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Sample records for minewaste,acidminedrainage,suspendedmatter,Fe-oxyhydroxides

  1. Kinetics of microbial Fe(III) oxyhydroxide reduction : The role of mineral properties

    NARCIS (Netherlands)

    Bonneville, S.C.

    2005-01-01

    In many soils, sediments and groundwaters, ferric iron is a major potential electron acceptor for the oxidation of organic matter. In contrast to other terminal electron acceptors (e.g. nitrate or sulfate), the concentration of Fe3+(aq), is limited by the low solubility of Fe(III) oxyhydroxides

  2. Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Goldsmith, Zachary K.; Harshan, Aparna K.; Gerken, James B.; Vörös, Márton; Galli, Giulia; Stahl, Shannon S.; Hammes-Schiffer, Sharon

    2017-03-06

    NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast, absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni2+ to Ni3+, followed by oxidation to a mixed Ni3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fedoped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixedmetal oxidation states in heterogeneous catalysts.

  3. Nanoscale Titanium Dioxide (nTiO2) Transport in Water-Saturated Natural Sediments: Influence of Soil Organic Matter and Fe/Al Oxyhydroxides

    Science.gov (United States)

    Fisher-Power, L.; Cheng, T.

    2017-12-01

    Transport of engineered nanoparticles (ENP) in subsurface environments has important implications to water quality and soil contamination. Although extensive research has been conducted to understand the effects of water chemistry on ENP transport, less attention has been paid to influences from the transport medium/matrix. The objective of this research is to investigate the effects of natural organic matter (NOM) and Fe/Al oxyhydroxides in a natural sediment on ENP transport. A sediment was collected and separated into four portions, one of which was unmodified, and the others treated to remove specific components (organic matter, Fe/Al oxyhydroxides, or both organic matter and Fe/Al oxyhydroxides). Transport of nanoscale titanium dioxide (nTiO2) in columns packed with quartz sand and each of the four types of the sediment under water-saturated conditions was studied. Our results showed that nTiO2 transport was strongly influenced by pH and sediment composition. When influent pH = 5, nTiO2 transport in all the sediments was low, as positively-charged nTiO2 was attracted to negatively charged NOM, quartz, and other minerals. nTiO2 transport was slightly enhanced in columns packed with untreated sediment or Fe/Al oxyhydroxides removed sediment due to dissolved organic matter generated by the partial dissolution of NOM, which adsorbed onto nTiO2 surface and reversed its zeta potential to negative. When influent pH = 9, nTiO2 transport was generally high since negatively-charged nTiO2 was repelled by negatively charged transport medium. However, in columns packed with the organic matter removed sediment or the Fe/Al oxyhydroxides removed sediment, nTiO2 transport was low. This was attributable to pH buffering by the sediment, which decreased pore water pH in the column, resulting in zeta potential change and electrostatic attraction between Fe/Al oxyhydroxides and nTiO2. This research demonstrates that electrostatic forces between nTiO2 and mineral/organic components

  4. Structural Properties of the Cr(III)-Fe(III) (Oxy)Hydroxide Compositional Series: Insights for a Nanomaterial 'Solid Solution'

    International Nuclear Information System (INIS)

    Tang, Y.; Zhang, L.; Michel, F.M.; Harrington, R.; Parise, J.B.; Reeder, R.J.

    2010-01-01

    Chromium(III) (oxy)hydroxide and mixed Cr(III)-Fe(III) (oxy)hydroxides are environmentally important compounds for controlling chromium speciation and bioaccessibility in soils and aquatic systems and are also industrially important as precursors for materials and catalyst synthesis. However, direct characterization of the atomic arrangements of these materials is complicated because of their amorphous X-ray properties. This study involves synthesis of the complete Cr(III)-Fe(III) (oxy)hydroxide compositional series, and the use of complementary thermal, microscopic, spectroscopic, and scattering techniques for the evaluation of their structural properties. Thermal analysis results show that the Cr end member has a higher hydration state than the Fe end member, likely associated with the difference in water exchange rates in the first hydration spheres of Cr(III) and Fe(III). Three stages of weight loss are observed and are likely related to the loss of surface/structural water and hydroxyl groups. As compared to the Cr end member, the intermediate composition sample shows lower dehydration temperatures and a higher exothermic transition temperature. XANES analysis shows Cr(III) and Fe(III) to be the dominant oxidation states. XANES spectra also show progressive changes in the local structure around Cr and Fe atoms over the series. Pair distribution function (PDF) analysis of synchrotron X-ray total scattering data shows that the Fe end member is nanocrystalline ferrihydrite with an intermediate-range order and average coherent domain size of ∼27 (angstrom). The Cr end member, with a coherent domain size of ∼10 (angstrom), has only short-range order. The PDFs show progressive structural changes across the compositional series. High-resolution transmission electron microscopy (HRTEM) results also show the loss of structural order with increasing Cr content. These observations provide strong structural evidence of chemical substitution and progressive structural

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

    Science.gov (United States)

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

    2017-08-01

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

  6. FeII induced mineralogical transformations of ferric oxyhydroxides into magnetite of variable stoichiometry and morphology

    International Nuclear Information System (INIS)

    Usman, M.; Abdelmoula, M.; Hanna, K.

    2012-01-01

    The Mössbauer spectroscopy was used to monitor the mineralogical transformations of ferrihydrite (F), lepidocrocite (L) and goethite (G) into magnetite as a function of aging time. Ferric oxyhydroxides were reacted with soluble Fe II and OH – in stoichiometric amounts to form magnetite at an initial pH of ∼9.7. Observed transformation extent into magnetite followed the order: F>L>G with almost 30% of untransformed G after 1 month. The departure from stoichiometry, δ, of magnetite (Fe 3−δ O 4 ) generated from F (δ∼0.04) and L (δ∼0.05) was relatively low as compared to that in magnetite from G (δ∼0.08). The analysis by transmission electron microscopy and BET revealed that generated magnetite was also different in terms of morphology, particle size and surface area depending on the nature of initial ferric oxyhydroxide. This method of preparation is a possible way to form nano-sized magnetite. - Graphical abstract: Mössbauer spectrum of the early stage of magnetite formation formed from the interaction of adsorbed Fe II species with goethite. Highlights: ► Ferric oxides were reacted with hydroxylated Fe II to form magnetite. ► Magnetite formation was quantified as a function of aging time. ► Complete transformation of ferrihydrite and lepidocrocite was achieved. ► Almost 70% of initial goethite was transformed. ► Resulting magnetites have differences in stoichiometry and morphological properties.

  7. Biogenic iron oxyhydroxide formation at mid-ocean ridge hydrothermal vents: Juan de Fuca Ridge

    Energy Technology Data Exchange (ETDEWEB)

    Toner, Brandy M.; Santelli, Cara M.; Marcus, Matthew A.; Wirth, Richard; Chan, Clara S.; McCollom, Thomas; Bach, Wolfgang; Edwards, Katrina J.

    2008-05-22

    Here we examine Fe speciation within Fe-encrusted biofilms formed during 2-month seafloor incubations of sulfide mineral assemblages at the Main Endeavor Segment of the Juan de Fuca Ridge. The biofilms were distributed heterogeneously across the surface of the incubated sulfide and composed primarily of particles with a twisted stalk morphology resembling those produced by some aerobic Fe-oxidizing microorganisms. Our objectives were to determine the form of biofilm-associated Fe, and identify the sulfide minerals associated with microbial growth. We used micro-focused synchrotron-radiation X-ray fluorescence mapping (mu XRF), X-ray absorption spectroscopy (mu EXAFS), and X-ray diffraction (mu XRD) in conjunction with focused ion beam (FIB) sectioning, and highresolution transmission electron microscopy (HRTEM). The chemical and mineralogical composition of an Fe-encrusted biofilm was queried at different spatial scales, and the spatial relationship between primary sulfide and secondary oxyhydroxide minerals was resolved. The Fe-encrusted biofilms formed preferentially at pyrrhotite-rich (Fe1-xS, 0<_ x<_ 0.2) regions of the incubated chimney sulfide. At the nanometer spatial scale, particles within the biofilm exhibiting lattice fringing and diffraction patterns consistent with 2-line ferrihydrite were identified infrequently. At the micron spatial scale, Fe mu EXAFS spectroscopy and mu XRD measurements indicate that the dominant form of biofilm Fe is a short-range ordered Fe oxyhydroxide characterized by pervasive edge-sharing Fe-O6 octahedral linkages. Double corner-sharing Fe-O6 linkages, which are common to Fe oxyhydroxide mineral structures of 2-line ferrihydrite, 6-line ferrihydrite, and goethite, were not detected in the biogenic iron oxyhydroxide (BIO). The suspended development of the BIO mineral structure is consistent with Fe(III) hydrolysis and polymerization in the presence of high concentrations of Fe-complexing ligands. We hypothesize that

  8. Biogenic iron oxyhydroxide formation at mid-ocean ridge hydrothermal vents: Juan de Fuca Ridge

    International Nuclear Information System (INIS)

    Toner, Brandy M.; Santelli, Cara M.; Marcus, Matthew A.; Wirth, Richard; Chan, Clara S.; McCollom, Thomas; Bach, Wolfgang; Edwards, Katrina J.

    2008-01-01

    Here we examine Fe speciation within Fe-encrusted biofilms formed during 2-month seafloor incubations of sulfide mineral assemblages at the Main Endeavor Segment of the Juan de Fuca Ridge. The biofilms were distributed heterogeneously across the surface of the incubated sulfide and composed primarily of particles with a twisted stalk morphology resembling those produced by some aerobic Fe-oxidizing microorganisms. Our objectives were to determine the form of biofilm-associated Fe, and identify the sulfide minerals associated with microbial growth. We used micro-focused synchrotron-radiation X-ray fluorescence mapping (mu XRF), X-ray absorption spectroscopy (mu EXAFS), and X-ray diffraction (mu XRD) in conjunction with focused ion beam (FIB) sectioning, and high-resolution transmission electron microscopy (HRTEM). The chemical and mineralogical composition of an Fe-encrusted biofilm was queried at different spatial scales, and the spatial relationship between primary sulfide and secondary oxyhydroxide minerals was resolved. The Fe-encrusted biofilms formed preferentially at pyrrhotite-rich (Fe 1-x S, 0 (le) x (le) 0.2) regions of the incubated chimney sulfide. At the nanometer spatial scale, particles within the biofilm exhibiting lattice fringing and diffraction patterns consistent with 2-line ferrihydrite were identified infrequently. At the micron spatial scale, Fe mu EXAFS spectroscopy and mu XRD measurements indicate that the dominant form of biofilm Fe is a short-range ordered Fe oxyhydroxide characterized by pervasive edge-sharing Fe-O 6 octahedral linkages. Double corner-sharing Fe-O 6 linkages, which are common to Fe oxyhydroxide mineral structures of 2-line ferrihydrite, 6-line ferrihydrite, and goethite, were not detected in the biogenic iron oxyhydroxide (BIO). The suspended development of the BIO mineral structure is consistent with Fe(III) hydrolysis and polymerization in the presence of high concentrations of Fe-complexing ligands. We hypothesize that

  9. Iron oxyhydroxide mineralization on microbial extracellular polysaccharides

    Energy Technology Data Exchange (ETDEWEB)

    Chan, Clara S.; Fakra, Sirine C.; Edwards, David C.; Emerson, David; Banfield, Jillian F.

    2010-06-22

    Iron biominerals can form in neutral pH microaerophilic environments where microbes both catalyze iron oxidation and create polymers that localize mineral precipitation. In order to classify the microbial polymers that influence FeOOH mineralogy, we studied the organic and mineral components of biominerals using scanning transmission X-ray microscopy (STXM), micro X-ray fluorescence ({mu}XRF) microscopy, and high-resolution transmission electron microscopy (HRTEM). We focused on iron microbial mat samples from a creek and abandoned mine; these samples are dominated by iron oxyhydroxide-coated structures with sheath, stalk, and filament morphologies. In addition, we characterized the mineralized products of an iron-oxidizing, stalk-forming bacterial culture isolated from the mine. In both natural and cultured samples, microbial polymers were found to be acidic polysaccharides with carboxyl functional groups, strongly spatially correlated with iron oxyhydroxide distribution patterns. Organic fibrils collect FeOOH and control its recrystallization, in some cases resulting in oriented crystals with high aspect ratios. The impact of polymers is particularly pronounced as the materials age. Synthesis experiments designed to mimic the biomineralization processes show that the polysaccharide carboxyl groups bind dissolved iron strongly but release it as mineralization proceeds. Our results suggest that carboxyl groups of acidic polysaccharides are produced by different microorganisms to create a wide range of iron oxyhydroxide biomineral structures. The intimate and potentially long-term association controls the crystal growth, phase, and reactivity of iron oxyhydroxide nanoparticles in natural systems.

  10. Comparison study on transformation of iron oxyhydroxides: Based on theoretical and experimental data

    International Nuclear Information System (INIS)

    Lu Bin; Guo Hui; Li Ping; Liu Hui; Wei Yu; Hou Denglu

    2011-01-01

    We have investigated the catalytic transformation of ferrihydrite, feroxyhyte, and lepidocrocite in the presence of Fe(II). In this paper, the transformation from akaganeite and goethite to hematite in the presence of trace Fe(II) was studied in detail. The result indicates that trace Fe(II) can accelerate the transformation of akaganeite and goethite. Compared with the transformation of other iron oxyhydroxides (e.g., ferrihydrite, feroxyhyte, lepidocrocite, and akaganeite), a complete transformation from goethite to hematite was not observed in the presence of Fe(II). On the basis of our earlier and present experimental results, the transformation of various iron oxyhydroxides was compared based on their thermodynamic stability, crystalline structure, transformation mechanism, and transformation time. - Graphical abstract: The transformation of various iron oxyhydroxides in the presence of trace Fe(II) was compared based on experimental results, thermodynamic stability, crystalline structure, and transformation mechanism. Highlights: → Fe(II) can accelerate the transformation from akaganeite to hematite. → Small particles of goethite can transform to hematite in the presence of Fe(II). → Some hematite particles were found to be embedded within the crystal of goethite. → The relationship between structure and transformation mechanism was revealed.

  11. Reactivity of Uranium and Ferrous Iron with Natural Iron Oxyhydroxides.

    Science.gov (United States)

    Stewart, Brandy D; Cismasu, A Cristina; Williams, Kenneth H; Peyton, Brent M; Nico, Peter S

    2015-09-01

    Determining key reaction pathways involving uranium and iron oxyhydroxides under oxic and anoxic conditions is essential for understanding uranium mobility as well as other iron oxyhydroxide mediated processes, particularly near redox boundaries where redox conditions change rapidly in time and space. Here we examine the reactivity of a ferrihydrite-rich sediment from a surface seep adjacent to a redox boundary at the Rifle, Colorado field site. Iron(II)-sediment incubation experiments indicate that the natural ferrihydrite fraction of the sediment is not susceptible to reductive transformation under conditions that trigger significant mineralogical transformations of synthetic ferrihydrite. No measurable Fe(II)-promoted transformation was observed when the Rifle sediment was exposed to 30 mM Fe(II) for up to 2 weeks. Incubation of the Rifle sediment with 3 mM Fe(II) and 0.2 mM U(VI) for 15 days shows no measurable incorporation of U(VI) into the mineral structure or reduction of U(VI) to U(IV). Results indicate a significantly decreased reactivity of naturally occurring Fe oxyhydroxides as compared to synthetic minerals, likely due to the association of impurities (e.g., Si, organic matter), with implications for the mobility and bioavailability of uranium and other associated species in field environments.

  12. Accessible reactive surface area and abiotic redox reactivity of iron oxyhydroxides in acidic brines

    Science.gov (United States)

    Strehlau, Jennifer H.; Toner, Brandy M.; Arnold, William A.; Penn, R. Lee

    2017-01-01

    The reactivity of iron oxyhydroxide nanoparticles in low pH and high ionic strength solutions was quantified to assess abiotic contributions to oxidation-reduction chemistry in acidic brine environments, such as mine groundwater seepage, lakes in Western Australia, and acid mine drainage settings, which are of global interest for their environmental impacts and unique geomicrobiology. Factors expected to influence accessible and reactive surface area, including Fe(II) adsorption and aggregate size, were measured as a function of pH and CaCl2 concentration and related to the kinetics of redox reactions in aqueous suspensions of synthetic goethite (α-FeOOH), akaganeite (β-FeOOH), and ferrihydrite (Fe10O14(OH)2) nanoparticles. Aqueous conditions and iron oxyhydroxides were chosen based on characterization of natural iron-rich mine microbial mats located in Soudan Underground Mine State Park, Minnesota, USA. Quinone species were used as redox sensors because they are well-defined probes and are present in natural organic matter. Fe(II) adsorption to the iron oxyhydroxide mineral surfaces from aqueous solution was measurable only at pH values above 4 and either decreased or was not affected by CaCl2 concentration. Concentrations at or above 0.020 M CaCl2 in acetate buffer (pH 4.5) induced particle aggregation. Assessment of Fe(II) adsorption and particle aggregation in acidic brine suggested that accessible reactive surface area may be limited in acidic brines. This was supported by observations of decreasing benzoquinone reduction rate by adsorbed Fe(II) at high CaCl2 concentration. In contrast, the hydroquinone oxidation rate increased at high CaCl2 concentrations, which may be due to suppressed adsorption of Fe(II) generated by the reaction. Results suggest that iron geochemical cycling in acidic brine environments will be substantially different than for iron oxyhydroxides in low-saline waters with circumneutral pH. These findings have implications for acidic

  13. The reduction of 4-chloronitrobenzene by Fe(II)-Fe(III) oxide systems - correlations with reduction potential and inhibition by silicate

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Adele M., E-mail: adele.jones1@unsw.edu.au; Kinsela, Andrew S.; Collins, Richard N.; Waite, T. David, E-mail: d.waite@unsw.edu.au

    2016-12-15

    Recent studies have demonstrated that the rate at which Fe(II)-Fe(III) oxyhydroxide systems catalyze the reduction of reducible contaminants, such as 4-chloronitrobenzene, is well correlated to their thermodynamic reduction potential. Here we confirm this effect in the presence of Fe(III) oxyhydroxide phases not previously assessed, namely ferrihydrite and nano-goethite, as well as Fe(III) oxyhydroxide phases previously examined. In addition, silicate is found to decrease the extent of Fe(II) sorption to the Fe(III) oxyhydroxide surface, increasing the reduction potential of the Fe(II)-Fe(III) oxyhydroxide suspension and, accordingly, decreasing the rate of 4-chloronitrobenzene reduction. A linear relationship between the reduction potential of the Fe(II)-Fe(III) oxyhydroxide suspensions and the reduction rate of 4-chloronitrobenzene (normalized to surface area and concentration of sorbed Fe(II)) was obtained in the presence and absence of silicate. However, when ferrihydrite was doped with Si (through co-precipitation) the reduction of 4-chloronitrobenzene was much slower than predicted from its reduction potential. The results obtained have significant implications to the likely effectiveness of naturally occurring contaminant degradation processes involving Fe(II) and Fe(III) oxyhydroxides in groundwater environments containing high concentrations of silicate, or other species which compete with Fe(II) for sorption sites.

  14. Synthesis of LiFePO{sub 4}/polyacenes using iron oxyhydroxide as an iron source

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Guiling; Zhang, Xianfa; Liu, Jing; He, Xingguang; Wang, Jiawei; Xie, Haiming; Wang, Rongshun [Institute of Functional Materials, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024 (China); LIB Engineering Laboratory, Materials Science and Technology Center, Changchun, Jilin 130024 (China)

    2010-02-15

    LiFePO{sub 4}/polyacenes (PAS) composite is synthesized by iron oxyhydroxide as a new raw material and phenol-formaldehyde resin as both reducing agent and carbon source. The mechanism of the reaction is outlined by the analysis of XRD, FTIR as well as TG/DSC. The results show that the formation of LiFePO{sub 4} is started at 300 C, and above 550 C, the product can be mainly ascribed to olivine LiFePO{sub 4}. The electrochemical properties of the synthesized composites are investigated by charge-discharge tests. It is found that the prepared sample at 750 C (S750) has a better electrochemical performance than samples prepared at other temperatures. A discharge capacity of 158 mAh g{sup -1} is delivered at 0.2 C. Under high discharge rate of 10 C, a discharge capacity of 145 mAh g{sup -1} and good capacity retention of 93% after 800 cycles are achieved. The morphology of S750 and PAS distribution in it are investigated by SEM and TEM. (author)

  15. Mechanism of pyrrhotite formation from ferric oxyhydroxide catalyst; Kokoritsu sekitan ekika shokubai no kaihatsu (Okishi suisankatetsu shokubai karano pyrrhotite seisei kyodo)

    Energy Technology Data Exchange (ETDEWEB)

    Tazawa, K.; Koyama, T.; Kaneko, T.; Shimasaki, K. [Nippon Brown Coal Liquefaction Co. Ltd., Tokyo (Japan)

    1996-10-28

    It is thought that iron-based catalysts for coal liquefaction exercise their catalytic activity by forming pyrrhotite (Fe(1-x)S). However, there are still a lot of unknown problems remained concerning the formation and agglomeration behaviors of pyrrhotite. These make a difficulty for improving the activity of iron-based catalysts. In this study, sulfiding behaviors of {alpha}-iron oxyhydroxide ({alpha}-FeOOH) and {gamma}-iron oxyhydroxide ({gamma}-FeOOH) were investigated to reveal the formation and agglomeration behaviors of pyrrhotite. It was found that pyrrhotite was easily converted from ferric oxyhydroxide catalysts having large specific surface areas at the sulfiding temperature below 250{degree}C, and fine crystallites of pyrrhotite were formed at the initial stage of sulfiding. Crystal growth of pyrrhotite at the sulfiding temperature over 350{degree}C depended on the catalyst forms. It was also found that smaller crystallites of pyrrhotite were formed from {gamma}-FeOOH than from {alpha}-FeOOH and amorphous iron oxyhydroxide. 5 refs., 7 figs., 1 tab.

  16. The desorption of Phosphorous (32 P) fixed on iron and aluminum oxy-hydroxide surfaces by the soil microbial biomass

    International Nuclear Information System (INIS)

    Araujo, Lilian Maria Cesar de.

    1995-02-01

    This work determines whether the soil microbial biomass, with an ample supply of available C, can utilize P adsorber in the surfaces of oxy-hydroxides of Fe or Al of soil-P deficient soils. To simulate the surfaces of the natural Fe and Al compounds, synthetic oxy-hydroxides of Fe and Al, impregnated in strips of filter paper, and containing P tagged with 32 P, were used. (author). 60 refs., 7 figs., 7 tabs

  17. Sorbents based on xerogels of zirconium, aluminum and manganese oxyhydroxides

    Directory of Open Access Journals (Sweden)

    R.V. Smotraiev

    2016-05-01

    Full Text Available The actual problem of water supply in the world and in Ukraine, in particular, is a high level of pollution in water resources and an insufficient level of drinking water purification. With industrial wastewater, a significant amount of pollutants falls into water bodies, including suspended particles, sulfates, iron compounds, heavy metals, etc. Aim: The aim of this work is to determine the impact of aluminum and manganese ions additives on surface and sorption properties of zirconium oxyhydroxide based sorbents during their production process. Materials and Methods: The sorbents based on xerogels of zirconium, aluminum and manganese oxyhydroxides were prepared by sol-gel method during the hydrolysis of metal chlorides (zirconium oxychloride ZrOCl2, aluminum chloride AlCl3 and manganese chloride MnCl2 with carbamide. Results: The surface and sorption properties of sorbents based on xerogels of zirconium, aluminum and manganese oxyhydroxides were investigated. X-ray amorphous structure and evolved hydroxyl-hydrate cover mainly characterize the obtained xerogels. The composite sorbents based on xerogels of zirconium oxyhydroxide doped with aluminum oxyhydroxide (aS = 537 m2/g and manganese oxyhydroxide (aS = 356 m2/g have more developed specific surface area than single-component xerogels of zirconium oxyhydroxide (aS = 236 m2/g and aluminum oxyhydroxide (aS = 327 m2/g. The sorbent based on the xerogel of zirconium and manganese oxyhydroxides have the maximum SO42--ions sorption capacity. It absorbs 1.5 times more SO42–-ions than the industrial anion exchanger AN-221. The sorbents based on xerogels of zirconium oxyhydroxide has the sorption capacity of Fe3+-ions that is 1.5…2 times greater than the capacity of the industrial cation exchanger KU-2-8. The Na+-ions absorption capacity is 1.47…1.56 mmol/g for each sorbent. Conclusions: Based on these data it can be concluded that the proposed method is effective for sorbents production based on

  18. Effects of Gold Substrates on the Intrinsic and Extrinsic Activity of High-Loading Nickel-Based Oxyhydroxide Oxygen Evolution Catalysts

    DEFF Research Database (Denmark)

    Chakthranont, Pongkarn; Kibsgaard, Jakob; Gallo, Alessandro

    2017-01-01

    We systematically investigate the effects of Au substrates on the oxygen evolution activities of cathodically electrodeposited nickel oxyhydroxide (NiOOH), nickel–iron oxyhydroxide (NiFeOOH), and nickel–cerium oxyhydroxide (NiCeOOH) at varying loadings from 0 to 2000 nmol of metal/cm2. We determi...... high geometric current densities on flat substrates. By investigating the mass and site specific activities as a function of loading, we bridge the practical geometric activity to the fundamental intrinsic activity....

  19. What's weathering? Mineralogy and field leach studies in mine waste, Leadville and Montezuma mining districts, Colorado

    Science.gov (United States)

    Diehl, S.F.; Hageman, Phil L.; Smith, Kathleen S.

    2006-01-01

    Weathering is important in the development of rock fabrics that control porosity in mine-waste materials, and in turn, porosity affects metal transport through and from mine-waste piles into watersheds. Mine-waste piles are dynamic physical and chemical systems as evidenced by remnant Fe-oxide boxwork structures after sulfide minerals, development of alteration rinds and etch pits on grains, and precipitation of secondary minerals under low temperature conditions. These microscale changes in the mine-waste materials are the result of partial to total dissolution of sulfide and other minerals. Mine-waste materials from the Dinero, Lower Chatauqua, and Saints John sites, Leadville and Montezuma mining districts, Colorado, exhibit rock fabrics that indicate that weathering products, e.g., Fe oxyhydroxides, jarosite, and clays, have been transported in suspension through the waste piles and deposited in voids and as coatings on rock fragments. Microscale characterization of weathered, partially dissolved minerals lends insight into the source of leachable metals in these mine-waste sites. Mineralogic studies show that galena in the Lower Chatauqua waste is enriched in Ag. Qualitative and semiquantitative microanalysis of weathered, altered galena grains from all three sites show that the Ag-bearing galena is more susceptible to dissolution. It is not surprising, then, that solutions experimentally leached from Lower Chatauqua waste are higher in Pb (2310 ppb) compared to leachates from the Dinero (31 ppb) and Saints John (1360 ppb) wastes. The mobility of metals is increased at acidic pH. Using the USGS Field Leach Test protocol, leachate derived from the Dinero waste has a pH of 3 and high concentrations of Al (443 ppb), Fe (441 ppb), and Zn (7970 ppb). Leachate from Sts. John tailings has a pH about 4 and high concentrations of Mn (1520 ppb), Zn (2240 ppb), and Pb (1360 ppb). Leachate from the Lower Chatauqua waste has an intermediate pH of 5, but in addition to the

  20. Acid drainage at the inactive Santa Lucia mine, western Cuba: Natural attenuation of arsenic, barium and lead, and geochemical behavior of rare earth elements

    Energy Technology Data Exchange (ETDEWEB)

    Romero, Francisco Martin, E-mail: fmrch@geologia.unam.mx [Instituto de Geologia, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, Delegacion Coyoacan, 04510 Mexico D.F. (Mexico); Prol-Ledesma, Rosa Maria; Canet, Carles [Instituto de Geofisica, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, Delegacion Coyoacan, 04510 Mexico D.F. (Mexico); Alvares, Laura Nunez; Perez-Vazquez, Ramon [Facultad de Geologia y Mecanica, Universidad de Pinar del Rio (Cuba)

    2010-05-15

    A detailed geochemical study was conducted at the inactive Zn-Pb mine of Santa Lucia, in western Cuba. The studied mine-wastes are characterized by high total concentrations of potentially toxic elements (PTE), with average values of 17.4% Fe, 5.47% Ba, 2.27% Pb, 0.83% Zn, 1724 mg/kg As and 811 mg/kg Cu. Oxidation of sulfide minerals in mine-waste dumps and in the open pit produces acid mine effluents (pH = 2.5-2.6) enriched in dissolved SO{sub 4}{sup 2-} (up to 6754 mg/L), Fe (up to 4620 mg/L) and Zn (up to 2090 mg/L). Low pH values (2.5-2.8) and high dissolved concentrations of the same PTE were found in surface waters, up to 1500 m downstream from the mine. Nevertheless, concentrations of As, Ba and Pb in acid mine effluents and impacted surface waters are relatively low: 0.01-0.3 mg/L As, 0.002-0.03 mg/L Ba and 0.3-4.3 mg/L Pb. Analysis by X-ray diffraction and electron microscopy revealed the occurrence of lead-bearing barite and beudantite and the more common solid phases, reported elsewhere in similar environments including Fe-oxyhydroxides, jarosite, anglesite and plumbojarosite. Because the reported solubilities for barite and beudantite are very low under acidic conditions, these minerals may serve as the most important control in the mobility of As, Ba and Pb. In contrast, Fe-oxyhydroxides are relatively soluble under acidic conditions and, therefore, they may have a less significant role in PTE on-site immobilization. Mine-wastes and stream sediments show a light REE (LREE) and middle REE (MREE) enrichment relative to heavy REE (HREE). In contrast, acid mine effluents and surface waters are enriched in HREE relative to LREE. These results suggest that the LREE released during the oxidation of sulfides are captured by secondary (weathering) minerals, while the MREE are removed from the altered rocks. The low concentrations of LREE in acid stream water suggest that these elements can be retained in the sediments more strongly than HREE and MREE. One

  1. P-V-T equation of state of rhodium oxyhydroxide

    Science.gov (United States)

    Suzuki, Akio

    2018-04-01

    A high pressure X-ray diffraction study of RhOOH was carried out up to 17.44 GPa to investigate the compression behavior of an oxyhydroxide with an InOOH-related structure. A fit to the third-order Birch-Murnaghan equation of state gave K0 = 208 ± 6 GPa, and K‧ = 9.4 ± 1.3. The temperature derivative of the bulk modulus was found to be ∂K/∂T = -0.06 ± 0.02 GPa K-1. The refined parameters for volume thermal expansion were α0 = 2.7 ± 0.3 × 10-5 K-1; α1 = 1.7 ± 1.1 × 10-8 K-2 in the polynomial form (α(T) = α0 + α1(T-300)). Our results show that RhOOH is very incompressible, and has a higher bulk modulus than other InOOH-structured oxyhydroxides (e.g. δ-AlOOH, ε-FeOOH, and γ-MnOOH).

  2. The role of SO{sub 4}{sup 2−} surface distribution in arsenic removal by iron oxy-hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Tresintsi, S. [Analytical Chemistry Laboratory, Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Simeonidis, K., E-mail: ksime@physics.auth.gr [Analytical Chemistry Laboratory, Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Department of Mechanical Engineering, University of Thessaly, 38334 Volos (Greece); Pliatsikas, N.; Vourlias, G.; Patsalas, P. [Laboratory of Applied Physics, Department of Physics, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Mitrakas, M. [Analytical Chemistry Laboratory, Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece)

    2014-05-01

    This study investigates the contribution of chemisorbed SO{sub 4}{sup 2−} in improving arsenic removal properties of iron oxy-hydroxides through an ion-exchange mechanism. An analytical methodology was developed for the accurate quantification of sulfate ion (SO{sub 4}{sup 2−}) distribution onto the surface and structural compartments of iron oxy-hydroxides synthesized by FeSO{sub 4} precipitation. The procedure is based on the sequential determination of SO{sub 4}{sup 2−} presence in the diffuse and Stern layers, and the structure of these materials as defined by the sulfate-rich environments during the reaction and the variation in acidity (pH 3–12). Physically sorbed SO{sub 4}{sup 2−}, extracted in distilled water, and physically/chemically adsorbed ions on the oxy-hydroxide's surface leached by a 5 mM NaOH solution, were determined using ion chromatography. Total sulfate content was gravimetrically measured by precipitation as BaSO{sub 4}. To validate the suggested method, results were verified by X-ray photoelectron and Fourier-transformed infrared spectroscopy. Results showed that low precipitation pH-values favor the incorporation of sulfate ions into the structure and the inner double layer, while under alkaline conditions ions shift to the diffuse layer. - Graphical abstract: An analytical methodology for the accurate quantification of sulfate ions (SO{sub 4}{sup 2−}) distribution onto the diffuse layer, the Stern layer and the structure of iron oxy-hydroxides used as arsenic removal agents. - Highlights: • Quantification of sulfate ions presence in FeOOH surface compartments. • Preparation pH defines the distribution of sulfates. • XPS and FTIR verify the presence of SO{sub 4}{sup 2−} in the structure, the Stern layer the diffuse layer of FeOOH. • Chemically adsorbed sulfates control the arsenic removal efficiency of iron oxyhydroxides.

  3. Characterization and comparison of iron oxyhydroxide precipitates from biotic and abiotic groundwater treatments

    DEFF Research Database (Denmark)

    Arturi, Katarzyna R.; Bender Koch, Christian; Søgaard, Erik G.

    2017-01-01

    Removal of iron is an important step in groundwater treatment for drinking water production. It is performed to prevent organoleptic issues and clogging in water supply systems. Iron can be eliminated with a purely physico-chemical (abiotic) method or biotically with the help of iron......-oxidizing bacteria (FeOB). Each of the purification methods requires different operating conditions and results in formation of iron oxyhydroxide (FeOOH) precipitates. Knowledge about the differences in composition and properties of the biotic and abiotic precipitates is desirable from a technical, but also...

  4. Local environments and lithium adsorption on the iron oxyhydroxides lepidocrocite (gamma-FeOOH) and goethite (alpha-FeOOH): A 2H-2 and 7Li solid-state MAS NMR study

    DEFF Research Database (Denmark)

    Nielsen, Ulla Gro; Grey, Clare P.; Paik, Jonkim

    2008-01-01

    2H and 7LiMAS NMR spectroscopy techniques were applied to study the local surface and bulk environments of iron oxyhydroxide lepiclocrocite (gamma-FeOOH). 2H variable-temperature (VT) MAS NMR experiments were performed, showing the presence of short-range, strong antiferromagnetic correlations......, even at temperatures above the Neel temperature, TN, 77 K. The formation of a Li+ inner-sphere complex on the surface of lepiclocrocite was confirmed by the observation of a signal with a large 7Li hyperfine shift in the 7Li  MAS NMR spectrum. The effect of pH and relative humidity (RH...

  5. The secret behind the success of doping nickel oxyhydroxide with iron.

    Science.gov (United States)

    Fidelsky, Vicky; Toroker, Maytal Caspary

    2017-03-15

    Discovering better catalysts for water splitting is the holy grail of the renewable energy field. One of the most successful water oxidation catalysts is nickel oxyhydroxide (NiOOH), which is chemically active only as a result of doping with Fe. In order to shed light on how Fe improves efficiency, we perform Density Functional Theory +U (DFT+U) calculations of water oxidation reaction intermediates of Fe substitutional doped NiOOH. The results are analyzed while considering the presence of vacancies that we use as probes to test the effect of adding charge to the surface. We find that the smaller electronegativity of the Fe dopant relative to Ni allows the dopant to have several possible oxidation states with less energy penalty. As a result, the presence of vacancies which alters local oxidation states does not affect the low overpotential of Fe-doped NiOOH. We conclude that the secret to the success of doping NiOOH with iron is the ability of iron to easily change oxidation states, which is critical during the chemical reaction of water oxidation.

  6. Biogenic Fe(III) minerals lower the efficiency of iron-mineral based commercial filter systems for arsenic removal

    DEFF Research Database (Denmark)

    Kleinert, Susanne; Muehe, Eva M.; Posth, Nicole

    2011-01-01

    Millions of people worldwide are affected by As (arsenic) contaminated groundwater. Fe(III) (oxy)hydroxides sorb As efficiently and are therefore used in water purification filters. Commercial filters containing abiogenic Fe(III) (oxy)hydroxides (GEH) showed varying As removal, and it was unclear...

  7. Redox characterization of the Fe(II)-catalyzed transformation of ferrihydrite to goethite

    Science.gov (United States)

    Jones, Adele M.; Collins, Richard N.; Waite, T. David

    2017-12-01

    The reduction potential of Fe(II)-Fe(III) (oxyhydr)oxide systems provides an important control on the biogeochemical cycling of redox-sensitive elements such as carbon and nitrogen as well as trace metals and organic contaminants in natural systems. As such, an in-depth understanding of the factors controlling the reduction potential of such systems is critical to predicting the likely transformation, transport and fate of these species in natural and perturbed environments. In this study the mineralogy and reduction potential of ferrihydrite suspensions at pH 6.50 and pH 7.00 were determined over the course of their Fe(II)-catalyzed transformation to lepidocrocite and goethite using X-ray absorption spectroscopy and mediated electrochemical approaches. The measured reduction potentials were compared to those of analogous Fe(II)-Fe(III) (oxyhydr)oxide suspensions reacted for 5 min containing pure ferrihydrite (Fh), lepidocrocite (L) and goethite (Gt). The reduction potentials of the pure Fe(II)-Fe(III) (oxyhydr)oxide suspensions were, respectively, +47.5, -13.5 and -122.3 mV vs. SHE at pH 6.5, and -22.9, -84.1 and -189.7 mV vs. SHE at pH 7. These values are in good agreement with reduction potentials calculated using the Nernst equation and reported thermodynamic solubility products indicating that these suspensions had reached equilibrium within 5 min. The reduction potential of the pH 6.50 Fe(II)-ferrihydrite suspension decreased from +47.4 mV to -126.4 mV over a week, and from -20.1 mV to -188.4 mV (all vs. SHE) after 24 h at pH 7. The changes in reduction potential over time matched well to those calculated from the relative proportion of each pure Fe(III) (oxyhydr)oxide present suggesting that Fe3+ activity was influenced by the mix of iron oxides present rather than the most insoluble solid species. Finally, evidence is provided that adsorbed Fe(II) has the capacity to reduce a significantly larger fraction of a reducible species than the aqueous Fe

  8. Magnetic properties of some selected, soil-related iron oxides and oxyhydroxides as probed by 57Fe Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    DeGrave, E.; Vandenberghe, R.E.; Bowen, L.H.

    1990-01-01

    In the last decade, Mossbauer spectroscopy has become an increasingly important and applied analytical tool for the characterization of environmental Fe-containing material. One of the most fastly growing application area of this technique is undoubtedly that of soils and sediments. Since such systems are commonly complex mixtures of various and mostly poorly crystalline compounds, much emphasis has been displayed towards the Mossbauer spectra of the pure constituents which, in the case of oxides and oxyhydroxides, usually concern well characterized synthetic samples. Many excellent and fairly complete review papers in that respect have been published in the recent literature and it is not the aim of the present authors to come up with still another one covering the same period. Only those results reported since 1985 and which have provided basically new insight concerning structural and/or magnetic properties have been selected. In addition, it has been attempted to collect some of the less-frequently dealt-with magnetic characteristics which more often have a fundamental importance rather than an analytical one, and which are therefore at the moment less-directly related and restricted to soil studies. A particular aspect that has received considerable attention in this paper is the effect on the Mossbauer spectra of the application of strong magnetic fields

  9. Efficiency of Iron-Based Oxy-Hydroxides in Removing Antimony from Groundwater to Levels below the Drinking Water Regulation Limits

    Directory of Open Access Journals (Sweden)

    Konstantinos Simeonidis

    2017-02-01

    Full Text Available This study evaluates the efficiency of iron-based oxy-hydroxides to remove antimony from groundwater to meet the requirements of drinking water regulations. Results obtained by batch adsorption experiments indicated that the qualified iron oxy-hydroxide (FeOOH, synthesized at pH 4 for maintaining a high positive charge density (2.5 mmol OH−/g achieved a residual concentration of Sb(III below the EU drinking water regulation limit of 5 μg/L by providing an adsorption capacity of 3.1 mg/g. This is more than twice greater compared either to similar commercial FeOOHs (GFH, Bayoxide or to tetravalent manganese feroxyhyte (Fe-MnOOH adsorbents. In contrast, all tested adsorbents failed to achieve a residual concentration below 5 μg/L for Sb(V. The higher efficiency of the qualified FeOOH was confirmed by rapid small-scale column tests, since an adsorption capacity of 3 mg Sb(III/g was determined at a breakthrough concentration of 5 μg/L. However, it completely failed to achieve Sb(V concentrations below 5 μg/L even at the beginning of the column experiments. The results of leaching tests classified the spent qualified FeOOH to inert wastes. Considering the rapid kinetics of this process (i.e., 85% of total removal was performed within 10 min, the developed qualified adsorbent may be promoted as a prospective material for point-of-use Sb(III removal from water in vulnerable communities, since the adsorbent’s cost was estimated to be close to 30 ± 3.4 €/103 m3 for every 10 μg Sb(III/L removed.

  10. Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

    Science.gov (United States)

    Leybourne, Matthew I.; Johannesson, Karen H.

    2008-12-01

    We have collected ˜500 stream waters and associated bed-load sediments over an ˜400 km 2 region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into "dissolved" (primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO 2/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.

  11. Synthesis of aluminum oxy-hydroxide nanofibers from porous anodic alumina

    Energy Technology Data Exchange (ETDEWEB)

    Jha, Himendra; Kikuchi, Tatsuya; Sakairi, Masatoshi; Takahashi, Hideaki [Laboratory of Interface Microstructure Analysis (LIMSA), Division of Materials Science and Engineering, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628 (Japan)], E-mail: himendra@eng.hokudai.ac.jp

    2008-10-01

    A novel method for the synthesis of aluminum oxy-hydroxide nanofibers from a porous anodic oxide film of aluminum is demonstrated. In the present method, the porous anodic alumina not only acts as a template, but also serves as the starting material for the synthesis. The porous anodic alumina film is hydrothermally treated for pore-sealing, which forms aluminum oxy-hydroxide inside the pores of the oxide film as well as on the surface of the film. The hydrothermally sealed porous oxide film is immersed in the sodium citrate solution, which selectively etches the porous aluminum oxide from the film, leaving the oxy-hydroxide intact. The method is simple and gives highly uniform aluminum oxy-hydroxide nanofibers. Moreover, the diameter of the nanofibers can be controlled by controlling the pore size of the porous anodic alumina film, which depends on the anodizing conditions. Nanofibers with diameters of about 38-85 nm, having uniform shape and size, were successfully synthesized using the present method.

  12. Synthesis of aluminum oxy-hydroxide nanofibers from porous anodic alumina

    International Nuclear Information System (INIS)

    Jha, Himendra; Kikuchi, Tatsuya; Sakairi, Masatoshi; Takahashi, Hideaki

    2008-01-01

    A novel method for the synthesis of aluminum oxy-hydroxide nanofibers from a porous anodic oxide film of aluminum is demonstrated. In the present method, the porous anodic alumina not only acts as a template, but also serves as the starting material for the synthesis. The porous anodic alumina film is hydrothermally treated for pore-sealing, which forms aluminum oxy-hydroxide inside the pores of the oxide film as well as on the surface of the film. The hydrothermally sealed porous oxide film is immersed in the sodium citrate solution, which selectively etches the porous aluminum oxide from the film, leaving the oxy-hydroxide intact. The method is simple and gives highly uniform aluminum oxy-hydroxide nanofibers. Moreover, the diameter of the nanofibers can be controlled by controlling the pore size of the porous anodic alumina film, which depends on the anodizing conditions. Nanofibers with diameters of about 38-85 nm, having uniform shape and size, were successfully synthesized using the present method

  13. Iron-reducing bacteria accumulate ferric oxyhydroxide nanoparticle aggregates that may support planktonic growth.

    Science.gov (United States)

    Luef, Birgit; Fakra, Sirine C; Csencsits, Roseann; Wrighton, Kelly C; Williams, Kenneth H; Wilkins, Michael J; Downing, Kenneth H; Long, Philip E; Comolli, Luis R; Banfield, Jillian F

    2013-02-01

    Iron-reducing bacteria (FeRB) play key roles in anaerobic metal and carbon cycling and carry out biogeochemical transformations that can be harnessed for environmental bioremediation. A subset of FeRB require direct contact with Fe(III)-bearing minerals for dissimilatory growth, yet these bacteria must move between mineral particles. Furthermore, they proliferate in planktonic consortia during biostimulation experiments. Thus, a key question is how such organisms can sustain growth under these conditions. Here we characterized planktonic microbial communities sampled from an aquifer in Rifle, Colorado, USA, close to the peak of iron reduction following in situ acetate amendment. Samples were cryo-plunged on site and subsequently examined using correlated two- and three-dimensional cryogenic transmission electron microscopy (cryo-TEM) and scanning transmission X-ray microscopy (STXM). The outer membranes of most cells were decorated with aggregates up to 150 nm in diameter composed of ∼3 nm wide amorphous, Fe-rich nanoparticles. Fluorescent in situ hybridization of lineage-specific probes applied to rRNA of cells subsequently imaged via cryo-TEM identified Geobacter spp., a well-studied group of FeRB. STXM results at the Fe L(2,3) absorption edges indicate that nanoparticle aggregates contain a variable mixture of Fe(II)-Fe(III), and are generally enriched in Fe(III). Geobacter bemidjiensis cultivated anaerobically in the laboratory on acetate and hydrous ferric oxyhydroxides also accumulated mixed-valence nanoparticle aggregates. In field-collected samples, FeRB with a wide variety of morphologies were associated with nano-aggregates, indicating that cell surface Fe(III) accumulation may be a general mechanism by which FeRB can grow while in planktonic suspension.

  14. Novel iron oxyhydroxide lepidocrocite nanosheet as ultrahigh power density anode material for asymmetric supercapacitors.

    Science.gov (United States)

    Chen, Ying-Chu; Lin, Yan-Gu; Hsu, Yu-Kuei; Yen, Shi-Chern; Chen, Kuei-Hsien; Chen, Li-Chyong

    2014-09-24

    A simple one-step electroplating route is proposed for the synthesis of novel iron oxyhydroxide lepidocrocite (γ-FeOOH) nanosheet anodes with distinct layered channels, and the microstructural influence on the pseudocapacitive performance of the obtained γ-FeOOH nanosheets is investigated via in situ X-ray absorption spectroscopy (XAS) and electrochemical measurement. The in situ XAS results regarding charge storage mechanisms of electrodeposited γ-FeOOH nanosheets show that a Li(+) can reversibly insert/desert into/from the 2D channels between the [FeO6 ] octahedral subunits depending on the applied potential. This process charge compensates the Fe(2+) /Fe(3+) redox transition upon charging-discharging and thus contributes to an ideal pseudocapacitive behavior of the γ-FeOOH electrode. Electrochemical results indicate that the γ-FeOOH nanosheet shows the outstanding pseudocapacitive performance, which achieves the extraordinary power density of 9000 W kg(-1) with good rate performance. Most importantly, the asymmetric supercapacitors with excellent electrochemical performance are further realized by using 2D MnO2 and γ-FeOOH nanosheets as cathode and anode materials, respectively. The obtained device can be cycled reversibly at a maximum cell voltage of 1.85 V in a mild aqueous electrolyte, further delivering a maximum power density of 16 000 W kg(-1) at an energy density of 37.4 Wh kg(-1). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Adsorption Mechanisms of Trivalent Gold onto Iron Oxy-Hydroxides: From the Molecular Scale to the Model

    International Nuclear Information System (INIS)

    Cances, Benjamin; Benedetti, Marc; Farges, Francois; Brown, Gordon E. Jr.

    2007-01-01

    Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxy-hydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au LIII-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl)4), with dominantly OH ligands at pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution - MUlti SIte Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite

  16. Textural and mineralogical characteristics of microbial fossils associated with modern and ancient iron (oxyhydr)oxides: terrestrial analogue for sediments in Gale Crater.

    Science.gov (United States)

    Potter-McIntyre, Sally L; Chan, Marjorie A; McPherson, Brian J

    2014-01-01

    Iron (oxyhydr)oxide microbial mats in modern to ∼100 ka tufa terraces are present in a cold spring system along Ten Mile Graben, southeastern Utah, USA. Mats exhibit morphological, chemical, and textural biosignatures and show diagenetic changes that occur over millennial scales. The Jurassic Brushy Basin Member of the Morrison Formation in the Four Corners region of the USA also exhibits comparable microbial fossils and iron (oxyhydr)oxide biosignatures in the lacustrine unit. Both the modern spring system and Brushy Basin Member represent alkaline, saline, groundwater-fed systems and preserve diatoms and other similar algal forms with cellular elaboration. Two distinct suites of elements (1. C, Fe, As and 2. C, S, Se, P) are associated with microbial fossils in modern and ancient iron (oxyhydr)oxides and may be potential markers for biosignatures. The presence of ferrihydrite in ∼100 ka fossil microbial mats and Jurassic rocks suggests that this thermodynamically unstable mineral may also be a potential biomarker. One of the most extensive sedimentary records on Mars is exposed in Gale Crater and consists of non-acidic clays and sulfates possibly of lacustrine origin. These terrestrial iron (oxyhydr)oxide examples are a valuable analogue because of similar iron- and clay-rich host rock compositions and will help (1) understand diagenetic processes in a non-acidic, saline lacustrine environment such as the sedimentary rocks in Gale Crater, (2) document specific biomediated textures, (3) demonstrate how biomediated textures might persist or respond to diagenesis over time, and (4) provide a ground truth library of textures to explore and compare in extraterrestrial iron (oxyhydr)oxides, where future explorations hope to detect past evidence of life.

  17. Sequestration of non-pure carbon dioxide streams in iron oxyhydroxide-containing saline repositories

    Science.gov (United States)

    Garcia, S.; Rosenbauer, Robert J.; Palandri, James L.; Maroto-Valer, M. Mercedes

    2012-01-01

    Iron oxyhydroxide, goethite (α-FeOOH), was evaluated as a potential formation mineral reactant for trapping CO2 in a mineral phase such as siderite (FeCO3), when a mixture of CO2-SO 2 flue gas is injected into a saline aquifer. Two thermodynamic simulations were conducted, equilibrating a CO2-SO2 fluid mixture with a NaCl-brine and Fe-rich rocks at 150 °C and 300 bar. The modeling studies evaluated mineral and fluid composition at equilibrium and the influence of pH buffering in the system. Results show siderite precipitates both in the buffered and unbuffered system; however, the presence of an alkaline pH buffer enhances the stability of the carbonate. Based on the model, an experiment was designed to compare with thermodynamic predictions. A CO2-SO2 gas mixture was reacted in 150 ml of NaCl-NaOH brine containing 10 g of goethite at 150 °C and 300 bar for 24 days. Mineralogical and brine chemistry confirmed siderite as the predominant reaction product in the system. Seventy-six mg of CO2 are sequestered in siderite per 10 g of goethite.

  18. Kinetics of microbial Fe(III) oxyhydroxidereduction: The role of mineral properties

    NARCIS (Netherlands)

    Bonneville, Steeve

    2005-01-01

    In many soils, sediments and groundwaters, ferric iron is a major potential electron acceptor for the oxidation of organic matter. In contrast to other terminal electron acceptors (e.g. nitrate or sulfate), the concentration of Fe3+(aq), is limited by the low solubility of Fe(III) oxyhydroxides

  19. Quantitative characterization of the atomic-scale structure of oxyhydroxides in rusts formed on steel surfaces

    International Nuclear Information System (INIS)

    Saito, M.; Suzuki, S.; Kimura, M.; Suzuki, T.; Kihira, H.; Waseda, Y.

    2005-01-01

    Quantitative X-ray structural analysis coupled with anomalous X-ray scattering has been used for characterizing the atomic-scale structure of rust formed on steel surfaces. Samples were prepared from rust layers formed on the surfaces of two commercial steels. X-ray scattered intensity profiles of the two samples showed that the rusts consisted mainly of two types of ferric oxyhydroxide, α-FeOOH and γ-FeOOH. The amounts of these rust components and the realistic atomic arrangements in the components were estimated by fitting both the ordinary and the environmental interference functions with a model structure calculated using the reverse Monte Carlo simulation technique. The two rust components were found to be the network structure formed by FeO 6 octahedral units, the network structure itself deviating from the ideal case. The present results also suggest that the structural analysis method using anomalous X-ray scattering and the reverse Monte Carlo technique is very successful in determining the atomic-scale structure of rusts formed on the steel surfaces

  20. Iron (III) oxyhydroxide in isopropyl alcohol preparation, characterization and solvothermal treatment

    International Nuclear Information System (INIS)

    Carvalho, E.L.C.N.; Jafelicci Junior, M.

    1989-01-01

    Iron (III) nitrate hydrolysis was carried out in isopropyl alcohol solution by an aqueous amonia gas stream resulting in iron (III) oxyhydroxide sol. It has been investigated in this work the solvothermal treatment of this colloidal system at 120 0 C and 24 hours. Iron (III) oxyhydroxide freshly obtained and solvothermally treated. Samples were dryed by lyophilization. Products obtained were characterized by the following techniques: spectrophotometric iron analysis by 1,10-orthophenantroline complexation method, powder X-ray diffraction, vibrational infrared spectra and differential thermal analysis. After solvothermal treatment resulting product was crystallized into hematite, while freshly iron (III) oxyhydroxide was non crystalline. Both of them are very active powder, showing high water adsorption [pt

  1. Geochemical and iron isotopic insights into hydrothermal iron oxyhydroxide deposit formation at Loihi Seamount

    Science.gov (United States)

    Rouxel, Olivier; Toner, Brandy; Germain, Yoan; Glazer, Brian

    2018-01-01

    Low-temperature hydrothermal vents, such as those encountered at Loihi Seamount, harbor abundant microbial communities and provide ideal systems to test hypotheses on biotic versus abiotic formation of hydrous ferric oxide (FeOx) deposits at the seafloor. Hydrothermal activity at Loihi Seamount produces abundant microbial mats associated with rust-colored FeOx deposits and variably encrusted with Mn-oxyhydroxides. Here, we applied Fe isotope systematics together with major and trace element geochemistry to study the formation mechanisms and preservation of such mineralized microbial mats. Iron isotope composition of warm (oxidation of Fe(II) during mixing of the hydrothermal fluid with seawater. By comparing the results with experimentally determined Fe isotope fractionation factors, we determined that less than 20% of Fe(II) is oxidized within active microbial mats, although this number may reach 80% in aged or less active deposits. These results are consistent with Fe(II) oxidation mediated by microbial processes considering the expected slow kinetics of abiotic Fe oxidation in low oxygen bottom water at Loihi Seamount. In contrast, FeOx deposits recovered at extinct sites have distinctly negative Fe-isotope values down to -1.77‰ together with significant enrichment in Mn and occurrence of negative Ce anomalies. These results are best explained by the near-complete oxidation of an isotopically light Fe(II) source produced during the waning stage of hydrothermal activity under more oxidizing conditions. Light Fe isotope values of FeOx are therefore generated by subsurface precipitation of isotopically heavy Fe-oxides rather than by the activity of dissimilatory Fe reduction in the subsurface. Overall, Fe-isotope compositions of microbial mats at Loihi Seamount display a remarkable range between -1.2‰ and +1.6‰ which indicate that Fe isotope compositions of hydrothermal Fe-oxide precipitates are particularly sensitive to local environmental conditions where

  2. 57Fe Moessbauer spectroscopic characterisation of a ferromanganese nodule from the Central Indian Ocean

    International Nuclear Information System (INIS)

    Dutta, R.K.; Chakravortty, V.

    1997-01-01

    The iron bearing phases present in a ferromanganese nodule from the Central Indian Ocean have been determined using 57 Fe Moessbauer spectroscopy. The Moessbauer results have been corroborated by XRD, IR and TG-DTA studies. The Moessbauer spectrum of a ferromanganese nodule shows a broad line width which indicates the presence of more than one iron bearing paramagnetic oxide or oxyhydroxide phases where iron is present as Fe 3+ . γ-FeOOH has been distinctly characterised as one of the iron bearing phases in the nodule. Other oxyhydroxide and oxide phases of iron in the nodule have been ruled out. A typical paramagnetic doublet persists even at very high temperature which has been proposed to be due to iron(III)phosphate. Formation of solid solution of Mn 2 O 3 -Fe 2 O 3 has been observed in the heat treated nodule at 1073 K, which has been characterised by the Moessbauer technique. (author)

  3. Galvanic Corrosion of Lead by Iron (Oxyhydr)Oxides: Potential Impacts on Drinking Water Quality.

    Science.gov (United States)

    Trueman, Benjamin F; Sweet, Gregory A; Harding, Matthew D; Estabrook, Hayden; Bishop, D Paul; Gagnon, Graham A

    2017-06-20

    Lead exposure via drinking water remains a significant public health risk; this study explored the potential effects of upstream iron corrosion on lead mobility in water distribution systems. Specifically, galvanic corrosion of lead by iron (oxyhydr)oxides was investigated. Coupling an iron mineral cathode with metallic lead in a galvanic cell increased lead release by 531 μg L -1 on average-a 9-fold increase over uniform corrosion in the absence of iron. Cathodes were composed of spark plasma sintered Fe 3 O 4 or α-Fe 2 O 3 or field-extracted Fe 3 O 4 and α-FeOOH. Orthophosphate immobilized oxidized lead as insoluble hydroxypyromorphite, while humic acid enhanced lead mobility. Addition of a humic isolate increased lead release due to uniform corrosion by 81 μg L -1 and-upon coupling lead to a mineral cathode-release due to galvanic corrosion by 990 μg L -1 . Elevated lead in the presence of humic acid appeared to be driven by complexation, with 208 Pb and UV 254 size-exclusion chromatograms exhibiting strong correlation under these conditions (R 2 average = 0.87). A significant iron corrosion effect was consistent with field data: lead levels after lead service line replacement were greater by factors of 2.3-4.7 at sites supplied by unlined cast iron distribution mains compared with the alternative, lined ductile iron.

  4. Long-term effects of the iron-based phosphate binder, sucroferric oxyhydroxide, in dialysis patients.

    Science.gov (United States)

    Floege, Jürgen; Covic, Adrian C; Ketteler, Markus; Mann, Johannes F E; Rastogi, Anjay; Spinowitz, Bruce; Chong, Edward M F; Gaillard, Sylvain; Lisk, Laura J; Sprague, Stuart M

    2015-06-01

    Hyperphosphatemia necessitates the use of phosphate binders in most dialysis patients. Long-term efficacy and tolerability of the iron-based phosphate binder, sucroferric oxyhydroxide (previously known as PA21), was compared with that of sevelamer carbonate (sevelamer) in an open-label Phase III extension study. In the initial Phase III study, hemo- or peritoneal dialysis patients with hyperphosphatemia were randomized 2:1 to receive sucroferric oxyhydroxide 1.0-3.0 g/day (2-6 tablets/day; n = 710) or sevelamer 2.4-14.4 g/day (3-18 tablets/day; n = 349) for 24 weeks. Eligible patients could enter the 28-week extension study, continuing the same treatment and dose they were receiving at the end of the initial study. Overall, 644 patients were available for efficacy analysis (n = 384 sucroferric oxyhydroxide; n = 260 sevelamer). Serum phosphorus concentrations were maintained during the extension study. Mean ± standard deviation (SD) change in serum phosphorus concentrations from extension study baseline to Week 52 end point was 0.02 ± 0.52 mmol/L with sucroferric oxyhydroxide and 0.09 ± 0.58 mmol/L with sevelamer. Mean serum phosphorus concentrations remained within Kidney Disease Outcomes Quality Initiative target range (1.13-1.78 mmol/L) for both treatment groups. Mean (SD) daily tablet number over the 28-week extension study was lower for sucroferric oxyhydroxide (4.0 ± 1.5) versus sevelamer (10.1 ± 6.6). Patient adherence was 86.2% with sucroferric oxyhydroxide versus 76.9% with sevelamer. Mean serum ferritin concentrations increased over the extension study in both treatment groups, but transferrin saturation (TSAT), iron and hemoglobin concentrations were generally stable. Gastrointestinal-related adverse events were similar and occurred early with both treatments, but decreased over time. The serum phosphorus-lowering effect of sucroferric oxyhydroxide was maintained over 1 year and associated with a lower pill burden, compared with sevelamer

  5. Synthesis, Structural Characterization, and Thermal Properties of the Poly(methylmethacrylate/δ-FeOOH Hybrid Material: An Experimental and Theoretical Study

    Directory of Open Access Journals (Sweden)

    Silviana Corrêa

    2016-01-01

    Full Text Available The δ-FeOOH/PMMA nanocomposites with 0.5 and 2.5 wt.% of δ-FeOOH were prepared by grafting 3-(trimethoxysilylpropyl methacrylate on the surface of the iron oxyhydroxide particles. The FTIR spectra of the δ-FeOOH/PMMA nanocomposites showed that the silane monomers were covalently attached to the δ-FeOOH particles. Because of the strong interaction between the PMMA and δ-FeOOH nanoparticles, the thermal stability of the δ-FeOOH/PMMA nanocomposites was improved compared to the pure PMMA. The SEM analysis conferred the size agglomerate of particles regarding the morphology of samples. The theoretical study enabled a better understanding of the interaction of the polymer with the iron oxyhydroxide. The DFT-based calculations reinforce the radical trapping mechanism of stabilization of nanocomposites; that is, Fe3+ species might be able to accept electrons coming from the organic phase that decomposes via radical unzipping. The radical scavenge effect delays the weight loss of polymer.

  6. Negative impact of oxygen molecular activation on Cr(VI) removal with core–shell Fe@Fe2O3 nanowires

    International Nuclear Information System (INIS)

    Mu, Yi; Wu, Hao; Ai, Zhihui

    2015-01-01

    Highlights: • The presence of oxygen inhibited Cr(VI) removal efficiency with nZVI by near 3 times. • Cr(VI) removal with nZVI was related to adsorption, reduction, co-precipitation, and adsorption reactions. • Molecular oxygen activation competed donor electrons from Fe 0 core and surface bound Fe(II) of nZVI. • Thicker Cr(III)/Fe(III)/Cr(VI) oxyhydroxides shell of nZVI leaded to the electron transfer inhibition. - Abstract: In this study, we demonstrate that the presence of oxygen molecule can inhibit Cr(VI) removal with core–shell Fe@Fe 2 O 3 nanowires at neutral pH of 6.1. 100% of Cr(VI) removal was achieved by the Fe@Fe 2 O 3 nanowires within 60 min in the anoxic condition, in contrast, only 81.2% of Cr(VI) was sequestrated in the oxic condition. Removal kinetics analysis indicated that the presence of oxygen could inhibit the Cr(VI) removal efficiency by near 3 times. XRD, SEM, and XPS analysis revealed that either the anoxic or oxic Cr(VI) removal was involved with adsorption, reduction, co-precipitation, and re-adsorption processes. More Cr(VI) was bound in a reduced state of Cr(III) in the anoxic process, while a thicker Cr(III)/Fe(III)/Cr(VI) oxyhydroxides shell, leading to inhibiting the electron transfer, was found under the oxic process. The negative impact of oxygen molecule was attributed to the oxygen molecular activation which competed with Cr(VI) adsorbed for the consumption of donor electrons from Fe 0 core and ferrous ions bound on the iron oxides surface under the oxic condition. This study sheds light on the understanding of the fate and transport of Cr(VI) in oxic and anoxic environment, as well provides helpful guide for optimizing Cr(VI) removal conditions in real applications

  7. Geochemical study of evaporite and clay mineral-oxyhydroxide samples from the Waste Isolation Pilot Plant site

    International Nuclear Information System (INIS)

    Brookins, D.G.

    1993-06-01

    Samples of clay minerals, insoluble oxyhydroxides, and their host evaporites from the WIPP site have been studied for their major and minor elements abundances, x-ray diffraction characteristics, K-Ar ages, and Rb-Sr ages. This study was undertaken to determine their overall geochemical characteristics and to investigate possible interactions between evaporates and insoluble constituents. The evaporite host material is water-soluble, having Cl/Br ratios typical of marine evaporites, although the Br content is low. Insoluble material (usually a mixture of clay minerals and oxyhydroxide phases) yields very high Cl/Br ratios, possibly because of Cl from admixed halide minerals. This same material yields K/Rb and Th/U ratios in the normal range for shales; suggesting little, if any, effect of evaporite-induced remobilization of U, K, or Rb in the insoluble material. The rare-earth element (REE) data also show normal REE/chondrite (REE/CHON) distribution patterns, supporting the K/Rb and Th/U data. Clay minerals yield K-Ar dates in the range 365 to 390 Ma and a Rb-Sr isochron age of 428 ± 7 Ma. These ages are well in excess of the 220- to 230-Ma formational age of the evaporites, and confirm the detrital origin of the clays. The ages also show that any evaporite or clay mineral reactions that might have occurred at or near the time of sedimentation and diagenesis were not sufficient to reset the K-Ar and Rb-Sr systematics of the clay minerals. Further, x-ray data indicate a normal evaporitic assemblage of clay minerals and Fe-rich oxyhydroxide phases. The clay minerals and other insoluble material appear to be resistant to the destructive effects of their entrapment in the evaporites, which suggests that these insoluble materials would be good getters for any radionuclides (hypothetically) released from the storage of radioactive wastes in the area

  8. Iron oxyhydroxide nanorods with high electrochemical reactivity as a sensitive and rapid determination platform for 4-chlorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yuanyuan [Key Laboratory for Material Chemistry of Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Britton Chance Center for Biomedical Photonics at Wuhan, National Laboratory for Optoelectronics-Hubei Bioinformatics & Molecular Imaging Key Laboratory, Systems Biology Theme, Department of Biomedical Engineering, College of Life Science and Technology, Huazhong University of Science and Technology, Wuhan 430074 (China); Cheng, Qin; Zheng, Meng [Key Laboratory for Material Chemistry of Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Liu, Xin [Britton Chance Center for Biomedical Photonics at Wuhan, National Laboratory for Optoelectronics-Hubei Bioinformatics & Molecular Imaging Key Laboratory, Systems Biology Theme, Department of Biomedical Engineering, College of Life Science and Technology, Huazhong University of Science and Technology, Wuhan 430074 (China); Wu, Kangbing, E-mail: kbwu@hust.edu.cn [Key Laboratory for Material Chemistry of Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2016-04-15

    Highlights: • Prepared FeOOH nanorods exhibited high reactivity toward the oxidation of 4-CP. • Response signals and detection sensitivity of 4-CP increased greatly by FeOOH. • Highly-sensitive and rapid determination platform was developed for 4-CP. • Practical application in water samples was studied, and the accuracy was good. - Abstract: Iron oxyhydroxide (FeOOH) nanorods were prepared through solvothermal reaction, and characterized using Raman spectroscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, transmission electron microscopy and scanning electron microscopy. Thereafter, the prepared FeOOH nanorods were used as sensing material to construct a novel detection platform for 4-chlorophenol (4-CP). The electrochemical behaviors of 4-CP were studied, and the oxidation peak currents increased greatly on the surface of FeOOH nanorods. The signal enhancement mechanism was studied for 4-CP, and it was found that the prepared FeOOH nanorods remarkably improved the electron transfer ability and surface adsorption efficiency of 4-CP. The influences of pH value, amount of FeOOH nanorods and accumulation time were examined. As a result, a highly-sensitive electrochemical method was developed for the rapid determination of 4-CP. The linear range was from 10 to 500 nM, and the detection limit was 3.2 nM. It was used in different water samples, and the results consisted with the values that obtained by high-performance liquid chromatography.

  9. STUDY ON PHYTO-EXTRACTION BALANCE OF ZN, CD AND PB FROM MINE-WASTE POLLUTED SOILS BY USING FESTUCA ARUNDINACEA AND LOLIUM PERENNE SPECIES

    Directory of Open Access Journals (Sweden)

    B. LIXANDRU

    2009-05-01

    Full Text Available Through the cultivation of tall fescue (Festuca arundinacea and of perennial ryegrass for two years on a chernozem type of soil, in the Banat's plain area we investigated the phyto-extraction potential of Zn, Cd and Pb. In the experimental plot it has been incorporated a quantity of 20 kg of mine-waste per square meter, in a mass ratio of 1:2,5. The mine-waste polluting "contribution" was of 1209 mg Zn / kg d.s., 4.70 mg Cd / kg d.s. and 188.2 mg Pb / kg d.s. The metals content in the soil was determined at the two moments of biomass harvesting, and through balance calculations we could establish the phyto-extraction efficiency of the two foragegrasses species. The obtained results indicate that Festuca arundinacea has an average phyto-extraction yield of 50% for Zn and Cd in the soil; in the case of an ionic excess of 3,5 to 4 times, the phyto-extraction efficiency is reduced, more obvious in the case of Pb (lead ions. The species Lolium perenne registers a yield of almost 92% in the process of phyto-extraction of Zn. The yield values for Cd si Pb are lower, but comparable with the control plot. Unlike Festuca arundinacea, the Lollium perenne species tolerates better the Cd and Pb ionic excess.

  10. Electron small polarons and their mobility in iron (oxyhydr)oxide nanoparticles

    DEFF Research Database (Denmark)

    Katz, Jordan E; Zhang, Xiaoyi; Attenkofer, Klaus

    2012-01-01

    Electron mobility within iron (oxyhydr)oxides enables charge transfer between widely separated surface sites. There is increasing evidence that this internal conduction influences the rates of interfacial reactions and the outcomes of redox-driven phase transformations of environmental interest....... To determine the links between crystal structure and charge-transport efficiency, we used pump-probe spectroscopy to study the dynamics of electrons introduced into iron(III) (oxyhydr)oxide nanoparticles via ultrafast interfacial electron transfer. Using time-resolved x-ray spectroscopy and ab initio...

  11. Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

    Science.gov (United States)

    Balistrieri, L.S.; Chao, T.T.

    1990-01-01

    This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites

  12. One-year efficacy and safety of the iron-based phosphate binder sucroferric oxyhydroxide in patients on peritoneal dialysis.

    Science.gov (United States)

    Floege, Jürgen; Covic, Adrian C; Ketteler, Markus; Mann, Johannes; Rastogi, Anjay; Spinowitz, Bruce; Rakov, Viatcheslav; Lisk, Laura J; Sprague, Stuart M

    2017-11-01

    Sucroferric oxyhydroxide is a noncalcium, iron-based phosphate binder that demonstrated sustained serum phosphorus control, good tolerability and lower pill burden compared with sevelamer carbonate (sevelamer) in a Phase 3 study conducted in dialysis patients. This subanalysis examines the efficacy and tolerability of sucroferric oxyhydroxide and sevelamer in the peritoneal dialysis (PD) patient population. The initial study (NCT01324128) and its extension (NCT01464190) were multicenter, Phase 3, open-label, randomized (2:1), active-controlled trials comparing sucroferric oxyhydroxide (1.0-3.0 g/day) with sevelamer (2.4-14.4 g/day) in dialysis patients over 52 weeks in total. In the overall study, 84/1055 (8.1%) patients received PD and were eligible for efficacy analysis (sucroferric oxyhydroxide, n = 56; sevelamer, n = 28). The two groups were broadly comparable to each other and to the overall study population. Serum phosphorus concentrations decreased comparably with both phosphate binders by week 12 (mean change from baseline - 0.6 mmol/L). Over 52 weeks, sucroferric oxyhydroxide effectively reduced serum phosphorus concentrations to a similar extent as sevelamer; 62.5% and 64.3% of patients, respectively, were below the Kidney Disease Outcomes Quality Initiative target range (≤1.78 mmol/L). This was achieved with a lower pill burden (3.4 ± 1.3 versus 8.1 ± 3.7 tablets/day) with sucroferric oxyhydroxide compared with sevelamer. Treatment adherence rates were 91.2% with sucroferric oxyhydroxide and 79.3% with sevelamer. The proportion of patients reporting at least one treatment-emergent adverse event was 86.0% with sucroferric oxyhydroxide and 93.1% with sevelamer. The most common adverse events with both treatments were gastrointestinal: diarrhea and discolored feces with sucroferric oxyhydroxide and nausea, vomiting and constipation with sevelamer. Sucroferric oxyhydroxide is noninferior to sevelamer for controlling serum

  13. Fate of Cd during microbial Fe(III) mineral reduction by a novel and Cd-tolerant Geobacter species.

    Science.gov (United States)

    Muehe, E Marie; Obst, Martin; Hitchcock, Adam; Tyliszczak, Tolek; Behrens, Sebastian; Schröder, Christian; Byrne, James M; Michel, F Marc; Krämer, Ute; Kappler, Andreas

    2013-12-17

    Fe(III) (oxyhydr)oxides affect the mobility of contaminants in the environment by providing reactive surfaces for sorption. This includes the toxic metal cadmium (Cd), which prevails in agricultural soils and is taken up by crops. Fe(III)-reducing bacteria can mobilize such contaminants by Fe(III) mineral dissolution or immobilize them by sorption to or coprecipitation with secondary Fe minerals. To date, not much is known about the fate of Fe(III) mineral-associated Cd during microbial Fe(III) reduction. Here, we describe the isolation of a new Geobacter sp. strain Cd1 from a Cd-contaminated field site, where the strain accounts for 10(4) cells g(-1) dry soil. Strain Cd1 reduces the poorly crystalline Fe(III) oxyhydroxide ferrihydrite in the presence of at least up to 112 mg Cd L(-1). During initial microbial reduction of Cd-loaded ferrihydrite, sorbed Cd was mobilized. However, during continuous microbial Fe(III) reduction, Cd was immobilized by sorption to and/or coprecipitation within newly formed secondary minerals that contained Ca, Fe, and carbonate, implying the formation of an otavite-siderite-calcite (CdCO3-FeCO3-CaCO3) mixed mineral phase. Our data shows that microbially mediated turnover of Fe minerals affects the mobility of Cd in soils, potentially altering the dynamics of Cd uptake into food or phyto-remediating plants.

  14. Study the properties of activated carbon and oxyhydroxide aluminum as sorbents for removal humic substances from natural waters

    International Nuclear Information System (INIS)

    Shiyan, L N; Machekhina, K I; Gryaznova, E N

    2016-01-01

    The present work relates to the problem of high-quality drinking water supply using processes of adsorption on activated carbon and aluminum oxyhydroxide for removal humic- type organic substances. Also the paper reports on sorbtion properties of the activeted carbon Norit SA UF and oxyhydroxide aluminum for removal humic substances. It was found out that the maximum adsorption capacity of activated carbon to organic substances is equal to 0.25 mg/mg and aluminum oxyhydroxide is equal to 0.3 mg/mg. It is shown that the maximum adsorption capacity of activated carbon Norit SA UF to iron (III) ions is equal to 0.0045 mg/mg and to silicon ions is equal to 0.024 mg/mg. Consequently, the aluminum oxyhydroxide has better adsorption characteristics in comparison with the activated carbon for removal of humic substances, iron and silicon ions. It is associated with the fact that activated carbon has a large adsorption surface, and this is due to its porous structure, but not all molecules can enter into these pores. Therefore, the fibrous structure of aluminum oxyhydroxide promotes better sorption capacity. The presented results suggest that activated carbon Norit SA UF and aluminum oxyhydroxide can be used as sorbents for removal humic substances or other organic substances from groundwater and natural waters. (paper)

  15. Abiotic and microbial interactions during anaerobic transformations of Fe(II and NOx-

    Directory of Open Access Journals (Sweden)

    Flynn ePicardal

    2012-03-01

    Full Text Available Microbial Fe(II oxidation using NO3- as the terminal electron acceptor (nitrate-dependent Fe(II oxidation; NDFO has been studied for over 15 years. Although there are reports of autotrophic isolates and stable enrichments, many of the bacteria capable of NDFO are known organotrophic NO3- -reducers that require the presence of an organic, primary substrate, e.g., acetate, for significant amounts of Fe(II oxidation. Although the thermodynamics of Fe(II oxidation are favorable when coupled to either NO3- or NO2- reduction, the kinetics of abiotic Fe(II oxidation by NO3- are relatively slow except under special conditions. NDFO is typically studied in batch cultures containing millimolar concentrations of Fe(II, NO3-, and the primary substrate. In such systems, NO2- is often observed to accumulate in culture media during Fe(II oxidation. Compared to NO3-, abiotic reactions of biogenic NO2- and Fe(II are relatively rapid. The kinetics and reaction pathways of Fe(II oxidation by NO2- are strongly affected by medium composition and pH, reactant concentration, and the presence of Fe(II-sorptive surfaces, e.g., Fe(III oxyhydroxides and cellular surfaces. In batch cultures, the combination of abiotic and microbial Fe(II oxidation can alter product distribution and, more importantly, results in the formation of intracellular precipitates and extracellular Fe(III oxyhydroxide encrustations that apparently limit further cell growth and Fe(II oxidation. Unless steps are taken to minimize or account for potential abiotic reactions, results of microbial NDFO studies can be obfuscated by artifacts of the chosen experimental conditions, the use of inappropriate analytical methods, and the resulting uncertainties about the relative importance of abiotic and microbial reactions.In this manuscript, abiotic reactions of NO3- and NO2- with aqueous Fe2+, chelated Fe(II, and solid-phase Fe(II are reviewed along with factors that can influence overall NDFO reac

  16. Synthesis of beta alumina from aluminum hydroxide and oxyhydroxide precursors

    CSIR Research Space (South Africa)

    Van Zyl, A

    1993-02-01

    Full Text Available Two aluminium oxyhydroxides, boehmite and pseudoboehmite, and two aluminium hydroxides, bayerite and gibbsite, have been investigated as precursors for the synthesis of the solid electrolyte, beta alumina. Reaction pathways and products have been...

  17. Rapid sedimentation of iron oxyhydroxides in an active hydrothermal shallow semi-enclosed bay at Satsuma Iwo-Jima Island, Kagoshima, Japan

    Science.gov (United States)

    Kiyokawa, Shoichi; Ueshiba, Takuya

    2015-04-01

    Hydrothermal activity is common in the fishing port of Nagahama Bay, a small semi-enclosed bay located on the southwest coast of Satsuma Iwo-Jima Island (38 km south of Kyushu Island, Japan). The bay contains red-brown iron oxyhydroxides and thick deposits of sediment. In this work, the high concentration and sedimentation rates of oxyhydroxide in this bay were studied and the sedimentary history was reconstructed. Since dredging work in 1998, a thickness of 1.0-1.5 m of iron oxyhydroxide-rich sediments has accumulated on the floor of the bay. To estimate the volume of iron oxyhydroxide sediments and the amount discharged from hydrothermal vents, sediment traps were operated for several years and 13 sedimentary core samples were collected to reconstruct the 10-year sedimentary history of Nagahama Bay. To confirm the timing of sedimentary events, the core data were compared with meteorological records obtained on the island, and the ages of characteristic key beds were thus identified. The sedimentation rate of iron oxyhydroxide mud was calculated, after correcting for sediment input from other sources. The sediments in the 13 cores from Nagahama Bay consist mainly of iron oxyhydroxide mud, three thick tephra beds, and a topmost thick sandy mud bed. Heavy rainfall events in 2000, 2001, 2002, and 2004-2005 coincide with tephra beds, which were reworked from Iwo-Dake ash deposits to form tephra-rich sediment. Strong typhoon events with gigantic waves transported outer-ocean-floor sediments and supplied quartz, cristobalite, tridymite, and albite sands to Nagahama Bay. These materials were redeposited together with bay sediments as the sandy mud bed. Based on the results from the sediment traps and cores, it is estimated that the iron oxyhydroxide mud accumulated in the bay at the relatively rapid rate of 33.3 cm/year (from traps) and 2.8-4.9 cm/year (from cores). The pore water contents within the sediment trap and core sediments are 73%-82% and 47%-67%, respectively

  18. Fe-Ni-bearing serpentines from the saprolite horizon of Caribbean Ni-laterite deposits: new insights from thermodynamic calculations

    Science.gov (United States)

    Villanova-de-Benavent, Cristina; Domènech, Cristina; Tauler, Esperança; Galí, Salvador; Tassara, Santiago; Proenza, Joaquín A.

    2017-10-01

    Fe-Ni-bearing serpentine from the saprolite horizon is the main Ni ores in hydrous silicate-type Ni laterites and formed by chemical weathering of partially serpentinized ultramafic rocks under tropical conditions. During lateritization, Mg, Si, and Ni are leached from the surface and transported downwards. Fe2+ is oxidized to Fe3+ and fixed as insoluble Fe-oxyhydroxides (mostly goethite) that incorporate Ni. This Ni is later leached from goethite and incorporated in secondary serpentine and garnierite. As a result, a serpentine-dominated saprolite horizon forms over the ultramafic protolith, overlapped by a Fe-oxyhydroxide-dominated limonite horizon. The serpentine from the protolith (serpentine I) is of hydrothermal origin and yields similar Ni (0.10-0.62 wt.% NiO) and lower Fe (mostly 1.37-5.81 wt.% FeO) concentrations than the primary olivine. In contrast, Fe-Ni-bearing serpentine from the saprolite (serpentine II) shows significantly higher and variable Fe and Ni contents, typically ranging from 2.23 to 15.59 wt.% Fe2O3 and from 1.30 to 7.67 wt.% NiO, suggesting that serpentine get enriched in Fe and Ni under supergene conditions. This study presents detailed mineralogical, textural, and chemical data on this serpentine II, as well as new insights by thermodynamic calculations assuming ideal solution between Fe-, Ni- and Mg-pure serpentines. The aim is to assess if at atmospheric pressure and temperature Fe-Ni-bearing serpentine can be formed by precipitation. Results indicate that the formation of serpentine II under atmospheric pressure and temperature is thermodynamically supported, and pH, Eh, and the equilibrium constant of the reaction are the parameters that affect the results more significantly.

  19. Green rusts synthesis by coprecipitation of Fe II-Fe III ions and mass-balance diagram

    Science.gov (United States)

    Ruby, Christian; Aïssa, Rabha; Géhin, Antoine; Cortot, Jérôme; Abdelmoula, Mustapha; Génin, Jean-Marie

    2006-06-01

    A basic solution is progressively added to various mixed Fe II-Fe III solutions. The nature and the relative quantities of the compounds that form can be visualised in a mass-balance diagram. The formation of hydroxysulphate green rust {GR( SO42-)} is preceded by the precipitation of a sulphated ferric basic salt that transforms in a badly ordered ferric oxyhydroxide. Then octahedrally coordinated Fe II species and SO42- anions are adsorbed on the FeOOH surface and GR( SO42-) is formed at the solid/solution interface. By using the same method of preparation, other types of green rust were synthesised, e.g. hydroxycarbonate green rust {GR( CO32-)}. Like other layered double hydroxides, green rusts obey the general chemical formula [ṡ[ṡmHO]x+ with x⩽1/3. Al-substituted hydroxysulphate green rust consists of small hexagonal crystals with a lateral size ˜50 nm, which is significantly smaller than the size of the GR( SO42-) crystals (˜500 nm). To cite this article: C. Ruby et al., C. R. Geoscience 338 (2006).

  20. Uranium accumulation in modern and ancient Fe-oxide sediments: Examples from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and Yubileynoe massive sulfide deposit (South Urals, Russia)

    Science.gov (United States)

    Ayupova, N. R.; Melekestseva, I. Yu.; Maslennikov, V. V.; Tseluyko, A. S.; Blinov, I. A.; Beltenev, V. E.

    2018-05-01

    Fe-oxyhydroxide sediments (gossans) from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and hematite-carbonate-quartz rocks (gossanites) from the Yubileynoe Cu-Zn VHMS deposit (South Urals) are characterized by anomalously high U contents (up to 352 ppm and 73 ppm, respectively). In gossans from the Ashadze-2 hydrothermal sulfide field, rare isometric anhedral uraninite grains (up to 2 μm) with outer P- and Ca-rich rims, and numerous smaller (<1 μm) grains, occur in Fe-oxyhydroxides and sepiolite, associated with pyrite, isocubanite, chalcopyrite, galena, atacamite and halite. In gossanites from the Yubileynoe deposit, numerous uraninite particles (<3 μm) are associated with apatite, V-rich Mg-chlorite, micro-nodules of pyrite, Se-bearing galena, hessite and acanthite in a hematite-carbonate-quartz matrix. Small (1-3 μm) round grains of uraninite, which locally coalesce to large grains up to 10 μm in size, are associated with authigenic chalcopyrite. The similar diagenetic processes of U accumulation in modern and ancient Fe-oxyhydroxide sediments were the result of U fixation from seawater during the oxidation of sulfide minerals. Uraninite in gossanites was mainly deposited from diagenetic pore fluids, which circulated in the sulfide-hyaloclast-carbonate sediments.

  1. Risk assessment of particle dispersion and trace element contamination from mine-waste dumps.

    Science.gov (United States)

    Romero, Antonio; González, Isabel; Martín, José María; Vázquez, María Auxiliadora; Ortiz, Pilar

    2015-04-01

    In this study, a model to delimit risk zones influenced by atmospheric particle dispersion from mine-waste dumps is developed to assess their influence on the soil and the population according to the concentration of trace elements in the waste. The model is applied to the Riotinto Mine (in SW Spain), which has a long history of mining and heavy land contamination. The waste materials are separated into three clusters according to the mapping, mineralogy, and geochemical classification using cluster analysis. Two of the clusters are composed of slag, fresh pyrite, and roasted pyrite ashes, which may contain high concentrations of trace elements (e.g., >1 % As or >4 % Pb). The average pollution load index (PLI) calculated for As, Cd, Co, Cu, Pb, Tl, and Zn versus the baseline of the regional soil is 19. The other cluster is primarily composed of sterile rocks and ochreous tailings, and the average PLI is 3. The combination of particle dispersion calculated by a Gaussian model, the PLI, the surface area of each waste and the wind direction is used to develop a risk-assessment model with Geographic Information System GIS software. The zone of high risk can affect the agricultural soil and the population in the study area, particularly if mining activity is restarted in the near future. This model can be applied to spatial planning and environmental protection if the information is complemented with atmospheric particulate matter studies.

  2. Zero-valent iron/iron oxide-oxyhydroxide/graphene as a magnetic sorbent for the enrichment of polychlorinated biphenyls, polyaromatic hydrocarbons and phthalates prior to gas chromatography-mass spectrometry.

    Science.gov (United States)

    Karamani, Anna A; Douvalis, Alexios P; Stalikas, Constantine D

    2013-01-04

    A composite magnetic material consisting of zero-valent iron, iron oxide-oxyhydroxide and graphene was synthesized and used successfully as a sorbent for the micro solid-phase extraction of PAHs, PCBs and phthalic acid esters. The components endow the composite with multiple characteristics such as adsorption capability and facile removal due to its magnetic properties. Due to the π-π electrostatic stacking property of graphene, the high specific surface area and the adsorption capability of both components, the resulting black flaky Fe(0)/iron oxide-oxyhydroxide/graphene composite showed high extraction efficiency for the target analytes from water samples. Compared with the neat graphene, the composite material has improved properties in terms of microextraction capabilities as both the hydrophobic graphene and zero-valent iron participate in the adsorption of the hydrophobic molecules. The precision from the extraction of all three groups of compounds was lower than 7% and the recoveries were from 90 to 93% from a spiked lake water sample. The high recoveries in relation to the low final volume of the desorption solvent ensure high preconcentration efficiency and a promising sorbent for analytical applications. Copyright © 2012 Elsevier B.V. All rights reserved.

  3. Radiolytic formation of iron oxyhydroxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Sutherland, T.; Wren, J.C., E-mail: tsuther4@uwo.ca [The Univ. of Western Ontario, London, ON (Canada)

    2014-07-01

    The formation of iron oxyhydroxide nanoparticles under gamma irradiation of ferrous ion solutions is a process in the infancy of its understanding. Herein we present work to probe the mechanism by which these nanoparticles are formed. These results can be used to better understand the activity transport processes occurring within a reactor environment which may pose both environmental and safety concerns. Initial ferrous concentrations and solution pH were modified and found to have little effect on final particle size and composition. The nanoparticles were formed in the presence of scavengers and it was found that hydroxyl radicals promote the particle formation while solvated electrons diminish it. Post-synthesis heating was found to shift the initially-formed lepidocrocite particles towards a mixture of goethite and maghemite. (author)

  4. Humic acid facilitates the transport of ARS-labeled hydroxyapatite nanoparticles in iron oxyhydroxide-coated sand

    Science.gov (United States)

    Wang, Dengjun; Bradford, Scott A.; Harvey, Ronald W.; Gao, Bin; Cang, Long; Zhou, Dongmei

    2012-01-01

    Hydroxyapatite nanoparticles (nHAP) have been widely used to remediate soil and wastewater contaminated with metals and radionuclides. However, our understanding of nHAP transport and fate is limited in natural environments that exhibit significant variability in solid and solution chemistry. The transport and retention kinetics of Alizarin red S (ARS)-labeled nHAP were investigated in water-saturated packed columns that encompassed a range of humic acid concentrations (HA, 0–10 mg L–1), fractional surface coverage of iron oxyhydroxide coatings on sand grains (λ, 0–0.75), and pH (6.0–10.5). HA was found to have a marked effect on the electrokinetic properties of ARS-nHAP, and on the transport and retention of ARS-nHAP in granular media. The transport of ARS-nHAP was found to increase with increasing HA concentration because of enhanced colloidal stability and the reduced aggregate size. When HA = 10 mg L–1, greater ARS-nHAP attachment occurred with increasing λ because of increased electrostatic attraction between negatively charged nanoparticles and positively charged iron oxyhydroxides, although alkaline conditions (pH 8.0 and 10.5) reversed the surface charge of the iron oxyhydroxides and therefore decreased deposition. The retention profiles of ARS-nHAP exhibited a hyperexponential shape for all test conditions, suggesting some unfavorable attachment conditions. Retarded breakthrough curves occurred in sands with iron oxyhydroxide coatings because of time-dependent occupation of favorable deposition sites. Consideration of the above effects is necessary to improve remediation efficiency of nHAP for metals and actinides in soils and subsurface environments.

  5. Formation of the Fe(II)-Fe(III) hydroxysulphate green rust during marine corrosion of steel

    International Nuclear Information System (INIS)

    Refait, Ph.; Memet, J.-B.; Bon, C.; Sabot, R.; Genin, J.-M.R.

    2003-01-01

    Rust layers formed on steel sheet piles immersed 1 m above the mud line for 25 years were analysed by Raman spectroscopy, scanning electron microscopy and elemental X-ray mappings (Fe, S, O). They consist of three main strata, the inner one mainly composed of magnetite, the intermediate one of iron(III) oxyhydroxides and the outer one of hydroxysulphate green rust GR(SO 4 2- ). Simulations of GRs formation in solutions having large [Cl - ]/[SO 4 2- ] ratios revealed that the hydroxysulphate GR(SO 4 2- ) was obtained instead of the hydroxychloride GR(Cl - ), as demonstrated by X-ray diffraction and transmission Moessbauer spectroscopy analyses. Measurements of the [S], [Fe] and [Cl] concentrations allowed us to establish that GR(SO 4 2- ) formed along with a drastic impoverishment of the solution in sulphate ions; the [Cl - ]/[SO 4 2- ] ratio increased from 12 to 240. The GR, acting like a 'sulphate pump', may favour the colonisation of the rust layers by sulphate reducing bacteria

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

    Directory of Open Access Journals (Sweden)

    Elizabeth D. Swanner

    2015-10-01

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

  7. Investigating the effect of ascorbate on the Fe(II)-catalyzed transformation of the poorly crystalline iron mineral ferrihydrite.

    Science.gov (United States)

    Xiao, Wei; Jones, Adele M; Collins, Richard N; Waite, T David

    2018-05-09

    The inorganic core of the iron storage protein, ferritin, is recognized as being analogous to the poorly crystalline iron mineral, ferrihydrite (Fh). Fh is also abundant in soils where it is central to the redox cycling of particular soil contaminants and trace elements. In geochemical circles, it is recognized that Fh can undergo Fe(II)-catalyzed transformation to form more crystalline iron minerals, vastly altering the reactivity of the iron oxide and, in some cases, the redox poise of the system. Of relevance to both geochemical and biological systems, we investigate here if the naturally occurring reducing agent, ascorbate, can effect such an Fe(II)-catalyzed transformation of Fh at 25 °C and circumneutral pH. The transformation of ferrihydrite to possible secondary Fe(III) mineralization products was quantified using Fourier transform infrared (FTIR) spectroscopy, with supporting data obtained using X-ray absorbance spectroscopy (XAS) and X-ray diffraction (XRD). Whilst the amount of Fe(II) formed in the presence of ascorbate has resulted in Fh transformation in previous studies, no transformation of Fh to more crystalline Fe(III) (oxyhydr)oxides was observed in this study. Further experiments indicated this was due to the ability of ascorbate to inhibit the formation of goethite, lepidocrocite and magnetite. The manner in which ascorbate associated with Fh was investigated using FTIR and total organic carbon (TOC) analysis. The majority of ascorbate was found to adsorb to the Fh surface under anoxic conditions but, under oxic conditions, ascorbate was initially adsorbed then became incorporated within the Fe(III) (oxyhydr)oxide structure (i.e., co-precipitated) over time. Copyright © 2018 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    Eitel, Eryn M.; Taillefert, Martial

    2017-10-01

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

  9. Modified composites based on mesostructured iron oxyhydroxide and synthetic minerals: A potential material for the treatment of various toxic heavy metals and its toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Chung, Seung-Gun [Center for Water Resource Cycle Research, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Ryu, Jae-Chun; Song, Mi-Kyung [Center for Integrated Risk Research, Cellular and Molecular Toxicology Laboratory, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); An, Byungryul [Center for Water Resource Cycle Research, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Kim, Song-Bae [Environmental Functional Materials and Biocolloids Laboratory, Seoul National University, Seoul 151-921 (Korea, Republic of); Lee, Sang-Hyup [Center for Water Resource Cycle Research, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Graduate School of Convergence Green Technology and Policy, Korea University, Seoul 136-701 (Korea, Republic of); Choi, Jae-Woo, E-mail: plead36@kist.re.kr [Center for Water Resource Cycle Research, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)

    2014-02-01

    Graphical abstract: - Highlights: • Meso-iron-oxyhydroxide was found to be efficient for anion heavy metal adsorption. • The composite bead can simultaneously remove the cations and anions of heavy metals. • Powdered form had stronger cytotoxicity than did the granular form. • Adsorbent recovery is facilitated by granulation process of powder-type. - Abstract: The composites of mesostructured iron oxyhydroxide and/or commercial synthetic zeolite were investigated for use in the removal of toxic heavy metals, such as cadmium, copper, lead and arsenic, from aqueous solution. Four types of adsorbents, dried alginate beads (DABs), synthetic-zeolite impregnated beads (SZIBs), meso-iron-oxyhydroxide impregnated beads (MIOIBs) and synthetic-zeolite/meso-iron-oxyhydroxide composite beads (SZMIOIBs), were prepared for heavy metal adsorption tests. Laboratory experiments were conducted to investigate the removal efficiencies of cations and anions of heavy metals and the possibility of regenerating the adsorbents. Among these adsorbents, the MIOIBs can simultaneously remove cations and anions of heavy metals; they have high adsorption capacities for lead (60.1 mg g{sup −1}) and arsenic (71.9 mg g{sup −1}) compared with other adsorbents, such as DABs (158.1 and 0.0 mg g{sup −1}), SZIB (42.9 and 0.0 mg g{sup −1}) and SZMIOIB (54.0 and 5.9 mg g{sup −1}) for lead and arsenic, respectively. Additionally, the removal efficiency was consistent at approximately 90%, notwithstanding repetitive regeneration. The characteristics of meso-iron-oxyhydroxide powder were confirmed by X-ray diffraction, Brunauer–Emmett–Teller and transmission electron microscopy. We also performed a comparative toxicity study that indicated that much lower concentrations of the powdered form of mesostructured iron oxyhydroxide had stronger cytotoxicity than the granular form. These results suggest that the granular form of meso iron oxyhydroxide is a more useful and safer adsorbent for

  10. Clay minerals, metallic oxides and oxy-hydroxides and soil organic carbon distribution within soil aggregates in temperate forest soils

    Science.gov (United States)

    Gartzia-Bengoetxea, Nahia; Fernández-Ugalde, Oihane; Virto, Iñigo; Arias-González, Ander

    2017-04-01

    Soil mineralogy is of primary importance for key environmental services provided by soils like carbon sequestration. However, current knowledge on the effects of clay mineralogy on soil organic carbon (SOC) stabilization is based on limited and conflicting data. In this study, we investigated the relationship between clay minerals, metallic oxides and oxy-hydroxides and SOC distribution within soil aggregates in mature Pinus radiata D.Don forest plantations. Nine forest stands located in the same geographical area of the Basque Country (North of Spain) were selected. These stands were planted on different parent material (3 on each of the following: sandstone, basalt and trachyte). There were no significant differences in climate and forest management among them. Moreover, soils under these plantations presented similar content of clay particles. We determined bulk SOC storage, clay mineralogy, the content of Fe-Si-Al-oxides and oxyhydroxides and the distribution of organic C in different soil aggregate sizes at different soil depths (0-5 cm and 5-20 cm). The relationship between SOC and abiotic factors was investigated using a factor analysis (PCA) followed by stepwise regression analysis. Soils developed on sandstone showed significantly lower concentration of SOC (29 g C kg-1) than soils developed on basalts (97 g C kg-1) and trachytes (119 g C kg-1). The soils on sandstone presented a mixed clay mineralogy dominated by illite, with lesser amounts of hydroxivermiculite, hydrobiotite and kaolinite, and a total absence of interstratified chlorite/vermiculite. In contrast, the major crystalline clay mineral identified in the soils developed on volcanic rocks was interstratified chlorite/vermiculite. Nevertheless, no major differences were observed between basaltic and trachytic soils in the clay mineralogy. The selective extraction of Fe showed that the oxalate extractable iron was significantly lower in soils on sandstone (3.7%) than on basalts (11.2%) and

  11. Modified composites based on mesostructured iron oxyhydroxide and synthetic minerals: a potential material for the treatment of various toxic heavy metals and its toxicity.

    Science.gov (United States)

    Chung, Seung-Gun; Ryu, Jae-Chun; Song, Mi-Kyung; An, Byungryul; Kim, Song-Bae; Lee, Sang-Hyup; Choi, Jae-Woo

    2014-02-28

    The composites of mesostructured iron oxyhydroxide and/or commercial synthetic zeolite were investigated for use in the removal of toxic heavy metals, such as cadmium, copper, lead and arsenic, from aqueous solution. Four types of adsorbents, dried alginate beads (DABs), synthetic-zeolite impregnated beads (SZIBs), meso-iron-oxyhydroxide impregnated beads (MIOIBs) and synthetic-zeolite/meso-iron-oxyhydroxide composite beads (SZMIOIBs), were prepared for heavy metal adsorption tests. Laboratory experiments were conducted to investigate the removal efficiencies of cations and anions of heavy metals and the possibility of regenerating the adsorbents. Among these adsorbents, the MIOIBs can simultaneously remove cations and anions of heavy metals; they have high adsorption capacities for lead (60.1mgg(-1)) and arsenic (71.9mgg(-1)) compared with other adsorbents, such as DABs (158.1 and 0.0mgg(-1)), SZIB (42.9 and 0.0mgg(-1)) and SZMIOIB (54.0 and 5.9mgg(-1)) for lead and arsenic, respectively. Additionally, the removal efficiency was consistent at approximately 90%, notwithstanding repetitive regeneration. The characteristics of meso-iron-oxyhydroxide powder were confirmed by X-ray diffraction, Brunauer-Emmett-Teller and transmission electron microscopy. We also performed a comparative toxicity study that indicated that much lower concentrations of the powdered form of mesostructured iron oxyhydroxide had stronger cytotoxicity than the granular form. These results suggest that the granular form of meso iron oxyhydroxide is a more useful and safer adsorbent for heavy metal treatment than the powdered form. This research provides promising results for the application of MIOIBs as an adsorbent for various heavy metals from wastewater and sewage. Copyright © 2013 Elsevier B.V. All rights reserved.

  12. Hard X-ray total scattering study on the structure of Si-dopped ferric oxyhydroxides and products of their transformation

    Science.gov (United States)

    Pieczara, Gabriela; Borkiewicz, Olaf; Manecki, Maciej; Rzepa, Grzegorz

    2016-04-01

    Here we report the results of a detailed structural investigation, using synchrotron-based pair distribution function analyses (PDF) and high-resolution X-ray diffraction (HR-XRD), on a series of Si-bearing synthetic analogues of ferrihydrite with a range of Si/Fe ratio relevant to geological environments and on products of their thermal transformation. Hard X-ray total scattering data suitable for PDF analyses have been collected at the PDF-dedicated beamline 11-ID-B and the HR-XRD data at beamline 11-BM of the Advanced Photon Source (APS) at Argonne National Laboratory (ANL). Ferrihydrite is a poorly crystalline, nano-sized hydrous ferric oxyhydroxide with a nominal/ideal formula Fe5HO8•4H2O. Its chemical composition however, can vary significantly and the atomic structure is yet to be fully understood despite multitude of structural studies undertaken over the past two decades (Michel et al., 2007; Manceau, 2009). One of the most commonly discussed and still unsettled contention points regarding the structural arrangements of ferrihydrite is related to the presence or absence of tetraherdally coordinated iron(III) within its structure. The majority of experimental work carried out to date focused on pure, synthetic ferrihydrite analogues with chemical composition close to ideal/nominal. This approach is clearly a significant oversimplification of natural ferrihydrite which always contains substantial amounts of admixtures, with Si, C, P, As, Ca, S and Al being the most common. One of the most important and the most commonly encountered impurities is Si, in the form of silicate ion that has strong affinity for ferrihydrite. SiO2content in natural ferrihydrites can vary substantially but generally falls with the range of 2.6-31.5 wt% (Cismasu et al., 2011). In certain environments however, such as modern seafloor hydrothermal vents, higher Si/Fe ratios (up to ca. 3) have been reported (Sun et al., 2013). The results of previous reports indicate that silicate

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

    Science.gov (United States)

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

    2012-06-19

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

  14. Synthesis of multi-walled carbon nanotubes/{beta}-FeOOH nanocomposites with high adsorption capacity

    Energy Technology Data Exchange (ETDEWEB)

    Song Haojie, E-mail: shj6922@163.com [School of Materials Science and Engineering, Jiangsu University (China); Liu Lei [Pharmaceutic College of Henan University (China); Jia Xiaohua; Min Chunying [School of Materials Science and Engineering, Jiangsu University (China)

    2012-12-15

    A hybrid nanostructure of multi-walled carbon nanotubes (CNTs) and {beta}-ferric oxyhydroxide ({beta}-FeOOH) nanoparticles is synthesized by ultrasonic-assisted in situ hydrolysis of the precursor ferric chloride and CNTs. Characterization by X-ray diffraction, scanning electron microscopy , and transmission electron microscopy establishes the nanohybrid structure of the synthesized sample. The results revealed that the surface of CNTs was uniformly assembled by numerous {beta}-FeOOH nanoparticles and had an average diameter of 3 nm. The formation route of anchoring {beta}-FeOOH nanoparticles onto CNTs was proposed as the intercalation and adsorption of iron ions onto the wall of CNTs, followed by the nucleation and growth of {beta}-FeOOH nanoparticles. The values of remanent magnetization (M{sub r}) and coercivity (H{sub c}) of the as-synthesized CNTs/{beta}-FeOOH nanocomposites were 0.1131 emu g, and 490.824 Oe, respectively. Furthermore, CNTs/{beta}-FeOOH nanocomposites showed a very high adsorption capacity of Congo red and thus these nanocomposites can be used as good adsorbents and can be used for the removal of the dye of Congo red from the waste water system.

  15. Primary sink and source of geogenic arsenic in sedimentary aquifers in the southern Choushui River alluvial fan, Taiwan

    International Nuclear Information System (INIS)

    Lu, Kuang-Liang; Liu, Chen-Wuing; Wang, Sheng-Wei; Jang, Cheng-Shin; Lin, Kao-Hung; Liao, Vivian Hsiu-Chuan; Liao, Chung-Min; Chang, Fi-John

    2010-01-01

    This work characterized the sink and source/mobility of As in the As-affected sedimentary aquifers of the southern Choushui River alluvial fan, central Taiwan. Major mineral phases and chemical components were determined by XRD and X-ray photoelectron spectroscopy (XPS). The partitioning of As and Fe among cores were determined by sequential extraction. Based on XPS results, the primary forms of Fe were hematite, goethite and magnetite. Sequential extraction data and the XRF analysis indicated that Fe oxyhydroxides and sulfides were likely to be the major sinks of As, particularly in the distal-fan. Furthermore, Fe oxyhydroxides retained higher As contents than As-bearing sulfides. The reductive dissolution of Fe oxyhydroxides, which accompanied high levels of HCO 3 - and NH 4 + concentrations, was likely the principal release mechanism of As into groundwater in this area. The dual roles of Fe oxyhydroxides which are governed by the local redox condition act as a sink and source in the aquifer. Ionic replacement by PO 4 3- and HCO 3 - along with seasonal water table fluctuation, caused by monsoons and excessive pumping, contributed specific parts of As in the groundwater. The findings can be used to account for the inconsistency between Fe and As concentrations observed in groundwater.

  16. Selective Dissolution Techniques, X-Ray Diffraction and Moessbauer Spectroscopy Studies of Forms of Fe in Particle-Size Fractions of an Entic Haplustoll

    International Nuclear Information System (INIS)

    Acebal, S. G.; Aguirre, M. E.; Santamaria, R. M.; Mijovilovich, A.; Petrick, S.; Saragovi, C.

    2003-01-01

    Particle-size fractions (o = mean diameter, 5-2 μm, 2-1 μm, and 57 Fe Moessbauer spectroscopy (MS). Quartz, feldspar, smectite, illite and interstratified illite-smectite are the dominant minerals whereas Fe oxides and oxy-hydroxides are present in low concentration but increase as particle size decreases. Poorly crystallized oxides (highly Al-substituted hematite and goethite) amounts are lower, comparable to or slightly higher than the hematite amounts in the o 5-2 μm, 2-1 μm and 3+ and Fe 2+ are associated to the clay minerals and/or hydroxyl-interlayered 2:1 type material present; part of this Fe 3+ is located in the hydroxy-interlayers its amount being higher in the smallest fraction. Any possible changes after the PY and NaOH treatments were not detected by MS.

  17. The gas phase oxide and oxyhydroxide chemistry of trace amounts of rhenium

    International Nuclear Information System (INIS)

    Eichler, R.; Eichler, B.; Jost, D.T.; Dressler, R.; Tuerler, A.; Gaeggeler, H.W.

    1999-01-01

    In preparation of experiments to investigate the chemical properties of bohrium (Bh, element 107) the behaviour of Re, its lighter homologue in group 7, was studied in different oxidizing chemical systems. The adsorption data of Re oxide and oxyhydroxide compounds on quartz surfaces were evaluated from results of thermochromatography experiments and confirmed in isothermal gas chromatography experiments applying 1 cm as standard state for the simple gas adsorption process: X(g) ↔ X(ads) (X = ReO 3 , HReO 4 ) ΔH ads (ReO 3 ) = -190 ± 10 kJ/mol; ΔS ads (ReO 3 ) = -179±30 J/mol K; ΔH ads (HReO 4 ) = -77 ± 5 kJ/mol; ΔS ads (HReO 4 ) = -187±50 J/mol K. An on-line separation method for oxides and oxyhydroxides of short lived Re isotopes using isothermal high temperature gas-solid adsorption chromatography was developed. Separation yields and times of group 7 elements from lanthanides (model for actinides), polonium and bismuth were determined using the model isotopes 169,170,174,176 Re, 152-155 Er, 151-154 Ho, 218 Po, and 214 Bi. An updated correlation function between the microscopic adsorption enthalpy and the macroscopic sublimation enthalpy was calculated from the experimental adsorption data of this work and literature data. (orig.)

  18. EMP and SIMS studies on Mn/Ca and Fe/Ca systematics in benthic foraminifera from the Peruvian OMZ: a contribution to the identification of potential redox proxies and the impact of cleaning protocols

    OpenAIRE

    Glock, N.; Eisenhauer, A.; Liebetrau, V.; Wiedenbeck, M.; Hensen, C.; Nehrke, G.

    2012-01-01

    In this study we present an initial dataset of Mn/Ca and Fe/Ca ratios in tests of benthic foraminifera from the Peruvian oxygen minimum zone (OMZ) determined with SIMS. These results are a contribution to a better understanding of the proxy potential of these elemental ratios for ambient redox conditions. Foraminiferal tests are often contaminated by diagenetic coatings, like Mn rich carbonate- or Fe and Mn rich (oxyhydr)oxide coatings. Thus, it is substantial to assure that...

  19. On the use of Mossbauer spectroscopy for characterisation of iron oxides and oxyhydroxides in soils

    DEFF Research Database (Denmark)

    Mørup, Steen; Ostenfeld, Christopher Worsøe

    2001-01-01

    An empirical expression for the dependence of the magnetic hyperfine field on the aluminium content and the particle size in iron oxides and oxyhydroxides is often used in Mossbauer studies of soil samples. According to this expression, the reduction of the hyperfine field in nanometer-sized part...... on the magnetic hyperfine splitting in Mossbauer spectra of magnetic nanoparticles. Therefore, an analysis of data, based on the empirical expression, which only takes into account the particle size and the aluminium content, can give erroneous results.......An empirical expression for the dependence of the magnetic hyperfine field on the aluminium content and the particle size in iron oxides and oxyhydroxides is often used in Mossbauer studies of soil samples. According to this expression, the reduction of the hyperfine field in nanometer...... discrepancy in the case of non-interacting hematite nanoparticles (accidentally) can be explained by the size dependence of the magnetic anisotropy constant. However, it is also pointed out that a third parameter, namely the strength of the inter-particle interactions, can have a significant influence...

  20. Stochastic Simulation of Isotopic Exchange Mechanisms for Fe(II)-Catalyzed Recrystallization of Goethite

    Energy Technology Data Exchange (ETDEWEB)

    Zarzycki, Piotr [Energy; Institute; Rosso, Kevin M. [Pacific Northwest

    2017-06-15

    Understanding Fe(II)-catalyzed transformations of Fe(III)- (oxyhydr)oxides is critical for correctly interpreting stable isotopic distributions and for predicting the fate of metal ions in the environment. Recent Fe isotopic tracer experiments have shown that goethite undergoes rapid recrystallization without phase change when exposed to aqueous Fe(II). The proposed explanation is oxidation of sorbed Fe(II) and reductive Fe(II) release coupled 1:1 by electron conduction through crystallites. Given the availability of two tracer exchange data sets that explore pH and particle size effects (e.g., Handler et al. Environ. Sci. Technol. 2014, 48, 11302-11311; Joshi and Gorski Environ. Sci. Technol. 2016, 50, 7315-7324), we developed a stochastic simulation that exactly mimics these experiments, while imposing the 1:1 constraint. We find that all data can be represented by this model, and unifying mechanistic information emerges. At pH 7.5 a rapid initial exchange is followed by slower exchange, consistent with mixed surface- and diffusion-limited kinetics arising from prominent particle aggregation. At pH 5.0 where aggregation and net Fe(II) sorption are minimal, that exchange is quantitatively proportional to available particle surface area and the density of sorbed Fe(II) is more readily evident. Our analysis reveals a fundamental atom exchange rate of ~10-5 Fe nm-2 s-1, commensurate with some of the reported reductive dissolution rates of goethite, suggesting Fe(II) release is the rate-limiting step in the conduction mechanism during recrystallization.

  1. Formation, aggregation and reactivity of amorphous ferric oxyhydroxides on dissociation of Fe(III)-organic complexes in dilute aqueous suspensions

    Science.gov (United States)

    Bligh, Mark W.; Waite, T. David

    2010-10-01

    While chemical reactions that take place at the surface of amorphous ferric oxides (AFO) are known to be important in aquatic systems, incorporation of these reactions into kinetic models is hindered by a lack of ability to reliably quantify the reactivity of the surface and the changes in reactivity that occur over time. Long term decreases in the reactivity of iron oxides may be considered to result from changes in the molecular structure of the solid, however, over shorter time scales where substantial aggregation may occur, the mechanisms of reactivity loss are less clear. Precipitation of AFO may be described as a combination of homogeneous and heterogeneous reactions, however, despite its potentially significant role, the latter reaction is usually neglected in kinetic models of aquatic processes. Here, we investigate the role of AFO in scavenging dissolved inorganic ferric (Fe(III)) species (Fe') via the heterogeneous precipitation reaction during the net dissociation of organically complexed Fe(III) in seawater. Using sulfosalicylic acid (SSA) as a model ligand, AFO was shown to play a significant role in inducing the net dissociation of the Fe-SSA complexes with equations describing both the heterogeneous precipitation reaction and the aging of AFO being required to adequately describe the experimental data. An aggregation based mechanism provided a good description of AFO aging over the short time scale of the experiments. The behaviour of AFO described here has implications for the bioavailability of iron in natural systems as a result of reactions involving AFO which are recognised to occur over time scales of minutes, including adsorption of Fe' and AFO dissolution, precipitation and ageing.

  2. 30 CFR 816.41 - Hydrologic-balance protection.

    Science.gov (United States)

    2010-07-01

    ... waste disposal areas and fills, so as to allow the movement of water to the ground-water system. (c...) Coal processing waste; (iii) Fly ash from a coal-fired facility; (iv) Sludge from an acid-mine-drainage... protection or replacement of water rights, and to support approved postmining land uses in accordance with...

  3. Fe-C-S systematics in Bengal Fan sediments

    Science.gov (United States)

    Volvoikar, S. P.; Mazumdar, A.; Goswami, H.; Pujari, S.; Peketi, A.

    2017-12-01

    Global biogeochemical cycles of iron, carbon and sulfur (Fe-C-S) are interrelated. Sulfate reduction in marine sediments is the major factor controlling the cycling and burial of carbon, sulfur and iron. Organoclastic sulfate reduction and anaerobic oxidation of methane (AOM) are the two main processes responsible for sulfate reduction in marine sediments. The amount and reactivity of organic matter, iron minerals and concentrations of dissolved sulfide in pore water control the burial of iron sulfide and organic bound sulfur in marine sediments. Here we investigate the sulfidization process in a sediment core from the western part of upper Bay of Bengal fan characterized by efficient burial of organic matter with siliclastic load. A 30 m long sediment core (MD 161/29, Lat. 170 18.04' N, Long. 870 22.56' E, water depth: 2434m) was collected onboard Marion Dufresne (May, 2007) and studied for Fe-S speciation and organic matter characterization. Buffered dithionite extractable iron (FeD) varies from 0.71 to 1.43 wt % (Avg. 0.79 wt %). FeD represents Fe oxides and oxyhydroxides mainly, ferrihydrite, lepidocrocite, goethite and hematite. Acid volatile sulfur (AVS) varies from 0.0015 to 0.63 wt % (avg: 0.058 wt %), while chromium reducible sulfur (CRS) varies from 0.00047 to 0.29 wt % (avg. 0.054 wt %). Based on the vertical distribution patterns of FeD, AVS and CRS, the core is divided into three zones, the lower (3000 to 1833 cm), middle (1833 to 398 cm) and upper (398 cm to surface) zones. FeD shows higher concentration in the lower zone. FeTR (FeOx + FeD + FeCRS + FeAVS) also exhibit higher concentration in this zone, suggesting higher availability of reactive iron for iron sulfide precipitation. AVS, elemental sulfur, spikes of CRS and gradual enrichment of δ34SAVS and δ34SCRS with sharp peaks in-between is noted in the lower zone. The gradual enrichment of δ34SAVS and δ34SCRS is the outcome of late diagenetic pyritization with higher availability of sulfide

  4. Formation of magnetic aluminium oxyhydroxide nanorods and use for hyperthermal effects

    International Nuclear Information System (INIS)

    Jha, Himendra; Schmidt-Stein, Felix; Shrestha, Nabeen K; Schmuki, Patrik; Kettering, Melanie; Hilger, Ingrid

    2011-01-01

    In the present work, we show that a porous alumina template can easily be filled with magnetic nanoparticles and then be sealed by a hot water treatment (by forming an aluminium oxyhydroxide (AlOOH) sealant layer). The porous layer then can be separated from the substrate by an etch to form free magnetic AlOOH nano-capsules. The process allows for a straightforward and highly defined size control of the magnetic units and can easily be scaled up. Furthermore, as AlOOH is biocompatible and has been used as a drug adjuvant for human use, the nanorod shaped capsules are highly promising for biomedical applications such as hyperthermal effects (heating in alternating magnetic fields).

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

    Science.gov (United States)

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

    2018-03-01

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

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

    Science.gov (United States)

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

    2013-01-01

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

  7. Multilayered films of cobalt oxyhydroxide nanowires/manganese oxide nanosheets for electrochemical capacitor

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Huajun [State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014 (China); ARC Centre of Excellence for Functional Nanomaterials, School of Chemical Engineering and AIBN, The University of Queensland, St Lucia, Brisbane, QLD 4072 (Australia); Tang, Fengqiu; Mukherji, Aniruddh; Yan, Xiaoxia; Wang, Lianzhou (Max) Lu, Gao Qing [ARC Centre of Excellence for Functional Nanomaterials, School of Chemical Engineering and AIBN, The University of Queensland, St Lucia, Brisbane, QLD 4072 (Australia); Lim, Melvin [Division of Environmental and Water Resources Engineering, School of Civil and Environmental Engineering, Nanyang Technological University, 639798 (Singapore)

    2010-01-15

    Multilayered films of cobalt oxyhydroxide nanowires (CoOOHNW) and exfoliated manganese oxide nanosheet (MONS) are fabricated by potentiostatic deposition and electrostatic self-assembly on indium-tin oxide coated glass substrates. The morphology and chemical composition of these films are characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectra (XPS) and the potential application as electrochemical supercapacitors are investigated using cyclic voltammetry and charge-discharge measurements. These ITO/CoOOHNW/MONS multilayered film electrodes exhibit excellent electrochemical capacitance properties, including high specific capacitance (507 F g{sup -1}) and long cycling durability (less 2% capacity loss after 5000 charge/discharge cycles). These characteristics indicate that these newly developed films may find important application for electrochemical capacitors. (author)

  8. Flow Velocity Effects on Fe(III Clogging during Managed Aquifer Recharge Using Urban Storm Water

    Directory of Open Access Journals (Sweden)

    Xinqiang Du

    2018-03-01

    Full Text Available Storm water harvesting and storage has been employed for nearly a hundred years, and using storm water to recharge aquifers is one of the most important ways to relieve water scarcity in arid and semi-arid regions. However, it cannot be widely adopted because of clogging problems. The risk of chemical clogging is mostly associated with iron oxyhydroxide precipitation; anhydrous ferric oxide (HFO clogging remains a problem in many wellfields. This paper investigates Fe(III clogging levels at three flow velocities (Darcy velocities, 0.46, 1.62 and 4.55 m/d. The results indicate that clogging increases with flow velocity, and is mostly affected by the first 0–3 cm of the column. The highest water velocity caused full clogging in 35 h, whereas the lowest took 53 h to reach an stable 60% reduction in hydraulic conductivity. For the high flow velocity, over 90% of the HFO was deposited in the 0–1 cm section. In contrast, the lowest flow velocity deposited only 75% in this section. Fe(III deposition was used as an approximation for Fe(OH3. High flow velocity may promote Fe(OH3 flocculent precipitate, thus increasing Fe(III deposition. The main mechanism for a porous matrix interception of Fe(III colloidal particles was surface filtration. Thus, the effects of deposition, clogging phenomena, and physicochemical mechanisms, are more significant at higher velocities.

  9. Structure of Fe(III) precipitates generated by Fe(0) electrocoagulation in the presence of groundwater ions

    Science.gov (United States)

    van Genuchten, C. M.; Pena, J.; Addy, S. E.; Gadgil, A. J.

    2012-12-01

    Electrocoagulation (EC) using Fe(0) electrodes is an inexpensive and efficient technology capable of removing a variety of contaminants from water supplies. Because of its ease of use and modest electricity and Fe(0) requirements, EC has potential as an arsenic-removal technology for rural South Asia, where millions drink groundwater contaminated by arsenic. In EC, a small external voltage applied to a sacrificial Fe(0) anode in contact with an electrolyte (e.g. pumped groundwater containing arsenic) promotes the oxidative dissolution of Fe ions, which polymerize and create reactive hydrous ferric oxides (HFO) in-situ with a high affinity for binding contaminants. The chemical composition of the electrolyte influences EC performance. For example, major inorganic ions present in groundwater (e.g. Ca, Mg, P, As(V), Si) alter the pathway by which FeO6 oligomers polymerize to form crystalline Fe (oxyhydr)oxide minerals. Because the precipitate structure largely determines properties that govern the efficiency of EC systems (e.g. precipitate reactivity and colloidal stability), it is essential to understand the individual and interdependent structural effects of common groundwater ions. In this work, we integrate Fe K-edge EXAFS spectroscopy with the Pair Distribution Function (PDF) technique to create a detailed description of EC precipitate structure as a function of electrolyte chemistry. EC precipitate samples were generated in a range of individual and combined concentrations of Ca, Mg, P, As(V), and Si, encompassing most of the typical levels found in natural groundwater. Combining complementary EXAFS and PDF techniques with batch uptake experiments and general chemical reasoning, we obtain structural representations of EC precipitates that are inaccessible with any single characterization technique. Our results indicate that the presence of As(V), P, and Si oxyanions promote the formation of nanoscale material bearing similar, but not identical, intermediate

  10. Effects of Sucroferric Oxyhydroxide Compared to Lanthanum Carbonate and Sevelamer Carbonate on Phosphate Homeostasis and Vascular Calcifications in a Rat Model of Chronic Kidney Failure

    Directory of Open Access Journals (Sweden)

    Olivier Phan

    2015-01-01

    Full Text Available Elevated serum phosphorus, calcium, and fibroblast growth factor 23 (FGF23 levels are associated with cardiovascular disease in chronic renal disease. This study evaluated the effects of sucroferric oxyhydroxide (PA21, a new iron-based phosphate binder, versus lanthanum carbonate (La and sevelamer carbonate (Se, on serum FGF23, phosphorus, calcium, and intact parathyroid hormone (iPTH concentrations, and the development of vascular calcification in adenine-induced chronic renal failure (CRF rats. After induction of CRF, renal function was significantly impaired in all groups: uremic rats developed severe hyperphosphatemia, and serum iPTH increased significantly. All uremic rats (except controls then received phosphate binders for 4 weeks. Hyperphosphatemia and increased serum iPTH were controlled to a similar extent in all phosphate binder-treatment groups. Only sucroferric oxyhydroxide was associated with significantly decreased FGF23. Vascular calcifications of the thoracic aorta were decreased by all three phosphate binders. Calcifications were better prevented at the superior part of the thoracic and abdominal aorta in the PA21 treated rats. In adenine-induced CRF rats, sucroferric oxyhydroxide was as effective as La and Se in controlling hyperphosphatemia, secondary hyperparathyroidism, and vascular calcifications. The role of FGF23 in calcification remains to be confirmed.

  11. The Redox Dynamics of Iron in a Seasonally Waterlogged Forest Soil (Chaux Forest, Eastern France) Traced with Rare Earth Element Distribution Patterns

    Science.gov (United States)

    Steinmann, M.; Floch, A. L.; Lucot, E.; Badot, P. M.

    2014-12-01

    The oxyhydroxides of iron are common soil minerals and known to control the availability of various major and trace elements essential for biogeochemical processes. We present a study from acidic natural forest soils, where reducing redox conditions due to seasonal waterlogging lead to the dissolution of Fe-oxyhydroxides, and to the release of Fe to soil water. In order to study in detail the mechanism of redox cycling of Fe, we used Rare Earth Element (REE) distribution patterns, because an earlier study has shown that they are a suitable tool to identify trace metal sources during soil reduction in wetland soils (Davranche et al., 2011). The REE patterns of soil leachates obtained with the modified 3-step BCR extraction scheme of Rauret et al., (1999) were compared with those of natural soil water. The adsorbed fractions (F1 leach), the reducible fraction of the deepest soil horizon H4 (F2 leach, 50-120 cm), and the oxidizable fractions of horizons H2 to H4 (F3 leachs, 24-120 cm) yielded REE patterns almost identical to soil water (see figure), showing that the REE and trace metal content of soil water was mainly derived from the F1 pool, and from the F2 and F3 pools of the clay mineral-rich deep soil horizons. In contrast, the F2 leach mobilized mainly Fe-oxyhydroxides associated with organic matter of the surface soil and yielded REE patterns significantly different from those of soil water. These results suggest that the trace metal content of soil water in hydromorphic soils is primarily controlled by the clay fraction of the deeper soil horizons and not by organic matter and related Fe-oxyhydroxides of the surface soil. Additional analyses are in progress in order to verify whether the REE and trace metals of the deeper soil horizons were directly derived from clay minerals or from associated Fe-oxyhydroxide coatings. Refs cited: Davranche et al. (2011), Chem. Geol. 284; Rauret et al. (1999), J. Environ. Monit. 1.

  12. Chemical Force Spectroscopy Evidence Supporting the Layer-by-Layer Model of Organic Matter Binding to Iron (oxy)Hydroxide Mineral Surfaces

    KAUST Repository

    Chassé , Alexander W.; Ohno, Tsutomu; Higgins, Steven R.; Amirbahman, Aria; Yildirim, Nadir; Parr, Thomas B.

    2015-01-01

    © 2015 American Chemical Society. The adsorption of dissolved organic matter (DOM) to metal (oxy)hydroxide mineral surfaces is a critical step for C sequestration in soils. Although equilibrium studies have described some of the factors controlling this process, the molecular-scale description of the adsorption process has been more limited. Chemical force spectroscopy revealed differing adhesion strengths of DOM extracted from three soils and a reference peat soil material to an iron (oxy)hydroxide mineral surface. The DOM was characterized using ultrahigh-resolution negative ion mode electrospray ionization Fourier Transform ion cyclotron resonance mass spectrometry. The results indicate that carboxyl-rich aromatic and N-containing aliphatic molecules of DOM are correlated with high adhesion forces. Increasing molecular mass was shown to decrease the adhesion force between the mineral surface and the DOM. Kendrick mass defect analysis suggests that mechanisms involving two carboxyl groups result in the most stable bond to the mineral surface. We conceptualize these results using a layer-by-layer "onion" model of organic matter stabilization on soil mineral surfaces.

  13. Chemical Force Spectroscopy Evidence Supporting the Layer-by-Layer Model of Organic Matter Binding to Iron (oxy)Hydroxide Mineral Surfaces

    KAUST Repository

    Chassé, Alexander W.

    2015-08-18

    © 2015 American Chemical Society. The adsorption of dissolved organic matter (DOM) to metal (oxy)hydroxide mineral surfaces is a critical step for C sequestration in soils. Although equilibrium studies have described some of the factors controlling this process, the molecular-scale description of the adsorption process has been more limited. Chemical force spectroscopy revealed differing adhesion strengths of DOM extracted from three soils and a reference peat soil material to an iron (oxy)hydroxide mineral surface. The DOM was characterized using ultrahigh-resolution negative ion mode electrospray ionization Fourier Transform ion cyclotron resonance mass spectrometry. The results indicate that carboxyl-rich aromatic and N-containing aliphatic molecules of DOM are correlated with high adhesion forces. Increasing molecular mass was shown to decrease the adhesion force between the mineral surface and the DOM. Kendrick mass defect analysis suggests that mechanisms involving two carboxyl groups result in the most stable bond to the mineral surface. We conceptualize these results using a layer-by-layer "onion" model of organic matter stabilization on soil mineral surfaces.

  14. Rates of As and trace-element mobilization caused by Fe reduction in mixed BTEX–ethanol experimental plumes

    Science.gov (United States)

    Ziegler, Brady A.; McGuire, Jennifer T.; Cozzarelli, Isabelle M.

    2015-01-01

    Biodegradation of organic matter, including petroleum-based fuels and biofuels, can create undesired secondary water-quality effects. Trace elements, especially arsenic (As), have strong adsorption affinities for Fe(III) (oxyhydr)-oxides and can be released to groundwater during Fe-reducing biodegradation. We investigated the mobilization of naturally occurring As, cobalt (Co), chromium (Cr), and nickel (Ni) from wetland sediments caused by the introduction of benzene, toluene, ethylbenzene, and xylenes (BTEX) and ethanol mixtures under iron- and nitrate-reducing conditions, using in situ push–pull tests. When BTEX alone was added, results showed simultaneous onset and similar rates of Fe reduction and As mobilization. In the presence of ethanol, the maximum rates of As release and Fe reduction were higher, the time to onset of reaction was decreased, and the rates occurred in multiple stages that reflected additional processes. The concentration of As increased from <1 μg/L to a maximum of 99 μg/L, exceeding the 10 μg/L limit for drinking water. Mobilization of Co, Cr, and Ni was observed in association with ethanol biodegradation but not with BTEX. These results demonstrate the potential for trace-element contamination of drinking water during biodegradation and highlight the importance of monitoring trace elements at natural and enhanced attenuation sites.

  15. Arsenic mobility in groundwater/surface water systems in carbonate-rich Pleistocene glacial drift aquifers (Michigan)

    International Nuclear Information System (INIS)

    Szramek, Kathryn; Walter, Lynn M.; McCall, Patti

    2004-01-01

    Within the Lower Peninsula of Michigan, groundwaters from the Marshall Formation (Mississippian) contain As derived from As-rich pyrites, often exceeding the World Heath Organization drinking water limit of 10 μg/L. Many Michigan watersheds, established on top of Pleistocene glacial drift derived from erosion of the underlying Marshall Formation, also have waters with elevated As. The Huron River watershed in southeastern Lower Michigan is a well characterized hydrogeochemical system of glacial drift deposits, proximate to the Marshall Fm. subcrop, which hosts carbonate-rich groundwaters, streams, and wetlands (fens), and well-developed soil profiles. Aqueous and solid phase geochemistry was determined for soils, soil waters, surface waters (streams and fens) and groundwaters from glacial drift aquifers to better understand the hydrogeologic and chemical controls on As mobility. Soil profiles established on the glacial drift exhibit enrichment in both Fe and As in the oxyhydroxide-rich zone of accumulation. The amounts of Fe and As present as oxyhydroxides are comparable to those reported from bulk Marshall Fm. core samples by previous workers. However, the As host in core samples is largely unaltered pyrite and arsenopyrite. This suggests that the transformation of Fe sulfides to Fe oxyhydroxides largely retains As and Fe at the oxidative weathering site. Groundwaters have the highest As values of all the waters sampled, and many were at or above the World Health limit. Most groundwaters are anaerobic, within the zones of Fe 3+ and As(V) reduction. Although reduction of Fe(III) oxyhydroxides is the probable source of As, there is no correlation between As and Fe concentrations. The As/Fe mole ratios in drift groundwaters are about an order of magnitude greater than those in soil profiles, suggesting that As is more mobile than Fe. This is consistent with the dominance of As(III) in these groundwaters and with the partitioning of Fe 2+ into carbonate cements. Soil

  16. X-Ray Absorption Spectroscopy of Fe-Substituted Allophane and Imogolite

    Science.gov (United States)

    Baker, L. L.; Strawn, D. G.; Nickerson, R. D.; McDaniel, P.

    2011-12-01

    substitution in tetrahedral sites occurs in allophane with Al:Si = 2:1, but not in higher-Si compositions. These results support the nanoball model for allophane (1) based on a rolled octahedral sheet and indicate that sheet is well ordered. They do not support proposed models of an incomplete octahedral sheet in high-Si allophanes. Analysis of Fe distribution suggests considerable Fe clustering in the octahedral sheet which increases with sample aging. This clustering could lead to eventual nucleation of a separate Fe (oxyhydr)oxide phase. (1) Creton et al. (2008) J Phys Chem C 112, 358.

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

    Science.gov (United States)

    Chen, Chunmei; Thompson, Aaron

    2018-01-16

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

  18. Iron Isotope Fractionation during Fe(II) Oxidation Mediated by the Oxygen-Producing Marine Cyanobacterium Synechococcus PCC 7002

    Energy Technology Data Exchange (ETDEWEB)

    Swanner, E. D.; Bayer, T.; Wu, W.; Hao, L.; Obst, M.; Sundman, A.; Byrne, J. M.; Michel, F. M.; Kleinhanns, I. C.; Kappler, A.; Schoenberg, R.

    2017-04-11

    In this study, we couple iron isotope analysis to microscopic and mineralogical investigation of iron speciation during circumneutral Fe(II) oxidation and Fe(III) precipitation with photosynthetically produced oxygen. In the presence of the cyanobacterium Synechococcus PCC 7002, aqueous Fe(II) (Fe(II)aq) is oxidized and precipitated as amorphous Fe(III) oxyhydroxide minerals (iron precipitates, Feppt), with distinct isotopic fractionation (ε56Fe) values determined from fitting the δ56Fe(II)aq (1.79‰ and 2.15‰) and the δ56Feppt (2.44‰ and 2.98‰) data trends from two replicate experiments. Additional Fe(II) and Fe(III) phases were detected using microscopy and chemical extractions and likely represent Fe(II) and Fe(III) sorbed to minerals and cells. The iron desorbed with sodium acetate (FeNaAc) yielded heavier δ56Fe compositions than Fe(II)aq. Modeling of the fractionation during Fe(III) sorption to cells and Fe(II) sorption to Feppt, combined with equilibration of sorbed iron and with Fe(II)aq using published fractionation factors, is consistent with our resulting δ56FeNaAc. The δ56Feppt data trend is inconsistent with complete equilibrium exchange with Fe(II)aq. Because of this and our detection of microbially excreted organics (e.g., exopolysaccharides) coating Feppt in our microscopic analysis, we suggest that electron and atom exchange is partially suppressed in this system by biologically produced organics. These results indicate that cyanobacteria influence the fate and composition of iron in sunlit environments via their role in Fe(II) oxidation through O2 production, the capacity of their cell surfaces to sorb iron, and the interaction of secreted organics with Fe(III) minerals.

  19. Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Du, Lei; Luo, Langli; Feng, Zhenxing; Engelhard, Mark; Xie, Xiaohong; Han, Binghong; Sun, Junming; Zhang, Jianghao; Yin, Geping; Wang, Chongmin; Wang, Yong; Shao, Yuyan

    2017-09-01

    Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhancing reaction kinetics but are limited by their scarce resource. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides etc. are their low electronic conductivity and durability. Herein, we report a highly active (360 mV overpotential at 10 mA cm–2GEO) and durable (no degradation after 20000 cycles) OER catalyst derived from bimetallic metal–organic frameworks (MOFs) precursors. This catalyst consists of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells. The electron-donation/deviation from Fe and tuned electronic structure of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity, whereas N concentration contributes negligibly. We further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by the chemical state of precursors.

  20. Ultrafast electron and energy transfer in dye-sensitized iron oxide and oxyhydroxide nanoparticles

    DEFF Research Database (Denmark)

    Gilbert, Benjamin; Katz, Jordan E.; Huse, Nils

    2013-01-01

    photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(iii) oxide nanoparticles has not been reported....... We addressed this topic by performing femtosecond transient absorption (TA) measurements of aqueous suspensions of uncoated and DCF-sensitized iron oxide and oxyhydroxide nanoparticles, and an aqueous iron(iii)–dye complex. Following light absorption, excited state relaxation times of the dye of 115...... a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye–oxide energy transfer...

  1. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    NARCIS (Netherlands)

    Van Der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; Van Der Velde, Y.

    2014-01-01

    The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from

  2. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water.

    NARCIS (Netherlands)

    Grift, van der B.; Rozemeijer, J.C.; Griffioen, J.; Velde, van der Y.

    2014-01-01

    The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and 5 P immobilization along the flow-path

  3. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    NARCIS (Netherlands)

    van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

    2014-01-01

    The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from

  4. Surface characteristics of the iron-oxyhydroxide layer formed during brick coatings by ESEM/EDS, {sup 23}Na and {sup 1}H MAS NMR, and ToF-SIMS

    Energy Technology Data Exchange (ETDEWEB)

    Allahdin, O. [Chaire Unesco « Sur la gestion de l' eau », Laboratoire Hydrosciences Lavoisier, Université de Bangui, Faculté des Sciences, B.P. 908 (Central African Republic); Wartel, M. [Université Lille1, Laboratoire LASIR (UMR CNRS 8516), Equipe Physico-chimie de l' Environnement, Bât. C8, 2" è" m" e étage, 59655 Villeneuve d' Ascq cedex (France); Mabingui, J. [Chaire Unesco « Sur la gestion de l' eau », Laboratoire Hydrosciences Lavoisier, Université de Bangui, Faculté des Sciences, B.P. 908 (Central African Republic); Revel, B. [Université Lille1, Service RMN, Bât. C4, 59655 Villeneuve d' Ascq cedex (France); Nuns, N. [Université Lille1, Institut Chevreul, 59655 Villeneuve d' Ascq cedex (France); Boughriet, A., E-mail: abdel.boughriet@univ-lille1.fr [Université Lille1, Laboratoire LASIR (UMR CNRS 8516), Equipe Physico-chimie de l' Environnement, Bât. C8, 2" è" m" e étage, 59655 Villeneuve d' Ascq cedex (France)

    2015-09-01

    Brick made locally by craftsmen in Bangui (Central African Republic) was modified first by HCl activation and second by iron-oxyhydroxide impregnation through the precipitation of ferric ions by NaOH at various fixed pH values (ranging from 3 to 13). The elemental analyses of synthesized compounds were performed using ICP-AES, and their surface chemistry/properties were investigated by environmental scanning electron microscopy (ESEM/EDS), {sup 1}H and {sup 23}Na MAS NMR spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The evidence of different {sup 23}Na chemical environments and the coexistence of Si and Al bound to ferrihydrite were made. The surface properties of this material which was found to be dependent upon synthesis pH, contributed to enhance metal uptake from water. - Highlights: • HCl-activated brick was coated at different Fe(III)-precipitation pH. • Surface properties were determined by ESEM, NMR and ToF-SIMS. • Al- and Si-bearing ferrihydrite and different Na environments were detected. • The pH used for modified-brick synthesis influenced metal uptake from water.

  5. Kinetics of Fe(II)-catalyzed transformation of 6-line ferrihydrite under anaerobic flow conditions

    Energy Technology Data Exchange (ETDEWEB)

    Yang, L.; Steefel, C.I.; Marcus, M.A.; Bargar, J.R.

    2010-04-01

    The readsorption of ferrous ions produced by the abiotic and microbially-mediated reductive dissolution of iron oxy-hydroxides drives a series of transformations of the host minerals. To further understand the mechanisms by which these transformations occur and their kinetics within a microporous flow environment, flow-through experiments were conducted in which capillary tubes packed with ferrihydrite-coated glass spheres were injected with inorganic Fe(II) solutions under circumneutral pH conditions at 25 C. Synchrotron X-ray diffraction was used to identify the secondary phase(s) formed and to provide data for quantitative kinetic analysis. At concentrations at and above 1.8 mM Fe(II) in the injection solution, magnetite was the only secondary phase formed (no intermediates were detected), with complete transformation following a nonlinear rate law requiring 28 hours and 150 hours of reaction at 18 and 1.8 mM Fe(II), respectively. However, when the injection solution consisted of 0.36 mM Fe(II), goethite was the predominant reaction product and formed much more slowly according to a linear rate law, while only minor magnetite was formed. When the rates are normalized based on the time to react half of the ferrihydrite on a reduced time plot, it is apparent that the 1.8 mM and 18 mM input Fe(II) experiments can be described by the same reaction mechanism, while the 0.36 input Fe(II) experiment is distinct. The analysis of the transformation kinetics suggest that the transformations involved an electron transfer reaction between the aqueous as well as sorbed Fe(II) and ferrihydrite acting as a semiconductor, rather than a simple dissolution and recrystallization mechanism. A transformation mechanism involving sorbed inner sphere Fe(II) alone is not supported, since the essentially equal coverage of sorption sites in the 18 mM and 1.8 mM Fe(II) injections cannot explain the difference in the transformation rates observed.

  6. Photoemission study of metallic iron nanoparticles surface aging in biological fluids. Influence on biomolecules adsorption

    International Nuclear Information System (INIS)

    Canivet, L.; Denayer, F.O.; Champion, Y.; Cenedese, P.; Dubot, P.

    2014-01-01

    Iron nanoparticles (nFe) prepared by vaporization and cryogenic condensation process (10–100 nm) has been exposed to Hank's balanced salt solution (HBSS) and the B-Ali cell growth fluids. These media can be used for cellular growth to study nFe penetration through cell membrane and its induced cytotoxicity. Surface chemistry of nFe exposed to such complex fluids has been characterized as the nanoparticles surface can be strongly changed by adsorption or corrosion processes before reaching intracellular medium. Particle size and surface chemistry have been characterized by scanning electron microscopy (SEM) and high-resolution X-ray photoelectron spectroscopy (HR-XPS). Exposition of nFe particles to growth and differentiation media leads to the formation of an oxy-hydroxide layer containing chlorinated species. We found that the passivated Fe 2 O 3 layer of the bare nFe particles is rapidly transformed into a thicker oxy-hydroxide layer that has a greater ability to adsorb molecular ions or ionic biomolecules like proteins or DNA.

  7. Influence of substrate rocks on Fe-Mn crust composition

    Science.gov (United States)

    Hein, J.R.; Morgan, C.L.

    1999-01-01

    Principal Component and other statistical analyses of chemical and mineralogical data of Fe-Mn oxyhydroxide crusts and their underlying rock substrates in the central Pacific indicate that substrate rocks do not influence crust composition. Two ridges near Johnston Atoll were dredged repetitively and up to seven substrate rock types were recovered from small areas of similar water depths. Crusts were analyzed mineralogically and chemically for 24 elements, and substrates were analyzed mineralogically and chemically for the 10 major oxides. Compositions of crusts on phosphatized substrates are distinctly different from crusts on substrates containing no phosphorite. However, that relationship only indicates that the episodes of phosphatization that mineralized the substrate rocks also mineralized the crusts that grew on them. A two-fold increase in copper contents in crusts that grew on phosphatized clastic substrate rocks, relative to crusts on other substrate rock types, is also associated with phosphatization and must have resulted from chemical reorganization during diagenesis. Phosphatized crusts show increases in Sr, Zn, Ca, Ba, Cu, Ce, V, and Mo contents and decreases in Fe, Si, and As contents relative to non-phosphatized crusts. Our statistical results support previous studies which show that crust compositions reflect predominantly direct precipitation from seawater (hydrogenetic), and to lesser extents reflect detrital input and diagenetic replacement of parts of the older crust generation by carbonate fluorapatite.

  8. Rare earth element studies of surficial sediments from the southwestern Carlsberg Ridge, Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Pattan, J.N.; Higgs, N.C.

    content. REEs show a strong positive correlation with Al+Fe+K+Mg+Na (r sup(2)=0.98) and Mn+Fe+Cu+Ni (r sup(2)=0.86) suggesting that the REE is associated with a combined phase of clays (mainly illite) and Mn-Fe oxyhydroxides. The aeolian input...

  9. Arsenic-Microbe-Mineral Interactions in Mining-Affected Environments

    Directory of Open Access Journals (Sweden)

    Karen A. Hudson-Edwards

    2013-10-01

    Full Text Available The toxic element arsenic (As occurs widely in solid and liquid mine wastes. Aqueous forms of arsenic are taken up in As-bearing sulfides, arsenides, sulfosalts, oxides, oxyhydroxides, Fe-oxides, -hydroxides, -oxyhydroxides and -sulfates, and Fe-, Ca-Fe- and other arsenates. Although a considerable body of research has demonstrated that microbes play a significant role in the precipitation and dissolution of these As-bearing minerals, and in the alteration of the redox state of As, in natural and simulated mining environments, the molecular-scale mechanisms of these interactions are still not well understood. Further research is required using traditional and novel mineralogical, spectroscopic and microbiological techniques to further advance this field, and to help design remediation schemes.

  10. Role of a unique population of lithotrophic, Fe-oxidizing bacteria in forming microbial Fe-mats at the Loihi Seamount.

    Science.gov (United States)

    Emerson, D.; Rentz, J. A.; Moyer, C. L.

    2005-12-01

    The Loihi Seamount, located 30 km SE of the island of Hawai'i, is among the most active volcanos on Earth. The summit, at a depth of 1100m, includes a 250m deep caldera (Pele's Pit) formed by an eruption in 1996. The summit, and especially Pele's Pit, are the site of extensive low to intermediate temperature (10° to 65°C) hydrothermal venting, emanating both from diffuse fissures and orifices that have substantial flow rates. The vent fluid is characterized by a low sulfide content, high CO2 concentrations and Fe(II) amounts in the 10s to 100s of μM. Associated with all vents are extensive deposits of iron oxyhydroxides that typically have 107 to 108 bacterial cells/cc associated with them. The morphology of the Fe-oxides are indicative of biological origins. We have isolated microaerophilic, obligately lithotrophic Fe-oxidizing bacteria from Loihi and describe here `Mariprofundus ferroxydans' a unique bacterium that forms a filamentous iron oxide mineral. `M. ferroxydans' is the first cultured representative of a novel division of the Proteobacteria, known previously only from clones from different hydrothermal vent sites. Molecular evidence from Loihi mats based on clone libraries and terminal restriction length polymorphism (T-RFLP) analysis of 16S rRNA genes indicate that this lineage of Fe-oxidizing organisms are common inhabitants at Loihi. We speculate that this organism and its relatives form the basis of an active microbial mat community that owe their existence to the inherent gradients of Fe(II) and O2 that exist at the Loihi vents. In a geological context this is interesting because the Loihi summit and caldera are in an O2-minima zone; O2 concentrations in the bulk seawater are around 0.5 mg/l. In effect, Loihi could serve as a proxy for the late Archaean and early Proterozoic periods when the Earth's atmosphere went from reducing to oxidizing, and it is speculated that abundant Fe(II) in the Earth's oceans served as a major sink for O2 production

  11. Change in catalyst properties during coal liquefaction; Kokoritsu sekitan ekika shokubai no kaihatsu (Hanno no shinko ni tomonau shokubai seijo no henka). 1

    Energy Technology Data Exchange (ETDEWEB)

    Koyama, T.; Sato, K.; Kaneko, T.; Shimasaki, K. [Nippon Brown Coal Liquefaction Co. Ltd., Tokyo (Japan)

    1996-10-28

    The purpose of this study is to prevent the deactivation of catalysts recycled in the 0.1 t/d bench scale unit (BSU). Catalysts recovered during reactions in the BSU and after reactions in the 5-liter autoclave were analyzed, to investigate the influences of the reaction condition on the property and activity of catalysts. Were used {gamma}-iron oxyhydroxide ({gamma}-FeOOH), {alpha}-iron oxyhydroxide ({alpha}-FeOOH), and natural pyrite (FeS2) as catalysts. At the S/Fe atomic ration of 1.2 under the BSU reaction condition, troilite was more easily formed from {gamma}-FeOOH compared with pyrite and {alpha}-FeOOH. As the reaction proceeded through the first, second, and third reactors, the crystal size increased, the pyrrhotite content decreased, and the troilite content increased. Deactivation due to the formation of troilite was irreversible. At the S/Fe of 3.0, however, both the formation of troilite and the crystal growth of pyrrhotite were not observed. It was found that the deactivation of catalysts can be remarkably suppressed. 5 refs., 6 figs., 1 tab.

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

    Directory of Open Access Journals (Sweden)

    Liang eShi

    2012-02-01

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

  13. Enhancement of particle aggregation in the presence of organic matter during neutralization of acid drainage in a stream confluence and its effect on arsenic immobilization.

    Science.gov (United States)

    Arce, Guillermo; Montecinos, Mauricio; Guerra, Paula; Escauriaza, Cristian; Coquery, Marina; Pastén, Pablo

    2017-08-01

    Acid drainage (AD) is an important environmental concern that impacts water quality. The formation of reactive Fe and Al oxyhydroxides during the neutralization of AD at river confluences is a natural attenuation process. Although it is known that organic matter (OM) can affect the aggregation of Fe and Al oxyhydroxides and the sorption of As onto their surfaces, the role of OM during the neutralization of AD at river confluences has not been studied. Field and experimental approaches were used to understand this role, using the Azufre River (pH 2) - Caracarani River (pH 8.6) confluence (northern Chile) as model system. Field measurements of organic carbon revealed a 10-15% loss of OM downstream the confluence, which was attributed to associations with Fe and Al oxyhydroxides that settle in the river bed. Laboratory mixtures of AD water with synthetic Caracarani waters under varying conditions of pH, concentration and type of OM revealed that OM promoted the aggregation of Fe oxyhydroxides without reducing As sorption, enhancing the removal of As at slightly acidic conditions (pH ∼4.5). At acidic conditions (pH ∼3), aggregation of OM - metal complexes at high OM concentrations could become the main removal mechanism. One type of OM promoted bimodal particle size distributions with larger mean sizes, possibly increasing the settling velocity of aggregates. This work contributes to a better understanding of the role of OM in AD affected basins, showing that the presence of OM during processes of neutralization of AD can enhance the removal of toxic elements. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Active slag filters-simple and sustainable phosphorus removal from wastewater using steel industry byproduct.

    Science.gov (United States)

    Pratt, C; Shilton, A

    2010-01-01

    Active filtration, where effluent is passed through a reactive substrate such as steel slag, offers a simple and cost-effective option for removing phosphorus (P) from effluent. This work summarises a series of studies that focused on the world's only full-scale active slag filter operated through to exhaustion. The filter achieved 75% P-removal during its first 5 years, reaching a retention capacity of 1.23 g P/kg slag but then its performance sharply declined. Scanning electron microscopy, X-ray diffraction, X-ray fluorescence, and chemical extractions revealed that P sequestration was primarily achieved via adsorption onto iron (Fe) oxyhydroxides on the slag's surface. It was concluded that batch equilibrium tests, whose use has been repeatedly proposed in the literature, cannot be used as an accurate predictor of filter adsorption capacity because Fe oxyhydroxides form via chemical weathering in the field, and laboratory tests don't account for this. Research into how chemical conditions affect slag's P retention capacity demonstrated that near-neutral pH and high redox are optimal for Fe oxyhydroxide stability and overall filter performance. However, as Fe oxyhydroxide sites fill up, removal capacity becomes exhausted. Attempts to regenerate P removal efficiency using physical techniques proved ineffective contrary to dogma in the literature. Based on the newly-developed understanding of the mechanisms of P removal, chemical regeneration techniques were investigated and were shown to strip large quantities of P from filter adsorption sites leading to a regenerated P removal efficiency. This raises the prospect of developing a breakthrough technology that can repeatedly remove and recover P from effluent.

  15. Magnetic and surface properties of Fe-Nb (Mo, V)-Cu-B-Si ribbons

    International Nuclear Information System (INIS)

    Butvinova, B.; Butvin, P.; Svec, P. Sr.; Matko, I.; Svec, P.; Janickovic, D.; Kadlecikova, M.

    2014-01-01

    The rapidly quenched Finemet (FeNbCuBSi) ribbons prepared by planar flow casting of the melt are very variable to obtain very good soft-magnetic properties. An appropriate thermal treatment leading to ultra-fine grain structure enables to attain such properties as desired for practical use. Increasing Fe percentage to the detriment of non-magnetic components lifts saturation induction above 1.3 T, preserves low coercivity and makes the alloy even cheaper to suit its mass production for use in power electronics. Apart from the plenty of benefits the ribbons show some risks. One of them is macroscopic heterogeneity, which often manifests via differences between surfaces and interior of a ribbon [3]. The surfaces squeeze (by in-plane force) the interior of many such ribbons and if engaged in magnetoelastic interaction, the force affects the resulting magnetic anisotropy [4]. Current research shows that changes of hysteresis loop shape come rather from surface crystallization and not from oxides namely in positively magnetostrictive alloys FeNbCuBSi known as low- Si Finemets. The object of this work is to verify whether the substitution of another element instead of Nb (usually incorporated as the grain-growth blocker) can change surface properties and affects the resulting magnetic properties. We chose V and Mo instead of Nb. Oxides, oxyhydroxides and a possible squeezing layer was looked for after higher temperature annealing which ensures partially nanocrystalline structure. (authors)

  16. Photoemission study of metallic iron nanoparticles surface aging in biological fluids. Influence on biomolecules adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Canivet, L.; Denayer, F.O. [Université de Lille 2, Droit et Santé, 42 rue P. Duez, 59000 Lille (France); Champion, Y.; Cenedese, P. [CNRS-ICMPE, 2 rue H. Dunant, 94320 Thiais (France); Dubot, P., E-mail: pdubot@icmpe.cnrs.fr [CNRS-ICMPE, 2 rue H. Dunant, 94320 Thiais (France)

    2014-07-01

    Iron nanoparticles (nFe) prepared by vaporization and cryogenic condensation process (10–100 nm) has been exposed to Hank's balanced salt solution (HBSS) and the B-Ali cell growth fluids. These media can be used for cellular growth to study nFe penetration through cell membrane and its induced cytotoxicity. Surface chemistry of nFe exposed to such complex fluids has been characterized as the nanoparticles surface can be strongly changed by adsorption or corrosion processes before reaching intracellular medium. Particle size and surface chemistry have been characterized by scanning electron microscopy (SEM) and high-resolution X-ray photoelectron spectroscopy (HR-XPS). Exposition of nFe particles to growth and differentiation media leads to the formation of an oxy-hydroxide layer containing chlorinated species. We found that the passivated Fe{sub 2}O{sub 3} layer of the bare nFe particles is rapidly transformed into a thicker oxy-hydroxide layer that has a greater ability to adsorb molecular ions or ionic biomolecules like proteins or DNA.

  17. Ab Initio Molecular Dynamics of Uranium Incorporated in Goethite (α-FeOOH): Interpretation of X-ray Absorption Spectroscopy of Trace Polyvalent Metals.

    Science.gov (United States)

    Kerisit, Sebastien; Bylaska, Eric J; Massey, Michael S; McBriarty, Martin E; Ilton, Eugene S

    2016-11-21

    Incorporation of economically or environmentally consequential polyvalent metals into iron (oxyhydr)oxides has applications in environmental chemistry, remediation, and materials science. A primary tool for characterizing the local coordination environment of such metals, and therefore building models to predict their behavior, is extended X-ray absorption fine structure spectroscopy (EXAFS). Accurate structural information can be lacking yet is required to constrain and inform data interpretation. In this regard, ab initio molecular dynamics (AIMD) was used to calculate the local coordination environment of minor amounts of U incorporated in the structure of goethite (α-FeOOH). U oxidation states (VI, V, and IV) and charge compensation schemes were varied. Simulated trajectories were used to calculate the U L III -edge EXAFS function and fit experimental EXAFS data for U incorporated into goethite under reducing conditions. Calculations that closely matched the U EXAFS of the well-characterized mineral uraninite (UO 2 ), and constrained the S 0 2 parameter to be 0.909, validated the approach. The results for the U-goethite system indicated that U(V) substituted for structural Fe(III) in octahedral uranate coordination. Charge balance was achieved by the loss of one structural proton coupled to addition of one electron into the solid (-1 H + , +1 e - ). The ability of AIMD to model higher energy states thermally accessible at room temperature is particularly relevant for protonated systems such as goethite, where proton transfers between adjacent octahedra had a dramatic effect on the calculated EXAFS. Vibrational effects as a function of temperature were also estimated using AIMD, allowing separate quantification of thermal and configurational disorder. In summary, coupling AIMD structural modeling and EXAFS experiments enables modeling of the redox behavior of polyvalent metals that are incorporated in conductive materials such as iron (oxyhydr)oxides, with

  18. Beam-induced redox transformation of arsenic during As K-edge XAS measurements: availability of reducing or oxidizing agents and As speciation.

    Science.gov (United States)

    Han, Young Soo; Jeong, Hoon Young; Hyun, Sung Pil; Hayes, Kim F; Chon, Chul Min

    2018-05-01

    During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O 2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O 2 during XAS measurements. With strict O 2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO 2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

  19. Surface oxidization-reduction reactions in Columbia Plateau basalts

    International Nuclear Information System (INIS)

    White, A.F.; Yee, A.

    1984-01-01

    Results are presented which define principal oxidation-reduction reactions expected between ground water and iron in the Umtanum and Cohassett basalt flows of south central Washington. Data include kinetics of aqueous iron speciation, rates of O 2 uptake and nature of oxyhydroxide precipitates. Such data are important in predicting behavior of radionuclides in basalt aquifers including determination of valence states, speciation, solubility, sorption, and coprecipitation on iron oxyhydroxide substrates and colloids. Analyses of the basalt by XPS indicates that ferrous iron is oxidized to ferric iron on the surface and that the total iron decreases as a function of pH during experimental weathering. Iron oxyhydroxide phases did not form surface coating on basalt surfaces but rather nucleated as separate plases in solution. No significant increases in Cs or Sr sorption were observed with increased weathering of the basalt. Concurrent increases in Fe(II) and decreases in Fe(III) in slightly to moderately acid solutions indicated continued oxidization of ferrous iron in the basalt. At neutral to basic pH, Fe(II) was strongly sorbed onto the basalt surface (Kd = 6.5 x 10 -3 1 x m 2 ) resulting in low dissolved concentrations even under anoxic conditions. The rate of O 2 uptake increased with decreasing pH. Diffusion rates (-- 10 -14 cm 2 x s -1 ), calculated using a one-dimensional analytical model, indicate grain boundary diffusion. Comparisons of Eh values calculated by Pt electrode, dissolved O 2 and Fe(II)/Fe(III) measurements showed considerable divergence, with the ferric-ferrous couple being the preferred method of estimating Eh

  20. Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Du, Lei; Luo, Langli; Feng, Zhenxing; Engelhard, Mark; Xie, Xiaohong; Han, Binghong; Sun, Junming; Zhang, Jianghao; Yin, Geping; Wang, Chongmin; Wang, Yong; Shao, Yuyan

    2017-09-01

    Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhanced reaction kinetics but are limited by their scarce resource. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides etc. are their low electronic conductivity and poor durability. Here, we report OER catalysts of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells derived from bimetallic metal–organic frameworks (MOFs) precursors. The optimal OER catalyst shows excellent activity (360 mV overpotential at 10 mA cm–2GEO) and durability (no obvious degradation after 20 000 cycles). The electron-donation from Fe and tuned electronic structure of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity. We further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by chemical state of precursors. Severe metal particle growth probably caused by oxidation of carbon shells and encapsulated nanoparticles is believed to the main mechanism for activity degradation in these catalysts.

  1. Electrochemical preparation of hematite nanostructured films for solar hydrogen production

    Directory of Open Access Journals (Sweden)

    Ebadzadeh T.

    2012-10-01

    Full Text Available Photoelectrochemical water splitting is a clean and promising technique for using a renewable source of energy, i.e., solar energy, to produce hydrogen. In this work electrochemical formation of iron oxyhydroxide and its conversion to hematite (α- Fe2O3 through thermal treatment have been studied. Oxyhydroxide iron compounds have been prepared onto SnO2/F covered glass substrate by potential cycling with two different potential sweep rate values; then calcined at 520 °C in air to obtain α-Fe2O3 nanostrutured films for their implementation as photoanode in a photoelectrochemical cell. X-ray diffraction analysis allowed finding that iron oxides films have nanocrystalline character. Scanning electron microscopy revealed that films have nanostructured morphology. The obtained results are discussed considering the influence of potential sweep rate employed during the preparation of iron oxyhydroxide film on optical, structural and morphological properties of hematite nanostructured films. Results show that films have acceptable characteristics as photoanode in a photoelectrochemical cell for hydrogen generation from water.

  2. Adsorption equilibrium of uranium on iron oxyhydroxide-PVA hydrogel spheres

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Armindo; Campos, Victor B.; Ribeiro, Luciana S.; Escanio, Camila A.; Silva, Edilaine F.; Oliveira, Felipe W., E-mail: santosa@cdtn.br, E-mail: vbc@cdtn.br, E-mail: lsr@cdtn.br, E-mail: cae@cdtn.br, E-mail: efd@cdtn.br, E-mail: fwfo@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2015-07-01

    Uranium and its compounds are considered strategic mineral resources due to its usage as an energy source and war material. They are harmful to human health. Thus, liquid waste containing low uranium content (≤100 mgU/L), from the mining and/or uranium reprocessing plants or even of the research center activities require the development of methods for their treatment, in a way to reduce its content to 15 μgU/L. Adsorption is one of these methods; it requires the synthesis of preferably spherical adsorbents, chemically and physically stable and with high adsorptive capacity. The sol-gel process can synthesize adsorbents having such characteristics, prioritizing the nanostructuring of iron oxyhydroxide in a hydrophilic PVA (polyvinyl alcohol) polymer network, which had an accessible pore structure (micro-, meso- and macropores + macroholes). We successfully obtained iron-PVA hydrogel spheres with (3433 ± 63 μm) and without (2833 ± 69 μm) macroholes. Both types of spheres have good mechanical strength and chemical stability in the 2-9 pH range. Adsorptive capacity: 413.22 mgU/g (with macroholes; Freundlich model) and 249.38 mgU/g (without macroholes; Langmuir and Freundlich models), at pH 5-6, 30 °C, and 6 h. With 280 mL of with-macrohole hydrogel spheres, we can treat 1 L of liquid waste (100 mgU/L) and reduce uranium content to 20 μgU/L. (author)

  3. Adsorption equilibrium of uranium on iron oxyhydroxide-PVA hydrogel spheres

    International Nuclear Information System (INIS)

    Santos, Armindo; Campos, Victor B.; Ribeiro, Luciana S.; Escanio, Camila A.; Silva, Edilaine F.; Oliveira, Felipe W.

    2015-01-01

    Uranium and its compounds are considered strategic mineral resources due to its usage as an energy source and war material. They are harmful to human health. Thus, liquid waste containing low uranium content (≤100 mgU/L), from the mining and/or uranium reprocessing plants or even of the research center activities require the development of methods for their treatment, in a way to reduce its content to 15 μgU/L. Adsorption is one of these methods; it requires the synthesis of preferably spherical adsorbents, chemically and physically stable and with high adsorptive capacity. The sol-gel process can synthesize adsorbents having such characteristics, prioritizing the nanostructuring of iron oxyhydroxide in a hydrophilic PVA (polyvinyl alcohol) polymer network, which had an accessible pore structure (micro-, meso- and macropores + macroholes). We successfully obtained iron-PVA hydrogel spheres with (3433 ± 63 μm) and without (2833 ± 69 μm) macroholes. Both types of spheres have good mechanical strength and chemical stability in the 2-9 pH range. Adsorptive capacity: 413.22 mgU/g (with macroholes; Freundlich model) and 249.38 mgU/g (without macroholes; Langmuir and Freundlich models), at pH 5-6, 30 °C, and 6 h. With 280 mL of with-macrohole hydrogel spheres, we can treat 1 L of liquid waste (100 mgU/L) and reduce uranium content to 20 μgU/L. (author)

  4. Magnetic Properties and Microstructure of FeOx/Fe/FePt and FeOx/FePt Films

    Directory of Open Access Journals (Sweden)

    Jai-Lin Tsai

    2013-01-01

    Full Text Available The Fe(6 nm/FePt film with perpendicular magnetization was deposited on the glass substrate. To study the oxygen diffusion effect on the coupling of Fe/FePt bilayer, the plasma oxidation with 0.5~7% oxygen flow ratio was performed during sputtered part of Fe layer and formed the FeOx(3 nm/Fe(3 nm/FePt trilayer. Two-step magnetic hysteresis loops were found in trilayer with oxygen flow ratio above 1%. The magnetization in FeOx and Fe/FePt layers was decoupled. The moments in FeOx layer were first reversed and followed by coupled Fe/FePt bilayer. The trilayer was annealed again at 500°C and 800°C for 3 minutes. When the FeOx(3 nm/Fe(3 nm/FePt trilayer was annealed at 500°C, the layers structure was changed to FeOx(6 nm/FePt bilayer due to oxygen diffusion. The hard-magnetic FeOx(6 nm/FePt film was coupled with single switching field. The FeOx/(disordered FePt layer structure was observed with further annealing at 800°C and presented soft-magnetic loop. In summary, the coupling between soft-magnetic Fe, FeOx layer, and hard-magnetic L10 FePt layer can be controlled by the oxygen diffusion behavior, and the oxidation of Fe layer was tuned by the annealing temperature. The ordered L10 FePt layer was deteriorated by oxygen and became disordered FePt when the annealed temperature was up to 800°C.

  5. Trace metals of an acid mine drainage stream using a chemical model (WATEQ) and sediment analysis

    International Nuclear Information System (INIS)

    West, K.A.; Wilson, T.P.

    1992-01-01

    The high metal contents common to the discharge of acid-mine drainage (AMD) from mines and mine spoils is an environmental concern to both government and industry. This paper reports the results of investigation of the behavior of metals in an AMD system at a former surface coal mine in Tuscarawas County, Oh. AMD discharges from seeps travels, in respective order through a laminar flow stream; a Typha-dominated wetland; a turbulent flow stream; and a sediment retention pond. Dissolved metals (Fe, Mn, Zn, Cr, Cd, Cu, and Al) major and minor components, and other parameters (pH, dissolved oxygen and Eh) were measured in the AMD water at each sample location. A chemical mineral equilibrium model (WATEQ) was used to predict the minerals which should precipitate at each site. Results suggest that the seeps are supersaturated and should be precipitating hematite, goethite and magnetite (iron oxides), and siderite (iron carbonate), whereas water of the other downstream sites were at or below equilibrium conditions for these minerals. The hydrogeochemistry of the AMD was further studied using sequential chemical attacks on the precipitate sediment surface coatings, in order to determine metal concentrations in the exchangeable, carbonate, Fe-Mn oxyhydroxide, and oxidizable fractions. The carbonate and exchangeable fractions of the precipitate are dominated by Ca and Fe, as well as Mg in the carbonate fraction. The Fe-Mn oxyhydroxide fraction contained Fe, Al, Mn, Mg, and trace metals, and also contained the greatest concentration of total elements in the system. The Fe-Mn oxyhydroxide is therefore, the major sink for metals of this AMD system. The decrease in the concentration of metals in the sediment precipitates in the downstream locations, is consistent with WATEQ and water analysis results

  6. Study of a low alloy steel rust using Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Maier, I.A.; Saragovi-Badler, C.; Labenski, F.

    1978-01-01

    Moessbauer spectroscopy has been used to analyze the internal and external rust layers of a weathering steel exposed for ten months to an urban-industrial atmosphere. Superparamagnetic α-FeOOH and γ-FeOOH were found in both layers. The external one also contained small sized delta-FeOOH and/or amorphous iron oxyhydroxide. These compounds were not present in the internal layer at this stage of the patina formation. (author)

  7. Microbial Diversity and Characteristics in Anaerobic Environments in KURT Groundwater

    International Nuclear Information System (INIS)

    Roh, Yul; Oh, Jong Min; Rhee, Sung Keun; Yong, Jong Joong

    2008-03-01

    The Underground Research Tunnel (URT) located in Korea Atomic Energy Research Institute (KAERI), Daejeon, South Korea was recently constructed as an experimental site to study radionuclide transport, biogeochemistry, radionuclide-mineral interactions for the geological disposal of high level nuclear waste. Groundwater sampled from URT was used to examine microbial diversity and to enrich metal reducing bacteria for studying microbe-metal interactions. Genomic analysis indicated that the groundwater contained diverse microorganisms such as metal reducers, metal oxidizers, anaerobic denitrifying bacteria, and bacteria for reductive dechlorination. Metal-reducing bacteria enriched from the groundwater was used to study metal reduction and biomineralization. The metal-reducing bacteria enriched with acetate or lactate as the electron donors showed the bacteria reduced Fe(III)-citrate, Fe(III) oxyhydroxide, Mn(IV) oxide, and Cr(VI) as the electron acceptors. Preliminary study indicated that the enriched bacteria were able to use glucose, lactate, acetate, and hydrogen as electron donors while reducing Fe(III)-citrate or Fe(III) oxyhydroxide as the electron acceptor. The bacteria exhibited diverse mineral precipitation capabilities including the formation of magnetite, siderite, and rhodochrosite. The results indicated that Fe(III)- and metal-reducing communities are present in URT at the KAERI

  8. Microbial Diversity in KURT Groundwater and Biomineralization Characteristics

    International Nuclear Information System (INIS)

    Roh, Yul; Rhee, Sung Keun; Oh, Jong Min; Park, Byung Jun

    2009-03-01

    The Underground Research Tunnel (URT) located in Korea Atomic Energy Research Institute (KAERI), Daejeon, South Korea was recently constructed as an experimental site to study radionuclide transport, biogeochemistry, radionuclide-mineral interactions for the geological disposal of high level nuclear waste. Groundwater sampled from URT was used to examine microbial diversity and to enrich metal reducing bacteria for studying microbe-metal interactions. Genomic analysis indicated that the groundwater contained diverse microorganisms such as metal reducers, metal oxidizers, anaerobic denitrifying bacteria, and bacteria for reductive dechlorination. Metal-reducing bacteria enriched from the groundwater was used to study metal reduction and biomineralization. The metal-reducing bacteria enriched with acetate or lactate as the electron donors showed the bacteria reduced Fe(III)-citrate, Fe(III) oxyhydroxides, Mn(IV) oxide, and Cr(VI) as the electron acceptors. Preliminary study indicated that the enriched bacteria were able to use glucose, lactate, acetate, and hydrogen as electron donors while reducing Fe(III)-citrate or Fe(III) oxyhydroxide as the electron acceptor. The bacteria exhibited diverse mineral precipitation capabilities including the formation of magnetite, siderite, and rhodochrosite. The results indicated that Fe(III)- and metal-reducing communities are present in URT at the KAERI

  9. Controls on Weathering of Pyrrhotite in a Low-Sulfide, Granitic Mine-Waste Rock in the Canadian Arctic

    Science.gov (United States)

    Langman, J. B.; Holland, S.; Sinclair, S.; Blowes, D.

    2013-12-01

    Increased environmental risk is incurred with expansion of mineral extraction in the Arctic. A greater understanding of geochemical processes associated with hard-rock mining in this cold climate is needed to evaluate and mitigate these risks. A laboratory and in-situ experiment was conducted to examine mineral weathering and the generation of acid rock drainage in a low-sulfide, run-of-mine waste rock in an Arctic climate. Rock with different concentrations of sulfides (primarily pyrrhotite [Fe7S8] containing small amounts of Co and Ni) and carbonates were weathered in the laboratory and in-situ, large-scale test piles to examine leachate composition and mineral weathering. The relatively larger sulfide-containing rock produced sufficient acid to overcome carbonate buffering and produced a declining pH environment with concomitant release of SO4, Fe, Co, and Ni. Following carbonate consumption, aluminosilicate buffering stabilized the pH above 4 until a reduction in acid generation. Results from the laboratory experiment assisted in determining that after consumption of 1.6 percent of the total sulfide, the larger sulfide-concentration test pile likely is at an internal steady-state or maximal weathering rate after seven years of precipitation input and weathering that is controlled by an annual freeze-thaw cycle. Further weathering of the test pile should be driven by external factors of temperature and precipitation in this Arctic, semi-arid region instead of internal factors of wetting and non-equilibrium buffering. It is predicted that maximal weathering will continue until at least 20 percent of the total sulfide is consumed. Using the identified evolution of sulfide consumption in this Arctic climate, a variable rate factor can now be assessed for the possible early evolution and maximal weathering of larger scale waste-rock piles and seasonal differences because of changes in the volume of a waste-rock pile undergoing active weathering due to the freeze

  10. The transformation of ferrihydrite in the presence of trace Fe(II): The effect of the anionic media

    International Nuclear Information System (INIS)

    Liu Hui; Guo Hui; Li Ping; Wei Yu

    2008-01-01

    The transformation from ferrihydrite to various iron oxides and iron oxyhydroxides has been given much attention not only in environmental science and geochemistry but also in biology and material science. This laboratory study attempted to investigate Fe(II)-induced transformation of ferrihydrite in sulfate-rich medium. The results indicate that the transformation in sulfate-rich medium differs from that in Cl - medium in the species, the amount and the morphology of products and transformation rate. Lepidocrocite is a main ingredient in the product in Cl - medium at room temperature (RT), while goethite is the only product in SO 4 2- medium at RT. Goethite particles obtained in Cl - medium are star-like but rod-like in SO 4 2- medium. The transformation rate in the latter medium is obviously slower than that in the former medium. The formation of lepidocrocite depends on both the ionic strength of the system and the dissolution rate of ferrihydrite. - Graphical abstract: Fe(II)-induced transformation of ferrihydrite in sulfate-rich medium was studied. Lepidocrocite is a main ingredient in the product in Cl - medium at room temperature (RT), while goethite is the only product in SO 4 2- medium. Goethite particles obtained in Cl - medium are star-like but rod-like in SO 4 2- medium

  11. The effect of aerobic corrosion on anaerobically-formed sulfide layers on carbon steel in dilute near-neutral pH saline solutions

    International Nuclear Information System (INIS)

    Sherar, B.W.A.; Keech, P.G.; Shoesmith, D.W.

    2013-01-01

    Highlights: •The corrosion rate is low when steel is exposed to anaerobic conditions (pH = 8.9). •An anaerobic corrosion with sulfide to aerobic switch increases the corrosion rate. •Aerobic conditions leads to corrosion and oxide deposition beneath FeS. •Continual air exposure leads to the blistering of the original FeS film. -- Abstract: The aerobic corrosion of pipeline steel was investigated in an aqueous sulfide solution by monitoring the corrosion potential and periodically measuring the polarization resistance. The properties and composition of the corrosion product deposits formed were determined using scanning electron microscopy, energy dispersive X-ray analysis, and Raman spectroscopy. The establishment of aerobic conditions leads to corrosion and (oxyhydr)oxide deposition beneath the anaerobically-formed mackinawite film originally present on the steel surface. This leads to blistering and spalling of the sulfide film. Chemical conversion of the mackinawite to Fe(III) (oxyhydr)oxides also occurs but is a relatively slow reaction

  12. Role of competing ions in the mobilization of arsenic in groundwater of Bengal Basin: insight from surface complexation modeling.

    Science.gov (United States)

    Biswas, Ashis; Gustafsson, Jon Petter; Neidhardt, Harald; Halder, Dipti; Kundu, Amit K; Chatterjee, Debashis; Berner, Zsolt; Bhattacharya, Prosun

    2014-05-15

    This study assesses the role of competing ions in the mobilization of arsenic (As) by surface complexation modeling of the temporal variability of As in groundwater. The potential use of two different surface complexation models (SCMs), developed for ferrihydrite and goethite, has been explored to account for the temporal variation of As(III) and As(V) concentration, monitored in shallow groundwater of Bengal Basin over a period of 20 months. The SCM for ferrihydrite appears as the better predictor of the observed variation in both As(III) and As(V) concentrations in the study sites. It is estimated that among the competing ions, PO4(3-) is the major competitor of As(III) and As(V) adsorption onto Fe oxyhydroxide, and the competition ability decreases in the order PO4(3-) ≫ Fe(II) > H4SiO4 = HCO3(-). It is further revealed that a small change in pH can also have a significant effect on the mobility of As(III) and As(V) in the aquifers. A decrease in pH increases the concentration of As(III), whereas it decreases the As(V) concentration and vice versa. The present study suggests that the reductive dissolution of Fe oxyhydroxide alone cannot explain the observed high As concentration in groundwater of the Bengal Basin. This study supports the view that the reductive dissolution of Fe oxyhydroxide followed by competitive sorption reactions with the aquifer sediment is the processes responsible for As enrichment in groundwater. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Preparation of FeO(OH Modified with Polyethylene Glycol and Its Catalytic Activity on the Reduction of Nitrobenzene with Hydrazine Hydrate

    Directory of Open Access Journals (Sweden)

    Ke Ying Cai

    2016-10-01

    Full Text Available Iron oxyhydroxide was prepared by dropping ammonia water to Fe(NO33.9H2O dispersed in polyethylene glycol (PEG 1000. The catalyst was characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy and laser particle size analyzer. The results showed the catalyst modified with polyethylene glycol was amorphous. The addition of PEG during the preparation make the particle size of the catalyst was smaller and more uniform. The catalytic performance was tested in the reduction of nitroarenes to corresponding amines with hydrazine hydrate, and the catalyst showed excellent activity and stability. Copyright © 2016 BCREC GROUP. All rights reserved Received: 2nd February 2016; Revised: 26th April 2016; Accepted: 7th June 2016 How to Cite: Cai, K.Y., Liu, Y.S., Song, M., Zhou, Y.M., Liu, Q., Wang, X.H. (2016. Preparation of FeO(OH Modified with Polyethylene Glycol and Its Catalytic Activity on the Reduction of Nitrobenzene with Hydrazine Hydrate. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (3: 363-368 (doi:10.9767/bcrec.11.3.576.363-368 Permalink/DOI: http://doi.org/10.9767/bcrec.11.3.576.363-368

  14. Effect of Organic Matter on Cr(VI Removal from Groundwaters by Fe(II Reductive Precipitation for Groundwater Treatment

    Directory of Open Access Journals (Sweden)

    Anna Gröhlich

    2017-06-01

    Full Text Available Due to its toxicity, Cr(VI is undesirable in groundwater. Its chemical reduction to Cr(III species, followed by precipitation is the most widely practiced treatment technique for the removal of Cr(VI from polluted waters. The resulting Cr(III species present low solubility, is much less toxic, and can be subsequently removed either by precipitation, or by adsorption onto iron oxy-hydroxides and co-precipitation. The effects of several parameters, such as the pH value of water to be treated, the applied Fe(II dose, and the presence of appropriate mineral surfaces, are well investigated and understood. However, the impact of the presence of humic acids (HAs in this process has only been considered by rather few studies. The main aim of this study was to determine the effect of humic substances on Fe(II reductive precipitation of Cr(VI within a pH range relevant for drinking water treatment. Jar test experiments were performed, using artificial groundwater of defined composition and initial Cr(VI concentration 100 μg/L, ferrous sulphate dosages 0.25–2 mg Fe(II/L, and pH values 6.5–8. It was found that Cr(VI and total chromium (Cr(total can be reliably removed in the absence of HAs in the tested pH range with the addition of Fe(II dosage of 1 mg Fe(II/L. Further on, the results indicated that the reduction of Cr(VI is only slightly affected by the presence of HAs. However, increased residual total Cr concentrations were found at lower Fe(II dosages and/or higher pH values. Additionally, the removal of the Cr(III species formed during Cr(VI reduction was strongly inhibited by the presence of HAs under the examined experimental conditions, since residual concentrations higher than 60 μg/L were determined. The results of this study will have implications to the ongoing discussion of a new, stricter, European Union regulation limit, regarding the presence of total chromium in drinking water.

  15. Ecological aspects of Moessbauer study of iron-containing atmospheric aerosols

    International Nuclear Information System (INIS)

    Kopcewicz, B.; Kopcewicz, M.

    2000-01-01

    Moessbauer spectroscopy was applied to analyze the iron compounds in atmospheric aerosol. Seasonal variations of iron concentration in atmospheric air measured over twenty years in Poland are discussed. It was observed that the concentration of iron sulfides (FeS, FeS 2 ) related to coal combustion dropped significantly, however, concentration of iron oxides and iron oxyhydroxides related to fuel combustion increased

  16. Arsenic partitioning among particle-size fractions of mine wastes and stream sediments from cinnabar mining districts.

    Science.gov (United States)

    Silva, Veronica; Loredo, Jorge; Fernández-Martínez, Rodolfo; Larios, Raquel; Ordóñez, Almudena; Gómez, Belén; Rucandio, Isabel

    2014-10-01

    Tailings from abandoned mercury mines represent an important pollution source by metals and metalloids. Mercury mining in Asturias (north-western Spain) has been carried out since Roman times until the 1970s. Specific and non-specific arsenic minerals are present in the paragenesis of the Hg ore deposit. As a result of intensive mining operations, waste materials contain high concentrations of As, which can be geochemically dispersed throughout surrounding areas. Arsenic accumulation, mobility and availability in soils and sediments are strongly affected by the association of As with solid phases and granular size composition. The objective of this study was to examine phase associations of As in the fine grain size subsamples of mine wastes (La Soterraña mine site) and stream sediments heavily affected by acid mine drainage (Los Rueldos mine site). An arsenic-selective sequential procedure, which categorizes As content into seven phase associations, was applied. In spite of a higher As accumulation in the finest particle-size subsamples, As fractionation did not seem to depend on grain size since similar distribution profiles were obtained for the studied granulometric fractions. The presence of As was relatively low in the most mobile forms in both sites. As was predominantly linked to short-range ordered Fe oxyhydroxides, coprecipitated with Fe and partially with Al oxyhydroxides and associated with structural material in mine waste samples. As incorporated into short-range ordered Fe oxyhydroxides was the predominant fraction at sediment samples, representing more than 80% of total As.

  17. Fissure fillings from the Klipperaas study site

    International Nuclear Information System (INIS)

    Tullborg, E.L.

    1986-07-01

    The Klipperaas study site is located within the Smaaland-Vaermland granitoid belt in southern Sweden. The area investigated can be subdivided into blocks with different hydraulic character and fracture frequency of the rocks. A fissure filling, study has been carried out within the area. This includes identification of the minerals, mineral frequency, textures within the fissures and isotope analyses of calcites. Four generation of fissure fillings, within the time space c. 1600 M.a. to present, has been distinguished. These are 1) quartz; 2) epidote + muscovite and adularia + hematite; 3) calcite + chlorite +/hematite; 4) calcite, clay minerals and Fe-oxyhydroxide. It is observed that the surface water affect the uppermost part of the bedrock resulting in calcite dissolution, break down of pyrite and precipitation of Fe-oxyhydroxide. It is also obvious from the fracture calcite frequency that calcite dissolution is more intensive close to and within the fracture zones. There, Fe-oxyhydroxide can be found down to at least 400 m depth. This gives valuable information about the physic-chemical character of the groundwater within the bedrock. Several fracture zones have been reactivated. It is also suspected that relatively late movements have taken place causing crushing of the rock and only a slight cementation of the crushed material is visible. Some of the fracture zones correspond to mafic dikes. These zones exhibit lower hydraulic conductivity than other zones due to fracture sealing by clay minerals but also by chlorite and calcite. (author)

  18. Controls on ferromanganese crust composition and reconnaissance resource potential, Ninetyeast Ridge, Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Hein, J.R.; Conrad, T.; Mizell, K.; Banakar, V.K.; Frey, F.A.; Sager, W.W.

    adsorbed on the Fe oxyhydroxide. The enrichment of Ni, Zn, and Cu in the phosphatized crust reflects preferential adsorption into the tunnel structure of todorokite. The rare earth element plus yttrium (REY) patterns indicate a lower oxidation potential...

  19. Enhanced As (V Removal from Aqueous Solution by Biochar Prepared from Iron-Impregnated Corn Straw

    Directory of Open Access Journals (Sweden)

    Jiaming Fan

    2018-01-01

    Full Text Available Fe-loaded adsorbents have received increasing attention for the removal of arsenic in contaminated water or soil. In this study, Fe-loaded biochar was prepared from iron-impregnated corn straw under a pyrolysis temperature of 600°C. The ratio of crystalline Fe oxides including magnetite and natrojarosite to amorphous iron oxyhydroxide in the composite was approximately 2 : 3. Consisting of 24.17% Fe and 27.76% O, the composite exhibited a high adsorption capacity of 14.77 mg g−1 despite low surface areas (4.81 m2 g−1. The pH range of 2.0–8.0 was optimal for arsenate removal and the adsorption process followed the Langmuir isotherms closely. In addition, pseudo-second-order kinetics best fit the As removal data. Fe oxide constituted a major As-adsorbing sink. Based on the X-ray diffraction spectra, saturation indices, and selective chemical extraction, the data suggested three main mechanisms for arsenate removal: sorption of arsenate, strong inner-sphere surface complexes with amorphous iron oxyhydroxide, and partial occlusion of arsenate into the crystalline Fe oxides or carbonized phase. The results indicated that the application of biochar prepared from iron-impregnated corn straw can be an efficient method for the remediation of arsenic contaminated water or soil.

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

    Science.gov (United States)

    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

  1. Characteristics and origin of rock varnish from the hyperarid coastal deserts of northern Peru

    Science.gov (United States)

    Jones, Charles E.

    1991-01-01

    The characteristics of a new type of rock varnish from the hyperarid coastal deserts of northern Peru, combined with laboratory experiments on associated soil materials, provide new insights into the formation of rock varnish. The Peruvian varnish consists of an Fe-rich, Mn-poor component covering up to 95% of a varnished surface and a Fe-rich, Mn-rich component found only in pits and along cracks and ridges. The alkaline soils plus the catalytic Fe oxyhydroxides that coat much of the varnish surfaces make the Peruvian situation ideal for physicochemical precipitation of Mn. However, the low Mn content of the dominant Fe-rich, Mn-poor component suggests that such precipitation is minor. This, plus the presence of abundant bacteria in the Mn-rich varnish and the recorded presence of Mn-precipitating bacteria in varnish elsewhere, suggests that bacteria are almost solely responsible for Mn-precipitation in rock varnish. A set of experiments involving Peruvian soil samples in contact with water-CO 2 solutions indicates that natural fogs or dews release Mn but not Fe when they come in contact with eolian materials on rock surfaces. This mechanism may efficiently provide Mn to bacteria on varnishing surfaces. The lack of Fe in solution suggests that a large but unknown proportion of Fe in varnish may be in the form of insoluble Fe oxyhydroxides sorbed onto the clay minerals that form the bulk of rock varnish. The results of this study do not substantively change R. I. Dorn's paleoenvironmental interpretations of varnish Mn:Fe ratios, but they do suggest areas for further inquiry.

  2. Iron oxide nanoparticles for plant nutrition? A preliminary Mössbauer study

    Energy Technology Data Exchange (ETDEWEB)

    Homonnay, Z., E-mail: homonnay@caesar.elte.hu [EötvösLoránd University, Institute of Chemistry (Hungary); Tolnai, Gy. [Research Centre for Natural Sciences, Institute of Materials and Environmental Chemistry (Hungary); Fodor, F.; Solti, Á. [EötvösLoránd University, Institute of Biology (Hungary); Kovács, K.; Kuzmann, E.; Ábrahám, A. [EötvösLoránd University, Institute of Chemistry (Hungary); Szabó, E. Gy.; Németh, P.; Szabó, L.; Klencsár, Z. [Research Centre for Natural Sciences, Institute of Materials and Environmental Chemistry (Hungary)

    2016-12-15

    One of the most important micronutrients for plants is iron. We have prepared iron(III) oxyhydroxide and magnetite nanoparticles with the aim to use them as possible nutrition source for plants. The iron(III)-oxide/oxyhydroxide nanoparticles prepared under our experimental conditions as colloidal suspensions proved to be 6-line ferrihydrite nanoparticles as verified by XRD, TEM/SAED and Mössbauer spectroscopy measurements. {sup 57}Fe Mössbauer spectra of magnetite nanoparticles prepared under different preparation conditions could be analyzed on the basis of a common model based on the superposition of four sextet components displaying Gaussian-shaped hyperfine magnetic field distributions.

  3. The potential impact of microbial Fe(III) reduction on subsurface U(VI) mobility at a low level radioactive waste storage site

    International Nuclear Information System (INIS)

    Wilkins, M.J.; Livens, F.R.; Vaughan, D.J.; Lloyd, J.R.; Beadle, I.; Small, J.S.

    2005-01-01

    Full text of publication follows: Fe(III) oxy-hydroxides have the potential to be utilised as terminal electron acceptors by indigenous microbial communities in the British Nuclear Fuels (BNFL) low level radioactive waste storage site at Drigg (Cumbria, UK) and these organisms may have a critical control on the biogeochemical cycling of several environmentally important radionuclides. In terms of radiological impact at Drigg, uranium is the most significant contributor to radiological impact and it is strongly influenced by biogeochemical processes. In terms of mass (moles) it is also the most abundant radionuclide in the Drigg inventory. Thus, the potential biotic and abiotic effects of Fe(III) reduction on U(VI) mobility in the Drigg subsurface are of interest. Culture-dependent and molecular techniques showed that the sediments in and around the Drigg site contained a diversity of Fe(III)-reducing bacteria. A series of microcosm experiments were utilised to create environmentally relevant experimental conditions. Microcosms set up using Drigg sediment and synthetic ground water were spiked with 100 μM U(VI) and acetate as an electron donor. U(VI) concentrations in groundwater were measured using a chemical assay while total U levels were determined using ICP-MS. Fe(II) levels were determined using the ferrozine method. Sediment surface areas were measured using BET analysis. The low surface area of the sediments resulted in only a small proportion of the 100 μM U(VI) spike sorbing onto mineral surfaces. The addition of ferri-hydrite to some microcosms resulted in an immediate lowering of soluble U(VI) concentrations, suggesting that the formation of soluble U(VI) complexes were not responsible for the minimal adsorption. The presence of biogenic Fe(II) in the microcosms did not affect the soluble U(VI) concentration. Similarly, soluble U(VI) levels remained unchanged when sediments were spiked with U(VI) post-microbial Fe(III) reduction. However, a lowering in

  4. Iron Availability in Tropical Soils and Iron Uptake by Plants

    Directory of Open Access Journals (Sweden)

    Guilherme Furlan Mielki

    Full Text Available ABSTRACT Given the increase in crop yields and the expansion of agriculture in low fertility soils, deficiency of micronutrients, such as iron, in plants grown in tropical soils has been observed. The aim of this study was to evaluate Fe availability and Fe uptake by corn (Zea mays L. plants in 13 different soils, at two depths. Iron was extracted by Mehlich-1, Mehlich-3, and CaCl2 (Fe-CC and was fractionated in forms related to low (Feo and high (Fed crystallinity pedogenic oxyhydroxides, and organic matter (Fep using ammonium oxalate, dithionite-citrate, and sodium pyrophosphate, respectively. In order to relate Fe availability to soil properties and plant growth, an experiment was carried out in a semi-hydroponic system in which part of the roots developed in a nutrient solution (without Fe and part in the soil (the only source of Fe. Forty-five days after seeding, we quantified shoot dry matter and leaf Fe concentration and content. Fed levels were high, from 5 to 132 g kg-1, and Feo and Fe-CC levels were low, indicating the predominance of Fe as crystalline oxyhydroxides and a low content of Fe readily available to plants. The extraction solutions showed significant correlations with various soil properties, many common to both, indicating that they act similarly. The correlation between the Mehlich-1 and Mehlich-3 extraction solutions was highly significant. However, these two extraction methods were inefficient in predicting Fe availability to plants. There was a positive correlation between dry matter and Fe levels in plant shoots, even within the ranges considered adequate in the soil and in the plant. Dry matter production and leaf Fe concentration and content were positively correlated with Fep concentration, indicating that the Fe fraction related to soil organic matter most contributes to Fe availability to plants.

  5. Properties and reactivity of Fe-organic matter associations formed by coprecipitation versus adsorption: Clues from arsenate batch adsorption

    Science.gov (United States)

    Mikutta, Robert; Lorenz, Dennis; Guggenberger, Georg; Haumaier, Ludwig; Freund, Anja

    2014-11-01

    Ferric oxyhydroxides play an important role in controlling the bioavailability of oxyanions such as arsenate and phosphate in soil. Despite this, little is known about the properties and reactivity of Fe(III)-organic matter phases derived from adsorption (reaction of organic matter (OM) to post-synthesis Fe oxide) versus coprecipitation (formation of Fe oxides in presence of OM). Coprecipitates and adsorption complexes were synthesized at pH 4 using two natural organic matter (NOM) types extracted from forest floor layers (Oi and Oa horizon) of a Haplic Podzol. Iron(III) coprecipitates were formed at initial molar metal-to-carbon (M/C) ratios of 1.0 and 0.1 and an aluminum (Al)-to-Fe(III) ratio of 0.2. Sample properties were studied by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), N2 gas adsorption, dynamic light scattering, and electrophoretic mobility measurements. Arsenic [As(V)] adsorption to Fe-OM phases was studied in batch experiments (168 h, pH 4, 100 μM As). The organic carbon (OC) contents of the coprecipitates (82-339 mg g-1) were higher than those of adsorption complexes (31 and 36 mg g-1), leading to pronounced variations in specific surface area (9-300 m2 g-1), average pore radii (1-9 nm), and total pore volumes (11-374 mm3 g-1) but being independent of the NOM type or the presence of Al. The occlusion of Fe solids by OM (XPS surface concentrations: 60-82 atom% C) caused comparable pHPZC (1.5-2) of adsorption complexes and coprecipitates. The synthesis conditions resulted in different Fe-OM association modes: Fe oxide particles in 'M/C 0.1' coprecipitates covered to a larger extent the outermost aggregate surfaces, for some 'M/C 1.0' coprecipitates OM effectively enveloped the Fe oxides, while OM in the adsorption complexes primarily covered the outer aggregate surfaces. Despite of their larger OC contents, adsorption of As(V) was fastest to coprecipitates formed at low Fe availability (M/C 0.1) and facilitated by desorption of weakly

  6. Municipal compost-based mixture for acid mine drainage bioremediation: Metal retention mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Oriol Gibert; Joan de Pablo; Jose Luis Cortina; Carlos Ayora [Universitat Politecnica de Catalunya, Barcelona (Spain). Departament d' Enginyeria Qumica

    2005-09-15

    An upflow packed column was operated to evaluate the potential of a mixture of municipal compost and calcite to promote sulphidogenesis in the remediation of a simulated mine water at high flows (>0.1 m d{sup -1}). Results showed that the pH was neutralised and metals (Fe, Al, Zn, Cu) were significantly removed. Metal removal was attributed to the combined result of precipitation as metal (oxy)hydroxides and carbonates, co-precipitation with these (oxy)hydroxides and sorption onto the compost surface rather than to precipitation as metal sulphides. The two last mechanisms are especially significant for Zn, whose hydroxide is not expected to precipitate at pH 6-7. Before the saturation of compost sorption sites, 60% of the influent Zn was estimated to have been removed by co-precipitation with Fe- and Al-(oxy)hydroxide and 40% by sorption onto the municipal compost.

  7. From 3D to 2D Co and Ni Oxyhydroxide Catalysts: Elucidation of the Active Site and Influence of Doping on the Oxygen Evolution Activity

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Hansen, Heine Anton; Vegge, Tejs

    2017-01-01

    Layered oxyhydroxides (ox-hys) of Ni and Co are among the most active catalysts for oxygen evolution in alkaline media. Their activities can be further tuned by delamination into single-layer oxide sheets or by means of doping. The active site for the reaction and how doping and delamination...... investigate the role of terrace and edge sites and use stability, catalytic activity, and electronic conductivity as evaluation criteria to pinpoint the best catalysts. We arrive at several important conclusions: the ox-hy surface is fully oxidized under oxygen evolution conditions, bulk terraces...

  8. Mobilisation and Bioavailability of Arsenic Around Mesothermal Gold Deposits in a Semiarid Environment, Otago, New Zealand

    Directory of Open Access Journals (Sweden)

    D. Craw

    2002-01-01

    Full Text Available Arsenopyrite (FeAsS is the principal arsenic (As mineral in mineralised mesothermal veins (typically 5,000 mg/kg As in southeastern New Zealand. Groundwater in contact with arsenopyrite-bearing rocks has elevated As concentrations (up to 0.1 mg/l. The arsenopyrite decomposes slowly on oxidation in soils and historic mine workings in a cool semiarid climate. Dissolved As is predominantly As(III in association with arsenopyrite, but this is rapidly oxidised over days to weeks to As(V in the vadose zone. Oxidation is facilitated by particulate Fe and/or Mn oxyhydroxides, and by bacteria in surface waters. Evaporative concentration of dissolved As(V in the vadose zone causes precipitation of scorodite (Fe(IIIAs(VO4.2H2O. Adsorption of As(V to Fe oxyhydroxides in soils and groundwater pathways lowers dissolved As concentrations. Soils over mineralised veins typically have <200 mg/kg As, as most As is removed in solution on geological time scales. Most plants on the mineralised rocks and soils do not take up As, although some inedible species can fix up to 18 mg/kg As. Hence, bioavailability of As(V is low in this environment, despite the substantial As flux.

  9. Redox front formation in an uplifting sedimentary rock sequence: An analogue for redox-controlling processes in the geosphere around deep geological repositories for radioactive waste

    International Nuclear Information System (INIS)

    Yoshida, H.; Metcalfe, R.; Yamamoto, K.; Murakami, Y.; Hoshii, D.; Kanekiyo, A.; Naganuma, T.; Hayashi, T.

    2008-01-01

    Subsurface redox fronts control the mobilization and fixation of many trace elements, including potential pollutants such as certain radionuclides. Any safety assessment for a deep geological repository for radioactive wastes needs to take into account adequately the long-term redox processes in the geosphere surrounding the repository. To build confidence in understanding these processes, a redox front in a reduced siliceous sedimentary rock distributed in an uplifting area in Japan has been studied in detail. Geochemical analyses show increased concentrations of Fe and trace elements, including rare earth elements (REEs), at the redox front, even though concentrations of reduced rock matrix constituents show little change. Detailed SEM observations revealed that fossilized microorganisms composed of amorphous granules made exclusively of Fe and Si occur in the rock's pore space. Microbial 16S rDNA analysis suggests that there is presently a zonation of different bacterial groups within the redox band, and bacterial zonation played an important role in the concentration of Fe-oxyhydroxides at the redox front. These water-rock-microbe interactions can be considered analogous to the processes occurring in the redox fronts that would develop around geological repositories for radioactive waste. Once formed, the Fe-oxyhydroxides within such a front would be preserved even after reducing conditions resume following repository closure

  10. Redox front formation in an uplifting sedimentary rock sequence: An analogue for redox-controlling processes in the geosphere around deep geological repositories for radioactive waste

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, H. [Nagoya University Museum, Material Research Section, Furocho, Nagoya 464-8602 (Japan)], E-mail: dora@num.nagoya-u.ac.jp; Metcalfe, R. [Quintessa Japan, Queen' s Tower A7-707, Minatomirai, Yokohama 220-6007 (Japan); Yamamoto, K. [Nagoya University Museum, Material Research Section, Furocho, Nagoya 464-8602 (Japan); Murakami, Y. [Japan Atomic Energy Agency (JAEA), Tono Geoscience Centre (Japan); Hoshii, D.; Kanekiyo, A.; Naganuma, T. [Hiroshima University, Higashi Hiroshima, Kagamiyama 1-4-4 (Japan); Hayashi, T. [Asahi University, Department of Dental Pharmacology, Hozumi, Gifu (Japan)

    2008-08-15

    Subsurface redox fronts control the mobilization and fixation of many trace elements, including potential pollutants such as certain radionuclides. Any safety assessment for a deep geological repository for radioactive wastes needs to take into account adequately the long-term redox processes in the geosphere surrounding the repository. To build confidence in understanding these processes, a redox front in a reduced siliceous sedimentary rock distributed in an uplifting area in Japan has been studied in detail. Geochemical analyses show increased concentrations of Fe and trace elements, including rare earth elements (REEs), at the redox front, even though concentrations of reduced rock matrix constituents show little change. Detailed SEM observations revealed that fossilized microorganisms composed of amorphous granules made exclusively of Fe and Si occur in the rock's pore space. Microbial 16S rDNA analysis suggests that there is presently a zonation of different bacterial groups within the redox band, and bacterial zonation played an important role in the concentration of Fe-oxyhydroxides at the redox front. These water-rock-microbe interactions can be considered analogous to the processes occurring in the redox fronts that would develop around geological repositories for radioactive waste. Once formed, the Fe-oxyhydroxides within such a front would be preserved even after reducing conditions resume following repository closure.

  11. The Effect of the Concentration of Oxidant, Cr(VI), on the Iron Oxidation in Saline Water

    Science.gov (United States)

    Ahn, H.; Jo, H. Y.; Ryu, J. H.; Koh, Y. K.

    2014-12-01

    Deep geological disposal is currently considered as the most appropriate method to isolate high level radioactive wastes (HLRWs) from the ecosystem. If groundwater seeps into underground disposal facilities, water molecules can be dissociated to radicals or peroxides, which can oxidize metal canisters and HLRWs. The oxidized radionuclides with a high solubility can be dissolved in the groundwater. Some dissolved radionuclides can act as oxidants. The continuous radiolysis of water molecules, which results from continuous seepage of groundwater, can enable the continuous production of the radioactive oxidants, resulting in an increase in concentration of oxidants. In this study, the effect of oxidant concentration on iron oxidation in the presence of salt was evaluated. Zero valent iron (ZVI) particles were reacted with Cr(VI) solutions with initial Cr(VI) concentrations ranged from 50 to 300 mg/L in reactors. The initial pH and NaCl concentration were fixed at 3 and 0.5 M, respectively. An increase in the initial Cr(VI) concentration caused an increase in the rate and extend of H2 gas production. The decrement of Cr(VI) was increased as the initial Cr(VI) concentration was increased. The penetration of H+ ions in the presence Cl- ions through the passive film on the ZVI particles caused the reaction between H+ ions and ZVI particles, producing H2 gas and Fe2+ ions. The passive film was damaged during the reaction due to the eruption of H2 gas or peptization by Cl- ions. The Fe2+ ions were reacted with Cr(VI) ions in the solution, producing Fe(III)-Cr(III) (oxy)hydroxides on the passive film of ZVI particles or in the solution as colloidal particles. The Fe(III)-Cr(III) (oxy)hydroxides tends to be precipitated as colloidal particles at a high Cr(VI) concentration and precipitated on the passive film at a low Cr(VI) concentration. The passive film was repaired or thickened by additional formation of Fe(III)-Cr(III) (oxy)hydroxides at a lower Cr(VI) concentration.

  12. Conversion electron Moessbauer study of low carbon steel polarized in aqueous sulfate solution containing sulfite in low concentration

    International Nuclear Information System (INIS)

    Vertes, Cs.; Lakatos-Varsanyi, M.; Vertes, A.; Kuzmann, E.; Meisel, W.; Guetlich, P.

    1992-01-01

    The passivation of low carbon steel was studied in aqueous solution of 0.5 M Na 2 SO 4 +0.001 M NaHSO 3 at pH=3.5 and 6.5. The found major components at pH=3.5 were: γ-FeOOH and Fe 3 C, and also FeSO 4 .H 2 O could be identified on the surface of the low carbon steel as a minor component. At pH=6.5, the passive film contained only amorphous iron(III)-oxide or oxyhydroxide. (orig.)

  13. Distribution of As, Cd, Pb, and Zn in redox features of mine-waste impacted wetland soils

    Energy Technology Data Exchange (ETDEWEB)

    Strawn, Daniel G.; Hickey, Patrick J.; McDaniel, Paul A.; Baker, Leslie L. [Idaho Univ., Moscow (United States). Soil and Land Resources Div.

    2012-08-15

    Purpose: Wetland soils of the Coeur d'Alene (CdA) River Basin of northern Idaho, USA are contaminated with toxic elements released during mining activities. In this paper, we report results from a multi-scale investigation of total As, Cd, Pb, and Zn distributions along a transect of these contaminated soils. Materials and methods: Four sites along an 80-m transect were established at the Black Rock Slough wetland in CdA River Basin. The elevation difference between the upslope and lowland site was 1.1 m. Soils were sampled from three depths, down to 45 cm. Redoximorphic features were isolated from the soils and categorized into five types of cemented particles, and Fe-enriched and depleted soil masses. Soils and isolated soil separates were analyzed for total elemental concentration. Results and discussion: Within soil profiles, contaminants are enriched in surface horizons as compared to the original depositional profiles. Enrichment was more dramatic in the upland sites than the lowland sites. Fe-enriched masses that ranged in size from a few millimeters to several centimeters were also enriched in As, Pb, and Zn. At the smallest scale investigated, five different soil aggregate types ranging in size from 1 to 2 mm in diameter had distinct contaminant associations: Fe-cemented aggregates were elevated in As and Zn; Mn-cemented aggregates had more than five times as much Pb as the bulk soil; root channels were elevated in As; and charcoal particles were elevated in all contaminants, particularly Pb and Cd. Conclusions: Results show that in wetland soils pedogenic processes differentially distribute contaminants amongst the redoximorphic features. The distribution is affected by landscape position and water table influence. At the pedon scale, there is an enrichment of As, Cd, Pb, and Zn in surface horizons, suggesting that upward flux of contaminants is occurring. This contaminant redistribution should be considered in design of management and remediation

  14. Adsorption and transformation of selected human-used macrolide antibacterial agents with iron(III) and manganese(IV) oxides

    International Nuclear Information System (INIS)

    Feitosa-Felizzola, Juliana; Hanna, Khalil; Chiron, Serge

    2009-01-01

    The adsorption/transformation of two members (clarithromycin and roxithromycin) of the macrolide (ML) antibacterial agents on the surface of three environmental subsurface sorbents (clay, iron(III) and manganese(IV) oxy-hydroxides) was investigated. The adsorption fitted well to the Freundlich model with a high sorption capacity. Adsorption probably occurred through a surface complexation mechanism and was accompanied by slow degradation of the selected MLs. Transformation proceeded through two parallel pathways: a major pathway was the hydrolysis of the cladinose sugar, and to a lesser extent the hydrolysis of the lactone ring. A minor pathway was the N-dealkylation of the amino sugar. This study indicates that Fe(III) and Mn(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of MLs. Such an attenuation route yields a range of intermediates that might retain some of their biological activity. - Iron(III) and manganese(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of macrolide antibacterial agents

  15. Adsorption and transformation of selected human-used macrolide antibacterial agents with iron(III) and manganese(IV) oxides

    Energy Technology Data Exchange (ETDEWEB)

    Feitosa-Felizzola, Juliana [Laboratoire Chimie Provence, Aix-Marseille Universites-CNRS (UMR 6264), 3 place Victor Hugo, 13331 Marseille Cedex 3 (France); Hanna, Khalil [Laboratoire de Chimie Physique et Microbiologie pour l' Environnement, CNRS-Universite Henri Poincare-Nancy 1 (UMR 7564), 405 rue de Vandoeuvre, 54600 Villers-les-Nancy (France); Chiron, Serge [Laboratoire Chimie Provence, Aix-Marseille Universites-CNRS (UMR 6264), 3 place Victor Hugo, 13331 Marseille Cedex 3 (France)], E-mail: serge.chiron@univ-provence.fr

    2009-04-15

    The adsorption/transformation of two members (clarithromycin and roxithromycin) of the macrolide (ML) antibacterial agents on the surface of three environmental subsurface sorbents (clay, iron(III) and manganese(IV) oxy-hydroxides) was investigated. The adsorption fitted well to the Freundlich model with a high sorption capacity. Adsorption probably occurred through a surface complexation mechanism and was accompanied by slow degradation of the selected MLs. Transformation proceeded through two parallel pathways: a major pathway was the hydrolysis of the cladinose sugar, and to a lesser extent the hydrolysis of the lactone ring. A minor pathway was the N-dealkylation of the amino sugar. This study indicates that Fe(III) and Mn(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of MLs. Such an attenuation route yields a range of intermediates that might retain some of their biological activity. - Iron(III) and manganese(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of macrolide antibacterial agents.

  16. Mineralogy and geochemistry of uranium mill tailings

    International Nuclear Information System (INIS)

    Pagel, M.; Somot, S.

    2002-01-01

    We have investigated three main types of uranium mill tailings: (1) acid mill tailings (Mounana, Gabon), (2) neutralized acid mill tailings (Ecarpiere and Jouac, France) and (3) alkaline mill tailings (Lodeve, France). We have focused especially on radium behaviour which is of major environmental concern in these tailings, but other metals were also studied. It is shown that in type 1 , trapping of 226 Ra by anglesite and barite is dominant whereas in types 2 and 3, 226 Ra is mainly or significantly scavenged by Fe- Mn oxyhydroxides. This study points out the importance of keeping conditions in which these oxyhydroxides will be stable for the long-term. Uranium would be also released during acidification of the tailings. This shows the importance to know more about the behavior of Ra during the crystallization of oxyhydroxides and during tailings diagenesis. Therefore, it is very important to study the sorption of Ra by clay minerals or late authigeneous minerals such as barite. (author)

  17. Green superlubricity of Nitinol 60 alloy against steel in presence of castor oil

    Science.gov (United States)

    Zeng, Qunfeng; Dong, Guangneng; Martin, Jean Michel

    2016-07-01

    In the present work, first, we show that sliding Nitinol 60 alloy against steel under castor oil lubrication exhibits a new case of superlubricity (coefficient of friction CoF ≪ 0.01). So far, CoF below 0.01 have never been achieved under boundary lubrication at high contact pressure and in presence of vegetable oil as a green lubricant. Next, it is demonstrated that superlubricity is controlled by tribochemical reactions, involving chemical degradation of castor oil and the formation of metal oxy-hydroxides. Finally, to explain these findings, we propose a novel superlubricity mechanism consisting of hexanoic acid molecules intercalated between nickel and iron oxy-hydroxide lamellar layers, a structure very similar to the one found in Fe-Ni batteries. We propose that superlubricity is achieved due to repulsive electrostatic forces acting between the intercalated metal oxy-hydroxide lamellar compounds. This system would be suitable for practical engineering applications in many fields including biotechnologies.

  18. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    Science.gov (United States)

    van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

    2014-11-01

    The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients

  19. Efficient photocatalytic degradation of perfluorooctanoic acid by a wide band gap p-block metal oxyhydroxide InOOH

    Science.gov (United States)

    Xu, Jingjing; Wu, Miaomiao; Yang, Jingwen; Wang, Zhengmei; Chen, Mindong; Teng, Fei

    2017-09-01

    In this work, we prepared a new wide band gap semiconductor, p-block metal oxyhydroxide InOOH, which exhibits efficient activity for perfluorooctanoic acid (PFOA) degradation under mild conditions and UV light irradiation. The apparent rate constant for PFOA degradation by InOOH is 27.6 times higher than that for P25 titania. Results show that ionized PFOA (C7F15COO-) can be adsorbed much more efficiently on the surface of InOOH than P25. Then, the adsorbed C7F15COO- can be decomposed directly by photo-generated holes to form C7F15COOrad radicals. This process is the key step for the photocalytic degradation of PFOA. Major degradation intermediates, fluoride ions and perfluorinated carboxylic acids (PFCAs) with shorter chain lengths were detected during PFOA degradation. A possible pathway for photocatalytic degradation of PFOA is proposed based on the experimental results. Therefore, this studies indicates a potential new material and method for the efficient treatment of PFCA pollutants under mild conditions.

  20. THE WEATHERING OF A SULFIDE OREBODY: SPECIATION AND FATE OF SOME POTENTIAL CONTAMINANTS

    Energy Technology Data Exchange (ETDEWEB)

    Courtin-Nomade, Alexandra; Grosbois, Cecile; Marcus, Matthew A.; Fakra, Sirine C.; Beny, Jean Michel; Foster, Andrea L.

    2010-07-16

    Various potentially toxic trace elements such as As, Cu, Pb and Zn have been remobilized by the weathering of a sulfide orebody that was only partially mined at Leona Heights, California. As a result, this body has both natural and anthropogenically modified weathering profiles only 500 m apart. The orebody is located in a heavily urbanized area in suburban Oakland, and directly affects water quality in at least one stream by producing acidic conditions and relatively high concentrations of dissolved elements (e.g., {approx}500 mg/L Cu, {approx}3700 mg/L Zn). Micrometric-scale mineralogical investigations were performed on the authigenic metal-bearing phases (less than 10 {mu}m in size) using electron-probe micro-analysis (EPMA), micro-Raman, micro X-ray absorption spectroscopy (mXAS), scanning X-ray diffraction (mSXRD) and scanning X-ray fluorescence (mSXRF) mapping techniques. Those measurements were coupled with classical mineralogical laboratory techniques, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Authigenic metal-bearing phases identified are mainly sulfates (jarosite, epsomite, schwertmannite), Fe (oxy-)hydroxides (goethite, hematite and poorly crystalline Fe products) and poorly crystalline Mn (hydr-)oxides. Sulfates and Fe (oxy-)hydroxides are the two main secondary products at both sites, whereas Mn (hydr-) oxides were only observed in the samples from the non-mining site. In these samples, the various trace elements show different affinities for Fe or Mn compounds. Lead is preferentially associated with Mn (hydr-)oxides and As with Fe (oxy-)hydroxides or sulfates. Copper association with Mn and Fe phases is questionable, and the results obtained rather indicate that Cu is present as individual Cu-rich grains (Cu hydroxides). Some ochreous precipitates were found at both sites and correspond to a mixture of schwertmannite, goethite and jarosite containing some potentially toxic trace elements such as Cu, Pb and Zn. According to the

  1. Influence of iron redox cycling on organo-mineral associations in arctic tundra soils

    Science.gov (United States)

    Herndon, E.; AlBashaireh, A.; Duroe, K.; Singer, D. M.

    2016-12-01

    Geochemical interactions between soil organic matter and minerals influence decomposition in many environments but remain poorly understood in arctic tundra systems. In tundra soils that are periodically to persistently saturated, the accumulation of iron oxyhydroxides and organo-iron precipitates at redox interfaces may inhibit decomposition by binding organic molecules and protecting them from microbial degradation. Here, we couple synchrotron-source spectroscopic techniques with chemical sequential extractions and physical density fractionations to evaluate the spatial distribution and speciation of Fe-bearing phases and associated organic matter in organic and mineral horizons of the seasonally thawed active layer in tundra soils from northern Alaska. Mineral-associated organic matter comprised 63 ± 9% of soil organic carbon stored in the active layer of ice wedge polygons. Ferrous iron produced in anoxic mineral horizons diffused upwards and precipitated as poorly-crystalline oxyhydroxides and organic-bound Fe(III) in the organic horizons. Ferrihydrite and goethite were present as coatings on mineral grains and plant debris and in aggregates with clays and particulate organic matter. Organic matter released through acid-dissolution of iron oxides may represent a small pool of readily-degradable organic molecules temporarily stabilized by sorption to iron oxyhydroxide surfaces, while larger quantities of particulate organic carbon and humic-like substances may be physically protected from decomposition by Fe-oxide coatings and aggregation. We conclude that formation of poorly-crystalline and crystalline iron oxides at redox interfaces contributes to mineral protection of organic matter through sorption, aggregation, and co-precipitation reactions. Further study of organo-mineral associations is necessary to determine the net impact of mineral-stabilization on carbon storage in rapidly warming arctic ecosystems.

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

    Science.gov (United States)

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

    2017-07-01

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

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

    Science.gov (United States)

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

    2017-01-01

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

  4. Anaerobic carbon mineralisation through sulphate reduction in the inner shelf sediments of eastern Arabian sea

    Digital Repository Service at National Institute of Oceanography (India)

    Naik, R.; Naqvi, S.W.A.; Araujo, J.

    ,G.-J. .Reichart and S. W. Poulton. 2012. Sedimentary phosphorus and iron cycling in and below the oxygen minimum zone of the northern Arabian Sea.Biogeosciences Discussion. 9, 3829–3880. Pratihary A.K, S. W. A. Naqvi, H. Naik,B.R. Thorat, G. Narvenkar...). Other factors such as sedimentation rate and the presence of anaerobic electron acceptors asnitrate, Fe and Mn oxyhydroxides also affect sedimentary Corg mineralization rates.Under anoxic conditions, reductive dissolution of Fe oxyhyroxides produces...

  5. Source and distribution of naturally occurring arsenic in groundwater from Alberta’s Southern Oil Sands Regions

    International Nuclear Information System (INIS)

    Moncur, Michael C.; Paktunc, Dogan; Jean Birks, S.; Ptacek, Carol J.; Welsh, Brent; Thibault, Yves

    2015-01-01

    Highlights: • Widespread naturally occurring As in groundwater with concentrations up to 179 μg/L. • 50% of the 816 water wells sampled exceeded 10 μg/L of As. • As(III) was the dominant species in 74% of the groundwater samples. • Shallow groundwater As is derived from arsenian pyrite oxidation. • In deeper sediments, As release is associated with Fe(III) reduction. - Abstract: Arsenic (As) concentrations as high as 179 μg/L have been observed in shallow groundwater in the Alberta’s Southern Oil Sand Regions. The geology of this area of Alberta includes a thick cover (up to 200 m) of unconsolidated glacial deposits, with a number of regional interglacial sand and gravel aquifers, underlain by marine shale. Arsenic concentrations observed in 216 unconsolidated sediment samples ranged from 1 and 17 ppm. A survey of over 800 water wells sampled for As in the area found that 50% of the wells contained As concentrations exceeding drinking water guidelines of 10 μg/L. Higher As concentrations in groundwater were associated with reducing conditions. Measurements of As speciation from 175 groundwater samples indicate that As(III) was the dominant species in 74% of the wells. Speciation model calculations showed that the majority of groundwater samples were undersaturated with respect to ferrihydrite, suggesting that reductive dissolution of Fe-oxyhydroxides may be the source of some As in groundwater. Detailed mineralogical characterization of sediment samples collected from two formations revealed the presence of fresh framboidal pyrite in the deeper unoxidized sediments. Electron microprobe analysis employing wavelength dispersive spectrometry indicated that the framboidal pyrite had variable As content with an average As concentration of 530 ppm, reaching up to 1840 ppm. In contrast, the oxidized sediments did not contain framboidal pyrite, but exhibited spheroidal Fe-oxyhydroxide grains with elevated As concentrations. The habit and composition suggest

  6. The distribution of rare earth and other elements and the mineralogy of the iron oxyhydroxide phase in marine ferromanganese concretions from within Slupsk Furrow in the southern Baltic

    International Nuclear Information System (INIS)

    Ali, A.; Ikuta, K.; Latka, K.; Goerlich, E.A.; Kunzendorf, H.; Glasby, G.P.; Szefer, P.

    1998-01-01

    Rare earth element concentrations in ferromanganese concretions sampled from Slupsk Furrow in the Polish Exclusive Economic Zone are similar to those of concretions from the Gulf of Bothnia. The lack of positive Ce anomalies in the concretions from Slupsk Furrow indicates that they are formed under less oxidizing conditions than spheroidal concretions from the Gulf of Bothnia. Moessbauer studies indicate that poorly crystalline lepidocrosite is the principal iron oxyhydroxide mineral present in these concretions. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  7. Geochemistry and jasper beds from the Ordovician Løkken ophiolite, Norway: origin of proximal and distal siliceous exhalites

    Science.gov (United States)

    Grenne, Tor; Slack, John F.

    2005-01-01

    Stratiform beds of jasper (hematitic chert), composed essentially of SiO2 (69-95 wt %) and Fe2O3 (3-25 wt %), can be traced several kilometers along strike in the Ordovician L??kken ophiolite, Norway. These siliceous beds are closely associated with volcanogenic massive sulfide (VMS) deposits and are interpreted as sea-floor gels that were deposited by fallout from hydrothermal plumes in silica-rich seawater, in which plume-derived Fe oxyhydroxide particles promoted flocculation and rapid settling of large (???200 ??m) colloidal particles of silica-iron oxyhydroxide. Concentrations of chalcophile elements in the jasper beds are at the parts per million level implying that sulfide particle fallout was insignificant and that the Si-Fe gel-forming plumes were mainly derived from intermediate- (100??-250??C) to high-temperature (>250??) white smoker-type vents with high Fe/S ratios. The interpreted setting is similar to that of the Lau basin, where high-temperature (280??-334??C) white smoker venting alternates or overlaps with sulfide mound-forming black smoker venting. Ratios of Al, Sc, Th, Hf, and REE to iron are very low and show that the detrital input was <0.1 percent of the bulk jasper. Most jasper beds are enriched in U, V, P, and Mo relative to the North American Shale Composite, reflecting a predominantly seawater source, whereas REE distribution patterns (positive Eu and negative Ce anomalies) reflect variable mixing of hydrothermal solutions with oxic seawater at dilution ratios of ???102 to 104. Trace element variations in the gel precursor to the jasper are thought to have been controlled by coprecipitation and/or adsorption by Fe oxyhydroxide particles that formed by the oxidation of hydrothermal Fe2+ within the variably seawater-diluted hydrothermal plume(s). Thick jasper layers near the H??ydal VMS orebody show distinct positive As/Fe and Sb/Fe anomalies that are attributed to near-vent rapid settling of Si-Fe particles derived from As- and Sb

  8. Trace-element evidence for the origin of desert varnish by direct aqueous atmospheric deposition

    Science.gov (United States)

    Thiagarajan, Nivedita; Aeolus Lee, Cin-Ty

    2004-07-01

    Smooth rock surfaces in arid environments are often covered with a thin coating of Fe-Mn oxyhydroxides known as desert varnish. It is debated whether such varnish is formed (a) by slow diagenesis of dust particles deposited on rock surfaces, (b) by leaching from the underlying rock substrate, or (c) by direct deposition of dissolved constituents in the atmosphere. Varnishes collected from smooth rock surfaces in the Mojave Desert and Death Valley, California are shown here to have highly enriched and fractionated trace-element abundances relative to upper continental crust (UCC). They are highly enriched in Co, Ni, Pb and the rare-earth elements (REEs). In particular, they have anomalously high Ce/La and low Y/Ho ratios. These features can only be explained by preferential scavenging of Co, Ni, Pb and the REEs by Fe-Mn oxyhydroxides in an aqueous environment. High field strength elements (HFSEs: Zr, Hf, Ta, Nb, Th), however, show only small enrichments despite the fact that these elements should also be strongly scavenged by Fe-Mn oxyhydroxides. This suggests that their lack of enrichment is a feature inherited from a solution initially poor in HFSEs. The first two scenarios for varnish formation can be ruled out as follows. The high enrichment factors of Fe, Mn and many trace elements cannot be generated by mass loss associated with post-depositional diagenesis of dust particles because such a process predicts only a small increase in concentration. In addition, the highly fractionated abundance patterns of particle reactive element pairs (e.g., Ce/La and Y/Ho) rules out leaching of the rock substrate. This is because if leaching were to occur, varnishes would grow from the inside to the outside, and thus any particle-reactive trace element leached from the substrate would be quantitatively sequestered in the Fe-Mn oxyhydroxide layers, prohibiting any significant elemental fractionations. One remaining possibility is that the Fe, Mn and trace metals in varnish are

  9. Untitled

    Indian Academy of Sciences (India)

    attributed to their incorporation in the CaCO lattice or adsorption of Fe-Mn oxyhydroxide coatings (Palmer 1985; Shaw and Wasserberg 1985; Wang et al 1986). REE distribution patterns and their association with a limited number of calcareous sediments from the Indian Ocean (Central Indian Basin and Wharton Basin) ...

  10. Microbially-induced Fe and Mn oxides in condensed pelagic sediments (Middle-Upper Jurassic, Western Sicily)

    Science.gov (United States)

    Préat, A.; Mamet, B.; Di Stefano, P.; Martire, L.; Kolo, K.

    2011-06-01

    This article presents a petrographic comparison of the Rosso Ammonitico facies of Western Sicily and the original Rosso Ammonitico Veronese of Northern Italy based on a total of 27 sections. The Rosso Ammonitico has been the subject of numerous controversies that range from bathyal to shallow-water platform sedimentation. Therefore it seemed interesting to verify if the term Rosso Ammonitico has the same geologic connotation from region to region. The Middle-Upper Jurassic Rosso Ammonitico of Western Sicily is a condensed succession formed during a period of extensional synsedimentary tectonics related to the spreading of the Ionian Ocean. Slope-to-basin or pelagic carbonate deposits characterize the sedimentation which consists of reddish mudstones and wackestones. The abundant fauna is composed of radiolarians, protoglobigerinids, Saccocoma, Bositra associated with ammonites. A few ferruginous hardgrounds, Fe-Mn oxide crusts and Mn-coated condensation horizons are also present. The red matrices contain abundant Fe-Mn encrusted, microbored and bioeroded bioclasts. Sporadic Fe-Mn oncolites composed of amorphous Mn-minerals and goethite are also conspicuous. The matrix, as well as the shells and the fillings of the complex associated veinlets, are frequently altered into calcite microsparite. Submicronic iron bacterial and fungal filaments associated with mineralized extracellular polymeric substances (EPS) are observed in the matrix. They record dysaerobic microenvironments at or near the sediment-water interfaces. Early mineralized discontinuities enhanced by subsequent pressure dissolution are reported in the succession. Mn-(Ni) bacterial filaments are exceptionally observed in the cortex of the Fe-Mn oncolites. As a consequence of an early lithification, the Mn filaments are poorly preserved. The pigmentation of the rock is due to the dispersion of submicronic oxyhydroxides (now goethite and amorphous iron) formed by bacterial mediation during early diagenesis

  11. Moessbauer-spectroscopic study of structure and magnetism of the exchange-coupled layer systems Fe/FeSn{sub 2}, and Fe/FeSi/Si and the ion-implanted diluted magnetic semiconductor SiC(Fe); Moessbauerspektroskopische Untersuchung von Struktur und Magnetismus der austauschgekoppelten Schichtsysteme Fe/FeSn{sub 2} und Fe/FeSi/Si und des ionenimplantierten verduennten magnetischen Halbleiters SiC(Fe)

    Energy Technology Data Exchange (ETDEWEB)

    Stromberg, Frank

    2009-07-07

    In line with this work the structural and magnetic properties of the exchange coupled layered systems Fe/FeSn{sub 2} and Fe/FeSi/Si and of the Fe ion implanted diluted magnetic semiconductor (DMS) SiC(Fe) were investigated. The main measuring method was the isotope selective {sup 57}Fe conversion electron Moessbauer spectroscopy (CEMS), mostly in connection with the {sup 57}Fe tracer layer technique, in a temperature range from 4.2 K to 340 K. Further measurement techniques were X-ray diffraction (XRD), electron diffraction (LEED, RHEED), SQUID magnetometry and FMR (Ferromagnetic Resonance). In the first part of this work the properties of thin AF FeSn{sub 2}(001) films and of the exchange-bias system Fe/FeSn{sub 2}(001) on InSb(001) were investigated. With the application of {sup 57}Fe-tracer layers and CEMS both the Fe-spin structure and the temperature dependence of the magnetic hyperfine field (B{sub hf}) of FeSn{sub 2} could be examined. The evaporation of Fe films on the FeSn{sub 2} films produced in the latter ones a high perpendicular spin component at the Fe/FeSn{sub 2} interface. In some distance from the interface the Fe spins rotate back into the sample plane. Furthermore {sup 57}Fe-CEMS provided a correlation between the absolute value of the exchange field vertical stroke He vertical stroke and the amount of magnetic defects within the FeSn{sub 2}. Temperature dependent CEMS-measurements yielded informations about the spin dynamics within the AF. The transition temperatures T{sub B}{sup *}, which were interpreted as superparamagnetic blocking temperatures, obtain higher values compared to the temperatures T{sub B} of the exchange-bias effect, obtained with magnetometry measurements. The second part of this work deals with the indirect exchange coupling within Fe/FeSi/Si/FeSi/Fe multilayers and FeSi diffusion barriers. The goal was to achieve Fe free Si interlayers. The CEMS results show that starting from a thickness of t{sub FeSi}=10-12 A of the

  12. Insights into iron sources and pathways in the Amazon River provided by isotopic and spectroscopic studies

    Science.gov (United States)

    Mulholland, Daniel Santos; Poitrasson, Franck; Boaventura, Geraldo Resende; Allard, Thierry; Vieira, Lucieth Cruz; Santos, Roberto Ventura; Mancini, Luiz; Seyler, Patrick

    2015-02-01

    ões River have δ57Fe consistent with strong mechanical erosion in the Andean Cordillera and upland soils, as evidenced by high concentrations of Fe3+-oxides sensu lato measured by EPR. The massive dissolved and colloidal Fe removal is associated with the evolution of the physical and chemical composition of the waters (i.e., ionic strength) during mixing, which influences organo-Fe3+ and Fe3+-oxyhydroxides stability. Several models are discussed to explain Fe non-conservative behavior, including dissociation of organo-Fe complexes and the subsequent formation of solid Fe3+-oxyhydroxides and semiquinone free radicals, as evidenced by EPR spectra demonstrating that organo-Fe signals decrease as Fe3+-oxyhydroxides and free radicals signals increase. As in estuarine regions, the mechanisms involving Fe transfer and loss in the mixing zone has a negligible effect on the bulk water Fe isotopic composition. This result suggests that a tropical basin similar to the Amazon River Basin delivers to the ocean waters with an Fe isotopic composition similar to that of the Earth's continental crust.

  13. MFM study of NdFeB and NdFeB/Fe/NdFeB thin films

    International Nuclear Information System (INIS)

    Gouteff, P.C.; Folks, L.; Street, R.

    1998-01-01

    Domain structures of NdFeB thin films, ranging in thickness between 1500 and 29 nm, have been studied qualitatively by magnetic force microscopy (MFM). Samples were prepared using a range of sputtering conditions resulting in differences in properties such as texture, coercivity and magnetic saturation. MFM images of all the films showed extensive interaction domain structures, similar to those observed in nanocrystalline bulk NdFeB. An exchange-coupled NdFeB/Fe/NdFeB trilayer with layer thicknesses 18 nm/15 nm/18 nm, respectively, was also examined using MFM. (orig.)

  14. Preparation and Mechanical Properties of TiC-Fe Cermets and TiC-Fe/Fe Bilayer Composites

    Science.gov (United States)

    Zheng, Yong; Zhou, Yang; Li, Runfeng; Wang, Jiaqi; Chen, Lulu; Li, Shibo

    2017-10-01

    TiC-Fe cermets and TiC-Fe/Fe bilayer composites consisting of a pure Fe layer and a TiC-Fe cermets layer were fabricated by hot-pressing sintering. The pure Fe layer contributes to the toughness of composites, and the TiC-Fe cermets layer endows the composites with an improved tensile strength and hardness. The effect of TiC contents (30-60 vol.%) on the mechanical properties of TiC-Fe cermets and TiC-Fe/Fe bilayer composites was investigated. Among the TiC-Fe cermets, the 40 vol.% TiC-Fe cermets possessed the highest tensile strength of 581 MPa and Vickers hardness of 5.1 GPa. The maximum fracture toughness of 17.0 MPa m1/2 was achieved for the TiC-Fe cermets with 30 vol.% TiC. For the TiC-Fe/Fe bilayer composites, the 40 vol.% TiC-Fe/Fe bilayer composite owns the maximum tensile strength of 588 MPa, which is higher than that of 40 vol.% TiC-Fe cermets. In addition, the 33.5% increment of tensile strength of 30 vol.% TiC-Fe/Fe bilayer composite comparing with the 30 vol.% TiC-Fe cermets, which is attributed to the 30 vol.% TiC-Fe/Fe bilayer composite exhibited the largest interlaminar shear strength of 335 MPa. The bilayer composites are expected to be used as wear resistance components in some heavy wear conditions.

  15. Concentration, distribution, and translocation of mercury and methylmercury in mine-waste, sediment, soil, water, and fish collected near the Abbadia San Salvatore mercury mine, Monte Amiata district, Italy

    Science.gov (United States)

    Rimondi, V.; Gray, J.E.; Costagliola, P.; Vaselli, O.; Lattanzi, P.

    2012-01-01

    The distribution and translocation of mercury (Hg) was studied in the Paglia River ecosystem, located downstream from the inactive Abbadia San Salvatore mine (ASSM). The ASSM is part of the Monte Amiata Hg district, Southern Tuscany, Italy, which was one of the world’s largest Hg districts. Concentrations of Hg and methyl-Hg were determined in mine-waste calcine (retorted ore), sediment, water, soil, and freshwater fish collected from the ASSM and the downstream Paglia River. Concentrations of Hg in calcine samples ranged from 25 to 1500 μg/g, all of which exceeded the industrial soil contamination level for Hg of 5 μg/g used in Italy. Stream and lake sediment samples collected downstream from the ASSM ranged in Hg concentration from 0.26 to 15 μg/g, of which more than 50% exceeded the probable effect concentration for Hg of 1.06 μg/g, the concentration above which harmful effects are likely to be observed in sediment-dwelling organisms. Stream and lake sediment methyl-Hg concentrations showed a significant correlation with TOC indicating considerable methylation and potential bioavailability of Hg. Stream water contained Hg as high as 1400 ng/L, but only one water sample exceeded the 1000 ng/L drinking water Hg standard used in Italy. Concentrations of Hg were elevated in freshwater fish muscle samples and ranged from 0.16 to 1.2 μg/g (wet weight), averaged 0.84 μg/g, and 96% of these exceeded the 0.3 μg/g (methyl-Hg, wet weight) USEPA fish muscle standard recommended to protect human health. Analysis of fish muscle for methyl-Hg confirmed that > 90% of the Hg in these fish is methyl-Hg. Such highly elevated Hg concentrations in fish indicated active methylation, significant bioavailability, and uptake of Hg by fish in the Paglia River ecosystem. Methyl-Hg is highly toxic and the high Hg concentrations in these fish represent a potential pathway of Hg to the human food chain.

  16. Weathering rind formation in buried terrace cobbles during periods of up to 300ka

    International Nuclear Information System (INIS)

    Yoshida, H.; Metcalfe, R.; Nishimoto, S.; Yamamoto, H.; Katsuta, N.

    2011-01-01

    Highlights: → Weathering rinds in sandstone and basalt cobbles buried for up to 300 ka have been investigated. → The aim was to determine the formation process and elemental mass balances during rind development. → Elemental mass balances across the rinds were determined by using open system mass balance (τ i,j ) calculations. → The formation rates are slower than the tropical areas due to the lower rainfall in the studied area. - Abstract: Weathering rinds formed in Mesozoic sandstone and basalt cobbles buried in terrace deposits for up to 300 ka have been investigated. The aim was to determine the formation process and elemental mass balances during rind development. The ages of terraces distributed in the western part of Fukui prefecture, central Japan have been determined as 50 ka, 120 ka and 300 ka based on a tephro-stratigraphic method. Detailed investigations across the weathering rinds, consisting of microscopic observations, porosity measurements, and mineralogical and geochemical analyses using X-ray diffractometry (XRD), X-ray fluorescence (XRF), secondary X-ray analytical microscopy (SXAM), scanning electron microanalyser (SEM) and electron probe microanalysis (EPMA) have been carried out. The results revealed that the Fe concentrations in the weathering rind of a basalt cobble slightly decreased from the cobble's surface (rim) towards the unweathered core. In contrast, in a sandstone cobble formed under the same environmental conditions over the same period of time there is an Fe-rich layer at some distance below the cobble's surface. Elemental mass balances across the rinds were determined by using open system mass balance (τ i,j ) calculations and show that the Fe was precipitated as Fe-oxyhydroxides in the basalt cobbles, although Fe was slightly removed from the rims. In sandstone cobbles, on the other hand, Fe migrated along a Fe concentration gradient by diffusion and precipitated as Fe-oxyhydroxide minerals to form the weathering rinds

  17. One-dimensional fossil-like γ-Fe2O3@carbon nanostructure: preparation, structural characterization and application as adsorbent for fast and selective recovery of gold ions from aqueous solution

    Science.gov (United States)

    Gunawan, Poernomo; Xiao, Wen; Hao Chua, Marcus Wen; Poh-Choo Tan, Cheryl; Ding, Jun; Zhong, Ziyi

    2016-10-01

    One-dimensional (1D) magnetic nanostructures with high thermal stability have important industrial applications, but their fabrication remains a big challenge. Herein we demonstrate a scalable approach for the preparation of stable 1D γ-Fe2O3@carbon, which is also applicable for other metal oxide-core and carbon-shell nanostructures, such as 1D TiO2@carbon. One-dimensional ferric oxyhydroxide (α-FeO(OH)) was initially prepared by a hydrothermal method, followed by carbon coating through hydrothermal treatment of the resulting metal oxide in glucose solution. After calcination in N2 gas at 500 °C and subsequent exposure to air, the initial carbon-coated 1D α-Fe2O3 was converted to 1D γ-Fe2O3@carbon, which was very stable without any observed changes even after 1.5 years of storage under ambient conditions. The materials were then used as adsorbents and found to be highly selective towards Au (III) adsorption, of which the maximum adsorption capacity is about 600 mg Au/g sorbent (1132 mg Au/g carbon). The spent sorbent containing Au after adsorption can be readily collected by applying a magnetic field due to the presence of the magnetic core, and the adsorbed Au particles are subsequently recovered after the combustion and dissolution of the sorbent. This work demonstrates not only a facile approach to the fabrication of robust 1D magnetic materials with a stable carbon shell, but also a possible cyanide-free process for the fast and selective recovery of gold from electronic waste and industrial water.

  18. Microstructural characterisation and corrosion performance of old railway girder bridge steel and modern weathering structural steel

    International Nuclear Information System (INIS)

    Tewary, N.K.; Kundu, A.; Nandi, R.; Saha, J.K.; Ghosh, S.K.

    2016-01-01

    Highlights: • Microstructure and corrosion performance are compared for two structural steels. • Microstructure evolution shows primarily ferrite-pearlite in both the steels. • Steels show higher corrosion rate in 1% HCl solution than in 3.5% NaCl solution. • The corrosion products show the presence of oxide, hydroxide and oxy-hydroxides. • The corroded surface reveals morphologies like flowery, cotton balls and rosette. - Abstract: A comparison on microstructure and corrosion performance has been made between the two structural steels used in old railway girder bridge (Sample A) and modern grades of weathering structural steel (Sample B). The microstructures, viewed under optical microscope and scanning electron microscope (SEM), show mainly ferrite-pearlite phase constituents in both the steels, A and B. The phase fraction analysis shows higher amount of pearlite in steel A compared to that of steel B. The grain size of steel A is larger than that of steel B under identical processing condition. The immersion corrosion test in 3.5% NaCl shows that the corrosion rate of steel A increases with time, while the same for steel B decreases with time. On the other hand, corrosion test in 1% HCl shows that the corrosion rate of both steel A and B is higher as compared to that of NaCl which always decreases with time. The XRD analysis of corrosion products show the presence of many oxides, hydroxide and oxy-hydroxide like Lepidocrocite (γ-FeOOH), Goethite (α-FeOOH), Akaganeite (β-FeOOH), Magnetite (Fe_3O_4) and Maghemite (γ-Fe_2O_3) in both the steels. The SEM images of corroded surfaces reveal different morphologies like flowery, cotton balls and rosette etc. which indicate that the corrosion products primarily contain Lepidocrocite (γ-FeOOH), Goethite (α-FeOOH) and Akaganeite (β-FeOOH).

  19. The influence of different electrodeposition E/t programs on the photoelectrochemical properties of α-Fe2O3 thin films

    International Nuclear Information System (INIS)

    Schrebler, Ricardo S.; Altamirano, Hernan; Grez, Paula; Herrera, Francisco V.; Munoz, Eduardo C.; Ballesteros, Luis A.; Cordova, Ricardo A.; Gomez, Humberto; Dalchiele, Enrique A.

    2010-01-01

    In this work morphological, structural and photoelectrochemical properties of n-type α-Fe 2 O 3 (hematite) thin films synthetized by means of two different electrochemical procedures: potential cycling electrodeposition (PC) and potential pulsed electrodeposition (PP) have been studied. The X-ray diffraction measurements showed that the films obtained after a thermal treatment at 520 o C present a nanocrystalline character. Scanning electron microscopy allowed finding that hematite films obtained by PP technique exhibit nanostructured morphology. The electrochemical and capacitance (Mott-Schottky and parallel capacitance) measurements showed that when in the PC and PP procedures the anodic limit E λ,A is being made more anodic, a decrease of the majority carriers concentration (N D ) and the surface states number has been observed. The photovoltammetry measurements indicated that the hematite films formed with the PP technique present a photocurrent one order of magnitude higher than the ones exhibited by the iron oxide films formed by PC. For instance, PP hematite films exhibit photovoltaic conversion efficiencies of 0.96% which are 2.5 times higher than the corresponding to the PC ones (0.38%). The maximum incident photon-to-current efficiency measured at λ = 370 and 600 nm was observed for hematite films grown by the PP procedure. By means of the photocurrent transient technique a decrease in the recombination process for those samples synthesized by PP was observed. The results obtained are discussed considering the influence of the anodic limit of the potential employed during the preparation of the iron oxyhydroxide (β-FeOOH) precursor film, all of this related to a decrease of the oxygen defects in this material and to a decrease of Fe(II) amount that is formed during the electrodeposition process.

  20. Fe atom exchange between aqueous Fe2+ and magnetite.

    Science.gov (United States)

    Gorski, Christopher A; Handler, Robert M; Beard, Brian L; Pasakarnis, Timothy; Johnson, Clark M; Scherer, Michelle M

    2012-11-20

    The reaction between magnetite and aqueous Fe(2+) has been extensively studied due to its role in contaminant reduction, trace-metal sequestration, and microbial respiration. Previous work has demonstrated that the reaction of Fe(2+) with magnetite (Fe(3)O(4)) results in the structural incorporation of Fe(2+) and an increase in the bulk Fe(2+) content of magnetite. It is unclear, however, whether significant Fe atom exchange occurs between magnetite and aqueous Fe(2+), as has been observed for other Fe oxides. Here, we measured the extent of Fe atom exchange between aqueous Fe(2+) and magnetite by reacting isotopically "normal" magnetite with (57)Fe-enriched aqueous Fe(2+). The extent of Fe atom exchange between magnetite and aqueous Fe(2+) was significant (54-71%), and went well beyond the amount of Fe atoms found at the near surface. Mössbauer spectroscopy of magnetite reacted with (56)Fe(2+) indicate that no preferential exchange of octahedral or tetrahedral sites occurred. Exchange experiments conducted with Co-ferrite (Co(2+)Fe(2)(3+)O(4)) showed little impact of Co substitution on the rate or extent of atom exchange. Bulk electron conduction, as previously invoked to explain Fe atom exchange in goethite, is a possible mechanism, but if it is occurring, conduction does not appear to be the rate-limiting step. The lack of significant impact of Co substitution on the kinetics of Fe atom exchange, and the relatively high diffusion coefficients reported for magnetite suggest that for magnetite, unlike goethite, Fe atom diffusion is a plausible mechanism to explain the rapid rates of Fe atom exchange in magnetite.

  1. The Moessbauer effect in Fe(III) HEDTA, Fe(III) EDTA, and Fe(III) CDTA compounds

    International Nuclear Information System (INIS)

    Prado, F.R.

    1989-01-01

    The dependence of Moessbauer spectra with pH value of Fe(III)HEDTA and Fe(III)CDTA compounds is studied. Informations on formation processes of LFe-O-FeL (L=ligand) type dimers by the relation of titration curves of Fe(III)EDTA, Fe(III)HEDTA and Fe(III)CDTA compounds with the series of Moessbauer spectra, are obtained. Some informations on Fe-O-Fe bond structure are also obtained. Comparing the titration curves with the series of Moessbauer spectra, it is concluded that the dimerization process begins when a specie of the form FeXOH α (X = EDTA, HEDTA, CDTA; α = -1, -2) arises. (M.C.K.) [pt

  2. Origin of middle rare earth element enrichments in acid waters of a Canadian high Arctic lake.

    Science.gov (United States)

    Johannesson, Kevin H.; Zhou, Xiaoping

    1999-01-01

    -Middle rare earth element (MREE) enriched rock-normalized rare earth element (REE) patterns of a dilute acidic lake (Colour Lake) in the Canadian High Arctic, were investigated by quantifying whole-rock REE concentrations of rock samples collected from the catchment basin, as well as determining the acid leachable REE fraction of these rocks. An aliquot of each rock sample was leached with 1 N HNO 3 to examine the readily leachable REE fraction of each rock, and an additional aliquot was leached with a 0.04 M NH 2OH · HCl in 25% (v/v) CH 3COOH solution, designed specifically to reduce Fe-Mn oxides/oxyhydroxides. Rare earth elements associated with the leachates that reacted with clastic sedimentary rock samples containing petrographically identifiable Fe-Mn oxide/oxyhydroxide cements and/or minerals/amorphous phases, exhibited whole-rock-normalized REE patterns similar to the lake waters, whereas whole-rock-normalized leachates from mafic igneous rocks and other clastic sedimentary rocks from the catchment basin differed substantially from the lake waters. The whole-rock, leachates, and lake water REE data support acid leaching or dissolution of MREE enriched Fe-Mn oxides/oxyhydroxides contained and identified within some of the catchment basin sedimentary rocks as the likely source of the unique lake water REE patterns. Solution complexation modelling of the REEs in the inflow streams and lake waters indicate that free metal ions (e.g., Ln 3+, where Ln = any REE) and sulfate complexes (LnSO 4+) are the dominant forms of dissolved REEs. Consequently, solution complexation reactions involving the REEs during weathering, transport to the lake, or within the lake, cannot be invoked to explain the MREE enrichments observed in the lake waters.

  3. Attenuation of landfill leachate by UK Triassic sandstone aquifer materials. 1. Fate of inorganic pollutants in laboratory columns

    Science.gov (United States)

    Thornton, Steven F.; Tellam, John H.; Lerner, David N.

    2000-05-01

    The attenuation of inorganic contaminants in acetogenic and methanogenic landfill leachate by calcareous and carbonate-deficient, oxide-rich Triassic sandstone aquifer materials from the English Midlands was examined in laboratory columns. Aqueous equilibrium speciation modelling, simple transport modelling and chemical mass balance approaches are used to evaluate the key processes and aquifer geochemical properties controlling contaminant fate. The results indicate that leachate-rock interactions are dominated by ion-exchange processes, acid-base and redox reactions and sorption/precipitation of metal species. Leachate NH 4 is attenuated by cation exchange with the aquifer sediments; however, NH 4 migration could be described with a simple model using retardation factors. Organic acids in the acetogenic leachate buffered the system pH at low levels during flushing of the calcareous aquifer material. In contrast, equilibrium with Al oxyhydroxide phases initially buffered pH (˜4.5) during flushing of the carbonate-deficient sandstone with methanogenic leachate. This led to the mobilisation of sorbed and oxide-bound heavy metals from the aquifer sediment which migrated as a concentrated pulse at the leachate front. Abiotic reductive dissolution of Mn oxyhydroxides on each aquifer material by leachate Fe 2+ maintains high concentrations of dissolved Mn and buffers the leachate inorganic redox system. This feature is analogous to the Mn-reducing zones found in leachate plumes and in the experiments provides a sink for the leachate Fe load and other heavy metals. The availability of reactive solid phase Mn oxyhydroxides limits the duration of redox buffering and Fe attenuation by these aquifer sediments. Aquifer pH and redox buffering capacity exert a fundamental influence on leachate inorganic contaminant fate in these systems. The implications for the assessment of aquifer vulnerability at landfills are discussed and simple measurements of aquifer properties which

  4. Precipitation pathways for ferrihydrite formation in acidic solutions

    DEFF Research Database (Denmark)

    Zhu, Mengqiang; Frandsen, Cathrine; Wallace, Adam F.

    2016-01-01

    to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe3+] = 0.2 M, 1.8 ... occurs prior to further condensation leading up to the nucleation of ferrihydrite. The structural reconfiguration is likely the rate-limiting step involved in the nucleation process....

  5. Effectiveness of FeEDDHA, FeEDDHMA, and FeHBED in Preventing Iron-Deficiency Chlorosis in Soybean.

    Science.gov (United States)

    Bin, Levi M; Weng, Liping; Bugter, Marcel H J

    2016-11-09

    The performance of FeHBED in preventing Fe deficiency chlorosis in soybean (Glycine max (L.) Merr.) in comparison to FeEDDHA and FeEDDHMA was studied, as well as the importance of the ortho-ortho and ortho-para/rest isomers in defining the performance. To this end, chlorophyll production (SPAD), plant dry matter yield, and the mass fractions of important mineral elements in the plant were quantified in a greenhouse pot experiment. All three Fe chelates increased SPAD index and dry matter yield compared to the control. The effect of FeHBED on chlorophyll production was visible over a longer time span than that of FeEDDHA and FeEDDHMA. Additionally, FeHBED did not suppress Mn uptake as much as the other Fe chelates. Compared to the other Fe chelates, total Fe content in the young leaves was lower in the FeHBED treatment; however, total Fe content was not directly related to chlorophyll production and biomass yield. For each chelate, the ortho-ortho isomer was found to be more effective than the other isomers evaluated.

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

    Science.gov (United States)

    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.

  7. The nanosphere iron mineral(s) in Mars soil

    Science.gov (United States)

    Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.

    1993-01-01

    A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.

  8. Arsenic mobilization in a freshening groundwater system formed within glaciomarine deposits

    International Nuclear Information System (INIS)

    Cavalcanti de Albuquerque, R.; Kirste, D.

    2012-01-01

    Arsenic release to groundwater and conditions favoring As mobility are investigated in a system of aquifers formed within unconsolidated Quaternary sediments. The studied groundwater system is comprised of unconfined aquifers formed in glaciofluvial sediments with Ca–Mg–HCO 3 groundwater, and confined aquifers formed within glaciomarine sediments with high As (above 10 μg/L) Na–HCO 3 or Na–Cl groundwater. A positive relationship of As concentrations with the Na/(Ca + Mg) ratio of groundwater indicates that As release occurs in glaciomarine sediments concurrent to cation exchange reactions related to groundwater freshening. Arsenic is mobile in confined aquifers as a result of groundwater basic pH which prevents arsenate from adsorbing to mineral surfaces, and reducing conditions that favor speciation to arsenite. Selected extractions applied to sediment core samples indicate that As occurs in sediments predominantly in sulfide minerals and in Mn oxides and/or Fe oxyhydroxides. General positive relationships between As and the reduced species Fe 2+ , NH 3 and dissolved S 2− suggest that As release occurs at increasingly reducing conditions. Despite likely As release via Fe oxyhydroxide reductive dissolution, Fe remains at relatively low concentrations in groundwater (up to 0.37 mg/L) as a result of possible Fe adsorption and Fe reprecipitation as carbonate minerals favored by basic pH and high alkalinity. The presence of S 2− in some samples, a negative relationship between δ 34 S of SO 4 and SO 4 2- concentrations, and a positive relationship between δ 34 S and δ 18 O of SO 4 indicate that groundwater in confined aquifers is undergoing bacterial SO 4 reduction.

  9. Ferrite grade iron oxides from ore rejects

    Indian Academy of Sciences (India)

    Iron oxyhydroxides and hydroxides were synthesized from chemically beneficiated high SiO2/Al2O3 low-grade iron ore (57.49% Fe2O3) rejects and heated to get iron oxides of 96–99.73% purity. The infrared band positions, isothermal weight loss and thermogravimetric and chemical analysis established the chemical ...

  10. Strong 3D and 1D magnetism in hexagonal Fe-chalcogenides FeS and FeSe vs. weak magnetism in hexagonal FeTe.

    Science.gov (United States)

    Parker, David S

    2017-06-13

    We present a comparative theoretical study of the hexagonal forms of the Fe-chalcogenides FeS, FeSe and FeTe with their better known tetragonal forms. While the tetragonal forms exhibit only an incipient antiferromagnetism and experimentally show superconductivity when doped, the hexagonal forms of FeS and FeSe display a robust magnetism. We show that this strong magnetism arises from a van Hove singularity associated with the direct Fe-Fe c-axis chains in the generally more three-dimensional NiAs structure. We also find that hexagonal FeTe is much less magnetic than the other two hexagonal materials, so that unconventional magnetically-mediated superconductivity is possible, although a large T c value is unlikely.

  11. Electron microscopy study of microbial mat in the North Fiji basin hydrothermal vent

    Science.gov (United States)

    Park, H.; Kim, J. W.; Lee, J. W.

    2017-12-01

    Hydrothermal vent systems consisting of hydrothermal vent, hydrothermal sediment and microbial mat are widely spread around the ocean, particularly spreading axis, continental margin and back-arc basin. Scientists have perceived that the hydrothermal systems, which reflect the primeval earth environment, are one of the best places to reveal the origin of life and extensive biogeochemical process of microbe-mineral interaction. In the present study multiline of analytical methods (X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM)) were utilized to investigate the mineralogy/chemistry of microbe-mineral interaction in hydrothermal microbial mat. Microbial mat samples were recovered by Canadian scientific submersible ROPOS on South Pacific North Fiji basin KIOST hydrothermal vent expedition 1602. XRD analysis showed that red-colored microbial mat contains Fe-oxides and Fe-oxyhydroxides. Various morphologies of minerals in the red-colored microbial mat observed by SEM are mainly showed sheath shaped, resembled with Leptothrix microbial structure, stalks shaped, similar with Marioprofundus microbial structure and globule shaped microbial structures. They are also detected with DNA analysis. The cross sectional observation of microbial structures encrusted with Fe-oxide and Fe-oxyhydroxide at a nano scale by Transmission Electron Microscopy (TEM) and Focused Ion Beam (FIB) technique was developed to verify the structural/biogeochemical properties in the microbe-mineral interaction. Systematic nano-scale measurements on the biomineralization in the microbial mat leads the understandings of biogeochemical environments around the hydrothermal vent.

  12. Strong 3D and 1D magnetism in hexagonal Fe-chalcogenides FeS and FeSe vs. weak magnetism in hexagonal FeTe

    Energy Technology Data Exchange (ETDEWEB)

    Parker, David S. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-06-13

    We present a comparative theoretical study of the hexagonal forms of the Fe-chalcogenides FeS, FeSe and FeTe with their better known tetragonal forms. While the tetragonal forms exhibit only an incipient antiferromagnetism and experimentally show superconductivity when doped, the hexagonal forms of FeS and FeSe display a robust magnetism. We show that this strong magnetism arises from a van Hove singularity associated with the direct Fe-Fe c-axis chains in the generally more three-dimensional NiAs structure. We also find that hexagonal FeTe is much less magnetic than the other two hexagonal materials, so that unconventional magnetically-mediated superconductivity is possible, although a large Tc value is unlikely.

  13. Influence of FeEDDS, FeEDTA, FeDTPA, FeEDDHA, and FeSO4 on Marigold Growth and Nutrition, and Substrate and Runoff Chemistry

    Science.gov (United States)

    Objectives of the study were to determine effects of Fe source on plant growth, plant nutrition, substrate chemistry and runoff chemistry. Iron source (FS) treatments consisted of Fe-aminopolycarboxylic acid (APCA) complexones iron ethylenediaminetetraacetic acid (FeEDTA), iron [S, S']-ethylenediam...

  14. Anomalous superconducting spin-valve effect in NbN/FeN/Cu/FeN/FeMn multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Tae Jong; Kim, Dong Ho [Yeungnam University, Gyeongsan (Korea, Republic of)

    2017-09-15

    We have studied magnetic and transport properties of NbN/FeN/Cu/FeN/FeMn spin-valve structure. In-plane magnetic moment exhibited typical hysteresis loops of spin valves in the normal state of NbN film at 20 K. On the other hand, the magnetic hysteresis loop in the superconducting state exhibited more complex behavior in which exchange bias provided by antiferrmagnetic FeMn layer to adjacent FeN layer was disturbed by superconductivity. Because of this, the ideal superconducting spin-valve effect was not detected. Instead the stray field originated from unsaturated magnetic states dominated the transport properties of NbN/FeN/Cu/FeN/FeMn multilayer.

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

    DEFF Research Database (Denmark)

    Ehlert, Katrin; Mikutta, Christian; Kretzschmar, Ruben

    2016-01-01

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

  16. Synthesis and characterization of boehmite γ-AIOOH and goethite α-FeOOH

    International Nuclear Information System (INIS)

    Corral C, N. G.; Granados C, F.

    2009-01-01

    The aluminum oxy-hydroxides (boehmite) and of iron (goethite) were synthesized by means of the Sol-Gel and oxidative hydrolysis methods, to be employees as adsorbent materials of the present Cd 2+ in aqueous solution. The synthesized materials were characterized by means of X-ray diffraction, infrared analysis and scanning electron microscopy, to identify their purity, elementary chemical composition and morphology. (Author)

  17. Soft magnetic properties of hybrid ferromagnetic films with CoFe, NiFe, and NiFeCuMo layers

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jong-Gu [Eastern-western Biomedical Engineering, Sangji University, Wonju 220-702 (Korea, Republic of); Hwang, Do-Guwn [Dept. of Oriental Biomedical Engineering, Sangji University, Wonju 220-702 (Korea, Republic of); Rhee, Jang-Roh [Dept. of Physics, Sookmyung Women' s University, Seoul 140-742 (Korea, Republic of); Lee, Sang-Suk, E-mail: sslee@sangji.ac.kr [Dept. of Oriental Biomedical Engineering, Sangji University, Wonju 220-702 (Korea, Republic of)

    2011-09-30

    Two-layered ferromagnetic alloy films (NiFe and CoFe) with intermediate NiFeCuMo soft magnetic layers of different thicknesses were investigated to understand the relationship between coercivity and magnetization process by taking into account the strength of hard-axis saturation field. The thickness dependence of H{sub EC} (easy-axis coercivity), H{sub HS} (hard-axis saturation field), and {chi} (susceptibility) of the NiFeCuMo thin films in glass/Ta(5 nm)/[CoFe or NiFe(5 nm-t/2)]/NiFeCuMo(t = 0, 4, 6, 8, 10 nm)/[CoFe or NiFe(5 nm-t/2)]/Ta(5 nm) films prepared using the ion beam deposition method was determined. The magnetic properties (H{sub EC}, H{sub HS}, and {chi}) of the ferromagnetic CoFe, NiFe three-layers with an intermediate NiFeCuMo super-soft magnetic layer were strongly dependent on the thickness of the NiFeCuMo layer.

  18. MIL-100-Fe derived N-doped Fe/Fe3C@C electrocatalysts for efficient oxygen reduction reaction

    Science.gov (United States)

    Guo, Dakai; Han, Sancan; Wang, Jiacheng; Zhu, Yufang

    2018-03-01

    N-doped porous Fe/Fe3C@C electrocatalysts were prepared by the pyrolysis of the hexamethylenetetramine (HMT)-incorporated MIL-100-Fe at different temperatures (700-1000 °C) under N2 atmosphere. Rotary evaporation of MIL-100-Fe and HMT solution could make more N-enriched HMT molecules enter into the pores of MIL-100-Fe, thus improving nitrogen contents of the final pyrolyzed samples. All pyrolyzed samples show porous textures with middle specific surface areas. The X-ray photoelectron spectroscopy (XPS) results demonstrate the successful introduction of N atoms into carbon framework. Sample Fe-N2-800 prepared by annealing the precursors with the HMT/MIL-100-Fe weight ratio of 2 at 800 °C exhibits the best electrocatalytic activity towards the oxygen reduction reaction (ORR) in terms of onset potential and current density because of high graphitic N and pyridinic N content. The enwrapped Fe/Fe3C nanoparticles and Fe-Nx active sites in these samples could also boost the ORR activity synergistically. Moreover, sample Fe-N2-800 demonstrates a dominant four electron reduction process, as well as excellent long-term operation stability and methanol crossover resistance. Thus, the N-doped Fe/Fe3C@C composites derived from the HMT-incorporated MIL-100-Fe are promising electrocatalysts to replace Pt/C for ORR in practical applications.

  19. The 54Fe(d,t)53Fe reaction and the neutron configuration in 54Fe

    International Nuclear Information System (INIS)

    England, J.B.A.; Ophel, T.R.; Johnston, A.; Zeller, A.F.

    1980-07-01

    The 54 Fe(d,t) 53 Fe reaction has been used to study the levels populated in 54 Fe in an attempt to establish the neutron configuration in 54 Fe. The states observed show clear evidence for a 2p-4h admixture in 54 Fe. In particular, the strength of the first 3/2 - level relative to the 7/2 - ground state transition is 3-4 times that in neighbouring N = 28 nuclei

  20. Statistical modeling of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2.

    Science.gov (United States)

    Ushakov, Vladimir G; Troe, Jürgen; Johnson, Ryan S; Guo, Hua; Ard, Shaun G; Melko, Joshua J; Shuman, Nicholas S; Viggiano, Albert A

    2015-08-14

    The rates of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2 are modeled by statistical rate theory accounting for energy- and angular momentum-specific rate constants for formation of the primary and secondary cationic adducts and their backward and forward reactions. The reactions are both suggested to proceed on sextet and quartet potential energy surfaces with efficient, but probably not complete, equilibration by spin-inversion of the populations of the sextet and quartet adducts. The influence of spin-inversion on the overall reaction rate is investigated. The differences of the two reaction rates mostly are due to different numbers of entrance states (atom + linear rotor or linear rotor + linear rotor, respectively). The reaction Fe(+) + N2O was studied either with (6)Fe(+) or with (4)Fe(+) reactants. Differences in the rate constants of (6)Fe(+) and (4)Fe(+) reacting with N2O are attributed to different contributions from electronically excited potential energy surfaces, such as they originate from the open-electronic shell reactants.

  1. Spin structure of exchange biased heterostructures. Fe/MnF{sub 2} and Fe/FeF{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Sahoo, B

    2006-12-18

    In this work, the {sup 57}Fe probe layer technique is used in order to investigate the depth- and temperature-dependent Fe-layer spin structure of exchange biased Fe/MnF{sub 2} and Fe/FeF{sub 2} (pseudo-twinned) antiferromagnetic (AFM) systems by conversion electron Moessbauer spectroscopy (CEMS) and nuclear resonant scattering (NRS) of synchrotron radiation. Two kinds of samples with a 10 A {sup 57}Fe probe layer directly at or 35 A away from the interface, labeled as interface and center sample, respectively, were studied in this work. The results obtained by CEMS for Fe/MnF{sub 2} suggests that, at 80 K, i.e., above T{sub N}=67 K of MnF{sub 2}, the remanent state Fe-layer spin structure of the two studied samples are slightly different due to their different microstructure. In the temperature range from 300 K to 80 K, the Fe-layer spin structure does not change just by zero-field cooling the sample in remanence. For Fe/FeF{sub 2}, a continuous non-monotonic change of the remanent-state Fe spin structure was observed by cooling from 300 K to 18 K. NRS of synchrotron radiation was used to investigate the temperature- and depth-dependent Fe-layer spin structure during magnetization reversal in pseudo-twinned Fe/MnF{sub 2}. A depthdependent Fe spin structure in an applied magnetic field (applied along the bisector of the twin domains) was observed at 10 K, where the Fe spins closer to the interface are not aligned along the field direction. The depth-dependence disappears at 150 K. (orig.)

  2. How oxygen attacks [FeFe] hydrogenases from photosynthetic organisms

    Science.gov (United States)

    Stripp, Sven T.; Goldet, Gabrielle; Brandmayr, Caterina; Sanganas, Oliver; Vincent, Kylie A.; Haumann, Michael; Armstrong, Fraser A.; Happe, Thomas

    2009-01-01

    Green algae such as Chlamydomonas reinhardtii synthesize an [FeFe] hydrogenase that is highly active in hydrogen evolution. However, the extreme sensitivity of [FeFe] hydrogenases to oxygen presents a major challenge for exploiting these organisms to achieve sustainable photosynthetic hydrogen production. In this study, the mechanism of oxygen inactivation of the [FeFe] hydrogenase CrHydA1 from C. reinhardtii has been investigated. X-ray absorption spectroscopy shows that reaction with oxygen results in destruction of the [4Fe-4S] domain of the active site H-cluster while leaving the di-iron domain (2FeH) essentially intact. By protein film electrochemistry we were able to determine the order of events leading up to this destruction. Carbon monoxide, a competitive inhibitor of CrHydA1 which binds to an Fe atom of the 2FeH domain and is otherwise not known to attack FeS clusters in proteins, reacts nearly two orders of magnitude faster than oxygen and protects the enzyme against oxygen damage. These results therefore show that destruction of the [4Fe-4S] cluster is initiated by binding and reduction of oxygen at the di-iron domain—a key step that is blocked by carbon monoxide. The relatively slow attack by oxygen compared to carbon monoxide suggests that a very high level of discrimination can be achieved by subtle factors such as electronic effects (specific orbital overlap requirements) and steric constraints at the active site. PMID:19805068

  3. Fe-vacancy and superconductivity in FeSe-based superconductors

    Science.gov (United States)

    Wang, C. H.; Chen, T. K.; Chang, C. C.; Lee, Y. C.; Wang, M. J.; Huang, K. C.; Wu, P. M.; Wu, M. K.

    2018-06-01

    This review summarizes recent advancements in FeSe and related systems. The FeSe and related superconductors are currently receiving considerable attention for the high Tcs observed and for many similar features to the high Tc cuprate superconductors. These similarities suggest that understanding the FeSe based compounds could potentially help our understanding of the cuprates. We shall first review the common features observed in the FeSe-based system. It was found that with a careful control of material synthesizing processes, numerous rich phases have been observed in the FeSe-based system. Detailed studies show that the Fe-vacancy ordered phases found in the FeSe based compounds, which are non-superconducting Mott insulators, are the parent compounds of the superconductors. Superconductivity emerges from the parent phases by disordering the Fe vacancy order, often by a simple annealing treatment. Recent high temperature X-ray diffraction experiments show that the degree of structural distortion associated with the disorder of Fe-vacancy is closely related to volume fraction of the superconductivity observed. These results suggest the strong lattice to spin coupling are important for the occurrence of superconductivity in FeSe based superconductors.

  4. Exchange bias variations of the seed and top NiFe layers in NiFe/FeMn/NiFe trilayer as a function of seed layer thickness

    International Nuclear Information System (INIS)

    Sankaranarayanan, V.K.; Yoon, S.M.; Kim, C.G.; Kim, C.O.

    2005-01-01

    Development of exchange bias at the seed and top NiFe layers in the NiFe (t nm)/FeMn(10 nm)/NiFe(5 nm) trilayer structure is investigated as a function of seed layer thickness, in the range of 2-20 nm. The seed NiFe layer shows maximum exchange bias at 4 nm seed layer thickness. The bias shows inverse thickness dependence with increasing thickness. The top NiFe layer on the other hand shows only half the bias of the seed layer which is retained even after the sharp fall in seed layer bias. The much smaller bias for the top NiFe layer is related to the difference in crystalline texture and spin orientations at the top FeMn/NiFe interface, in comparison to the bottom NiFe/FeMn interface which grows on a saturated NiFe layer with (1 1 1) orientation

  5. Structural and magnetic properties of NdFeB and NdFeB/Fe films with Mo addition

    Energy Technology Data Exchange (ETDEWEB)

    Urse, M; Grigoras, M; Lupu, N; Chiriac, H, E-mail: urse@phys-iasi.ro [National Institute of R and D for Technical Physics, 47 Mangeron Blvd., 700050 Iasi (Romania)

    2011-07-06

    The influence of the Mo addition on the microstructure and magnetic properties of Nd-Fe-B and Nd-Fe-B/Fe films was studied. The coercivity is a key parameter in the control of technical performances of Nd-Fe-B films. A small amount of about 1 at.% Mo can enhance the coercivity of Nd-Fe-B film by controlling the growth of soft and hard magnetic grains. A coercivity of 22.1 kOe, a remanence ratio, M{sub r}/M{sub s}, of 0.83 and a maximum energy product of 8 MGOe were obtained for Ta/[NdFeBMo(1at.%)(540nm)/Ta films annealed at 650{sup 0}C for 20 minutes due to Mo precipitates formed at the Nd{sub 2}Fe{sub 14}B phase boundaries which prevent the nucleation and expansion of the magnetic domains. Simultaneous use of Mo as addition and the stratification of Nd-Fe-B-Mo films using Fe as spacer layer are important tools for the improvement of the hard magnetic properties of Nd-Fe-B films. The Ta/[NdFeBMo(1at.%)(180nm)/Fe(1nm)]x3/Ta multilayer film annealed at 620{sup 0}C exhibits an increase in the coercivity from 12.1 kOe to 22.8 kOe, in the remanence ratio from 0.77 to 0.80, and in the maximum energy product from 4.5 to 7.1 MGOe in comparison with Ta/Nd-Fe-B/Ta film. As compared to Ta/Nd-Fe-B/Ta film, the Ta/[NdFeBMo(1at.%)(180nm)/Fe(1nm)]x3/Ta film presents a decrease in the crystallization temperature of about 30{sup 0}C.

  6. Isotopic fractionation associated with [NiFe]- and [FeFe]-hydrogenases

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Hui; Gandhi, Hasand; Cornish, Adam J.; Moran, James J.; Kreuzer, Helen W.; Ostrom, Nathaniel; Hegg, Eric L.

    2016-01-30

    Hydrogenases catalyze the reversible formation of H2 from electrons and protons with high efficiency. Understanding the relationships between H2 production, H2 uptake, and H2-H2O exchange can provide insight into the metabolism of microbial communities in which H2 is an essential component in energy cycling. In this manuscript, we used stable H isotopes (1H and 2H) to probe the isotope effects associated with three [FeFe]-hydrogenases and three [NiFe]-hydrogenases. All six hydrogenases displayed fractionation factors for H2 formation that were significantly less than 1, producing H2 that was severely depleted in 2H relative to the substrate, water. Consistent with differences in their active site structure, the fractionation factors for each class appear to cluster, with the three [NiFe]-hydrogenases (α = 0.27-0.40) generally having smaller values than the three [FeFe]-hydrogenases (α = 0.41-0.55). We also obtained isotopic fractionation factors associated with H2 uptake and H2-H2O exchange under conditions similar to those utilized for H2 production, providing us with a more complete picture of the three reactions catalyzed by hydrogenases. The fractionation factors determined in our studies can be used as signatures for different hydrogenases to probe their activity under different growth conditions and to ascertain which hydrogenases are most responsible for H2 production and/or uptake in complex microbial communities.

  7. Influence of an Fe cap layer on the structural and magnetic properties of Fe49Pt51/Fe bi-layers

    International Nuclear Information System (INIS)

    Chao-Yang, Duan; Bin, Ma; Zong-Zhi, Zhang; Qing-Yuan, Jin; Fu-Lin, Wei

    2009-01-01

    The influences of an Fe cap layer on the structural and magnetic properties of FePt/Fe bi-layers are investigated. Compared with single FePt alloy films, a thin Fe layer can affect the crystalline orientation and improve the chemical ordering of L1 0 FePt films. Moreover, the coercivity increases when a thin Fe layer covers the FePt layer. Beyond a critical thickness, however, the Fe cover layer quickens the magnetization reversal of Fe 49 Pt 51 /Fe bi-layers by their exchange coupling

  8. Synthesis of aqueous suspensions of magnetic nanoparticles with the co-precipitation of iron ions in the presence of aspartic acid

    Energy Technology Data Exchange (ETDEWEB)

    Pušnik, Klementina; Goršak, Tanja [Department for Materials Synthesis, Jožef Stefan Institute, 1000 Ljubljana (Slovenia); Jožef Stefan International Postgraduate School, 1000 Ljubljana (Slovenia); Drofenik, Miha [Department for Materials Synthesis, Jožef Stefan Institute, 1000 Ljubljana (Slovenia); Faculty of Chemistry and Chemical Engineering, University of Maribor, 2000 Maribor (Slovenia); Makovec, Darko [Department for Materials Synthesis, Jožef Stefan Institute, 1000 Ljubljana (Slovenia); Jožef Stefan International Postgraduate School, 1000 Ljubljana (Slovenia)

    2016-09-01

    There is increasing demand for the production of large quantities of aqueous suspensions of magnetic iron-oxide nanoparticles. Amino acids are one possible type of inexpensive, nontoxic, and biocompatible molecules that can be used as the surfactants for the preparation of stable suspensions. This preparation can be conducted in a simple, one-step process based on the co-precipitation of Fe{sup 3+}/Fe{sup 2+} ions in the presence of the amino acid. However, the presence of this amino acid changes the mechanism of the magnetic nanoparticles' formation. In this investigation we analyzed the influence of aspartic amino acid (Asp) on the formation of magnetic iron-oxide nanoparticles during the co-precipitation. The process of the nanoparticles’ formation was followed using a combination of TEM, x-ray diffractometry, magnetic measurements, in-situ FT-IR spectroscopy, and chemical analysis, and compared with the formation of nanoparticles without the Asp. The Asp forms a coordination complex with the Fe{sup 3+} ions, which impedes the formation of the intermediate iron oxyhydroxide phase and suppresses the growth of the final magnetic iron-oxide nanoparticles. Slower reaction kinetics can lead to the formation of nonmagnetic secondary phases. The aspartic-acid-absorbed nanoparticles can be dispersed to form relatively concentrated aqueous suspensions displaying a good colloidal stability at an increased pH. - Highlights: • Co-precipitation of Fe{sup 3+}/Fe{sup 2+} ions in the presence of aspartic amino acid (Asp). • Through analysis of nanoparticle formation mechanism. • Presence of Asp changes the mechanism of the nanoparticles’ formation. • Asp forms a coordination complex with the Fe{sup 3+} ions. • Asp impedes the formation of iron oxyhydroxide phase and suppresses the growth of iron-oxide nanoparticles. • The aspartic-acid-absorbed nanoparticles form stable aqueous suspensions.

  9. Synthesis of aqueous suspensions of magnetic nanoparticles with the co-precipitation of iron ions in the presence of aspartic acid

    International Nuclear Information System (INIS)

    Pušnik, Klementina; Goršak, Tanja; Drofenik, Miha; Makovec, Darko

    2016-01-01

    There is increasing demand for the production of large quantities of aqueous suspensions of magnetic iron-oxide nanoparticles. Amino acids are one possible type of inexpensive, nontoxic, and biocompatible molecules that can be used as the surfactants for the preparation of stable suspensions. This preparation can be conducted in a simple, one-step process based on the co-precipitation of Fe 3+ /Fe 2+ ions in the presence of the amino acid. However, the presence of this amino acid changes the mechanism of the magnetic nanoparticles' formation. In this investigation we analyzed the influence of aspartic amino acid (Asp) on the formation of magnetic iron-oxide nanoparticles during the co-precipitation. The process of the nanoparticles’ formation was followed using a combination of TEM, x-ray diffractometry, magnetic measurements, in-situ FT-IR spectroscopy, and chemical analysis, and compared with the formation of nanoparticles without the Asp. The Asp forms a coordination complex with the Fe 3+ ions, which impedes the formation of the intermediate iron oxyhydroxide phase and suppresses the growth of the final magnetic iron-oxide nanoparticles. Slower reaction kinetics can lead to the formation of nonmagnetic secondary phases. The aspartic-acid-absorbed nanoparticles can be dispersed to form relatively concentrated aqueous suspensions displaying a good colloidal stability at an increased pH. - Highlights: • Co-precipitation of Fe 3+ /Fe 2+ ions in the presence of aspartic amino acid (Asp). • Through analysis of nanoparticle formation mechanism. • Presence of Asp changes the mechanism of the nanoparticles’ formation. • Asp forms a coordination complex with the Fe 3+ ions. • Asp impedes the formation of iron oxyhydroxide phase and suppresses the growth of iron-oxide nanoparticles. • The aspartic-acid-absorbed nanoparticles form stable aqueous suspensions.

  10. Microstructure and properties of multiphase sintered cermets Fe-Fe{sub 2}B; Mikrostruktura i wlasnosci spiekanych reakcyjnie cermetali Fe-Fe{sub 2}B

    Energy Technology Data Exchange (ETDEWEB)

    Nowacki, J. [Wydzial Inzynierii Materialowej, Politechnika Szczecinska, Szczecin (Poland); Klimek, L. [Instytut Inzynierii Materialowej i Technik Bezwiorowych, Politechnika Lodzka, Lodz (Poland)

    1998-12-31

    The process of multiphase sintering of iron in the vacuum has been analysed. As a result of the process iron-iron boride cermets have been produced. Fe-Fe{sub 2}B cermets were obtained as a result of sintering of the Fe and B pure elements in the vacuum. Attemps at sintering in the solid phase and with the participation of the liquid phase, the Fe-Fe{sub 2}B eutectic, have been made. Metallographic qualitative and quantitative studies, X-ray structural qualitative and qauantitative analysis allowed to determine the structure of Fe{sub 2}B cermets, as well as a description of the kinetics of quantitative changes in phase proportions in the course of sintering. It has been found that their structure varies widely depending on sintering parameters and the composition of the sinters. Measurements of the Fe-Fe{sub 2}B cermets hardness and measurements on wear during dry friction by the pin-on-disc method have shown distinct advantages of the cermets as a modern constructional materials. The hardness of Fe-Fe{sub 2}B cermets, depending on their chemical composition and sintering parameters, ranges widely from 150 to 1500 HV, and their resistance to wear is comparable to that of diffusively boronized steels. FeFe{sub 2}B cermets are a composite material in which iron boride, Fe{sub 2}B, with a hardness of about 1800 HV plays the role of the reinforcement,while iron-iron boride, Fe-Fe{sub 2}B, with a hardness of about 500 HV plays the role of matrix. The eutectic in the spaces between iron boride grains is composed of boron solid solution plates in iron with a hardness of arround 250 HV, and iron boride, Fe{sub 2}B, plates with a hardness of approximaly 1800 HV. The combination of such different materials, a hard reinforcement and a relatively plastic matrix produces favourable properties of the cermet thus produced high hardness (1500 HV) constant over whole cross section of the material, resistance of abrasive wear and acceptable ductility. The properties mentioned above

  11. Equilibrium Fe isotope fractionation between inorganic aqueous Fe(III) and the siderophore complex, Fe(III)-desferrioxamine B

    DEFF Research Database (Denmark)

    Dideriksen, Knud; Baker, Joel A.; Stipp, Susan Louise Svane

    2008-01-01

    be controlled by isotope fractionation between the free and complexed iron.We have determined the equilibrium Fe isotope fractionation induced by organic ligand activity in experiments with solutions having co-existing inorganic Fe(III) species and siderophore complexes, Fedesferrioxamine B (at pH 2). The two......-type fractionation during precipitation, this experiment yielded an isotope fractionation factor of a56Fesolution-solid=1.00027. Calculations based on these results indicate that isotopic re-equilibration is unlikely to significantly affect our determined equilibrium Fe isotope fractionation between inorganically...... and organically complexed Fe. To determine the equilibrium Fe isotope fractionation between inorganically and organically bound Fe(III), experiments with variable proportions of inorganic Fe were carried out at 25 °C. Irrespective of the proportion of inorganic Fe, equilibrium fractionation factors were within...

  12. Trace metal concentrations in tropical mangrove sediments, NE Brazil.

    Science.gov (United States)

    Miola, Brígida; Morais, Jáder Onofre de; Pinheiro, Lidriana de Souza

    2016-01-15

    Sediment cores were taken from the mangroves of the Coreaú River estuary off the northeast coast of Brazil. They were analyzed for grain size, CaCO3, organic matter, and trace metal (Cd, Pb, Zn, Cu, Al, and Fe) contents. Mud texture was the predominant texture. Levels of trace metals in surface sediments indicated strong influence of anthropogenic processes, and diagenetic processes controlled the trace metal enrichment of core sediments of this estuary. The positive relationships between trace metals and Al and Fe indicate that Cu, Zn, Pb, and Cd concentrations are associated mainly with Al and Fe oxy-hydroxides and have natural sources. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Characterisation of zinc in slags originated from a contaminated sediment by coupling /μ-PIXE, /μ-RBS, /μ-EXAFS and powder EXAFS spectroscopy

    Science.gov (United States)

    Isaure, M. P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

    2001-07-01

    Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2O 3·9H 2O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation.

  14. Characterisation of zinc in slags originated from a contaminated sediment by coupling μ-PIXE, μ-RBS, μ-EXAFS and powder EXAFS spectroscopy

    International Nuclear Information System (INIS)

    Isaure, M.P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

    2001-01-01

    Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2 O 3 ·9H 2 O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation

  15. Effectiveness of FeEDDHA, FeEDDHMA, and FeHBED in Preventing Iron-Deficiency Chlorosis in Soybean

    NARCIS (Netherlands)

    Bin, Levi M.; Weng, Liping; Bugter, Marcel H.J.

    2016-01-01

    The performance of FeHBED in preventing Fe deficiency chlorosis in soybean (Glycine max (L.) Merr.) in comparison to FeEDDHA and FeEDDHMA was studied, as well as the importance of the ortho-ortho and ortho-para/rest isomers in defining the performance. To this end, chlorophyll production (SPAD),

  16. Development of a reactive force field for iron-oxyhydroxide systems.

    Science.gov (United States)

    Aryanpour, Masoud; van Duin, Adri C T; Kubicki, James D

    2010-06-03

    We adopt a classical force field methodology, ReaxFF, which is able to reproduce chemical reactions, and train its parameters for the thermodynamics of iron oxides as well as energetics of a few iron redox reactions. Two parametrizations are developed, and their results are compared with quantum calculations or experimental measurements. In addition to training, two test cases are considered: the lattice parameters of a selected set of iron minerals, and the molecular dynamics simulation of a model for alpha-FeOOH (goethite)-water interaction. Reliability and limitations of the developed force fields in predicting structure and energetics are discussed.

  17. Raman-spectroscopic (Fe/Fe+Mg, CO2) and Structural studies of Mg-Fe cordierites

    International Nuclear Information System (INIS)

    Haefeker, U.

    2013-01-01

    In the course of this dissertation synthetic hexagonal and orthorhombic Mg-Fe-cordierites have been investigated with Raman-spectroscopy and XRD methods. Cordierite´s Mg- and Fe-end-members as well as their Mg-Fe solid solutions with the chemical formula (Mg, Fe 2+ ) 2 Al 4 Si 5 O 18 *nH 2 O have been synthesized. Raman-data of synthetic hydrous Mg- and Fe-cordierites have been obtained in the wavenumber-region 100-1250 cm-1 and the experimental data were then compared with the results of quantum-mechanical calculations. 86 theoretical bands could be related to specific vibrational modes of the tetrahedral and octahedral sites of the cordierite structure. Maximum and mean deviation between experimentally-derived bands and calculated modes were ±7 cm -1 for Mg-cordierite and ±19 cm -1 for Fe-cordierite. Spectra comparison revealed a trend of peak downshifting as a consequence of Fe-incorporation. The calculations now allow more accurate interpretation of the Raman spectra with respect to structural changes of cordierite, resulting from Al-Si ordering and Mg-Fe exchange. Atomic motions in cordierite have been compared with those of the structurally similar mineral beryl. Investigations of 16 H 2 O-bearing synthetic well-ordered Mg-Fe-cordierites (XFe =0-1) with micro-Raman spectroscopy revealed a linear correlation between the Fe/Mg ratio and the position of certain Raman peaks. The peaks (wave-number Mg-/Fe-cordierite) at 122/111, 262/257, 430/418, 579/571, 974/967, and 1012/1007 cm -1 were selected for a detailed deconvolution analysis . The shifts of these peaks were then plotted vs. XFe and regression of the data lead to the formulation of a set of linear equations. In addition, the effect of different H 2 O contents and the degree of Al-Si ordering on the Fe/Mg determination were also investigated. Testing the calibration against data from six well-characterized natural cordierite samples yielded excellent agreement. Existing calibration diagrams for CO 2

  18. In situ fabrication of Ni-Co (oxy)hydroxide nanowire-supported nanoflake arrays and their application in supercapacitors.

    Science.gov (United States)

    Zheng, Xiaoyu; Quan, Honglin; Li, Xiaoxin; He, Hai; Ye, Qinglan; Xu, Xuetang; Wang, Fan

    2016-09-29

    Three-dimensional (3D) hybrid nanostructured arrays grown on a flexible substrate have recently attracted great attention owing to their potential application as supercapacitor electrodes in portable and wearable electronic devices. Here, we report an in situ conversion of Ni-Co active electrode materials for the fabrication of high-performance electrodes. Ni-Co carbonate hydroxide nanowire arrays on carbon cloth were initially synthesized via a hydrothermal method, and they were gradually converted to Ni-Co (oxy)hydroxide nanowire-supported nanoflake arrays after soaking in an alkaline solution. The evolution of the supercapacitor performance of the soaked electrode was investigated in detail. The areal capacitance increases from 281 mF cm -2 at 1 mA cm -2 to 3710 and 3900 mF cm -2 after soaking for 36 h and 48 h, respectively. More interestingly, the electrode also shows an increased capacitance with charge/discharge cycles due to the long-time soaking in KOH solution, suggesting novel cycling durability. The enhancement in capacitive performance should be related to the formation of a unique nanowire-supported nanoflake array architecture, which controls the agglomeration of nanoflakes, making them fully activated. As a result, the facile in situ fabrication of the hybrid architectural design in this study provides a new approach to fabricate high-performance Ni/Co based hydroxide nanostructure arrays for next-generation energy storage devices.

  19. Construction and evaluation of As(V) selective electrodes based on iron oxyhydroxide embedded in silica gel membrane

    International Nuclear Information System (INIS)

    Rodriguez, J.A.; Barrado, E.; Vega, M.; Prieto, F.; Lima, J.L.F.C.

    2005-01-01

    Two As(V) selective electrodes (with and without inner reference solution) have been developed using selective membranes based on iron oxyhydroxide embedded on silica gel mixed with ultrapure graphite at a 2/98 (w/w) ratio. The active component of the membrane was synthesised by means of the sol-gel technique and characterized by X-ray and FTIR spectroscopy. This compound shows a great affinity towards As(V) ions adsorbing 408 mg g -1 . Using 1 mol l -1 phosphate buffer (at a 1/1, v/v ratio) to adjust the pH and the ionic strength to 7 and 0.5 mol l -1 , respectively, the calibration curve is linear from 1.0 x 10 -1 to 1.0 x 10 -6 mol l -1 As(V), with a practical detection limit of 4 x 10 -7 mol l -1 (0.03 mg l -1 ) and a slope close to 30 mV decade -1 . The effect of potentially interfering ions was investigated. The accuracy and precision of the procedure have been tested on arsenic-free drinking water samples spiked with known amounts of arsenic and on groundwater samples containing high levels of arsenic. Total arsenic in these samples was determined after oxidation of As(III) with iodine at pH 7. The results of total As were comparable to those generated by ET-AAS

  20. Giant magnetoimpedance effect in sputtered single layered NiFe film and meander NiFe/Cu/NiFe film

    International Nuclear Information System (INIS)

    Chen, L.; Zhou, Y.; Lei, C.; Zhou, Z.M.; Ding, W.

    2010-01-01

    Giant magnetoimpedance (GMI) effect on NiFe thin film is very promising due to its application in developing the magnetic field sensors with highly sensitivity and low cost. In this paper, the single layered NiFe thin film and NiFe/Cu/NiFe thin film with a meander structure are prepared by the MEMS technology. The influences of sputtering parameters, film structure and conductor layer width on GMI effect in NiFe single layer and meander NiFe/Cu/NiFe film are investigated. Maximum of the GMI ratio in single layer and sandwich film is 5% and 64%, respectively. The results obtained are useful for developing the high-performance magnetic sensors based on NiFe thin film.

  1. Iron geochemistry and organic carbon preservation by iron (oxyhydr)oxides in surface sediments of the East China Sea and the south Yellow Sea

    Science.gov (United States)

    Ma, Wei-Wei; Zhu, Mao-Xu; Yang, Gui-Peng; Li, Tie

    2018-02-01

    In marine sediments factors that influence iron (Fe) geochemistry and its interactions with other elements are diverse and remain poorly understood. Here we comparatively study Fe speciation and reactive Fe-bound organic carbon (Fe-OC) in surface sediments of the East China Sea (ECS) and the south Yellow Sea (SYS). The objectives are to better understand the potential impacts of geochemically distinct sediment sources and depositional/diagenetic settings on Fe geochemistry and OC preservation by Fe (hydr)oxides in sediments of the two extensive shelf seas around the world. Contents of carbonate- and acid-volatile-sulfide (AVS)-associated Fe(II) (FeAVS + carb) and magnetite (Femag) in the ECS sediments are about 5 and 9 times higher, respectively, than in the SYS. This could be ascribed to the ferruginous conditions of the ECS sediments that favor the formation/accumulation of Fecarb and Femag, a unique feature of marine unsteady depositional regimes. Much lower total Fe(II) contents in the SYS than in the ECS suggest that lower availability of highly reactive Fe (FeHR) and/or weak Fe reduction is a factor limiting Fe(II) formation and accumulation in the SYS sediments. The ratio of FeHR to total Fe is, on average, markedly higher (2.4 times) in the ECS sediments than in the SYS, which may be a combined result of several factors relevant to different sediment sources and depositional/diagenetic settings. In comparison with many other marine sediments, the percent fractions (fFe-OC) of Fe-OC to total organic carbon (TOC) in the ECS and the SYS are low, which can be ascribed to surface adsorption of OC rather than coprecipitation or organic complexation as the dominant binding mechanisms. Based on the fFe-OC in this study, total Fe-OC estimated for global continental shelves is equivalent to 38% of the atmospheric CO2 pool, which indicates the important role of sorptive stabilization of Fe-OC in continental shelf sediments for buffering CO2 release to the atmosphere

  2. Shewanella putrefaciens mtrB encodes an outer membrane protein required for Fe(III) and Mn(IV) reduction.

    Science.gov (United States)

    Beliaev, A S; Saffarini, D A

    1998-12-01

    Iron and manganese oxides or oxyhydroxides are abundant transition metals, and in aquatic environments they serve as terminal electron acceptors for a large number of bacterial species. The molecular mechanisms of anaerobic metal reduction, however, are not understood. Shewanella putrefaciens is a facultative anaerobe that uses Fe(III) and Mn(IV) as terminal electron acceptors during anaerobic respiration. Transposon mutagenesis was used to generate mutants of S. putrefaciens, and one such mutant, SR-21, was analyzed in detail. Growth and enzyme assays indicated that the mutation in SR-21 resulted in loss of Fe(III) and Mn(IV) reduction but did not affect its ability to reduce other electron acceptors used by the wild type. This deficiency was due to Tn5 inactivation of an open reading frame (ORF) designated mtrB. mtrB encodes a protein of 679 amino acids and contains a signal sequence characteristic of secreted proteins. Analysis of membrane fractions of the mutant, SR-21, and wild-type cells indicated that MtrB is located on the outer membrane of S. putrefaciens. A 5.2-kb DNA fragment that contains mtrB was isolated and completely sequenced. A second ORF, designated mtrA, was found directly upstream of mtrB. The two ORFs appear to be arranged in an operon. mtrA encodes a putative 10-heme c-type cytochrome of 333 amino acids. The N-terminal sequence of MtrA contains a potential signal sequence for secretion across the cell membrane. The amino acid sequence of MtrA exhibited 34% identity to NrfB from Escherichia coli, which is involved in formate-dependent nitrite reduction. To our knowledge, this is the first report of genes encoding proteins involved in metal reduction.

  3. Molecular [(Fe3)–(Fe3)] and [(Fe4)–(Fe4)] coordination cluster pairs as single or composite arrays.

    Science.gov (United States)

    Sañudo, E Carolina; Uber, Jorge Salinas; Pons Balagué, Alba; Roubeau, Olivier; Aromí, Guillem

    2012-08-06

    The synthesis of molecular cluster pairs is a challenge for coordination chemists due to the potential applications of these species in molecular spintronics or quantum computing. The ligand H(4)L, 1,3-bis-(3-oxo-3-(2-hydroxyphenyl)-propionyl)-2-methoxybenzene, has been successfully used to obtain a series of such complexes using the basic Fe(III) trinuclear carboxylates as starting materials. Synthetic control has allowed the isolation of the two molecular cluster pairs that form the composite [Fe(4)O(2)(PhCO(2))(6)(H(2)L)(pz)](2)[Fe(3)O(PhCO(2))(5)(py)(H(2)L)](2) (1). The dimers of trinuclear units, [Fe(3)O(PhCO(2))(5)(H(2)O)(H(2)L)](2) (2) and [Fe(3)O(o-MePhCO(2))(5)(H(2)L)(py)](2) (3), and the dimers of tetranuclear units, [Fe(4)O(2)(PhCO(2))(6)(H(2)L)(pz)](2) (4) and [Fe(4)O(2)(o-MePhCO(2))(6)(H(2)L)(pz)](2) (5), are presented here. The magnetic properties of the reported aggregates show that they are pairs of semi-independent clusters weakly interacting magnetically as required for two-qubit quantum gates.

  4. Timescales of carbon turnover in soils with mixed crystalline mineralogies

    Science.gov (United States)

    Khomo, Lesego; Trumbore, Susan; Bern, Carleton R.; Chadwick, Oliver A.

    2017-01-01

    Organic matter-mineral associations stabilize much of the carbon (C) stored globally in soils. Metastable short-range-order (SRO) minerals such as allophane and ferrihydrite provide one mechanism for long-term stabilization of organic matter in young soil. However, in soils with few SRO minerals and a predominance of crystalline aluminosilicate or Fe (and Al) oxyhydroxide, C turnover should be governed by chemisorption with those minerals. Here, we correlate mineral composition from soils containing small amounts of SRO minerals with mean turnover time (TT) of C estimated from radiocarbon (14C) in bulk soil, free light fraction and mineral-associated organic matter. We varied the mineral amount and composition by sampling ancient soils formed on different lithologies in arid to subhumid climates in Kruger National Park (KNP), South Africa. Mineral contents in bulk soils were assessed using chemical extractions to quantify Fe oxyhydroxides and SRO minerals. Because of our interest in the role of silicate clay mineralogy, particularly smectite (2 : 1) and kaolinite (1 : 1), we separately quantified the mineralogy of the clay-sized fraction using X-ray diffraction (XRD) and measured 14C on the same fraction. Density separation demonstrated that mineral associated C accounted for 40-70 % of bulk soil organic C in A and B1 horizons for granite, nephelinite and arid-zone gabbro soils, and > 80 % in other soils. Organic matter strongly associated with the isolated clay-sized fraction represented only 9-47 % of the bulk soil C. The mean TT of C strongly associated with the clay-sized fraction increased with the amount of smectite (2 : 1 clays); in samples with > 40 % smectite it averaged 1020 ± 460 years. The C not strongly associated with clay-sized minerals, including a combination of low-density C, the C associated with minerals of sizes between 2 µm and 2 cm (including Fe oxyhydroxides as coatings), and C removed from clay-sized material by 2 % hydrogen peroxide had

  5. A [4Fe-4S]-Fe(CO)(CN)-l-cysteine intermediate is the first organometallic precursor in [FeFe] hydrogenase H-cluster bioassembly

    Science.gov (United States)

    Rao, Guodong; Tao, Lizhi; Suess, Daniel L. M.; Britt, R. David

    2018-05-01

    Biosynthesis of the [FeFe] hydrogenase active site (the 'H-cluster') requires the interplay of multiple proteins and small molecules. Among them, the radical S-adenosylmethionine enzyme HydG, a tyrosine lyase, has been proposed to generate a complex that contains an Fe(CO)2(CN) moiety that is eventually incorporated into the H-cluster. Here we describe the characterization of an intermediate in the HydG reaction: a [4Fe-4S][(Cys)Fe(CO)(CN)] species, 'Complex A', in which a CO, a CN- and a cysteine (Cys) molecule bind to the unique 'dangler' Fe site of the auxiliary [5Fe-4S] cluster of HydG. The identification of this intermediate—the first organometallic precursor to the H-cluster—validates the previously hypothesized HydG reaction cycle and provides a basis for elucidating the biosynthetic origin of other moieties of the H-cluster.

  6. Study on adsorption of 99Tc on Fe, Fe2O3 and Fe3O4

    International Nuclear Information System (INIS)

    Liu Dejun; Fan Xianhua; Zhang Yingjie; Yao Jun; Zhou Duo; Wang Yong

    2004-01-01

    The absorption behavior of 99 Tc on Fe, Fe 2 O 3 and Fe 3 O 4 powders from aqueous 99 TcO 4 - solutions is studied by batch method in atmospheric conditions. After the adsorption reaches equilibrium, the valence state of 99 Tc in the aqueous solution is examined by extraction with tetraphenylarsonium chloride. The experimental results show that the adsorption ratio of 99 Tc on iron powders decreases with the increase of pH (in the range of 5-8) and of CO 3 2- concentration (in the range of 1 x 10 -8 -1 x 10 -2 mol/L). In opposite, the two factors have no significant influence on the absorption of 99 Tc on both Fe 2 O 3 and Fe 3 O 4 powders. The adsorption isotherms of 99 TcO 4 - on Fe, Fe 2 O 3 and Fe 3 O 4 powders can be well described by the Freundlich's equation. The major valence state of 99 Tc is deduced to be Tc(IV) when iron powders is used as the absorbent. In the case of Fe 2 O 3 or Fe 3 O 4 as an absorbent, the 99 Tc remains as the TcO 4 - form

  7. Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

    Science.gov (United States)

    Neumann, Anke; Wu, Lingling; Li, Weiqiang; Beard, Brian L; Johnson, Clark M; Rosso, Kevin M; Frierdich, Andrew J; Scherer, Michelle M

    2015-03-03

    Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

  8. Novel Pelagic Iron-Oxidizing Zetaproteobacteria from the Chesapeake Bay Oxic–Anoxic Transition Zone

    Science.gov (United States)

    Chiu, Beverly K.; Kato, Shingo; McAllister, Sean M.; Field, Erin K.; Chan, Clara S.

    2017-01-01

    Chemolithotrophic iron-oxidizing bacteria (FeOB) could theoretically inhabit any environment where Fe(II) and O2 (or nitrate) coexist. Until recently, marine Fe-oxidizing Zetaproteobacteria had primarily been observed in benthic and subsurface settings, but not redox-stratified water columns. This may be due to the challenges that a pelagic lifestyle would pose for Zetaproteobacteria, given low Fe(II) concentrations in modern marine waters and the possibility that Fe oxyhydroxide biominerals could cause cells to sink. However, we recently cultivated Zetaproteobacteria from the Chesapeake Bay oxic–anoxic transition zone, suggesting that they can survive and contribute to biogeochemical cycling in a stratified estuary. Here we describe the isolation, characterization, and genomes of two new species, Mariprofundus aestuarium CP-5 and Mariprofundus ferrinatatus CP-8, which are the first Zetaproteobacteria isolates from a pelagic environment. We looked for adaptations enabling strains CP-5 and CP-8 to overcome the challenges of living in a low Fe redoxcline with frequent O2 fluctuations due to tidal mixing. We found that the CP strains produce distinctive dreadlock-like Fe oxyhydroxide structures that are easily shed, which would help cells maintain suspension in the water column. These oxides are by-products of Fe(II) oxidation, likely catalyzed by the putative Fe(II) oxidase encoded by the cyc2 gene, present in both CP-5 and CP-8 genomes; the consistent presence of cyc2 in all microaerophilic FeOB and other FeOB genomes supports its putative role in Fe(II) oxidation. The CP strains also have two gene clusters associated with biofilm formation (Wsp system and the Widespread Colonization Island) that are absent or rare in other Zetaproteobacteria. We propose that biofilm formation enables the CP strains to attach to FeS particles and form flocs, an advantageous strategy for scavenging Fe(II) and developing low [O2] microenvironments within more oxygenated waters

  9. Process and genes for expression and overexpression of active [FeFe] hydrogenases

    Science.gov (United States)

    Seibert, Michael; King, Paul W; Ghirardi, Maria Lucia; Posewitz, Matthew C; Smolinski, Sharon L

    2014-09-16

    A process for expression of active [FeFe]-hydrogenase in a host organism that does not contain either the structural gene(s) for [FeFe]-hydrogenases and/or homologues for the maturation genes HydE, HydF and HyG, comprising: cloning the structural hydrogenase gene(s) and/or the maturation genes HydE, HydF and HydG from an organisms that contains these genes into expression plasmids; transferring the plasmids into an organism that lacks a native [FeFe]-hydrogenase or that has a disrupted [FeFe]-hydrogenase and culturing it aerobically; and inducing anaerobiosis to provide [FeFe] hydrogenase biosynthesis and H?2#191 production.

  10. Photoelectron spectroscopy study of Fe-diluted Au-Fe alloys

    CERN Document Server

    Nahm, T U; Choi, B; Park, J S; Oh, S J; Cho, E J

    2003-01-01

    The electronic structure of Fe-diluted Au-Fe alloys has been studied by taking core-level and valence-band spectra using x-ray photoemission spectroscopy and synchrotron radiation. From the core-level spectroscopy, we found that the Fe 2p spectrum is composed of d sup 6 and d sup 7 multiplets from Fe impurity atoms. This behaviour is qualitatively discussed within the context of electron-electron interaction. In order to explore the electron-correlation effects in the valence band, we obtained Fe 3d partial spectral weights by taking advantage of the Cooper-minimum phenomenon of an Au 5d photoionization cross section. It was found that the spin-down states have an appreciable amount of spectral weights throughout the host Au 5d band, contrary to previous one-electron calculations predicting two-peak structure of the Fe 3d states. We suggest that this discrepancy results from the correlation effect of the Fe 3d electrons.

  11. Colorimeter determination of Fe(II)/Fe(III) ratio in glass

    International Nuclear Information System (INIS)

    Baumann, E.W.; Coleman, C.J.; Karraker, D.G.; Scott, W.H.

    1987-01-01

    A colorimetric method has been developed to determine the Fe(II)/Fe(III) ratio in glass containing nuclear waste. Fe(II) is stabilized with pentavalent vanadium during dissolution in sulfuric and hydrofluoric acids. The chromogen is FerroZine (Hach Chemical Company), which forms a magenta complex with Fe(II). The two-step color development consists of determining the Fe(II) by adding FerroZine, followed by determining total Fe after the Fe(III) present is reduced with ascorbic acid. The method was validated by analyzing mixtures of ferrous/ferric solutions and nonferrous glass frit, and by comparison with Moessbauer spectroscopy. The effect of gamma radiation was established. The procedure is generally applicable to nonradioactive materials such as minerals and other glasses

  12. Detailed characterization and preliminary adsorption model for materials for an intermediate-scale reactive-transport experiment

    International Nuclear Information System (INIS)

    Ward, D.B.; Bryan, C.R.

    1994-01-01

    An experiment involving migration of fluid and tracers (Li, Br, Ni) through a 6-m-high x 3-m-dia caisson Wedron 510 sand, is being carried out for Yucca Mountain Site Characterization Project. Sand's surface chemistry of the sand was studied and a preliminary surface-complexation model of Ni adsorption formulated for transport calculations. XPS and leaching suggest that surface of the quartz sand is partially covered by thin layers of Fe-oxyhydroxide and Ca-Mg carbonate and by flakes of kaolinite. Ni adsorption by the sand is strongly pH-dependent, showing no adsorption at pH 5 and near-total adsorption at pH 7. Location of adsorption edge is independent of ionic strength and dissolved Ni concentration; it is shifted to slightly lower pH with higher pCO2 and to slightly higher pH by competition with Li. Diminished adsorption at alkiline pH with higher pCO2 implies formation of dissolved Ni-carbonato complexes. Ni adsorption edges for goethite and quartz, two components of the sand were also measured. Ni adsorption on pure quartz is only moderately pH-dependent and differs in shape and location from that of the sand, whereas Ni adsorption by goethite is strongly pH-dependent. A triple-layer surface-complexation model developed for goethite provides a good fit to the Ni-adsorption curve of the sand. Based on this model, the apparent surface area of the Fe-oxyhydroxide coating is estimated to be 560 m 2 /g, compatible with its occurrence as amorphous Fe-oxyhydroxide. Potentiometric titrations on sand also differ from pure quartz and suggest that effective surface area of sand may be much greater than that measured by N 2 -BET gas adsorption. Attempts to model the adsorption of bulk sand in terms of properties of pure end member components suggest that much of the sand surface is inert. Although the exact Ni adsorption mechanisms remain ambiguous, this preliminary adsorption model provides an initial set of parameters that can be used in transport calculations

  13. Mineralogy, geochemistry and petrophysics of red coloured granite adjacent to fractures

    International Nuclear Information System (INIS)

    Eliasson, T.

    1993-03-01

    Mineralogical, geochemical and petrophysical investigations were conducted of red-coloured alteration rims and of the neighbouring unaltered equivalents along fractures within granite from Aespoe. An investigation was made also of a weak to rather strong, red-coloured granite from the Stripa mine, as well as a weak brownish-red colouration, definitely no hydrothermal in origin, of weathered rinds at a glacial polished rock surface in the Bohus granite. When approaching the fracture planes in the Aespoe granite, the most diagnostic alteration features are * the saussuritisation and Fe-oxyhydroxide staining of plagioclase, * the crystallisation chlorite pseudomorphs after biotite and * the hematisation of magnetite. The porosity within the alteration zones increases generally 2 to 3 times compared with the protolith rock, whereas the densities decrease by some 5 to 10%. The oxidation of magnetite gives as much as a tenfold lowering of the magnetic susceptibility. The red colouration of the Stripa granite is caused by hematite ± Fe-oxyhydroxide formation along microfractures, grain boundaries and, subordinately, the main minerals. Oxidation and re-precipitation of iron liberated during a retrograde muscovitisation of principally chlorite is interpreted to be the cause of the formation of the ferric oxides. The rather homogeneous density and porosity values of the grey and of the red-coloured granites reflect the minor change in the mineralogy when going from fresh into altered granite. Weathering and whitening of plagioclase in the bleached, outer zone and precipitation of small quantities of Fe-oxyhydroxides/hydroxides in the brownish-red zone cause the macroscopic colouration of the weathering rind below the glacial polished rock surface of Bohus granite. There is a marked increase in porosity from the interior fresh (c. 0.4-0.5%) towards the exterior bleached zone (c.1.5-2%) of the subaerialy, weathered Bohus granite surface. The incipient decomposition of

  14. Nature of impurities in fertilizers containing EDDHMA/Fe(3+), EDDHSA/Fe(3+), and EDDCHA/Fe(3+) chelates.

    Science.gov (United States)

    Alvarez-Fernández, Ana; Cremonini, Mauro A; Sierra, Miguel A; Placucci, Giuseppe; Lucena, Juan J

    2002-01-16

    Iron chelates derived from ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA), ethylenediaminedi(o-hydroxy-p-methylphenylacetic) acid (EDDHMA), ethylenediaminedi(2-hydroxy-5-sulfophenylacetic) acid (EDDHSA), and ethylenediaminedi(5-carboxy-2-hydroxyphenylacetic) acid (EDDCHA) are remarkably efficient in correcting iron chlorosis in plants growing in alkaline soils. This work reports the determination of impurities in commercial samples of fertilizers containing EDDHMA/Fe(3+), EDDHSA/Fe(3+), and EDDCHA/Fe(3+). The active components (EDDHMA/Fe(3+), EDDHSA/Fe(3+), and EDDCHA/Fe(3+)) were separated easily from other compounds present in the fertilizers by HPLC. Comparison of the retention times and the UV-visible spectra of the peaks obtained from commercial EDDHSA/Fe(3+) and EDDCHA/Fe(3+) samples with those of standard solutions showed that unreacted starting materials (p-hydroxybenzenesulfonic acid and p-hydroxybenzoic acid, respectively) were always present in the commercial products. 1D and 2D NMR experiments showed that commercial fertilizers based on EDDHMA/Fe(3+) contained impurities having structures tentatively assigned to iron chelates of two isomers of EDDHMA. These findings suggest that current production processes of iron chelates used in agriculture need to be improved.

  15. Melting relations in the Fe-rich portion of the system FeFeS at 30 kb pressure

    Science.gov (United States)

    Brett, R.; Bell, P.M.

    1969-01-01

    The melting relations of FeFeS mixtures covering the composition range from Fe to Fe67S33 have been determined at 30 kb pressure. The phase relations are similar to those at low pressure. The eutectic has a composition of Fe72.9S27.1 and a temperature of 990??C. Solubility of S in Fe at elevated temperatures at 30 kb is of the same order of magnitude as at low pressure. Sulfur may have significantly lowered the melting point of iron in the upper mantle during the period of coalescence of metal prior to core formation in the primitive earth. ?? 1969.

  16. Comparison of Ab initio low-energy models for LaFePO, LaFeAsO, BaFe2As2, LiFeAs, FeSe, and FeTe. Electron correlation and covalency

    International Nuclear Information System (INIS)

    Miyake, Takashi; Nakamura, Kazuma; Arita, Ryotaro; Imada, Masatoshi

    2010-01-01

    Effective low-energy Hamiltonians for several different families of iron-based superconductors are compared after deriving them from the downfolding scheme based on first-principles calculations. Systematic dependences of the derived model parameters on the families are elucidated, many of which are understood from the systematic variation of the covalency between Fe-3d and pnictogen-/chalcogen-p orbitals. First, LaFePO, LaFeAsO (1111), BaFe 2 As 2 (122), LiFeAs (111), FeSe, and FeTe (11) have overall similar band structures near the Fermi level, where the total widths of 10-fold Fe-3d bands are mostly around 4.5 eV. However, the derived effective models of the 10-fold Fe-3d bands (d model) for FeSe and FeTe have substantially larger effective onsite Coulomb interactions U - 4.2 and 3.4 eV, respectively, after the screening by electrons on other bands and after averaging over orbitals, as compared to ∼2.5 eV for LaFeAsO. The difference is similar in the effective models containing p orbitals of As, Se or Te (dp or dpp model), where U ranges from ∼4 eV for the 1111 family to ∼7 eV for the 11 family. The exchange interaction J has a similar tendency. The family dependence of models indicates a wide variation ranging from weak correlation regime (LaFePO) to substantially strong correlation regime (FeSe). The origin of the larger effective interaction in the 11 family is ascribed to smaller spread of the Wannier orbitals generating larger bare interaction, and to fewer screening channels by the other bands. This variation is primarily derived from the distance h between the pnictogen/chalcogen position and the Fe layer: The longer h for the 11 family generates more ionic character of the bonding between iron and anion atoms, while the shorter h for the 1111 family leads to more covalent-bonding character, the larger spread of the Wannier orbitals, and more efficient screening by the anion p orbitals. The screened interaction of the d model is strongly orbital

  17. Sources of acid and metals from the weathering of the Dinero waste pile, Lake Fork watershed, Leadville, Colorado

    Science.gov (United States)

    Diehl, S.F.; Hageman, Phil L.; Smith, Kathleen S.; Herron, J.T.; Desborough, G.A.

    2005-01-01

    Two trenches were dug into the south Dinero mine-waste pile near Leadville, Colorado, to study the weathering of rock fragments and the mineralogic sources of metal contaminants in the surrounding wetland and Lake Fork Watershed. Water seeping from the base of the south Dinero waste-rock pile was pH 2.9, whereas leachate from a composite sample of the rock waste was pH 3.3. The waste pile was mostly devoid of vegetation, open to infiltration of precipitation, and saturated at the base because of placement in the wetland. The south mine-waste pile is composed of poorly sorted material, ranging from boulder-size to fine-grained rock fragments. The trenches showed both matrix-supported and clast-supported zones, with faint horizontal color banding, suggesting zonation of Fe oxides. Secondary minerals such as jarosite and gypsum occurred throughout the depth of the trenches. Infiltration of water and transport of dissolved material through the pile is evidenced by optically continuous secondary mineral deposits that fill or line voids. Iron-sulfate material exhibits microlaminations with shrinkage cracking and preferential dissolution of microlayers that evidence drying and wetting events. In addition to fluids, submicron-sized to very fine-grained particles such as jarosite are transported through channel ways in the pile. Rock fragments are coated with a mixture of clay, jarosite, and manganese oxides. Dissolution of minerals is a primary source of metals. Skeletal remnants of grains, outlined by Fe-oxide minerals, are common. Potassium jarosite is the most abundant jarosite phase, but Pb-and Ag-bearing jarosite are common. Grain-sized clusters of jarosite suggest that entire sulfide grains were replaced by very fine-grained jarosite crystals. The waste piles were removed from the wetland and reclaimed upslope in 2003. This was an opportunity to test methods to identify sources of acid and metals and metal transport processes within a waste pile. A series of

  18. Magnetostrictive GMR spin valves with composite FeGa/FeCo free layers

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Luping [Key Laboratory of Magnetic Materials and Devices & Zhejiang Province Key Laboratory of Magnetic Materials and Application Technology, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); Institute of Materials Science, School of Materials Science and Engineering, Shanghai University, Shanghai 200072 (China); Zhan, Qingfeng, E-mail: zhanqf@nimte.ac.cn, E-mail: runweili@nimte.ac.cn; Yang, Huali; Li, Huihui; Zhang, Shuanglan; Liu, Yiwei; Wang, Baomin; Li, Run-Wei, E-mail: zhanqf@nimte.ac.cn, E-mail: runweili@nimte.ac.cn [Key Laboratory of Magnetic Materials and Devices & Zhejiang Province Key Laboratory of Magnetic Materials and Application Technology, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); Tan, Xiaohua [Institute of Materials Science, School of Materials Science and Engineering, Shanghai University, Shanghai 200072 (China)

    2016-03-15

    We have fabricated strain-sensitive spin valves on flexible substrates by utilizing the large magnetostrictive FeGa alloy to promote the strain sensitivity and the composite free layer of FeGa/FeCo to avoid the drastic reduction of giant magnetoresistance (GMR) ratio. This kind of spin valve (SV-FeGa/FeCo) displays a MR ratio about 5.9%, which is comparable to that of the conventional spin valve (SV-FeCo) with a single FeCo free layer. Different from the previously reported works on magnetostrictive spin valves, the SV-FeGa/FeCo displays an asymmetric strain dependent GMR behavior. Upon increasing the lateral strain, the MR ratio for the ascending branch decreases more quickly than that for the descending branch, which is ascribed to the formation of a spiraling spin structure around the FeGa/FeCo interface under the combined influences of both magnetic field and mechanical strain. A strain sensitivity of GF = 7.2 was achieved at a magnetic bias field of -30 Oe in flexible SV-FeGa/FeCo, which is significantly larger than that of SV-FeCo.

  19. Magnetostrictive GMR spin valves with composite FeGa/FeCo free layers

    International Nuclear Information System (INIS)

    Liu, Luping; Zhan, Qingfeng; Yang, Huali; Li, Huihui; Zhang, Shuanglan; Liu, Yiwei; Wang, Baomin; Li, Run-Wei; Tan, Xiaohua

    2016-01-01

    We have fabricated strain-sensitive spin valves on flexible substrates by utilizing the large magnetostrictive FeGa alloy to promote the strain sensitivity and the composite free layer of FeGa/FeCo to avoid the drastic reduction of giant magnetoresistance (GMR) ratio. This kind of spin valve (SV-FeGa/FeCo) displays a MR ratio about 5.9%, which is comparable to that of the conventional spin valve (SV-FeCo) with a single FeCo free layer. Different from the previously reported works on magnetostrictive spin valves, the SV-FeGa/FeCo displays an asymmetric strain dependent GMR behavior. Upon increasing the lateral strain, the MR ratio for the ascending branch decreases more quickly than that for the descending branch, which is ascribed to the formation of a spiraling spin structure around the FeGa/FeCo interface under the combined influences of both magnetic field and mechanical strain. A strain sensitivity of GF = 7.2 was achieved at a magnetic bias field of -30 Oe in flexible SV-FeGa/FeCo, which is significantly larger than that of SV-FeCo.

  20. Magnetostrictive GMR spin valves with composite FeGa/FeCo free layers

    Science.gov (United States)

    Liu, Luping; Zhan, Qingfeng; Yang, Huali; Li, Huihui; Zhang, Shuanglan; Liu, Yiwei; Wang, Baomin; Tan, Xiaohua; Li, Run-Wei

    2016-03-01

    We have fabricated strain-sensitive spin valves on flexible substrates by utilizing the large magnetostrictive FeGa alloy to promote the strain sensitivity and the composite free layer of FeGa/FeCo to avoid the drastic reduction of giant magnetoresistance (GMR) ratio. This kind of spin valve (SV-FeGa/FeCo) displays a MR ratio about 5.9%, which is comparable to that of the conventional spin valve (SV-FeCo) with a single FeCo free layer. Different from the previously reported works on magnetostrictive spin valves, the SV-FeGa/FeCo displays an asymmetric strain dependent GMR behavior. Upon increasing the lateral strain, the MR ratio for the ascending branch decreases more quickly than that for the descending branch, which is ascribed to the formation of a spiraling spin structure around the FeGa/FeCo interface under the combined influences of both magnetic field and mechanical strain. A strain sensitivity of GF = 7.2 was achieved at a magnetic bias field of -30 Oe in flexible SV-FeGa/FeCo, which is significantly larger than that of SV-FeCo.

  1. Subsurface injection of dissolved ferric chloride to form a chemical barrier: Laboratory investigations

    International Nuclear Information System (INIS)

    Morrison, S.J.; Spangler, R.R.; Morris, S.A.

    1996-01-01

    A chemical barrier is a permeable zone of reactive materials emplaced in the subsurface to remove ground-water contaminants while allowing clean ground water to pass through. Because dissolved ferric chloride hydrolyzes to amorphous ferric oxyhydroxide when it contacts calcite (CaCO 3 ), it may be viable to emplace a zone of amorphous ferric oxyhydroxide (an absorbent for U, Mo, and other inorganic contaminants) into calcite-bearing geologic units by injecting ferric chloride through wells. For a chemical barrier to be successful, it must remain permeable and must be immobile. This investigation monitored chemical compositions, hydraulic conductivity, and iron mobility in laboratory columns and in a two-dimensional tank to determine the viability of injecting ferric chloride to form an amorphous ferric oxyhydroxide chemical barrier. The authors introduced a ferric chloride solution (1,345 mg/1[0.024 m] Fe) to calcite-bearing alluvial gravel to form a chemical barrier of amorphous ferric oxyhydroxide, followed by solutions contaminated with U and Mo. The simulated chemical barriers decreased U and Mo concentrations to less than 0.05 mg/l (2.1 x 10 -7 m) and 0.01 (1.0 x 10 -7 m), respectively; however, the breakthrough front is spread out with concentrations increasing to more than regulatory guideline values sooner than predicted. The hydraulic conductivity of calcite-bearing alluvial gravel decreased substantially during ferric chloride introduction because of the formation of carbon dioxide but increased to within factors of 1 to 5 of the original value as synthetic ground water flowed through the system. Amorphous ferric oxyhydroxide that formed in these experiments remained immobile at flow rates exceeding those typical of ground water. These laboratory results, in conjunction with site-specific characterization data, can be used to design chemical barriers emplaced by injection of ferric chloride

  2. Computed oscillator strengths and energy levels for Fe III, Fe IV, Fe V, and Fe VI with calculated wavelengths and wavelengths derived from established data

    International Nuclear Information System (INIS)

    Fawcett, B.C.

    1989-01-01

    Calculated weighted oscillator strengths are tabulated for spectral lines of Fe III, Fe IV, Fe V, and Fe VI. The lines belong to transition arrays 3d 6 -3d 5 4p and 3d 5 4s-3d 5 4p in Fe III, 3d 5 -3d 4 4p and 3d 4 4s-3d 4 4p in Fe IV, 3d 4 -3d 3 4p and 3d 3 4s-3d 3 4p in Fe V, and 3d 3 -3d 2 4p and 3d 2 4s-3d 2 4p in Fe VI. For the calculations, Slater parameters are optimized on the basis of minimizing the discrepancies between observed and computed wavelengths. Configuration interaction was included among the 3d n , 3d n-1 4s, 3d n-2 4s 2 , 3d n-1 4d, and 3d n-1 5s even configurations and among the 3d n-1 4p, 3d n-2 4s4p, and 3d n-1 5p odd configurations, with 3p 5 3d n+1 added for Fe VI. Calculated wavelengths are compared with observational data, and the compositions of energy levels are listed. This completes a series of similar computations for these complex configurations covering Fe I to Fe VI

  3. Clarifying roughness and atomic diffusion contributions to the interface broadening in exchange-biased NiFe/FeMn/NiFe heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Nascimento, V.P., E-mail: valberpn@yahoo.com.br [Departamento de Física, Universidade Federal do Espírito Santo, 29075-910 Vitória (Brazil); Merino, I.L.C.; Passamani, E.C. [Departamento de Física, Universidade Federal do Espírito Santo, 29075-910 Vitória (Brazil); Alayo, W. [Departamento de Física, Universidade de Pelotas, 96010-610 Pelotas (Brazil); Tafur, M. [Instituto de Ciências Exatas, Universidade Federal de Itajubá, 37500-903 Itajubá (Brazil); Pelegrini, F. [Instituto de Física, Universidade Federal de Goiás, 74001-970 Goiânia (Brazil); Magalhães-Paniago, R. [Universidade Federal de Minas Gerais, Belo Horizonte (Brazil); Alvarenga, A.D. [Instituto Nacional de Metrologia, 25250-020 Xerém (Brazil); Saitovitch, E.B. [Coordenação de Física Experimental e Baixas Energias, Centro Brasileiro de Pesquisas Físicas, 22290-180 Rio de Janeiro (Brazil)

    2013-09-02

    NiFe(30 nm)/FeMn(13 nm)/NiFe(10 nm) heterostructures prepared by magnetron sputtering at different argon working pressures (0.27, 0.67 and 1.33 Pa) were systematically investigated by using specular and off-specular diffuse X-ray scattering experiments, combined with ferromagnetic resonance technique, in order to distinguish the contribution from roughness and atomic diffusion to the total structural disorder at NiFe/FeMn interfaces. It was shown that an increase in the working gas pressure from 0.27 to 1.33 Pa causes an enhancement of the atomic diffusion at the NiFe/FeMn interfaces, an effect more pronounced at the top FeMn/NiFe interface. In particular, this atomic diffusion provokes a formation of non-uniform magnetic dead-layers at the NiFe/FeMn interfaces (NiFeMn regions with paramagnetic or weak antiferromagnetic properties); that are responsible for the substantial reduction of the exchange bias field in the NiFe/FeMn system. Thus, this work generically helps to understand the discrepancies found in the literature regarding the influence of the interface broadening on the exchange bias properties (e.g., exchange bias field) of the NiFe/FeMn system. - Highlights: • Roughness and atomic diffusion contributions to the interface broadening • Clarification of the exchange bias field dependence on the interface disorder • Ferromagnetic, paramagnetic and antiferromagnetic phases at the magnetic interface • Magnetic dead layers formed by increasing the argon work pressure • Atomic diffusion in heterostructures prepared at higher argon pressure.

  4. Point defects in B.C.C. Fe-Al, Fe-Co, and Fe-Co-V ordered alloys

    International Nuclear Information System (INIS)

    Riviere, J.P.; Dinhut, J.F.

    1982-01-01

    Radiation damage produced at 20 K by 2.5 MeV electrons is studied in three B 2 type Fe-40 at % Al, Fe-Co, Fe-Co-V ordered alloys. The resistivity damage in Fe-40 at % Al ordered single crystals is found less effective in the directions. The results suggest that replacement collision chains are difficult to propagate along the direction. Frenkel pair creation superimposed with disordering can account for the resistivity damage in the initially ordered Fe-Co alloy. Informations concerning replacement collision sequences in direction are derived. During the recovery of all the alloys, three main stages are observed and an ordering enhancement occurs. (author)

  5. Weathering processes in waste materials from a mining area in a semiarid zone

    International Nuclear Information System (INIS)

    Navarro-Hervás, Cortes; Pérez-Sirvent, Carmen; Martínez-Sánchez, María José; García-Lorenzo, Mari Luz; Molina, José

    2012-01-01

    Chemical and mineralogical characterization of waste materials present in an abandoned Pb, Zn–Ag mining site (SE, Spain) was carried out. In unaltered rocks, the mineralogy is characterized by plagioclase, pyroxene, magnetite, ilmenite, amphibole, biotite and quartz. Trace-element contents of these samples represent unaltered values. In mine-waste materials, pH ranged from acidic to slightly acidic and trace-element content was generally high, especially for Pb and Zn, although there were also substantial As concentrations. X-ray diffraction results suggested that these samples have a complex mineralogy, including alteration products. Surficial materials in the study area were affected by weathering processes, generating supergene assemblages, including Fe and Mn oxides and hydroxides, carbonates, hydrated sulfates and jarosite. Knowledge of the geochemical processes that took place in the past and which are still taking place provide an important tool for assessing associated environmental problems in this area.

  6. Thermodynamics of the Mo-Fe-C and W-Fe-C systems

    International Nuclear Information System (INIS)

    Kleykamp, H.

    1978-01-01

    A study on the reaction behaviour of the components of the Mo 2 C-Fe and WC-Fe systems is presented. Both systems are stable if the mono-phase carbides are in equilibrium with the Fe-C solid solution within fixed carbon concentrations, the limits of which are calculated in this paper. Gibbs energies of formation at 1273 K of the intermetallic phases, of the binary and of the ternary carbides in the Mo-Fe-C and W-Fe-C systems were determined. The Fe corner in the phase diagrams of both systems and the calculated C boundaries in the two-phase field γ-Fe(Mo,C)-Mo 2 C and the γ-Fe(W,C)-WC, respectively, based on this study, are shown in figures. (GSC) [de

  7. Subsurface variations in arsenic mineralogy and geochemistry following long-term weathering of gold mine tailings

    International Nuclear Information System (INIS)

    DeSisto, Stephanie L.; Jamieson, Heather E.; Parsons, Michael B.

    2016-01-01

    Variations in arsenic (As) mineralogy and geochemical controls on its mobility were evaluated in subsurface tailings at the historical Montague and Goldenville mine sites in Nova Scotia, Canada. Tailings at these sites contain some of the highest As concentrations in Nova Scotia and are located in close proximity to local communities. Pore water in the subsurface tailings is characterized by circumneutral to alkaline pH (6.2 to 8.7) and mildly reducing to oxidizing redox conditions (+130 mV to +347 mV). Bulk chemistry, scanning electron microscopy, and synchrotron micro-X-ray diffraction analyses showed As mineral hosts differ with depth. The deepest tailings (max. 2 m) are in direct contact with partially decomposed vegetation, which supports reducing conditions and the precipitation of authigenic As and Fe sulfides. Under reducing conditions, dissolved As concentrations are also controlled by desorption of As from dissolution of Fe and Mn oxides and the sorption or co-precipitation of As with carbonates. These geochemical controls differ from those influencing dissolved As concentrations under oxidizing conditions. In the near surface, As mobility is controlled by oxidative dissolution of primary arsenopyrite, precipitation of secondary Fe arsenates, Fe oxyhydroxides and Mn oxides, secondary Ca-Fe arsenates, and sorption onto Fe oxyhydroxides and gangue minerals. Some of these mineral species are stable under different conditions yet occur in close association, indicating the importance of microenvironments. The results of this study show that the weathering characteristics of these tailings vary with depth, leading to the formation of new As hosts that are distinct from those observed in the near surface. Identification of these As hosts provides an understanding of current controls on As mobility and has implications for future reprocessing and/or remediation efforts. - Highlights: • Subsurface mineralogy does not reflect surface tailings end

  8. Al/Fe isomorphic substitution versus Fe{sub 2}O{sub 3} clusters formation in Fe-doped aluminosilicate nanotubes (imogolite)

    Energy Technology Data Exchange (ETDEWEB)

    Shafia, Ehsan [Politecnico di Torino, Department of Applied Science and Technology and INSTM Unit of Torino-Politecnico (Italy); Esposito, Serena [Università degli Studi di Cassino e del Lazio Meridionale, Department of Civil and Mechanical Engineering (Italy); Manzoli, Maela; Chiesa, Mario [Università di Torino, Dipartimento di Chimica and Centro Interdipartimentale NIS (Italy); Tiberto, Paola [Electromagnetism, I.N.Ri.M. (Italy); Barrera, Gabriele [Università di Torino, Dipartimento di Chimica and Centro Interdipartimentale NIS (Italy); Menard, Gabriel [Harvard University, Department of Chemistry and Chemical Biology (United States); Allia, Paolo, E-mail: paolo.allia@polito.it [Politecnico di Torino, Department of Applied Science and Technology and INSTM Unit of Torino-Politecnico (Italy); Freyria, Francesca S. [Massachusetts Institute of Technology, Department of Chemistry (United States); Garrone, Edoardo; Bonelli, Barbara, E-mail: barbara.bonelli@polito.it [Politecnico di Torino, Department of Applied Science and Technology and INSTM Unit of Torino-Politecnico (Italy)

    2015-08-15

    Textural, magnetic and spectroscopic properties are reported of Fe-doped aluminosilicate nanotubes (NTs) of the imogolite type, IMO, with nominal composition (OH){sub 3}Al{sub 2−x}Fe{sub x}O{sub 3}SiOH (x = 0, 0.025, 0.050). Samples were obtained by either direct synthesis (Fe-0.025-IMO, Fe-0.050-IMO) or post-synthesis loading (Fe-L-IMO). The Fe content was either 1.4 wt% (both Fe-0.050-IMO and Fe-L-IMO) or 0.7 wt% (Fe-0.025-IMO). Textural properties were characterized by High-Resolution Transmission Electron Microscopy, X-ray diffraction and N{sub 2} adsorption/desorption isotherms at 77 K. The presence of different iron species was studied by magnetic moment measurements and three spectroscopies: Mössbauer, UV–Vis and electron paramagnetic resonance, respectively. Fe{sup 3+}/Al{sup 3+} isomorphic substitution (IS) at octahedral sites at the external surface of NTs is the main process occurring by direct synthesis at low Fe loadings, giving rise to the formation of isolated high-spin Fe{sup 3+} sites. Higher loadings give rise, besides IS, to the formation of Fe{sub 2}O{sub 3} clusters. IS occurs up to a limit of Al/Fe atomic ratio of ca. 60 (corresponding to x = 0.032). A fraction of the magnetism related to NCs is pinned by the surface anisotropy; also, clusters are magnetically interacting with each other. Post-synthesis loading leads to a system rather close to that obtained by direct synthesis, involving both IS and cluster formations. Slightly larger clusters than with direct synthesis samples, however, are formed. The occurrence of IS indicates a facile cleavage/sealing of Al–O–Al bonds: this opens the possibility to exchange Al{sup 3+} ions in pre-formed IMO NTs, a much simpler procedure compared with direct synthesis.

  9. Diffusion of Nb in Fe and in some Fe alloys

    International Nuclear Information System (INIS)

    Kurokawa, S.; Ruzzante, J.E.; Hey, A.M.; Dyment, F.

    1981-01-01

    Diffusion data of microalloying elements such as Nb, V, Ti, are required when analysing the transformation and recrystallization behaviour of HSLA steels in order to optimize grain refinement and precipitation hardening. The diffusion behaviour of Nb in pure Fe, Fe 1.5 Mn, Fe 0.6 Si and Fe 1.5 Mn 0.6 Si has been measured between 1080 and 1200 0 C. Results indicate that Si increases Nb diffusivity while Mn decreases it. The sequence of diffusion coeficients values is: D sup(Nb) sub(Fe 1.5 Mn) [pt

  10. First principles calculations of the magnetic and hyperfine properties of Fe/N/Fe and Fe/O/Fe multilayers in the ground state of cohesive energy

    Science.gov (United States)

    dos Santos, A. V.; Samudio Pérez, C. A.; Muenchen, D.; Anibele, T. P.

    2015-01-01

    The ground state properties of Fe/N/Fe and Fe/O/Fe multilayers were investigated using the first principles calculations. The calculations were performed using the Linearized Augmented Plane Wave (LAPW) method implemented in the Wien2k code. A supercell consisting of one layer of nitride (or oxide) between two layers of Fe in the bcc structure was used to model the structure of the multilayer. The research in new materials also stimulated theoretical and experimental studies of iron-based nitrides due to their variety of structural and magnetic properties for the potential applications as in high strength steels and for high corrosion resistance. It is obvious from many reports that magnetic iron nitrides such as γ-Fe4N and α-Fe16N2 have interesting magnetic properties, among these a high magnetisation saturation and a high density crimp. However, although Fe-N films and multilayers have many potential applications, they can be produced in many ways and are being extensively studied from the theoretical point of view there is no detailed knowledge of their electronic structure. Clearly, efforts to understand the influence of the nitrogen atoms on the entire electronic structure are needed as to correctly interpret the observed changes in the magnetic properties when going from Fe-N bulk compounds to multilayer structures. Nevertheless, the N atoms are not solely responsible for electronics alterations in solid compounds. Theoretical results showed that Fe4X bulk compounds, where X is a variable atom with increasing atomic number (Z), the nature of bonding between X and adjacent Fe atoms changes from more covalent to more ionic and the magnetic moments of Fe also increase for Z=7, i.e. N. This is an indicative that atoms with a Z number higher than 7, i.e., O, can produce several new alterations in the entire magnetic properties of Fe multilayers. This paper presents the first results of an ab-initio electronic structure calculations, performed for Fe-N and Fe

  11. Influence of the surface topography, morphology and structure on magnetic properties of ion beam sputtered iron layers, Fe/Cr/Fe- and Fe/MgO/Fe multilayers; Untersuchung der Morphologie und magnetische Eigenschaften von ionenstrahl-gesputterten Eisen-Einzelschichten, Fe/Cr/Fe- und Fe/MgO/Fe-Schichtsystemen

    Energy Technology Data Exchange (ETDEWEB)

    Steeb, Alexandra

    2007-04-05

    In this PhD Thesis, the influence of the surface topography, morphology and structure on magnetic properties of ion beam sputtered iron layers on GaAs is examined. To analyze the structure of the produced iron films, low energy electron diffraction and scanning tunneling microscopy is employed. The utilized methods to investigate the magnetic properties are Kerr- and SQUID-magnetometry and ferromagnetic resonance. It is demonstrated that on untreated as well as on presputtered and heated GaAs substrates the sputtered iron films grow epitaxially. The least surface roughness of 1 A exhibit iron films grown on untreated GaAs, while iron films on heated GaAs have the highest roughness of 30 A. The largest crystal anisotropy constant is found for the presputtered GaAs/Fe-System. For this preparation method, two monolayers of iron are determined to be magnetically dead layers. At a film thickness of 100 A, 83% of the value for saturation magnetization of bulk iron are achieved. The small observed FMR-linewidths confirm the good bulk properties of the ion beam sputtered iron. Furthermore, an antiferromagnetic interlayer exchange coupling in sputtered Fe/Cr/Fe-films was achieved. For a thickness of 12 to 17 A of the chrome interlayer, a coupling strength up to 0.2 mJ/m{sup 2} is found. To account for the small coupling strength, a strong intermixing at the interface is assumed. Finally, epitaxial Fe/MgO/Fe/FeMn multilayers are deposited on GaAs. After the structuring, it is possible to detect tunneling processes in the tunneling contacts with current-voltage measurements. The tunnel magneto resistance values of 2% are small, which can be explained by the absence of sharp, well-defined interfaces between the Fe/FeMn and the Fe/MgO interfaces. These results demonstrate, that analog to MBE the ion beam sputtering method realizes good magnetic bulk properties. However, interface sensitive phenomena are weakened because of a strong intermixing at the interfaces. (orig.)

  12. Hydrogeochemistry of Groundwater and Arsenic Adsorption Characteristics of Subsurface Sediments in an Alluvial Plain, SW Taiwan

    Directory of Open Access Journals (Sweden)

    Libing Liao

    2016-12-01

    Full Text Available Many studies were conducted to investigate arsenic mobilization in different alluvial plains worldwide. However, due to the unique endemic disease associated with arsenic (As contamination in Taiwan, a recent research was re-initiated to understand the transport behavior of arsenic in a localized alluvial plain. A comprehensive approach towards arsenic mobility, binding, and chemical speciation was applied to correlate groundwater hydrogeochemistry with parameters of the sediments that affected the As fate and transport. The groundwater belongs to a Na-Ca-HCO3 type with moderate reducing to oxidizing conditions (redox potential = −192 to 8 mV. Groundwater As concentration in the region ranged from 8.89 to 1131 μg/L with a mean of 343 ± 297 μg/L, while the As content in the core sediments varied from 0.80 to 22.8 mg/kg with a mean of 9.9 ± 6.2 mg/kg. A significant correlation was found between As and Fe, Mn, or organic matter, as well as other elements such as Ni, Cu, Zn, and Co in the core sediments. Sequential extraction analysis indicated that the organic matter and Fe/Mn oxyhydroxides were the major binding pools of As. Batch adsorption experiments showed that the sediments had slightly higher affinity for As(III than for As(V under near neutral pH conditions and the As adsorption capacity increased as the contents of Fe oxyhydroxides as well as the organic matter increased.

  13. Fe65-PTB2 Dimerization Mimics Fe65-APP Interaction

    Directory of Open Access Journals (Sweden)

    Lukas P. Feilen

    2017-05-01

    Full Text Available Physiological function and pathology of the Alzheimer’s disease causing amyloid precursor protein (APP are correlated with its cytosolic adaptor Fe65 encompassing a WW and two phosphotyrosine-binding domains (PTBs. The C-terminal Fe65-PTB2 binds a large portion of the APP intracellular domain (AICD including the GYENPTY internalization sequence fingerprint. AICD binding to Fe65-PTB2 opens an intra-molecular interaction causing a structural change and altering Fe65 activity. Here we show that in the absence of the AICD, Fe65-PTB2 forms a homodimer in solution and determine its crystal structure at 2.6 Å resolution. Dimerization involves the unwinding of a C-terminal α-helix that mimics binding of the AICD internalization sequence, thus shielding the hydrophobic binding pocket. Specific dimer formation is validated by nuclear magnetic resonance (NMR techniques and cell-based analyses reveal that Fe65-PTB2 together with the WW domain are necessary and sufficient for dimerization. Together, our data demonstrate that Fe65 dimerizes via its APP interaction site, suggesting that besides intra- also intermolecular interactions between Fe65 molecules contribute to homeostatic regulation of APP mediated signaling.

  14. Fe65-PTB2 Dimerization Mimics Fe65-APP Interaction.

    Science.gov (United States)

    Feilen, Lukas P; Haubrich, Kevin; Strecker, Paul; Probst, Sabine; Eggert, Simone; Stier, Gunter; Sinning, Irmgard; Konietzko, Uwe; Kins, Stefan; Simon, Bernd; Wild, Klemens

    2017-01-01

    Physiological function and pathology of the Alzheimer's disease causing amyloid precursor protein (APP) are correlated with its cytosolic adaptor Fe65 encompassing a WW and two phosphotyrosine-binding domains (PTBs). The C-terminal Fe65-PTB2 binds a large portion of the APP intracellular domain (AICD) including the GYENPTY internalization sequence fingerprint. AICD binding to Fe65-PTB2 opens an intra-molecular interaction causing a structural change and altering Fe65 activity. Here we show that in the absence of the AICD, Fe65-PTB2 forms a homodimer in solution and determine its crystal structure at 2.6 Å resolution. Dimerization involves the unwinding of a C-terminal α-helix that mimics binding of the AICD internalization sequence, thus shielding the hydrophobic binding pocket. Specific dimer formation is validated by nuclear magnetic resonance (NMR) techniques and cell-based analyses reveal that Fe65-PTB2 together with the WW domain are necessary and sufficient for dimerization. Together, our data demonstrate that Fe65 dimerizes via its APP interaction site, suggesting that besides intra- also intermolecular interactions between Fe65 molecules contribute to homeostatic regulation of APP mediated signaling.

  15. Formation mechanisms of neutral Fe layers in the thermosphere at Antarctica studied with a thermosphere-ionosphere Fe/Fe+ (TIFe) model

    Science.gov (United States)

    Chu, Xinzhao; Yu, Zhibin

    2017-06-01

    With a thermosphere-ionosphere Fe/Fe+ (TIFe) model developed from first principles at the University of Colorado, we present the first quantitative investigation of formation mechanisms of thermospheric Fe layers observed by lidar in Antarctica. These recently discovered neutral metal layers in the thermosphere between 100 and 200 km provide unique tracers for studies of fundamental processes in the space-atmosphere interaction region. The TIFe model formulates and expands the TIFe theory originally proposed by Chu et al. that the thermospheric Fe layers are produced through the neutralization of converged Fe+ layers. Through testing mechanisms and reproducing the 28 May 2011 event at McMurdo, we conceive the lifecycle of meteoric metals via deposition, transport, chemistry, and wave dynamics for thermospheric Fe layers with gravity wave signatures. While the meteor injection of iron species is negligible above 120 km, the polar electric field transports metallic ions Fe+ upward from their main deposition region into the E-F regions, providing the major source of Fe+ (and accordingly Fe) in the thermosphere. Atmospheric wave-induced vertical shears of vertical and horizontal winds converge Fe+ to form dense Fe+ layers. Direct electron-Fe+ recombination is the major channel to neutralize Fe+ layers to form Fe above 120 km. Fe layer shapes are determined by multiple factors of neutral winds, electric field, and aurora activity. Gravity-wave-induced vertical wind plays a key role in forming gravity-wave-shaped Fe layers. Aurora particle precipitation enhances Fe+ neutralization by increasing electron density while accelerating Fe loss via charge transfer with enhanced NO+ and O2+ densities.Plain Language SummaryThe discoveries of neutral metal layers reaching near 200 km in the thermosphere have significant scientific merit because such discoveries challenge the current understandings of upper atmospheric composition, chemistry, dynamics, electrodynamics, and

  16. Effects of Fe fine powders doping on hot deformed NdFeB magnets

    International Nuclear Information System (INIS)

    Lin, Min; Wang, Huijie; Zheng, Jingwu; Yan, Aru

    2015-01-01

    The composite NdFeB magnets with blending melt-spun flakes and Fe fine powders were prepared by the hot-pressed and hot-deformed route. Characterizations of the hot-deformed NdFeB magnets affected by the doped Fe powders were tested. The doped Fe powders decrease the hot-deformed pressure when the strain is between 15 and 50%. XRD patterns show that the doped Fe powders have little influence on the c-axis alignment of hot-deformed NdFeB magnets in the press direction. The B r and the (BH) max get improved when the doped Fe powders are less than 3 wt%. The doped Fe of hot-deformed NdFeB magnets exists in the elongated state and the spherical state surrounded by the Nd-rich phase. With the Fe fraction increasing, the potential of magnet moves to the positive direction and the diameter of the Nyquist arc becomes larger, which indicate that the corrosion resistance improved effectively. The bending strength was enhanced by the elongated α-Fe phase embedded in the matrix 2:14:1 phase. - Highlights: • The doped Fe powders have little influence on the c-axis alignment of magnets. • The elongated Fe powders are more than the spherical Fe powders in the magnets. • The corrosion resistance is improved effectively with the increasing Fe fraction. • The bending strength is enhanced by the elongated α-Fe phase embedded in the matrix

  17. Effects of Fe fine powders doping on hot deformed NdFeB magnets

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Min, E-mail: linm@nimte.ac.cn [Ningbo Institute of Material Technology & Engineering Chinese Academy of Science, Ningbo 315201 (China); Wang, Huijie [Ningbo Jinji Strong Magnetic Material Company, Ningbo 315041 (China); Zheng, Jingwu [Zhejiang University of Technology, Hangzhou 310014 (China); Yan, Aru [Ningbo Institute of Material Technology & Engineering Chinese Academy of Science, Ningbo 315201 (China)

    2015-04-01

    The composite NdFeB magnets with blending melt-spun flakes and Fe fine powders were prepared by the hot-pressed and hot-deformed route. Characterizations of the hot-deformed NdFeB magnets affected by the doped Fe powders were tested. The doped Fe powders decrease the hot-deformed pressure when the strain is between 15 and 50%. XRD patterns show that the doped Fe powders have little influence on the c-axis alignment of hot-deformed NdFeB magnets in the press direction. The B{sub r} and the (BH){sub max} get improved when the doped Fe powders are less than 3 wt%. The doped Fe of hot-deformed NdFeB magnets exists in the elongated state and the spherical state surrounded by the Nd-rich phase. With the Fe fraction increasing, the potential of magnet moves to the positive direction and the diameter of the Nyquist arc becomes larger, which indicate that the corrosion resistance improved effectively. The bending strength was enhanced by the elongated α-Fe phase embedded in the matrix 2:14:1 phase. - Highlights: • The doped Fe powders have little influence on the c-axis alignment of magnets. • The elongated Fe powders are more than the spherical Fe powders in the magnets. • The corrosion resistance is improved effectively with the increasing Fe fraction. • The bending strength is enhanced by the elongated α-Fe phase embedded in the matrix.

  18. Pr2Fe14B/α-Fe nanocomposites for thermal applications

    International Nuclear Information System (INIS)

    Silva, Suelanny Carvalho da

    2012-01-01

    In this work, Pr x Fe 94 - x B 6 (x = 6, 8, 10 and 12) nanostructured powders were prepared by a combination of hydrogenation, disproportionation, desorption and recombination (HDDR) process with high energy milling applied to the mixture of an as-cast alloy (Pr 14 Fe 80 B 6 ) and α-Fe. The produced nanoparticles showed magnetic properties comparable to those reported in hyperthermia studies. The optimal time to obtain the magnetic nanoparticles is 5 hours (at 900 rpm). It was verified that longer milling times cause an increase in carbon percentage on the particles. The carbon is derived from oleic acid added as a surfactant in the milling step. The nanocomposites exhibit coercive force ranging from 80 Oe (6.5 kAm -1 ) to 170 Oe (13.5 kAm -1 ) and magnetic moments in the range of 81 129 Am2kg -1 . From the X-ray diffraction analyses, only two phases were found in all samples: α-Fe and the magnetic phase Pr 2 Fe 14 B. Individual nanoparticles with diameter of about 20 nm were verified. The samples studied presented heating when exposed to an alternating magnetic field (f = 222 kHz e H max ∼3.7 kAm -1 ) comparable to reported in literature. Temperature variations (ΔT) of the powders were: 51 K for Pr 6 Fe 88 B 6 , 41 K for Pr 8 Fe 86 B 6 , 38 K for Pr 10 Fe 8 4 B 6 and T = 34 K for Pr 12 Fe 82 B 6 . The specific absorption rates (SARs) of the powders were 201 Wkg -1 for Pr 6 Fe 88 B 6 composition, 158 Wkg -1 on the composition Pr 8 Fe 86 B 6 , and 114 Wkg -1 for Pr 10 Fe 84 B 6 and Pr 12 Fe 82 B 6 compositions. (author)

  19. Microstructure and properties of multiphase sintered cermets Fe-Fe2B

    International Nuclear Information System (INIS)

    Nowacki, J.; Klimek, L.

    1998-01-01

    The process of multiphase sintering of iron in the vacuum has been analysed. As a result of the process iron-iron boride cermets have been produced. Fe-Fe 2 B cermets were obtained as a result of sintering of the Fe and B pure elements in the vacuum. Attemps at sintering in the solid phase and with the participation of the liquid phase, the Fe-Fe 2 B eutectic, have been made. Metallographic qualitative and quantitative studies, X-ray structural qualitative and qauantitative analysis allowed to determine the structure of Fe 2 B cermets, as well as a description of the kinetics of quantitative changes in phase proportions in the course of sintering. It has been found that their structure varies widely depending on sintering parameters and the composition of the sinters. Measurements of the Fe-Fe 2 B cermets hardness and measurements on wear during dry friction by the pin-on-disc method have shown distinct advantages of the cermets as a modern constructional materials. The hardness of Fe-Fe 2 B cermets, depending on their chemical composition and sintering parameters, ranges widely from 150 to 1500 HV, and their resistance to wear is comparable to that of diffusively boronized steels. FeFe 2 B cermets are a composite material in which iron boride, Fe 2 B, with a hardness of about 1800 HV plays the role of the reinforcement,while iron-iron boride, Fe-Fe 2 B, with a hardness of about 500 HV plays the role of matrix. The eutectic in the spaces between iron boride grains is composed of boron solid solution plates in iron with a hardness of arround 250 HV, and iron boride, Fe 2 B, plates with a hardness of approximaly 1800 HV. The combination of such different materials, a hard reinforcement and a relatively plastic matrix produces favourable properties of the cermet thus produced high hardness (1500 HV) constant over whole cross section of the material, resistance of abrasive wear and acceptable ductility. The properties mentioned above, resulting from the cermet

  20. Tuning high frequency magnetic properties and damping of FeGa, FeGaN and FeGaB thin films

    Directory of Open Access Journals (Sweden)

    Derang Cao

    2017-11-01

    Full Text Available A series of FeGa, FeGaN and FeGaB films with varied oblique angles were deposited by sputtering method on silicon substrates, respectively. The microstructure, soft magnetism, microwave properties, and damping factor for the films were investigated. The FeGa films showed a poor high frequency magnetic property due to the large stress itself. The grain size of FeGa films was reduced by the additional N element, while the structure of FeGa films was changed from the polycrystalline to amorphous phase by the involved B element. As a result, N content can effectively improve the magnetic softness of FeGa film, but their high frequency magnetic properties were still poor both when the N2/Ar flow rate ratio is 2% and 5% during the deposition. The additional B content significantly led to the excellent magnetic softness and the self-biased ferromagnetic resonance frequency of 1.83 GHz for FeGaB film. The dampings of FeGa films were adjusted by the additional N and B contents from 0.218 to 0.139 and 0.023, respectively. The combination of these properties for FeGa films are helpful for the development of magnetostrictive microwave devices.

  1. Interparticle interactions of FePt core and Fe{sub 3}O{sub 4} shell in FePt/Fe{sub 3}O{sub 4} magnetic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Akbari, Hossein, E-mail: Akbari.ph@iauardabil.ac.ir [Department of Physics, Ardabil Branch, Islamic Azad University, Ardabil (Iran, Islamic Republic of); Zeynali, Hossein [Department of Physics, Kashan Branch, Islamic Azad University, Kashan (Iran, Islamic Republic of); Bakhshayeshi, Ali [Department of Physics, Mashhad Branch, Islamic Azad University, Mashhad (Iran, Islamic Republic of)

    2016-02-22

    Monodisperse FePt nanoparticles were successfully synthesized using simple wet chemical method. Fe{sub 3}O{sub 4} was used as a magnetic shell around each FePt nanoparticles. In FePt/Fe{sub 3}O{sub 4} core/shell system, core thickness is 2 nm and shell thickness varies from zero to 2.5 nm. A theoretical model presented to calculate the shell thickness dependence of Coercivity. Presented model is compared with the results from Stoner–Wohlfarth model to interpret the shell thickness dependence of Coercivity in FePt/Fe{sub 3}O{sub 4} core/shell nanoparticles. There is a difference between the results from Stoner–Wohlfarth model and experimental data when the shell thickness increases. In the presented model, the effects of interparticle exchange and random magneto crystalline anisotropy are added to the previous models of magnetization reversal for core/shell nanostructures in order to achieve a better agreement with experimental data. For magnetic shells in FePt/Fe{sub 3}O{sub 4} core/shell, effective coupling between particles increases with increasing shell thickness which leads to Coercivity destruction for stronger couplings. According to the boundary conditions, in the harder regions with higher exchange stiffness, there is small variation in magnetization and so the magnetization modes become more localized. We discussed both localized and non-localized magnetization modes. For non-zero shell thickness, non-localized modes propagate in the soft phase which effects the quality of particle exchange interactions. - Highlights: • Monodisperse FePt nanoparticles were successfully synthesized using simple wet chemical method. • Fe{sub 3}O{sub 4} was used as a magnetic shell around each FePt nanoparticles. • A theoretical model presented to calculate the shell thickness dependence of Coercivity. • Magnetic shells increase effective coupling between particles with increasing shell thickness. • Magnetization modes are more localized in the regions with

  2. Corrosion-resistant amorphous alloy ribbons for electromagnetic filtration of iron rusts from water

    International Nuclear Information System (INIS)

    Kawashima, Asahi; Asami, Katsuhiko; Sato, Takeaki; Hashimoto, Koji

    1985-01-01

    An attempt was made to use corrosion-resistant amorphous Fe-9Cr-13P-7C alloy ribbons as an electromagnetic filter material for trapping various iron rusts suspended in water at 40 0 C. The ferrimagnetic Fe 3 O 4 rust was trapped with the 100 % efficiency and paramagnetic rusts such as α-Fe 2 O 3 , α-FeOOH and amorphous ferric oxyhydroxide were trapped with certain efficiencies at the magnetic field strength of 0.5-10 kOe. The regeneration of the filter by back-washing was easy. The trapping capacity of electromagnetic filter was proportional to the edge length of the filter material where the high magnetic field strength existed. Therefore, melt-spun thin and narrow amorphous alloy ribbons having the high corrosion resistance have the potential utility as electromagnetic filter material. (author)

  3. Strengthening mechanisms of Fe nanoparticles for single crystal Cu–Fe alloy

    International Nuclear Information System (INIS)

    Shi, Guodong; Chen, Xiaohua; Jiang, Han; Wang, Zidong; Tang, Hao; Fan, Yongquan

    2015-01-01

    A single crystal Cu–Fe alloy with finely dispersed precipitate Fe nanoparticles was fabricated in this study. The interface relationship of iron nanoparticle and copper matrix was analyzed with a high-resolution transmission electron microscope (HRTEM), and the effect of Fe nanoparticles on mechanical properties of single crystal Cu–Fe alloy was discussed. Results show that, the finely dispersed Fe nanoparticles can be obtained under the directional solidification condition, with the size of 5–50 nm and the coherent interface between the iron nanoparticle and the copper matrix. Single crystal Cu–Fe alloy possesses improved tensile strength of 194.64 MPa, and total elongation of 44.72%, respectively, at room temperature, in contrast to pure Cu sample. Nanoparticles which have coherent interface with matrix can improve the dislocation motion state. Some dislocations can slip through the nanoparticle along the coherent interface and some dislocations can enter into the nanoparticles. Thus to improve the tensile strength of single crystal Cu–Fe alloy without sacrificing the ductility simultaneously. Based on the above analyses, strengthening mechanisms of Fe nanoparticles for single crystal Cu–Fe alloy was described

  4. Experimental phases diagram Zr-Fe and Zr-Sn-Fe of the Fe rich zone at a temperature of 1100oC

    International Nuclear Information System (INIS)

    Nieva, N.; Jimenez, J.; Gomez, A; Granovsky, M.S

    2010-01-01

    Zr-based alloys are frequently used in the nuclear energy industry; among these are the Zr-based Zircaloys whose main alloys are Sn and Fe. In order to experimentally evaluate part of the diagram of the binary Zr-Fe phases and the ternary Zr-Sn-Fe in the Fe-rich zone, different binary alloys in the area closest to the composition of the ZrFe 2 and Zr 6 Fe 23 compounds were designed as well as a ternary alloy of Zr-Sn-Fe in the Fe-rich region of the ternary system. All the alloys underwent a two month heat treatment at a temperature of 1100 o C. Later the phases that were present were identified using different complementary techniques (mainly X-ray diffraction and microanalysis). The clear presence of the Zr 6 Fe 23 phase was not observed in any of the alloys. A new ternary phase consisting approximately of Zr 2 0Sn 14 Fe 66 was verified in the ternary alloy

  5. The aquatic geochemistry of arsenic in volcanic groundwaters from southern Italy

    International Nuclear Information System (INIS)

    Aiuppa, Alessandro; D'Alessandro, Walter; Federico, Cinzia; Palumbo, Barbara; Valenza, Mariano

    2003-01-01

    This paper discusses the abundance, speciation and mobility of As in groundwater systems from active volcanic areas in Italy. Using literature data and new additional determinations, the main geochemical processes controlling the fate of As during gas-water-rock interaction in these systems are examined. Arsenic concentrations in the fluids range from 0.1 to 6940 μg/l, with wide differences observed among the different volcanoes and within each area. The dependence of As content on water temperature, pH, redox potential and major ions is investigated. Results demonstrate that As concentrations are highest where active hydrothermal circulation takes place at shallow levels, i.e. at Vulcano Island and the Phlegrean Fields. In both areas the dissolution of As-bearing sulphides is likely to be the main source of As. Mature Cl-rich groundwaters, representative of the discharge from the deep thermal reservoirs, are typically enriched in As with respect to SO 4 -rich ''steam heated groundwaters''. In the HCO 3 - groundwaters recovered at Vesuvius and Etna, aqueous As cycling is limited by the absence of high-temperature interactions and by high-Fe content of the host rocks, resulting in oxidative As adsorption. Thermodynamic modelling suggests that reducing H 2 S-rich groundwaters are in equilibrium with realgar, whereas in oxidising environments over-saturation with respect to Fe oxy-hydroxides is indicated. Under these oxidising conditions, As solubility decreases controlled by As co-precipitation with, or adsorption on, Fe oxy-hydroxides. Consistent with thermodynamic considerations, As mobility in the studied areas is enhanced in intermediate redox environments, where both sulphides and Fe hydroxides are unstable

  6. Modification of interlayer exchange coupling in Fe/V/Fe trilayers using hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Skoryna, J., E-mail: jskoryna@ifmpan.poznan.pl [Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17 St., 60-179 Poznań (Poland); Marczyńska, A. [Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17 St., 60-179 Poznań (Poland); Lewandowski, M. [NanoBioMedical Centre, Adam Mickiewicz University, Umultowska 85 St., 61-614 Poznań (Poland); Smardz, L. [Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17 St., 60-179 Poznań (Poland)

    2015-10-05

    Highlights: • Magnetic films and multilayers. • Thin films. • Hydrogen absorbing materials. • Magnetic measurements. • Exchange coupling. - Abstract: Fe/V/Fe trilayers with constant-thickness Fe and step-like wedged V sublayers were prepared at room temperature using UHV magnetron sputtering. The bottom Fe layer grows onto oxidised Si(1 0 0) substrate and shows relatively high coercivity. The top Fe layer grows on vanadium spacer and shows considerably lower coercivity. The planar growth of the Fe and V sublayers was confirmed in-situ by X-ray photoelectron spectroscopy. Results show that the Fe sublayers are weakly exchange coupled for d{sub V} > 1.4 nm. Results on the coercivity studies as a function of the V interlayer thickness show near d{sub V} ∼ 1.95 nm (∼2.45 nm) weak antiferromagnetic (ferromagnetic) coupling, respectively. The hydrogenation of the Fe/V/Fe trilayers leads to increase of the strength of the ferromagnetic interlayer exchange coupling.

  7. Oxyhydroxide of metallic nanowires in a molecular H2O and H2O2 environment and their effects on mechanical properties.

    Science.gov (United States)

    Aral, Gurcan; Islam, Md Mahbubul; Wang, Yun-Jiang; Ogata, Shigenobu; Duin, Adri C T van

    2018-06-14

    To avoid unexpected environmental mechanical failure, there is a strong need to fully understand the details of the oxidation process and intrinsic mechanical properties of reactive metallic iron (Fe) nanowires (NWs) under various aqueous reactive environmental conditions. Herein, we employed ReaxFF reactive molecular dynamics (MD) simulations to elucidate the oxidation of Fe NWs exposed to molecular water (H2O) and hydrogen peroxide (H2O2) environment, and the influence of the oxide shell layer on the tensile mechanical deformation properties of Fe NWs. Our structural analysis shows that oxidation of Fe NWs occurs with the formation of different iron oxide and hydroxide phases in the aqueous molecular H2O and H2O2 oxidizing environments. We observe that the resulting microstructure due to pre-oxide shell layer formation reduces the mechanical stress via increasing the initial defect sites in the vicinity of the oxide region to facilitate the onset of plastic deformation during tensile loading. Specifically, the oxide layer of Fe NWs formed in the H2O2 environment has a relatively significant effect on the deterioration of the mechanical properties of Fe NWs. The weakening of the yield stress and Young modulus of H2O2 oxidized Fe NWs indicates the important role of local oxide microstructures on mechanical deformation properties of individual Fe NWs. Notably, deformation twinning is found as the primary mechanical plastic deformation mechanism of all Fe NWs, but it is initially observed at low strain and stress level for the oxidized Fe NWs.

  8. Adhesive and Cohesive Strength in FeB/Fe2B Systems

    Science.gov (United States)

    Meneses-Amador, A.; Blancas-Pérez, D.; Corpus-Mejía, R.; Rodríguez-Castro, G. A.; Martínez-Trinidad, J.; Jiménez-Tinoco, L. F.

    2018-05-01

    In this work, FeB/Fe2B systems were evaluated by the scratch test. The powder-pack boriding process was performed on the surface of AISI M2 steel. The mechanical parameters, such as yield stress and Young's modulus of the boride layer, were obtained by the instrumented indentation technique. Residual stresses produced on the boride layer were estimated by using the x-ray diffraction (XRD) technique. The scratch test was performed in order to evaluate the cohesive/adhesive strength of the FeB/Fe2B coating. In addition, a numerical evaluation of the scratch test on boride layers was performed by the finite element method. Maximum principal stresses were related to the failure mechanisms observed by the experimental scratch test. Shear stresses at the interfaces of the FeB/Fe2B/substrate system were also evaluated. Finally, the results obtained provide essential information about the effect of the layer thickness, the residual stresses, and the resilience modulus on the cohesive/adhesive strength in FeB/Fe2B systems.

  9. Fungal Iron Biomineralization in Río Tinto

    Directory of Open Access Journals (Sweden)

    Monike Oggerin

    2016-04-01

    Full Text Available Although there are many studies on biomineralization processes, most of them focus on the role of prokaryotes. As fungi play an important role in different geological and biogeochemical processes, it was considered of interest to evaluate their role in a natural extreme acidic environment, Río Tinto, which has a high level of fungal diversity and a high concentration of metals. In this work we report, for the first time, the generation of iron oxyhydroxide minerals by the fungal community in a specific location of the Tinto basin. Using Transmission Electron Microscopy (TEM and High Angle Angular Dark Field coupled with Scanning Transmission Electron Microscopy (HAADF-STEM and Energy-Dispersive X-ray Spectroscopy (EDX, we observed fungal structures involved in the formation of iron oxyhydroxide minerals in mineralized sediment samples from the Río Tinto basin. Although Río Tinto waters are supersaturated in these minerals, they do not precipitate due to their slow precipitation kinetics. The presence of fungi, which simply provide charged surfaces for metal binding, favors the precipitation of Fe oxyhydroxides by overcoming these kinetic barriers. These results prove that the fungal community of Río Tinto participates very actively in the geochemical processes that take place there.

  10. Calculation of Site-specific Carbon-isotope Fractionation in Pedogenic Oxide Minerals

    Energy Technology Data Exchange (ETDEWEB)

    Rustad, James R.; Zarzycki, Piotr

    2008-07-29

    Ab initio molecular dynamics and quantum chemistry techniques are used to calculate the structure, vibrational frequencies, and carbon-isotope fractionation factors of the carbon dioxide component [CO2(m)] of soil (oxy)hydroxide minerals goethite, diaspore, and gibbsite. We have identified two possible pathways of incorporation of CO2(m) into (oxy)hydroxide crystal structures: one in which the C4+ substitutes for four H+ [CO2(m)A] and another in which C4+ substitutes for (Al3+,Fe3+) + H+ [CO2(m)B]. Calculations of isotope fractionation factors give large differences between the two structures, with the CO2(m)A being isotopically lighter than CO2(m)B by ≈10 per mil in the case of gibbsite and nearly 20 per mil in the case of goethite. The reduced partition function ratio of CO2(m)B structure in goethite differs from CO2(g) by <1 per mil. The predicted fractionation for gibbsite is >10 per mil higher, close to those measured for calcite and aragonite. The surprisingly large difference in the carbon-isotope fractionation factor between the CO2(m)A and CO2(m)B structures within a given mineral suggests that the isotopic signatures of soil (oxy)hydroxide could be heterogeneous.

  11. Protonation/reduction dynamics at the [4Fe-4S] cluster of the hydrogen-forming cofactor in [FeFe]-hydrogenases.

    Science.gov (United States)

    Senger, Moritz; Mebs, Stefan; Duan, Jifu; Shulenina, Olga; Laun, Konstantin; Kertess, Leonie; Wittkamp, Florian; Apfel, Ulf-Peter; Happe, Thomas; Winkler, Martin; Haumann, Michael; Stripp, Sven T

    2018-01-31

    The [FeFe]-hydrogenases of bacteria and algae are the most efficient hydrogen conversion catalysts in nature. Their active-site cofactor (H-cluster) comprises a [4Fe-4S] cluster linked to a unique diiron site that binds three carbon monoxide (CO) and two cyanide (CN - ) ligands. Understanding microbial hydrogen conversion requires elucidation of the interplay of proton and electron transfer events at the H-cluster. We performed real-time spectroscopy on [FeFe]-hydrogenase protein films under controlled variation of atmospheric gas composition, sample pH, and reductant concentration. Attenuated total reflection Fourier-transform infrared spectroscopy was used to monitor shifts of the CO/CN - vibrational bands in response to redox and protonation changes. Three different [FeFe]-hydrogenases and several protein and cofactor variants were compared, including element and isotopic exchange studies. A protonated equivalent (HoxH) of the oxidized state (Hox) was found, which preferentially accumulated at acidic pH and under reducing conditions. We show that the one-electron reduced state Hred' represents an intrinsically protonated species. Interestingly, the formation of HoxH and Hred' was independent of the established proton pathway to the diiron site. Quantum chemical calculations of the respective CO/CN - infrared band patterns favored a cysteine ligand of the [4Fe-4S] cluster as the protonation site in HoxH and Hred'. We propose that proton-coupled electron transfer facilitates reduction of the [4Fe-4S] cluster and prevents premature formation of a hydride at the catalytic diiron site. Our findings imply that protonation events both at the [4Fe-4S] cluster and at the diiron site of the H-cluster are important in the hydrogen conversion reaction of [FeFe]-hydrogenases.

  12. Lattice locations and properties of Fe in Co/Fe co-implanted ZnO

    DEFF Research Database (Denmark)

    Gunnlaugsson, H.P.; Johnston, K.; Mølholt, T.E.

    2012-01-01

    The lattice locations and electronic configurations of Fe in 57Co/57Fe implanted ZnO (to (5‐6) × 1014 Fe/cm−2) have been studied by 57Fe Mössbauer emission spectroscopy. The spectra acquired upon room temperature implantation show ∼20% of the probe atoms as Fe2+ on perturbed Zn sites and the rema......The lattice locations and electronic configurations of Fe in 57Co/57Fe implanted ZnO (to (5‐6) × 1014 Fe/cm−2) have been studied by 57Fe Mössbauer emission spectroscopy. The spectra acquired upon room temperature implantation show ∼20% of the probe atoms as Fe2+ on perturbed Zn sites...... and the remaining fraction as Fe2+ in damage sites of interstitial character. After annealing at 773 K, ∼20% remain on crystalline sites, while the damage fraction has partly disappeared and instead a ∼30% fraction occurs as high‐spin Fe3+, presumably in precipitates. This suggests that precipitation of Co/Fe in ZnO...... likely takes place at relatively low temperatures, thus explaining some of the discrepancies in the literature regarding magnetic properties of 3d metal‐doped ZnO....

  13. Geochemical partitioning of Cu and Ni in mangrove sediments: Relationships with their bioavailability

    International Nuclear Information System (INIS)

    Chakraborty, Parthasarathi; Ramteke, Darwin; Chakraborty, Sucharita

    2015-01-01

    Highlights: • Metal speciation controls bioavailability in mangrove ecosystem. • Bioavailability of Ni was controlled by Fe/Mn-oxyhydroxide and organic phases • Bioavailability of Cu in mangrove roots was controlled by organic phase in the sediments. • Cu interacts more strongly with organic phases than Ni in mangrove sediment. - Abstract: Sequential extraction study was performed to determine the concentrations of non-residual metal-complexes in the mangrove sediments from the Divar Island, (west coast of India). Accumulation of metal in the mangrove roots (from the same location) was determined and used as an indicator of bioavailability of metal. An attempt was made to establish a mechanistic linkage between the non-residual metal complexes and their bioavailability in the mangrove system. The non-residual fractions of Cu and Ni were mainly associated with Fe/Mn oxyhydroxide and organic phases in the sediments. A part of these metal fractions were bioavailable in the system. These two phases were the major controlling factors for Ni speciation and their bioavailability in the studied sediments. However, Cu was found to interact more strongly with the organic phases than Ni in the mangrove sediments. Organic phases in the mangrove sediments acted as buffer to control the speciation and bioavailability of Cu in the system

  14. Iron persistence in a distal hydrothermal plume supported by dissolved-particulate exchange

    Science.gov (United States)

    Fitzsimmons, Jessica N.; John, Seth G.; Marsay, Christopher M.; Hoffman, Colleen L.; Nicholas, Sarah L.; Toner, Brandy M.; German, Christopher R.; Sherrell, Robert M.

    2017-02-01

    Hydrothermally sourced dissolved metals have been recorded in all ocean basins. In the oceans' largest known hydrothermal plume, extending westwards across the Pacific from the Southern East Pacific Rise, dissolved iron and manganese were shown by the GEOTRACES program to be transported halfway across the Pacific. Here, we report that particulate iron and manganese in the same plume also exceed background concentrations, even 4,000 km from the vent source. Both dissolved and particulate iron deepen by more than 350 m relative to 3He--a non-reactive tracer of hydrothermal input--crossing isopycnals. Manganese shows no similar descent. Individual plume particle analyses indicate that particulate iron occurs within low-density organic matrices, consistent with its slow sinking rate of 5-10 m yr-1. Chemical speciation and isotopic composition analyses reveal that particulate iron consists of Fe(III) oxyhydroxides, whereas dissolved iron consists of nanoparticulate Fe(III) oxyhydroxides and an organically complexed iron phase. The descent of plume-dissolved iron is best explained by reversible exchange onto slowly sinking particles, probably mediated by organic compounds binding iron. We suggest that in ocean regimes with high particulate iron loadings, dissolved iron fluxes may depend on the balance between stabilization in the dissolved phase and the reversibility of exchange onto sinking particles.

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

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  16. Colorimetric determination of Fe2+/Fe3+ ratio in radioactive glasses

    International Nuclear Information System (INIS)

    Coleman, C.J.; Baumann, E.W.; Bibler, N.E.

    1992-01-01

    In the vitrification of nuclear wastes, the Fe 2+ /Fe 3+ ratio in the glass is a measure of the redox properties of the glass melt. It is necessary to measure this ratio to ensure that the melt redox properties are suitable for the glass melter. A colorimetric method for measuring the Fe 2+ /Fe 3+ ratio in highly radioactive glasses was developed and tested remotely in a shielded cell. The tests were performed on glasses similar in composition and radioactivity to those that will be produced in the Savannah River Site Defense Waste Processing Facility. The first step of the method is dissolution of finely crushed glass with a hydrofluoric/sulfuric acid mixture with ammonium vanadate added to preserve the Fe 2+ content of the glass during the dissolution. Boric acid is then added to complex fluoride and to destroy iron-fluoride complexes. After adjusting the solution to pH 5, FerroZine TM (trademark of the Hach Company, Loveland, CO) reagent is added to form a magenta-colored complex with Fe 2+ . The absorbance at 562 nm is measured by using a fiber optic-coupled photodiode array spectrophotometer. Ascorbic acid is then used to reduce all the iron in solution to Fe 2+ and the absorbance is again measured. The difference in absorbance measurements corresponds to the Fe 3+ in the sample and the Fe 2+ /Fe 3+ ratio can be calculated

  17. Behaviour of Fe4O5-Mg2Fe2O5 solid solutions and their relation to coexisting Mg-Fe silicates and oxide phases

    Science.gov (United States)

    Uenver-Thiele, Laura; Woodland, Alan B.; Miyajima, Nobuyoshi; Ballaran, Tiziana Boffa; Frost, Daniel J.

    2018-03-01

    Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe4O5-Mg2Fe2O5 solid solutions and (2) to explore the phase relations involving (Mg,Fe)2Fe2O5 (denoted as O5-phase) and Mg-Fe silicates. Multi-anvil experiments were performed at 11-20 GPa and 1100-1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O5-phase coexists with Fe2O3, hp-(Mg,Fe)Fe2O4, (Mg,Fe)3Fe4O9 or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O5-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe3+-bearing phase B. However, (Mg,Fe)2Fe2O5 does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe2+ and Fe3+ (at least 1.0 cations Fe per formula unit). Fe-L2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe3+/Fetot = 0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si4+ + [6]Mg2+ = 2Fe3+. The ability to accommodate Fe2+ and Fe3+ makes this potential "water-storing" mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg2Fe2O5 have been refined, yielding H°1bar,298 = - 1981.5 kJ mol- 1. Solid solution is complete across the Fe4O5-Mg2Fe2O5 binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe2+ with silicates indicates that (Mg,Fe)2Fe2O5 has a strong preference for Fe2+. Modelling of partitioning with olivine is consistent with the O5-phase exhibiting ideal mixing behaviour. Mg-Fe2+ partitioning between (Mg,Fe)2Fe2O5 and ringwoodite or wadsleyite is influenced by the presence of Fe3+ and OH incorporation in the silicate phases.

  18. Timescales of carbon turnover in soils with mixed crystalline mineralogies

    Science.gov (United States)

    Khomo, Lesego; Trumbore, Susan E.; Bern, Carleton R.; Chadwick, Oliver A.

    2017-01-01

    Organic matter–mineral associations stabilize much of the carbon (C) stored globally in soils. Metastable short-range-order (SRO) minerals such as allophane and ferrihydrite provide one mechanism for long-term stabilization of organic matter in young soil. However, in soils with few SRO minerals and a predominance of crystalline aluminosilicate or Fe (and Al) oxyhydroxide, C turnover should be governed by chemisorption with those minerals. Here, we correlate mineral composition from soils containing small amounts of SRO minerals with mean turnover time (TT) of C estimated from radiocarbon (14C) in bulk soil, free light fraction and mineral-associated organic matter. We varied the mineral amount and composition by sampling ancient soils formed on different lithologies in arid to subhumid climates in Kruger National Park (KNP), South Africa. Mineral contents in bulk soils were assessed using chemical extractions to quantify Fe oxyhydroxides and SRO minerals. Because of our interest in the role of silicate clay mineralogy, particularly smectite (2 : 1) and kaolinite (1 : 1), we separately quantified the mineralogy of the clay-sized fraction using X-ray diffraction (XRD) and measured 14C on the same fraction. Density separation demonstrated that mineral associated C accounted for 40–70 % of bulk soil organic C in A and B1 horizons for granite, nephelinite and arid-zone gabbro soils, and > 80 % in other soils. Organic matter strongly associated with the isolated clay-sized fraction represented only 9–47 % of the bulk soil C. The mean TT of C strongly associated with the clay-sized fraction increased with the amount of smectite (2 : 1 clays); in samples with > 40 % smectite it averaged 1020 ± 460 years. The C not strongly associated with clay-sized minerals, including a combination of low-density C, the C associated with minerals of sizes between 2 µm and 2 cm (including Fe oxyhydroxides as coatings), and C removed from clay

  19. 57Fe Moessbauer and magnetic studies of ErFe12-xNbx

    International Nuclear Information System (INIS)

    Wang, J L; Campbell, S J; Cadogan, J M; Tegus, O; Edge, A V J

    2005-01-01

    The structural and magnetic properties of ErFe 12-x Nb x compounds (x 0.6, 0.7 and 0.8) have been investigated by x-ray diffraction, ac susceptibility and dc magnetization measurements and 57 Fe Moessbauer spectroscopy. Refinements of the x-ray diffraction patterns show that the Nb atoms preferentially occupy the 8i sites; this can be understood in the terms of enthalpy effects and differences in the metallic radii. The average Fe-Fe distance at the different sites is found to behave as d Fe-Fe (8i)> d Fe-Fe (8j)> d Fe-Fe (8f). The unit cell volume increases slightly with increasing Nb content, consistent with the larger radius of Nb compared with Fe. A spin reorientation from easy-axis at room temperature to easy-cone at low temperatures has been detected for all compounds. The spin reorientation temperatures T sr in ErFe 12-x Nb x compounds remain essentially unchanged (T sr ∼42-44 K) with increasing Nb concentration, whereas a significant decrease in T sr (T sr1 ∼236-204 K; T sr2 ∼154-94 K) is obtained in DyFe 12-x Nb x from x = 0.6 to 0.8. This can be understood by taking the different crystal-field terms responsible for the spin reorientation in the two systems into account. We find that the spin-reorientation process is particularly sensitive to the sixth-order term B 60 O 60 of the crystal field acting on the Er 3+ ion, due to its large and positive value of γ J . 57 Fe hyperfine interaction parameters and magnetic moments values have been determined for the 8i, 8j and 8f sites from the Moessbauer spectra. The weighted average 57 Fe hyperfine field values were found to follow a T 2 dependence; this suggests that a single-particle excitation mechanism is responsible for reduction of the 3d-sublattice magnetization with increasing temperature

  20. Hyperfine fields of Fe in Nd2Fe14BandSm2Fe17N3

    Science.gov (United States)

    Akai, Hisazumi; Ogura, Masako

    2015-03-01

    High saturation magnetization of rare-earth magnets originates from Fe and the strong magnetic anisotropy stems from f-states of rare-earth elements such as Nd and Sm. Therefore the hyperfine fields of both Fe and rare-earth provide us with important pieces of information: Fe NMR enable us to detect site dependence of the local magnetic moment and magnetic anisotropy (Fe sites also contribute to the magnetic anisotropy) while rare-earth NQR directly give the information of electric field gradients (EFG) that are related to the shape of the f-electron cloud as well as the EFG produced by ligands. In this study we focus on the hyperfine fields of materials used as permanent magnets, Nd2Fe14BandSm2Fe17N3 from theoretical points of view. The detailed electronic structure together with the hyperfine interactions are discussed on the basis of the first-principles calculation. In particular, the relations between the observed hyperfine fields and the magnetic properties are studies in detail. The effects of doping of those materials by other elements such as Dy and the effects of N adding in Sm2Fe17N3 will be discussed. This work was supported by Elements Strategy Initiative Center for Magnetic Materials Project, the Ministry of Education, Culture, Sports, Science and Technology, Japan.

  1. Ferromagnetic resonance on oxideless magnetic Fe and FeRh nanoparticles; Ferromagnetische Resonanz an oxidfreien magnetischen Fe und FeRh Nanopartikeln

    Energy Technology Data Exchange (ETDEWEB)

    Trunova, Anastasia

    2009-05-25

    This work is dedicated to investigations of structural and magnetic properties of the colloidal Fe/Fe{sub x}O{sub y} nanocubes (13 nm) and the Fe{sub x}Rh{sub 100-x} core/shell nanoparticles (2 nm). As compared with other works, where the measurements on oxidized nanoparticles were carried out, we additionally performed investigations on nanoparticles in an oxide free state. In order to make the measurements on oxide free particles possible, oxygen- and hydrogenplasma was used to remove the ligands and reduce the oxide shell of the Fe nanocubes. The oxide free Fe nanocubes were covered with a Ag/Pt protective coating to prevent them from new oxidation. This method allowed carrying out the magnetic measurements on oxide free Fe nanocubes. Micromagnetic simulations as well as simulations of the high frequency susceptibility were used for the data analysing. It was found that both the g-factor g=2.09{+-}0.01 and the anisotropy constant K{sub 4}=(4.8{+-}0.5).10{sup 4} J/m{sup 3} coincide with that of bulk iron. However, the saturation magnetization M{sub S}(5 K)=(1.2{+-}0.12).10{sup 6} A/m differs from the bulk value by 30%. The reduction by 30% compared to the bulk value in the case of nanoparticles may be caused by the following possible reasons: a) the presence of inner oxide layer (approx. 10 at.%) that cannot be reduced; b) the anti-parallel order between magnetic moments of iron core and magnetic moments of antiferomagnetic iron oxide; c) some structural changes of the surface after plasma treatment. The obtained damping parameter {alpha}=0.03{+-}0.005 is ten times larger than that of the Fe layers as it is known for nanoparticles systems in general. The core/shell Fe{sub x}Rh{sub 100-x} nanoparticles (x=80,50) were produced under Ar-atmosphere and were sealed into a quartz tube to prevent oxidation. The analysis of g-factors shows that the value for the FePh nanoparticles with Fe-rich core is larger (g=2.08{+-}0.01) than that for the nanoparticles with Rh

  2. Evolution of the local structure of ferric gels and polymers during the crystallisation of iron oxides. Application to uranium trapping

    International Nuclear Information System (INIS)

    Combes, Jean-Marie

    1988-01-01

    A first part of this research thesis reports the study of the structure of the main iron oxides and oxy-hydroxides, and of the protocols for the synthesis of ferric gels. The second part reports a topological approach by EXAFS (Extended X-Ray Absorption Fine Structure) of the structure of Mn and Fe oxides and oxy-hydroxides. The third part reports the study of the formation of ferric oxides from aqueous solutions by using a polyhedral approach by X-ray absorption spectroscopy in the case of hydrolysis and formation of ferric gels, and in the case of haematite formation from ferric gels. The next parts respectively report the study of the local structure of gels synthesised from iron(II), and the study of the local structure of natural ferric gels. Then, the author reports the study of sites of uranium bonding on ferric gels [fr

  3. Kerr microscopy study of exchange-coupled FePt/Fe exchange spring magnets

    Energy Technology Data Exchange (ETDEWEB)

    Hussain, Zaineb; Kumar, Dileep [UGC-DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore 452001 (India); Reddy, V. Raghavendra, E-mail: varimalla@yahoo.com [UGC-DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore 452001 (India); Gupta, Ajay [Amity Center for Spintronic Materials, Amity University, Noida 201303 (India)

    2017-05-15

    Magnetization reversal and magnetic microstructure of top soft magnetic layer (Fe) in exchange spring coupled L1{sub 0} FePt/Fe is studied using high resolution Kerr microscopy. With remnant state of the hard magnetic layer (L1{sub 0} FePt) as initial condition, magnetization loops along with magnetic domains are recorded for the top soft magnetic layer (Fe) using Kerr microscopy. Considerable shifting of Fe layer hysteresis loop from center which is similar to exchange bias phenomena is observed. It is also observed that one can tune the magnitude of hysteresis shift by reaching the remanent state from different saturating fields (H{sub SAT}) and also by varying the angle between measuring field and H{sub SAT}. The hysteresis loops and magnetic domains of top soft Fe layer demonstrate unambiguously that soft magnetic layer at remanent state in such exchange coupled system is having unidirectional anisotropy. An analogy is drawn and the observations are explained in terms of established model of exchange bias phenomena framed for field-cooled ferromagnetic - antiferromagnetic bilayer systems. - Highlights: • Kerr microscopy of top soft magnetic Fe layer in exchange spring coupled L1{sub 0} FePt (30 nm)/Fe (22 nm) is reported. • Considerable shifting of Fe layer hysteresis loop from center which is similar to exchange bias phenomena is observed. • Tuneable nature of magnitude of hysteresis shift is shown. • It is unambiguously shown that the top soft Fe magnetic layer at remanent state is having unidirectional anisotropy.

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

    Science.gov (United States)

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

    2016-11-09

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

  5. Ferromagnetic resonance study of sputtered NiFe/V/NiFe heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Alayo, W., E-mail: willian.rodriguez@ufpel.edu.br [Departamento de Física – IFM, Universidade Federal de Pelotas, 96010-900 Rio Grande do Sul (Brazil); Pelegrini, F. [Instituto de Física, Universidade Federal de Goiás, Goiânia, 74001-970 (Brazil); Baggio-Saitovitch, E. [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro, RJ, 22290-180 (Brazil)

    2015-03-01

    The Ni{sub 81}Fe{sub 19}/V/Ni{sub 81}Fe{sub 19} heterostructures has been produced by magnetron sputtering and analyzed by ferromagnetic resonance. Two systems were investigated: the non symmetrical NiFe(50 Å)/V(t)/NiFe(30 Å) trilayers and the symmetrical NiFe(80 Å)/V(t)/NiFe(80 Å) trilayers, with variable ultrathin V thickness t. Ferromagnetic exchange coupling was evidenced for t below 10 Å by the excitation of the optic mode, in the case of the non symmetrical samples, and by the observation of a single resonance mode for the symmetrical trilayers. For larger V thickness, all samples exhibited two modes, which were attributed to the resonance of the individual NiFe layers with different effective magnetizations. The analysis with the equilibrium and resonance conditions provided the exchange coupling constants and effective magnetizations. - Highlights: • We present a study of symmetrical and non symmetrical NiFe/V/NiFe trilayers deposited on Si single crystals by ferromagnetic resonance (FMR) at room temperature. • For the non symmetrical trilayers, the FMR spectra show the optic and acoustic modes for samples with very thin V layer thicknesses, evidencing ferromagnetic exchange coupling, whereas, for larger V thickness, the spectra exhibited two well resolved modes associated to each independent NiFe layer. For the symmetrical trilayers, strong ferromagnetic exchange coupling is evidenced by the observation of a single resonance mode. • The analysis with the equilibrium condition and dispersion relation provides the exchange coupling constants and effective magnetizations.

  6. Fe-Vacancy-Induced Ferromagnetism in Tetragonal FeSe Thin Films

    International Nuclear Information System (INIS)

    Yong-Feng, Li; Gui-Bin, Liu; Li-Jie, Shi; Bang-Gui, Liu

    2009-01-01

    Motivated by recent experiments, we investigate structural, electronic, and magnetic properties of tetragonal FeSe with Fe vacancies using the state-of-the-art first-principles method. We show that Fe vacancies tend to stay in the same one of the two sublattices and thus induce ferromagnetism in the ground-state phase. Our calculated net moment is in good agreement with the experimental data available. Therefore, the ferromagnetism observed in tetragonal FeSe thin films is explained. It could be made controllable soon for spintronic applications

  7. Mössbauer Studies of Core-Shell FeO/Fe3O4 Nanoparticles

    Science.gov (United States)

    Kamzin, A. S.; Valiullin, A. A.; Khurshid, H.; Nemati, Z.; Srikanth, H.; Phan, M. H.

    2018-02-01

    FeO/Fe3O4 nanoparticles were synthesized by thermal decomposition. Electron microscopy revealed that these nanoparticles were of the core-shell type and had a spherical shape with an average size of 20 nm. It was found that the obtained FeO/Fe3O4 nanoparticles had exchange coupling. The effect of anisotropy on the efficiency of heating (hyperthermic effect) of FeO/Fe3O4 nanoparticles by an external alternating magnetic field was examined. The specific absorption rate (SAR) of the studied nanoparticles was 135 W/g in the experiment with an external alternating magnetic field with a strength of 600 Oe and a frequency of 310 kHz. These data led to an important insight: the saturation magnetization is not the only factor governing the SAR, and the efficiency of heating of magnetic FeO/Fe3O4 nanoparticles may be increased by enhancing the effective anisotropy. Mössbauer spectroscopy of the phase composition of the synthesized nanoparticles clearly revealed the simultaneous presence of three phases: magnetite Fe3O4, maghemite γ-Fe2O3, and wustite FeO.

  8. Neutron irradiation effects in Fe and Fe-Cr at 300 °C

    International Nuclear Information System (INIS)

    Chen, Wei-Ying; Miao, Yinbin; Gan, Jian; Okuniewski, Maria A.; Maloy, Stuart A.; Stubbins, James F.

    2016-01-01

    Fe and Fe-Cr (Cr = 10–16 at.%) specimens were neutron-irradiated at 300 °C to 0.01, 0.1 and 1 dpa. The TEM observations indicated that the Cr significantly reduced the mobility of dislocation loops and suppressed vacancy clustering, leading to distinct damage microstructures between Fe and Fe-Cr. Irradiation-induced dislocation loops in Fe were heterogeneously observed in the vicinity of grown-in dislocations, whereas the loop distribution observed in Fe-Cr is much more uniform. Voids were observed in the irradiated Fe samples, but not in irradiated Fe-Cr samples. Increasing Cr content in Fe-Cr results in a higher density, and a smaller size of irradiation-induced dislocation loops. Orowan mechanism was used to correlate the observed microstructure and hardening, which showed that the hardening in Fe-Cr can be attributed to the formation of dislocation loops and α′ precipitates. -- Graphical abstract: Addition of Cr in Fe suppressed the mobility of mobile 1/2<111> dislocation loops and increased the proportion of immobile <100> dislocation loops, leading to a transition of loop distribution from highly heterogeneous to uniform. Display Omitted

  9. Migration of {sup 75}Se(IV) in crushed Beishan granite: Effects of the iron content

    Energy Technology Data Exchange (ETDEWEB)

    He, Jiangang; Ma, Bin; Kang, Mingliang; Wang, Chunli; Nie, Zhe; Liu, Chunli, E-mail: liucl@pku.edu.cn

    2017-02-15

    Highlights: • The diffusion of {sup 75}SeO{sub 3}{sup 2−} in crushed BsG was slowest at approximately pH 5. • The D{sub a} values under aerobic conditions were nearly one order of magnitude lower than those under anaerobic conditions. • Fe(II)-bearing mineralogical components can be responsible for the great difference in D{sub a} values. • Se{sup IV} can be reduced to Se{sup 0} by BsG under anaerobic conditions. - Abstract: The diffusion of selenite (labeled with {sup 75}Se) in compacted Beishan granite (BsG) was investigated using the in-diffusion capillary method at pH values from ∼2.0 to ∼11.0 under oxic and anoxic conditions. The results indicate that the apparent diffusion coefficient (D{sub a}) values of selenite in BsG always reached the minimum at approximately pH 5. Unexpectedly, the D{sub a} values under oxic conditions are nearly one order of magnitude lower than those under the anoxic conditions. Further characterization reveals the existence of redox-sensitive Fe(II)-containing components, which can be responsible for the great difference in D{sub a} values. Fe(2p) X-ray photoelectron spectroscopy (XPS) results show that more Fe(III)-oxyhydroxide coating is formed on the granite’s surface under aerobic conditions than is formed under anaerobic conditions. Correspondingly, Se(3d) spectra indicate that more selenium is sorbed under oxic conditions, and the sorbed amount always reached the maximum at pH values from ∼4 to ∼5. A linear combination fit of X-ray absorption near edge structure (XANES) spectroscopy data revealed that Se(0) was formed under anoxic condition and that selenite preferred to form inner-sphere complexes with Fe(III)-oxyhydroxide. Overall, this study indicates that natural Fe-bearing minerals can greatly attenuate selenite diffusion and the retardation would be enhanced under aerobic conditions.

  10. Fe-N and (Fe, Ni)-N Fine Powders for Magnetic Recording

    International Nuclear Information System (INIS)

    Chen Ziyu; Li Fashen

    1998-01-01

    Combining Moessbauer spectroscopy with magnetic property measurement, we have studied Fe-N and (Fe, Ni)-N powders for magnetic recording. The typical particles of the core (α-Fe)/shell (γ'-Fe 4 N) structure have been successfully prepared. All the products are stabilized in a multi-organic solution. It has been found that the coercivity can be changed from 300 to 800 Oe by adjusting the shape of the particles. The special saturation magnetization of the particles can be adjusted from 120 to 180emu/g and their chemical stability is improved by substituting nickel for iron in γ'-Fe 4 N. Following experiments for corrosion resistance, it is expected that (Fe, Ni)-N and the core/shell particles will be applied as recording media in the near future

  11. Fe-N and (Fe, Ni)-N Fine Powders for Magnetic Recording

    Energy Technology Data Exchange (ETDEWEB)

    Chen Ziyu; Li Fashen [Lanzhou University, Department of Physics (China)

    1998-12-15

    Combining Moessbauer spectroscopy with magnetic property measurement, we have studied Fe-N and (Fe, Ni)-N powders for magnetic recording. The typical particles of the core ({alpha}-Fe)/shell ({gamma}'-Fe{sub 4}N) structure have been successfully prepared. All the products are stabilized in a multi-organic solution. It has been found that the coercivity can be changed from 300 to 800 Oe by adjusting the shape of the particles. The special saturation magnetization of the particles can be adjusted from 120 to 180emu/g and their chemical stability is improved by substituting nickel for iron in {gamma}'-Fe{sub 4}N. Following experiments for corrosion resistance, it is expected that (Fe, Ni)-N and the core/shell particles will be applied as recording media in the near future.

  12. Exchange biased FeNi/FeMn bilayers with coercivity and switching field enhanced by FeMn surface oxidation

    Directory of Open Access Journals (Sweden)

    A. V. Svalov

    2013-09-01

    Full Text Available FeNi/FeMn bilayers were grown in a magnetic field and subjected to heat treatments at temperatures of 50 to 350 °C in vacuum or in a gas mixture containing oxygen. In the as-deposited state, the hysteresis loop of 30 nm FeNi layer was shifted. Low temperature annealing leads to a decrease of the exchange bias field. Heat treatments at higher temperatures in gas mixture result in partial oxidation of 20 nm thick FeMn layer leading to a nonlinear dependence of coercivity and a switching field of FeNi layer on annealing temperature. The maximum of coercivity and switching field were observed after annealing at 300 °C.

  13. The nanophase iron mineral(s) in Mars soil

    Science.gov (United States)

    Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.

    1993-01-01

    A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism

  14. Spin-dependent electronic transport characteristics in Fe4N/BiFeO3/Fe4N perpendicular magnetic tunnel junctions

    Science.gov (United States)

    Yin, Li; Wang, Xiaocha; Mi, Wenbo

    2018-01-01

    Perpendicular magnetic tunnel junctions (MTJs) have attracted increasing attention owing to the low energy consumption and wide application prospects. Herewith, against Julliere's formula, an inverse tunnel magnetoresistance (TMR) appears in tetragonal Fe4N/BiFeO3/Fe4N perpendicular MTJs, which is attributed to the binding between the interface resonant tunneling state and central (bordered) hot spots. Especially, antiferromagnetic BiFeO3 shows an extra spin-polarized resonant state in the barrier, which provides a magnetic-barrier factor to affect the tunneling transport in MTJs. Meanwhile, due to the spin-polarized transport in Fe4N/BiFeO3/Fe4N MTJs, the sign of TMR can be tuned by the applied bias. The tunable TMR and resonant magnetic barrier effect pave the way for clarifying the tunneling transport in other junctions and spintronic devices.

  15. Effect of Fe-Mn addition on microstructure and magnetic properties of NdFeB magnetic powders

    Science.gov (United States)

    Kurniawan, C.; Purba, A. S.; Setiadi, E. A.; Simbolon, S.; Warman, A.; Sebayang, P.

    2018-03-01

    In this paper, the effect of Fe-Mn alloy addition on microstructures and magnetic properties of NdFeB magnetic powders was investigated. Varied Fe-Mn compositions of 1, 5, and 10 wt% were mixed with commercial NdFeB type MQA powders for 15 minutes using shaker mill. The characterizations were performed by powder density, PSA, XRD, SEM, and VSM. The Fe-Mn addition increased the powder density of NdFeB/Fe-Mn powders. On the other side, particle size distribution slightly decreased as the Fe-Mn composition increases. Magnetic properties of NdFeB/Fe-Mn powders changed with the increasing of Fe-Mn content. SEM analysis showed the particle size of NdFeB/Fe-Mn powder was smaller as the Fe-Mn composition increases. It showed that NdFeB/Fe-Mn particles have different size and shape for NdFeB and Fe-Mn particles separately. The optimum magnetic properties of NdFeB/Fe-Mn powder was achieved on the 5 wt% Fe-Mn composition with remanence M r = 49.45 emu/g, coercivity H c = 2.201 kOe, and energy product, BH max = 2.15 MGOe.

  16. Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

    Science.gov (United States)

    Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

    2013-05-01

    Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

  17. Effects of metal ions on the reactivity and corrosion electrochemistry of Fe/FeS nanoparticles.

    Science.gov (United States)

    Kim, Eun-Ju; Kim, Jae-Hwan; Chang, Yoon-Seok; Turcio-Ortega, David; Tratnyek, Paul G

    2014-04-01

    Nano-zerovalent iron (nZVI) formed under sulfidic conditions results in a biphasic material (Fe/FeS) that reduces trichloroethene (TCE) more rapidly than nZVI associated only with iron oxides (Fe/FeO). Exposing Fe/FeS to dissolved metals (Pd(2+), Cu(2+), Ni(2+), Co(2+), and Mn(2+)) results in their sequestration by coprecipitation as dopants into FeS and FeO and/or by electroless precipitation as zerovalent metals that are hydrogenation catalysts. Using TCE reduction rates to probe the effect of metal amendments on the reactivity of Fe/FeS, it was found that Mn(2+) and Cu(2+) decreased TCE reduction rates, while Pd(2+), Co(2+), and Ni(2+) increased them. Electrochemical characterization of metal-amended Fe/FeS showed that aging caused passivation by growth of FeO and FeS phases and poisoning of catalytic metal deposits by sulfide. Correlation of rate constants for TCE reduction (kobs) with electrochemical parameters (corrosion potentials and currents, Tafel slopes, and polarization resistance) and descriptors of hydrogen activation by metals (exchange current density for hydrogen reduction and enthalpy of solution into metals) showed the controlling process changed with aging. For fresh Fe/FeS, kobs was best described by the exchange current density for activation of hydrogen, whereas kobs for aged Fe/FeS correlated with electrochemical descriptors of electron transfer.

  18. Asymmetric interfaces in Fe/Ag and Ag/Fe bilayers prepared by molecular beam evaporation

    Energy Technology Data Exchange (ETDEWEB)

    Tunyogi, A. [KFKI Research Institute for Particle and Nuclear Physics, P.O. Box 49, H-1525 Budapest (Hungary)]. E-mail: tunyogi@rmki.kfki.hu; Paszti, F. [KFKI Research Institute for Particle and Nuclear Physics, P.O. Box 49, H-1525 Budapest (Hungary); Osvath, Z. [MTA Research Institute for Technical Physics and Materials Science, P.O. Box 49, H-1525 Budapest (Hungary); Tancziko, F. [KFKI Research Institute for Particle and Nuclear Physics, P.O. Box 49, H-1525 Budapest (Hungary); Major, M. [KFKI Research Institute for Particle and Nuclear Physics, P.O. Box 49, H-1525 Budapest (Hungary); Szilagyi, E. [KFKI Research Institute for Particle and Nuclear Physics, P.O. Box 49, H-1525 Budapest (Hungary)

    2006-08-15

    Single layers of Fe and Ag, as well as Fe/Ag (iron deposited first) and Ag/Fe bilayers were prepared by molecular beam evaporation onto Si. The samples were investigated with backscattering spectrometry (BS) and atomic force microscopy (AFM). BS spectra of Fe/Ag and Ag/Fe indicate a significant difference at the interface. In the case of Fe/Ag the Ag peak has a long tail at the interface, while for Ag/Fe the interface is abrupt. The tail in the Fe/Ag spectrum is too large to be caused by double or plural scattering. According to AFM, the effect of surface roughness is also negligible. In spite of the fact that Fe and Ag are completely immiscible in equilibrium, this tail, however, suggests that some Ag is located in the Fe layer. After annealing, both samples show mixing between the two layers; this is much larger again for Fe/Ag.

  19. Influence of ruthenium ions on the precipitation of α-FeOOH, α-Fe2O3 and Fe3O4 in highly alkaline media

    International Nuclear Information System (INIS)

    Krehula, Stjepko; Music, Svetozar

    2006-01-01

    The influence of ruthenium ions on the precipitation of goethite (α-FeOOH), α-Fe 2 O 3 and Fe 3 O 4 in highly alkaline media was investigated by 57 Fe Moessbauer and FT-IR spectroscopies, thermal field emission scanning electron microscope (FE SEM) and EDS. The presence of Ru-dopant strongly affected the precipitation of α-FeOOH at highly alkaline pH, i.e. the formation of α-Fe 2 O 3 was also noticed. A decrease of hyperfine magnetic field (HMF) at RT from 35.1 T (undoped α-FeOOH) to 31.3 T for sample with [Ru]/([Ru] + [Fe]) = 0.0196 was assigned to the incorporation of ruthenium ions into the α-FeOOH structure. Moessbauer spectroscopy showed the formation of stoichiometric Fe 3 O 4 for [Ru]/([Ru] + [Fe]) = 0.0291-0.0909. α-Fe 2 O 3 and Fe 3 O 4 did not show a tendency to the formation of solid solutions with ruthenium ions. FE SEM observations of the samples showed that reference α-FeOOH sample contained acicular particles of good uniformity, which increased the length up to ∼5 times with increase of concentration of ruthenium ions. On the other hand, large octahedral Fe 3 O 4 crystals (particles) were associated with small particles of ruthenium (hydrous) oxide with a size in the range ∼100 nm or less. A possible catalytic action of ruthenium that created reduction conditions for Fe 3+ ions and formation of Fe 2+ ions for precipitation of Fe 3 O 4 was discussed

  20. Experimental and thermodynamic assessments of substitutions in the AlFeSi, FeMnSi, FeSiZr and AlCaFeSi systems (65 wt % Si) - solidification simulation

    International Nuclear Information System (INIS)

    Gueneau, C.; Ansara, I.

    1994-01-01

    The substitutions of Al Si, Fe Mn and Fe Zr in some intermetallic compounds of the Al-Fe-Si, Fe-Mn-Si and Fe-Si-Zr systems are modelled in the Si-rich corner using a two sublattice model. The solidification paths of the studied alloys are determined at equilibrium. The ascalculated phase volume fractions of the alloys are compared to the experimental ones. Finally, a solidification simulation using the Gulliver-Scheil's model is performed in order to explain the formation of some precipitates experimentally observed. (authors). 14 figs., 19 refs

  1. Mineralogical study on agricultural soils using mossbauer spectrometry

    International Nuclear Information System (INIS)

    Ceron L, M.L.; Fabian S, J.; Bravo C, J.

    1999-01-01

    Iron (Fe) compounds are very common in nature. In the case of soils, they occur in the form of Fe sesquioxides, such as oxides, hydroxides and oxyhydroxides, as well as substitution cations in clay minerals. These minerals occur in crystalline and amorphous states. The isotopic selective nature of mossbauer spectroscopy (nuclear gamma resonance) allows the indentification of minerals containing Fe even when they are present in low concentrations and in amorphous state. In this work we report the preliminary results of a current study of soil samples collected from the area of Chinchero, Cusco. The experimental data were obtained by mossbauer spectroscopy and x-ray diffraction; these data were complemented with data reported by other workers. Standard procedures were used for sample preparation and the mossbauer spectra were taken at room and liquid nitrogen temperatures

  2. FeEDDHA-facilitated Fe uptake in relation to the behaviour of FeEDDHA components in the soil-plant system as a function of time and dosage.

    OpenAIRE

    Schenkeveld, W.D.C.; Temminghoff, E.J.M.; Reichwein, A.M.; Riemsdijk, van, W.H.

    2010-01-01

    FeEDDHA products are widely used to prevent and remedy Fe chlorosis in crops grown on calcareous soils. These products consist of a mixture of FeEDDHA components: racemic o,o-FeEDDHA, meso o,o-FeEDDHA, o,p-FeEDDHA and rest-FeEDDHA. The FeEDDHA components differ in physical and chemical properties, and as a consequence also in effectiveness as Fe fertilizer. In order to efficiently match dose, frequency and moment of FeEDDHA application with the Fe requirements of plants, it is important to un...

  3. Preparation of nanoscale iron (oxide, oxyhydroxides and zero-valent) particles derived from blueberries: Reactivity, characterization and removal mechanism of arsenate.

    Science.gov (United States)

    Manquián-Cerda, Karen; Cruces, Edgardo; Angélica Rubio, María; Reyes, Camila; Arancibia-Miranda, Nicolás

    2017-11-01

    The application of iron nanoparticles (FeNPs) to the removal of various pollutants has received wide attention over the last few decades. A synthesis alternative to obtain these nanoparticles without using harmful chemical reagents, such as NaBH 4 , is the use of extracts from different natural sources that allow a lesser degree of agglomeration, in a process known as green synthesis. In this study, FeNPs were synthesized by 'green' (hereafter, BB-Fe NPs) and 'chemical' (hereafter, nZVI) methods. Extracts of leaves and blueberry shoots (Vaccinium corymbosum) were used as reducing agents for FeCl 3 ·6H 2 O solution in the green synthesis method. FeNPs were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), electrophoretic migration, Brunauer-Emmett-Teller (BET) surface area analysis and X-ray diffraction (XRD) and evaluated for the removal of As(V) from aqueous systems. In both synthesis methods, XRD analysis confirmed the presence of the different kinds of iron nanoparticles. SEM analysis showed that the average size of BB-Fe NPs was 52.4nm and that a variety of nanoparticles of different forms and associated structures, such as lepidocrocite, magnetite, and nZVI, were present, while the dimensions of nZVI were 80.2nm. Comparatively significant differences regarding the electrophoretic mobility were found between both materials pre- and post-sorption of As(V). The velocity of As(V) removal by BB-Fe NPs was slower than that by nZVI, reaching equilibrium at 120min compared to 60min for nZVI. The removal kinetics of As(V) were adequately described by the pseudo-second-order kinetic model, and the maximum adsorbed amounts of this analyte are in close accordance with the experimental results. The Langmuir-Freundlich model is in good agreement with our experimental data, where the sorption capacity of nZVI and BB-Fe NPs was found to be 52.23 ± 6.06 and 50.40 ± 5.90 (mg·g -1 ), respectively. The use of leaves of Vaccinium

  4. Synthesis and characterization of magnetic Fe/CNTs composites with controllable Fe nanoparticle concentration

    International Nuclear Information System (INIS)

    Zhao Fan; Duan Hongyan; Wang Weigao; Wang Jun

    2012-01-01

    Fe/CNTs composites, with different concentrations of Fe nanoparticles (NPs) on carbon nanotube (CNT) surfaces, were successfully fabricated via a facile solvothermal method. The lengths of CNTs are up to 10 μm and the mean diameter of the Fe nanoparticles is about 25 nm. The structures, composition and magnetic properties of the Fe/CNTs were characterized by XRD, FTIR, FE-SEM, TEM and PPMS. We found that the concentrations of Fe nanoparticles depositing on the CNTs could be controlled by adjusting the initial mass ratio of ferrocene to CNTs. The Fe/CNTs composites display good ferromagnetic properties at room temperature, with a saturation magnetization of 125 emu/g-Fe and a coercivity of 276 Oe. The Curie temperature of the sample is about 1038 K, slightly lower than that (1043 K) of the bulk iron.

  5. Formation and stability of Fe-rich precipitates in dilute Zr(Fe) single-crystal alloys

    International Nuclear Information System (INIS)

    Zou, H.; Hood, G.M.; Roy, J.A.; Schultz, R.J.

    1993-02-01

    The formation and stability of Fe-rich precipitates in two α-Zr(Fe) single-crystal alloys with nominal compositions (I, 50 ppma Fe, and II, 650 ppma Fe) have been investigated (the maximum solid solubility of Fe in α-Zr is 180 ppma - 800 C). Optical microscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have been used to examine the characteristics of Fe-rich precipitates. SEM and TEM micrographs show that in as-grown alloy II, Zr 2 Fe precipitates are located at 'stringers'. Precipitates were not observed in as-grown alloy I. During annealing, below the solvus, Fe diffuses to the surfaces to form Zr 3 Fe precipitates in both alloys. The precipitates on the surfaces of alloy I tend to be star-like (0001) or pyramidal (1010), and their distribution is heterogeneous. Dissolution of Zr 3 Fe surface precipitates of alloy I (annealing above the solvus) leaves precipitate-like features on the surfaces. Zr 2 Fe precipitates in as-grown alloy II can be dissolved only by β-phase annealing. (Author) 8 figs., 18 refs

  6. FeEDDHA-facilitated Fe uptake in relation to the behaviour of FeEDDHA components in the soil-plant system as a function of time and dosage.

    NARCIS (Netherlands)

    Schenkeveld, W.D.C.; Temminghoff, E.J.M.; Reichwein, A.M.; Riemsdijk, van W.H.

    2010-01-01

    FeEDDHA products are widely used to prevent and remedy Fe chlorosis in crops grown on calcareous soils. These products consist of a mixture of FeEDDHA components: racemic o,o-FeEDDHA, meso o,o-FeEDDHA, o,p-FeEDDHA and rest-FeEDDHA. The FeEDDHA components differ in physical and chemical properties,

  7. Iron Isotope Fractionation in Microbial and Non-Biological Precipitates, and the Human Body

    Science.gov (United States)

    von Blanckenburg, F.; Boettcher, M. E.; Hofmann, B.; Walczyk, T.

    2001-12-01

    We have investigated biotic and abiotic stable iron isotope fractionation pathways in experiments, the low-T natural environment, and the human body. Fe samples were analysed using a Nu Plasma Multicollector ICP-MS. All measured samples plot on the theoretically predicted exponential fractionation line in the Delta57Fe versus Delta56Fe space, demonstrating absence of ArN or ArO interferences. An experimental calibration of Fe isotope fractionation during abiotic formation of iron (III) oxyhydroxide and iron(II) minerals from aqueous solution resulted in significant differences: (a) During fast precipitation of FeOOH during alkalization of a Fe(III)Cl3 solution at room temperature the solid is only slightly enriched by about 0.1permil in 57Fe compared to the solution. (b) Slow precipitation of akaganeite (beta-FeOOH) from aqueous Fe(III)Cl3 solution leads to a depletion of 57Fe by about -2.2permil in the solid phase without a significant influence of temperature. (c) Precipitation of FeOOH during oxidation of aqueous Fe(II) solutions by oxygen yields an enrichment of up to 4.8permil in 57Fe in the solid phase. (d) Iron(II) carbonate precipitation between 20 and 60C leads to an almost negligible depletion in 57Fe compared to aqueous ferrous ions. Interpretation: Large enrichment of the heavy isotope is observed where Fe is oxidised, whereas small to interme-diate depletions of heavy Fe isotopes occur upon forma-tion of Fe-minerals without change in redox state. Addi-tionally, kinetic effects, the speciation of the aqueous solution, or the effect of crystal structures may have to be considered. Biotic isotope fractionation by microorganisms was investigated at two field sites. In a Fe mine (Gonzen, Switzerland), Fe-precipitating microbes (Gallionella ferrugina and Leptohrix ochtraceae) have formed Fe(III)-oxyhydroxides that are ca. 0.6permil heavier in Delta57Fe than the Fe-rich parent solutions. At Cady Mts, California, filamentous fabrics of goethite, thought to

  8. Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.

    Science.gov (United States)

    Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo

    2018-02-02

    The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.

  9. Mössbauer spectroscopic studies in U-Fe and U-Fe-Zr alloys

    Energy Technology Data Exchange (ETDEWEB)

    Panda, Alaka; Singh, L. Herojit; Rajagopalan, S.; Govindaraj, R., E-mail: govind@igcar.gov.in; Ramachandran, Renjith; Kalavathi, S.; Amarendra, G. [Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam (India)

    2016-05-23

    {sup 57}Fe Mössbauer studies have been carried out in an alloy of U and Fe with atomic percentage in the ratio of 68%:32% in order to understand the local structure and valence of Fe atoms associated with different phases that may get formed. The effect of changes in the hyperfine parameters such as isomer shift and quadrupole splitting at Fe sites due to additional alloying of Zr has been studied in an alloy of U, Fe and Zr in the ratio of 44%:33%:23% respectively with respect to that of the U-Fe alloy chosen in the present study. Possible effect of solute clustering in these systems has been addressed in an analogous alloy of uranium and zirconium using positron lifetime spectroscopy.

  10. Reactions of laser-ablated iron atoms and cations with carbon monoxide: Infrared spectra of FeCO+, Fe(CO)2+, Fe(CO)x, and Fe(CO)x- (x=1-4) in solid neon

    Science.gov (United States)

    Zhou, Mingfei; Andrews, Lester

    1999-06-01

    Laser-ablated iron atoms, cations, and electrons have been reacted with CO molecules during condensation in excess neon. The FeCO molecule is observed at 1933.7 cm-1 in solid neon. Based on isotopic shifts and density functional calculations, the FeCO molecule has the same 3Σ- ground state in solid neon that has been observed at 1946.5 cm-1 in a recent high resolution gas phase investigation [Tanaka et al., J. Chem. Phys. 106, 2118 (1997)]. The C-O stretching vibration of the Fe(CO)2 molecule is observed at 1917.1 cm-1 in solid neon, which is in excellent agreement with the 1928.2 cm-1 gas phase value for the linear molecule. Anions and cations are also produced and trapped, absorptions at 1782.0, 1732.9, 1794.5, and 1859.7 cm-1 are assigned to the linear FeCO-, Fe(CO)2-, trigonal planar Fe(CO)3-, and C3v Fe(CO)4- anions, respectively, and 2123.0, 2134.0 cm-1 absorptions to the linear FeCO+ and Fe(CO)2+ cations. Doping these experiments with CCl4 virtually eliminates the anion absorptions and markedly increases the cation absorptions, which confirms the charge identifications. Higher iron carbonyl Fe(CO)3, Fe(CO)4, and Fe(CO)5 absorptions are produced on photolysis.

  11. Hydrological and geochemical constraints on the mechanism of formation of arsenic contaminated groundwater in Sonargaon, Bangladesh

    Energy Technology Data Exchange (ETDEWEB)

    Itai, Takaaki [Institute for Study of the Earth' s Interior, Okayama University, Misasa, Tottori 682-0193 (Japan)], E-mail: itai-epss@hiroshima-u.ac.jp; Masuda, Harue [Department of Geosciences, Osaka-City University, Sugimoto-tyo, Sumiyoshi, Osaka 558-8585 (Japan); Seddique, Ashraf A. [Department of Geosciences, Osaka-City University, Sugimoto-tyo, Sumiyoshi, Osaka 558-8585 (Japan); Department of Geology, University of Dhaka, Dhaka 1000 (Bangladesh); Mitamura, Muneki [Department of Geosciences, Osaka-City University, Sugimoto-tyo, Sumiyoshi, Osaka 558-8585 (Japan); Maruoka, Teruyuki [Department of Integrative Environmental Science, University of Tsukuba, Tsukuba, Ibaraki 305-8572 (Japan); Li, Xiaodong [Department of Geosciences, Osaka-City University, Sugimoto-tyo, Sumiyoshi, Osaka 558-8585 (Japan); Kusakabe, Minoru [Institute for Study of the Earth' s Interior, Okayama University, Misasa, Tottori 682-0193 (Japan); Dipak, Biswas K. [Department of Geology, University of Dhaka, Dhaka 1000 (Bangladesh); Farooqi, Abida [Department of Geosciences, Osaka-City University, Sugimoto-tyo, Sumiyoshi, Osaka 558-8585 (Japan); Yamanaka, Toshiro [Department of Earth Systems Science, Okayama University, 3-1-1 Tsushima-naka Okayama 700-8530 (Japan); Nakaya, Shinji [Department of Civil Engineering, Shinshu University, Wakazato, Nagano 380-8553 (Japan); Matsuda, Jun-ichi [Department of Earth and Space Science, Osaka University, 1-1 Machikaneyama-tyo, Toyonaka-shi, Osaka 560-0043 (Japan); Ahmed, Kazi Matin [Department of Geology, University of Dhaka, Dhaka 1000 (Bangladesh)

    2008-11-15

    The geochemical characteristics and hydrological constraints of high As groundwater in Sonargaon, in mid-eastern Bangladesh were investigated in order to ascertain the mechanism of As release into the groundwaters from host sediments in the Ganges-Brahmaputra delta. Samples of groundwater were collected from ca. 230 tube wells in both the rainy and dry seasons. Similar to previous studies, high As groundwater was found in the Holocene unconfined aquifer but not in the Pleistocene aquifer. Groundwaters in the Holocene aquifer were of the Ca-Mg-HCO{sub 3} type with major solutes derived from chemical weathering of detrital minerals such as plagioclase and biotite. Groundwater with high As was generally characterized by high NH{sub 4}{sup +}, possibly derived from the agricultural application of fertilizer as suggested by the small variation of {delta}{sup 15}N{sub NH4} (mostly 2-4 per mille ). Concentrations of Fe changed between the rainy and dry seasons by precipitation/dissolution of Fe oxyhydroxide and siderite, whilst there was not an apparent concomitant change in As. Inhomogeneous spatial distribution of {delta}{sup 18}O in the Holocene unconfined aquifer indicates poor mixing of groundwater in the horizontal direction. Spatial variation of redox conditions is associated with localized variations in subsurface permeability and the recharge/discharge cycle of groundwater. Hydrogeochemical data presented in this paper suggest that reduction of Fe oxyhydroxide is not the only mechanism of As mobilization, and chemical weathering of biotite and/or other basic minerals in the Holocene aquifer could also be important as a primary cause of As mobilization.

  12. Stability of the high pressure phase Fe3S2 up to Earth's core pressures in the Fe-S-O and the Fe-S-Si systems

    Science.gov (United States)

    Zurkowski, C. C.; Chidester, B.; Davis, A.; Brauser, N.; Greenberg, E.; Prakapenka, V. B.; Campbell, A.

    2017-12-01

    Earth's core is comprised of an iron-nickel alloy that contains 5-15% of a light element component. The abundance and alloying capability of sulfur, silicon and oxygen in the bulk Earth make them important core alloy candidates; therefore, the high-pressure phase equilibria of the Fe-S-O and Fe-S-Si systems are relevant for understanding the possible chemistry of Earth's core. Previously, a Fe3S2 phase was recognized as a low-pressure intermediate phase in the Fe-FeS system that is stable from 14-21 GPa, but the structure of this phase has not been resolved. We report in-situ XRD and chemical analysis of recovered samples to further examine the stability and structure of Fe3S2 as it coexists with other phases in the Fe-S-O and Fe-S-Si systems. In situ high P-T synchrotron XRD experiments were conducted in the laser-heated diamond anvil cell to determine the equilibrium phases in Fe75S7O18 and Fe80S5Si15 compositions between 30 and 174 GPa and up to 3000 K. In the S,O-rich samples, an orthorhombic Fe3S2 phase coexists with hcp-Fe, Fe3S and FeO and undergoes two monoclinic distortions between 60 and 174 GPa. In the S,Si-rich samples, the orthorhombic Fe3S2 phase was observed up to 115 GPa. With increasing pressure, the Fe3S2 phase becomes stable to higher temperatures in both compositions, suggesting possible Fe3(S,O)2 or Fe3(S,Si)2 solid solutions. SEM analysis of a laser heated Fe75S7O18 sample recovered from 40 GPa and 1450 K confirms a Fe3(S,O)2 phase with O dissolved into the structure. Based on the current melting data in the Fe-S-O and Fe-S-Si systems, the Fe3(S,O)2 stability field intersects the solidus in the outer core and could be a possible liquidus phase in Fe,S,O-rich planetary cores, whereas Fe3S is the stable sulfide at outer core pressures in Fe,S,Si-rich systems.

  13. Moessbauer and XRD study of pulse plated Fe-P and Fe-Ni thin layers

    International Nuclear Information System (INIS)

    Miko, Annamaria; Kuzmann, Erno; Lakatos-Varsanyi, Magda; Kakay, Attila; Nagy, Ferenc; Varga, Lajos Karoly

    2005-01-01

    57 Fe conversion electron Moessbauer spectroscopy, X-ray diffraction, electrochemical and magnetic measurements were used to study pulse electroplated Fe-P and Ni-Fe coatings. XRD and 57 Fe CEMS measurements revealed the amorphous character of the novel pulse plated Fe-P alloys. CEM spectra indicated significant differences in the short range order and in the magnetic anisotropy between the Fe-P deposits pulse plated at medium long deposition time (t on = 2 ms), with short relaxation time (t off = 9 ms) and low current density (I p = 0.05 Acm -2 ) or at short deposition time (t on = 1 ms) with long relaxation time (t off = 250 ms) and high current density (I p = 1.0 Acm -2 ). The broad peaks centred around the fcc reflections in XRD of the pulse plated Ni-22 wt.% Fe deposit reflected a microcrystalline Ni-Fe alloy with a very fine, 5-8 nm, grain size. The CEM spectrum of the pulse plated Ni-22 wt.% Fe coating corresponded to a highly disordered solid solution alloy containing a minute amount of ferrihydrite. Extreme favourable soft magnetic properties were observed with these Ni-Fe and Fe-P pulse plated thin layers.

  14. Characterization of rust layer formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich environment by Cl and Fe K-edge XANES measurements

    International Nuclear Information System (INIS)

    Konishi, Hiroyuki; Mizuki, Jun'ichiro; Yamashita, Masato; Uchida, Hitoshi

    2005-01-01

    Chloride in atmosphere considerably reduces the corrosion resistance of conventional weathering steel containing a small amount of Cr. Ni is an effective anticorrosive element for improving the corrosion resistance of steel in a Cl-rich environment. In order to clarify the structure of the protective rust layer of weathering steel, Cl and Fe K-edge X-ray absorption near edge structure (XANES) spectra of atmospheric corrosion products (rust) formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich atmosphere were measured. The Fe K-XANES measurements enable the characterization of mixture of iron oxides such as rust. The chemical composition of the rust was determined by performing pattern fitting of the measured spectra. All the rust is composed mainly of goethite, akaganeite, lepidocrocite and magnetite. Among these iron oxides, akaganeite in particular is the major component in the rust. Additionally, the amount of akaganeite in the rust of Fe-Ni alloy is much greater than that in rust of Fe-Cr alloy. Akaganeite is generally considered to facilitate the corrosion of steel, but our results indicate that akaganeite in the rust of Fe-Ni alloy is quantitatively different from that in rust of Fe-Cr alloy and does not facilitate the corrosion of steel. The shoulder peak observed in Cl K-XANES spectra reveals that the rust contains a chloride other than akaganeite. The energy of the shoulder peak does not correspond to that of any well-known chlorides. In the measured spectra, there is no proof that Cl, by combining with the alloying element, inhibits the alloying element from acting in corrosion resistance. The shoulder peak appears only when the content of the alloying element is lower than a certain value. This suggests that the generation of the unidentified chloride is related to the corrosion rate of steel. (author)

  15. XAS studies on selenite reduction by pyrite

    International Nuclear Information System (INIS)

    Kang Mingliang; Liu Chunli; Chen Fanrong; Charlet, Laurnet

    2012-01-01

    The interaction of aqueous Se (IV) with pyrite were systematically investigated in light of thermodynamic calculations and X-ray Absorption Spectroscopy (XAS). The results from the speciation study reveal that the reduction product is Se (O) when natural pyrite reacts with Se (N) at pH≤5.65, while small amount of FeSeO 3 or iron selenides may be formed at pH 6.1. At pH≥6.94, due to the precipitation of Fe (Ⅲ) -oxyhydroxide, the formation of the thermodynamically most stable species, FeSe 2 , is inhibited. However, when the reactive nanopyrite-greigite was used for reaction, the thermodynamically most stable species, FeSe 2 , was found for the first time as the predominant product in the present study, suggesting that 79 Se can be immobilized in its most insoluble form, FeSe 2 , in Fe (Ⅱ) -sulfide containing environment. This study confirms that pyrite can significantly attenuate the mobility of Se by reductive precipitation, and that the reaction process does not produce protons under acidic or neutral condition when Se (O) is formed. (authors)

  16. Speciative Determination of Dissolved Inorganic Fe(II), Fe(III) and Total Fe in Natural Waters by Coupling CPE with FAAS

    International Nuclear Information System (INIS)

    Gurkan, R.; Altunay, N.

    2013-01-01

    A new cloud point extraction (CPE) method for the preconcentration of trace iron speciation in natural waters prior to determination by flame atomic absorption spectrometry (FAAS) was developed in the present study. In this method, Fe(II) sensitively and selectively reacts with Calcon carboxylic acid (CCA) in presence of cetylpyridinium chloride (CPC) yielding a hydrophobic complex at pH 10.5, which is then entrapped in surfactant-rich phase. Total Fe was accurately and reliably determined after the reduction of Fe(III) to Fe(II) with sulfite. The amount of Fe(III) in samples was determined from the difference between total Fe and Fe(II). CPC was used not only as an auxiliary ligand in CPE, but also as sensitivity enhancement agent in FAAS. The nonionic surfactant, polyethylene glycol tert-octylphenyl ether (Triton X-114) was used as an extracting agent. The analytical variables affecting CPE efficiency were investigated in detail. The preconcentration/enhancement factors of 50 and 82 respectively, were obtained for the preconcentration of Fe(II) with 50 mL solution. Under the optimized conditions, the detection limit of Fe(II) in linear range of 0.2-60 μg L/sup -1/ was 0.06 μg L/sup -1/. The relative standard deviation was 2.7 percentage (20 μg L/sup -1/, N: 5), recoveries for Fe(II) were in range of 99.0-102.0 percentage for all water samples including certified reference materials (CRMs). In order to verify its accuracy, two CRMs were analyzed and the results obtained were statistically in good agreement with the certified values. (author)

  17. Properties of porous FeAlOy/FeAlx ceramic matrix composite ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 36; Issue 7. Properties of porous FeAlO/FeAl ceramic matrix composite influenced by mechanical activation of FeAl powder. V Usoltsev S Tikhov A Salanov V Sadykov G Golubkova O Lomovskii. Volume 36 Issue 7 December 2013 pp 1195-1200 ...

  18. Obtention of the TiFe compound by high-energy milling of Ti+Fe and TiH{sub 2}+Fe powder mixtures; Obtencao do composto TiFe a partir da moagem de alta energia de misturas Ti+Fe e TiH{sub 2}+Fe

    Energy Technology Data Exchange (ETDEWEB)

    Falcao, R.B.; Dammann, E.D.C.C.; Rocha, C.J.; Leal Neto, R.M., E-mail: railson.falcao@usp.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Ciencias e Tecnologia de Materiais. Lab. de Intermetalicos

    2010-07-01

    In this work TiFe compound was obtained by two process routes involving high-energy ball milling: mechanical alloying from Ti and Fe powders (route 1) and mechanical milling from TiH{sub 2} and Fe powders, both followed by an annealing heat treatment. Shaker and planetary ball mills were utilized for times varying from 1-25 hours. Milled and annealed powders were characterized by SEM and X-ray diffraction analyses. TiFe compound was formed in both routes. A strong powder adherence in the milling vial and balls occurred with route 1 in both mills. Powder adherence was significantly reduced by using TiH{sub 2} (route 2) mainly in the planetary mill, in spite of TiFe formation has only occurred after the annealing treatment. (author)

  19. Natural nanomaterials : reappraising the elusive structure of the nano-sized mineral ferrihydrite through X-Ray absorption spectroscopy at the iron K-edge

    OpenAIRE

    Figueiredo, M. Ondina; Silva, Teresa Pereira; Veiga, João Pedro

    2013-01-01

    Ferrihydrite is natural ferric oxyhydroxide occurring exclusively nanocrystalline. With ideal formula 5 Fe2 O3 . 9 H2 O, ferrihydrite is quite abundant in sediments, weathering crusts and mine wastes, being characteristic of red pre-soils formed by loose weathered rock plus mineral debris (regoliths) and commonly designated as “2-line” or “6-line” on the basis of the broadened maxima observed in the X-ray diffraction pattern. Synthetic nanocrystalline “6-line” ferrihydrite was...

  20. Spectrophotometric speciation of Fe(II) and Fe(III) using hydrazone-micelle systems and flow injections

    International Nuclear Information System (INIS)

    Khojali, Inas Osman

    1999-04-01

    Two hydrazones were synthesised, namely salicylhyrazone (SH) and trihydroxyacetophenone (THAPH) were synthesised with the objective of developing a method for determining of Fe(II) and Fe(III) in the presence of each other and hence the total iron.those hydrazones were selected so as to combine the ability of phenolic compounds to complex Fe(III) ions and the complexing characteristics of hydrazones. The complexes of Fe(II) S H and Fe(III) S H as well those of Fe(II)-THAPH and Fe(III)-THAPH had shown maximum absorbance at λ=412 nm which was not not modified by presence of micelles i.e. sodium n-dodecyl sulphate (SDS) and n-hexa dodecyl pyridinium bromide. The maximum absorbance for all complexes takes place around a neutral pH. Generally, in addition, of n-hexa dodecylpyridinium bromide to fe(II)-SH and Fe(III)-SH absorbance of the complexes increases with increasing the concentration of the micelle. The effects of the addition of sodium n-dodecyle sulphate (SDS) to Fe(III)-SH is also studied. Generally, increasing the concentration of the micelle decrease the absorbance of the complexes. To study the effect of the presence of Fe(II) and Fe(III) on the determination of each other,mixtures of Fe(II)-SH and Fe(III)-SH are studied. However, the use of ascorbic acid as a reducing reagent for Fe(III) did not produce the needed results but non reducible results, which may be due to the masking effect of ascorbic acid and thus making the metal not available to the ligand. However, conversion of Fe(II) to Fe(III) prior to the determination was avoided as this requires the use of oxidant, which will oxidise the ligand as well. To establish the condition for the maximum absorbance of THAPH complexes, the effect of the base was investigated by using sodium and ammonium hydroxide. Generally, increasing the concentration of the base decreases the abosrbance. as expected, ammonium hydroxide produced positive results than sodium hydroxide. After establishing the optimum Fi

  1. CO-Bridged H-Cluster Intermediates in the Catalytic Mechanism of [FeFe]-Hydrogenase CaI.

    Science.gov (United States)

    Ratzloff, Michael W; Artz, Jacob H; Mulder, David W; Collins, Reuben T; Furtak, Thomas E; King, Paul W

    2018-06-20

    The [FeFe]-hydrogenases ([FeFe] H 2 ases) catalyze reversible H 2 activation at the H-cluster, which is composed of a [4Fe-4S] H subsite linked by a cysteine thiolate to a bridged, organometallic [2Fe-2S] ([2Fe] H ) subsite. Profoundly different geometric models of the H-cluster redox states that orchestrate the electron/proton transfer steps of H 2 bond activation have been proposed. We have examined this question in the [FeFe] H 2 ase I from Clostridium acetobutylicum (CaI) by Fourier-transform infrared (FTIR) spectroscopy with temperature annealing and H/D isotope exchange to identify the relevant redox states and define catalytic transitions. One-electron reduction of H ox led to formation of H red H + ([4Fe-4S] H 2+ -Fe I -Fe I ) and H red ' ([4Fe-4S] H 1+ -Fe II -Fe I ), with both states characterized by low frequency μ-CO IR modes consistent with a fully bridged [2Fe] H . Similar μ-CO IR modes were also identified for H red H + of the [FeFe] H 2 ase from Chlamydomonas reinhardtii (CrHydA1). The CaI proton-transfer variant C298S showed enrichment of an H/D isotope-sensitive μ-CO mode, a component of the hydride bound H-cluster IR signal, H hyd . Equilibrating CaI with increasing amounts of NaDT, and probed at cryogenic temperatures, showed H red H + was converted to H hyd . Over an increasing temperature range from 10 to 260 K catalytic turnover led to loss of H hyd and appearance of H ox , consistent with enzymatic turnover and H 2 formation. The results show for CaI that the μ-CO of [2Fe] H remains bridging for all of the "H red " states and that H red H + is on pathway to H hyd and H 2 evolution in the catalytic mechanism. These results provide a blueprint for designing small molecule catalytic analogs.

  2. Magnetic and structural characterizations on nanoparticles of FePt, FeRh and their composites

    International Nuclear Information System (INIS)

    Ko, Hnin Yu Yu; Suzuki, Takao; Nam, Nguyen T.; Phuoc, Nguyen N.; Cao Jiangwei; Hirotsu, Yoshihiko

    2008-01-01

    The various compositions of FePt and FeRh nanoparticles, and their composite particles have been fabricated by the solution-phase chemical method and their magnetic properties characterized. High-resolution transmission electron microscopic observations indicate that mono-dispersed FeRh and FePt/FeRh nanoparticles are fabricated with the average size of 3-5 nm. However, larger size particles are distributed in the annealed state. From X-ray diffraction results, the as-deposited FeRh nanoparticles reveal a chemically disordered fcc structure which can be transformed into CsCl-type structure through thermal annealing. Similarly, the annealed FePt nanoparticles show the L1 0 -phase fct structure although the fcc structure is apparent in the as-deposited state. It is also found that the first time in the exchange bias effect in the composite of ferromagnetic (FePt) and anti-ferromagnetic (FeRh) nanoparticles; result in a shift of the hysteresis loop after field cooling process

  3. Moessbauer and XRD study of pulse plated Fe-P and Fe-Ni thin layers

    Energy Technology Data Exchange (ETDEWEB)

    Miko, Annamaria [Bay Zoltan Institute for Material Science (Hungary); Kuzmann, Erno, E-mail: kuzmann@para.chem.elte.hu [Eoetvoes Lorand University, Research Group for Nuclear Methods in Structural Chemistry, Hungarian Academy of Sciences, Department of Nuclear Chemistry (Hungary); Lakatos-Varsanyi, Magda [Bay Zoltan Institute for Material Science (Hungary); Kakay, Attila [Research Institute for Solid State Physics and Optics (Hungary); Nagy, Ferenc [Eoetvoes Lorand University, Research Group for Nuclear Methods in Structural Chemistry, Hungarian Academy of Sciences, Department of Nuclear Chemistry (Hungary); Varga, Lajos Karoly [Research Institute for Solid State Physics and Optics (Hungary)

    2005-09-15

    {sup 57}Fe conversion electron Moessbauer spectroscopy, X-ray diffraction, electrochemical and magnetic measurements were used to study pulse electroplated Fe-P and Ni-Fe coatings. XRD and {sup 57}Fe CEMS measurements revealed the amorphous character of the novel pulse plated Fe-P alloys. CEM spectra indicated significant differences in the short range order and in the magnetic anisotropy between the Fe-P deposits pulse plated at medium long deposition time (t{sub on} = 2 ms), with short relaxation time (t{sub off} = 9 ms) and low current density (I{sub p} = 0.05 Acm{sup -2}) or at short deposition time (t{sub on} = 1 ms) with long relaxation time (t{sub off} = 250 ms) and high current density (I{sub p} = 1.0 Acm{sup -2}). The broad peaks centred around the fcc reflections in XRD of the pulse plated Ni-22 wt.% Fe deposit reflected a microcrystalline Ni-Fe alloy with a very fine, 5-8 nm, grain size. The CEM spectrum of the pulse plated Ni-22 wt.% Fe coating corresponded to a highly disordered solid solution alloy containing a minute amount of ferrihydrite. Extreme favourable soft magnetic properties were observed with these Ni-Fe and Fe-P pulse plated thin layers.

  4. Accumulation of iron and arsenic in the Chandina alluvium of the lower delta plain, Southeastern Bangladesh

    Science.gov (United States)

    Zahid, A.; Hassan, M.Q.; Breit, G.N.; Balke, K.-D.; Flegr, M.

    2009-01-01

    Accumulations of iron, manganese, and arsenic occur in the Chandina alluvium of southeastern Bangladesh within 2.5 m of the ground surface. These distinctive orange-brown horizons are subhorizontal and consistently occur within 1 m of the contact of the aerated (yellow-brown) and water-saturated (gray) sediment. Ferric oxyhydroxide precipitates that define the horizons form by oxidation of reduced iron in pore waters near the top of the saturated zone when exposed to air in the unsaturated sediment. Hydrous Fe-oxide has a high specific surface area and thus a high adsorption capacity that absorbs the bulk of arsenic also present in the reduced pore water, resulting in accumulations containing as much as 280 ppm arsenic. The steep redox gradient that characterizes the transition of saturated and unsaturated sediment also favors accumulation of manganese oxides in the oxidized sediment. Anomalous concentrations of phosphate and molybdenum also detected in the ferric oxyhydroxide-enriched sediment are attributed to sorption processes. ?? Springer Science+Business Media B.V. 2008.

  5. Structural and magnetic study of mechanically deformed Fe rich FeAlSi ternary alloys

    International Nuclear Information System (INIS)

    Legarra, E.; Apiñaniz, E.; Plazaola, F.

    2012-01-01

    Highlights: ► Addition of Si to binary Fe–Al alloys makes the disordering more difficult. ► Si addition opposes the large volume increase found in FeAl alloys with deformation. ► Disordering induces a redistribution of non-ferrous atoms around Fe atoms in Fe 75 Al 25−x Si x and Fe 70 Al 30−x Si x . ► Addition of Si to binary Fe 75 Al 25 and Fe 70 Al 30 alloys opposes the magnetic behavior induced by Al in the magnetism of Fe. ► Si inhibits the para-ferro transition found in Fe 60 Al 40 alloy with disordering. - Abstract: In this work we study systematically the influence of different Al/Si ratios on the magnetic and structural properties of mechanically disordered powder Fe 75 Al 25−x Si x , Fe 70 Al 30−x Si x and Fe 60 Al 40−x Si x alloys by means of Mössbauer spectroscopy, X-ray diffraction and magnetic measurements. In order to obtain different stages of disorder the alloys were deformed by different methods: crushing induction melted alloys and ball milling annealed (ordered) alloys using different number of balls and speed. X-ray and Mössbauer data show that mechanical deformation induces the disordered A2 structure in these alloys. The results indicate that addition of Si to binary Fe–Al alloys makes the disordering more difficult. In addition, X-ray diffraction patterns show that the normalized lattice parameter variation of the disordered alloys of each composition decreases monotonically with Si content, indicating clearly that Si addition opposes the large volume increase found in FeAl alloys with deformation. The study of the hyperfine fields indicates that there is a redistribution of non-ferrous atoms around Fe atoms with the disordering; indeed, there is an inversion of the behavior of the hyperfine field of the Fe atoms. On the other hand, the magnetic measurements indicate that addition of Si to binary Fe 75 Al 25 and Fe 70 Al 30 alloys opposes the magnetic behavior induced by Al in the magnetism of Fe.

  6. Spectral distribution of Fe2+ photoionization cross section in InP:Fe

    International Nuclear Information System (INIS)

    Iikawa, F.

    1985-01-01

    Measurements of Fe 2+ ( 5 E) photoionization cross section in InP at 80 0 K, using constant current photoconductivity technique, were done. The spectrum presents a threshold energy of ∼ 0,65 eV due to the transition from Fe 2+ charge state, in the ground state, to Fe 3+ with an electron emission for the minimum conduction band. In the measurement of photoluminescence at ∼ 2 0 K, a wide emission of Fe complexe with the strong lattice interaction. In order to analyse the experimental data of Fe 2+ cross section in InP, a theoretical model was used. (M.C.K.) [pt

  7. Insights into Resistance to Fe Deficiency Stress from a Comparative Study of In Vitro-Selected Novel Fe-Efficient and Fe-Inefficient Potato Plants

    Directory of Open Access Journals (Sweden)

    Georgina A. Boamponsem

    2017-09-01

    Full Text Available Iron (Fe deficiency induces chlorosis (IDC in plants and can result in reduced plant productivity. Therefore, development of Fe-efficient plants is of great interest. To gain a better understanding of the physiology of Fe-efficient plants, putative novel plant variants were regenerated from potato (Solanum tubersosum L. var. ‘Iwa’ callus cultures selected under Fe deficient or low Fe supply (0–5 μM Fe. Based on visual chlorosis rating (VCR, 23% of callus-derived regenerants were classified as Fe-efficient (EF and 77% as Fe-inefficient (IFN plant lines when they were grown under Fe deficiency conditions. Stem height was found to be highly correlated with internodal distance, leaf and root lengths in the EF plant lines grown under Fe deficiency conditions. In addition, compared to the IFN plant lines and control parental biotype, the EF plants including the lines named A1, B2, and B9, exhibited enhanced formation of lateral roots and root hairs as well as increased expression of ferritin (fer3 in the leaf and iron-regulated transporter (irt1 in the root. These morphological adaptations and changes in expression the fer3 and irt1 genes of the selected EF potato lines suggest that they are associated with resistance to low Fe supply stress.

  8. Interstitial Fe in MgO

    CERN Document Server

    Mølholt, T E; Gunnlaugsson, H P; Svane, A; Masenda, H; Naidoo, D; Bharuth-Ram, K; Fanciulli, M; Gislason, H P; Johnston, K; Langouche, G; Ólafsson, S; Sielemann, R; Weyer, G

    2014-01-01

    Isolated Fe-57 atoms were studied in MgO single-crystals by emission Mossbauer spectroscopy following implantation of Mn-57 decaying to Fe-57. Four Mossbauer spectral components were found corresponding to different Fe lattice positions and/or charge states. Two components represent Fe atoms substituting Mg as Fe2+ and Fe3+, respectively; a third component is due to Fe in a strongly implantation-induced disturbed region. The fourth component, which is the focus of this paper, can be assigned to Fe at an interstitial site. Comparison of its measured isomer shift with ab initio calculations suggests that the interstitial Fe is located on, or close to, the face of the rock-salt MgO structure. To harmonize such an assignment with the measured near-zero quadrupole interaction a local motion process (cage motion) of the Fe has to be stipulated. The relation of such a local motion as a starting point for long range diffusion is discussed.

  9. Synthesis of Nano sized Zinc-Doped Cobalt Oxyhydroxide Parties by a Dropping Method and Their Carbon Monoxide Gas Sensing Properties

    International Nuclear Information System (INIS)

    Wang, J.W.; Kuo, Y.M.

    2013-01-01

    Two nano structures of cobalt oxyhydroxide (CoOOH) and Zinc-(Zn-) doped CoOOH (1–4% Zn) are prepared from Co(NO 3 ) 2 solution via microtitration with NaOH and oxidation in air. The X-ray diffraction (XRD) analysis results show that a pure state of nano-CoOOH can be obtained at an alkalinity (OH−/Co + ) of 5 with 40°C heat treatment after 6 h. The Zn ions preferentially substitute Co ions in the CoOOH structure, resulting in a decrease of its crystallinity. The disc-like CoOOH nano structure exhibits good sensitivity to carbon monoxide (CO) in a temperature range of 40–110°C with maximum sensitivity to CO at around 70–80°C. When CoOOH nano structure is doped with 1% Zn, its sensitivity and selectivity for CO gas are improved at 70–80°C; further Zn doping to 2% degraded the CO sensing properties of nano-CoOOH. The results of a cross-sensitivity investigation of the sensor to various gases coexisting at early stages of a fire show that the sensitivity of Zn-doped nano-CoOOH is the highest toward CO. Zn-doped nano-CoOOH film exhibits a high sensitivity to CO at room temperature, making it a promising sensor for early-stage fire detection.

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

    Science.gov (United States)

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

    2017-10-01

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

  11. Electric-field tunable perpendicular magnetic anisotropy in tetragonal Fe4N/BiFeO3 heterostructures

    Science.gov (United States)

    Yin, Li; Wang, Xiaocha; Mi, Wenbo

    2017-07-01

    Electric field control on perpendicular magnetic anisotropy (PMA) is indispensable for spintronic devices. Herewith, in tetragonal Fe4N/BiFeO3 heterostructures with the FeAFeB/Fe-O2 interface, PMA in each Fe4N layer, not merely interfacial layers, is modulated by the electric field, which is attributed to the broken spin screening of the electric field in highly spin-polarized Fe4N. Moreover, the periodical dx y+dy z+dz2 and dx y+dx2-y2 orbital-PMA oscillation enhances the interactions between adjacent FeAFeB and (FeB)2N atomic layers, which benefits the electric field modulation on PMA in the whole Fe4N atomic layers. The electric-field control on PMA in Fe4N/BiFeO3 heterostructures is favored by the electric-field-lifted potential in Fe4N.

  12. Metal cycling during sediment early diagenesis in a water reservoir affected by acid mine drainage

    DEFF Research Database (Denmark)

    Torres, Ester; Ayora, Carlos; Canovas, C. R.

    2013-01-01

    The discharge of acid mine drainage (AMD) into a reservoir may seriously affect the water quality. To investigate the metal transfer between the water and the sediment, three cores were collected from the Sancho Reservoir (Iberian Pyrite Belt, SW Spain) during different seasons: turnover event......; oxic, stratified period; anoxic and under shallow perennially oxic conditions. The cores were sliced in an oxygen-free atmosphere, after which pore water was extracted by centrifugation and analyzed. A sequential extraction was then applied to the sediments to extract the water-soluble, monosulfide......, low crystallinity Fe(III)-oxyhydroxide, crystalline Fe(III)-oxide, organic, pyrite and residual phases. The results showed that, despite the acidic chemistry of the water column (pH

  13. Magnetic nanowires (Fe, Fe-Co, Fe-Ni – magnetic moment reorientation in respect of wires composition

    Directory of Open Access Journals (Sweden)

    Kalska-Szostko Beata

    2015-03-01

    Full Text Available Magnetic nanowires of Fe, Fe-Co, and Fe-Ni alloy and layered structure were prepared by electrochemical alternating current (AC deposition method. The morphology of the nanowires in and without the matrix was studied by energy dispersive X-ray spectroscopy (EDX, scanning electron microscopy (SEM, and X-ray diffraction (XRD, respectively. The wires either show strong dependence on the combination of elements deposition (alloy or layered or chemical composition (Co or Ni. The magnetic properties of the nanostructures were determined on the basis of Mössbauer spectroscopy (MS.

  14. Thallium isotope evidence for a permanent increase in marine organic carbon export in the early Eocene

    Science.gov (United States)

    Nielsen, S.G.; Mar-Gerrison, S.; Gannoun, A.; LaRowe, D.; Klemm, V.; Halliday, A.N.; Burton, K.W.; Hein, J.R.

    2009-01-01

    The first high resolution thallium (Tl) isotope records in two ferromanganese crusts (Fe-Mn crusts), CD29 and D11 from the Pacific Ocean are presented. The crusts record pronounced but systematic changes in 205Tl/203Tl that are unlikely to reflect diagenetic overprinting or changes in isotope fractionation between seawater and Fe-Mn crusts. It appears more likely that the Fe-Mn crusts track the Tl isotope composition of seawater over time. The present-day oceanic residence time of Tl is estimated to be about 20,000??yr, such that the isotopic composition should reflect ocean-wide events. New and published Os isotope data are used to construct age models for these crusts that are consistent with each other and significantly different from previous age models. Application of these age models reveals that the Tl isotope composition of seawater changed systematically between ~ 55??Ma and ~ 45??Ma. Using a simple box model it is shown that the present day Tl isotope composition of seawater depends almost exclusively on the ratio between the two principal output fluxes of marine Tl. These fluxes are the rate of removal of Tl from seawater via scavenging by authigenic Fe-Mn oxyhydroxide precipitation and the uptake rate of Tl during low temperature alteration of oceanic crust. It is highly unlikely that the latter has changed greatly. Therefore, assuming that the marine Tl budget has also not changed significantly during the Cenozoic, the low 205Tl/203Tl during the Paleocene is best explained by a more than four-fold higher sequestration of Tl by Fe-Mn oxyhydroxides compared with at the present day. The calculated Cenozoic Tl isotopic seawater curve displays a striking similarity to that of S, providing evidence that both systems may have responded to the same change in the marine environment. A plausible explanation is a marked and permanent increase in organic carbon export from ~ 55??Ma to ~ 45??Ma, which led to higher pyrite burial rates and a significantly reduced

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

    Science.gov (United States)

    Li, Yue; Machala, Libor; Yan, Weile

    2016-02-02

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

  16. Rapid thermal annealing of FePt and FePt/Cu thin films

    Energy Technology Data Exchange (ETDEWEB)

    Brombacher, Christoph

    2011-01-10

    Chemically ordered FePt is one of the most promising materials to reach the ultimate limitations in storage density of future magnetic recording devices due to its high uniaxial magnetocrystalline anisotropy and a corrosion resistance superior to rare-earth based magnets. In this study, FePt and FePt/Cu bilayers have been sputter deposited at room temperature onto thermally oxidized silicon wafers, glass substrates and self-assembled arrays of spherical SiO{sub 2} particles with diameters down to 10 nm. Millisecond flash lamp annealing, as well as conventional rapid thermal annealing was employed to induce the phase transformation from the chemically disordered A1 phase into the chemically ordered L1{sub 0} phase. The influence of the annealing temperature, annealing time and the film thickness on the ordering transformation and (001) texture evolution of FePt films with near equiatomic composition was studied. Whereas flash lamp annealed FePt films exhibit a polycrystalline morphology with high chemical L1{sub 0} order, rapid thermal annealing can lead to the formation of chemically ordered FePt films with (001) texture on amorphous SiO{sub 2}/Si substrates. The resultant high perpendicular magnetic anisotropy and large coercivities up to 40 kOe are demonstrated. Simultaneously to the ordering transformation, rapid thermal annealing to temperatures exceeding 600 C leads to a break up of the continuous FePt film into separated islands. This dewetting behavior was utilized to create regular arrays of FePt nanostructures on SiO{sub 2} particle templates with periods down to 50 nm. The addition of Cu improves the (001) texture formation and chemical ordering for annealing temperatures T{sub a} {<=}600 C. In addition, the magnetic anisotropy and the coercivity of the ternary FePtCu alloy can be effectively tailored by adjusting the Cu content. The prospects of FePtCu based exchange spring media, as well as the magnetic properties of FePtCu nanostructures fabricated

  17. High-frequency permeability of electroplated CoNiFe and CoNiFe-C alloys

    International Nuclear Information System (INIS)

    Rhen, Fernando M.F.; McCloskey, Paul; O'Donnell, Terence; Roy, Saibal

    2008-01-01

    We have investigated CoNiFe and CoNiFe-C electrodeposited by pulse reverse plating (PRP) and direct current (DC) techniques. CoNiFe(PRP) films with composition Co 59.4 Fe 27.7 Ni 12.8 show coercivity of 95 A m -1 (1.2 Oe) and magnetization saturation flux (μ 0 M s ) of 1.8 T. Resistivity of CoNiFe (PRP) is about 24 μΩ cm and permeability remains almost constant μ r ' ∼475 up to 30 MHz with a quality factor (Q) larger than 10. Additionally, the permeability spectra analysis shows that CoNiFe exhibits a classical eddy current loss at zero bias field and ferromagnetic resonance (FMR) when biased with 0.05 T. Furthermore, a crossover between eddy current and FMR loss is observed for CoNiFe-PRP when baised with 0.05 T. DC and PRP plated CoNiFe-C, which have resistivity and permeability of 85, 38 μΩ cm, μ r '=165 and 35 with Q>10 up to 320 MHz, respectively, showed only ferromagnetic resonance losses. The ferromagnetic resonance peaks in CoNiFe and CoNiFe-C are broad and resembles a Gaussian distribution of FMR frequencies. The incorporation of C to CoNiFe reduces eddy current loss, but also reduces the FMR frequency

  18. NifI inhibits nitrogenase by competing with Fe protein for binding to the MoFe protein

    International Nuclear Information System (INIS)

    Dodsworth, Jeremy A.; Leigh, John A.

    2007-01-01

    Reduction of substrate by nitrogenase requires direct electron transfer from the Fe protein to the MoFe protein. Inhibition of nitrogenase activity in Methanococcus maripaludis occurs when the regulatory protein NifI 1,2 binds the MoFe protein. This inhibition is relieved by 2-oxoglutarate. Here we present evidence that NifI 1,2 binding prevents association of the two nitrogenase components. Increasing amounts of Fe protein competed with NifI 1,2 , decreasing its inhibitory effect. NifI 1,2 prevented the co-purification of MoFe protein with a mutant form of the Fe protein that forms a stable complex with the MoFe protein, and NifI 1,2 was unable to bind to an AlF 4 - -stabilized Fe protein:MoFe protein complex. NifI 1,2 inhibited ATP- and MoFe protein-dependent oxidation of the Fe protein, and 2OG relieved this inhibition. These results support a model where NifI 1,2 competes with the Fe protein for binding to MoFe protein and prevents electron transfer

  19. Na7 [Fe2S6 ] , Na2 [FeS2 ] and Na2 [FeSe2 ] : New 'reduced' sodium chalcogenido ferrates

    Science.gov (United States)

    Stüble, Pirmin; Peschke, Simon; Johrendt, Dirk; Röhr, Caroline

    2018-02-01

    Three new 'reduced' FeII containing sodium chalcogenido ferrates were obtained applying a reductive synthetic route. The mixed-valent sulfido ferrate Na7 [Fe2S6 ] , which forms bar-shaped crystals with metallic greenish luster, was synthesized in pure phase from natural pyrite and elemental sodium at a maximum temperature of 800 °C. Its centrosymmetric triclinic structure (SG P 1 bar , a = 764.15(2), b = 1153.70(2), c = 1272.58(3) pm, α = 62.3325 (7) , β = 72.8345 (8) , γ = 84.6394 (8) ° , Z = 3, R1 = 0.0185) exhibits two crystallographically different [Fe2S6 ] 7 - dimers of edge-sharing [FeS4 ] tetrahedra, with somewhat larger Fe-S distances than in the fully oxidized FeIII dimers of e.g. Na6 [Fe2III S6 ] . In contrast to the localized AFM ordered pure di-ferrates(III), the Curie-Weiss behavior of the magnetic susceptibility proves the rarely observed valence-delocalized S = 9/2 state of the mixed-valent FeIII /FeII dimer. The nearly spin-only value of the magnetic moment combined with the chemical bonding not generally differing from that in pure ferrates(II) and (III), provides a striking argument, that the reduction of the local Fe spin moments observed in all condensed sulfido ferrate moieties is connected with the AFM spin ordering. The two isotypic ferrates(II) Na2 [FeS2 ] and Na2 [FeSe2 ] with chain-like structural units (SG Ibam, a = 643.54(8)/ 660.81(1), b = 1140.2(2)/1190.30(2) c = 562.90(6)/585.59(1) pm, Z = 4, R1 = 0.0372/0.0466) crystallize in the K2 [ZnO2 ] -type structure. Although representing merely further members of the common series of chalcogenido metallates(II) Na2 [MIIQ2 ] , these two new phases, together with Na6 [FeS4 ] and Li2 [FeS2 ] , are the only examples of pure FeII alkali chalcogenido ferrates. The new compounds allow for a general comparison of di- and chain ferrates(II) and (III) and mixed-valent analogs concerning the electronic and magnetic properties (including Heisenberg super-exchange and double-exchange interactions

  20. Structural and magnetic properties of Ce/Fe and Ce/FeCoV multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Tixier, S; Boeni, P [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Mannix, D; Stirling, W G [Liverpool Univ. (United Kingdom); Lander, G H

    1997-09-01

    Ce/Fe and Ce/FeCoV multilayers have been grown by magnetron sputtering. The interfaces are well defined and the layers are crystalline down to an individual layer thickness of 20 A. Ce/FeCoV multilayers show sharper interfaces than Ce/Fe but some loss of crystallinity is observed. Hysteresis loops obtained by SQUID show different behaviour of the bulk magnetisation as a function of the layer thickness. Fe moments are found by Moessbauer spectroscopy to be perpendicular to the interfaces for multilayers with small periodicity. (author) 2 figs., 2 refs.

  1. Electronic Properties of LiFePO4 and Li doped LiFePO4

    International Nuclear Information System (INIS)

    Zhuang, G.V.; Allen, J.L.; Ross, P.N.; Guo, J.-H.; Jow, T.R.

    2005-01-01

    The potential use of different iron phosphates as cathode materials in lithium-ion batteries has recently been investigated.1 One of the promising candidates is LiFePO4. This compound has several advantages in comparison to the state-of-the-art cathode material in commercial rechargeable lithium batteries. Firstly, it has a high theoretical capacity (170 mAh/g). Secondly, it occurs as mineral triphylite in nature and is inexpensive, thermally stable, non-toxic and non-hygroscopic. However, its low electronic conductivity (∼10-9 S/cm) results in low power capability. There has been intense worldwide research activity to find methods to increase the electronic conductivity of LiFePO4, including supervalent ion doping,2 introducing non-carbonaceous network conduction3 and carbon coating, and the optimization of the carbon coating on LiFePO4 particle surfaces.4 Recently, the Li doped LiFePO4 (Li1+xFe1-xPO4) synthesized at ARL has yield electronic conductivity increase up to 106.5 We studied electronic structure of LiFePO4 and Li doped LiFePO4 by synchrotron based soft X-ray emission (XES) and X-ray absorption (XAS) spectroscopies. XAS probes the unoccupied partial density of states, while XES the occupied partial density of states. By combining XAS and XES measurements, we obtained information on band gap and orbital character of both LiFePO4 and Li doped LiFePO4. The occupied and unoccupied oxygen partial density of states (DOS) of LiFePO4 and 5 percent Li doped LiFePO4 are presented in Fig. 1. Our experimental results clearly indicate that LiFePO4 has wideband gap (∼ 4 eV). This value is much larger than what is predicted by DFT calculation. For 5 percent Li doped LiFePO4, a new doping state was created closer to the Fermi level, imparting p-type conductivity, consistent with thermopower measurement. Such observation substantiates the suggestion that high electronic conductivity in Li1.05Fe0.95 PO4 is due to available number of charge carriers in the material

  2. Effect of the oxidation rate and Fe(II) state on microbial nitrate-dependent Fe(III) mineral formation

    Science.gov (United States)

    Senko, John M.; Dewers , Thomas A.; Krumholz, Lee R.

    2005-01-01

    A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems.

  3. Magnetic properties of FeZr{sub 2} and Fe{sub 2}Zr intermetallic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Prajapat, C. L., E-mail: prajapat@barc.gov.in; Singh, M. R.; Mishra, P. K. [Technical Physics Division, Bhabha Atomic Research Centre, Mumbai, INDIA-400085 (India); Chattaraj, D. [Product Development Division, Bhabha Atomic Research Centre, Mumbai, INDIA-400085 (India); Mishra, R. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai, INDIA-400085 (India); Ravikumar, G. [Scientific Information Resources Division, Bhabha Atomic Research Centre, Mumbai, INDIA-400085 (India)

    2016-05-23

    Magnetic properties of Fe-Zr system, viz., FeZr{sub 2} and Fe{sub 2}Zr have been studied. Both the compounds show soft ferromagnetic behavior. Curie temperature is well above the room temperature. Lower saturation magnetization for the zirconium rich sample, FeZr{sub 2}, could be due to possible donation of electrons from the Zr-rich neighbors to Fe atoms or diminution of long range magnetic order by defects.

  4. Microbial iron cycling in acidic geothermal springs of Yellowstone National Park: Integrating molecular surveys, geochemical processes and isolation of novel Fe-active microorganisms

    Directory of Open Access Journals (Sweden)

    Mark A Kozubal

    2012-03-01

    Full Text Available Geochemical, molecular, and physiological analyses of microbial isolates were combined to study the geomicrobiology of acidic iron oxide mats in Yellowstone National Park (YNP. Nineteen sampling locations from 11 geothermal springs were studied ranging in temperature from 53 to 84 °C and pH 2.4 to 3.6. All iron-oxide mats exhibited high diversity of crenarchaeal sequences from the Sulfolobales, Thermoproteales, and Desulfurococcales. The predominant Sulfolobales sequences were highly similar to Metallosphaera yellowstonensis str. MK1, previously isolated from one of these sites. Other groups of archaea were consistently associated with different types of iron oxide mats, including undescribed members of the phyla Thaumarchaeota and Euryarchaeota. Bacterial sequences were dominated by relatives of Hydrogenobaculum spp. above 65-70 °C, but increased in diversity below 60 °C. Cultivation of relevant iron-oxidizing and iron-reducing microbial isolates included Sulfolobus str. MK3, Sulfobacillus str. MK2, Acidicaldus str. MK6, and a new candidate genus in the Sulfolobales referred to as Sulfolobales str. MK5. Strains MK3 and MK5 are capable of oxidizing ferrous iron autotrophically, while strain MK2 oxidizes iron mixotrophically. Similar rates of iron oxidation were observed for M. yellowstonensis str. MK1 and Sulfolobales str. MK5 cultures, and these rates are close to those measured in situ. Biomineralized phases of ferric iron varied among cultures and field sites, and included ferric oxyhydroxides, K-jarosite, goethite, hematite, and scorodite depending on geochemical conditions. Strains MK5 and MK6 are capable of reducing ferric iron under anaerobic conditions with complex carbon sources. The combination of geochemical and molecular data as well as physiological observations of isolates suggests that the community structure of acidic Fe mats is linked with Fe cycling across temperatures ranging from 53 to 88 oC.

  5. Removal of FePO4 and Fe3(PO4)2 crystals on the surface of passive fillers in Fe0/GAC reactor using the acclimated bacteria

    International Nuclear Information System (INIS)

    Lai, Bo; Zhou, Yuexi; Yang, Ping; Wang, Juling; Yang, Jinghui; Li, Huiqiang

    2012-01-01

    Highlights: ► Fe 3 (PO 4 ) 2 and FePO 4 crystals would weaken treatment efficiency of Fe 0 /GAC reactor. ► Fe 3 (PO 4 ) 2 and FePO 4 crystals could be removed by the acclimated bacteria. ► FeS and sulfur in the passive film would be removed by the sulfur-oxidizing bacteria. ► Develop a cost-effective bio-regeneration technology for the passive fillers. - Abstract: As past studies presented, there is obvious defect that the fillers in the Fe 0 /GAC reactor begin to be passive after about 60 d continuous running, although the complicated, toxic and refractory ABS resin wastewater can be pretreated efficiently by the Fe 0 /GAC reactor. During the process, the Fe 3 (PO 4 ) 2 and FePO 4 crystals with high density in the passive film are formed by the reaction between PO 4 3− and Fe 2+ /Fe 3+ . Meanwhile, they obstruct the formation of macroscopic galvanic cells between Fe 0 and GAC, which will lower the wastewater treatment efficiency of Fe 0 /GAC reactor. In this study, in order to remove the Fe 3 (PO 4 ) 2 and FePO 4 crystals on the surface of the passive fillers, the bacteria were acclimated in the passive Fe 0 /GAC reactor. According to the results, it can be concluded that the Fe 3 (PO 4 ) 2 and FePO 4 crystals with high density in the passive film could be decomposed or removed by the joint action between the typical propionic acid type fermentation bacteria and sulfate reducing bacteria (SRB), whereas the PO 4 3− ions from the decomposition of the Fe 3 (PO 4 ) 2 and FePO 4 crystals were released into aqueous solution which would be discharged from the passive Fe 0 /GAC reactor. Furthermore, the remained FeS and sulfur (S) in the passive film also can be decomposed or removed easily by the oxidation of the sulfur-oxidizing bacteria. This study provides some theoretical references for the further study of a cost-effective bio-regeneration technology to solve the passive problems of the fillers in the zero-valent iron (ZVI) or Fe 0 /GAC reactor.

  6. Optimization of Fe2+ supplement in anaerobic digestion accounting for the Fe-bioavailability.

    Science.gov (United States)

    Cai, Yafan; Zhao, Xiaoling; Zhao, Yubin; Wang, Hongliang; Yuan, Xufeng; Zhu, Wanbin; Cui, Zongjun; Wang, Xiaofen

    2018-02-01

    Fe is widely used as an additive in anaerobic digestion, but its bioavailability and the mechanism by which it enhances digestion are unclear. In this study, sequential extraction was used to measure Fe bioavailability, while biochemical parameters, kinetics model and Q-PCR (fluorescence quantitative PCR) were used to explore its mechanism of stimulation. The results showed that sequential extraction is a suitable method to assess the anaerobic system bioavailability of Fe, which is low and fluctuates to a limited extent (1.7 to -3.1wt%), indicating that it would be easy for Fe levels to be insufficient. Methane yield increased when the added Fe 2+ was 10-500mg/L. Appropriate amounts of Fe 2+ accelerated the decomposition of rice straw and facilitated methanogen metabolism, thereby improving reactor performance. The modified Gompertz model better fitted the results than the first-order kinetic model. Feasibility analysis showed that addition of Fe 2+ at ≤50mg/L was suitable. Copyright © 2017. Published by Elsevier Ltd.

  7. Chemical consequences of the nuclear reactions 58Fe(n,γ)59Fe and 57Co(EC)57Fe in soluble Prussian Blue

    DEFF Research Database (Denmark)

    Fenger, Jes; Maddock, A. G.; Siekierska, K. E.

    1970-01-01

    KFe[Fe(CN)6],H2O was prepared with 58Fe in either the cation or the complex, and both samples were neutron-irradiated and analysed for free and complexed 59Fe. Parallel experiments were performed on K4[Fe(CN)6],3H2O. In Prussian Blue the retention in the hexacyano-complex is ca. 5% and can be inc...

  8. Adsorption of antimony onto iron oxyhydroxides: Adsorption behavior and surface structure

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Xuejun; Wu, Zhijun [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19 Xinjiekouwai Street, Beijing 100875 (China); He, Mengchang, E-mail: hemc@bnu.edu.cn [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19 Xinjiekouwai Street, Beijing 100875 (China); Meng, Xiaoguang [Center for Environmental Systems, Stevens Institute of Technology, Hoboken, NJ 07030 (United States); Jin, Xin [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19 Xinjiekouwai Street, Beijing 100875 (China); Qiu, Nan; Zhang, Jing [Beijing Synchrotron Radiation Facility (BSRF), Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

    2014-07-15

    Graphical abstract: - Highlights: • Antimony adsorption depended on the Sb species, pH, and the type of iron oxides. • Sb(V) adsorption favored at acidic pH, Sb(III) adsorption optimized in wider pH. • Antimony was adsorbed onto the iron oxides by the inner-sphere surface complex. • Bidentate mononuclear ({sup 2}E) was the dominant form of Sb incorporated into HFO. • XAFS and XPS indicated Sb(III) adsorbed was slowly oxidized to Sb(V). - Abstract: Antimony is detected in soil and water with elevated concentration due to a variety of industrial applications and mining activities. Though antimony is classified as a pollutant of priority interest by the United States Environmental Protection Agency (USEPA) and Europe Union (EU), very little is known about its environmental behavior and adsorption mechanism. In this study, the adsorption behaviors and surface structure of antimony (III/V) on iron oxides were investigated using batch adsorption techniques, surface complexation modeling (SCM), X-ray photon spectroscopy (XPS) and extended X-ray absorption fine structure spectroscopy (EXAFS). The adsorption isotherms and edges indicated that the affinity of Sb(V) and Sb(III) toward the iron oxides depended on the Sb species, solution pH, and the characteristics of iron oxides. Sb(V) adsorption was favored at acidic pH and decreased dramatically with increasing pH, while Sb(III) adsorption was constant over a broad pH range. When pH is higher than 7, Sb(III) adsorption by goethite and hydrous ferric oxide (HFO) was greater than Sb(V). EXAFS analysis indicated that the majority of Sb(III), either adsorbed onto HFO or co-precipitated by FeCl{sub 3}, was oxidized into Sb(V) probably due to the involvement of O{sub 2} in the long duration of sample preservation. Only one Sb–Fe subshell was filtered in the EXAFS spectra of antimony adsorption onto HFO, with the coordination number of 1.0–1.9 attributed to bidentate mononuclear edge-sharing ({sup 2}E) between Sb and

  9. Perpendicular exchange coupling effects in ferrimagnetic TbFeCo/GdFeCo hard/soft structures

    Science.gov (United States)

    Wang, Ke; Wang, Yahong; Ling, Fujin; Xu, Zhan

    2018-04-01

    Bilayers consisting of magnetically hard TbFeCo and soft GdFeCo alloy were fabricated. Exchange-spring and sharp switching in a step-by-step fashion were observed in the TbFeCo/GdFeCo hard/soft bilayers with increasing GdFeCo thickness. A perpendicular exchange bias field of several hundred Oersteds is observed from the shift of minor loops pinned by TbFeCo layer. The perpendicular exchange energy is derived to be in the range of 0.18-0.30 erg/cm2. The exchange energy is shown to increase with the thickness of GdFeCo layer in the bilayers, which can be attributed to the enhanced perpendicular anisotropy of GdFeCo layer in our experimental range.

  10. The distribution of phosphorus in Popes Creek, VA, and in the Pocomoke River, MD: Two watersheds with different land management practices in the Chesapeake Bay Basin

    Science.gov (United States)

    Simon, N.S.; Bricker, O.P.; Newell, W.; McCoy, J.; Morawe, R.

    2005-01-01

    This paper compares phosphorus (P) concentrations in sediments from two watersheds, one with, and one without, intensive animal agriculture. The watersheds are in the coastal plain of the Chesapeake Bay and have similar physiographic characteristics. Agriculture in the Pocomoke River, MD, watershed supplied 2.7 percent of all broiler chickens produced in the USA in 1997. Poultry litter is an abundant, local source of manure for crops. Broiler chickens are not produced in the Popes Creek, VA, watershed and poultry manure is, therefore, not a major source of fertilizer. The largest concentrations of P in sediment samples are found in floodplain and main-stem bottom sediment in both watersheds. Concentrations of total P and P extracted with 1N HCl are significantly larger in main-stem bottom sediments from the Pocomoke River than in main-stem bottom sediments from Popes Creek. Larger concentrations of P are associated with what are potentially redox sensitive iron oxyhydroxides in sediment samples from the Pocomoke River watershed than are associated with what are potentially redox sensitive iron oxyhydroxides in sediment samples from the Popes Creek watershed. Data for P and iron (Fe) concentrations in sediments from the Popes Creek watershed provide a numerical framework (baseline) with which to compare P and Fe concentrations in sediment from the Pocomoke River watershed. ?? Springer 2005.

  11. Trace metal enrichments in core sediments in Muthupet mangroves, SE coast of India: Application of acid leachable technique

    International Nuclear Information System (INIS)

    Janaki-Raman, D.; Jonathan, M.P.; Srinivasalu, S.; Armstrong-Altrin, J.S.; Mohan, S.P.; Ram-Mohan, V.

    2007-01-01

    Core sediments from Mullipallam Creek of Muthupet mangroves on the southeast coast of India were analyzed for texture, CaCO 3 , organic carbon, sulfur and acid leachable trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd). Textural analysis reveals a predominance of mud while CaCO 3 indicates dissolution in the upper half of the core, and reprecipitation of carbonates in reduction zones. Trace metals are diagenetically modified and anthropogenic processes control Pb and, to some extent, Ni, Zn and Fe. A distinct event is identified at 90 cm suggesting a change in deposition. Strong relationship of trace metals with Fe indicates that they are associated with Fe-oxyhydroxides. The role of carbonates in absorbing trace metals is evident from their positive relationship with trace metals. Comparison of acid leachable trace metals indicates increase in concentrations in the study area and the sediments act as a sink for trace metals contributed from multiple sources. - Natural and anthropogenic trace metals afeecting mangrove sediments

  12. Assessment of acid leachable trace metals in sediment cores from River Uppanar, Cuddalore, Southeast coast of India

    International Nuclear Information System (INIS)

    Ayyamperumal, T.; Jonathan, M.P.; Srinivasalu, S.; Armstrong-Altrin, J.S.; Ram-Mohan, V.

    2006-01-01

    An acid leachable technique is employed in core samples (C1, C2 and C3) to develop a baseline data on the sediment quality for trace metals of River Uppanar, Cuddalore, southeast coast of India. Acid leachable metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd) indicate peak values at the sulphidic phase and enrichment of metals in the surface layers are due to the anthropogenic activities. Association of trace metals with Fe, Mn indicates their adsorption onto Fe-Mn oxyhydroxides and their correlation with S indicate that they are precipitated as metal sulphides. Factor analysis identified three possible types of geochemical associations and the supremacy of trace metals along with Fe, Mn, S and mud supports their geochemical associations. Factor analysis also signifies that anthropogenic activities have affected both the estuarine and fresh water regions of River Uppanar. - Both natural and anthropogenic factors are affecting metals in sediments

  13. Exchange-coupled Fe3O4/CoFe2O4 nanoparticles for advanced magnetic hyperthermia

    Science.gov (United States)

    Glassell, M.; Robles, J.; Das, R.; Phan, M. H.; Srikanth, H.

    Iron oxide nanoparticles especially Fe3O4, γ-Fe2O3 have been extensively studied for magnetic hyperthermia because of their tunable magnetic properties and stable suspension in superparamagnetic regime. However, their relatively low heating capacity hindered practical application. Recently, a large improvement in heating efficiency has been reported in exchange-coupled nanoparticles with exchange coupling between soft and hard magnetic phases. Here, we systematically studied the effect of core and shell size on the heating efficiency of the Fe3O4/CoFe2O4 core/shell nanoparticles. The nanoparticles were synthesized using thermal decomposition of organometallic precursors. Transmission electron microscopy (TEM) showed formation of spherical shaped Fe3O4 and Fe3O-/CoFe2O4 nanoparticles. Magnetic measurements showed high magnetization (≅70 emu/g) and superparamagnetic behavior for the nanoparticles at room temperature. Magnetic hyperthermia results showed a large increase in specific absorption rate (SAR) for 8nm Fe3O4/CoFe2O4 compared to Fe3O4 nanoparticles of the same size. The heating efficiency of the Fe3O4/CoFe2O4 with 1 nm CoFe2O4 (shell) increased from 207 to 220 W/g (for 800 Oe) with increase in core size from 6 to 8 nm. The heating efficiency of the Fe3O4/CoFe2O4 with 2 nm CoFe2O4 (shell) and core size of 8 nm increased from 220 to 460 W/g (for 800 Oe). These exchange-coupled Fe3O4/CoFe2O4 core/shell nanoparticles can be a good candidate for advanced hyperthermia application.

  14. [{sup 18}F]FE-SUPPY and [{sup 18}F]FE-SUPPY:2 - metabolic considerations

    Energy Technology Data Exchange (ETDEWEB)

    Haeusler, Daniela [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Pharmaceutical Technology and Biopharmaceutics, Univ. of Vienna, A-1090 Vienna (Austria); Nics, Lukas [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Nutritional Sciences, Univ. of Vienna, A-1090 Vienna (Austria); Mien, Leonhard-Key [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Pharmaceutical Technology and Biopharmaceutics, Univ. of Vienna, A-1090 Vienna (Austria); Ungersboeck, Johanna [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Inorganic Chemistry, Univ. of Vienna, A-1090 Vienna (Austria); Lanzenberger, Rupert R. [Dept. of Psychiatry and Psychotherapy, Medical Univ. of Vienna, A-1090 Vienna (Austria); Shanab, Karem [Dept. of Drug and Natural Product Synthesis, Univ. of Vienna, A-1090 Vienna (Austria); Sindelar, Karoline M. [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Viernstein, Helmut [Dept. of Pharmaceutical Technology and Biopharmaceutics, Univ. of Vienna, A-1090 Vienna (Austria); Wagner, Karl-Heinz [Dept. of Nutritional Sciences, Univ. of Vienna, A-1090 Vienna (Austria); Dudczak, Robert; Kletter, Kurt [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Wadsak, Wolfgang [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Inorganic Chemistry, Univ. of Vienna, A-1090 Vienna (Austria); Mitterhauser, Markus [Dept. of Nuclear Medicine, Medical Univ. of Vienna, A-1090 Vienna (Austria); Dept. of Pharmaceutical Technology and Biopharmaceutics, Univ. of Vienna, A-1090 Vienna (Austria); Hospital Pharmacy of the General Hospital of Vienna, A-1090 Vienna (Austria)], E-mail: markus.mitterhauser@meduniwien.ac.at

    2010-05-15

    Introduction: Recently, [{sup 18}F]FE-SUPPY and [{sup 18}F]FE-SUPPY:2 were introduced as the first positron emission tomography (PET) tracers for the adenosine A{sub 3} receptor. Thus, aim of the present study was the metabolic characterization of the two adenosine A{sub 3} receptor PET tracers. Methods: In vitro carboxylesterase (CES) experiments were conducted using incubation mixtures containing different concentrations of the two substrates, porcine CES and phosphate-buffered saline. Enzymatic reactions were stopped by adding acetonitrile/methanol (10:1) after various time points and analyzed by a high-performance liquid chromatography (HPLC) standard protocol. In vivo experiments were conducted in male wild-type rats; tracers were injected through a tail vein. Rats were sacrificed after various time points (n=3), and blood and brain samples were collected. Sample cleanup was performed by an HPLC standard protocol. Results: The rate of enzymatic hydrolysis by CES demonstrated Michaelis-Menten constants in a micromolar range (FE-SUPPY, 20.15 {mu}M, and FE-SUPPY:2, 13.11 {mu}M) and limiting velocities of 0.035 and 0.015 {mu}M/min for FE-SUPPY and FE-SUPPY:2, respectively. Degree of metabolism in blood showed the following: 15 min pi 47.7% of [{sup 18}F]FE-SUPPY was intact compared to 33.1% of [{sup 18}F]FE-SUPPY:2; 30 min pi 30.3% intact [{sup 18}F]FE-SUPPY was found compared to 15.6% [{sup 18}F]FE-SUPPY:2. In brain, [{sup 18}F]FE-SUPPY:2 formed an early hydrophilic metabolite, whereas metabolism of [{sup 18}F]FE-SUPPY was not observed before 30 min pi Conclusion: Knowing that metabolism in rats is several times faster than in human, we conclude that [{sup 18}F]FE-SUPPY should be stable for the typical time span of a clinical investigation. As a consequence, from a metabolic point of view, one would tend to decide in favor of [{sup 18}F]FE-SUPPY.

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

    Directory of Open Access Journals (Sweden)

    Jennyfer eMIOT

    2015-09-01

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

  16. Cysteine as a ligand platform in the biosynthesis of the FeFe hydrogenase H cluster.

    Science.gov (United States)

    Suess, Daniel L M; Bürstel, Ingmar; De La Paz, Liliana; Kuchenreuther, Jon M; Pham, Cindy C; Cramer, Stephen P; Swartz, James R; Britt, R David

    2015-09-15

    Hydrogenases catalyze the redox interconversion of protons and H2, an important reaction for a number of metabolic processes and for solar fuel production. In FeFe hydrogenases, catalysis occurs at the H cluster, a metallocofactor comprising a [4Fe-4S]H subcluster coupled to a [2Fe]H subcluster bound by CO, CN(-), and azadithiolate ligands. The [2Fe]H subcluster is assembled by the maturases HydE, HydF, and HydG. HydG is a member of the radical S-adenosyl-L-methionine family of enzymes that transforms Fe and L-tyrosine into an [Fe(CO)2(CN)] synthon that is incorporated into the H cluster. Although it is thought that the site of synthon formation in HydG is the "dangler" Fe of a [5Fe] cluster, many mechanistic aspects of this chemistry remain unresolved including the full ligand set of the synthon, how the dangler Fe initially binds to HydG, and how the synthon is released at the end of the reaction. To address these questions, we herein show that L-cysteine (Cys) binds the auxiliary [4Fe-4S] cluster of HydG and further chelates the dangler Fe. We also demonstrate that a [4Fe-4S]aux[CN] species is generated during HydG catalysis, a process that entails the loss of Cys and the [Fe(CO)2(CN)] fragment; on this basis, we suggest that Cys likely completes the coordination sphere of the synthon. Thus, through spectroscopic analysis of HydG before and after the synthon is formed, we conclude that Cys serves as the ligand platform on which the synthon is built and plays a role in both Fe(2+) binding and synthon release.

  17. Seasonal water quality variations in a river affected by acid mine drainage: the Odiel River (South West Spain)

    Energy Technology Data Exchange (ETDEWEB)

    Olias, M.; Nieto, J.M.; Sarmiento, A.M.; Ceron, J.C.; Canovas, C.R

    2004-10-15

    This paper intends to analyse seasonal variations of the quality of the water of the Odiel River. This river, together with the Tinto River, drains the Iberian Pyrite Belt (IPB), a region containing an abundance of massive sulphide deposits. Because of mining activity dating back to prehistoric times, these two rivers are heavily contaminated. The Odiel and Tinto Rivers drain into a shared estuary known as the Ria of Huelva. This work studies dissolved contaminant data in water of the Odiel River collected by various organisations, between October 1980 and October 2002, close to the rivers entry into the estuary. Flow data for this location were also obtained. The most abundant metals in the water, in order of abundance, are zinc (Zn), iron (Fe), manganese (Mn) and copper (Cu). Arsenic (As), cadmium (Cd) and lead (Pb) are also present but in much lower quantities. The quality of the river water is linked to precipitation; the maximum sulphate, Fe, Zn, Mn, Cd and Pb concentrations occur during the autumn rains, which dissolve the Fe hydroxysulphates that were precipitated during the summer months. In winter, the intense rains cause an increase in the river flow, producing a dilution of the contaminants and a slight increase in the pH. During spring and summer, the sulphate and metal concentration (except Fe) recover and once again increase. The Fe concentration pattern displays a low value during summer due to increased precipitation of ferric oxyhydroxides. The arsenic concentration displays a different evolution, with maximum values in winter, and minimum in spring and summer as they are strongly adsorbed and/or coprecipitated by the ferric oxyhydroxides. Mn and sulphates are the most conservative species in the water. Relative to sulphate, Mn, Zn and Cd, copper displays greater values in winter and lower ones in summer, probably due to its coprecipitation with hydroxysulphates during the spring and summer months. Cd and Zn also appear to be affected by the same

  18. Resonant Ni and Fe KLL Auger spectra photoexcited from NiFe alloys

    International Nuclear Information System (INIS)

    Koever, L.; Cserny, I.; Berenyi, Z.; Egri, S.; Novak, M.

    2005-01-01

    Complete text of publication follows. KLL Auger spectra of 3d transition metal atoms in solid environment, measured using high energy resolution, give an insight into the details of the local electronic structure surrounding the particular atoms emitting the signal Auger electrons. Fine tuning the energy of the exciting monochromatic photons across the K-absorption edge, features characteristic to resonant phenomena can be identified in the spectra. The shapes of the resonantly photoexcited KLL Auger spectra induced from 3d transition metals and alloys are well interpreted by the single step model of the Auger process, based on the resonant scattering theory. The peak shapes are strongly influenced by the 4p partial density of unoccupied electronic states around the excited atom. High energy resolution studies of KLL Auger spectra of 3d transition metals using laboratory X-ray sources, however, request very demanding experiments and yield spectra of limited statistical quality making the evaluation of the fine details in the spectra difficult. The Tunable High Energy XPS (THE- XPS) instrument at BW2 offers optimum photon x and energy resolution for spectroscopy of deep core Auger transitions. For the present measurements high purity polycrystalline Ni and Fe sheets as well as NiFe alloy samples of different compositions (Ni 80 Fe 20 , Ni 50 Fe 50 , Ni 20 Fe 80 ) were used. The surfaces of the samples were cleaned by in-situ argon ion sputtering. The measurements of the Ni and Fe KL 23 L 23 Auger spectra of the metal and alloy samples were performed with the THE-XPS instrument using high electron energy resolution (0.2 eV). In Fig.1, the measured Fe KL 23 L 23 spectrum, photoexcited at the Fe K absorption edge from Fe metal, is compared with the respective spectrum excited from a Ni 50 Fe 50 alloy. A significant broadening of the 1 D 2 peak and an enhancement of the spectral intensity at the low energy loss part of this peak observed in the alloy sample, while the

  19. Electrical resistivity surface for FeO-Fe2O3-P2O5 glasses

    Science.gov (United States)

    Vaughan, J. G.; Kinser, D. L.

    1975-01-01

    The dc electrical properties and microstructure of x(FeO-Fe2O3)-(100-x)P2O5 glasses were investigated up to a maximum of x = 75 mol %. Results indicate that, in general, the minimum resistivity of the glass does not occur at equal Fe(2+) and Fe(3+) concentrations, although for the special case where x = 55 mol % the minimum does occur at Fe(2+)/Fe total = 0.5, as reported by other investigators. Evidence presented shows that the position of the minimum resistivity is a function of total iron content. The minimum shifts to glasses richer in Fe(2+) at higher total iron concentrations.

  20. Role of PO4 tetrahedron in LiFePO4 and FePO4 system.

    Science.gov (United States)

    Zeng, Yuewu

    2015-06-01

    Using high resolution transmission electron microscopy with image simulation and Fourier analysis, the Li1- x FePO4 (x < 0.01), Li1- x FePO4 (x ∼ 0.5), and FePO4 particles, prepared by charging or discharging the 053048 electrochemical cells (thickness: 5 mm, width: 30 mm, height: 48 mm) and dismantled inside an Ar-filled dry box, were investigated. The high resolution images reveal: (1) the solid solution of Li1- x FePO4 (x < 0.01) contains some missing Li ions leading PO4 group distorted around M1 tunnel of the unit cell; (2) the texture of the particles of Li1- x FePO4 (x ∼0.5) has homogeneously distributed compositional domains of LiFePO4 and FePO4 resulting from spinodal decomposition which promote Li ion easily getting into the particle due to uphill diffusion, (3) the particles of FePO4 formed in charging have heavily distorted lattice and contain some isolated LiFePO4 , (4) interface between LiFePO4 and FePO4 and between amorphous and crystal region provides the lattice distortion of small polarons. © 2015 Wiley Periodicals, Inc.

  1. Microstructure, magnetic and Moessbauer studies on spark-plasma sintered Sm-Co-Fe/Fe(Co) nanocomposite magnets

    Energy Technology Data Exchange (ETDEWEB)

    Rao, N V Rama; Saravanan, P; Gopalan, R; Raja, M Manivel; Rao, D V Sreedhara; Chandrasekaran, V [Defence Metallurgical Research Laboratory, Hyderabad-500 058 (India); Sivaprahasam, D [International Advanced Research Centre for Powder Metallurgy and New Materials Hyderabad-500 005 (India); Ranganathan, R [Saha Institute of Nuclear Physics, Kolkata-700 064 (India)], E-mail: rg_gopy@yahoo.com

    2008-03-21

    Nanocomposite powders comprising Sm-Co-Fe intermetallic phases and Fe(Co) were synthesized by high-energy ball milling and were consolidated into bulk magnets by the spark-plasma sintering (SPS) technique. While the microstructure of the SPS samples was characterized by transmission electron microscopy (TEM), the solubility of Fe in different phases was investigated using Moessbauer spectroscopy. TEM studies revealed that the spark-plasma sintered sample has Sm(Co,Fe){sub 5} as a major phase with Sm{sub 2}(Co,Fe){sub 17}, Sm(Co,Fe){sub 2} and Fe(Co) as secondary phases. The size of the nanocrystalline grains of all these phases was found to be in the range 50-100 nm. The Moessbauer spectra of the as-milled powders exhibited two different subspectra: a sextet corresponding to the Fe phase and a broad sextet associated with the Fe(Co) phase; while that of the SPS sample showed four different subspectra: a sextet corresponding to Fe and other three sextets corresponding to the Fe(Co), Sm(Co,Fe){sub 5} and Sm{sub 2}(Co,Fe){sub 17} phases; these results are in accordance with the TEM observation. Recoil magnetization and reversible susceptibility measurements revealed magnetically single phase behaviour of the SPS magnets.

  2. Exchange bias in sputtered FeNi/FeMn systems: Effect of short low-temperature heat treatments

    Energy Technology Data Exchange (ETDEWEB)

    Savin, Peter, E-mail: peter.savin@urfu.ru [Department of Magnetism and Magnetic Nanomaterials, Laboratory of Magnetic Sensors, Ural Federal University, 620002 Ekaterinburg (Russian Federation); Guzmán, Jorge [Instituto de Ciencia de Materiales de Madrid-CSIC, 28049 Madrid (Spain); Lepalovskij, Vladimir [Department of Magnetism and Magnetic Nanomaterials, Laboratory of Magnetic Sensors, Ural Federal University, 620002 Ekaterinburg (Russian Federation); Svalov, Andrey; Kurlyandskaya, Galina [Department of Magnetism and Magnetic Nanomaterials, Laboratory of Magnetic Sensors, Ural Federal University, 620002 Ekaterinburg (Russian Federation); Departamento de Electricidad y Electrónica, Universidad del País Vasco (UPV/EHU), 48940 Leioa, Vizcaya (Spain); Asenjo, Agustina [Instituto de Ciencia de Materiales de Madrid-CSIC, 28049 Madrid (Spain); Vas’kovskiy, Vladimir [Department of Magnetism and Magnetic Nanomaterials, Laboratory of Magnetic Sensors, Ural Federal University, 620002 Ekaterinburg (Russian Federation); Vazquez, Manuel [Department of Magnetism and Magnetic Nanomaterials, Laboratory of Magnetic Sensors, Ural Federal University, 620002 Ekaterinburg (Russian Federation); Instituto de Ciencia de Materiales de Madrid-CSIC, 28049 Madrid (Spain)

    2016-03-15

    Short (5 min) post-deposition thermal treatments under magnetic field at low temperature (up to 200 °C) performed in exchange-coupled FeNi(40 nm)/FeMn(20 nm) bilayer thin films prepared by magnetron sputtering are shown to be effective to significantly modify their exchange field (from around 40 Oe down to 27 Oe) between FeNi and FeMn layers. A similar exchange field decrease was observed for the first deposited FeNi layer of the FeNi(40 nm)/FeMn(20 nm)/FeNi(40 nm) trilayer films after the same thermal treatments. The exchange field value for the second FeNi layer was not substantially changed. The X-ray diffraction patterns indicates that such a heat treatment has no effect on the grain size and crystalline texture of the films, while atomic force microscope studies reveal an increase of the surface roughness after the treatment which is more noticeable in the case of the trilayer film. Analysis of the experimental results leads us to conclude that the variations of the exchange field after heat treatment are likely caused by a modification of interfacial roughness and/or interfacial magnetic structure, but unlikely by the changes in the microstructure and/or changes of composition of the antiferromagnetic FeMn layer. - Highlights: • FeNi/FeMn bilayers and FeNi/FeMn/FeNi trilayers were prepared by magnetron sputtering. • Post-deposition heat treatments at the temperatures below 200 °C during 5 min were made. • Annealing reduces the exchange field for the first FeNi layer in trilayers. • The exchange field value for the second FeNi layer was not substantially changed. • Exchange field changes are most likely caused by a modification of interface roughness.

  3. Fe/V and Fe/Co (0 0 1) superlattices: growth, anisotropy, magnetisation and magnetoresistance

    International Nuclear Information System (INIS)

    Nordblad, P.; Broddefalk, A.; Mathieu, R.; Blomqvist, P.; Eriksson, O.; Waeppling, R.

    2003-01-01

    Some physical properties of BCC Fe/V and Fe/Co (0 0 1) superlattices are reviewed. The dependence of the magnetic anisotropy on the in-plane strain introduced by the lattice mismatch between Fe and V is measured and compared to a theoretical derivation. The dependence of the magnetic anisotropy (and saturation magnetisation) on the layer thickness ratio Fe/Co is measured and a value for the anisotropy of BCC Co is derived from extrapolation. The interlayer exchange coupling of Fe/V superlattices is studied as a function of the V layer thickness (constant Fe thickness) and layer thickness of Fe (constant V thickness). A region of antiferromagnetic coupling and GMR is found for V thicknesses 12-14 monolayers. However, surprisingly, a 'cutoff' of the antiferromagnetic coupling and GMR is found when the iron layer thickness exceeds about 10 monolayers

  4. High Temperature Magnetic Properties of Indirect Exchange Spring FePt/M(Cu,C/Fe Trilayer Thin Films

    Directory of Open Access Journals (Sweden)

    Anabil Gayen

    2013-01-01

    Full Text Available We report the investigation of temperature dependent magnetic properties of FePt and FePt(30/M(Cu,C/Fe(5 trilayer thin films prepared by using magnetron sputtering technique at ambient temperature and postannealed at different temperatures. L10 ordering, hard magnetic properties, and thermal stability of FePt films are improved with increasing postannealing temperature. In FePt/M/Fe trilayer, the formation of interlayer exchange coupling between magnetic layers depends on interlayer materials and interface morphology. In FePt/C/Fe trilayer, when the C interlayer thickness was about 0.5 nm, a strong interlayer exchange coupling between hard and soft layers was achieved, and saturation magnetization was enhanced considerably after using interlayer exchange coupling with Fe. In addition, incoherent magnetization reversal process observed in FePt/Fe films changes into coherent switching process in FePt/C/Fe films giving rise to a single hysteresis loop. High temperature magnetic studies up to 573 K reveal that the effective reduction in the coercivity decreases largely from 34 Oe/K for FePt/Fe film to 13 Oe/K for FePt/C(0.5/Fe film demonstrating that the interlayer exchange coupling seems to be a promising approach to improve the stability of hard magnetic properties at high temperatures, which is suitable for high-performance magnets and thermally assisted magnetic recording media.

  5. Ferromagnetic resonance on oxideless magnetic Fe and FeRh nanoparticles

    International Nuclear Information System (INIS)

    Trunova, Anastasia

    2009-01-01

    This work is dedicated to investigations of structural and magnetic properties of the colloidal Fe/Fe x O y nanocubes (13 nm) and the Fe x Rh 100-x core/shell nanoparticles (2 nm). As compared with other works, where the measurements on oxidized nanoparticles were carried out, we additionally performed investigations on nanoparticles in an oxide free state. In order to make the measurements on oxide free particles possible, oxygen- and hydrogenplasma was used to remove the ligands and reduce the oxide shell of the Fe nanocubes. The oxide free Fe nanocubes were covered with a Ag/Pt protective coating to prevent them from new oxidation. This method allowed carrying out the magnetic measurements on oxide free Fe nanocubes. Micromagnetic simulations as well as simulations of the high frequency susceptibility were used for the data analysing. It was found that both the g-factor g=2.09±0.01 and the anisotropy constant K 4 =(4.8±0.5).10 4 J/m 3 coincide with that of bulk iron. However, the saturation magnetization M S (5 K)=(1.2±0.12).10 6 A/m differs from the bulk value by 30%. The reduction by 30% compared to the bulk value in the case of nanoparticles may be caused by the following possible reasons: a) the presence of inner oxide layer (approx. 10 at.%) that cannot be reduced; b) the anti-parallel order between magnetic moments of iron core and magnetic moments of antiferomagnetic iron oxide; c) some structural changes of the surface after plasma treatment. The obtained damping parameter α=0.03±0.005 is ten times larger than that of the Fe layers as it is known for nanoparticles systems in general. The core/shell Fe x Rh 100-x nanoparticles (x=80,50) were produced under Ar-atmosphere and were sealed into a quartz tube to prevent oxidation. The analysis of g-factors shows that the value for the FePh nanoparticles with Fe-rich core is larger (g=2.08±0.01) than that for the nanoparticles with Rh-rich core and coincides within error bars with the g-factor of bulk

  6. Effect of Iron Fe (II and Fe (III in a Binary System Evaluated Bioluminescent Method

    Directory of Open Access Journals (Sweden)

    Elena Sorokina

    2013-01-01

    Full Text Available The effect of iron ions Fe2+ and Fe3+ on the bioluminescent recombinant strain of Escherichia coli in a single-component and binary system. Found that for the bacteria E. coli Fe3+ ions are more toxic than Fe2+. Under the combined effect of iron toxicity increases, the percentage of luminescence quenching increases, but the value is much less than the sum of the indicator for the Fe2+ and Fe3+. The biological effect of insertion of iron is not proportional to their content in the mixture.

  7. Magnetic structure of molecular magnet Fe[Fe(CN) 6

    Indian Academy of Sciences (India)

    We have studied the magnetic structure of Fe[Fe(CN)6]·4H2O, prepared by precipitation method, using neutron diffraction technique. Temperature dependent DC magnetization study down to 4.2 K shows that the compound undergoes from a high temperature disordered (paramagnetic) to an ordered magnetic phase ...

  8. 57Fe Moessbauer and magnetization study of the Th7Fe3 and the hydride Th7Fe3H/sub n/

    International Nuclear Information System (INIS)

    Viccaro, P.J.; Shenoy, G.K.; Dunlap, B.D.; Westlake, D.G.; Malik, S.K.; Wallace, W.E.

    1978-01-01

    Th 7 Fe 3 is known to be a Pauli paramagnet and to undergo a superconducting transition at 1.86K. Its hydride Th 7 Fe 3 H/sub n/ is shown to possess magnetic ordering. The 57 Fe saturated hyperfine field in the hydride is estimated to be aproximately 20kG. A positive isomer shift of 0.30 +- 0.02 mm/s at 300 K relative to Th 7 Fe 3 would be consistent with an increase in d-like electrons on Fe. Preliminary magnetization results indicate a magnetic moment of about 0.5 μ/sub B/ for the hydride and a transition temperature near 300 K

  9. Kinetics and mechanism of diclofenac removal using ferrate(VI): roles of Fe3+, Fe2+, and Mn2.

    Science.gov (United States)

    Zhao, Junfeng; Wang, Qun; Fu, Yongsheng; Peng, Bo; Zhou, Gaofeng

    2018-06-01

    In this study, the effect of Fe 3+ , Fe 2+ , and Mn 2+ dose, solution pH, reaction temperature, background water matrix (i.e., inorganic anions, cations, and natural organic matters (NOM)), and the kinetics and mechanism for the reaction system of Fe(VI)/Fe 3+ , Fe(VI)/Fe 2+ , and Fe(VI)/Mn 2+ were investigated systematically. Traces of Fe 3+ , Fe 2+ , and Mn 2+ promoted the DCF removal by Fe(VI) significantly. The pseudo-first-order rate constant (k obs ) of DCF increased with decreasing pH (9-6) and increasing temperature (10-30 °C) due to the gradually reduced stability and enhanced reactivity of Fe(VI). Cu 2+ and Zn 2+ ions evidently improved the DCF removal, while CO 3 2- restrained it. Besides, SO 4 2- , Cl - , NO 3 - , Mg 2+ , and Ca 2+ almost had no influence on the degradation of DCF by Fe(VI)/Fe 3+ , Fe(VI)/Fe 2+ , and Fe(VI)/Mn 2+ within the tested concentration. The addition of 5 or 20 mg L -1 NOM decreased the removal efficiency of DCF. Moreover, Fe 2 O 3 and Fe(OH) 3 , the by-products of Fe(VI), slightly inhibited the DCF removal, while α-FeOOH, another by-product of Fe(VI), showed no influence at pH 7. In addition, MnO 2 and MnO 4 - , the by-products of Mn 2+ , enhanced the DCF degradation due to catalysis and superposition of oxidation capacity, respectively. This study indicates that Fe 3+ and Fe 2+ promoted the DCF removal mainly via the self-catalysis for Fe(VI), and meanwhile, the catalysis of Mn 2+ and the effect of its by-products (i.e., MnO 2 and MnO 4 - ) contributed synchronously for DCF degradation. Graphical abstract ᅟ.

  10. Accumulating the hydride state in the catalytic cycle of [FeFe]-hydrogenases

    Science.gov (United States)

    Winkler, Martin; Senger, Moritz; Duan, Jifu; Esselborn, Julian; Wittkamp, Florian; Hofmann, Eckhard; Apfel, Ulf-Peter; Stripp, Sven Timo; Happe, Thomas

    2017-07-01

    H2 turnover at the [FeFe]-hydrogenase cofactor (H-cluster) is assumed to follow a reversible heterolytic mechanism, first yielding a proton and a hydrido-species which again is double-oxidized to release another proton. Three of the four presumed catalytic intermediates (Hox, Hred/Hred and Hsred) were characterized, using various spectroscopic techniques. However, in catalytically active enzyme, the state containing the hydrido-species, which is eponymous for the proposed heterolytic mechanism, has yet only been speculated about. We use different strategies to trap and spectroscopically characterize this transient hydride state (Hhyd) for three wild-type [FeFe]-hydrogenases. Applying a novel set-up for real-time attenuated total-reflection Fourier-transform infrared spectroscopy, we monitor compositional changes in the state-specific infrared signatures of [FeFe]-hydrogenases, varying buffer pH and gas composition. We selectively enrich the equilibrium concentration of Hhyd, applying Le Chatelier's principle by simultaneously increasing substrate and product concentrations (H2/H+). Site-directed manipulation, targeting either the proton-transfer pathway or the adt ligand, significantly enhances Hhyd accumulation independent of pH.

  11. Simulation of radiation damage in Fe and Fe-Cr

    International Nuclear Information System (INIS)

    Lagerstedt, Christina

    2005-11-01

    Steel is an important structural material in nuclear reactors used for example in pressure vessels and fast reactor cladding. In reactor environments it has been observed that ferritic steels are more resistant to swelling than the austenitic steels typically used. Much effort has been put into developing basic models of FeCr alloys which can serve as model alloys for describing ferritic steels. As a result, a number of interatomic potentials for Fe and FeCr alloys exist today. For the work in this thesis, basic material properties coming from experiments or ab initio calculations were used to fit interatomic potentials for Fe, Cr and FeCr implementing both the embedded atom method and the Finnis-Sinclair formalisms. The potentials were then validated by molecular dynamic calculations of material properties such as defect formation energies, migration energies and thermal expansion. Further studies of potential performance were carried out in simulations of radiation damage cascades and thermal aging. The influence of the interatomic potential on the primary defect state in materials under irradiation was analyzed in a study comparing results obtained using four different potentials. The objective of the study was to find correlations between potential properties and the primary damage state produced in simulations of displacement cascades. The defect evolution and clustering during different cascade stages were also investigated to try to gain a better understanding of these processes

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

    International Nuclear Information System (INIS)

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

    1999-01-01

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

  13. Investigation of Synthesis and Magnetic Properties of Rod-Shaped CoFe2O4 via Precipitation-Topotactic Reaction Employing α-FeOOH and γ-FeOOH As Templates

    Science.gov (United States)

    Cao, Xiaohui; Dong, Hongfei; Tan, Yuzhuo; Meng, Jinhong

    2018-03-01

    Rod-shaped CoFe2O4 was prepared by chemical precipitation-topotactic reaction method, and in this preparation needle-like γ-FeOOH and α-FeOOH were synthesized to use as template materials. The evolution of phase and morphology in the process of calcination exhibits that α-FeOOH and γ-FeOOH experienced different routes to form the α-Fe2O3 middle phase with different crystallinity and morphology. The synthesis process of CoFe2O4 revealed that the crystallinity, purity and morphology of CoFe2O4 depend on the α-Fe2O3 middle phase. The magnetic measurement showed that the CoFe2O4 prepared from α-FeOOH has higher saturation magnetization and coercivity, and the crystallinity and morphology may play important roles in achieving a better magnetic performance.

  14. Fe-Ti/Fe (II)-loading on ceramic filter materials for residual chlorine removal from drinking water.

    Science.gov (United States)

    Man, Kexin; Zhu, Qi; Guo, Zheng; Xing, Zipeng

    2018-06-01

    Ceramic filter material was prepared with silicon dioxide (SiO 2 ), which was recovered from red mud and then modified with Fe (II) and Fe-Ti bimetal oxide. Ceramic filter material can be used to reduce the content of residual chlorine from drinking water. The results showed that after a two-step leaching process with 3 M hydrochloric acid (HCl) and 90% sulfuric acid (H 2 SO 4 ), the recovery of SiO 2 exceeded 80%. Fe (II)/Fe-Ti bimetal oxide, with a high adsorption capacity of residual chlorine, was prepared using a 3:1 M ratio of Fe/Ti and a concentration of 0.4 mol/L Fe 2+ . According to the zeta-potential, scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) analysis, Fe (II) and Fe-Ti bimetal oxide altered the zeta potential and structural properties of the ceramic filter material. There was a synergistic interaction between Fe and Ti in which FeOTi bonds on the material surface and hydroxyl groups provided the active sites for adsorption. Through a redox reaction, Fe (II) transfers hypochlorite to chloride, and FeOTiCl bonds were formed after adsorption. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Determination of the 54Fe(n, 2n)53gFe and 54Fe(n, 2n)53mFe cross sections averaged over a 235U fission neutron spectrum

    International Nuclear Information System (INIS)

    Ribeiro Guevara, S.; Arribere, M.; Kestelman, A.J.

    2002-01-01

    The reaction cross sections averaged over a 235 U fission neutron spectrum have been measured for the 54 Fe(n, 2n) 53g Fe and 54 Fe(n, 2n) 53m Fe threshold reactions. The values found are, respectively: (1.14 ± 0.13) μb, and (0.52 ± 0.16) μb. The measured cross sections are referred to the (111± 3) mb standard cross section of the 58 Ni(n, p) 58m+g Co reaction. The (81.7 ± 2.2) mb standard cross section value for the 54 Fe(n, p) 54 Mn reaction, was also used as a monitor to check the results obtained with the Ni standard, leading to an excellent agreement. (author)

  16. Modeling Equilibrium Fe Isotope Fractionation in Fe-Organic Complexes: Implications for the use of Fe Isotopes as a Biomarker and Trends Based on the Properties of Bound Ligands

    Science.gov (United States)

    Domagal-Goldman, S.; Kubicki, J. D.

    2006-05-01

    Fe Isotopes have been proposed as a useful tracer of biological and geochemical processes. Key to understanding the effects these various processes have on Fe isotopes is accurate modeling of the reactions responsible for the isotope fractionations. In this study, we examined the theoretical basis for the claims that Fe isotopes can be used as a biomarker. This was done by using molecular orbital/density functional theory (MO/DFT) calculations to predict the equilibrium fractionation of Fe isotopes due to changes in the redox state and the bonding environment of Fe. Specifically, we predicted vibrational frequencies for iron desferrioxamine (Fe-DFOB), iron triscatechol (Fe(cat)3), iron trisoxalate (Fe(ox)3), and hexaaquo iron (Fe(H2O)6) for complexes containing both ferrous (Fe2+) and ferric (Fe3+) iron. Using these vibrational frequencies, we then predicted fractionation factors between these six complexes. The predicted fractionation factors resulting from changes in the redox state of Fe fell in the range 2.5- 3.5‰. The fractionation factors resulting from changes in the bonding environment of Fe ranged from 0.2 to 1.4‰. These results indicate that changes in the bonding strength of Fe ligands are less important to Fe isotope fractionation processes than are changes to the redox state of Fe. The implications for use of Fe as a tracer of biological processes is clear: abiological redox changes must be ruled out in a sample before Fe isotopes are considered as a potential biomarker. Furthermore, the use of Fe isotopes to measure the redox state of the Earths surface environment through time is supported by this work, since changes in the redox state of Fe appear to be the more important driver of isotopic fractionations. In addition to the large differences between redox-driven fractionations and ligand-driven fractionations, we will also show general trends in the demand for heavy Fe isotopes as a function of properties of the bound ligand. This will help the

  17. Ferromagnetic alloy material CoFeC with high thermal tolerance in MgO/CoFeC/Pt structure and comparable intrinsic damping factor with CoFeB

    Science.gov (United States)

    Chen, Shaohai; Zhou, Jing; Lin, Weinan; Yu, Jihang; Guo, Rui; Poh, Francis; Shum, Danny; Chen, Jingsheng

    2018-02-01

    The thermal tolerance and perpendicular magnetic anisotropy (PMA) of ferromagnetic alloy Co40Fe40C20 in the structure MgO/CoFeC/Pt (or Ta) were investigated and compared with the commonly used CoFeB alloy. It is found that the PMA of CoFeC with {{K}i,CoFeC}=2.21 erg c{{m}-2} , which is 59% higher than that of CoFeB, can be obtained after proper post-annealing treatment. Furthermore, CoFeC alloy provides better thermal tolerance to temperature of 400 °C than CoFeB. The studies on ferromagnetic resonance show that the intrinsic damping constant α in of Co40Fe40C20 alloy is 0.0047, which is similar to the reported value of 0.004 for Co40Fe40B20 alloy. The comprehensive comparisons indicate that CoFeC alloy is a promising candidate for the application of the integration of spin torque transfer magnetic random access memory with complementary metal-oxide semiconductor processes.

  18. Fe++/Fe+++ concentration relationship and mechanical properties of phosphate glasses useful for wastes immobilization

    International Nuclear Information System (INIS)

    Garcia, D.A.; Prado, Miguel O.

    2007-01-01

    Under different melting conditions, glasses with different Fe(II)/Fe(III) concentration relationship were prepared within each type of glass 43Fe 2 O 3 -57P 2 O 5 and 33,33Fe 2 O 3 - 66,67P 2 O 5 . Using Moessbauer spectroscopy Fe(II)/Fe(III) concentration values were determined. Vickers and Knoop indentations were used for determining their hardness, toughness, Young modulus and brittleness. The same measurements were carried on some silicate and aluminosilicate glasses. Also Weibull statistics was done to determine the characteristics (Weibull modulus and and fracture probability) of glass fracture. We found that silicate glasses (SG) are harder than phosphate glasses (PG). Toughness values for PG, are in the same range than for SG, although for the same density exhibit larger values or smaller brittleness than silicate glasses. For one of the glasses it was found that the mechanical load P 0 needed for a fracture probability of 63% increases with the Fe(II) content. (author)

  19. Ion-irradiation induced chemical ordering of FePt and FePtAu nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Seetala, Naidu V. [Department of Physics, Grambling State University, RWE Jones Drive, Carver Hall 81, Grambling, LA 71245 (United States)]. E-mail: naidusv@gram.edu; Harrell, J.W. [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Lawson, Jeremy [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Nikles, David E. [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States); Williams, John R. [Department of Physics, Auburn University, Auburn, AL 36849 (United States); Isaacs-Smith, Tamara [Department of Physics, Auburn University, Auburn, AL 36849 (United States)

    2005-12-15

    We have studied the effect of ion-beam irradiation on reducing the ordering temperature of FePt and FePtAu nanoparticles. FePt and FePt(Au14%) 4 nm particles dispersed on a Si-substrate were irradiated by 300 keV Al-ions with a dose of 1 x 10{sup 16} ions/cm{sup 2} at 43 {sup o}C using a water-cooled flange in order to minimize the vacancy migration and voids formation within the collision cascades. Partial chemical ordering has been observed in as-irradiated particles with coercivity of 60-130 Oe. Post-irradiation annealing at 220 {sup o}C enhanced chemical ordering in FePt nanoparticles with coercivity of 3500 Oe, magnetic anisotropy of 1.5 x 10{sup 7} erg/cc, and thermal stability factor of 130. A much higher 375 {sup o}C post-irradiation annealing was required in FePtAu, presumably because Au atoms were trapped at Fe/Pt lattice sites at lower temperatures. As the annealing temperature increased, anomalous features in the magnetization reversal curves were observed that disappeared at higher annealing temperatures.

  20. Magnetic properties of Fe/NiO/Fe(001) trilayers

    International Nuclear Information System (INIS)

    Biagioni, P.; Brambilla, A.; Portalupi, M.; Rougemaille, N.; Schmid, A.K.; Lanzara, A.; Vavassori, P.; Zani, M.; Finazzi, M.; Duo, L.; Ciccacci, F.

    2005-01-01

    We have investigated the magnetic properties of epitaxially grown Fe/NiO/Fe(001) trilayers, for different thicknesses of the NiO spacer. Magneto Optical Kerr Effect has been exploited to study the in-plane magnetization reversal processes in the iron layers. We found that the NiO thickness t AFM has a critical value t C for the magnetic coupling between the Fe layers: for t AFM C the magnetization directions align perpendicularly, with zero applied field, while the alignment is collinear for thicker spacers. A phenomenological model has been developed to reproduce and discuss the results. Complementary information has been obtained by means of spin polarized low energy electron microscopy

  1. Magnetic properties of Fe/NiO/Fe(001) trilayers

    Energy Technology Data Exchange (ETDEWEB)

    Biagioni, P [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Brambilla, A [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Portalupi, M [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Rougemaille, N [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Schmid, A K [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Lanzara, A [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Department of Physics, University of California at Berkeley, Berkeley, CA 94720 (United States); Vavassori, P [INFM - Dipartimento di Fisica, Universita di Ferrara, Via Paradiso 12, 44100 Ferrara (Italy); Zani, M [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Finazzi, M [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Duo, L [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy); Ciccacci, F [INFM - Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy)

    2005-04-15

    We have investigated the magnetic properties of epitaxially grown Fe/NiO/Fe(001) trilayers, for different thicknesses of the NiO spacer. Magneto Optical Kerr Effect has been exploited to study the in-plane magnetization reversal processes in the iron layers. We found that the NiO thickness t{sub AFM} has a critical value t{sub C} for the magnetic coupling between the Fe layers: for t{sub AFM}

  2. Beyond clay - using selective extractions to improve predictions of soil carbon content

    Science.gov (United States)

    Rasmussen, C.; Berhe, A. A.; Blankinship, J. C.; Crow, S. E.; Druhan, J. L.; Heckman, K. A.; Keiluweit, M.; Lawrence, C. R.; Marin-Spiotta, E.; Plante, A. F.; Schaedel, C.; Schimel, J.; Sierra, C. A.; Thompson, A.; Wagai, R.; Wieder, W. R.

    2016-12-01

    A central component of modern soil carbon (C) models is the use of clay content to scale the relative partitioning of decomposing plant material to respiration and mineral stabilized soil C. However, numerous pedon to plot scale studies indicate that other soil mineral parameters, such as Fe- or Al-oxyhydroxide content and specific surface area, may be more effective than clay alone for predicting soil C content and stabilization. Here we directly address the following question: Are there soil physicochemical parameters that represent mineral C association and soil C content that can replace or be used in conjunction with clay content as scalars in soil C models. We explored the relationship of soil C content to a number of soil physicochemical and physiographic parameters using the National Cooperative Soil Survey database that contains horizon level data for > 62,000 pedons spanning global ecoregions and geographic areas. The data indicated significant variation in the degree of correlation among soil C, clay and Fe-/Al-oxyhydroxides with increasing moisture variability. Specifically, dry, water-limited systems (PET/MAP > 1) presented strong positive correlations between clay and soil C, that decreased significantly to little or no correlation in wet, energy-limited systems (PET/MAP soil C to oxalate extractable Al+Fe increased significantly with increasing moisture availability. This pattern was particularly well expressed for subsurface B horizons. Multivariate analyses indicated similar patterns, with clear climate and ecosystem level variation in the degree of correlation among soil C and soil physicochemical properties. The results indicate a need to modify current soil C models to incorporate additional C partitioning parameters that better account for climate and ecoregion variability in C stabilization mechanisms.

  3. Thermodynamic Description Of Ternary Fe-B-X Systems. Part 2: Fe-B-Ni

    Directory of Open Access Journals (Sweden)

    Miettinen J.

    2014-06-01

    Full Text Available Przedstawiono termodynamiczny opis trójskładnikowego układu Fe-B-Ni w kontekście nowej bazy danych dla układów Fe-B-X (X = Cr, Ni, Mn, Si, Ti, V, C. Parametry termodynamiczne dwuskładnikowych stopów Fe-B. Fe-Ni i B-Ni zostały są zaczerpnięte z wcześniejszych opracowań, przy tym opis B-Ni został nieznacznie zmodyfikowany. Parametry dla układu Fe-B-Ni zostały zoptymalizowane w tej pracy w oparciu o eksperymentalne równowagi fazowe i dane termodynamiczne zaczerpnięte z literatury. Roztwory stałe w układzie Fe-B-Ni opisano przy użyciu modelu roztworu substytucyjnego, a borki traktowane są jako fazy stechiometryczne lub półstechiometryczne typu (A.BpCq opisane przy użyciu modelu dwu podsieci.

  4. Structure, magnetism, and interface properties of epitactical thin Fe and FePt films on GaAs(001) substrates; Struktur, Magnetismus und Grenzflaecheneigenschaften epitaktischer duenner Fe- und FePt-Filme auf GaAs(001)-Substraten

    Energy Technology Data Exchange (ETDEWEB)

    Schuster, Ellen Ursula

    2007-12-17

    The research in this thesis is focused on the study of the Fe spin structure and interface magnetism of thin epitaxial Fe layers or epitaxial FePt alloy films with chemical L1{sub 0} order on GaAs(001) surfaces. The main method of investigation was isotope-specific conversion electron Moessbauer spectroscopy (CEMS) combined with the {sup 57}Fe probe-layer technique in the temperature range of 4.2-300 K. The film structure was studied using electron diffraction (RHEED) and X-ray diffraction (XRD). The chemical order parameter S determined by XRD was found to increase with rising growth temperature, T{sub S}, to a maximum value of 0.71, until long range order is destroyed at T{sub S}>350 C by alloying with the substrate. As an important result a linear correlation between short-range order (revealed by the relative spectral area of the L1{sub 0} phase) and long-range order S was observed. The observed perpendicular Fe spin texture, characterized by the mean tilting angle left angle {theta} right angle of the Fe spins (relative to the film normal direction), was found to correlate with the L1{sub 0} phase content and with S. Furthermore, epitaxial Fe(001) films on GaAs(001)-(4 x 6) and on GaAs(001)-LED surfaces were grown successfully. In the initial stage of Fe film growth non-monotonous behavior of the in-plane lattice parameter was observed by RHEED. The magnetic hyperfine field distributions P(B{sub hf}) at the Fe/GaAs interface extracted from CEMS spectra for T{sub S}=-140 C or room temperature (RT) were found to be very similar. The observed large mean hyperfine fields of left angle B{sub hf} right angle {approx}25-27 T at the interface indicate the presence of high average Fe moments of 1.7-1.8 {mu}{sub B}. Nonmagnetic interface layers either can be excluded (Fe/GaAs) or are very thin (0.5 ML,Fe/GaAs-LED). Owing to its island structure an ultrathin (1.9 ML thick) uncoated Fe(001) film on GaAs(001)-(4 x 6) shows superparamagnetism with a blocking temperature of

  5. Exchange coupling behavior in bimagnetic CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Leite, G.C.P. [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Chagas, E.F., E-mail: efchagas@fisica.ufmt.br [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Pereira, R.; Prado, R.J. [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Terezo, A.J. [Departamento de Quimica, Universidade Federal do Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Alzamora, M.; Baggio-Saitovitch, E. [Centro Brasileiro de Pesquisas Fisicas, Rua Xavier Sigaud 150 Urca, Rio de Janeiro (Brazil)

    2012-09-15

    In this work we report a study of the magnetic behavior of ferrimagnetic oxide CoFe{sub 2}O{sub 4} and ferrimagnetic oxide/ferromagnetic metal CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite. The latter compound is a good system to study hard ferrimagnet/soft ferromagnet exchange coupled. Two steps were followed to synthesize the bimagnetic CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite: (i) first, preparation of CoFe{sub 2}O{sub 4} nanoparticles using a simple hydrothermal method, and (ii) second, reduction reaction of cobalt ferrite nanoparticles using activated charcoal in inert atmosphere and high temperature. The phase structures, particle sizes, morphology, and magnetic properties of CoFe{sub 2}O{sub 4} nanoparticles were investigated by X-Ray diffraction (XRD), Mossbauer spectroscopy (MS), transmission electron microscopy (TEM), and vibrating sample magnetometer (VSM) with applied field up to 3.0 kOe at room temperature and 50 K. The mean diameter of CoFe{sub 2}O{sub 4} particles is about 16 nm. Mossbauer spectra revealed two sites for Fe{sup 3+}. One site is related to Fe in an octahedral coordination and the other one to the Fe{sup 3+} in a tetrahedral coordination, as expected for a spinel crystal structure of CoFe{sub 2}O{sub 4}. TEM measurements of nanocomposite showed the formation of a thin shell of CoFe{sub 2} on the cobalt ferrite and indicate that the nanoparticles increase to about 100 nm. The magnetization of the nanocomposite showed a hysteresis loop that is characteristic of exchange coupled systems. A maximum energy product (BH){sub max} of 1.22 MGOe was achieved at room temperature for CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposites, which is about 115% higher than the value obtained for CoFe{sub 2}O{sub 4} precursor. The exchange coupling interaction and the enhancement of product (BH){sub max} in nanocomposite CoFe{sub 2}O{sub 4}/CoFe{sub 2} are discussed. - Highlights: Black-Right-Pointing-Pointer CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite

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

    Science.gov (United States)

    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.

  7. Ordering phenomena in FeCo-films and Fe/Cr-multilayers: an X-ray and neutron scattering study

    Energy Technology Data Exchange (ETDEWEB)

    Nickel, B.

    2001-07-01

    The following topics are covered: critical phenomena in thin films, critical adsorption, finite size scaling, FeCo Ising model, kinematical scattering theory for thin films, FeCo thin films, growth and characterisation of single crystal FeCo thin films, X-ray study of ordering in FeCo films, antiferromagnetic coupling in Fe/Cr multilayers, neutron scattering on Fe/Cr multilayers (WL)

  8. Shape anisotropy and hybridization enhanced magnetization in nanowires of Fe/MgO/Fe encapsulated in carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Aryee, Dennis [Army Research Laboratory, Weapons and Materials Research Directorate, Aberdeen Proving Ground, MD 21005 (United States); Department of Physics and Engineering Physics, Morgan State University, Baltimore, MD 21251 (United States); Seifu, Dereje, E-mail: dereje.seifu@morgan.edu [Department of Physics and Engineering Physics, Morgan State University, Baltimore, MD 21251 (United States)

    2017-05-01

    Arrays of tunneling magnetoresistance (TMR) nanowires were synthesized for the first time by filling Fe/MgO/Fe inside vertically grown and substrate supported carbon nanotubes. The magnetic properties of nanowires and planar nanoscale thin films of Fe/MgO/Fe showed several similarities, such as two-fold magnetic symmetry and ratio of orbital moment to spin moment. Nanowires of Fe/MgO/Fe showed higher saturation magnetization by a factor of 2.7 compared to planar thin films of Fe/MgO/Fe at 1.5 kOe. The enhanced magnetic properties likely resulted from shape anisotropy of the nanowires and as well as the hybridization that occur between the π- electronic states of carbon and 3d-bands of the Fe-surface.

  9. Fabrication and magnetic properties of Fe/GaAs/Fe hybrid structures

    OpenAIRE

    Wong, P.K.J.; Zhang, W.; Zhang, W.; Wu, J.; Will, I.G.; Xu, Y.B.; Farrer, I.; Ritchie, D.A.

    2010-01-01

    In this contribution, experimental results on the fabrication and magnetic characterization of a novel type vertical Fe/GaAs(100)/Fe spin-valve (SV) spintronic device are presented. An array of techniques has been developed by combining use of ex-situ chemical and selective etching of GaAs/AlGaAs/n-GaAs epilayers and ultrahigh vacuum deposition of Fe by molecular beam epitaxy (MBE). The thinnest achievable GaAs membrane by these sequences can be as thin as 50 nm.

  10. A synthetic system links FeFe-hydrogenases to essential E. coli sulfur metabolism

    Directory of Open Access Journals (Sweden)

    Grandl Gerald

    2011-05-01

    Full Text Available Abstract Background FeFe-hydrogenases are the most active class of H2-producing enzymes known in nature and may have important applications in clean H2 energy production. Many potential uses are currently complicated by a crucial weakness: the active sites of all known FeFe-hydrogenases are irreversibly inactivated by O2. Results We have developed a synthetic metabolic pathway in E. coli that links FeFe-hydrogenase activity to the production of the essential amino acid cysteine. Our design includes a complementary host strain whose endogenous redox pool is insulated from the synthetic metabolic pathway. Host viability on a selective medium requires hydrogenase expression, and moderate O2 levels eliminate growth. This pathway forms the basis for a genetic selection for O2 tolerance. Genetically selected hydrogenases did not show improved stability in O2 and in many cases had lost H2 production activity. The isolated mutations cluster significantly on charged surface residues, suggesting the evolution of binding surfaces that may accelerate hydrogenase electron transfer. Conclusions Rational design can optimize a fully heterologous three-component pathway to provide an essential metabolic flux while remaining insulated from the endogenous redox pool. We have developed a number of convenient in vivo assays to aid in the engineering of synthetic H2 metabolism. Our results also indicate a H2-independent redox activity in three different FeFe-hydrogenases, with implications for the future directed evolution of H2-activating catalysts.

  11. Molecular magnetism of a linear Fe(III)-Mn(II)-Fe(III) complex. Influence of long-range exchange interaction

    International Nuclear Information System (INIS)

    Lengen, M.; Chaudhuri, P.

    1994-01-01

    The magnetic properties of [L-Fe(III)-dmg 3 Mn(II)-Fe(III)-L] (ClO 4 ) 2 have been characterized by magnetic susceptibility, EPR, and Moessbauer studies. L represents 1,4,7-trimethyl-,1,4,7-triazacyclononane and dmg represents dimethylglyoxime. X-ray diffraction measurements yield that the arrangement of the three metal centers is strictly linear with atomic distances d Fe-Mn 0.35 nm and d Fe-Fe = 0.7 nm. Magnetic susceptibility measurements (3-295 K) were analyzed in the framework of the spin-Hamiltonian formalism considering Heisenberg exchange and Zeeman interaction: H = J Fe-Mn (S Fe1 + S Fe2 )S Mn + J Fe-Fe S Fe1 S Fe2 + gμ B S total B. The spins S Fe1 = S Fe2 = S Mn = 5/2 of the complex are antiferromagnetically coupled, yielding a total spin of S total = 5/2 with exchange coupling constants F Fe-Mn = 13.4 cm -1 and J Fe-Fe = 4.5 cm -1 . Magnetically split Moessbauer spectra were recorded at 1.5 K under various applied fields (20 mT, 170 mT, 4 T). The spin-Hamiltonian analysis of these spectra yields isotropic magnetic hyperfine coupling with A total /(g N μ N ) = -18.5 T. The corresponding local component A Fe is related to A total via spin-projection: A total = (6/7)A Fe . The resulting A Fe /(g N μ N ) -21.6 T is in agreement with standard values of ferric high-spin complexes. Spin-Hamiltonian parameters as obtained from Moessbauer studies and exchange coupling constants as derived from susceptibility measurements are corroborated by temperature-dependent EPR studies. (orig.)

  12. Redox reactions of [FeFe]-hydrogenase models containing an internal amine and a pendant phosphine.

    Science.gov (United States)

    Zheng, Dehua; Wang, Mei; Chen, Lin; Wang, Ning; Sun, Licheng

    2014-02-03

    A diiron dithiolate complex with a pendant phosphine coordinated to one of the iron centers, [(μ-SCH2)2N(CH2C6H4-o-PPh2){Fe2(CO)5}] (1), was prepared and structurally characterized. The pendant phosphine is dissociated together with a CO ligand in the presence of excess PMe3, to afford [(μ-SCH2)2N(CH2C6H4-o-PPh2){Fe(CO)2(PMe3)}2] (2). Redox reactions of 2 and related complexes were studied in detail by in situ IR spectroscopy. A series of new Fe(II)Fe(I) ([3](+) and [6](+)), Fe(II)Fe(II) ([4](2+)), and Fe(I)Fe(I) (5) complexes relevant to Hox, Hox(CO), and Hred states of the [FeFe]-hydrogenase active site were detected. Among these complexes, the molecular structures of the diferrous complex [4](2+) with the internal amine and the pendant phosphine co-coordinated to the same iron center and the triphosphine diiron complex 5 were determined by X-ray crystallography. To make a comparison, the redox reactions of an analogous complex, [(μ-SCH2)2N(CH2C6H5){Fe(CO)2(PMe3)}2] (7), were also investigated by in situ IR spectroscopy in the absence or presence of extrinsic PPh3, which has no influence on the oxidation reaction of 7. The pendant phosphine in the second coordination sphere makes the redox reaction of 2 different from that of its analogue 7.

  13. Characterization of Bi and Fe co-doped PZT capacitors for FeRAM.

    Science.gov (United States)

    Cross, Jeffrey S; Kim, Seung-Hyun; Wada, Satoshi; Chatterjee, Abhijit

    2010-08-01

    Ferroelectric random access memory (FeRAM) has been in mass production for over 15 years. Higher polarization ferroelectric materials are needed for future devices which can operate above about 100 °C. With this goal in mind, co-doping of thin Pb(Zr 40 ,Ti 60 )O 3 (PZT) films with 1 at.% Bi and 1 at.% Fe was examined in order to enhance the ferroelectric properties as well as characterize the doped material. The XRD patterns of PZT-5% BiFeO 3 (BF) and PZT 140-nm thick films showed (111) orientation on (111) platinized Si wafers and a 30 °C increase in the tetragonal to cubic phase transition temperature, often called the Curie temperature, from 350 to 380 °C with co-doping, indicating that Bi and Fe are substituting into the PZT lattice. Raman spectra revealed decreased band intensity with Bi and Fe co-doping of PZT compared to PZT. Polarization hysteresis loops show similar values of remanent polarization, but square-shaped voltage pulse-measured net polarization values of PZT-BF were higher and showed higher endurance to repeated cycling up to 10 10 cycles. It is proposed that Bi and Fe are both in the +3 oxidation state and substituting into the perovskite A and B sites, respectively. Substitution of Bi and Fe into the PZT lattice likely creates defect dipoles, which increase the net polarization when measured by the short voltage pulse positive-up-negative-down (PUND) method.

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

    International Nuclear Information System (INIS)

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

    2011-01-01

    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, 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Monnot, Andrew D.; Behl, Mamta; Ho, Sanna; Zheng, Wei, E-mail: wzheng@purdue.edu

    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, 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.

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

    Science.gov (United States)

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

    2009-01-01

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

  17. Influence of chemical composition of CoFeB on tunneling magnetoresistance and microstructure in polycrystalline CoFeB/MgO/CoFeB magnetic tunnel junctions

    International Nuclear Information System (INIS)

    Tsunekawa, Koji; Choi, Young-Suk; Nagamine, Yoshinori; Djayaprawira, David D.; Takeuchi, Takashi; Kitamoto, Yoshitaka

    2006-01-01

    We report, for the first time, the correlation between tunneling magnetoresistance (TMR) and the microstructure of polycrystalline CoFeB/MgO/CoFeB magnetic tunnel junctions with various Co/Fe ratios in the (CoFe) 81 B 19 reference and free layers. It is found that the Co/Fe ratio in the (CoFe) 81 B 19 reference layer strongly affects the (001) out-of-plane texture of the MgO tunnel barrier, resulting in the variation in TMR ratio. Further microstructure characterization of the magnetic tunnel junction with a higher TMR ratio and a stronger (001) out-of-plane texture in the MgO tunnel barrier reveals a grain-to-grain lattice match between the crystallized bcc CoFeB reference layer and MgO with a 45deg rotational epitaxial relationship, that is, CoFeB(001)[110]//MgO(001)[100]. (author)

  18. A pulse synthesis of beta-FeSi sub 2 layers on silicon implanted with Fe sup + ions

    CERN Document Server

    Batalov, R I; Terukov, E I; Kudoyarova, V K; Weiser, G; Kuehne, H

    2001-01-01

    The synthesis of thin beta-FeSi sub 2 films was performed by means of the Fe sup + ion implantation into Si (100) and the following nanosecond pulsed ion treatment of implanted layer. Using the beta-FeSi sub 2 beta-FeSi sub 2 e X-ray diffraction it is shown that the pulsed ion treatment results in the generation of the mixture of two phases: FeSi and beta-FeSi sub 2 with stressed crystal lattices. The following short-time annealing leads to the total transformation of the FeSi phase into the beta-FeSi sub 2 one. The Raman scattering data prove the generation of the beta-FeSi sub 2 at the high degree of the silicon crystallinity. The experimental results of the optical absorption testify to the formation of beta-FeSi sub 2 layers and precipitates with the straight-band structure. The photoluminescence signal at lambda approx = 1.56 mu m observes up to 210 K

  19. In situ QXAFS observation of the reduction of Fe2O3 and CaFe2O4

    International Nuclear Information System (INIS)

    Kimura, Masao; Takayama, Toru; Murao, Reiko; Nomura, Masaharu; Uemura, Yohei; Asakura, Kiyotaka

    2013-01-01

    In situ QXAFS studies of the reduction of α-Fe 2 O 3 and CaFe 2 O 4 were conducted to determine their reduction kinetics and mechanisms. The reduction of α-Fe 2 O 3 involved two steps, the first being a very fast process in which Fe 3+ was reduced to Fe 2+ and the second being the reduction of Fe 2+ to Fe metal over a longer period. In contrast, the reduction of Fe in CaFe 2 O 4 was a single first-order reaction, although an induction period was clearly observed at the beginning of the reduction process. The reduction processes were successfully studied using a combination of in situ QXAFS spectra at the Ca and Fe K-edges.

  20. Presence of 60Fe in eucrite Piplia Kalan: A new perspective to the initial 60Fe/ 56Fe in the early solar system

    Digital Repository Service at National Institute of Oceanography (India)

    Rudraswami, N.G.; Sahijpal, S.; Bhandari, N.

    Fe-Ni isotope measurements of ferrous pyroxenes of the Piplia Kalan eucrite using Secondary Ion Mass Spectrometer revealed the presence of sup (60) Ni excess corresponding to the initial 60Fe/56Fe of (5.2 + or - 2.4) × 10 sup(-9). Combining...

  1. Coercivity Recovery Effect of Sm-Fe-Cu-Al Alloy on Sm2Fe17N3 Magnet

    Science.gov (United States)

    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.

  2. Effect of Soil Parameters on the Kinetics of the Displacement of Fe from FeEDDHA Chelates by Cu

    NARCIS (Netherlands)

    Schenkeveld, W.D.C.; Reichwein, A.M.; Temminghoff, E.J.M.; Riemsdijk, van W.H.

    2012-01-01

    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

  3. A new rhodamine-based fluorescent probe for the discrimination of Fe"3"+ from Fe"2"+

    International Nuclear Information System (INIS)

    You, Qi Hua; Huang, Hua Bin; Zhuang, Zhi Xia; Wang, Xiao Ru; Chan, Wing Hong

    2016-01-01

    A new rhodamine-based fluorescent probe for the discrimination of Fe"3"+ from Fe"2"+ has been designed and investigated. The probe shows an immediate visual color change in response to Fe"3"+ and Cu"2"+, while only Fe"3"+ triggers the fluorescent change of the probe. The existence of large amount of other metal ions shows negligible interference in the detection of Fe"3"+. The association constant K_a_s_s of 4.64 × 10"8 M"-"2 (R"2 = 0.994) and 5.38 × 10"8 M"-"2 (R"2 = 0.991) of the complex was derived from UV/Vis and fluorescence titration assuming 1:2 stoichiometry of probe–Fe"3"+ complex, respectively

  4. Determination of K shell fluorescence cross-section and Kβ/Kα intensity ratios for Fe, Se, Te, FeSe, FeTe and TeSe

    International Nuclear Information System (INIS)

    Saydam, M.; Aksoy, C.; Cengiz, E.; Alaşalvar, C.; Tıraşoğlu, E.; Apaydın, G.

    2012-01-01

    The fluorescence cross-sections (σ Ki ) and the intensity ratios K β /K α for pure Fe, Se, Te elements and FeSe, FeTe, TeSe complexes have been investigated. The samples were excited by 59.5 keV γ-rays from 241 Am annular radioactive source and emitted X-rays. They were counted by an Ultra-LEGe detector with resolution of 150 eV at 5.9 keV. For pure elements results have been compared with the theoretical calculated values. According to our results band length and mutual interaction of atoms affected the results. We claimed that these effects would help researchers who study on superconductors, especially determining which compound can be show the superconductor properties. - Highlights: ► TeSe, FeSe and FeTe complexes have affected each other in terms of charge transfer. ► Fe excitement and enhancement have been made by Se and Te. ► Attractive interactions between electrons can help to becoming superconductivity.

  5. Crystallization behavior and magnetic properties in High Fe content FeBCSiCu alloy system

    Energy Technology Data Exchange (ETDEWEB)

    Fan, X.D., E-mail: fanxd@seu.edu.cn; Shen, B.L., E-mail: blshen@seu.edu.cn

    2015-07-01

    High Fe content FeBCSiCu nanocrystalline alloys are prepared by annealing melt-spun amorphous ribbons with aim at increasing saturation magnetic flux density. Microstructures identified by XRD and TEM reveal that Cu addition inhibits the surface crystallization of Fe{sub 86}B{sub 7}C{sub 7} alloy and improve its glass-forming ability. Activation energy of crystallization calculated by Kissinger's equation indicates that both Cu and Si addition promotes the precipitation of α-Fe phase and improves the thermal stability. VSM and DC B–H loop tracer measurements show that the Fe{sub 85.5}B{sub 7}C{sub 6}Si{sub 1}Cu{sub 0.5} nanocrystalline alloy exhibits high saturation magnetic flux density of 1.8 T and low coercivity of 10 A/m, respectively. AC properties measured by AC B–H analyzer show this alloy exhibits low core loss of 0.35 W/kg at 1 T at 50 Hz. Low material cost and convenient productivity make the Fe{sub 85.5}B{sub 7}C{sub 6}Si{sub 1}Cu{sub 0.5} nanocrystalline alloy an economical application in industry. - Highlights: • Cu addition inhibits the surface crystallization and improves the GFA. • The competitive formation of Fe{sub 3}C and α-Fe phase impedes the devitrification. • Fe{sub 85.5}B{sub 7}C{sub 6}Si{sub 1}Cu{sub 0.5} nanocrystalline alloy exhibits excellent magnetic properties. • The alloy system has an economical advantage and convenient productivity.

  6. Gas phase synthesis of core-shell Fe@FeO{sub x} magnetic nanoparticles into fluids

    Energy Technology Data Exchange (ETDEWEB)

    Aktas, Sitki, E-mail: aksitki61@gmail.com; Thornton, Stuart C.; Binns, Chris [University of Leicester, Department of Physics and Astronomy (United Kingdom); Denby, Phil [Ensol As, Nesttun (Norway)

    2016-12-15

    Sorbitol, short chain molecules, have been used to stabilise of Fe@FeO{sub x} nanoparticles produced in the gas phase under the ultra-high vacuum (UHV) conditions. The sorbitol coated Fe@FeO{sub x} nanoparticles produced by our method have a narrow size distribution with a hydrodynamic diameter of 35 nm after NaOH is added to the solution. Magnetisation measurement shows that the magnetic nanoparticles are superparamagnetic at 100 K and demonstrate hysteresis at 5 K with an anisotropy constant of 5.31 × 10{sup 4} J/m{sup 3} (similar to bulk iron). Also, it is shown that sorbitol is only suitable for stabilising the Fe@FeO{sub x} suspensions, and it does not prevent further oxidation of the metallic Fe core. According to MRI measurement, the nanoparticles have a high transverse relaxation rate of 425 mM{sup −1} s{sup −1}.

  7. Sulfide phase in the Fe-Ti-S and Fe-C-Ti-S alloys

    International Nuclear Information System (INIS)

    Malinochka, Ya.N.; Balakina, N.A.; Shmelev, Yu.S.

    1976-01-01

    The nature of the sulfide phases in Fe-Ti-S and Fe-C-Ti-S alloys was studied. The carbide and the sulfide phase were identified the aid of X-ray spectral microanalysis. It was established that for a small content of titanium and sulfur in ternary Fe-Ti-S alloys the solidification of the γ-solution on the boundaries of dendritic branches is accompanied, along with the precipitation of a sulfide rich in iron of the (Fe, Ti) S type where a small quantity of titanium is dissolved, by the formation of a titanium-bearing sulfide eutectic γ + TiS. The amount of the sulfide eutectic increases with the contents of titanium and sulfur until a purely eutectic alloy is formed. Both carbides and sulfides may be formed in the solidification of quaternary alloys Fe-C-Ti-S

  8. Accelerated Removal of Fe-Antisite Defects while Nanosizing Hydrothermal LiFePO4 with Ca(2).

    Science.gov (United States)

    Paolella, Andrea; Turner, Stuart; Bertoni, Giovanni; Hovington, Pierre; Flacau, Roxana; Boyer, Chad; Feng, Zimin; Colombo, Massimo; Marras, Sergio; Prato, Mirko; Manna, Liberato; Guerfi, Abdelbast; Demopoulos, George P; Armand, Michel; Zaghib, Karim

    2016-04-13

    Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances.

  9. Fabrication of FeSi and Fe{sub 3}Si compounds by electron beam induced mixing of [Fe/Si]{sub 2} and [Fe{sub 3}/Si]{sub 2} multilayers grown by focused electron beam induced deposition

    Energy Technology Data Exchange (ETDEWEB)

    Porrati, F.; Sachser, R.; Huth, M. [Physikalisches Institut, Goethe-Universität, Max-von-Laue-Str. 1, D-60438 Frankfurt am Main (Germany); Gazzadi, G. C. [S3 Center, Nanoscience Institute-CNR, Via Campi 213/a, 41125 Modena (Italy); Frabboni, S. [S3 Center, Nanoscience Institute-CNR, Via Campi 213/a, 41125 Modena (Italy); FIM Department, University of Modena and Reggio Emilia, Via G. Campi 213/a, 41125 Modena (Italy)

    2016-06-21

    Fe-Si binary compounds have been fabricated by focused electron beam induced deposition by the alternating use of iron pentacarbonyl, Fe(CO){sub 5}, and neopentasilane, Si{sub 5}H{sub 12} as precursor gases. The fabrication procedure consisted in preparing multilayer structures which were treated by low-energy electron irradiation and annealing to induce atomic species intermixing. In this way, we are able to fabricate FeSi and Fe{sub 3}Si binary compounds from [Fe/Si]{sub 2} and [Fe{sub 3}/Si]{sub 2} multilayers, as shown by transmission electron microscopy investigations. This fabrication procedure is useful to obtain nanostructured binary alloys from precursors which compete for adsorption sites during growth and, therefore, cannot be used simultaneously.

  10. Magnetic properties of Fe-oxide and (Fe, Co) oxide nanoparticles synthesized in polystyrene resin matrix

    Science.gov (United States)

    Rodak, D.; Kroll, E.; Tsoi, G. M.; Vaishnava, P. P.; Naik, R.; Wenger, L. E.; Suryanarayanan, R.; Naik, V. M.; Boolchand, P.

    2003-03-01

    Magnetic nanoparticles have potential applications ranging from drug delivery and imaging in the medical field to sensing and memory storage in technology. The preparation, structure, and physical properties of iron oxide-based nanoparticles synthesized by ion exchange in a polystyrene resin matrix have been investigated. Employing a synthesis method developed originally by Ziolo, et. al^1, nanoparticles were prepared in a sulfonated divinyl benzene polystyrene resin matrix using various aqueous solutions of (1) FeCl_2, (2) FeCl_3, (3) FeCl2 : 2FeCl3 , (4) 9FeCl2 : CoCl_2, and (5) 4FeCl2 : CoCl_2. Powder x-ray diffraction measurements were used to identify the phases present while transmission electron microscopy was used for particle size distribution determinations. SQUID magnetization measurements (field-cooled and zero-field-cooled) and Fe^57 Mössbauer effect measurements indicate the presence of ferromagnetic iron oxide phases and a superparamagnetic behavior with blocking temperatures (T_B) varying from 50 K to room temperature. Nanoparticles synthesized using a stoichiometric mixture of FeCl2 and FeCl3 exhibit the lowest TB and smallest particle size distribution. The Mössbauer effect measurements have also been used to identify the iron oxides phases present and their relative amounts in the nanoparticles ^1R.F. Ziolo, et al., Science 207, 219 (1992). *Permanent address: Kettering University, Flint, MI 48504

  11. Magnetism and metal insulator transition in FeSi and FeGe. Ab Initio investigations of the electronic structure; Magnetismus und Metall-Isolator-Uebergang in FeSi und FeGe. Ab-initio-Untersuchungen der elektronischen Struktur

    Energy Technology Data Exchange (ETDEWEB)

    Neef, Matthias

    2007-03-19

    Aim of this thesis was to reach by a systematic study of different ab initio procedures an improved description of the electronic properties of FeSi and FeGe. Central result is the itinerant description of FeSi as a semiconductor in the neighbourhood of a ferromagnetic instability. The regardment of the nonlocal exchange in the effective one-particle approximation leads to a metastable magnetic state scarcely above the magnetic ground state. The application of the hybrid functional leads to a 1st order metal-isolator transition for large lattice parameters: FeSi transforms at increasement of the lattice parameter from an unmagnetic isolator to a magnetic metal. A similar behavior is found in the isostructural compound FeGe. The two systems FeSi and FeGe were systematically and detailedly analyzed by means of ab initio procedures. Thereby the structural, electronic, and magnetic properties were studied with DFT and HF calculations. Both calculations with spin polarization and without spin polarization were performed.

  12. Timing for a sustainable fertilisation of Glycine max by using HBED/Fe3+ and EDDHA/Fe3+ chelates.

    Science.gov (United States)

    Martín-Fernández, Clara; López-Rayo, Sandra; Hernández-Apaolaza, Lourdes; Lucena, Juan J

    2017-07-01

    Efficient use of Fe chelates is crucial to avoid environmental risks and reduce economic losses. HBED/Fe 3+ has been recently approved by the European Union for soil fertilisation, but studies delving into the best timing for its application are necessary. In this work, a batch incubation experiment and two biological experiments were developed to determine the optimal physiological stage for a sustainable application of HBED/Fe 3+ in soil fertilisation compared with EDDHA/Fe 3+ fertilisers using 57 Fe. HBED/Fe 3+ demonstrated a high durability in soils and soil materials, maintaining more than 80% of Fe chelated after 70 days, and its application at an early physiological stage resulted in a high Fe accumulation in soybean and soil after 36 days. In contrast, the stability of EDDHA/Fe 3+ decreased because of the retention of its lowest stable isomers. The best timing for chelates application was confirmed in a 52 day experiment. The application of HBED/Fe 3+ at the early stage increased the Fe translocation to fruits; while o,o-EDDHA/Fe 3+ accumulated more Fe in fruits when added at the fructification stage. The high HBED/Fe 3+ stability in calcareous soil requires a differentiate application timing, and its addition at early physiological stages leads into the most efficient fertilisation. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  13. N2O decomposition over Fe/ZSM-5: reversible generation of highly active cationic Fe species

    NARCIS (Netherlands)

    Zhu, Q.; Hensen, E.J.M.; Mojet, B.L.; Wolput, van J.H.M.C.; Santen, van R.A.

    2002-01-01

    Fe-oxide species in Fe/ZSM-5 (prepared by chemical vapor deposition of FeCl3)-active in N2O decomposition-react with zeolite protons during high temperature calcination to give highly active cationic Fe species, this transformation being reversible upon exposure to water vapor at lower temperature

  14. Magnetic properties of ball-milled TbFe2 and TbFe2B

    Indian Academy of Sciences (India)

    Unknown

    1. Introduction. The RFe2 (R = rare earth) Laves phase compounds are known to possess large cubic anisotropy (Clark et al 1972) and highest Curie temperature (TC) of all RT2 compounds. (T = transition metal). RFe2 ... TbFe2 and TbFe2B were prepared by arc melting the high pure elements (Tb and B, 99⋅9% purity; Fe, ...

  15. μ(4)-Orthothio-carbonato-tetra-kis-[tri-carbonyl-iron(I)](2 Fe-Fe).

    Science.gov (United States)

    Shi, Yao-Cheng; Cheng, Huan-Ren; Yuan, Li-Min; Li, Qian-Kun

    2011-11-01

    The fused bis-butterfly-shaped title compound, [Fe(4)(CS(4))(CO)(12)], possesses an orthothio-carbonate (CS(4) (4-)) ligand that acts as a bridge between two Fe(2)(CO)(6) units. A short intra-molecular S⋯S contact [2.6984 (8) and 2.6977 (8) Å] occurs in each S(2)Fe(2)(CO)(6) fragment.

  16. Protein profile of Beta vulgaris leaf apoplastic fluid and changes induced by Fe deficiency and Fe resupply

    Directory of Open Access Journals (Sweden)

    Laura eCeballos-Laita

    2015-03-01

    Full Text Available The fluid collected by direct leaf centrifugation has been used to study the proteome of the sugar beet apoplastic fluid as well as the changes induced by Fe deficiency and Fe resupply to Fe-deficient plants in the protein profile. Plants were grown in Fe-sufficient and Fe-deficient conditions, and Fe resupply was carried out with 45 μM Fe(III-EDTA for 24 h. Protein extracts of leaf apoplastic fluid were analyzed by two-dimensional isoelectric focusing-SDS-PAGE electrophoresis. Gel image analysis revealed 203 consistent spots, and proteins in 81% of them (164 were identified by nLC-MS/MS using a custom made reference repository of beet protein sequences. When redundant UniProt entries were deleted, a non-redundant leaf apoplastic proteome consisting of 109 proteins was obtained. TargetP and SecretomeP algorithms predicted that 63% of them were secretory proteins. Functional classification of the non-redundant proteins indicated that stress and defense, protein metabolism, cell wall and C metabolism accounted for approximately 75% of the identified proteome. The effects of Fe-deficiency on the leaf apoplast proteome were limited, with only five spots (2.5% changing in relative abundance, thus suggesting that protein homeostasis in the leaf apoplast fluid is well maintained upon Fe shortage. The identification of three chitinase isoforms among proteins increasing in relative abundance with Fe-deficiency suggests that one of the few effects of Fe deficiency in the leaf apoplast proteome includes cell wall modifications. Iron resupply to Fe deficient plants changed the relative abundance of 16 spots when compared to either Fe-sufficient or Fe-deficient samples. Proteins identified in these spots can be broadly classified as those responding to Fe-resupply, which included defense and cell wall related proteins, and non-responsive, which are mainly protein metabolism related proteins and whose changes in relative abundance followed the same trend as

  17. Phase analysis of Fe-nanowires encapsulated into multi-walled carbon nanotubes via 57Fe Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Ruskov, T.; Spirov, I.; Ritschel, M.; Mueller, C.; Leonhardt, A.; Ruskov, R.

    2007-01-01

    We have performed morphological analysis of samples of Fe-nanowires encapsulated into aligned multi-walled carbon nanotubes (Fe-MWCNT) via 57 Fe Moessbauer spectroscopy. The aligned Fe-MWCNTs were obtained by pyrolysis of ferrocene onto an oxidized Si substrate. Transmission Moessbauer spectroscopy (TMS) and back scattered conversion electron Moessbauer spectroscopy (CEMS) were applied in order to distinguish different Fe-phases and their spatial distribution within the whole sample and along the tubes' height. A characterization (on a large spatial scale) of the aligned CNT samples were performed by obtaining TMS spectra for selected spots positioned at different locations of the sample. While the total Fe content changes considerably from one location to another, the γ-Fe/α-Fe phase ratio is constant onto a relatively large area. Using TMS and CEMS for all aligned Fe-MWCNTs samples it is also shown that along the CNT axes, going to the top of the nanotube the relative content of the γ-Fe phase increases. Going to the opposite direction, i.e. towards the silicon substrate, the relative content of the Fe 3 C phase increases, that is in agreement with our previous works. The results of an additional Moessbauer spectroscopy experiment in TMS and CEMS modes performed on a non-aligned sample support the conclusion that in our case the iron phases in the channels of carbon nanotubes are spatially separated as individual nanoparticles. The relative intensity ratio of the α-Fe phase Moessbauer sextets show good magnetic texture along nanotubes axis for one of the aligned samples and the lack of such orientation for the others. (authors)

  18. Magnetic properties of {alpha}-Fe and Fe{sub 3}C nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Lutz, M U; Weissker, U; Wolny, F; Mueller, C; Loeffler, M; Muehl, T; Leonhardt, A; Buechner, B; Klingeler, R, E-mail: m.lutz@ifw-dresden.d [Leibniz Institute for Solid State and Materials Research IFW Dresden, Helmholtzstrasse 20, 01069 Dresden (Germany)

    2010-01-01

    The magnetic properties of single domain {alpha}-Fe and Fe{sub 3}C nanowires encapsulated within Multi Walled Carbon Nanotubes (MWNT) are investigated with a Magnetic Force Microscope (MFM). The wires are formed during the Chemical Vapour Deposition growth process, partially filling the hollow center of the MWNTs. The wires have a diameter variation of 10-60nm and can be several {mu}m long. The phase and crystal orientation of the filling relative to the long tube axis are probed by Transmission Electron Microscopy. The remanent magnetization states of the wires are investigated by MFM imaging. The {alpha}-Fe wires show shape dominated magnetization along the tube axis, whereas the FesC wires show a perpendicular magnetization imposed by magneto-crystalline anisotropy. Switching fields of {alpha}-Fe nanowires are determined by the application of an in-situ magnetic field, revealing a tip triggered magnetization reversal by localized nucleation.

  19. A subsurface Fe-silicate weathering microbiome

    Science.gov (United States)

    Napieralski, S. A.; Buss, H. L.; Roden, E. E.

    2017-12-01

    Traditional models of microbially mediated weathering of primary Fe-bearing minerals often invoke organic ligands (e.g. siderophores) used for nutrient acquisition. However, it is well known that the oxidation of Fe(II) governs the overall rate of Fe-silicate mineral dissolution. Recent work has demonstrated the ability of lithtrophic iron oxidizing bacteria (FeOB) to grow via the oxidation of structural Fe(II) in biotite as a source of metabolic energy with evidence suggesting a direct enzymatic attack on the mineral surface. This process necessitates the involvement of dedicated outer membrane proteins that interact with insoluble mineral phases in a process known as extracellular electron transfer (EET). To investigate the potential role FeOB in a terrestrial subsurface weathering system, samples were obtained from the bedrock-saprolite interface (785 cm depth) within the Rio Icacos Watershed of the Luquillo Mountains in Puerto Rico. Prior geochemical evidence suggests the flux of Fe(II) from the weathering bedrock supports a robust lithotrophic microbial community at depth. Current work confirms the activity of microorganism in situ, with a marked increase in ATP near the bedrock-saprolite interface. Regolith recovered from the interface was used as inoculum to establish enrichment cultures with powderized Fe(II)-bearing minerals serving as the sole energy source. Monitoring of the Fe(II)/Fe(total) ratio and ATP generation suggests growth of microorganisms coupled to the oxidation of mineral bound Fe(II). Analysis of 16S rRNA gene and shotgun metagenomic libraries from in situ and enrichment culture samples lends further support to FeOB involvement in the weathering process. Multiple metagenomic bins related to known FeOB, including Betaproteobacteria genera, contain homologs to model EET systems, including Cyc2 and MtoAB. Our approach combining geochemistry and metagenomics with ongoing microbiological and genomic characterization of novel isolates obtained

  20. Epitaxial Fe3Si/Ge/Fe3Si thin film multilayers grown on GaAs(001)

    International Nuclear Information System (INIS)

    Jenichen, B.; Herfort, J.; Jahn, U.; Trampert, A.; Riechert, H.

    2014-01-01

    We demonstrate Fe 3 Si/Ge/Fe 3 Si/GaAs(001) structures grown by molecular-beam epitaxy and characterized by transmission electron microscopy, electron backscattered diffraction, and X-ray diffraction. The bottom Fe 3 Si epitaxial film on GaAs is always single crystalline. The structural properties of the Ge film and the top Fe 3 Si layer depend on the substrate temperature during Ge deposition. Different orientation distributions of the grains in the Ge and the upper Fe 3 Si film were found. The low substrate temperature T s of 150 °C during Ge deposition ensures sharp interfaces, however, results in predominantly amorphous films. We find that the intermediate T s (225 °C) leads to a largely [111] oriented upper Fe 3 Si layer and polycrystal films. The high T s of 325 °C stabilizes the [001] oriented epitaxial layer structure, i.e., delivers smooth interfaces and single crystal films over as much as 80% of the surface area. - Highlights: • Fe 3 Si/Ge/Fe 3 Si/GaAs(001) structures are grown by MBE. • The bottom Fe 3 Si film is always single crystalline. • The properties of the Ge film depend on the substrate temperature during deposition. • Optimum growth conditions lead to almost perfect epitaxy of Ge on Fe 3 Si

  1. Study of the reaction of astrophysical interest 60Fe(n,γ)61Fe via (d,pγ) transfer reaction

    International Nuclear Information System (INIS)

    Giron, S.

    2011-12-01

    60 Fe is of special interest in nuclear astrophysics. Indeed the recent observations of 60 Fe characteristic gamma-ray lines by the RHESSI and INTEGRAL spacecrafts allowed to measure the total flux of 60 Fe over the Galaxy. Moreover the observation in presolar grains of an excess of the daughter-nuclei of 60 Fe, 60 Ni, gives constraints on the conditions of formation of the early solar system. However, the cross-sections of some reactions involved in 60 Fe nucleosynthesis and included to stellar models are still uncertain. The destruction reaction of 60 Fe, 60 Fe(n, γ) 61 Fe, is one of them. The total cross-section can be separate into two contributions: the direct one, involving states below the neutron separation threshold of 61 Fe, and the resonant one.We improved 61 Fe spectroscopy in order to evaluate the direct capture part of the 60 Fe(n, γ) 61 Fe reaction cross-section. 60 Fe(n, γ) 61 Fe was thus studied via d( 60 Fe, pγ) 61 Fe transfer reaction with the CATS/MUST2/EXOGAM setup at LISE-GANIL. DWBA analysis of experimental proton differential cross-sections allowed to extract orbital angular momentum and spectroscopic factors of different populated states identified below the neutron threshold. A comparison of experimental results for 61 Fe with experimental results for similar nuclei and with shell-model calculations was also performed. (author) [fr

  2. Magnetization reversal in textured NdFeB-Fe composites observed by domain imaging

    Energy Technology Data Exchange (ETDEWEB)

    Thielsch, Juliane, E-mail: j.thielsch@ifw-dresden.d [IFW Dresden, Institute for Metallic Materials, P.O. Box 27 01 16, D-01171 Dresden (Germany); Hinz, Dietrich; Schultz, Ludwig; Gutfleisch, Oliver [IFW Dresden, Institute for Metallic Materials, P.O. Box 27 01 16, D-01171 Dresden (Germany)

    2010-10-15

    Textured composite samples consisting of Nd{sub 13.6}Fe{sub 73.6}Ga{sub 0.6}Co{sub 6.6}B{sub 5.6} (MQU-F{sup TM}) and micron-sized Fe particles with weight ratios from 100:0 to 70:30 have been prepared by hot deformation. Microstructure studies revealed a layered structure of both phases with the layer normal parallel to the pressing direction. Magnetic measurements showed single-phase hysteresis curves for all samples when measured along the pressing direction, which is also the easy axis of magnetization. Coercivity decreased drastically from 1.32 T for pure NdFeB samples to 0.154 T for a sample with 30 wt% Fe. Magneto-optical Kerr microscopy with a digitally enhanced imaging technique has been used to examine the evolution of magnetic domains in the hard and soft phase during demagnetizing a sample consisting of 70 wt% NdFeB and 30 wt% Fe. It is shown that demagnetization takes place via domain rearrangements within the soft phase, which lead to and support the nucleation of reversed interaction domains at phase boundaries. Also nucleation of interaction domains within the hard magnetic phase could be revealed.

  3. Magnetization reversal in textured NdFeB-Fe composites observed by domain imaging

    International Nuclear Information System (INIS)

    Thielsch, Juliane; Hinz, Dietrich; Schultz, Ludwig; Gutfleisch, Oliver

    2010-01-01

    Textured composite samples consisting of Nd 13.6 Fe 73.6 Ga 0.6 Co 6.6 B 5.6 (MQU-F TM ) and micron-sized Fe particles with weight ratios from 100:0 to 70:30 have been prepared by hot deformation. Microstructure studies revealed a layered structure of both phases with the layer normal parallel to the pressing direction. Magnetic measurements showed single-phase hysteresis curves for all samples when measured along the pressing direction, which is also the easy axis of magnetization. Coercivity decreased drastically from 1.32 T for pure NdFeB samples to 0.154 T for a sample with 30 wt% Fe. Magneto-optical Kerr microscopy with a digitally enhanced imaging technique has been used to examine the evolution of magnetic domains in the hard and soft phase during demagnetizing a sample consisting of 70 wt% NdFeB and 30 wt% Fe. It is shown that demagnetization takes place via domain rearrangements within the soft phase, which lead to and support the nucleation of reversed interaction domains at phase boundaries. Also nucleation of interaction domains within the hard magnetic phase could be revealed.

  4. High saturation magnetization FeB(C) nanocapsules

    International Nuclear Information System (INIS)

    Ma, S.; Si, P.Z.; Zhang, Y.; Wu, B.; Li, Y.B.; Liu, J.J.; Feng, W.J.; Ma, X.L.; Zhang, Z.D.

    2007-01-01

    FeB(C) nanocapsules were prepared by arc-discharging Fe 80 B 20 alloy in Ar and CH 4 . X-ray diffraction and transmission electron microscopy analyses showed that the FeB(C) nanocapsules had a core-shell structure with α-Fe and Fe 3 B as cores and graphite as shells. The formation mechanism of the FeB(C) nanocapsules is discussed. The graphite shells display a strong anti-acid effect. The saturation magnetization at room temperature of the FeB(C) nanocapsules is much higher than that of Fe(B) nanocapsules. The blocking temperature of FeB(C) nanocapsules is above 300 K

  5. Enhanced antibacterial performance of Fe3O4–Ag and MnFe2O4 ...

    Indian Academy of Sciences (India)

    sity in our daily life. ... enhances the biological activity of Ag NPs, but many stud- ... against Gram-positive and Gram-negative bacteria in this ..... Antimicrobial effects of Fe3O4@Nico@Ag, Fe3O4@His@Ag and Fe3O4@HA@Ag against Fe3O4 ...

  6. Microstructure and Properties of Fe3Al-Fe3AlC x Composite Prepared by Reactive Liquid Processing

    Science.gov (United States)

    Verona, Maria Nalu; Setti, Dalmarino; Paredes, Ramón Sigifredo Cortés

    2018-04-01

    A Fe3Al-Fe3AlC x composite was prepared using reactive liquid processing (RLP) through controlled mixture of carbon steel and aluminum in the liquid state. The microstructure and phases of the composite were assessed using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, optical microscopy, and differential scanning calorimetry. In addition, the density, hardness, microhardness, and elastic modulus were evaluated. The Fe3Al-Fe3AlC x composite consisted of 65 vol pct Fe3Al and 35 vol pct Fe3AlC x ( κ). The κ phase contained 10.62 at. pct C, resulting in the stoichiometry Fe3AlC0.475. The elastic modulus of the Fe3Al-Fe3AlC0.475 composite followed the rule of mixtures. The RLP technique was shown to be capable of producing Fe3Al-Fe3AlC0.475 with a microstructure and properties similar to those achieved using other processing techniques reported in the literature.

  7. Efficacy of Fe(o,o-EDDHA) and Fe(o,p-EDDHA) isomers in supplying Fe to strategy I plants differs in nutrient solution and calcareous soil.

    Science.gov (United States)

    Rojas, Carmen L; Romera, Francisco J; Alcántara, Esteban; Pérez-Vicente, Rafael; Sariego, Cristina; Garcaí-Alonso, J Ignacio; Boned, Javier; Marti, Gabriel

    2008-11-26

    The FeEDDHA [iron(3+) ethylenediamine di(o-hydroxyphenylacetic) acid] is one of the most efficient iron chelates employed in the correction of iron clorosis in calcareous soils. FeEDDHA presents different positional isomers: the ortho-ortho (o,o), the ortho-para (o,p), and the para-para (p,p). Of these isomers, the p,p cannot chelate Fe in soil solution in a wide range of pH values, while both o,o and o,p can. The objective of this work was to compare the efficiency of both isomers (o,o and o,p) to provide Fe to two Strategy I plants (tomato and peach) in nutrient solution (pH approximately 6.0), as well as in calcareous soil (pH approximately 8.4; CALCIXEREPT). For this, chelates of both o,o-EDDHA and o,p-EDDHA with 57Fe (a nonradioactive isotope of Fe) were used, where the 57Fe acts as a tracer. The results obtained showed that the o,o isomer is capable of providing sufficient Fe to plants in both nutrient solution and calcareous soil. However, the o,p isomer is capable of providing sufficient Fe to plants in nutrient solution but not in calcareous soil.

  8. Fabrication of NdFeB microstructures using a silicon molding technique for NdFeB/Ta multilayered films and NdFeB magnetic powder

    International Nuclear Information System (INIS)

    Jiang Yonggang; Fujita, Takayuki; Uehara, Minoru; Iga, Yuki; Hashimoto, Taichi; Hao, Xiuchun; Higuchi, Kohei; Maenaka, Kazusuke

    2011-01-01

    The silicon molding technique is described for patterning of NdFeB/Ta multilayered magnetic films and NdFeB magnetic powder at the micron scale. Silicon trenches are seamlessly filled by 12-μm-thick NdFeB/Ta multilayered magnetic films with a magnetic retentivity of 1.3 T. The topography image and magnetic field distribution image are measured using an atomic force microscope and a magnetic force microscope, respectively. Using a silicon molding technique complemented by a lift-off process, NdFeB magnetic powder is utilized to fabricate magnetic microstructures. Silicon trenches as narrow as 20 μm are filled by a mixture of magnetic powder and wax powder. The B-H hysteresis loop of the patterned magnetic powder is characterized using a vibrating sample magnetometer, which shows a magnetic retentivity of approximately 0.37 T. - Highlights: → We demonstrate the fabrication of micro-magnets using silicon molding processes. → NdFeB/Ta films are well filled in silicon trenches with a thickness of 12 μm. → The 12-μm-thick NdFeB/Ta magnetic film shows a retentivity of 1.3 T. → Magnetic structures as narrow as 20 μm are fabricated using NdFeB magnetic powder. → VSM measurement shows a retentivity of 0.37 T for patterned NdFeB magnetic powder.

  9. Fabrication of NdFeB microstructures using a silicon molding technique for NdFeB/Ta multilayered films and NdFeB magnetic powder

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Yonggang, E-mail: yonggangj@gmail.com [School of Mechanical Engineering and Automation, Beihang University, Xueyuan Road No. 37, Haidian District, Beijing 100191 (China); Maenaka Human-Sensing Fusion project, Japan Science and Technology Agency, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Fujita, Takayuki [Maenaka Human-Sensing Fusion project, Japan Science and Technology Agency, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Uehara, Minoru [NEOMAX Co. Ltd., 2-15-17, Egawa, Shimamoto-Cho, Mishima-gun, Osaka 618-0013 (Japan); Iga, Yuki [Maenaka Human-Sensing Fusion project, Japan Science and Technology Agency, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Hashimoto, Taichi [Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Hao, Xiuchun; Higuchi, Kohei [Maenaka Human-Sensing Fusion project, Japan Science and Technology Agency, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Maenaka, Kazusuke [Maenaka Human-Sensing Fusion project, Japan Science and Technology Agency, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan); Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280 (Japan)

    2011-11-15

    The silicon molding technique is described for patterning of NdFeB/Ta multilayered magnetic films and NdFeB magnetic powder at the micron scale. Silicon trenches are seamlessly filled by 12-{mu}m-thick NdFeB/Ta multilayered magnetic films with a magnetic retentivity of 1.3 T. The topography image and magnetic field distribution image are measured using an atomic force microscope and a magnetic force microscope, respectively. Using a silicon molding technique complemented by a lift-off process, NdFeB magnetic powder is utilized to fabricate magnetic microstructures. Silicon trenches as narrow as 20 {mu}m are filled by a mixture of magnetic powder and wax powder. The B-H hysteresis loop of the patterned magnetic powder is characterized using a vibrating sample magnetometer, which shows a magnetic retentivity of approximately 0.37 T. - Highlights: > We demonstrate the fabrication of micro-magnets using silicon molding processes. > NdFeB/Ta films are well filled in silicon trenches with a thickness of 12 {mu}m. > The 12-{mu}m-thick NdFeB/Ta magnetic film shows a retentivity of 1.3 T. > Magnetic structures as narrow as 20 {mu}m are fabricated using NdFeB magnetic powder. > VSM measurement shows a retentivity of 0.37 T for patterned NdFeB magnetic powder.

  10. Fabrication of α-Fe/Fe3C/Woodceramic Nanocomposite with Its Improved Microwave Absorption and Mechanical Properties

    Directory of Open Access Journals (Sweden)

    Weihong Zhou

    2018-05-01

    Full Text Available Furan resin and fir powder pretreated by FeCl3 and aqueous ammonia solution were used to fabricate α-Fe/Fe3C/woodceramic nanocomposite. The bands of the pretreated wood powder were characterized by Fourier transform infrared spectroscopy (FTIR. The structural characterization of the nanocomposites was performed by scanning electron microscopy (SEM and X-ray diffraction (XRD. The microwave absorption of the nanocomposites was measured by a vector network analyzer in the range of 2–18 GHz. The mechanical properties of the composites were also investigated. XRD and SEM results show that the α-Fe and Fe3C nanoparticles are in-situ generated and disperse in the matrix of the woodceramic. The diameters of these nanoparticles increase with the increasing of concentration of FeCl3 solution. The experimental results show that both the complex permittivity and the complex permeability of α-Fe/Fe3C/woodceramic nanocomposites increase as the concentration of FeCl3 solution increases. The composites pretreated with 0.60 mol·L−1 FeCl3 have the best absorption properties. The maximum value of reflection loss (RL at 3 mm thickness reaches −25.60 dB at 10.16 GHz and the bandwidth below −10 dB is about 2.5 GHz. Compared to woodceramic, the bending strength and compressive strength of α-Fe/Fe3C/woodceramic nanocomposites increase by 22.5% and 18.7% at most, respectively.

  11. Swelling of Fe-Mn and Fe-Cr-Mn alloys at high neutron fluence

    International Nuclear Information System (INIS)

    Garner, F.A.; Brager, H.R.

    1986-06-01

    Swelling data on neutron-irradiated simple Fe-Cr-Mn and Fe-Mn alloys, as well as commercial Fe-Cr-Mn base alloys are now becoming available at exposure levels approaching 50 dpa. The swelling rate decreases from the ∼1%/dpa found at lower exposures, probably due to the extensive formation of ferritic phases. As expected, commercial alloys swell less than the simple alloys

  12. Structural Investigation of Fe-Ni-S and Fe-Ni-Si Melts by High-temperature Fluorescence XAFS Measurements

    International Nuclear Information System (INIS)

    Manghnani, Murli H.; Balogh, John; Hong Xinguo; Newville, Matthew; Amulele, G.

    2007-01-01

    Iron-nickel (Fe-Ni) alloy is regarded as the most abundant constituent of Earth's core, with an amount of 5.5 wt% Ni in the core based on geochemical and cosmochemical models. The structural role of nickel in liquid Fe-Ni alloys with light elements such as S or Si is poorly understood, largely because of the experimental difficulties of high-temperature melts. Recently, we have succeeded in acquiring Ni K-edge fluorescence x-ray absorption fine structure (XAFS) spectra of Fe-Ni-S and Fe-Ni-Si melts and alloys. Different structural environment of Ni atoms in Fe-Ni-S and Fe-Ni-Si melts is observed, supporting the effect of light elements in Fe-Ni melts

  13. Silicon induced Fe deficiency affects Fe, Mn, Cu and Zn distribution in rice (Oryza sativa L.) growth in calcareous conditions.

    Science.gov (United States)

    Carrasco-Gil, Sandra; Rodríguez-Menéndez, Sara; Fernández, Beatriz; Pereiro, Rosario; de la Fuente, Vicenta; Hernandez-Apaolaza, Lourdes

    2018-04-01

    A protective effect by silicon in the amelioration of iron chlorosis has recently been proved for Strategy 1 species, at acidic pH. However in calcareous conditions, the Si effect on Fe acquisition and distribution is still unknown. In this work, the effect of Si on Fe, Mn, Cu and Zn distribution was studied in rice (Strategy 2 species) under Fe sufficiency and deficiency. Plants (+Si or-Si) were grown initially with Fe, and then Fe was removed from the nutrient solution. The plants were then analysed using a combined approach including LA-ICP-MS images for each element of interest, the analysis of the Fe and Si concentration at different cell layers of root and leaf cross sections by SEM-EDX, and determining the apoplastic Fe, total micronutrient concentration and oxidative stress indexes. A different Si effect was observed depending on plant Fe status. Under Fe sufficiency, Si supply increased Fe root plaque formation, decreasing Fe concentration inside the root and increasing the oxidative stress in the plants. Therefore, Fe acquisition strategies were activated, and Fe translocation rate to the aerial parts was increased, even under an optimal Fe supply. Under Fe deficiency, +Si plants absorbed Fe from the plaque more rapidly than -Si plants, due to the previous activation of Fe deficiency strategies during the growing period (+Fe + Si). Higher Fe plaque formation due to Si supply during the growing period reduced Fe uptake and could activate Fe deficiency strategies in rice, making it more efficient against Fe chlorosis alterations. Silicon influenced Mn and Cu distribution in root. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

  14. Magnetostrictive properties of FeAl/polyester and FeAl/silicone composites

    Energy Technology Data Exchange (ETDEWEB)

    Riesgo, G. [Dpto. de Ciencias y Técnicas de la Navegación, Universidad de Oviedo, Campus universitario de Gijón, 33203 Gijón (Spain); Carrizo, J. [Dpto. de Física de la Universidad de Oviedo, c/ Calvo Sotelo s/n, 33007 Oviedo (Spain); Elbaile, L., E-mail: elbaile@uniovi.es [Dpto. de Física de la Universidad de Oviedo, c/ Calvo Sotelo s/n, 33007 Oviedo (Spain); Crespo, R.D. [Dpto. de Física de la Universidad de Oviedo, c/ Calvo Sotelo s/n, 33007 Oviedo (Spain); Sepúlveda, R. [Dpto. de Ingeniería Mecánica y de los Materiales, Universidad de Sevilla, Isla Cartuja, 41092 Sevilla (Spain); García, J.A. [Dpto. de Física de la Universidad de Oviedo, c/ Calvo Sotelo s/n, 33007 Oviedo (Spain)

    2017-01-15

    Highlights: • Nanocrystalline powders of FeAl have been obtained from the Fe{sub 81}Al{sub 19} ribbon produced by melt spinning. • The method allows the obtainment of a FeAl solid solution from the starting process. • The microstructure and magnetic properties of the powders were investigated. • Composites with a magnetostriction of 45 ppm have been obtained. - Abstract: Ribbons of composition Fe{sub 81}Al{sub 19} obtained by the melt spinning method have been used to yield powder by mechanical milling. Using this method, a rapid nanocrystallization and a FeAl solid solution phase was obtained from the start of the process. The microstructural and magnetic properties as well as the XRD patterns of the powders were studied in function of the milling time. Grain refinement and an increase of the coercive field were the main transformations resulting from increasing the milling time. Two sets of magnetostrictive composites were produced from the 100 h-milled powder. In one of them polyester was used as matrix and in the other one silicone. In the case of the silicone composites cured in a magnetic field of 140 mT in the longitudinal direction a saturation magnetostriction as high as 45 ppm was obtained.

  15. Fe II/Fe III mixed-valence state induced by Li-insertion into the metal-organic-framework Mil53(Fe): A DFT+U study

    Science.gov (United States)

    Combelles, C.; Ben Yahia, M.; Pedesseau, L.; Doublet, M.-L.

    The iron-based metal-organic-framework MIL53(Fe) has recently been tested as a cathode materials for Li-Ion batteries, leading to promising cycling life and rate capability. Despite a poor capacity of 70 mAh g -1 associated with the exchange of almost 0.5Li/Fe, this result is the first evidence of a reversible lithium insertion never observed in a MOF system. In the present study, the MIL53(Fe) redox mechanism is investigated through first-principles DFT+U calculations. The results show that MIL53(Fe) is a weak antiferromagnetic charge transfer insulator at T = 0 K, with iron ions in the high-spin S = 5/2 state. Its reactivity vs elemental lithium is then investigated as a function of lithium composition and distribution over the most probable Li-sites of the MOF structure. The redox mechanism is fully interpreted as a two-step insertion/conversion mechanism, associated with the stabilization of the Fe 3+/Fe 2+ mixed-valence state prior to the complete decomposition of the inorganic-organic interactions within the porous MOF architecture.

  16. Acetone sensors based on microsheet-assembled hierarchical Fe2O3 with different Fe3+ concentrations

    Science.gov (United States)

    Wang, Han; Yan, Lei; Li, Shuo; Li, Yu; Liu, Li; Du, Liting; Duan, Haojie; Cheng, Yali

    2018-02-01

    Several different morphologies of microsheet-assembled Fe2O3 have been fabricated by hydrothermal method using diverse concentrations of Fe3+ precursor solutions (0.025, 0.020, 0.015, 0.010 mol/L Fe3+). The as-synthesized materials have been characterized by scanning electron microscope (SEM), X-ray powder diffraction (XRD), and energy-dispersive X-ray spectrometry (EDS). The SEM images reflect that the morphologies of as-synthesized materials are affected by the concentrations of Fe3+ in precursor solutions. The less concentration of Fe3+, the more porous of Fe2O3 microflowers, and thinner of slices distributed on the surface. Furthermore, gas sensors based on these Fe2O3 microflowers manufactured and tested to various common gases. The optimum response value to 100 ppm acetone is 52 at the working temperature of 220 °C. Meanwhile, the Fe2O3 microflower sensors possess ultrafast response-recovery speed, which are 8 and 19 s, respectively. The possible sensing mechanism was mainly attributed to the high surface area, three-dimensional porous structure.

  17. Chemical synthesis of magnetic Fe-B and Fe-Co-B particles and chains

    International Nuclear Information System (INIS)

    Fulmer, P.; Kim, J.; Manthiram, A.; Sanchez, J.M.

    1999-04-01

    With an objective to develop magnetic materials with high saturation magnetization for the Magnetically Assisted Chemical Separation (MACS) process the chemical synthesis of Fe-B and Fe-Co-B alloys by reducing iron and cobalt chloride solutions with potassium borohydride has been investigated systematically. The influence of the concentration of the reactants, applied magnetic field, reaction atmosphere, and method of mixing the reactants on the microstructure, particle size, composition and magnetic properties has been studied. Both M-B (M = Fe and Co) particles and elongated chains composed of nanometer size M-B particles have been obtained depending on the reaction conditions. The Fe-B samples exhibit saturation magnetization of M S of 120--190 emu/g, remanent magnetization M r of 10--22 emu/g, and coercive field H c of 400--900 Oe. A high M S value of 190 emu/g, which is close to the theoretical value of 218 emu/g for pure Fe, has been achieved particularly for samples with well-defined chain structures. Increasing the Co content in the Fe-Co-B alloys increases the boron content and thereby decreases the crystallinity and M S values although marginal increase in H c (1,250 Oe) and M r (36 emu/g) values could be made in some Fe-Co-B compositions. The chain structure with high M S may be attractive for other magnetic separation processes as well

  18. Uptake and Release of Cerium During Fe-Oxide Formation and Transformation in Fe(II) Solutions

    DEFF Research Database (Denmark)

    Nedel, Sorin; Dideriksen, Knud; Christiansen, Bo C.

    2010-01-01

    Fe-oxides are ubiquitous in soils and sediments and form during Fe(0) corrosion. Depending on redox conditions and solution composition, Fe-oxides such as ferrihydrite, goethite, magnetite, and green rust (GR) may form. These phases typically have high surface area and large affinity for adsorption......(III) release. X-ray photoelectron spectroscopy revealed Ce(III) adsorbed on magnetite. When Fe-oxides were synthesized by air oxidation of Fe(II) solutions at pH 7, GR(Na,SO4) played a catalytic role in the oxidation of Ce(III) to Ce(IV) by O-2, removing more than 90% of the dissolved Ce. Transmission electron...

  19. Adsorption induced modification of in-plane magnetic anisotropy in epitaxial Co and Fe/Co films on Fe(110)

    Science.gov (United States)

    Ślezak, M.; Ślezak, T.; Matlak, K.; DróŻdŻ, P.; Korecki, J.

    2018-05-01

    A study of in-plane magnetic anisotropy (MA) in epitaxial bcc Co films and Fe/Co bilayers on a Fe(110) surface is reported. Surface MA of as-deposited Co films and Fe/Co bilayers strongly depends on the Co (dCo) and Fe (dFe) thickness. Adsorption of residual gases drastically modifies in-plane MA of both Co films and Fe/Co bilayers. We present two dimensional MA maps in the (dCo, dFe) space for both as grown and adsorption-modified films. Our results indicate how to precisely engineer in-plane MA that can be controlled by dCo, dFe and is sensitive to the residual gas adsorption.

  20. Thermodynamical properties of 56Fe

    International Nuclear Information System (INIS)

    Tavukcu, E.; Becker, J. A.; Bernstein, L. A.; Garrett, P. E.; Younes, W.; Guttormsen, M.; Rekstad, J.; Siem, S.; Mitchell, G. E.; Schiller, A.; Voinov, A.

    2003-01-01

    Average nuclear level densities close to the nuclear binding energy in 56Fe and 57Fe are extracted from primary γ-ray spectra. A step structure is observed in the level density for both isotopes, and is interpreted as breaking of Cooper pairs. Thermal properties of 56Fe are studied within the statistical canonical ensemble. The experimental heat capacity in 56Fe is compared with the theoretical heat capacity calculated within the shell model Monte Carlo approach

  1. Ab-initio study of the interfacial properties in ultrathin MgO films on O-rich FeO/Fe(001) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Junjin; Yu, Byungdeok [University of Seoul, Seoul (Korea, Republic of)

    2014-09-15

    Using ab-initio simulations based on density functional theory, we systematically studied the interfacial properties of MgO films on O-rich FeO/Fe(001) surfaces with increasing number of MgO layers from one to three monolayers (MLs). The structural and the adhesion properties of the MgO/FeO/Fe(001) system were assessed and compared with those of simple MgO/Fe(001) interfaces. Our calculated results showed that the adhesion energy for MgO/FeO/Fe(001) was smaller than that for simple MgO/Fe(001). An analysis of the electronic structures and the charge rearrangements of the MgO/FeO/Fe(001) interfaces was also performed. The work functions of the MgO/FeO/Fe(001) systems upon the deposition of MgO films exhibited smaller decreases (0.45 - 0.67 eV) than those (1.43 - 1.74 eV) of the MgO/Fe(001) systems. In addition, the obtained work functions (3.77 - 3.99 eV) for MgO/FeO/Fe(001) were much larger than those (2.12 - 2.43 eV) for MgO/Fe(001).

  2. Fabricating Fe3O4/Fe/Biocarbon Fibers using Cellulose Nanocrystals for High-Rate Li-ion Battery Anode

    International Nuclear Information System (INIS)

    Zhang, Shuzhen; He, Wen; Zhang, Xudong; Yang, Guihua; Ma, Jingyun; Yang, Xuena; Song, Xin

    2015-01-01

    Highlights: • Mesoporous biocarbon fibers adhered with Fe 3 O 4 /Fe nanoparticles (Fe 3 O 4 /Fe/MBCFs) are synthesized. • This method uses the natural cotton as a template and carbon source. • Fe 3 O 4 /Fe/MBCFs exhibit excellent cycling performance at higher current. - ABSTRACT: Searching the high rate Fe 3 O 4 -based materials for lithium ion batteries (LIBs) is still a great challenge. Here we tackle this problem by developing a facile and green method which uses the natural cotton as a biotemplate and a activity biocarbon source. By this new method, we synthesized the mesoporous biocarbon fibers adhered with Fe 3 O 4 /Fe nanoparticles (Fe 3 O 4 /Fe/MBCFs). Fe 3 O 4 /Fe/MBCFs are a highly stable anode material for high-rate LIBs due to its excellent cycling performance at higher current and fast charging feature. This anode shows a high reversible capacity of 472 mAh g −1 after 500 cycles and can be rapidly charge to 100% in 28.3 min. After 160 cycles at varied current densities from 1 A g −1 to 10 A g −1 , it still delivered a high discharge capacity of 524.6 mAh g −1 and an ultra-high coulombic efficiency close to 100%. This is attributed to the synergistic effects of several factors including the unique mesoporous hybrid construction, the graphitized biocarbon fibers and the chemical bonding between Fe 3 O 4 and Fe nanoparticles. This work is instructive for fabrication and design of nanostructured electrodes with extraordinary properties from biomass renewable resources

  3. Formation of hard magnetic L1{sub 0}-FePt/FePd monolayers from elemental multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Goo, Nam Hoon

    2007-06-18

    In this thesis, ordered L1{sub 0}-FePt and FePd films of different nominal compositions are prepared from Fe/Pt and Fe/Pd multilayers by annealing. In case of the L1{sub 0}-FePt films the composition of the films is modified by changing the individual elemental layer thicknesses in the multilayer precursors. This simple variation of the composition is the great advantage of the multilayer approach compared to sputtering single alloy layer from an alloy target. The formation mechanism of the fct phase from the multilayers and the microstructural properties are investigated. The characteristics of the hysteresis loop (coercivity {mu}{sub 0}H{sub c}, remanence J{sub r}) and of the intrinsic magnetic properties (anisotropy constant K{sub l}, spontaneous polarization J{sub s}, exchange constant A) of the ordered L1{sub 0}-FePt and FePd films are studied. The effects of the composition of the L1{sub 0}-FePt films on the microstructural and magnetic properties are investigated. The microstructure of these ordered L1{sub 0}-FePt films are then correlated to the magnetic properties with microstructural parameters by investigating the temperature dependence of the coercivity. (orig.)

  4. CoFeRh alloys

    International Nuclear Information System (INIS)

    Tabakovic, Ibro; Qiu Jiaoming; Riemer, Steve; Sun Ming; Vas'ko, Vlad; Kief, Mark

    2008-01-01

    The electrochemical behavior of Rh(III) species in CoFe solution containing RhCl 3 , NH 4 Cl, H 3 BO 3 , CoSO 4 , FeSO 4 , saccharin, and NaLS (Na lauryl sulfate) has been investigated. The electrochemistry of Rh(III) species is influenced by each of the compounds present in CoFe plating solution, but especially by addition of saccharin and H 3 BO 3 to the RhCl 3 -NH 4 Cl solution. The nucleation and growth of Rh on GC (glassy carbon), Ru, and Cu electrodes from NH 4 Cl solution was studied using the potentiostatic current-transient methods. The results support a predominantly progressive nucleation of Rh on all three-electrode surfaces. The nucleation kinetic parameters ANo (steady state nucleation r