Sample records for nanophase metallic iron

  1. Lunar dust simulant containing nanophase iron and method for making the same

    NASA Technical Reports Server (NTRS)

    Hung, Chin-cheh (Inventor); McNatt, Jeremiah (Inventor)

    2012-01-01

    A lunar dust simulant containing nanophase iron and a method for making the same. Process (1) comprises a mixture of ferric chloride, fluorinated carbon powder, and glass beads, treating the mixture to produce nanophase iron, wherein the resulting lunar dust simulant contains .alpha.-iron nanoparticles, Fe.sub.2O.sub.3, and Fe.sub.3O.sub.4. Process (2) comprises a mixture of a material of mixed-metal oxides that contain iron and carbon black, treating the mixture to produce nanophase iron, wherein the resulting lunar dust simulant contains .alpha.-iron nanoparticles and Fe.sub.3O.sub.4.

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

    NASA Technical Reports Server (NTRS)

    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

  3. Simulations of Effects of Nanophase Iron Space Weather Products on Lunar Regolith Reflectance Spectra

    NASA Astrophysics Data System (ADS)

    Escobar-Cerezo, J.; Penttilä, A.; Kohout, T.; Muñoz, O.; Moreno, F.; Muinonen, K.

    2018-01-01

    Lunar soil spectra differ from pulverized lunar rocks spectra by reddening and darkening effects, and shallower absorption bands. These effects have been described in the past as a consequence of space weathering. In this work, we focus on the effects of nanophase iron (npFe0) inclusions on the experimental reflectance spectra of lunar regolith particles. The reflectance spectra are computed using SIRIS3, a code that combines ray optics with radiative-transfer modeling to simulate light scattering by different types of scatterers. The imaginary part of the refractive index as a function of wavelength of immature lunar soil is derived by comparison with the measured spectra of the corresponding material. Furthermore, the effect of adding nanophase iron inclusions on the reflectance spectra is studied. The computed spectra qualitatively reproduce the observed effects of space weathered lunar regolith.

  4. Nuclear fuel elements made from nanophase materials

    DOEpatents

    Heubeck, Norman B.

    1998-01-01

    A nuclear reactor core fuel element is composed of nanophase high temperature materials. An array of the fuel elements in rod form are joined in an open geometry fuel cell that preferably also uses such nanophase materials for the cell structures. The particular high temperature nanophase fuel element material must have the appropriate mechanical characteristics to avoid strain related failure even at high temperatures, in the order of about 3000.degree. F. Preferably, the reactor type is a pressurized or boiling water reactor and the nanophase material is a high temperature ceramic or ceramic composite. Nanophase metals, or nanophase metals with nanophase ceramics in a composite mixture, also have desirable characteristics, although their temperature capability is not as great as with all-ceramic nanophase material. Combinations of conventional or nanophase metals and conventional or nanophase ceramics can be employed as long as there is at least one nanophase material in the composite. The nuclear reactor so constructed has a number of high strength fuel particles, a nanophase structural material for supporting a fuel rod at high temperature, a configuration to allow passive cooling in the event of a primary cooling system failure, an ability to retain a coolable geometry even at high temperatures, an ability to resist generation of hydrogen gas, and a configuration having good nuclear, corrosion, and mechanical characteristics.

  5. Nuclear fuel elements made from nanophase materials

    DOEpatents

    Heubeck, N.B.

    1998-09-08

    A nuclear reactor core fuel element is composed of nanophase high temperature materials. An array of the fuel elements in rod form are joined in an open geometry fuel cell that preferably also uses such nanophase materials for the cell structures. The particular high temperature nanophase fuel element material must have the appropriate mechanical characteristics to avoid strain related failure even at high temperatures, in the order of about 3000 F. Preferably, the reactor type is a pressurized or boiling water reactor and the nanophase material is a high temperature ceramic or ceramic composite. Nanophase metals, or nanophase metals with nanophase ceramics in a composite mixture, also have desirable characteristics, although their temperature capability is not as great as with all-ceramic nanophase material. Combinations of conventional or nanophase metals and conventional or nanophase ceramics can be employed as long as there is at least one nanophase material in the composite. The nuclear reactor so constructed has a number of high strength fuel particles, a nanophase structural material for supporting a fuel rod at high temperature, a configuration to allow passive cooling in the event of a primary cooling system failure, an ability to retain a coolable geometry even at high temperatures, an ability to resist generation of hydrogen gas, and a configuration having good nuclear, corrosion, and mechanical characteristics. 5 figs.

  6. Nanophase cobalt, nickel and zinc ferrites: synchrotron XAS study on the crystallite size dependence of metal distribution.

    PubMed

    Nordhei, Camilla; Ramstad, Astrid Lund; Nicholson, David G

    2008-02-21

    Nanophase cobalt, nickel and zinc ferrites, in which the crystallites are in the size range 4-25 nm, were synthesised by coprecipitation and subsequent annealing. X-Ray absorption spectroscopy using synchrotron radiation (supported by X-ray powder diffraction) was used to study the effects of particle size on the distributions of the metal atoms over the tetrahedral and octahedral sites of the spinel structure. Deviations from the bulk structure were found which are attributed to the significant influence of the surface on very small particles. Like the bulk material, nickel ferrite is an inverse spinel in the nanoregime, although the population of metals on the octahedral sites increases with decreasing particle size. Cobalt ferrite and zinc ferrite take the inverse and normal forms of the spinel structure respectively, but within the nanoregime both systems show similar trends in being partially inverted. Further, in zinc ferrite, unlike the normal bulk structure, the nanophase system involves mixed coordinations of zinc(ii) and iron(iii) consistent with increasing partial inversion with size.

  7. Nanophase Iron Oxides as an Ultraviolet Sunscreen for Ancient Photosynthetic Microbes: A Possible Link Between Early Organisms, Banded-Iron Formations, and the Oxygenation of the Atmosphere

    NASA Technical Reports Server (NTRS)

    Bishop, Janice L.; Rothschild, Lynn J.; Rothschild, Lynn J.; Rogoff, Dana A.

    2006-01-01

    We propose that nanophase iron oxide-bearing materials provided important niches for ancient photosynthetic microbes on the early Earth that ultimately led to the oxygenation of the Earth s atmosphere and the formation of iron oxide deposits. Atmospheric oxygen and ozone attenuate UV radiation on the Earth today providing substantial protection for photosynthetic organisms. With ultraviolet radiation fluxes likely to have been even higher on the early Earth than today, accessing solar radiation was particularly risky for early organisms. Yet, we know that photosynthesis arose then and played a critical role in subsequent evolution. Of primary importance was protection at approx.250-290 nm, where peak nucleic acid (approx.260 nm) and protein (approx.280 nm) absorptions occur. Nanophase ferric oxide/oxyhydroxide minerals absorb, and thus block, the lethal UV radiation, while transmitting light through much of the visible and near-infrared regions of interest to photosynthesis (400 to 1100 nm). Further, they were available in early environments, and are synthesized by many organisms. Based on ferric oxide/oxyhydroxide spectral properties, likely geologic processes, and the results of experiments with the photosynthetic organisms, Euglena sp. and Chlumydomonus reinhardtii, we propose a scenario where photosynthesis, and ultimately the oxygenation of the atmosphere, depended on the protection of early microbes by nanophase ferric oxides/oxyhydroxides. The results of this study are also applicable to other potentially habitable iron-bearing planetary bodies because of the evolutionary pressure to utilize solar radiation when available as an energy source.

  8. Nanophase Nickel-Zirconium Alloys for Fuel Cells

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram; Whitacre, jay; Valdez, Thomas

    2008-01-01

    Nanophase nickel-zirconium alloys have been investigated for use as electrically conductive coatings and catalyst supports in fuel cells. Heretofore, noble metals have been used because they resist corrosion in the harsh, acidic fuel cell interior environments. However, the high cost of noble metals has prompted a search for less-costly substitutes. Nickel-zirconium alloys belong to a class of base metal alloys formed from transition elements of widely different d-electron configurations. These alloys generally exhibit unique physical, chemical, and metallurgical properties that can include corrosion resistance. Inasmuch as corrosion is accelerated by free-energy differences between bulk material and grain boundaries, it was conjectured that amorphous (glassy) and nanophase forms of these alloys could offer the desired corrosion resistance. For experiments to test the conjecture, thin alloy films containing various proportions of nickel and zirconium were deposited by magnetron and radiofrequency co-sputtering of nickel and zirconium. The results of x-ray diffraction studies of the deposited films suggested that the films had a nanophase and nearly amorphous character.

  9. Quantifying the VNIR Effects of Nanophase Iron Generated through the Space Weathering of Silicates: Reconciling Modeled Data with Laboratory Observations

    NASA Astrophysics Data System (ADS)

    Legett, C., IV; Glotch, T. D.; Lucey, P. G.

    2015-12-01

    Space weathering is a diverse set of processes that occur on the surfaces of airless bodies due to exposure to the space environment. One of the effects of space weathering is the generation of nanophase iron particles in glassy rims on mineral grains due to sputtering of iron-bearing minerals. These particles have a size-dependent effect on visible and near infrared (VNIR) reflectance spectra with smaller diameter particles (< 50 nm) causing both reddening and darkening of the spectra with respect to unweathered material (Britt-Pieters particle behavior), while larger particles (> 300 nm) darken without reddening. Between these two sizes, a gradual shift between these two behaviors occurs. In this work, we present results from the Multiple Sphere T-Matrix (MSTM) scattering model in combination with Hapke theory to explore the particle size and iron content parameter spaces with respect to VNIR (700-1700 nm) spectral slope. Previous work has shown that the MSTM-Hapke hybrid model offers improvements over Mie-Hapke models. Virtual particles are constructed out of an arbitrary number of spheres, and each sphere is assigned a refractive index and extinction coefficient for each wavelength of interest. The model then directly solves Maxwell's Equations at every wave-particle interface to predict the scattering, extinction and absorption efficiencies. These are then put into a simplified Hapke bidirectional reflectance model that yields a predicted reflectance. Preliminary results show an area of maximum slopes for iron particle diameters < 80 nm and iron concentrations of ~1-10wt% in an amorphous silica matrix. Further model runs are planned to better refine the extent of this region. Companion laboratory work using mixtures of powdered aerogel and nanophase iron particles provides a point of comparison to modeling efforts. The effects on reflectance and emissivity values due to particle size in a nearly ideal scatterer (aerogel) are also observed with comparisons to

  10. Metallic Iron and Iron Oxide as an Explanation for the Dark Material Observed on Saturn's Icy Satellites and Rings with Cassini VIMS

    NASA Astrophysics Data System (ADS)

    Clark, Roger Nelson; Cruikshank, D. P.; Jaumann, R.; Brown, R. H.; Dalle Ore, C.; Stephan, K.; Hoefen, T. M.; Curchin, J. M.; Buratti, B. J.; Filacchione, G.; Baines, K. H.; Nicholson, P. D.

    2010-10-01

    The Visual and Infrared Mapping Spectrometer (VIMS) on Cassini has obtained spatially resolved spectra on satellites of Saturn. The Cassini Rev 49 Iapetus fly-by on September 10, 2007, provided data on both the dark material and the transition zone between the dark material and the visually bright ice. The dark material has low albedo with a linear increase in reflectance with wavelength, 3-micron water, and CO2 absorptions. The transition between bright and dark regions shows mixing with unusual optical properties including increased blue scattering and increasing strength of a UV absorber in areas with stronger ice absorptions. Similar spectral effects are observed on other Saturnian satellites and in the rings. We have been unable to match these spectral properties and trends using tholins and carbon compounds. However, the dark material is spectrally matched by fine-grained metallic iron plus nano-phase hematite and adsorbed water which contribute UV and 3-micron absorption, respectively. The blue scattering peak and UV absorption can be explained by Rayleigh scattering from sub-micron particles with a UV absorption, or a combination of Rayleigh scattering and Rayleigh absorption as has been attributed to spectral properties of the Moon. A new radiative transfer model that includes Rayleigh scattering and Rayleigh absorption has been constructed. Models of ice, sub-micron metallic iron, hydrated iron oxide, and trace CO2 explain the observed spectra. Rayleigh absorption requires high absorption coefficient nano-sized particles, which is also consistent with metallic iron. The UV absorber appears to have increased strength on satellite surfaces close to Saturn, with a corresponding decrease in metallic iron signature. A possible explanation is that the iron is oxidized closer to Saturn by oxygen in the extended atmosphere of Saturn's rings, or the dark material is simply covered by clean fine-grained ice particles, for example, from the E-ring.

  11. [Cytocompatibility of nanophase hydroxyapatite ceramics].

    PubMed

    Wen, Bo; Chen, Zhi-qing; Jiang, Yin-shan; Yang, Zheng-wen; Xu, Yong-zhong

    2004-12-01

    To evaluate the cytocompatibility of nanophase hydroxyapatite ceramics in vitro. Hydroxyapatite (HA) was prepared via wet method. The grain size of the hydroxyapatite in the study was determined by scanning electron microscope and atomic force microscope with image analysis software. Primary osteoblast culture was established from rat calvaria. Cell adherence and proliferation on nanophase hydroxyapatite ceramics and conventional hydroxyapatite ceramics were examined at 1, 3, 5, 7 days. Morphology of the cells was observed by microscope. The average grain size of the nanophase and conventional HA was 55 nm and 780 nm, respectively. Throughout 7 days period, osteoblast proliferation on the HA was similar to that on tissue culture borosilicate glass controls, osteoblasts could attach, spread and proliferate on HA. However, compared to conventional ceramics, osteoblast proliferation on nanophase HA was significantly better after 1, 3, 5 and 7 days. Cytocompatibility of nanophase HA was significantly better than conventional ceramics.

  12. High Resolution Transmission Electron Microscopy (HRTEM) of nanophase ferric oxides

    NASA Technical Reports Server (NTRS)

    Golden, D. C.; Morris, R. V.; Ming, D. W.; Lauer, H. V., Jr.

    1994-01-01

    Iron oxide minerals are the prime candidates for Fe(III) signatures in remotely sensed Martian surface spectra. Magnetic, Mossbauer, and reflectance spectroscopy have been carried out in the laboratory in order to understand the mineralogical nature of Martian analog ferric oxide minerals of submicron or nanometer size range. Out of the iron oxide minerals studied, nanometer sized ferric oxides are promising candidates for possible Martian spectral analogs. 'Nanophase ferric oxide (np-Ox)' is a generic term for ferric oxide/oxihydroxide particles having nanoscale (less than 10 nm) particle dimensions. Ferrihydrite, superparamagnetic particles of hematite, maghemite and goethite, and nanometer sized particles of inherently paramagnetic lepidocrocite are all examples of nanophase ferric oxides. np-Ox particles in general do not give X-ray diffraction (XRD) patterns with well defined peaks and would often be classified as X-ray amorphous. Therefore, different np-Oxs preparations should be characterized using a more sensitive technique e.g., high resolution transmission electron microscopy (HRTEM). The purpose of this study is to report the particle size, morphology and crystalline order, of five np-Ox samples by HRTEM imaging and electron diffraction (ED).

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

    NASA Technical Reports Server (NTRS)

    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.

  14. Synthesis and Stability of Iron Nanoparticles for Lunar Environment Studies

    NASA Technical Reports Server (NTRS)

    Hung, Ching-cheh; McNatt, Jeremiah

    2009-01-01

    Simulant of lunar dust is needed when researching the lunar environment. However, unlike the true lunar dust, today s simulants do not contain nanophase iron. Two different processes have been developed to fabricate nanophase iron to be used as part of the lunar dust simulant: (1) Sequentially treating a mixture of ferric chloride, fluorinated carbon, and soda lime glass beads at about 300 C in nitrogen, at room temperature in air, and then at 1050 C in nitrogen. The product includes glass beads that are grey in color, can be attracted by a magnet, and contain alpha-iron nanoparticles (which seem to slowly lose their lattice structure in ambient air during a period of 12 months). This product may have some similarity to the lunar glassy regolith that contains Fe(sup 0). (2) Heating a mixture of carbon black and a lunar simulant (a mixed metal oxide that includes iron oxide) at 1050 C in nitrogen. This process simulates lunar dust reaction to the carbon in a micrometeorite at the time of impact. The product contains a chemically modified simulant that can be attracted by a magnet and has a surface layer whose iron concentration increased during the reaction. The iron was found to be alpha-iron and Fe3O4 nanoparticles, which appear to grow after the fabrication process, but stabilizes after 6 months of ambient air storage.

  15. Pigmenting agents in Martian soils: inferences from spectral, Mossbauer, and magnetic properties of nanophase and other iron oxides in Hawaiian palagonitic soil PN-9

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Golden, D. C.; Lauer, H. V. Jr; Adams, J. B.

    1993-01-01

    We have examined a Hawaiian palagonitic tephra sample (PN-9) that has spectroscopic similarities to Martian bright regions using a number of analytical techniques, including Mossbauer and reflectance spectroscopy, X-ray diffraction, instrumental neutron activation analysis, electron probe microanalysis, transmission electron microscopy, and dithionite-citrate-bicarbonate extraction. Chemically, PN-9 has a Hawaiitic composition with alkali (and presumably silica) loss resulting from leaching by meteoric water during palagonitization; no Ce anomaly is present in the REE pattern. Mineralogically, our results show that nanophase ferric oxide (np-Ox) particles (either nanophase hematite (np-Hm) or a mixture of ferrihydrite and np-Hm) are responsible for the distinctive ferric doublet and visible-wavelength ferric absorption edge observed in Mossbauer and reflectivity spectra, respectively, for this and other spectrally similar palagonitic samples. The np-Ox particles appear to be imbedded in a hydrated aluminosilicate matrix material; no evidence was found for phyllosilicates. Other iron-bearing phases observed are titanomagnetite, which accounts for the magnetic nature of the sample; olivine; pyroxene; and glass. By analogy, np-Ox is likely the primary pigmenting agent of the bright soils and dust of Mars.

  16. Nanophase change for data storage applications.

    PubMed

    Shi, L P; Chong, T C

    2007-01-01

    Phase change materials are widely used for date storage. The most widespread and important applications are rewritable optical disc and Phase Change Random Access Memory (PCRAM), which utilizes the light and electric induced phase change respectively. For decades, miniaturization has been the major driving force to increase the density. Now the working unit area of the current data storage media is in the order of nano-scale. On the nano-scale, extreme dimensional and nano-structural constraints and the large proportion of interfaces will cause the deviation of the phase change behavior from that of bulk. Hence an in-depth understanding of nanophase change and the related issues has become more and more important. Nanophase change can be defined as: phase change at the scale within nano range of 100 nm, which is size-dependent, interface-dominated and surrounding materials related. Nanophase change can be classified into two groups, thin film related and structure related. Film thickness and clapping materials are key factors for thin film type, while structure shape, size and surrounding materials are critical parameters for structure type. In this paper, the recent development of nanophase change is reviewed, including crystallization of small element at nano size, thickness dependence of crystallization, effect of clapping layer on the phase change of phase change thin film and so on. The applications of nanophase change technology on data storage is introduced, including optical recording such as super lattice like optical disc, initialization free disc, near field, super-RENS, dual layer, multi level, probe storage, and PCRAM including, superlattice-like structure, side edge structure, and line type structure. Future key research issues of nanophase change are also discussed.

  17. Mid-infrared transmission spectra of crystalline and nanophase iron oxides/oxyhydroxides and implications for remote sensing of Mars

    NASA Technical Reports Server (NTRS)

    Bell, James F., III; Roush, Ted L.; Morris, Richard V.

    1995-01-01

    Ferric-iron-bearing materials play an important role in the interpretation of visible to near-IR Mars spectra, and they may play a similarly important role in the analysis of new mid-IR spacecraft spectral observations to be obtained over the next decade. We review existing data on mid-IR transmission spectra of ferric oxides/oxyhydroxides and present new transmission spectra for ferric-bearing materials spanning a wide range of mineralogy and crystallinity. These materials include 11 samples of well-crystallized ferric oxides (hematite, maghemite, and magnetite) and ferric oxyhydroxides (goethite, lepidocrocite). We also report the first transmission spectra for purely nanophase ferric oxide samples that have been shown to exhibit spectral similarities to Mars in the visible to near-IR and we compare these data to previous and new transmission spectra of terrestrial palagonites. Most of these samples show numerous, diagnostic absorption features in the mid-IR due to Fe(3+)-O(2-) vibrational transitions, structural and/or bound OH, and/or silicates. These data indicate that high spatial resolution, moderate spectral resolution mid-IR ground-based and spacecraft observations of Mars may be able to detect and uniquely discriminate among different ferric-iron-bearing phases on the Martian surface or in the airborne dust.

  18. Mid-infrared transmission spectra of crystalline and nanophase iron oxides/oxyhydroxides and implications for remote sensing of Mars

    NASA Technical Reports Server (NTRS)

    Bell, James F., III; Roush, Ted L.; Morris, Richard V.

    1995-01-01

    Ferric-iron-bearing materials play an important role in the interpretation of visible to near-IR Mars spectra, and they may play a similarly important role in the analysis of new mid-IR spacecraft spectral observations to be obtained over the next decade. We review exisiting data on mid-IR transmission spectra of ferric oxides/oxyhydroxides and present new transmission spectra for ferric-bearing materials spanning a wide range of mineralogy and crystallinity. These materials include 11 samples of well-crystallized ferric oxides (hematite, maghemite, and magnetite) and ferric oxyhydroxides (goethite, lepidocrocite). We also report the first transmission spectra for purely nanophase ferric oxide samples that have been shown to exhibit spectral similarities to Mars in the visible to near-IR and we compare these data to previous and new transmission spectra of terrestial palagonites. Most of these samples show numerous, diagnostic absorption features in the mid-IR due to Fe(3+) - 0(2-) vibrational transitions, structural and/or bound OH, and/or silicates. These data indicate that high spatial resolution, moderate spectral resolution mid-IR ground-based and spacecraft observations of Mars may be able to detect and uniquely discriminate among different ferric-iron-bearing phases on the Martian surface or in the airborne dust.

  19. Formation of Nanophase Iron in Lunar Soil Simulant for Use in ISRU Studies

    NASA Technical Reports Server (NTRS)

    Liu, Yang; Taylor, Lawrence A.; Hill, Eddy; Day, James D. M.

    2005-01-01

    For the prospective return of humans to the Moon and the extensive amount of premonitory studies necessary, large quantities of lunar soil simulants are required, for a myriad of purposes from construction/engineering purposes all the way to medical testing of its effects from ingestion by humans. And there is only a limited and precious quantity of lunar soil available on Earth (i.e., Apollo soils) - therefore, the immediate need for lunar soil simulants. Since the Apollo era, there have been several simulants; of these JSC-1 (Johnson Space Center) and MLS-1 (Minnesota Lunar Simulant) have been the most widely used. JSC-1 was produced from glassy volcanic tuff in order to approximate lunar soil geotechnical properties; whereas, MLS-1 approximates the chemistry of Apollo 11 high-Ti soil, 10084. Stocks of both simulants are depleted, but JSC-1 has recently gone back into production. The lunar soil simulant workshop, held at Marshall Space Flight Center in January 2005, identified the need to make new simulants for the special properties of lunar soil, such as nanophase iron (np-Fe(sup 0). Hill et al. (2005, this volume) showed the important role of microscale Fe(sup 0) in microwave processing of the lunar soil simulants JSC-1 and MLS-1. Lunar soil is formed by space weathering of lunar rocks (e.g., micrometeorite impact, cosmic particle bombardment). Glass generated during micrometeorite impact cements rock and mineral fragments together to form aggregates called agglutinates, and also produces vapor that is deposited and coats soil grains. Taylor et al. (2001) showed that the relative amount of impact glass in lunar soil increases with decreasing grain size and is the most abundant component in lunar dust (less than 20 micrometer fraction). Notably, the magnetic susceptibility of lunar soil also increases with the decreasing grain size, as a function of the amount of nanophase-sized Fe(sup 0) in impact-melt generated glass. Keller et al. (1997, 1999) also

  20. Mammalian Cell Interactions with Nanophase Materials

    DTIC Science & Technology

    2005-01-01

    alumina , titania and hydroxylapatite) as well as on composites of these ceramics with either poly(L-lactic) acid or poly(methyl) methacrylate. Most...osteoblasts on flat, nanophase (versus microphase/conventional) ceramics ( alumina , titania and hydroxylapatite) as a function of decreasing ceramic grain size...acid (PLA) and nanophase (but not on polymer/conventional) ceramics ( alumina , titania and hydroxylapatite) composites [4]. Specifically, osteoblast

  1. Nanophase materials assembled from clusters

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

    Siegel, R.W.

    1992-02-01

    The preparation of metal and ceramic atom clusters by means of the gas-condensation method, followed by their in situ collection and consolidation under high-vacuum conditions, has recently led to the synthesis of a new class of ultrafine-grained materials. These nanophase materials, with typical average grain sizes of 5 to 50 nm and, hence, a large fraction of their atoms in interfaces, exhibit properties that are often considerably improved relative to those of conventional materials. Furthermore, their synthesis and processing characteristics should enable the design of new materials with unique properties. Some examples are ductile ceramics that can be formed andmore » sintered to full density at low temperatures without the need for binding or sintering aids, and metals with dramatically increased strength. The synthesis of these materials is briefly described along with what is presently known of their structure and properties. Their future impact on materials science and technology is also considered.« less

  2. Recognizing Sulfate and Phosphate Complexes Adsorbed onto Nanophase Weathering Products on Mars

    NASA Technical Reports Server (NTRS)

    Rampe, E. B.; Morris, R. V.; Archer, P. D., Jr.

    2015-01-01

    Nanophase weathering products (i.e., secondary phases that lack long-range atomic order) have been recognized on the martian surface via orbital observations and in-situ measurements from landed missions. Allophane, a poorly crystalline, hydrated aluminosilicate, has been identified at the regional scale in models of thermal-infrared (TIR) data from the Thermal Emission Spectrometer (TES) and at the local scale from visible/near-IR (VNIR) data from the Compact Reconnaissance Impact Spectrometer for Mars (CRISM) instrument and phase calculations of Alpha Particle X-ray Spectrometer (APXS) data of rocks encountered by the Mars Exploration Rovers (MER) Spirit and Opportunity. Nanophase iron oxides (npOx) have been recognized in rocks and soils measured by the Mössbauer Spectrometer on Spirit and Opportunity. Furthermore, analyses of X-ray diffraction data measured by the CheMin instrument onboard the Mars Science Laboratory rover Curiosity indicate rock and soil samples are comprised of approx. 20-50 wt.% X-ray amorphous materials. Chemical measurements by landed missions indicate the presence of sulfur and phosphorus in martian rocks in soils, and APXS data from Gusev crater demonstrate abundances of up to approx. 5 wt.% P2O5 and approx. 30 wt.% SO3. However, the speciation of phosphorus and sulfur is not always evident. On Earth, phosphate and sulfate anions can be chemisorbed onto the surfaces of nanophase weathering products. This process may also occur on Mars, and calculations of the composition of the amorphous component at Gale crater using CheMin mineral models and APXS data show that amorphous material is enriched in volatiles, including S. Here, we examine the ability to detect chemisorbed sulfate and phosphate complexes by analyzing sulfate- and phosphate-adsorbed nanophase weathering products using instruments similar to those on landed and orbital missions.

  3. Metal-metal interaction mediates the iron induction of Drosophila MtnB

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

    Qiang, Wenjia; Huang, Yunpeng; Wan, Zhihui

    Metallothionein (MT) protein families are a class of small and universal proteins rich in cysteine residues. They are synthesized in response to heavy metal stresses to sequester the toxic ions by metal-thiolate bridges. Five MT family members, namely MtnA, MtnB, MtnC, MtnD and MtnE, have been discovered and identified in Drosophila. These five isoforms of MTs are regulated by metal responsive transcription factor dMTF-1 and play differentiated but overlapping roles in detoxification of metal ions. Previous researches have shown that Drosophila MtnB responds to copper (Cu), cadmium (Cd) and zinc (Zn). Interestingly in this study we found that Drosophila MtnBmore » expression also responds to elevated iron levels in the diet. Further investigations revealed that MtnB plays limited roles in iron detoxification, and the direct binding of MtnB to ferrous iron in vitro is also weak. The induction of MtnB by iron turns out to be mediated by iron interference of other metals, because EDTA at even a partial concentration of that of iron can suppress this induction. Indeed, in the presence of iron, zinc homeostasis is altered, as reflected by expression changes of zinc transporters dZIP1 and dZnT1. Thus, iron-mediated MtnB induction appears resulting from interrupted homeostasis of other metals such as zinc, which in turns induced MtnB expression. Metal-metal interaction may more widely exist than we expected. - Highlights: • Metallothionein B expression is regulated by iron in Drosophila melanogaster. • MtnB has limited physiological roles in iron detoxification. • Binding affinity of MtnB to iron is weak in vitro. • Induction of Drosophila MtnB by iron is mediated indirectly through metal-metal interaction.« less

  4. Detecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane, Aluminosilicate Gel, and Ferrihydrite

    NASA Technical Reports Server (NTRS)

    Rampe, E. B.; Bish, D. L.; Chipera, S. J.; Morris, R. V.; Achilles, C. N.; Ming, D W.; Blake, D. F.; Anderson, R. C.; Bristow, T. F.; Crisp, A.; hide

    2013-01-01

    X-ray diffraction (XRD) data collected of the Rocknest samples by the CheMin instrument on Mars Science Laboratory suggest the presence of poorly crystalline or amorphous materials [1], such as nanophase weathering products or volcanic and impact glasses. The identification of the type(s) of X-ray amorphous material at Rocknest is important because it can elucidate past aqueous weathering processes. The presence of volcanic and impact glasses would indicate that little chemical weathering has occurred because glass is highly susceptible to aqueous alteration. The presence of nanophase weathering products, such as allophane, nanophase iron-oxides, and/or palagonite, would indicate incipient chemical weathering. Furthermore, the types of weathering products present could help constrain pH conditions and identify which primary phases altered to form the weathering products. Quantitative analysis of phases from CheMin data is achieved through Reference Intensity Ratios (RIRs) and Rietveld refinement. The RIR of a mineral (or mineraloid) that relates the scattering power of that mineral (typically the most intense diffraction line) to the scattering power of a separate mineral standard such as corundum [2]. RIRs can be calculated from XRD patterns measured in the laboratory by mixing a mineral with a standard in known abundances and comparing diffraction line intensities of the mineral to the standard. X-ray amorphous phases (e.g., nanophase weathering products) have broad scattering signatures rather than sharp diffraction lines. Thus, RIRs of X-ray amorphous materials are calculated by comparing the area under one of these broad scattering signals with the area under a diffraction line in the standard. Here, we measured XRD patterns of nanophase weathering products (allophane, aluminosilicate gel, and ferrihydrite) mixed with a mineral standard (beryl) in the CheMinIV laboratory instrument and calculated their RIRs to help constrain the abundances of these phases in

  5. [Experimental research on the effect of nanophase ceramics on osteoblasts functions].

    PubMed

    Wen, Bo; Chen, Zhiqing; Jiang, Yinshan; Yang, Zhengwen; Xu, Yongzhong

    2005-06-01

    In order to study the cytocompatibility of nanophase hydroxyapatite ceramic in vitro, we prepared hydroxyapatite by use of the wet chemistry techniques. The grain size of hydroxyapatite of interest to the present study was determined by scanning electron microscopy and atomic force microscopy with image analysis software. Primary culture of osteoblast from rat calvaria was established. Protein content, synthesis of alkaline phosphatase and deposition of calcium-containing mineral by osteoblasts cultured on nanophase hydroxyapatite ceramics and on conventional hydroxyapatite ceramics for 7, 14, 21 and 28 days were examined. The results showed that the average surface grain size of the nanophase and that of the conventional HA compact formulations was 55 (nanophase) and 780 (conventional) nm, respectively. More importantly, compared to the synthesis of alkaline phosphatase and deposition of calcium-containing mineral by osteoblasts cultured on nanophase was significantly greater than that on conventional ceramics after 21 and 28 days. The cytocompatibility was significantly greater on nanophase HA than on conventional formulations of the same ceramic.

  6. Quantitative EPMA of Nano-Phase Iron-Silicides in Apollo 16 Lunar Regolith

    NASA Astrophysics Data System (ADS)

    Gopon, P.; Fournelle, J.; Valley, J. W.; Pinard, P. T.; Sobol, P.; Horn, W.; Spicuzza, M.; Llovet, X.; Richter, S.

    2013-12-01

    Until recently, quantitative EPMA of phases under a few microns in size has been extremely difficult. In order to achieve analytical volumes to analyze sub-micron features, accelerating voltages between 5 and 8 keV need to be used. At these voltages the normally used K X-ray transitions (of higher Z elements) are no longer excited, and we must rely of outer shell transitions (L and M). These outer shell transitions are difficult to use for quantitative EPMA because they are strongly affected by different bonding environments, the error associated with their mass attenuation coefficients (MAC), and their proximity to absorption edges. These problems are especially prevalent for the transition metals, because of the unfilled M5 electron shell where the Lα transition originates. Previous studies have tried to overcome these limitations by using standards that almost exactly matched their unknowns. This, however, is cumbersome and requires accurate knowledge of the composition of your sample beforehand, as well as an exorbitant number of well characterized standards. Using a 5 keV electron beam and utilizing non-standard X-ray transitions (Ll) for the transition metals, we are able to conduct accurate quantitative analyses of phases down to ~300nm. The Ll transition in the transition metals behaves more like a core-state transition, and unlike the Lα/β lines, is unaffected by bonding effects and does not lie near an absorption edge. This allows for quantitative analysis using standards do not have to exactly match the unknown. In our case pure metal standards were used for all elements except phosphorus. We present here data on iron-silicides in two Apollo 16 regolith grains. These plagioclase grains (A6-7 and A6-8) were collected between North and South Ray Craters, in the lunar highlands, and thus are associated with one or more large impact events. We report the presence of carbon, nickel, and phosphorus (in order of abundance) in these iron-silicide phases

  7. Iron metal optical constants: Assessing the effects of metal composition and oxidation on laboratory reflectance spectra of planetary materials

    NASA Astrophysics Data System (ADS)

    Blewett, D. T.; Cahill, J. T.; Lawrence, S. J.; Denevi, B. W.; Nguyen, N. V.

    2012-12-01

    Many planetary surfaces contain Fe or FeNi metal. These metals are present as macroscopic grains (larger than the wavelength of light) in a variety of meteorites and are inferred to exist on/in their asteroid parent bodies. In addition, much smaller (nano- to micrometer) grains of metallic Fe are produced to varying degrees in the surfaces of airless bodies by exposure to the space environment. Space weathering, which includes solar wind sputtering and micrometeoroid impact melting and vaporization, results in the reduction of ferrous Fe harvested from silicates and oxides to a single-domain metallic state, present as nanophase blebs and coatings on and within regolith particles. Nanophase Fe (npFe0) is optically active and has a strong effect on reflectance spectra. For example, a mature lunar soil that has accumulated npFe0 is darker and has a redder spectral slope compared with an unweathered powder of the same lithology; mineralogical absorption bands are also attenuated in space-weathered material. Here we report progress on a comprehensive program undertaken to measure the optical constants of Fe and Ni. The optical constants (real and imaginary parts of the index of refraction) are fundamental physical parameters that govern how light reflects from and transmits through a material. We use ellipsometry to measure the optical constants of high-purity metal films from 160 to 4000 nm, including bare films exposed to the atmosphere and films protected from the atmosphere via a novel technique involving a metal coating on a fused silica prism. Air-exposed Fe films have optical constants that are markedly different from those of the protected film, despite the fact that the air-exposed films appear bright and mirror-like to the eye. X-ray photoelectron spectroscopy confirms the presence of Fe2O3 on the surface of the air-exposed Fe film. Hence, we conclude that oxidation layers form rapidly (minutes to hours) on air-exposed metal and measurably alter the optical

  8. Influence of nanophase titania topography on bacterial attachment and metabolism

    PubMed Central

    Park, Margaret R; Banks, Michelle K; Applegate, Bruce; Webster, Thomas J

    2008-01-01

    Surfaces with nanophase compared to conventional (or nanometer smooth) topographies are known to have different properties of area, charge, and reactivity. Previously published research indicates that the attachment of certain bacteria (such as Pseudomonas fluorescens 5RL) is higher on surfaces with nanophase compared to conventional topographies, however, their effect on bacterial metabolism is unclear. Results presented here show that the adhesion of Pseudomonas fluorescens 5RL and Pseudomonas putida TVA8 was higher on nanophase than conventional titania. Importantly, in terms of metabolism, bacteria attached to the nanophase surfaces had higher bioluminescence rates than on the conventional surfaces under all nutrient conditions. Thus, the results from this study show greater select bacterial metabolism on nanometer than conventional topographies, critical results with strong consequences for the design of improved biosensors for bacteria detection. PMID:19337418

  9. An Iron Reservoir to the Catalytic Metal

    PubMed Central

    Liu, Fange; Geng, Jiafeng; Gumpper, Ryan H.; Barman, Arghya; Davis, Ian; Ozarowski, Andrew; Hamelberg, Donald; Liu, Aimin

    2015-01-01

    The rubredoxin motif is present in over 74,000 protein sequences and 2,000 structures, but few have known functions. A secondary, non-catalytic, rubredoxin-like iron site is conserved in 3-hydroxyanthranilate 3,4-dioxygenase (HAO), from single cellular sources but not multicellular sources. Through the population of the two metal binding sites with various metals in bacterial HAO, the structural and functional relationship of the rubredoxin-like site was investigated using kinetic, spectroscopic, crystallographic, and computational approaches. It is shown that the first metal presented preferentially binds to the catalytic site rather than the rubredoxin-like site, which selectively binds iron when the catalytic site is occupied. Furthermore, an iron ion bound to the rubredoxin-like site is readily delivered to an empty catalytic site of metal-free HAO via an intermolecular transfer mechanism. Through the use of metal analysis and catalytic activity measurements, we show that a downstream metabolic intermediate can selectively remove the catalytic iron. As the prokaryotic HAO is often crucial for cell survival, there is a need for ensuring its activity. These results suggest that the rubredoxin-like site is a possible auxiliary iron source to the catalytic center when it is lost during catalysis in a pathway with metabolic intermediates of metal-chelating properties. A spare tire concept is proposed based on this biochemical study, and this concept opens up a potentially new functional paradigm for iron-sulfur centers in iron-dependent enzymes as transient iron binding and shuttling sites to ensure full metal loading of the catalytic site. PMID:25918158

  10. Formation and characterization of metallic iron grains in coal-based reduction of oolitic iron ore

    NASA Astrophysics Data System (ADS)

    Sun, Yong-sheng; Han, Yue-xin; Li, Yan-feng; Li, Yan-jun

    2017-02-01

    To reveal the formation and characteristics of metallic iron grains in coal-based reduction, oolitic iron ore was isothermally reduced in various reduction times at various reduction temperatures. The microstructure and size of the metallic iron phase were investigated by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and a Bgrimm process mineralogy analyzer. In the results, the reduced Fe separates from the ore and forms metallic iron protuberances, and then the subsequent reduced Fe diffuses to the protuberances and grows into metallic iron grains. Most of the metallic iron grains exist in the quasi-spherical shape and inlaid in the slag matrix. The cumulative frequency of metallic iron grain size is markedly influenced by both reduction time and temperature. With increasing reduction temperature and time, the grain size of metallic iron obviously increases. According to the classical grain growth equation, the growth kinetic parameters, i.e., time exponent, growth activation energy, and pre-exponential constant, are estimated to be 1.3759 ± 0.0374, 103.18 kJ·mol-1, and 922.05, respectively. Using these calculated parameters, a growth model is established to describe the growth behavior of metallic iron grains.

  11. Characterization of Nanophase Materials

    NASA Astrophysics Data System (ADS)

    Wang, Zhong Lin

    2000-01-01

    Engineering of nanophase materials and devices is of vital interest in electronics, semiconductors and optics, catalysis, ceramics and magnetism. Research associated with nanoparticles has widely spread and diffused into every field of scientific research, forming a trend of nanocrystal engineered materials. The unique properties of nanophase materials are entirely determined by their atomic scale structures, particularly the structures of interfaces and surfaces. Development of nanotechnology involves several steps, of which characterization of nanoparticles is indespensable to understand the behavior and properties of nanoparticles, aiming at implementing nanotechnolgy, controlling their behavior and designing new nanomaterials systems with super performance. The book will focus on structural and property characterization of nanocrystals and their assemblies, with an emphasis on basic physical approach, detailed techniques, data interpretation and applications. Intended readers of this comprehensive reference work are advanced graduate students and researchers in the field, who are specialized in materials chemistry, materials physics and materials science.

  12. Raman Mapping for the Investigation of Nano-phased Materials

    NASA Astrophysics Data System (ADS)

    Gouadec, G.; Bellot-Gurlet, L.; Baron, D.; Colomban, Ph.

    Nanosized and nanophased materials exhibit special properties. First they offer a good compromise between the high density of chemical bonds by unit volume, needed for good mechanical properties and the homogeneity of amorphous materials that prevents crack initiation. Second, interfaces are in very high concentration and they have a strong influence on many electrical and redox properties. The analysis of nanophased, low crystallinity materials is not straigtforward. The recording of Raman spectra with a geometric resolution close to 0.5 \\upmu {text{ m}^3} and the deep understanding of the Raman signature allow to locate the different nanophases and to predict the properties of the material. Case studies are discussed: advanced polymer fibres, ceramic fibres and composites, textured piezoelectric ceramics and corroded (ancient) steel.

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

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

    Iron-enriched smectites have been suggested as important mineral compounds of the Martian soil. They were shown to comply with the chemical analysis of the Martian soil, to simulate many of the findings of the Viking Labeled Release Experiments on Mars, to have spectral reflectance in the VIS-NIR strongly resembling the bright regions on Mars. The analogy with Mars soil is based, in a number of aspects, on the nature and behavior of the iron oxides and oxyhydroxides deposited on the surface of the clay particles. A summary of the properties of these iron phases and some recent findings are presented. Their potential relevance to Mars surface processes is discussed.

  14. Top-down approach for nanophase reconstruction in bulk heterojunction solar cells.

    PubMed

    Kong, Jaemin; Hwang, In-Wook; Lee, Kwanghee

    2014-09-01

    "Top-Down" nanophase reconstruction via a post-additive soaking process is first presented with various BHJ binary composites. By simply rinsing as-cast BHJ films with a solvent mixture containing a few traces of a nanophase-control reagent such as 1,8-diiodooctane, oversized fullerene-rich clusters (>100 nm in dia-meter) in the BHJ film are instataneously disassembled and entirely reorganized into finely intermixed donor/acceptor nanophases (ca. 10 nm) with a 3D compositional homogeneity, without surface segregation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Nanophase iron phosphate, iron arsenate, iron vanadate, and iron molybdate minerals synthesized within the protein cage of ferritin.

    PubMed

    Polanams, Jup; Ray, Alisha D; Watt, Richard K

    2005-05-02

    Nanoparticles of iron phosphate, iron arsenate, iron molybdate, and iron vanadate were synthesized within the 8 nm interior of ferritin. The synthesis involved reacting Fe(II) with ferritin in a buffered solution at pH 7.4 in the presence of phosphate, arsenate, vanadate, or molybdate. O2 was used as the oxidant to deposit the Fe(III) mineral inside ferritin. The rate of iron incorporation into ferritin was stimulated when oxo-anions were present. The simultaneous deposition of both iron and the oxo-anion was confirmed by elemental analysis and energy-dispersive X-ray analysis. The ferritin samples containing iron and one of the oxo-anions possessed different UV/vis spectra depending on the anion used during mineral formation. TEM analysis showed mineral cores with approximately 8 nm mineral particles consistent with the formation of mineral phases inside ferritin.

  16. Center for Nanophase Materials Sciences

    NASA Astrophysics Data System (ADS)

    Horton, Linda

    2002-10-01

    The Center for Nanophase Materials Sciences (CNMS) will be a user facility with a strong component of joint, collaborative research. CNMS is being developed, together with the scientific community, with support from DOE's Office of Basic Energy Sciences. The Center will provide a thriving, multidisciplinary environment for research as well as the education of students and postdoctoral scholars. It will be co-located with the Spallation Neutron Source (SNS) and the Joint Institute for Neutron Sciences (JINS). The CNMS will integrate nanoscale research with neutron science, synthesis science, and theory/modeling/simulation, bringing together four areas in which the United States has clear national research and educational needs. The Center's research will be organized under three scientific thrusts: nano-dimensioned "soft" materials (including organic, hybrid, and interfacial nanophases); complex "hard" materials systems (including the crosscutting areas of interfaces and reduced dimensionality that become scientifically critical on the nanoscale); and theory/modeling/simulation. This presentation will summarize the progress towards identification of the specific research focus topics for the Center. Currently proposed topics, based on two workshops with the potential user community, include catalysis, nanomagnetism, synthetic and bio-inspired macromolecular materials, nanophase biomaterials, nanofluidics, optics/photonics, carbon-based nanostructures, collective behavior, nanoscale interface science, virtual synthesis and nanomaterials design, and electronic structure, correlations, and transport. In addition, the proposed 80,000 square foot facility (wet/dry labs, nanofabrication clean rooms, and offices) and the associated technical equipment will be described. The CNMS is scheduled to begin construction in spring, 2003. Initial operations are planned for late in 2004.

  17. Iron phosphate compositions for containment of hazardous metal waste

    DOEpatents

    Day, Delbert E.

    1998-01-01

    An improved iron phosphate waste form for the vitrification, containment and long-term disposition of hazardous metal waste such as radioactive nuclear waste is provided. The waste form comprises a rigid iron phosphate matrix resulting from the cooling of a melt formed by heating a batch mixture comprising the metal waste and a matrix-forming component. The waste form comprises from about 30 to about 70 weight percent P.sub.2 O.sub.5 and from about 25 to about 50 weight percent iron oxide and has metals present in the metal waste chemically dissolved therein. The concentration of iron oxide in the waste form along with a high proportion of the iron in the waste form being present as Fe.sup.3+ provide a waste form exhibiting improved chemical resistance to corrosive attack. A method for preparing the improved iron phosphate waste forms is also provided.

  18. Iron phosphate compositions for containment of hazardous metal waste

    DOEpatents

    Day, D.E.

    1998-05-12

    An improved iron phosphate waste form for the vitrification, containment and long-term disposition of hazardous metal waste such as radioactive nuclear waste is provided. The waste form comprises a rigid iron phosphate matrix resulting from the cooling of a melt formed by heating a batch mixture comprising the metal waste and a matrix-forming component. The waste form comprises from about 30 to about 70 weight percent P{sub 2}O{sub 5} and from about 25 to about 50 weight percent iron oxide and has metals present in the metal waste chemically dissolved therein. The concentration of iron oxide in the waste form along with a high proportion of the iron in the waste form being present as Fe{sup 3+} provide a waste form exhibiting improved chemical resistance to corrosive attack. A method for preparing the improved iron phosphate waste forms is also provided. 21 figs.

  19. Composition and molecular scale structure of nanophases formed by precipitation of biotite weathering products

    NASA Astrophysics Data System (ADS)

    Tamrat, Wuhib Zewde; Rose, Jérôme; Grauby, Olivier; Doelsch, Emmanuel; Levard, Clément; Chaurand, Perrine; Basile-Doelsch, Isabelle

    2018-05-01

    Because of their large surface area and reactivity, nanometric-size soil mineral phases have a high potential for soil organic matter stabilization, contaminant sorption or soil aggregation. In the literature, Fe and Al phases have been the main targets of batch-synthesized nanomineral studies while nano-aluminosilicates (Al and Si phases) have been mainly studied in Andic soils. In the present work, we synthesized secondary nanophases of Fe, Al and Si. To simulate a system as close as possible to soil conditions, we conducted laboratory simulations of the processes of (1) biotite alteration in acidic conditions producing a Al Si Fe Mg K leachate solution and (2) the following neoformation of secondary nanophases by titrating the leachate solution to pH 4.2, 5 and 7. The morphology of the nanophases, their size, crystallinity and chemistry were characterized by TEM-EDX on single particles and their local atomic structure by EXAFS (Extended X-ray Absorption Fine Structure) at the Fe absorption K-edge. The main nanophases formed were amorphous particles 10-60 nm in size whose composition (dominated by Fe and Si) was strongly controlled by the pH conditions at the end of the titration. At pH 4.2 and pH 7, the structure of the nanophases was dominated by the polymerization of Fe, which was hindered by Al, Si, Mg and K. Conversely, at pH 5, the polymerization of Fe was counteracted by precipitation of high amounts of Si. The synthetized nanophases were estimated to be rather analogous to nanophases formed in natural biotite-bearing soils. Because of their small size and potential high surface reactivity, the adsorption capacities of these nanophases with respect to the OM should be revisited in the framework of soil C storage.

  20. Process to Produce Iron Nanoparticle Lunar Dust Simulant Composite

    NASA Technical Reports Server (NTRS)

    Hung, Ching-cheh; McNatt, Jeremiah

    2010-01-01

    A document discusses a method for producing nanophase iron lunar dust composite simulant by heating a mixture of carbon black and current lunar simulant types (mixed oxide including iron oxide) at a high temperature to reduce ionic iron into elemental iron. The product is a chemically modified lunar simulant that can be attracted by a magnet, and has a surface layer with an iron concentration that is increased during the reaction. The iron was found to be -iron and Fe3O4 nanoparticles. The simulant produced with this method contains iron nanoparticles not available previously, and they are stable in ambient air. These nanoparticles can be mass-produced simply.

  1. Reactive oxygen species-related activities of nano-iron metal and nano-iron oxides.

    PubMed

    Wu, Haohao; Yin, Jun-Jie; Wamer, Wayne G; Zeng, Mingyong; Lo, Y Martin

    2014-03-01

    Nano-iron metal and nano-iron oxides are among the most widely used engineered and naturally occurring nanostructures, and the increasing incidence of biological exposure to these nanostructures has raised concerns about their biotoxicity. Reactive oxygen species (ROS)-induced oxidative stress is one of the most accepted toxic mechanisms and, in the past decades, considerable efforts have been made to investigate the ROS-related activities of iron nanostructures. In this review, we summarize activities of nano-iron metal and nano-iron oxides in ROS-related redox processes, addressing in detail the known homogeneous and heterogeneous redox mechanisms involved in these processes, intrinsic ROS-related properties of iron nanostructures (chemical composition, particle size, and crystalline phase), and ROS-related bio-microenvironmental factors, including physiological pH and buffers, biogenic reducing agents, and other organic substances. Copyright © 2014. Published by Elsevier B.V.

  2. Mechanisms of Nanophase-Induced Desorption in LDI-MS. A Short Review

    PubMed Central

    Picca, Rosaria Anna; Calvano, Cosima Damiana; Cioffi, Nicola; Palmisano, Francesco

    2017-01-01

    Nanomaterials are frequently used in laser desorption ionization mass spectrometry (LDI-MS) as DI enhancers, providing excellent figures of merit for the analysis of low molecular weight organic molecules. In recent years, literature on this topic has benefited from several studies assessing the fundamental aspects of the ion desorption efficiency and the internal energy transfer, in the case of model analytes. Several different parameters have been investigated, including the intrinsic chemical and physical properties of the nanophase (chemical composition, thermal conductivity, photo-absorption efficiency, specific heat capacity, phase transition point, explosion threshold, etc.), along with morphological parameters such as the nanophase size, shape, and interparticle distance. Other aspects, such as the composition, roughness and defects of the substrate supporting the LDI-active nanophases, the nanophase binding affinity towards the target analyte, the role of water molecules, have been taken into account as well. Readers interested in nanoparticle based LDI-MS sub-techniques (SALDI-, SELDI-, NALDI- MS) will find here a concise overview of the recent findings in the specialized field of fundamental and mechanistic studies, shading light on the desorption ionization phenomena responsible of the outperforming MS data offered by these techniques. PMID:28368330

  3. Metal ion binding to iron oxides

    NASA Astrophysics Data System (ADS)

    Ponthieu, M.; Juillot, F.; Hiemstra, T.; van Riemsdijk, W. H.; Benedetti, M. F.

    2006-06-01

    The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

  4. The Center for Nanophase Materials Sciences

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

    Christen, Hans; Ovchinnikova, Olga; Jesse, Stephen

    2016-03-11

    The Center for Nanophase Materials Sciences (CNMS) at Oak Ridge National Laboratory (ORNL) integrates nanoscale science with neutron science; synthesis science; and theory, modeling, and simulation. Operating as a national user facility, the CNMS supports a multidisciplinary environment for research to understand nanoscale materials and phenomena.

  5. The Center for Nanophase Materials Sciences

    ScienceCinema

    Christen, Hans; Ovchinnikova, Olga; Jesse, Stephen; Mazumder, Baishakhi; Norred, Liz; Idrobo, Juan Carlos; Berlijn, Tom

    2018-06-25

    The Center for Nanophase Materials Sciences (CNMS) at Oak Ridge National Laboratory (ORNL) integrates nanoscale science with neutron science; synthesis science; and theory, modeling, and simulation. Operating as a national user facility, the CNMS supports a multidisciplinary environment for research to understand nanoscale materials and phenomena.

  6. Derivation of optical constants for nanophase hematite and application to modeled abundances from in-situ Martian reflectance spectra

    NASA Astrophysics Data System (ADS)

    Lucey, Paul G.; Trang, David; Johnson, Jeffrey R.; Glotch, Timothy D.

    2018-01-01

    Several studies have detected the presence of nanophase ferric oxide, such as nanophase hematite, across the martian surface through spacecraft and rover data. In this study, we used the radiative transfer method to detect and quantify the abundance of these nanophase particles. Because the visible/near-infrared spectral characteristics of hematite > 10 nm in size are different from nanophase hematite < 10 nm, there are not any adequate optical constants of nanophase hematite to study visible to near-infrared rover/spacecraft data of the martian surface. Consequently, we found that radiative transfer models based upon the optical constants of crystalline hematite are unable to reproduce laboratory spectra of nanophase hematite. In order to match the model spectra to the laboratory spectra, we developed a new set of optical constants of nanophase hematite in the visible and near-infrared and found that radiative transfer models based upon these optical constants consistently model the laboratory spectra. We applied our model to the passive bidirectional reflectance spectra data from the Chemistry and Camera (ChemCam) instrument onboard the Mars Science Laboratory rover, Curiosity. After modeling six spectra representing different major units identified during the first year of rover operations, we found that the nanophase hematite abundance was no more than 4 wt%.

  7. Nanophase-separated Ni3Nb as an automobile exhaust catalyst.

    PubMed

    Tanabe, Toyokazu; Imai, Tsubasa; Tokunaga, Tomoharu; Arai, Shigeo; Yamamoto, Yuta; Ueda, Shigenori; Ramesh, Gubbala V; Nagao, Satoshi; Hirata, Hirohito; Matsumoto, Shin-Ichi; Fujita, Takeshi; Abe, Hideki

    2017-05-01

    Catalytic remediation of automobile exhaust has relied on precious metals (PMs) including platinum (Pt). Herein, we report that an intermetallic phase of Ni and niobium (Nb) ( i.e. , Ni 3 Nb) exhibits a significantly higher activity than that of Pt for the remediation of the most toxic gas in exhaust ( i.e. , nitrogen monoxide (NO)) in the presence of carbon monoxide (CO). When subjected to the exhaust-remediation atmosphere, Ni 3 Nb spontaneously evolves into a catalytically active nanophase-separated structure consisting of filamentous Ni networks (thickness < 10 nm) that are incorporated in a niobium oxide matrix ( i.e. , NbO x ( x < 5/2)). The exposure of the filamentous Ni promotes NO dissociation, CO oxidation and N 2 generation, and the NbO x matrix absorbs excessive nitrogen adatoms to retain the active Ni 0 sites at the metal/oxide interface. Furthermore, the NbO x matrix immobilizes the filamentous Ni at elevated temperatures to produce long-term and stable catalytic performance over hundreds of hours.

  8. Interactions between microbial iron reduction and metal geochemistry: effect of redox cycling on transition metal speciation in iron bearing sediments.

    PubMed

    Cooper, D Craig; Picardal, Flynn F; Coby, Aaron J

    2006-03-15

    Microbial iron reduction is an important biogeochemical process that can affect metal geochemistry in sediments through direct and indirect mechanisms. With respectto Fe(III) (hydr)oxides bearing sorbed divalent metals, recent reports have indicated that (1) microbial reduction of goethite/ferrihydrite mixtures preferentially removes ferrihydrite, (2) this process can incorporate previously sorbed Zn(II) into an authigenic crystalline phase that is insoluble in 0.5 M HCl, (3) this new phase is probably goethite, and (4) the presence of nonreducible minerals can inhibit this transformation. This study demonstrates that a range of sorbed transition metals can be selectively sequestered into a 0.5 M HCl insoluble phase and that the process can be stimulated through sequential steps of microbial iron reduction and air oxidation. Microbial reduction experiments with divalent Cd, Co, Mn, Ni, Pb, and Zn indicate that all metals save Mn experienced some sequestration, with the degree of metal incorporation into the 0.5 M HCl insoluble phase correlating positively with crystalline ionic radius at coordination number = 6. Redox cycling experiments with Zn adsorbed to synthetic goethite/ferrihydrite or iron-bearing natural sediments indicate that redox cycling from iron reducing to iron oxidizing conditions sequesters more Zn within authigenic minerals than microbial iron reduction alone. In addition, the process is more effective in goethite/ferrihydrite mixtures than in iron-bearing natural sediments. Microbial reduction alone resulted in a -3x increase in 0.5 M HCl insoluble Zn and increased aqueous Zn (Zn-aq) in goethite/ferrihydrite, but did not significantly affect Zn speciation in natural sediments. Redox cycling enhanced the Zn sequestration by approximately 12% in both goethite/ferrihydrite and natural sediments and reduced Zn-aq to levels equal to the uninoculated control in goethite/ferrihydrite and less than the uninoculated control in natural sediments. These

  9. System and method for producing metallic iron

    DOEpatents

    Englund, David J.; Schlichting, Mark; Meehan, John; Crouch, Jeremiah; Wilson, Logan

    2014-07-29

    A method of production of metallic iron nodules comprises assembling a hearth furnace having a moveable hearth comprising refractory material and having a conversion zone and a fusion zone, providing a hearth material layer comprising carbonaceous material on the refractory material, providing a layer of reducible material comprising and iron bearing material arranged in discrete portions over at least a portion of the hearth material layer, delivering oxygen gas into the hearth furnace to a ratio of at least 0.8:1 ponds of oxygen to pounds of iron in the reducible material to heat the conversion zone to a temperature sufficient to at least partially reduce the reducible material and to heat the fusion zone to a temperature sufficient to at least partially reduce the reducible material, and heating the reducible material to form one or more metallic iron nodules and slag.

  10. On the Size Dependence of Molar and Specific Properties of Independent Nano-phases and Those in Contact with Other Phases

    NASA Astrophysics Data System (ADS)

    Kaptay, George

    2018-05-01

    Nano-materials are materials with at least one nano-phase. A nano-phase is a phase with at least one of its dimensions below 100 nm. It is shown here that nano-phases have at least 1% of their atoms along their surface layer. The ratio of surface atoms is proportional to the specific surface area of the phase, defined as the ratio of its surface area to its volume. Each specific/molar property has its bulk value and its surface value for the given phase, being always different, as the energetic states of the atoms in the bulk and in the surface layer of a phase are different. The average specific/molar property of a nano-phase is modeled here as a linear combination of the bulk and surface values of the same property, scaled with the ratio of the surface atoms. That makes the performance of all nano-phases proportional to their specific surface area. As the characteristic size of the nano-phase is inversely proportional to its specific surface area, all specific/molar properties of nano-phases are inversely proportional to the characteristic size of the phase. This is applied to the size dependence of the molar Gibbs energy of the nano-phase, which appears to be in agreement with the thermodynamics of Gibbs. This agreement proves the general validity of the present model on the size dependence of the specific/molar properties of independent nano-phases. It is shown that the properties of nano-phases are different for independent nano-phases (surrounded only by their equilibrium vapor phase) and for nano-phases in multi-phase situations, such as a liquid nano-droplet in the sessile drop configuration.

  11. Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation.

    PubMed

    Zhang, Peili; Li, Lin; Nordlund, Dennis; Chen, Hong; Fan, Lizhou; Zhang, Biaobiao; Sheng, Xia; Daniel, Quentin; Sun, Licheng

    2018-01-26

    Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2 . The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.

  12. Method and system for producing metallic iron nuggets

    DOEpatents

    Iwasaki, Iwao; Kiesel, Richard F.; Englund, David J; Hendrickson, Dave

    2012-12-18

    A method and system for producing metallic iron nuggets may include providing multiple layers of agglomerates, such as briquettes, balls and extrusions, of a reducible mixture of reducing material (such as carbonaceous material) and of a reducible iron bearing material (such as iron oxide) on a hearth material layer (such as carbonaceous material) and providing a coarse overlayer of carbonaceous material over at least some of the agglomerates. Heating the agglomerates of reducible mixture to 1425.degree. C. or 1400.degree. C. or 1375.degree. C. results in formation of an intermediate product of one or more metallic iron nuggets, which may have a sulfur content of less than 0.03%, and slag, which may have less than 5% mass MgO, which may have a ratio of percent by weight sulfur in the slag over percent by weight sulfur in the metallic nuggets of at least about 12 or at least about 15.

  13. Metal regeneration of iron chelates in nitric oxide scrubbing

    DOEpatents

    Chang, S.G.; Littlejohn, D.; Shi, Y.

    1997-08-19

    The present invention relates to a process of using metal particles to reduce NO to NH{sub 3}. More specifically, the invention concerns an improved process to regenerate iron (II) (CHELATE) by reduction of iron (II) (CHELATE) (NO) complex, which process comprises: (a) contacting an aqueous solution containing iron (II) (CHELATE) (NO) with metal particles at between about 20 and 90 C to reduce NO present, produce ammonia or an ammonium ion, and produce free iron (II) (CHELATE) at a pH of between about 3 and 8. The process is useful to remove NO from flue gas and reduce pollution. 34 figs.

  14. Metal regeneration of iron chelates in nitric oxide scrubbing

    DOEpatents

    Chang, Shih-Ger; Littlejohn, David; Shi, Yao

    1997-08-19

    The present invention relates to a process of using metal particles to reduce NO to NH.sub.3. More specifically, the invention concerns an improved process to regenerate iron (II) (CHELATE) by reduction of iron (II) (CHELATE) (NO) complex, which process comprises: a) contacting an aqueous solution containing iron (II) (CHELATE) (NO) with metal particles at between about 20.degree. and 90.degree. C. to reduce NO present, produce ammonia or an ammonium ion, and produce free iron (II) (CHELATE) at a pH of between about 3 and 8. The process is useful to remove NO from flue gas and reduce pollution.

  15. Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

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

    Zhang, Peili; Li, Lin; Nordlund, Dennis

    Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

  16. Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

    DOE PAGES

    Zhang, Peili; Li, Lin; Nordlund, Dennis; ...

    2018-01-26

    Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

  17. Chromium doped nano-phase separated yttria-alumina-silica glass based optical fiber preform: fabrication and characterization

    NASA Astrophysics Data System (ADS)

    Dutta, Debjit; Dhar, Anirban; Das, Shyamal; Bysakh, Sandip; Kir'yanov, Alexandar; Paul, Mukul Chandra

    2015-06-01

    Transition metal (TM) doping in silica core optical fiber is one of the research area which has been studied for long time and Chromium (Cr) doping specially attracts a lot of research interest due to their broad emission band covering U, C and L band with many potential application such as saturable absorber or broadband amplifier etc. This paper present fabrication of Cr doped nano-phase separated silica fiber within yttria-alumina-silica core glass through conventional Modified Chemical Vapor Deposition (MCVD) process coupled with solution doping technique along with different material and optical characterization. For the first time scanning electron microscope (SEM) / energy dispersive X-ray (EDX) analysis of porous soot sample and final preform has been utilized to investigate incorporation mechanism of Crions with special emphasis on Cr-species evaporation at different stages of fabrication. We also report that optimized annealing condition of our fabricated preform exhibited enhanced fluorescence emission and a broad band within 550- 800 nm wavelength region under pumping at 532 nm wavelength due to nano-phase restructuration.

  18. Supercritical Fluid Infusion of Iron Additives in Polymeric Matrices

    NASA Technical Reports Server (NTRS)

    Nazem, Negin; Taylor, Larry T.

    1999-01-01

    The objective of this project was the experimentation to measure preparation of iron nanophases within polymeric matrices via supercritical fluid infusion of iron precursors followed by thermal reduction. Another objective was to determine if supercritical CO2 could infuse into the polymer. The experiment is described along with the materials, and the supercritical fluid infusion and cure procedures. X-ray photoelectron spectra and transmission electron micrographs were obtained. The results are summarized in charts, and tables.

  19. Possible Evidence for Iron Sulfates, Iron Sulfides, and Elemental Sulfur at Gusev Crater, Mars, from Mer, Crism, and Analog Data

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Ming, D. W.; Yen, A.; Arvidson, R. E.; Gruener, J.; Humm, D.; Klingelhoefer, G.; Murchie, S.; Schroeder, C.; Seelos, F., IV; hide

    2007-01-01

    The Mossbauer (MB) spectrometers on the Mars Exploration Rovers (MER) Spirit (Gusev crater) and Opportunity (Meridiani Planum) have detected 14 Fe-bearing phases, and mineralogical assignments have been made for all except 3. Identified Fe2+-bearing phases are olivine, pyroxene, ilmenite, and troilite. Magnetite and chromite are present as mixed Fe(2+) and Fe(3+) phases. Identified Fe(3+) phase are jarosite, hematite, goethite, and nanophase ferric oxide (npOx). Fe(sup 0) (iron metal) is present as kamacite. Nanophase ferric oxide (npOx) is a generic name for octahedrally coordinated Fe(3+) alteration products that cannot be otherwise mineralogically assigned on the basis of MER data. On the Earth, npOx would include ferrihydrite, iddingsite, schwertmannite, akaganeite, and superparamagnetic hematite and goethite. The Mars Reconnaissance Orbiter CRISM instrument, a visible, near-IR hyperspectral imager (approximately 0.35 to 4 micron) enables mineralogical examination of Mars with a tool that is sensitive to H2O and to M-OH (M = Al, Si, Fe, Mg, etc.) at spatial resolution of about 20 m/pixel. We examined a CRISM image of the MER region of Gusev crater (Columbia Hills and plains to the west), looking for spectral evidence of the aqueous process apparent from the MER analyses. We also searched for spectral constraints for the mineralogical composition of our unidentified Fe-bearing phases and the forms of npOx present on Mars. We also consider evidence from analogue samples that the precursor for the goethite detected by MB in Clovis Class rocks is an iron sulfide. We suggest that there is some indirect evidence that elemental sulfur might be present to different extents in Clovis Class rocks, the Fe3Sulfate-rich soils, and perhaps even typical (Laguna Class) surface soils.

  20. System and method for producing metallic iron nodules

    DOEpatents

    Bleifuss, Rodney L [Grand Rapids, MN; Englund, David J [Bovey, MN; Iwasaki, Iwao [Grand Rapids, MN; Lindgren, Andrew J [Grand Rapids, MN; Kiesel, Richard F [Hibbing, MN

    2011-09-20

    A method for producing metallic iron nodules by assembling a shielding entry system to introduce coarse carbonaceous material greater than 6 mesh in to the furnace atmosphere at location(s) where the temperature of the furnace atmosphere adjacent at least partially reduced reducible iron bearing material is between about 2200 and 2650.degree. F. (1200 and 1450.degree. C.), the shielding entry system adapted to inhibit emission of infrared radiation from the furnace atmosphere and seal the furnace atmosphere from exterior atmosphere while introducing coarse carbonaceous material greater than 6 mesh into the furnace to be distributed over the at least partially reduced reducible iron bearing material, and heating the covered at least partially reduced reducible iron bearing material in a fusion atmosphere to assist in fusion and inhibit reoxidation of the reduced material during fusion to assist in fusion and inhibit reoxidation of the reduced material in forming metallic iron nodules.

  1. Synthesis and electronic properties of nanophase semiconductor materials

    NASA Astrophysics Data System (ADS)

    Sailor, Michael J.

    1993-05-01

    The objective of the research effort is to understand and learn to control the morphologic and electronic properties of electrodeposited nanophase semiconductors. The initial work has focused on electrodeposition of nanophase CdSe, using a sequential monolayer deposition technique that we are developing. We are currently extending the synthesis phase of this project into silicon, silicon carbide, and phosphor materials. This work also encompasses studying semiconductor electrodeposition into materials with restricted dimensions, such as microporous alumina and porous silicon membranes. By growing films with very small grain sizes, we hope to produce and study materials that display unusual electronic or luminescent effects. We are primarily interested in the electronic properties of the II-VI and group IV materials, for potential applications in nanoscale electronics and optical detector technologies. The phosphors are being studied for their potential as efficient high-resolution display materials.

  2. Manufacturing and Application of Metalized Ore-Coal Pellets in Synthetic Pig Iron Smelting

    NASA Astrophysics Data System (ADS)

    Nokhrina, O. I.; Rozhikhina, I. D.; Khodosov, I. E.

    2016-08-01

    The article presents research data on manufacturing and application of metalized ore-coal pellets in synthetic pig iron smelting. A technology of pellets metallization by means of solid-phase reduction of iron from oxides using hematite-magnetite iron ore and low-caking coal as raw materials is described. Industrial testing of replacing 10, 15, and 20% of waste metal by the metalized ore-coal pellets in the coreless induction furnace IST-1 is described. Optimal temperature and time conditions of feeding the metalized pellets into the furnace in smelting pig iron of SCh-40-60 grade are determined.

  3. Method and system for producing metallic iron nuggets

    DOEpatents

    Iwasaki, Iwao; Lindgren, Andrew J.; Kiesel, Richard F.

    2013-06-25

    Method and system for producing metallic nuggets includes providing reducible mixture of reducing material (such as carbonaceous material) and reducible iron bearing material (such as iron oxide) that may be arranged in discrete portions, such as mounds or briquettes, on at least a portion of a hearth material layer (such as carbonaceous material). A coarse overlayer of carbonaceous material may be provided over at least some of the discrete portions. Heating the reducible mixture to 1425.degree. C. or 1400.degree. C. or 1375.degree. C. results in formation of an intermediate product of one or more metallic iron nuggets, which may have a sulfur content of less than 0.03%, and slag, which may have less than 5% mass MgO, which may have a ratio of percent by weight sulfur in the slag over percent by weight sulfur in the metallic nuggets of at least about 12 or at least about 15.

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

    PubMed

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

    2012-12-01

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

  5. Biogenic iron oxide transformation by hyperthermophiles: spectral and physiological potentials

    NASA Astrophysics Data System (ADS)

    Kashyap, S.; Sklute, E.; Dyar, M. D.; Holden, J. F.

    2017-12-01

    It is likely that any putative life in our Solar System beyond Earth, extinct or extant, is microbial. However, to detect such life, distinct organic or mineral biosignatures need to be established. Microbe-mineral interactions and mineral transformations deserve further examination in this regard. This study focused on hyperthermophilic iron oxide-reducing archaea and addressed the types of iron-oxide minerals that are favored for growth, the kinetics of such reactions, and the mineral transformations that occur depending upon the electron acceptor. Two hyperthermophilic archaea (Pyrodictium delaneyi and Pyrobaculum islandicum) and six laboratory-synthesized nanophase iron oxide minerals (2-line ferrihydrite, lepidocrocite, akaganéite, goethite, hematite and maghemite) were tested for cell growth and Fe(II) production. The mineral end-products were further characterized by examining the spectral signatures associated with these transformations using reflectance, Raman, and Mössbauer spectroscopies and electron diffraction patterns. Additionally, we critically examined how sample preparation techniques influence the end products of these transformations by comparing freeze-dried samples against those still in solution. Results showed that both organisms utilize all six nanophase iron oxides, although with varying success. The best candidates for microbial reduction were ferrihydrite, akaganéite, and lepidocrocite. The mineral transformation products and the extent of reduction varied and showed subtle differences based on organism and the type of iron oxide used. The subtle spectral differences were best characterized using combined spectroscopy techniques. This research provides new insights into microbe-mineral interactions and the discrimination of potential biosignatures in the search for life beyond Earth.

  6. Surveying the South Pole-Aitken basin magnetic anomaly for remnant impactor metallic iron

    USGS Publications Warehouse

    Cahill, Joshua T.S.; Hagerty, Justin J.; Lawrence, David M.; Klima, Rachel L.; Blewett, David T.

    2014-01-01

    The Moon has areas of magnetized crust ("magnetic anomalies"), the origins of which are poorly constrained. A magnetic anomaly near the northern rim of South Pole-Aitken (SPA) basin was recently postulated to originate from remnant metallic iron emplaced by the SPA basin-forming impactor. Here, we remotely examine the regolith of this SPA magnetic anomaly with a combination of Clementine and Lunar Prospector derived iron maps for any evidence of enhanced metallic iron content. We find that these data sets do not definitively detect the hypothesized remnant metallic iron within the upper tens of centimeters of the lunar regolith.

  7. Release of iron, zinc, and lead from common iron construction bars and zinc metallic bars in water solutions and meals.

    PubMed

    Lechtig, Aarón; Lòpez de Romaña, Daniel; Boy, Erick; Vargas, Alejandro; Rosas del Portal, Mauricio; Huaylinos, María Luisa

    2007-12-01

    The use of iron pots has decreased the prevalence of anemia. To investigate the release of iron, zinc, and lead from metallic iron and zinc bars incubated in water and in meals. Iron, zinc, and lead concentrations were measured at different incubation conditions in water and in meals. The iron concentration in water was 1.26 mg/L after incubation with one iron bar at pH 7 and 100 degrees C for 20 minutes and in meals was 0.97 mg per 100 g of wet meals, rich in phytate, cooking at 100 degrees C during 20 minutes. The maximum contents were 7720 mg/L of iron and 1826 mg/L of zinc in vinegar at pH 3 and 20 degrees C after 90 and 32 days, respectively. Lead was released from the bars, but at concentrations well below the upper tolerable limits. In outreach populations, the use of iron and zinc metallic bars in water and meals could contribute to sustainable, very low-cost prevention of iron and zinc deficiencies, and home-fortified vinegar could be used for treatment of both deficiencies. Field trials should be performed to determine the impact that the use of iron and zinc metallic bars in water and meals might have on the iron and zinc status of population groups.

  8. Process for removing technetium from iron and other metals

    DOEpatents

    Leitnaker, J.M.; Trowbridge, L.D.

    1999-03-23

    A process for removing technetium from iron and other metals comprises the steps of converting the molten, alloyed technetium to a sulfide dissolved in manganese sulfide, and removing the sulfide from the molten metal as a slag. 4 figs.

  9. Use of bimodal carbon distribution in compacts for producing metallic iron nodules

    DOEpatents

    Iwasaki, Iwao

    2012-10-16

    A method for use in production of metallic iron nodules comprising providing a reducible mixture into a hearth furnace for the production of metallic iron nodules, where the reducible mixture comprises a quantity of reducible iron bearing material, a quantity of first carbonaceous reducing material of a size less than about 28 mesh of an amount between about 65 percent and about 95 percent of a stoichiometric amount necessary for complete iron reduction of the reducible iron bearing material, and a quantity of second carbonaceous reducing material with an average particle size greater than average particle size of the first carbonaceous reducing material and a size between about 3 mesh and about 48 mesh of an amount between about 20 percent and about 60 percent of a stoichiometric amount of necessary for complete iron reduction of the reducible iron bearing material.

  10. Use of bimodal carbon distribution in compacts for producing metallic iron nodules

    DOEpatents

    Iwasaki, Iwao

    2014-04-08

    A method for use in production of metallic iron nodules comprising providing a reducible mixture into a hearth furnace for the production of metallic iron nodules, where the reducible mixture comprises a quantity of reducible iron bearing material, a quantity of first carbonaceous reducing material of a size less than about 28 mesh of an amount between about 65 percent and about 95 percent of a stoichiometric amount necessary for complete iron reduction of the reducible iron bearing material, and a quantity of second carbonaceous reducing material with an average particle size greater than average particle size of the first carbonaceous reducing material and a size between about 3 mesh and about 48 mesh of an amount between about 20 percent and about 60 percent of a stoichiometric amount of necessary for complete iron reduction of the reducible iron bearing material.

  11. Microscopic iron metal on glass and minerals - A tool for studying regolith maturity

    NASA Technical Reports Server (NTRS)

    Allen, C. C.; Morris, R. V.; Lauer, H. V., Jr.; Mckay, D. S.

    1993-01-01

    A novel method of producing mixtures of glass or minerals with iron metal is presented. A portion of the Fe(2+) in basaltic glass and minerals can be reduced to metal in a few hours at 1100 C and an oxygen fugacity well below the iron-wustite buffer. Part of the iron metals forms rounded submicrometer blebs on the surfaces and in some cases within the grains. A concentration of such blebs equivalent to 20-30 percent of a grain's surface area can totally dominate the reflectance spectra of basaltic glass, pyroxene, and olivine. The production of optically opaque iron metal blebs, combined with the decline in Fe(2+), affects the glass and mineral reflectance spectra in three ways: by lowering the overall reflectivity, reducing the spectral contrast of absorption features, and producing a continuum with a general rise in reflectivity toward longer wavelengths.

  12. Isolation and characterization of iron chelators from turmeric (Curcuma longa): selective metal binding by curcuminoids.

    PubMed

    Messner, Donald J; Surrago, Christine; Fiordalisi, Celia; Chung, Wing Yin; Kowdley, Kris V

    2017-10-01

    Iron overload disorders may be treated by chelation therapy. This study describes a novel method for isolating iron chelators from complex mixtures including plant extracts. We demonstrate the one-step isolation of curcuminoids from turmeric, the medicinal food spice derived from Curcuma longa. The method uses iron-nitrilotriacetic acid (NTA)-agarose, to which curcumin binds rapidly, specifically, and reversibly. Curcumin, demethoxycurcumin, and bisdemethoxycurcumin each bound iron-NTA-agarose with comparable affinities and a stoichiometry near 1. Analyses of binding efficiencies and purity demonstrated that curcuminoids comprise the primary iron binding compounds recovered from a crude turmeric extract. Competition of curcuminoid binding to the iron resin was used to characterize the metal binding site on curcumin and to detect iron binding by added chelators. Curcumin-Iron-NTA-agarose binding was inhibited by other metals with relative potency: (>90% inhibition) Cu 2+  ~ Al 3+  > Zn 2+  ≥ Ca 2+  ~ Mg 2+  ~ Mn 2+ (<20% inhibition). Binding was also inhibited by pharmaceutical iron chelators (desferoxamine or EDTA) or by higher concentrations of weak iron chelators (citrate or silibinin). Investigation of the physiological effects of iron binding by curcumin revealed that curcumin uptake by cultured cells was reduced >80% by addition of iron to the media; uptake was completely restored by desferoxamine. Ranking of metals by relative potencies for blocking curcumin uptake agreed with their relative potencies in blocking curcumin binding to iron-NTA-agarose. We conclude that curcumin can selectively bind toxic metals including iron in a physiological setting, and propose inhibition of curcumin binding to iron-NTA-agarose for iron chelator screening.

  13. Optimization Review, Peck Iron and Metal Superfund Site, Portsmouth, Virginia

    EPA Pesticide Factsheets

    The Peck Iron and Metal Superfund Site is a 33-acre property located in Norfolk County, Portsmouth, Virginia. PIM (Figure 1) is the site of a former scrap metal storage and recycling facility that began operation in the 1940s.

  14. Formation of nanophases in epoxy thermosets containing amphiphilic block copolymers with linear and star-like topologies.

    PubMed

    Wang, Lei; Zhang, Chongyin; Cong, Houluo; Li, Lei; Zheng, Sixun; Li, Xiuhong; Wang, Jie

    2013-07-11

    In this work, we investigated the effect of topological structures of block copolymers on the formation of the nanophase in epoxy thermosets containing amphiphilic block copolymers. Two block copolymers composed of poly(ε-caprolactone) (PCL) and poly(2,2,2-trifluoroethyl acrylate) (PTFEA) blocks were synthesized to possess linear and star-shaped topologies. The star-shaped block copolymer composed a polyhedral oligomeric silsesquioxane (POSS) core and eight poly(ε-caprolactone)-block-poly(2,2,2-trifluoroethyl acrylate) (PCL-b-PTFEA) diblock copolymer arms. Both block copolymers were synthesized via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) process; they were controlled to have identical compositions of copolymerization and lengths of blocks. Upon incorporating both block copolymers into epoxy thermosets, the spherical PTFEA nanophases were formed in all the cases. However, the sizes of PTFEA nanophases from the star-like block copolymer were significantly lower than those from the linear diblock copolymer. The difference in the nanostructures gave rise to the different glass transition behavior of the nanostructured thermosets. The dependence of PTFEA nanophases on the topologies of block copolymers is interpreted in terms of the conformation of the miscible subchain (viz. PCL) at the surface of PTFEA microdomains and the restriction of POSS cages on the demixing of the thermoset-philic block (viz. PCL).

  15. Continuous-flow extraction system for elemental association study: a case of synthetic metal-doped iron hydroxide.

    PubMed

    Hinsin, Duangduean; Pdungsap, Laddawan; Shiowatana, Juwadee

    2002-12-06

    A continuous-flow extraction system originally developed for sequential extraction was applied to study elemental association of a synthetic metal-doped amorphous iron hydroxide phase. The homogeneity and metal association of the precipitates were evaluated by gradual leaching using the system. Leachate was collected in fractions for determination of elemental concentrations. The result obtained as extractograms indicated that the doped metals were adsorbed more on the outermost surface rather than homogeneously distributed in the precipitates. The continuous-flow extraction method was also used for effective removal of surface adsorbed metals to obtain a homogeneous metal-doped synthetic iron hydroxide by a sequential extraction using acetic acid and small volume of hydroxylamine hydrochloride solution. The system not only ensures complete washing, but the extent of metal immobilization in the synthetic iron hydroxide could be determined with high accuracy from the extractograms. The initial metal/iron mole ratio (M/Fe) in solution affected the M/Fe mole ratio in homogeneous doped iron hydroxide phase. The M/Fe mole ratio of metal incorporation was approximately 0.01-0.02 and 0.03-0.06, for initial solution M/Fe mole ratio of 0.025 and 0.100, respectively.

  16. Nanophase Carbonates on Mars: Does Evolved Gas Analysis of Nanophase Carbonates Reveal a Large Organic Carbon Budget in Near-surface Martian Materials?

    NASA Astrophysics Data System (ADS)

    Archer, P. D., Jr.; Ming, D. W.; Sutter, B.; Niles, P. B.; Eigenbrode, J. L.

    2015-12-01

    Evolved Gas Analysis (EGA), which involves heating a sample and monitoring the gases released, has been performed on Mars by the Viking gas chromatography/mass spectrometry instruments, the Thermal and Evolved Gas Analyzer (TEGA) on the Phoenix lander, and the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory. All of these instruments detected CO2 released during sample analysis at abundances of ~0.1 to 5 wt% assuming a carbonate source. The source of the CO2 can be constrained by evaluating the temperature of the gas release, a capability of both the TEGA and SAM instruments. The samples analyzed by SAM show that the majority of the CO2is released below 400 °C, much lower than traditional carbonate decomposition temperatures which can be as low as 400 °C for some siderites, with magnesites and calcites decomposing at even higher temperatures. In addition to mineralogy, decomposition temperature can depend on particle size (among other factors). If carbonates formed on Mars under low temperature and relative humidity conditions, the resulting small particle size (nanophase) carbonates could have low decomposition temperatures. We have found that calcite can be synthesized by exposing CaO to water vapor and CO2 and that the resulting mineral has an EGA peak of ~550 °C for CO2, which is about 200 °C lower than for other calcites. Work is ongoing to produce Fe and Mg-bearing carbonates using the same process. Current results suggest that nanophase calcium carbonates cannot explain the CO2 released from martian samples. If the decomposition temperatures of Mg and Fe-bearing nanophase carbonates are not significantly lower than 400 °C, other candidate sources include oxalates and carboxylated organic molecules. If present, the abundance of organic carbon in these samples could be > 0.1 wt % (1000s of ppm), a signficant departure from the paradigm of the organic-poor Mars based on Viking results.

  17. Nanophase Carbonates on Mars: Does Evolved Gas Analysis of Nanophase Carbonates Reveal a Large Organic Carbon Budget in Near-Surface Martian Materials?

    NASA Technical Reports Server (NTRS)

    Archer, P. Douglas, Jr.; Niles, Paul B.; Ming, Douglas W.; Sutter, Brad; Eigenbrode, Jen

    2015-01-01

    Evolved Gas Analysis (EGA), which involves heating a sample and monitoring the gases released, has been performed on Mars by the Viking gas chromatography/mass spectrometry instruments, the Thermal and Evolved Gas Analyzer (TEGA) on the Phoenix lander, and the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory. All of these instruments detected CO2 released during sample analysis at abundances of approx. 0.1 to 5 wt% assuming a carbonate source. The source of the CO2 can be constrained by evaluating the temperature of the gas release, a capability of both the TEGA and SAM instruments. The samples analyzed by SAM show that the majority of the CO2 is released below 400C, much lower than traditional carbonate decomposition temperatures which can be as low as 400C for some siderites, with magnesites and calcites decomposing at even higher temperatures. In addition to mineralogy, decomposition temperature can depend on particle size (among other factors). If carbonates formed on Mars under low temperature and relative humidity conditions, the resulting small particle size (nanophase) carbonates could have low decomposition temperatures. We have found that calcite can be synthesized by exposing CaO to water vapor and CO2 and that the resulting mineral has an EGA peak of approx. 550C for CO2, which is about 200C lower than for other calcites. Work is ongoing to produce Fe and Mg-bearing carbonates using the same process. Current results suggest that nanophase calcium carbonates cannot explain the CO2 released from martian samples. If the decomposition temperatures of Mg and Fe-bearing nanophase carbonates are not significantly lower than 400C, other candidate sources include oxalates and carboxylated organic molecules. If present, the abundance of organic carbon in these samples could be greater than 0.1 wt % (1000s of ppm), a signficant departure from the paradigm of the organic-poor Mars based on Viking results.

  18. Mixed-valent dicobalt and iron-cobalt complexes with high-spin configurations and short metal-metal bonds.

    PubMed

    Zall, Christopher M; Clouston, Laura J; Young, Victor G; Ding, Keying; Kim, Hyun Jung; Zherebetskyy, Danylo; Chen, Yu-Sheng; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C

    2013-08-19

    Cobalt-cobalt and iron-cobalt bonds are investigated in coordination complexes with formally mixed-valent [M2](3+) cores. The trigonal dicobalt tris(diphenylformamidinate) compound, Co2(DPhF)3, which was previously reported by Cotton, Murillo, and co-workers (Inorg. Chim. Acta 1996, 249, 9), is shown to have an energetically isolated, high-spin sextet ground-state by magnetic susceptibility and electron paramagnetic resonance (EPR) spectroscopy. A new tris(amidinato)amine ligand platform is introduced. By tethering three amidinate donors to an apical amine, this platform offers two distinct metal-binding sites. Using the phenyl-substituted variant (abbreviated as L(Ph)), the isolation of a dicobalt homobimetallic and an iron-cobalt heterobimetallic are demonstrated. The new [Co2](3+) and [FeCo](3+) cores have high-spin sextet and septet ground states, respectively. Their solid-state structures reveal short metal-metal bond distances of 2.29 Å for Co-Co and 2.18 Å for Fe-Co; the latter is the shortest distance for an iron-cobalt bond to date. To assign the positions of iron and cobalt atoms as well as to determine if Fe/Co mixing is occurring, X-ray anomalous scattering experiments were performed, spanning the Fe and Co absorption energies. These studies show only a minor amount of metal-site mixing in this complex, and that FeCoL(Ph) is more precisely described as (Fe0.94(1)Co0.06(1))(Co0.95(1)Fe0.05(1))L(Ph). The iron-cobalt heterobimetallic has been further characterized by Mössbauer spectroscopy. Its isomer shift of 0.65 mm/s and quadrupole splitting of 0.64 mm/s are comparable to the related diiron complex, Fe2(DPhF)3. On the basis of spectroscopic data and theoretical calculations, it is proposed that the formal [M2](3+) cores are fully delocalized.

  19. Ionic liquid-based extraction followed by graphite-furnace atomic absorption spectrometry for the determination of trace heavy metals in high-purity iron metal.

    PubMed

    Matsumiya, Hiroaki; Kato, Tatsuya; Hiraide, Masataka

    2014-02-01

    The analysis of high-purity materials for trace impurities is an important and challenging task. The present paper describes a facile and sensitive method for the determination of trace heavy metals in high-purity iron metal. Trace heavy metals in an iron sample solution were rapidly and selectively preconcentrated by the extraction into a tiny volume of an ionic liquid [1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide] for the determination by graphite-furnace atomic absorption spectrometry (GFAAS). A nitrogen-donating neutral ligand, 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ), was found to be effective in the ionic liquid-based selective extraction, allowing the nearly complete (~99.8%) elimination of the iron matrix. The combination with the optimized GFAAS was successful. The detectability reached sub-μg g(-1) levels in iron metal. The novel use of TPTZ in ionic liquid-based extraction followed by GFAAS was successfully applied to the determination of traces of Co, Ni, Cu, Cd, and Pb in certified reference materials for high-purity iron metal. © 2013 Published by Elsevier B.V.

  20. Multiscale correlations of iron phases and heavy metals in technogenic magnetic particles from contaminated soils.

    PubMed

    Yu, Xiuling; Lu, Shenggao

    2016-12-01

    Technogenic magnetic particles (TMPs) are carriers of heavy metals and organic contaminants, which derived from anthropogenic activities. However, little information on the relationship between heavy metals and TMP carrier phases at the micrometer scale is available. This study determined the distribution and association of heavy metals and magnetic phases in TMPs in three contaminated soils at the micrometer scale using micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy. Multiscale correlations of heavy metals in TMPs were elucidated using wavelet transform analysis. μ-XRF mapping showed that Fe was enriched and closely correlated with Co, Cr, and Pb in TMPs from steel industrial areas. Fluorescence mapping and wavelet analysis showed that ferroalloy was a major magnetic signature and heavy metal carrier in TMPs, because most heavy metals were highly associated with ferroalloy at all size scales. Multiscale analysis revealed that heavy metals in the TMPs were from multiple sources. Iron K-edge μ-XANES spectra revealed that metallic iron, ferroalloy, and magnetite were the main iron magnetic phases in the TMPs. The relative percentage of these magnetic phases depended on their emission sources. Heatmap analysis revealed that Co, Pb, Cu, Cr, and Ni were mainly derived from ferroalloy particles, while As was derived from both ferroalloy and metallic iron phases. Our results indicated the scale-dependent correlations of magnetic phases and heavy metals in TMPs. The combination of synchrotron based X-ray microprobe techniques and multiscale analysis provides a powerful tool for identifying the magnetic phases from different sources and quantifying the association of iron phases and heavy metals at micrometer scale. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Wetting of nanophases: Nanobubbles, nanodroplets and micropancakes on hydrophobic surfaces.

    PubMed

    An, Hongjie; Liu, Guangming; Craig, Vincent S J

    2015-08-01

    The observation by Atomic Force Microscopy of a range of nanophases on hydrophobic surfaces poses some challenging questions, not only related to the stability of these objects but also regarding their wetting properties. Spherical capped nanobubbles are observed to exhibit contact angles that far exceed the macroscopic contact angle measured for the same materials, whereas nanodroplets exhibit contact angles that are much the same as the macroscopic contact angle. Micropancakes are reported to consist of gas, in which case their wetting properties are mysterious. They should only be stable when the van der Waals forces act to thicken the film whereas for a gas, the van der Waals forces will always act to thin the film. Here we examine the available evidence and contribute some additional experiments in order to review our understanding of the wetting properties of these nanophases. We demonstrate that if in fact micropancakes consist of a contaminant their wetting properties can be explained, though the very high contact angles of nanobubbles remain unexplained. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Biogenic catalysis of soil formation on Mars?

    NASA Technical Reports Server (NTRS)

    Bishop, J. L.

    1998-01-01

    The high iron abundance and the weak ferric iron spectral features of martian surface material are consistent with nanophase (nm-sized) iron oxide minerals as a major source of iron in the bright region soil on Mars. Nanophase iron oxide minerals, such as ferrihydrite and schwertmannite, and nanophase forms of hematite and goethite are formed by both biotic and abiotic processes on Earth. The presence of these minerals on Mars does not indicate biological activity on Mars, but it does raise the possibility. This work includes speculation regarding the possibility of biogenic soils on Mars based on previous observations and analyses. A remote sensing goal of upcoming missions should be to determine if nanophase iron oxide minerals, clay silicates and carbonates are present in the martian surface material. These minerals are important indicators for exobiology and their presence on Mars would invoke a need for further investigation and sample return from these sites.

  3. Experimental segregation of iron-nickel metal, iron-sulfide, and olivine in a thermal gradient: Preliminary results

    NASA Technical Reports Server (NTRS)

    Jurewicz, Stephen R.; Jones, J. H.

    1993-01-01

    Speculation about the possible mechanisms for core formation in small asteroids raises more questions than answers. Petrologic evidence from iron meteorites, pallasites, and astronomical observations of M asteroids suggests that many small bodies were capable of core formation. Recent work by Taylor reviews the geochemical evidence and examines the possible physical/mechanical constraints on segregation processes. Taylor's evaluation suggests that extensive silicate partial melting (preferably 50 vol. percent or greater) is required before metal can segregate from the surrounding silicate and form a metal core. The arguments for large degrees of silicate partial melting are two-fold: (1) elemental trends in iron meteorites require that the metal was at is liquidus; and (2) experimental observations of metal/sulfide inclusions in partially molten silicate meteorites show that the metal/sulfide tends to form spherules in the liquid silicate due to surface tension effects. Taylor points out that for these metal spherules to sink through a silicate mush, high degrees of silicate partial melting are required to lower the silicate yield strength. Although some qualitative experimental data exists, little is actually known about the behavior of metals and liquid sulfides dispersed in silicate systems. In addition, we have been impressed with the ability of cumulative olivine to expel trapped liquid when placed in a thermal gradient. Consequently, we undertook to accomplish the following: (1) experimentally evaluate the potential for metal/sulfide/silicate segregation in a thermal gradient; and (2) obtain quantitative data of the wetting parameters of metal-sulfide melts among silicate grains.

  4. Bioaccessibility of micron-sized powder particles of molybdenum metal, iron metal, molybdenum oxides and ferromolybdenum--Importance of surface oxides.

    PubMed

    Mörsdorf, Alexander; Odnevall Wallinder, Inger; Hedberg, Yolanda

    2015-08-01

    The European chemical framework REACH requires that hazards and risks posed by chemicals, including alloys and metals, that are manufactured, imported or used in different products (substances or articles) are identified and proven safe for humans and the environment. Metals and alloys need hence to be investigated on their extent of released metals (bioaccessibility) in biologically relevant environments. Read-across from available studies may be used for similar materials. This study investigates the release of molybdenum and iron from powder particles of molybdenum metal (Mo), a ferromolybdenum alloy (FeMo), an iron metal powder (Fe), MoO2, and MoO3 in different synthetic body fluids of pH ranging from 1.5 to 7.4 and of different composition. Spectroscopic tools and cyclic voltammetry have been employed to characterize surface oxides, microscopy, light scattering and nitrogen absorption for particle characterization, and atomic absorption spectroscopy to quantify released amounts of metals. The release of molybdenum from the Mo powder generally increased with pH and was influenced by the fluid composition. The mixed iron and molybdenum surface oxide of the FeMo powder acted as a barrier both at acidic and weakly alkaline conditions. These findings underline the importance of the surface oxide characteristics for the bioaccessibility of metal alloys. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  5. Formation of iron metal and grain coagulation in the solar nebula

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A., III; Berg, Otto

    1994-01-01

    The interstellar grain population in the giant molecular cloud from which the sun formed contained little or no iron metal. However, thermal processing of individual interstellar silicates in the solar nebula is likely to result in the formation of a population of very small iron metal grains. If such grains are exposed to even transient magnetic fields, each will become a tiny dipole magnet capable of interacting with other such dipoles over spatial scale orders of magnitude larger than the radii of individual grains. Such interactions will greatly increase the coagulation cross-section for this grain population. Furthermore, the magnetic attraction between two iron dipoles will significantly increase both the collisional sticking coefficient and the strength of the interparticle binding energy for iron aggregates. Formation of iron metal may therefore be a key step in the aggregation of planetesimals in a protoplanetary nebula. Such aggregates may have already been observed in protoplanetary systems. The enhancement in the effective interaction distance between two magnetic dipoles is directly proportional to the strength of the magnetic dipoles and inversely proportional to the relative velocity. It is less sensitive to the reduced mass of the interacting particles (alpha M(exp -1/2)) and almost insensitive to the initial number density of magnetic dipoles (alpha n(sub o)(exp 1/6)). We are in the process of measuring the degree of coagulation in our condensation flow apparatus as a function of applied magnetic field and correlating these results by means of magnetic remanance acquisition measurements on our iron grains with the strength of the magnetic field to which the grains are exposed. Results of our magnetic remanance acquisition measurements and the magnetic-induced coagulation study will be presented as well as an estimate of the importance of such processes near the nebular midplane.

  6. Effect of iron sulfides on the space weathering of airless silicate bodies: Laboratory simulation

    NASA Astrophysics Data System (ADS)

    Sasaki, Sho; Hiroi, Takahiro; Okazaki, Mizuki

    The spectral mismatch between S-type asteroids and ordinary chondrites is explained by the process "space weathering", which should change the optical properties of the surface of airless silicate bodies: darkening, spectral reddening, and attenuation of absorption bands in reflectance spectra. It is caused by nanophase metallic iron (nanoFe) particles within the amorphous rims, which are formed on regolith particles by high velocity dust impacts as well as irradiation of the solar wind ions. Those nanoFe particles were discovered in lunar soils, Kapoeta meteorite, and regolith grains from the surface of S-type asteroid Itokawa. Experimental studies using nano-second pulse laser confirmed that nanoFe should control the spectral darkening and reddening. In ordinary chondrites, iron sulfides, especially troilite FeS is the main sulfur-bearing mineral. TEM observation of a dust grain of Itokawa showed the presence of not only iron, but also nanophase FeS particles, which would be formed within a surface vapor-deposited thin layer (<10 to 15nm) (Noguchi et al., 2011). Among dust grains of Itokawa, one grain is composed mainly of FeS (-40 mum) with smaller olivine and pyroxene grains embedded in the FeS (Yada et al., 2014). Previously surface sulfur depletion of S-type asteroid Eros was explained by the same causes (high velocity dust impacts as well as irradiation of the solar wind ions) as space weathering (Loeffler et al. 2008), but the effect of FeS on the surface optical properties of silicate bodies has not discussed well. To examine this effect, we conducted pulse laser irradiation experiments on mixture of olivine (and pyroxene) and FeS particles with sizes typically 45-75micron, under various FeS fraction (0-20wt%). We found that addition of FeS promotes the change of optical properties in accordance with space weathering. Compared with the cases where Fe particles are mixed, darkening of 1.0 - 2.5 micron region is observed. Probably FeS nanoparticles would be

  7. Increased osteoblast and decreased Staphylococcus epidermidis functions on nanophase ZnO and TiO2.

    PubMed

    Colon, Gabriel; Ward, Brian C; Webster, Thomas J

    2006-09-01

    Many engineers and surgeons trace implant failure to poor osseointegration (or the bonding of an orthopedic implant to juxtaposed bone) and/or bacteria infection. By using novel nanotopographies, researchers have shown that nanostructured ceramics, carbon fibers, polymers, metals, and composites enhance osteoblast adhesion and calcium/phosphate mineral deposition. However, the function of bacteria on materials with nanostructured surfaces remains largely uninvestigated. This is despite the fact that during normal surgical insertion of an orthopedic implant, bacteria from the patient's own skin and/or mucosa enters the wound site. These bacteria (namely, Staphylococcus epidermidis) irreversibly adhere to an implant surface while various physiological stresses induce alterations in the bacterial growth rate leading to biofilm formation. Because of their integral role in determining the success of orthopedic implants, the objective of this in vitro study was to examine the functions of (i) S. epidermidis and (ii) osteoblasts (or bone-forming cells) on ZnO and titania (TiO(2)), which possess nanostructured compared to microstructured surface features. ZnO is a well-known antimicrobial agent and TiO(2) readily forms on titanium once implanted. Results of this study provided the first evidence of decreased S. epidermidis adhesion on ZnO and TiO(2) with nanostructured when compared with microstructured surface features. Moreover, compared with microphase formulations, results of this study showed increased osteoblast adhesion, alkaline phosphatase activity, and calcium mineral deposition on nanophase ZnO and TiO(2). In this manner, this study suggests that nanophase ZnO and TiO(2) may reduce S. epidermidis adhesion and increase osteoblast functions necessary to promote the efficacy of orthopedic implants.

  8. Reflectance spectroscopy of palagonite and iron-rich montmorillonite clay mixtures: Implications for the surface composition of Mars

    NASA Technical Reports Server (NTRS)

    Orenberg, J. B.; Handy, J.

    1991-01-01

    Because of the power of remote sensing reflectance spectroscopy in determining mineralogy, it was used as the major method of identifying possible mineral analogs of the Martian surface. A summary of proposed Martian surface compositions from reflectance spectroscopy before 1979 was presented. Since that time, iron-rich montmorillonite clay, nanocrystalline or nanophase hematite, and palagonite were suggested as Mars soil analog materials.

  9. UPTAKE OF HEAVY METALS IN BATCH SYSTEMS BY A RECYCLED IRON-BEARING MATERIAL

    EPA Science Inventory

    An iron-bearing material deriving from surface finishing operations in the manufacturing of cast-iron components demonstrates potential for removal of heavy metals from aqueous waste streams. Batch isotherm and rate experiments were conducted for uptake of cadmium, zinc, and lead...

  10. Ultrasmall water-soluble metal-iron oxide nanoparticles as T1-weighted contrast agents for magnetic resonance imaging.

    PubMed

    Zeng, Leyong; Ren, Wenzhi; Zheng, Jianjun; Cui, Ping; Wu, Aiguo

    2012-02-28

    Using an improved hydrolysis method of inorganic salts assisted with water-bath incubation, ultrasmall water-soluble metal-iron oxide nanoparticles (including Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles) were synthesized in aqueous solutions, which were used as T(1)-weighted contrast agents for magnetic resonance imaging (MRI). The morphology, structure, MRI relaxation properties and cytotoxicity of the as-prepared metal-iron oxide nanoparticles were characterized, respectively. The results showed that the average sizes of nanoparticles were about 4 nm, 4 nm and 5 nm for Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles, respectively. Moreover, the nanoparticles have good water dispersibility and low cytotoxicity. The MRI test showed the strong T(1)-weighted, but the weak T(2)-weighted MRI performance of metal-iron oxide nanoparticles. The high T(1)-weighted MRI performance can be attributed to the ultrasmall size of metal-iron oxide nanoparticles. Therefore, the as-prepared metal-iron oxide nanoparticles with good water dispersibility and ultrasmall size can have potential applications as T(1)-weighted contrast agent materials for MRI.

  11. The Process of Nanostructuring of Metal (Iron) Matrix in Composite Materials for Directional Control of the Mechanical Properties

    PubMed Central

    Zemtsova, Elena

    2014-01-01

    We justified theoretical and experimental bases of synthesis of new class of highly nanostructured composite nanomaterials based on metal matrix with titanium carbide nanowires as dispersed phase. A new combined method for obtaining of metal iron-based composite materials comprising the powder metallurgy processes and the surface design of the dispersed phase is considered. The following stages of material synthesis are investigated: (1) preparation of porous metal matrix; (2) surface structuring of the porous metal matrix by TiC nanowires; (3) pressing and sintering to give solid metal composite nanostructured materials based on iron with TiC nanostructures with size 1–50 nm. This material can be represented as the material type “frame in the frame” that represents iron metal frame reinforcing the frame of different chemical compositions based on TiC. Study of material functional properties showed that the mechanical properties of composite materials based on iron with TiC dispersed phase despite the presence of residual porosity are comparable to the properties of the best grades of steel containing expensive dopants and obtained by molding. This will solve the problem of developing a new generation of nanostructured metal (iron-based) materials with improved mechanical properties for the different areas of technology. PMID:24695459

  12. The process of nanostructuring of metal (iron) matrix in composite materials for directional control of the mechanical properties.

    PubMed

    Zemtsova, Elena; Yurchuk, Denis; Smirnov, Vladimir

    2014-01-01

    We justified theoretical and experimental bases of synthesis of new class of highly nanostructured composite nanomaterials based on metal matrix with titanium carbide nanowires as dispersed phase. A new combined method for obtaining of metal iron-based composite materials comprising the powder metallurgy processes and the surface design of the dispersed phase is considered. The following stages of material synthesis are investigated: (1) preparation of porous metal matrix; (2) surface structuring of the porous metal matrix by TiC nanowires; (3) pressing and sintering to give solid metal composite nanostructured materials based on iron with TiC nanostructures with size 1-50 nm. This material can be represented as the material type "frame in the frame" that represents iron metal frame reinforcing the frame of different chemical compositions based on TiC. Study of material functional properties showed that the mechanical properties of composite materials based on iron with TiC dispersed phase despite the presence of residual porosity are comparable to the properties of the best grades of steel containing expensive dopants and obtained by molding. This will solve the problem of developing a new generation of nanostructured metal (iron-based) materials with improved mechanical properties for the different areas of technology.

  13. Effect of iron sulfides on space weathering: Lessons from the Itokawa particles and laboratory simulations

    NASA Astrophysics Data System (ADS)

    Okazaki, M.; Sasaki, S.; Tsuchiyama, A.; Miyake, A.; Matsumoto, T.; Hirata, T.; Hiroi, T.

    2014-07-01

    Space weathering is the process invoked to explain the spectral mismatch between S-type asteroids and ordinary chondrites: darkening, spectral reddening, and attenuation of absorption bands in the reflectance spectra. These changes of optical properties of the surface of airless silicate bodies are explained by nanophase metallic iron (nanoFe) particles, which are formed on regolith particles by high-velocity dust impacts as well as irradiation of the solar-wind ions (Hapke 2001). Those nanoFe particles were discovered in lunar soils, Kapoeta meteorite, and regolith grains from the surface of S-type asteroid Itokawa. Experimental studies using a nano-second-pulse laser confirmed that nanoFe should control the spectral darkening and reddening. The observed reddening of S-type asteroid families is correlated with dynamical asteroid ages after family-forming disruption (Jedicke, et al. 2004). Still, experiments showed that the weathering degree should depend on the composition such as the olivine/pyroxene ratio (Hiroi and Sasaki 2001). In ordinary chondrites, iron sulfides, typically, troilite FeS is the main sulfur-bearing mineral. TEM observation of a dust grain of Itokawa showed the presence of not only iron, but also nanophase FeS particles, which are embedded within a vapor-deposited thin surface layer (thinner than 10-15 nm; Noguchi et al. 2011). One of the Itokawa grains is composed mainly of FeS (about 40 microns) with smaller olivine and pyroxene particles (Yada et al., 2014). On the other hand, the surface sulfur depletion of S-type asteroid Eros was explained by the same mechanism (high-velocity dust and solar-wind particle impacts) of space weathering (Loeffler et al. 2008). To examine the effect of FeS on the surface optical properties of silicate bodies, we conducted pulse-laser irradiation experiments on mixtures of olivine (and pyroxene) and FeS particles with typical sizes of 45--75 micron, for varying FeS fractions (0--0.2 by weight). We find that

  14. Effects of sulfate on heavy metal release from iron corrosion scales in drinking water distribution system.

    PubMed

    Sun, Huifang; Shi, Baoyou; Yang, Fan; Wang, Dongsheng

    2017-05-01

    Trace heavy metals accumulated in iron corrosion scales within a drinking water distribution system (DWDS) could potentially be released to bulk water and consequently deteriorate the tap water quality. The objective of this study was to identify and evaluate the release of trace heavy metals in DWDS under changing source water conditions. Experimental pipe loops with different iron corrosion scales were set up to simulate the actual DWDS. The effects of sulfate levels on heavy metal release were systemically investigated. Heavy metal releases of Mn, Ni, Cu, Pb, Cr and As could be rapidly triggered by sulfate addition but the releases slowly decreased over time. Heavy metal release was more severe in pipes transporting groundwater (GW) than in pipes transporting surface water (SW). There were strong positive correlations (R 2  > 0.8) between the releases of Fe and Mn, Fe and Ni, Fe and Cu, and Fe and Pb. When switching to higher sulfate water, iron corrosion scales in all pipe loops tended to be more stable (especially in pipes transporting GW), with a larger proportion of stable constituents (mainly Fe 3 O 4 ) and fewer unstable compounds (β-FeOOH, γ-FeOOH, FeCO 3 and amorphous iron oxides). The main functional iron reducing bacteria (IRB) communities were favorable for the formation of Fe 3 O 4 . The transformation of corrosion scales and the growth of sulfate reducing bacteria (SRB) accounted for the gradually reduced heavy metal release with time. The higher metal release in pipes transporting GW could be due to increased Fe 6 (OH) 12 CO 3 content under higher sulfate concentrations. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Aggregation in complex triacylglycerol oils: coarse-grained models, nanophase separation, and predicted x-ray intensities

    NASA Astrophysics Data System (ADS)

    Quinn, Bonnie; Peyronel, Fernanda; Gordon, Tyler; Marangoni, Alejandro; Hanna, Charles B.; Pink, David A.

    2014-11-01

    Triacylglycerols (TAGs) are biologically important molecules which form crystalline nanoplatelets (CNPs) and, ultimately, fat crystal networks in edible oils. Characterizing the self-assembled hierarchies of these networks is important to understanding their functionality and oil binding capacity. We have modelled CNPs in multicomponent oils and studied their aggregation. The oil comprises (a) a liquid componentt, and (b) components which phase separately on a nano-scale (nano-phase separation) to coat the surfaces of the CNPs impenetrably, either isotropically or anisotropically, with either liquid-like coatings or crystallites, forming a coating of thickness Δ. We modelled three cases: (i) liquid-liquid nano-phase separation, (ii) solid-liquid nano-phase separation, with CNPs coated isotropically, and (iii) CNPs coated anisotropically. The models were applied to mixes of tristearin and triolein with fully hydrogenated canola oil, shea butter with high oleic sunflower oil, and cotton seed oil. We performed Monte Carlo simulations, computed structure functions and concluded: (1) three regimes arose: (a) thin coating regime, Δ \\lt 0.0701 u (b) transition regime, 0.0701 u≤slant Δ ≤slant 0.0916 u and (c) thick coating regime, Δ \\gt 0.0916 u . (arbitrary units, u) (2) The thin coating regime exhibits 1D TAGwoods, which aggregate, via DLCA/RLCA, into fractal structures which are uniformly distributed in space. (3) In the thick coating regime, for an isotropic coating, TAGwoods are not formed and coated CNPs will not aggregate but will be uniformly distributed in space. For anisotropic coating, TAGwoods can be formed and might form 1D strings but will not form DLCA/RLCA clusters. (4) The regimes are, approximately: thin coating, 0\\lt Δ \\lt 7.0 \\text{nm} transition regime, 7.0\\ltΔ \\lt 9.2 \\text{nm} and thick coating, Δ \\gt 9.2 \\text{nm} (5) The minimum minority TAG concentration required to undergo nano-phase separation is, approximately, 0.29% (thin

  16. Aggregation in complex triacylglycerol oils: coarse-grained models, nanophase separation, and predicted x-ray intensities.

    PubMed

    Quinn, Bonnie; Peyronel, Fernanda; Gordon, Tyler; Marangoni, Alejandro; Hanna, Charles B; Pink, David A

    2014-11-19

    Triacylglycerols (TAGs) are biologically important molecules which form crystalline nanoplatelets (CNPs) and, ultimately, fat crystal networks in edible oils. Characterizing the self-assembled hierarchies of these networks is important to understanding their functionality and oil binding capacity. We have modelled CNPs in multicomponent oils and studied their aggregation. The oil comprises (a) a liquid component, and (b) components which phase separately on a nano-scale (nano-phase separation) to coat the surfaces of the CNPs impenetrably, either isotropically or anisotropically, with either liquid-like coatings or crystallites, forming a coating of thickness ?. We modelled three cases: (i) liquid?liquid nano-phase separation, (ii) solid?liquid nano-phase separation, with CNPs coated isotropically, and (iii) CNPs coated anisotropically. The models were applied to mixes of tristearin and triolein with fully hydrogenated canola oil, shea butter with high oleic sunflower oil, and cotton seed oil. We performed Monte Carlo simulations, computed structure functions and concluded: (1) three regimes arose: (a) thin coating regime, Δ < 0.0701 u (b) transition regime, 0.0701 u ≤ Δ ≤ 0.0916 u and (c) thick coating regime, Δ > 0.0916 u. (arbitrary units, u) (2) The thin coating regime exhibits 1D TAGwoods, which aggregate, via DLCA/RLCA, into fractal structures which are uniformly distributed in space. (3) In the thick coating regime, for an isotropic coating, TAGwoods are not formed and coated CNPs will not aggregate but will be uniformly distributed in space. For anisotropic coating, TAGwoods can be formed and might form 1D strings but will not form DLCA/RLCA clusters. (4) The regimes are, approximately: thin coating, 0 < Δ < 7.0 nm transition regime, 7.0 < Δ < 9.2 nm and thick coating, Δ > 9.2 nm (5) The minimum minority TAG concentration required to undergo nano-phase separation is, approximately, 0.29% (thin coatings) and 0.94% (thick coatings). Minority

  17. Iron and alloys of iron. [lunar resources

    NASA Technical Reports Server (NTRS)

    Sastri, Sankar

    1992-01-01

    All lunar soil contains iron in the metallic form, mostly as an iron-nickel alloy in concentrations of a few tenths of 1 percent. Some of this free iron can be easily separated by magnetic means. It is estimated that the magnetic separation of 100,000 tons of lunar soil would yield 150-200 tons of iron. Agglutinates contain metallic iron which could be extracted by melting and made into powder metallurgy products. The characteristics and potential uses of the pure-iron and iron-alloy lunar products are discussed. Processes for working iron that might be used in a nonterrestrial facility are also addressed.

  18. Iron plaque formation and heavy metal uptake in Spartina alterniflora at different tidal levels and waterlogging conditions.

    PubMed

    Xu, Yan; Sun, Xiangli; Zhang, Qiqiong; Li, Xiuzhen; Yan, Zhongzheng

    2018-05-30

    Tidal flat elevation in the estuarine wetland determines the tidal flooding time and flooding frequency, which will inevitably affect the formation of iron plaque and accumulations of heavy metals (HMs) in wetland plants. The present study investigated the formation of iron plaque and HM's (copper, zinc, lead, and chromium) accumulation in S. alterniflora, a typical estuarine wetland species, at different tidal flat elevations (low, middle and high) in filed and at different time (3, 6, 9, 12 h per day) of waterlogging treatment in greenhouse conditions. Results showed that the accumulation of copper, zinc, lead, and chromium in S. alterniflora was proportional to the exchangeable fraction of these metals in the sediments, which generally increased with the increase of waterlogging time, whereas the formations of iron plaque in roots decreased with the increase of waterlogging time. Under field conditions, the uptake of copper and zinc in the different parts of the plants generally increased with the tidal levels despite the decrease in the metals' exchangeable fraction with increasing tidal levels. The formation of iron plaque was found to be highest in the middle tidal positions and significantly lower in low and high tidal positions. Longer waterlogging time increased the metals' accumulation but decreased the formation of iron plaque in S. alterniflora. The binding of metal ions on iron plaque helped impede the uptake and accumulation of copper and chromium in S. alterniflora. Copyright © 2018 Elsevier Inc. All rights reserved.

  19. Rescuing iron-overloaded macrophages by conservative relocation of the accumulated metal

    PubMed Central

    Sohn, Yang-Sung; Mitterstiller, Anna-Maria; Breuer, William; Weiss, Guenter; Cabantchik, Z Ioav

    2011-01-01

    BACKGROUND AND PURPOSE Systemic iron deficiency concomitant with macrophage iron retention is characteristic of iron-refractory anaemias associated with chronic disease. The systemic misdistribution of iron, which is further exacerbated by parenteral iron supplementation, is mainly attributable to iron retention exerted on resident macrophages by hepcidin-mediated down-regulation of the iron exporter ferroportin. We aimed at developing an experimental macrophage-based cell model that recapitulates pathophysiological features of iron misdistribution found in chronic disorders and use it as a screening platform for identifying agents with the potential for relocating the accumulated metal and restoring affected functions. EXPERIMENTAL APPROACH A RAW macrophage subline was selected as cell model of iron retention based on their capacity to take up polymeric iron or aged erythrocytes excessively, resulting in a demonstrable increase of cell labile iron pools and oxidative damage that are aggravated by hepcidin. KEY RESULTS This model provided a three-stage high throughput screening platform for identifying agents with the combined ability to: (i) scavenge cell iron and thereby rescue macrophage cells damaged by iron-overload; (ii) bypass the ferroportin blockade by conveying the scavenged iron to other iron-starved cells in co-culture via transferrin but (iii) without promoting utilization of the scavenged iron by intracellular pathogens. As test agents we used chelators in clinical practice and found the oral chelator deferiprone fulfilled essentially all of the three criteria. CONCLUSIONS AND IMPLICATIONS We provide a proof of principle for conservative iron relocation as complementary therapeutic approach for correcting the misdistribution of iron associated with chronic disease and exacerbated by parenteral iron supplementation. PMID:21091647

  20. Hydrogenation and dehydrogenation iron pincer catalysts capable of metal-ligand cooperation by aromatization/dearomatization.

    PubMed

    Zell, Thomas; Milstein, David

    2015-07-21

    The substitution of expensive and potentially toxic noble-metal catalysts by cheap, abundant, environmentally benign, and less toxic metals is highly desirable and in line with green chemistry guidelines. We have recently discovered a new type of metal-ligand cooperation, which is based on the reversible dearomatization/aromatization of different heteroaromatic ligand cores caused by deprotonation/protonation of the ligand. More specifically, we have studied complexes of various transition metals (Ru, Fe, Co, Rh, Ir, Ni, Pd, Pt, and Re) bearing pyridine- and bipyridine-based PNP and PNN pincer ligands, which have slightly acidic methylene protons. In addition, we have discovered long-range metal-ligand cooperation in acridine-based pincer ligands, where the cooperation takes place at the electrophilic C-9 position of the acridine moiety leading to dearomatization of its middle ring. This type of metal-ligand cooperation was used for the activation of chemical bonds, including H-H, C-H (sp(2) and sp(3)), O-H, N-H, and B-H bonds. This unusual reactivity likely takes place in various catalytic hydrogenation, dehydrogenation, and related reactions. In this Account, we summarize our studies on novel bifunctional iron PNP and PNN pincer complexes, which were designed on the basis of their ruthenium congeners. Iron PNP pincer complexes serve as efficient (pre)catalysts for hydrogenation and dehydrogenation reactions under remarkably mild conditions. Their catalytic applications include atom-efficient and industrially important hydrogenation reactions of ketones, aldehydes, and esters to the corresponding alcohols. Moreover, they catalyze the hydrogenation of carbon dioxide to sodium formate in the presence of sodium hydroxide, the selective decomposition of formic acid to carbon dioxide and hydrogen, and the E-selective semihydrogenation of alkynes to give E-alkenes. These catalysts feature, compared to other iron-based catalysts, very high catalytic activities which in

  1. Electrochemical synthesis of hard-alloy compositions based on tungsten carbide and an iron triad metal

    NASA Astrophysics Data System (ADS)

    Kushkhov, Kh. B.; Adamokova, M. N.; Kvashin, V. A.; Kardanov, A. L.

    2010-08-01

    Single and cyclic voltammetry is used to study the electrode processes that occur during electrochemical synthesis of hard-alloy compositions based on tungsten carbide and an iron triad metal in tungstate and tungstate-carbonate Na2WO4-Li2WO4-Li2CO3 (5.0-22.0 wt %) melts. The conditions of bringing the electroprecipitation potentials of tungsten, carbon, and an iron triad metal into coincidence are determined.

  2. Structure and Growth of Quasi One-Dimensional YSi2 Nanophases on Si(100)

    PubMed Central

    Iancu, V.; Kent, P.R.C.; Hus, S.; Hu, H.; Zeng, C.G.; Weitering, H.H.

    2013-01-01

    Quasi one-dimensional YSi2 nanostructures are formed via self-assembly on the Si(100) surface. These epitaxial nanowires are metastable and their formation strongly depends on the growth parameters. Here, we explore the various stages of yttrium silicide formation over a range of metal coverages and growth temperatures, and establish a rudimentary phase diagram for these novel and often coexisting nanophases. In addition to previously identified stoichiometric wires, we identify several new nanowire systems. These nanowires exhibit a variety of surface reconstructions, which sometimes coexist on a single wire. From a comparison of scanning tunneling microcopy images, tunneling spectra, and first-principles density functional theory calculations, we determine that these surface reconstructions arise from local orderings of yttrium vacancies. Nanowires often agglomerate into nanowire bundles, the thinnest of which are formed by single wire pairs. The calculations show that such bundles are energetically favored compared to well-separated single wires. Thicker bundles are formed at slightly higher temperature. They extend over several microns, forming a robust network of conducting wires that could possibly be employed in nanodevice applications. PMID:23221350

  3. Iron-based amorphous alloys and methods of synthesizing iron-based amorphous alloys

    DOEpatents

    Saw, Cheng Kiong; Bauer, William A.; Choi, Jor-Shan; Day, Dan; Farmer, Joseph C.

    2016-05-03

    A method according to one embodiment includes combining an amorphous iron-based alloy and at least one metal selected from a group consisting of molybdenum, chromium, tungsten, boron, gadolinium, nickel phosphorous, yttrium, and alloys thereof to form a mixture, wherein the at least one metal is present in the mixture from about 5 atomic percent (at %) to about 55 at %; and ball milling the mixture at least until an amorphous alloy of the iron-based alloy and the at least one metal is formed. Several amorphous iron-based metal alloys are also presented, including corrosion-resistant amorphous iron-based metal alloys and radiation-shielding amorphous iron-based metal alloys.

  4. Iron isotopic fractionation between silicate mantle and metallic core at high pressure

    PubMed Central

    Liu, Jin; Dauphas, Nicolas; Roskosz, Mathieu; Hu, Michael Y.; Yang, Hong; Bi, Wenli; Zhao, Jiyong; Alp, Esen E.; Hu, Justin Y.; Lin, Jung-Fu

    2017-01-01

    The +0.1‰ elevated 56Fe/54Fe ratio of terrestrial basalts relative to chondrites was proposed to be a fingerprint of core-mantle segregation. However, the extent of iron isotopic fractionation between molten metal and silicate under high pressure–temperature conditions is poorly known. Here we show that iron forms chemical bonds of similar strengths in basaltic glasses and iron-rich alloys, even at high pressure. From the measured mean force constants of iron bonds, we calculate an equilibrium iron isotope fractionation between silicate and iron under core formation conditions in Earth of ∼0–0.02‰, which is small relative to the +0.1‰ shift of terrestrial basalts. This result is unaffected by small amounts of nickel and candidate core-forming light elements, as the isotopic shifts associated with such alloying are small. This study suggests that the variability in iron isotopic composition in planetary objects cannot be due to core formation. PMID:28216664

  5. Effect of Transport and Aging Processes on Metal Speciation in Iron Oxyhydroxide Aggregates, Tar Creek Superfund Site, Oklahoma

    NASA Astrophysics Data System (ADS)

    Estes, E. R.; Schaider, L. A.; Shine, J. P.; Brabander, D. J.

    2010-12-01

    Following the cessation of mining activity in the late 20th century, Tar Creek Superfund Site was left highly contaminated by Pb, Zn, and Cd. Tar Creek, which flows through the site and into the Neosho River, has been studied extensively because of its potential to transport metals from the mining site to downstream communities. Previous research identified aggregated iron oxyhydroxide material, which forms when mine seepage mixes with Tar Creek surface water, as a major transport vector of metals. Frequent flooding in Tar Creek deposits aggregates on downstream floodplains, where wetting and drying processes alter the speciation of iron and other metals. This study seeks to better quantify those changes and to determine how transport and aging affects the human and ecological health risk. Sequential extractions of aggregate samples collected from the creek demonstrate that Fe is present in both amorphous (10-35% of Fe extracted) and more crystalline (8-23% of Fe extracted) phases. Substantial portions of heavy metals sorb to amorphous iron oxyhydroxide phases (accounting for 10-30% of Pb and Zn extracted) but are not associated with more crystalline iron oxide phases (representing only 1% or less of the Pb and Zn extracted). Samples have a high organic matter content (18-25% mass loss on ignition), but only Fe was significantly extracted by the oxidizing step targeting organic matter (1-2% of Pb and Zn extracted, but 10-26% of Fe extracted). The majority of metals were extracted by the soluble or residual steps. If metals and organic matter inhibit transformation of amorphous iron oxyhydroxide material to nano and crystalline iron oxides, then a steady-state volume of amorphous iron oxyhydroxide material with a high total sorption capacity may exist within Tar Creek, enhancing the metal flux accommodated by this transport mechanism. Once transported downstream and deposited on floodplains, however, it is hypothesized that repeated changes in soil matrix

  6. Metal matrix composite of an iron aluminide and ceramic particles and method thereof

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

    Schneibel, Joachim H.

    A metal matrix composite comprising an iron aluminide binder phase and a ceramic particulate phase such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide is made by heating a mixture of iron aluminide powder and particulates of one of the ceramics such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide in a alumina crucible at about 1450.degree. C. for about 15 minutes in an evacuated furnace and cooling the mixture to room temperature. The ceramic particulates comprise greater than 40 volume percent to about 99 volume percent of the metal matrix composite.

  7. Metal matrix composite of an iron aluminide and ceramic particles and method thereof

    DOEpatents

    Schneibel, J.H.

    1997-06-10

    A metal matrix composite comprising an iron aluminide binder phase and a ceramic particulate phase such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide is made by heating a mixture of iron aluminide powder and particulates of one of the ceramics such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide in a alumina crucible at about 1,450 C for about 15 minutes in an evacuated furnace and cooling the mixture to room temperature. The ceramic particulates comprise greater than 40 volume percent to about 99 volume percent of the metal matrix composite.

  8. Metal matrix composite of an iron aluminide and ceramic particles and method thereof

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

    Schneibel, J.H.

    A metal matrix composite comprising an iron aluminide binder phase and a ceramic particulate phase such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide is made by heating a mixture of iron aluminide powder and particulates of one of the ceramics such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide in a alumina crucible at about 1,450 C for about 15 minutes in an evacuated furnace and cooling the mixture to room temperature. The ceramic particulates comprise greater than 40 volume percent to about 99 volume percent of the metal matrix composite.

  9. DIVALENT METAL TRANSPORTER-1 REGULATION BY IRON AND VANADIUM MODULATES HYDROGEN PEROXIDE-INDUCED DNA DAMAGE IN LUNG CELLS

    EPA Science Inventory

    The divalent metal transporter-1 (DMT1) participates in the detoxification of metals that can damage lung epithelium. Elevated iron levels increase the expression of DMT1 in bronchial epithelial cells stimulating its uptake and storage in ferritin, thus making iron unavailable t...

  10. High efficiency iron electrode and additives for use in rechargeable iron-based batteries

    DOEpatents

    Narayan, Sri R.; Prakash, G. K. Surya; Aniszfeld, Robert; Manohar, Aswin; Malkhandi, Souradip; Yang, Bo

    2017-02-21

    An iron electrode and a method of manufacturing an iron electrode for use in an iron-based rechargeable battery are disclosed. In one embodiment, the iron electrode includes carbonyl iron powder and one of a metal sulfide additive or metal oxide additive selected from the group of metals consisting of bismuth, lead, mercury, indium, gallium, and tin for suppressing hydrogen evolution at the iron electrode during charging of the iron-based rechargeable battery. An iron-air rechargeable battery including an iron electrode comprising carbonyl iron is also disclosed, as is an iron-air battery wherein at least one of the iron electrode and the electrolyte includes an organosulfur additive.

  11. Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

    PubMed Central

    Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

    2016-01-01

    The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

  12. System and method for making metallic iron with reduced CO.sub.2 emissions

    DOEpatents

    Kiesel, Richard F; Englund, David J; Schlichting, Mark; Meehan, John; Crouch, Jeremiah; Wilson, Logan

    2014-10-14

    A method and system for making metallic iron nodules with reduced CO.sub.2 emissions is disclosed. The method includes: assembling a linear hearth furnace having entry and exit portions, at least a conversion zone and a fusion zone, and a moving hearth adapted to move reducible iron bearing material through the furnace on contiguous hearth sections; assembling a shrouded return substantially free of air ingress extending adjacent at least the conversion and fusion zones of the furnace through which hearth sections can move from adjacent the exit portion to adjacent the entry portion of the furnace; transferring the hearth sections from the furnace to the shrouded return adjacent the exit portion; reducing reducible material in the linear hearth furnace to metallic iron nodules; and transporting gases from at least the fusion zone to the shrouded return to heat the hearth sections while in the shrouded return.

  13. Metals, Oxidative Stress and Neurodegeneration: A focus on Iron, Manganese and Mercury

    PubMed Central

    Farina, Marcelo; Avila, Daiana Silva; da Rocha, João Batista Teixeira

    2013-01-01

    Essential metals are crucial for the maintenance of cell homeostasis. Among the 23 elements that have known physiological functions in humans, 12 are metals, including iron (Fe) and manganese (Mn). Nevertheless, excessive exposure to these metals may lead to pathological conditions, including neurodegeneration. Similarly, exposure to metals that do not have known biological functions, such as mercury (Hg), also present great health concerns. This reviews focuses on the neurodegenerative mechanisms and effects of Fe, Mn and Hg. Oxidative stress (OS), particularly in mitochondria, is a common feature of Fe, Mn and Hg toxicity. However, the primary molecular targets triggering OS are distinct. Free cationic iron is a potent pro-oxidant and can initiate a set of reactions that form extremely reactive products, such as OH•. Mn can oxidize dopamine (DA), generating reactive species and also affect mitochondrial function, leading to accumulation of metabolites and culminating with OS. Cationic Hg forms have strong affinity for nucleophiles, such as –SH and –SeH. Therefore, they target critical thiol- and selenol-molecules with antioxidant properties. Finally, we address the main sources of exposure to these metals, their transport mechanisms into the brain, and therapeutic modalities to mitigate their neurotoxic effects. PMID:23266600

  14. Nanophase hydroxyapatite coatings for dental and orthopedic applications

    NASA Astrophysics Data System (ADS)

    Sato, Michiko

    In order to improve dental and orthopedic implant performance, the objective of this study was to synthesize nanocrystalline hydroxyapatite (HA) powders to coat metals (specifically, titanium and tantalum). Precipitated HA powders were either sintered in order to produce UltraCaP HA (or microcrystalline size HA) or were treated hydrothermally to produce nanocrystalline HA. Some of the UltraCaP and nanocrystalline HA powders were doped with yttrium (Y) since previous in vitro studies demonstrated that Y-doped HA in bulk improved osteoblast (or bone-forming cell) function over undoped HA. The nanocrystalline HA powders were also mixed with nanophase titania powders because previous studies demonstrated that titania/HA composite coatings increased coating adhesive strength and HA nucleation. These powders were then deposited onto titanium by a novel room-temperature process, called IonTiteT(TM). The results demonstrated that the chemical properties and crystallite size of the original HA powders were maintained in the coatings. More importantly, in vitro studies showed increased osteoblast (bone-forming cell) adhesion on the single phase nanocrystalline HA and nano-titania/HA coatings compared to traditionally used plasma-sprayed HA coatings and uncoated metals. Results further demonstrated greater amounts of calcium deposition by osteoblasts cultured on nanocrystalline HA coatings compared to UltraCaP coatings and conventionally used plasma-sprayed HA coatings. To elucidate mechanisms that influenced osteoblast functions on the HA coatings, the amount of proteins (fibronectin and vitronectin) onto the HA powders and the adsorbed fibronectin conformation were investigated. Exposure of cell integrin binding domains (in fibronectin III10 segments) was greater in fibronectin adsorbed onto 1.2 mole% Y-doped UltraCaP HA coatings compared to nanocrystalline HA coatings tested. However, 1.2 mole% Y-doped UltraCaP HA coatings did not increase mineralization by osteoblasts

  15. The magnetohydrodynamic force experienced by spherical iron particles in liquid metal

    NASA Astrophysics Data System (ADS)

    Ščepanskis, Mihails; Jakovičs, Andris

    2016-04-01

    The paper contains a theoretical investigation of magnetohydrodynamic force experienced by iron particles (well-conducting and ferromagnetic) in well-conducting liquid. The investigation is performed by extending the Leenov and Kolin's theory to take into account the second-order effect. Therefore, the limits of the parent model are taken over to the present results. It is found that the effective conductivity of iron particles in liquid metal, which is important for practical application of the theoretically obtained force, is approximately equal to 1.5·106 S/m. The last result is obtained using a quasi-empirical approach - a comparison of experimental results with the results of the numerical simulation that was performed for various conductivities of the iron particles.

  16. Removal of metals from landfill leachate by sorption to activated carbon, bone meal and iron fines.

    PubMed

    Modin, Hanna; Persson, Kenneth M; Andersson, Anna; van Praagh, Martijn

    2011-05-30

    Sorption filters based on granular activated carbon, bone meal and iron fines were tested for their efficiency of removing metals from landfill leachate. Removal of Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sr and Zn were studied in a laboratory scale setup. Activated carbon removed more than 90% of Co, Cr, Cu, Fe, Mn and Ni. Ca, Pb, Sr and Zn were removed but less efficiently. Bone meal removed over 80% of Cr, Fe, Hg, Mn and Sr and 20-80% of Al, Ca, Cu, Mo, Ni, Pb and Zn. Iron fines removed most metals (As, Ca, Co, Cr, Cu, Fe, Mg, Mn, Pb, Sr and Zn) to some extent but less efficiently. All materials released unwanted substances (metals, TOC or nutrients), highlighting the need to study the uptake and release of a large number of compounds, not only the target metals. To remove a wide range of metals using these materials two or more filter materials may need to be combined. Sorption mechanisms for all materials include ion exchange, sorption and precipitation. For iron fines oxidation of Fe(0) seems to be important for metal immobilisation. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Reverse micelle synthesis of nanoscale metal containing catalysts. [Nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide nanoscale powders

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

    Darab, J.G.; Fulton, J.L.; Linehan, J.C.

    1993-03-01

    The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction andmore » precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni[sub 3]Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.« less

  18. Interaction between tungsten monocarbide and an iron-based metallic melt

    NASA Astrophysics Data System (ADS)

    Chumanov, I. V.; Anikeev, A. N.

    2015-12-01

    A technique and results of investigation of compacted tungsten carbide substrates by scanning microscopy are reported. Samples are prepared in the course of studies of the wettability of tungsten carbide substrates with the iron melt, which are performed in accordance with the sessile drop method using two different heating strategies, namely, contact and noncontact heating of metal.

  19. Interphase Transformations at Metal (Copper, Iron)-Polymer Gel-Electrolyte Interfaces

    NASA Astrophysics Data System (ADS)

    Lyamina, G. V.; Dubinina, O. V.; Vaitulevich, E. A.; Mokrousov, G. M.

    2018-07-01

    The results from studies of the interface boundaries between metals (copper and iron) and gel electrolyte based on methacrylic copolymers are organized systematically. In contrast to processes in liquid electrolytes, a number of key features of the reactions that occur at such interfaces are revealed: a diffusion limiting stage; a lack of reverse reactions; and the formation of coordination compounds of metal ions with the functional groups of polymers, the stabilities of which are several orders of magnitude greater than that of coordination with their low-molecular weight counterparts. It is shown that processes which employ polymeric organogels can be used for the careful cleaning of the metal surfaces, and for the formation of a desired phase composition on the latter.

  20. In situ monitoring magnetism and resistance of nanophase platinum upon electrochemical oxidation.

    PubMed

    Steyskal, Eva-Maria; Topolovec, Stefan; Landgraf, Stephan; Krenn, Heinz; Würschum, Roland

    2013-01-01

    Controlled tuning of material properties by external stimuli represents one of the major topics of current research in the field of functional materials. Electrochemically induced property tuning has recently emerged as a promising pathway in this direction making use of nanophase materials with a high fraction of electrode-electrolyte interfaces. The present letter reports on electrochemical property tuning of porous nanocrystalline Pt. Deeper insight into the underlying processes could be gained by means of a direct comparison of the charge-induced response of two different properties, namely electrical resistance and magnetic moment. For this purpose, four-point resistance measurements and SQUID magnetometry were performed under identical in situ electrochemical control focussing on the regime of electrooxidation. Fully reversible variations of the electrical resistance and the magnetic moment of 6% and 1% were observed upon the formation or dissolution of a subatomic chemisorbed oxygen surface layer, respectively. The increase of the resistance, which is directly correlated to the amount of deposited oxygen, is considered to be primarily caused by charge-carrier scattering processes at the metal-electrolyte interfaces. In comparison, the decrease of the magnetic moment upon positive charging appears to be governed by the electric field at the nanocrystallite-electrolyte interfaces due to spin-orbit coupling.

  1. Hybrid zero valent iron (ZVI)/H2O2 oxidation process for landfill leachate treatment with novel nanosize metallic calcium/iron composite.

    PubMed

    Lee, Son Dong; Mallampati, Srinivasa Reddy; Lee, Byoung Ho

    2017-04-01

    A novel nanosize metallic calcium/iron dispersed reagent was synthesized and tested as coagulant/catalyst in a hybrid zero valent iron (ZVI)/H 2 O 2 oxidation process to treat leachate. Two different types of leachates, one from municipal solid waste (MSW) tipping hall (MSWIL) and second from an MSW landfill site (MSWLL), were collected and characterized. The morphology, elemental composition, and mineral phases of the nano-Ca/CaO and nano-Fe/Ca/CaO were characterized by scanning electron microscopy-electron dispersive spectroscopy (SEM-EDS) and x-ray powder diffraction (XRD) analysis. The coagulation process with 2.5 g L -1 nano-Ca/CaO attained 64.0, 56.0, and 20.7% removal of color, chemical oxygen demand (COD), and total suspended solids (TSS) in MSWLL. With only 1.0 g L -1 of nano-Fe/Ca/CaO, relatively high color, COD and TSS removal was achieved in MSWLL at 67.5, 60.2, and 37.7%, respectively. The heavy metal removal efficiency reached 91-99% after treatment with nano-Fe/Ca/CaO in both leachate samples. The coupling process, using 1.0 g L -1 of nano-Fe/Ca/CaO and 20 mM H 2 O 2 doses, achieved enhancement removal of color, COD, and TSS, up to 95%, 96%, and 66%, respectively, without initial pH control. After this treatment, the color, COD, TSS, and heavy metals were significantly decreased, fitting the Korean discharge regulation limit. A hybrid coupled zero valent iron (ZVI)/H 2 O 2 oxidation process with novel nanosized metallic calcium/iron dispersed reagent proved to be a suitable treatment for dealing with leachate samples. Conventional treatments (biological or physicochemical) are not sufficient anymore to reach the level of purification needed to fully reduce the negative impact of landfill leachates on the environment. This implies that new treatment alternatives species must be proposed. A coupled zero valent iron (ZVI)/H 2 O 2 oxidation process proved to be a suitable treatment for dealing with leachate samples. Coagulation with nFe/Ca/CaO allows 91

  2. Mechanisms and efficiency of the simultaneous removal of metals and cyanides by using ferrate(VI): crucial roles of nanocrystalline iron(III) oxyhydroxides and metal carbonates.

    PubMed

    Filip, Jan; Yngard, Ria A; Siskova, Karolina; Marusak, Zdenek; Ettler, Vojtech; Sajdl, Petr; Sharma, Virender K; Zboril, Radek

    2011-08-29

    The reaction of potassium ferrate(VI), K(2)FeO(4), with weak-acid dissociable cyanides--namely, K(2)[Zn(CN)(4)], K(2)[Cd(CN)(4)], K(2)[Ni(CN)(4)], and K(3)[Cu(CN)(4)]--results in the formation of iron(III) oxyhydroxide nanoparticles that differ in size, crystal structure, and surface area. During cyanide oxidation and the simultaneous reduction of iron(VI), zinc(II), copper(II), and cadmium(II), metallic ions are almost completely removed from solution due to their coprecipitation with the iron(III) oxyhydroxides including 2-line ferrihydrite, 7-line ferrihydrite, and/or goethite. Based on the results of XRD, Mössbauer and IR spectroscopies, as well as TEM, X-ray photoelectron emission spectroscopy, and Brunauer-Emmett-Teller measurements, we suggest three scavenging mechanisms for the removal of metals including their incorporation into the ferrihydrite crystal structure, the formation of a separate phase, and their adsorption onto the precipitate surface. Zn and Cu are preferentially and almost completely incorporated into the crystal structure of the iron(III) oxyhydroxides; the formation of the Cd-bearing, X-ray amorphous phase, together with Cd carbonate is the principal mechanism of Cd removal. Interestingly, Ni remains predominantly in solution due to the key role of nickel(II) carbonate, which exhibits a solubility product constant several orders of magnitude higher than the carbonates of the other metals. Traces of Ni, identified in the iron(III) precipitate, are exclusively adsorbed onto the large surface area of nanoparticles. We discuss the relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal, as well as the linear relationship observed between the rate constant and the surface area of precipitates. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Heavy Metals Induce Iron Deficiency Responses at Different Hierarchic and Regulatory Levels.

    PubMed

    Lešková, Alexandra; Giehl, Ricardo F H; Hartmann, Anja; Fargašová, Agáta; von Wirén, Nicolaus

    2017-07-01

    In plants, the excess of several heavy metals mimics iron (Fe) deficiency-induced chlorosis, indicating a disturbance in Fe homeostasis. To examine the level at which heavy metals interfere with Fe deficiency responses, we carried out an in-depth characterization of Fe-related physiological, regulatory, and morphological responses in Arabidopsis ( Arabidopsis thaliana ) exposed to heavy metals. Enhanced zinc (Zn) uptake closely mimicked Fe deficiency by leading to low chlorophyll but high ferric-chelate reductase activity and coumarin release. These responses were not caused by Zn-inhibited Fe uptake via IRON-REGULATED TRANSPORTER (IRT1). Instead, Zn simulated the transcriptional response of typical Fe-regulated genes, indicating that Zn affects Fe homeostasis at the level of Fe sensing. Excess supplies of cobalt and nickel altered root traits in a different way from Fe deficiency, inducing only transient Fe deficiency responses, which were characterized by a lack of induction of the ethylene pathway. Cadmium showed a rather inconsistent influence on Fe deficiency responses at multiple levels. By contrast, manganese evoked weak Fe deficiency responses in wild-type plants but strongly exacerbated chlorosis in irt1 plants, indicating that manganese antagonized Fe mainly at the level of transport. These results show that the investigated heavy metals modulate Fe deficiency responses at different hierarchic and regulatory levels and that the interaction of metals with physiological and morphological Fe deficiency responses is uncoupled. Thus, this study not only emphasizes the importance of assessing heavy metal toxicities at multiple levels but also provides a new perspective on how Fe deficiency contributes to the toxic action of individual heavy metals. © 2017 American Society of Plant Biologists. All Rights Reserved.

  4. Trace metals related to historical iron smelting at Hopewell Furnace National Historic Site, Berks and Chester Counties, Pennsylvania

    USGS Publications Warehouse

    Sloto, Ronald A.

    2011-01-01

    Iron ore containing elevated concentrations of trace metals was smelted at Hopewell Furnace during its 113 years of operation (1771-1883). The ore used at Hopewell Furnace was obtained from iron mines within 5 miles of the furnace. The iron-ore deposits were formed about 200 million years ago and contain abundant magnetite, the primary iron mineral, and accessory minerals enriched in arsenic, cobalt, copper, lead, and other metals. Hopewell Furnace, built by Mark Bird during 1770-71, was one of the last of the charcoal-burning, cold-blast iron furnaces operated in Pennsylvania. The most productive years for Hopewell Furnace were from 1830 to 1837. Castings were the most profitable product, especially the popular Hopewell Stove. More than 80,000 stoves were cast at Hopewell, which produced as many as 23 types and sizes of cooking and heating stoves. Beginning in the 1840s, the iron industry shifted to large-scale, steam-driven coke and anthracite furnaces. Independent rural enterprises like Hopewell could no longer compete when the iron and steel industries consolidated in urban manufacturing centers. The furnace ceased operation in 1883 (Kurjack, 1954). The U.S. Geological Survey (USGS), in cooperation with the National Park Service, completed a study at Hopewell Furnace National Historic Site (NHS) in Berks and Chester Counties, Pennsylvania, to determine the fate of toxic trace metals, such as arsenic, cobalt, and lead, released into the environment during historical iron-smelting operations. The results of the study, conducted during 2008-10, are presented in this fact sheet.

  5. Immobilization of heavy metals in electroplating sludge by biochar and iron sulfide.

    PubMed

    Lyu, Honghong; Gong, Yanyan; Tang, Jingcshun; Huang, Yao; Wang, Qilin

    2016-07-01

    Electroplating sludge (ES) containing large quantities of heavy metals is regarded as a hazardous waste in China. This paper introduced a simple method of treating ES using environmentally friendly fixatives biochar (BC) and iron sulfide (FeS), respectively. After 3 days of treatment with FeS at a FeS-to-ES mass ratio of 1:5, the toxicity characteristic leaching procedure (TCLP)-based leachability of total Cr (TCr), Cu(II), Ni(II), Pb(II), and Zn(II) was decreased by 59.6, 100, 63.8, 73.5, and 90.5 %, respectively. After 5 days of treatment with BC at a BC-to-ES mass ratio of 1:2, the TCLP-based leachability was declined by 35.1, 30.6, 22.3, 23.1, and 22.4 %, respectively. Pseudo first-order kinetic model adequately simulated the sorption kinetic data. Structure and morphology analysis showed that adsorption, electrostatic attraction, surface complexation, and chemical precipitation were dominant mechanisms for heavy metals immobilization by BC, and that chemical precipitation (formation of metal sulfide and hydroxide precipitates), iron exchange (formation of CuFeS2), and surface complexation were mainly responsible for heavy metals removal by FeS. Economic costs of BC and FeS were 500 and 768 CNY/t, lower than that of Na2S (940 CNY/t). The results suggest that BC and FeS are effective, economic, and environmentally friendly fixatives for immobilization of heavy metals in ES before landfill disposal.

  6. Carbon Solubility in Silicon-Iron-Bearing Metals during Core Formation on Mercury

    NASA Technical Reports Server (NTRS)

    Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Ross, D. Kent; Rapp, Jennifer F.; Danielson, Lisa R.; Keller, Lindsay P.; Righter, Kevin

    2016-01-01

    Recent results obtained from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft showed the surface of Mercury has high S abundances (approximately 4 wt%) and low Iron(II) Oxide abundances (less than 2 wt%). Based on these extreme values, the oxygen fugacity of Mercury's surface materials was estimated to be approximately 3 to 7 log(sub 10) units below the IW buffer (Delta IW-3 to Delta IW-7). This highly reducing nature of the planet has resulted in a large core and relatively thin mantle, extending to only approximately 420 km depth (corresponding to a core-mantle boundary pressure of approximately 4-7 GPa) within the planet. Furthermore, MESSENGER results have suggested the presence of carbon on the surface of the planet. Previous experimental results from have also suggested the possibility of a primary floatation crust on Mercury composed of graphite, produced after a global magma ocean event. With these exotic conditions of this compositional end-member planet, it begs the question, what is the core composition of Mercury? Although no definitive conclusion has been reached, previous studies have made advances towards answering this question. Riner et al. and Chen et al. looked at iron sulfide systems and implemented various crystallization and layered core scenarios to try and determine the composition and structure of Mercury's core. Malavergne et al. examined core crystallization scenarios in the presence of sulfur and silicon. Hauck et al. used the most recent geophysical constraints from the MESSENGER spacecraft to model the internal structure of Mercury, including the core, in a iron-sulfur-silicon system. More recently, Chabot et al. conducted a series of metal-silicate partitioning experiments in a iron-sulfur-silicon system. These results showed the core of Mercury has the potential to contain more than 15 wt% silicon. However, with the newest results from MESSENGER's low altitude campaign, carbon is another

  7. Metallic iron for water treatment: leaving the valley of confusion

    NASA Astrophysics Data System (ADS)

    Makota, Susanne; Nde-Tchoupe, Arnaud I.; Mwakabona, Hezron T.; Tepong-Tsindé, Raoul; Noubactep, Chicgoua; Nassi, Achille; Njau, Karoli N.

    2017-12-01

    Researchers on metallic iron (Fe0) for environmental remediation and water treatment are walking in a valley of confusion for 25 years. This valley is characterized by the propagation of different beliefs that have resulted from a partial analysis of the Fe0/H2O system as (1) a reductive chemical reaction was considered an electrochemical one and (2) the mass balance of iron has not been really addressed. The partial analysis in turn has been undermining the scientific method while discouraging any real critical argumentation. This communication re-establishes the complex nature of the Fe0/H2O system while recalling that, finally, proper system analysis and chemical thermodynamics are the most confident ways to solve any conflicting situation in Fe0 environmental remediation.

  8. Effects of thermomechanical processing on strength and toughness of iron - 12-percent-nickel - reactive metal alloys at -196 C

    NASA Technical Reports Server (NTRS)

    Stephens, J. R.; Witzke, W. R.

    1978-01-01

    Thermomechanical processing (TMP) was evaluated as a method of strengthening normally tough iron-12-nickel-reactive metal alloys at cryogenic temperatures. Five iron-12 nickel alloys with reactive metal additions of aluminum, niobium, titanium, vanadium, and aluminum plus niobium were investigated. Primary evaluation was based on the yield strength and fracture toughness of the thermomechanically processed alloys at -196 C.

  9. Active catalysts of sonoelectrochemically prepared iron metal nanoparticles for the electroreduction of chloroacetates

    NASA Astrophysics Data System (ADS)

    Sáez, V.; González-García, J.; Marken, F.

    2010-01-01

    A new methodology for the sonoelectro-deposition and stripping of highly reactive iron at boron-doped diamond electrodes has been studied. In aqueous 1 M NH4F iron metal readily and reversibly electro-deposits onto boron-doped diamond electrodes. The effects of deposition potential, FeF63- concentration, deposition time, and mass transport are investigated and also the influence of power ultrasound (24 kHz, 8 Wcm-2). Scanning electron microscopy images of iron nanoparticles grown to typically 20-30 nm diameters are obtained. It is shown that a strongly and permanently adhering film of iron at boron-doped diamond can be formed and transferred into other solution environments. The catalytic reactivity of iron deposits at boron-doped diamond is investigated for the reductive dehalogenation of chloroacetate. The kinetically limited multi-electron reduction of trichloroacetate is dependent on the FeF63- deposition conditions and the solution composition. It is demonstrated that a stepwise iron-catalysed dechlorination via dichloroacetate and monochloroacetate to acetate is feasible. This sonoelectrochemical methodology offers a novel, clean and very versatile electro-dehalogenation methodology. The role of fluoride in the surface electrochemistry of iron deserves further attention.

  10. Sources and fates of heavy metals in a mining-impacted stream: Temporal variability and the role of iron oxides

    PubMed Central

    Schaider, Laurel A.; Senn, David B.; Estes, Emily R.; Brabander, Daniel J.; Shine, James P.

    2014-01-01

    Heavy metal contamination of surface waters at mining sites often involves complex interactions of multiple sources and varying biogeochemical conditions. We compared surface and subsurface metal loading from mine waste pile runoff and mine drainage discharge and characterized the influence of iron oxides on metal fate along a 0.9-km stretch of Tar Creek (Oklahoma, USA), which drains an abandoned Zn/Pb mining area. The importance of each source varied by metal: mine waste pile runoff contributed 70% of Cd, while mine drainage contributed 90% of Pb, and both sources contributed similarly to Zn loading. Subsurface inputs accounted for 40% of flow and 40-70% of metal loading along this stretch. Streambed iron oxide aggregate material contained highly elevated Zn (up to 27,000 μg g−1), Pb (up to 550 μg g−1) and Cd (up to 200 μg g−1) and was characterized as a heterogeneous mixture of iron oxides, fine-grain mine waste, and organic material. Sequential extractions confirmed preferential sequestration of Pb by iron oxides, as well as substantial concentrations of Zn and Cd in iron oxide fractions, with additional accumulation of Zn, Pb, and Cd during downstream transport. Comparisons with historical data show that while metal concentrations in mine drainage have decreased by more than an order of magnitude in recent decades, the chemical composition of mine waste pile runoff has remained relatively constant, indicating less attenuation and increased relative importance of pile runoff. These results highlight the importance of monitoring temporal changes at contaminated sites associated with evolving speciation and simultaneously addressing surface and subsurface contamination from both mine waste piles and mine drainage. PMID:24867708

  11. Red mud (RM)-Induced enhancement of iron plaque formation reduces arsenic and metal accumulation in two wetland plant species.

    PubMed

    Yang, J X; Guo, Q J; Yang, J; Zhou, X Y; Ren, H Y; Zhang, H Z; Xu, R X; Wang, X D; Peters, M; Zhu, G X; Wei, R F; Tian, L Y; Han, X K

    2016-01-01

    Human activities have resulted in arsenic (As) and heavy metals accumulation in paddy soils in China. Phytoremediation has been suggested as an effective and low-cost method to clean up contaminated soils. A combined soil-sand pot experiment was conducted to investigate the influence of red mud (RM) supply on iron plaque formation and As and heavy metal accumulation in two wetland plant species (Cyperus alternifolius Rottb., Echinodorus amazonicus Rataj), using As and heavy metals polluted paddy soil combined with three rates of RM application (0, 2%, 5%). The results showed that RM supply significantly decreased As and heavy metals accumulation in shoots of the two plants due to the decrease of As and heavy metal availability and the enhancement of the formation of iron plaque on the root surface and in the rhizosphere. Both wetland plants supplied with RM tended to have more Fe plaque, higher As and heavy metals on roots and in their rhizospheres, and were more tolerant of As and heavy metal toxicity. The results suggest that RM-induced enhancement of the formation of iron plaque on the root surface and in the rhizosphere of wetland plants may be significant for remediation of soils contaminated with As and heavy metals.

  12. Iron-targeting antitumor activity of gallium compounds and novel insights into triapine(®)-metal complexes.

    PubMed

    Chitambar, Christopher R; Antholine, William E

    2013-03-10

    Despite advances made in the treatment of cancer, a significant number of patients succumb to this disease every year. Hence, there is a great need to develop new anticancer agents. Emerging data show that malignant cells have a greater requirement for iron than normal cells do and that proteins involved in iron import, export, and storage may be altered in cancer cells. Therefore, strategies to perturb these iron-dependent steps in malignant cells hold promise for the treatment of cancer. Recent studies show that gallium compounds and metal-thiosemicarbazone complexes inhibit tumor cell growth by targeting iron homeostasis, including iron-dependent ribonucleotide reductase. Chemical similarities of gallium(III) with iron(III) enable the former to mimic the latter and interpose itself in critical iron-dependent steps in cellular proliferation. Newer gallium compounds have emerged with additional mechanisms of action. In clinical trials, the first-generation-compound gallium nitrate has exhibited activity against bladder cancer and non-Hodgkin's lymphoma, while the thiosemicarbazone Triapine(®) has demonstrated activity against other tumors. Novel gallium compounds with greater cytotoxicity and a broader spectrum of antineoplastic activity than gallium nitrate should continue to be developed. The antineoplastic activity and toxicity of the existing novel gallium compounds and thiosemicarbazone-metal complexes should be tested in animal tumor models and advanced to Phase I and II clinical trials. Future research should identify biologic markers that predict tumor sensitivity to gallium compounds. This will help direct gallium-based therapy to cancer patients who are most likely to benefit from it.

  13. Nitrogen activation of carbon-encapsulated zero-valent iron nanoparticles and influence of the activation temperature on heavy metals removal

    NASA Astrophysics Data System (ADS)

    Bonaiti, Stefania; Calderon, Blanca; Collina, Elena; Lasagni, Marina; Mezzanotte, Valeria; Aracil, Ignacio; Fullana, Andrés

    2017-05-01

    Nanoparticles of zero-valent iron (nZVI) represent a promising agent for environmental remediation. This is due to their core-shell structure which presents the characteristics of both metallic and oxidised iron, leading to sorption and reductive precipitation of metal ions. Nevertheless, nZVI application presents some limitations regarding their rapid oxidation and aggregation in the media which leads to the delivery of the ions after some hours (the “aging effect”). To address these issues, modifications of nZVI structure and synthesis methods have been developed in the last years. The aging problem was solved by using nZVI encapsulated inside carbon spheres (CE-nZVI), synthetized through Hydrothermal Carbonization (HTC). Results showed high heavy metals removal percentage. Furthermore, CE-nZVI were activated with nitrogen in order to increase the metallic iron content. The aim of this study was to test CE-nZVI post-treated with nitrogen at different temperatures in heavy metals removal, demonstrating that the influence of the temperature was negligible in nanoparticles removal efficiency.

  14. [Effect of the change in sulphate and dissolved oxygen mass concentration on metal release in old cast iron distribution pipes].

    PubMed

    Wu, Yong-li; Shi, Bao-you; Sun, Hui-fang; Zhang, Zhi-huan; Gu, Jun-nong; Wang, Dong-sheng

    2013-09-01

    To understand the processes of corrosion by-product release and the consequent "red water" problems caused by the variation of water chemical composition in drinking water distribution system, the effect of sulphate and dissolved oxygen (DO) concentration on total iron release in corroded old iron pipe sections historically transporting groundwater was investigated in laboratory using small-scale pipe section reactors. The release behaviors of some low-level metals, such as Mn, As, Cr, Cu, Zn and Ni, in the process of iron release were also monitored. The results showed that the total iron and Mn release increased significantly with the increase of sulphate concentration, and apparent red water occurred when sulphate concentration was above 400 mg x L(-1). With the increase of sulfate concentration, the effluent concentrations of As, Cr, Cu, Zn and Ni also increased obviously, however, the effluent concentrations of these metals were lower than the influent concentrations under most circumstances, which indicated that adsorption of these metals by pipe corrosion scales occurred. Increasing DO within a certain range could significantly inhibit the iron release.

  15. ZIP14 and DMT1 in the liver, pancreas, and heart are differentially regulated by iron deficiency and overload: implications for tissue iron uptake in iron-related disorders

    PubMed Central

    Nam, Hyeyoung; Wang, Chia-Yu; Zhang, Lin; Zhang, Wei; Hojyo, Shintaro; Fukada, Toshiyuki; Knutson, Mitchell D.

    2013-01-01

    The liver, pancreas, and heart are particularly susceptible to iron-related disorders. These tissues take up plasma iron from transferrin or non-transferrin-bound iron, which appears during iron overload. Here, we assessed the effect of iron status on the levels of the transmembrane transporters, ZRT/IRT-like protein 14 and divalent metal-ion transporter-1, which have both been implicated in transferrin- and non-transferrin-bound iron uptake. Weanling male rats (n=6/group) were fed an iron-deficient, iron-adequate, or iron-overloaded diet for 3 weeks. ZRT/IRT-like protein 14, divalent metal-ion transporter-1 protein and mRNA levels in liver, pancreas, and heart were determined by using immunoblotting and quantitative reverse transcriptase polymerase chain reaction analysis. Confocal immunofluorescence microscopy was used to localize ZRT/IRT-like protein 14 in the liver and pancreas. ZRT/IRT-like protein 14 and divalent metal-ion transporter-1 protein levels were also determined in hypotransferrinemic mice with genetic iron overload. Hepatic ZRT/IRT-like protein 14 levels were found to be 100% higher in iron-loaded rats than in iron-adequate controls. By contrast, hepatic divalent metal-ion transporter-1 protein levels were 70% lower in iron-overloaded animals and nearly 3-fold higher in iron-deficient ones. In the pancreas, ZRT/IRT-like protein 14 levels were 50% higher in iron-overloaded rats, and in the heart, divalent metal-ion transporter-1 protein levels were 4-fold higher in iron-deficient animals. At the mRNA level, ZRT/IRT-like protein 14 expression did not vary with iron status, whereas divalent metal-ion transporter-1 expression was found to be elevated in iron-deficient livers. Immunofluorescence staining localized ZRT/IRT-like protein 14 to the basolateral membrane of hepatocytes and to acinar cells of the pancreas. Hepatic ZRT/IRT-like protein 14, but not divalent metal-ion transporter-1, protein levels were elevated in iron-loaded hypotransferrinemic

  16. Comprehensive Utilization of Iron and Phosphorus from High-Phosphorus Refractory Iron Ore

    NASA Astrophysics Data System (ADS)

    Sun, Yongsheng; Zhang, Qi; Han, Yuexin; Gao, Peng; Li, Guofeng

    2018-02-01

    An innovative process of coal-based reduction followed by magnetic separation and dephosphorization was developed to simultaneously recover iron and phosphorus from one typical high-phosphorus refractory iron ore. The experimental results showed that the iron minerals in iron ore were reduced to metallic iron during the coal-based reduction and the phosphorus was enriched in the metallic iron phase. The CaO-SiO2-FeO-Al2O3 slag system was used in the dephosphorization of metallic iron. A hot metal of 99.17% Fe and 0.10% P was produced with Fe recovery of 84.41%. Meanwhile, a dephosphorization slag of 5.72% P was obtained with P recovery of 67.23%. The contents of impurities in hot metal were very low, and it could be used as feedstock for steelmaking after a secondary refining. Phosphorus in the dephosphorization slag mainly existed in the form of a 5CaO·P2O5·SiO2 solid solution where the P2O5 content is 13.10%. At a slag particle size of 20.7 μm (90% passing), 94.54% of the P2O5 could be solubilized in citric acid, indicating the slag met the feedstock requirements in phosphate fertilizer production. Consequently, the proposed process achieved simultaneous Fe and P recovery, paving the way to comprehensive utilization of high-phosphorus refractory iron ore.

  17. Microwave Permittivity and Permeability Measurement on Lunar Soils

    NASA Technical Reports Server (NTRS)

    Barmatz, Martin; Steinfeld, David; Begley, Shelley B.; Winterhalter, Daniel; Allen, Carlton

    2011-01-01

    There has been interest in finding ways to process the lunar regolith since the early analyses of lunar samples returned from the Apollo moon missions. This fact has led to proposals for using microwaves to perform in-situ processing of the lunar soil to support future colonization of the moon. More recently, there has been speculation that the excellent microwave absorption of lunar soil came from the nanophase iron content in the regolith. The motivation for the present study was to begin obtaining a more fundamental understanding of the dielectric and magnetic properties of the regolith at microwave frequencies. A major objective of this study was to obtain information that would help answer the question about whether nanophase iron plays a major role in heating lunar soils. These new measurements over a wide frequency range can also determine the magnitude of the dielectric and magnetic absorption and if there are any resonant features that could be used to enhance processing of the regolith in the future. In addition, these microwave measurements would be useful in confirming that new simulants being developed, particularly those containing nanophase iron, would have the correct composition to simulate the lunar regolith. The results of this study suggest that nanophase iron does not play a major role in heating lunar regolith.

  18. Metallic iron for safe drinking water provision: Considering a lost knowledge.

    PubMed

    Mwakabona, Hezron T; Ndé-Tchoupé, Arnaud Igor; Njau, Karoli N; Noubactep, Chicgoua; Wydra, Kerstin D

    2017-06-15

    Around year 1890, the technology of using metallic iron (Fe 0 ) for safe drinking water provision was already established in Europe. The science and technology to manufacture suitable Fe 0 materials were known and further developed in this period. Scientists had then developed skills to (i) explore the suitability of individual Fe 0 materials (e.g. iron filling, sponge iron) for selected applications, and (ii) establish treatment processes for households and water treatment plants. The recent (1990) discovery of Fe 0 as reactive agent for environmental remediation and water treatment has not yet considered this ancient knowledge. In the present work, some key aspects of the ancient knowledge are presented together with some contemporised interpretations, in an attempt to demonstrate the scientific truth contained therein. It appears that the ancient knowledge is an independent validation of the scientific concept that in water treatment (Fe 0 /H 2 O system) Fe 0 materials are generators of contaminant collectors. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Evaluation of the effect of divalent metal transporter 1 gene polymorphism on blood iron, lead and cadmium levels

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

    Kayaaltı, Zeliha, E-mail: kayaalti@ankara.edu.tr; Akyüzlü, Dilek Kaya; Söylemezoğlu, Tülin

    Divalent metal transporter 1 (DMT1), a member of the proton-coupled metal ion transporter family, mediates transport of ferrous iron from the lumen of the intestine into the enterocyte and export of iron from endocytic vesicles. It has an affinity not only for iron but also for other divalent cations including manganese, cobalt, nickel, cadmium, lead, copper, and zinc. DMT1 is encoded by the SLC11a2 gene that is located on chromosome 12q13 in humans and express four major mammalian isoforms (1A/+IRE, 1A/-IRE, 2/+IRE and 2/-IRE). Mutations or polymorphisms of DMT1 gene may have an impact on human health by disturbing metalmore » trafficking. To study the possible association of DMT1 gene with the blood levels of some divalent cations such as iron, lead and cadmium, a single nucleotide polymorphism (SNP) (IVS4+44C/A) in DMT1 gene was investigated in 486 unrelated and healthy individuals in a Turkish population by method of polymerase chain reaction–restriction fragment length polymorphism (PCR–RFLP). The genotype frequencies were found as 49.8% homozygote typical (CC), 38.3% heterozygote (CA) and 11.9% homozygote atypical (AA). Metal levels were analyzed by dual atomic absorption spectrometer system and the average levels of iron, lead and cadmium in the blood samples were 446.01±81.87 ppm, 35.59±17.72 ppb and 1.25±0.87 ppb, respectively. Individuals with the CC genotype had higher blood iron, lead and cadmium levels than those with AA and CA genotypes. Highly statistically significant associations were detected between IVS4+44 C/A polymorphism in the DMT1 gene and iron and lead levels (p=0.001 and p=0.036, respectively), but no association was found with cadmium level (p=0.344). This study suggested that DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, lead and cadmium levels. - Highlights: • DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, cadmium and lead levels.

  20. Effect of nanoscale zero-valent iron and magnetite (Fe3O4) on the fate of metals during anaerobic digestion of sludge.

    PubMed

    Suanon, Fidèle; Sun, Qian; Mama, Daouda; Li, Jiangwei; Dimon, Biaou; Yu, Chang-Ping

    2016-01-01

    Anaerobic digestion (AD) is one of the most widely used processes to stabilize waste sewage sludge and produce biogas renewable energy. In this study, two different iron nanoparticles [nanoscale zero-valent iron (nZVI) and magnetite (Fe3O4)] were used in the mesophilic AD processes (37 ± 1 °C) to improve biogas production. In addition, changes of heavy metal (Cd, Co, Cu, Zn, Ni and Cr) speciation during AD of sludge with and without iron nanoparticles have been investigated. Concentrations of metals in the initial sludge were as follows: 63.1, 73.4, 1102.2, 2060.3, 483.9 and 604.1 mg kg(-1) (dry sludge basis) for Cd, Co, Cu, Zn, Ni and Cr, respectively. Sequential fractionation showed that metals were predominantly bonded to organic matter and carbonates in the initial sludge. Compared with AD without iron nanoparticles, the application of iron nanoparticles (at dose of 0.5% in this study) showed positive impact not only on biogas production, but also on improvement of metals stabilization in the digestate. Metals were found concentrated in Fe-Mn bound and residual fractions and little was accumulated in the liquid digestate and most mobile fractions of solid digestate (water soluble, exchangeable and carbonates bound). Therefore, iron nanoparticles when properly used, could improve not only biogas yield, but also regulate and control the mobilization of metals during AD process. However, our study also observed that iron nanoparticles could promote the immobilization of phosphorus within the sludge during AD, and more research is needed to fully address the mechanism behind this phenomenon and the impact on future phosphorus reuse. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Iron-Targeting Antitumor Activity of Gallium Compounds and Novel Insights Into Triapine®-Metal Complexes

    PubMed Central

    Antholine, William E.

    2013-01-01

    Abstract Significance: Despite advances made in the treatment of cancer, a significant number of patients succumb to this disease every year. Hence, there is a great need to develop new anticancer agents. Recent Advances: Emerging data show that malignant cells have a greater requirement for iron than normal cells do and that proteins involved in iron import, export, and storage may be altered in cancer cells. Therefore, strategies to perturb these iron-dependent steps in malignant cells hold promise for the treatment of cancer. Recent studies show that gallium compounds and metal-thiosemicarbazone complexes inhibit tumor cell growth by targeting iron homeostasis, including iron-dependent ribonucleotide reductase. Chemical similarities of gallium(III) with iron(III) enable the former to mimic the latter and interpose itself in critical iron-dependent steps in cellular proliferation. Newer gallium compounds have emerged with additional mechanisms of action. In clinical trials, the first-generation-compound gallium nitrate has exhibited activity against bladder cancer and non-Hodgkin's lymphoma, while the thiosemicarbazone Triapine® has demonstrated activity against other tumors. Critical Issues: Novel gallium compounds with greater cytotoxicity and a broader spectrum of antineoplastic activity than gallium nitrate should continue to be developed. Future Directions: The antineoplastic activity and toxicity of the existing novel gallium compounds and thiosemicarbazone-metal complexes should be tested in animal tumor models and advanced to Phase I and II clinical trials. Future research should identify biologic markers that predict tumor sensitivity to gallium compounds. This will help direct gallium-based therapy to cancer patients who are most likely to benefit from it. Antioxid. Redox Signal. 00, 000–000. PMID:22900955

  2. Structural, morphological, magnetic and dielectric characterization of nano-phased antimony doped manganese zinc ferrites

    NASA Astrophysics Data System (ADS)

    Sridhar, Ch. S. L. N.; Lakshmi, Ch. S.; Govindraj, G.; Bangarraju, S.; Satyanarayana, L.; Potukuchi, D. M.

    2016-05-01

    Nano-phased doped Mn-Zn ferrites, viz., Mn0.5-x/2Zn0.5-x/2SbXFe2O4 for x=0 to 0.3 (in steps of 0.05) prepared by hydrothermal method are characterized by X-ray diffraction, Infrared and scanning electron microscopy. XRD and SEM infer the growth of nano-crystalline cubic and hematite (α-Fe2O3) phase structures. IR reveals the ferrite phase abundance and metal ion replacement with dopant. Decreasing trend of lattice constant with dopant reflects the preferential replacement of Fe3+ions by Sb5+ion. Doping is found to cause for the decrease (i.e., 46-14 nm) of grain size. An overall trend of decreasing saturation magnetization is observed with doping. Low magnetization is attributed to the diamagnetic nature of dopant, abundance of hematite (α-Fe2O3) phase, non-stoichiometry and low temperature (800 °C) sintering conditions. Increasing Yafet-Kittel angle reflects surface spin canting to pronounce lower Ms. Lower coercivity is observed for x≤0.1, while a large Hc results for higher concentrations. High ac resistivity (~106 ohm-cm) and low dielectric loss factor (tan δ~10-2-10-3) are witnessed. Resistivity is explained on the base of a transformation in the Metal Cation-to-Oxide anion bond configuration and blockade of conductivity path. Retarded hopping (between adjacent B-sites) of carriers across the grain boundaries is addressed. Relatively higher resistivity and low dielectric loss in Sbdoped Mn-Zn ferrite systems pronounce their utility in high frequency applications.

  3. Binding of heavy metal ions in aggregates of microbial cells, EPS and biogenic iron minerals measured in-situ using metal- and glycoconjugates-specific fluorophores

    NASA Astrophysics Data System (ADS)

    Hao, Likai; Guo, Yuan; Byrne, James M.; Zeitvogel, Fabian; Schmid, Gregor; Ingino, Pablo; Li, Jianli; Neu, Thomas R.; Swanner, Elizabeth D.; Kappler, Andreas; Obst, Martin

    2016-05-01

    Aggregates consisting of bacterial cells, extracellular polymeric substances (EPS) and Fe(III) minerals formed by Fe(II)-oxidizing bacteria are common at bulk or microscale chemical interfaces where Fe cycling occurs. The high sorption capacity and binding capacity of cells, EPS, and minerals controls the mobility and fate of heavy metals. However, it remains unclear to which of these component(s) the metals will bind in complex aggregates. To clarify this question, the present study focuses on 3D mapping of heavy metals sorbed to cells, glycoconjugates that comprise the majority of EPS constituents, and Fe(III) mineral aggregates formed by the phototrophic Fe(II)-oxidizing bacteria Rhodobacter ferrooxidans SW2 using confocal laser scanning microscopy (CLSM) in combination with metal- and glycoconjugates-specific fluorophores. The present study evaluated the influence of glycoconjugates, microbial cell surfaces, and (biogenic) Fe(III) minerals, and the availability of ferrous and ferric iron on heavy metal sorption. Analyses in this study provide detailed knowledge on the spatial distribution of metal ions in the aggregates at the sub-μm scale, which is essential to understand the underlying mechanisms of microbe-mineral-metal interactions. The heavy metals (Au3+, Cd2+, Cr3+, CrO42-, Cu2+, Hg2+, Ni2+, Pd2+, tributyltin (TBT) and Zn2+) were found mainly sorbed to cell surfaces, present within the glycoconjugates matrix, and bound to the mineral surfaces, but not incorporated into the biogenic Fe(III) minerals. Statistical analysis revealed that all ten heavy metals tested showed relatively similar sorption behavior that was affected by the presence of sorbed ferrous and ferric iron. Results in this study showed that in addition to the mineral surfaces, both bacterial cell surfaces and the glycoconjugates provided most of sorption sites for heavy metals. Simultaneously, ferrous and ferric iron ions competed with the heavy metals for sorption sites on the organic

  4. System and method for producing metallic iron

    DOEpatents

    Bleifuss, Rodney L; Englund, David J; Iwasaki, Iwao; Fosnacht, Donald R; Brandon, Mark M; True, Bradford G

    2013-09-17

    A hearth furnace for producing metallic iron material has a furnace housing having a drying/preheat zone, a conversion zone, a fusion zone, and optionally a cooling zone, the conversion zone is between the drying/preheat zone and the fusion zone. A moving hearth is positioned within the furnace housing. A hood or separation barrier within at least a portion of the conversion zone, fusion zone or both separates the fusion zone into an upper region and a lower region with the lower region adjacent the hearth and the upper region adjacent the lower region and spaced from the hearth. An injector introduces a gaseous reductant into the lower region adjacent the hearth. A combustion region may be formed above the hood or separation barrier.

  5. Iron Isotope Systematics

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

    Dauphas, Nicolas; John, Seth G.; Rouxel, Olivier

    Iron is a ubiquitous element with a rich (i.e., complex) chemical behavior. It possesses three oxidation states, metallic iron (Fe0), ferrous iron (Fe2+) and ferric iron (Fe3+). The distribution of these oxidation states is markedly stratified in the Earth.

  6. Metallation and mismetallation of iron and manganese proteins in vitro and in vivo: the class I ribonucleotide reductases as a case study.

    PubMed

    Cotruvo, Joseph A; Stubbe, Joanne

    2012-10-01

    How cells ensure correct metallation of a given protein and whether a degree of promiscuity in metal binding has evolved are largely unanswered questions. In a classic case, iron- and manganese-dependent superoxide dismutases (SODs) catalyze the disproportionation of superoxide using highly similar protein scaffolds and nearly identical active sites. However, most of these enzymes are active with only one metal, although both metals can bind in vitro and in vivo. Iron(ii) and manganese(ii) bind weakly to most proteins and possess similar coordination preferences. Their distinct redox properties suggest that they are unlikely to be interchangeable in biological systems except when they function in Lewis acid catalytic roles, yet recent work suggests this is not always the case. This review summarizes the diversity of ways in which iron and manganese are substituted in similar or identical protein frameworks. As models, we discuss (1) enzymes, such as epimerases, thought to use Fe(II) as a Lewis acid under normal growth conditions but which switch to Mn(II) under oxidative stress; (2) extradiol dioxygenases, which have been found to use both Fe(II) and Mn(II), the redox role of which in catalysis remains to be elucidated; (3) SODs, which use redox chemistry and are generally metal-specific; and (4) the class I ribonucleotide reductases (RNRs), which have evolved unique biosynthetic pathways to control metallation. The primary focus is the class Ib RNRs, which can catalyze formation of a stable radical on a tyrosine residue in their β2 subunits using either a di-iron or a recently characterized dimanganese cofactor. The physiological roles of enzymes that can switch between iron and manganese cofactors are discussed, as are insights obtained from the studies of many groups regarding iron and manganese homeostasis and the divergent and convergent strategies organisms use for control of protein metallation. We propose that, in many of the systems discussed

  7. Characterizing Nanophase Materials on Mars: Spectroscopic Studies of Allophane and Imogolite

    NASA Technical Reports Server (NTRS)

    Jeute, Thomas; Baker, Leslie; Bishop, Janice; Rampe, Elizabeth; Abidin, Zaenal

    2017-01-01

    Allophane is an amorphous or poorly crystalline hydrous aluminosilicate material. Allophane's chemical structure represents a hollow nanosphere, 5-6 nm in diameter with 4-7 large pores in the structure. Identification of allophane and other amorphous and nanophase minerals on Mars has provided clues about the aqueous geochemical environment there. These materials likely represent partially altered or leached basaltic ash and therefore, could represent a geologic marker for where water was present on the Martian surface; as well as indicate regions of climate change, where surface water was not present long enough or sufficiently warm to form clays. Characterization of these materials is important for increasing spectral recognition capabilities using visible/near-infrared (VNIR) and thermal infrared (TIR) spectra of Mars. A suite of synthetic allophane samples was created using a method that has been modified to produce allophane with Fe isomorphically substituted for Al in octahedral coordination. Compositions of the materials range from high-Si allophane (molar Al:Si = 1:2) to protoimogolite (Al:Si = 2:1), with Fe(3+) and Fe(2+) isomorphically substituted for Al from 0-10 mol% of total Al. These compositions span the range observed in natural terrestrial allophanes. Fe K-edge X-ray absorption spectroscopy provided information on the speciation and electrochemical and structural position of Fe in the framework. Fourier transform infrared spectroscopy confirmed syntheses and demonstrated changes in infrared spectroscopic signature with Fe substitution. VNIR reflectance spectra and TIR Thermal infrared emissivity spectra were also collected for direct comparison to Martian data. By increasing spectral recognition capacities of nanophase materials, more accurate estimates can be made on the aqueous geochemical environment of Mars.

  8. 35. GREY IRON TUMBLERS, IN THE GREY IRON FOUNDRY ROTATE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    35. GREY IRON TUMBLERS, IN THE GREY IRON FOUNDRY ROTATE CASTINGS WITH SHOT TO REMOVE AND SURFACE OXIDES AND REMAINING EXCESS METALS. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

  9. 75 FR 81212 - Floor-Standing Metal-Top Ironing Tables and Certain Parts Thereof from the People's Republic of...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-12-27

    ... Ironing Tables and Certain Parts Thereof from the People's Republic of China: Extension of Time Limit for... parts thereof from the People's Republic of China. See Floor-Standing, Metal-Top Ironing Tables and Certain Parts Thereof From the People's Republic of China: Preliminary Results of Antidumping Duty...

  10. 77 FR 1455 - Floor-Standing, Metal-Top Ironing Tables and Certain Parts Thereof From the People's Republic of...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-01-10

    ... Ironing Tables and Certain Parts Thereof From the People's Republic of China: Extension of Time Limit for... parts thereof from the People's Republic of China. See Floor-Standing, Metal-Top Ironing Tables and Certain Parts Thereof From the People's Republic of China: Preliminary Results of Antidumping Duty...

  11. Experimental evidence for the absence of iron isotope fractionation between metal and silicate liquids at 1 GPa and 1250-1300 °C and its cosmochemical consequences

    NASA Astrophysics Data System (ADS)

    Hin, Remco C.; Schmidt, Max W.; Bourdon, Bernard

    2012-09-01

    Iron isotope fractionation during metal-silicate differentiation has been proposed as a cause for differences in iron isotope compositions of chondrites, iron meteorites and the bulk silicate Earth. Stable isotope fractionation, however, rapidly decreases with increasing temperature. We have thus performed liquid metal-liquid silicate equilibration experiments at 1250-1300 °C and 1 GPa to address whether Fe isotope fractionation is resolvable at the lowest possible temperatures for magmatic metal-silicate differentiation. A centrifuging piston cylinder apparatus enabled quantitative metal-silicate segregation. Elemental tin or sulphur was used in the synthetic metal-oxide mixtures to lower the melting temperature of the metal. The analyses demonstrate that eight of the 10 experimental systems equilibrated in a closed isotopic system, as was assessed by varying run durations and starting Fe isotope compositions. Statistically significant iron isotope fractionation between quenched metals and silicates was absent in nine of the 10 experiments and all 10 experiments yield an average metal-silicate fractionation factor of 0.01 ± 0.04‰, independent of whether graphite or silica glass capsules were used. This implies that Fe isotopes do not fractionate during low pressure metal-silicate segregation under magmatic conditions. In large bodies such as the Earth, fractionation between metal and high pressure (>20 GPa) silicate phases may still be a possible process for equilibrium fractionation during metal-silicate differentiation. However, the 0.07 ± 0.02‰ heavier composition of bulk magmatic iron meteorites relative to the average of bulk ordinary/carbonaceous chondrites cannot result from equilibrium Fe isotope fractionation during core segregation. The up to 0.5‰ lighter sulphide than metal fraction in iron meteorites and in one ordinary chondrite can only be explained by fractionation during subsolidus processes.

  12. Catalytic decomposition of toxic chemicals over iron group metals supported on carbon nanotubes.

    PubMed

    Li, Lili; Chen, Can; Chen, Long; Zhu, Zixue; Hu, Jianli

    2014-03-18

    This study explores catalytic decomposition of phosphine (PH3) using iron group metals (Co, Ni) and metal oxides (Fe2O3, Co(3)O4, NiO) supported on carbon nanotubes (CNTs). The catalysts are synthesized by means of a deposition-precipitation method. The morphology, structure, and composition of the catalysts are characterized using a number of analytical instrumentations, including high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, BET surface area measurement, and inductively coupled plasma. The activity of the catalysts in the PH3 decomposition reaction is measured and correlated with their surface and structural properties. The characterization results show that phosphidation occurs on the catalyst surface, and the resulting metal phosphides act as an active phase in the PH3 decomposition reaction. Cobalt phosphide, CoP, is formed on Co/CNTs and Co(3)O4/CNTs, whereas iron phosphide, FeP, is formed on Fe2O3/CNTs. In contrast, phosphorus-rich phosphide NiP2 is formed on Ni/CNTs and NiO/CNTs. The initial activities of the catalysts are shown in the following sequence: Ni/CNTs > Co/CNTs > Co(3)O4/CNTs >NiO/CNTs > Fe2O3/CNTs, whereas activities of metal phosphides are shown in the following order: CoP > NiP2 > FeP. The catalytic activity of metal phosphides is attributed to their electronic properties. Cobalt phosphide formed on Co/CNTs and Co(3)O4/CNTs exhibits not only the highest activity, but also long-term stability in the PH3 decomposition reaction.

  13. Low-pressure hydrogenation of carbon dioxide catalyzed by an iron pincer complex exhibiting noble metal activity.

    PubMed

    Langer, Robert; Diskin-Posner, Yael; Leitus, Gregory; Shimon, Linda J W; Ben-David, Yehoshoa; Milstein, David

    2011-10-10

    A highly active iron catalyst for the hydrogenation of carbon dioxide and bicarbonates works under remarkably low pressures and achieves activities similar to some of the best noble metal catalysts. A mechanism is proposed involving the direct attack of an iron trans-dihydride on carbon dioxide, followed by ligand exchange and dihydrogen coordination. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Metal transports and enrichments in iron depositions hosted in basaltic rocks. II: Metal rich fluids and Fe origin

    NASA Astrophysics Data System (ADS)

    Zhang, Ronghua; Zhang, Xuetong; Hu, Shumin

    2015-12-01

    This study focuses on revealing the mechanism of metal transport, enrichment and Fe origin of iron deposition during water basalt interactions occurred in basaltic rocks. Observations of the iron deposits (anhydrite-magnetite-pyroxene type deposits) hosted in K-rich basaltic rocks in the Mesozoic volcanic area of the Middle-Lower Yangtze River valley, China, indicate that the mechanism of metal transport and enrichment for those deposits are significant objective to scientists, and the Fe origin problem is not well resolved. Here the metal transport, enrichment and iron origin have been investigated in high temperature experiments of water basaltic interactions. These deposits were accompanying a wide zone with metal alteration. The effects of hydrothermal alteration on major rock-forming element concentrations in basaltic rock were investigated by systematically comparing the chemical compositions of altered rocks with those of fresh rocks. In the deposits, these metals are distributed throughout altered rocks that exhibit vertical zoning from the deeper to the shallow. Then, combined with the investigations of the metal-alterations, we performed kinetic experiments of water-basaltic rock interactions using flow-through reactors in open systems at temperatures from 20 °C to 550 °C, 23-34 MPa. Release rates for the rock-forming elements from the rocks have been measured. Experiments provide the release rates for various elements at a large temperature range, and indicate that the dissolution rates (release rates) for various elements vary with temperature. Si, Al, and K have high release rates at temperatures from 300 °C to 500 °C; the maximum release rates (RMX) for Si are reached at temperatures from 300 °C to 400 °C. The RMXs for Ca, Mg, and Fe are at low temperatures from 20 °C to 300 °C. Results demonstrate that Fe is not released from 400 °C to 550 °C, and indicate that when deep circling fluids passed through basaltic rocks, Fe was not mobile, and

  15. Insights into solar nebula formation of pyrrhotite from nanoscale disequilibrium phases produced by H2S sulfidation of Fe metal

    DOE PAGES

    Gainsforth, Z; Lauretta, DS; Tamura, N; ...

    2017-09-01

    © 2017 by Walter de Gruyter Berlin/Boston. Lauretta (2005) produced sulfide in the laboratory by exposing canonical nebular metal analogs to H 2 S gas under temperatures and pressures relevant to the formation of the Solar System. The resulting reactions produced a suite of sulfides and nanophase materials not visible at the microprobe scale, but which we have now analyzed by TEM for comparison with interplanetary dust samples and comet Wild 2 samples returned by the Stardust mission. We find the unexpected result that disequilibrium formation favors pyrrhotite over troilite and also produces minority schreibersite, daubréelite, barringerite, taenite, oldhamite, andmore » perryite at the metal-sulfide interface. TEM identification of nanophases and analysis of pyrrhotite superlattice reflections illuminate the formation pathway of disequilibrium sulfide. We discuss the conditions under which such disequilibrium can occur, and implications for formation of sulfide found in extraterrestrial materials.« less

  16. Metal mobilization by iron- and sulfur-oxidizing bacteria in a multiple extreme mine tailings in the Atacama Desert, Chile.

    PubMed

    Korehi, H; Blöthe, M; Sitnikova, M A; Dold, B; Schippers, A

    2013-03-05

    The marine shore sulfidic mine tailings dump at the Chañaral Bay in the Atacama Desert, northern Chile, is characterized by extreme acidity, high salinity, and high heavy metals concentrations. Due to pyrite oxidation, metals (especially copper) are mobilized under acidic conditions and transported toward the tailings surface and precipitate as secondary minerals (Dold, Environ. Sci. Technol. 2006, 40, 752-758.). Depth profiles of total cell counts in this almost organic-carbon free multiple extreme environment showed variable numbers with up to 10(8) cells g(-1) dry weight for 50 samples at four sites. Real-time PCR quantification and bacterial 16S rRNA gene diversity analysis via clone libraries revealed a dominance of Bacteria over Archaea and the frequent occurrence of the acidophilic iron(II)- and sulfur-oxidizing and iron(III)-reducing genera Acidithiobacillus, Alicyclobacillus, and Sulfobacillus. Acidophilic chemolithoautotrophic iron(II)-oxidizing bacteria were also frequently found via most-probable-number (MPN) cultivation. Halotolerant iron(II)-oxidizers in enrichment cultures were active at NaCl concentrations up to 1 M. Maximal microcalorimetrically determined pyrite oxidation rates coincided with maxima of the pyrite content, total cell counts, and MPN of iron(II)-oxidizers. These findings indicate that microbial pyrite oxidation and metal mobilization preferentially occur in distinct tailings layers at high salinity. Microorganisms for biomining with seawater salt concentrations obviously exist in nature.

  17. Recent advances in research applications of nanophase hydroxyapatite.

    PubMed

    Fox, Kate; Tran, Phong A; Tran, Nhiem

    2012-07-16

    Hydroxyapatite, the main inorganic material in natural bone, has been used widely for orthopaedic applications. Due to size effects and surface phenomena at the nanoscale, nanophase hydroxyapatite possesses unique properties compared to its bulk-phase counterpart. The high surface-to-volume ratio, reactivities, and biomimetic morphologies make nano-hydroxyapatite more favourable in applications such as orthopaedic implant coating or bone substitute filler. Recently, more efforts have been focused on the possibility of combining hydroxyapatite with other drugs and materials for multipurpose applications, such as antimicrobial treatments, osteoporosis treatments and magnetic manipulation. To build more effective nano-hydroxyapatite and composite systems, the particle synthesis processes, chemistry, and toxicity have to be thoroughly investigated. In this Minireview, we report the recent advances in research regarding nano-hydroxyapatite. Synthesis routes and a wide range of applications of hydroxyapatite nanoparticles will be discussed. The Minireview also addresses several challenges concerning the biosafety of the nanoparticles. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Heavy Metals Induce Iron Deficiency Responses at Different Hierarchic and Regulatory Levels1[OPEN

    PubMed Central

    2017-01-01

    In plants, the excess of several heavy metals mimics iron (Fe) deficiency-induced chlorosis, indicating a disturbance in Fe homeostasis. To examine the level at which heavy metals interfere with Fe deficiency responses, we carried out an in-depth characterization of Fe-related physiological, regulatory, and morphological responses in Arabidopsis (Arabidopsis thaliana) exposed to heavy metals. Enhanced zinc (Zn) uptake closely mimicked Fe deficiency by leading to low chlorophyll but high ferric-chelate reductase activity and coumarin release. These responses were not caused by Zn-inhibited Fe uptake via IRON-REGULATED TRANSPORTER (IRT1). Instead, Zn simulated the transcriptional response of typical Fe-regulated genes, indicating that Zn affects Fe homeostasis at the level of Fe sensing. Excess supplies of cobalt and nickel altered root traits in a different way from Fe deficiency, inducing only transient Fe deficiency responses, which were characterized by a lack of induction of the ethylene pathway. Cadmium showed a rather inconsistent influence on Fe deficiency responses at multiple levels. By contrast, manganese evoked weak Fe deficiency responses in wild-type plants but strongly exacerbated chlorosis in irt1 plants, indicating that manganese antagonized Fe mainly at the level of transport. These results show that the investigated heavy metals modulate Fe deficiency responses at different hierarchic and regulatory levels and that the interaction of metals with physiological and morphological Fe deficiency responses is uncoupled. Thus, this study not only emphasizes the importance of assessing heavy metal toxicities at multiple levels but also provides a new perspective on how Fe deficiency contributes to the toxic action of individual heavy metals. PMID:28500270

  19. Iron and iron-related proteins in asbestosis.

    EPA Science Inventory

    ABSTRACT: We tested the postulate that iron homeostasis is altered among patients diagnosed to have asbestosis. Lung tissue from six individuals diagnosed to have had asbestosis at autopsy was stained for iron, ferritin, divalent metal transporter 1 (DMT1), and ferroportin 1 (FP...

  20. Magnetization and Magnetoresistance in Iron Intercalated Transition Metal Dichalcogenides

    NASA Astrophysics Data System (ADS)

    Choe, Jesse

    The understanding of magnetism in strongly correlated electronic systems is a vital area of research. Not only is it linked to other phenomena like high temperature superconductivity in the cuprates and iron pnictides, but magnetic materials have been used in electronics since before the computer. As it becomes harder to prop up Moore's law by increasing the density of transistors, mankind must look towards new methods to improve technology or risk stagnation. Research into alternative materials for technology, such as transition metal dichalcogenides, is a promising direction of research to maintain the rate of technological improvement. Our work focuses on the effect of iron intercalation in TiS2. Single crystals of FexTiS 2 (0 ≤ x ≤ 1) were grown using vapor transport. Anisotropic susceptibility and magnetization measurements of the samples were measured, showing ferromagnetism and sharp switching behavior in the magnetization. Finally electrical transport measurements were taken, both with and without field. Measurements of magnetoresistance for x = 0.2 and 0.3 show large magnetoresistance (up to ˜ 60%) and an atypical 'bowtie' shape.

  1. Synthesis Functional and Constructional Nanomaterials on a Basis Carbide Tungsten, Molybdenum and Metals of a Triad of Iron in Ionic Melts

    NASA Astrophysics Data System (ADS)

    Kushkhov, H. B.; Adamokova, M. N.; Kvashin, V. A.; Kardanov, A. L.

    2011-04-01

    Single and cyclic voltammetry is used to study the electrode processes that occur during electrochemical synthesis of hard-alloy compositions based on tungsten carbide and an iron triad metal in tungstate and tungstate-carbonate Na2WO4-Li2WO4-Li2CO3 (5.0-22.0 wt %) melts. The conditions of bringing the electroprecipitation potentials of tungsten, carbon, and an iron triad metal into coincidence are determined.

  2. Method for producing iron-based catalysts

    DOEpatents

    Farcasiu, Malvina; Kaufman, Phillip B.; Diehl, J. Rodney; Kathrein, Hendrik

    1999-01-01

    A method for preparing an acid catalyst having a long shelf-life is provided comprising doping crystalline iron oxides with lattice-compatible metals and heating the now-doped oxide with halogen compounds at elevated temperatures. The invention also provides for a catalyst comprising an iron oxide particle having a predetermined lattice structure, one or more metal dopants for said iron oxide, said dopants having an ionic radius compatible with said lattice structure; and a halogen bound with the iron and the metal dopants on the surface of the particle.

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

    PubMed

    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.

  4. System and method for producing metallic iron

    DOEpatents

    Bleifuss, Rodney L [Grand Rapids, MN; Englund, David J [Bovey, MN; Iwasaki, Iwao [Grand Rapids, MN; Fosnacht, Donald R [Hermantown, MN; Brandon, Mark M [Charlotte, NC; True, Bradford G [Charlotte, NC

    2012-01-17

    A hearth furnace 10 for producing metallic iron material has a furnace housing 11 having a drying/preheat zone 12, a conversion zone 13, a fusion zone 14, and optionally a cooling zone 15, the conversion zone 13 is between the drying/preheat zone 12 and the fusion zone 14. A moving hearth 20 is positioned within the furnace housing 11. A hood or separation barrier 30 within at least a portion of the conversion zone 13, fusion zone 14 or both separates the fusion zone 14 into an upper region and a lower region with the lower region adjacent the hearth 20 and the upper region adjacent the lower region and spaced from the hearth 20. An injector introduces a gaseous reductant into the lower region adjacent the hearth 20. A combustion region may be formed above the hood or separation barrier.

  5. Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

    NASA Technical Reports Server (NTRS)

    Napier, Mary E.; Stair, Peter C.

    1992-01-01

    Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

  6. Removal of heavy metals using bentonite supported nano-zero valent iron particles

    NASA Astrophysics Data System (ADS)

    Zarime, Nur Aishah; Yaacob, Wan Zuhari Wan; Jamil, Habibah

    2018-04-01

    This study reports the composite nanoscale zero-valent iron (nZVI) which was successfully synthesized using low cost natural clay (bentonite). Bentonite composite nZVI (B-nZVI) was introduced to reduce the agglomeration of nZVI particles, thus will used for heavy metals treatment. The synthesized material was analyzed using physical, mineralogy and morphology analysis such as Brunnaer-Emmett-Teller (BET) surface area, Field Emission Scanning Electron Microscopy (FESEM), X-Ray Diffraction (XRD), Fourier Transform Infrared (FTIR) and X-ray Photoelectron Spectroscopy (XPS). The batch adsorption test of Bentonite and B-nZVI with heavy metals solutions (Pb, Cu, Cd, Co, Ni and Zn) was also conducted to determine their effectiveness in removing heavy metals. Through Batch test, B-nZVI shows the highest adsorption capacity (qe= 50.25 mg/g) compared to bentonite (qe= 27.75 mg/g). This occurred because B-nZVI can reduce aggregation of nZVI, dispersed well in bentonite layers thus it can provide more sites for adsorbing heavy metals.

  7. Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites.

    PubMed

    Xiao, Dianne J; Bloch, Eric D; Mason, Jarad A; Queen, Wendy L; Hudson, Matthew R; Planas, Nora; Borycz, Joshua; Dzubak, Allison L; Verma, Pragya; Lee, Kyuho; Bonino, Francesca; Crocellà, Valentina; Yano, Junko; Bordiga, Silvia; Truhlar, Donald G; Gagliardi, Laura; Brown, Craig M; Long, Jeffrey R

    2014-07-01

    Enzymatic haem and non-haem high-valent iron-oxo species are known to activate strong C-H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron-oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)-oxo compounds. In particular, although nature's non-haem iron(IV)-oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal-organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal-organic framework Fe2(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc), are able to activate the C-H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)-oxo species.

  8. Fabrication of Conductive Macroporous Structures Through Nano-phase Separation Method

    NASA Astrophysics Data System (ADS)

    Kim, Soohyun; Lee, Hyunjung

    2018-03-01

    Thermoelectric power generation performance is characterized on the basis of the figure of merit, which tends to be high in thermoelectric materials with high electrical conductivity and low thermal conductivity. Porous structures cause phonon scattering, which decreases thermal conductivity. In this study, we fabricated porous structures for thermoelectric devices via nano-phase separation of silica particles from a polyacrylonitrile (PAN) matrix via a sol-gel process. The porosity was determined by control of silica particle size with various the mixing ratio of tetraethylorthosilicate as the precursor of silica particles to PAN. High electrical conductivity was maintained by subsequent carbonization of the PAN matrix in spited of a high porosity. As the results, the conductive porous structures having porosity from 13.9 to 83.3 (%) was successfully fabricated, keeping their electrical conductivities.

  9. A novel approach for rapidly and cost-effectively assessing toxicity of toxic metals in acidic water using an acidophilic iron-oxidizing biosensor.

    PubMed

    Yang, Shih-Hung; Cheng, Kuo-Chih; Liao, Vivian Hsiu-Chuan

    2017-11-01

    Contamination by heavy metals and metalloids is a serious environmental and health concern. Acidic wastewaters are often associated with toxic metals which may enter and spread into agricultural soils. Several biological assays have been developed to detect toxic metals; however, most of them can only detect toxic metals in a neutral pH, not in an acidic environment. In this study, an acidophilic iron-oxidizing bacterium (IOB) Strain Y10 was isolated, characterized, and used to detect toxic metals toxicity in acidic water at pH 2.5. The colorimetric acidophilic IOB biosensor was based on the inhibition of the iron oxidizing ability of Strain Y10, an acidophilic iron-oxidizing bacterium, by metals toxicity. Our results showed that Strain Y10 is acidophilic iron-oxidizing bacterium. Thiobacillus caldus medium (TCM) (pH 2.5) supplied with both S 4 O 6 2- and glucose was the optimum growth medium for Strain Y10. The optimum temperature and pH for the growth of Strain Y10 was 45 °C and pH 2.5, respectively. Our study demonstrates that the color-based acidophilic IOB biosensor can be semi-quantitatively observed by eye or quantitatively measured by spectrometer to detect toxicity from multiple toxic metals at pH 2.5 within 45 min. Our study shows that monitoring toxic metals in acidic water is possible by using the acidophilic IOB biosensor. Our study thus provides a novel approach for rapid and cost-effective detection of toxic metals in acidic conditions that can otherwise compromise current methods of chemical analysis. This method also allows for increased efficiency when screening large numbers of environmental samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Defect Clustering and Nano-phase Structure Characterization of Multicomponent Rare Earth-Oxide-Doped Zirconia-Yttria Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Chen, Yuan L.; Miller, Robert A.

    2004-01-01

    Advanced thermal barrier coatings (TBCs) have been developed by incorporating multicomponent rare earth oxide dopants into zirconia-based thermal barrier coatings to promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nanophases within the coating systems. In this paper, the defect clusters, induced by Nd, Gd, and Yb rare earth dopants in the zirconia-yttria thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The TEM lattice imaging, selected area diffraction (SAD), and electron energy-loss spectroscopy (EELS) analyses demonstrated that the extensive nanoscale rare earth dopant segregation exists in the plasma-sprayed and electron-physical-vapor-deposited (EB PVD) thermal barrier coatings. The nanoscale concentration heterogeneity and the resulting large lattice distortion promoted the formation of parallel and rotational defective lattice clusters in the coating systems. The presence of the 5-to 100-nm-sized defect clusters and nanophases is believed to be responsible for the significant reduction of thermal conductivity, improved sintering resistance, and long-term high temperature stability of the advanced thermal barrier coating systems.

  11. Production of iron from metallurgical waste

    DOEpatents

    Hendrickson, David W; Iwasaki, Iwao

    2013-09-17

    A method of recovering metallic iron from iron-bearing metallurgical waste in steelmaking comprising steps of providing an iron-bearing metallurgical waste containing more than 55% by weight FeO and FeO equivalent and a particle size of at least 80% less than 10 mesh, mixing the iron-bearing metallurgical waste with a carbonaceous material to form a reducible mixture where the carbonaceous material is between 80 and 110% of the stoichiometric amount needed to reduce the iron-bearing waste to metallic iron, and as needed additions to provide a silica content between 0.8 and 8% by weight and a ratio of CaO/SiO.sub.2 between 1.4 and 1.8, forming agglomerates of the reducible mixture over a hearth material layer to protect the hearth, heating the agglomerates to a higher temperature above the melting point of iron to form nodules of metallic iron and slag material from the agglomerates by melting.

  12. The role of iron in cancer.

    PubMed

    Weinberg, E D

    1996-02-01

    Numerous laboratory and clinical investigations over the past few decades have observed that one of the dangers of iron is its ability to favour neoplastic cell growth. The metal is carcinogenic due to its catalytic effect on the formation of hydroxyl radicals, suppression of the activity of host defence cells and promotion of cancer cell multiplication. In both animals and humans, primary neoplasms develop at body sites of excessive iron deposits. The invaded host attempts to withhold iron from the cancer cells via sequestration of the metal in newly formed ferritin. The host also endeavours to withdraw the metal from cancer cells via macrophage synthesis of nitric oxide. Quantitative evaluation of body iron and of iron-withholding proteins has prognostic value in cancer patients. Procedures associated with lowering host iron intake and inducing host cell iron efflux can assist in prevention and management of neoplastic diseases. Pharmaceutical methods for depriving neoplastic cells of iron are being developed in experimental and clinical protocols.

  13. Inhibition of cellulase-catalyzed lignocellulosic hydrolysis by iron and oxidative metal ions and complexes.

    PubMed

    Tejirian, Ani; Xu, Feng

    2010-12-01

    Enzymatic lignocellulose hydrolysis plays a key role in microbially driven carbon cycling and energy conversion and holds promise for bio-based energy and chemical industries. Cellulases (key lignocellulose-active enzymes) are prone to interference from various noncellulosic substances (e.g., metal ions). During natural cellulolysis, these substances may arise from other microbial activities or abiotic events, and during industrial cellulolysis, they may be derived from biomass feedstocks or upstream treatments. Knowledge about cellulolysis-inhibiting reactions is of importance for the microbiology of natural biomass degradation and the development of biomass conversion technology. Different metal ions, including those native to microbial activity or employed for biomass pretreatments, are often tested for enzymatic cellulolysis. Only a few metal ions act as inhibitors of cellulases, which include ferrous and ferric ions as well as cupric ion. In this study, we showed inhibition by ferrous/ferric ions as part of a more general effect from oxidative (or redox-active) metal ions and their complexes. The correlation between inhibition and oxidation potential indicated the oxidative nature of the inhibition, and the dependence on air established the catalytic role that iron ions played in mediating the dioxygen inhibition of cellulolysis. Individual cellulases showed different susceptibilities to inhibition. It is likely that the inhibition exerted its effect more on cellulose than on cellulase. Strong iron ion chelators and polyethylene glycols could mitigate the inhibition. Potential microbiological and industrial implications of the observed effect of redox-active metal ions on enzymatic cellulolysis, as well as the prevention and mitigation of this effect in industrial biomass conversion, are discussed.

  14. Sulfur-Mediated Electron Shuttling Sustains Microbial Long-Distance Extracellular Electron Transfer with the Aid of Metallic Iron Sulfides.

    PubMed

    Kondo, Katsuhito; Okamoto, Akihiro; Hashimoto, Kazuhito; Nakamura, Ryuhei

    2015-07-07

    In addition to serving as an energy source for microbial growth, iron sulfides are proposed to act as naturally occurring electrical wires that mediate long-distance extracellular electron transfer (EET) and bridge spatially discrete redox environments. These hypothetical EET reactions stand on the abilities of microbes to use the interfacial electrochemistry of metallic/semiconductive iron sulfides to maintain metabolisms; however, the mechanisms of these phenomena remain unexplored. To obtain insight into EET to iron sulfides, we monitored EET at the interface between Shewanella oneidensis MR-1 cells and biomineralized iron sulfides in an electrochemical cell. Respiratory current steeply increased with the concomitant formation of poorly crystalline mackinawite (FeS) minerals, indicating that S. oneidensis has the ability to exploit extracellularly formed metallic FeS for long-distance EET. Deletion of major proteins of the metal-reduction (Mtr) pathway (OmcA, MtrC, CymA, and PilD) caused only subtle effects on the EET efficiency, a finding that sharply contrasts the majority of studies that report that the Mtr pathway is indispensable for the reduction of metal oxides and electrodes. The gene expression analyses of polysulfide and thiosulfate reductase suggest the existence of a sulfur-mediated electron-shuttling mechanism by which HS(-) ions and water-soluble polysulfides (HS(n)(-), where n ≥ 2) generated in the periplasmic space deliver electrons from cellular metabolic processes to cell surface-associated FeS. The finding of this Mtr-independent pathway indicates that polysulfide reductases complement the function of outer-membrane cytochromes in EET reactions and, thus, significantly expand the number of microbial species potentially capable of long-distance EET in sulfur-rich anoxic environments.

  15. MASS TRANSPORT EFFECTS ON THE KINETICS OF NITROBENZENE REDUCTION BY IRON METAL. (R827117)

    EPA Science Inventory

    To evaluate the importance of external mass transport on the overall rates of
    contaminant reduction by iron metal (Fe0), we have compared measured
    rates of surface reaction for nitrobenzene (ArNO2) to estimated rates
    of external mass transport...

  16. Iron Homeostasis in Mycobacterium tuberculosis: Mechanistic Insights into Siderophore-Mediated Iron Uptake

    PubMed Central

    2016-01-01

    Mycobacterium tuberculosis requires iron for normal growth but faces a limitation of the metal ion due to its low solubility at biological pH and the withholding of iron by the mammalian host. The pathogen expresses the Fe3+-specific siderophores mycobactin and carboxymycobactin to chelate the metal ion from insoluble iron and the host proteins transferrin, lactoferrin, and ferritin. Siderophore-mediated iron uptake is essential for the survival of M. tuberculosis, as knockout mutants, which were defective in siderophore synthesis or uptake, failed to survive in low-iron medium and inside macrophages. But as excess iron is toxic due to its catalytic role in the generation of free radicals, regulation of iron uptake is necessary to maintain optimal levels of intracellular iron. The focus of this review is to present a comprehensive overview of iron homeostasis in M. tuberculosis that is discussed in the context of mycobactin biosynthesis, transport of iron across the mycobacterial cell envelope, and storage of excess iron. The clinical significance of the serum iron status and the expression of the iron-regulated protein HupB in tuberculosis (TB) patients is presented here, highlighting the potential of HupB as a marker, notably in extrapulmonary TB cases. PMID:27402628

  17. A study of the dispersity of iron oxide and iron oxide-noble metal (Me = Pd, Pt) supported systems

    NASA Astrophysics Data System (ADS)

    Cherkezova-Zheleva, Z. P.; Shopska, M. G.; Krstić, J. B.; Jovanović, D. M.; Mitov, I. G.; Kadinov, G. B.

    2007-09-01

    Samples of one-(Fe) and two-component (Fe-Pd and Fe-Pt) catalysts were prepared by incipient wetness impregnation of four different supports: TiO2 (anatase), γ-Al2O3, activated carbon, and diatomite. The chosen synthesis conditions resulted in the formation of nanosized supported phases—iron oxide (in the one-component samples), or iron oxide-noble metal (in the two-component ones). Different agglomeration degrees of these phases were obtained as a result of thermal treatment. Ultradisperse size of the supported phase was maintained in some samples, while a process of partial agglomeration occurred in others, giving rise to nearly bidisperse (ultra-and highdisperse) supported particles. The different texture of the used supports and their chemical composition are the reasons for the different stability of the nanosized supported phases. The samples were tested as heterogeneous catalysts in total benzene oxidation reaction.

  18. Treatment of heavy metals by iron oxide coated and natural gravel media in Sustainable urban Drainage Systems.

    PubMed

    Norris, M J; Pulford, I D; Haynes, H; Dorea, C C; Phoenix, V R

    2013-01-01

    Sustainable urban Drainage Systems (SuDS) filter drains are simple, low-cost systems utilized as a first defence to treat road runoff by employing biogeochemical processes to reduce pollutants. However, the mechanisms involved in pollution attenuation are poorly understood. This work aims to develop a better understanding of these mechanisms to facilitate improved SuDS design. Since heavy metals are a large fraction of pollution in road runoff, this study aimed to enhance heavy metal removal of filter drain gravel with an iron oxide mineral amendment to increase surface area for heavy metal scavenging. Experiments showed that amendment-coated and uncoated (control) gravel removed similar quantities of heavy metals. Moreover, when normalized to surface area, iron oxide coated gravels (IOCGs) showed poorer metal removal capacities than uncoated gravel. Inspection of the uncoated microgabbro gravel indicated that clay particulates on the surface (a natural product of weathering of this material) augmented heavy metal removal, generating metal sequestration capacities that were competitive compared with IOCGs. Furthermore, when the weathered surface was scrubbed and removed, metal removal capacities were reduced by 20%. When compared with other lithologies, adsorption of heavy metals by microgabbro was 10-70% higher, indicating that both the lithology of the gravel, and the presence of a weathered surface, considerably influence its ability to immobilize heavy metals. These results contradict previous assumptions which suggest that gravel lithology is not a significant factor in SuDS design. Based upon these results, weathered microgabbro is suggested to be an ideal lithology for use in SuDS.

  19. Polarization of IRON-REGULATED TRANSPORTER 1 (IRT1) to the plant-soil interface plays crucial role in metal homeostasis.

    PubMed

    Barberon, Marie; Dubeaux, Guillaume; Kolb, Cornelia; Isono, Erika; Zelazny, Enric; Vert, Grégory

    2014-06-03

    In plants, the controlled absorption of soil nutrients by root epidermal cells is critical for growth and development. IRON-REGULATED TRANSPORTER 1 (IRT1) is the main root transporter taking up iron from the soil and is also the main entry route in plants for potentially toxic metals such as manganese, zinc, cobalt, and cadmium. Previous work demonstrated that the IRT1 protein localizes to early endosomes/trans-Golgi network (EE/TGN) and is constitutively endocytosed through a monoubiquitin- and clathrin-dependent mechanism. Here, we show that the availability of secondary non-iron metal substrates of IRT1 (Zn, Mn, and Co) controls the localization of IRT1 between the outer polar domain of the plasma membrane and EE/TGN in root epidermal cells. We also identify FYVE1, a phosphatidylinositol-3-phosphate-binding protein recruited to late endosomes, as an important regulator of IRT1-dependent metal transport and metal homeostasis in plants. FYVE1 controls IRT1 recycling to the plasma membrane and impacts the polar delivery of this transporter to the outer plasma membrane domain. This work establishes a functional link between the dynamics and the lateral polarity of IRT1 and the transport of its substrates, and identifies a molecular mechanism driving polar localization of a cell surface protein in plants.

  20. The Center for Nanophase Materials Sciences

    NASA Astrophysics Data System (ADS)

    Lowndes, Douglas

    2005-03-01

    The Center for Nanophase Materials Sciences (CNMS) located at Oak Ridge National Laboratory (ORNL) will be the first DOE Nanoscale Science Research Center to begin operation, with construction to be completed in April 2005 and initial operations in October 2005. The CNMS' scientific program has been developed through workshops with the national community, with the goal of creating a highly collaborative research environment to accelerate discovery and drive technological advances. Research at the CNMS is organized under seven Scientific Themes selected to address challenges to understanding and to exploit particular ORNL strengths (see http://cnms.ornl.govhttp://cnms.ornl.gov). These include extensive synthesis and characterization capabilities for soft, hard, nanostructured, magnetic and catalytic materials and their composites; neutron scattering at the Spallation Neutron Source and High Flux Isotope Reactor; computational nanoscience in the CNMS' Nanomaterials Theory Institute and utilizing facilities and expertise of the Center for Computational Sciences and the new Leadership Scientific Computing Facility at ORNL; a new CNMS Nanofabrication Research Laboratory; and a suite of unique and state-of-the-art instruments to be made reliably available to the national community for imaging, manipulation, and properties measurements on nanoscale materials in controlled environments. The new research facilities will be described together with the planned operation of the user research program, the latter illustrated by the current ``jump start'' user program that utilizes existing ORNL/CNMS facilities.

  1. Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks

    PubMed Central

    Jones, J. Graham; Warner, C. G.

    1972-01-01

    Graham Jones, J., and Warner, C. G. (1972).Brit. J. industr. Med.,29, 169-177. Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks. Occupational and medical histories, smoking habits, respiratory symptoms, chest radiographs, and ventilatory capacities were studied in 14 steelworkers employed as deseamers of steel ingots for periods of up to 16 years. The men were exposed for approximately five hours of each working shift to fume concentrations ranging from 1·3 to 294·1 mg/m3 made up mainly of iron oxide with varying proportions of chromium oxide and nickel oxide. Four of the men, with 14 to 16 years' exposure, showed radiological evidence of pneumoconiosis classified as ILO categories 2 or 3. Of these, two had pulmonary function within the normal range and two had measurable loss of function, moderate in one case and mild in the other. Many observers would diagnose these cases as siderosis but the authors consider that this term should be reserved for cases exposed to pure iron compounds. The correct diagnosis is mixed-dust pneumoconiosis and the loss of pulmonary function is caused by the effects of the mixture of metallic oxides. It is probable that inhalation of pure iron oxide does not cause fibrotic pulmonary changes, whereas the inhalation of iron oxide plus certain other substances obviously does. Images PMID:5021996

  2. Metals removal from aqueous solution by iron-based bonding agents.

    PubMed

    Deliyanni, Eleni A; Lazaridis, Nikolaos K; Peleka, Efrosini N; Matis, Konstantinos A

    2004-01-01

    GOAL AND SCOPE AND BACKGROUND: The application of a promising method, termed sorptive flotation, for the removal of chromium(VI) and zinc ions was the aim of the present paper. A special case of sorptive flotation is adsorbing colloid flotation. Suitable sorbent preparation techniques have been developed in the laboratory. Sorptive flotation, consisting of the sorption and flotation processes combined in series, has proved to give fast and satisfactory treatment of the industrial streams and effluents bearing dilute aqueous solutions of zinc and chromium(VI). Goethite has proved to be effective for the removal of chromium(VI) and zinc ions. Also, adsorbing colloid flotation with ferric hydroxide (as the co-precipitant) could be an alternative method to the above-mentioned separation of metal ions. In both cases, chromium(VI) (pH=4) and zinc (pH=7) removal was about 100%. The reasons for selecting the iron-based bonding materials, like goethite and/or in-situ produced ferric hydroxide, are that they are cheap, easily synthesized, suitable both for cation and anion sorption, and, furthermore, that they present low risks for adding a further pollutant to the system. Promising results were obtained. The application of goethite and in-situ produced ferric hydroxide has demonstrated their effectiveness in the removal of heavy metal ions, such as chromium anions and zinc cations. A proposed continuation of current work is the utilization of similar iron oxides, for instance synthesized akaganeite. The comparison between the results reported in this paper with the results reported in the literature, also deserves attention.

  3. Two-State Reactivity in Low-Valent Iron-Mediated C-H Activation and the Implications for Other First-Row Transition Metals.

    PubMed

    Sun, Yihua; Tang, Hao; Chen, Kejuan; Hu, Lianrui; Yao, Jiannian; Shaik, Sason; Chen, Hui

    2016-03-23

    C-H bond activation/functionalization promoted by low-valent iron complexes has recently emerged as a promising approach for the utilization of earth-abundant first-row transition metals to carry out this difficult transformation. Herein we use extensive density functional theory and high-level ab initio coupled cluster calculations to shed light on the mechanism of these intriguing reactions. Our key mechanistic discovery for C-H arylation reactions reveals a two-state reactivity (TSR) scenario in which the low-spin Fe(II) singlet state, which is initially an excited state, crosses over the high-spin ground state and promotes C-H bond cleavage. Subsequently, aryl transmetalation occurs, followed by oxidation of Fe(II) to Fe(III) in a single-electron transfer (SET) step in which dichloroalkane serves as an oxidant, thus promoting the final C-C coupling and finalizing the C-H functionalization. Regeneration of the Fe(II) catalyst for the next round of C-H activation involves SET oxidation of the Fe(I) species generated after the C-C bond coupling. The ligand sphere of iron is found to play a crucial role in the TSR mechanism by stabilization of the reactive low-spin state that mediates the C-H activation. This is the first time that the successful TSR concept conceived for high-valent iron chemistry is shown to successfully rationalize the reactivity for a reaction promoted by low-valent iron complexes. A comparative study involving other divalent middle and late first-row transition metals implicates iron as the optimum metal in this TSR mechanism for C-H activation. It is predicted that stabilization of low-spin Mn(II) using an appropriate ligand sphere should produce another promising candidate for efficient C-H bond activation. This new TSR scenario therefore emerges as a new strategy for using low-valent first-row transition metals for C-H activation reactions.

  4. Metabolic crossroads of iron and copper

    PubMed Central

    Collins, James F; Prohaska, Joseph R; Knutson, Mitchell D

    2013-01-01

    Interactions between the essential dietary metals, iron and copper, have been known for many years. This review highlights recent advances in iron-copper interactions with a focus on tissues and cell types important for regulating whole-body iron and copper homeostasis. Cells that mediate dietary assimilation (enterocytes) and storage and distribution (hepatocytes) of iron and copper are considered, along with the principal users (erythroid cells) and recyclers of red cell iron (reticuloendothelial macrophages). Interactions between iron and copper in the brain are also discussed. Many unanswered questions regarding the role of these metals and their interactions in health and disease emerge from this synopsis, highlighting extensive future research opportunities. PMID:20384844

  5. Response of Southern Ocean Phytoplankton Communities to Trace Metal (including Iron) and Light Availability

    NASA Astrophysics Data System (ADS)

    Fietz, S.; Roychoudhury, A. N.; Thomalla, S.; Mtshali, T. N.; Philibert, R.; Van Horsten, N.; Loock, J. C.; Cloete, R.

    2016-02-01

    Phytoplankton primary productivity depends on macro- and micronutrient availability and in turn plays a key role in the marine biogeochemical cycles. The role of iron in regulating phytoplankton primary production and thus biogeochemical cycles in the Southern Ocean has been widely recognized; however, it also became obvious that iron is not the sole factor limiting primary production in the Southern Ocean and that light, for instance, might aggravate or relief trace nutrient limitation. We conducted a suite of ship-board incubation experiments in austral summer 2013/14, 2014/15 and winter 2015 to shed light on the complex interplay between trace metal and light limitation. We observed a strong difference in acclimation and photophysiological response depending on the environmental conditions of the in-situ communities prior to the experiment. The differences in acclimation and photophysiological responses resulted in different growth and macronutrient uptake rates. Revisited stations did, however, not always show the same responses. At at least one station we will link the incubation experiments to the in-situ vertical profiles of trace metals, macronutrients and primary productivity.

  6. Iron Containing Metal-Organic Frameworks: Structure, Synthesis, and Applications in Environmental Remediation.

    PubMed

    Liu, Xiaocheng; Zhou, Yaoyu; Zhang, Jiachao; Tang, Lin; Luo, Lin; Zeng, Guangming

    2017-06-21

    Metal-organic frameworks (MOFs) with Fe content are gradually developing into an independent branch in environmental remediation, requiring economical, effective, low-toxicity strategies to the complete procedure. In this review, recent advancements in the structure, synthesis, and environmental application focusing on the mechanism are presented. The unique structure of novel design proposed specific characteristics of different iron-containing MOFs with potential innovation. Synthesis of typical MILs, NH 2 -MILs and MILs based materials reveal the basis and defect of the current method, indicating the optimal means for the actual requirements. The adsorption of various contamination with multiple interaction as well as the catalytic degradation over radicals or electron-hole pairs are reviewed. This review implied considerable prospects of iron-containing MOFs in the field of environment and a more comprehensive cognition into the challenges and potential improvement.

  7. Potential ecological and human health risks of heavy metals in surface soils associated with iron ore mining in Pahang, Malaysia.

    PubMed

    Diami, Siti Merryan; Kusin, Faradiella Mohd; Madzin, Zafira

    2016-10-01

    The composition of heavy metals (and metalloid) in surface soils of iron ore mine-impacted areas has been evaluated of their potential ecological and human health risks. The mining areas included seven selected locations in the vicinity of active and abandoned iron ore-mining sites in Pahang, Malaysia. Heavy metals such as Fe, Mn, Cu, Zn, Co, Pb, Cr, Ni, and Cd and metalloid As were present in the mining soils of the studied area, while Cu was found exceeding the soil guideline value at all sampling locations. However, the assessment of the potential ecological risk index (RI) indicated low ecological risk (RI between 44 and 128) with respect to Cd, Pb, Cu, As, Zn, Co, and Ni in the surface soils. Contributions of potential ecological risk [Formula: see text]by metal elements to the total potential ecological RI were evident for Cd, As, Pb, and Cu. Contribution of Cu appears to be consistently greater in the abandoned mining area compared to active iron ore-mining site. For non-carcinogenic risk, no significant potential health risk was found to both children and adults as the hazard indices (HIs) were all below than 1. The lifetime cancer risk (LCR) indicated that As has greater potential carcinogenic risk compared to other metals that may induce carcinogenic effects such as Pb, Cr, and Cd, while the LCR of As for children fell within tolerable range for regulatory purposes. Irrespective of carcinogenic or non-carcinogenic risk, greater potential health risk was found among children (by an order of magnitude higher for most metals) compared to adults. The hazard quotient (HQ) and cancer risk indicated that the pathways for the risk to occur were found to be in the order of ingestion > dermal > inhalation. Overall, findings showed that some metals and metalloid were still present at comparable concentrations even long after cessation of the iron ore-mining activities.

  8. Reducing bacteria and macrophage density on nanophase hydroxyapatite coated onto titanium surfaces without releasing pharmaceutical agents

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Garima; Yazici, Hilal; Webster, Thomas J.

    2015-04-01

    Reducing bacterial density on titanium implant surfaces has been a major concern because of the increasing number of nosocomial infections. Controlling the inflammatory response post implantation has also been an important issue for medical devices due to the detrimental effects of chronic inflammation on device performance. It has recently been demonstrated that manipulating medical device surface properties including chemistry, roughness and wettability can control both infection and inflammation. Here, we synthesized nanophase (that is, materials with one dimension in the nanoscale) hydroxyapatite coatings on titanium to reduce bacterial adhesion and inflammatory responses (as measured by macrophage functions) and compared such results to bare titanium and plasma sprayed hydroxyapatite titanium coated surfaces used clinically today. This approach is a pharmaceutical-free approach to inhibit infection and inflammation due to the detrimental side effects of any drug released in the body. Here, nanophase hydroxyapatite was synthesized in sizes ranging from 110-170 nm and was subsequently coated onto titanium samples using electrophoretic deposition. Results indicated that smaller nanoscale hydroxyapatite features on titanium surfaces alone decreased bacterial attachment in the presence of gram negative (P. aeruginosa), gram positive (S. aureus) and ampicillin resistant gram-negative (E. coli) bacteria as well as were able to control inflammatory responses; properties which should lead to their further investigation for improved medical applications.

  9. The iron-chelate transporter OsYSL9 plays a role in iron distribution in developing rice grains.

    PubMed

    Senoura, Takeshi; Sakashita, Emi; Kobayashi, Takanori; Takahashi, Michiko; Aung, May Sann; Masuda, Hiroshi; Nakanishi, Hiromi; Nishizawa, Naoko K

    2017-11-01

    Rice OsYSL9 is a novel transporter for Fe(II)-nicotianamine and Fe(III)-deoxymugineic acid that is responsible for internal iron transport, especially from endosperm to embryo in developing seeds. Metal chelators are essential for safe and efficient metal translocation in plants. Graminaceous plants utilize specific ferric iron chelators, mugineic acid family phytosiderophores, to take up sparingly soluble iron from the soil. Yellow Stripe 1-Like (YSL) family transporters are responsible for transport of metal-phytosiderophores and structurally similar metal-nicotianamine complexes. Among the rice YSL family members (OsYSL) whose functions have not yet been clarified, OsYSL9 belongs to an uncharacterized subgroup containing highly conserved homologs in graminaceous species. In the present report, we showed that OsYSL9 localizes mainly to the plasma membrane and transports both iron(II)-nicotianamine and iron(III)-deoxymugineic acid into the cell. Expression of OsYSL9 was induced in the roots but repressed in the nonjuvenile leaves in response to iron deficiency. In iron-deficient roots, OsYSL9 was induced in the vascular cylinder but not in epidermal cells. Although OsYSL9-knockdown plants did not show a growth defect under iron-sufficient conditions, these plants were more sensitive to iron deficiency in the nonjuvenile stage compared with non-transgenic plants. At the grain-filling stage, OsYSL9 expression was strongly and transiently induced in the scutellum of the embryo and in endosperm cells surrounding the embryo. The iron concentration was decreased in embryos of OsYSL9-knockdown plants but was increased in residual parts of brown seeds. These results suggested that OsYSL9 is involved in iron translocation within plant parts and particularly iron translocation from endosperm to embryo in developing seeds.

  10. Tissue distribution of manganese in iron-sufficient or iron-deficient rats after stainless steel welding-fume exposure.

    PubMed

    Park, Jung-Duck; Kim, Ki-Young; Kim, Dong-Won; Choi, Seong-Jin; Choi, Byung-Sun; Chung, Yong Hyun; Han, Jeong Hee; Sung, Jae Hyuck; Kwon, Il Hoon; Mun, Je-Hyeok; Yu, Il Je

    2007-05-01

    Welders can be exposed to high levels of manganese through welding fumes. Although it has already been suggested that excessive manganese exposure causes neurotoxicity, called manganism, the pathway of manganese transport to the brain with welding-fume exposure remains unclear. Iron is an essential metal that maintains a homeostasis in the body. The divalent metal transporter 1 (DMT1) transports iron and other divalent metals, such as manganese, and the depletion of iron is known to upregulate DMT1 expression. Accordingly, this study investigated the tissue distribution of manganese in iron-sufficient and iron-deficient rats after welding-fume exposure. The feeding of an iron-deficient diet for 4 wk produced a depletion of body iron, such as decreased iron levels in the serum and tissues, and upregulated the DMT1 expression in the rat duodenum. The iron-sufficient and iron-deficient rats were then exposed to welding fumes generated from manual metal arc stainless steel at a concentration of 63.5 +/- 2.3 mg/m3 for 2 h per day over a 30-day period. Animals were sacrificed on days 1, 15, and 30. The level of body iron in the iron-deficient rats was restored to the control level after the welding-fume exposure. However, the tissue distributions of manganese after the welding-fume exposure showed similar patterns in both the iron-sufficient and iron-deficient groups. The concentration of manganese increased in the lungs and liver on days 15 and 30, and increased in the olfactory bulb on day 30. Slight and heterogeneous increases of manganese were observed in different brain regions. Consequently, these findings suggest that the presence of Fe in the inhaled welding fumes may not have a significant effect on the uptake of Mn into the brain. Thus, the condition of iron deficiency did not seem to have any apparent effect on the transport of Mn into the brain after the inhalation of welding fumes.

  11. A Mossbauer investigation of iron-rich terrestrial hydrothermal vent systems: lessons for Mars exploration.

    PubMed

    Wade, M L; Agresti, D G; Wdowiak, T J; Armendarez, L P; Farmer, J D

    1999-04-25

    Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite

  12. A Mossbauer investigation of iron-rich terrestrial hydrothermal vent systems: lessons for Mars exploration

    NASA Technical Reports Server (NTRS)

    Wade, M. L.; Agresti, D. G.; Wdowiak, T. J.; Armendarez, L. P.; Farmer, J. D.

    1999-01-01

    Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite

  13. A feasible strategy to balance the crystallinity and specific surface area of metal oxide nanocrystals

    NASA Astrophysics Data System (ADS)

    Zhang, Q. P.; Xu, X. N.; Liu, Y. T.; Xu, M.; Deng, S. H.; Chen, Y.; Yuan, H.; Yu, F.; Huang, Y.; Zhao, K.; Xu, S.; Xiong, G.

    2017-04-01

    Practical, efficient synthesis of metal oxide nanocrystals with good crystallinity and high specific surface area by a modified polymer-network gel method is demonstrated, taking ZnO nanocrystals as an example. A novel stepwise heat treatment yields significant improvement in crystal quality. Such nanophase materials can effectively degrade common organic dyes under solar radiation and can perform very well in photo-assisted detection of NO2 gas. Other typical metal oxide nanocrystals with good crystallinity and high specific surface area were also synthesized successfully under similar conditions. This work provides a general strategy for the synthesis of metal oxide nanocrystals, balancing the crystallinity and specific surface area.

  14. Corrosion resistance of cast irons and titanium alloys as reference engineered metal barriers for use in basalt geologic storage: a literature assessment

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

    Charlot, L.A.; Westerman, R.E.

    A survey and assessment of the literature on the corrosion resistance of cast irons and low-alloy titanium are presented. Selected engineering properties of cast iron and titanium are briefly described; however, the corrosion resistance of cast iron and titanium in aqueous solutions or in soils and their use in a basalt repository are emphasized. In evaluating the potential use of cast iron and titanium as structural barrier materials for long-lived nuclear waste packages, it is assumed that titanium has the general corrosion resistance to be used in relatively thin cross sections whereas the cost and availability of cast iron allowsmore » its use even in very thick cross sections. Based on this assumption, the survey showed that: The uniform corrosion of low-alloy titanium in a basalt environment is expected to be extremely low. A linear extrapolation of general corrosion rates with an added corrosion allowance suggests that a 3.2- to 6.4-mm-thick wall may have a life of 1000 yr. Pitting and crevice corrosion are not likely corrosion modes in basalt ground waters. It is also unlikely that stress corrosion cracking (SCC) will occur in the commercially pure (CP) titanium alloy or in palladiumor molybdenum-alloyed titanium materials. Low-alloy cast irons may be used as barrier metals if the environment surrounding the metal keeps the alloy in the passive range. The solubility of the corrosion product and the semipermeable nature of the oxide film allow significant uniform corrosion over long time periods. A linear extrapolation of high-temperature corrosion rates on carbon steels and corrosion rates of cast irons in soils gives an estimated metal penetration of 51 to 64 mm after 1000 yr. A corrosion allowance of 3 to 5 times that suggests that an acceptable cast iron wall may be from 178 to 305 mm thick. Although they cannot be fully assessed, pitting and crevice corrosion should not affect cast iron due to the ground-water chemistry of basalt.« less

  15. Iron homeostasis and its disruption in mouse lung in iron deficiency and overload.

    PubMed

    Giorgi, Gisela; D'Anna, María Cecilia; Roque, Marta Elena

    2015-10-01

    What is the central question of this study? The aim was to explore the role and hitherto unclear mechanisms of action of iron proteins in protecting the lung against the harmful effects of iron accumulation and the ability of pulmonary cells to mobilize iron in iron deficiency. What is the main finding and its importance? We show that pulmonary hepcidin appears not to modify cellular iron mobilization in the lung. We propose pathways for supplying iron to the lung in iron deficiency and for protecting the lung against iron excess in iron overload, mediated by the co-ordinated action of iron proteins, such as divalent metal transporter 1, ZRT-IRE-like-protein 14, transferrin receptor, ferritin, haemochromatosis-associated protein and ferroportin. Iron dyshomeostasis is associated with several forms of chronic lung disease, but its mechanisms of action remain to be elucidated. The aim of the present study was to determine the role of the lung in whole-animal models with iron deficiency and iron overload, studying the divalent metal transporter 1 (DMT1), ZRT-IRE-like protein 14 (ZIP14), transferrin receptor (TfR), haemochromatosis-associated protein (HFE), hepcidin, ferritin and ferroportin (FPN) expression. In each model, adult CF1 mice were divided into the following groups (six mice per group): (i) iron-overload model, iron saccharate i.p. and control group (iron adequate), 0.9% NaCl i.p.; and (ii) iron-deficiency model, induced by repeated bleeding, and control group (sham operated). Proteins were assessed by immunohistochemistry and Western blot. In control mice, DMT1 was localized in the cytoplasm of airway cells, and in iron deficiency and overload it was in the apical membrane. Divalent metal transporter 1 and TfR increased in iron deficiency, without changes in iron overload. ZRT-IRE-like protein 14 decreased in airway cells in iron deficiency and increased in iron overload. In iron deficiency, HFE and FPN were immunolocalized close to the apical membrane

  16. Assessment of heavy metal accumulation in macrophyte, agricultural soil, and crop plants adjacent to discharge zone of sponge iron factory

    NASA Astrophysics Data System (ADS)

    Gupta, S.; Nayek, S.; Saha, R. N.; Satpati, S.

    2008-08-01

    The present study deals with the characterization of effluent released from sponge iron industries and distribution of heavy metals in soil and macrophytes near to effluent discharge channel. Apart from this, accumulation of heavy metals in nearby soil and vegetation system irrigated with effluent-contaminated water is also the subject of this study. Physico-chemical analysis of effluent reveals that the concentration of total suspended solids (TSS), total hardness (TH), iron (Fe2+), and oil and grease are greater than the IS (1981) norms for discharge of water into inland water body. The soil along the sides of the effluent channel also shows higher concentration of heavy metals than the background soil. The enrichment of the heavy metals are in the order of Chromium (Cr) > Iron (Fe) > Manganese (Mn) > Zinc (Zn) > Copper (Cu) > Cadmium (Cd). Macrophytes growing along the sides of the effluent channel also show significant accumulation of heavy metals almost in the same order as accumulated in soil. Higher uptake of heavy metals by these varieties reveals that these species can be used for future phytoremediation. The effluent as well as contaminated water is extensively used for irrigation for growing vegetables like tomato ( Lycopersicon esculatum) in the surrounding areas. Heavy metal accumulation in this agricultural soil are in the sequence of Cr > Fe > Mn > Zn > Cu > Cd. More or less similar type of accumulation pattern are also found in tomato plants except Fe and Zn exceeding Cr and Mn. Transfer Factor of heavy metals from soil to tomato plants (TFS) shows average value of <1, suggesting less uptake of heavy metals from soil. Among the plant parts studied, fruit shows least accumulation. Although tomato plants show some phenotypic changes, the survival of tomato plants as well as least accumulation of metals in fruit reveals their tolerance to heavy metals. Therefore it may be suggested that this plant can be grown successfully in the heavy metal

  17. Silicate Inclusions in IAB Irons: Correlations Between Metal Composition and Inclusion Properties, and Inferences for Their Origin

    NASA Astrophysics Data System (ADS)

    Benedix, G. K.; McCoy, T. J.; Keil, K.

    1995-09-01

    IAB irons are the largest group of iron meteorites, exhibit a large range of siderophile element concentrations in their metal, and commonly contain silicate inclusions with roughly chondritic composition. They are closely related to IIICD irons [1,2] and their inclusions resemble winonaites [3]. It has been suggested that IAB's and IIICD's formed in individual impact melt pools [4,2] on a common parent body. However, it has also been suggested that fractional crystallization [5,6] of a S-saturated core could produce the observed siderophile element trends. Metal composition is correlated with silicate inclusion mineralogy in IIICD's [1], indicating reactions between solid silicates and the metallic magma in a core. These trends observed in IIICD's differ from those in IAB's, suggesting different parent bodies. A bi-modal grouping, based primarily on mineralogy and mineral abundances, was suggested for IAB inclusions [7]. However, recent recoveries of several new silicate-bearing IAB's, along with the emergence of new ideas on their origins, prompted a comprehensive study to document more fully the range of inclusions within IAB irons, to examine possible correlations between the compositions of the metallic host and the silicate inclusions, and to elucidate the origin of IAB irons. We are studying troilite-graphite-silicate inclusions in 24 IAB irons with Ni concentrations ranging from 6.6-25.0%. These include Odessa and Copiapo types [7], newly recovered meteorites (e.g., Lueders [8]) and meteorites with extreme Ni contents (e.g., Jenny's Creek, 6.8%; San Cristobal, 25.0% [9]). The inclusions exhibit a range of textures from recrystallized to partial melts (e.g., Caddo County [10]). Rigorous classification [7] is hampered by heterogeneities between group meteorites, between different samples of distinct meteorites, and within individual inclusions. While intergroup heterogeneities make comparisons between the suite of IAB's somewhat difficult, some general trends

  18. Mammalian iron metabolism and its control by iron regulatory proteins☆

    PubMed Central

    Anderson, Cole P.; Shen, Lacy; Eisenstein, Richard S.; Leibold, Elizabeth A.

    2013-01-01

    Cellular iron homeostasis is maintained by iron regulatory proteins 1 and 2 (IRP1 and IRP2). IRPs bind to iron-responsive elements (IREs) located in the untranslated regions of mRNAs encoding protein involved in iron uptake, storage, utilization and export. Over the past decade, significant progress has been made in understanding how IRPs are regulated by iron-dependent and iron-independent mechanisms and the pathological consequences of IRP2 deficiency in mice. The identification of novel IREs involved in diverse cellular pathways has revealed that the IRP–IRE network extends to processes other than iron homeostasis. A mechanistic understanding of IRP regulation will likely yield important insights into the basis of disorders of iron metabolism. This article is part of a Special Issue entitled: Cell Biology of Metals. PMID:22610083

  19. Chemical classification of iron meteorites. XI. Multi-element studies of 38 new irons and the high abundance of ungrouped irons from Antarctica

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

    Wasson, J.T.; Ouyang, Xinwei; Wang, Jianmin

    1989-03-01

    The authors report concentrations of 14 elements in the metal of 38 iron meteorites and a pallasite. The meteorites are classified based on these data and on structural observations. Three samples are paired with previously classified irons; thus, these additional 35 irons raise the number of well-classified, independent iron meteorites to 598. One Yamato iron contains 342 mg/g Ni, the second highest Ni content in an IAB iron after Oktibbeha County. Two small irons from Western Australia appear to be metal nodules from mesosiderites. Several of the new irons are from Antarctica. Of 24 independent irons from Antarctica, 8 aremore » ungrouped. The fraction, 0.333, is much higher than the fraction 0.161 among all 598 classified irons. Statistical tests show that it is highly improbably ({approximately}2.9% probability) that the Antarctic population is a random sample of the larger population. The difference is probably related to the fact that the median mass of Antarctic irons is about two orders of magnitude smaller than that of non-Antarctic irons. It is doubtful that the difference results from fragmentation patterns yielding different size distributions favoring smaller masses among ungrouped irons. More likely is the possibility that smaller meteoroids tend to sample a larger number of asteroidal source regions, perhaps because small meteoroids tend to have higher ejection velocities or because small meteoroids have random-walked a greater increment of orbital semimajor axis away from that of the parent body.« less

  20. Moessbauer spectra of olivine-rich achondrites - Evidence for preterrestrial redox reactions

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Martinez, S. L.

    1991-01-01

    Moessbauer spectral measurements at 4.2 K were made on several ureilites and the two shergottites found in Antarctica, as well as two ureilite falls, three SNC meteorite falls, and two finds in order to distinguish products of preterrestrial redox reactions from phases formed during oxidative weathering on the earth. The spectra indicated that several ureilites contain major proportions of metallic iron, much of which resulted from preterrestrial carbon-induced reduction of ferrous iron in the outermost 10-100 microns of olivine grains in contact with carbonaceous material in the ureilites. The cryptocrystalline nature of these Fe inclusions in olivine renders the metal extremely vulnerable to aerial oxidation, even in ureilites collected as falls. It is inferred that the nanophase ferric oxides or oxyhydroxides identified in Brachina and Lafayette were produced by terrestrial weather of olivines before the meteorites were found. The absence of goethite in two olivine-bearing Antarctic shergottites suggests that the 2 percent ferric iron determined in their Moessbauer spectra also originated from oxidation on Mars.

  1. Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) for dissolved metal ion removal.

    PubMed

    Su, Yiming; Adeleye, Adeyemi S; Keller, Arturo A; Huang, Yuxiong; Dai, Chaomeng; Zhou, Xuefei; Zhang, Yalei

    2015-05-01

    Sulfide-modified nanoscale zerovalent iron (S-nZVI) is attracting a lot of attention due to its ease of production and high reactivity with organic pollutants. However, its structure is still poorly understood and its potential application in heavy metal remediation has not been explored. Herein, the structure of S-nZVI and its cadmium (Cd) removal performance under different aqueous conditions were carefully investigated. Transmission electron microscopy (TEM) with an energy-dispersive X-ray spectroscopy (EDS) analysis suggested that sulfur was incorporated into the zerovalent iron core. Scanning electron microscopy (SEM) with EDS analysis demonstrated that sulfur was also homogeneously distributed within the nanoparticles. When the concentration of Na2S2O4 was increased during synthesis, a flake-like structure (FeSx) increased significantly. S-nZVI had an optimal Cd removal capacity of 85 mg/g, which was >100% higher than for pristine nZVI. Even at pH 5, over 95% removal efficiency was observed, indicating sulfide compounds played a crucial role in metal ion removal and particle chemical stability. Oxygen impaired the structure of S-nZVI but enhanced Cd removal capacity to about 120 mg/g. Particle aging had no negative effect on removal capacity of S-nZVI, and Cd-containing mixtures remained stable in a two months experiment. S-nZVI can efficiently sequester dissolved metal ions from different contaminated water matrices. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Reactions of metal ions at surfaces of hydrous iron oxide

    USGS Publications Warehouse

    Hem, J.D.

    1977-01-01

    Cu, Ag and Cr concentrations in natural water may be lowered by mild chemical reduction involving ferric hydroxide-ferrous ion redox processes. V and Mo solubilities may be controlled by precipitation of ferrous vanadate or molybdate. Concentrations as low as 10-8.00 or 10-9.00 M are readily attainable for all these metals in oxygen-depleted systems that are relatively rich in Fe. Deposition of manganese oxides such as Mn3O4 can be catalyzed in oxygenated water by coupling to ferrous-ferric redox reactions. Once formed, these oxides may disproportionate, giving Mn4+ oxides. This reaction produces strongly oxidizing conditions at manganese oxide surfaces. The solubility of As is significantly influenced by ferric iron only at low pH. Spinel structures such as chromite or ferrites of Cu, Ni, and Zn, are very stable and if locally developed on ferric hydroxide surfaces could bring about solubilities much below 10-9.00 M for divalent metals near neutral pH. Solubilities calculated from thermodynamic data are shown graphically and compared with observed concentrations in some natural systems. ?? 1977.

  3. Iron Isotope Constraints on Planetesimal Core Formation

    NASA Astrophysics Data System (ADS)

    Jordan, M.; Young, E. D.

    2016-12-01

    The prevalence of iron in both planetary cores and silicate mantles renders the element a valuable tool for understanding core formation. Magmatic iron meteorites exhibit an enrichment in 57Fe/54Fe relative to chondrites and HED meteorites. This is suggestive of heavy Fe partitioning into the cores of differentiated bodies. If iron isotope fractionation accompanies core formation, we can elucidate details about the history of accretion for planetary bodies as well as their compositions and relative core sizes. The equilibrium 57Fe/54Fe between metal and silicate is necessary for understanding observed iron isotope compositions and placing constraints on core formation. We measure this fractionation in two Aubrite meteorites, Norton County and Mount Egerton, which have known temperatures of equilibration and equilibrated silicon isotopes. Iron was purified using ion-exchange chromatography. Data were collected on a ThermoFinnigan NeptuneTM multiple-collector inductively coupled plasma-source mass spectrometer (MC-ICP-MS) run in wet plasma mode. The measured fractionation Δ57Femetal-silicate is 0.08‰ ± 0.039 (2 SE) for Norton County and 0.09‰ ± 0.019 (2 SE) for Mount Egerton, indicating that the heavy isotopes of Fe partition into the metallic phase. These rocks are in isotopic equilibrium at a temperature of 1130 K and 1200 K ± 80 K, respectively. The concentration of the heavy isotopes of iron in the metallic phase is consistent with recent experimental studies. Using our measured metal-silicate Fe isotope fractionation and the resulting temperature calibration, while taking into account impurities in the metallic phase and temperatures of equilibration, determine that core formation could explain the observed difference between magmatic iron meteorites and chondrites if parent bodies have small cores. In order to verify that Rayleigh distillation during fractional crystallization was not a cause of iron isotope fractionation in iron meteorites, we measured

  4. Production and early preservation of lipid biomarkers in iron hot springs.

    PubMed

    Parenteau, Mary N; Jahnke, Linda L; Farmer, Jack D; Cady, Sherry L

    2014-06-01

    The bicarbonate-buffered anoxic vent waters at Chocolate Pots hot springs in Yellowstone National Park are 51-54°C, pH 5.5-6.0, and are very high in dissolved Fe(II) at 5.8-5.9 mg/L. The aqueous Fe(II) is oxidized by a combination of biotic and abiotic mechanisms and precipitated as primary siliceous nanophase iron oxyhydroxides (ferrihydrite). Four distinct prokaryotic photosynthetic microbial mat types grow on top of these iron deposits. Lipids were used to characterize the community composition of the microbial mats, link source organisms to geologically significant biomarkers, and investigate how iron mineralization degrades the lipid signature of the community. The phospholipid and glycolipid fatty acid profiles of the highest-temperature mats indicate that they are dominated by cyanobacteria and green nonsulfur filamentous anoxygenic phototrophs (FAPs). Diagnostic lipid biomarkers of the cyanobacteria include midchain branched mono- and dimethylalkanes and, most notably, 2-methylbacteriohopanepolyol. Diagnostic lipid biomarkers of the FAPs (Chloroflexus and Roseiflexus spp.) include wax esters and a long-chain tri-unsaturated alkene. Surprisingly, the lipid biomarkers resisted the earliest stages of microbial degradation and diagenesis to survive in the iron oxides beneath the mats. Understanding the potential of particular sedimentary environments to capture and preserve fossil biosignatures is of vital importance in the selection of the best landing sites for future astrobiological missions to Mars. This study explores the nature of organic degradation processes in moderately thermal Fe(II)-rich groundwater springs--environmental conditions that have been previously identified as highly relevant for Mars exploration.

  5. Metal Tolerance Protein 8 Mediates Manganese Homeostasis and Iron Reallocation during Seed Development and Germination.

    PubMed

    Eroglu, Seckin; Giehl, Ricardo F H; Meier, Bastian; Takahashi, Michiko; Terada, Yasuko; Ignatyev, Konstantin; Andresen, Elisa; Küpper, Hendrik; Peiter, Edgar; von Wirén, Nicolaus

    2017-07-01

    Metal accumulation in seeds is a prerequisite for germination and establishment of plants but also for micronutrient delivery to humans. To investigate metal transport processes and their interactions in seeds, we focused on METAL TOLERANCE PROTEIN8 (MTP8), a tonoplast transporter of the manganese (Mn) subclade of cation diffusion facilitators, which in Arabidopsis ( Arabidopsis thaliana ) is expressed in embryos of seeds. The x-ray fluorescence imaging showed that expression of MTP8 was responsible for Mn localization in subepidermal cells on the abaxial side of the cotyledons and in cortical cells of the hypocotyl. Accordingly, under low Mn availability, MTP8 increased seed stores of Mn, required for efficient seed germination. In mutant embryos lacking expression of VACUOLAR IRON TRANSPORTER1 ( VIT1 ), MTP8 built up iron (Fe) hotspots in MTP8 -expressing cells types, suggesting that MTP8 transports Fe in addition to Mn. In mtp8 vit1 double mutant seeds, Mn and Fe were distributed in all cell types of the embryo. An Fe transport function of MTP8 was confirmed by its ability to complement Fe hypersensitivity of a yeast mutant defective in vacuolar Fe transport. Imbibing mtp8-1 mutant seeds in the presence of Mn or subjecting seeds to wet-dry cycles showed that MTP8 conferred Mn tolerance. During germination, MTP8 promoted reallocation of Fe from the vasculature. These results indicate that cell type-specific accumulation of Mn and Fe in seeds depends on MTP8 and that this transporter plays an important role in the generation of seed metal stores as well as for metal homeostasis and germination efficiency under challenging environmental conditions. © 2017 American Society of Plant Biologists. All Rights Reserved.

  6. Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

    PubMed Central

    2016-01-01

    The current status of homogeneous iron catalysis in organic chemistry is contemplated, as are the reasons why this particular research area only recently starts challenging the enduring dominance of the late and mostly noble metals over the field. Centered in the middle of the d-block and able to support formal oxidation states ranging from −II to +VI, iron catalysts hold the promise of being able to encompass organic synthesis at large. They are expected to serve reductive as well as oxidative regimes, can emulate “noble tasks”, but are also able to adopt “early” transition metal character. Since a comprehensive coverage of this multidimensional agenda is beyond the scope of an Outlook anyway, emphasis is laid in this article on the analysis of the factors that perhaps allow one to control the multifarious chemical nature of this earth-abundant metal. The challenges are significant, not least at the analytical frontier; their mastery mandates a mindset that differs from the routines that most organic chemists interested in (noble metal) catalysis tend to cultivate. This aspect notwithstanding, it is safe to predict that homogeneous iron catalysis bears the chance to enable a responsible paradigm for chemical synthesis and a sustained catalyst economy, while potentially providing substantial economic advantages. This promise will spur the systematic and in-depth investigations that it takes to upgrade this research area to strategy-level status in organic chemistry and beyond. PMID:27981231

  7. Grains of Nonferrous and Noble Metals in Iron-Manganese Formations and Igneous Rocks of Submarine Elevations of the Sea of Japan

    NASA Astrophysics Data System (ADS)

    Kolesnik, O. N.; Astakhova, N. V.

    2018-01-01

    Iron-manganese formations and igneous rocks of submarine elevations in the Sea of Japan contain overlapping mineral phases (grains) with quite identical morphology, localization, and chemical composition. Most of the grains conform to oxides, intermetallic compounds, native elements, sulfides, and sulfates in terms of the set of nonferrous, noble, and certain other metals (Cu, Zn, Sn, Pb, Ni, Mo, Ag, Pd, and Pt). The main conclusion that postvolcanic hydrothermal fluids are the key sources of metals is based upon a comparison of the data of electron microprobe analysis of iron-manganese formations and igneous rocks dredged at the same submarine elevations in the Sea of Japan.

  8. Mean-Square Amplitudes of Vibration and Anisotropic Motion of Metal Atoms in Iron Organometallics

    NASA Astrophysics Data System (ADS)

    Herber, Rolfe H.; Nowik, Israel

    2002-12-01

    Mössbauer recoil-free fraction (f) data for ferrocene [(η5-(C5H5)2Fe] over the temperature range 90≤T≤370 K have been used to calculate the mean-square-amplitude-of-vibration (msav) of the iron atom, and these data have been compared to the thermal factors (U ij ) extracted from X-ray diffraction data reported in the literature. The agreement between these two independent data sets is taken as a validation of the interpretation of the Mössbauer data in terms of the mean-square-amplitude-of-vibration of the metal atom in iron organometallic solids. The contribution of three low-frequency IR active modes of ferrocene (ω11, ω21, and ω22) to the f(T) parameter is discussed in detail.

  9. Ferritin iron minerals are chelator targets, antioxidants, and coated, dietary iron.

    PubMed

    Theil, Elizabeth C

    2010-08-01

    Cellular ferritin is central for iron balance during transfusions therapies; serum ferritin is a small fraction of body ferritin, albeit a convenient reporter. Iron overload induces extra ferritin protein synthesis but the protein is overfilled with the extra iron that damages ferritin, with conversion to toxic hemosiderin. Three new approaches that manipulate ferritin to address excess iron, hemosiderin, and associated oxidative damage in Cooley's Anemia and other iron overload conditions are faster removal of ferritin iron with chelators guided to ferritin gated pores by peptides; more ferritin protein synthesis using ferritin mRNA activators, by metal complexes that target mRNA 3D structures; and determining if endocytotic absorption of iron from legumes, which is mostly ferritin, is regulated during iron overload to prevent excess iron entry while providing protein. More of a focus on ferritin features, including protein cage structure, iron mineral, regulatable mRNA, and specific gut absorption properties, will achieve the three novel experimental goals for managing iron homeostasis with transfusion therapies.

  10. Integrated System of Thermal/Dimensional Analysis for Quality Control of Metallic Melt and Ductile Iron Casting Solidification

    NASA Astrophysics Data System (ADS)

    Stan, Stelian; Chisamera, Mihai; Riposan, Iulian; Neacsu, Loredana; Cojocaru, Ana Maria; Stan, Iuliana

    2018-03-01

    The main objective of the present work is to introduce a specific experimental instrument and technique for simultaneously evaluating cooling curves and expansion or contraction of cast metals during solidification. Contraction/expansion analysis illustrates the solidification parameters progression, according to the molten cast iron characteristics, which are dependent on the melting procedure and applied metallurgical treatments, mold media rigidity and thermal behavior [heat transfer parameters]. The first part of the paper summarizes the performance of this two-mold device. Its function is illustrated by representative shrinkage tendency results in ductile cast iron as affected by mold rigidity (green sand and furan resin sand molds) and inoculant type (FeSi-based alloys), published in part previously. The second part of the paper illustrates an application of this equipment adapted for commercial foundry use. It conducts thermal analysis and volume change measurements in a single ceramic cup so that mold media as well as solidification conditions are constants, with cast iron quality as the variable. Experiments compared gray and ductile cast iron solidification patterns. Gray iron castings are characterized by higher undercooling at the beginning and at the end of solidification and lower graphitic expansion. Typically, ductile cast iron exhibits higher graphitic, initial expansion, conducive for shrinkage formation in soft molds.

  11. IRON INCREASES EXPRESSION OF IRON-EXPORT PROTEIN MTP1 IN LUNG CELLS

    EPA Science Inventory

    Accumulation of reactive iron in acute and chronic lung disease suggests that iron-driven free radical formation could contribute to tissue injury. Safe transport and sequestration of this metal is likely to be of importance in lung defense. We provide evidence for the expression...

  12. Iron aluminide alloy coatings and joints, and methods of forming

    DOEpatents

    Wright, Richard N.; Wright, Julie K.; Moore, Glenn A.

    1994-01-01

    A method of joining two bodies together, at least one of the bodies being predominantly composed of metal, the two bodies each having a respective joint surface for joining with the joint surface of the other body, the two bodies having a respective melting point, includes the following steps: a) providing aluminum metal and iron metal on at least one of the joint surfaces of the two bodies; b) after providing the aluminum metal and iron metal on the one joint surface, positioning the joint surfaces of the two bodies in juxtaposition against one another with the aluminum and iron positioned therebetween; c) heating the aluminum and iron on the juxtaposed bodies to a temperature from greater than or equal to 600.degree. C. to less than the melting point of the lower melting point body; d) applying pressure on the juxtaposed surfaces; and e) maintaining the pressure and the temperature for a time period effective to form the aluminum and iron into an iron aluminide alloy joint which bonds the juxtaposed surfaces and correspondingly the two bodies together. The method can also effectively be used to coat a body with an iron aluminide coating.

  13. Iron aluminide alloy coatings and joints, and methods of forming

    DOEpatents

    Wright, R.N.; Wright, J.K.; Moore, G.A.

    1994-09-27

    Disclosed is a method of joining two bodies together, at least one of the bodies being predominantly composed of metal, the two bodies each having a respective joint surface for joining with the joint surface of the other body, the two bodies having a respective melting point, includes the following steps: (a) providing aluminum metal and iron metal on at least one of the joint surfaces of the two bodies; (b) after providing the aluminum metal and iron metal on the one joint surface, positioning the joint surfaces of the two bodies in juxtaposition against one another with the aluminum and iron positioned therebetween; (c) heating the aluminum and iron on the juxtaposed bodies to a temperature from greater than or equal to 600 C to less than the melting point of the lower melting point body; (d) applying pressure on the juxtaposed surfaces; and (e) maintaining the pressure and the temperature for a time period effective to form the aluminum and iron into an iron aluminide alloy joint which bonds the juxtaposed surfaces and correspondingly the two bodies together. The method can also effectively be used to coat a body with an iron aluminide coating.

  14. Metallic corrosion processes reactivation sustained by iron-reducing bacteria: Implication on long-term stability of protective layers

    NASA Astrophysics Data System (ADS)

    Esnault, L.; Jullien, M.; Mustin, C.; Bildstein, O.; Libert, M.

    In deep geological environments foreseen for the disposal of radioactive waste, metallic containers will undergo anaerobic corrosion. In this context, the formation of corrosion products such as magnetite may reduce the rate of corrosion processes through the formation of a protective layer. This study aims at determining the direct impact of iron-reducing bacteria (IRB) activity on the stability of corrosion protective layers. Batch experiments investigating iron corrosion processes including the formation of secondary magnetite and its subsequent alteration in the presence of IRB show the bacteria ability to use structural Fe(III) for respiration which leads to the sustainment of a high corrosion rate. With the bio-reduction of corrosion products such as magnetite, and H 2 as electron donor, IRB promote the reactivation of corrosion processes in corrosive environments by altering the protective layer. This phenomenon could have a major impact on the long-term stability of metallic compounds involved in multi-barrier system for high-level radioactive waste containment.

  15. Air pollution particles and iron homeostasis | Science ...

    EPA Pesticide Factsheets

    Background: The mechanism underlying biological effects of particles deposited in the lung has not been defined. Major Conclusions: A disruption in iron homeostasis follows exposure of cells to all particulate matter including air pollution particles. Following endocytosis, functional groups at the surface of retained particle complex iron available in the cell. In response to a reduction in concentrations of requisite iron, a functional deficiency can result intracellularly. Superoxide production by the cell exposed to a particle increases ferrireduction which facilitates import of iron with the objective being the reversal of the metal deficiency. Failure to resolve the functional iron deficiency following cell exposure to particles activates kinases and transcription factors resulting in a release of inflammatory mediators and inflammation. Tissue injury is the end product of this disruption in iron homeostasis initiated by the particle exposure. Elevation of available iron to the cell precludes deficiency of the metal and either diminishes or eliminates biological effects.General Significance: Recognition of the pathway for biological effects after particle exposure to involve a functional deficiency of iron suggests novel therapies such as metal supplementation (e.g. inhaled and oral). In addition, the demonstration of a shared mechanism of biological effects allows understanding the common clinical, physiological, and pathological presentation fol

  16. Recovery of Iron from Chromium Vanadium-Bearing Titanomagnetite Concentrate by Direct Reduction

    NASA Astrophysics Data System (ADS)

    Wang, Mingyu; Zhou, Shengfan; Wang, Xuewen; Chen, Bianfang; Yang, Haoxiang; Wang, Saikui; Luo, Pengfei

    2016-10-01

    The recovery of iron from chromium vanadium-bearing titanomagnetite concentrate was investigated by direct reduction, followed by magnetic separation. The results indicated that the metallization rate of iron can reach 98.9% at a temperature of 1200°C for a reduction duration of 60 min with the addition of 16% graphite powder and 0.5% sodium oxalate. Although the addition of borax, sodium carbonate and sodium oxalate to the chromium vanadium-bearing titanomagnetite concentrate can all improve the metallization rate of iron, the effect of sodium oxalate was the best. Sodium oxalate not only increases the metallization rate of iron but also promotes the growth of metallic iron. After magnetic separating, the recovery of iron was 92.8% and the iron content of magnetic concentrate was 88.4%.

  17. Monomeric Yeast Frataxin is an Iron-Binding Protein

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

    Cook,J.; Bencze, K.; Jankovic, A.

    Friedreich's ataxia, an autosomal cardio- and neurodegenerative disorder that affects 1 in 50 000 humans, is caused by decreased levels of the protein frataxin. Although frataxin is nuclear-encoded, it is targeted to the mitochondrial matrix and necessary for proper regulation of cellular iron homeostasis. Frataxin is required for the cellular production of both heme and iron-sulfur (Fe-S) clusters. Monomeric frataxin binds with high affinity to ferrochelatase, the enzyme involved in iron insertion into porphyrin during heme production. Monomeric frataxin also binds to Isu, the scaffold protein required for assembly of Fe-S cluster intermediates. These processes (heme and Fe-S cluster assembly)more » share requirements for iron, suggesting that monomeric frataxin might function as the common iron donor. To provide a molecular basis to better understand frataxin's function, we have characterized the binding properties and metal-site structure of ferrous iron bound to monomeric yeast frataxin. Yeast frataxin is stable as an iron-loaded monomer, and the protein can bind two ferrous iron atoms with micromolar binding affinity. Frataxin amino acids affected by the presence of iron are localized within conserved acidic patches located on the surfaces of both helix-1 and strand-1. Under anaerobic conditions, bound metal is stable in the high-spin ferrous state. The metal-ligand coordination geometry of both metal-binding sites is consistent with a six-coordinate iron-(oxygen/nitrogen) based ligand geometry, surely constructed in part from carboxylate and possibly imidazole side chains coming from residues within these conserved acidic patches on the protein. On the basis of our results, we have developed a model for how we believe yeast frataxin interacts with iron.« less

  18. Monomeric Yeast Frataxin is an Iron Binding Protein†

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

    Cook, J.; Bencze, K; Jankovic, A

    Friedreich's ataxia, an autosomal cardio- and neurodegenerative disorder that affects 1 in 50000 humans, is caused by decreased levels of the protein frataxin. Although frataxin is nuclear-encoded, it is targeted to the mitochondrial matrix and necessary for proper regulation of cellular iron homeostasis. Frataxin is required for the cellular production of both heme and iron-sulfur (Fe-S) clusters. Monomeric frataxin binds with high affinity to ferrochelatase, the enzyme involved in iron insertion into porphyrin during heme production. Monomeric frataxin also binds to Isu, the scaffold protein required for assembly of Fe-S cluster intermediates. These processes (heme and Fe-S cluster assembly) sharemore » requirements for iron, suggesting that monomeric frataxin might function as the common iron donor. To provide a molecular basis to better understand frataxin's function, we have characterized the binding properties and metal-site structure of ferrous iron bound to monomeric yeast frataxin. Yeast frataxin is stable as an iron-loaded monomer, and the protein can bind two ferrous iron atoms with micromolar binding affinity. Frataxin amino acids affected by the presence of iron are localized within conserved acidic patches located on the surfaces of both helix-1 and strand-1. Under anaerobic conditions, bound metal is stable in the high-spin ferrous state. The metal-ligand coordination geometry of both metal-binding sites is consistent with a six-coordinate iron-(oxygen/nitrogen) based ligand geometry, surely constructed in part from carboxylate and possibly imidazole side chains coming from residues within these conserved acidic patches on the protein. On the basis of our results, we have developed a model for how we believe yeast frataxin interacts with iron.« less

  19. Disruption of iron homeostasis and lung disease.

    PubMed

    Ghio, Andrew J

    2009-07-01

    As a result of a direct exchange with the external environment, the lungs are exposed to both iron and agents with a capacity to disrupt the homeostasis of this metal (e.g. particles). An increased availability of catalytically reactive iron can result from these exposures and, by generating an oxidative stress, this metal can contribute to tissue injury. By importing this Fe(3+) into cells for storage in a chemically less reactive form, the lower respiratory tract demonstrates an ability to mitigate both the oxidative stress presented by iron and its potential for tissue injury. This means that detoxification is accomplished by chemical reduction to Fe(2+) (e.g. by duodenal cytochrome b and other ferrireductases), iron import (e.g. by divalent metal transporter 1 and other transporters), and storage in ferritin. The metal can subsequently be exported from the cell (e.g. by ferroportin 1) in a less reactive state relative to that initially imported. Iron is then transported out of the lung via the mucociliary pathway or blood and lymphatic pathways to the reticuloendothelial system for long term storage. This coordinated handling of iron in the lung appears to be disrupted in several acute diseases on the lung including infections, acute respiratory distress syndrome, transfusion-related acute lung injury, and ischemia-reperfusion. Exposures to bleomycin, dusts and fibers, and paraquat similarly alter iron homeostasis in the lung to affect an oxidative stress. Finally, iron homeostasis is disrupted in numerous chronic lung diseases including pulmonary alveolar proteinosis, transplantation, cigarette smoking, and cystic fibrosis.

  20. ISOLATION AND PROPERTIES OF AN IRON-OXIDIZING THIOBACILLUS

    PubMed Central

    Razzell, W. E.; Trussell, P. C.

    1963-01-01

    Razzell, W. E. (British Columbia Research Council, Vancouver, Canada) and P. C. Trussell. Isolation and properties of an iron-oxidizing Thiobacillus. J. Bacteriol. 85:595–603. 1963. — An organism isolated from acidic copper-leaching waters has been shown to oxidize ferrous ions, sulfur, and metallic sulfides but exhibit peculiar responses to thiosulfate. The name Thiobacillus ferrooxidans has been used to describe it. A pH of 2.5 is optimal for growth on iron, sulfur, and metallic sulfides, but cells free from iron can be obtained from growth at pH 1.6, and sulfur cultures adjusted to pH 5.5 readily attain a pH of 1.8. A stationary cultivation procedure appears superior to percolation techniques for studying the oxidation of finely divided metallic sulfides. Concentrations of soluble copper in excess of 1 g per liter were obtained from chalcopyrite in less than 4 weeks. Chalcocite oxidation proceeded in the absence of iron. Sodium chloride inhibits iron oxidation without preventing oxidation of metallic sulfides by the organism. PMID:14042937

  1. Iron and aluminium oxides containing industrial wastes as adsorbents of heavy metals: Application possibilities and limitations.

    PubMed

    Jacukowicz-Sobala, Irena; Ociński, Daniel; Kociołek-Balawejder, Elżbieta

    2015-07-01

    Industrial wastes with a high iron or aluminium oxide content are produced in huge quantities as by-products of water treatment (water treatment residuals), bauxite processing (red mud) and hard and brown coal burning in power plants (fly ash). Although they vary in their composition, the wastes have one thing in common--a high content of amorphous iron and/or aluminium oxides with a large specific surface area, whereby this group of wastes shows very good adsorbability towards heavy metals, arsenates, selenates, etc. But their physical form makes their utilisation quite difficult, since it is not easy to separate the spent sorbent from the solution and high bed hydraulic resistances occur in dynamic regime processes. Nevertheless, because of the potential benefits of utilising the wastes in industrial effluent treatment, this issue attracts much attention today. This study describes in detail the waste generation processes, the chemical structure of the wastes, their physicochemical properties, and the mechanisms of fixing heavy metals and semimetals on the surface of iron and aluminium oxides. Typical compositions of wastes generated in selected industrial plants are given. A detailed survey of the literature on the adsorption applications of the wastes, including methods of their thermal and chemical activation, as well as regeneration of the spent sorbents, is presented. The existing and potential ways of modifying the physical form of the discussed group of wastes, making it possible to overcome the basic limitation on their practical use, are discussed. © The Author(s) 2015.

  2. Metal-metal bond lengths in complexes of transition metals.

    PubMed

    Pauling, L

    1976-12-01

    In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths.

  3. Transition metals at the host–pathogen interface: How Neisseria exploit human metalloproteins for acquiring iron and zinc

    PubMed Central

    Neumann, Wilma; Hadley, Rose C.; Nolan, Elizabeth M.

    2017-01-01

    Transition metals are essential nutrients for all organisms and important players in the host-microbe interaction. During bacterial infection, a tug-of-war between the host and microbe for nutrient metals occurs: the host innate immune system responds to the pathogen by reducing metal availability and the pathogen tries to outmaneuver this response. The outcome of this competition, which involves metal-sequestering host-defense proteins and microbial metal acquisition machinery, is an important variable for whether infection occurs. One strategy bacterial pathogens employ to overcome metal restriction involves hijacking abundant host metalloproteins. The obligate human pathogens Neisseria spp. express TonB-dependent transport systems that capture human metalloproteins, extract the bound metal ions, and deliver these nutrients into the bacterial cell. This Essay highlights structural and mechanistic investigations that provide insights into how Neisseria acquire iron from the Fe(III)-transport protein transferrin, the Fe(III)-chelating host-defense protein lactoferrin, and the oxygen-transport protein hemoglobin, and obtain zinc from the metal-sequestering antimicrobial protein calprotectin. PMID:28487398

  4. Redox inactive metal ion triggered N-dealkylation by an iron catalyst with dioxygen activation: a lesson from lipoxygenases.

    PubMed

    Zhang, Jisheng; Wang, Yujuan; Luo, Nengchao; Chen, Zhuqi; Wu, Kangbing; Yin, Guochuan

    2015-06-07

    Utilization of dioxygen as the terminal oxidant at ambient temperature is always a challenge in redox chemistry, because it is hard to oxidize a stable redox metal ion like iron(III) to its high oxidation state to initialize the catalytic cycle. Inspired by the dioxygenation and co-oxidase activity of lipoxygenases, herein, we introduce an alternative protocol to activate the sluggish iron(III) species with non-redox metal ions, which can promote its oxidizing power to facilitate substrate oxidation with dioxygen, thus initializing the catalytic cycle. In oxidations of N,N-dimethylaniline and its analogues, adding Zn(OTf)2 to the [Fe(TPA)Cl2]Cl catalyst can trigger the amine oxidation with dioxygen, whereas [Fe(TPA)Cl2]Cl alone is very sluggish. In stoichiometric oxidations, it has also been confirmed that the presence of Zn(OTf)2 can apparently improve the electron transfer capability of the [Fe(TPA)Cl2]Cl complex. Experiments using different types of substrates as trapping reagents disclosed that the iron(IV) species does not occur in the catalytic cycle, suggesting that oxidation of amines is initialized by electron transfer rather than hydrogen abstraction. Combined experiments from UV-Vis, high resolution mass spectrometry, electrochemistry, EPR and oxidation kinetics support that the improved electron transfer ability of iron(III) species originates from its interaction with added Lewis acids like Zn(2+) through a plausible chloride or OTf(-) bridge, which has promoted the redox potential of iron(III) species. The amine oxidation mechanism was also discussed based on the available data, which resembles the co-oxidase activity of lipoxygenases in oxidative dealkylation of xenobiotic metabolisms where an external electron donor is not essential for dioxygen activation.

  5. Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate

    PubMed Central

    Root, Robert A.; Hayes, Sarah M.; Hammond, Corin M.; Maier, Raina M.; Chorover, Jon

    2015-01-01

    Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3 to 2.3). Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mM kg-1 (3080, 2200, and 2570 mg kg-1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2 fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25-54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe

  6. Nanophase Iron Globules in Lunar Soil

    NASA Technical Reports Server (NTRS)

    James, C. L.; Letsinger, S. L.; Wentworth, S. J.; McKay, D. S.; Basu, A.

    2003-01-01

    Micrometeoritic impacts on lunar soils produce melt and vapor. A patina of condensed vapor is deposited on lunar grains, the melt forms agglutinitic glass. In lunar soils, agglutinitic glass and rinds of grains host submicron-sized globules of pure Fe0 (Fe-rich globules larger than 1 micron usually contain other elements such as Ni, P, and S). Observation and measurement of such small size requires either back scattered electron (BSE) imaging with a high-resolution SEM or transmitted electron imaging with a TEM. The two techniques impose different limitations on the size-range of measurements. Resolution of BSE imaging of polished thin sections or grain mounts of lunar soils is at best around 4-5nm (JEOL 6340F field-emission (FE)-SEM at JSC). Therefore, Fe0 globules below 10nm in cross-sectional diameter are not truly measured. The upper limit of a millimeter or so is not a hindrance. In fact, it is an advantage because whole grains can be observed and mapped at varying magnifications. Angstrom-scale resolution of TEM images is more than sufficient to observe and measure the smallest of Fe0 globules that are about 1nm in cross-section. Microtoming edges of lunar grains; however, puts an upper size limitation of 50nm, at best, on the wafer, which more or less limits measuring Fe0 globules up to 30nm or so. Clearly, SEM and TEM techniques complement each other in obtaining the complete range of size distribution of Fe0 globules in lunar soils. Below we describe, in brief, our method of determining the size distribution of Fe0 globules in agglutinitic glass using BSE-SEM imaging and size measurement. Although our work is incomplete, we also include a table of results obtained so far, which understandably would be refined as we collect more data.

  7. Production and Early Preservation of Lipid Biomarkers in Iron Hot Springs

    PubMed Central

    Jahnke, Linda L.; Farmer, Jack D.; Cady, Sherry L.

    2014-01-01

    Abstract The bicarbonate-buffered anoxic vent waters at Chocolate Pots hot springs in Yellowstone National Park are 51–54°C, pH 5.5–6.0, and are very high in dissolved Fe(II) at 5.8–5.9 mg/L. The aqueous Fe(II) is oxidized by a combination of biotic and abiotic mechanisms and precipitated as primary siliceous nanophase iron oxyhydroxides (ferrihydrite). Four distinct prokaryotic photosynthetic microbial mat types grow on top of these iron deposits. Lipids were used to characterize the community composition of the microbial mats, link source organisms to geologically significant biomarkers, and investigate how iron mineralization degrades the lipid signature of the community. The phospholipid and glycolipid fatty acid profiles of the highest-temperature mats indicate that they are dominated by cyanobacteria and green nonsulfur filamentous anoxygenic phototrophs (FAPs). Diagnostic lipid biomarkers of the cyanobacteria include midchain branched mono- and dimethylalkanes and, most notably, 2-methylbacteriohopanepolyol. Diagnostic lipid biomarkers of the FAPs (Chloroflexus and Roseiflexus spp.) include wax esters and a long-chain tri-unsaturated alkene. Surprisingly, the lipid biomarkers resisted the earliest stages of microbial degradation and diagenesis to survive in the iron oxides beneath the mats. Understanding the potential of particular sedimentary environments to capture and preserve fossil biosignatures is of vital importance in the selection of the best landing sites for future astrobiological missions to Mars. This study explores the nature of organic degradation processes in moderately thermal Fe(II)-rich groundwater springs—environmental conditions that have been previously identified as highly relevant for Mars exploration. Key Words: Lipid biomarkers—Photosynthesis—Iron—Hot springs—Mars. Astrobiology 14, 502–521. PMID:24886100

  8. Production and Early Preservation of Lipid Biomarkers in Iron Hot Springs

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

    Parenteau, Mary N.; Jahnke, Linda L.; Farmer, Jack D.

    2014-06-01

    The bicarbonate-buffered anoxic vent waters at Chocolate Pots hot springs in Yellowstone National Park are 51–54°C, pH 5.5–6.0, and are very high in dissolved Fe(II) at 5.8–5.9 mg/L. The aqueous Fe(II) is oxidized by a combination of biotic and abiotic mechanisms and precipitated as primary siliceous nanophase iron oxyhydroxides (ferrihydrite). Four distinct prokaryotic photosynthetic microbial mat types grow on top of these iron deposits. Lipids were used to characterize the community composition of the microbial mats, link source organisms to geologically significant biomarkers, and investigate how iron mineralization degrades the lipid signature of the community. The phospholipid and glycolipid fattymore » acid profiles of the highest-temperature mats indicate that they are dominated by cyanobacteria and green nonsulfur filamentous anoxygenic phototrophs (FAPs). Diagnostic lipid biomarkers of the cyanobacteria include midchain branched mono- and dimethylalkanes and, most notably, 2-methylbacteriohopanepolyol. Diagnostic lipid biomarkers of the FAPs (Chloroflexus and Roseiflexus spp.) include wax esters and a long-chain tri-unsaturated alkene. Surprisingly, the lipid biomarkers resisted the earliest stages of microbial degradation and diagenesis to survive in the iron oxides beneath the mats. Understanding the potential of particular sedimentary environments to capture and preserve fossil biosignatures is of vital importance in the selection of the best landing sites for future astrobiological missions to Mars. Finally, this study explores the nature of organic degradation processes in moderately thermal Fe(II)-rich groundwater springs—environmental conditions that have been previously identified as highly relevant for Mars exploration.« less

  9. Biogeochemistry: Deep ocean iron balance

    NASA Astrophysics Data System (ADS)

    Homoky, William B.

    2017-02-01

    Dissolved iron is mysteriously pervasive in deep ocean hydrothermal plumes. An analysis of gas, metals and particles from a 4,000 km plume transect suggests that dissolved iron is maintained by rapid and reversible exchanges with sinking particles.

  10. Mineral resource of the month: Iron and steel

    USGS Publications Warehouse

    Fenton, Michael D.

    2014-01-01

    Iron is one of the most abundant elements on Earth, but it does not occur in nature in a useful metallic form. Although ancient people may have recovered some iron from meteorites, it wasn’t until smelting was invented that iron metal could be derived from iron oxides. After the beginning of the Iron Age in about 1200 B.C., knowledge of iron- and steelmaking spread from the ancient Middle East through Greece to the Roman Empire, then to Europe and, in the early 17th century, to North America. The first successful furnace in North America began operating in 1646 in what is now Saugus, Mass. Introduction of the Bessemer converter in the mid-19th century made the modern steel age possible.

  11. Metal Tolerance Protein 8 Mediates Manganese Homeostasis and Iron Reallocation during Seed Development and Germination1[OPEN

    PubMed Central

    Takahashi, Michiko; Terada, Yasuko

    2017-01-01

    Metal accumulation in seeds is a prerequisite for germination and establishment of plants but also for micronutrient delivery to humans. To investigate metal transport processes and their interactions in seeds, we focused on METAL TOLERANCE PROTEIN8 (MTP8), a tonoplast transporter of the manganese (Mn) subclade of cation diffusion facilitators, which in Arabidopsis (Arabidopsis thaliana) is expressed in embryos of seeds. The x-ray fluorescence imaging showed that expression of MTP8 was responsible for Mn localization in subepidermal cells on the abaxial side of the cotyledons and in cortical cells of the hypocotyl. Accordingly, under low Mn availability, MTP8 increased seed stores of Mn, required for efficient seed germination. In mutant embryos lacking expression of VACUOLAR IRON TRANSPORTER1 (VIT1), MTP8 built up iron (Fe) hotspots in MTP8-expressing cells types, suggesting that MTP8 transports Fe in addition to Mn. In mtp8 vit1 double mutant seeds, Mn and Fe were distributed in all cell types of the embryo. An Fe transport function of MTP8 was confirmed by its ability to complement Fe hypersensitivity of a yeast mutant defective in vacuolar Fe transport. Imbibing mtp8-1 mutant seeds in the presence of Mn or subjecting seeds to wet-dry cycles showed that MTP8 conferred Mn tolerance. During germination, MTP8 promoted reallocation of Fe from the vasculature. These results indicate that cell type-specific accumulation of Mn and Fe in seeds depends on MTP8 and that this transporter plays an important role in the generation of seed metal stores as well as for metal homeostasis and germination efficiency under challenging environmental conditions. PMID:28461400

  12. Surprising abundance of Gallionella-related iron oxidizers in creek sediments at pH 4.4 or at high heavy metal concentrations

    USGS Publications Warehouse

    Fabisch, Maria; Beulig, Felix; Akob, Denise M.; Küsel, Kirsten

    2013-01-01

    We identified and quantified abundant iron-oxidizing bacteria (FeOB) at three iron-rich, metal-contaminated creek sites with increasing sediment pH from extremely acidic (R1, pH 2.7), to moderately acidic (R2, pH 4.4), to slightly acidic (R3, pH 6.3) in a former uranium-mining district. The geochemical parameters showed little variations over the 1.5 year study period. The highest metal concentrations found in creek sediments always coincided with the lowest metal concentrations in creek water at the slightly acidic site R3. Sequential extractions of R3 sediment revealed large portions of heavy metals (Ni, Cu, Zn, Pb, U) bound to the iron oxide fraction. Light microscopy of glass slides exposed in creeks detected twisted stalks characteristic of microaerobic FeOB of the family Gallionellaceae at R3 but also at the acidic site R2. Sequences related to FeOB such as Gallionella ferruginea, Sideroxydans sp. CL21, Ferritrophicum radicicola, and Acidovorax sp. BrG1 were identified in the sediments. The highest fraction of clone sequences similar to the acidophilic “Ferrovum myxofaciens” was detected in R1. Quantitative PCR using primer sets specific for Gallionella spp., Sideroxydans spp., and “Ferrovum myxofaciens” revealed that ~72% (R2 sediment) and 37% (R3 sediment) of total bacterial 16S rRNA gene copies could be assigned to groups of FeOB with dominance of microaerobic Gallionella spp. at both sites. Gallionella spp. had similar and very high absolute and relative gene copy numbers in both sediment communities. Thus, Gallionella-like organisms appear to exhibit a greater acid and metal tolerance than shown before. Microaerobic FeOB from R3 creek sediment enriched in newly developed metal gradient tubes tolerated metal concentrations of 35 mM Co, 24 mM Ni, and 1.3 mM Cd, higher than those in sediments. Our results will extend the limited knowledge of FeOB at contaminated, moderately to slightly acidic environments.

  13. Changes of the corrosion potential of iron in stagnation and flow conditions and their relationship with metal release.

    PubMed

    Fabbricino, Massimiliano; Korshin, Gregory V

    2014-10-01

    This study examined the behavior of corrosion potential (Ecorr) of iron exposed to drinking water during episodes of stagnation and flow. These measurements showed that during stagnation episodes, Ecorr values decrease prominently and consistently. This decrease is initially rapid but it becomes slower as the stagnation time increases. During flow episodes, the Ecorr values increase and reach a quasi-steady state. Experiments with varying concentrations of dissolved oxygen showed that the decrease of Ecorr values characteristic for stagnation is likely to be associated with the consumption of dissolved oxygen by the exposed metal. The corrosion potential of iron and its changes during stagnation were sensitive to the concentrations of sulfate and chloride ions. Measurements of iron release showed that both the absolute values of Ecorr measured prior to or after stagnation episodes were well correlated with the logarithms of concentrations of total iron. The slope of this dependence showed that the observed correlations between Ecorr values and Fe concentrations corresponded to the coupling between the oxidant consumption and changes of Fe redox status. These results demonstrate that in situ Ecorr measurements can be a sensitive method with which to ascertain effects of hydrodynamic conditions and short-term variations of water chemistry on metal release and corrosion in drinking water. This approach is valuable practically because Ecorr measurements are precise, can be carried out in situ with any desired time resolution, do not affect the state of exposed surface in any extent and can be carried out with readily available equipment. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Cytosolic iron chaperones: Proteins delivering iron cofactors in the cytosol of mammalian cells.

    PubMed

    Philpott, Caroline C; Ryu, Moon-Suhn; Frey, Avery; Patel, Sarju

    2017-08-04

    Eukaryotic cells contain hundreds of metalloproteins that are supported by intracellular systems coordinating the uptake and distribution of metal cofactors. Iron cofactors include heme, iron-sulfur clusters, and simple iron ions. Poly(rC)-binding proteins are multifunctional adaptors that serve as iron ion chaperones in the cytosolic/nuclear compartment, binding iron at import and delivering it to enzymes, for storage (ferritin) and export (ferroportin). Ferritin iron is mobilized by autophagy through the cargo receptor, nuclear co-activator 4. The monothiol glutaredoxin Glrx3 and BolA2 function as a [2Fe-2S] chaperone complex. These proteins form a core system of cytosolic iron cofactor chaperones in mammalian cells. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  15. Chemical classification of iron meteorites. XI - Multi-element studies of 38 new irons and the high abundance of ungrouped irons from Antarctica

    NASA Technical Reports Server (NTRS)

    Wasson, John T.; Ouyang, Xinwei; Wang, Jianmin; Jerde, Eric

    1989-01-01

    Concentrations of 14 elements in the metal of 38 iron meteorites and a pallasite are reported. Three samples are paired with previously classified irons, raising the number of well-classified, independent iron meteorites to 598. Several of the new irons are from Antarctica. Of 24 independent irons from Antarctica, eight are ungrouped, a much higher fraction than that among all classified irons. The difference is probably related to the fact that the median mass of Antarctic irons is about two orders of magnitude smaller than that of non-Antarctic irons. Smaller meteoroids may tend to sample a larger number of asteroidal source regions, perhaps because small meteoroids tend to have higher ejection velocities or because they have random-walked a greater increment of orbital semimajor axis away from that of the parent body.

  16. Divalent metal transporter 1 (DMT1) in the brain: implications for a role in iron transport at the blood-brain barrier, and neuronal and glial pathology.

    PubMed

    Skjørringe, Tina; Burkhart, Annette; Johnsen, Kasper Bendix; Moos, Torben

    2015-01-01

    Iron is required in a variety of essential processes in the body. In this review, we focus on iron transport in the brain and the role of the divalent metal transporter 1 (DMT1) vital for iron uptake in most cells. DMT1 locates to cellular membranes and endosomal membranes, where it is a key player in non-transferrin bound iron uptake and transferrin-bound iron uptake, respectively. Four isoforms of DMT1 exist, and their respective characteristics involve a complex cell-specific regulatory machinery all controlling iron transport across these membranes. This complexity reflects the fine balance required in iron homeostasis, as this metal is indispensable in many cell functions but highly toxic when appearing in excess. DMT1 expression in the brain is prominent in neurons. Of serious dispute is the expression of DMT1 in non-neuronal cells. Recent studies imply that DMT1 does exist in endosomes of brain capillary endothelial cells denoting the blood-brain barrier. This supports existing evidence that iron uptake at the BBB occurs by means of transferrin-receptor mediated endocytosis followed by detachment of iron from transferrin inside the acidic compartment of the endosome and DMT1-mediated pumping iron into the cytosol. The subsequent iron transport across the abluminal membrane into the brain likely occurs by ferroportin. The virtual absent expression of transferrin receptors and DMT1 in glial cells, i.e., astrocytes, microglia and oligodendrocytes, suggest that the steady state uptake of iron in glia is much lower than in neurons and/or other mechanisms for iron uptake in these cell types prevail.

  17. Divalent metal transporter 1 (DMT1) in the brain: implications for a role in iron transport at the blood-brain barrier, and neuronal and glial pathology

    PubMed Central

    Skjørringe, Tina; Burkhart, Annette; Johnsen, Kasper Bendix; Moos, Torben

    2015-01-01

    Iron is required in a variety of essential processes in the body. In this review, we focus on iron transport in the brain and the role of the divalent metal transporter 1 (DMT1) vital for iron uptake in most cells. DMT1 locates to cellular membranes and endosomal membranes, where it is a key player in non-transferrin bound iron uptake and transferrin-bound iron uptake, respectively. Four isoforms of DMT1 exist, and their respective characteristics involve a complex cell-specific regulatory machinery all controlling iron transport across these membranes. This complexity reflects the fine balance required in iron homeostasis, as this metal is indispensable in many cell functions but highly toxic when appearing in excess. DMT1 expression in the brain is prominent in neurons. Of serious dispute is the expression of DMT1 in non-neuronal cells. Recent studies imply that DMT1 does exist in endosomes of brain capillary endothelial cells denoting the blood-brain barrier. This supports existing evidence that iron uptake at the BBB occurs by means of transferrin-receptor mediated endocytosis followed by detachment of iron from transferrin inside the acidic compartment of the endosome and DMT1-mediated pumping iron into the cytosol. The subsequent iron transport across the abluminal membrane into the brain likely occurs by ferroportin. The virtual absent expression of transferrin receptors and DMT1 in glial cells, i.e., astrocytes, microglia and oligodendrocytes, suggest that the steady state uptake of iron in glia is much lower than in neurons and/or other mechanisms for iron uptake in these cell types prevail. PMID:26106291

  18. Metal-metal bond lengths in complexes of transition metals*

    PubMed Central

    Pauling, Linus

    1976-01-01

    In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths. PMID:16592368

  19. Iron Oxide Minerals in Dust: New Insights from Magnetism, Spectroscopy, and Microscopy

    NASA Astrophysics Data System (ADS)

    Reynolds, R. L.; Moskowitz, B. M.; Goldstein, H. L.; Cattle, S.; Bristow, C. S.; Berquo, T. S.; Kokaly, R. F.

    2016-12-01

    Although iron oxide minerals typically compose only a few weight percent of bulk atmospheric dust, they exert important effects on weather, climate, melting of snow and ice, and ocean fertilization. Moreover, the partition between hematite and goethite is important to know to improve models for radiative effects of ferric oxide minerals. The combination of magnetic property measurements, Mössbauer spectroscopy, reflectance spectroscopy, chemical analysis, and scanning electron microscopy at 9-nm resolution reveals types, sizes, abundances, and occurrences of iron oxide minerals in samples from the 2009 "Red Dawn" dust storm (Australia), the Bodélé Depression (Chad), and dust and dust-source sediments in the American West. In each case, discrete nano-phase and microcrystalline iron oxides, hematite and (or) goethite were identified on and within clay coatings on composite dust particles. "Red Dawn" dust samples across eastern Australia each contained hematite, goethite, and magnetite. Goethite and hematite composed approximately 25-45% of the Fe-bearing phases as indicated by Mössbauer spectroscopy at 300K and 4.2K. Magnetite concentrations (as much as 0.29 wt %) were much higher in eastern, urban sites than in remote western sites (0.01 wt %), suggesting local addition of magnetite from urban sources. In samples from the Bodélé Depression, dominant goethite and subordinate hematite composed about 2% of yellow-reddish dust-source sediments. Magnetite was ubiquitous (0.002-0.57 wt %). The average iron apportionment was 32% in ferric oxide minerals, 1.4 % in magnetite, and 65% in ferric silicates. In all cases, high abundance of ferric oxides correlated with low reflectance, indicating their capacity to absorb solar radiation. Moreover, the high surface-to-volume ratios of ferric oxide nanoparticles may facilitate atmospheric processing and affect iron solubility and bioavailability in marine ecosystems and in human lungs.

  20. From iron coordination compounds to metal oxide nanoparticles.

    PubMed

    Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel; Cazacu, Maria

    2016-01-01

    Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe 2 III Fe II O(CH 3 COO) 6 (H 2 O) 3 ]·2H 2 O (FeAc1), μ 3 -oxo trinuclear iron(III) acetate, [Fe 3 O(CH 3 COO) 6 (H 2 O) 3 ]NO 3 ∙4H 2 O (FeAc2), iron furoate, [Fe 3 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeF), iron chromium furoate, FeCr 2 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles.

  1. From iron coordination compounds to metal oxide nanoparticles

    PubMed Central

    Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel

    2016-01-01

    Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe2 IIIFeIIO(CH3COO)6(H2O)3]·2H2O (FeAc1), μ3-oxo trinuclear iron(III) acetate, [Fe3O(CH3COO)6(H2O)3]NO3∙4H2O (FeAc2), iron furoate, [Fe3O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeF), iron chromium furoate, FeCr2O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles. PMID:28144555

  2. Hydrolysis of soybean protein improves iron bioavailability

    USDA-ARS?s Scientific Manuscript database

    Iron is an important trace metal element in human body. Iron deficiency affects human health, especially pregnant women and children. Soybean protein is a popular food in Asia and can contain a high amount of iron (145.70±0.74 ug/g); however, it is usually reported as an inhibitor of iron absorption...

  3. PIC1, an Ancient Permease in Arabidopsis Chloroplasts, Mediates Iron Transport[W

    PubMed Central

    Duy, Daniela; Wanner, Gerhard; Meda, Anderson R.; von Wirén, Nicolaus; Soll, Jürgen; Philippar, Katrin

    2007-01-01

    In chloroplasts, the transition metals iron and copper play an essential role in photosynthetic electron transport and act as cofactors for superoxide dismutases. Iron is essential for chlorophyll biosynthesis, and ferritin clusters in plastids store iron during germination, development, and iron stress. Thus, plastidic homeostasis of transition metals, in particular of iron, is crucial for chloroplast as well as plant development. However, very little is known about iron uptake by chloroplasts. Arabidopsis thaliana PERMEASE IN CHLOROPLASTS1 (PIC1), identified in a screen for metal transporters in plastids, contains four predicted α-helices, is targeted to the inner envelope, and displays homology with cyanobacterial permease-like proteins. Knockout mutants of PIC1 grew only heterotrophically and were characterized by a chlorotic and dwarfish phenotype reminiscent of iron-deficient plants. Ultrastructural analysis of plastids revealed severely impaired chloroplast development and a striking increase in ferritin clusters. Besides upregulation of ferritin, pic1 mutants showed differential regulation of genes and proteins related to iron stress or transport, photosynthesis, and Fe-S cluster biogenesis. Furthermore, PIC1 and its cyanobacterial homolog mediated iron accumulation in an iron uptake–defective yeast mutant. These observations suggest that PIC1 functions in iron transport across the inner envelope of chloroplasts and hence in cellular metal homeostasis. PMID:17337631

  4. Fabrication of Iron-Containing Carbon Materials From Graphite Fluoride

    NASA Technical Reports Server (NTRS)

    Hung, Ching-cheh

    1996-01-01

    Carbon materials containing iron alloy, iron metal, iron oxide or iron halide were fabricated. Typical samples of these metals were estimated to contain 1 iron atom per 3.5 to 5 carbon atoms. Those carbon materials containing iron alloy, iron metal, and/or Fe3O4 were magnetic. The kinetics of the fabrication process were studied by exposing graphite fluoride (CF(0.68)) to FeCl3 over a 280 to 420 C temperature range. Between 280 and 295 C, FeCl3 quickly entered the structure of CF(0.68), broke the carbon-fluorine bonds, and within 10 to 30 min, completely converted it to carbon made up of graphite planes between which particles of crystalline FeF3 and noncrystalline FeCl3 were located. Longer reaction times (e.g., 28 hr) or higher reaction temperatures (e.g., 420 C) produced materials containing graphite, a FeCl3-graphite intercalation compound, FeCl2(center dot)4H2O, and FeCl2(center dot)2H2O. These products were further heat treated to produce iron-containing carbon materials. When the heating temperature was kept in the 750 to 850 C range, and the oxygen supply was kept at the optimum level, the iron halides in the carbon structure were converted to iron oxides. Raising the heat to temperatures higher than 900 C reduced such iron oxides to iron metal. The kinetics of these reactions were used to suggest processes for fabricating carbon materials containing iron alloy. Such processes were then tested experimentally. In one of the successful trial runs, commercially purchased CF(0.7) powder was used as the reactant, and NiO was added during the final heating to 1200 C as a source of both nickel and oxygen. The product thus obtained was magnetic and was confirmed to be a nickel-iron alloy in carbon.

  5. DISRUPTION OF NORMAL IRON HOMEOSTASIS AFTER BRONCHIAL INSTILLATION OF AN IRON-CONTAINING PARTICLE

    EPA Science Inventory


    The atmosphere constitutes a prime vehicle for the movement and redistribution of metals. Metal exposure can be associated with an oxidative stress. We tested the hypothesis that, in response to an iron-containing particle, the human respiratory tract will demonstrate an incr...

  6. Potential for iron oxides to control metal releases in CO2 sequestration scenarios

    USGS Publications Warehouse

    Berger, P.M.; Roy, W.R.

    2011-01-01

    The potential for the release of metals into groundwater following the injection of carbon dioxide (CO2) into the subsurface during carbon sequestration projects remains an open research question. Changing the chemical composition of even the relatively deep formation brines during CO2 injection and storage may be of concern because of the recognized risks associated with the limited potential for leakage of CO2-impacted brine to the surface. Geochemical modeling allows for proactive evaluation of site geochemistry before CO2 injection takes place to predict whether the release of metals from iron oxides may occur in the reservoir. Geochemical modeling can also help evaluate potential changes in shallow aquifers were CO2 leakage to occur near the surface. In this study, we created three batch-reaction models that simulate chemical changes in groundwater resulting from the introduction of CO2 at two carbon sequestration sites operated by the Midwest Geological Sequestration Consortium (MGSC). In each of these models, we input the chemical composition of groundwater samples into React??, and equilibrated them with selected mineral phases and CO 2 at reservoir pressure and temperature. The model then simulated the kinetic reactions with other mineral phases over a period of up to 100 years. For two of the simulations, the water was also at equilibrium with iron oxide surface complexes. The first model simulated a recently completed enhanced oil recovery (EOR) project in south-central Illinois in which the MGSC injected into, and then produced CO2, from a sandstone oil reservoir. The MGSC afterwards periodically measured the brine chemistry from several wells in the reservoir for approximately two years. The sandstone contains a relatively small amount of iron oxide, and the batch simulation for the injection process showed detectable changes in several aqueous species that were attributable to changes in surface complexation sites. After using the batch reaction

  7. Mechanisms of mammalian iron homeostasis

    PubMed Central

    Pantopoulos, Kostas; Porwal, Suheel Kumar; Tartakoff, Alan; Devireddy, L.

    2012-01-01

    Iron is vital for almost all organisms because of its ability to donate and accept electrons with relative ease. It serves as a cofactor for many proteins and enzymes necessary for oxygen and energy metabolism, as well as for several other essential processes. Mammalian cells utilize multiple mechanisms to acquire iron. Disruption of iron homeostasis is associated with various human diseases: iron deficiency resulting from defects in acquisition or distribution of the metal causes anemia; whereas iron surfeit resulting from excessive iron absorption or defective utilization causes abnormal tissue iron deposition, leading to oxidative damage. Mammals utilize distinct mechanisms to regulate iron homeostasis at the systemic and cellular levels. These involve the hormone hepcidin and iron regulatory proteins, which collectively ensure iron balance. This review outlines recent advances in iron regulatory pathways, as well as in mechanisms underlying intracellular iron trafficking, an important but less-studied area of mammalian iron homeostasis. PMID:22703180

  8. Regulation of cellular iron metabolism

    PubMed Central

    Wang, Jian; Pantopoulos, Kostas

    2011-01-01

    Iron is an essential but potentially hazardous biometal. Mammalian cells require sufficient amounts of iron to satisfy metabolic needs or to accomplish specialized functions. Iron is delivered to tissues by circulating transferrin, a transporter that captures iron released into the plasma mainly from intestinal enterocytes or reticuloendothelial macrophages. The binding of iron-laden transferrin to the cell-surface transferrin receptor 1 results in endocytosis and uptake of the metal cargo. Internalized iron is transported to mitochondria for the synthesis of haem or iron–sulfur clusters, which are integral parts of several metalloproteins, and excess iron is stored and detoxified in cytosolic ferritin. Iron metabolism is controlled at different levels and by diverse mechanisms. The present review summarizes basic concepts of iron transport, use and storage and focuses on the IRE (iron-responsive element)/IRP (iron-regulatory protein) system, a well known post-transcriptional regulatory circuit that not only maintains iron homoeostasis in various cell types, but also contributes to systemic iron balance. PMID:21348856

  9. Iron regulatory proteins and their role in controlling iron metabolism.

    PubMed

    Kühn, Lukas C

    2015-02-01

    Cellular iron homeostasis is regulated by post-transcriptional feedback mechanisms, which control the expression of proteins involved in iron uptake, release and storage. Two cytoplasmic proteins with mRNA-binding properties, iron regulatory proteins 1 and 2 (IRP1 and IRP2) play a central role in this regulation. Foremost, IRPs regulate ferritin H and ferritin L translation and thus iron storage, as well as transferrin receptor 1 (TfR1) mRNA stability, thereby adjusting receptor expression and iron uptake via receptor-mediated endocytosis of iron-loaded transferrin. In addition splice variants of iron transporters for import and export at the plasma-membrane, divalent metal transporter 1 (DMT1) and ferroportin are regulated by IRPs. These mechanisms have probably evolved to maintain the cytoplasmic labile iron pool (LIP) at an appropriate level. In certain tissues, the regulation exerted by IRPs influences iron homeostasis and utilization of the entire organism. In intestine, the control of ferritin expression limits intestinal iron absorption and, thus, whole body iron levels. In bone marrow, erythroid heme biosynthesis is coordinated with iron availability through IRP-mediated translational control of erythroid 5-aminolevulinate synthase mRNA. Moreover, the translational control of HIF2α mRNA in kidney by IRP1 coordinates erythropoietin synthesis with iron and oxygen supply. Besides IRPs, body iron absorption is negatively regulated by hepcidin. This peptide hormone, synthesized and secreted by the liver in response to high serum iron, downregulates ferroportin at the protein level and thereby limits iron absorption from the diet. Hepcidin will not be discussed in further detail here.

  10. The crystal structure of the Yersinia pestis iron chaperone YiuA reveals a basic triad binding motif for the chelated metal

    PubMed Central

    2017-01-01

    Biological chelating molecules called siderophores are used to sequester iron and maintain its ferric state. Bacterial substrate-binding proteins (SBPs) bind iron–siderophore complexes and deliver these complexes to ATP-binding cassette (ABC) transporters for import into the cytoplasm, where the iron can be transferred from the siderophore to catalytic enzymes. In Yersinia pestis, the causative agent of plague, the Yersinia iron-uptake (Yiu) ABC transporter has been shown to improve iron acquisition under iron-chelated conditions. The Yiu transporter has been proposed to be an iron–siderophore transporter; however, the precise siderophore substrate is unknown. Therefore, the precise role of the Yiu transporter in Y. pestis survival remains uncharacterized. To better understand the function of the Yiu transporter, the crystal structure of YiuA (YPO1310/y2875), an SBP which functions to present the iron–siderophore substrate to the transporter for import into the cytoplasm, was determined. The 2.20 and 1.77 Å resolution X-ray crystal structures reveal a basic triad binding motif at the YiuA canonical substrate-binding site, indicative of a metal-chelate binding site. Structural alignment and computational docking studies support the function of YiuA in binding chelated metal. Additionally, YiuA contains two mobile helices, helix 5 and helix 10, that undergo 2–3 Å shifts across crystal forms and demonstrate structural breathing of the c-clamp architecture. The flexibility in both c-clamp lobes suggest that YiuA substrate transfer resembles the Venus flytrap mechanism that has been proposed for other SBPs. PMID:29095164

  11. Virus templated metallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Aljabali, Alaa A. A.; Barclay, J. Elaine; Lomonossoff, George P.; Evans, David J.

    2010-12-01

    Plant viruses are considered as nanobuilding blocks that can be used as synthons or templates for novel materials. Cowpea mosaic virus (CPMV) particles have been shown to template the fabrication of metallic nanoparticles by an electroless deposition metallization process. Palladium ions were electrostatically bound to the virus capsid and, when reduced, acted as nucleation sites for the subsequent metal deposition from solution. The method, although simple, produced highly monodisperse metallic nanoparticles with a diameter of ca. <=35 nm. CPMV-templated particles were prepared with cobalt, nickel, iron, platinum, cobalt-platinum and nickel-iron.Plant viruses are considered as nanobuilding blocks that can be used as synthons or templates for novel materials. Cowpea mosaic virus (CPMV) particles have been shown to template the fabrication of metallic nanoparticles by an electroless deposition metallization process. Palladium ions were electrostatically bound to the virus capsid and, when reduced, acted as nucleation sites for the subsequent metal deposition from solution. The method, although simple, produced highly monodisperse metallic nanoparticles with a diameter of ca. <=35 nm. CPMV-templated particles were prepared with cobalt, nickel, iron, platinum, cobalt-platinum and nickel-iron. Electronic supplementary information (ESI) available: Additional experimental detail, agarose gel electrophoresis results, energy dispersive X-ray spectra, ζ-potential measurements, dynamic light scattering data, nanoparticle tracking analysis and an atomic force microscopy image of Ni-CPMV. See DOI: 10.1039/c0nr00525h

  12. Deep-Earth Equilibration between Molten Iron and Solid Silicates

    NASA Astrophysics Data System (ADS)

    Brennan, M.; Zurkowski, C. C.; Chidester, B.; Campbell, A.

    2017-12-01

    Elemental partitioning between iron-rich metals and silicate minerals influences the properties of Earth's deep interior, and is ultimately responsible for the nature of the core-mantle boundary. These interactions between molten iron and solid silicates were influential during planetary accretion, and persist today between the mantle and liquid outer core. Here we report the results of diamond anvil cell experiments at lower mantle conditions (40 GPa, >2500 K) aimed at examining systems containing a mixture of metals (iron or Fe-16Si alloy) and silicates (peridotite). The experiments were conducted at pressure-temperature conditions above the metallic liquidus but below the silicate solidus, and the recovered samples were analyzed by FIB/SEM with EDS to record the compositions of the coexisting phases. Each sample formed a three-phase equilibrium between bridgmanite, Fe-rich metallic melt, and an oxide. In one experiment, using pure Fe, the quenched metal contained 6 weight percent O, and the coexisting oxide was ferropericlase. The second experiment, using Fe-Si alloy, was highly reducing; its metal contained 10 wt% Si, and the coexisting mineral was stishovite. The distinct mineralogies of the two experiments derived from their different starting metals. These results imply that metallic composition is an important factor in determining the products of mixed phase iron-silicate reactions. The properties of deep-Earth interfaces such as the core-mantle boundary could be strongly affected by their metallic components.

  13. Zinc deficiency-induced iron accumulation, a consequence of alterations in iron regulatory protein-binding activity, iron transporters, and iron storage proteins.

    PubMed

    Niles, Brad J; Clegg, Michael S; Hanna, Lynn A; Chou, Susan S; Momma, Tony Y; Hong, Heeok; Keen, Carl L

    2008-02-22

    One consequence of zinc deficiency is an elevation in cell and tissue iron concentrations. To examine the mechanism(s) underlying this phenomenon, Swiss 3T3 cells were cultured in zinc-deficient (D, 0.5 microM zinc), zinc-supplemented (S, 50 microM zinc), or control (C, 4 microM zinc) media. After 24 h of culture, cells in the D group were characterized by a 50% decrease in intracellular zinc and a 35% increase in intracellular iron relative to cells in the S and C groups. The increase in cellular iron was associated with increased transferrin receptor 1 protein and mRNA levels and increased ferritin light chain expression. The divalent metal transporter 1(+)iron-responsive element isoform mRNA was decreased during zinc deficiency-induced iron accumulation. Examination of zinc-deficient cells revealed increased binding of iron regulatory protein 2 (IRP2) and decreased binding of IRP1 to a consensus iron-responsive element. The increased IRP2-binding activity in zinc-deficient cells coincided with an increased level of IRP2 protein. The accumulation of IRP2 protein was independent of zinc deficiency-induced intracellular nitric oxide production but was attenuated by the addition of the antioxidant N-acetylcysteine or ascorbate to the D medium. These data support the concept that zinc deficiency can result in alterations in iron transporter, storage, and regulatory proteins, which facilitate iron accumulation.

  14. Cloud iron speciation: Experimental simulations

    NASA Astrophysics Data System (ADS)

    Sofikitis, A. M.; Colin, J. L.; Desboeufs, K. V.; Losno, R.

    2003-04-01

    The aim of our contribution is to identify major processes controlling iron speciation in the atmospheric aqueous phase. Fe is known to participate in a variety of redox reactions in cloud chemistry, as well as controlling free radical production in the troposphere. Iron cycling is slower than cycles with other catalytic transition metals (Cu, Mn). The residence time of each iron species is around ten minutes, this allows analytical separation and determination of each iron redox species and therefore its ratio. As the only source of trace metals in aqueous atmospheric phase is due to the solubilization of aerosols, we present here dissolution rate measurements obtained by laboratory experiments with an open flow reactor. This reactor enables us to reproduce the dissolution of a particle in aqueous atmospheric water. The dissolution rate and the speciation of iron are dependent on the mineralogy of the solid phase. Our experiments included Goethite, hematite and vermiculite, which are typical mineral constituents of dust particles. Comparisons were made with natural loess which is a blend of various crystalline and amorphous phases. We will present results of crustal origin particles dissolution experiments where kinetic parameters are determined, including iron speciation. Major functions of variation are pH and photochemistry in the aqueous weathering solution.

  15. Isolation of Acetogenic Bacteria That Induce Biocorrosion by Utilizing Metallic Iron as the Sole Electron Donor

    PubMed Central

    Yumoto, Isao; Kamagata, Yoichi

    2014-01-01

    Corrosion of iron occurring under anoxic conditions, which is termed microbiologically influenced corrosion (MIC) or biocorrosion, is mostly caused by microbial activities. Microbial activity that enhances corrosion via uptake of electrons from metallic iron [Fe(0)] has been regarded as one of the major causative factors. In addition to sulfate-reducing bacteria and methanogenic archaea in marine environments, acetogenic bacteria in freshwater environments have recently been suggested to cause MIC under anoxic conditions. However, no microorganisms that perform acetogenesis-dependent MIC have been isolated or had their MIC-inducing mechanisms characterized. Here, we enriched and isolated acetogenic bacteria that induce iron corrosion by utilizing Fe(0) as the sole electron donor under freshwater, sulfate-free, and anoxic conditions. The enriched communities produced significantly larger amounts of Fe(II) than the abiotic controls and produced acetate coupled with Fe(0) oxidation prior to CH4 production. Microbial community analysis revealed that Sporomusa sp. and Desulfovibrio sp. dominated in the enrichments. Strain GT1, which is closely related to the acetogen Sporomusa sphaeroides, was eventually isolated from the enrichment. Strain GT1 grew acetogenetically with Fe(0) as the sole electron donor and enhanced iron corrosion, which is the first demonstration of MIC mediated by a pure culture of an acetogen. Other well-known acetogenic bacteria, including Sporomusa ovata and Acetobacterium spp., did not grow well on Fe(0). These results indicate that very few species of acetogens have specific mechanisms to efficiently utilize cathodic electrons derived from Fe(0) oxidation and induce iron corrosion. PMID:25304512

  16. Isolation of acetogenic bacteria that induce biocorrosion by utilizing metallic iron as the sole electron donor.

    PubMed

    Kato, Souichiro; Yumoto, Isao; Kamagata, Yoichi

    2015-01-01

    Corrosion of iron occurring under anoxic conditions, which is termed microbiologically influenced corrosion (MIC) or biocorrosion, is mostly caused by microbial activities. Microbial activity that enhances corrosion via uptake of electrons from metallic iron [Fe(0)] has been regarded as one of the major causative factors. In addition to sulfate-reducing bacteria and methanogenic archaea in marine environments, acetogenic bacteria in freshwater environments have recently been suggested to cause MIC under anoxic conditions. However, no microorganisms that perform acetogenesis-dependent MIC have been isolated or had their MIC-inducing mechanisms characterized. Here, we enriched and isolated acetogenic bacteria that induce iron corrosion by utilizing Fe(0) as the sole electron donor under freshwater, sulfate-free, and anoxic conditions. The enriched communities produced significantly larger amounts of Fe(II) than the abiotic controls and produced acetate coupled with Fe(0) oxidation prior to CH4 production. Microbial community analysis revealed that Sporomusa sp. and Desulfovibrio sp. dominated in the enrichments. Strain GT1, which is closely related to the acetogen Sporomusa sphaeroides, was eventually isolated from the enrichment. Strain GT1 grew acetogenetically with Fe(0) as the sole electron donor and enhanced iron corrosion, which is the first demonstration of MIC mediated by a pure culture of an acetogen. Other well-known acetogenic bacteria, including Sporomusa ovata and Acetobacterium spp., did not grow well on Fe(0). These results indicate that very few species of acetogens have specific mechanisms to efficiently utilize cathodic electrons derived from Fe(0) oxidation and induce iron corrosion. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

  17. Metal-Organic Heat Carrier Nanofluids

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

    McGrail, B. Peter; Thallapally, Praveen K.; Blanchard, Jeremy

    2013-09-01

    Nanofluids, dispersions of metal or oxide nanoparticles in a base working fluid, are being intensively studied due to improvements they offer in thermal properties of the working fluid. However, these benefits have been erratically demonstrated and proven impacts on thermal conductivity are modest and well described from long-established effective medium theory. In this paper, we describe a new class of metal-organic heat carrier (MOHC) nanofluid that offers potential for a larger performance boost in thermal vapor-liquid compression cycles. MOHCs are nanophase porous coordination solids designed to reversibly uptake the working fluid molecules in which the MOHCs are suspended. Additional heatmore » can be extracted in a heat exchanger or solar collector from the endothermic enthalpy of desorption, which is then released as the nanofluid transits through a power generating device such as a turboexpander. Calculations for an R123 MOHC nanofluid indicated potential for up to 15% increase in power output. Capillary tube experiments show that liquid-vapor transitions occur without nanoparticle deposition on the tube walls provided entrance Reynolds number exceeds approximately 100.« less

  18. Iron, transferrin and myelinogenesis

    NASA Astrophysics Data System (ADS)

    Sergeant, C.; Vesvres, M. H.; Devès, G.; Baron, B.; Guillou, F.

    2003-09-01

    Transferrin (Tf), the iron binding protein of vertebrates serum, is known to be synthesized by oligodendrocytes (Ols) in the central nervous system. It has been postulated that Tf is involved in Ols maturation and myelinogenesis. This link is particularly important in the understanding of a severe human pathology: the multiple sclerosis, which remains without efficient treatment. We generated transgenic mice containing the complete human Tf gene and extensive regulatory sequences from the 5 ' and 3 ' untranslated regions that specifically overexpress Tf in Ols. Brain cytoarchitecture of the transgenic mice appears to be normal in all brain regions examined, total myelin content is increased by 30% and motor coordination is significantly improved when compared with non-transgenic littermates. Tf role in the central nervous system may be related to its affinity for metallic cations. Normal and transgenic mice were used for determination of trace metals (iron, copper and zinc) and minerals (potassium and calcium) concentration in cerebellum and corpus callosum. The freeze-dried samples were prepared to allow proton-induced X-ray emission and Rutherford backscattering spectrometry analyses with the nuclear microprobe in Bordeaux. Preliminary results were obtained and carbon distribution was revealed as a very good analysis to distinguish precisely the white matter region. A comparison of metallic and mineral elements contents in brain between normal and transgenic mice shows that iron, copper and zinc levels remained constant. This result provides evidence that effects of Tf overexpression in the brain do not solely relate to iron transport.

  19. Near-Earth asteroids: Metals occurrence, extraction, and fabrication

    NASA Astrophysics Data System (ADS)

    Westfall, Richard

    Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength

  20. Near-Earth asteroids: Metals occurrence, extraction, and fabrication

    NASA Technical Reports Server (NTRS)

    Westfall, Richard

    1991-01-01

    Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength

  1. Rapid kinetics of iron responsive element (IRE) RNA/iron regulatory protein 1 and IRE-RNA/eIF4F complexes respond differently to metal ions.

    PubMed

    Khan, Mateen A; Ma, Jia; Walden, William E; Merrick, William C; Theil, Elizabeth C; Goss, Dixie J

    2014-06-01

    Metal ion binding was previously shown to destabilize IRE-RNA/IRP1 equilibria and enhanced IRE-RNA/eIF4F equilibria. In order to understand the relative importance of kinetics and stability, we now report rapid rates of protein/RNA complex assembly and dissociation for two IRE-RNAs with IRP1, and quantitatively different metal ion response kinetics that coincide with the different iron responses in vivo. kon, for FRT IRE-RNA binding to IRP1 was eight times faster than ACO2 IRE-RNA. Mn(2+) decreased kon and increased koff for IRP1 binding to both FRT and ACO2 IRE-RNA, with a larger effect for FRT IRE-RNA. In order to further understand IRE-mRNA regulation in terms of kinetics and stability, eIF4F kinetics with FRT IRE-RNA were determined. kon for eIF4F binding to FRT IRE-RNA in the absence of metal ions was 5-times slower than the IRP1 binding to FRT IRE-RNA. Mn(2+) increased the association rate for eIF4F binding to FRT IRE-RNA, so that at 50 µM Mn(2+) eIF4F bound more than 3-times faster than IRP1. IRP1/IRE-RNA complex has a much shorter life-time than the eIF4F/IRE-RNA complex, which suggests that both rate of assembly and stability of the complexes are important, and that allows this regulatory system to respond rapidly to change in cellular iron. © The Author(s) 2014. Published by Oxford University Press on behalf of Nucleic Acids Research.

  2. Accumulation and distribution of iron, cadmium, lead and nickel in cucumber plants grown in hydroponics containing two different chelated iron supplies.

    PubMed

    Csog, Árpád; Mihucz, Victor G; Tatár, Eniko; Fodor, Ferenc; Virág, István; Majdik, Cornelia; Záray, Gyula

    2011-07-01

    Cucumber plants grown in hydroponics containing 10 μM Cd(II), Ni(II) and Pb(II), and iron supplied as Fe(III) EDTA or Fe(III) citrate in identical concentrations, were investigated by total-reflection X-ray fluorescence spectrometry with special emphasis on the determination of iron accumulation and distribution within the different plant compartments (root, stem, cotyledon and leaves). The extent of Cd, Ni and Pb accumulation and distribution were also determined. Generally, iron and heavy-metal contaminant accumulation was higher when Fe(III) citrate was used. The accumulation of nickel and lead was higher by about 20% and 100%, respectively, if the iron supply was Fe(III) citrate. The accumulation of Cd was similar. In the case of Fe(III) citrate, the total amounts of Fe taken up were similar in the control and heavy-metal-treated plants (27-31 μmol/plant). Further, the amounts of iron transported from the root towards the shoot of the control, lead- and nickel-contaminated plants were independent of the iron(III) form. Although Fe mobility could be characterized as being low, its distribution within the shoot was not significantly affected by the heavy metals investigated. Copyright © 2011 Elsevier GmbH. All rights reserved.

  3. Metallic glass composition

    DOEpatents

    Kroeger, Donald M.; Koch, Carl C.

    1986-01-01

    A metallic glass alloy that is either iron-based or nickel-based or based on a mixture of iron and nickel, containing lesser amounts of elements selected from the group boron, silicon carbon and phosphorous to which is added an amount of a ductility enhancing element selected from the group cerium, lanthanum, praseodymium and neodymium sufficient to increase ductility of the metallic glass upon annealing.

  4. Analysis of ablation debris from natural and artificial iron meteorites

    NASA Technical Reports Server (NTRS)

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

    1977-01-01

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

  5. Amelioration of iron mine soils with biosolids: Effects on plant tissue metal content and earthworms.

    PubMed

    Cele, Emmanuel Nkosinathi; Maboeta, Mark

    2016-11-01

    The achievement of environmentally sound and economically feasible disposal strategies for biosolids is a major issue in the wastewater treatment industry around the world, including Swaziland. Currently, an iron ore mine site, which is located within a wildlife sanctuary, is being considered as a suitable place where controlled disposal of biosolids may be practiced. Therefore, this study was conducted to investigate the effects of urban biosolids on iron mine soils with regard to plant metal content and ecotoxicological effects on earthworms. This was done through chemical analysis of plants grown in biosolid-amended mine soil. Earthworm behaviour, reproduction and bioaccumulation tests were also conducted on biosolid-amended mine soil. According to the results obtained, the use of biosolids led to creation of soil conditions that were generally favourable to earthworms. However, plants were found to have accumulated Zn up to 346 mg kg -1 (in shoots) and 462 mg kg -1 (in roots). This was more than double the normal Zn content of plants. It was concluded that while biosolids can be beneficial to mine soils and earthworms, they can also lead to elevated metal content in plant tissues, which might be a concern to plant-dependant wildlife species. Nonetheless, it was not possible to satisfactorily estimate risks to forage quality since animal feeding tests with hyperaccumulator plants have not been reported. Quite possibly, there may be no cause for alarm since the uptake of metals from soil is greater in plants grown in pots in the greenhouse than from the same soil in the field since pot studies fail to mimic field conditions where the soil is heterogeneous and where the root system possesses a complex topology. It was thought that further field trials might assist in arriving at more satisfactory conclusions.

  6. Iron hydrides formation in interstellar clouds

    NASA Astrophysics Data System (ADS)

    Bar-Nun, A.; Pasternak, M.; Barrett, P. H.

    1980-07-01

    A recent Moessbauer study with Fe-57 in a solid hydrogen or hydrogen-argon matrix demonstrated the formation of an iron hydride molecule (FeH2) at 2.5-5 K. Following this and other studies, the possible existence of iron hydride molecules in interstellar clouds is proposed. In clouds, the iron hydrides FeH and FeH2 would be formed only on grains, by encounters of H atoms or H2 molecules with Fe atoms which are adsorbed on the grains. The other transition metals, Sc, Ti, V, Cr, Mn, Co, N, Cd and also Cu and Ca form hydrides of the type M-H, which could be responsible, at least in part, for the depletion of these metals in clouds.

  7. More Evidence of the Importance of Amorphous Silicates in CM Carbonaceous Chondrites: New Observations from a Fine-Grained Rim in the CM2 Chondrite, TIL 91722

    NASA Astrophysics Data System (ADS)

    Brearley, A. J.; Le Guillou, C.

    2015-07-01

    A fine-grained rim in TIL 91722 contains abundant amorphous silicate material containing nanophase sulfides. Phyllosilicates are rare. The amorphous material has a high ferric iron content indicative of oxidation coupled with hydration.

  8. Effect of chromium and phosphorus on the physical properties of iron and titanium-based amorphous metallic alloy films

    NASA Technical Reports Server (NTRS)

    Distefano, S.; Rameshan, R.; Fitzgerald, D. J.

    1991-01-01

    Amorphous iron and titanium-based alloys containing various amounts of chromium, phosphorus, and boron exhibit high corrosion resistance. Some physical properties of Fe and Ti-based metallic alloy films deposited on a glass substrate by a dc-magnetron sputtering technique are reported. The films were characterized using differential scanning calorimetry, stress analysis, SEM, XRD, SIMS, electron microprobe, and potentiodynamic polarization techniques.

  9. Porous Iron-Carboxylate Metal-Organic Framework: A Novel Bioplatform with Sustained Antibacterial Efficacy and Nontoxicity.

    PubMed

    Lin, Sha; Liu, Xiangmei; Tan, Lei; Cui, Zhenduo; Yang, Xianjin; Yeung, Kelvin W K; Pan, Haobo; Wu, Shuilin

    2017-06-07

    Sustained drug release plays a critical role in targeting the therapy of local diseases such as bacterial infections. In the present work, porous iron-carboxylate metal-organic framework [MOF-53(Fe)] nanoparticles (NPs) were designed to entrap the vancomycin (Van) drugs. This system exhibited excellent chemical stability under acidic conditions (pH 7.4, 6.5, and 5.5) and much higher drug-loading capability because of the high porosity and large surface area of MOF NPs. The results showed that the drug-loading ratio of Van could reach 20 wt % and that the antibacterial ratio of the MOF-53(Fe)/Van system against Staphylococcus aureus could reach up to 90%. In addition, this MOF-53(Fe)/Van system exhibited excellent biocompatibility because of its chemical stability and sustained release of iron ions. Hence, these porous MOF NPs are a promising bioplatform not only for local therapy of bacterial infections but also for other biomedical therapies for tissue regeneration.

  10. Environmental Risk Implications of Metals in Sludges from Waste Water Treatment Plants: The Discovery of Vast Stores of Metal-Containing Nanoparticles.

    PubMed

    Tou, Feiyun; Yang, Yi; Feng, Jingnan; Niu, Zuoshun; Pan, Hui; Qin, Yukun; Guo, Xingpan; Meng, Xiangzhou; Liu, Min; Hochella, Michael F

    2017-05-02

    Nanoparticle (NP) assessment in sludge materials, although of growing importance in eco- and biotoxicity studies, is commonly overlooked and, at best, understudied. In the present study, sewage sludge samples from across the mega-city of Shanghai, China were investigated for the first time using a sequential extraction method coupled with single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) to quantify the abundance of metal-containing NPs in the extraction fractions and transmission electron microscopy to specifically identify the nanophases present. In general, most sludges observed showed high concentrations of Cr, Cu, Cd, Ni, Zn, and Pb, exceeding the maximum permitted values in the national application standard of acid soil in China. NPs in these sludges contribute little to the volume and mass but account for about half of the total particle number. Based on electron microscopy techniques, various NPs were further identified, including Ti-, Fe-, Zn-, Sn-, and Pb-containing NPs. All NPs, ignored by traditional metal risk evaluation methods, were observed at a concentration of 10 7 -10 11 particles/g within the bioavailable fraction of metals. These results indicate the underestimate or misestimation in evaluating the environmental risks of metals based on traditional sequential extraction methods. A new approach for the environmental risk assessment of metals, including NPs, is urgently needed.

  11. Iron Absorption in Drosophila melanogaster

    PubMed Central

    Mandilaras, Konstantinos; Pathmanathan, Tharse; Missirlis, Fanis

    2013-01-01

    The way in which Drosophila melanogaster acquires iron from the diet remains poorly understood despite iron absorption being of vital significance for larval growth. To describe the process of organismal iron absorption, consideration needs to be given to cellular iron import, storage, export and how intestinal epithelial cells sense and respond to iron availability. Here we review studies on the Divalent Metal Transporter-1 homolog Malvolio (iron import), the recent discovery that Multicopper Oxidase-1 has ferroxidase activity (iron export) and the role of ferritin in the process of iron acquisition (iron storage). We also describe what is known about iron regulation in insect cells. We then draw upon knowledge from mammalian iron homeostasis to identify candidate genes in flies. Questions arise from the lack of conservation in Drosophila for key mammalian players, such as ferroportin, hepcidin and all the components of the hemochromatosis-related pathway. Drosophila and other insects also lack erythropoiesis. Thus, systemic iron regulation is likely to be conveyed by different signaling pathways and tissue requirements. The significance of regulating intestinal iron uptake is inferred from reports linking Drosophila developmental, immune, heat-shock and behavioral responses to iron sequestration. PMID:23686013

  12. Iron ore mines leachate potential for oxyradical production.

    PubMed

    Hamoutene, D; Rahimtula, A; Payne, J

    2000-06-01

    The ecotoxicological effects of mining effluents is coming under much greater scrutiny. It appears necessary to explore possible health effects in association with iron ore mining effluents. The present results clearly demonstrate that iron-ore leachate is not an inert media but has the potential to induce lipid peroxidation. Peroxidation was assessed by measuring oxygen consumption in the presence of a reducing agent such as ascorbate or NADPH and a chelator such as EDTA. Labrador iron ore is an insoluble complex crystalline material containing a mixture of metals (Fe, Al, Ti, Mn, Mg,ellipsis, ) in contrast to the iron sources used for normal lipid peroxidation studies. The metal of highest percentage is iron (59. 58%), a metal known to induce oxyradical production. Iron ore powder initiated ascorbic acid-dependent lipid peroxidation (nonenzymatic) in liposomes, lipids extracted from rat and salmon liver microsomes, and intact salmon liver microsomes. It also revealed an inhibitory effect of NADPH-dependent microsomes lipid peroxidation as well as on NADPH cytochrome c reductase activity. However, nonenzymatic peroxidation in rat liver microsomes was not significantly inhibited. Cytochrome P450 IA1- and IIB1-dependent enzymatic activities as well as P450 levels were not affected. The inhibition could be due to one of the other components of iron ore leachate (Mn, Al,ellipsis, ). These effects of iron-ore leachate indicate that a potential toxicity could be associated with its release into lakes. Further studies are necessary to explore in vivo effects on aquatic animals. Copyright 2000 Academic Press.

  13. Lithium-aluminum-iron electrode composition

    DOEpatents

    Kaun, Thomas D.

    1979-01-01

    A negative electrode composition is presented for use in a secondary electrochemical cell. The cell also includes an electrolyte with lithium ions such as a molten salt of alkali metal halides or alkaline earth metal halides that can be used in high-temperature cells. The cell's positive electrode contains a a chalcogen or a metal chalcogenide as the active electrode material. The negative electrode composition includes up to 50 atom percent lithium as the active electrode constituent in an alloy of aluminum-iron. Various binary and ternary intermetallic phases of lithium, aluminum and iron are formed. The lithium within the intermetallic phase of Al.sub.5 Fe.sub.2 exhibits increased activity over that of lithium within a lithium-aluminum alloy to provide an increased cell potential of up to about 0.25 volt.

  14. Nanophase-separated Ni3Nb as an automobile exhaust catalyst† †Electronic supplementary information (ESI) available: Demonstration procedure, experimental and characterization details. See DOI: 10.1039/c6sc05473k Click here for additional data file. Click here for additional data file.

    PubMed Central

    Tanabe, Toyokazu; Imai, Tsubasa; Tokunaga, Tomoharu; Arai, Shigeo; Yamamoto, Yuta; Ueda, Shigenori; Ramesh, Gubbala V.; Nagao, Satoshi; Hirata, Hirohito; Matsumoto, Shin-ichi

    2017-01-01

    Catalytic remediation of automobile exhaust has relied on precious metals (PMs) including platinum (Pt). Herein, we report that an intermetallic phase of Ni and niobium (Nb) (i.e., Ni3Nb) exhibits a significantly higher activity than that of Pt for the remediation of the most toxic gas in exhaust (i.e., nitrogen monoxide (NO)) in the presence of carbon monoxide (CO). When subjected to the exhaust-remediation atmosphere, Ni3Nb spontaneously evolves into a catalytically active nanophase-separated structure consisting of filamentous Ni networks (thickness < 10 nm) that are incorporated in a niobium oxide matrix (i.e., NbOx (x < 5/2)). The exposure of the filamentous Ni promotes NO dissociation, CO oxidation and N2 generation, and the NbOx matrix absorbs excessive nitrogen adatoms to retain the active Ni0 sites at the metal/oxide interface. Furthermore, the NbOx matrix immobilizes the filamentous Ni at elevated temperatures to produce long-term and stable catalytic performance over hundreds of hours. PMID:28507707

  15. Chemically bonded phosphate ceramics of trivalent oxides of iron and manganese

    DOEpatents

    Wagh, Arun S.; Jeong, Seung-Young

    2002-01-01

    A new method for combining elemental iron and other metals to form an inexpensive ceramic to stabilize arsenic, alkaline red mud wastes, swarfs, and other iron or metal-based additives, to create products and waste forms which can be poured or dye cast.

  16. Rapid magnetic removal of aqueous heavy metals and their relevant mechanisms using nanoscale zero valent iron (nZVI) particles.

    PubMed

    Huang, Pengpeng; Ye, Zhengfang; Xie, Wuming; Chen, Qi; Li, Jing; Xu, Zhencheng; Yao, Maosheng

    2013-08-01

    Much work is devoted to heavy metal sorption, reduction and relevant mechanisms by nanoscale zero valent iron (nZVI) particle, but fewer studies utilize its magnetic properties in aqueous metal removals. Here, we have investigated the use of nZVI particles both electrosprayed (E-nZVI) and non-electrosprayed (NE-nZVI) with different concentration levels (0.186-1.86 mg/mL) in removing aqueous Cd(II), Cr(IV), and Pb(II) through the magnetic separation means. The effects of the reaction time (5-20 min) and magnetic treatment time (1-30 min) on relevant magnetic removal efficiencies were studied. Metal ion concentration was analyzed using inductively coupled plasma (ICP), and the magnetically obtained metal-nZVI mixtures were further analyzed using X-ray photoelectron spectroscopy (XPS). Results showed that the magnetic removal efficiencies of heavy metals varied with the metal species, nZVI loading, reaction and magnetic separation time. In most cases, use of 1.5 mg/mL E-nZVI or NE-nZVI resulted in removal efficiencies of more than 80% for Pb(II), Cd(II), and Cr(IV). Increasing the magnetic treatment time from 1 to 20 min was shown to lead to ≈ 20% increase in Pb(II) removal efficiency, but no improvements for Cd(II) and Cr(IV). In contrast, increasing the reaction time decreased the Pb(II) removal efficiency, yet no effects observed for Cd(II) and Cr(IV). In general, 1 min reaction and 5 min magnetic treatment were found sufficient to achieve considerable heavy metal removals. For comparable efficiencies, use of magnetic method could significantly reduce nZVI loading. XPS analysis results indicated that atomic percentages of O 1s, Fe 2p, Cd 3d, Pb 4f and Cr 2p varied with metal exposures. Different from Cd(II) and Cr(IV), aqueous iron ions might be possibly present when treating Pb(II). This study demonstrated a rapid heavy metal removal method using the magnetic property of nZVI particles, while contributing to understanding of the relevant removal mechanisms

  17. Iron, zinc, and copper in retinal physiology and disease.

    PubMed

    Ugarte, Marta; Osborne, Neville N; Brown, Laurence A; Bishop, Paul N

    2013-01-01

    The essential trace metals iron, zinc, and copper play important roles both in retinal physiology and disease. They are involved in various retinal functions such as phototransduction, the visual cycle, and the process of neurotransmission, being tightly bound to proteins and other molecules to regulate their structure and/or function or as unbound free metal ions. Elevated levels of "free" or loosely bound metal ions can exert toxic effects, and in order to maintain homeostatic levels to protect retinal cells from their toxicity, appropriate mechanisms exist such as metal transporters, chaperones, and the presence of certain storage molecules that tightly bind metals to form nontoxic products. The pathways to maintain homeostatic levels of metals are closely interlinked, with various metabolic pathways directly and/or indirectly affecting their concentrations, compartmentalization, and oxidation/reduction states. Retinal deficiency or excess of these metals can result from systemic depletion and/or overload or from mutations in genes involved in maintaining retinal metal homeostasis, and this is associated with retinal dysfunction and pathology. Iron accumulation in the retina, a characteristic of aging, may be involved in the pathogenesis of retinal diseases such as age-related macular degeneration (AMD). Zinc deficiency is associated with poor dark adaptation. Zinc levels in the human retina and RPE decrease with age in AMD. Copper deficiency is associated with optic neuropathy, but retinal function is maintained. The changes in iron and zinc homeostasis in AMD have led to the speculation that iron chelation and/or zinc supplements may help in its treatment. Copyright © 2013 Elsevier Inc. All rights reserved.

  18. Communication: Influence of nanophase segregation on ion transport in room temperature ionic liquids

    DOE PAGES

    Griffin, Philip J.; Wang, Yangyang; Holt, Adam P.; ...

    2016-04-21

    In this paper, we report measurements of the ionic conductivity, shear viscosity, and structural dynamics in a homologous series of quaternary ammonium ionic liquids (ILs) and a prototypical imidazolium-based IL over a wide range of temperatures down to the glass transition. We find that the ionic conductivity of these materials generally decreases, while the shear viscosity correspondingly increases, with increasing volume fraction of aliphatic side groups. Upon crossing an aliphatic volume fraction of ~0.40, we observe a sharp, order-of-magnitude decrease in ionic conductivity and enhancement of viscosity, which coincides with the presence of long-lived, nanometer-sized alkyl aggregates. These strong changesmore » in dynamics are not mirrored in the ionicity of these ILs, which decreases nearly linearly with aliphatic volume fraction. Finally, our results demonstrate that nanophase segregation in neat ILs strongly reduces ionic conductivity primarily due to an aggregation-induced suppression of dynamics.« less

  19. Unique Properties of Lunar Impact Glass: Nanophase Metallic Fe Synthesis

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

    Liu, Yang; Taylor, Lawrence A.; Thompson, James R

    2007-01-01

    Lunar regolith contains important materials that can be used for in-situ resource utilization (ISRU) on the Moon, thereby providing for substantial economic savings for development of a manned base. However, virtually all activities on the Moon will be affected by the deleterious effects of the adhering, abrasive, and pervasive nature of lunar dust (<20 {micro}m portion of regolith, which constitutes {approx}20 wt% of the soil). In addition, the major impact-produced glass in the lunar soil, especially agglutinitic glass (60-80 vol% of the dust), contains unique nanometer-sized metallic Fe (np-Fe{sup 0}), which may pose severe pulmonary problems for humans. The presencemore » of the np-Fe0 imparts considerable magnetic susceptibility to the fine portion of the lunar soil, and dust mitigation techniques can be designed using these magnetic properties. The limited availability of Apollo lunar soils for ISRU research has made it necessary to produce materials that simulate this unique np-Fe{sup 0} property, for testing different dust mitigation methods using electromagnetic fields, and for toxicity studies of human respiratory and pulmonary systems, and for microwave treatment of lunar soil to produce paved roads, etc. A method for synthesizing np-Fe{sup 0} in an amorphous silica matrix is presented here. This type of specific simulant can be used as an additive to other existing lunar soil simulants.« less

  20. Iron decreases biological effects of ozone exposure

    EPA Science Inventory

    CONTEXT: Ozone (0(3)) exposure is associated with a disruption of iron homeostasis and increased availability of this metal which potentially contributes to an oxidative stress and biologicaleffects. OBJECTIVE: We tested the postulate that increased concentrations of iron in c...

  1. A single low-energy, iron-poor supernova as the source of metals in the star SMSS J031300.36-670839.3.

    PubMed

    Keller, S C; Bessell, M S; Frebel, A; Casey, A R; Asplund, M; Jacobson, H R; Lind, K; Norris, J E; Yong, D; Heger, A; Magic, Z; Da Costa, G S; Schmidt, B P; Tisserand, P

    2014-02-27

    The element abundance ratios of four low-mass stars with extremely low metallicities (abundances of elements heavier than helium) indicate that the gas out of which the stars formed was enriched in each case by at most a few--and potentially only one--low-energy supernova. Such supernovae yield large quantities of light elements such as carbon but very little iron. The dominance of low-energy supernovae seems surprising, because it had been expected that the first stars were extremely massive, and that they disintegrated in pair-instability explosions that would rapidly enrich galaxies in iron. What has remained unclear is the yield of iron from the first supernovae, because hitherto no star has been unambiguously interpreted as encapsulating the yield of a single supernova. Here we report the optical spectrum of SMSS J031300.36-670839.3, which shows no evidence of iron (with an upper limit of 10(-7.1) times solar abundance). Based on a comparison of its abundance pattern with those of models, we conclude that the star was seeded with material from a single supernova with an original mass about 60 times that of the Sun (and that the supernova left behind a black hole). Taken together with the four previously mentioned low-metallicity stars, we conclude that low-energy supernovae were common in the early Universe, and that such supernovae yielded light-element enrichment with insignificant iron. Reduced stellar feedback both chemically and mechanically from low-energy supernovae would have enabled first-generation stars to form over an extended period. We speculate that such stars may perhaps have had an important role in the epoch of cosmic reionization and the chemical evolution of early galaxies.

  2. Impact of two iron(III) chelators on the iron, cadmium, lead and nickel accumulation in poplar grown under heavy metal stress in hydroponics.

    PubMed

    Mihucz, Victor G; Csog, Árpád; Fodor, Ferenc; Tatár, Enikő; Szoboszlai, Norbert; Silaghi-Dumitrescu, Luminiţa; Záray, Gyula

    2012-04-15

    Poplar (Populus jacquemontiana var. glauca cv. Kopeczkii) was grown in hydroponics containing 10 μM Cd(II), Ni(II) or Pb(II), and Fe as Fe(III) EDTA or Fe(III) citrate in identical concentrations. The present study was designed to compare the accumulation and distribution of Fe, Cd, Ni and Pb within the different plant compartments. Generally, Fe and heavy-metal accumulation were higher by factor 2-7 and 1.6-3.3, respectively, when Fe(III) citrate was used. Iron transport towards the shoot depended on the Fe(III) chelate and, generally, on the heavy metal used. Lead was accumulated only in the root. The amounts of Fe and heavy metals accumulated by poplar were very similar to those of cucumber grown in an identical way, indicating strong Fe uptake regulation of these two Strategy I plants: a cultivar and a woody plant. The Strategy I Fe uptake mechanism (i.e. reducing Fe(III) followed by Fe(II) uptake), together with the Fe(III) chelate form in the nutrient solution had significant effects on Fe and heavy metal uptake. Poplar appears to show phytoremediation potential for Cd and Ni, as their transport towards the shoot was characterized by 51-54% and 26-48% depending on the Fe(III) supply in the nutrient solution. Copyright © 2012 Elsevier GmbH. All rights reserved.

  3. Exploring Iron Silicate Precursors of Ancient Iron Formations through Rock Record, Laboratory and Field Analogue Investigations

    NASA Astrophysics Data System (ADS)

    Johnson, J. E.; Rasmussen, B.; Muhling, J.; Benzerara, K.; Jezequel, D.; Cosmidis, J.; Templeton, A. S.

    2016-12-01

    In direct contrast to today's oceans, iron-rich chemical precipitates dominate the deep marine sedimentary record > 2.3 billion years ago. The deposition of these minerals resulted in massive iron formations and indicate that the ocean was previously ferruginous and largely anoxic. To precipitate and concentrate iron in the sediments, many hypotheses have centered on the oxidation of soluble Fe(II) to solid Fe(III)-oxyhydroxides; these ideas have stimulated extensive research using iron-oxidizing bacteria to produce Fe(III)-oxides and trace metal sorption experiments on Fe(III)-oxides, leading to inferences of trace metal availability and implications for enzymatic and microbial evolution as well as pO2 levels and seawater chemistry. However, recent discoveries of disseminated iron-silicate nanoparticles in early-silicifying chert indicate that iron-silicates may have instead been the primary precipitates from these Archean ferruginous oceans (Rasmussen et al, 2015). Considering the significant paradigm shift this discovery implies for interpretations of Archean elemental cycling, redox state and potential microbial metabolisms, we investigated these iron-silicate inclusions and their implications for ancient seawater chemistry in a multi-faceted approach using spectroscopic- and diffraction-based techniques. The crystal structure, Fe oxidation state and Fe coordination environment of iron-silicate nanoparticles have been interrogated using microscale X-ray absorption spectroscopy, TEM and nanoscale scanning transmission X-ray microscopy. To further explore the chemical and potential biological controls on iron-silicate formation, we have also performed laboratory experiments to mimic Archean seawater and precipitate iron-bearing silicate minerals under abiotic conditions and in the presence of iron-oxidizing bacteria. In a complementary study, sediments from a natural Archean analogue system were sampled to determine if iron-silicate minerals form in Mexican

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

    PubMed

    Nilsson, M; Andreas, L; Lagerkvist, A

    2016-05-01

    About 85% of the ashes produced in Sweden originated from the incineration of municipal solid waste and biofuel. The rest comes from the thermal treatment of recycled wood, peat, charcoal and others. About 68% of all ashes annually produced in Sweden are used for constructions on landfills, mainly slopes, roads and embankments, and only 3% for construction of roads and working surfaces outside the landfills (SCB, 2013). Since waste bottom ash (BA) often has similar properties to crushed bedrock or gravel, it could be used for road constructions to a larger extent. However, the leaching of e.g. Cr, Cu, Mo, Pb and Zn can cause a threat to the surrounding environment if the material is used as it is. Carbonation is a commonly used pre-treatment method, yet it is not always sufficient. As leaching from aged ash is often controlled by adsorption to iron oxides, increasing the number of Fe oxide sorption sites can be a way to control the leaching of several critical elements. The importance of iron oxides as sorption sites for metals is known from both mineralogical studies of bottom ash and from the remediation of contaminated soil, where iron is used as an amendment. In this study, zero valent iron (Fe(0)) was added prior to accelerated carbonation in order to increase the number of adsorption sites for metals and thereby reduce leaching. Batch, column and pHstat leaching tests were performed and the leaching behaviour was evaluated with multivariate data analysis. It showed that leaching changed distinctly after the tested treatments, in particular after the combined treatment. Especially, the leaching of Cr and Cu clearly decreased as a result of accelerated carbonation. The combination of accelerated carbonation with Fe(0) addition reduced the leaching of Cr and Cu even further and reduced also the leaching of Mo, Zn, Pb and Cd compared to untreated BA. Compared with only accelerated carbonation, the Fe(0) addition significantly reduced the leaching of Cr, Cu and Mo

  5. Heavy metal mining using microbes.

    PubMed

    Rawlings, Douglas E

    2002-01-01

    The use of acidiphilic, chemolithotrophic iron- and sulfur-oxidizing microbes in processes to recover metals from certain types of copper, uranium, and gold-bearing minerals or mineral concentrates is now well established. During these processes insoluble metal sulfides are oxidized to soluble metal sulfates. Mineral decomposition is believed to be mostly due to chemical attack by ferric iron, with the main role of the microorganisms being to reoxidize the resultant ferrous iron back to ferric iron. Currently operating industrial biomining processes have used bacteria that grow optimally from ambient to 50 degrees C, but thermophilic microbes have been isolated that have the potential to enable mineral biooxidation to be carried out at temperatures of 80 degrees C or higher. The development of higher-temperature processes will extend the variety of minerals that can be commercially processed.

  6. Adsorption of poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) polymers on zinc, zinc oxide, iron, and iron oxide surfaces.

    PubMed

    Seifert, Susan; Simon, Frank; Baumann, Giesela; Hietschold, Michael; Seifert, Andreas; Spange, Stefan

    2011-12-06

    The adsorption of poly(vinyl formamide) (PVFA) and the statistic copolymers poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) onto zinc and iron metal particles as well as their oxides was investigated. The adsorbates were characterized by means of XPS, DRIFT spectroscopy, wet chemical analysis, and solvatochromic probes. Dicyano-bis-(1,10-phenanthroline)-iron(II) (1), 3-(4-amino-3-methylphenyl)-7-phenyl-benzo-[1,2-b:4,5-b']difuran-2,6-dione (2), and 4-tert-butyl-2-(dicyano-methylene)-5-[4-(diethylamino)-benzylidene]-Δ(3)-thiazoline (3) as solvatochromic probes were coadsorbed onto zinc oxide to measure various effects of surface polarity. The experimental findings showed that the adsorption mechanism of PVFA and PVFA-co-PVAm strongly depends on the degree of hydrolysis of PVFA and pH values and also on the kind of metal or metal oxide surfaces that were employed as adsorbents. The adsorption mechanism of PVFA/PVFA-co-PVAm onto zinc oxide and iron oxide surfaces is mainly affected by electrostatic interactions. Particularly in the region of pH 5, the adsorption of PVFA/PVFA-co-PVAm onto zinc and iron metal particles is additionally influenced by redox processes, dissolution, and complexation reactions. © 2011 American Chemical Society

  7. A long-term high-fat diet changes iron distribution in the body, increasing iron accumulation specifically in the mouse spleen.

    PubMed

    Yamano, Noriko; Ikeda, Yasumasa; Sakama, Minoru; Izawa-Ishizawa, Yuki; Kihira, Yoshitaka; Ishizawa, Keisuke; Miyamoto, Licht; Tomita, Shuhei; Tsuchiya, Koichiro; Tamaki, Toshiaki

    2015-01-01

    Although iron is an essential trace metal, its presence in excess causes oxidative stress in the human body. Recent studies have indicated that iron storage is a risk factor for type 2 diabetes mellitus. Dietary iron restriction or iron chelation ameliorates symptoms of type 2 diabetes in mouse models. However, whether iron content in the body changes with the development of diabetes is unknown. Here, we investigated the dynamics of iron accumulation and changes in iron absorption-related genes in mice that developed obesity and diabetes by consuming a high-fat diet (HFD-fed mice). HFD-fed mice (18-20 wk) were compared with control mice for hematologic features, serum ferritin levels, and iron contents in the gastrocnemius muscle, heart, epididymal fat, testis, liver, duodenum, and spleen. In addition, the spleen was examined histologically. Iron absorption-related gene expression in the liver and duodenum was also examined. Hemoglobin and serum ferritin levels were increased in HFD-fed mice. The HFD-fed mice showed iron accumulation in the spleen, but not in the heart or liver. Increased percentages of the splenic red pulp and macrophages were observed in HFD-fed mice and iron accumulation in the spleen was found mainly in the splenic red pulp. The HFD-fed mice also showed decreased iron content in the duodenum. The mRNA expression of divalent metal transporter-1 (DMT-1), an iron absorption-related gene, was elevated in the duodenum of HFD-fed mice. These results indicate that iron accumulation (specifically accumulation in the spleen) is enhanced by the development of type 2 diabetes induced by HFD.

  8. Soluble Iron in Alveolar Macrophages Modulates Iron Oxide Particle-Induced Inflammatory Response via Prostaglandin E2 Synthesis

    EPA Science Inventory

    Ambient particulate matter (PM)-associated metals have been shown to play an important role in cardiopulmonary health outcomes. To study the modulation of inflammation by PM-associated soluble metal, we investigated intracellular solubility of radiolabelled iron oxide (59

  9. Iron and Mechanisms of Emotional Behavior

    PubMed Central

    Kim, Jonghan; Wessling-Resnick, Marianne

    2014-01-01

    Iron is required for appropriate behavioral organization. Iron deficiency results in poor brain myelination and impaired monoamine metabolism. Glutamate and GABA homeostasis is modified by changes in brain iron status. Such changes not only produce deficits in memory/learning capacity and motor skills, but also emotional and psychological problems. An accumulating body of evidence indicates that both energy metabolism and neurotransmitter homeostasis influence emotional behavior, and both functions are influenced by brain iron status. Like other neurobehavioral aspects, the influence of iron metabolism on mechanisms of emotional behavior are multifactorial: brain region-specific control of behavior, regulation of neurotransmitters and associated proteins, temporal and regional differences in iron requirements, oxidative stress responses to excess iron, sex differences in metabolism, and interactions between iron and other metals. To better understand the role that brain iron plays in emotional behavior and mental health, this review discusses the pathologies associated with anxiety and other emotional disorders with respect to body iron status. PMID:25154570

  10. Separations of actinides, lanthanides and other metals

    DOEpatents

    Smith, Barbara F.; Jarvinen, Gordon D.; Ensor, Dale D.

    1995-01-01

    An organic extracting solution comprised of a bis(acylpyrazolone or a substituted bis(acylpyrazolone) and an extraction method useful for separating certain elements of the actinide series of the periodic table having a valence of four from one other, and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also useful for separating hexavalent actinides from one or more of the substances in a group consisting of trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals.

  11. Heavy metal removal using nanoscale zero-valent iron (nZVI): Theory and application.

    PubMed

    Li, Shaolin; Wang, Wei; Liang, Feipeng; Zhang, Wei-Xian

    2017-01-15

    Treatment of wastewater containing heavy metals requires considerations on simultaneous removal of different ions, system reliability and quick separation of reaction products. In this work, we demonstrate that nanoscale zero-valent iron (nZVI) is an ideal reagent for removing heavy metals from wastewater. Batch experiments show that nZVI is able to perform simultaneous removal of different heavy metals and arsenic; reactive nZVI in uniform dispersion brings rapid changes in solution E h , enabling a facile way for reaction regulation. Microscope characterizations and settling experiments suggest that nZVI serves as solid seeds that facilitate products separation. A treatment process consisting of E h -controlled nZVI reaction, gravitational separation and nZVI recirculation is then demonstrated. Long-term (>12 months) operation shows that the process achieves >99.5% removal of As, Cu and a number of other toxic elements. The E h -controlled reaction system sustains a highly-reducing condition in reactor and reduces nZVI dosage. The process produces effluent of stable quality that meets local discharge guidelines. The gravitational separator shows high efficacy of nZVI recovery and the recirculation improves nZVI material efficiency, resulting in extraordinarily high removal capacities ((245mg As+226 mg-Cu)/g-nZVI). The work provides proof that nanomaterials can offer truly green and cost-effective solutions for wastewater treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Organometallic iron complexes as potential cancer therapeutics.

    PubMed

    Mojžišová, Gabriela; Mojžiš, Ján; Vašková, Janka

    2014-01-01

    Metal-containing drugs have long been used for medicinal purposes in more or less empirical way. The potential of these anticancer agents has only been fully realised and explored since the discovery of the biological activity of cisplatin. Cisplatin and carboplatin have been two of the most successful anti-cancer agents ever developed, and are currently used to treat ovarian, lung and testicular cancers. They share certain side effects, so their clinical use is severely limited by dose-limiting toxicity. Inherent or acquired resistance is a second problem often associated with platinum-based drugs, with further limits of their clinical use. These problems have prompted chemists to employ different strategies in development of the new metal-based anticancer agents with different mechanisms of action. There are various metal complexes still under development and investigation for the future cancer treatment use. In the search for novel bio-organometallic molecules, iron containing anti-tumoral agents are enjoying an increasing interest and appear very promising as the potential drug candidates. Iron, as an essential cofactor in a number of enzymes and physiological processes, may be less toxic than non essential metals, such as platinum. Up to now, some of iron complexes have been tested as cytotoxic agents and found to be endowed with an antitumor activity in several in vitro tests (on cultured cancer cell lines) and few in vivo experiments (e. g. on Ehrlich's ascites carcinoma). Although the precise molecular mechanism is yet to be defined, a number of observations suggest that the reactive oxygen species can play important role in iron-induced cytotoxicty. This review covers some relevant examples of research on the novel iron complexes.

  13. Scavenging iron: a novel mechanism of plant immunity activation by microbial siderophores.

    PubMed

    Aznar, Aude; Chen, Nicolas W G; Rigault, Martine; Riache, Nassima; Joseph, Delphine; Desmaële, Didier; Mouille, Grégory; Boutet, Stéphanie; Soubigou-Taconnat, Ludivine; Renou, Jean-Pierre; Thomine, Sébastien; Expert, Dominique; Dellagi, Alia

    2014-04-01

    Siderophores are specific ferric iron chelators synthesized by virtually all microorganisms in response to iron deficiency. We have previously shown that they promote infection by the phytopathogenic enterobacteria Dickeya dadantii and Erwinia amylovora. Siderophores also have the ability to activate plant immunity. We have used complete Arabidopsis transcriptome microarrays to investigate the global transcriptional modifications in roots and leaves of Arabidopsis (Arabidopsis thaliana) plants after leaf treatment with the siderophore deferrioxamine (DFO). Physiological relevance of these transcriptional modifications was validated experimentally. Immunity and heavy-metal homeostasis were the major processes affected by DFO. These two physiological responses could be activated by a synthetic iron chelator ethylenediamine-di(o-hydroxyphenylacetic) acid, indicating that siderophores eliciting activities rely on their strong iron-chelating capacity. DFO was able to protect Arabidopsis against the pathogenic bacterium Pseudomonas syringae pv tomato DC3000. Siderophore treatment caused local modifications of iron distribution in leaf cells visible by ferrocyanide and diaminobenzidine-H₂O₂ staining. Metal quantifications showed that DFO causes a transient iron and zinc uptake at the root level, which is presumably mediated by the metal transporter iron regulated transporter1 (IRT1). Defense gene expression and callose deposition in response to DFO were compromised in an irt1 mutant. Consistently, plant susceptibility to D. dadantii was increased in the irt1 mutant. Our work shows that iron scavenging is a unique mechanism of immunity activation in plants. It highlights the strong relationship between heavy-metal homeostasis and immunity.

  14. Dissolved and particulate trace metal micronutrients under the McMurdo Sound seasonal sea ice: basal sea ice communities as a capacitor for iron

    NASA Astrophysics Data System (ADS)

    Noble, Abigail; Saito, Mak; Moran, Dawn; Allen, Andrew

    2013-10-01

    Dissolved and particulate metal concentrations are reported from three sites beneath and at the base of the McMurdo Sound seasonal sea ice in the Ross Sea of Antarctica. This dataset provided insight into Co and Mn biogeochemistry, supporting a previous hypothesis for water column mixing occurring faster than scavenging. Three observations support this: first, Mn-containing particles with Mn/Al ratios in excess of the sediment were present in the water column, implying the presence of bacterial Mn-oxidation processes. Second, dissolved and labile Co were uniform with depth beneath the sea ice after the winter season. Third, dissolved Co:PO43- ratios were consistent with previously observed Ross Sea stoichiometry, implying that over-winter scavenging was slow relative to mixing. Abundant dissolved Fe and Mn were consistent with a winter reserve concept, and particulate Al, Fe, Mn, and Co covaried, implying that these metals behaved similarly. Elevated particulate metals were observed in proximity to the nearby Islands, with particulate Fe/Al ratios similar to that of nearby sediment, consistent with a sediment resuspension source. Dissolved and particulate metals were elevated at the shallowest depths (particularly Fe) with elevated particulate P/Al and Fe/Al ratios in excess of sediments, demonstrating a sea ice biomass source. The sea ice biomass was extremely dense (chl a >9500 μg/L) and contained high abundances of particulate metals with elevated metal/Al ratios. A hypothesis for seasonal accumulation of bioactive metals at the base of the McMurdo Sound sea ice by the basal algal community is presented, analogous to a capacitor that accumulates iron during the spring and early summer. The release and transport of particulate metals accumulated at the base of the sea ice by sloughing is discussed as a potentially important mechanism in providing iron nutrition during polynya phytoplankton bloom formation and could be examined in future oceanographic expeditions.

  15. Rapid, sensitive, and selective fluorescent DNA detection using iron-based metal-organic framework nanorods: Synergies of the metal center and organic linker.

    PubMed

    Tian, Jingqi; Liu, Qian; Shi, Jinle; Hu, Jianming; Asiri, Abdullah M; Sun, Xuping; He, Yuquan

    2015-09-15

    Considerable recent attention has been paid to homogeneous fluorescent DNA detection with the use of nanostructures as a universal "quencher", but it still remains a great challenge to develop such nanosensor with the benefits of low cost, high speed, sensitivity, and selectivity. In this work, we report the use of iron-based metal-organic framework nanorods as a high-efficient sensing platform for fluorescent DNA detection. It only takes about 4 min to complete the whole "mix-and-detect" process with a low detection limit of 10 pM and a strong discrimination of single point mutation. Control experiments reveal the remarkable sensing behavior is a consequence of the synergies of the metal center and organic linker. This work elucidates how composition control of nanostructures can significantly impact their sensing properties, enabling new opportunities for the rational design of functional materials for analytical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Carbon on Mercury's Surface - Origin, Distribution, and Concentration

    NASA Technical Reports Server (NTRS)

    Klima, Rachel L.; Blewett, David T.; Denevi, Brett W.; Ernst, Carolyn M.; Murchie, Scott L.; Peplowski, Patrick N.; Perera, Virange; Vander Kaaden, Kathleen

    2018-01-01

    Distinctive low-reflectance material (LRM) was first observed on Mercury in Mariner 10 flyby images. Visible to near-infrared reflectance spectra of LRM are flatter than the average reflectance spectrum of Mercury, which is strongly red sloped (increasing in reflectance with wavelength). From Mariner 10 and early MErcury, Surface, Space, ENvironment, GEochemistry, and Ranging (MESSENGER) flyby observations, it was suggested that a higher content of ilmenite, ulvospinel, carbon, or iron metal could cause both the characteristic dark, flat spectrum of LRM and the globally low reflectance of Mercury. Once MESSENGER entered orbit, low Fe and Ti abundances measured by the X-Ray and Gamma-Ray Spectrometers ruled out ilmenite, and ulvospinel as important surface constituents and implied that LRM was darkened by a different phase, such as carbon or small amounts of micro- or nanophase iron or iron sulfide dispersed in a silicate matrix. Low-altitude thermal neutron measurements of three LRM-rich regions confirmed an enhancement of 1-3 weight-percent carbon over the global abundance, supporting the hypothesis that LRM is darkened by carbon.

  17. An innovative method for nondestructive analysis of cast iron artifacts at Hopewell Furnace National Historic Site, Pennsylvania

    USGS Publications Warehouse

    Sloto, R.A.; Helmke, M.F.

    2011-01-01

    Iron ore containing elevated concentrations of trace metals was smelted at Hopewell Furnace during its 113 years of operation (1771-1883). For this study, we sampled iron ore, cast iron furnace products, slag, soil, groundwater, streamflow, and streambed sediment to determine the fate of trace metals released into the environment during the iron-smelting process. Standard techniques were used to sample and analyze all media except cast iron. We analyzed the trace-metal content of the cast iron using a portable X-ray fluorescence spectrometer, which provided rapid, on-site, nondestructive analyses for 23 elements. The artifacts analyzed included eight cast iron stoves, a footed pot, and a kettle in the Hopewell Furnace museum. We measured elevated concentrations of arsenic, copper, lead, and zinc in the cast iron. Lead concentrations as great as 3,150 parts per million were measured in the stoves. Cobalt was detectable but not quantifiable because of interference with iron. Our study found that arsenic, cobalt, and lead were not released to soil or slag, which could pose a significant health risk to visitors and employees. Instead, our study demonstrates these heavy metals remained with the cast iron and were removed from the site.

  18. Chalcogenide and pnictide nanocrystals from the silylative deoxygenation of metal oxides

    DOE PAGES

    Lin, Chia-Cheng; Tan, Shannon J.; Vela, Javier

    2017-09-11

    Transition metal chalcogenide and pnictide nanocrystals are of interest for optoelectronic and catalytic applications. In this paper, we present a generalized route to the synthesis of these materials from the silylative deoxygenation of metal oxides with trimethylsilyl reagents. Specific nanophases produced in this way include Ni 3S 2, Ni 5Se 5, Ni 2P, Co 9S 8, Co 3Se 4, CoP, Co 2P, and heterobimetallic (Ni/Co) 9S 8. The resulting chalcogenide nanocrystals are hollow, likely due to differential rates of ion diffusion during the interfacial phase transformation reaction (Kirkendall-type effect). In contrast, the phosphide nanocrystals are solid, likely because they formmore » at higher reaction temperatures. Finally, in all cases, simultaneous partial decomposition of the deoxygenating silyl reagent produces a coating of amorphous silica around the newly formed nanocrystals, which could impact their stability and recyclability.« less

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

    NASA Astrophysics Data System (ADS)

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

    2017-10-01

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

  20. Electroslag Treatment of Liquid Cast Iron

    NASA Astrophysics Data System (ADS)

    Grachev, V. A.

    2018-01-01

    The processes that occur in the liquid metal-slag system during electroslag treatment of cast iron are studied from an electrochemical standpoint. The role of electrolysis in the electroslag process is shown, and a method for producing high-strength cast iron with globular graphite using electrolysis of a slag containing magnesium oxides and fluorides is proposed and tested.

  1. Elemental and iron isotopic composition of aerosols collected in a parking structure.

    PubMed

    Majestic, Brian J; Anbar, Ariel D; Herckes, Pierre

    2009-09-01

    The trace metal contents and iron isotope composition of size-resolved aerosols were determined in a parking structure in Tempe, AZ, USA. Particulate matter (PM)<2.5 microm in diameter (the fine fraction) and PM>2.5 microm were collected. Several air toxics (e.g., arsenic, cadmium, and antimony) were enriched above the crustal average, implicating automobiles as an important source. Extremely high levels of fine copper (up to 1000 ng m(-3)) were also observed in the parking garage, likely from brake wear. The iron isotope composition of the aerosols were found to be +0.15+/-0.03 per thousand and +0.18+/-0.03 per thousand for the PM<2.5 microm and PM>2.5 microm fractions, respectively. The similarity of isotope composition indicates a common source for each size fraction. To better understand the source of iron in the parking garage, the elemental composition in four brake pads (two semi-metallic and two ceramic), two tire tread samples, and two waste oil samples were determined. Striking differences in the metallic and ceramic brake pads were observed. The ceramic brake pads contained 10-20% copper by mass, while the metallic brake pads contained about 70% iron, with very little copper. Both waste oil samples contained significant amounts of calcium, phosphorous, and zinc, consistent with the composition of some engine oil additives. Differences in iron isotope composition were observed between the source materials; most notably between the tire tread (average=+0.02 per thousand) and the ceramic brake linings (average=+0.65 per thousand). Differences in isotopic composition were also observed between the metallic (average=+0.18 per thousand) and ceramic brake pads, implying that iron isotope composition may be used to resolve these sources. The iron isotope composition of the metallic brake pads was found to be identical to the aerosols, implying that brake dust is the dominant source of iron in a parking garage.

  2. Iron metal production in silicate melts through the direct reduction of Fe/II/ by Ti/III/, Cr/II/, and Eu/II/. [in lunar basalts

    NASA Technical Reports Server (NTRS)

    Schreiber, H. D.; Balazs, G. B.; Shaffer, A. P.; Jamison, P. L.

    1982-01-01

    The production of metallic iron in silicate melts by chemical reactions of Ti(3+), Cr(2+), and Eu(2+) with Fe(2+) is demonstrated under experimental conditions in a simplified basaltic liquid. These reactions form a basis for interpreting the role of isochemical valency exchange models in explanations for the reduced nature of lunar basalts. The redox couples are individually investigated in the silicate melt to ascertain reference redox ratios that are independent of mutual interactions. These studies also provide calibrations of spectral absorptions of the Fe(2+) and Ti(2+) species in these glasses. Subsequent spectrophotometric analyses of Fe(2+) and Ti(2+) in glasses doped with both iron and titanium and of Fe(2+) in glasses doped with either iron and chromium or iron and europium ascertain the degree of mutual interactions in these dual-doped glasses.

  3. Native iron in the continental lower crust - Petrological and geophysical implications

    NASA Technical Reports Server (NTRS)

    Haggerty, S. E.; Toft, P. B.

    1985-01-01

    Lower crustal granulite xenoliths recovered from a kimberlite pipe in western Africa contain native iron (Fe) as a decomposition product of garnet and ilmenite. Magnetic measurements show that less than 0.1 percent (by volume) of iron metal is present. Data from geothermometry and oxygen geobarometry indicate that the oxide and metal phases equilibrated between iron-wuestite and magnetite-wuestite buffers, which may represent the oxidation state of the continental lower crust, and the depleted lithospheric upper mantle. Ferromagnetic native iron could be stable to a depth of about 95 kilometers and should be considered in the interpretation of long-wavelength static magnetic anomalies.

  4. Native iron in the continental lower crust - Petrological and geophysical implications

    NASA Astrophysics Data System (ADS)

    Haggerty, S. E.; Toft, P. B.

    1985-08-01

    Lower crustal granulite xenoliths recovered from a kimberlite pipe in western Africa contain native iron (Fe) as a decomposition product of garnet and ilmenite. Magnetic measurements show that less than 0.1 percent (by volume) of iron metal is present. Data from geothermometry and oxygen geobarometry indicate that the oxide and metal phases equilibrated between iron-wuestite and magnetite-wuestite buffers, which may represent the oxidation state of the continental lower crust, and the depleted lithospheric upper mantle. Ferromagnetic native iron could be stable to a depth of about 95 kilometers and should be considered in the interpretation of long-wavelength static magnetic anomalies.

  5. Mining for metals in society's waste

    USGS Publications Warehouse

    Smith, Kathleen S.; Plumlee, Geoffrey S.; Hageman, Philip L.

    2015-01-01

    Metals and minerals are natural resources that human beings have been mining for thousands of years. Contemporary metal mining is dominated by iron ore, copper and gold, with 2 billion tons of iron ore, nearly 20 million tons of copper and 2,000 tons of gold produced every year. Tens to hundreds of tons of other metals that are essential components for electronics, green energy production, and high-technology products are produced annually.

  6. Covalence of atoms in the heavier transition metals*

    PubMed Central

    Pauling, Linus

    1977-01-01

    The observed magnetic properties of the heavier transition metals permit them to have larger metallic valences than their iron-group congeners. With 0.72 metallic orbital, as found for the iron-group metals, the maximum metallic valence and minimum interatomic distance would occur for 8.28 transargononic electrons. The curves of observed interatomic distances for the close-packed metals of the second and third long periods have minima at this point, supporting the assignment of high valences to these metals. Values of the single-bond radii corresponding to these valences are calculated. PMID:16592407

  7. Iron-Terephthalate Coordination Network Thin Films Through In-Situ Atomic/Molecular Layer Deposition.

    PubMed

    Tanskanen, A; Karppinen, M

    2018-06-12

    Iron terephthalate coordination network thin films can be fabricated using the state-of-the-art gas-phase atomic/molecular layer deposition (ALD/MLD) technique in a highly controlled manner. Iron is an Earth-abundant and nonhazardous transition metal, and with its rich variety of potential applications an interesting metal constituent for the inorganic-organic coordination network films. Our work underlines the role of the metal precursor used when aiming at in-situ ALD/MLD growth of crystalline inorganic-organic thin films. We obtain crystalline iron terephthalate films when FeCl 3 is employed as the iron source whereas depositions based on the bulkier Fe(acac) 3 precursor yield amorphous films. The chemical composition and structure of the films are investigated with GIXRD, XRR, FTIR and XPS.

  8. Amorphous metal composites

    DOEpatents

    Byrne, Martin A.; Lupinski, John H.

    1984-01-01

    An improved amorphous metal composite and process of making the composite. The amorphous metal composite comprises amorphous metal (e.g. iron) and a low molecular weight thermosetting polymer binder. The process comprises placing an amorphous metal in particulate form and a thermosetting polymer binder powder into a container, mixing these materials, and applying heat and pressure to convert the mixture into an amorphous metal composite.

  9. Thermodynamics and Charging of Interstellar Iron Nanoparticles

    NASA Astrophysics Data System (ADS)

    Hensley, Brandon S.; Draine, B. T.

    2017-01-01

    Interstellar iron in the form of metallic iron nanoparticles may constitute a component of the interstellar dust. We compute the stability of iron nanoparticles to sublimation in the interstellar radiation field, finding that iron clusters can persist down to a radius of ≃4.5 Å, and perhaps smaller. We employ laboratory data on small iron clusters to compute the photoelectric yields as a function of grain size and the resulting grain charge distribution in various interstellar environments, finding that iron nanoparticles can acquire negative charges, particularly in regions with high gas temperatures and ionization fractions. If ≳10% of the interstellar iron is in the form of ultrasmall iron clusters, the photoelectric heating rate from dust may be increased by up to tens of percent relative to dust models with only carbonaceous and silicate grains.

  10. Characterization of ferromagnetic or conductive properties of metallic foreign objects embedded within the human body with magnetic iron detector (MID): Screening patients for MRI.

    PubMed

    Gianesin, Barbara; Zefiro, Daniele; Paparo, Francesco; Caminata, Alessio; Balocco, Manuela; Carrara, Paola; Quintino, Sabrina; Pinto, Valeria; Bacigalupo, Lorenzo; Rollandi, Gian Andrea; Marinelli, Mauro; Forni, Gian Luca

    2015-05-01

    A preliminary assessment of the MRI-compatibility of metallic object possibly embedded within the patient is required before conducting the MRI examination. The Magnetic Iron Detector (MID) is a highly sensitive susceptometer that uses a weak magnetic field to measure iron overload in the liver. MID might be used to perform a screening procedure for MRI by determining the ferromagnetic/conductive properties of embedded metallic objects. The study was composed by: (i) definition of MID sensitivity threshold; (ii) application of MID in a procedure to characterize the ferromagnetic/conductive properties of metallic foreign objects in 958 patients scheduled for MID examination. The detection threshold for ferromagnetic objects was found to be the equivalent of a piece of wire of length 2 mm and gauge 0.8 mm(2) and, representing purely conductive objects, an aluminum sheet of area 2 × 2 cm(2) . Of 958 patients, 165 had foreign bodies of unknown nature. MID was able to detect those with ferromagnetic and/or conducting properties based on fluctuations in the magnetic and eddy current signals versus control. The high sensitivity of MID makes it suitable for assessing the ferromagnetic/conductive properties of metallic foreign objects embedded within the body of patients scheduled for MRI. © 2015 Wiley Periodicals, Inc.

  11. The biological effect of asbestos exposure is dependent on changes in iron homeostasis

    EPA Science Inventory

    Abstract Functional groups on the surface of fibrous silicates can complex iron. We tested the postulate that 1) asbestos complexes and sequesters host cell iron resulting in a disruption of metal homeostasis and 2) this loss of essential metal results in an oxidative stress and...

  12. Remediation of Ni(2+)-contaminated water using iron powder and steel manufacturing byproducts.

    PubMed

    Jin, Jian; Zhao, Wei-Rong; Xu, Xin-Hua; Hao, Zhi-Wei; Liu, Yong; He, Ping; Zhou, Mi

    2006-01-01

    Steel manufacturing byproducts and commercial iron powders were tested in the treatment of Ni(2+)-contaminated water. Ni2+ is a priority pollutant of some soils and groundwater. The use of zero-valent iron, which can reduce Ni2+ to its neural form appears to be an alternative approach for the remediation of Ni(2+)-contaminated sites. Our experimental data show that the removal efficiencies of Ni2+ were 95.15% and 94.68% at a metal to solution ratio of 20 g/L for commercial iron powders and the steel manufacturing byproducts in 60 min at room temperature, respectively. The removal efficiency reached 98.20% when the metal to solution ratio was 40 g/L for commercial iron powders. Furthermore, we found that the removal efficiency was also largely affected by other factors such as the pHs of the treated water, the length of time for the metal to be in contact with the Ni(2+)-contaminated water, initial concentrations of metal solutions, particle sizes and the amount of iron powders. Surprisingly, the reaction temperature appeared to have little effect on the removal efficiency. Our study opens the way to further optimize the reaction conditions of in situ remediation of Ni2+ or other heavy metals on contaminated sites.

  13. Current understanding of iron homeostasis.

    PubMed

    Anderson, Gregory J; Frazer, David M

    2017-12-01

    Iron is an essential trace element, but it is also toxic in excess, and thus mammals have developed elegant mechanisms for keeping both cellular and whole-body iron concentrations within the optimal physiologic range. In the diet, iron is either sequestered within heme or in various nonheme forms. Although the absorption of heme iron is poorly understood, nonheme iron is transported across the apical membrane of the intestinal enterocyte by divalent metal-ion transporter 1 (DMT1) and is exported into the circulation via ferroportin 1 (FPN1). Newly absorbed iron binds to plasma transferrin and is distributed around the body to sites of utilization with the erythroid marrow having particularly high iron requirements. Iron-loaded transferrin binds to transferrin receptor 1 on the surface of most body cells, and after endocytosis of the complex, iron enters the cytoplasm via DMT1 in the endosomal membrane. This iron can be used for metabolic functions, stored within cytosolic ferritin, or exported from the cell via FPN1. Cellular iron concentrations are modulated by the iron regulatory proteins (IRPs) IRP1 and IRP2. At the whole-body level, dietary iron absorption and iron export from the tissues into the plasma are regulated by the liver-derived peptide hepcidin. When tissue iron demands are high, hepcidin concentrations are low and vice versa. Too little or too much iron can have important clinical consequences. Most iron deficiency reflects an inadequate supply of iron in the diet, whereas iron excess is usually associated with hereditary disorders. These disorders include various forms of hemochromatosis, which are characterized by inadequate hepcidin production and, thus, increased dietary iron intake, and iron-loading anemias whereby both increased iron absorption and transfusion therapy contribute to the iron overload. Despite major recent advances, much remains to be learned about iron physiology and pathophysiology. © 2017 American Society for Nutrition.

  14. Biomineralization of metal-containing ores and concentrates.

    PubMed

    Rawlings, Douglas E; Dew, David; du Plessis, Chris

    2003-01-01

    Biomining is the use of microorganisms to extract metals from sulfide and/or iron-containing ores and mineral concentrates. The iron and sulfide is microbially oxidized to produce ferric iron and sulfuric acid, and these chemicals convert the insoluble sulfides of metals such as copper, nickel and zinc to soluble metal sulfates that can be readily recovered from solution. Although gold is inert to microbial action, microbes can be used to recover gold from certain types of minerals because as they oxidize the ore, they open its structure, thereby allowing gold-solubilizing chemicals such as cyanide to penetrate the mineral. Here, we review a strongly growing microbially-based metal extraction industry, which uses either rapid stirred-tank or slower irrigation technology to recover metals from an increasing range of minerals using a diversity of microbes that grow at a variety of temperatures.

  15. Friction and transfer of copper, silver, and gold to iron in the presence of various adsorbed surface films

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1979-01-01

    Sliding friction experiments were conducted with the noble metals copper, silver, and gold and two binary alloys of these metals contacting iron in the presence of various adsorbates including, oxygen, methyl mercaptan, and methyl chloride. A pin on disk specimen configuration was used with a load of 100 grams, sliding velocity of 60 mm/min; at 25 C with the surfaces saturated with the adsorbates. Auger emission spectroscopy was used to monitor surface films. Results of the experiments indicate that friction and transfer characteristics are highly specific with respect to both the noble metal and surface film present. With all three metals and films transfer of the noble metal to iron occurred very rapidly. With all metals and films transfer of the noble metal to iron continuously increased with repeated passes except for silver and copper sliding on iron sulfide.

  16. Economic Geology (Metals)

    ERIC Educational Resources Information Center

    Gair, Jacob E.

    1972-01-01

    Reviews metalliferous ore-deposit research reported in 1971. Research was dominated by isotopic studies, and worldwide metals exploration was marked by announcements of important new discoveries of base metals, iron ore, nickel, titanium, and uranium. (Author/PR)

  17. Metallic transfer between metals in sliding contact examined by auger emission spectroscopy

    NASA Technical Reports Server (NTRS)

    Pepper, S. V.

    1972-01-01

    Metallic transfer between polycrystalline metals in sliding contact was examined. Hemispherical riders of iron, nickel, and cobalt were slid on tungsten, tantalum, niobium, and molybdenum disks in ultrahigh vacuum. Auger emission spectroscopy was used to monitor the elemental composition of the disk surfaces. Iron, nickel, and cobalt transferred to tungsten, whereas only cobalt transferred to tantalum, niobium, and molybdenum. The results of this investigation are discussed in terms of the cohesive energy and strain hardening characteristics of the specimen materials.

  18. Electrochemically controlled iron isotope fractionation

    NASA Astrophysics Data System (ADS)

    Black, Jay R.; Young, Edward D.; Kavner, Abby

    2010-02-01

    Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.

  19. Distribution and Multivariate Pollution Risks Assessment of Heavy Metals and Natural Radionuclides Around Abandoned Iron-Ore Mines in North Central Nigeria

    NASA Astrophysics Data System (ADS)

    Isinkaye, Omoniyi Matthew

    2018-02-01

    The Itakpe abandoned iron-ore mines constitute the largest iron-ore deposits in Nigeria with an estimated reserve of about three million metric tons of ore. The present effort is a part of a comprehensive study to estimate the environmental and radiological health hazards associated with previous mining operations in the study area. In this regard, heavy metals (Fe, Zn, Cu, Cd, Cr, Mn, Pb, Ni, Co and As) and natural radionuclides (U, Th and K) were measured in rock, soil and water samples collected at different locations within the mining sites. Atomic absorption and gamma-ray spectrometry were utilized for the measurements. Fe, Mn, Zn, Cu, Ni, Cd, Cr, Co Pb and As were detected at varying concentrations in rock and soil samples. Cd, Cr, Pb and As were not detected in water samples. The concentrations of heavy metals vary according to the following pattern; rock ˃ soil ˃ water. The mean elemental concentrations of K, U and Th are 2.9%, 0.8 and 1.2 ppm and 1.3%, 0.7 and 1.7 ppm, respectively, for rock and soil samples. Pearson correlation analyses of the results indicate that the heavy metals are mostly negatively correlated with natural radionuclides in the study area. Cancer and non-cancer risks due to heavy metals and radiological hazards due to natural radionuclides to the population living within the vicinity of the abandoned mines are lower than acceptable limits. It can, therefore, be concluded that no significant environmental or radiological health hazard is envisaged.

  20. INTERIOR VIEW, LOOKING NORTH, TOWARDS CUPOLA WHERE SCRAP METAL AND ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    INTERIOR VIEW, LOOKING NORTH, TOWARDS CUPOLA WHERE SCRAP METAL AND OTHER COMPONENTS ARE MELTED TO CREATE DUCTILE IRON. BRIGHT FLASH IN BACKGROUND RESULTS FROM MOLTEN METAL (DUCTILE IRON) BEING POURED FROM CUPOLA INTO TRANSFER LADLE. - McWane Cast Iron Pipe Company, Pipe Casting Area, 1201 Vanderbilt Road, Birmingham, Jefferson County, AL

  1. CARBON MONOXIDE REVERSIBLY DISRUPTS IRON HOMEOSTATIS AND RESPIRATORY EPITHELIAL CELLS FUNCTION

    EPA Science Inventory

    Iron dissociation from heme is a major factor in iron metabolism and cellular concentrations of the metal correlate inversely with the expression of heme oxygenase (HO). We tested the hypothesis that 1) exposure to a product of HO, carbon monoxide (CO), disturbs iron homeostas...

  2. Mixed-Valent Dicobalt and Iron-Cobalt Complexes with High-Spin Configurations and Short Metal-Metal Bonds

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

    Zall, Christopher M.; Clouston, Laura J.; Young, Jr., Victor G.

    2013-09-23

    Cobalt–cobalt and iron–cobalt bonds are investigated in coordination complexes with formally mixed-valent [M 2] 3+ cores. The trigonal dicobalt tris(diphenylformamidinate) compound, Co 2(DPhF) 3, which was previously reported by Cotton, Murillo, and co-workers (Inorg. Chim. Acta 1996, 249, 9), is shown to have an energetically isolated, high-spin sextet ground-state by magnetic susceptibility and electron paramagnetic resonance (EPR) spectroscopy. A new tris(amidinato)amine ligand platform is introduced. By tethering three amidinate donors to an apical amine, this platform offers two distinct metal-binding sites. Using the phenyl-substituted variant (abbreviated as L Ph), the isolation of a dicobalt homobimetallic and an iron–cobalt heterobimetallic aremore » demonstrated. The new [Co 2] 3+ and [FeCo] 3+ cores have high-spin sextet and septet ground states, respectively. Their solid-state structures reveal short metal–metal bond distances of 2.29 Å for Co–Co and 2.18 Å for Fe–Co; the latter is the shortest distance for an iron–cobalt bond to date. To assign the positions of iron and cobalt atoms as well as to determine if Fe/Co mixing is occurring, X-ray anomalous scattering experiments were performed, spanning the Fe and Co absorption energies. These studies show only a minor amount of metal-site mixing in this complex, and that FeCoL Ph is more precisely described as (Fe 0.94(1)Co 0.06(1))(Co 0.95(1)Fe 0.05(1))L Ph. The iron–cobalt heterobimetallic has been further characterized by Mössbauer spectroscopy. Its isomer shift of 0.65 mm/s and quadrupole splitting of 0.64 mm/s are comparable to the related diiron complex, Fe 2(DPhF) 3. On the basis of spectroscopic data and theoretical calculations, it is proposed that the formal [M 2] 3+ cores are fully delocalized.« less

  3. Intestinal HIF2α promotes tissue-iron accumulation in disorders of iron overload with anemia

    PubMed Central

    Anderson, Erik R.; Taylor, Matthew; Xue, Xiang; Ramakrishnan, Sadeesh K.; Martin, Angelical; Xie, Liwei; Bredell, Bryce X.; Gardenghi, Sara; Rivella, Stefano; Shah, Yatrik M.

    2013-01-01

    Several distinct congenital disorders can lead to tissue-iron overload with anemia. Repeated blood transfusions are one of the major causes of iron overload in several of these disorders, including β-thalassemia major, which is characterized by a defective β-globin gene. In this state, hyperabsorption of iron is also observed and can significantly contribute to iron overload. In β-thalassemia intermedia, which does not require blood transfusion for survival, hyperabsorption of iron is the leading cause of iron overload. The mechanism of increased iron absorption in β-thalassemia is unclear. We definitively demonstrate, using genetic mouse models, that intestinal hypoxia-inducible factor-2α (HIF2α) and divalent metal transporter-1 (DMT1) are activated early in the pathogenesis of β-thalassemia and are essential for excess iron accumulation in mouse models of β-thalassemia. Moreover, thalassemic mice with established iron overload had significant improvement in tissue-iron levels and anemia following disruption of intestinal HIF2α. In addition to repeated blood transfusions and increased iron absorption, chronic hemolysis is the major cause of tissue-iron accumulation in anemic iron-overload disorders caused by hemolytic anemia. Mechanistic studies in a hemolytic anemia mouse model demonstrated that loss of intestinal HIF2α/DMT1 signaling led to decreased tissue-iron accumulation in the liver without worsening the anemia. These data demonstrate that dysregulation of intestinal hypoxia and HIF2α signaling is critical for progressive iron overload in β-thalassemia and may be a novel therapeutic target in several anemic iron-overload disorders. PMID:24282296

  4. Green Synthesis of Iron Nanoparticles and Their Environmental Applications and Implications

    PubMed Central

    Saif, Sadia; Tahir, Arifa; Chen, Yongsheng

    2016-01-01

    Recent advances in nanoscience and nanotechnology have also led to the development of novel nanomaterials, which ultimately increase potential health and environmental hazards. Interest in developing environmentally benign procedures for the synthesis of metallic nanoparticles has been increased. The purpose is to minimize the negative impacts of synthetic procedures, their accompanying chemicals and derivative compounds. The exploitation of different biomaterials for the synthesis of nanoparticles is considered a valuable approach in green nanotechnology. Biological resources such as bacteria, algae fungi and plants have been used for the production of low-cost, energy-efficient, and nontoxic environmental friendly metallic nanoparticles. This review provides an overview of various reports of green synthesised zero valent metallic iron (ZVMI) and iron oxide (Fe2O3/Fe3O4) nanoparticles (NPs) and highlights their substantial applications in environmental pollution control. This review also summarizes the ecotoxicological impacts of green synthesised iron nanoparticles opposed to non-green synthesised iron nanoparticles. PMID:28335338

  5. Angiotensin II inhibits uptake of transferrin-bound iron but not non-transferrin-bound iron by cultured astrocytes.

    PubMed

    Huang, Suna; Du, Fang; Li, Lan; Liu, Yong; Liu, Yuhong; Zhang, Chao; Qian, Zhong Ming

    2014-06-01

    The existence of all components of the renin-angiotensin system (RAS) and the iron metabolism system, and the recent findings on the functions of angiotensin II (ANGII) in peripheral iron metabolism imply that ANGII might play a role in iron homeostasis by regulating expression of iron transport proteins in the brain. Here, we investigated effects of ANGII on uptake and release of iron as well as expression of cell iron transport proteins in cultured astrocytes. We demonstrated that ANGII could significantly inhibit transferrin-bound iron (Tf-Fe) uptake and iron release as well as the expression of transferrin receptor 1 (TfR1) and the iron exporter ferroportin 1 (Fpn1) in cultured astrocytes. This indicated that the inhibitory role of ANGII on Tf-Fe uptake and iron release is mediated by its negative effect on the expression of TfR1 and Fpn1. We also provided evidence that ANGII had no effect on divalent metal transporter 1 (DMT1) expression as well as non-transferrin-bound iron (NTBI) uptake in the cells. Our findings showed that ANGII has a role to affect expression of iron transport proteins in astrocytes in vitro and also suggested that ANGII might have a physiological function in brain iron homeostasis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration.

    PubMed

    Birkner, Nancy; Navrotsky, Alexandra

    2014-04-29

    Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings.

  7. Pathogenic implications of distinct patterns of iron and zinc in chronic MS lesions

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

    Popescu, Bogdan F.; Frischer, Josa M.; Webb, Samuel M.

    Multiple sclerosis (MS) is a chronic inflammatory demyelinating disease of the central nervous system (CNS) in which oligodendrocytes, the CNS cells that stain most robustly for iron and myelin are the targets of injury. Metals are essential for normal CNS functioning, and metal imbalances have been linked to demyelination and neurodegeneration. Using a multidisciplinary approach involving synchrotron techniques, iron histochemistry and immunohistochemistry, we compared the distribution and quantification of iron and zinc in MS lesions to the surrounding normal appearing and periplaque white matter, and assessed the involvement of these metals in MS lesion pathogenesis. We found that the distributionmore » of iron and zinc is heterogeneous in MS plaques, and with few remarkable exceptions they do not accumulate in chronic MS lesions. We show that brain iron tends to decrease with increasing age and disease duration of MS patients; reactive astrocytes organized in large astrogliotic areas in a subset of smoldering and inactive plaques accumulate iron and safely store it in ferritin; a subset of smoldering lesions do not contain a rim of iron-loaded macrophages/microglia; and the iron content of shadow plaques varies with the stage of remyelination. Zinc in MS lesions was generally decreased, paralleling myelin loss. Iron accumulates concentrically in a subset of chronic inactive lesions suggesting that not all iron rims around MS lesions equate with smoldering plaques. Furthermore, upon degeneration of iron-loaded microglia/macrophages, astrocytes may form an additional protective barrier that may prevent iron-induced oxidative damage.« less

  8. Pathogenic implications of distinct patterns of iron and zinc in chronic MS lesions

    DOE PAGES

    Popescu, Bogdan F.; Frischer, Josa M.; Webb, Samuel M.; ...

    2017-03-22

    Multiple sclerosis (MS) is a chronic inflammatory demyelinating disease of the central nervous system (CNS) in which oligodendrocytes, the CNS cells that stain most robustly for iron and myelin are the targets of injury. Metals are essential for normal CNS functioning, and metal imbalances have been linked to demyelination and neurodegeneration. Using a multidisciplinary approach involving synchrotron techniques, iron histochemistry and immunohistochemistry, we compared the distribution and quantification of iron and zinc in MS lesions to the surrounding normal appearing and periplaque white matter, and assessed the involvement of these metals in MS lesion pathogenesis. We found that the distributionmore » of iron and zinc is heterogeneous in MS plaques, and with few remarkable exceptions they do not accumulate in chronic MS lesions. We show that brain iron tends to decrease with increasing age and disease duration of MS patients; reactive astrocytes organized in large astrogliotic areas in a subset of smoldering and inactive plaques accumulate iron and safely store it in ferritin; a subset of smoldering lesions do not contain a rim of iron-loaded macrophages/microglia; and the iron content of shadow plaques varies with the stage of remyelination. Zinc in MS lesions was generally decreased, paralleling myelin loss. Iron accumulates concentrically in a subset of chronic inactive lesions suggesting that not all iron rims around MS lesions equate with smoldering plaques. Furthermore, upon degeneration of iron-loaded microglia/macrophages, astrocytes may form an additional protective barrier that may prevent iron-induced oxidative damage.« less

  9. Impairment of Interrelated Iron- and Copper Homeostatic Mechanisms in Brain Contributes to the Pathogenesis of Neurodegenerative Disorders

    PubMed Central

    Skjørringe, Tina; Møller, Lisbeth Birk; Moos, Torben

    2012-01-01

    Iron and copper are important co-factors for a number of enzymes in the brain, including enzymes involved in neurotransmitter synthesis and myelin formation. Both shortage and an excess of iron or copper will affect the brain. The transport of iron and copper into the brain from the circulation is strictly regulated, and concordantly protective barriers, i.e., the blood-brain barrier (BBB) and the blood-cerebrospinal fluid (CSF) barrier (BCB) have evolved to separate the brain environment from the circulation. The uptake mechanisms of the two metals interact. Both iron deficiency and overload lead to altered copper homeostasis in the brain. Similarly, changes in dietary copper affect the brain iron homeostasis. Moreover, the uptake routes of iron and copper overlap each other which affect the interplay between the concentrations of the two metals in the brain. The divalent metal transporter-1 (DMT1) is involved in the uptake of both iron and copper. Furthermore, copper is an essential co-factor in numerous proteins that are vital for iron homeostasis and affects the binding of iron-response proteins to iron-response elements in the mRNA of the transferrin receptor, DMT1, and ferroportin, all highly involved in iron transport. Iron and copper are mainly taken up at the BBB, but the BCB also plays a vital role in the homeostasis of the two metals, in terms of sequestering, uptake, and efflux of iron and copper from the brain. Inside the brain, iron and copper are taken up by neurons and glia cells that express various transporters. PMID:23055972

  10. THERMODYNAMICS AND CHARGING OF INTERSTELLAR IRON NANOPARTICLES

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

    Hensley, Brandon S.; Draine, B. T., E-mail: brandon.s.hensley@jpl.nasa.gov

    Interstellar iron in the form of metallic iron nanoparticles may constitute a component of the interstellar dust. We compute the stability of iron nanoparticles to sublimation in the interstellar radiation field, finding that iron clusters can persist down to a radius of ≃4.5 Å, and perhaps smaller. We employ laboratory data on small iron clusters to compute the photoelectric yields as a function of grain size and the resulting grain charge distribution in various interstellar environments, finding that iron nanoparticles can acquire negative charges, particularly in regions with high gas temperatures and ionization fractions. If ≳10% of the interstellar ironmore » is in the form of ultrasmall iron clusters, the photoelectric heating rate from dust may be increased by up to tens of percent relative to dust models with only carbonaceous and silicate grains.« less

  11. Electrochemistry of Simple Organometallic Models of Iron-Iron Hydrogenases in Organic Solvent and Water.

    PubMed

    Gloaguen, Frederic

    2016-01-19

    Synthetic models of the active site of iron-iron hydrogenases are currently the subjects of numerous studies aimed at developing H2-production catalysts based on cheap and abundant materials. In this context, the present report offers an electrochemist's view of the catalysis of proton reduction by simple binuclear iron(I) thiolate complexes. Although these complexes probably do not follow a biocatalytic pathway, we analyze and discuss the interplay between the reduction potential and basicity and how these antagonist properties impact the mechanisms of proton-coupled electron transfer to the metal centers. This question is central to any consideration of the activity at the molecular level of hydrogenases and related enzymes. In a second part, special attention is paid to iron thiolate complexes holding rigid and unsaturated bridging ligands. The complexes that enjoy mild reduction potentials and stabilized reduced forms are promising iron-based catalysts for the photodriven evolution of H2 in organic solvents and, more importantly, in water.

  12. Dissolved and particulate trace metal micronutrients under the McMurdo Sound seasonal sea ice: basal sea ice communities as a capacitor for iron

    PubMed Central

    Noble, Abigail E.; Moran, Dawn M.; Allen, Andrew E.; Saito, Mak A.

    2013-01-01

    Dissolved and particulate metal concentrations are reported from three sites beneath and at the base of the McMurdo Sound seasonal sea ice in the Ross Sea of Antarctica. This dataset provided insight into Co and Mn biogeochemistry, supporting a previous hypothesis for water column mixing occurring faster than scavenging. Three observations support this: first, Mn-containing particles with Mn/Al ratios in excess of the sediment were present in the water column, implying the presence of bacterial Mn-oxidation processes. Second, dissolved and labile Co were uniform with depth beneath the sea ice after the winter season. Third, dissolved Co:PO3−4 ratios were consistent with previously observed Ross Sea stoichiometry, implying that over-winter scavenging was slow relative to mixing. Abundant dissolved Fe and Mn were consistent with a winter reserve concept, and particulate Al, Fe, Mn, and Co covaried, implying that these metals behaved similarly. Elevated particulate metals were observed in proximity to the nearby Islands, with particulate Fe/Al ratios similar to that of nearby sediment, consistent with a sediment resuspension source. Dissolved and particulate metals were elevated at the shallowest depths (particularly Fe) with elevated particulate P/Al and Fe/Al ratios in excess of sediments, demonstrating a sea ice biomass source. The sea ice biomass was extremely dense (chl a >9500 μg/L) and contained high abundances of particulate metals with elevated metal/Al ratios. A hypothesis for seasonal accumulation of bioactive metals at the base of the McMurdo Sound sea ice by the basal algal community is presented, analogous to a capacitor that accumulates iron during the spring and early summer. The release and transport of particulate metals accumulated at the base of the sea ice by sloughing is discussed as a potentially important mechanism in providing iron nutrition during polynya phytoplankton bloom formation and could be examined in future oceanographic

  13. IRON COATED URANIUM AND ITS PRODUCTION

    DOEpatents

    Gray, A.G.

    1960-03-15

    A method of applying a protective coating to a metallic uranium article is given. The method comprises etching the surface of the article with an etchant solution containlng chloride ions, such as a solution of phosphoric acid and hydrochloric acid, cleaning the etched surface, electroplating iron thereon from a ferrous ammonium sulfate electroplating bath, and soldering an aluminum sheath to the resultant iron layer.

  14. Iron Export through the Transporter Ferroportin 1 Is Modulated by the Iron Chaperone PCBP2*

    PubMed Central

    Yanatori, Izumi; Richardson, Des R.; Imada, Kiyoshi; Kishi, Fumio

    2016-01-01

    Ferroportin 1 (FPN1) is an iron export protein found in mammals. FPN1 is important for the export of iron across the basolateral membrane of absorptive enterocytes and across the plasma membrane of macrophages. The expression of FPN1 is regulated by hepcidin, which binds to FPN1 and then induces its degradation. Previously, we demonstrated that divalent metal transporter 1 (DMT1) interacts with the intracellular iron chaperone protein poly(rC)-binding protein 2 (PCBP2). Subsequently, PCBP2 receives iron from DMT1 and then disengages from the transporter. In this study, we investigated the function of PCBP2 in iron export. Mammalian genomes encode four PCBPs (i.e. PCBP1–4). Here, for the first time, we demonstrated using both yeast and mammalian cells that PCBP2, but not PCBP1, PCBP3, or PCBP4, binds with FPN1. Importantly, iron-loaded, but not iron-depleted, PCBP2 interacts with FPN1. The PCBP2-binding domain of FPN1 was identified in its C-terminal cytoplasmic region. The silencing of PCBP2 expression suppressed FPN1-dependent iron export from cells. These results suggest that FPN1 exports iron received from the iron chaperone PCBP2. Therefore, it was found that PCBP2 modulates cellular iron export, which is an important physiological process. PMID:27302059

  15. Investigations of Heavy Metal Ion Sorption Using Nanocomposites of Iron-Modified Biochar

    NASA Astrophysics Data System (ADS)

    Kołodyńska, D.; Bąk, J.; Kozioł, M.; Pylypchuk, L. V.

    2017-06-01

    Magnetic biochar nanocomposites were obtained by modification of biochar by zero-valent iron. The article provides information on the impact of contact time, initial Cd(II), Co(II), Zn(II), and Pb(II) ion concentrations, dose of the sorbents, solution pH and temperature on the adsorption capacity. On the basis of experiments, it was found that the optimum parameters for the sorption process are phase contact time 360 min (after this time, the equilibrium of all concentrations is reached), the dose of sorbent equal to 5 g/dm3, pH 5 and the temperature 295 K. The values of parameters calculated from the kinetic models and isotherms present the best match to the pseudo second order and Langmuir isotherm models. The calculated thermodynamic parameters ΔH 0, ΔS 0 and ΔG 0 indicate that the sorption of heavy metal ions is an exothermic and spontaneous process as well as favoured at lower temperatures, suggesting the physical character of sorption. The solution of nitric acid(V) at the concentration 0.1 mol/dm3 was the best acidic desorbing agent used for regeneration of metal-loaded magnetic sorbents. The physicochemical properties of synthesized composites were characterized by FTIR, SEM, XRD, XPS and TG analyses. The point characteristics of the double layer for biochar pHPZC and pHIEP were designated.

  16. Iron Abundances in Lunar Impact Basin Melt Sheets From Orbital Magnetic Field Data

    NASA Astrophysics Data System (ADS)

    Oliveira, Joana S.; Wieczorek, Mark A.; Kletetschka, Gunther

    2017-12-01

    Magnetic field data acquired from orbit shows that the Moon possesses many magnetic anomalies. Though most of these are not associated with known geologic structures, some are found within large impact basins within the interior peak ring. The primary magnetic carrier in lunar rocks is metallic iron, but indigenous lunar rocks are metal poor and cannot account easily for the observed field strengths. The projectiles that formed the largest impact basins must have contained a significant quantity of metallic iron, and a portion of this iron would have been retained on the Moon's surface within the impact melt sheet. Here we use orbital magnetic field data to invert for the magnetization within large impact basins using the assumption that the crust is unidirectionally magnetized. We develop a technique based on laboratory thermoremanent magnetization acquisition to quantify the relationship between the strength of the magnetic field at the time the rock cooled and the abundance of metal in the rock. If we assume that the magnetized portion of the impact melt sheet is 1 km thick, we find average abundances of metallic iron ranging from 0.11% to 0.45 wt %, with an uncertainty of a factor of about 3. This abundance is consistent with the metallic iron abundances in sampled lunar impact melts and the abundance of projectile contamination in terrestrial impact melts. These results help constrain the composition of the projectile, the impact process, and the time evolution of the lunar dynamo.

  17. Mössbauer studies of iron hydride at high pressure

    NASA Astrophysics Data System (ADS)

    Choe, I.; Ingalls, R.; Brown, J. M.; Sato-Sorensen, Y.; Mills, R.

    1991-07-01

    We have measured in situ Mössbauer spectra of iron hydride made in a diamond anvil cell at high pressure and room temperature. The spectra show a sudden change at 3.5+/-0.5 GPa from a single hyperfine pattern to a superposition of three. The former pattern results from normal α-iron with negligible hydrogen content, and the latter from residual α-iron plus newly formed iron hydride. Between 3.5 and 10.4 GPa, the extra hydride pattern have hyperfine fields for one ranging from 276 to 263 kOe, and the other, from 317 to 309 kOe. Both have isomer shifts of about 0.4 mm/sec, and negligible quadrupole splittings. X-ray studies on quenched samples have shown that iron hydride is of double hexagonal close-packed structure, whose two nonequivalent iron sites may account for the observation of two different patterns. Even allowing for the effect of volume expansion, the observed isomer shifts for the hydride are considerably more positive than those of other metallic phases of iron. At the same time, the hyperfine fields are slightly smaller than that of α-iron. As a possible explanation, one may expect a bonding of hydrogen with iron, which would result in a small reduction of 4s electrons, possibly accompanied by a small increase of 3d electrons compared with the neutral atom in metallic iron. The difference between the hyperfine fields in the two spectra are presumably due to the different symmetry at the two iron sites.

  18. A Comparison of Golf Shoe Designs Highlights Greater Ground Reaction Forces with Shorter Irons

    PubMed Central

    Worsfold, Paul; Smith, Neal A.; Dyson, Rosemary J.

    2007-01-01

    In an effort to reduce golf turf damage the traditional metal spike golf shoe has been redesigned, but shoe-ground biomechanical evaluations have utilised artificial grass surfaces. Twenty-four golfers wore three different golf shoe traction designs (traditional metal spikes, alternative spikes, and a flat-soled shoe with no additional traction) when performing shots with a driver, 3 iron and 7 iron. Ground action forces were measured beneath the feet by two natural grass covered force platforms. The maximum vertical force recorded at the back foot with the 3 iron and 7 iron was 0.82 BW (body weight) and at the front foot 1.1 BW approximately in both the metal spike and alternative spike golf shoe designs. When using the driver these maximal vertical values were 0.49 BW at the back foot and 0.84 BW at the front foot. Furthermore, as performance of the backswing and then downswing necessitates a change in movement direction the range of force generated during the complete swing was calculated. In the metal spike shoe the vertical force generated at the back foot with both irons was 0.67 BW and at the front foot 0.96 BW with the 3 iron and 0.92 BW with the 7 iron. The back foot vertical force generated with the driver was 0.33 BW and at the front foot 0.83 BW wearing the metal spike shoe. Results indicated the greater force generation with the irons. When using the driver the more horizontal swing plane associated with the longer club reduced vertical forces at the back and front foot. However, the mediolateral force generated across each foot in the metal and alternative spike shoes when using the driver was greater than when the irons were used. The coefficient of friction was 0. 62 at the back and front foot whichever shoe was worn or club used. Key pointsDuring the golf swing ground reaction forces at the golf shoe to natural grass turf interface were greater with irons than with the longer driver.In the golf swing maximal vertical forces were greater at the

  19. Dominance of 'Gallionella capsiferriformans' and heavy metal association with Gallionella-like stalks in metal-rich pH 6 mine water discharge

    USGS Publications Warehouse

    Fabisch, Maria; Freyer, Gina; Johnson, Carol A.; Buchel, Georg; Akob, Denise M.; Neu, Thomas R.; Kusel, Kirsten

    2016-01-01

    Heavy metal-contaminated, pH 6 mine water discharge created new streams and iron-rich terraces at a creek bank in a former uranium-mining area near Ronneburg, Germany. The transition from microoxic groundwater with ~5 mm Fe(II) to oxic surface water may provide a suitable habitat for microaerobic iron-oxidizing bacteria (FeOB). In this study, we investigated the potential contribution of these FeOB to iron oxidation and metal retention in this high-metal environment. We (i) identified and quantified FeOB in water and sediment at the outflow, terraces, and creek, (ii) studied the composition of biogenic iron oxides (Gallionella-like twisted stalks) with scanning and transmission electron microscopy (SEM, TEM) as well as confocal laser scanning microscopy (CLSM), and (iii) examined the metal distribution in sediments. Using quantitative PCR, a very high abundance of FeOB was demonstrated at all sites over a 6-month study period. Gallionella spp. clearly dominated the communities, accounting for up to 88% ofBacteria, with a minor contribution of other FeOB such as Sideroxydans spp. and ‘Ferrovum myxofaciens’. Classical 16S rRNA gene cloning showed that 96% of the Gallionella-related sequences had ≥97% identity to the putatively metal-tolerant ‘Gallionella capsiferriformans ES-2’, in addition to known stalk formers such as Gallionella ferruginea and Gallionellaceae strain R-1. Twisted stalks from glass slides incubated in water and sediment were composed of the Fe(III) oxyhydroxide ferrihydrite, as well as polysaccharides. SEM and scanning TEM-energy-dispersive X-ray spectroscopy revealed that stalk material contained Cu and Sn, demonstrating the association of heavy metals with biogenic iron oxides and the potential for metal retention by these stalks. Sequential extraction of sediments suggested that Cu (52–61% of total sediment Cu) and other heavy metals were primarily bound to the iron oxide fractions. These results show the importance of

  20. Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base.

    PubMed

    Lyons, Michael E G; Doyle, Richard L; Brandon, Michael P

    2011-12-28

    Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.

  1. Characterization and structural properties of iron in plants.

    NASA Astrophysics Data System (ADS)

    Dewanamuni, Udya; Dehipawala, Sunil; Gafney, Harry

    Iron is one of the most abundant metals in the soil and occurs in a wide range of chemical forms. Humans receive iron through either meat products or plants. Non meat eaters depend on plant product for their daily iron requirement. The iron absorption by plants depends on other minerals present in the soil and soil pH value. The amount of iron present in plants grown with different soil compositions were investigated using X-ray absorption spectroscopy (XAS) and Mossbauer spectroscopy. Based on the X-ray absorption data, the amount of iron in plants vary significantly with soil pH value. The Mossbauer spectroscopy reveals that iron present in the samples has the form Fe3+ or electron density at the site of the iron nucleus similar to that of Fe3+. CUNY Research Scholar Program, MSEIP.

  2. Understanding the Reactivity of Lunar Dust for Future Lunar Missions

    NASA Technical Reports Server (NTRS)

    Wallace, W. T.; Jeevarajan, A. S.; Taylor, L. A.

    2010-01-01

    Fluorescence and EPR can be used to measure the reactivity of lunar soil. Lunar soil is highly activated by grinding. Reactivity is dependent upon soil maturity and locale. Maturity is based on the amount of nanophase iron (np-Fe) in a soil relative to the total iron (FeO). Lunar soil activity ia a direct function of the amount of np-Fe present. Reactive soil can be "deactivated" by humid atmosphere.

  3. Conversion of mill-scale waste to nanoscale zero valent iron (nZVI) for 'green' hydrogen generation via metal-steam reforming

    NASA Astrophysics Data System (ADS)

    Kesavan, Sathees Kumar

    The Proton Exchange Membrane Fuel Cells (PEMFCs) are the most preferred and efficient energy conversion devices for automotive applications but demand high purity hydrogen which comes at a premium price. The currently pursued hydrogen generation methods suffer from issues such as, low efficiency, high cost, environmental non-benignity, and, in some cases, commercial non-viability. Many of these drawbacks including the CO contamination and, storage and delivery can be overcome by resorting to metal-steam reforming (MSR) using iron from steel industry's mill-scale waste. A novel solution-based room temperature technique using sodium borohydride (NaBH4) as the reducing agent has been developed that produces highly active nanoscale (30-40 nm) iron particles. A slightly modified version of this technique using a surfactant and water oil microemulsion resulted in the formation of 5 nm Fe particles. By using hydrazine (N2H4) as an inexpensive and more stable (compared to NaBH4) reductant, body centered cubic iron particles with edge dimensions ˜5 nm were obtained under mild solvothermal conditions in ethanol. The nanoscale zero valent iron (nZVI) powder showed improved kinetics and greater propensity for hydrogen generation than the coarser microscale iron obtained through traditional reduction techniques. To initiate and sustain the somewhat endothermic MSR process, a solar concentrator consisting of a convex polyacrylic sheet with aluminum reflective coating was fabricated. This unique combination of mill-scale waste as iron source, hydrazine as the reductant, mild process conditions for nZVI generation and solar energy as the impetus for actuating MSR, obviates several drawbacks plaguing the grand scheme of producing, storing and delivering pure and humidified H2 to a PEMFC stack.

  4. Iron-Virus Interactions in the Oceans

    NASA Astrophysics Data System (ADS)

    Bonnain, C. C.; Buck, K. N.; Breitbart, M.

    2016-02-01

    Iron is an essential nutrient in the oceans, with the sub-nanomolar concentrations found in open ocean surface waters often insufficient for supporting biological activity. More than 99.9% of dissolved iron is bound to organic ligands, yet identifying the sources of these ligands in seawater remains a major challenge. A significant portion of iron-binding ligands fall into the colloidal fraction, which is operationally defined as the fraction collected between a 0.02 µm and a 0.45 µm filter. Among the organic ligands in this fraction persists an extremely abundant biological candidate: viruses. On average there are 107 viruses per milliliter of seawater, most of which are phages (viruses that infect bacteria). The impact of viruses on ocean biogeochemistry is often evoked purely through the act of lysing hosts and very few studies have considered the geochemical potential of the viral particles themselves. Recent work in non-marine model systems has revealed the presence of iron atoms within the structure of diverse phages infecting Escherichia coli. Combined with the small size and sheer abundance of phages in the oceans, the inclusion of iron in phage structures would translate into a major factor for cycling of this important trace metal. In addition, iron is so critical for growth that bacteria have evolved multiple uptake systems for assimilating iron, such as siderophores. Certain outer membrane proteins serve a dual function in siderophore uptake and as a phage receptor, suggesting that some of the strategies utilized for iron acquisition make bacteria vulnerable to phage infection. Given the constant arms race between bacteria and phages to develop resistance and counter-resistance, respectively, it is not surprising that phage would have evolved to utilize critical regions of surface-exposed proteins which are indispensable for bacterial growth as receptors. The research presented here explores the potential of marine phages to serve as iron

  5. DoD Metal Finishing Workshop: Chromate Alternatives for Metal Treatment and Sealing

    DTIC Science & Technology

    2007-05-17

    always) contain Co inhibitors and nanophase SiO2 to fill scratches. For many materials trivalent processes are now as good as (and in some cases better...6 2.4. Trivalent and non-chrome technology ..................................................... 6 3...5 Figure 3. Trivalent passivate market (1000 gals).................................................. 6 Figure 4. Protection

  6. Reflectance spectroscopy and GEX simulation of palagonite and iron-rich montmorillonite clay mixtures: Implications for the surface composition of Mars

    NASA Technical Reports Server (NTRS)

    Orenberg, J. B.; Handy, J.; Quinn, R.

    1992-01-01

    Because of the power of remote sensing reflectance spectroscopy in determining mineralogy, it has been used as the major method of identifying a possible mineral analogue of the martian surface. A summary of proposed martian surface compositions from reflectance spectroscopy before 1979 was presented by Singer et al. Since that time, iron-rich montmorillonite clay, nanocrystalline or nanophase hematite, and palagonite have been suggested as Mars soil analogue materials. Palagonite in petrological terms is best described as an amorphous, hydrated, ferric iron, silica gel. Montmorillonite is a member of the smectite clay group, and its structure is characterized by an octahedral sheet in coordination with two tetrahedral sheets in which oxygen atoms are shared. The crystal unity of montmorillonite is well defined in contrast to palagonite where it is considered amorphous or poorly crystalline at best. Because of the absence of the diagnostic strong 2.2-micron reflectance band characteristic of clays in the near-infrared (NIR) spectrum of Mars and palagonite and based upon a consideration of wide wavelength coverage (0.3-50 microns), Roush et al. concluded that palagonite is a more likely Mars surface analogue. In spite of the spectral agreement of palagonite and the Mars reflectance spectrum in the 2.2-micron region, palagonite shows poor correspondence with the results of the Viking LR experiment. In contrast, iron-rich montmorillonite clays show relatively good agreement with the results of the Viking LR experiment. This spectral study was undertaken to evaluate the spectral properties of mixtures of palagonite and Mars analogue iron-rich montmorillonite clay (16-18 wt. percent Fe as Fe2O3) as a Mars surface mineralogical model. Mixtures of minerals as Mars surface analogue materials have been studied before, but the mixtures were restricted to crystalline clays and iron oxides.

  7. Heavy metal contamination of the soils used for stocking raw materials in the former ILVA iron-steel industrial plant of Bagnoli (southern Italy).

    PubMed

    Adamo, P; Arienzo, M; Bianco, M R; Terribile, F; Violante, P

    2002-08-05

    The total contents and the chemical and mineralogical forms of the metals Fe, Al, Cu, Co, Cr, Pb, Zn, Ni and Mn in the horizons of a soil profile, representative of an area devoted to stocking raw materials in the dismantled iron-steel industrial plant of ILVA of Bagnoli (Naples), were studied by physical and chemical methods. The geological setting of the study area is the result of volcanic activity in the Phlegrean Fields, a group of polygenic volcanoes to the west of Naples, which give rise to the parent soil material. Soil morphology appeared to be strongly disturbed by the occurrence and stratification of materials used in the industrial process. Fine sediments illuviation down the profile resulted in the occurrence of silt and clay coatings. The total contents of Cu, Co, Cr, Pb, Zn and Ni, in the whole soil samples, especially in the surface layers, were above the regulatory levels (Cu 120, Co 20, Cr 150, Pb 100, Zn 150, Ni 120 mg kg(-1)) stated by the Italian Ministry of Environment for soils in public, private and residential areas, and below the levels (Cu 600, Co 250, Cr 800, Pb 1000, Zn 1500, Ni 500 mg kg(-1)) outlined for soils and subsoils of industrial and commercial areas (Gazzetta Ufficiale della Repubblica Italiana, 1999). Speciation of heavy metals and the determination of the different chemical pools in the fraction < 2 mm identified the large presence of elements trapped in the mineralogical structure of oxides and silicates and occluded in easily reducible manganese or iron oxides. A constant amount of Cu was associated with organic compounds. A significant amount of Zn (> 20%) was extracted in diluted acetic acid solution, indicating that the element was present in a more readily and potentially available form. In the clay fraction (< 2 microm) heavy metals were associated with both amorphous and crystalline iron forms. The presence of iron-rich clay coatings was evident in the illuvial pores of deeper horizons. Enrichment in Cu, Co, Cr and

  8. Psyche: Journey to a Metal World

    NASA Astrophysics Data System (ADS)

    Elkins-Tanton, L. T.; Psyche Team

    2015-01-01

    We propose to visit the exposed iron core of a protoplanet by sending a mission to (16) Psyche, by far the largest iron metal body in the asteroid belt. At Psyche we will explore, for the first time, a world made not of rock or ice, but of iron.

  9. Scavenging Iron: A Novel Mechanism of Plant Immunity Activation by Microbial Siderophores1[C][W

    PubMed Central

    Aznar, Aude; Chen, Nicolas W.G.; Rigault, Martine; Riache, Nassima; Joseph, Delphine; Desmaële, Didier; Mouille, Grégory; Boutet, Stéphanie; Soubigou-Taconnat, Ludivine; Renou, Jean-Pierre; Thomine, Sébastien; Expert, Dominique; Dellagi, Alia

    2014-01-01

    Siderophores are specific ferric iron chelators synthesized by virtually all microorganisms in response to iron deficiency. We have previously shown that they promote infection by the phytopathogenic enterobacteria Dickeya dadantii and Erwinia amylovora. Siderophores also have the ability to activate plant immunity. We have used complete Arabidopsis transcriptome microarrays to investigate the global transcriptional modifications in roots and leaves of Arabidopsis (Arabidopsis thaliana) plants after leaf treatment with the siderophore deferrioxamine (DFO). Physiological relevance of these transcriptional modifications was validated experimentally. Immunity and heavy-metal homeostasis were the major processes affected by DFO. These two physiological responses could be activated by a synthetic iron chelator ethylenediamine-di(o-hydroxyphenylacetic) acid, indicating that siderophores eliciting activities rely on their strong iron-chelating capacity. DFO was able to protect Arabidopsis against the pathogenic bacterium Pseudomonas syringae pv tomato DC3000. Siderophore treatment caused local modifications of iron distribution in leaf cells visible by ferrocyanide and diaminobenzidine-H2O2 staining. Metal quantifications showed that DFO causes a transient iron and zinc uptake at the root level, which is presumably mediated by the metal transporter iron regulated transporter1 (IRT1). Defense gene expression and callose deposition in response to DFO were compromised in an irt1 mutant. Consistently, plant susceptibility to D. dadantii was increased in the irt1 mutant. Our work shows that iron scavenging is a unique mechanism of immunity activation in plants. It highlights the strong relationship between heavy-metal homeostasis and immunity. PMID:24501001

  10. Stable Nickel Isotopes in Fusion Crusts from Iron Meteorites and from Metallic Particles in a Black Wabar Impact Glass

    NASA Astrophysics Data System (ADS)

    Xue, S.; Herzog, G. F.; Hall, G. S.

    1993-07-01

    Iron and nickel isotopes may undergo mass fractionation in systems subjected to high-temperature vaporization [1-3]. We report here a search for nickel fractionation in fusion crusts from iron meteorites and in metal-rich material separated from Wabar impact glasses. Fusion-crust bearing samples of Bogou (IA), N'Goureyma (I-an), and Pitts (IB) were potted in epoxy and were "shaved" with a milling machine. Microscopic examination of the shavings showed the presence of some material from the interior of the meteorites as well as from the fusion crust. A fourth meteorite, Cape of Good Hope (IVB), was prepared for use as a reference standard. About 1.4 mg of magnetic material was collected from a 2-g sample of black Wabar impact glass ground in a Spex mill; microscopic examination indicated that adhering silicates comprised ~5% of the sample. These (terrestrial) silicates contain relatively little Ni [4] so their presence does not interfere with the nickel analysis. Nickel was separated from all samples and its isotopic composition determined as in [2]. Results and Discussion: Nickel isotopic abundances are given in Table 1 both as delta values and as an average fractionation, PHI, where PHI is the slope of a plot of delta vs. mass for each sample. Within the precision of our measurements (from 0.3 to 1.5%, depending on the isotope) all the samples had normal (i.e., terrestrial) isotopic abundances of Ni. Clayton et al. [5] reported that delta-18O in fusion crust is lower than in the atmosphere, probably as a result of a kinetic isotope effect, while in metallic deep-sea spheres, heavy oxygen isotopes are enriched. They inferred that the metallic spheres are not the ablation products of larger meteorites. Similarly, the Ni isotopic abundances in fusion crust are normal, while those in deep-sea metallic spheres are enriched in the heavier isotopes [1]. We note, however, that material ablated from the surface of an iron could have undergone fractionation after separation

  11. Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration

    PubMed Central

    Birkner, Nancy; Navrotsky, Alexandra

    2014-01-01

    Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings. PMID:24733903

  12. Zn(II) stimulation of Fe(II)-activated repression in the iron-dependent repressor from Mycobacterium tuberculosis.

    PubMed

    Stapleton, Brian; Walker, Lawrence R; Logan, Timothy M

    2013-03-19

    Thermodynamic measurements of Fe(II) binding and activation of repressor function in the iron-dependent repressor from Mycobacterium tuberculosis (IdeR) are reported. IdeR, a member of the diphtheria toxin repressor family of proteins, regulates iron homeostasis and contributes to the virulence response in M. tuberculosis. Although iron is the physiological ligand, this is the first detailed analysis of iron binding and activation in this protein. The results showed that IdeR binds 2 equiv of Fe(II) with dissociation constants that differ by a factor of 25. The high- and low-affinity iron binding sites were assigned to physical binding sites I and II, respectively, using metal binding site mutants. IdeR was also found to contain a high-affinity Zn(II) binding site that was assigned to physical metal binding site II through the use of binding site mutants and metal competition assays. Fe(II) binding was modestly weaker in the presence of Zn(II), but the coupled metal binding-DNA binding affinity was significantly stronger, requiring 30-fold less Fe(II) to activate DNA binding compared to Fe(II) alone. Together, these results suggest that IdeR is a mixed-metal repressor, where Zn(II) acts as a structural metal and Fe(II) acts to trigger the physiologically relevant promoter binding. This new model for IdeR activation provides a better understanding of IdeR and the biology of iron homeostasis in M. tuberculosis.

  13. A simple route to diverse noble metal-decorated iron oxide nanoparticles for catalysis

    NASA Astrophysics Data System (ADS)

    Walker, Joan M.; Zaleski, Jeffrey M.

    2016-01-01

    Developing facile synthetic routes to multifunctional nanoparticles combining the magnetic properties of iron oxides with the optical and catalytic utility of noble metal particles remains an important goal in realizing the potential of hybrid nanomaterials. To this end, we have developed a single route to noble metal-decorated magnetic nanoparticles (Fe3O4@SiO2-M M = Au, Pd, Ag, and PtAg) and characterized them by HRTEM and STEM/EDX imaging to reveal their nanometer size (16 nm Fe3O4 and 1-5 nm M seeds) and uniformity. This represents one of the few examples of genuine multifunctional particles on the nanoscale. We show that these hybrid structures have excellent catalytic activity for the reduction of 4-nitrophenol (knorm = 2 × 107 s-1 mol(Pd)-1 5 × 106 s-1 mol(Au)-1 5 × 105 s-1 mol(PtAg)-1 7 × 105 s-1 mol(Ag)-1). These rates are the highest reported for nano-sized comparables, and are competitive with mesoparticles of similar composition. Due to their magnetic response, the particles are also suitable for magnetic recovery and maintain >99% conversion for at least four cycles. Using this synthetic route, Fe3O4@SiO2-M particles show great promise for further development as a precursor to complicated anisotropic materials or for applications ranging from nanocatalysis to biomedical sensing.Developing facile synthetic routes to multifunctional nanoparticles combining the magnetic properties of iron oxides with the optical and catalytic utility of noble metal particles remains an important goal in realizing the potential of hybrid nanomaterials. To this end, we have developed a single route to noble metal-decorated magnetic nanoparticles (Fe3O4@SiO2-M M = Au, Pd, Ag, and PtAg) and characterized them by HRTEM and STEM/EDX imaging to reveal their nanometer size (16 nm Fe3O4 and 1-5 nm M seeds) and uniformity. This represents one of the few examples of genuine multifunctional particles on the nanoscale. We show that these hybrid structures have excellent catalytic

  14. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, W.M.H.; Tzou, M.S.; Jiang, H.J.

    1987-03-31

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  15. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, Wolfgang M. H.; Tzou, Ming-Shin; Jiang, Hui-Jong

    1987-01-01

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  16. Metallic iron for environmental remediation: A review of reviews.

    PubMed

    Noubactep, Chicgoua

    2015-11-15

    This article critically evaluates recent review articles on using metallic iron (Fe(0)) for environmental remediation in order to provide insight for more efficient Fe(0)-based systems. The presentation is limited to peer-reviewed articles published during 2014 and 2015, excluding own contributions, dealing mostly with granular Fe(0). A literature search was conducted up to June 15th 2015 using Science Direct, SCOPUS, Springer and Web of Science databases. The search yielded eight articles that met the final inclusion criteria. The evaluation clearly shows that seven articles provide a narrative description of processes occurring in the Fe(0)/H20 system according to the concept that Fe(0) is a reducing agent. Only one article clearly follows a different path, presenting Fe(0) as a generator of adsorbing (hydroxides, oxides) and reducing (Fe(II), H/H2) agents. The apparent discrepancies between the two schools are identified and extensively discussed based on the chemistry of the Fe(0)/H20 system. The results of this evaluation indicate clearly that research on 'Fe(0) for environmental remediation' is in its infancy. Despite the current paucity of reliable data for the design of efficient Fe(0)-based systems, this review demonstrates that sensible progress could be achieved within a short period of time, specific recommendations to help guide future research are suggested. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Toxic metal immobilization in contaminated sediment using bentonite- and kaolinite-supported nano zero-valent iron

    NASA Astrophysics Data System (ADS)

    Tomašević, D. D.; Kozma, G.; Kerkez, Dj. V.; Dalmacija, B. D.; Dalmacija, M. B.; Bečelić-Tomin, M. R.; Kukovecz, Á.; Kónya, Z.; Rončević, S.

    2014-08-01

    The objective of this study was to investigate the possibility of using supported nanoscale zero-valent iron with bentonite and kaolinite for immobilization of As, Pb and Zn in contaminated sediment from the Nadela river basin (Serbia). Assessment of the sediment quality based on the pseudo-total metal content (As, Pb and Zn) according to the corresponding Serbian standards shows its severe contamination, such that it requires disposal in special reservoirs and, if possible, remediation. A microwave-assisted sequential extraction procedure was employed to assess potential metal mobility and risk to the aquatic environment. According to these results, As showed lower risk to the environment than Pb and Zn, which both represent higher risk to the environment. The contaminated sediment, irrespective of the different speciation of the treated metals, was subjected to the same treatment. Semi-dynamic leaching test, based on leachability index and effective diffusion coefficients, was conducted for As-, Pb- and Zn-contaminated sediments in order to assess the long-term leaching behaviour. In order to simulate "worst case" leaching conditions, the test was modified using acetic and humic acid solution as leachants instead of deionized water. A diffusion-based model was used to elucidate the controlling leaching mechanisms; in the majority of samples, the controlling leaching mechanism appeared to be diffusion. Three different single-step leaching tests were applied to evaluate the extraction potential of examined metals. Generally, the test results indicated that the treated sediment is safe for disposal and could even be considered for "controlled utilization".

  18. Iron promotes protein insolubility and aging in C. elegans

    PubMed Central

    Klang, Ida M.; Schilling, Birgit; Sorensen, Dylan J.; Sahu, Alexandria K.; Kapahi, Pankaj; Andersen, Julie K.; Swoboda, Peter; Killilea, David W.; Gibson, Bradford W.; Lithgow, Gordon J.

    2014-01-01

    Many late-onset proteotoxic diseases are accompanied by a disruption in homeostasis of metals (metallostasis) including iron, copper and zinc. Although aging is the most prominent risk factor for these disorders, the impact of aging on metallostasis and its role in proteotoxic disease remain poorly understood. Moreover, it is not clear whether a loss of metallostasis influences normal aging. We have investigated the role of metallostasis in longevity of Caenorhabditis elegans. We found that calcium, copper, iron, and manganese levels increase as a function of age, while potassium and phosphorus levels tend to decrease. Increased dietary iron significantly accelerated the age-related accumulation of insoluble protein, a molecular pathology of aging. Proteomic analysis revealed widespread effects of dietary iron in multiple organelles and tissues. Pharmacological interventions to block accumulation of specific metals attenuated many models of proteotoxicity and extended normal lifespan. Collectively, these results suggest that a loss of metallostasis with aging contributes to age-related protein aggregation. PMID:25554795

  19. Iron promotes protein insolubility and aging in C. elegans.

    PubMed

    Klang, Ida M; Schilling, Birgit; Sorensen, Dylan J; Sahu, Alexandria K; Kapahi, Pankaj; Andersen, Julie K; Swoboda, Peter; Killilea, David W; Gibson, Bradford W; Lithgow, Gordon J

    2014-11-01

    Many late-onset proteotoxic diseases are accompanied by a disruption in homeostasis of metals (metallostasis) including iron, copper and zinc. Although aging is the most prominent risk factor for these disorders, the impact of aging on metallostasis and its role in proteotoxic disease remain poorly understood. Moreover, it is not clear whether a loss of metallostasis influences normal aging. We have investigated the role of metallostasis in longevity ofCaenorhabditis elegans. We found that calcium, copper, iron, and manganese levels increase as a function of age, while potassium and phosphorus levels tend to decrease. Increased dietary iron significantly accelerated the age-related accumulation of insoluble protein, a molecular pathology of aging. Proteomic analysis revealed widespread effects of dietary iron in multiple organelles and tissues. Pharmacological interventions to block accumulation of specific metals attenuated many models of proteotoxicity and extended normal lifespan. Collectively, these results suggest that a loss of metallostasis with aging contributes to age-related protein aggregation.

  20. Chromium metal organic frameworks and synthesis of metal organic frameworks

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

    Zhou, Hong-Cai; Liu, Tian-Fu; Lian, Xizhen

    The present invention relates to monocrystalline metal organic frameworks comprising chromium ions and carboxylate ligands and the use of the same, for example their use for storing a gas. The invention also relates to methods for preparing metal organic frameworks comprising chromium, titanium or iron ions and carboxylate ligands. The methods of the invention allow such metal organic frameworks to be prepared in monocrystalline or polycrystalline forms.

  1. Silicate Inclusions in the Kodaikanal IIE Iron Meteorite

    NASA Technical Reports Server (NTRS)

    Kurat, G.; Varela, M. E.; Zinner, E.

    2005-01-01

    Silicate inclusions in iron meteorites display an astonishing chemical and mineralogical variety, ranging from chondritic to highly fractionated, silica- and alkali-rich assemblages. In spite of this, their origin is commonly considered to be a simple one: mixing of silicates, fractionated or unfractionated, with metal. The latter had to be liquid in order to accommodate the former in a pore-free way which all models accomplish by assuming shock melting. II-E iron meteorites are particularly interesting because they contain an exotic zoo of silicate inclusions, including some chemically strongly fractionated ones. They also pose a formidable conundrum: young silicates are enclosed by very old metal. This and many other incompatibilities between models and reality forced the formulation of an alternative genetic model for irons. Here we present preliminary findings in our study of Kodaikanal silicate inclusions.

  2. Buried treasure: evolutionary perspectives on microbial iron piracy

    PubMed Central

    Barber, Matthew F.; Elde, Nels C.

    2015-01-01

    Host-pathogen interactions provide valuable systems for the study of evolutionary genetics and natural selection. The sequestration of essential iron has emerged as a critical innate defense system termed nutritional immunity, leading pathogens to evolve mechanisms of `iron piracy' to scavenge this metal from host proteins. This battle for iron carries numerous consequences not only for host-pathogen evolution, but also microbial community interactions. Here we highlight recent and potential future areas of investigation on the evolutionary implications of microbial iron piracy in relation to molecular arms races, host range, competition, and virulence. Applying evolutionary genetic approaches to the study of microbial iron acquisition could also provide new inroads for understanding and combating infectious disease. PMID:26431675

  3. Iron Isotopic Fractionation in Earth's Lower Mantle

    NASA Astrophysics Data System (ADS)

    Yang, H.; Lin, J. F.; Hu, M. Y.; Bi, W.; Zhao, J.; Alp, E. E.; Roskosz, M.; Dauphas, N.; Okuchi, T.

    2017-12-01

    The Earth's bulk chemical composition is vital for deciphering the origin of this planet. Our estimation of the iron isotopic composition of the bulk Earth relies on the iron isotopic composition difference between the metallic core and silicate mantle. Previous studies1,2,3 on this fractionation scale have mostly focused on the alloying effects of light elements in the iron metal phases, while the pressure effects of the silicate mantle phases especially due to iron partitioning4 in the lower mantle minerals have not been fully addressed. For instance, Polyakov (2009) simply assumed equal iron distribution between ferropericlase and post-perovskite in his model. Shahar et al. (2016) only used bridgmanite as a proxy for the mantle while another lower mantle mineral ferropericlase was neglected. Here we have investigated the force constant of iron bonds in lower-mantle ferropericlase and bridgmanite crystals up to 104GPa using NRIXS(Nuclear Resonant Inelastic X-ray Scattering) and SMS(Synchrotron Mössbauer Spectroscopy) in a diamond anvil cell at sector-3 of the Advance Photon Source. These results are used to evaluate the pressure effects as well as the spin/valence states of iron5,6 on the force constant of iron bonds and the iron isotope distributions within the lower mantle and at the core-mantle boundary. We found that the liquid-solid iron isotopic fractionation during magma ocean crystallization was limited, however, the inter-mineral fractionation between ferropericlase and bridgmanite could be significant influenced by the spin/valence states at the lowermost mantle conditions. 1.Polyakov, V. B. Science 323, 912-914 (2009). 2.Shahar, A. et al. Science 352, 580-582 (2016). 3.Liu, J. et al. Nat. Commun. 8, 14377 (2017). 4.Irifune, T. et al. Science 327, 193-195 (2010). 5.Lin, J. F., Speziale, S., Mao, Z. & Marquardt, Rev. Geophys. 51, 244-275 (2013). 6.Mao, Z. et al. Am. Mineral. 102 (2017).

  4. Drosophila melanogaster Models of Metal-Related Human Diseases and Metal Toxicity.

    PubMed

    Calap-Quintana, Pablo; González-Fernández, Javier; Sebastiá-Ortega, Noelia; Llorens, José Vicente; Moltó, María Dolores

    2017-07-06

    Iron, copper and zinc are transition metals essential for life because they are required in a multitude of biological processes. Organisms have evolved to acquire metals from nutrition and to maintain adequate levels of each metal to avoid damaging effects associated with its deficiency, excess or misplacement. Interestingly, the main components of metal homeostatic pathways are conserved, with many orthologues of the human metal-related genes having been identified and characterized in Drosophila melanogaster . Drosophila has gained appreciation as a useful model for studying human diseases, including those caused by mutations in pathways controlling cellular metal homeostasis. Flies have many advantages in the laboratory, such as a short life cycle, easy handling and inexpensive maintenance. Furthermore, they can be raised in a large number. In addition, flies are greatly appreciated because they offer a considerable number of genetic tools to address some of the unresolved questions concerning disease pathology, which in turn could contribute to our understanding of the metal metabolism and homeostasis. This review recapitulates the metabolism of the principal transition metals, namely iron, zinc and copper, in Drosophila and the utility of this organism as an experimental model to explore the role of metal dyshomeostasis in different human diseases. Finally, a summary of the contribution of Drosophila as a model for testing metal toxicity is provided.

  5. Drosophila melanogaster Models of Metal-Related Human Diseases and Metal Toxicity

    PubMed Central

    Calap-Quintana, Pablo; González-Fernández, Javier; Sebastiá-Ortega, Noelia; Moltó, María Dolores

    2017-01-01

    Iron, copper and zinc are transition metals essential for life because they are required in a multitude of biological processes. Organisms have evolved to acquire metals from nutrition and to maintain adequate levels of each metal to avoid damaging effects associated with its deficiency, excess or misplacement. Interestingly, the main components of metal homeostatic pathways are conserved, with many orthologues of the human metal-related genes having been identified and characterized in Drosophila melanogaster. Drosophila has gained appreciation as a useful model for studying human diseases, including those caused by mutations in pathways controlling cellular metal homeostasis. Flies have many advantages in the laboratory, such as a short life cycle, easy handling and inexpensive maintenance. Furthermore, they can be raised in a large number. In addition, flies are greatly appreciated because they offer a considerable number of genetic tools to address some of the unresolved questions concerning disease pathology, which in turn could contribute to our understanding of the metal metabolism and homeostasis. This review recapitulates the metabolism of the principal transition metals, namely iron, zinc and copper, in Drosophila and the utility of this organism as an experimental model to explore the role of metal dyshomeostasis in different human diseases. Finally, a summary of the contribution of Drosophila as a model for testing metal toxicity is provided. PMID:28684721

  6. Mesosiderites. I - Compositions of their metallic portions and possible relationship to other metal-rich meteorite groups

    NASA Technical Reports Server (NTRS)

    Wasson, J. T.; Schaudy, R.; Bild, R. W.; Chou, C.-L.

    1974-01-01

    The metal from 17 mesosiderites has been analyzed for Ni, Ga, Ge, and Ir by the techniques of atomic-absorption spectrometry and neutron activation. Most mesosiderite metal samples fall in a narrow compositional range: Ni, 7.0-9.0%; Ga, 13-16 ppm; Ge, 47-58 ppm; and Ir, 2.4-4.4 ppm. Most of those falling outside these ranges belong to Powell's (1971) least-metamorphosed type. Mesosiderite metal falls in the same general composition range as IIIAB irons, IIIE irons, pallasites and H-group chondrite metal. There are distinct differences in detail, however, and firm evidence for a close genetic relationship between any of these groups and the mesosiderites is lacking.

  7. Discrete Responses to Limitation for Iron and Manganese in Agrobacterium tumefaciens: Influence on Attachment and Biofilm Formation

    PubMed Central

    Hibbing, Michael E.; Xu, Jing; Natarajan, Ramya; Buechlein, Aaron M.

    2015-01-01

    ABSTRACT Transition metals such as iron and manganese are crucial trace nutrients for the growth of most bacteria, functioning as catalytic cofactors for many essential enzymes. Dedicated uptake and regulatory systems have evolved to ensure their acquisition for growth, while preventing toxicity. Transcriptomic analysis of the iron- and manganese-responsive regulons of Agrobacterium tumefaciens revealed that there are discrete regulatory networks that respond to changes in iron and manganese levels. Complementing earlier studies, the iron-responsive gene network is quite large and includes many aspects of iron-dependent metabolism and the iron-sparing response. In contrast, the manganese-responsive network is restricted to a limited number of genes, many of which can be linked to transport and utilization of the transition metal. Several of the target genes predicted to drive manganese uptake are required for growth under manganese-limited conditions, and an A. tumefaciens mutant with a manganese transport deficiency is attenuated for plant virulence. Iron and manganese limitation independently inhibit biofilm formation by A. tumefaciens, and several candidate genes that could impact biofilm formation were identified in each regulon. The biofilm-inhibitory effects of iron and manganese do not rely on recognized metal-responsive transcriptional regulators, suggesting alternate mechanisms influencing biofilm formation. However, under low-manganese conditions the dcpA operon is upregulated, encoding a system that controls levels of the cyclic di-GMP second messenger. Mutation of this regulatory pathway dampens the effect of manganese limitation. IMPORTANCE Responses to changes in transition metal levels, such as those of manganese and iron, are important for normal metabolism and growth in bacteria. Our study used global gene expression profiling to understand the response of the plant pathogen Agrobacterium tumefaciens to changes of transition metal availability

  8. Old iron, young copper: from Mars to Venus.

    PubMed

    Crichton, R R; Pierre, J L

    2001-06-01

    Iron and copper are metals which play an important role in the living world. From a brief consideration of their chemistry and biochemistry we conclude that the early chemistry of life used water soluble ferrous iron while copper was in the water-insoluble Cu(I) state as highly insoluble sulphides. The advent of oxygen was a catastrophic event for most living organisms, and can be considered to be the first general irreversible pollution of the earth. In contrast to the oxidation of iron and its loss of bioavailability as insoluble Fe(III), the oxidation of insoluble Cu(I) led to soluble Cu(II). A new iron biochemistry became possible after the advent of oxygen, with the development of chelators of Fe(III), which rendered iron once again accessible, and with the control of the potential toxicity of iron by its storage in a water soluble, non-toxic, bio-available storage protein (ferritin). Biology also discovered that whereas enzymes involved in anaerobic metabolism were designed to operate in the lower portion of the redox spectrum, the arrival of dioxygen created the need for a new redox active metal which could attain higher redox potentials. Copper, now bioavailable, was ideally suited to exploit the oxidizing power of dioxygen. The arrival of copper also coincided with the development of multicellular organisms which had extracellular cross-linked matrices capable of resisting attack by oxygen free radicals. After the initial 'iron age' subsequent evolution moved, not towards a 'copper age', but rather to an 'iron-copper' age. In the second part of the review, this symbiosis of iron and copper is examined in yeast. We then briefly consider iron and copper metabolism in mammals, before looking at iron-copper interactions in mammals, particularly man, and conclude with the reflection that, as in Greek and Roman mythology, a better understanding of the potentially positive interactions between Mars (iron) and Venus (copper) can only be to the advantage of our

  9. Immune Cells and Microbiota Response to Iron Starvation.

    PubMed

    Chieppa, Marcello; Giannelli, Gianluigi

    2018-01-01

    Metal ions are essential for life on Earth, mostly as crucial components of all living organisms; indeed, they are necessary for bioenergetics functions as crucial redox catalysts. Due to the essential role of iron in biological processes, body iron content is finely regulated and is the battlefield of a tug-of-war between the host and the microbiota.

  10. Targeting Iron Homeostasis in Acute Kidney Injury

    PubMed Central

    Walker, Vyvyca J.; Agarwal, Anupam

    2017-01-01

    Summary Iron is an essential metal involved in several major cellular processes required to maintain life. Because of iron’s ability to cause oxidative damage, its transport, metabolism, and storage is strictly controlled in the body, especially in the small intestine, liver, and kidney. Iron plays a major role in acute kidney injury and has been a target for therapeutic intervention. However, the therapies that have been effective in animal models of acute kidney injury have not been successful in human beings. Targeting iron trafficking via ferritin, ferroportin, or hepcidin may offer new insights. This review focuses on the biology of iron, particularly in the kidney, and its implications in acute kidney injury. PMID:27085736

  11. Iron plaque decreases cadmium accumulation in Oryza sativa L. and serves as a source of iron.

    PubMed

    Sebastian, A; Prasad, M N V

    2016-11-01

    Cadmium (Cd) contamination occurs in paddy soils; hence it is necessary to reduce Cd content of rice. Application and mode of action of ferrous sulphate in minimizing Cd in rice was monitored in the present study. Pot culture with Indian rice variety Swarna (MTU 7029) was maintained in Cd-spiked soil containing ferrous sulphates, which is expected to reduce Cd accumulation in rice. Responses in rhizosphere pH, root surface, metal accumulation in plant and molecular physiological processes were monitored. Iron plaque was induced on root surfaces after FeSO4 application and the amount of Fe in plaque reduced with increases in Cd in the soil. Rhizosphere pH decreased during plaque formation and became more acidic due to secretion of organic acids from the roots under Cd treatment. Moreover, iron chelate reductase activity increased with Cd treatment, but in the absence of Cd, activity of this enzyme increased in plaque-induced plants. Cd treatment caused expression of OsYSL18, whereas OsYSL15 was expressed only in roots without iron plaque. Fe content of plants increased during plaque formation, which protected plants from Cd-induced Fe deficiency and metal toxicity. This was corroborated with increased biomass, chlorophyll content and quantum efficiency of photo-synthesis among plaque-induced plants. We conclude that ferrous sulphate-induced iron plaque prevents Cd accumulation and Fe deficiency in rice. Iron released from plaque via organic acid mediated dissolution during Cd stress. © 2016 German Botanical Society and The Royal Botanical Society of the Netherlands.

  12. Method of making metal matrix composites reinforced with ceramic particulates

    DOEpatents

    Cornie, James A.; Kattamis, Theodoulos; Chambers, Brent V.; Bond, Bruce E.; Varela, Raul H.

    1989-01-01

    Composite materials and methods for making such materials are disclosed in which dispersed ceramic particles are at chemical equilibrium with a base metal matrix, thereby permitting such materials to be remelted and subsequently cast or otherwise processed to form net weight parts and other finished (or semi-finished) articles while maintaining the microstructure and mechanical properties (e.g. wear resistance or hardness) of the original composite. The composite materials of the present invention are composed of ceramic particles in a base metal matrix. The ceramics are preferably carbides of titanium, zirconium, tungsten, molybdenum or other refractory metals. The base metal can be iron, nickel, cobalt, chromium or other high temperature metal and alloys thereof. For ferrous matrices, alloys suitable for use as the base metal include cast iron, carbon steels, stainless steels and iron-based superalloys.

  13. Method of making metal matrix composites reinforced with ceramic particulates

    DOEpatents

    Cornie, J.A.; Kattamis, T.; Chambers, B.V.; Bond, B.E.; Varela, R.H.

    1989-08-01

    Composite materials and methods for making such materials are disclosed in which dispersed ceramic particles are at chemical equilibrium with a base metal matrix, thereby permitting such materials to be remelted and subsequently cast or otherwise processed to form net weight parts and other finished (or semi-finished) articles while maintaining the microstructure and mechanical properties (e.g. wear resistance or hardness) of the original composite. The composite materials of the present invention are composed of ceramic particles in a base metal matrix. The ceramics are preferably carbides of titanium, zirconium, tungsten, molybdenum or other refractory metals. The base metal can be iron, nickel, cobalt, chromium or other high temperature metal and alloys thereof. For ferrous matrices, alloys suitable for use as the base metal include cast iron, carbon steels, stainless steels and iron-based superalloys. 2 figs.

  14. Total and labile metals in surface sediments of the tropical river-estuary system of Marabasco (Pacific coast of Mexico): Influence of an iron mine.

    PubMed

    Marmolejo-Rodríguez, Ana Judith; Prego, Ricardo; Meyer-Willerer, Alejandro; Shumilin, Evgueni; Cobelo-García, Antonio

    2007-01-01

    Marabasco is a tropical river-estuary system comprising the Marabasco river and the Barra de Navidad Lagoon. The river is impacted by the Peña Colorada iron mine, which produces 3.5 million tons of pellets per year. Thirteen surface sediment samples were collected in May 2005 (dry season) in order to establish background levels of Al, Cd, Co, Cu, Fe, Ni, Pb, and Zn in the system and to ascertain the potential mobility of metals in the sediments. Analyses were carried out in the fraction finer than 63 microm, and labile metals extracted according the BCR procedure. Certified reference materials were used for validation of methods. Total concentrations of Cd, Co, Cu, Ni, Pb, and Zn were in the range of 0.05-0.34, 6-95, 0.7-31, 9-26, 2-18, and 53-179 mgkg(-1), respectively; Al and Fe ranges of 24-127, and 26-69 mgg(-1) correspondingly. Cadmium was found to be significantly labile in the sediments (20-100%), followed by Co (0-35%), Ni (3-16%) and Zn (0-25%), whereas the labile fraction for Cu, Fe and Pb was almost negligible (<4%). According with the total metal concentrations, background levels and normalised enrichment factors (NEF) of the metals studied, the impact of the Peña Colorada iron mine on the Marabasco system is lower than expected when compared with other similar World systems influenced by mining activities.

  15. Nitric Oxide Improves Internal Iron Availability in Plants1

    PubMed Central

    Graziano, Magdalena; Beligni, María Verónica; Lamattina, Lorenzo

    2002-01-01

    Iron deficiency impairs chlorophyll biosynthesis and chloroplast development. In leaves, most of the iron must cross several biological membranes to reach the chloroplast. The components involved in the complex internal iron transport are largely unknown. Nitric oxide (NO), a bioactive free radical, can react with transition metals to form metal-nitrosyl complexes. Sodium nitroprusside, an NO donor, completely prevented leaf interveinal chlorosis in maize (Zea mays) plants growing with an iron concentration as low as 10 μm Fe-EDTA in the nutrient solution. S-Nitroso-N-acetylpenicillamine, another NO donor, as well as gaseous NO supply in a translucent chamber were also able to revert the iron deficiency symptoms. A specific NO scavenger, 2-(4-carboxy-phenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, blocked the effect of the NO donors. The effect of NO treatment on the photosynthetic apparatus of iron-deficient plants was also studied. Electron micrographs of mesophyll cells from iron-deficient maize plants revealed plastids with few photosynthetic lamellae and rudimentary grana. In contrast, in NO-treated maize plants, mesophyll chloroplast appeared completely developed. NO treatment did not increase iron content in plant organs, when expressed in a fresh matter basis, suggesting that root iron uptake was not enhanced. NO scavengers 2-(4-carboxy-phenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and methylene blue promoted interveinal chlorosis in iron-replete maize plants (growing in 250 μm Fe-EDTA). Even though results support a role for endogenous NO in iron nutrition, experiments did not establish an essential role. NO was also able to revert the chlorotic phenotype of the iron-inefficient maize mutants yellow stripe1 and yellow stripe3, both impaired in the iron uptake mechanisms. All together, these results support a biological action of NO on the availability and/or delivery of metabolically active iron within the plant. PMID:12481068

  16. Inert electrode containing metal oxides, copper and noble metal

    DOEpatents

    Ray, Siba P.; Woods, Robert W.; Dawless, Robert K.; Hosler, Robert B.

    2001-01-01

    A cermet composite material is made by treating at an elevated temperature a mixture comprising a compound of iron and a compound of at least one other metal, together with an alloy or mixture of copper and a noble metal. The alloy or mixture preferably comprises particles having an interior portion containing more copper than noble metal and an exterior portion containing more noble metal than copper. The noble metal is preferably silver. The cermet composite material preferably includes alloy phase portions and a ceramic phase portion. At least part of the ceramic phase portion preferably has a spinel structure.

  17. Inert electrode containing metal oxides, copper and noble metal

    DOEpatents

    Ray, Siba P.; Woods, Robert W.; Dawless, Robert K.; Hosler, Robert B.

    2000-01-01

    A cermet composite material is made by treating at an elevated temperature a mixture comprising a compound of iron and a compound of at least one other metal, together with an alloy or mixture of copper and a noble metal. The alloy or mixture preferably comprises particles having an interior portion containing more copper than noble metal and an exterior portion containing more noble metal than copper. The noble metal is preferably silver. The cermet composite material preferably includes alloy phase portions and a ceramic phase portion. At least part of the ceramic phase portion preferably has a spinel structure.

  18. Iron and manganese in anaerobic respiration: environmental significance, physiology, and regulation

    NASA Technical Reports Server (NTRS)

    Nealson, K. H.; Saffarini, D.

    1994-01-01

    Dissimilatory iron and/or manganese reduction is known to occur in several organisms, including anaerobic sulfur-reducing organisms such as Geobacter metallireducens or Desulfuromonas acetoxidans, and facultative aerobes such as Shewanella putrefaciens. These bacteria couple both carbon oxidation and growth to the reduction of these metals, and inhibitor and competition experiments suggest that Mn(IV) and Fe(III) are efficient electron acceptors similar to nitrate in redox abilities and capable of out-competing electron acceptors of lower potential, such as sulfate (sulfate reduction) or CO2 (methanogenesis). Field studies of iron and/or manganese reduction suggest that organisms with such metabolic abilities play important roles in coupling the oxidation of organic carbon to metal reduction under anaerobic conditions. Because both iron and manganese oxides are solids or colloids, they tend to settle downward in aquatic environments, providing a physical mechanism for the movement of oxidizing potential into anoxic zones. The resulting biogeochemical metal cycles have a strong impact on many other elements including carbon, sulfur, phosphorous, and trace metals.

  19. Iron pentacarbonyl detection limits in the cigarette smoke matrix using FT-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Parrish, Milton E.; Plunkett, Susan E.; Harward, Charles N.

    2005-11-01

    Endogenous metals present in tobacco from agricultural practices have been purported to generate metal carbonyls in cigarette smoke. Transition metal catalysts, such as iron oxide, have been investigated for the reduction of carbon monoxide (CO) in cigarette smoke. These studies motivated the development of an analytical method to determine if iron pentacarbonyl [Fe(CO) 5] is present in mainstream smoke from cigarette models having cigarette paper made with iron oxide. An FT-IR puff-by-puff method was developed and the detection limit was determined using two primary reference spectra from different sources to estimate the amount of Fe(CO) 5 present in a high-pressure steel cylinder of CO. We do not detect Fe(CO) 5 in a single 35 mL puff from reference cigarettes or from those cigarette models having cigarette paper made with iron oxide, with a 30-ppbV limit of detection (LOD). Also, it was shown that a filter containing activated carbon would remove Fe(CO) 5.

  20. Rare-Earth Metals and Their Applications in Aviation

    DTIC Science & Technology

    1984-08-01

    metals are not as common as iron and steel which are visible everywhere, yet they are not unfamiliar to us. We often encounter them in everyday life...the flint of a lighter. It is an alloy of rare-earth metal and iron . It contains about 30% iron and the remainder is a composite rare-earth alloy...used to manufacture the detonators of bullets and shells as well as the pyrophoric alloys of firing devices. This type of alloy has a 49.5% content of

  1. Amyloid Precursor Protein and Alpha Synuclein Translation, Implications for Iron and Inflammation in Neurodegenerative diseases

    PubMed Central

    Cahill, Catherine M.; Lahiri, Debomoy K.; Huang, Xudong; Rogers, Jack T.

    2014-01-01

    Summary Recent studies that alleles in the hemochromatosis gene may accelerate the onset of Alzheimer's disease (AD) by five years have validated interest in the model in which metals (particularly iron) accelerate disease course. Biochemical and biophysical measurements demonstrated the presence of elevated levels of neurotoxic copper, zinc and iron in the brains of AD patients. Intracellular levels of amyloid precursor protein (APP) holoprotein were shown to be modulated via iron by a mechanism that is similar to the translation control of the ferritin L- and H mRNAs by Iron-responsive Element (IRE) RNA stem loops in their 5′untranslated regions (5′UTRs). Recently, we reported a putative IRE-like sequence to be present in the 5′UTR of the Parkinson's disease (PD) specific alpha synuclein (ASYN) transcript. ASYN encodes the non-Aβ component (NAC) of amyloid plaques. The demonstration of iron-dependent translation of APP mRNA, the involvement of metals in the plaque of AD patients and of increased iron in striatal neurons in the Substantia nigra (SN) of PD patients, have each encouraged the development of metal attenuating agents and iron chelators as a major new therapeutic strategy for the treatment of these neurodegenerative diseases. In the case of AD, metal based therapeutics may ultimately prove more cost effective than the use of an amyloid vaccine as the preferred anti-amyloid therapeutic strategy to ameliorate the cognitive decline of AD patients. PMID:19166904

  2. Impact of wine production on the fractionation of copper and iron in Chardonnay wine: Implications for oxygen consumption.

    PubMed

    Rousseva, Michaela; Kontoudakis, Nikolaos; Schmidtke, Leigh M; Scollary, Geoffrey R; Clark, Andrew C

    2016-07-15

    Copper and iron in wine can influence oxidative, reductive and colloidal stability. The current study utilises a solid phase extraction technique to fractionate these metals into hydrophobic, cationic and residual forms, with quantification by ICP-OES. The impact of aspects of wine production on the metal fractions was examined, along with the relationship between metal fractions and oxygen decay rates. Addition of copper and iron to juice, followed by fermentation, favoured an increase in all of their respective metal fractions in the wine, with the largest increase observed for the cationic form of iron. Bentonite fining of the protein-containing wines led to a significant reduction in the cationic fraction of copper and an increase in the cationic form of iron. Total copper correlated more closely with oxygen consumption in the wine compared to total iron, and the residual and cationic forms of copper provided the largest contribution to this impact. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Impregnated metal-polymeric functional beads

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Volksen, Willi (Inventor)

    1980-01-01

    Amine containing polymeric microspheres such as polyvinyl pyridine are complexed with metal salts or acids containing metals such as gold, platinum or iron. After reduction with sodium borohydride, the salt is reduced to finely divided free metal or metal oxides, useful as catalysts. Microspheres containing covalent bonding sites can be used for labeling or separating proteins.

  4. Impregnated metal-polymeric functional beads

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Volksen, Willi (Inventor)

    1978-01-01

    Amine containing polymeric microspheres such as polyvinyl pyridine are complexed with metal salts or acids containing metals such as gold, platinum or iron. After reduction with sodium borohydride, the salt is reduced to finely divided free metal or metal oxides, useful as catalysts. Microspheres containing covalent bonding sites can be used for labeling or separating proteins.

  5. Anaerobic microbial remobilization of coprecipitated metals

    DOEpatents

    Francis, Arokiasamy J.; Dodge, Cleveland J.

    1994-10-11

    A process is provided for solubilizing coprecipitated metals. Metals in wastestreams are concentrated by treatment with an iron oxide coprecipitating agent. The coprecipitated metals are solubilized by contacting the coprecipitate with a bacterial culture of a Clostridium species ATCC 53464. The remobilized metals can then be recovered and recycled.

  6. Characterization of tetraethylene glycol passivated iron nanoparticles

    NASA Astrophysics Data System (ADS)

    Nunes, Eloiza da Silva; Viali, Wesley Renato; da Silva, Sebastião William; Coaquira, José Antonio Huamaní; Garg, Vijayendra Kumar; de Oliveira, Aderbal Carlos; Morais, Paulo César; Jafelicci Júnior, Miguel

    2014-10-01

    The present study describes the synthesis and characterization of iron@iron oxide nanoparticles produced by passivation of metallic iron in tetraethylene glycol media. Structural and chemical characterizations were performed using transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mössbauer spectroscopy. Pomegranate-like core@shell nanoparticulate material in the size range of 90-120 nm was obtained. According to quantitative phase analysis using Rietveld structure refinement the synthesized iron oxide was identified as magnetite (Fe3O4) whereas the iron to magnetite mass fractions was found to be 47:53. These findings are in good agreement with the data obtained from Mössbauer and thermal gravimetric analysis (TGA). The XPS data revealed the presence of a surface organic layer with higher hydrocarbon content, possibly due to the tetraethylene glycol thermal degradation correlated with iron oxidation. The room-temperature (300 K) saturation magnetization measured for the as-synthesized iron and for the iron-iron oxide were 145 emu g-1 and 131 emu g-1, respectively. The measured saturation magnetizations are in good agreement with data obtained from TEM, XRD and Mössbauer spectroscopy.

  7. Influence of indigenous and added iron on copper extraction from soil.

    PubMed

    Di Palma, Luca

    2009-10-15

    Experimental tests of copper leaching from a low permeability soil are presented and discussed. The objective of the experiments was to investigate the influence of indigenous and added iron in the soil towards copper mobilization. Metals' leaching was performed by flushing (column tests) or washing (batch tests) the soil with an aqueous solution of ethylenediaminetetraacetic acid, EDTA. An excess of EDTA was used in flushing tests (up to a EDTA:Cu molar ratio of about 26.2:1), while, in washing tests, the investigated EDTA vs. copper molar ratios were in the range between 1 (equimolar tests) and 8. Copper extraction yield in flushing tests (up to about 85%) was found to depend upon contact time between the soil and the leaching solution and the characteristics of the conditioning solution. The saturation of the soil with a NaNO(3) solution before the treatment, favoured the flushing process reducing the time of percolation, but resulted in a lower metal extraction during the following percolation of EDTA. The indigenous iron was competitive with copper to form EDTA complexes only when it was present in the organic and oxides-hydroxides fractions. Artificial iron addition to the soil resulted in an increase of both the exchangeable iron and the iron bonded to the organic fraction of the soil, thus increasing the overall amount of iron available to extraction. In both batch and continuous tests, the mechanism of copper extraction was found to involve the former dissolution of metal salts, that lead to an initial high concentration of both copper and selected competitive cations (essentially Ca(2+)), and the following EDTA exchange reaction between calcium and copper complexes. The initial metal salts dissolution was found to be pH-dependant.

  8. A proof for substitution of endogenous iron (II) in lipoxygenase by exogenous Cu2+.

    PubMed

    Cai, Yan; Xu, Hong; Xia, Yongmei; Su, Yafen; Fang, Yun

    2010-10-01

    Soybean lipoxygenase (LOX) contains endogenous iron (II) at the active site, which is important for the enzyme activity. The activity of LOX can be accelerated by some exogenous metal ions including Cu2+. However, the mechanism of the activity improvement caused by exogenous metal ions remains unclear, not only for LOX but for most other metalloenzymes. Meanwhile, the possibility that exogenous metal ions can displace endogenous iron (II) is still in discussion for a lack of a direct and quantitative proof. In this paper, a quantitative proof of replacing iron (II) inside LOX by exogenous Cu2+ was provided, simply using UV-Vis spectrometry with two indicators p-carboxylantipyrylazo and 9-(4-carboxyphenyl)-2,3,7-trihydroxyl-6-fluorine. A 0.56 microM free iron (II) was observed in the bulk solution after incubating 9.45 microM Cu2+ with 16.10 microM LOX at 20 degrees C for 5 min, which is in coincidence with the decrement of Cu2+ in the bulk solution (0.53 microM), implying that iron (II) was replaced by Cu2+.

  9. Increased metal concentrations in exhaled breath condensate of industrial welders.

    PubMed

    Hoffmeyer, Frank; Weiss, Tobias; Lehnert, Martin; Pesch, Beate; Berresheim, Hans; Henry, Jana; Raulf-Heimsoth, Monika; Broding, Horst Christoph; Bünger, Jürgen; Harth, Volker; Brüning, Thomas

    2011-01-01

    It was the aim of this study to evaluate the effect of different devices on the metal concentration in exhaled breath condensate (EBC) and to prove whether working conditions in different welding companies result in diverse composition of metallic elements. The influence of two collection devices (ECoScreen, ECoScreen2) on detection of metallic elements in EBC was evaluated in 24 control subjects. Properties of ECoScreen and a frequent use can alter EBC metal content due to contamination from metallic components. ECoScreen2 turned out to be favourable for metal assessment. Concentrations of iron, nickel and chromium in EBC sampled with ECoScreen2 were compared between non-exposed controls and industrial welders. Metal concentrations in EBC were higher in 36 welders recruited from three companies. Exposure to welding fumes could be demonstrated predominantly for increased iron concentrations. Concentrations of iron and nickel differed by working conditions, but chromium could not be detected in EBC.

  10. A complementary set of electrochemical and X-ray synchrotron techniques to determine the passivation mechanism of iron treated in a new corrosion inhibitor solution specifically developed for the preservation of metallic artefacts

    NASA Astrophysics Data System (ADS)

    Mirambet, F.; Reguer, S.; Rocca, E.; Hollner, S.; Testemale, D.

    2010-05-01

    Metallic artefacts of the cultural heritage are often stored in uncontrolled environmental conditions. They are very sensitive to atmospheric corrosion caused by a succession of wet and dry periods due to variations of relative humidity and temperature. To avoid the complete degradation of the metallic artefacts, new preventive strategies must be developed. In this context, we have studied new compounds based on sodium carboxylates solutions CH3(CH2) n-2COO-, Na+ hereafter called NaC n . They allow the formation of a passive layer at the metallic surface composed of a metal-carboxylate complex. To understand the action of those inhibitors in the passivation process of iron we have performed electrochemical measurements and surface characterisation. Moreover, to monitor in real time the growth of the coating, in situ X-ray absorption spectroscopy (XAS) experiments at iron K-edge were carried out in an electrochemical cell. These analyses have shown that in the case of NaC10 solution, the protection of iron surface is correlated to the precipitation of a well-organised layer of FeC10. These experiments confirmed that this compound is a fully oxidised trinuclear Fe(III) complex containing decanoate anions as ligands. Such information concerning the passive layer is a key factor to evaluate its stability and finally the long-term efficiency of the protection treatment.

  11. Disorders of metal metabolism

    PubMed Central

    Ferreira, Carlos R.; Gahl, William A.

    2017-01-01

    Trace elements are chemical elements needed in minute amounts for normal physiology. Some of the physiologically relevant trace elements include iodine, copper, iron, manganese, zinc, selenium, cobalt and molybdenum. Of these, some are metals, and in particular, transition metals. The different electron shells of an atom carry different energy levels, with those closest to the nucleus being lowest in energy. The number of electrons in the outermost shell determines the reactivity of such an atom. The electron shells are divided in sub-shells, and in particular the third shell has s, p and d sub-shells. Transition metals are strictly defined as elements whose atom has an incomplete d sub-shell. This incomplete d sub-shell makes them prone to chemical reactions, particularly redox reactions. Transition metals of biologic importance include copper, iron, manganese, cobalt and molybdenum. Zinc is not a transition metal, since it has a complete d sub-shell. Selenium, on the other hand, is strictly speaking a nonmetal, although given its chemical properties between those of metals and nonmetals, it is sometimes considered a metalloid. In this review, we summarize the current knowledge on the inborn errors of metal and metalloid metabolism. PMID:29354481

  12. The ColRS signal transduction system responds to the excess of external zinc, iron, manganese, and cadmium

    PubMed Central

    2014-01-01

    Background The ColRS two-component system has been shown to contribute to the membrane functionality and stress tolerance of Pseudomonas putida as well as to the virulence of Pseudomonas aeruginosa and plant pathogenic Xanthomonas species. However, the conditions activating the ColRS pathway and the signal(s) sensed by ColS have remained unknown. Here we aimed to analyze the role of the ColRS system in metal tolerance of P. putida and to test whether ColS can respond to metal excess. Results We show that the ColRS system is necessary for P. putida to tolerate the excess of iron and zinc, and that it also contributes to manganese and cadmium tolerance. Excess of iron, zinc, manganese or cadmium activates ColRS signaling and as a result modifies the expression of ColR-regulated genes. Our data suggest that the genes in the ColR regulon are functionally redundant, as several loci have to be deleted to observe a significant decrease in metal tolerance. Site-directed mutagenesis of ColS revealed that excess of iron and, surprisingly, also zinc are sensed by a conserved ExxE motif in ColS’s periplasmic domain. While ColS is able to sense different metals, it still discriminates between the two oxidation states of iron, specifically responding to ferric and not ferrous iron. We propose a signal perception model involving a dimeric ColS, where each monomer donates one ExxE motif for metal binding. Conclusions Several transition metals are essential for living organisms in certain amounts, but toxic in excess. We show that ColRS is a sensor system which detects and responds to the excess of physiologically important metals such as zinc, iron and manganese. Thus, the ColRS system is an important factor for metal homeostasis and tolerance in P. putida. PMID:24946800

  13. Desferrithiocin: A Search for Clinically Effective Iron Chelators

    PubMed Central

    2015-01-01

    The successful search for orally active iron chelators to treat transfusional iron-overload diseases, e.g., thalassemia, is overviewed. The critical role of iron in nature as a redox engine is first described, as well as how primitive life forms and humans manage the metal. The problems that derive when iron homeostasis in humans is disrupted and the mechanism of the ensuing damage, uncontrolled Fenton chemistry, are discussed. The solution to the problem, chelator-mediated iron removal, is clear. Design options for the assembly of ligands that sequester and decorporate iron are reviewed, along with the shortcomings of the currently available therapeutics. The rationale for choosing desferrithiocin, a natural product iron chelator (a siderophore), as a platform for structure–activity relationship studies in the search for an orally active iron chelator is thoroughly developed. The study provides an excellent example of how to systematically reengineer a pharmacophore in order to overcome toxicological problems while maintaining iron clearing efficacy and has led to three ligands being evaluated in human clinical trials. PMID:25207964

  14. Roman mystery iron blades from Serbia

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

    Balos, Sebastian; Benscoter, Arlan; Pense, Alan

    A First to Forth Century Roman spear blade from Serbia was found to have an unusual microstructure inconsistent with typical Roman Period iron. An analysis of the blade undertaken at Lehigh University in the US and at the Faculty of Technical Sciences in Novi Sad, Serbia established that it was metallic in appearance, magnetic and had an external layer of red rust. But as metallographically polished, it appeared to contain multiple internal phases and internal cracking. Even after aggressive etching, no typical low carbon microstructure was developed. Scanning electron microscopy, classical and energy dispersive X-ray analysis indicated that the specimenmore » was essentially iron, although its microhardness was too high for typical Roman iron. It was then dubbed 'Mystery Iron.' Analysis of all the data led to the proposal that it was essentially a Roman iron 'fossil' in which the iron had been converted to high temperature iron oxide while retaining the form of the blade, conversion probably occurring in a fire. Subsequent X-ray diffraction analysis confirmed that the blade consisted of FeO and Fe{sub 3}O{sub 4} and the mystery of the iron fossil was at least partially solved. A hypothesis is proposed regarding a potential cause for the fire.« less

  15. Coal Ash Aerosol in East Asian Outflow as a Source for Oceanic Deposition of Iron and Other Metals

    NASA Astrophysics Data System (ADS)

    Anderson, J. R.; Hua, X.

    2008-12-01

    While ocean deposition of East Asian dust is given significant emphasis as a source of biologically-active trace elements, iron in particular, dust events are episodic and highly seasonal. There is, however, a constant source of aerosol that is chemically similar to dust (albeit amorphous in structure rather than crystalline) in the ash particles emitted from many hundreds of coal-fired power plants that are sited along the entire coastal region of China and Korea. The emission controls on these facilities vary widely and, in even cases of state-of-the-art emission controls, the secondary release of ash can be significant. There are of course even more small industrial and household sources of coal combustion emissions, in most cases with little or no emissions controls. Ash from a modern coal-fired power facility in Korea has been examined chemically and morphologically with electron microscopic techniques. As is characteristic of all such facilities, two principal types of ash are present: (1) flyash, silicate glass spheres that are emitted with the smoke and removed by electrostatic precipitators; and (2) bottom ash, "clinkers" and noncombustible material sticking to the furnace walls that are mixed with water and ground after cooling, then removed as a slurry to a dumping area. In addition, iron sulfide (pyrite) is a common constituent of coal and provides both a source of sulfur dioxide gas and also molten iron spherical particles in the ash. The iron spheres then are rapidly oxidized upon cooling. Bottom ash is a more complex material than flyash in that it contains more iron and other trace metals, plus it contains varying amounts of uncombusted carbon. The post-combustion handling of bottom ash can lead to significant emissions despite the fact that little or none goes out the stack. The iron oxide spheres can also be emitted by this secondary method. The concentrations of ash can be very high in close proximity to power plants (PM10 of several hundred

  16. Iron oxide - clay composite vectors on long-distance transport of arsenic and toxic metals in mining-affected areas.

    PubMed

    Gomez-Gonzalez, Miguel A; Villalobos, Mario; Marco, Jose Francisco; Garcia-Guinea, Javier; Bolea, Eduardo; Laborda, Francisco; Garrido, Fernando

    2018-04-01

    Mine wastes from abandoned exploitations are sources of high concentrations of hazardous metal(oid)s. Although these contaminants can be attenuated by sorbing to secondary minerals, in this work we identified a mechanism for long-distance dispersion of arsenic and metals through their association to mobile colloids. We characterize the colloids and their sorbed contaminants using spectrometric and physicochemical fractionation techniques. Mechanical action through erosion may release and transport high concentrations of colloid-associated metal(oid)s towards nearby stream waters, promoting their dispersion from the contamination source. Poorly crystalline ferrihydrite acts as the principal As-sorbing mineral, but in this study we find that this nanomineral does not mobilize As independently, rather, it is transported as surface coatings bound to mineral particles, perhaps through electrostatic biding interactions due to opposing surface charges at acidic to circumneutral pH values. This association is very stable and effective in carrying along metal(oid)s in concentrations above regulatory levels. The unlimited source of toxic elements in mine residues causes ongoing, decades-long mobilization of toxic elements into stream waters. The ferrihydrite-clay colloidal composites and their high mobility limit the attenuating role that iron oxides alone show through adsorption of metal(oid)s and their immobilization in situ. This may have important implications for the potential bioavailability of these contaminants, as well as for the use of this water for human consumption. Copyright © 2018 Elsevier Ltd. All rights reserved.

  17. Metallurgy Beyond Iron

    NASA Astrophysics Data System (ADS)

    Gallino, Isabella; Busch, Ralf

    2009-08-01

    Metallurgy is one of the oldest sciences. Its history can be traced back to 6000 BCE with the discovery of Gold, and each new discovery - Copper, Silver, Lead, Tin, Iron and Mercury - marked the beginning of a new era of civilization. Currently there are 86 known metals, but until the end of the 17th century, only 12 of these were known. Steel (Fe-C alloy) was discovered in the 11th century BCE; however, it took until 1709 CE before we mastered the smelting of pig-iron by using coke instead of charcoal and started the industrial revolution. The metallurgy of nowadays is mainly about discovering better materials with superior properties to fulfil the increasing demand of the global market. Promising are the Glassy Metals or Bulk Metallic Glasses (BMGs) - discovered at first in the late 50s at the California Institute of Technology - which are several times stronger than the best industrial steels and 10-times springier. The unusual structure that lacks crystalline grains makes BMGs so promising. They have a liquid-like structure that means they melt at lower temperatures, can be moulded nearly as easily as plastics, and can be shaped into features just 10 nm across. The best BMG formers are based on Zr, Pd, Pt, Ca, Au and, recently discovered, also Fe. They have typically three to five components with large atomic size mismatch and a composition close to a deep eutectic. Packing in such liquids is very dense, with a low content of free volume, resulting in viscosities that are several orders of magnitude higher than in pure metal melts.

  18. Preparation of nanoporous metal foam from high nitrogen transition metal complexes

    DOEpatents

    Tappan, Bryce C.; Huynh, My Hang V.; Hiskey, Michael A.; Son, Steven F.; Oschwald, David M.; Chavez, David E.; Naud, Darren L.

    2006-11-28

    Nanoporous metal foams are prepared by ignition of high nitrogen transition metal complexes. The ammonium salts of iron(III) tris[bi(tetrazolato)-amine], cobalt(III) tris(bi(tetrazolato)amine), and high nitrogen compounds of copper and silver were prepared as loose powders, pressed into pellets and wafers, and ignited under an inert atmosphere to form nanoporous metal foam monoliths having very high surface area and very low density.

  19. Regulation of copper and iron homeostasis by metal chelators: a possible chemotherapy for Alzheimer's disease.

    PubMed

    Robert, Anne; Liu, Yan; Nguyen, Michel; Meunier, Bernard

    2015-05-19

    With the increase of life expectancy of humans in more than two-thirds of the countries in the World, aging diseases are becoming the frontline health problems. Alzheimer's disease (AD) is now one of the major challenges in drug discovery, since, with the exception of memantine in 2003, all clinical trials with drug candidates failed over the past decade. If we consider that the loss of neurons is due to a high level of oxidative stress produced by nonregulated redox active metal ions like copper linked to amyloids of different sizes, regulation of metal homeostasis is a key target. The difficulty for large copper-carrier proteins to directly extract copper ions from metalated amyloids might be considered as being at the origin of the rupture of the copper homeostasis regulation in AD brains. So, there is an urgent need for new specific metal chelators that should be able to regulate the homeostasis of metal ions, specially copper and iron, in AD brains. As a consequence of that concept, chelators promoting metal excretion from brain are not desired. One should favor ligands able to extract copper ions from sinks (amyloids being the major one) and to transfer these redox-active metal ions to copper-carrier proteins or copper-containing enzymes. Obviously, the affinity of these chelators for the metal ion should not be a sufficient criterion, but the metal specificity and the ability of the chelators to release the metal under specific biological conditions should be considered. Such an approach is still largely unexplored. The requirements for the chelators are very high (ability to cross the brain-blood barrier, lack of toxicity, etc.), few chemical series were proposed, and, among them, biochemical or biological data are scarce. As a matter of fact, the bioinorganic pharmacology of AD represents less than 1% of all articles dedicated to AD drug research. The major part of these articles deals with an old and rather toxic drug, clioquinol and related analogs, that

  20. Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

    NASA Astrophysics Data System (ADS)

    Tomyn, Stefania; Shylin, Sergii I.; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O.

    2017-01-01

    In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge.

  1. Indefinitely stable iron(IV) cage complexes formed in water by air oxidation.

    PubMed

    Tomyn, Stefania; Shylin, Sergii I; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O

    2017-01-19

    In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge.

  2. Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

    PubMed Central

    Tomyn, Stefania; Shylin, Sergii I.; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O.

    2017-01-01

    In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge. PMID:28102364

  3. Nifedipine Increases Iron Content in WKPT-0293 Cl.2 Cells via Up-Regulating Iron Influx Proteins

    PubMed Central

    Yu, Shuang-Shuang; Jiang, Li-Rong; Ling, Yan; Qian, Zhong-Ming; Zhou, Yu-Fu; Li, Juan; Ke, Ya

    2017-01-01

    Nifedipine was reported to enhance urinary iron excretion in iron overloaded mice. However, it remains unknown how nifedipine stimulates urinary iron excretion in the kidney. We speculated that nifedipine might inhibit the TfR1/ DMT1 (transferrin receptor 1/divalent metal transporter1)-mediated iron uptake by proximal tubule cells in addition to blocking L-type Ca2+ channels, leading to an increase in iron in lumen-fluid and then urinary iron excretion. To test this hypothesis, we investigated the effects of nifedipine on iron content and expression of TfR1, DMT1 and ferroportin1 (Fpn1) in WKPT-0293 Cl.2 cells of the S1 segment of the proximal tubule in rats, using a graphite furnace atomic absorption spectrophotometer and Western blot analysis, respectively. We demonstrated for the first time that nifedipine significantly enhanced iron content as well as TfR1 and DMT1 expression and had no effect on Fpn1 levels in the cells. We also found that ferric ammonium citrate decreased TfR1 levels, increased Fpn1 expression and had no effect on DMT1 content, while co-treatment with nifedipine and FAC increase TfR1 and DMT1 expression and also had no effect on Fpn1 levels. These findings suggest that the nifedipine-induced increase in cell iron may mainly be due to the corresponding increase in TfR1 and DMT1 expression and also imply that the effects of nifedipine on iron transport in proximal tubule cells can not explain the increase in urinary iron excretion. PMID:28243203

  4. The solubility of metals in Pb17Li liquid alloy

    NASA Astrophysics Data System (ADS)

    Borgstedt, H. U.; Feuerstein, H.

    1992-09-01

    The solubility data of iron in the eutectic alloy Pb17Li which were evaluated from corrosion tests in a turbulent flow of the molten alloy are discussed in the frame of solubilities of the transition metals in liquid lead. It is shown that the solubility of iron in the alloy is close to that in lead. This is also the fact for several other alloying elements of steels.A comparison of all known data shows that they are in agreement with generally shown trends for the solubility of the transition metals in low melting metals. These trends indicate comparably high solubilities of nickel and manganese in the liquid metals, lower saturation concentrations of vanadium, chromium, iron, and cobalt, and extremely low solubility of molybdenum.

  5. Shock Wave Response of Iron-based In Situ Metallic Glass Matrix Composites

    PubMed Central

    Khanolkar, Gauri R.; Rauls, Michael B.; Kelly, James P.; Graeve, Olivia A.; Hodge, Andrea M.; Eliasson, Veronica

    2016-01-01

    The response of amorphous steels to shock wave compression has been explored for the first time. Further, the effect of partial devitrification on the shock response of bulk metallic glasses is examined by conducting experiments on two iron-based in situ metallic glass matrix composites, containing varying amounts of crystalline precipitates, both with initial composition Fe49.7Cr17.7Mn1.9Mo7.4W1.6B15.2C3.8Si2.4. The samples, designated SAM2X5-600 and SAM2X5-630, are X-ray amorphous and partially crystalline, respectively, due to differences in sintering parameters during sample preparation. Shock response is determined by making velocity measurements using interferometry techniques at the rear free surface of the samples, which have been subjected to impact from a high-velocity projectile launched from a powder gun. Experiments have yielded results indicating a Hugoniot Elastic Limit (HEL) to be 8.58 ± 0.53 GPa for SAM2X5-600 and 11.76 ± 1.26 GPa for SAM2X5-630. The latter HEL result is higher than elastic limits for any BMG reported in the literature thus far. SAM2X5-600 catastrophically loses post-yield strength whereas SAM2X5-630, while showing some strain-softening, retains strength beyond the HEL. The presence of crystallinity within the amorphous matrix is thus seen to significantly aid in strengthening the material as well as preserving material strength beyond yielding. PMID:26932846

  6. Shock Wave Response of Iron-based In Situ Metallic Glass Matrix Composites.

    PubMed

    Khanolkar, Gauri R; Rauls, Michael B; Kelly, James P; Graeve, Olivia A; Hodge, Andrea M; Eliasson, Veronica

    2016-03-02

    The response of amorphous steels to shock wave compression has been explored for the first time. Further, the effect of partial devitrification on the shock response of bulk metallic glasses is examined by conducting experiments on two iron-based in situ metallic glass matrix composites, containing varying amounts of crystalline precipitates, both with initial composition Fe49.7Cr17.7Mn1.9Mo7.4W1.6B15.2C3.8Si2.4. The samples, designated SAM2X5-600 and SAM2X5-630, are X-ray amorphous and partially crystalline, respectively, due to differences in sintering parameters during sample preparation. Shock response is determined by making velocity measurements using interferometry techniques at the rear free surface of the samples, which have been subjected to impact from a high-velocity projectile launched from a powder gun. Experiments have yielded results indicating a Hugoniot Elastic Limit (HEL) to be 8.58 ± 0.53 GPa for SAM2X5-600 and 11.76 ± 1.26 GPa for SAM2X5-630. The latter HEL result is higher than elastic limits for any BMG reported in the literature thus far. SAM2X5-600 catastrophically loses post-yield strength whereas SAM2X5-630, while showing some strain-softening, retains strength beyond the HEL. The presence of crystallinity within the amorphous matrix is thus seen to significantly aid in strengthening the material as well as preserving material strength beyond yielding.

  7. Environmental Remediation and Application of Nanoscale Zero-Valent Iron and Its Composites for the Removal of Heavy Metal Ions: A Review.

    PubMed

    Zou, Yidong; Wang, Xiangxue; Khan, Ayub; Wang, Pengyi; Liu, Yunhai; Alsaedi, Ahmed; Hayat, Tasawar; Wang, Xiangke

    2016-07-19

    The presence of heavy metals in the industrial effluents has recently been a challenging issue for human health. Efficient removal of heavy metal ions from environment is one of the most important issues from biological and environmental point of view, and many studies have been devoted to investigate the environmental behavior of nanoscale zerovalent iron (NZVI) for the removal of toxic heavy metal ions, present both in the surface and underground wastewater. The aim of this review is to show the excellent removal capacity and environmental remediation of NZVI-based materials for various heavy metal ions. A new look on NZVI-based materials (e.g., modified or matrix-supported NZVI materials) and possible interaction mechanism (e.g., adsorption, reduction and oxidation) and the latest environmental application. The effects of various environmental conditions (e.g., pH, temperature, coexisting oxy-anions and cations) and potential problems for the removal of heavy metal ions on NZVI-based materials with the DFT theoretical calculations and EXAFS technology are discussed. Research shows that NZVI-based materials have satisfactory removal capacities for heavy metal ions and play an important role in the environmental pollution cleanup. Possible improvement of NZVI-based materials and potential areas for future applications in environment remediation are also proposed.

  8. Wood smoke particle sequesters cell iron to impact a biological effect.

    EPA Science Inventory

    The biological effect of an inorganic particle (i.e., silica) can be associated with a disruption in cell iron homeostasis. Organic compounds included in particles originating from combustion processes can also complex sources of host cell iron to disrupt metal homeostasis. We te...

  9. Anaerobic microbial remobilization of coprecipitated metals

    DOEpatents

    Francis, A.J.; Dodge, C.J.

    1994-10-11

    A process is provided for solubilizing coprecipitated metals. Metals in waste streams are concentrated by treatment with an iron oxide coprecipitating agent. The coprecipitated metals are solubilized by contacting the coprecipitate with a bacterial culture of a Clostridium species ATCC 53464. The remobilized metals can then be recovered and recycled. 4 figs.

  10. Angiotensin II inhibits iron uptake and release in cultured neurons.

    PubMed

    Liu, Yong; Huang, Suna; Du, Fang; Yang, Guang; Jiang, Li Rong; Zhang, Chao; Qian, Zhong-ming

    2014-05-01

    Based on the well-confirmed roles of angiotensin II (ANGII) in iron transport of peripheral organs and cells, the causative link of excess brain iron with and the involvement of ANGII in neurodegenerative disorders, we speculated that ANGII might also have an effect on expression of iron transport proteins in the brain. In the present study, we investigated effects of ANGII on iron uptake and release using the radio-isotope methods as well as expression of cell iron transport proteins by Western blot analysis in cultured neurons. Our findings demonstrated for the first time that ANGII significantly reduced transferrin-bound iron and non-transferrin bound iron uptake and iron release as well as expression of two major iron uptake proteins transferrin receptor 1 and divalent metal transporter 1 and the key iron exporter ferroportin 1 in cultured neurons. The findings suggested that endogenous ANGII might have a physiological significance in brain iron metabolism.

  11. Impact of biostimulated redox processes on metal dynamics in an iron-rich creek soil of a former uranium mining area.

    PubMed

    Burkhardt, Eva-Maria; Akob, Denise M; Bischoff, Sebastian; Sitte, Jana; Kostka, Joel E; Banerjee, Dipanjan; Scheinost, Andreas C; Küsel, Kirsten

    2010-01-01

    Understanding the dynamics of metals and radionuclides in soil environments is necessary for evaluating risks to pristine sites. An iron-rich creek soil of a former uranium-mining district (Ronneburg, Germany) showed high porewater concentrations of heavy metals and radionuclides. Thus, this study aims to (i) evaluate metal dynamics during terminal electron accepting processes (TEAPs) and (ii) characterize active microbial populations in biostimulated soil microcosms using a stable isotope probing (SIP) approach. In biostimulated soil slurries, concentrations of soluble Co, Ni, Zn, As, and unexpectedly U increased during Fe(III)-reduction. This suggests that there was a release of sorbed metals and As during reductive dissolution of Fe(III)-oxides. Subsequent sulfate-reduction was concurrent with a decrease of U, Co, Ni, and Zn concentrations. The relative contribution of U(IV) in the solid phase changed from 18.5 to 88.7% after incubation. The active Fe(III)-reducing population was dominated by delta-Proteobacteria (Geobacter) in (13)C-ethanol amended microcosms. A more diverse community was present in (13)C-lactate amended microcosms including taxa related to Acidobacteria, Firmicutes, delta-Proteobacteria, and beta-Proteobacteria. Our results suggested that biostimulated Fe(III)-reducing communities facilitated the release of metals including U to groundwater which is in contrast to other studies.

  12. Environmental Effects on the Metallicities of Early-Type Galaxies

    NASA Technical Reports Server (NTRS)

    Jones, Christine; Oliversen, Ronald (Technical Monitor)

    2004-01-01

    We completed and published two papers in the Astrophysical Journal based on research from grant. In the first paper we analyzed nine X-ray-bright Virgo early-type galaxies observed by both ASCA and ROSAT. Through spatially resolved spectroscopy, we determined the radial temperature profiles and abundances of Mg, Si, and Fe for six galaxies. The temperature profiles are consistent with isothermal temperatures outside of cooler regions at the galaxies' centers. We present new evidence for iron abundance gradients in NGC 4472 and NGC 4649 and confirm the previous results on NGC 4636. Mg and Si abundance gradients on average are flatter than those of iron and correspond to an underabundance of α-process elements at high Fe values, while at low iron the element ratios favor enrichment by Type II supernovae (SNe). We explain the observed trend using the metallicity dependence of SN Ia metal production and present constraints on the available theoretical modeling for low-metallicity inhibition of SNe Ia. In the second paper We analyzed nine X-ray-bright Virgo early-type galaxies observed by both ASCA and ROSAT. Through spatially resolved spectroscopy, we determined the radial temperature profiles and abundances of Mg, Si, and Fe for six galaxies. The temperature profiles are consistent with isothermal temperatures outside of cooler regions at the galaxies' centers. We present new evidence for iron abundance gradients in NGC 4472 and NGC 4649 and confirm the previous results on NGC 4636. Mg and Si abundance gradients on average are flatter than those of iron and correspond to an underabundance of α-process elements at high Fe values, while at low iron the element ratios favor enrichment by Type I1 supernovae (SNe). We explain the observed trend using the metallicity dependence of SN Ia metal production and present constraints on the available theoretical modeling for low-metallicity inhibition of SNe Ia.

  13. Electronic structure and reactivity of three-coordinate iron complexes.

    PubMed

    Holland, Patrick L

    2008-08-01

    [Reaction: see text]. The identity and oxidation state of the metal in a coordination compound are typically thought to be the most important determinants of its reactivity. However, the coordination number (the number of bonds to the metal) can be equally influential. This Account describes iron complexes with a coordination number of only three, which differ greatly from iron complexes with octahedral (six-coordinate) geometries with respect to their magnetism, electronic structure, preference for ligands, and reactivity. Three-coordinate complexes with a trigonal-planar geometry are accessible using bulky, anionic, bidentate ligands (beta-diketiminates) that steer a monodentate ligand into the plane of their two nitrogen donors. This strategy has led to a variety of three-coordinate iron complexes in which iron is in the +1, +2, and +3 oxidation states. Systematic studies on the electronic structures of these complexes have been useful in interpreting their properties. The iron ions are generally high spin, with singly occupied orbitals available for pi interactions with ligands. Trends in sigma-bonding show that iron(II) complexes favor electronegative ligands (O, N donors) over electropositive ligands (hydride). The combination of electrostatic sigma-bonding and the availability of pi-interactions stabilizes iron(II) fluoride and oxo complexes. The same factors destabilize iron(II) hydride complexes, which are reactive enough to add the hydrogen atom to unsaturated organic molecules and to take part in radical reactions. Iron(I) complexes use strong pi-backbonding to transfer charge from iron into coordinated alkynes and N 2, whereas iron(III) accepts charge from a pi-donating imido ligand. Though the imidoiron(III) complex is stabilized by pi-bonding in the trigonal-planar geometry, addition of pyridine as a fourth donor weakens the pi-bonding, which enables abstraction of H atoms from hydrocarbons. The unusual bonding and reactivity patterns of three

  14. Thermodynamics of Iron Oxidation in Metallurgical Slags

    NASA Astrophysics Data System (ADS)

    Matousek, Jan

    2012-11-01

    The state of oxidation of a pyrometallurgical process, given by the partial pressure of oxygen and the temperature, is one of the important properties monitored and controlled in the smelting and refining of iron and the nonferrous metals. This article reviews the thermodynamic background for this quantity and examines some empirical methods for its estimation and use. The emphasis is on copper smelting, but the same principles apply to iron, nickel, lead, and zinc processes.

  15. Iron, copper, zinc, and manganese transport and regulation in pathogenic Enterobacteria: correlations between strains, site of infection and the relative importance of the different metal transport systems for virulence

    PubMed Central

    Porcheron, Gaëlle; Garénaux, Amélie; Proulx, Julie; Sabri, Mourad; Dozois, Charles M.

    2013-01-01

    For all microorganisms, acquisition of metal ions is essential for survival in the environment or in their infected host. Metal ions are required in many biological processes as components of metalloproteins and serve as cofactors or structural elements for enzymes. However, it is critical for bacteria to ensure that metal uptake and availability is in accordance with physiological needs, as an imbalance in bacterial metal homeostasis is deleterious. Indeed, host defense strategies against infection either consist of metal starvation by sequestration or toxicity by the highly concentrated release of metals. To overcome these host strategies, bacteria employ a variety of metal uptake and export systems and finely regulate metal homeostasis by numerous transcriptional regulators, allowing them to adapt to changing environmental conditions. As a consequence, iron, zinc, manganese, and copper uptake systems significantly contribute to the virulence of many pathogenic bacteria. However, during the course of our experiments on the role of iron and manganese transporters in extraintestinal Escherichia coli (ExPEC) virulence, we observed that depending on the strain tested, the importance of tested systems in virulence may be different. This could be due to the different set of systems present in these strains, but literature also suggests that as each pathogen must adapt to the particular microenvironment of its site of infection, the role of each acquisition system in virulence can differ from a particular strain to another. In this review, we present the systems involved in metal transport by Enterobacteria and the main regulators responsible for their controlled expression. We also discuss the relative role of these systems depending on the pathogen and the tissues they infect. PMID:24367764

  16. Molecular imaging of labile iron(II) pools in living cells with a turn-on fluorescent probe.

    PubMed

    Au-Yeung, Ho Yu; Chan, Jefferson; Chantarojsiri, Teera; Chang, Christopher J

    2013-10-09

    Iron is an essential metal for living organisms, but misregulation of its homeostasis at the cellular level can trigger detrimental oxidative and/or nitrosative stress and damage events. Motivated to help study the physiological and pathological consequences of biological iron regulation, we now report a reaction-based strategy for monitoring labile Fe(2+) pools in aqueous solution and living cells. Iron Probe 1 (IP1) exploits a bioinspired, iron-mediated oxidative C-O bond cleavage reaction to achieve a selective turn-on response to Fe(2+) over a range of cellular metal ions in their bioavailable forms. We show that this first-generation chemical tool for fluorescence Fe(2+) detection can visualize changes in exchangeable iron stores in living cells upon iron supplementation or depletion, including labile iron pools at endogenous, basal levels. Moreover, IP1 can be used to identify reversible expansion of labile iron pools by stimulation with vitamin C or the iron regulatory hormone hepcidin, providing a starting point for further investigations of iron signaling and stress events in living systems as well as future probe development.

  17. The iron-nickel-phosphorus system: Effects on the distribution of trace elements during the evolution of iron meteorites

    NASA Astrophysics Data System (ADS)

    Corrigan, Catherine M.; Chabot, Nancy L.; McCoy, Timothy J.; McDonough, William F.; Watson, Heather C.; Saslow, Sarah A.; Ash, Richard D.

    2009-05-01

    To better understand the partitioning behavior of elements during the formation and evolution of iron meteorites, two sets of experiments were conducted at 1 atm in the Fe-Ni-P system. The first set examined the effect of P on solid metal/liquid metal partitioning behavior of 22 elements, while the other set explored the effect of the crystal structures of body-centered cubic (α)- and face-centered cubic (γ)-solid Fe alloys on partitioning behavior. Overall, the effect of P on the partition coefficients for the majority of the elements was minimal. As, Au, Ga, Ge, Ir, Os, Pt, Re, and Sb showed slightly increasing partition coefficients with increasing P-content of the metallic liquid. Co, Cu, Pd, and Sn showed constant partition coefficients. Rh, Ru, W, and Mo showed phosphorophile (P-loving) tendencies. Parameterization models were applied to solid metal/liquid metal results for 12 elements. As, Au, Pt, and Re failed to match previous parameterization models, requiring the determination of separate parameters for the Fe-Ni-S and Fe-Ni-P systems. Experiments with coexisting α and γ Fe alloy solids produced partitioning ratios close to unity, indicating that an α versus γ Fe alloy crystal structure has only a minor influence on the partitioning behaviors of the trace element studied. A simple relationship between an element's natural crystal structure and its α/γ partitioning ratio was not observed. If an iron meteorite crystallizes from a single metallic liquid that contains both S and P, the effect of P on the distribution of elements between the crystallizing solids and the residual liquid will be minor in comparison to the effect of S. This indicates that to a first order, fractional crystallization models of the Fe-Ni-S-P system that do not take into account P are appropriate for interpreting the evolution of iron meteorites if the effects of S are appropriately included in the effort.

  18. Iron versus Copper II. Principles and Applications in Bioinorganic Chemistry.

    ERIC Educational Resources Information Center

    Ochiai, Ei-Ichiro

    1986-01-01

    Discusses the differences between iron and copper. Describes various aspects of the behaviors of these two elements, including those of biological and environmental significance. Addresses the evolution of the atmosphere and sedimentary ore formation, the phylogeny of iron and copper, and some anthropological notes regarding the use of the metals.…

  19. 1,4-Iron Migration for Expedient Allene Annulations through Iron-Catalyzed C-H/N-H/C-O/C-H Functionalizations.

    PubMed

    Mo, Jiayu; Müller, Thomas; Oliveira, João C A; Ackermann, Lutz

    2018-06-25

    C-H activation bears great potential for enabling sustainable molecular syntheses in a step- and atom-economical manner, with major advances having been realized with precious 4d and 5d transition metals. In contrast, we employed earth abundant, nontoxic iron catalysts for versatile allene annulations through a unique C-H/N-H/C-O/C-H functionalization sequence. The powerful iron catalysis occurred under external-oxidant-free conditions even at room temperature, while detailed mechanistic studies revealed an unprecedented 1,4-iron migration regime for facile C-H activations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Metals and lipid oxidation. Contemporary issues.

    PubMed

    Schaich, K M

    1992-03-01

    Lipid oxidation is now recognized to be a critically important reaction in physiological and toxicological processes as well as in food products. This provides compelling reasons to understand what causes lipid oxidation in order to be able to prevent or control the reactions. Redox-active metals are major factors catalyzing lipid oxidation in biological systems. Classical mechanisms of direct electron transfer to double bonds by higher valence metals and of reduction of hydroperoxides by lower valence metals do not always account for patterns of metal catalysis of lipid oxidation in multiphasic or compartmentalized biological systems. To explain why oxidation kinetics, mechanisms, and products in molecular environments which are both chemically and physically complex often do not follow classical patterns predicted by model system studies, increased consideration must be given to five contemporary issues regarding metal catalysis of lipid oxidation: hypervalent non-heme iron or iron-oxygen complexes, heme catalysis mechanism(s), compartmentalization of reactions and lipid phase reactions of metals, effects of metals on product mixes, and factors affecting the mode of metal catalytic action.

  1. Impacts of iron and steelmaking facilities on soil quality.

    PubMed

    Strezov, Vladimir; Chaudhary, Chandrakant

    2017-12-01

    Iron and steel are highly important materials used in a wide range of products with important contribution to the economic development. The processes for making iron and steel are energy intensive and known to contribute to local pollution. Deposition of the metals may also have adverse impacts on soil quality, which requires detailed assessment. The aim of this study was to investigate the impacts of iron and steelmaking facilities on the local soil quality. Soil samples were collected in the vicinity of two steelmaking sites in Australia, one based on blast furnace steelmaking operation, while the second site was based on electric arc furnace steel recycling. The soil samples were compared to a background site where no industrial impact is expected. The soil collected near industrial facilities contained larger toxic metal contents, however this concentration for all priority metals was within the Australian National Environmental Protection Measure guidelines for the acceptable recreational soil quality. When compared to the international soil quality guidelines, some of the soils collected near the industrial sites, particularly near the blast furnace operated steelmaking, exceeded the arsenic, iron and manganese (according to United States Environmental Protection Agency guidelines) and chromium, copper and nickel concentrations (according to the Canadian guidelines). The work further provided a novel environmental assessment model taking into consideration the environmental and health impacts of each element. The environmental assessment revealed most significant contribution of manganese, followed by titanium, zinc, chromium and lead. Titanium was the second most important contributor to the soil quality, however this metal is currently not included in any of the international soil quality guidelines. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Zinc transport by respiratory epithelial cells and interaction with iron homeostasis.

    PubMed

    Deng, Zhongping; Dailey, Lisa A; Soukup, Joleen; Stonehuerner, Jacqueline; Richards, Judy D; Callaghan, Kimberly D; Yang, Funmei; Ghio, Andrew J

    2009-10-01

    Despite recurrent exposure to zinc through inhalation of ambient air pollution particles, relatively little information is known about the homeostasis of this metal in respiratory epithelial cells. We describe zinc uptake and release by respiratory epithelial cells and test the postulate that Zn(2+) transport interacts with iron homeostasis in these same cells. Zn(2+) uptake after 4 and 8 h of exposure to zinc sulfate was concentration- and time-dependent. A majority of Zn(2+) release occurred in the 4 h immediately following cell exposure to ZnSO(4). Regarding metal importers, mRNA for Zip1 and Zip2 showed no change after respiratory epithelial cell exposure to zinc while mRNA for divalent metal transporter (DMT)1 increased. Western blot assay for DMT1 protein supported an elevated expression of this transport protein following zinc exposure. RT-PCR confirmed mRNA for the metal exporters ZnT1 and ZnT4 with the former increasing after ZnSO(4). Cell concentrations of ferritin increased with zinc exposure while oxidative stress, measured as lipid peroxides, was decreased supporting an anti-oxidant function for Zn(2+). Increased DMT1 expression, following pre-incubations of respiratory epithelial cells with TNF-alpha, IFN-gamma, and endotoxin, was associated with significantly decreased intracellular zinc transport. Finally, incubations of respiratory epithelial cells with both zinc sulfate and ferric ammonium citrate resulted in elevated intracellular concentrations of both metals. We conclude that exposure to zinc increases iron uptake by respiratory epithelial cells. Elevations in cell iron can possibly affect an increased expression of DMT1 and ferritin which function to diminish oxidative stress. Comparable to other metal exposures, changes in iron homeostasis may contribute to the biological effects of zinc in specific cells and tissues.

  3. mRNA Regulation of Cardiac Iron Transporters and Ferritin Subunits in a Mouse Model of Iron Overload

    PubMed Central

    Brewer, Casey J.; Wood, Ruth I.; Wood, John C.

    2014-01-01

    Iron cardiomyopathy is the leading cause of death in iron overload. Men have twice the mortality rate of women, though the cause is unknown. In hemojuvelin-knockout mice, a model of the disease, males load more cardiac iron than females. We postulated that sex differences in cardiac iron import cause differences in cardiac iron concentration. RT-PCR was used to measure mRNA of cardiac iron transporters in hemojuvelin-knockout mice. No sex differences were discovered among putative importers of non-transferrin bound iron (L-type and T-type calcium channels, ZRT/IRT-like protein 14 zinc channels). Transferrin-bound iron transporters were also analyzed; these are controlled by the iron regulatory element/iron regulatory protein (IRE/IRP) system. There was a positive relationship between cardiac iron and ferroportin mRNA in both sexes, but it was significantly steeper in females (p<0.05). Transferrin receptor 1 and divalent metal transporter 1 were more highly expressed in females than males (p<0.01 and p<0.0001, respectively), consistent with their lower cardiac iron levels, as predicted by IRE/IRP regulatory pathways. Light-chain (L) ferritin showed a positive correlation with cardiac iron that was nearly identical in males and females (R2=0.41, p<0.01 and R2=0.56, p<0.05, respectively), while heavy-chain (H) ferritin was constitutively expressed in both sexes. This represents the first report of IRE/IRP regulatory pathways in the heart. Transcriptional regulation of ferroportin was suggested in both sexes, creating a potential mechanism for differential set points for iron export. Constitutive H-ferritin expression suggests a logical limit to cardiac iron buffering capacity at levels known to produce heart failure in humans. PMID:25220979

  4. Fabrication of high-performance metal ion doped iron oxide electrode for supercapacitor applications through a novel platform

    NASA Astrophysics Data System (ADS)

    Aghazadeh, Mustafa; Karimzadeh, Isa

    2017-10-01

    We provide a novel electrodeposition platform of undoped and Eu3+ doped iron oxide nanoparticles (Eu-IONPs) from an additive-free electrolyte containing Fe(NO3)3, FeCl2 and EuCl3. The prepared IONPs were analyzed using x-ray diffraction, field emission electron microscopy and energy-dispersive x-ray techniques, and the obtained data showed successful electrosynthesis of magnetite nanoparticles (size  ≈  10 nm) doped with about 10 wt% Eu3+ ions. The Eu-IONPs were used as supercapacitor electrode materials, and characterized by cyclic voltammetry and galvanostatic charge-discharge measurements. The as-synthesized Eu-IONPs exhibit remarkable pseudocapacitive activities including high specific capacitances of 212.5 and 153.2 F g-1 at 0.5 and 2 A g-1, respectively, and excellent cycling stabilities of 93.9% and 86.5% after 2000 discharging cycles. Furthermore, vibrational sample magnetometer data confirmed better superparamagnetic performance of Eu-IONPs (Ms  =  72.8 emu g-1, Mr  =  0.24 emu g-1 and H Ci  =  3.48 G) as compared with pure IONPs (Ms  =  51.92 emu g-1, Mr  =  0.95 emu g-1 and H Ci  =  14.62 G) due to exhibiting lower Mr and H Ci values. This novel synthetic platform of metal ion doped iron oxide is potentially a convenient way to fabricate high-performance iron oxide electrodes for energy storage systems.

  5. Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses

    NASA Astrophysics Data System (ADS)

    Das, Santanu; Choudhary, Kamal; Chernatynskiy, Aleksandr; Choi Yim, Haein; Bandyopadhyay, Asis K.; Mukherjee, Sundeep

    2016-06-01

    High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe-Co metallic glass system of composition [(Co1-x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent ‘Stoner type’ magnetization for the amorphous alloys in contrast to ‘Heisenberg type’ in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study.

  6. Implications of nutrient release from iron metal for microbial regrowth in water distribution systems.

    PubMed

    Morton, Siyuan C; Zhang, Yan; Edwards, Marc A

    2005-08-01

    Control of microbial regrowth in iron pipes is a major challenge for water utilities. This work examines the inter-relationship between iron corrosion and bacterial regrowth, with a special focus on the potential of iron pipe to serve as a source of phosphorus. Under some circumstances, corroding iron and steel may serve as a source for all macronutrients necessary for bacterial regrowth including fixed carbon, fixed nitrogen and phosphorus. Conceptual models and experimental data illustrate that levels of phosphorus released from corroding iron are significant relative to that necessary to sustain high levels of biofilm bacteria. Consequently, it may not be possible to control regrowth on iron surfaces by limiting phosphorus in the bulk water.

  7. Effect of the metals iron, copper and silver on fluorobenzene biodegradation by Labrys portucalensis.

    PubMed

    Moreira, Irina S; Amorim, Catarina L; Carvalho, Maria F; Ferreira, António C; Afonso, Carlos M; Castro, Paula M L

    2013-04-01

    Organic and metallic pollutants are ubiquitous in the environment. Many metals are reported to be toxic to microorganisms and to inhibit biodegradation. The effect of the metals iron, copper and silver on the metabolism of Labrys portucalensis F11 and on fluorobenzene (FB) biodegradation was examined. The results indicate that the addition of 1 mM of Fe(2+) to the culture medium has a positive effect on bacterial growth and has no impact in the biodegradation of 1 and 2 mM of FB. The presence of 1 mM of Cu(2+) was found to strongly inhibit the growth of F11 cultures and to reduce the biodegradation of 1 and 2 mM of FB to ca. 50 %, with 80 % of stoichiometrically expected fluoride released. In the experiments with resting cells, the FB degraded (from 2 mM supplied) was reduced ca. 20 % whereas the fluoride released was reduced to 45 % of that stoichiometrically expected. Ag(+) was the most potent inhibitor of FB degradation. In experiments with growing cells, the addition of 1 mM of Ag(+) to the culture medium containing 1 and 2 mM of FB resulted in no fluoride release, whereas FB degradation was only one third of that observed in control cultures. In the experiments with resting cells, the addition of Ag(+) resulted in 25 % reduction in substrate degradation and fluoride release was only 20 % of that stoichiometrically expected. The accumulation of catechol and 4-fluorocatechol in cultures supplemented with Cu(2+) or Ag(+) suggest inhibition of the key enzyme of FB metabolism-catechol 1,2-dioxygenase.

  8. Role of microbial iron reduction in the dissolution of iron hydroxysulfate minerals

    USGS Publications Warehouse

    Jones, E.J.P.; Nadeau, T.-L.; Voytek, M.A.; Landa, E.R.

    2006-01-01

    Iron-hydroxysulfate minerals can be important hosts for metals such as lead, mercury, copper, zinc, silver, chromium, arsenic, and selenium and for radionuclides such as 226Ra. These mineral-bound contaminants are considered immobilized under oxic conditions. However, when anoxic conditions develop, the activities of sulfate- or iron-reducing bacteria could result in mineral dissolution, releasing these bound contaminants. Reduction of structural sulfate in the iron-hydroxysulfate mineral jarosite by sulfate-reducing bacteria has previously been demonstrated. The primary objective of this work was to evaluate the potential for anaerobic dissolution of the iron-hydroxysulfate minerals jarosite and schwertmannite at neutral PH by iron-reducing bacteria. Mineral dissolution was tested using a long-term cultivar, Geobacter metallireducens strain GS-15, and a fresh isolate Geobacter sp. strain ENN1, previously undescribed. ENN1 was isolated from the discharge site of Shadle Mine, in the southern anthracite coalfield of Pennsylvania, where schwertmannite was the predominant iron-hydroxysulfate mineral. When jarosite from Elizabeth Mine (Vermont) was provided as the sole terminal electron acceptor, resting cells of both G. metallireducens and ENN1 were able to reduce structural Fe(III), releasing Fe+2, SO4-2, and K+ ions. A lithified jarosite sample from Utah was more resistant to microbial attack, but slow release of Fe+2 was observed. Neither bacterium released Fe+2 from poorly crystalline synthetic schwertmannite. Our results indicate that exposure of jarosite to iron-reducing conditions at neutral pH is likely to promote the mobility of hazardous constituents and should therefore be considered in evaluating waste disposal and/or reclamation options involving jarosite-bearing materials.

  9. Greek "red mud" residue: a study of microwave reductive roasting followed by magnetic separation for a metallic iron recovery process.

    PubMed

    Samouhos, Michail; Taxiarchou, Maria; Tsakiridis, Petros E; Potiriadis, Konstantinos

    2013-06-15

    The present research work is focused on the development of an alternative microwave reductive roasting process of red mud using lignite (30.15 wt.%Cfix), followed by wet magnetic separation, in order to produce a raw material suitable for sponge or cast iron production. The reduction degree of iron was controlled by both the reductive agent content and the microwave heating time. The reduction followed the Fe₂O₃ → Fe₃O₄ → FeO → Fe sequence. The dielectric constants [real (ε') and imaginary (ε″) permittivities] of red mud-lignite mixture were determined at 2.45 GHz, in the temperature range of 25-1100 °C. The effect of parameters such as temperature, intensity of reducing conditions, intensity of magnetic field and dispersing agent addition rate on the result of both processes was investigated. The phase's transformations in reduction process with microwave heating were determined by X-ray diffraction analysis (XRD) in combination with thermogravimetric/differential thermal analysis (TGA/DTA). The microstructural and morphological characterization of the produced calcines was carried out by scanning electron microscopy (SEM). At the optimum conditions a magnetic concentrate with total iron concentration of 35.15 and 69.3 wt.% metallization degree was obtained. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. ESD Test Apparatus for Soldering Irons

    NASA Technical Reports Server (NTRS)

    Sancho, Jose; Esser, Robert

    2013-01-01

    ESDA (Electrostatic Discharge Association) ESD STM 13.1-2000 requires frequent testing of the voltage leakage from the tip of a soldering iron and the resistance from the tip of the soldering iron to the common point ground. Without this test apparatus, the process is time-consuming and requires several wires, alligator clips, or test probes, as well as additional equipment. Soldering iron tips must be tested for electrostatic discharge risks frequently, and this typically takes a lot of time in setup and testing. This device enables the operator to execute the full test in one minute or less. This innovation is a simple apparatus that plugs into a digital multimeter (DMM) and the Common Point Ground (CPG) reference. It enables the user to perform two of the electrostatic discharge tests required in ESD STM 13.1-2000. The device consists of a small black box with two prongs sticking out of one end, two inputs on the opposite end (one of the inputs is used to connect the reference CPG to the DMM), and a metal tab on one side. Inside the box are wires, several washers of various materials, and assembly hardware (nuts and screws/bolts). The device is a passive electronic component that is plugged into a DMM. The operator sets the DMM to read voltage. The operator places the heated tip of the soldering iron onto the metal tab with a small amount of solder to ensure a complete connection. The voltage is read and recorded. The operator switches the DMM to read resistance. The operator places the heated tip of the soldering iron onto the metal tab with a small amount of solder to ensure a complete connection. The resistance is recorded. If the recorded voltage and resistance are below a number stated in ESDA ESD STM 13.1-2000, the test is considered to pass. The device includes all the necessary wiring internal to its body so the operator does not need to do any independent wiring, except for grounding. It uses a stack of high-thermal-resistance washers to minimize the

  11. Angiotensin II alters the expression of duodenal iron transporters, hepatic hepcidin, and body iron distribution in mice.

    PubMed

    Tajima, Soichiro; Ikeda, Yasumasa; Enomoto, Hideaki; Imao, Mizuki; Horinouchi, Yuya; Izawa-Ishizawa, Yuki; Kihira, Yoshitaka; Miyamoto, Licht; Ishizawa, Keisuke; Tsuchiya, Koichiro; Tamaki, Toshiaki

    2015-08-01

    Angiotensin II (ANG II) has been shown to affect iron metabolism through alteration of iron transporters, leading to increased cellular and tissue iron contents. Serum ferritin, a marker of body iron storage, is elevated in various cardiovascular diseases, including hypertension. However, the associated changes in iron absorption and the mechanism underlying increased iron content in a hypertensive state remain unclear. The C57BL6/J mice were treated with ANG II to generate a model of hypertension. Mice were divided into three groups: (1) control, (2) ANG II-treated, and (3) ANG II-treated and ANG II receptor blocker (ARB)-administered (ANG II-ARB) groups. Mice treated with ANG II showed increased serum ferritin levels compared to vehicle-treated control mice. In ANG II-treated mice, duodenal divalent metal transporter-1 and ferroportin (FPN) expression levels were increased and hepatic hepcidin mRNA expression and serum hepcidin concentration were reduced. The mRNA expression of bone morphogenetic protein 6 and CCAAT/enhancer-binding protein alpha, which are regulators of hepcidin, was also down-regulated in the livers of ANG II-treated mice. In terms of tissue iron content, macrophage iron content and renal iron content were increased by ANG II treatment, and these increases were associated with reduced expression of transferrin receptor 1 and FPN and increased expression of ferritin. These changes induced by ANG II treatment were ameliorated by the administration of an ARB. Angiotensin II (ANG II) altered the expression of duodenal iron transporters and reduced hepcidin levels, contributing to the alteration of body iron distribution.

  12. Protocol to determine accurate absorption coefficients for iron containing transferrins

    PubMed Central

    James, Nicholas G.; Mason, Anne B.

    2008-01-01

    An accurate protein concentration is an essential component of most biochemical experiments. The simplest method to determine a protein concentration is by measuring the A280, using an absorption coefficient (ε), and applying the Beer-Lambert law. For some metalloproteins (including all transferrin family members) difficulties arise because metal binding contributes to the A280 in a non-linear manner. The Edelhoch method is based on the assumption that the ε of a denatured protein in 6 M guanidine-HCl can be calculated from the number of the tryptophan, tyrosine, and cystine residues. We extend this method to derive ε values for both apo- and iron-bound transferrins. The absorbance of an identical amount of iron containing protein is measured in: 1) 6 M guanidine-HCl (denatured, no iron); 2) pH 7.4 buffer (non-denatured with iron); and 3) pH 5.6 (or lower) buffer with a chelator (non-denatured without iron). Since the iron free apo-protein has an identical A280 under non-denaturing conditions, the difference between the reading at pH 7.4 and the lower pH directly reports the contribution of the iron. The method is fast and consumes ~1 mg of sample. The ability to determine accurate ε values for transferrin mutants that bind iron with a wide range of affinities has proven very useful; furthermore a similar approach could easily be followed to determine ε values for other metalloproteins in which metal binding contributes to the A280. PMID:18471984

  13. Regulatory mechanisms for iron transport across the blood-brain barrier.

    PubMed

    Duck, Kari A; Simpson, Ian A; Connor, James R

    2017-12-09

    Many critical metabolic functions in the brain require adequate and timely delivery of iron. However, most studies when considering brain iron uptake have ignored the iron requirements of the endothelial cells that form the blood-brain barrier (BBB). Moreover, current models of BBB iron transport do not address regional regulation of brain iron uptake or how neurons, when adapting to metabolic demands, can acquire more iron. In this study, we demonstrate that both iron-poor transferrin (apo-Tf) and the iron chelator, deferoxamine, stimulate release of iron from iron-loaded endothelial cells in an in vitro BBB model. The role of the endosomal divalent metal transporter 1 (DMT1) in BBB iron acquisition and transport has been questioned. Here, we show that inhibition of DMT1 alters the transport of iron and Tf across the endothelial cells. These data support an endosome-mediated model of Tf-bound iron uptake into the brain and identifies mechanisms for local regional regulation of brain iron uptake. Moreover, our data provide an explanation for the disparity in the ratio of Tf to iron transport into the brain that has confounded the field. Copyright © 2017 Elsevier Inc. All rights reserved.

  14. Spall behavior of cast iron with varying microstructures

    NASA Astrophysics Data System (ADS)

    Plume, Gifford; Rousseau, Carl-Ernst

    2014-07-01

    The spall strength of cast iron with varying microstructures has been investigated using plate impact at moderate speed. Stress history measurements were made with manganin stress gauges embedded between the back face of the specimen and a low impedance polycarbonate backing. Five separate cast irons were tested. Four of these consisted of gray cast iron with graphite in flake form, with three classified as Type VII A2 and the fourth containing a bimodal distribution of Types VII A4 and VII D8. The fifth casting consisted of ductile cast iron with graphite in nodular form, classified as Type I, size class 5. The spall strength for the Type VII A2 gray cast irons varied between 40 and 370 MPa, and that of the additional gray cast iron, between 410 and 490 MPa. The spall strength of the ductile cast iron fell within the range of 0.94-1.2 GPa. It is shown that the spall strength is linked to the damage level at the spall plane, where an increased level of tensile stress is required to generate higher levels of damage. Post mortem analysis was performed on the recovered samples, revealing the graphite phase to be the primary factor governing the spall fracture of cast irons, where crack nucleation is directly correlated to the debonding of graphite from the metal matrix. The average length of graphite found within a casting is linked to the material's strength, where strength increases as a function of decreasing length. The morphology and mean free path of graphite precipitates further govern the subsequent coalescence of initiated cracks to form a complete fracture plane. In cases where graphite spacing is large, increased energy level is required to complete the fracture process. A secondary factor governing the spall fracture of cast irons has also been linked to the microstructure of the metal matrix, with pearlite yielding higher spall strengths than free ferrite.

  15. [Partitioning of taxifolin-iron ions complexes in octanol-water system].

    PubMed

    Shatalin, Iu V; Shubina, V S

    2014-01-01

    The composition of taxifolin-iron ions complexes in an octanol-water biphasic system was studied using the method of absorption spectrophotometry. It was found that at pH 5.0 in an aqueous biphasic system the complex of [Tf2 x Fe x (OH)k(H2O)8-k] is present, but at pH 7.0 and 9.0 the complexes of [Tf2 x Fe x (OH)k(H2O)2-k] and [Tf x Fe x OH)k(H2O)4-k] are predominantly observed. The formation of a stable [Tf3 x Fe] complex occurred in octanol phase. The charged iron ion of this complex is surrounded by taxifolin molecules, which shield the iron ion from lipophilic solvent. During transition from water to octanol phase the changes of the composition of complexes are accompanied by reciprocal changes in portion of taxifolin and iron ions in these phases. It was shown that the portion of taxifolin in aqueous solution in the presence of iron ions is increased at high pH values, and the portion of iron ions is minimal at pH 7.0. In addition, the parameters of solubility limits of taxifolin-iron ions complexes in an aqueous solution were determined. The data obtained gain a better understanding of the role of complexation of polyphenol with metal of variable valency in passive transport of flavonoids and metal ions across lipid membranes.

  16. Frataxin Depletion in Yeast Triggers Up-regulation of Iron Transport Systems before Affecting Iron-Sulfur Enzyme Activities*

    PubMed Central

    Moreno-Cermeño, Armando; Obis, Èlia; Bellí, Gemma; Cabiscol, Elisa; Ros, Joaquim; Tamarit, Jordi

    2010-01-01

    The primary function of frataxin, a mitochondrial protein involved in iron homeostasis, remains controversial. Using a yeast model of conditional expression of the frataxin homologue YFH1, we analyzed the primary effects of YFH1 depletion. The main conclusion unambiguously points to the up-regulation of iron transport systems as a primary effect of YFH1 down-regulation. We observed that inactivation of aconitase, an iron-sulfur enzyme, occurs long after the iron uptake system has been activated. Decreased aconitase activity should be considered part of a group of secondary events promoted by iron overloading, which includes decreased superoxide dismutase activity and increased protein carbonyl formation. Impaired manganese uptake, which contributes to superoxide dismutase deficiency, has also been observed in YFH1-deficient cells. This low manganese content can be attributed to the down-regulation of the metal ion transporter Smf2. Low Smf2 levels were not observed in AFT1/YFH1 double mutants, indicating that high iron levels could be responsible for the Smf2 decline. In summary, the results presented here indicate that decreased iron-sulfur enzyme activities in YFH1-deficient cells are the consequence of the oxidative stress conditions suffered by these cells. PMID:20956517

  17. Potential of siderophore-producing bacteria for improving heavy metal phytoextraction.

    PubMed

    Rajkumar, Mani; Ae, Noriharu; Prasad, Majeti Narasimha Vara; Freitas, Helena

    2010-03-01

    Phytoremediation holds promise for in situ treatment of heavy metal contaminated soils. Recently, the benefits of combining siderophore-producing bacteria (SPB) with plants for metal removal from contaminated soils have been demonstrated. Metal-resistant SPB play an important role in the successful survival and growth of plants in contaminated soils by alleviating the metal toxicity and supplying the plant with nutrients, particularly iron. Furthermore, bacterial siderophores are able to bind metals other than iron and thus enhance their bioavailability in the rhizosphere of plants. Overall, an increase in plant growth and metal uptake will further enhance the effectiveness of phytoremediation processes. Here, we highlight the diversity and ecology of metal resistant SPB and discuss their potential role in phytoremediation of heavy metals.

  18. Calcium channel blockers ameliorate iron overload-associated hepatic fibrosis by altering iron transport and stellate cell apoptosis

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

    Zhang, Ying

    Liver fibrosis is the principal cause of morbidity and mortality in patients with iron overload. Calcium channel blockers (CCBs) can antagonize divalent cation entry into renal and myocardial cells and inhibit fibrogenic gene expression. We investigated the potential of CCBs to resolve iron overload-associated hepatic fibrosis. Kunming mice were assigned to nine groups (n = 8 per group): control, iron overload, deferoxamine, high and low dose verapamil, high and low dose nimodipine, and high and low dose diltiazem. Iron deposition and hepatic fibrosis were measured in mouse livers. Expression levels of molecules associated with transmembrane iron transport were determined bymore » molecular biology approaches. In vitro HSC-T6 cells were randomized into nine groups (the same groups as the mice). Changes in proliferation, apoptosis, and metalloproteinase expression in cells were detected to assess the anti-fibrotic effects of CCBs during iron overload conditions. We found that CCBs reduced hepatic iron content, intracellular iron deposition, the number of hepatic fibrotic areas, collagen expression levels, and hydroxyproline content. CCBs rescued abnormal expression of α1C protein in L-type voltage-dependent calcium channel (LVDCC) and down-regulated divalent metal transporter-1 (DMT-1) expression in mouse livers. In iron-overloaded HSC-T6 cells, CCBs reduced iron deposition, inhibited proliferation, induced apoptosis, and elevated expression of matrix metalloproteinase-13 (MMP-13) and tissue inhibitor of metalloproteinase-1 (TIMP-1). CCBs are potential therapeutic agents that can be used to address hepatic fibrosis during iron overload. They resolve hepatic fibrosis probably correlated with regulating transmembrane iron transport and inhibiting HSC growth. - Highlights: • Calcium channel blockers (CCBs) reduced hepatic iron content. • CCBs decreased hepatic fibrotic areas and collagen expression levels. • CCBs resolve fibrosis by regulating iron transport

  19. Oxidation-Induced Degradable Nanogels for Iron Chelation

    NASA Astrophysics Data System (ADS)

    Liu, Zhi; Wang, Yan; Purro, Max; Xiong, May P.

    2016-02-01

    Iron overload can increase cellular oxidative stress levels due to formation of reactive oxygen species (ROS); untreated, it can be extremely destructive to organs and fatal to patients. Since elevated oxidative stress levels are inherent to the condition in such patients, oxidation-induced degradable nanogels for iron chelation were rationally designed by simultaneously polymerizing oxidation-sensitive host-guest crosslinkers between β-cyclodextrin (β-CD) and ferrocene (Fc) and iron chelating moieties composed of deferoxamine (DFO) into the final gel scaffold in reverse emulsion reaction chambers. UV-Vis absorption and atomic absorption spectroscopy (AAS) was used to verify iron chelating capability of nanogels. These materials can degrade into smaller chelating fragments at rates proportional to the level of oxidative stress present. Conjugating DFO reduces the cytotoxicity of the chelator in the macrophage cells. Importantly, the nanogel can effectively reduce cellular ferritin expression in iron overloaded cells and regulate intracellular iron levels at the same time, which is important for maintaining a homeostatic level of this critical metal in cells.

  20. Reductive dechlorination of trichloroethylene by iron bimetallics

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

    Orth, R.G.; Dauda, T.; McKenzie, D.E.

    1998-07-01

    Reductive dechlorination using a zero valence metal such as iron has seen an increase in interest with the extension of iron dechlorination to in-situ treatment of ground water. Studies to increase the rate of dechlorination and the long term stability have lead many to examine the use of bimetallic iron systems. Results are shown for bimetallic iron systems of Cu, Sn, Ni, Ag, Au, and Pd. All of these bimetallic couples form a galvanic couple which increase corrosion rates and the production of hydrogen. Increased rates of reaction normalized to surface area were observed for all the couples. The reactionmore » rates were found to depended on surface area and surface coverage of the iron. The results of studies in deuterium oxide indicate that the pathways changed as the bimetallic is changed and that the pathway in all cases could be a combination of dehydrohalgenation and sequential dechlorination. Degradation of DNAPL TCE by iron was found to be zero order and the type of product observed was different from that observed for TCE dissolved in water.« less

  1. Oxidation-Induced Degradable Nanogels for Iron Chelation

    PubMed Central

    Liu, Zhi; Wang, Yan; Purro, Max; Xiong, May P.

    2016-01-01

    Iron overload can increase cellular oxidative stress levels due to formation of reactive oxygen species (ROS); untreated, it can be extremely destructive to organs and fatal to patients. Since elevated oxidative stress levels are inherent to the condition in such patients, oxidation-induced degradable nanogels for iron chelation were rationally designed by simultaneously polymerizing oxidation-sensitive host-guest crosslinkers between β-cyclodextrin (β-CD) and ferrocene (Fc) and iron chelating moieties composed of deferoxamine (DFO) into the final gel scaffold in reverse emulsion reaction chambers. UV-Vis absorption and atomic absorption spectroscopy (AAS) was used to verify iron chelating capability of nanogels. These materials can degrade into smaller chelating fragments at rates proportional to the level of oxidative stress present. Conjugating DFO reduces the cytotoxicity of the chelator in the macrophage cells. Importantly, the nanogel can effectively reduce cellular ferritin expression in iron overloaded cells and regulate intracellular iron levels at the same time, which is important for maintaining a homeostatic level of this critical metal in cells. PMID:26868174

  2. Metal-ligand Covalency of Iron Complexes from High-Resolution Resonant Inelastic X-ray Scattering

    PubMed Central

    Lundberg, Marcus; Kroll, Thomas; DeBeer, Serena; Bergmann, Uwe; Wilson, Samuel A.; Glatzel, Pieter; Nordlund, Dennis; Hedman, Britt; Hodgson, Keith O.; Solomon, Edward I.

    2013-01-01

    Data from Kα resonant inelastic X-ray scattering (RIXS) have been used to extract electronic structure information, i.e., the covalency of metal-ligand bonds, for four iron complexes using an experimentally based theoretical model. Kα RIXS involves resonant 1s → 3d excitation and detection of the 2p → 1s (Kα) emission. This two-photon process reaches similar final states as single-photon L-edge (2p → 3d) X-ray absorption spectroscopy (XAS), but involves only hard X-rays and can therefore be used to get high-resolution L-edge-like spectra for metal proteins, solution catalysts and their intermediates. To analyze the information content of Kα RIXS spectra, data have been collected for four characteristic σ-donor and π-backdonation complexes; ferrous tacn [FeII(tacn)2]Br2, ferrocyanide [FeII(CN)6]K4, ferric tacn [FeIII(tacn)2]Br3 and ferricyanide [FeIII(CN)6]K3. From these spectra metal-ligand covalencies can be extracted using a charge-transfer multiplet model, without previous information from the L-edge XAS experiment. A direct comparison of L-edge XAS and Kα RIXS spectra show that the latter reaches additional final states, e.g., when exciting into the eg (σ*) orbitals, and the splitting between final states of different symmetry provides an extra dimension that makes Kα RIXS a more sensitive probe of σ-bonding. Another key difference between L-edge XAS and Kα RIXS is the π-backbonding features in ferro- and ferricyanide that are significantly more intense in L-edge XAS compared to Kα RIXS. This shows that two methods are complimentary in assigning electronic structure. The Kα RIXS approach can thus be used as a stand-alone method, in combination with L-edge XAS for strongly covalent systems that are difficult to probe by UV/Vis spectroscopy, or as an extension to conventional absorption spectroscopy for a wide range of transition metal enzymes and catalysts. PMID:24131028

  3. Maternal Cadmium, Iron and Zinc Levels, DNA Methylation and Birth Weight

    EPA Science Inventory

    BACKGROUND:Cadmium (Cd) is a ubiquitous and environmentally persistent toxic metal that has been implicated in neurotoxicity, carcinogenesis and obesity and essential metals including zinc (Zn) and iron (Fe) may alter these outcomes. However mechanisms underlying these relationsh...

  4. A method for recovery of iron, titanium, and vanadium from vanadium-bearing titanomagnetite

    NASA Astrophysics Data System (ADS)

    Zhang, Yi-min; Wang, Li-na; Chen, De-sheng; Wang, Wei-jing; Liu, Ya-hui; Zhao, Hong-xin; Qi, Tao

    2018-02-01

    An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures: low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.

  5. Determination of natural organic matter and iron binding capacity in fen samples

    NASA Astrophysics Data System (ADS)

    Kügler, Stefan; Cooper, Rebecca E.; Frieder Mohr, Jan; Wichard, Thomas; Küsel, Kirsten

    2017-04-01

    Natural organic matter (NOM) plays an important role in ecosystem processes such as soil carbon stabilization, nutrient availability and metal complexation. Iron-NOM-complexes, for example, are known to increase the solubility and, as a result, the bioavailability of iron in natural environments leading to several effects on the microbial community. Due to the various functions of NOM in natural environments, there is a high level of interest in the characterization of the molecular composition. The complexity of NOM presents a significant challenge in the elucidation of its composition. However, the development and utilization of high resolution mass spectrometry (HR-MS) as a tool to detect single compounds in complex samples has spearheaded the effort to elucidate the composition of NOM. Over the past years, the accuracy of ion cyclotron- or Orbitrap mass spectrometers has increased dramatically resulting in the possibility to obtain a mass differentiation of the large number of compounds in NOM. Together these tools provide significant and powerful insight into the molecular composition of NOM. In the current study, we aim to understand abiotic and biotic interactions between NOM and metals, such as iron, found in the Schlöppnerbrunnen fen (Fichtelgebirge, Germany) and how these interactions impact the microbial consortia. We characterized the dissolved organic matter (DOM) as well as basic chemical parameters in the iron-rich (up to 20 mg (g wt peat)-1), slightly acidic (pH 4.8) fen to gain more information about DOM-metal interactions. This minerotrophic peatland connected to the groundwater has received Fe(II) released from the surrounding soils in the Lehstenbach catchment. Absorption spectroscopy (AAS), differential pulse polarography (DPP) and high resolution electrospray ionization mass spectrometry (HR-ESI-Orbitrap-MS) was applied to characterize the molecular composition of DOM in the peat water extract (PWE). We identified typical patterns for DOM

  6. Stabilization of biosolids with nanoscale zero-valent iron (nZVI)

    NASA Astrophysics Data System (ADS)

    Li, Xiao-qin; Brown, Derick G.; Zhang, Wei-xian

    2007-04-01

    Biosolids are the treated organic residuals, also known as sludge, that are generated from domestic wastewater treatment plants. According to the USEPA, over 7 millions tons (dry weight) of biosolids are generated every year in the US by more than the 16,000 wastewater treatment plants and a large portion of these biosolids is disposed on land. Nuisance odors, the potential of pathogen transmission, and presence of toxic and persistent organic chemicals and metals in biosolids have for the most part limited the use of land applications. This paper presents zero-valent iron nanoparticles (1-100 nm) for the treatment and stabilization of biosolids. Iron nanoparticles have been shown to form stable and nonvolatile surface complexes with malodorous sulfur compounds such as hydrogen sulfide and methyl sulfides, degrade persistent organic pollutants such as PCBs and chlorinated pesticides, and sequestrate toxic metal ions such as mercury and lead. The end products from the nanoparticle reactions are iron oxides and oxyhydroxides, similar to the ubiquitous iron minerals in the environment. Due to the large surface area and high surface reactivity, only a relatively low dose (<0.1% wt) of iron nanoparticles is needed for effective biosolids stabilization. The iron nanoparticle technology may thus offer an economically and environmentally sustainable and unique solution to one of the most vexing environmental problems.

  7. Heavy metal accumulation in Pseudevernia furfuracea (L.) Zopf from the Karabük iron-steel factory in Karabük, Turkey.

    PubMed

    Cansaran-Duman, Demet; Atakol, Orhan; Atasoy, Ilknur; Kahya, Didem; Aras, Sümer; Beyaztaş, Taylan

    2009-01-01

    Pseudevernia furfuracea (L.) Zopf lichen specimens were collected every 5 km starting from around an iron-steel factory located in the central area of Karabük province, up to Yenice Forest. Zn, Cu, Mn, Fe, Pb, Ni, Cd, Cr contents were analyzed in the samples collected from polluted and unpolluted areas. A Pseudevernia furfuracea (L.) Zopf sample from Yenice Forest was used as a control. The reason for this choise was the abundance of species diversity, and therefore sample collection might cause a very low impact on natural population density. The forest is among the 100 forested areas that must be urgently taken under protection according to WWF (World Wildlife Fund) researches. Results of the current study manifested significant variations among the contents of these elements between stations. As expected, the pollution sources, such as iron-steel factory, roads and railroads, industry, heavy traffic, and waste treatment plants, have major impact on the heavy metal accumulation in P. furfuracea (L.) Zopf, and, in accordance to their location, samples 8 and 10 displayed high element accumulation. Surprisingly, although Yenice Forest is under protection, results of our study showed that the region is becoming polluted by the influence of many pollution sources in the area. The present study also confirms the efficient metal accumulation capacity of lichens.

  8. Genomic insights into microbial iron oxidation and iron uptake strategies in extremely acidic environments.

    PubMed

    Bonnefoy, Violaine; Holmes, David S

    2012-07-01

    This minireview presents recent advances in our understanding of iron oxidation and homeostasis in acidophilic Bacteria and Archaea. These processes influence the flux of metals and nutrients in pristine and man-made acidic environments such as acid mine drainage and industrial bioleaching operations. Acidophiles are also being studied to understand life in extreme conditions and their role in the generation of biomarkers used in the search for evidence of existing or past extra-terrestrial life. Iron oxidation in acidophiles is best understood in the model organism Acidithiobacillus ferrooxidans. However, recent functional genomic analysis of acidophiles is leading to a deeper appreciation of the diversity of acidophilic iron-oxidizing pathways. Although it is too early to paint a detailed picture of the role played by lateral gene transfer in the evolution of iron oxidation, emerging evidence tends to support the view that iron oxidation arose independently more than once in evolution. Acidic environments are generally rich in soluble iron and extreme acidophiles (e.g. the Leptospirillum genus) have considerably fewer iron uptake systems compared with neutrophiles. However, some acidophiles have been shown to grow as high as pH 6 and, in the case of the Acidithiobacillus genus, to have multiple iron uptake systems. This could be an adaption allowing them to respond to different iron concentrations via the use of a multiplicity of different siderophores. Both Leptospirillum spp. and Acidithiobacillus spp. are predicted to synthesize the acid stable citrate siderophore for Fe(III) uptake. In addition, both groups have predicted receptors for siderophores produced by other microorganisms, suggesting that competition for iron occurs influencing the ecophysiology of acidic environments. Little is known about the genetic regulation of iron oxidation and iron uptake in acidophiles, especially how the use of iron as an energy source is balanced with its need to take up

  9. Theoretical research program to predict the properties of molecules and clusters containing transition metal atoms

    NASA Technical Reports Server (NTRS)

    Walch, S.

    1984-01-01

    The primary focus of this research has been the theoretical study of transition metal (TM) chemistry. A major goal of this work is to provide reliable information about the interaction of H atoms with iron metal. This information is needed to understand the effect of H atoms on the processes of embrittlement and crack propagation in iron. The method in the iron hydrogen studies is the cluster method in which the bulk metal is modelled by a finite number of iron atoms. There are several difficulties in the application of this approach to the hydrogen iron system. First the nature of TM-TM and TM-H bonding for even diatomic molecules was not well understood when these studies were started. Secondly relatively large iron clusters are needed to provide reasonable results.

  10. Absorption of Manganese and Iron in a Mouse Model of Hemochromatosis

    PubMed Central

    Kim, Jonghan; Buckett, Peter D.; Wessling-Resnick, Marianne

    2013-01-01

    Hereditary hemochromatosis, an iron overload disease associated with excessive intestinal iron absorption, is commonly caused by loss of HFE gene function. Both iron and manganese absorption are regulated by iron status, but the relationships between the transport pathways of these metals and how they are affected by HFE-associated hemochromatosis remain poorly understood. Loss of HFE function is known to alter the intestinal expression of DMT1 (divalent metal transporter-1) and Fpn (ferroportin), transporters that have been implicated in absorption of both iron and manganese. Although the influence of HFE deficiency on dietary iron absorption has been characterized, potential effects on manganese metabolism have yet to be explored. To investigate the role of HFE in manganese absorption, we characterized the uptake and distribution of the metal in Hfe −/− knockout mice after intravenous, intragastric, and intranasal administration of 54Mn. These values were compared to intravenous and intragastric administration of 59Fe. Intestinal absorption of 59Fe was increased and clearance of injected 59Fe was also increased in Hfe−/− mice compared to controls. Hfe −/− mice displayed greater intestinal absorption of 54Mn compared to wild-type Hfe+/+ control mice. After intravenous injection, the distribution of 59Fe to heart and liver was greater in Hfe −/− mice but no remarkable differences were observed for 54Mn. Although olfactory absorption of 54Mn into blood was unchanged in Hfe −/− mice, higher levels of intranasally-instilled 54Mn were associated with Hfe−/− brain compared to controls. These results show that manganese transport and metabolism can be modified by HFE deficiency. PMID:23705020

  11. Iron homeostasis and toxicity in retinal degeneration.

    PubMed

    He, Xining; Hahn, Paul; Iacovelli, Jared; Wong, Robert; King, Chih; Bhisitkul, Robert; Massaro-Giordano, Mina; Dunaief, Joshua L

    2007-11-01

    Iron is essential for many metabolic processes but can also cause damage. As a potent generator of hydroxyl radical, the most reactive of the free radicals, iron can cause considerable oxidative stress. Since iron is absorbed through diet but not excreted except through menstruation, total body iron levels buildup with age. Macular iron levels increase with age, in both men and women. This iron has the potential to contribute to retinal degeneration. Here we present an overview of the evidence suggesting that iron may contribute to retinal degenerations. Intraocular iron foreign bodies cause retinal degeneration. Retinal iron buildup resulting from hereditary iron homeostasis disorders aceruloplasminemia, Friedreich's ataxia, and panthothenate kinase-associated neurodegeneration cause retinal degeneration. Mice with targeted mutation of the iron exporter ceruloplasmin have age-dependent retinal iron overload and a resulting retinal degeneration with features of age-related macular degeneration (AMD). Post mortem retinas from patients with AMD have more iron and the iron carrier transferrin than age-matched controls. Over the past 10 years much has been learned about the intricate network of proteins involved in iron handling. Many of these, including transferrin, transferrin receptor, divalent metal transporter-1, ferritin, ferroportin, ceruloplasmin, hephaestin, iron-regulatory protein, and histocompatibility leukocyte antigen class I-like protein involved in iron homeostasis (HFE) have been found in the retina. Some of these proteins have been found in the cornea and lens as well. Levels of the iron carrier transferrin are high in the aqueous and vitreous humors. The functions of these proteins in other tissues, combined with studies on cultured ocular tissues, genetically engineered mice, and eye exams on patients with hereditary iron diseases provide clues regarding their ocular functions. Iron may play a role in a broad range of ocular diseases, including

  12. Iron homeostasis and toxicity in retinal degeneration

    PubMed Central

    He, Xining; Hahn, Paul; Iacovelli, Jared; Wong, Robert; King, Chih; Bhisitkul, Robert; Massaro-Giordano, Mina; Dunaief, Joshua L.

    2007-01-01

    Iron is essential for many metabolic processes but can also cause damage. As a potent generator of hydroxyl radical, the most reactive of the free radicals, iron can cause considerable oxidative stress. Since iron is absorbed through diet but not excreted except through menstruation, total body iron levels build up with age. Macular iron levels increase with age, in both men and women. This iron has the potential to contribute to retinal degeneration. Here we present an overview of the evidence suggesting that iron may contribute to retinal degenerations. Intraocular iron foreign bodies cause retinal degeneration. Retinal iron buildup resulting from hereditary iron homeostasis disorders aceruloplasminemia, Friedreich’s Ataxia, and panthothenate kinase associated neurodegeneration cause retinal degeneration. Mice with targeted mutation of the iron exporter ceruloplasmin have age-dependent retinal iron overload and a resulting retinal degeneration with features of age-related macular degeneration (AMD). Post mortem retinas from patients with AMD have more iron and the iron carrier transferrin than age- matched controls. Over the past ten years much has been learned about the intricate network of proteins involved in iron handling. Many of these, including transferrin, transferrin receptor, divalent metal transporter 1, ferritin, ferroportin, ceruloplasmin, hephaestin, iron regulatory protein, and histocompatibility leukocyte antigen class I-like protein involved in iron homeostasis (HFE) have been found in the retina. Some of these proteins have been found in the cornea and lens as well. Levels of the iron carrier transferrin are high in the aqueous and vitreous humors. The functions of these proteins in other tissues, combined with studies on cultured ocular tissues, genetically engineered mice, and eye exams on patients with hereditary iron diseases provide clues regarding their ocular functions. Iron may play a role in a broad range of ocular diseases, including

  13. Pressure-induced superconductivity in the iron-based ladder material BaFe2S3.

    PubMed

    Takahashi, Hiroki; Sugimoto, Akira; Nambu, Yusuke; Yamauchi, Touru; Hirata, Yasuyuki; Kawakami, Takateru; Avdeev, Maxim; Matsubayashi, Kazuyuki; Du, Fei; Kawashima, Chizuru; Soeda, Hideto; Nakano, Satoshi; Uwatoko, Yoshiya; Ueda, Yutaka; Sato, Taku J; Ohgushi, Kenya

    2015-10-01

    All the iron-based superconductors identified so far share a square lattice composed of Fe atoms as a common feature, despite having different crystal structures. In copper-based materials, the superconducting phase emerges not only in square-lattice structures but also in ladder structures. Yet iron-based superconductors without a square-lattice motif have not been found, despite being actively sought out. Here, we report the discovery of pressure-induced superconductivity in the iron-based spin-ladder material BaFe2S3, a Mott insulator with striped-type magnetic ordering below ∼120 K. On the application of pressure this compound exhibits a metal-insulator transition at about 11 GPa, followed by the appearance of superconductivity below Tc = 14 K, right after the onset of the metallic phase. Our findings indicate that iron-based ladder compounds represent promising material platforms, in particular for studying the fundamentals of iron-based superconductivity.

  14. Molecular dissection of a putative iron reductase from Desulfotomaculum reducens MI-1

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

    Li, Zhi; Kim, David D.; Nelson, Ornella D.

    2015-10-08

    Desulfotomaculum reducens MI-1 is a Firmicute strain capable of reducing a variety of heavy metal ions and has a great potential in heavy metal bioremediation.We recently identified Dred_2421 as a potential iron reductase through proteomic study of D. reducens. The current study examines its iron-reduction mechanism. Dred_2421, like its close homolog from Escherichia coli (2, 4-dienoyl-CoA reductase), has an FMN-binding N-terminal domain (NTD), an FAD-binding C-terminal domain (CTD), and a 4Fee4S cluster between the two domains. To understand the mechanism of the iron-reduction activity and the role of each domain, we generated a series of variants for each domain andmore » investigated their iron reduction activity. Our results suggest that CTD is the main contributor of the iron-reduction activity, and that NTD and the 4Fee4S cluster are not directly involved in such activity. This study provides a mechanistic understanding of the ironereductase activity of Dred_2421 and may also help to elucidate other physiological activities this enzyme may have.« less

  15. Metal-ceramic joint assembly

    DOEpatents

    Li, Jian

    2002-01-01

    A metal-ceramic joint assembly in which a brazing alloy is situated between metallic and ceramic members. The metallic member is either an aluminum-containing stainless steel, a high chromium-content ferritic stainless steel or an iron nickel alloy with a corrosion protection coating. The brazing alloy, in turn, is either an Au-based or Ni-based alloy with a brazing temperature in the range of 9500 to 1200.degree. C.

  16. In vivo bioluminescence imaging of labile iron accumulation in a murine model of Acinetobacter baumannii infection.

    PubMed

    Aron, Allegra T; Heffern, Marie C; Lonergan, Zachery R; Vander Wal, Mark N; Blank, Brian R; Spangler, Benjamin; Zhang, Yaofang; Park, Hyo Min; Stahl, Andreas; Renslo, Adam R; Skaar, Eric P; Chang, Christopher J

    2017-11-28

    Iron is an essential metal for all organisms, yet disruption of its homeostasis, particularly in labile forms that can contribute to oxidative stress, is connected to diseases ranging from infection to cancer to neurodegeneration. Iron deficiency is also among the most common nutritional deficiencies worldwide. To advance studies of iron in healthy and disease states, we now report the synthesis and characterization of iron-caged luciferin-1 (ICL-1), a bioluminescent probe that enables longitudinal monitoring of labile iron pools (LIPs) in living animals. ICL-1 utilizes a bioinspired endoperoxide trigger to release d-aminoluciferin for selective reactivity-based detection of Fe 2+ with metal and oxidation state specificity. The probe can detect physiological changes in labile Fe 2+ levels in live cells and mice experiencing iron deficiency or overload. Application of ICL-1 in a model of systemic bacterial infection reveals increased iron accumulation in infected tissues that accompany transcriptional changes consistent with elevations in both iron acquisition and retention. The ability to assess iron status in living animals provides a powerful technology for studying the contributions of iron metabolism to physiology and pathology.

  17. Removal of metal(oid)s from contaminated water using iron-coated peat sorbent.

    PubMed

    Kasiuliene, Alfreda; Carabante, Ivan; Bhattacharya, Prosun; Caporale, Antonio Giandonato; Adamo, Paola; Kumpiene, Jurate

    2018-05-01

    This study aimed at combining iron and peat to produce a sorbent suitable for a simultaneous removal of cations and anions from a solution. Peat powder, an industrial residue, was coated with iron by immersing peat into iron salt solutions. The adsorption efficiency of the newly produced sorbent towards As, Cr, Cu and Zn was tested by means of batch adsorption experiments at a constant pH value of 5. Coating of Fe on peat significantly increased the adsorption of As (from <5% to 80%) and Cr (from <3% to 25%) in comparison to uncoated peat. Removal of cations on coated peat slightly decreased (by 10-15%), yet remained within acceptable range. Electron Microscopy combined with X-Ray Energy Dispersive Spectroscopy revealed that iron coating on the peat was rather homogenous and As and Cr were abundantly adsorbed on the surface. By contrast, Cu and Zn displayed a sparing distribution on the surface of the iron coated peat. These results indicate that iron-peat simultaneously target sufficient amounts of both cations and anions and can be used for a one-step treatment of contaminated groundwater. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

  18. Iron oxide surfaces

    NASA Astrophysics Data System (ADS)

    Parkinson, Gareth S.

    2016-03-01

    The current status of knowledge regarding the surfaces of the iron oxides, magnetite (Fe3O4), maghemite (γ-Fe2O3), haematite (α-Fe2O3), and wüstite (Fe1-xO) is reviewed. The paper starts with a summary of applications where iron oxide surfaces play a major role, including corrosion, catalysis, spintronics, magnetic nanoparticles (MNPs), biomedicine, photoelectrochemical water splitting and groundwater remediation. The bulk structure and properties are then briefly presented; each compound is based on a close-packed anion lattice, with a different distribution and oxidation state of the Fe cations in interstitial sites. The bulk defect chemistry is dominated by cation vacancies and interstitials (not oxygen vacancies) and this provides the context to understand iron oxide surfaces, which represent the front line in reduction and oxidation processes. Fe diffuses in and out from the bulk in response to the O2 chemical potential, forming sometimes complex intermediate phases at the surface. For example, α-Fe2O3 adopts Fe3O4-like surfaces in reducing conditions, and Fe3O4 adopts Fe1-xO-like structures in further reducing conditions still. It is argued that known bulk defect structures are an excellent starting point in building models for iron oxide surfaces. The atomic-scale structure of the low-index surfaces of iron oxides is the major focus of this review. Fe3O4 is the most studied iron oxide in surface science, primarily because its stability range corresponds nicely to the ultra-high vacuum environment. It is also an electrical conductor, which makes it straightforward to study with the most commonly used surface science methods such as photoemission spectroscopies (XPS, UPS) and scanning tunneling microscopy (STM). The impact of the surfaces on the measurement of bulk properties such as magnetism, the Verwey transition and the (predicted) half-metallicity is discussed. The best understood iron oxide surface at present is probably Fe3O4(100); the structure is

  19. Leaching behavior of lanthanum, nickel and iron from spent catalyst using inorganic acids

    NASA Astrophysics Data System (ADS)

    Astuti, W.; Prilitasari, N. M.; Iskandar, Y.; Bratakusuma, D.; Petrus, H. T. B. M.

    2018-01-01

    Highly technological applications of rare earth metals (REs) and scarcity of supply have become an incentive torecover the REs from various resources, which include high grade and low grade ores, as well as recycledwaste materials. Spent hydrocracking catalyst contain lanthanum and a variety of valuable metals such as nickel and iron. This study investigated the recovery of lanthanum, nickel and iron from spent hydrocracking catalyst by leaching using various inorganic acid (sulfuric acid, hydrochloric acid, and nitric acid). The effect of acid concentration, type of acid and leaching temperature was conducted to study the leaching behavior of each valuable metal from spent-catalyst. It has been shown that it is possible to recover more than 90% of lanthanum, however the leaching efficiency of nickel and iron in this process was very low. It can be concluded that the leaching process is selective for lanthanum recovery from hydrocracking spent-catalyst.

  20. The chemistry of iron, aluminum, and dissolved organic material in three acidic, metal-enriched, mountain streams, as controlled by watershed and in-stream processes

    USGS Publications Warehouse

    McKnight, Diane M.; Bencala, Kenneth E.

    1990-01-01

    Several studies were conducted in three acidic, metal-enriched, mountain streams, and the results are discussed together in this paper to provide a synthesis of watershed and in-stream processes controlling Fe, Al, and DOC (dissolved organic carbon) concentrations. One of the streams, the Snake River, is naturally acidic; the other two, Peru Creek and St. Kevin Gulch, receive acid mine drainage. Analysis of stream water chemistry data for the acidic headwaters of the Snake River shows that some trace metal solutes (Al, Mn, Zn) are correlated with major ions, indicating that watershed processes control their concentrations. Once in the stream, biogeochemical processes can control transport if they occur over time scales comparable to those for hydrologic transport. Examples of the following in-stream reactions are presented: (1) photoreduction and dissolution of hydrous iron oxides in response to an experimental decrease in stream pH, (2) precipitation of Al at three stream confluences, and (3) sorption of dissolved organic material by hydrous iron and aluminum oxides in a stream confluence. The extent of these reactions is evaluated using conservative tracers and a transport model that includes storage in the substream zone.

  1. Iron and molecular opacities and the evolution of Population I stars

    NASA Technical Reports Server (NTRS)

    Stothers, Richard B.; Chin, Chao-Wen

    1993-01-01

    Effects of recent opacity revisions on the evolution of Population I stars are explored over the range 1.5-60 solar masses. Opacity parameters considered include the angular momentum coupling scheme for iron, the relative iron abundance, the total metal abundance, and diatomic and triatomic molecular sources. Only the total metal abundance exerts an important control over the evolutionary tracks. Blue loops on the H-R diagram during core helium burning can be very sensitive to opacity, but only insofar as the simple formation or suppression of a blue loop is concerned. The blue loops are most robust for stellar masses around 10 solar masses. We confirm, from a comparison of stellar models with observational data, that the total metal abundance is close to solar and that convective core overshooting is likely to be very slight. The new models predict the existence of an iron convection zone in the envelope and a great widening of the main-sequence band in the H-R diagram at luminosities brighter than 100,000 solar luminosities.

  2. ASTM Committee G-4 metals flammability test program - Data and discussion

    NASA Technical Reports Server (NTRS)

    Stoltzfus, Joel M.; Homa, John M.; Williams, Ralph E.; Benz, Frank J.

    1988-01-01

    Results of metals flammability tests performed on twenty-six metals in the NASA/White Sands Test Facility are discussed together with the test systems. The promoted combustion and ignition characteristics of these metals are described, and the metals are ranked according to their suitability for use in oxygen systems. In general, alloys with high copper and nickel contents and low iron content were found to rank higher than those that had high iron content, while alloys that had high aluminum content were ranked the lowest.

  3. Removal of trace metal contaminants from potable water by electrocoagulation.

    PubMed

    Heffron, Joe; Marhefke, Matt; Mayer, Brooke K

    2016-06-21

    This study investigated the effects of four operational and environmental variables on the removal of trace metal contaminants from drinking water by electrocoagulation (EC). Removal efficiencies for five metals (arsenic, cadmium, chromium, lead and nickel) were compared under varying combinations of electrode material, post-treatment, water composition and pH. Iron electrodes out-performed aluminum electrodes in removing chromium and arsenic. At pH 6.5, aluminum electrodes were slightly more effective at removing nickel and cadmium, while at pH 8.5, iron electrodes were more effective for these metals. Regardless of electrode, cadmium and nickel removal efficiencies were higher at pH 8.5 than at pH 6.5. Post-EC treatment using membrane filtration (0.45 μm) enhanced contaminant removal for all metals but nickel. With the exception of lead, all metals exhibited poorer removal efficiencies as the ionic strength of the background electrolyte increased, particularly in the very high-solids synthetic groundwaters. Residual aluminum concentrations were lowest at pH 6.5, while iron residuals were lowest in low ionic strength waters. Both aluminum and iron residuals required post-treatment filtration to meet drinking water standards. EC with post-treatment filtration appears to effectively remove trace metal contaminants to potable water standards, but both reactor and source water parameters critically impact removal efficiency.

  4. Removal of trace metal contaminants from potable water by electrocoagulation

    PubMed Central

    Heffron, Joe; Marhefke, Matt; Mayer, Brooke K.

    2016-01-01

    This study investigated the effects of four operational and environmental variables on the removal of trace metal contaminants from drinking water by electrocoagulation (EC). Removal efficiencies for five metals (arsenic, cadmium, chromium, lead and nickel) were compared under varying combinations of electrode material, post-treatment, water composition and pH. Iron electrodes out-performed aluminum electrodes in removing chromium and arsenic. At pH 6.5, aluminum electrodes were slightly more effective at removing nickel and cadmium, while at pH 8.5, iron electrodes were more effective for these metals. Regardless of electrode, cadmium and nickel removal efficiencies were higher at pH 8.5 than at pH 6.5. Post-EC treatment using membrane filtration (0.45 μm) enhanced contaminant removal for all metals but nickel. With the exception of lead, all metals exhibited poorer removal efficiencies as the ionic strength of the background electrolyte increased, particularly in the very high-solids synthetic groundwaters. Residual aluminum concentrations were lowest at pH 6.5, while iron residuals were lowest in low ionic strength waters. Both aluminum and iron residuals required post-treatment filtration to meet drinking water standards. EC with post-treatment filtration appears to effectively remove trace metal contaminants to potable water standards, but both reactor and source water parameters critically impact removal efficiency. PMID:27324564

  5. Removal of trace metal contaminants from potable water by electrocoagulation

    NASA Astrophysics Data System (ADS)

    Heffron, Joe; Marhefke, Matt; Mayer, Brooke K.

    2016-06-01

    This study investigated the effects of four operational and environmental variables on the removal of trace metal contaminants from drinking water by electrocoagulation (EC). Removal efficiencies for five metals (arsenic, cadmium, chromium, lead and nickel) were compared under varying combinations of electrode material, post-treatment, water composition and pH. Iron electrodes out-performed aluminum electrodes in removing chromium and arsenic. At pH 6.5, aluminum electrodes were slightly more effective at removing nickel and cadmium, while at pH 8.5, iron electrodes were more effective for these metals. Regardless of electrode, cadmium and nickel removal efficiencies were higher at pH 8.5 than at pH 6.5. Post-EC treatment using membrane filtration (0.45 μm) enhanced contaminant removal for all metals but nickel. With the exception of lead, all metals exhibited poorer removal efficiencies as the ionic strength of the background electrolyte increased, particularly in the very high-solids synthetic groundwaters. Residual aluminum concentrations were lowest at pH 6.5, while iron residuals were lowest in low ionic strength waters. Both aluminum and iron residuals required post-treatment filtration to meet drinking water standards. EC with post-treatment filtration appears to effectively remove trace metal contaminants to potable water standards, but both reactor and source water parameters critically impact removal efficiency.

  6. Metabolic changes of iron uptake in N(2)-fixing common bean nodules during iron deficiency.

    PubMed

    Slatni, Tarek; Vigani, Gianpiero; Salah, Imen Ben; Kouas, Saber; Dell'Orto, Marta; Gouia, Houda; Zocchi, Graziano; Abdelly, Chedly

    2011-08-01

    Iron is an important nutrient in N(2)-fixing legume nodules. The demand for this micronutrient increases during the symbiosis establishment, where the metal is utilized for the synthesis of various iron-containing proteins in both the plant and the bacteroid. Unfortunately, in spite of its importance, iron is poorly available to plant uptake since its solubility is very low when in its oxidized form Fe(III). In the present study, the effect of iron deficiency on the activity of some proteins involved in Strategy I response, such as Fe-chelate reductase (FC-R), H(+)-ATPase, and phosphoenolpyruvate carboxylase (PEPC) and the protein level of iron regulated transporter (IRT1) and H(+)-ATPase proteins has been investigated in both roots and nodules of a tolerant (Flamingo) and a susceptible (Coco blanc) cultivar of common bean plants. The main results of this study show that the symbiotic tolerance of Flamingo can be ascribed to a greater increase in the FC-R and H(+)-ATPase activities in both roots and nodules, leading to a more efficient Fe supply to nodulating tissues. The strong increase in PEPC activity and organic acid content, in the Flamingo root nodules, suggests that under iron deficiency nodules can modify their metabolism in order to sustain those activities necessary to acquire Fe directly from the soil solution. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  7. PROTON GENERATION BY DISSOLUTION OF INTRINSIC OR AUGMENTED ALUMINOSILICATE MINERALS FOR IN SITU CONTAMINANT REMEDIATION BY ZERO-VALENCE-STATE IRON

    EPA Science Inventory

    Metallic, or zero-valence-state, iron is being incorporated into permeable reactive subsurface barriers for remediating a variety of contaminant plume types. The remediation occurs via reductive processes that are associated with surface corrosion of the iron metal. Reaction rate...

  8. Metals in fungal virulence

    PubMed Central

    Gerwien, Franziska; Skrahina, Volha; Kasper, Lydia; Brunke, Sascha

    2017-01-01

    Abstract Metals are essential for life, and they play a central role in the struggle between infecting microbes and their hosts. In fact, an important aspect of microbial pathogenesis is the ‘nutritional immunity’, in which metals are actively restricted (or, in an extended definition of the term, locally enriched) by the host to hinder microbial growth and virulence. Consequently, fungi have evolved often complex regulatory networks, uptake and detoxification systems for essential metals such as iron, zinc, copper, nickel and manganese. These systems often differ fundamentally from their bacterial counterparts, but even within the fungal pathogens we can find common and unique solutions to maintain metal homeostasis. Thus, we here compare the common and species-specific mechanisms used for different metals among different fungal species—focusing on important human pathogens such as Candida albicans, Aspergillus fumigatus or Cryptococcus neoformans, but also looking at model fungi such as Saccharomyces cerevisiae or A. nidulans as well-studied examples for the underlying principles. These direct comparisons of our current knowledge reveal that we have a good understanding how model fungal pathogens take up iron or zinc, but that much is still to learn about other metals and specific adaptations of individual species—not the least to exploit this knowledge for new antifungal strategies. PMID:29069482

  9. Copper Deficiency Leads to Anemia, Duodenal Hypoxia, Upregulation of HIF-2α and Altered Expression of Iron Absorption Genes in Mice

    PubMed Central

    Matak, Pavle; Zumerle, Sara; Mastrogiannaki, Maria; El Balkhi, Souleiman; Delga, Stephanie; Mathieu, Jacques R. R.; Canonne-Hergaux, François; Poupon, Joel; Sharp, Paul A.; Vaulont, Sophie; Peyssonnaux, Carole

    2013-01-01

    Iron and copper are essential trace metals, actively absorbed from the proximal gut in a regulated fashion. Depletion of either metal can lead to anemia. In the gut, copper deficiency can affect iron absorption through modulating the activity of hephaestin - a multi-copper oxidase required for optimal iron export from enterocytes. How systemic copper status regulates iron absorption is unknown. Mice were subjected to a nutritional copper deficiency-induced anemia regime from birth and injected with copper sulphate intraperitoneally to correct the anemia. Copper deficiency resulted in anemia, increased duodenal hypoxia and Hypoxia inducible factor 2α (HIF-2α) levels, a regulator of iron absorption. HIF-2α upregulation in copper deficiency appeared to be independent of duodenal iron or copper levels and correlated with the expression of iron transporters (Ferroportin - Fpn, Divalent Metal transporter – Dmt1) and ferric reductase – Dcytb. Alleviation of copper-dependent anemia with intraperitoneal copper injection resulted in down regulation of HIF-2α-regulated iron absorption genes in the gut. Our work identifies HIF-2α as an important regulator of iron transport machinery in copper deficiency. PMID:23555700

  10. Gallium and its competing roles with iron in biological systems.

    PubMed

    Chitambar, Christopher R

    2016-08-01

    Gallium, a group IIIa metal, shares chemical properties with iron. Studies have shown that gallium-based compounds have potential therapeutic activity against certain cancers and infectious microorganisms. By functioning as an iron mimetic, gallium perturbs iron-dependent proliferation processes in tumor cells. Gallium's action on iron homeostasis leads to disruption of ribonucleotide reductase, mitochondrial function, and the regulation of transferrin receptor and ferritin. In addition, gallium nitrate stimulates an increase in mitochondrial reactive oxygen species in cells which triggers downstream upregulation of metallothionein and hemoxygenase-1. Gallium's anti-infective activity against bacteria and fungi results from disruption of microbial iron utilization through mechanisms which include gallium binding to siderophores and downregulation of bacterial iron uptake. Gallium compounds lack cross-resistance to conventional chemotherapeutic drugs and antibiotics thus making them attractive agents for drug development. This review will focus on the mechanisms of action of gallium with emphasis on its interaction with iron and iron proteins. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Local environment of iron in garden soil Vs Plants

    NASA Astrophysics Data System (ADS)

    Dehipawala, Sunil; Dong, Chaojung; Smith, Stephen; Schneider, Patricia; Gafney, Harry

    2015-03-01

    Iron is an essential nutrient not only for humans, but also for all types of plants. Plants use iron for chlorophyll formation, RNA metabolism, and transpiration process regulation. Iron is one of the most abundant metals in the soil and occurs in a wide range of chemical forms. The correlation between the iron species presents in soil and in Petroselinum crispum (parsley) plants were investigated using the room temperature Mossbauer spectroscopy. Mossbauer spectrum of garden soil consists of two doublets. Based on the established isomer shift and quadrupole splitting values of iron, these doublets can be identified as due to octahedrally coordinated Fe3+ and tetrahedrally coordinated Fe2+. Most of the iron present in the parsley has the form Fe3+ or electron density at the site of the iron nucleus similar to that of Fe3+. These findings will help establish soil conditions necessary to increase Fe2+ intake by plants similar to the form of iron present in most supplements. Sunil Dehipawala acknowledges financial support provided by PSC-CUNY.

  12. The Rehbinder effect in iron during giga-cycle fatigue loading

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

    Bannikov, M. V., E-mail: mbannikov@icmm.ru; Naimark, O. B.

    The influence of the adsorptive strength reduction effect (the Rehbinder effect) on the fatigue life of pure iron under the giga-cycle loading regime was investigated. Specimens were loaded by an ultrasonic testing machine with a frequency of 20 kHz in air and in contact with eutectic alloy of gallium with tin and indium. A significant (by several orders of magnitude) worsening of the life-time of iron in contact with a molten metal as compared with tests in air was established. The liquid metal penetrates into the material to a depth of 200 μm to the center of a fatigue crack. Themore » mechanism of the fatigue crack initiation in the giga-cycle regime of loading in contact with a surfactant is differing: the crack is formed on the surface of the specimen rather than within it as is the case for air. Based on the electron and optical microscopy data for the fracture surface, it can be concluded that exactly the change in the crack initiation mechanism reduces the fatigue life of iron in contact with a liquid metal because the initiated crack propagates regardless of the surfactant.« less

  13. The Rehbinder effect in iron during giga-cycle fatigue loading

    NASA Astrophysics Data System (ADS)

    Bannikov, M. V.; Naimark, O. B.

    2015-10-01

    The influence of the adsorptive strength reduction effect (the Rehbinder effect) on the fatigue life of pure iron under the giga-cycle loading regime was investigated. Specimens were loaded by an ultrasonic testing machine with a frequency of 20 kHz in air and in contact with eutectic alloy of gallium with tin and indium. A significant (by several orders of magnitude) worsening of the life-time of iron in contact with a molten metal as compared with tests in air was established. The liquid metal penetrates into the material to a depth of 200 μm to the center of a fatigue crack. The mechanism of the fatigue crack initiation in the giga-cycle regime of loading in contact with a surfactant is differing: the crack is formed on the surface of the specimen rather than within it as is the case for air. Based on the electron and optical microscopy data for the fracture surface, it can be concluded that exactly the change in the crack initiation mechanism reduces the fatigue life of iron in contact with a liquid metal because the initiated crack propagates regardless of the surfactant.

  14. Application of Emulsified Zero-Valent Iron to Marine Environments

    NASA Technical Reports Server (NTRS)

    Quinn, Jacqueline W.; Brooks, Kathleen B.; Geiger, Cherie L.; Clausen, Christian A.; Milum, Kristen M.

    2006-01-01

    Contamination of marine waters and sediments with heavy metals and dense non-aqueous phase liquids (DNAPLs) including chlorinated solvents, pesticides and PCBs pose ecological and human health risks through the potential of the contaminant to bioaccumulate in fish, shellfish and avian populations. The contaminants enter marine environments through improper disposal techniques and storm water runoff. Current remediation technologies for application to marine environments include costly dredging and off-site treatment of the contaminated media. Emulsified zero-valent iron (EZVI) has been proven to effectively degrade dissolved-phase and DNAPL-phase contaminants in freshwater environments on both the laboratory and field-scale level. Emulsified Zero-Valent Metal (EZVM) using metals such as iron and/or magnesium have been shown in the laboratory and on the bench scale to be effective at removing metals contamination in freshwater environments. The application to marine environments, however, is only just being explored. This paper discusses. the potential use of EZVI or EZVM in brackish and saltwater environments, with supporting laboratory data detailing its effectiveness on trichloroethylene, lead, copper, nickel and cadmium.

  15. Equilibrium carbon and hydrogen isotope fractionation in iron

    NASA Astrophysics Data System (ADS)

    Schauble, E. A.

    2009-12-01

    Recent theoretical and experimental studies (e.g., [1-3]) have suggested that Si- and Fe-isotopic signatures can be used to characterize the compositions and conditions of segregation of metallic cores in planetary interiors. This study expands the theoretical framework to include carbon and hydrogen, which may also be alloying elements. Hydrogen (D/H) and carbon (13C/12C) fractionations in iron-rich metallic melts are estimated by modeling analogous iron-rich crystals, i.e., dhcp-FeH and η-Fe2C. C- and H-atoms in these crystals are completely coordinated by iron. The driving energy for equilibrium fractionation is assumed to come from the reduction of vibrational frequencies when heavy isotopes are substituted for light ones; vibrations are assumed to be harmonic. This treatment is crude at high temperature, and for the relatively anharmonic vibrations typical of hydrogen-bearing substances, but may provide a reasonably accurate, semi-quantitative approximation of real fractionation behavior. Vibrational frequencies of all crystals are modeled with density functional theory, using gradient-corrected functionals and ultrasoft pseudopotentials. For both carbon and hydrogen, the models suggest that the metal phase will be strongly depleted in heavy isotopes. At 2000 K, 1 atm, η-Fe2C will have 3‰ lower 13C/12C than coexisting diamond. Combining this result with previous high-temperature theoretical and experimental studies (e.g., [4]), metal-graphite fractionation is expected to be very similar, while metal-CO2 fractionation will be almost twice as large, ca. -5‰. Deuterium/hydrogen fractionations are expected to be an order of magnitude larger, with 50-70‰ lower D/H in dhcp-FeH than in coexisting H2 gas at 2000 K, and approximately 100‰ lower D/H than water vapor. These fractionations are much larger than those inferred for silicon and iron, as expected given the differences in atomic mass. References: 1. Georg et al. (2007) Nature 447:1102; 2. Rustad & Yin

  16. Catalytic production of metal carbonyls from metal oxides

    DOEpatents

    Sapienza, Richard S.; Slegeir, William A.; Foran, Michael T.

    1984-01-01

    This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150.degree.-260.degree. C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO.sub.4 and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect.

  17. Catalytic production of metal carbonyls from metal oxides

    DOEpatents

    Sapienza, R.S.; Slegeir, W.A.; Foran, M.T.

    1984-01-06

    This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150 to 260/sup 0/C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO/sub 4/ and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect. 3 tables.

  18. Carbon Isotopic Heterogeneity of Graphite in the San Juan Mass of the Campo Del Cielo IAB Iron Meteorite

    NASA Technical Reports Server (NTRS)

    Maruoka, T.; Kurat, G.; Zinner, E.; Varela, M. E.; Ametrano, S. J.

    2003-01-01

    The origin of IAB iron meteorites is still a matter of debate. It is generally believed that iron meteorites originated from molten cores in small planetesimals because the fractionation trend of trace elements (e.g., Ir, Ge, Ga, etc. vs. Ni) for most iron meteorites can be more or less explained by fractional crystallization from metal melts. However, this process cannot produce trace element characteristics of the IAB (and other) iron meteorites. To explain these trace element abundance patterns, several models have been proposed. Although most of these models require a high temperature, clear evidence has recently been obtained for a sub-solidus formation of IAB iron meteorites from noble gas analyses. Moreover, heterogeneous distributions of some trace elements in metal and other phases also suggest a low temperature origin of at least some IAB iron meteorites. Here we use the carbon isotopic compositions of graphite to constrain the origin of IAB iron meteorites. Our data confirm a possible low temperature origin of IAB iron meteorites.

  19. Iron-Based Redox Polymerization of Acrylic Acid for Direct Synthesis of Hydrogel/Membranes, and Metal Nanoparticles for Water Treatment

    PubMed Central

    Hernández, Sebastián; Papp, Joseph K.; Bhattacharyya, Dibakar

    2014-01-01

    Functionalized polymer materials with ion exchange groups and integration of nano-structured materials is an emerging area for catalytic and water pollution control applications. The polymerization of materials such as acrylic acid often requires persulfate initiator and a high temperature start. However, is generally known that metal ions accelerate such polymerizations starting from room temperature. If the metal is properly selected, it can be used in environmental applications adding two advantages simultaneously. This paper deals with this by polymerizing acrylic acid using iron as accelerant and its subsequent use for nanoparticle synthesis in hydrogel and PVDF membranes. Characterizations of hydrogel, membranes and nanoparticles were carried out with different techniques. Nanoparticles sizes of 30–60 nm were synthesized. Permeability and swelling measurements demonstrate an inverse relationship between hydrogel mesh size (6.30 to 8.34 nm) and membrane pores (222 to 110 nm). Quantitative reduction of trichloroethylene/chloride generation by Fe/Pd nanoparticles in hydrogel/membrane platforms was also performed. PMID:24954975

  20. Application of a water cooling treatment and its effect on coal-based reduction of high-chromium vanadium and titanium iron ore

    NASA Astrophysics Data System (ADS)

    Yang, Song-tao; Zhou, Mi; Jiang, Tao; Guan, Shan-fei; Zhang, Wei-jun; Xue, Xiang-xin

    2016-12-01

    A water cooling treatment was applied in the coal-based reduction of high-chromium vanadium and titanium (V-Ti-Cr) iron ore from the Hongge region of Panzhihua, China. Its effects on the metallization ratio ( η), S removal ratio ( R S), and P removal ratio ( R P) were studied and analyzed on the basis of chemical composition determined via inductively coupled plasma optical emission spectroscopy. The metallic iron particle size and the element distribution of Fe, V, Cr, and Ti in a reduced briquette after water cooling treatment at 1350°C were determined and observed via scanning electron microscopy. The results show that the water cooling treatment improved the η, R S, and R P in the coal-based reduction of V-Ti-Cr iron ore compared to those obtained with a furnace cooling treatment. Meanwhile, the particle size of metallic iron obtained via the water cooling treatment was smaller than that of metallic iron obtained via the furnace cooling treatment; however, the particle size reached 70 μm at 1350°C, which is substantially larger than the minimum particle size required (20 μm) for magnetic separation. Therefore, the water cooling treatment described in this work is a good method for improving the quality of metallic iron in coal-based reduction and it could be applied in the coal-based reduction of V-Ti-Cr iron ore followed by magnetic separation.

  1. Recovering heavy rare earth metals from magnet scrap

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

    Ott, Ryan T.; McCallum, Ralph W.; Jones, Lawrence L.

    A method of treating rare earth metal-bearing permanent magnet scrap, waste or other material in a manner to recover the heavy rare earth metal content separately from the light rare earth metal content. The heavy rare earth metal content can be recovered either as a heavy rare earth metal-enriched iron based alloy or as a heavy rare earth metal based alloy.

  2. Pharmacokinetics study of Zr-89-labeled melanin nanoparticle in iron-overload mice.

    PubMed

    Zhang, Pengjun; Yue, Yuanyuan; Pan, Donghui; Yang, Runlin; Xu, Yuping; Wang, Lizhen; Yan, Junjie; Li, Xiaotian; Yang, Min

    2016-09-01

    Melanin, a natural biological pigment present in many organisms, has been found to exhibit multiple functions. An important property of melanin is its ability to chelate metal ions strongly, which might be developed as an iron chelator for iron overload therapy. Herein, we prepared the ultrasmall water-soluble melanin nanoparticle (MP) and firstly evaluate the pharmacokinetics of MP in iron-overload mice to provide scientific basis for treating iron-overload. To study the circulation time and biodistribution, MP was labeled with (89)Zr, a long half-life (78.4h) positron-emitting metal which is suited for the labeling of nanoparticles and large bioactive molecule. MP was chelated with (89)Zr directly at pH5, resulting in non-decay-corrected yield of 89.6% and a radiochemical purity of more than 98%. The specific activity was at least190 MBq/μmol. The (89)Zr-MP was stable in human plasma and PBS for at least 48h. The half-life of (89)Zr-MP was about 15.70±1.74h in iron-overload mice. Biodistribution studies and MicroPET imaging showed that (89)Zr-MP mainly accumulated in liver and spleen, which are the target organ of iron-overload. The results indicate that the melanin nanoparticle is promising for further iron overload therapy. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. Iron in neurodegenerative disorders: being in the wrong place at the wrong time?

    PubMed

    Apostolakis, Sotirios; Kypraiou, Anna-Maria

    2017-11-27

    Brain iron deposits have been reported consistently in imaging and histologic examinations of patients with neurodegenerative disorders. While the origins of this finding have not been clarified yet, it is speculated that impaired iron homeostasis or deficient transport mechanisms result in the accumulation of this highly toxic metal ultimately leading to formation of reactive oxygen species and cell death. On the other hand, there are also those who support that iron is just an incidental finding, a by product of neuronal loss. A literature review has been performed in order to present the key findings in support of the iron hypothesis of neurodegeneration, as well as to identify conditions causing or resulting from iron overload and compare and contrast their features with the most prominent neurodegenerative disorders. There is an abundance of experimental and observational findings in support of the hypothesis in question; however, as neurodegeneration is a rare incident of commonly encountered iron-associated disorders of the nervous system, and this metal is found in non-neurodegenerative disorders as well, it is possible that iron is the result or even an incidental finding in neurodegeneration. Understanding the underlying processes of iron metabolism in the brain and particularly its release during cell damage is expected to provide a deeper understanding of the origins of neurodegeneration in the years to come.

  4. Role of iron in the pathogenesis of cysteamine-induced duodenal ulceration in rats

    PubMed Central

    Khomenko, Tetyana; Szabo, Sandor; Deng, Xiaoming; Ishikawa, Hideki; Anderson, Gregory J.; McLaren, Gordon D.

    2009-01-01

    Cysteamine induces perforating duodenal ulcers in rats within 24–48 h. This reducing aminothiol generates hydrogen peroxide in the presence of transition metals (e.g., ferric iron), producing oxidative stress, which may contribute to organ-specific tissue damage. Since most intestinal iron absorption takes place in the proximal duodenum, we hypothesized that cysteamine may disrupt regulation of mucosal iron transport, and iron may facilitate cysteamine-induced duodenal ulceration. We show here that cysteamine-induced ulceration was aggravated by pretreatment of rats with Fe3+ or Fe2+ compounds, which elevated iron concentration in the duodenal mucosa. In contrast, feeding rats an iron-deficient diet was associated with a 4.6-fold decrease in ulcer formation, accompanied by a 34% decrease (P < 0.05) in the duodenal mucosal iron concentration. Administration of deferoxamine inhibited ulceration by 65%. We also observed that the antiulcer effect of H2 receptor antagonist cimetidine included a 35% decrease in iron concentration in the duodenal mucosa. Cysteamine-induced duodenal ulcers were also decreased in iron-deficient Belgrade rats (P < 0.05). In normal rats, cysteamine administration increased the iron concentration in the proximal duodenal mucosa by 33% in the preulcerogenic stage but at the same time decreased serum iron (P < 0.05). Cysteamine also enhanced activation of mucosal iron regulatory protein 1 and increased the expression of divalent metal transporter 1 mRNA and protein. Transferrin receptor 1 protein expression was also increased, although mucosal ferroportin and ferritin remained almost unchanged. These results indicate an expansion of the intracellular labile iron pool in the duodenal mucosa, increasing its susceptibility to oxidative stress, and suggest a role for iron in the pathogenesis of organ-specific tissue injury such as duodenal ulcers. PMID:19342511

  5. Effective Construction of High-quality Iron Oxy-hydroxides and Co-doped Iron Oxy-hydroxides Nanostructures: Towards the Promising Oxygen Evolution Reaction Application

    NASA Astrophysics Data System (ADS)

    Zhang, Xinyu; An, Li; Yin, Jie; Xi, Pinxian; Zheng, Zhiping; Du, Yaping

    2017-03-01

    Rational design of high efficient and low cost electrocatalysts for oxygen evolution reaction (OER) plays an important role in water splitting. Herein, a general gelatin-assisted wet chemistry method is employed to fabricate well-defined iron oxy-hydroxides and transitional metal doped iron oxy-hydroxides nanomaterials, which show good catalytic performances for OER. Specifically, the Co-doped iron oxy-hydroxides (Co0.54Fe0.46OOH) show the excellent electrocatalytic performance for OER with an onset potential of 1.52 V, tafel slope of 47 mV/dec and outstanding stability. The ultrahigh oxygen evolution activity and strong durability, with superior performance in comparison to the pure iron oxy-hydroxide (FeOOH) catalysts, originate from the branch structure of Co0.54Fe0.46OOH on its surface so as to provide many active edge sites, enhanced mass/charge transport capability, easy release oxygen gas bubbles, and strong structural stability, which are advantageous for OER. Meanwhile, Co-doping in FeOOH nanostructures constitutes a desirable four-electron pathway for reversible oxygen evolution and reduction, which is potentially useful for rechargeable metal-air batteries, regenerative fuel cells, and other important clean energy devices. This work may provide a new insight into constructing the promising water oxidation catalysts for practical clean energy application.

  6. Effective Construction of High-quality Iron Oxy-hydroxides and Co-doped Iron Oxy-hydroxides Nanostructures: Towards the Promising Oxygen Evolution Reaction Application.

    PubMed

    Zhang, Xinyu; An, Li; Yin, Jie; Xi, Pinxian; Zheng, Zhiping; Du, Yaping

    2017-03-08

    Rational design of high efficient and low cost electrocatalysts for oxygen evolution reaction (OER) plays an important role in water splitting. Herein, a general gelatin-assisted wet chemistry method is employed to fabricate well-defined iron oxy-hydroxides and transitional metal doped iron oxy-hydroxides nanomaterials, which show good catalytic performances for OER. Specifically, the Co-doped iron oxy-hydroxides (Co 0.54 Fe 0.46 OOH) show the excellent electrocatalytic performance for OER with an onset potential of 1.52 V, tafel slope of 47 mV/dec and outstanding stability. The ultrahigh oxygen evolution activity and strong durability, with superior performance in comparison to the pure iron oxy-hydroxide (FeOOH) catalysts, originate from the branch structure of Co 0.54 Fe 0.46 OOH on its surface so as to provide many active edge sites, enhanced mass/charge transport capability, easy release oxygen gas bubbles, and strong structural stability, which are advantageous for OER. Meanwhile, Co-doping in FeOOH nanostructures constitutes a desirable four-electron pathway for reversible oxygen evolution and reduction, which is potentially useful for rechargeable metal-air batteries, regenerative fuel cells, and other important clean energy devices. This work may provide a new insight into constructing the promising water oxidation catalysts for practical clean energy application.

  7. Hypobaric Hypoxia Regulates Brain Iron Homeostasis in Rats.

    PubMed

    Li, Yaru; Yu, Peng; Chang, Shi-Yang; Wu, Qiong; Yu, Panpan; Xie, Congcong; Wu, Wenyue; Zhao, Baolu; Gao, Guofen; Chang, Yan-Zhong

    2017-06-01

    Disruption of iron homeostasis in brain has been found to be closely involved in several neurodegenerative diseases. Recent studies have reported that appropriate intermittent hypobaric hypoxia played a protective role in brain injury caused by acute hypoxia. However, the mechanisms of this protective effect have not been fully understood. In this study, Sprague-Dawley (SD) rat models were developed by hypobaric hypoxia treatment in an altitude chamber, and the iron level and iron related protein levels were determined in rat brain after 4 weeks of treatment. We found that the iron levels significantly decreased in the cortex and hippocampus of rat brain as compared to that of the control rats without hypobaric hypoxia treatment. The expression levels of iron storage protein L-ferritin and iron transport proteins, including transferrin receptor-1 (TfR1), divalent metal transporter 1 (DMT1), and ferroportin1 (FPN1), were also altered. Further studies found that the iron regulatory protein 2 (IRP2) played a dominant regulatory role in the changes of iron hemostasis, whereas iron regulatory protein 1 (IRP1) mainly acted as cis-aconitase. These results, for the first time, showed the alteration of iron metabolism during hypobaric hypoxia in rat models, which link the potential neuroprotective role of hypobaric hypoxia treatment to the decreased iron level in brain. This may provide insight into the treatment of iron-overloaded neurodegenerative diseases. J. Cell. Biochem. 118: 1596-1605, 2017. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  8. Polybenzimidazole block copolymers for fuel cell: synthesis and studies of block length effects on nanophase separation, mechanical properties, and proton conductivity of PEM.

    PubMed

    Maity, Sudhangshu; Jana, Tushar

    2014-05-14

    A series of meta-polybenzimidazole-block-para-polybenzimidazole (m-PBI-b-p-PBI), segmented block copolymers of PBI, were synthesized with various structural motifs and block lengths by condensing the diamine terminated meta-PBI (m-PBI-Am) and acid terminated para-PBI (p-PBI-Ac) oligomers. NMR studies and existence of two distinct glass transition temperatures (Tg), obtained from dynamical mechanical analysis (DMA) results, unequivocally confirmed the formation of block copolymer structure through the current polymerization methodology. Appropriate and careful selection of oligomers chain length enabled us to tailor the block length of block copolymers and also to make varieties of structural motifs. Increasingly distinct Tg peaks with higher block length of segmented block structure attributed the decrease in phase mixing between the meta-PBI and para-PBI blocks, which in turn resulted into nanophase segregated domains. The proton conductivities of proton exchange membrane (PEM) developed from phosphoric acid (PA) doped block copolymer membranes were found to be increasing substantially with increasing block length of copolymers even though PA loading of these membranes did not alter appreciably with varying block length. For example when molecular weight (Mn) of blocks were increased from 1000 to 5500 then the proton conductivities at 160 °C of resulting copolymers increased from 0.05 to 0.11 S/cm. Higher block length induced nanophase separation between the blocks by creating less morphological barrier within the block which facilitated the movement of the proton in the block and hence resulting higher proton conductivity of the PEM. The structural varieties also influenced the phase separation and proton conductivity. In comparison to meta-para random copolymers reported earlier, the current meta-para segmented block copolymers were found to be more suitable for PBI-based PEM.

  9. Effects of Na2SO4 on iron and nickel reduction in a high-iron and low-nickel laterite ore

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-ping; Sun, Ti-chang; Chen, Chao; Kou, Jue

    2018-04-01

    This study investigates the reactions of Na2SO4 and its effects on iron and nickel reduction in the roasting of a high-iron and low-nickel laterite ore through gas composition, X-ray diffraction, and scanning electron microscope analyses. Results showed that a reduction reaction of Na2SO4 to SO2 was performed with roasting up to 600°C. However, no clear influence on iron and nickel reductions appeared, because only a small amount of Na2SO4 reacted to produce SO2. Na2SO4 reacted completely at 1000°C, mainly producing troilite and nepheline, which remarkably improves selective reduction of nickel. Furthermore, the production of low-melting-point minerals, including troilite and nepheline, accelerated nickel reduction and delayed iron reduction, which is attributed to the concurrent production of magnesium magnetite, whose structure is more stable than the structure of magnetite. Reduction reactions of Na2SO4 resulted in weakening of the reduction atmosphere, and the main product of Na2SO4 changed and delayed the reduction of iron. Eventually, iron metallization was effectively controlled during laterite ore reduction roasting, leading to iron mainly being found in wustite and high iron-containing olivine.

  10. Nitric oxide activation by distal redox modulation in tetranuclear iron nitrosyl complexes.

    PubMed

    de Ruiter, Graham; Thompson, Niklas B; Lionetti, Davide; Agapie, Theodor

    2015-11-11

    A series of tetranuclear iron complexes displaying a site-differentiated metal center was synthesized. Three of the metal centers are coordinated to our previously reported ligand, based on a 1,3,5-triarylbenzene motif with nitrogen and oxygen donors. The fourth (apical) iron center is coordinatively unsaturated and appended to the trinuclear core through three bridging pyrazolates and an interstitial μ4-oxide moiety. Electrochemical studies of complex [LFe3(PhPz)3OFe][OTf]2 revealed three reversible redox events assigned to the Fe(II)4/Fe(II)3Fe(III) (-1.733 V), Fe(II)3Fe(III)/Fe(II)2Fe(III)2 (-0.727 V), and Fe(II)2Fe(III)2/Fe(II)Fe(III)3 (0.018 V) redox couples. Combined Mössbauer and crystallographic studies indicate that the change in oxidation state is exclusively localized at the triiron core, without changing the oxidation state of the apical metal center. This phenomenon is assigned to differences in the coordination environment of the two metal sites and provides a strategy for storing electron and hole equivalents without affecting the oxidation state of the coordinatively unsaturated metal. The presence of a ligand-binding site allowed the effect of redox modulation on nitric oxide activation by an Fe(II) metal center to be studied. Treatment of the clusters with nitric oxide resulted in binding of NO to the apical iron center, generating a {FeNO}(7) moiety. As with the NO-free precursors, the three reversible redox events are localized at the iron centers distal from the NO ligand. Altering the redox state of the triiron core resulted in significant change in the NO stretching frequency, by as much as 100 cm(-1). The increased activation of NO is attributed to structural changes within the clusters, in particular, those related to the interaction of the metal centers with the interstitial atom. The differences in NO activation were further shown to lead to differential reactivity, with NO disproportionation and N2O formation performed by the more

  11. iron phase control during pressure leaching at elevated temperature

    NASA Astrophysics Data System (ADS)

    Fleuriault, Camille

    Iron is a common contaminant encountered in most metal recovery operations, and particularly hydrometallurgical processes. For example, the Hematite Process uses autoclaves to precipitate iron oxide out of the leaching solution, while other metals are solubilized for further hydrometallurgical processing. In some cases, Basic Iron Sulfate (BIS) forms in place of hematite. The presence of BIS is unwanted in the autoclave discharge because it diminishes recovery and causes environmental matters. The focus of this master thesis is on the various iron phases forming during the pressure oxidation of sulfates. Artificial leaching solutions were produced from CuSO4, FeSO4 and H2SO4 in an attempt to recreate the matrix composition and conditions used for copper sulfides autoclaving. The following factors were investigated in order to determine which conditions hinder the formation of BIS: initial free acidity (5 -- 98 g/L), initial copper concentration (12.7 -- 63.5 g/L), initial iron concentration (16.7 -- 30.7 g/L) and initial iron oxidation state. There were three solid species formed in the autoclave: hematite, BIS and hydronium jarosite. The results show that free acid is the main factor influencing the composition of the residue. At an initial concentration of 22.3 g/L iron and no copper added, the upper limit for iron oxide formation is 41 g/L H2SO4. The increase of BIS content in the residue is not gradual and occurs over a change of a few grams per liter around the aforementioned limit. Increasing copper sulfate concentration in the solution hinders the formation of BIS. At 63.5g/L copper, the upper free acidity limit is increased to 61g/L. This effect seems to be related to the buffering action of copper sulfate, decreasing the overall acid concentration and thus extending the stability range of hematite. The effect of varying iron concentration on the precipitate chemistry is unclear. At high iron levels, the only noticeable effect was the inhibition of jarosite

  12. Metallic glass composition. [That does not embrittle upon annealing

    DOEpatents

    Kroeger, D.M.; Koch, C.C.

    1984-09-14

    This patent pertains to a metallic glass alloy that is either iron-based or nickel-based or based on a mixture of iron and nickel, containing lesser amounts of elements selected from the group boron, silicon, carbon and phosphorous to which is added an amount of a ductility-enhancing element selected from the group cerium, lanthanum, praseodymium and neodymium sufficient to increase ductility of the metallic glass upon annealing.

  13. Nramp1 promotes efficient macrophage recycling of iron following erythrophagocytosis in vivo

    PubMed Central

    Soe-Lin, Shan; Apte, Sameer S.; Andriopoulos, Billy; Andrews, Marc C.; Schranzhofer, Matthias; Kahawita, Tanya; Garcia-Santos, Daniel; Ponka, Prem

    2009-01-01

    Natural resistance-associated macrophage protein 1 (Nramp1) is a divalent metal transporter expressed exclusively in phagocytic cells. We hypothesized that macrophage Nramp1 may participate in the recycling of iron acquired from phagocytosed senescent erythrocytes. To evaluate the role of Nramp1 in vivo, the iron parameters of WT and KO mice were analyzed after acute and chronic induction of hemolytic anemia. We found that untreated KO mice exhibited greater serum transferrin saturation and splenic iron content with higher duodenal ferroportin (Fpn) and divalent metal transporter 1 (DMT1) expression. Furthermore, hepatocyte iron content and hepcidin mRNA levels were dramatically lower in KO mice, indicating that hepcidin levels can be regulated by low-hepatocyte iron stores despite increased transferrin saturation. After acute treatment with the hemolytic agent phenylhydrazine (Phz), KO mice experienced a significant decrease in transferrin saturation and hematocrit, whereas WT mice were relatively unaffected. After a month-long Phz regimen, KO mice retained markedly increased quantities of iron within the liver and spleen and exhibited more pronounced splenomegaly and reticulocytosis than WT mice. After injection of 59Fe-labeled heat-damaged reticulocytes, KO animals accumulated erythrophagocytosed 59Fe within their liver and spleen, whereas WT animals efficiently recycled phagocytosed 59Fe to the marrow and erythrocytes. These data imply that without Nramp1, iron accumulates within the liver and spleen during erythrophagocytosis and hemolytic anemia, supporting our hypothesis that Nramp1 promotes efficient hemoglobin iron recycling in macrophages. Our observations suggest that mutations in Nramp1 could result in a novel form of human hereditary iron overload. PMID:19321419

  14. Nramp1 promotes efficient macrophage recycling of iron following erythrophagocytosis in vivo.

    PubMed

    Soe-Lin, Shan; Apte, Sameer S; Andriopoulos, Billy; Andrews, Marc C; Schranzhofer, Matthias; Kahawita, Tanya; Garcia-Santos, Daniel; Ponka, Prem

    2009-04-07

    Natural resistance-associated macrophage protein 1 (Nramp1) is a divalent metal transporter expressed exclusively in phagocytic cells. We hypothesized that macrophage Nramp1 may participate in the recycling of iron acquired from phagocytosed senescent erythrocytes. To evaluate the role of Nramp1 in vivo, the iron parameters of WT and KO mice were analyzed after acute and chronic induction of hemolytic anemia. We found that untreated KO mice exhibited greater serum transferrin saturation and splenic iron content with higher duodenal ferroportin (Fpn) and divalent metal transporter 1 (DMT1) expression. Furthermore, hepatocyte iron content and hepcidin mRNA levels were dramatically lower in KO mice, indicating that hepcidin levels can be regulated by low-hepatocyte iron stores despite increased transferrin saturation. After acute treatment with the hemolytic agent phenylhydrazine (Phz), KO mice experienced a significant decrease in transferrin saturation and hematocrit, whereas WT mice were relatively unaffected. After a month-long Phz regimen, KO mice retained markedly increased quantities of iron within the liver and spleen and exhibited more pronounced splenomegaly and reticulocytosis than WT mice. After injection of (59)Fe-labeled heat-damaged reticulocytes, KO animals accumulated erythrophagocytosed (59)Fe within their liver and spleen, whereas WT animals efficiently recycled phagocytosed (59)Fe to the marrow and erythrocytes. These data imply that without Nramp1, iron accumulates within the liver and spleen during erythrophagocytosis and hemolytic anemia, supporting our hypothesis that Nramp1 promotes efficient hemoglobin iron recycling in macrophages. Our observations suggest that mutations in Nramp1 could result in a novel form of human hereditary iron overload.

  15. Radiogenic Xenon-129 in Silicate Inclusions in the Campo Del Cielo Iron Meteorite

    NASA Technical Reports Server (NTRS)

    Meshik, A.; Kurat, G.; Pravdivtseva, O.; Hohenberg, C. M.

    2004-01-01

    Iron meteorites present a challenge for the I-Xe dating technique because it is usually the inclusions, not metal, that contain radiogenic xenon and iodine. Silicate inclusions are frequent in only types IAB and IIE, and earlier studies of irons have demonstrated that I-Xe system can survive intact in these inclusions preserving valuable age information. Our previous studies of the I-Xe record in pyroxene grains from Toluca iron suggested an intriguing relationship between apparent I-Xe ages and (Mg+Fe)/Fe ratios. The I-Xe system in K-feldspar inclusions from Colomera (IIE) had the fingerprint of slow cooling, with an indicated cooling rate of 2-4 C/Ma. Here we present studies of the iodine-xenon system in a silicate-graphite-metal (SiGrMet) inclusion of the IA Campo del Cielo iron meteorite from the collection of the Museum of Natural History in Vienna.

  16. Thermal and Evolved Gas Analysis of "Nanophase" Carbonates: Implications for Thermal and Evolved Gas Analysis on Mars Missions

    NASA Technical Reports Server (NTRS)

    Lauer, Howard V., Jr.; Archer, P. D., Jr.; Sutter, B.; Niles, P. B.; Ming, Douglas W.

    2012-01-01

    Data collected by the Mars Phoenix Lander's Thermal and Evolved Gas Analyzer (TEGA) suggested the presence of calcium-rich carbonates as indicated by a high temperature CO2 release while a low temperature (approx.400-680 C) CO2 release suggested possible Mg- and/or Fe-carbonates [1,2]. Interpretations of the data collected by Mars remote instruments is done by comparing the mission data to a database on the thermal properties of well-characterized Martian analog materials collected under reduced and Earth ambient pressures [3,4]. We are proposing that "nano-phase" carbonates may also be contributing to the low temperature CO2 release. The objectives of this paper is to (1) characterize the thermal and evolved gas proper-ties of carbonates of varying particle size, (2) evaluate the CO2 releases from CO2 treated CaO samples and (3) examine the secondary CO2 release from reheated calcite of varying particle size.

  17. Iron-magnesium alloy in the Earth's Core

    NASA Astrophysics Data System (ADS)

    Dubrovinskaia, N.; Dubrovinsky, L.; Abrikosov, I.

    2005-12-01

    Composition of the Earth's outer core is a geochemical parameter crucial for understanding the evolution and current dynamics of our planet. Since it was recognized that the liquid metallic outer core is about 10% less dense than pure iron, different elements lighter than iron, including Si, S, O, C, and H, were proposed as major or at least significantly abundant in Earth's core. However, combination of experimental results with theoretical and geochemical considerations shows that it is unlikely that any one of these elements can account for the density deficit on its own. In series of experiments in a multianvil apparatus and in electrically- and laser-heated diamond anvil cells, we demonstrate that high pressure promotes solubility of magnesium in iron and at megabar pressure range more than 10 at% of Mg can dissolve in Fe. At pressures above 95 to 100 GPa, molten iron reacts with periclase MgO forming an iron-magnesium alloy and iron oxide. Our observations suggest that magnesium can be an important light element in Earth's outer core, but it cannot account for the seismologically determined density deficit on its own.

  18. Iron Homeostasis in Peripheral Nervous System, Still a Black Box?

    PubMed Central

    Taveggia, Carla

    2014-01-01

    Abstract Significance: Iron is the most abundant transition metal in biology and an essential cofactor for many cellular enzymes. Iron homeostasis impairment is also a component of peripheral neuropathies. Recent Advances: During the past years, much effort has been paid to understand the molecular mechanism involved in maintaining systemic iron homeostasis in mammals. This has been stimulated by the evidence that iron dyshomeostasis is an initial cause of several disorders, including genetic and sporadic neurodegenerative disorders. Critical Issues: However, very little has been done to investigate the physiological role of iron in peripheral nervous system (PNS), despite the development of suitable cellular and animal models. Future Directions: To stimulate research on iron metabolism and peripheral neuropathy, we provide a summary of the knowledge on iron homeostasis in the PNS, on its transport across the blood–nerve barrier, its involvement in myelination, and we identify unresolved questions. Furthermore, we comment on the role of iron in iron-related disorder with peripheral component, in demyelinating and metabolic peripheral neuropathies. Antioxid. Redox Signal. 21, 634–648. PMID:24409826

  19. Effects of ferrous carbamoyl glycine on iron state and absorption in an iron-deficient rat model.

    PubMed

    Zhang, Yuzhe; Sun, Xiaoming; Xie, Chunyan; Shu, Xugang; Oso, Abimbola Oladele; Ruan, Zheng; Deng, Ze-Yuan; Wu, Xin; Yin, Yulong

    2015-11-01

    An iron-deficient rat model was established and used to determine the effects of different iron sources on iron metabolism and absorption. Iron-deficient rats were assigned to one of three treatment groups, and their diet was supplemented with deionized water (control), Fe-CGly, or FeSO4 for 8 days via intragastric administration. Blood samples were obtained for analysis of iron-related properties, and the small intestine and liver were removed for quantitative reverse transcription PCR of genes related to iron metabolism. The serum total iron-binding capacity (TIBC) levels of rats in Fe-CGly and FeSO4 supplementation groups was lower (P < 0.05) than that of the rats in the control group. The rats in Fe-CGly group exhibited higher (P < 0.05) plasma Fe and ferritin levels and lower (P < 0.05) TIBC levels compared with the rats in FeSO4 groups. The relative expression of liver hepcidin increased (P < 0.05) by tenfold and 80-fold in the Fe-CGly and FeSO4 groups, respectively, whereas divalent metal transporter 1, duodenal cytochrome b, and ferroportin 1 expression decreased (P < 0.05) in the duodenum in both Fe-CGly and FeSO4 group. A comparison between Fe-CGly and FeSO4 group showed that iron regulatory protein 1 (IRP1) and iron regulatory protein (IRP2) expressions were reduced (P < 0.05) in rats administered FeSO4 than in rats administered with Fe-Cgly. These results indicate that Fe-CGly rapidly improves the blood iron status and that IRP1 and IRP2 may play an important role in the intestinal absorption of Fe-CGly.

  20. Mechanisms of iron and copper-frataxin interactions.

    PubMed

    Han, T H L; Camadro, J M; Santos, R; Lesuisse, E; El Hage Chahine, J M; Ha-Duong, N T

    2017-08-16

    Frataxin is a mitochondrial protein whose deficiency is the cause of Friedreich's ataxia, a hereditary neurodegenerative disease. This protein plays a role in iron-sulfur cluster biosynthesis, protection against oxidative stress and iron metabolism. In an attempt to provide a better understanding of the role played by metals in its metabolic functions, the mechanisms of mitochondrial metal binding to frataxin in vitro have been investigated. A purified recombinant yeast frataxin homolog Yfh1 binds two Cu(ii) ions with a K d1 (Cu II ) of 1.3 × 10 -7 M and a K d2 (Cu II ) of 3.1 × 10 -4 M and a single Cu(i) ion with a higher affinity than for Cu(ii) (K d (Cu I ) = 3.2 × 10 -8 M). Mn(ii) forms two complexes with Yfh1 (K d1 (Mn II ) = 4.0 × 10 -8 M; K d2 (Mn II ) = 4.0 × 10 -7 M). Cu and Mn bind Yfh1 with higher affinities than Fe(ii). It is established for the first time that the mechanisms of the interaction of iron and copper with frataxin are comparable and involve three kinetic steps. The first step occurs in the 50-500 ms range and corresponds to a first metal uptake. This is followed by two other kinetic processes that are related to a second metal uptake and/or to a change in the conformation leading to thermodynamic equilibrium. Frataxin deficient Δyfh1 yeast cells exhibited a marked growth defect in the presence of exogenous Cu or Mn. Mitochondria from Δyfh1 strains also accumulated higher amounts of copper, suggesting a functional role of frataxin in vivo in copper homeostasis.