top atomic layers of the host substrate. Estimates of the positron binding energy and positron annihilation characteristics reveal their strong sensitivity to the nanoparticle coverage. Computed core annihilation probabilities are compared with experimental ones estimated from the measured Auger peak intensities. The observed behavior of the Fe and Cu PAES signal intensities is explained by theoretical calculations as being due to trapping of positrons in the regions of Cu nanoparticles embedded in the top atomic layers of Fe.

Oxidation behaviour of zirconium alloys and their precipitates - A mechanistic study

NASA Astrophysics Data System (ADS)

Proff, C.; Abolhassani, S.; Lemaignan, C.

2013-01-01

The precipitate oxidation behaviour of binary zirconium alloys containing 1 wt.% Fe, Ni, Cr or 0.6 wt.% Nb was characterised in TEM on FIB prepared transverse sections of the oxide and reported in previous studies [1,2]. In the present study the following alloys: Zr1%Cu, Zr0.5%Cu0.5%Mo and pure Zr are analysed to add to the available information. In all cases, the observed precipitate oxidation behaviour in the oxide close to the metal-oxide interface could be described either with delayed oxidation with respect to the matrix or simultaneous oxidation as the surrounding zirconium matrix. Attempt was made to explain these observations, with different parameters such as precipitate size and structure, composition and thermodynamic properties. It was concluded that the thermodynamics with the new approach presented could explain most precisely their behaviour, considering the precipitate stoichiometry and the free energy of oxidation of the constituting elements. The surface topography of the oxidised materials, as well as the microstructure of the oxide presenting microcracks have been examined. A systematic presence of microcracks above the precipitates exhibiting delayed oxidation has been found; the height of these crack calculated using the Pilling-Bedworth ratios of different phases present, can explain their origin. The protrusions at the surface in the case of materials containing large precipitates can be unambiguously correlated to the presence of these latter, and the height can be correlated to the Pilling-Bedworth ratios of the phases present as well as the diffusion of the alloying elements to the surface and their subsequent oxidation. This latter behaviour was much more considerable in the case of Fe and Cu with Fe showing systematically diffusion to the outer surface.

Evaluated the Twenty-Six Elements in the Pectoral Muscle of As-Treated Chicken by Inductively Coupled Plasma Mass Spectrometry.

PubMed

Sun, Bonan; Xing, Mingwei

2016-02-01

This study assessed the impacts of dietary arsenic trioxide on the contents of 26 elements in the pectoral muscle of chicken. A total of 100 Hy-line laying cocks were randomly divided into two groups (n = 50), including an As-treated group (basic diet supplemented with arsenic trioxide at 30 mg/kg) and a control group (basal diet). The feeding experiment lasted for 90 days and the experimental animals were given free access to feed and drinking water. The elements lithium (Li), boron (B), natrum (Na), magnesium (Mg), aluminium (AI), silicium (Si), kalium (K), calcium (Ca), vanadium (V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co.), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), molybdenum (Mo), cadmium (Cd), stannum (Sn), stibium (Sb), barium (Ba), hydrargyrum (Hg), thallium (Tl) and plumbum (Pb) in the pectoral muscles were determined using inductively coupled plasma mass spectrometry (ICP-MS). The resulted data indicated that Li, Na, AI, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ba, Tl and Pb were significantly increased (P < 0.05) in chicken exposed to As2O3 compared to control chicken, while Mg, Si, K, As and Cd decreased significantly (P < 0.05). These results suggest that ICP-MS determination of elements in chicken tissues enables a rapid analysis with good precision and accuracy. Supplementation of high levels of As affected levels of 20 elements (Li, Na, AI, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Ba, Tl, Pb, Mg, Si, K, As and Cd) in the pectoral muscles of chicken. Thus, it is needful to monitor the concentration of toxic metal (As) in chicken for human health.

Synthesis of Cu-Fe{sub 3}O{sub 4}@graphene composite: A magnetically separable and efficient catalyst for the reduction of 4-nitrophenol

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

Xu, Ran; Bi, Huiping, E-mail: hpbi@njust.edu.cn; He, Guangyu

2014-09-15

Highlights: • The Cu-Fe{sub 3}O{sub 4}@GE composite was prepared by one-step solvent–thermal method. • The Cu-Fe{sub 3}O{sub 4}@GE composite exhibited the highest catalytic activity with excellent stability. • The Cu-Fe{sub 3}O{sub 4}@GE composite was magnetically separable. - Abstract: In this work, the Cu-Fe{sub 3}O{sub 4}@GE composite was prepared easily by a one-step solvent–thermal method, which achieved the formation of Cu nanoparticles (Cu NPs), Fe{sub 3}O{sub 4} nanoparticles (Fe{sub 3}O{sub 4} NPs) and reduction of GO simultaneously. The morphology and structure of the composite was fully characterized by means of X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy, transmission electron microscopymore » (TEM). The time-dependent adsorption spectra of the reaction mixture was measured by UV–vis absorption spectroscopy. The results demonstrated that the Cu NPs and Fe{sub 3}O{sub 4} NPs were densely and evenly deposited on the graphene (GE) sheets. It was found that the Cu-Fe{sub 3}O{sub 4}@GE composite exhibited high catalytic activities on the reduction of p-nitrophenol to p-aminophenol. Furthermore, the composite catalyst can be easily recovered due to its magnetic separability and high stability.« less

Phase equilibria in the nominally Al65Cu23Fe12 system at 3, 5 and 21 GPa: Implications for the quasicrystal-bearing Khatyrka meteorite

NASA Astrophysics Data System (ADS)

Stagno, Vincenzo; Bindi, Luca; Steinhardt, Paul J.; Fei, Yingwei

2017-10-01

Two of the three natural quasiperiodic crystals found in the Khatyrka meteorite show a composition within the Al-Cu-Fe system. Icosahedrite, with formula Al63Cu24Fe13, coexists with the new Al62Cu31Fe7 quasicrystal plus additional Al-metallic minerals such as stolperite (AlCu), kryachkoite [(Al,Cu)6(Fe,Cu)], hollisterite (AlFe3), khatyrkite (Al2Cu) and cupalite (AlCu), associated to high-pressure phases like ringwoodite/ahrensite, coesite, and stishovite. These high-pressure minerals represent the evidence that most of the Khatyrka meteoritic fragments formed at least at 5 GPa and 1200 °C, if not at more extreme conditions. On the other hand, experimental studies on phase equilibria within the representative Al-Cu-Fe system appear mostly limited to ambient pressure conditions, yet. This makes the interpretation of the coexisting mineral phases in the meteoritic sample quite difficult. We performed experiments at 3, 5 and 21 GPa and temperatures of 800-1500 °C using the multi-anvil apparatus to investigate the phase equilibria in the Al65Cu23Fe12 system representative of the first natural quasicrystal, icosahedrite. Our results, supported by single-crystal X-ray diffraction and analyses by scanning electron microscopy, confirm the stability of icosahedrite at high pressure and temperature along with additional coexisting Al-bearing phases representative of khatyrkite and stolperite as those found in the natural meteorite. One reversal experiment performed at 5 GPa and 1200 °C shows the formation of the icosahedral quasicrystal from a pure Al, Cu and Fe mixture, a first experimental synthesis of icosahedrite under those conditions. Pressure appears to not play a major role in the distribution of Al, Cu and Fe between the coexisting phases, icosahedrite in particular. Results from this study extend our knowledge on the stability of icosahedral AlCuFe at higher temperature and pressure than previously examined, and provide a new constraint on the stability of icosahedrite.

Coping with iron limitation: A metabolomic study of Synechocystis sp. PCC 6803

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

Rivas-Ubach, Albert; Poret-Peterson, Amisha T.; Peñuelas, Josep

Iron (Fe) is a key element for all living systems, especially for photosynthetic organisms because of its important role in the photosynthetic electron transport chain. Fe limitation in cyanobacteria leads to several physiological and morphological changes. However, the overall metabolic responses to Fe limitation are still poorly understood. In this study, we integrated elemental, stoichiometric, macromolecular, and metabolomic data to shed light on the responses of Synechocystis sp. PCC 6803, a non-N2-fixing freshwater cyanobacterium, to Fe limitation. Compared to Synechocystis growing at nutrient replete conditions, Fe-limited cultures had lower growth rates and amounts of chlorophyll a, RNA, RNA:DNA, C, N,more » and P and higher ratios of Protein:RNA, C:N, C:P and N:P, in accordance with the growth rate hypothesis which predicts faster growing organisms will have decreased biomass RNA contents and C:P and N:P ratios. Fe-limited Synechocystis had lower amounts Fe, Mn and Mo, and higher amount of Cu. Several changes in amino acids of cultures growing under Fe limitation suggest nitrogen limitation. Additionally, we found substantial increases in stress-related metabolites in Fe-limited cyanobacteria such antioxidants. This study represents an advance in understanding the stoichiometric, macromolecular and metabolic strategies that cyanobacteria use to cope with Fe limitation. This information, moreover, may further understanding of changes in cyanobacterial functions under scenarios of Fe limitation in aquatic ecosystems.« less

Impact of Ficoll density gradient centrifugation on major and trace element concentrations in erythrocytes and blood plasma.

PubMed

Lu, Ying; Ahmed, Sultan; Harari, Florencia; Vahter, Marie

2015-01-01

Ficoll density gradient centrifugation is widely used to separate cellular components of human blood. We evaluated the suitability to use erythrocytes and blood plasma obtained from Ficoll centrifugation for assessment of elemental concentrations. We determined 22 elements (from Li to U) in erythrocytes and blood plasma separated by direct or Ficoll density gradient centrifugation, using inductively coupled plasma mass spectrometry. Compared with erythrocytes and blood plasma separated by direct centrifugation, those separated by Ficoll had highly elevated iodine and Ba concentration, due to the contamination from the Ficoll-Paque medium, and about twice as high concentrations of Sr and Mo in erythrocytes. On the other hand, the concentrations of Ca in erythrocytes and plasma were markedly reduced by the Ficoll separation, to some extent also Li, Co, Cu, and U. The reduced concentrations were probably due to EDTA, a chelator present in the Ficoll medium. Arsenic concentrations seemed to be lowered by Ficoll, probably in a species-specific manner. The concentrations of Mg, P, S, K, Fe, Zn, Se, Rb, and Cs were not affected in the erythrocytes, but decreased in plasma. Concentrations of Mn, Cd, and Pb were not affected in erythrocytes, but in plasma affected by EDTA and/or pre-analytical contamination. Ficoll separation changed the concentrations of Li, Ca, Co, Cu, As, Mo, I, Ba, and U in erythrocytes and blood plasma, Sr in erythrocytes, and Mg, P, S, K, Fe, Zn, Se, Rb and Cs in blood plasma, to an extent that will invalidate evaluation of deficiencies or excess intakes. Copyright © 2014 Elsevier GmbH. All rights reserved.

Heavy metals pollution levels and children health risk assessment of Yerevan kindergartens soils.

PubMed

Tepanosyan, Gevorg; Maghakyan, Nairuhi; Sahakyan, Lilit; Saghatelyan, Armen

2017-08-01

Children, the most vulnerable urban population group, are exceptionally sensitive to polluted environments, particularly urban soils, which can lead to adverse health effects upon exposure. In this study, the total concentrations of Ag, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Ti, V, and Zn were determined in 111 topsoil samples collected from kindergartens in Yerevan. The objectives of this study were to evaluate heavy metal pollution levels of kindergarten's soils in Yerevan, compare with national legal and international requirements on heavy metal contents in kindergarten soil, and assess related child health risk. Multivariate geostatistical analyses suggested that the concentrations of Ag, As, Ba, Cd, Cu, Hg, Mo, Pb, and Zn observed in the kindergarten's topsoil may have originated from anthropogenic sources, while Co, Cr, Fe, Mn, Ni, Ti, and V mostly come from natural sources. According to the Summary pollution index (Zc), 102 kindergartens belong to the low pollution level, 7 to the moderate and only 2 to the high level of pollution. Summary concentration index (SCI) showed that 109 kindergartens were in the allowable level, while 2 featured in the low level of pollution. The health risk assessment showed that in all kindergartens except for seven, non-carcinogenic risk for children was detected (HI>1), while carcinogenic risk from arsenic belongs to the very low (allowable) level. Cr and multi-element carcinogenic risk (RI) exceeded the safety level (1.0E- 06) in all kindergartens and showed that the potential of developing cancer, albeit small, does exist. Therefore, city's kindergartens require necessary remedial actions to eliminate or reduce soil pollution and heavy metal-induced health risks. Copyright © 2017 Elsevier Inc. All rights reserved.

A GREEN CHEMISTRY APPROACH TO PREPARATION OF CORE (FE OR CU)-SHELL (NOBLE METALS) NANOCOMPOSITES USING AQUEOUS ASCORBIC ACID

EPA Science Inventory

A greener method to fabricate novel core (Fe or Cu)-shell (noble metals) nanocomposites of transition metals such as Fe and Cu and noble metals such as Au, Pt, Pd, and Ag using aqueous ascorbic acid is described. Transition metal salts such as Cu and Fe were reduced using ascor...

Fluorescent and colorimetric detection of Fe(III) and Cu(II) by a difunctional rhodamine-based probe

NASA Astrophysics Data System (ADS)

Wang, Lei; Ye, Dandan; Li, Wenxuan; Liu, Yuanyuan; Li, Longhua; Zhang, Wenli; Ni, Liang

2017-08-01

A new rhodamine B hydrazone derivative (probe L) was synthesized and characterized. The probe L had sufficiently satisfactory selective response to Fe3 + and Cu2 + ions among various interferential metal ions, and high sensitivity with the detection limit of 4.63 × 10- 9 M and 5.264 × 10- 7 M for Fe3 + and Cu2 + ions, respectively. In the presence of Fe3 +, the probe L exhibited turn-on orange fluorescence accompanied by color change from colorless to pink. Toward Cu2 +, the probe L showed significant color change from colorless to red purple. These remarkable orange fluorescence and color change made probe L suitable naked-eye identify for Fe3 + and Cu2 + ions. By means of Job's plot, Benesi-Hildebrand studies and FTIR spectra, both 1:1 binding modes (L-Fe3 + and L-Cu2 +) were confirmed. The coordination mechanism and turn on/off fluorescence for L-Fe3 + and L-Cu2 + complexes were well explained by theoretical calculations. Moreover, probe L could be used as a quick, simple, visual test strip for Fe3 + and Cu2 + detection.

Pulsed Laser Deposition Growth of Delafossite (CuFeO2) thin films and multilayers

NASA Astrophysics Data System (ADS)

Joshi, Toyanath; Ferrari, Piero; Borisov, Pavel; Cabrera, Alejandro; Lederman, David

2014-03-01

Owing to its narrow band gap (<2 eV) and p-type conductivity delafossite CuFeO2 is attractive for applications in the field of solar energy conversion. Obtaining pure phase CuFeO2 thin films, however, is relatively difficult. It is necessary to maintain the lowest possible Cu valency (+1) in order to avoid forming the comparably stable spinel compound CuFe2O4. We present a systematic study of the pulsed laser deposition (PLD) growth conditions for epitaxial (00.1) oriented CuFeO2 thin films on Al2O3 (00.1) substrates. The secondary impurity phase, CuFe2O4, was removed completely by optimizing the growth conditions. RHEED, XRD and TEM showed that the pure phase delafossite films are highly epitaxial to the substrate. The chemical purity was verified by Raman and XPS. The indirect bandgap of 1.15 eV was measured using infrared reflectivity, and is in agreement with the CuFeO2 bulk value. Finally, we discuss the growth and structural characterization of delafossite multilayers, CuFeO2/CuGaO2. This work was supported by a Research Challenge Grant from the West Virginia Higher Education Policy Commission (HEPC.dsr.12.29) and the Microelectronics Advanced Research Corporation (Contract # 2013-MA-2382) at WVU.

Theoretical Investigation of Calculating Temperatures in the Combining Zone of Cu/Fe Composite Plate Jointed by Explosive Welding

NASA Astrophysics Data System (ADS)

Qu, Y. D.; Zhang, W. J.; Kong, X. Q.; Zhao, X.

2016-03-01

The heat-transfer behavior of the interface of Flyer plate (or Base Plate) has great influence on the microcosmic structures, stress distributions, and interface distortion of the welded interface of composite plates by explosive welding. In this paper, the temperature distributions in the combing zone are studied for the case of Cu/Fe composite plate jointed by explosive welding near the lower limit of explosive welding. The results show that Flyer plate (Cu plate) and Base Plate (Fe plate) firstly almost have the same melting rate in the explosive welding process. Then, the melting rate of Cu plate becomes higher than that of Fe plate. Finally, the melt thicknesses of Cu plate and Fe plate trend to be different constants, respectively. Meanwhile, the melting layer of Cu plate is thicker than that of Fe plate. The research could supply some theoretical foundations for calculating the temperature distribution and optimizing the explosive welding parameters of Cu/Fe composite plate to some extent.

Fe(II)/Cu(II) interaction on goethite stimulated by an iron-reducing bacteria Aeromonas Hydrophila HS01 under anaerobic conditions.

PubMed

Tao, Liang; Zhu, Zhen-Ke; Li, Fang-Bai; Wang, Shan-Li

2017-11-01

Copper is a trace element essential for living creatures, but copper content in soil should be controlled, as it is toxic. The physical-chemical-biological features of Cu in soil have a significant correlation with the Fe(II)/Cu(II) interaction in soil. Of significant interest to the current study is the effect of Fe(II)/Cu(II) interaction conducted on goethite under anaerobic conditions stimulated by HS01 (a dissimilatory iron reduction (DIR) microbial). The following four treatments were designed: HS01 with α-FeOOH and Cu(II) (T1), HS01 with α-FeOOH (T2), HS01 with Cu(II) (T3), and α-FeOOH with Cu(II) (T4). HS01 presents a negligible impact on copper species transformation (T3), whereas the presence of α-FeOOH significantly enhanced copper aging contributing to the DIR effect (T1). Moreover, the violent reaction between adsorbed Fe(II) and Cu(II) leads to the decreased concentration of the active Fe(II) species (T1), further inhibiting reactions between Fe(II) and iron (hydr)oxides and decelerating the phase transformation of iron (hydr)oxides (T1). From this study, the effects of the Fe(II)/Cu(II) interaction on goethite under anaerobic conditions by HS01 are presented in three aspects: (1) the accelerating effect of copper aging, (2) the reductive transformation of copper, and (3) the inhibition effect of the phase transformation of iron (hydr)oxides. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evaluation of constitutive iron reductase (AtFRO2) expression on mineral accumulation and distribution in soybean (Glycine max. L)

PubMed Central

Vasconcelos, Marta W.; Clemente, Thomas E.; Grusak, Michael A.

2014-01-01

Iron is an important micronutrient in human and plant nutrition. Adequate iron nutrition during crop production is central for assuring appropriate iron concentrations in the harvestable organs, for human food or animal feed. The whole-plant movement of iron involves several processes, including the reduction of ferric to ferrous iron at several locations throughout the plant, prior to transmembrane trafficking of ferrous iron. In this study, soybean plants that constitutively expressed the AtFRO2 iron reductase gene were analyzed for leaf iron reductase activity, as well as the effect of this transgene’s expression on root, leaf, pod wall, and seed mineral concentrations. High Fe supply, in combination with the constitutive expression of AtFRO2, resulted in significantly higher concentrations of different minerals in roots (K, P, Zn, Ca, Ni, Mg, and Mo), pod walls (Fe, K, P, Cu, and Ni), leaves (Fe, P, Cu, Ca, Ni, and Mg) and seeds (Fe, Zn, Cu, and Ni). Leaf and pod wall iron concentrations increased as much as 500% in transgenic plants, while seed iron concentrations only increased by 10%, suggesting that factors other than leaf and pod wall reductase activity were limiting the translocation of iron to seeds. Protoplasts isolated from transgenic leaves had three-fold higher reductase activity than controls. Expression levels of the iron storage protein, ferritin, were higher in the transgenic leaves than in wild-type, suggesting that the excess iron may be stored as ferritin in the leaves and therefore unavailable for phloem loading and delivery to the seeds. Also, citrate and malate levels in the roots and leaves of transgenic plants were significantly higher than in wild-type, suggesting that organic acid production could be related to the increased accumulation of minerals in roots, leaves, and pod walls, but not in the seeds. All together, these results suggest a more ubiquitous role for the iron reductase in whole-plant mineral accumulation and distribution. PMID:24765096

[MoS4]2- Cluster Bridges in Co-Fe Layered Double Hydroxides for Mercury Uptake from S-Hg Mixed Flue Gas.

PubMed

Xu, Haomiao; Yuan, Yong; Liao, Yong; Xie, Jiangkun; Qu, Zan; Shangguan, Wenfeng; Yan, Naiqiang

2017-09-05

[MoS 4 ] 2- clusters were bridged between CoFe layered double hydroxide (LDH) layers using the ion-exchange method. [MoS 4 ] 2- /CoFe-LDH showed excellent Hg 0 removal performance under low and high concentrations of SO 2 , highlighting the potential for such material in S-Hg mixed flue gas purification. The maximum mercury capacity was as high as 16.39 mg/g. The structure and physical-chemical properties of [MoS 4 ] 2- /CoFe-LDH composites were characterized with FT-IR, XRD, TEM&SEM, XPS, and H 2 -TPR. [MoS 4 ] 2- clusters intercalated into the CoFe-LDH layered sheets; then, we enlarged the layer-to-layer spacing (from 0.622 to 0.880 nm) and enlarged the surface area (from 41.4 m 2 /g to 112.1 m 2 /g) of the composite. During the adsorption process, the interlayer [MoS 4 ] 2- cluster was the primary active site for mercury uptake. The adsorbed mercury existed as HgS on the material surface. The absence of active oxygen results in a composite with high sulfur resistance. Due to its high efficiency and SO 2 resistance, [MoS 4 ] 2- /CoFe-LDH is a promising adsorbent for mercury uptake from S-Hg mixed flue gas.

Models for aerobic carbon monoxide dehydrogenase: synthesis, characterization and reactivity of paramagnetic MoVO(μ-S)CuI complexes† †Electronic supplementary information (ESI) available: Synthetic yields and microanalytical, mass spectrometric and IR spectroscopic data for all new compounds. CCDC 1576257–1576260. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04239f

PubMed Central

Gourlay, Craig; Nielsen, David J.; Evans, David J.; White, Jonathan M.

2017-01-01

Reaction of [CoCp2][TpiPrMoOS(OAr)] [Cp = η5-cyclopentadienyl; TpiPr = hydrotris(3-isopropylpyrazol-1-yl)borate; OAr = phenolate or derivative thereof] with [Cu(NCMe)(Me3tcn)]BF4 (Me3tcn = 1,4,7-trimethyl-1,4,7-triazacyclononane) in MeCN at –30 °C results in the formation of red-brown/black, paramagnetic, μ-sulfido-Mo(v)/Cu(i) complexes, TpiPrMoO(OAr)(μ-S)Cu(Me3tcn). The complexes possess the MoO(μ-S)Cu core found in aerobic carbon monoxide dehydrogenases (CODHs) and exhibit X-band EPR spectra closely related to those of semi-reduced CODH, with giso ∼ 1.937, hyperfine coupling to 95,97Mo (aiso = 39–42 × 10–4 cm–1) and strong superhyperfine coupling to 63,65Cu (aiso = 34–63 × 10–4 cm–1). Anisotropic spectra exhibit monoclinic symmetry with g1 ∼ 1.996, g2 ∼ 1.944 and g3 ∼ 1.882, and nearly isotropic ACu values (75–90 × 10–4 cm–1). The X-ray structures of four derivatives (Ar = Ph, C6H4tBu-2, C6H4sBu-2, C6H4Ph-4) are reported and discussed along with that of the Ar = C6H3tBu2-3,5 derivative (communicated in C. Gourlay, D. J. Nielsen, J. M. White, S. Z. Knottenbelt, M. L. Kirk and C. G. Young, J. Am. Chem. Soc., 2006, 128, 2164). The complexes exhibit distorted octahedral oxo-Mo(v) and distorted tetrahedral Cu(i) centres bridged by a single bent μ-sulfido ligand, with Mo–S and Cu–S distances and Mo–S–Cu angles in the ranges 2.262–2.300 Å, 2.111–2.134 Å and 115.87–134.27°, respectively. The 2 t-butyl derivative adopts a unique phenolate conformation with O 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 Mo–O–Cα and O 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 Mo–S–Cu torsion angles of 92.7 and 21.1°, respectively, very different from those of the other structurally characterized derivatives (31–47 and 33–45°, respectively) and exhibits a relatively short Mo···Cu distance [3.752(2) Å vs. 3.806(7)–4.040(2) Å]. As well, the aCu value of this complex (34.3 × 10–4 cm–1) is much lower than the values observed for other members of the series (55–63 × 10–4 cm–1), supporting the hypothesis that the electronic structure of the MoO(μ-S)Cu core unit and the degree of intermetallic communication are strongly dependent on the geometry of the MoO(OR)(μ-S)Cu unit. The complexes participate in an electrochemically reversible Mo(vi)/Mo(v) redox couple and react with cyanide undergoing decupration and desulfurization reactions of the type observed for CODH. PMID:29629154

Origin of the Lengshuigou porphyry-skarn Cu deposit in the Zha-Shan district, South Qinling, central China, and implications for differences between porphyry Cu and Mo deposits

NASA Astrophysics Data System (ADS)

Xie, Guiqing; Mao, Jingwen; Wang, Ruiting; Meng, Deming; Sun, Jia; Dai, Junzhi; Ren, Tao; Li, Jianbi; Zhao, Haijie

2017-04-01

Porphyry Cu and Mo deposits are two economically important types of metal deposits worldwide, but factors controlling their difference remain enigmatic. Compared with the well-studied large porphyry Mo province in the south margin of the North China Block (S-NCB), the origin of newly discovered porphyry Cu deposits in the South Qinling (SQB) is poorly constrained. Integrated zircon LA-ICPMS U-Pb and molybdenite Re-Os ages and geological evidence indicate three stages of magmatism at Lengshuigou: (1) late Neoproterozoic (718 to 704 Ma) quartz diorite + albitite + granite association during the pre-ore stage, (2) 146 to 145 Ma granodiorite porphyry during the syn-ore stage, and (3) 145 Ma granite porphyry during the post-ore stage. Elemental and Sr-Nd isotopic evidence provide important constraints on their magma source. Pre-ore Neoproterozoic quartz diorite + albitite + granite was derived by re-melting of a mixture of crustal and juvenile mantle materials, and stronger fractional crystallization was involved in these ore-hosting intrusions than in contemporary granitoids hosted in the Douling Group. Syn-ore granodiorite porphyry was derived from mantle-derived magma with contributions from different proportions of crustal components. Post-ore granite porphyry was derived mainly from a crustal source. Nearly contemporaneous porphyry Cu and Mo systems were identified in Qinling Province, including the 147-139 Ma porphyry Mo systems in the S-NCB and 150-146 Ma porphyry Cu systems in the SQB. Granitic stocks related to porphyry Cu systems in the SQB are characterized by moderate SiO2 contents (58.01-69.07 %) and less radiogenic Nd-Hf isotopes (ɛNd(t) = -3.8 to -6.3, ɛHf(t) = -4.5 to +1.6), whereas the granitic stocks related to porphyry Mo deposits in the S-NCB have high SiO2 concentrations (64.00-76.00 %) and more radiogenic Nd-Hf isotopes (ɛNd(t) = -18.0 to -11.6, ɛHf(t) = -26.3 to -13.5). In addition, molybdenite from the Chigou and Lengshuigou porphyry Cu deposits in the S-NCB show higher Re contents (77.50-394.3 ppm) than those from nearly contemporaneous porphyry Mo deposits (9.34-49.7 ppm) in the S-NCB. These lines of evidence indicate that a higher proportion of mantle component was involved in the formation of porphyry Cu deposits in the SQB than nearly contemporaneous porphyry Mo deposits in the S-NCB. It is most likely that the nature of the magma source plays an essential role in the differences between porphyry Cu and Mo deposits.

Magnetic properties of quadruple perovskite solid solutions Ca{sub 1–x}Y{sub x}Cu{sub 3}Fe{sub 4}O{sub 12} and Y{sub 1–y}Ce{sub x}Cu{sub 3}Fe{sub 4}O{sub 12}

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

Murakami, Makoto; Mori, Shigeo; Yamada, Ikuya, E-mail: i-yamada@21c.osakafu-u.ac.jp

Magnetic properties of the quadruple perovskite solid solutions Ca{sub 1–x}Y{sub x}Cu{sub 3}Fe{sub 4}O{sub 12} and Y{sub 1–y}Ce{sub y}Cu{sub 3}Fe{sub 4}O{sub 12} are investigated. Ca{sub 1–x}Y{sub x}Cu{sub 3}Fe{sub 4}O{sub 12} shows continuous increase in the ferromagnetic transition temperature as x increases. Y{sub 1–y}Ce{sub y}Cu{sub 3}Fe{sub 4}O{sub 12} exhibits a ferromagnetic-antiferromagnetic transition in the vicinity of y = 0.5. These observations demonstrate the electron doping effect on magnetic properties of charge-disproportionated ACu{sub 3}Fe{sub 4}O{sub 12} phases.

Activities in Cu2S-FeS-PbS melts at 1200 °C

NASA Astrophysics Data System (ADS)

Eriç, H.; Timuçin, M.

1981-09-01

The dew-point method was used to determine the vapor pressures of PbS over liquid sulfides of the system Cu2S-FeS-PbS at 1200 °C. From the PbS activity data, activities of Cu2S and FeS were evaluated both in binary and ternary melts by Gibbs-Duhem calculations. The systems Cu2S-PbS and Cu2S-FeS exhibit negative departures from ideal behavior, while the FeS-PbS melts are ideal solutions at 1200 °C.

High efficient removal of molybdenum from water by Fe2(SO4)3: Effects of pH and affecting factors in the presence of co-existing background constituents.

PubMed

Zhang, Xiang; Ma, Jun; Lu, Xixin; Huangfu, Xiaoliu; Zou, Jing

2015-12-30

Comparatively investigated the different effects of Fe2(SO4)3 coagulation-filtration and FeCl3 coagulation-filtration on the removal of Mo (VI). And the influence of calcium, sulfate, silicate, phosphate and humic acid (HA) were also studied. The following conclusions can be obtained: (1) compared with the case of FeCl3, Fe2(SO4)3 showed a higher Mo (VI) removal efficiency at pH 4.00-5.00, but an equal removal efficiency at pH 6.00-9.00. (2) The optimum Mo (VI) removal by Fe2(SO4)3 was achieved at pH 5.00-6.00; (3) The presence of calcium can reduce the removal of Mo (VI) over the entire pH range in the present study; (4) The effect of co-existing background anions (including HA) was dominated by three factors: Firstly the influence of co-existing background anions on the content of Fe intercepted from water (intercepted Fe). Secondly the competition of co-existing anions with Mo (VI) for adsorption sites. Thirdly the influence of co-existing background anions on the Zeta potential of the iron flocs. Copyright © 2015 Elsevier B.V. All rights reserved.

Growth and photo-response of NbSe2 and NbS2 crystals

NASA Astrophysics Data System (ADS)

Patel, Kunjal; Solanki, G. K.; Pataniya, Pratik; Patel, K. D.

2018-05-01

Transition metal dichalcogenides(TMDCs) have attracted intense research efforts due to their drastic properties change as we move towards ultra-thin crystalline layers from their bulk counterparts. Many well studied members of this family such as MoS2, WS2, WSe2, WS2 etc. have shown potential for flexible electronic devices including photovoltaic applications. The TMDCs like NbSe2 and NbS2 are relatively less studied layered compounds consisting of staked sandwiches of Se-Nb-Se/S-Nb-Se tri-layers with strong covalent/ionic intra layer bonds and weak Van der Waals interlayer interactions. In the present work, author have grown the crystals of NbSe2 and NbS2 by Direct Vapour Transport (DVT) technique and the material composition is confirmed using EDAX data. Photoelectrochemical (PEC) solar cell measurements are performed under monochromatic light illumination at different intensities and various solar cell parameters are calculated. These crystalline semiconductor electrodes were also analysed by photocurrent-voltage characteristics in a PEC solar cell structure (Cu/NbSe2/(0.1M K4Fe(CN)6 + 0.1M K3Fe(CN)6) and Cu/NbS2/(0.1M K4Fe(CN)6 +0.1M K3Fe(CN)6)). Blue coloured light gave the maximum efficiency. For further analysis of photodetection properties of the grown crystals, Ag painted broad low contact resistance electrical contacts were drawn from the crystals and its transient photoresponse was studied to evaluate different detector parameters.

Rosette iron deficiency transcript and microRNA profiling reveals links between copper and iron homeostasis in Arabidopsis thaliana

PubMed Central

Waters, Brian M.; Stein, Ricardo J.

2012-01-01

Iron (Fe) is an essential plant micronutrient, and its deficiency limits plant growth and development on alkaline soils. Under Fe deficiency, plant responses include up-regulation of genes involved in Fe uptake from the soil. However, little is known about shoot responses to Fe deficiency. Using microarrays to probe gene expression in Kas-1 and Tsu-1 ecotypes of Arabidopsis thaliana, and comparison with existing Col-0 data, revealed conserved rosette gene expression responses to Fe deficiency. Fe-regulated genes included known metal homeostasis-related genes, and a number of genes of unknown function. Several genes responded to Fe deficiency in both roots and rosettes. Fe deficiency led to up-regulation of Cu,Zn superoxide dismutase (SOD) genes CSD1 and CSD2, and down-regulation of FeSOD genes FSD1 and FSD2. Eight microRNAs were found to respond to Fe deficiency. Three of these (miR397a, miR398a, and miR398b/c) are known to regulate transcripts of Cu-containing proteins, and were down-regulated by Fe deficiency, suggesting that they could be involved in plant adaptation to Fe limitation. Indeed, Fe deficiency led to accumulation of Cu in rosettes, prior to any detectable decrease in Fe concentration. ccs1 mutants that lack functional Cu,ZnSOD proteins were prone to greater oxidative stress under Fe deficiency, indicating that increased Cu concentration under Fe limitation has an important role in oxidative stress prevention. The present results show that Cu accumulation, microRNA regulation, and associated differential expression of Fe and CuSOD genes are coordinated responses to Fe limitation. PMID:22962679

Metal and metalloid accumulation in shrews (Soricomorpha, Mammalia) from two protected Mediterranean coastal sites.

PubMed

Sánchez-Chardi, Alejandro; López-Fuster, María José

2009-04-01

Although ecotoxicological data on heavy metals are abundant, information on other potentially toxic elements with attributed deficiency and/or toxic disturbances is scarce. Here we quantify zinc, copper, iron, manganese, chromium, molybdenum, strontium, barium, and boron in bones of greater white-toothed shrews, Crocidura russula, inhabiting two protected Mediterranean coastal sites: the Ebro Delta, a wetland impacted by human activities, and the Medas Islands, a reference site. Natural and anthropogenic inputs significantly increase Fe, Mn, Mo, Sr, Ba, and B in specimens from the Ebro Delta, whereas Cu and Cr were higher in Medas' shrews. Principal component analysis allowed complete separation between sites along the first two axes in particular due to B, Sr, and Cu. This study provides metal reference values in bones of insectivores, explores their variability and bioaccumulation patterns in depth, and assesses the potential environmental risk and toxicity for biota exposed to the above elements.

Thermal transport properties of polycrystalline Pb2FeMoO6

NASA Astrophysics Data System (ADS)

Yuan, Xueping; Xu, Mingxiang

2018-06-01

Thermoelectric properties and specific heat of polycrystalline Pb2FeMoO6 have been systematically studied. The thermal conductivity increases monotonically with increasing of temperature, and reaches the maximum value 1.50 W m‑1 K‑1 at 350 K. The relatively low thermal conductivity is mainly attributed to the strong scattering effect of phonons at Fe/Mo sites. The negative Seebeck coefficient indicates the n-type conduction of the sample. The absolute value of S increases up to 20 μV K‑1 at 350 K. Due to the inhomogeneity resulting from Fe/Mo ions disorder, no distinct λ-type specific heat peak or anomaly typical for second-order transitions are observed.

Methyl transfer from Fe (and Mo) to Sn: formation of (eta(5)-C(5)H(5))M(CO)(n)Sn(t)Bu(2)Me (M = Fe, n = 2; M = Mo, n = 3) complexes from photochemical irradiation of (eta(5)-C(5)H(5))M(CO)(n)Me and (t)Bu(2)SnH(2).

PubMed

Sharma, Hemant K; Arias-Ugarte, Renzo; Metta-Magana, Alejandro; Pannell, Keith H

2010-07-07

Formation of an Sn-CH(3) bond, concomitantly with an Sn-M (M = Fe, Mo), is readily achieved from the photochemical reactions of (t)Bu(2)SnH(2) with (eta(5)-C(5)H(5))M(CO)(n)Me (M = Fe, n = 2; M = Mo, n = 3) via the intermediacy of (eta(5)-C(5)H(5))M(CO)(n)Sn(t)Bu(2)H.

Microstructure and Room-Temperature Mechanical Properties of FeCrMoVTi x High-Entropy Alloys

NASA Astrophysics Data System (ADS)

Guo, Jun; Huang, Xuefei; Huang, Weigang

2017-07-01

FeCrMoVTi x ( x values represent the molar ratio, where x = 0, 0.5, 1.0, 1.5, and 2.0) high-entropy alloys were prepared by a vacuum arc melting method. The effects of Ti element on the microstructure and room-temperature mechanical properties of the as-cast FeCrMoVTi x alloys were investigated. The results show that the prepared alloys exhibited typical dendritic microstructure and the size of the microstructure became fine with increasing Ti content. The FeCrMoV alloy exhibited a single body-centered cubic structure (BCC1) and the alloys prepared with Ti element exhibited BCC1 + BCC2 mixed structure. The new BCC2 phase is considered as (Fe, Ti)-rich phase and was distributed in the dendrite region. With the increase of Ti content, the volume fraction of the BCC2 phase increased and its shape changed from a long strip to a network. For the FeCrMoV alloy, the fracture strength, plastic strain, and hardness reached as high as 2231 MPa, 28.2%, and 720 HV, respectively. The maximum hardness of 887 HV was obtained in the FeCrMoVTi alloy. However, the fracture strength, yield stress, and plastic strain of the alloys decreased continuously as Ti content increased. In the room-temperature compressive test, the alloys showed typical brittle fracture characteristics.

Petrogenesis of the mineralized granitoids from the Kounrad and Borly porphyry Cu deposits and the East Kounrad porphyry Mo deposit in Kazakhstan: Implication for tectonic evolution and mineralization of the western part of the Central Asian Orogenic Belt

NASA Astrophysics Data System (ADS)

Shen, Ping; Pan, Hongdi; Seitmuratova, Eleonora

2017-08-01

The Kounrad region, located in the western part of the Central Asian Orogenic Belt, hosts the Kounrad porphyry Cu, the Borly porphyry Cu-Mo, and the East Kounrad porphyry Mo deposits. Secondary ion mass spectrometry (SIMS) zircon U-Pb dating indicates that the mineralized granitoids from the Kounrad, the Borly and the East Kounrad deposits emplaced at 331.7 ± 2.2 Ma, 311.6 ± 2.6 Ma, and 295.4 ± 2.9 Ma, respectively. The mineralized granodiorite porphyries at Kounrad show a geochemical affinity to adakitic rocks with high Sr (357-670 ppm), Sr/Y (40-68) and Mg numbers (Mg# = molar Mg/(Mg + Fe2 +)) from 0.43 to 0.51, low Yb (0.97-1.1 ppm) and Y (8.3-11.1 ppm). They have variable Sr-Nd-Hf-O isotopic compositions ((87Sr/86Sr)i = 0.7046 to 0.7051, εNd(t) = - 0.1 to + 1.1, εHf(t) = + 5.2 to + 9.0, δ18O = + 5.7 to + 6.8). These features indicate that the Kounrad adakitic magmas derived from the MASH (melting, assimilation, storage, homogenization) zone at depth of 40 km with 5-15% ancient basement rocks contamination. The mineralized granodiorite porphyries at Borly have a normal arc magma geochemical signature (e.g., enrichment of light rare earth elements (LREE) and depletion of heavy REE, Nb and Ti) and experienced fractional crystallization. They also have variable Sr-Nd-Hf-O isotopic compositions ((87Sr/86Sr)i = 0.7047 to 0.7053, εNd(t) = 0 to - 1.3, εHf(t) = - 0.6 to + 7.4, δ18O = + 5.5 to + 6.7) and Mg# (0.45 to 0.51), indicating that they were generated by melting of juvenile basaltic lower crust with normal thickness, followed by 10-30% ancient crustal contamination. The East Kounrad mineralized intrusions, consisting of granite and leucogranite, have experienced advanced degrees of fractional crystallization and have similar Sr-Nd-Hf-O isotopic compositions ((87Sr/86Sr)i = 0.7048, ɛNd (t) = + 1.0 to + 2.8, εHf(t) = + 4.8 to + 8.9, δ18O = + 5.6 to + 6.4) and low Mg# (0.18-0.37), indicating a juvenile lower crust source at depths of < 27 km with 10-20% ancient crustal contamination. The link between geochemistry and mineralization indicate that the subduction of the Junggar-Balkhash Ocean at 332 Ma resulted in the formation of the Kounrad adakitic rocks and assocatied Cu deposit, and continuing subduction at around 311 Ma resulted in the formation of the Borly granodiorite porphyry and assocatied Cu-Mo deposit, but entered a collisional stage by the Early-Permian ( 295 Ma) and resulted in the formation of the East Kounrad granite and leucogranite and assocatied Mo deposit. It is likely that evolution from porphyry Cu to Mo mineralization in the Kounrad region is owing to tectonic evolution from subduction to collision settings, crust depth variation from thickness to thinness, and magma evolution from adaktic and normal arc magma to highly fractionated I-type granitic magma.

Characterization of Cu buffer layers for growth of L10-FeNi thin films

NASA Astrophysics Data System (ADS)

Mizuguchi, M.; Sekiya, S.; Takanashi, K.

2010-05-01

A Cu(001) layer was fabricated on a Au(001) layer to investigate the use of Cu as a buffer layer for growing L10-FeNi thin films. The epitaxial growth of a Cu buffer layer was observed using reflection high-energy electron diffraction. The flatness of the layer improved drastically with an increase in the substrate temperature although the layer was an alloy (AuCu3). An FeNi thin film was epitaxially grown on the AuCu3 buffer layer by alternate monatomic layer deposition and the formation of an L10-FeNi ordered alloy was expected. The AuCu3 buffer layer is thus a promising candidate material for the growth of L10-FeNi thin films.

Iron deficiency, but not anemia, upregulates iron absorption in breast-fed peruvian infants.

PubMed

Hicks, Penni D; Zavaleta, Nelly; Chen, Zhensheng; Abrams, Steven A; Lönnerdal, Bo

2006-09-01

Iron absorption in adults is regulated by homeostatic mechanisms that decrease absorption when iron status is high. There are few data, however, regarding the existence of a similar homeostatic regulation in infants. We studied 2 groups of human milk-fed infants using (57)Fe (given as ferrous sulfate without any milk) and (58)Fe (given at the time of a breast-milk feeding) stable isotopes to determine whether healthy infants at risk for iron deficiency would regulate their iron absorption based on their iron status. We studied 20 Peruvian infants at 5-6 mo of age and 18 infants at 9-10 mo of age. We found no effect of infant hemoglobin concentration on iron absorption with 5-6 mo-old infants absorbing 19.2 +/- 2.1% and 9- to 10-mo-old infants absorbing 25.8 +/- 2.6% of the (57)Fe dose. For (58)Fe, 5- to 6-mo-old infants absorbed 42.6 +/- 5.0% and 9 to 10-mo-old infants absorbed 51.9 +/- 10.3%. Following log transformation, iron absorption from (57)Fe (r = -0.61, P = < 0.001) and (58)Fe (r = -0.61, P = < 0.001) were inversely correlated to serum ferritin (S-Ft). For both the (57)Fe and (58)Fe doses, infants with S-Ft <12 mg/L (n = 11) had significantly higher iron absorption than those with S-Ft >12 mg/L. We concluded that iron absorption in infants is related to iron status as assessed by serum ferritin but not hemoglobin concentration. Infants with low iron status upregulate iron absorption from breast milk at both 5-6 and 9-10 mo of age.

High Efficient Photo-Fenton Catalyst of α-Fe2O3/MoS2 Hierarchical Nanoheterostructures: Reutilization for Supercapacitors

NASA Astrophysics Data System (ADS)

Yang, Xijia; Sun, Haiming; Zhang, Lishu; Zhao, Lijun; Lian, Jianshe; Jiang, Qing

2016-08-01

A novel three-dimensional (3D) α-Fe2O3/MoS2 hierarchical nanoheterostructure is effectively synthesized via a facile hydrothermal method. The zero-dimensional (0D) Fe2O3 nanoparticles guide the growth of two-dimensional (2D) MoS2 nanosheets and formed 3D flower-like structures, while MoS2 facilitates the good dispersion of porous Fe2O3 with abundant oxygen vacancies. This charming 3D-structure with perfect match of non-equal dimension exhibits high recyclable photo-Fenton catalytic activity for Methyl orange pollutant and nice specific capacity in reusing as supercapacitor after catalysis. The synergistic effect between Fe2O3 and MoS2, the intermediate nanointerfaces, the 3D porous structures, and the abundant oxygen vacancies both contribute to highly active catalysis, nice electrochemical performance and stable cycling. This strategy is simple, cheap, and feasible for maximizing the value of the materials, as well as eliminating the secondary pollution.

High Efficient Photo-Fenton Catalyst of α-Fe2O3/MoS2 Hierarchical Nanoheterostructures: Reutilization for Supercapacitors.

PubMed

Yang, Xijia; Sun, Haiming; Zhang, Lishu; Zhao, Lijun; Lian, Jianshe; Jiang, Qing

2016-08-16

A novel three-dimensional (3D) α-Fe2O3/MoS2 hierarchical nanoheterostructure is effectively synthesized via a facile hydrothermal method. The zero-dimensional (0D) Fe2O3 nanoparticles guide the growth of two-dimensional (2D) MoS2 nanosheets and formed 3D flower-like structures, while MoS2 facilitates the good dispersion of porous Fe2O3 with abundant oxygen vacancies. This charming 3D-structure with perfect match of non-equal dimension exhibits high recyclable photo-Fenton catalytic activity for Methyl orange pollutant and nice specific capacity in reusing as supercapacitor after catalysis. The synergistic effect between Fe2O3 and MoS2, the intermediate nanointerfaces, the 3D porous structures, and the abundant oxygen vacancies both contribute to highly active catalysis, nice electrochemical performance and stable cycling. This strategy is simple, cheap, and feasible for maximizing the value of the materials, as well as eliminating the secondary pollution.

The effect of ionic interactions on the oxidation of metals in natural waters

NASA Astrophysics Data System (ADS)

Millero, Frank J.

1985-02-01

The effect of ionic interactions of the major components of natural waters on the oxidation of Cu(I) and Fe(II) has been examined. The various ion pairs of these metals have been shown to have different rates of oxidation. For Fe(II), the chloride and sulfate ion pairs are not easily oxidized. The measured decrease in the rate constant at a fixed pH in chloride and sulfate solutions agrees very well with the values predicted. The effect of pH (6 to 8) on the oxidation of Fe(II) in water and seawater have been shown to follow the rate equation -d in [Fe(II)]/dt = k 1β 1α Fe/[H +] + k 2β 2α Fe/[H +] 2 where k1 and k2 are the pseudo first order rate constants, β1 and β2 are the hydrolysis constants for Fe(OH) + and Fe(OH) 0. The value of αFE is the fraction of free Fe 2+. The value of k1 (2.0 ±0.5 min-1) in water and seawater are similar within experimental error. The value of k2 (1.2 × 10 5 min -1) in seawater is 28% of its value in water in reasonable agreement with predictions using an ion pairing model. For the oxidation of Cu(I) a rate equation of the form -d ln [Cu(I)]/dt = k 0α Cu+ k 1β 1α Cu[Cl] was found where k0 (14.1 sec -1) and k1 (3.9 sec -1) are the pseudo first order rate constants for the oxidation of Cu + and CuCl 0, β1 is the formation constant for CuCl 0 and αCu is the fraction of free Cu +. Thus, unlike the results for Fe(II), Cu(I) chloride complexes have measurable rates of oxidation.

Spatial distribution and source identification of heavy metals in surface soils in a typical coal mine city, Lianyuan, China.

PubMed

Liang, Jie; Feng, Chunting; Zeng, Guangming; Gao, Xiang; Zhong, Minzhou; Li, Xiaodong; Li, Xin; He, Xinyue; Fang, Yilong

2017-06-01

In this study, we investigated the pollution degree and spatial distribution of heavy metals and determined their sources in topsoil in a typical coal mine city, Lianyuan, Hunan Province, China. We collected 6078 soil surface samples in different land use types. And the concentrations of Zn, Cd, Cu, Hg, Pb, Sb, As, Mo, V, Mn, Fe and Cr were measured. The average contents of all heavy metals were lower than their corresponding Grade II values of Chinese Soil Quality Standard with the exception of Hg. However, average contents of twelve heavy metals, except for Mn, exceeded their background level in soils in Hunan Province. Based on one-way analysis of variance (ANOVA), the contents of Cu, Zn, Cd, Pb, Hg, Mo and V were related to the anthropogenic source and there were statistically significant differences in their concentrations among different land use patterns. The spatial variation of heavy metal was visualized by GIS. The PMF model was used to ascertain contamination sources of twelve heavy metals and apportion their source contributions in Lianyuan soils. The results showed that the source contributions of the natural source, atmospheric deposition, industrial activities and agricultural activities accounted for 33.6%, 26.05%, 23.44% and 16.91%, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Copper:molybdenum sub-oxide blend as transparent conductive electrode (TCE) indium free

NASA Astrophysics Data System (ADS)

Hssein, Mehdi; Cattin, Linda; Morsli, Mustapha; Addou, Mohammed; Bernède, Jean-Christian

2016-05-01

Oxide/metal/oxide structures have been shown to be promising alternatives to ITO. In such structures, in order to decrease the high light reflection of the metal film it is embedded between two metal oxides dielectric. MoO3-x is often used as oxide due to its capacity to be a performing anode buffer layer in organic solar cells, while silver is the metal the most often used [1]. Some attempts to use cheaper metal such as copper have been done. However it was shown that Cu diffuses strongly into MoO3-x [2]. Here we used this property to grow simple new transparent conductive oxide (TCE), i.e., Cu: MoO3-x blend. After the deposition of a thin Cu layer, a film of MoO3-x is deposited by sublimation. An XPS study shows more than 50% of Cu is present at the surface of the structure. In order to limit the Cu diffusion an ultra-thin Al layer is deposited onto MoO3-x. Then, in order to obtain a good hole collecting contact with the electron donor of the organic solar cells, a second MoO3-x layer is deposited. After optimization of the thickness of the different layers, the optimum structure is as follow: Cu (12 nm) : MoO3-x (20 nm)/Al (0.5 nm)/ MoO3-x (10 nm). The sheet resistance of this structure is Rsq = 5.2 Ω/sq. and its transmittance is Tmax = 65%. The factor of merit ϕM = T10/Rsq. = 2.41 × 10-3 Ω-1, which made this new TCE promising as anode in organic solar cells. Contribution to the topical issue "Materials for Energy Harvesting, Conversion and Storage (ICOME 2015) - Elected submissions", edited by Jean-Michel Nunzi, Rachid Bennacer and Mohammed El Ganaoui

Diamonds in ophiolitic mantle rocks and podiform chromitites: An unsolved mystery

NASA Astrophysics Data System (ADS)

Yang, J.; Zhang, Z.; Xu, X.; Ba, D.; Bai, W.; Fabg, Q.; Meng, F.; Chen, S.; Robinson, P. T.; Dobrzhinetskaya, L.

2009-05-01

In recent years ultrahigh pressure minerals, such as diamond and coesite, and other unusual minerals were discovered in chromitites of the Luobusa ophiolite in Tibet, and 4 new minerals have been approved by the CNMMN. These results have raised many questionsWhat are the occurrences of the diamonds, what is the source of their carbon and how were they formed? What is the origin of the chromites hosting the diamonds and at what depth did they form? What is the genetic relationship between the diamonds and the host chromitites? In what geological, geophysical and geochemical environments can the diamonds be formed and how are they preserved? The UHP minerals from Luobusa are controversial because they have not been found in situ and because ophiolites are currently believed to form at shallow levels above oceanic spreading centers in suprasubduction zone environments. More detailed study and experimental work are needed to understand the origin and significance of these unusual minerals and investigations of other ophiolites are needed to determine if such minerals occur elsewhere To approach these problems, we have collected two one-ton samples of harzburgite hosting chromitite orebodies in the Luobusa ophiolite in Tibet. The harzburgite samples were taken close to chromitite orebody 31, from which the diamonds, coesite and other unusual minerals were recovered. We processed these two samples in the same manner as the chromitites and discovered numerous diamonds and more than 50 other mineral species. These preliminary results show that the minerals in the harzburgites are similar to those in the chromitites, suggesting a genetic relationship between them. To determine if such UHP and unusual minerals occur elsewhere, we collected about 1.5 t of chromitite from two orebodies in an ultramafic body in the Polar Urals. Thus far, more than 60 different mineral species have been separated from these ores. The most exciting discovery is the common occurrence of diamond, a typical UHP mineral in the Luobusa chromitites. Other minerals include: (1) native elements: Cr, W, Ni, Co, Si, Al and Ta; (2) carbides: SiC and WC; (3) alloys: Cr-Fe, Si-Al-Fe, Ni-Cu, Ag-Au, Ag-Sn, Fe-Si, Fe-P, and Ag-Zn-Sn; (4) oxides: NiCrFe, PbSn, REE, rutile and Si-bearing rutile, ilmenite, corundum, chromite, MgO, and SnO2; (5) silicates: kyanite, pseudomorphs of octahedral olivine, zircon, garnet, feldspar, and quartz,; (6) sulfides of Fe, Ni, Cu, Mo, Pb, Ab, AsFe, FeNi, CuZn, and CoFeNi; and (7) iron groups: native Fe, FeO, and Fe2O3. These minerals are very similar in composition and structure to those reported from the Luobusa chromitites.

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

Liu, Hongying, E-mail: liuhongying@hdu.edu.cn; Gu, Chunchuan; Li, Dujuan

Graphical abstract: A non-enzymatic H{sub 2}O{sub 2} sensor with high selectivity and sensitivity based on rose-shaped FeMoO{sub 4} synthesized by the convenient microwave-assisted hydrothermal method, was fabricated. - Highlights: • Rose-shaped FeMoO{sub 4} is synthesized within 10 min via microwave-assisted hydrothermal approach. • Non-enzymatic hydrogen peroxide biosensor based on FeMoO{sub 4} nanomaterials is fabricated. • The biosensor exhibits good performance. - Abstract: In this work, we demonstrated a simple, rapid and reliable microwave-assisted hydrothermal approach to synthesize the uniform rose-shaped FeMoO{sub 4} within 10 min. The morphologies of the synthesized materials were characterized by X-ray powder diffraction and scanning electronmore » microscopy. Moreover, a non-enzymatic amperometric sensor for the detection of hydrogen peroxide (H{sub 2}O{sub 2}) was fabricated on the basis of the FeMoO{sub 4} as electrocatalysis. The resulting FeMoO{sub 4} exhibited high sensitivity and good stability for the detection of H{sub 2}O{sub 2}, which may be attributed to the rose-shaped structure of the material and the catalytic property of FeMoO{sub 4}. Amperometric response showed that the modified electrode had a good response for H{sub 2}O{sub 2} with a linear range from 1 μM to 1.6 mM, a detection limit of 0.5 μM (S/N = 3), high selectivity and short response time. Additionally, good recoveries of analytes in real milk samples confirm the reliability of the prepared sensor in practical applications.« less

NH 3-SCR on Cu, Fe and Cu + Fe exchanged beta and SSZ-13 catalysts: Hydrothermal aging and propylene poisoning effects

DOE PAGES

Wang, Aiyong; Wang, Yilin; Walter, Eric D.; ...

2017-10-07

Cu, Fe and Cu + Fe ion exchanged Beta and SSZ-13 catalysts were prepared by solution ion exchange using commercial NH 4/Beta, and NH 4/SSZ-13 that was prepared in-house. To study hydrothermal aging effects, Beta supported catalysts were aged hydrothermally at 700 °C and SSZ-13 supported catalysts were aged at 750 °C. In order to reveal the effects of Fe addition in the co-exchanged catalysts, these catalysts were characterized by means of powder X-ray diffraction (XRD), N 2 adsorption-desorption, electron paramagnetic resonance (EPR), 27Al-nuclear magnetic resonance ( 27Al-NMR) and propylene coking followed with temperature programmed reaction (TPR), and further testedmore » with standard NH 3-SCR with and without the presence of propylene. Collectively, the catalyst characterizations and reaction testing indicated minor beneficial effects of Fe addition in Cu,Fe/Beta, where NH 3-SCR activity, N 2 selectivity and hydrothermal stability were all slightly improved. In contrast, Fe addition did not show apparent beneficial effects in low-temperature SCR for the Cu,Fe/SSZ-13 case. In conclusion, at elevated reaction temperatures, however, the presence of Fe indeed considerably improved NO conversion and N 2 selectivity for the hydrothermally aged Cu,Fe/SSZ-13 catalyst in the presence of propylene.« less

NH 3-SCR on Cu, Fe and Cu + Fe exchanged beta and SSZ-13 catalysts: Hydrothermal aging and propylene poisoning effects

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

Wang, Aiyong; Wang, Yilin; Walter, Eric D.

Cu, Fe and Cu + Fe ion exchanged Beta and SSZ-13 catalysts were prepared by solution ion exchange using commercial NH 4/Beta, and NH 4/SSZ-13 that was prepared in-house. To study hydrothermal aging effects, Beta supported catalysts were aged hydrothermally at 700 °C and SSZ-13 supported catalysts were aged at 750 °C. In order to reveal the effects of Fe addition in the co-exchanged catalysts, these catalysts were characterized by means of powder X-ray diffraction (XRD), N 2 adsorption-desorption, electron paramagnetic resonance (EPR), 27Al-nuclear magnetic resonance ( 27Al-NMR) and propylene coking followed with temperature programmed reaction (TPR), and further testedmore » with standard NH 3-SCR with and without the presence of propylene. Collectively, the catalyst characterizations and reaction testing indicated minor beneficial effects of Fe addition in Cu,Fe/Beta, where NH 3-SCR activity, N 2 selectivity and hydrothermal stability were all slightly improved. In contrast, Fe addition did not show apparent beneficial effects in low-temperature SCR for the Cu,Fe/SSZ-13 case. In conclusion, at elevated reaction temperatures, however, the presence of Fe indeed considerably improved NO conversion and N 2 selectivity for the hydrothermally aged Cu,Fe/SSZ-13 catalyst in the presence of propylene.« less

Failure Mechanisms of SAC/Fe-Ni Solder Joints During Thermal Cycling

NASA Astrophysics Data System (ADS)

Gao, Li-Yin; Liu, Zhi-Quan; Li, Cai-Fu

2017-08-01

Thermal cycling tests have been conducted on Sn-Ag-Cu/Fe- xNi ( x = 73 wt.% or 45 wt.%) and Sn-Ag-Cu/Cu solder joints according to the Joint Electron Device Engineering Council industrial standard to study their interfacial reliability under thermal stress. The interfacial intermetallic compounds formed for solder joints on Cu, Fe-73Ni, and Fe-45Ni were 4.5 μm, 1.7 μm, and 1.4 μm thick, respectively, after 3000 cycles, demonstrating excellent diffusion barrier effect of Fe-Ni under bump metallization (UBM). Also, two deformation modes, viz. solder extrusion and fatigue crack formation, were observed by scanning electron microscopy and three-dimensional x-ray microscopy. Solder extrusion dominated for solder joints on Cu, while fatigue cracks dominated for solder joints on Fe-45Ni and both modes were detected for those on Fe-73Ni. Solder joints on Fe-Ni presented inferior reliability during thermal cycling compared with those on Cu, with characteristic lifetime of 3441 h, 3190 h, and 1247 h for Cu, Fe-73Ni, and Fe-45Ni UBM, respectively. This degradation of the interfacial reliability for solder joints on Fe-Ni is attributed to the mismatch in coefficient of thermal expansion (CTE) at interconnection level. The CTE mismatch at microstructure level was also analyzed by electron backscatter diffraction for clearer identification of recrystallization-related deformation mechanisms.

Preparation of Mo-Re-C samples containing Mo7Re13C with the β-Mn-type structure by solid state reaction of planetary-ball-milled powder mixtures of Mo, Re and C, and their crystal structures and superconductivity

NASA Astrophysics Data System (ADS)

Oh-ishi, Katsuyoshi; Nagumo, Kenta; Tateishi, Kazuya; Takafumi, Ohnishi; Yoshikane, Kenta; Sugiyama, Machiko; Oka, Kengo; Kobayashi, Ryota

2017-01-01

Mo-Re-C compounds containing Mo7Re13C with the β-Mn structure were synthesized with high-melting-temperature metals Mo, Re, and C powders using a conventional solid state method with a planetary ball milling machine instead of the arc melting method. Use of the ball milling machine was necessary to obtain Mo7Re13C with the β-Mn structure using the solid state method. Almost single-phase Mo7Re13C with a trace of impurity were obtained using the synthesis method. By XRF and lattice parameter measurements on the samples, Fe element existed in the compound synthesized using the planetary ball milling machine with a pot and balls made of steel, though Fe element was not detected in the compound synthesized using a pot and balls made of tungsten carbide. The former compound containg the Fe atom did not show superconductivity but the latter compound without the Fe atom showed superconductivity at 6.1 K.

Electronic, Magnetic, and Redox Properties of [MFe(3)S(4)] Clusters (M = Cd, Cu, Cr) in Pyrococcus furiosus Ferredoxin.

PubMed

Staples, Christopher R.; Dhawan, Ish K.; Finnegan, Michael G.; Dwinell, Derek A.; Zhou, Zhi Hao; Huang, Heshu; Verhagen, Marc F. J. M.; Adams, Michael W. W.; Johnson, Michael K.

1997-12-03

The ground- and excited-state properties of heterometallic [CuFe(3)S(4)](2+,+), [CdFe(3)S(4)](2+,+), and [CrFe(3)S(4)](2+,+) cubane clusters assembled in Pyrococcus furiosus ferredoxin have been investigated by the combination of EPR and variable-temperature/variable-field magnetic circular dichroism (MCD) studies. The results indicate Cd(2+) incorporation into [Fe(3)S(4)](0,-) cluster fragments to yield S = 2 [CdFe(3)S(4)](2+) and S = (5)/(2) [CdFe(3)S(4)](+) clusters and Cu(+) incorporation into [Fe(3)S(4)](+,0) cluster fragments to yield S = (1)/(2) [CuFe(3)S(4)](2+) and S = 2 [CuFe(3)S(4)](+) clusters. This is the first report of the preparation of cubane type [CrFe(3)S(4)](2+,+) clusters, and the combination of EPR and MCD results indicates S = 0 and S = (3)/(2) ground states for the oxidized and reduced forms, respectively. Midpoint potentials for the [CdFe(3)S(4)](2+,+), [CrFe(3)S(4)](2+,+), and [CuFe(3)S(4)](2+,+) couples, E(m) = -470 +/- 15, -440 +/- 10, and +190 +/- 10 mV (vs NHE), respectively, were determined by EPR-monitored redox titrations or direct electrochemistry at a glassy carbon electrode. The trends in redox potential, ground-state spin, and electron delocalization of [MFe(3)S(4)](2+,+) clusters in P. furiosus ferredoxin are discussed as a function of heterometal (M = Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Tl).

Copper-nickel superalloys as inert alloy anodes for aluminum electrolysis

NASA Astrophysics Data System (ADS)

Shi, Zhongning; Xu, Junli; Qiu, Zhuxian; Wang, Zhaowen; Gao, Bingliang

2003-11-01

The superalloys Cu-Ni-Al, Cu-Ni-Fe, and Cu-Ni-Cr were studied as anodes for aluminum electrolysis. The alloys were tested for corrosion in acidic electrolyte molten salt and for oxidation in both air and oxygen. The results showed that the Cu-Ni-Al anodes possess excellent resistance to oxidation and corrosion, and the oxidation rates of Cu-Ni-Fe and Cu-Ni-Al anodes were slower than those of pure copper or nickel. During electrolysis, the cell voltage of the Cu-Ni-Al anode was affected most by the concentration of alumina in cryolite molten salt. The Cu-Ni-Fe anode exhibited corrosion resistance in electrolyte molten salt. Comparatively, the Cu-Ni-Cr anode showed poor resistance to oxidation and corrosion. The testing found that further study is warranted on the use of Cu-Ni-Al and Cu-Ni-Fe as inert alloy anodes.

Activities in Cu2S-FeS-SnS melts at 1200 °C

NASA Astrophysics Data System (ADS)

Eric, R. Hurman

1993-04-01

The dew-point technique was used to measure the vapor pressures of SnS over liquid sulfides of the system Cu2S-FeS-SnS at 1200 °C. Activities of SnS were generated from the measured vapor pressures of SnS. Activities of Cu2S and FeS were evaluated both in binary and ternary melts by Gibbs-Duhem calculations from the known SnS activity data. The systems Cu2S-SnS and Cu2S-FeS exhibit negative departures from ideal behavior, while FeS-SnS melts exhibit positive deviations.

Band gap tuning in transition metal oxides by site-specific substitution

DOEpatents

Lee, Ho Nyung; Chisholm, Jr., Matthew F; Jellison, Jr., Gerald Earle; Singh, David J; Choi, Woo Seok

2013-12-24

A transition metal oxide insulator composition having a tuned band gap includes a transition metal oxide having a perovskite or a perovskite-like crystalline structure. The transition metal oxide includes at least one first element selected form the group of Bi, Ca, Ba, Sr, Li, Na, Mg, K, Pb, and Pr; and at least one second element selected from the group of Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Hf, Ta, W, Re, Os, Ir, and Pt. At least one correlated insulator is integrated into the crystalline structure, including REMO.sub.3, wherein RE is at least one Rare Earth element, and wherein M is at least one element selected from the group of Co, V, Cr, Ni, Mn, and Fe. The composition is characterized by a band gap of less of 4.5 eV.

Fraction distribution and risk assessment of heavy metals in waste clay sediment discharged through the phosphate beneficiation process in Jordan.

PubMed

Al-Hwaiti, Mohammad Salem; Brumsack, Hans Jurgen; Schnetger, Bernhard

2015-07-01

Heavy metal contamination of clay waste through the phosphate beneficiation process is a serious problem faced by scientists and regulators worldwide. Through the beneficiation process, heavy metals naturally present in the phosphate rocks became concentrated in the clay waste. This study evaluated the concentration of heavy metals and their fractions in the clay waste in order to assess the risk of environmental contamination. A five-step sequential extraction method, the risk assessment code (RAC), effects range low (ERL), effects range medium (ERM), the lowest effect level (LEL), the severe effect level (SEL), the redistribution index (U tf), the reduced partition index (I), residual partition index (I R), and the Nemerow multi-factor index (PC) were used to assess for clay waste contamination. Heavy metals were analyzed using high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) and inductively coupled plasma optical emission spectroscopy (ICP-OES). Correlation analyses were carried out to better understand the relationships between the chemical characteristics and the contents of the different phase fractions. Concentrations of Cd and Cu confirmed that both were bound to the exchangeable fraction (F1) and the carbonate fraction (F2), presenting higher mobility, whereas Pb was most abundant in the Fe-Mn oxide fraction (F3) and organic matter fraction (F4). The residual fraction (F5) contained the highest concentrations (>60%) of As, Cr, Mo, V, and Zn, with lower mobility. Application of the RAC index showed that Cd and Cu should be considered a moderate risk, whereas As, Cr, Mo, Pb, and Zn presented a low risk. Cadmium and Cu contents in mobile fractions F1 and F2 were higher than ERL but lower than ERM. On the other hand, As, Pb, and Zn contents of mobile fractions F1 and F2 were lower than ERL and ERM guideline values. Moreover, total Pb concentrations in the clay waste were below the lowest effect level (LEL) threshold value period, Cr and Zn values in the clay waste were determined to have exceeded the severe effect level (SEL) limit values, whereas Cd and Cu level ranges between LEL and SEL indicate moderate contamination. I R values of heavy metals in the clay waste confirmed that Cd and Cu were bound to the exchangeable and carbonate fractions and presented higher mobility, whereas As, Cr, Mo, Pb, V, and Zn were bound to organic or residual fractions and consequently exhibit lower mobility. A Nemerow multi-factor index revealed that the mine site contains high levels of Cd, Cu, V, and Zn pollution. As and Cr were found at a moderate level of contamination, whereas Pb was present at a safe level of contamination. The order of the comprehensive contamination indices was Cd > Cu > Mo > Zn > V > Cr > As > Pb, indicating that the assessment of clay waste, especially with Cd and Cu, should be undertaken to control heavy metal contamination in adjacent urban and mine areas at the Eshidiya mines.

Atomic-absorption determination of rhodium in chromite concentrates

USGS Publications Warehouse

Schnepfe, M.M.; Grimaldi, F.S.

1969-01-01

Rhodium is determined in chromite concentrates by atomic absorption after concentration either by co-precipitation with tellurium formed by the reduction of tellurite with tin(II) chloride or by fire assay into a gold bead. Interelement interferences in the atomic-absorption determination are removed by buffering the solutions with lanthanum sulphate (lanthanum concentration 1%). Substantial amounts of Ag, Al, Au, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ho, Hg, K, La, Mg, Mn, Mo, Na, Ni, Pb, Te, Ti, V, Y, Zn and platinum metals can be tolerated. A lower limit of approximately 0.07 ppm Rh can be determined in a 3-g sample. ?? 1969.

Novel "203" type of heterostructured MoS2-Fe3O4-C ternary nanohybrid: Synthesis, and enhanced microwave absorption properties

NASA Astrophysics Data System (ADS)

Yang, Erqi; Qi, Xiaosi; Xie, Ren; Bai, Zhongchen; Jiang, Yang; Qin, Shuijie; Zhong, Wei; Du, Youwei

2018-06-01

It is widely recognized that constructing multiple interface structures to enhance interface polarization is very good for the attenuation of electromagnetic (EM) wave. Here, a novel "203" type of heterostructured nanohybrid consisting of two-dimensional (2D) MoS2 nanosheets, zero-dimensional (0D) Fe3O4 nanoparticles and three-dimensional (3D) carbon layers was elaborately designed and successfully synthesized by a two-step method: Fe3O4 nanoparticles were deposited onto the surface of few-layer MoS2 nanosheets by a hydrothermal method, followed by the carbonation process by a chemical vapor deposition method. Compared to that of "20" type MoS2-Fe3O4, the as-prepared heterostructured "203" type MoS2-Fe3O4-C ternary nanohybrid exhibited remarkably enhanced EM and microwave absorption properties. And the minimum reflection loss (RL) value of the obtained MoS2-Fe3O4-C ternary nanohybrid could reach -53.03 dB at 14.4 GHz with a matching thickness of 7.86 mm. Moreover, the excellent EM wave absorption property of the as-prepared ternary nanohybrid was proved to be attributed to the quarter-wavelength matching model. Therefore, a simple and effective route was proposed to produce MoS2-based mixed-dimensional van der Waals heterostructure, which provided a new platform for the designing and production of high performance microwave absorption materials.

As(V) removal capacity of FeCu bimetallic nanoparticles in aqueous solutions: The influence of Cu content and morphologic changes in bimetallic nanoparticles.

PubMed

Sepúlveda, Pamela; Rubio, María A; Baltazar, Samuel E; Rojas-Nunez, J; Sánchez Llamazares, J L; Garcia, Alejandra García; Arancibia-Miranda, Nicolás

2018-08-15

In this study, bimetallic nanoparticles (BMNPs) with different mass ratios of Cu and Fe were evaluated. The influence of the morphology on the removal of pollutants was explored through theoretical and experimental studies, which revealed the best structure for removing arsenate (As(V)) in aqueous systems. To evidence the surface characteristics and differences among BMNPs with different mass proportions of Fe and Cu, several characterization techniques were used. Microscopy techniques and molecular dynamics simulations were applied to determine the differences in morphology and structure. In addition, X-ray diffraction (XRD) was used to determine the presence of various oxides. Finally, the magnetization response was evaluated, revealing differences among the materials. Our cumulative data show that BMNPs with low amounts of Cu (Fe 0.9 Cu 0.1 ) had a non-uniform core-shell structure with agglomerate-type chains of magnetite, whereas a Janus-like structure was observed in BMNPs with high amounts of Cu (Fe 0.5 Cu 0.5 ). However, a non-uniform core-shell structure (Fe 0.9 Cu 0.1 ) facilitated electron transfer among Fe, Cu and As, which increased the adsorption rate (k), capacity (q e ) and intensity (n). The mechanism of As removal was also explored in a comparative study of the phase and morphology of BMNPs pre- and post-sorption. Copyright © 2018 Elsevier Inc. All rights reserved.

Adsorption of multi-heavy metals Zn and Cu onto surficial sediments: modeling and adsorption capacity analysis.

PubMed

Li, Shanshan; Zhang, Chen; Wang, Meng; Li, Yu

2014-01-01

Improved multiple regression adsorption models (IMRAMs) was developed to estimate the adsorption capacity of the components [Fe oxides (Fe), Mn oxides (Mn), organic materials (OMs), residuals] in surficial sediments for multi-heavy metal Zn and Cu. IMRAM is an improved version over MRAM, which introduces a computer program in the model developing process. As MRAM, Zn(Cu) IMRAM, and Cu(Zn) IMRAM again confirmed that there is significant interaction effects that control the adsorption of compounded Zn and Cu, which was neglected by additional adsorption model. The verification experiment shows that the relative deviation of the IMRAMs is less than 13%. It is revealed by the IMRAMs that Mn, which has the greatest adsorption capability for compounded Zn and Cu (54.889 and 161.180 mg/l, respectively), follows by interference adsorption capacity of Fe/Mn (-1.072 and -24.591 mg/l respectively). Zn and Cu influence each other through different mechanisms. When Zn is the adsorbate, compounded Cu mainly affects the adsorption capacities of Fe/Mn and Fe/Mn/OMs; while when Cu is the adsorbate, compounded Zn mainly exerts its effect on Mn, Fe/Mn, and Mn/OMs. It also shows that the compounded Zn or Cu weakened the interference adsorption of Fe/Mn, and meanwhile, strengthened the interference adsorption of Mn/OMs.

Giant magnetoresistance (GMR) behavior of electrodeposited NiFe/Cu multilayers: Dependence of non-magnetic and magnetic layer thicknesses

NASA Astrophysics Data System (ADS)

Kuru, Hilal; Kockar, Hakan; Alper, Mursel

2017-12-01

Giant magnetoresistance (GMR) behavior in electrodeposited NiFe/Cu multilayers was investigated as a function of non-magnetic (Cu) and ferromagnetic (NiFe) layer thicknesses, respectively. Prior to the GMR analysis, structural and magnetic analyses of the multilayers were also studied. The elemental analysis of the multilayers indicated that the Cu and Ni content in the multilayers increase with increasing Cu and NiFe layer thickness, respectively. The structural studies by X-ray diffraction revealed that all multilayers have face centred cubic structure with preferred (1 1 0) crystal orientation as their substrates. The magnetic properties studied with the vibrating sample magnetometer showed that the magnetizations of the samples are significantly affected by the layer thicknesses. Saturation magnetisation, Ms increases from 45 to 225 emu/cm3 with increasing NiFe layer thickness. The increase in the Ni content of the multilayers with a small Fe content causes an increase in the Ms. And, the coercivities ranging from 2 to 24 Oe are between the soft and hard magnetic properties. Also, the magnetic easy axis of the multilayers was found to be in the film plane. Magnetoresistance measurements showed that all multilayers exhibited the GMR behavior. The GMR magnitude increases with increasing Cu layer thickness and reaches its maximum value of 10% at the Cu layer thickness of 1 nm, then it decreases. And similarly, the GMR magnitude increases and reaches highest value of pure GMR (10%) for the NiFe layer thickness of 3 nm, and beyond this point GMR decreases with increasing NiFe layer thickness. Some small component of the anisotropic magnetoresistance was also observed at thin Cu and thick NiFe layer thicknesses. It is seen that the highest GMR values up to 10% were obtained in electrodeposited NiFe/Cu multilayers up to now. The structural, magnetic and magnetoresistance properties of the NiFe/Cu were reported via the variations of the thicknesses of Cu and NiFe layers with stressing the role of layer thicknesses on the high GMR behavior.

A comprehensive study of magnetic exchanges in the layered oxychalcogenides Sr 3 Fe 2 O 5 Cu 2 Q 2 ( Q = S, Se)

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

Lü, Minfeng; Mentré, Olivier; Gordon, Elijah E.

2017-12-01

The layered oxysulfide Sr3Fe2O5Cu2S2 was prepared, and its crystal structure and magnetic properties were characterized by synchrotron X-ray diffraction (XRD), powder neutron diffraction (PND), Mössbauer spectroscopy measurements and by density functional theory (DFT) calculations. In addition, the spin exchange interactions leading to the ordered magnetic structure of Sr3Fe2O5Cu2S2 were compared with those of its selenium analogue Sr3Fe2O5Cu2Se2. The oxysulfide Sr3Fe2O5Cu2S2 adopts a G-type antiferromagnetic (AFM) structure at a temperature in the range 485–512 K, which is comparable with the three-dimensional (3D) AFM ordering temperature, TN ≈ 490 K, found for Sr3Fe2O5Cu2Se2. Consistent with this observation, the spin exchange interactions ofmore » the magnetic (Sr3Fe2O5)2+ layers are slightly greater (but comparable) for oxysulfide than for the oxyselenide. Attempts to reduce or oxidize Sr3Fe2O5Cu2S2 using topochemical routes yield metallic Fe.« less

Conditions and mechanisms for the formation of nano-sized Delafossite (CuFeO2) at temperatures ≤90 °C in aqueous solution

NASA Astrophysics Data System (ADS)

John, Melanie; Heuss-Aßbichler, Soraya; Ullrich, Aladin

2016-02-01

In this study, we present the mechanism of CuFeO2 formation in aqueous solution at low temperatures ≤90 °C, using sulfate salts as reactants. Furthermore, we demonstrate the influence of experimental conditions (alkalization, reaction and ageing temperature and time) on the synthesized nanoparticles. In all cases, GR-SO4, a Fe(II-III) layered double hydroxysulphate (Fe2+4Fe3+2(OH)12·SO4) and Cu2O precipitate first. During further OH- supply GR-SO4 oxidizes and forms Fe10O14(OH)2, Cu2O and CuFeO2 crystals. Due to the high pH further CuFeO2 crystals grow at the cost of the unstable intermediate products. The reaction rate increases with increasing ageing temperature, reaction pH and, in particular, NaOH concentrations in the solution. As a result, highly crystalline CuFeO2 (3R and 2H polytypes) nanoparticles showing hexagonal morphology can be synthesized at 70 °C within 10 h or at 50 °C within 1 week. The formation of 2H polytype is favored by additional OH- supply during the pH-stat time and rather low temperatures.

Arsenic and Other Metals’ Presence in Biomarkers of Cambodians in Arsenic Contaminated Areas

PubMed Central

Chanpiwat, Penradee; Himeno, Seiichiro; Sthiannopkao, Suthipong

2015-01-01

Chemical analyses of metal (Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Ba, and Pb) concentrations in hair, nails, and urine of Cambodians in arsenic-contaminated areas who consumed groundwater daily showed elevated levels in these biomarkers for most metals of toxicological interest. The levels of metals in biomarkers corresponded to their levels in groundwater, especially for As, whose concentrations exceeded the WHO guidelines for drinking water. About 75.6% of hair samples from the population in this study contained As levels higher than the normal level in unexposed individuals (1 mg·kg−1). Most of the population (83.3%) showed As urinary levels exceeding the normal (<50 ng·mg−1). These results indicate the possibility of arsenicosis symptoms in residents of the areas studied. Among the three biomarkers tested, hair has shown to be a reliable indicator of metal exposures. The levels of As (r2 = 0.633), Ba (r2 = 0.646), Fe (r2 = 0.595), and Mo (r2 = 0.555) in hair were strongly positively associated with the levels of those metals in groundwater. In addition, significant weak correlations (p < 0.01) were found between levels of exposure to As and As concentrations in both nails (r2 = 0.544) and urine (r2 = 0.243). PMID:26569276

Thermodynamic analysis of binary Fe{sub 85}B{sub 15} to quinary Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloys for primary crystallizations of α-Fe in nanocrystalline soft magnetic alloys

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

Takeuchi, A., E-mail: takeuchi@imr.tohoku.ac.jp; Zhang, Y.; Takenaka, K.

2015-05-07

Fe-based Fe{sub 85}B{sub 15}, Fe{sub 84}B{sub 15}Cu{sub 1}, Fe{sub 82}Si{sub 2}B{sub 15}Cu{sub 1}, Fe{sub 85}Si{sub 2}B{sub 12}Cu{sub 1}, and Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} (NANOMET{sup ®}) alloys were experimental and computational analyzed to clarify the features of NANOMET that exhibits high saturation magnetic flux density (B{sub s}) nearly 1.9 T and low core loss than conventional nanocrystalline soft magnetic alloys. The X-ray diffraction analysis for ribbon specimens produced experimentally by melt spinning from melts revealed that the samples were almost formed into an amorphous single phase. Then, the as-quenched samples were analyzed with differential scanning calorimeter (DSC) experimentally for exothermicmore » enthalpies of the primary and secondary crystallizations (ΔH{sub x1} and ΔH{sub x2}) and their crystallization temperatures (T{sub x1} and T{sub x2}), respectively. The ratio ΔH{sub x1}/ΔH{sub x2} measured by DSC experimentally tended to be extremely high for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy, and this tendency was reproduced by the analysis with commercial software, Thermo-Calc, with database for Fe-based alloys, TCFE7 for Gibbs free energy (G) assessments. The calculations exhibit that a volume fraction (V{sub f}) of α-Fe tends to increase from 0.56 for the Fe{sub 85}B{sub 15} to 0.75 for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy. The computational analysis of the alloys for G of α-Fe and amorphous phases (G{sub α-Fe} and G{sub amor}) shows that a relationship G{sub α-Fe} ∼ G{sub amor} holds for the Fe{sub 85}Si{sub 2}B{sub 12}Cu{sub 1}, whereas G{sub α-Fe} < G{sub amor} for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy at T{sub x1} and that an extremely high V{sub f} = 0.75 was achieved for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy by including 2.8 at. % Si and 4.5 at. % P into α-Fe. These computational results indicate that the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy barely forms amorphous phase, which, in turn, leads to high V{sub f} and resultant high B{sub s}.« less

Minor-Cu doped soft magnetic Fe-based FeCoBCSiCu amorphous alloys with high saturation magnetization

NASA Astrophysics Data System (ADS)

Li, Yanhui; Wang, Zhenmin; Zhang, Wei

2018-05-01

The effects of Cu alloying on the amorphous-forming ability (AFA) and magnetic properties of the P-free Fe81Co5B11C2Si1 amorphous alloy were investigated. Addition of ≤ 1.0 at.% Cu enhances the AFA of the base alloy without significant deterioration of the soft magnetic properties. The Fe80.5Co5B11C2Si1Cu0.5 alloy with the largest critical thickness for amorphous formation of ˜35 μm possesses a high saturation magnetization (Bs) of ˜1.78 T, low coercivity of ˜14.6 A/m, and good bending ductility upon annealing in a wide temperature range of 513-553 K with maintaining the amorphous state. The fabrication of the new high-Fe-content Fe-Co-B-C-Si-Cu amorphous alloys by minor doping of Cu gives a guideline to developing high Bs amorphous alloys with excellent AFA.

Effects of B and Mo on the magnetic properties of NdFeTi-nitrides with ThMn[sub 12]-type structure

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

Kim, Y.B.; Kim, H.T.; Kim, C.S.

1993-11-01

The alloys having nearly single phase of ThMn[sub 12]-type structure (1-12 phase) have been successfully synthesized in NdFe[sub 10.7]Ti[sub 1.3[minus]y]M[sub y] (M = B/Mo) alloy systems by substituting B or Mo up to 23% of Ti (y=0.3). After nitrification, the unit cell volume of 1--12 phase has increased by about 2--3% and a-Fe phase of 5--15 wt.% has been formed depending on the substitutional elements. The nitrides, NdFe[sub 10.7]TiB[sub 0.3]N[sub x] and Nd Fe[sub 10.7]TiMo[sub 0.3]N[sub x], were confirmed to have uniaxial anisotropy by X-ray diffractometry. The results of magnetic measurements for the nitrides have shown that B is verymore » effective for the increase of both Curie temperature and magnetization. On the other band, Mo is effective for the increase of anisotropy field, but it decreases the magnetization. The Curie temperature and magnetization of NdFe[sub 10.7]TiB[sub 0.3]N[sub x] are 560 C and 148 Am[sup 2] /kg, respectively, by about 20% and 15% higher than those of NdFe[sub 10.7]Ti[sub 1.3]N[sub x]. The anisotropy field of NdFe[sub 10.7]TiMo[sub 0.3]N[sub x] is about 7960 kA/m (100 kOe) which is about 25% higher than that of NdFe[sub 10.7]Ti[sub 1.3]N[sub x].« less

Atomic-scale understanding of high thermal stability of the Mo/CoFeB/MgO spin injector for spin-injection in remanence.

PubMed

Tao, Bingshan; Barate, Philippe; Devaux, Xavier; Renucci, Pierre; Frougier, Julien; Djeffal, Abdelhak; Liang, Shiheng; Xu, Bo; Hehn, Michel; Jaffrès, Henri; George, Jean-Marie; Marie, Xavier; Mangin, Stéphane; Han, Xiufeng; Wang, Zhanguo; Lu, Yuan

2018-05-31

Remanent spin injection into a spin light emitting diode (spin-LED) at zero magnetic field is a prerequisite for future application of spin optoelectronics. Here, we demonstrate the remanent spin injection into GaAs based LEDs with a thermally stable Mo/CoFeB/MgO spin injector. A systematic study of magnetic properties, polarization-resolved electroluminescence (EL) and atomic-scale interfacial structures has been performed in comparison with the Ta/CoFeB/MgO spin injector. The perpendicular magnetic anisotropy (PMA) of the Mo/CoFeB/MgO injector shows more advanced thermal stability than that of the Ta/CoFeB/MgO injector and robust PMA can be maintained up to 400 °C annealing. The remanent circular polarization (PC) of EL from the Mo capped spin-LED reaches a maximum value of 10% after 300 °C annealing, and even remains at 4% after 400 °C annealing. In contrast, the Ta capped spin-LED almost completely loses the remanent PC under 400 °C annealing. Combined advanced electron microscopy and spectroscopy studies reveal that a large amount of Ta diffuses into the MgO tunneling barrier through the CoFeB layer after 400 °C annealing. However, the diffusion of Mo into CoFeB is limited and never reaches the MgO barrier. These findings afford a comprehensive perspective to use the highly thermally stable Mo/CoFeB/MgO spin injector for efficient electrical spin injection in remanence.

Microstructural control of FeCrAl alloys using Mo and Nb additions

DOE PAGES

Sun, Zhiqian; Bei, Hongbin; Yamamoto, Yukinori

2017-08-14

The effects of Mo and Nb additions on the microstructure and mechanical properties of two FeCrAl alloys were studied in this paper. Fine and uniform recrystallized grain structures (~ 20–30 μm) were achieved in both alloys through suitable annealing after warm-rolling. The formation of Fe 2Nb-type Laves phase precipitates in the Nb-containing FeCrAl alloy effectively stabilized the deformed and recrystallized microstructures. The Mo-containing FeCrAl alloy exhibited strong γ texture fiber after annealing at 650–900 °C, whereas the annealed Nb-containing FeCrAl alloy had much weaker texture. Finally, both strength and ductility decreased as the grain size increased in both alloys.

Influence of inserted Mo layer on the thermal stability of perpendicularly magnetized Ta/Mo/Co{sub 20}Fe{sub 60}B{sub 20}/MgO/Ta films

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

Li, Minghua, E-mail: mhli@ustb.edu.cn; Department of Electrical Engineering, University of California, Los Angeles, California 90095; Lu, Jinhui

2016-04-15

We studied the thermal stability of perpendicular magnetic anisotropy (PMA) in Ta/Mo/CoFeB/MgO/Ta films with and without inserted Mo layers. In the absence of a Mo layer, the films show PMA at annealing temperatures below 300 °C. On the other hand, the insertion of a Mo layer preserves PMA at annealing temperatures of up to 500 °C; however, a higher annealing temperature leads to the collapse of PMA. X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM) were used to study the microstructure of the films to understand the deterioration of PMA. The XPS results show that the segregation ofmore » Ta is partly suppressed by inserting a Mo layer. Once inserted, Mo does not remain at the interface of Ta and CoFeB but migrates to the surface of the films. The HRTEM results show that the crystallization of the MgO (001) texture is improved owing to the higher annealing temperature of the Mo inserted sample. A smooth and clear CoFeB/MgO interface is evident. The inserted Mo layer not only helps to obtain sharper and smoother interfaces but also contributes to the crystallization after the higher annealing temperature of films.« less

Reduction of CO2 to low carbon alcohols on CuO FCs/Fe2O3 NTs catalyst with photoelectric dual catalytic interfaces

NASA Astrophysics Data System (ADS)

Li, Peiqiang; Wang, Huying; Xu, Jinfeng; Jing, Hua; Zhang, Jun; Han, Haixiang; Lu, Fusui

2013-11-01

In this paper, the CuO FCs/Fe2O3 NTs catalyst was obtained after Fe2O3 nanotubes (Fe2O3 NTs) were decorated with CuO flower clusters (CuO FCs) by the pulse electrochemical deposition method. The in situ vertically aligned Fe2O3 NTs were prepared on the ferrous substrate by a potentiostatic anodization method. The SEM result showed the volcano-like Fe2O3 NTs were arranged in order and the CuO FCs constituted of flaky CuO distributed on the Fe2O3 NTs surface uniformly. After CuO FCs were loaded on Fe2O3 NTs, the absorption of visible light was enhanced noticeably, and its band gap narrowed to 1.78 eV from 2.03 eV. The conduction band and valence band locating at -0.73 eV and 1.05 eV, respectively were further obtained. In the PEC reduction of CO2 process, methanol and ethanol were two major products identified by chromatography. Their contents reached 1.00 mmol L-1 cm-2 and 107.38 μmol L-1 cm-2 after 6 h, respectively. This high-efficiency catalyst with photoelectric dual catalytic interfaces has a great guidance and reference significance for CO2 reduction to liquid carbon fuels.In this paper, the CuO FCs/Fe2O3 NTs catalyst was obtained after Fe2O3 nanotubes (Fe2O3 NTs) were decorated with CuO flower clusters (CuO FCs) by the pulse electrochemical deposition method. The in situ vertically aligned Fe2O3 NTs were prepared on the ferrous substrate by a potentiostatic anodization method. The SEM result showed the volcano-like Fe2O3 NTs were arranged in order and the CuO FCs constituted of flaky CuO distributed on the Fe2O3 NTs surface uniformly. After CuO FCs were loaded on Fe2O3 NTs, the absorption of visible light was enhanced noticeably, and its band gap narrowed to 1.78 eV from 2.03 eV. The conduction band and valence band locating at -0.73 eV and 1.05 eV, respectively were further obtained. In the PEC reduction of CO2 process, methanol and ethanol were two major products identified by chromatography. Their contents reached 1.00 mmol L-1 cm-2 and 107.38 μmol L-1 cm-2 after 6 h, respectively. This high-efficiency catalyst with photoelectric dual catalytic interfaces has a great guidance and reference significance for CO2 reduction to liquid carbon fuels. Electronic supplementary information (ESI) available: Reduction of CO2 to low carbon alcohols on CuO FCs/Fe2O3 NTs catalyst with photoelectric dual catalytic interfaces. See DOI: 10.1039/c3nr03352j

Microwave synthesis of molybdenum doped LiFePO4/C and its electrochemical studies.

PubMed

Naik, Amol; P, Sajan C

2016-05-10

A Mo-doped LiFePO4 composite was prepared successfully from an iron carbonyl complex by adopting a facile and rapid microwave assisted solid state method. The evolution of gases from the iron precursor produces a highly porous product. The formation and substitution of Mo in LiFePO4 were confirmed by X-ray diffraction; surface analysis was carried out by scanning electron microscopy, field emission scanning electron microscopy, and transmission electron microscopy. The electrochemical properties of the substituted LiFePO4 were examined by cyclic voltammetry, electrochemical impedance spectroscopy and by recording charge-discharge cycles. It was observed that the as prepared composites consisted of a single phase orthorhombic olivine-type structure, where Mo(6+) was successfully introduced into the M2(Fe) sites. Incorporation of supervalent Mo(6+) introduced Li(+) ion vacancies in LiFePO4. The synthesized material facilitated lithium ion diffusion during charging/discharging due to the charge compensation effect and porosity. The battery performance studies showed that LiMo0.05Fe0.095PO4 exhibited a maximum capacity of 169.7 mA h g(-1) at 0.1 C current density, with admirable stability retention. Even at higher current densities, the retention of the specific capacity was exceptional.

Thermodynamic controls on element partitioning between titanomagnetite and andesitic-dacitic silicate melts

NASA Astrophysics Data System (ADS)

Sievwright, R. H.; Wilkinson, J. J.; O'Neill, H. St. C.; Berry, A. J.

2017-08-01

Titanomagnetite-melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity ( fO2) and temperature ( T) in an andesitic-dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite-melt partitioning of the divalent cations (Mg2+, Mn2+, Co2+, Ni2+, Zn2+) and Cu2+/Cu+ with increasing fO2 between 0.2 and 3.7 log units above the fayalite-magnetite-quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral-melt partitioning of divalent cations, a more rigorous justification of magnetite-melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO2 implies a reciprocal relationship between a(Fe2+O) and a(Fe3+O1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite-melt partitioning of divalent cations with fO2 in magnetite-rich spinel. As a result of this, titanomagnetite-melt partitioning of divalent cations is indirectly sensitive to changes in fO2 in silicic, but less so in mafic bulk systems.

Has irrigated water from Mahaweli River contributed to the kidney disease of uncertain etiology in the dry zone of Sri Lanka?

PubMed

Diyabalanage, Saranga; Abekoon, Sumith; Watanabe, Izumi; Watai, Chie; Ono, Yuko; Wijesekara, Saman; Guruge, Keerthi S; Chandrajith, Rohana

2016-06-01

The Mahaweli is the largest river basin in Sri Lanka that provides water to the dry zone region through multipurpose irrigation schemes . Selenium, arsenic, cadmium, and other bioimportant trace elements in surface waters of the upper Mahaweli River were measured using ICP-MS. Trace element levels were then compared with water from two other rivers (Maha Oya, Kalu Ganga) and from six dry zone irrigation reservoirs. Results showed that the trace metal concentrations in the Mahaweli upper catchment were detected in the order of Fe > Cu > Zn > Se > Cr > Mn > As > Ni > Co > Mo. Remarkably high levels of Ca, Cr, Co, Ni, Cu, As, and Se were observed in the Mahaweli Basin compared to other study rivers. Considerably high levels of Cr, Mn, Fe, Co, Ni, Cu, Zn, As, and Se were found in upstream tributaries of the Mahaweli River. Such metals possibly originated from phosphate and organic fertilizers that are heavily applied for tea and vegetable cultivations within the drainage basin. Cadmium that is often attributed to the etiology of unknown chronic kidney diseases in certain parts of the dry zone is much lower than previously reported levels. Decrease in these metals in the lower part of the Mahaweli River could be due to adsorption of trace metals onto sediment and consequent deposition in reservoirs.

Fe{sub 3}O{sub 4}/CuO/ZnO/Nano graphene platelets (Fe{sub 3}O{sub 4}/CuO/ZnO/NGP) composites prepared by sol-gel method with enhanced sonocatalytic activity for the removal of dye

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

Hendry, Tju; Taufik, Ardiansyah; Saleh, Rosari, E-mail: rosari.saleh@gmail.com, E-mail: rosari.saleh@ui.ac.id

2016-04-19

In this study, an attempt has been made to synthesize nanographene platelets coupled with Fe3O4/CuO/ZnO (Fe3O4/CuO/ZnO/NGP) with various ZnO loadings using a two step methods, sol-gel followed by hydrothermal method. Characterization was carried out by X-ray diffraction, energy-dispersive X-ray spectroscopy and vibrating sample magnetometer. The sonocatalytic performance was evaluated by degradation of methylene blue under ultrasonic irradiation.The Fe3O4/CuO/ZnO/NGP showed superior sonocatalytic activity than the Fe3O4/CuO/ZnO materials. They also showed high stability and can be easily separated from the reaction system for recycling process.

Project VeSElkA: abundance analysis of chemical species in HD 41076 and HD 148330

NASA Astrophysics Data System (ADS)

Khalack, V.; Gallant, G.; Thibeault, C.

2017-10-01

A new semi-automatic approach is employed to carry out the abundance analysis of high-resolution spectra of HD 41076 and HD 148330 obtained recently with the spectropolarimetre Echelle SpectroPolarimetric Device for Observations of Stars at the Canada-France-Hawaii Telescope. This approach allows to prepare in a semi-automatic mode the input data for the modified zeeman2 code and to analyse several hundreds of line profiles in sequence during a single run. It also provides more information on abundance distribution for each chemical element at the deeper atmospheric layers. Our analysis of the Balmer profiles observed in the spectra of HD 41076 and HD 148330 has resulted in the estimates of their effective temperature, gravity, metallicity and radial velocity. The respective models of stellar atmosphere have been calculated with the code phoenix and used to carry out abundance analysis employing the modified zeeman2 code. The analysis shows a deficit of the C, N, F, Mg, Ca, Ti, V, Cu, Y, Mo, Sm and Gd, and overabundance of Cr, Mn, Fe, Co, Ni, Sr, Zr, Ba, Ce, Nd and Dy in the stellar atmosphere of HD 41076. In the atmosphere of HD 148330, the C, N and Mo appear to be underabundant, while the Ne, Na, Al, Si, P, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Sr, Y, Zr, Ba, Ce, Pr, Nd, Sm, Eu, Gd and Dy are overabundant. We also have found signatures of vertical abundance stratification of Fe, Ti, Cr and Mn in HD 41076, and of Fe, Ti, V, Cr, Mn, Y, Zr, Ce, Nd, Sm and Gd in HD 148330.

Recombinant Escherichia coli as a biofactory for various single- and multi-element nanomaterials.

PubMed

Choi, Yoojin; Park, Tae Jung; Lee, Doh C; Lee, Sang Yup

2018-06-05

Nanomaterials (NMs) are mostly synthesized by chemical and physical methods, but biological synthesis is also receiving great attention. However, the mechanisms for biological producibility of NMs, crystalline versus amorphous, are not yet understood. Here we report biosynthesis of 60 different NMs by employing a recombinant Escherichia coli strain coexpressing metallothionein, a metal-binding protein, and phytochelatin synthase that synthesizes a metal-binding peptide phytochelatin. Both an in vivo method employing live cells and an in vitro method employing the cell extract are used to synthesize NMs. The periodic table is scanned to select 35 suitable elements, followed by biosynthesis of their NMs. Nine crystalline single-elements of Mn 3 O 4 , Fe 3 O 4 , Cu 2 O, Mo, Ag, In(OH) 3 , SnO 2 , Te, and Au are synthesized, while the other 16 elements result in biosynthesis of amorphous NMs or no NM synthesis. Producibility and crystallinity of the NMs are analyzed using a Pourbaix diagram that predicts the stable chemical species of each element for NM biosynthesis by varying reduction potential and pH. Based on the analyses, the initial pH of reactions is changed from 6.5 to 7.5, resulting in biosynthesis of various crystalline NMs of those previously amorphous or not-synthesized ones. This strategy is extended to biosynthesize multi-element NMs including CoFe 2 O 4 , NiFe 2 O 4 , ZnMn 2 O 4 , ZnFe 2 O 4 , Ag 2 S, Ag 2 TeO 3 , Ag 2 WO 4 , Hg 3 TeO 6 , PbMoO 4, PbWO 4 , and Pb 5 (VO 4 ) 3 OH NMs. The strategy described here allows biosynthesis of NMs with various properties, providing a platform for manufacturing various NMs in an environmentally friendly manner.

Microstructure and mechanical properties of aluminium matrix composites reinforced by Al{sub 62}Cu{sub 25.5}Fe{sub 12.5} melt spun ribbon

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

Lityńska-Dobrzyńska, Lidia, E-mail: l.litynska@imim.pl; Mitka, Mikołaj; Góral, Anna

Aluminium matrix composites containing 15, 30 and 50 vol.% of pulverized Al{sub 62}Cu{sub 25.5}Fe{sub 12.5} (in at.%) melt spun ribbons have been prepared by a vacuum hot pressing (T = 673 K, P = 600 MPa). The microstructure of the initial ribbon and the composites was investigated using X-ray, scanning and transmission electron microscopy. In the as-spun ribbon the quasicrystalline icosahedral phase (i-phase) coexisted with the cubic copper rich β-Al(Cu, Fe) intermetallic compound. The phase composition of Al-Cu-Fe particles changed after consolidation process and the i-phase transformed partially to the ω-Al{sub 70}Cu{sub 20}Fe{sub 10} phase. Additionally, the Θ-Al{sub 2}Cu phasemore » formed at the α(Al)/Al-Cu-Fe particle interfaces. With an increase in volume fraction of the reinforcement the hardness of the composites increased up to HV = 180 for the highest amount of added particles. The ultimate compression strength of the same sample reached the value of 545 MPa. - Highlights: • Al and 15, 30, 50% of pulverized Al{sub 62}Cu{sub 25.5}Fe{sub 12.5} melt spun ribbon were consolidated. • The initial ribbon consisted of the icosahedral i-phase and copper rich β-Al(Cu, Fe). • The i-phase partially transforms to ω-Al{sub 7}Cu{sub 2}Fe phase in all composites. • Increase of microhardness and compressive strength with content of reinforcement • Ultimate compression strength 545 MPa for 50% of added particles.« less

Solid state 31phosphorus nuclear magnetic resonance of iron-, manganese-, and copper-containing synthetic hydroxyapatites

NASA Technical Reports Server (NTRS)

Sutter, B.; Taylor, R. E.; Hossner, L. R.; Ming, D. W.

2002-01-01

The incorporation of micronutrients into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in the National Aeronautics and Space Administration's (NASA's) Advanced Life Support (ALS) program for Lunar or Martian outposts. Solid state 31P nuclear magnetic resonance (NMR) was utilized to examine the paramagnetic effects of Fe3+, Mn2+, and Cu2+ to determine if they were incorporated into the SHA structure. Separate Fe3+, Mn2+, and Cu2+ containing SHA materials along with a transition metal free SHA (pure-SHA) were synthesized using a precipitation method. The proximity (<1 nm) of the transition metals to the 31P nuclei of SHA were apparent when comparing the integrated 31P signal intensities of the pure-SHA (87 arbitrary units g-1) with the Fe-, Mn-, and Cu-SHA materials (37-71 arbitrary units g-1). The lower integrated 31P signal intensities of the Fe-, Mn-, and Cu-SHA materials relative to the pure-SHA suggested that Fe3+, Mn2+, and Cu2+ were incorporated in the SHA structure. Further support for Fe3+, Mn2+, and Cu2+ incorporation was demonstrated by the reduced spin-lattice relaxation constants of the Fe-, Mn-, and Cu-SHA materials (T'=0.075-0.434s) relative to pure-SHA (T1=58.4s). Inversion recovery spectra indicated that Fe3+, Mn2+, and Cu2+ were not homogeneously distributed about the 31P nuclei in the SHA structure. Extraction with diethylene-triamine-penta-acetic acid (DTPA) suggested that between 50 and 80% of the total starting metal concentrations were incorporated in the SHA structure. Iron-, Mn-, and Cu-containing SHA are potential slow release sources of Fe, Mn, and Cu in the ALS cropping system.

Growth and sacrificial oxidation of transition metal nanolayers

NASA Astrophysics Data System (ADS)

Tsarfati, Tim; Zoethout, Erwin; van de Kruijs, Robbert; Bijkerk, Fred

2009-04-01

Growth and oxidation of Au, Pt, Pd, Rh, Cu, Ru, Ni and Co layers of 0.3-4.3 nm thickness on Mo have been investigated with ARPES and AFM. Co and Ni layers oxidize while the Mo remains metallic. For nobler metals, the on top O and oxidation state of subsurface Mo increase, suggesting sacrificial e - donation by Mo. Au and Cu, in spite of their significantly lower surface free energy, grow in islands on Mo and actually promote Mo oxidation. Applications of the sacrificial oxidation in nanometer thin layers exist in a range of nanoscopic devices, such as nano-electronics and protection of e.g. multilayer X-ray optics for astronomy, medicine and lithography.

Influence of Cu on modifying the beta phase and enhancing the mechanical properties of recycled Al-Si-Fe cast alloys.

PubMed

Basak, C B; Babu, N Hari

2017-07-18

High iron impurity affects the castability and the tensile properties of the recycled Al-Si alloys due to the presence of the Fe containing intermetallic β-Al 9 Fe 2 Si 2 phase. To date only Mn addition is known to transform the β-Al 9 Fe 2 Si 2 phase in the Al-Si-Fe system. However, for the first time, as reported here, it is shown that β-phase transforms to the ω-Al 7 Cu 2 Fe phase in the presence of Cu, after solutionization at 793 K. The ω-phase decomposes below 673 K resulting into the formation of θ-Al 2 Cu phase. However, the present thermodynamic description of the Al-Si-Fe-Cu system needs finer tuning to accurately predict the stability of the ω-phase in these alloys. In the present study, an attempt was made to enhance the strength of Al-6wt%Si-2wt%Fe model recycled cast alloy with different amount of Cu addition. Microstructural and XRD analysis were carried out in detail to show the influence of Cu and the stability range of the ω-phase. Tensile properties and micro-hardness values are also reported for both as-cast and solutionized alloys with different amount of Cu without and with ageing treatment at 473 K. The increase in strength due to addition of Cu, in Fe-rich Al-Si alloys is promising from the alloy recyclability point of view.

Spinel, YbFe2O4, and Yb2Fe3O7 types of structure for compounds in the In2O3 and Sc2O3-A2O3-BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, Cu, or Zn) at temperatures over 1000C

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

Kimizuka, N.; Mohri, T.

In the Sc2O3-Ga2O3-CuO, Sc2O3-Ga2O3-ZnO, and Sc2O3-Al2O3-CuO systems, ScGaCuO4, ScGaZnO4, and ScAlCuO4 with the YbFe2O4-type structure and Sc2Ga2CuO7 with the Yb2Fe3O7-type structure were obtained. In the In2O3-A2O3-BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, or Zn), InGaFeO4, InGaNiO4, and InFeT MgO4 with the spinel structure, InGaZnO4, InGaMgO4, and InAl-CuO4 with the YbFe2O4-type structure, and In2Ga2MnO7 and In2Ga2ZnO7 with the Yb2Fe3O7-type structure were obtained. InGaMnO4 and InFe2O4 had both the YbFe2O4-type and spinel-type structures. The revised classification for the crystal structures of AB2O4 compounds is presented, based upon the coordination numbers of constituent A and B cations. 5more » references, 2 tables.« less

Speciation of Energy Critical Elements in Marine Ferromanganese Crusts and Nodules by Principal Component Analysis and Least-squares fits to XAFS Spectra

NASA Astrophysics Data System (ADS)

Foster, A. L.; Klofas, J. M.; Hein, J. R.; Koschinsky, A.; Bargar, J.; Dunham, R. E.; Conrad, T. A.

2011-12-01

Marine ferromanganese crusts and nodules ("Fe-Mn crusts") are considered a potential mineral resource due to their accumulation of several economically-important elements at concentrations above mean crustal abundances. They are typically composed of intergrown Fe oxyhydroxide and Mn oxide; thicker (older) crusts can also contain carbonate fluorapatite. We used X-ray absorption fine-structure (XAFS) spectroscopy, a molecular-scale structure probe, to determine the speciation of several elements (Te, Bi, Mo, Zr, Pt) in Fe-Mn crusts. As a first step in analysis of this dataset, we have conducted principal component analysis (PCA) of Te K-edge and Mo K-edge, k3-weighted XAFS spectra. The sample set consisted of 12 homogenized, ground Fe-Mn crust samples from 8 locations in the global ocean. One sample was subjected to a chemical leach to selectively remove Mn oxides and the elements associated with it. The samples in the study set contain 50-205 mg/kg Te (average = 88) and 97-802 mg/kg Mo (average = 567). PCAs of background-subtracted, normalized Te K-edge and Mo K-edge XAFS spectra were performed on a data matrix of 12 rows x 122 columns (rows = samples; columns = Te or Mo fluorescence value at each energy step) and results were visualized without rotation. The number of significant components was assessed by the Malinowski indicator function and ability of the components to reconstruct the features (minus noise) of all sample spectra. Two components were significant by these criteria for both Te and Mo PCAs and described a total of 74 and 75% of the total variance, respectively. Reconstruction of potential model compounds by the principal components derived from PCAs on the sample set ("target transformation") provides a means of ranking models in terms of their utility for subsequent linear-combination, least-squares (LCLS) fits (the next step of data analysis). Synthetic end-member models of Te4+, Te6+, and Mo adsorbed to Fe(III) oxyhydroxide and Mn oxide were tested. Te6+ sorbed to Fe oxyhydroxide and Mo sorbed to Fe oxyhydroxide were identified as the best models for Te and Mo PCAs, respectively. However, in the case of Mo, least-squares fits contradicted these results, indicating that about 80% of Mo in crust samples was associated with Mn oxides. Ultimately it was discovered that the sample from which Mn oxide had been leached was skewing the results in the Mo PCA but not in the Te PCA. When the leached sample was removed and the Mo PCA repeated (n = 11), target transformation indicated that Mo sorbed to Mn oxide was indeed the best model for the set. Our results indicate that Te and Mo are strongly partitioned into different phases in these Fe-Mn crusts, and emphasize the importance of evaluating outliers and their effects on PCA.

Effect of Solutes on Grain Refinement of As-Cast Fe-4Si Alloy

NASA Astrophysics Data System (ADS)

Li, Ming; Li, Jian-Min; Zheng, Qing; Wang, Geoff; Zhang, Ming-Xing

2018-06-01

Grain size is one of the key microstructural factors that control the mechanical properties of steels. The present work aims to extend the theories of grain refinement which were established for cast light alloys to steel systems. Using a designed Fe-4 wt pct Si alloy (all-ferrite structure during whole solidification process), the solute effect on grain refinement/grain coarsening in ferritic systems was comprehensively investigated. Experimental results showed that boron (B), which is associated with the highest Q value (growth restriction factor) in ferrite, significantly refined the as-cast structure of the Fe-4 wt pct Si alloy. Cu and Mo with low Q values had no effect on grain refinement. However, although Y and Zr have relatively high Q values, addition of these two solutes led to grain coarsening in the Fe-4Si alloy. Understanding the results in regards to the growth restriction factor and the driving force for the solidification led to the conclusion that in addition to the grain growth restriction effect, the changes of thermodynamic driving force for solidification due to the solute addition also played a key role in grain refinement in ferritic alloys.

Effect of Solutes on Grain Refinement of As-Cast Fe-4Si Alloy

NASA Astrophysics Data System (ADS)

Li, Ming; Li, Jian-Min; Zheng, Qing; Wang, Geoff; Zhang, Ming-Xing

2018-03-01

Grain size is one of the key microstructural factors that control the mechanical properties of steels. The present work aims to extend the theories of grain refinement which were established for cast light alloys to steel systems. Using a designed Fe-4 wt pct Si alloy (all-ferrite structure during whole solidification process), the solute effect on grain refinement/grain coarsening in ferritic systems was comprehensively investigated. Experimental results showed that boron (B), which is associated with the highest Q value (growth restriction factor) in ferrite, significantly refined the as-cast structure of the Fe-4 wt pct Si alloy. Cu and Mo with low Q values had no effect on grain refinement. However, although Y and Zr have relatively high Q values, addition of these two solutes led to grain coarsening in the Fe-4Si alloy. Understanding the results in regards to the growth restriction factor and the driving force for the solidification led to the conclusion that in addition to the grain growth restriction effect, the changes of thermodynamic driving force for solidification due to the solute addition also played a key role in grain refinement in ferritic alloys.

Integrated photooxidative-extractive desulfurization system for fuel oil using Cu, Fe and Cu-Fe/TiO2 and eutectic based ionic liquids: Effect of calcination temperature and duration

NASA Astrophysics Data System (ADS)

Zaid, Hayyiratul Fatimah Mohd; Kait, Chong Fai; Mutalib, Mohamed Ibrahim Abdul

2014-10-01

Photocatalyts TiO2 doped with Cu, Fe and Cu-Fe metal at different calcination temperature and duration were successfully prepared and characterized. Photocatalytic oxidative desulfurization of model oil containing dibenzothiophene as the sulfur compound (100 ppm) using the prepared photocatalyst was investigated. The photocatalyst calcined at 500°C and duration of 1 h showed the best performance.

Microstructures and Mechanical Properties of NiTiFeAlCu High-Entropy Alloys with Exceptional Nano-precipitates

NASA Astrophysics Data System (ADS)

Zhang, Yanqiu; Wang, Sibing; Jiang, Shuyong; Zhu, Xiaoming; Sun, Dong

2017-01-01

Three novel NiTiFeAlCu high-entropy alloys, which consist of nano-precipitates with face-centered cubic structure and matrix with body-centered cubic structure, were fabricated to investigate microstructures and mechanical properties. With the increase in Ni and Ti contents, the strength of NiTiFeAlCu alloy is enhanced, while the plasticity of NiTiFeAlCu alloy is lowered. Plenty of dislocations can be observed in the Ni32Ti32Fe12Al12Cu12 high-entropy alloy. The size of nano-precipitates decreases with the increase in Ni and Ti contents, while lattice distortion becomes more and more severe with the increase in Ni and Ti contents. The existence of nano-precipitates, dislocations and lattice distortion is responsible for the increase in the strength of NiTiFeAlCu alloy, but it has an adverse influence on the plasticity of NiTiFeAlCu alloy. Ni20Ti20Fe20Al20Cu20 alloy exhibits the substantial ability of plastic deformation and a characteristic of steady flow at 850 and 1000 °C. This phenomenon is attributed to a competition between the increase in the dislocation density induced by plastic strain and the decrease in the dislocation density due to the dynamic recrystallization.

Copper(II) cyanido-bridged bimetallic nitroprusside-based complexes: Syntheses, X-ray structures, magnetic properties, 57Fe Mössbauer spectroscopy and thermal studies

NASA Astrophysics Data System (ADS)

Trávníček, Zdeněk; Herchel, Radovan; Mikulík, Jiří; Zbořil, Radek

2010-05-01

Three heterobimetallic cyanido-bridged copper(II) nitroprusside-based complexes of the compositions [Cu(tet)Fe(CN) 5NO]·H 2O ( 1), where tet= N,N' -bis(3-aminopropyl)ethylenediamine, [Cu(hto)Fe(CN) 5NO]·2H 2O ( 2), where hto=1,3,6,9,11,14-hexaazatricyclo[12.2.1.1 6,9]octadecane and [Cu(nme) 2Fe(CN) 5NO]·H 2O ( 3), where nme= N-methylethylenediamine, were synthesized and characterized by elemental analyses, 57Fe Mössbauer and FTIR spectroscopies, thermal analysis, magnetic measurements and single-crystal X-ray analysis. The products of thermal degradation processes of 2 and 3 were studied by XRD, 57Fe Mössbauer spectroscopy, SEM and EDS, and they were identified as mixtures of CuFe 2O 4 and CuO.

Preparation of TbCu7-type Sm-Fe powders by low-temperature HDDR treatment

NASA Astrophysics Data System (ADS)

Takagi, Kenta; Jinno, Miho; Ozaki, Kimihiro

2018-05-01

Low-temperature hydrogen-disproportionation-desorption-recombination (HDDR) treatment of Sm-Fe alloy powder was conducted to prepare a metastable TbCu7 type Sm-Fe alloy powder with a grain size of more than a few hundreds of nanometers. While a treatment temperature above 700 °C produced the familiar Th2Zn17 type alloy, one below 600 °C resulted in successful synthesis of the TbCu7 type Sm-Fe alloy with submicron-size grains. This TbCu7 type alloy powder, however, showed no significant improvement in magnetic properties compared to the Th2Zn17 type, as its composition was estimated to be near SmFe8.5 and thus did not achieve the expected Fe-rich composition. Therefore, cross-sectional transmission electron microscope observation of the unfinished TbCu7 type alloy powder was conducted in order to explore means of forming the Fe-rich phase.

Synthesis, characterization and optical non-linearity of two heterobimetallic copper clusters containing tetraselenometalates

NASA Astrophysics Data System (ADS)

Zhang, Qian-Feng; Zhang, Chi; Song, Ying-Lin; Xin, Xin-Quan

2000-07-01

Cluster [{MoCu 3Se 3Br}(PPh 3) 3Se]·3THF·H 2O ( 1·3THF·H 2O) was prepared from reaction of [Et 4N] 2[MoSe] 4, Cu(PPh 3) 2NO 3 and Et 4N·Br in CH 2Cl 2 solution; also, 1 can be also obtained from the reaction of [MoSe 4Cu 4Py 6Br 2] and excess PPh 3 in a DMF-CH 2Cl 2 mixture solvent. The 95Mo NMR technique was used to monitor the above two reaction processes. X-ray crystallographic structure determination shows that it contains a strongly distorted cubane-like {MoCu 3Se 3Br} core. The coordination of the central Mo atom and each Cu atom are distorted from tetrahedral. Cluster [{WCu 3Se 3Cl}(PPh 3) 3Se] ( 2) was synthesized by the reaction of [Et 4N] 2[WSe] 4 and Cu(PPh 3) 2Cl in the solid state for nonlinear optical (NLO) studies. Its structure was reported by Ibers (Inorg. Chem. 31 (1992) 4365). The NLO properties of clusters 1 and 2 were studied. Both NLO absorption and refraction were obtained, and their effective third-order non-linearities were detected with α2=3.4×10 -10 and 5.9×10 -10 m/W and n2=-1.5×10 -17 and -1.3×10 -17 m 2/W , respectively, for the same concentration CH 2Cl 2 solution of 1 and 2. Influence of skeletal atoms to nonlinear absorption is also discussed in the paper.

Copper-promoted circumneutral activation of H2O2 by magnetic CuFe2O4 spinel nanoparticles: Mechanism, stoichiometric efficiency, and pathway of degrading sulfanilamide.

PubMed

Feng, Yong; Liao, Changzhong; Shih, Kaimin

2016-07-01

To evaluate the heterogeneous degradation of sulfanilamide by external energy-free Fenton-like reactions, magnetic CuFe2O4 spinel nanoparticles (NPs) were synthesized and used as catalysts for activation of hydrogen peroxide (H2O2). The physicochemical properties of the CuFe2O4 NPs were characterized with several techniques, including X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and magnetometry. In the catalytic experiments, CuFe2O4 NPs/H2O2 oxidation showed the best degradation performance in the circumneutral conditions that resulted from the presence of Cu(II) on the surface of the CuFe2O4 NPs. The surface area-normalized pseudo-first-order rate constants were calculated as 2.60 × 10(-2) L m(-1) min(-1), 2.58 × 10(-3) L m(-1) min(-1), 1.92 × 10(-3) L m(-1) min(-1), and 7.30 × 10(-4) L m(-1) min(-1) for CuO, CuFe2O4 NPs, Fe3O4, and α-Fe2O3 catalysts, respectively. Thus, solid state Cu(II) was more reactive and efficient than Fe(III) in the circumneutral activation of H2O2; this finding was further supported by the results regarding the stoichiometric efficiency of H2O2. The effects of experimental parameters such as the oxidant dosage and catalyst loading were investigated. The mechanism for H2O2 activation on the spinel surface was explored and could be explained by the solid redox cycles of Fe(II)/Fe(III) and Cu(II)/Cu(I). Based on the products detected, a degradation pathway via the CS bond cleavage is proposed for the degradation of sulfanilamide. The findings of this study suggest that copper can be used as a doping metal to improve the reactivity and expand the effective pH range of iron oxides. Copyright © 2016 Elsevier Ltd. All rights reserved.

Optimizing Heat Treatment Process of Fe-13Cr-3Mo-3Ni Martensitic Stainless of Steel

NASA Astrophysics Data System (ADS)

Anwar, M. S.; Prifiharni, S.; Mabruri, E.

2017-05-01

The Fe-13Cr-3Mo-3Ni stainless steels are modified into martensitic stainless steels for steam turbine blades application. The working temperature of steam turbine was around 600 - 700 °C. The improvement properties of turbine blade material is necessary to maintain steam turbine work. The previous research revealed that it has corrosion resistance of Fe-13Cr-3Mo-3Ni which is better than 13Cr stainless steels in the chloride environment. In this work, the effect of heat treatment on microstructure and hardness of Fe-13Cr-3Mo-3Ni stainless steels has been studied. The steel was prepared by induction melting followed by hot forging. The steels were austenitized at 1000, 1050, and 1100 °C for 1 hour and were tempered at 600, 650, and 700 °C for 1 hour. The steels were then subjected to metallographic observation and hardness test of Rockwell C. The optimal heat treatment of Fe-13Cr-3Mo-3Ni was carried out austenitized in 1050 °C and tempered in 600 - 700 °C.

Role of Cu During Sintering of Fe0.96Cu0.04 Nanoparticles

NASA Astrophysics Data System (ADS)

Sivaprahasam, D.; Sriramamurthy, A. M.; Bysakh, S.; Sundararajan, G.; Chattopadhyay, K.

2018-04-01

Nanoparticle agglomerates of passivated Fe ( n-Fe) and Fe0.96Cu0.04 ( n-Fe0.96Cu0.04), synthesized through the levitational gas condensation (LGC) process, were compacted and sintered using the conventional powder metallurgy method. The n-Fe0.96Cu0.04 agglomerates produced lower green density than n-Fe, and when compacted under pressure beyond 200 MPa, they underwent lateral cracking during ejection attributed to the presence of a passive oxide layer. Sintering under dynamic hydrogen atmosphere can produce a higher density of compact in n-Fe0.96Cu0.04 in comparison to n-Fe. Both the results of dilatometry and thermogravimetric (TG) measurements of the samples under flowing hydrogen revealed enhancement of the sintering process as soon as the reduction of oxide layers could be accomplished. The shrinkage rate of n-Fe0.96Cu0.04 reached a value three times higher than n-Fe at a low temperature of 723 K (450 °C) during heating. This enhanced shrinkage rate was the manifestation of accumulation of Cu at the surface of the particles. The formation of a thin-surface melted layer enriched with copper during heating to isothermal holding facilitated as a medium of transport for diffusion of the elements. The compacts produced by sintering at 773 K (500 °C), with relative density 82 pct, were found to be unstable and oxidized instantly when exposed to ambient atmosphere. The stable compacts of density more than 92 pct with 300- to 450-nm grain size could only be produced when sintering was carried out at 973 K (700 °C) and beyond. The 0.22 wt pct residual oxygen obtained in the sintered compact is similar to what is used for conventional ferrous powder metallurgy products.

Trace element concentrations in needles and bark of Larix Sibirica within the Mo-W ore field (Buryat Republic, Russia)

NASA Astrophysics Data System (ADS)

Timofeev, Ivan; Kosheleva, Natalia

2016-04-01

The present study aims to assess the changes in the trace element (TE) composition of Larix Sibirica species growing in the impact area of Dzhida Mo-W plant in the Zakamensk city. The objectives of the study were: (1) to reveal the biogeochemical background features and changes in the TE composition of larch needles and bark in the mining region; (2) to determine patterns of spatial distribution of TE content in larch organs; (3) to assess the ecological state of larch plantation in different land-use zones of the city. A landscape-geochemical survey of the territory was carried out in summer of 2013. Total of 21 mixed (taken from 3-5 trees) samples of needles and bark were collected in undisturbed and different land-use areas. The bulk contents of TEs in dry plant samples were analyzed by mass spectrometry with induced coupled plasma. Sixteen priority pollutants were selected for thorough analysis, including elements of hazard classes I (Zn, As, Pb, Cd), II (Cr, Co, Ni, Cu, Mo, Sb), III (V, Sr, Ba, W), and some others (Sn, Bi). Concentrations of TEs (C_b) in background trees were compared with the global clarks (C_g) for annual increment of terrestrial vegetation (Dobrovol'skii 2003) via calculating the global enrichment EF_g=C_b/Cg and dispersion factors DF_g=C_g/C_b}. The concentrations of the elements in the urban samples Ci were grouped depending on the type of land use and compared with the background (C_b) via calculating the local enrichment EF_l=C_i/Cb and dispersion factors DF_l=C_b/C_i. The ecological state of the urban plants was diagnosed using three TE ratios. The Fe/Mn ratio represents photosynthetic activity with optimum value 1.5-2.5. The Pb/Mn ratio characterizes balance between technogenic and biophilic elements, its value for unpolluted terrestrial plants is 0.006. The Cu/Zn ratio determines the proportionality in the provision of enzyme synthesis with these metals, its optimum value is 0.27. TE composition of needles of background larch is characterized by increased concentrations of ?? ? Mn (EF_g=2.9) ? Sr (1.5), and reduced ones for Ni, Co, Pb, Mo, Sn, V (DF_l=5.1-22.1), that of Cd, Cu, Zn are close to global clarks. Ba, Pb, Cd (EF_g=3.5-2.3) are accumulated in the bark, Cu, Zn, Co, Cr, Ni, Sn dissipate (DF_g=2.1-3.7), and the content of Mn, Sr, Mo, V, As is close to Cg. In the city larch needles accumulate Cr (EF_l=37.8), W (18.9), V, Pb, Bi (8.6-11.4), Sb, Ni, Cd, Sn (6.6-2.5); Mn (DF_l=3.1) is among scattered. Changes in the TE composition of larch bark is most clearly evident in the industrial area, where high concentrations of W, Sn (EF_l=5.4-6.6), Sb, Pb, As (2.8-3.4), Mo, Cd, V, Bi, Zn (1.5-2.0) and low ones -- of Cr, Ni, Co, Ba (DF_l=4.6-2.1) are observed. As an indicator of long-term pollution, bark displays that vegetation of industrial zone has been subject previously to most intense anthropogenic impact, so, Pb/Mn=0.06 was there the highest. After plant closing residential area experiences the greatest impact according to Fe/Mn=4.7; Pb/Mn=0.04 values in the needles. This is caused by the active transport of aeolian dry material of tailings. 1. Dobrovol'skii VV (2003) Basics of biogeochemistry: the textbook for students of higher educational institutions. Moscow, "Academia" Publ., 400 p.

Effect of soil parameters on the kinetics of the displacement of Fe from FeEDDHA chelates by Cu.

PubMed

Schenkeveld, Walter D C; Reichwein, Arjen M; Temminghoff, Erwin J M; van Riemsdijk, Willem H

2012-06-28

In soil application, o,o-FeEDDHA (iron (3+) ethylene diamine-N,N'-bis(2-hydroxy phenyl acetic acid) complex) is the active ingredient of FeEDDHA chelate-based Fe fertilizers. The effectiveness of o,o-FeEDDHA is potentially compromised by the displacement of Fe from FeEDDHA by Cu. The actual impact of Cu competition is codetermined by the kinetics of the displacement reaction. In this study, the influence of soil parameters on the displacement kinetics has been examined in goethite suspensions. The displacement reaction predominantly takes place on the reactive surface rather than in solution. The rate at which the o,o-FeEDDHA concentration declined depended on the available reactive surface area, the Cu loading, and the FeEDDHA loading. Soil factors reducing FeEDDHA adsorption (high ionic strength, humic acid adsorption onto the goethite surface, and monovalent instead of divalent cations in the electrolyte) decreased the displacement rate. For meso o,o-FeEDDHA, the displacement rate equation was derived, which is first order in FeEDDHA loading and half order in Cu loading. For soil conditions, the equation can be simplified to an exponential decay function in meso o,o-FeEDDHA solution concentration.

Investigation of iron adsorption on composite transition metal carbides in steel by first-principles calculation

NASA Astrophysics Data System (ADS)

Xiong, Hui-Hui; Gan, Lei; Tong, Zhi-Fang; Zhang, Heng-Hua; Zhou, Yang

2018-05-01

The nucleation potential of transition metal (TM) carbides formed in steel can be predicted by the behavior of iron adsorption on their surface. Therefore, Fe adsorption on the (001) surface of (A1-xmx)C (A = Nb, Ti, m = Mo, V) was investigated by the first-principles method to reveal the initialization of Fe nucleation. The Mulliken population and partial density of state (PDOS) were also calculated and analyzed in this work. The results show that Fe adsorption depends on the composition and configuration of the composite carbides. The adsorption energy (Wads) of Fe on most of (A1-xmx)C is larger than that of Fe on pure TiC or NbC. The maximum Wads is found for Fe on (Nb0.5Mo0.5)C complex carbide, indicating that this carbide has the high nucleation capacity at early stage. The Fe adsorption could be improved by the segregation of Cr and Mn atoms on the surfaces of (Nb0.5Mo0.5)C and (Ti0.5Mo0.5)C. The PDOS analysis of (Cr, Mn)-doped systems further explains the strong interactions between Fe and Cr or Mn atoms.

Size and elemental distributions of nano- to micro-particulates in the geochemically-stratified Great Salt Lake

USGS Publications Warehouse

Diaz, X.; Johnson, W.P.; Fernandez, D.; Naftz, D.L.

2009-01-01

The characterization of trace elements in terms of their apportionment among dissolved, macromolecular, nano- and micro-particulate phases in the water column of the Great Salt Lake carries implications for the potential entry of toxins into the food web of the lake. Samples from the anoxic deep and oxic shallow brine layers of the lake were fractionated using asymmetric flow field-flow fractionation (AF4). The associated trace elements were measured via online collision cell inductively-coupled plasma mass spectrometry (CC-ICP-MS). Results showed that of the total (dissolved + particulate) trace element mass, the percent associated with particulates varied from negligible (e.g. Sb), to greater than 50% (e.g. Al, Fe, Pb). Elements such as Cu, Zn, Mn, Co, Au, Hg, and U were associated with nanoparticles, as well as being present as dissolved species. Particulate-associated trace elements were predominantly associated with particulates larger than 450 nm in size. Among the smaller nanoparticulates (<450 nm), some trace elements (Ni, Zn, Au and Pb) showed higher percent mass (associated with nanoparticles) in the 0.9-7.5 nm size range relative to the 10-250 nm size range. The apparent nanoparticle size distributions were similar between the two brine layers; whereas, important differences in elemental associations to nanoparticles were discerned between the two layers. Elements such as Zn, Cu, Pb and Mo showed increasing signal intensities from oxic shallow to anoxic deep brine, suggesting the formation of sulfide nanoparticles, although this may also reflect association with dissolved organic matter. Aluminum and Fe showed greatly increased concentration with depth and equivalent size distributions that differed from those of Zn, Cu, Pb and Mo. Other elements (e.g. Mn, Ni, and Co) showed no significant change in signal intensity with depth. Arsenic was associated with <2 nm nanoparticles, and showed no increase in concentration with depth, possibly indicating dissolved arsenite. Mercury was associated with <2 nm nanoparticles, and showed greatly increased concentration with depth, possibly indicating association with dissolved organic matter. ?? 2009 Elsevier Ltd.

Novel approach for removing brominated flame retardant from aquatic environments using Cu/Fe-based metal-organic frameworks: A case of hexabromocyclododecane (HBCD).

PubMed

Li, Xiang; Liu, Hongli; Jia, Xiaoshan; Li, Guiying; An, Taicheng; Gao, Yanpeng

2018-04-15

Cu and Fe based metal-organic frameworks (Cu-BTC and Fe-BTC) were synthesized via a simple solvothermal method and innovatively utilized to remove a typical nonionic brominated flame retardant, hexabromocyclododecane (HBCD), from aquatic environment. Results show that over 80% of HBCD was removed by Cu-BTC within 5h, which is 1.3 times higher than removal by Fe-BTC. Thermodynamic analysis confirms spontaneous adsorption of HBCD onto the metal-organic frameworks (MOFs). Furthermore, the Gibbs free energy of Cu-BTC (-9.11kJ/mol) is more negative than that of Fe-BTC (-5.04kJ/mol). Both adsorption isotherms of HBCD onto Cu-BTC and Fe-BTC followed the Langmuir model, indicating a typical monomolecular-layer adsorption mechanism. In addition, the water stability test of these MOFs shows that the collapse of the Cu-BTC crystal structure is significantly hindered in the aquatic environment due to adsorption of the hydrophobic HBCD. The proposed adsorption mechanism includes van der Waals and hydrophobic interactions. These findings demonstrate that Cu/Fe-BTC are promising adsorbents for the removal of hydrophobic organic pollutants from aquatic environments, and may further improve the understanding of MOF materials for environmental applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Phase diagram and neutron spin resonance of superconducting NaFe 1 - x Cu x As

DOE PAGES

Tan, Guotai; Song, Yu; Zhang, Rui; ...

2017-02-03

In this paper, we use transport and neutron scattering to study the electronic phase diagram and spin excitations of NaFe 1-xCu xAs single crystals. Similar to Co- and Ni-doped NaFeAs, a bulk superconducting phase appears near x≈2% with the suppression of stripe-type magnetic order in NaFeAs. Upon further increasing Cu concentration the system becomes insulating, culminating in an antiferromagnetically ordered insulating phase near x≈50%. Using transport measurements, we demonstrate that the resistivity in NaFe 1-xCu xAs exhibits non-Fermi-liquid behavior near x≈1.8%. Our inelastic neutron scattering experiments reveal a single neutron spin resonance mode exhibiting weak dispersion along c axis inmore » NaFe 0.98Cu 0.02As. The resonance is high in energy relative to the superconducting transition temperature T c but weak in intensity, likely resulting from impurity effects. These results are similar to other iron pnictides superconductors despite that the superconducting phase in NaFe 1-xCu xAs is continuously connected to an antiferromagnetically ordered insulating phase near x≈50% with significant electronic correlations. Finally, therefore, electron correlations is an important ingredient of superconductivity in NaFe 1-xCu xAs and other iron pnictides.« less

Activation of persulfate/copper by hydroxylamine via accelerating the cupric/cuprous redox couple.

PubMed

Zhou, Peng; Zhang, Jing; Liang, Juan; Zhang, Yongli; Liu, Ya; Liu, Bei

2016-01-01

Cuprous copper [Cu(I)] reacts with sodium persulfate (PDS) to generate sulfate radical SO4(-)•, but it has been seldom investigated owing to its instability and difficulty in dissolving it. This study proposes a new method to regenerate Cu(I) from cupric copper [Cu(II)] by addition of hydroxylamine (HA) to induce the continuous production of radicals through active PDS, and investigates the resulting enhanced methyl orange (MO) degradation efficiency and mechanism in the new system. HA accelerated the degradation of MO markedly in the pH range from 6.0 to 8.0 in the HA/Cu(II)/PDS process. Both SO4(-)• and hydroxyl radicals (•OH) were considered as the primary reactive radicals in the process. The MO degradation in the HA/Cu(II)/PDS process can be divided into three stages: the fast stage, the transitory stage, and the low stage. MO degradation was enhanced with increased dosage of PDS. Although high dosage of HA could accelerate the transformation of the Cu(II)/Cu(I) cycle to produce more reactive radicals, excess HA can quench the reactive radicals. This study indicates that through a copper-redox cycling mechanism by HA, the production of SO4(-)• and •OH can be strongly enhanced, and the effective pH range can be expanded to neutral conditions.

Introducing a 2-His-1-Glu Nonheme Iron Center into Myoglobin Confers Nitric Oxide Reductase Activity

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

Lin, Y.W.; Robinson, H.; Yeung, N.

2010-07-28

A conserved 2-His-1-Glu metal center, as found in natural nonheme iron-containing enzymes, was engineered into sperm whale myoglobin by replacing Leu29 and Phe43 with Glu and His, respectively (swMb L29E, F43H, H64, called Fe{sub B}Mb(-His)). A high resolution (1.65 {angstrom}) crystal structure of Cu(II)-CN?-Fe{sub B}Mb(-His) was determined, demonstrating that the unique 2-His-1-Glu metal center was successfully created within swMb. The Fe{sub B}Mb(-His) can bind Cu, Fe, or Zn ions, with both Cu(I)-Fe{sub B}Mb(-His) and Fe(II)-Fe{sub B}Mb(-His) exhibiting nitric oxide reductase (NOR) activities. Cu dependent NOR activity was significantly higher than that of Fe in the same metal binding site. EPRmore » studies showed that the reduction of NO to N{sub 2}O catalyzed by these two enzymes resulted in different intermediates; a five-coordinate heme-NO species was observed for Cu(I)-Fe{sub B}Mb(-His) due to the cleavage of the proximal heme Fe-His bond, while Fe(II)-Fe{sub B}Mb(-His) remained six-coordinate. Therefore, both the metal ligand, Glu29, and the metal itself, Cu or Fe, play crucial roles in NOR activity. This study presents a novel protein model of NOR and provides insights into a newly discovered member of the NOR family, gNOR.« less

Cu3Mo2O9: An Ultralow-Firing Microwave Dielectric Ceramic with Good Temperature Stability and Chemical Compatibility with Aluminum

NASA Astrophysics Data System (ADS)

Wen, Wangxi; Li, Chunchun; Sun, Yihua; Tang, Ying; Fang, Liang

2018-02-01

An ultralow-firing microwave dielectric ceramic Cu3Mo2O9 with orthorhombic structure has been fabricated via a solid-state reaction method. X-ray diffraction analysis, Rietveld refinement, Raman spectroscopy, energy-dispersive spectrometry, and scanning electron microscopy were employed to explore the phase purity, crystal structure, and microstructure. Pure and dense Cu3Mo2O9 ceramics could be obtained in the sintering temperature range from 580°C to 680°C. The sample sintered at 660°C for 4 h exhibited the highest relative density (˜ 97.2%) and best microwave dielectric properties with ɛ r = 7.2, Q × f = 19,300 GHz, and τ f = - 7.8 ppm/°C. Chemical compatibility with aluminum electrodes was also confirmed. All the results suggest that Cu3Mo2O9 ceramic is a promising candidate for use in ultralow-temperature cofired ceramic applications.

Catalytic ozonation of petroleum refinery wastewater utilizing Mn-Fe-Cu/Al2O 3 catalyst.

PubMed

Chen, Chunmao; Yoza, Brandon A; Wang, Yandan; Wang, Ping; Li, Qing X; Guo, Shaohui; Yan, Guangxu

2015-04-01

There is of great interest to develop an economic and high-efficient catalytic ozonation system (COS) for the treatment of biologically refractory wastewaters. Applications of COS require options of commercially feasible catalysts. Experiments in the present study were designed to prepare and investigate a novel manganese-iron-copper oxide-supported alumina-assisted COS (Mn-Fe-Cu/Al2O3-COS) for the pretreatment of petroleum refinery wastewater. The highly dispersed composite metal oxides on the catalyst surface greatly promoted the performance of catalytic ozonation. Hydroxyl radical mediated oxidation is a dominant reaction in Mn-Fe-Cu/Al2O3-COS. Mn-Fe-Cu/Al2O3-COS enhanced COD removal by 32.7% compared with a single ozonation system and by 8-16% compared with Mn-Fe/Al2O3-COS, Mn-Cu/Al2O3-COS, and Fe-Cu/Al2O3-COS. The O/C and H/C ratios of oxygen-containing polar compounds significantly increased after catalytic ozonation, and the biodegradability of petroleum refinery wastewater was significantly improved. This study illustrates potential applications of Mn-Fe-Cu/Al2O3-COS for pretreatment of biologically refractory wastewaters.

Characteristics of Catalytic Gasification of Natural Coke with H2O in a Fluidized Bed

NASA Astrophysics Data System (ADS)

Lin, L. S.; Zhao, C. S.; Wang, S.; Zhu, G.; Xiang, W. G.

The experimental investigation on gasification characteristics of natural coke from Peicheng, Jiangsu with steam were conducted in a fluidized bed gasifier setup. The effects of several parameters, in terms of the catalyst type, the catalyst mixed manner and the dosage of catalyst over coke on the yield, the components, the heating value of fuel gas and the carbon conversion rate were examined. Results indicate that the fluidized bed gasification technology could overcome the shortcomings of natural coke. Ca-, Fe- and Cu-based nitrates could improve the gasification reaction effectively with a little difference, they could be listed in a descending sequence as follows: Cu-based>Fe-based>Ca-based according to their catalytic effect. The influences of Fe/Ca ratio and Cu/Ca ratio on gasification are similar, gas yield, carbon conversion rate and gas heating value per hour increase as Fe/Ca ratio or Cu/Ca ratio increases, but all of them go up first and then drop with decrease in Fe/Cu ratio. When the dosage of Ca-, Fe- and Cu-based nitrates mixed with the ratio of Ca/Fe/Cu= 10/35/55 is 3%, the best catalytic effect is achieved.

Microstructure and mechanical behavior of Zr substrates coated with FeCrAl and Mo by cold-spraying

NASA Astrophysics Data System (ADS)

Park, Dong Jun; Kim, Hyun Gil; Jung, Yang Il; Park, Jung Hwan; Yang, Jae Ho; Koo, Yang Hyun

2018-06-01

FeCrAl and Mo layers were cold-sprayed onto a Zr surface, with the Mo layer introduced between the FeCrAl coating and the Zr matrix preventing high-temperature interdiffusion. Microstructural characterization of the first-deposited Mo layer and the Zr matrix immediately below the Mo/Zr interface was performed using transmission electron microscopy, and near-interface elemental distributions were obtained using energy-dispersive X-ray spectroscopy. The deformation of the coated Mo powder induced the formation of microbands and mechanically interlocked nanoscale structures. The mechanical behavior of Zr with a coating layer was compared with those characteristic of conventional Zr samples. The coated sample showed smaller strength reduction in the test conducted at elevated temperature. The hardness and fracture morphology of the Zr matrix near the interface region were investigated to determine the effect of impacting Mo particles on the matrix microstructure. The enhanced hardness and cleavage fracture morphology of the Zr matrix immediately below the Mo/Zr interface indicated the occurrence of localized deformation owing to Mo particle impact.

Charge dynamics of 57Fe probe atoms in La2Li0.5Cu0.5O4

NASA Astrophysics Data System (ADS)

Presniakov, I. A.; Sobolev, A. V.; Rusakov, V. S.; Moskvin, A. S.; Baranov, A. V.

2018-06-01

The objective of this study is to characterize the electronic state and local surrounding of 57Fe Mössbauer probe atoms within iron-doped layered perovskite La2Li0.5Cu0.5O4 containing transition metal in unusual formal oxidation states "+3". An approach based on the qualitative energy diagrams analysis and the calculations within the cluster configuration interaction method have been developed. It was shown that a large amount of charge is transferred via Cu-O bonds from the O: 2p bands to the Cu: 3d orbitals and the ground state is dominated by the d9L configuration ("Cu2+-O-" state). The dominant d9L ground state for the (CuO6) sublattice induces in the environment of the 57Fe probe cations a charge transfer Fe3+ + O-(L) → Fe4+ + O2-, which transforms "Fe3+" into "Fe4+" state. The experimental spectra in the entire temperature range 77-300 K were described with the use of the stochastic two-level model based on the assumption of dynamic equilibrium between two Fe3+↔Fe4+ valence states related to the iron atom in the [Fe(1)O4]4- center. The relaxation frequencies and activation energies of the corresponding charge fluctuations were estimated based on Mössbauer data. The results are discussed assuming a temperature-induced change in the electronic state of the [CuO4]5- clusters in the layered perovskite.

Evidence of cross-cutting and redox reaction in Khatyrka meteorite reveals metallic-Al minerals formed in outer space.

PubMed

Lin, Chaney; Hollister, Lincoln S; MacPherson, Glenn J; Bindi, Luca; Ma, Chi; Andronicos, Christopher L; Steinhardt, Paul J

2017-05-09

We report on a fragment of the quasicrystal-bearing CV3 carbonaceous chondrite Khatyrka recovered from fine-grained, clay-rich sediments in the Koryak Mountains, Chukotka (Russia). We show higher melting-point silicate glass cross-cutting lower melting-point Al-Cu-Fe alloys, as well as unambiguous evidence of a reduction-oxidation reaction history between Al-Cu-Fe alloys and silicate melt. The redox reactions involve reduction of FeO and SiO 2 to Fe and Fe-Si metal, and oxidation of metallic Al to Al 2 O 3 , occurring where silicate melt was in contact with Al-Cu-Fe alloys. In the reaction zone, there are metallic Fe and Fe-Si beads, aluminous spinel rinds on the Al-Cu-Fe alloys, and Al 2 O 3 enrichment in the silicate melt surrounding the alloys. From this and other evidence, we demonstrate that Khatyrka must have experienced at least two distinct events: first, an event as early as 4.564 Ga in which the first Al-Cu-Fe alloys formed; and, second, a more recent impact-induced shock in space that led to transformations of and reactions between the alloys and the meteorite matrix. The new evidence firmly establishes that the Al-Cu-Fe alloys (including quasicrystals) formed in outer space in a complex, multi-stage process.

Microstructure and Mechanical Properties of Highly Alloyed FeCrMoVC Steel Fabricated by Spark Plasma Sintering

NASA Astrophysics Data System (ADS)

Oh, Seung-Jin; Jun, Joong-Hwan; Lee, Min-Ha; Shon, In-Jin; Lee, Seok-Jae

2018-05-01

In this study, we successfully fabricated highly alloyed FeCrMoVC specimens within 2 min by using the spark plasma sintering (SPS) method. The densities of the sintered specimens were almost identical to their theoretical values. Fine (Mo, V)-rich carbides with lamellar structure were precipitated along the grain boundaries of the as-sintered specimen, whereas relatively large carbides were formed additionally in the transgranular region during the tempering treatment. Compared with the specimen produced by a conventional casting method, the FeCrMoVC specimens from SPS showed smaller grain size with finer carbides and higher hardness values.

The role of impurity ions in the formation of phase composition of Norilsk ore types

NASA Astrophysics Data System (ADS)

Mashukov, Anatoly; Mashukova, Alla

2013-04-01

Using the methods of X-ray and Mössbauer spectroscopy, scanning electron microscopy, there were studied the samples of Norilsk ore types in order to identify compounds containing Cu and Ni. Depending on elemental composition there were singled out two sample series. Maximum concentration in percentage of selected elements for this series is presented below. 1: Ni (0), Cu (0,42), S (11,2), O (20,2), H (0.02), Fe(46,8), Ca (5,85), Mg (1,75), K (0,47), Na (0). 2: Ni (4,93), Cu (0), S (14,9), O (27,1), H (0,11), Fe (28,1), Ca (14,9), Mg (0), K (0), Na (1,61). The research conducted by using the method of scanning electron microscopy and the X-ray microanalysis showed that iron and sulfur are spread uniformly over the scanned area. Sulfur is absent in the inclusions containing Fe and Ni. There are areas, sizes 8 - 120 microns, strongly enriched by Fe. The inclusions of rectangular and rhomboid shapes sizes 8 - 15 microns contain Ni as the content of Fe increases. There were identified the inclusions having a high content of Cu, with a maximum concentration of Ni. The presence of native elements testifies to the reducing mode of ore formation processes. The phases, containing Cu ? Ni, have a complex composition: pentlandite (FeNiS2), chalcopyrite (CuFeS2), bornite (CuFeS4), nickelhexahydrite (NiSO4 [6H2O]), wroewolfeite (Cu4 (OH) 6 (SO4) • 2H2O), pyrrhotine (Fe7S8), pyrite (FeS2). The position of the absorption lines in the magnetically ordered areas indicates the presence of stoichiometric FeS and CuFeS2. Some of the samples of this group have broadened lines, indicating the existence of various positions of the Fe ions in the sublattices. The ingrowths of CuFeS2 are characterized by the degree of the structure defectiveness, by various impurities, which is reflected in the studied parameters. As regards the other sample series, containing FeS and CuFeS2 in pyrrhotine matrix of Fe 1-xSx, the spectra are the superposition of the unsolved doublet, which shows the presence of paramagnetic areas. The magnetic phase has the spectrum composed of two six-linear spectrums. The peaks on the spectrum borders show the oxide presence. The isomer shifts of the samples range from 0 to 1.394 mm/s, quadrupole splitting ranges from 0 to 2.688 mm/s. This indicates that the local electronic structure depends on the genesis of compounds. Thus, most of the bulk of Cu, Ni is not dissipated in the crystal lattices of the ore, but it is part of the ore sulphides. The presence of the characteristic structures of the solid solutions decomposition shows a wide temperature range of sulphide crystallization.

Fabrication of Fe{sub 3}O{sub 4}@CuO core-shell from MOF based materials and its antibacterial activity

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

Rajabi, S.K.; Sohrabnezhad, Sh., E-mail: sohrabnezhad@guilan.ac.ir; Ghafourian, S.

Magnetic Fe{sub 3}O{sub 4}@CuO nanocomposite with a core/shell structure was successfully synthesized via direct calcinations of magnetic Fe{sub 3}O{sub 4}@HKUST-1 in air atmosphere. The morphology, structure, magnetic and porous properties of the as-synthesized nano composites were characterized by using scanning electron microscope (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), and vibration sample magnetometer (VSM). The results showed that the nanocomposite material included a Fe{sub 3}O{sub 4} core and a CuO shell. The Fe{sub 3}O{sub 4}@CuO core-shell can be separated easily from the medium by a small magnet. The antibacterial activity of Fe{sub 3}O{sub 4}-CuO core-shell was investigated againstmore » gram-positive and gram-negative bacteria. A new mechanism was proposed for inactivation of bacteria over the prepared sample. It was demonstrated that the core-shell exhibit recyclable antibacterial activity, acting as an ideal long-acting antibacterial agent. - Graphical abstract: Fe{sub 3}O{sub 4}@CuO core-shell release of copper ions. These Cu{sup 2+} ions were responsible for the exhibited antibacterial activity. - Highlights: • The Fe{sub 3}O{sub 4}@CuO core-shell was prepared by MOF method. • This is the first study of antibacterial activity of core-shell consist of CuO and Fe{sub 3}O{sub 4}. • The core-shell can be reused effectively. • Core-shell was separated from the reaction solution by external magnetic field.« less

Environmental application of millimeter-scale sponge iron (s-Fe(0)) particles (II): the effect of surface copper.

PubMed

Ju, Yongming; Liu, Xiaowen; Liu, Runlong; Li, Guohua; Wang, Xiaoyan; Yang, Yanyan; Wei, Dongyang; Fang, Jiande; Dionysiou, Dionysios D

2015-04-28

To enhance the catalytic reactivity of millimeter-scale particles of sponge iron (s-Fe(0)), Cu(2+) ions were deposited on the surface of s-Fe(0) using a simple direct reduction reaction, and the catalytic properties of the bimetallic system was tested for removal of rhodamine B (RhB) from an aqueous solution. The influence of Cu(0) loading, catalyst dosage, particle size, initial RhB concentration, and initial pH were investigated, and the recyclability of the catalyst was also assessed. The results demonstrate that the 3∼5 millimeter s-Fe(0) particles (s-Fe(0)(3∼5mm)) with 5wt% Cu loading gave the best results. The removal of RhB followed two-step, pseudo-first-order reaction kinetics. Cu(0)-s-Fe(0) showed excellent stability after five reuse cycles. Cu(0)-s-Fe(0) possesses great advantages compared to nanoscale zero-valent iron, iron power, and iron flakes as well as its bimetals. The surface Cu(0) apparently catalyzes the production of reactive hydrogen atoms for indirect reaction and generates Fe-Cu galvanic cells that enhance electron transfer for direct reaction. This bimetallic catalyst shows great potential for the pre-treatment of recalcitrant wastewaters. Additionally, some oxides containing iron element are selected to simulate the adsorption process. The results prove that the adsorption process of FeOOH, Fe2O3 and Fe3O4 played minor role for the removal of RhB. Copyright © 2015 Elsevier B.V. All rights reserved.

The bioinformatics of nucleotide sequence coding for proteins requiring metal coenzymes and proteins embedded with metals

NASA Astrophysics Data System (ADS)

Tremberger, G.; Dehipawala, Sunil; Cheung, E.; Holden, T.; Sullivan, R.; Nguyen, A.; Lieberman, D.; Cheung, T.

2015-09-01

All metallo-proteins need post-translation metal incorporation. In fact, the isotope ratio of Fe, Cu, and Zn in physiology and oncology have emerged as an important tool. The nickel containing F430 is the prosthetic group of the enzyme methyl coenzyme M reductase which catalyzes the release of methane in the final step of methano-genesis, a prime energy metabolism candidate for life exploration space mission in the solar system. The 3.5 Gyr early life sulfite reductase as a life switch energy metabolism had Fe-Mo clusters. The nitrogenase for nitrogen fixation 3 billion years ago had Mo. The early life arsenite oxidase needed for anoxygenic photosynthesis energy metabolism 2.8 billion years ago had Mo and Fe. The selection pressure in metal incorporation inside a protein would be quantifiable in terms of the related nucleotide sequence complexity with fractal dimension and entropy values. Simulation model showed that the studied metal-required energy metabolism sequences had at least ten times more selection pressure relatively in comparison to the horizontal transferred sequences in Mealybug, guided by the outcome histogram of the correlation R-sq values. The metal energy metabolism sequence group was compared to the circadian clock KaiC sequence group using magnesium atomic level bond shifting mechanism in the protein, and the simulation model would suggest a much higher selection pressure for the energy life switch sequence group. The possibility of using Kepler 444 as an example of ancient life in Galaxy with the associated exoplanets has been proposed and is further discussed in this report. Examples of arsenic metal bonding shift probed by Synchrotron-based X-ray spectroscopy data and Zn controlled FOXP2 regulated pathways in human and chimp brain studied tissue samples are studied in relationship to the sequence bioinformatics. The analysis results suggest that relatively large metal bonding shift amount is associated with low probability correlation R-sq outcome in the bioinformatics simulation.

Photo Degradation of Methyl Orange by Persulfate Activated with Zero Valent Iron

NASA Astrophysics Data System (ADS)

Munkoeva, V. A.; Sizykh, M. R.; Batoeva, A. A.

2017-11-01

The oxidative degradation of Methyl Orange (MO) subjected to direct photolysis (Solar) and various oxidative systems was studied. The comparative experiments have shown that MO conversion and mineralization increases in the following order: Solar ∼ Solar/Fe0 ∼ Solar/S2O82- < S2O82-/Fe0 < Solar/S2O82-/Fe0. The influence of the main factors (duration of exposure, the ratio of initial concentrations of MO:S2O82-:Fe0, pH and temperature of the reaction medium) on the degree of MO conversion and mineralization was studied. The optimal pH and temperature of the reaction medium were 5.8 and 25°C, respectively. The rate of MO decomposition and mineralization increased proportionally to the initial concentration of the oxidant at the molar ratios [S2O82-] :[MO] ≤ 12. Judging by the nature of the kinetic curves, a further increase of this ratio is impractical. However, an increase in the oxidant concentration had a positive effect on the degrees of conversion and mineralization of total organic carbon (TOC). Thus, at the ratios of 12:1 and 48:1, the conversion efficiency of TOC was 23 and 60 %, respectively. The optimal concentration of Fe0 was 100 mg/l.

Synthesis, spectroscopy, and binding constants of ketocatechol-containing iminodiacetic acid and its Fe(III), Cu(II), and Zn(II) complexes and reaction of Cu(II) complex with H₂O₂ in aqueous solution.

PubMed

Gao, Jiaojiao; Xing, Feifei; Bai, Yueling; Zhu, Shourong

2014-06-07

A new neuromelanin-like ketocatechol-containing iminodiacetic acid ligand, (N-(3,4-dihydroxyl)phenacylimino)diacetic acid (H4L), which is also quite similar to compounds found in insect cuticle, has been synthesized and characterized. The X-ray crystal structure of H4L has been successfully determined. Proton binding and coordination with Fe(III), Cu(II), and Zn(II) have been studied by potentiometric titrations and UV-vis spectrophotometry in aqueous solution. UV spectra of H4L in the absence and presence of different metal ions indicate complexes formed with the catechol moiety of H4L in aqueous solution. Visible spectra and NMR reveal that H4L with Fe(III), Cu(II), and Zn(II) can all give stable mono-(ML) and dinuclear complexes [M(ML)]. Fe(III) can also form {Fe(FeL)2} and {Fe(FeL)3} species with sufficient base. The process is accompanied by a drastic color change from light blue to deep-blue to wine-red. The Fe(III)-Cu(II) heteronuclear complex also exists in aqueous solution whose spectra are similar to the homonuclear Fe(III) complex. However, the spectra of {Fe(CuL)} shifted to a longer wavelength and {Fe(CuL)2} and {Fe(CuL)3} shifted to a shorter wavelength. Keto-enol tautomerism was observed in weak basic aqueous solution as indicated by (1)H NMR spectra. The reaction products of Cu(II) complex with H2O2 depend on the H2O2 concentration and pH value. Low concentrations of H2O2 oxidize H4L to a series of semiquinone and quinone compounds with absorption maxima at 314-400 nm, while a high concentration of H2O2 oxidizes H4L to colorless muconic acid derivatives. NaIO4 gives different oxidase products, but no 2,4,5-trihydroxyphenylalanine quinone (TPQ)-like hydroxyquinone can be found.

Copper-tuned magnetic order and excitations in iron-based superconductors Fe1+yTe1-xSex

NASA Astrophysics Data System (ADS)

Wen, Jinsheng; Xu, Zhijun; Xu, Guangyong; Lumsden, Mark; Matsuda, Masaaki; Valdivia, Patrick; Bourret, Edith; Lee, Dunghai; Gu, Genda; Tranquada, John; Birgeneau, Robert

2012-02-01

We report neutron scattering results on the Cu-substitution effects in the iron-based superconductors, Fe1+yTe1-xSex. In the parent compound, it is found that Cu drives the low-temperature magnetic ground state from long-range commensurate antiferromagnetic order in Fe1.06TeCu0.04 to short-range incommensurate order in FeTeCu0.1. In the former sample, the structural and magnetic ordering temperature is 40 K; in FeTeCu0.1, the structural phase transition is not obvious and a transition to the spin-glass state is found at 22 K. Cu suppresses superconductivity in FeTe0.5Se0.5---Tc is reduced to 7 K with a 2% Cu doping, and no superconductivity is found in the 10% Cu-doped sample. In the meantime, the intensity and energy of the resonance mode are suppressed in the 2% Cu-doped sample, while there is no resonance in the non-superconducting sample. Besides, the low-temperature magnetic excitation spectra are distinct for these two samples, with the superconducting one having an ``hour-glass" shape and the other one having a ``waterfall" shape. Our results provide further insights on the interplay between magnetism and superconductivity in the iron-based superconductors.

Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst

DOE PAGES

Lu, Yongwu; Yu, Fei; Hu, Jin; ...

2012-04-12

Zn-Mn promoted Cu-Fe based catalyst was synthesized by the co-precipitation method. Mixed alcohols synthesis from syngas was studied in a half-inch tubular reactor system after the catalyst was reduced. Zn-Mn promoted Cu-Fe based catalyst was characterized by SEM-EDS, TEM, XRD, and XPS. The liquid phase products (alcohol phase and hydrocarbon phase) were analyzed by GC-MS and the gas phase products were analyzed by GC. The results showed that Zn-Mn promoted Cu-Fe based catalyst had high catalytic activity and high alcohol selectivity. The maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbons were also very high. Cumore » (111) was the active site for mixed alcohols synthesis, Fe 2C (101) was the active site for olefin and paraffin synthesis. The reaction mechanism of mixed alcohols synthesis from syngas over Zn-Mn promoted Cu-Fe based catalyst was proposed. Here, Zn-Mn promoted Cu-Fe based catalyst can be regarded as a potential candidate for catalytic conversion of biomass-derived syngas to mixed alcohols.« less

Fabrication and photocatalytic property of magnetic NiFe2O4/Cu2O composites

NASA Astrophysics Data System (ADS)

He, Zuming; Xia, Yongmei; Tang, Bin; Su, Jiangbin

2017-09-01

Magnetically separable NiFe2O4/Cu2O composites were successfully synthesized by a two-step method. The samples were characterized by XRD, XPS, SEM and VSM as well as their PL spectra and UV-vis adsorption spectra. The results showed that the NiFe2O4/Cu2O composites were composed of cubic-structured Cu2O and spinel-structured NiFe2O4, were able to absorb a large amount of visible light, exhibited excellent photocatalytic activity under simulated solar light irradiation and could be easily separated by an external magnetic field. The NiFe2O4/Cu2O composites exhibited higher photocatalytic performance than that of a single semiconductor. It was found that the prominently enhanced photocatalytic performance of NiFe2O4/Cu2O composites was ascribed to the effective separation of photo-generated electron-hole pairs and the effective generation of the hydroxyl radical •OH.

Structural, electronic, and elastic properties of CuFeS2: first-principles study

NASA Astrophysics Data System (ADS)

Zhou, Meng; Gao, Xiang; Cheng, Yan; Chen, Xiangrong; Cai, Lingcang

2015-03-01

The structural, electronic, and elastic properties of CuFeS2 have been investigated by using the generalized gradient approximation (GGA), GGA + U (on-site Coulomb repulsion energy), the local density approximation (LDA), and the LDA + U approach in the frame of density functional theory. It is shown that when the GGA + U formalism is selected with a U value of 3 eV for the 3d state of Fe, the calculated lattice constants agree well with the available experimental and other theoretical data. Our GGA + U calculations indicate that CuFeS2 is a semiconductor with a band gap of 0.552 eV and with a magnetic moment of 3.64 µB per Fe atom, which are well consistent with the experimental results. Combined with the density of states, the band structure characteristics of CuFeS2 have been analyzed and their origins have been specified, which reveals a hybridization existing between Fe-3d, Cu-3s, and S-3p, respectively. The charge and Mulliken population analyses indicate that CuFeS2 is a covalent crystal. Moreover, the calculated elastic constants prove that CuFeS2 is mechanically stable but anisotropic. The bulk modulus obtained from elastic constants is 87.1 GPa, which agrees well with the experimental value of 91 ± 15 GPa and better than the theoretical bulk modulus 74 GPa obtained from GGA method by Lazewski et al. The obtained shear modulus and Debye temperature are 21.0 GPa and 287 K, respectively, and the latter accords well with the available experimental value. It is expected that our work can provide useful information to further investigate CuFeS2 from both the experimental and theoretical sides.

Enhanced thermal stability of Cu alloy films by strong interaction between Ni and Zr (or Fe)

NASA Astrophysics Data System (ADS)

Zheng, Yuehong; Li, Xiaona; Cheng, Xiaotian; Li, Zhuming; Liu, Yubo; Dong, Chuang

2018-04-01

Low resistivity, phase stability and nonreactivity with surrounding dielectrics are the key to the application of Cu to ultra-large-scale integrated circuits. Here, a stable solid solution cluster model was introduced to design the composition of barrierless Cu-Ni-Zr (or Fe) seed layers. The third elements Fe and Zr were dissolved into Cu via a second element Ni, which is soluble in both Cu and Zr (or Fe). The films were prepared by magnetron sputtering on the single-crystal p-Si (1 0 0) wafers. Since the diffusion characteristics of the alloying elements are different, the effects of the strong interaction between Ni and Zr (or Fe) on the film’s stability and resistivity were studied. The results showed that a proper addition of Zr-Ni (Zr/Ni  ⩽  0.6/12) into Cu could form a large negative lattice distortion, which inhibits Cu-Si interdiffusion and enhances the stability of Cu film. When Fe-Ni was co-added into Cu, the lattice distortion of Cu reached a lower value, 0.0029 Å  ⩽  |Δa|  ⩽  0.0046 Å, and the films showed poor stability. Therefore, when the model is applied to the composition design of the films, the strong interaction between the elements and the addition ratio should be taken into consideration.

Facile synthesis, characterization and magnetic property of CuFe12O19 nanostructures via a sol-gel auto-combustion process

NASA Astrophysics Data System (ADS)

Ansari, Fatemeh; Sobhani, Azam; Salavati-Niasari, Masoud

2016-03-01

Copper hexaferrite (CuFe12O19) nanostructures were prepared by a simple route utilizing maltose-assisted sol-gel process. The morphology, phase structure, composition and purity of nanostructures can be controlled by type of surfactant and also adjusting the Cu:surfactant, Cu:Fe and Cu:reductant ratios. The bean-shape structures are formed in the absence of the surfactant when the molar ratio of Cu:Fe and Cu:reductant are 1:12 and 1:26, respectively. The agglomerated spherical nanoparticles with diameters ranging from 7 to 20 nm are obtained in the presence of triplex, when ratio of Cu:reductant is 1:26. In the absence of surfactant and also in the presence of triplex, the samples are found to be CuFe12O19. When polymer is used, there are still the peaks of CuFe12O19 and also some boad peaks in XRD patterns, because of the small size and encapsulation of nanostructures with polymer. Magnetic measurments show superparamagnetic behavior for the all samples. The Ms for the samples obtained in the presence of polymer shows that the coating of magnetic nanostructures does not always increase Ms. FT-IR frequency bands in the range 463-626, 607 and 542 cm-1 correspond to the formation of metal oxides in ferrites.

The dynamics of copper intercalated molybdenum ditelluride

NASA Astrophysics Data System (ADS)

Onofrio, Nicolas; Guzman, David; Strachan, Alejandro

2016-11-01

Layered transition metal dichalcogenides are emerging as key materials in nanoelectronics and energy applications. Predictive models to understand their growth, thermomechanical properties, and interaction with metals are needed in order to accelerate their incorporation into commercial products. Interatomic potentials enable large-scale atomistic simulations connecting first principle methods and devices. We present a ReaxFF reactive force field to describe molybdenum ditelluride and its interactions with copper. We optimized the force field parameters to describe the energetics, atomic charges, and mechanical properties of (i) layered MoTe2, Mo, and Cu in various phases, (ii) the intercalation of Cu atoms and small clusters within the van der Waals gap of MoTe2, and (iii) bond dissociation curves. The training set consists of an extensive set of first principles calculations computed using density functional theory (DFT). We validate the force field via the prediction of the adhesion of a single layer MoTe2 on a Cu(111) surface and find good agreement with DFT results not used in the training set. We characterized the mobility of the Cu ions intercalated into MoTe2 under the presence of an external electric field via finite temperature molecular dynamics simulations. The results show a significant increase in drift velocity for electric fields of approximately 0.4 V/Å and that mobility increases with Cu ion concentration.

β-K3Fe(MoO4)2Mo2O7

PubMed Central

Souilem, Amira; Zid, Mohamed Faouzi; Driss, Ahmed

2014-01-01

The title compound, tripotassium iron(III) bis­(ortho­molyb­date) dimolybdate, was obtained by a solid-state reaction. The main structural building units are one FeO6 octa­hedron, two MoO4 tetra­hedra and one Mo2O7 dimolybdate group, all with point group symmetries m. These units are linked via corner-sharing to form ribbons parallel to [010]. The three K+ cations are located between the ribbons on mirror planes and have coordination numbers of 10 and 12. Two O atoms of one of the MoO4 tetra­hedra of the dimolybdate group are disordered over two positions in a 0.524 (11):0.476 (11) ratio. The structure of the title compound is compared briefly with that of Rb3FeMo4O15. PMID:25161509

Influence of trace elements mixture on bacterial diversity and fermentation characteristics of liquid diet fermented with probiotics under air-tight condition.

PubMed

He, Yuyong; Chen, Zhiyu; Liu, Xiaolan; Wang, Chengwei; Lu, Wei

2014-01-01

Cu2+, Zn2+, Fe2+ and I- are often supplemented to the diet of suckling and early weaning piglets, but little information is available regarding the effects of different Cu2+, Zn2+, Fe2+ and I- mixtures on bacteria growth, diversity and fermentation characteristics of fermented liquid diet for piglets. Pyrosequencing was performed to investigate the effect of Cu2+, Zn2+, Fe2+ and I- mixtures on the diversity, growth and fermentation characteristics of bacteria in the liquid diet fermented with Bacillus subtilis and Enterococcus faecalis under air-tight condition. Results showed that the mixtures of Cu2+, Zn2+, Fe2+ and I- at different concentrations promoted Bacillus growth, increased bacterial diversity and lactic acid production and lowered pH to about 5. The importance of Cu2+, Zn2+, Fe2+ and I- is different for Bacillus growth with the order Zn2+> Fe2+>Cu2+> I- in a 21-d fermentation and Cu2+>I->Fe2+>Zn2+ in a 42-d fermentation. Cu2+, Zn2+, Fe2+ and I- is recommended at a level of 150, 60, 150 and 0.6 mg/kg respectively for the production of fermented liquid diet with Bacillus subtilis. The findings improve our understanding of the influence of trace elements on liquid diet fermentation with probiotics and support the proper use of trace elements in the production of fermented liquid diet for piglets.

Magnetization reversal process and evaluation of thermal stability factor in Cu doped granular L10 FePt films

NASA Astrophysics Data System (ADS)

Jain, S.; Papusoi, C.; Admana, R.; Yuan, H.; Acharya, R.

2018-05-01

Curie temperature TC distributions and magnetization reversal mechanism in Cu doped L10 FePt granular films is investigated as a function of film thickness in the range of ˜5-12 nm with Cu mol. % varying in the range of 0%-6%. It is shown that Cu doping increases the FePt tetragonality and chemical ordering. For Cu doped FePt-X films, coercivity (HC) exhibits a non-monotonic behavior with increasing film thickness, i.e., HC increases initially up to tcr ˜ 7 nm, and decreases thereafter. We attribute this behavior to the change in magnetization reversal mechanism from coherent to an incoherent (domain-wall driven) mode. While in un-doped films, the domain-walls nucleate at the grain boundaries, in doped films the Cu atoms may act as domain-wall nucleation and pinning sites, isolating magnetic spin clusters of reduced dimensionality with respect to the physical grain size. This is experimentally supported by a much poorer dependence of the AC susceptibility (both, real and imaginary components) on the film thickness above 7 nm than in the case of un-doped films. The formation of magnetic spin clusters inside the grains as a consequence of the reduced coupling between Fe-Fe and Fe-Pt-Fe atoms with increasing Cu doping can explain the experimentally evidenced reduction of both, the film Curie temperature, TC, and intrinsic anisotropy energy density, KC, with increasing Cu doping.

Possibility to Use Hydrothermally Synthesized CuFeS2 Nanocomposite as an Acceptor in Hybrid Solar Cell

NASA Astrophysics Data System (ADS)

Sil, Sayantan; Dey, Arka; Halder, Soumi; Datta, Joydeep; Ray, Partha Pratim

2018-01-01

Here we have approached the plausible use of CuFeS2 nanocomposite as an acceptor in organic-inorganic hybrid solar cell. To produce CuFeS2 nanocomposite, hydrothermal strategy was employed. The room-temperature XRD pattern approves the synthesized material as CuFeS2 with no phase impurity (JCPDS Card no: 37-0471). The elemental composition of the material was analyzed from the TEM-EDX data. The obtained selected area electron diffraction (SAED) planes harmonized with the XRD pattern of the synthesized product. Optical band gap (4.14 eV) of the composite from UV-Vis analysis depicts that the synthesized material is belonging to wide band gap semiconductor family. The HOMO (- 6.97 eV) and LUMO (- 2.93 eV) positions from electrochemical study reveal that there is a possibility of electron transfer from MEH-PPV to CuFeS2. The optical absorption and photoluminescence spectra of MEH-PPV:CuFeS2 (donor:acceptor) composite were recorded sequentially by varying weight ratios. The monotonic blue shifting of the absorption peak position indicated the interaction between donor and acceptor materials. The possibility of electron transfer from donor (MEH-PPV) to acceptor (CuFeS2) was approved with photoluminescence analysis. Subsequently, we have fabricated a hybrid solar cell by incorporating CuFeS2 nanocomposite with MEH-PPV in open atmosphere and obtained 0.3% power conversion efficiency.

Covalent Electron Transfer Theory of Superconductivity

DTIC Science & Technology

1992-06-19

carriers. This situation is analogous to a vacuum diode without space charge, where each electron emitted from the cathode arrives at the anode before...Generic MO energy level diagram for a do cation in an oxygen octahedral complex. 89 53 Band model approximation of the MO states of a Cu perovskite ...C2) CuO4 complex. 94 57 p-type 3d 2,2-2p a Cu2+-O-Cu3+ covalent transfer in I 80-deg perovskite bond 95 geometry for d9 - d8(low-spin). xi LIST OF