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Sample records for nanophase ferric oxide

  1. 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).

  2. Irradiation of Anorthite by Iron Ions-A Simulation of the Solar Wind Origin of Nanophase Iron in Lunar Soil

    NASA Astrophysics Data System (ADS)

    Li, Y.; Li, X. Y.; Wu, Y. X.; Li, S. J.; Wang, S. J.

    2015-07-01

    We present a simulant study of the origin of nanophase iron particles that implanted into the lunar soil particles by solar wind. Iron, ferroferric oxide and ferric oxide were identified and their origins were discussed.

  3. 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.

  4. Microwave drying of ferric oxide pellets

    SciTech Connect

    Pickles, C.A.; Xia, D.K.

    1997-12-31

    The application of microwave energy for the drying of ferric oxide pellets has been investigated and evaluated. It is shown that the microwave drying rates are much higher than those observed in the conventional process. Also there is some potential for improved quality of the product. As a stand-alone technology it is unlikely that microwave drying would be economical for pellets due to the low cost of conventional fuels. However, based on an understanding of the drying mechanisms in the conventional process and in the microwave process, it is shown that microwave-assisted drying offers considerable potential. In this hybrid process, the advantages of the two drying techniques are combined to provide an improved drying process.

  5. ADSORPTION OF TRACE METALS BY HYDROUS FERRIC OXIDE IN SEAWATER

    EPA Science Inventory

    The adsorption of trace metals by amorphous hydrous ferric oxide in seawater is studied with reference to simple model systems designed to isolate the factors which may have an effect on the isotherms. Results show that the complex system behaves in a remarkably simple way and th...

  6. What ferric oxide/oxyhydroxide phases are present on Mars

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.

    1988-01-01

    The weathering history of Mars can be deduced largely from the mineralogy and distribution of ferric oxide/oxyhydroxide phases. As discussed, some insights can be gained through spectrophotometric remote sensing, but absolute determinations must depend on direct laboratory analysis of returned Martian samples.

  7. 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.

  8. 21 CFR 186.1300 - Ferric oxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... , CAS Reg. No. 1309-37-1) occurs naturally as the mineral hematite. It may be prepared synthetically by heating brown...hydroxide oxide. The product is red-brown to black trigonal crystals. (b) In accordance with §...

  9. 21 CFR 186.1300 - Ferric oxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... , CAS Reg. No. 1309-37-1) occurs naturally as the mineral hematite. It may be prepared synthetically by heating brown...hydroxide oxide. The product is red-brown to black trigonal crystals. (b) In accordance with §...

  10. 21 CFR 186.1300 - Ferric oxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... , CAS Reg. No. 1309-37-1) occurs naturally as the mineral hematite. It may be prepared synthetically by heating brown...hydroxide oxide. The product is red-brown to black trigonal crystals. (b) In accordance with §...

  11. Ferric oxide quantum dots in stable phosphate glass system and their magneto-optical study

    SciTech Connect

    Garaje, Sunil N.; Apte, Sanjay K.; Kumar, Ganpathy; Panmand, Rajendra P.; Naik, Sonali D.; Mahajan, Satish M.; Chand, Ramesh; Kale, Bharat B.

    2013-02-15

    Graphical abstract: We report synthesis of ferric oxide embedded low melting phosphate glass nanocomposite and also the effect of ferric oxide nanoparticles (NCs) content on the optical and magneto-optical properties of the glasses. Faraday rotation of the glass nanocomposites was measured and showed variation in Verdet constant with concentration of ferric oxide. Interestingly, the host glass itself showed fairly good Verdet constant (11.5°/T cm) and there is a threefold enhancement in the Verdet constant of ferric oxide quantum dot-glass nanocomposite. Highlights: ? We synthesize ferric oxide embedded low melting stable phosphate glass nanocomposite. ? Glasses doped with 0.25 and 2% ferric oxide show particle size in the range of 4–12 nm. ? The host phosphate glass itself shows fairly good Verdet constant (11.5°/T cm). ? Glasses doped with 0.25% ferric oxide show high Verdet constant (30.525°/T cm). ? The as synthesis glasses may have potential application in magneto optical devices. -- Abstract: Herein, we report the synthesis of ferric oxide embedded low melting phosphate glass nanocomposite and also the effect of ferric oxide nanoparticles content on the optical and magneto-optical properties of the glasses. The optical study clearly showed red shift in optical cut off with increasing ferric oxide concentration. The band gap of the host glass was observed to be 3.48 eV and it shifted to 3.14 eV after doping with ferric oxide. The glasses doped with 0.25 and 2% ferric oxide showed particle size of 4–6 nm and 8–12 nm, respectively. Faraday rotation of the glass nanocomposites was measured and showed variation in the Verdet constant as per increasing concentration of ferric oxide. Interestingly, the host glass itself showed fairly good Verdet constant (11.5°/T cm) and threefold enhancement was observed in the Verdet constant of ferric oxide quantum dot-glass nanocomposite.

  12. 21 CFR 186.1300 - Ferric oxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...hematite. It may be prepared synthetically by heating brown iron hydroxide oxide. The product is red-brown to black trigonal crystals. (b) In accordance with § 186.1(b)(1), the ingredient is used as an indirect human food ingredient...

  13. 21 CFR 186.1300 - Ferric oxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...hematite. It may be prepared synthetically by heating brown iron hydroxide oxide. The product is red-brown to black trigonal crystals. (b) In accordance with § 186.1(b)(1), the ingredient is used as an indirect human food ingredient...

  14. Role of nanophase oxides in short-term atmospheric corrosion of structural steels

    NASA Astrophysics Data System (ADS)

    Balasubramanian, Rama

    Systematic studies on the development of nanophase iron oxides in the corrosion products of carbon and weathering steel were performed to understand the role of nanophase oxides in short-term atmospheric corrosion. Similarities and/or differences between short-term and long-term atmospheric corrosion were established by studying carbon steel and weathering steel coupons exposed in mild marine environments for short-term and comparing it with previously established long-term data. Influence of substitutional elements, in particular chromium, in forming nanophase goethite was investigated. Crystallographic, magnetic and morphological properties of nanophase chromium substituted goethite have been characterized in order to understand the protective nature of chromium-substituted goethite in a naturally weathered steel surface. Spectroscopic investigation of the corrosion products of both carbon and weathering steel indicated that lepidocrocite and goethite were the predominant oxides to form following short-term exposures. The corrosion coatings were well layered for exposure times as early as 2 months. The layering was very similar to that observed on steel coupons exposed for more than 8 years. The outer layer was composed of lepidocrocite and occasionally goethite. The inner layer was mainly composed of nanophase goethite. The relative fraction of nanophase goethite was significantly higher in weathering steel compared to carbon steel at the end of six months of exposure. The data analysis also revealed that during the first two months of exposure weathering steel corrodes faster than carbon steel. However carbon steel corrodes more rapidly after 6 months of exposure. At the end of one year, the corrosion rate of carbon steel is higher than weathering steel. It is proposed that during the couple of months, nucleation of oxides is the dominant process in both carbon and weathering steel. At the end of six months, a considerable amount of nanophase goethite formed on carbon steel continues to grow into bigger crystals. On the other hand, in weathering steel the crystal growth of a significant fraction of initially formed nanophase goethite is inhibited. It is proposed that substitutional elements like chromium inhibit the crystal growth in weathering steel. The crystallographic and spectroscopic data for showed that with increasing chromium concentration, the crystallite size of synthetic goethite measured from X-ray diffraction and particle length of goethite measured from Mossbauer spectroscopy and Transmission Electron Microscopy, became smaller. (Abstract shortened by UMI.)

  15. 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.

  16. Nickel adsorption to hydrous ferric oxide in the presence of EDTA: Effects of component addition sequence

    SciTech Connect

    Bryce, A.L.; Kornicker, W.A.; Elzerman, A.W. ); Clark, S.B. )

    1994-12-01

    Nickel, EDTA, and hydrous ferric oxide were combined in different sequences to study the effect on equilibration. In this system, the fraction of nickel adsorbed to the hydrous ferric oxide depended on the component addition sequence, but the fraction of EDTA adsorbed did not. In one sequence, nickel and EDTA were combined to preform a NiEDTA[sup 2[minus

  17. Dietary bioavailability of Cu adsorbed to colloidal hydrous ferric oxide

    USGS Publications Warehouse

    Cain, Daniel J.; Croteau, Marie-Noële; Fuller, Christopher C.

    2013-01-01

    The dietary bioavailability of copper (Cu) adsorbed to synthetic colloidal hydrous ferric oxide (HFO) was evaluated from the assimilation of 65Cu by two benthic grazers, a gastropod and a larval mayfly. HFO was synthesized, labeled with 65Cu to achieve a Cu/Fe ratio comparable to that determined in naturally formed HFO, and then aged. The labeled colloids were mixed with a food source (the diatom Nitzschia palea) to yield dietary 65Cu concentrations ranging from 211 to 2204 nmol/g (dry weight). Animals were pulse fed the contaminated diet and assimilation of 65Cu from HFO was determined following 1–3 days of depuration. Mass transfer of 65Cu from HFO to the diatom was less than 1%, indicating that HFO was the source of 65Cu to the grazers. Estimates of assimilation efficiency indicated that the majority of Cu ingested as HFO was assimilated (values >70%), implying that colloidal HFO potentially represents a source of dietary Cu to benthic grazers, especially where there is active formation and infiltration of these particles into benthic substrates.

  18. RATES OF HYDROUS FERRIC OXIDE CRYSTALLIZATION AND THE INFLUENCE ON COPRECIPITATED ARSENATE: JOURNAL ARTICLE

    EPA Science Inventory

    NRMRL-ADA-02101 Ford*, R. Rates of Hydrous Ferric Oxide Crystallization and the Influence on Coprecipitated Arsenate. Environmental Science & Technology 36 (11):2459-2463 (2002). EPA/600/J-02/240. Arsenate coprecipitated with hydrous fer...

  19. 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

  20. Interaction of nanoparticles of ferric oxide with brain nerve terminals and blood platelets

    NASA Astrophysics Data System (ADS)

    Borisova, Tatiana; Krisanova, Natalia; Sivko, Roman; Borisov, Arseniy

    2012-07-01

    Nanoparticles of ferric oxide are the components of Lunar and Martian soil simulants. The observations suggest that exposure to Lunar soli simulant can be deleterious to human physiology and the components of lunar soil may be internalized by lung epithelium and may overcome the blood-brain barrier. The study focused on the effects of nanoparticles of ferric oxide on the functional state of rat brain nerve terminals (synaptosomes) and rabbit blood platelets. Using photon correlation spectroscopy, we demonstrated the binding of nanoparticles of ferric oxide with nerve terminals and platelets. Nanoparticles did not depolarize the plasma membrane of nerve terminals and platelets that was shown by fluorimetry with potential-sensitive fluorescent dye rhodamine 6G. Using pH-sensitive fluorescent dye acridine orange, we revealed that the acidification of synaptic vesicles of nerve terminals and secretory granules of platelets did not change in the presence of nanoparticles. The initial velocity of uptake of excitatory neurotransmitter glutamate was not influenced by nanoparticles of ferric oxide, whereas glutamate binding to nerve terminals was altered. Thus, it was suggested that nanoparticles of ferric oxide might disturb glutamate transport in the mammalian CNS.

  1. RATES OF HYDROUS FERRIC OXIDE CRYSTALLIZATION AND THE INFLUENCE ON COPRECIPITATED ARSENATE

    EPA Science Inventory

    Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 ?C. Compa...

  2. Complexation of ferric oxide particles with pectins of ordered and random distribution of charged units

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Complexation between ferric oxide particles and pectins with degree of methylation 50%, but having blockwise (ordered) or random arrangement of free carboxyl groups, are investigated by electric light scattering and electrophoresis. The influence of charge distribution in pectin chain on the electri...

  3. Nanophase semiconductors embedded within transparent conductive oxides matrices as optical sensitizers for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Allen, C. G.; Shih, G. H.; Beal, R. J.; Potter, B. G., Jr.

    2010-08-01

    The optical absorption of a transparent conductive oxide (TCO), which is often used as the basis for junction or contact layers in thin film photovoltaics, can be tailored by incorporating a nanophase semiconductor (SC) component. Using a, dual-source, sequential R.F. magnetron sputter deposition technique, we manipulate the optical and electronic properties of SC:TCO composites by varying the local and extended nanophase assembly and composition. The present study explores nanocomposite systems based on Ge:ZnO and Ge:ITO. The impact of host material (ITO vs. ZnO) on the evolution of nanostructure is investigated. Heat treatment of the as-deposited films results in an increased crystallinity of the TCO and SC components, confirmed by X-ray diffraction and Raman spectroscopy studies. The presence of the SC phase is found to influence TCO grain growth and crystallographic orientation, and modification of the SC phase distribution is coincident with the morphological development of the TCO phase in both composite systems. Upon heattreatment, the high-energy optical absorption edge of the nanocomposite is blue-shifted compared to that of the corresponding as-deposited material. This indicates the development of quantum-confinement conditions for photocarriers within the Ge phase which leads to an increased energy gap over that expected for the more bulk-like, asdeposited Ge material. Under the deposition and thermal treatment conditions used in the present study, the spectral absorption response is consistent between the ZnO and ITO-based thin films examined. This suggests that carrier confinement conditions are mediated by the development of similar Ge-phase local spatial extent and Ge:TCO interfacial structures in both systems, regardless of TCO identity.

  4. Location of nanophase Fe-oxides in palagonitic soils: Implication for Martian pigments

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

    Palagonitic materials from Mauna Kea, Hawaii, were identified as Mars analogs based on their spectral and magnetic properties. These materials probably resulted from hydrothermal alteration during eruption of the volcano and/or from weathering under ambient conditions. The reflectance spectra of the Mars surface obtained by Earth-based telescopes and the reflectance spectra of analogs obtained in the laboratory show features due to electronic transitions of Fe(III) in oxide particles that range in size from nanometer (nanophase) to micrometer sized or larger. The presence of Fe(III) suggests oxidizing conditions during the alteration process in Mars that may have occurred in the past or during a slow ongoing process. Two naturally altered basaltic samples from Hawaii (HWMK12 and HWMK13) and a laboratory-altered (PH-13-DCGT2) basaltic glass similar in elemental composition to the above two samples was examined. All three samples exhibited spectral characteristics similar to martian bright-region spectra. Chemical and mineralogical changes occurring at the surface of these basalts were studied in order to understand the basis for their Mars-like properties. The spectral properties of the three samples were examined after the removal of Fe oxides by chemical extractants.

  5. Transmission Mössbauer Analysis of Nanophased Oxides Formed on High Strength Steels

    NASA Astrophysics Data System (ADS)

    Balasubramanian, R.; Cook, D. C.; Townsend, H.

    2002-06-01

    Nanophased oxides found in the corrosion coatings of atmospherically weathered steels have properties that are scientifically significant and industrially important. Mössbauer spectroscopy proves to be a very useful tool to accurately characterize the corrosion coatings. Samples of carbon steel were exposed in Campeche, along the Gulf of Mexico for up to one year and the development of corrosion products as a function of steel type and exposure time were studied using Mössbauer spectroscopy, micro-Raman spectrometry and X-ray diffraction. Both X-ray diffraction and transmission Mössbauer spectroscopic results indicated that lepidocrocite, maghemite and goethite were the dominant oxides. Transmission Mössbauer analysis at 77 K indicated that for up to three months of exposure, lepidocrocite and maghemite accounted for nearly 80% of the relative amount, with goethite contributing only 20% to the mixture. However, as the exposure time increased to 6 months, the relative contribution of goethite increased at the expense of decreasing amounts of maghemite. Monitoring the environment during the exposure time indicated that the average time of wetness decreased. The decrease in the relative contribution of maghemite to the total oxide concentration is related to the decreasing time of wetness, with increasing exposure time.

  6. The biostimulation of anaerobic digestion with (semi)conductive ferric oxides: their potential for enhanced biomethanation.

    PubMed

    Baek, Gahyun; Kim, Jaai; Cho, Kyungjin; Bae, Hyokwan; Lee, Changsoo

    2015-12-01

    The effect of biostimulation with ferric oxides, semiconductive ferric oxyhydroxide, and conductive magnetite on the anaerobic digestion of dairy wastewater was examined in a batch mode. The reactors supplemented with ferric oxyhydroxide (R2) and magnetite (R3) showed significantly enhanced biomethanation performance compared with the control (R1). The removal of chemical oxygen demand (COD) after 30 days was 31.9, 59.3, and 82.5 % in R1, R2, and R3, respectively. The consumed COD was almost fully recovered as biogas in R2 and R3, while only 79 % was recovered in R1. The total energy production as biogas was accordingly 32.2, 71.0, and 97.7 kJ in R1, R2, and R3, respectively. The reactors also differed in the acid formation profile with more propionate and butyrate found in R1 and more acetate found in R3. The enhanced biomethanation seems to be associated with variations in the bacterial community structure supposedly induced by the ferric oxides added. In contrast, no evident variation was observed in the archaeal community structure among the reactors. The potential electric syntrophy formed between Methanosaeta concilii-like methanogens and electroactive iron-reducing bacteria, particularly Trichococcus, was likely responsible for the enhanced performance. The stimulated growth of fermentative iron reducers may also have contributed by altering the metabolic characteristics of the bacterial communities to produce more favorable acidogenic products for methanogenesis. The overall results suggest the potential of biostimulation with (semi)conductive ferric oxides to enhance the rate and efficiency of the biomethanation of organic wastes. This seems to be potentially attractive, as increasing attention is being paid to the energy self-sufficiency of waste/wastewater treatment processes today. PMID:26272096

  7. Formation of ferric oxides from aqueous solutions: A polyhedral approach by X-ray absorption spectroscdpy: I. Hydrolysis and formation of ferric gels

    NASA Astrophysics Data System (ADS)

    Combes, J. M.; Manceau, A.; Calas, G.; Bottero, J. Y.

    1989-03-01

    X-ray absorption spectroscopy (XAS) was used to follow the evolution of local structural environments around ferric ions during the formation of ferric hydrous oxide gels from 1 M chloride and 0.1 M nitrate solutions. Fe K-XANES and EXAFS confirm that ferric ions remain 6-fold coordinated during this evolution. EXAFS spectra obtained on partially hydrolyzed ferric chloride solutions indicate the presence of aqua-chloro ferric complexes up to OH/Fe = 2.2. When OH/Fe < 1 in the solution, iron mainly occurs in trans-[ FeCl2( H2O) 4] 2+ octahedra with Fe-Cl and Fe-O distances of 2.31 and 2.01 Å, respectively. With increasing OH availability in the solution, Cl - anions tend gradually to be exchanged for (O,OH,OH 2) ligands. Below OH/Fe = 1, no structural order is detected beyond the first coordination sphere. Above this ratio, two Fe-Fe distances at 3.05 Å and 3.44 Å are observed and correspond to the presence of edge- and vertex-sharing Fe-octahedra. XAS results show that ferric gels and highly polymerized aqueous species are short-range ordered. The main contribution to disorder in the gels arises from the small size of coherently scattering domains also responsible for their X-ray 'amorphous' character. From the initial to the final stage of hydrolysis, particles possess a nearly spherical shape with a minimum average diameter ranging from 10-30 Å for polymers formed from chloride and nitrate solutions. As polymerization proceeds, the local order extends to several tens of angströms and the particle structures becomes progressively closer to that of akaganeite (?-FeOOH) or goethite (?-FeOOH). This local structure is distinct from that of the lepidocrocite (?-FeOOH)-like structure of ferric gels precipitated after oxidation of divalent Fe solutions. The growth of the crystalline Fe-oxyhydroxides from gels takes place by the progressive long-range ordering in the ferric polymers without modifying the short-range order around Fe.

  8. Charge-coupled device imaging spectroscopy of Mars. II - Results and implications for Martian ferric mineralogy

    NASA Technical Reports Server (NTRS)

    Bell, James F., III

    1992-01-01

    Materials similar to nanophase ferric oxides are presently seen to dominate the spectral behavior of the Martian surface in the visible-to-near-IR, in view of imaging spectroscopic observations of Mars. Attention is accordingly given to models for the formation of hematite and other ferric minerals in both current terrestrial environments and in the current and past, possibly wetter Martian climate. It is noted that imaging spectroscopy is an ideal tool for high spatial resolution spacecraft and telescopic studies of the Martian surface.

  9. The mechanism of selenate adsorption on goethite and hydrous ferric oxide

    SciTech Connect

    Manceau, A.; Charlet, L. . Environmental Geochemistry Group)

    1994-11-01

    Sorption of anions on mineral surfaces, and specifically on Fe oxides, is a topic of continued interest in soil and environmental chemistry. EXAFS spectroscopy has been used to investigate the structure of selenate surface complexes sorbed on dry and wet goethite and hydrous ferric oxide. It is shown that selenate oxyanions always form inner-sphere surface complexes on both sorbents regardless of the hydration state. Selenate, like phosphate and selenite, forms binuclear bridging complexes on (hk0) planes with two singly coordinated A-type OH groups. Furthermore evidence is provided for the attachment of selenate oxyanions on (001) planes by the sharing of edges with Fe octahedra. Selenite and arsenate appear to form the same types of surface complexes as selenate at the surface of goethite and hydrous ferric oxide. It is likely that this sorption mechanism is operative for other anions including phosphate and sulfate. A consequence of this study is the conclusion that the crystallographic planes of Fe oxides (hk0 and 001) do not appear to selectivity bond either cations or anions, at least at high surface coverage.

  10. Arsenic and antimony removal from drinking water by adsorption on granular ferric oxide.

    PubMed

    Sazakli, Eleni; Zouvelou, Stavroula V; Kalavrouziotis, Ioannis; Leotsinidis, Michalis

    2015-01-01

    Arsenic and antimony occur in drinking water due to natural weathering or anthropogenic activities. There has been growing concern about their impact on health. The aim of this study was to assess the efficiency of a granular ferric oxide adsorbent medium to remove arsenic and antimony from drinking water via rapid small-scale column tests (RSSCTs). Three different water matrices - deionized, raw water treated with a reverse osmosis domestic device and raw water - were spiked with arsenic and/or antimony to a concentration of 100 ?g L?¹. Both elements were successfully adsorbed onto the medium. The loadings until the guideline value was exceeded in the effluent were found to be 0.35-1.63 mg g?¹ for arsenic and 0.12-2.11 mg g?¹ for antimony, depending on the water matrix. Adsorption of one element was not substantially affected by the presence of the other. Aeration did not affect significantly the adsorption capacity. Granular ferric oxide could be employed for the simultaneous removal of arsenic and antimony from drinking water, whereas full-scale systems should be assessed via laboratory tests before their implementation. PMID:25746656

  11. Moessbauer search for ferric oxide phases in lunar materials and simulated lunar materials

    NASA Technical Reports Server (NTRS)

    Forester, D. W.

    1973-01-01

    Moessbauer studies were carried out on lunar fines and on simulated lunar glasses containing magnetic-like precipitates with the primary objective of determining how much, if any, ferric oxide is present in the lunar soils. Although unambiguous evidence of lunar Fe(3+) phases was not obtained, an upper limit was estimated from different portions of the Moessbauer spectra to be between 0.1 and 0.4 wt.% (as Fe3O4). A smaller than 62 microns fraction of 15021,118 showed 0.5 wt.% ferromagnetic iron at 300 K in as-returned condition. After heating to 650 C in an evacuated, sealed quartz tube for 1400 hours, the same sample exhibited 1 wt.% ferromagnetic iron at room temperature. An accompanying decrease in excess absorption area near zero velocity was noted. Thus, the result of the vacuum heat treatment was to convert fine grained iron to larger particles, apparently without the oxidation effects commonly reported.

  12. Hydrous ferric oxide precipitation in the presence of nonmetabolizing bacteria: Constraints on the mechanism of a biotic effect

    NASA Astrophysics Data System (ADS)

    Rancourt, Denis G.; Thibault, Pierre-Jean; Mavrocordatos, Denis; Lamarche, Gilles

    2005-02-01

    We have used room temperature and cryogenic 57Fe Mössbauer spectroscopy, powder X-ray diffraction (pXRD), mineral magnetometry, and transmission electron microscopy (TEM), to study the synthetic precipitation of hydrous ferric oxides (HFOs) prepared either in the absence (abiotic, a-HFO) or presence (biotic, b-HFO) of nonmetabolizing bacterial cells ( Bacillus subtilis or Bacillus licheniformis, ˜10 8 cells/mL) and under otherwise identical chemical conditions, starting from Fe(II) (10 -2, 10 -3, or 10 -4 mol/L) under open oxic conditions and at different pH (6-9). We have also performed the first Mössbauer spectroscopy measurements of bacterial cell wall ( Bacillus subtilis) surface complexed Fe, where Fe(III) (10 -3.5-10 -4.5 mol/L) was added to a fixed concentration of cells (˜10 8 cells/mL) under open oxic conditions and at various pH (2.5-4.3). We find that non-metabolic bacterial cell wall surface complexation of Fe is not passive in that it affects Fe speciation in at least two ways: (1) it can reduce Fe(III) to sorbed-Fe 2+ by a proposed steric and charge transfer effect and (2) it stabilizes Fe(II) as sorbed-Fe 2+ against ambient oxidation. The cell wall sorption of Fe occurs in a manner that is not compatible with incorporation into the HFO structure (different coordination environment and stabilization of the ferrous state) and the cell wall-sorbed Fe is not chemically bonded to the HFO particle when they coexist (the sorbed Fe is not magnetically polarized by the HFO particle in its magnetically ordered state). This invalidates the concept that sorption is the first step in a heterogeneous nucleation of HFO onto bacterial cell walls. Both the a-HFOs and the b-HFOs are predominantly varieties of ferrihydrite (Fh), often containing admixtures of nanophase lepidocrocite (nLp), yet they show significant abiotic/biotic differences: Biotic Fh has less intraparticle (including surface region) atomic order (Mössbauer quadrupole splitting), smaller primary particle size (magnetometry blocking temperature), weaker Fe to particle bond strength (Mössbauer center shift), and no six-line Fh (6L-Fh) admixture (pXRD, magnetometry). Contrary to current belief, we find that 6L-Fh appears to be precipitated directly, under a-HFO conditions, from either Fe(II) or Fe(III), and depending on Fe concentration and pH, whereas the presence of bacteria disables all such 6L-Fh precipitation and produces two-line Fh (2L-Fh)-like biotic coprecipitates. Given the nature of the differences between a-HFO and b-HFO and their synthesis condition dependences, several biotic precipitation mechanisms (template effect, near-cell environment effect, catalyzed nucleation and/or growth effect, and substrate-based coprecipitation) are ruled out. The prevailing present view of a template or heterogeneous nucleation barrier reduction effect, in particular, is shown not to be the cause of the large observed biotic effects on the resulting HFOs. The only proposed mechanism (relevant to Fh) that is consistent with all our observations is coprecipitation with and possible surface poisoning by ancillary bacteriagenic compounds. That bacterial cell wall functional groups are redox active and the characteristics of biotic (i.e., natural) HFOs compared to those of abiotic (i.e., synthetic) HFOs have several possible biogeochemical implications regarding Fe cycling, in the photic zones of water columns in particular.

  13. Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

    PubMed Central

    Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

    2013-01-01

    Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

  14. Magnetic ordering of ferric oxide within SiO{sub 2}-based mesoporous materials

    SciTech Connect

    Guo Haiquan; Zhang Xiaoming; Cui Minhui; Sharma, Renu; Yang Nanloh; Akins, Daniel L. . E-mail: akins@sci.ccny.cuny.edu

    2005-10-06

    Nanostructural ferric oxide was encapsulated within one-dimensional (1-D) silicate mesoporous molecular materials, resulting in the formation of nanocomposites. The resulting nanocomposites were characterized by UV-vis, IR, TEM, EPR and X-ray diffraction. The occluded Fe{sub 2}O{sub 3} nanostructures were found to evince optical spectra and magnetic properties that were significantly different from that of bulk Fe{sub 2}O{sub 3}. EPR measurements indicate that the various nanocomposites (whose dimensions were controllable by the pore sizes of the silicate materials), when sufficiently loaded with small Fe{sub 2}O{sub 3} nanoparticles, possess nonzero absorptions at zero applied magnetic field, as well as significant microwave absorption capacities as a function of applied magnetic field strength.

  15. Abstract No. pan0505 Sorption of Heavy Metal Contaminants onto Hydrated Ferric Oxides: Mechanistic Modeling using X-ray

    E-print Network

    Sparks, Donald L.

    Abstract No. pan0505 Sorption of Heavy Metal Contaminants onto Hydrated Ferric Oxides: Mechanistic, competing ions, and the nature of the background electrolyte. Macroscopic isotherm studies demonstrated sulfate and phosphate as background electrolytes. The XAS spectra were analyzed using WinXAS (Version 2

  16. Ion sorption onto hydrous ferric oxides: Effect on major element fluid chemistry at Aspo, Sweden

    SciTech Connect

    Bruton, C.J.; Viani, B.E.

    1996-06-01

    The observed variability of fluid chemistry at the Aespoe Hard Rock Laboratory is not fully described by conservative fluid mixing models. Ion exchange may account for some of the observed discrepancies. It is also possible that variably charged solids such as oxyhydroxides of Fe can serve as sources and sinks of anions and cations through surface complexation. Surface complexation reactions on hydrous ferric oxides involve sorption of both cations and anions. Geochemical modeling of the surface chemistry of hydrous ferric oxides (HFOs) in equilibrium with shallow HBH02 and deep KA0483A waters shows that HFOs can serve as significant, pH-sensitive sources and sinks for cations and anions. Carbonate sorption is favored especially at below-neutral pH. A greater mass of carbonate is sorbed onto HFO surfaces than is contained in the fluid when 10 g goethite, used as a proxy for HFOs, is in contact with 1 kg H{sub 2}O. The masses of sorbent required to significantly impact fluid chemistry through sorption/desorption reactions seem to be reasonable when compared to the occurrences of HFOs at Aespoe. Thus, it is possible that small changes in fluid chemistry can cause significant releases of cations or anions from HFOs into the fluid phase or, alternately, result in uptake of aqueous species onto HFO surfaces. Simulations of the mixing of shallow HBH02 and native KA0483A waters in the presence of a fixed mass of goethite show that surface complexation does not cause the concentrations of Ca, Sr, and SO{sub 4} to deviate from those that are predicted using conservative mixing models. Results for HCO{sub 3} are more difficult to interpret and cannot be addressed adequately at this time.

  17. Stable iron isotope fractionation between aqueous Fe(II) and hydrous ferric oxide.

    PubMed

    Wu, Lingling; Beard, Brian L; Roden, Eric E; Johnson, Clark M

    2011-03-01

    Despite the ubiquity of poorly crystalline ferric hydrous oxides (HFO, or ferrihydrite) in natural environments, stable Fe isotopic fractionation between HFO and other Fe phases remains unclear. In particular, it has been difficult to determine equilibrium Fe isotope fractionation between aqueous Fe(II) and HFO due to fast transformation of the latter to more stable minerals. Here we used HFO stabilized by the presence of dissolved silica (2.14 mM), or a Si-HFO coprecipitate, to determine an equilibrium Fe(II)-HFO fractionation factor using a three-isotope method. Iron isotope exchange between Fe(II) and HFO was rapid and near complete with the Si-HFO coprecipitate, and rapid but incomplete for HFO in the presence of dissolved silica, the latter case likely reflecting blockage of oxide surface sites by sorbed silica. Equilibrium Fe(II)-HFO (56)Fe/(54)Fe fractionation factors of -3.17 ± 0.08 (2?)‰ and -2.58 ± 0.14 (2?)‰ were obtained for HFO plus silica and the Si-HFO coprecipitate, respectively. Structural similarity between ferrihydrite and hematite, as suggested by spectroscopic studies, combined with the minor isotopic effect of dissolved silica, imply that the true equilibrium Fe(II)-HFO (56)Fe/(54)Fe fractionation factor in the absence of silica may be ?-3.2‰. These results provide a critical interpretive context for inferring the stable isotope effects of Fe redox cycling in nature. PMID:21294566

  18. Proton binding by hydrous ferric oxide and aluminum oxide surfaces interpreted using fully optimized continuous pKa spectra.

    PubMed

    Smith, D S; Ferris, F G

    2001-12-01

    A modified regularized least squares pKa spectrum approach is proposed to determine proton stability constants and concentrations for binding sites on hydrous ferric oxide (HFO) and aluminum oxide surfaces. Acid-base titration data are fit to a continuous binding site model for the system represented as a pKa spectrum. The modified parameter fitting method optimizes simultaneously for both smoothness of the pKa spectrum and goodness-of-fit, whereas other methods optimize for goodness-of-fit given a fixed smoothness factor. The modified method is tested with aluminum oxide and recovers values consistent with theoretical values. The regularized pKa spectrum method optimized for smoothness is applied to prepared samples of two types of HFO. The prepared HFO samples differ only in the total iron concentration of the parent solution. The resultant pKa distributions are compared to proton binding constants from MUSIC model results for crystalline iron oxides. The types of binding sites in the HFO sample are consistent with theoretical binding site stability constants for crystalline iron oxides. Overall, the prepared HFO samples have binding constants most consistent with values for lepidocrocite and goethite. PMID:11770764

  19. Synergistic Competitive Inhibition of Ferrous Iron Oxidation by Thiobacillus ferrooxidans by Increasing Concentrations of Ferric Iron and Cells

    PubMed Central

    Lizama, Hector M.; Suzuki, Isamu

    1989-01-01

    Oxidation of ferrous iron by Thiobacillus ferrooxidans SM-4 was inhibited competitively by increasing concentrations of ferric iron or cells. A kinetic analysis showed that binding of one inhibitor did not exclude binding of the other and led to synergistic inhibition by the two inhibitors. Binding of one inhibitor, however, was affected by the other inhibitor, and the apparent inhibition constant increased with increasing concentrations of the other inhibitor. PMID:16348031

  20. The kinetics of the oxidation of pyrite by ferric ions and dissolved oxygen: An electrochemical study

    SciTech Connect

    Holmes, P.R.; Crundwell, F.K.

    2000-01-01

    The dissolution of pyrite is important in the geochemical cycling of iron and sulphur, in the formation of acid mine drainage, and in the extraction of metals by bacterial leaching. Many researchers have studied the kinetics of dissolution, and the rate of dissolution has often been found to be half-order in ferric ions or oxygen. Previous work has not adequately explained the kinetics of dissolution of pyrite. The dissolution of pyrite is an oxidation-reduction reaction. The kinetics of the oxidation and reduction half-reactions was studied independently using electrochemical techniques of voltammetry. The kinetics of the overall reaction was studied by the electrochemical technique of potentiometry, which consisted of measuring the mixed potential of a sample of corroding pyrite in solutions of different compositions. The kinetics of the half reactions are related to the kinetics of the overall dissolution reaction by the condition that there is no accumulation of charge. This principle is used to derive expressions for the mixed potential and the rate of dissolution, which successfully describe the mixed potential measurements and the kinetics of dissolution reported in the literature. It is shown that the observations of half-order kinetics and that the oxygen in the sulphate product arises from water are both a direct consequence of the electrochemical mechanism. Thus it is concluded that the electrochemical reaction steps occurring at the mineral-solution interface control the rate of dissolution. Raman spectroscopy was used to analyze reaction products formed on the pyrite surface. The results indicated that small amounts of polysulphides form on the surface of the pyrite. However, it was also found that the mixed (corrosion) potential does not change over a 14-day leaching period. This indicates that even though polysulphide material is present on the surface, it does not influence the rate of the reactions occurring at the surface. Measurement of the sulphur yields as a function of electrode potential indicate that thiosulphate is not the only source of the sulphur product.

  1. Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

    USGS Publications Warehouse

    Verplanck, P.L.; Nordstrom, D.K.; Taylor, H.E.; Kimball, B.A.

    2004-01-01

    Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH. ?? 2004 Elsevier Ltd. All rights reserved.

  2. 21 CFR 184.1297 - Ferric chloride.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ferric chloride. 184.1297 Section 184.1297 Food and... Substances Affirmed as GRAS § 184.1297 Ferric chloride. (a) Ferric chloride (iron (III) chloride, FeC13, CAS Reg. No. 7705-08-0) may be prepared from iron and chlorine or from ferric oxide and hydrogen...

  3. 21 CFR 184.1297 - Ferric chloride.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Ferric chloride. 184.1297 Section 184.1297 Food... GRAS § 184.1297 Ferric chloride. (a) Ferric chloride (iron (III) chloride, FeC13, CAS Reg. No. 7705-08-0) may be prepared from iron and chlorine or from ferric oxide and hydrogen chloride. The...

  4. Synthesis of waste cooking oil based biodiesel via ferric-manganese promoted molybdenum oxide / zirconia nanoparticle solid acid catalyst: influence of ferric and manganese dopants.

    PubMed

    Alhassan, Fatah H; Rashid, Umer; Taufiq-Yap, Yun Hin

    2015-01-01

    The utilization of ferric-manganese promoted molybdenum oxide/zirconia (Fe-Mn- MoO3/ZrO2) (FMMZ) solid acid catalyst for production of biodiesel was demonstrated. FMMZ is produced through impregnation reaction followed by calcination at 600°C for 3 h. The characterization of FMMZ had been done using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), transmission electron microscopy(TEM) and Brunner-Emmett-Teller (BET) surface area measurement. The effect of waste cooking oil methyl esters (WCOME's) yield on the reactions variables such as reaction temperature, catalyst loading, molar ratio of methanol/oil and reusability were also assessed. The catalyst was used to convert the waste cooking oil into corresponding methyl esters (95.6%±0.15) within 5 h at 200? reaction temperature, 600 rpm stirring speed, 1:25 molar ratio of oil to alcohol and 4% w/w catalyst loading. The reported catalyst was successfully recycled in six connective experiments without loss in activity. Moreover, the fuel properties of WCOME's were also reported using ASTM D 6751 methods. PMID:25843280

  5. Biogenic iron mineralization accompanying the dissimilatory reduction of hydrous ferric oxide by a groundwater bacterium

    NASA Astrophysics Data System (ADS)

    Fredrickson, James K.; Zachara, John M.; Kennedy, David W.; Dong, Hailang; Onstott, Tullis C.; Hinman, Nancy W.; Li, Shu-mei

    1998-10-01

    Dissimilatory iron-reducing bacteria (DIRB) couple the oxidation of organic matter or H 2 to the reduction of iron oxides. The factors controlling the rate and extent of these reduction reactions and the resulting solid phases are complex and poorly understood. Batch experiments were conducted with amorphous hydrous ferric oxide (HFO) and the DIRB Shewanella putrefaciens, strain CN32, in well-defined aqueous solutions to investigate the reduction of HFO and formation of biogenic Fe(II) minerals. Lactate-HFO solutions buffered with either bicarbonate or 1,4-piperazinediethanesulfonic acid (PIPES) containing various combinations of phosphate and anthraquinone-2,6-disulfonate (AQDS), were inoculated with S. putrefaciens CN32. AQDS, a humic acid analog that can be reduced to dihydroanthraquinone by CN32, was included because of its ability to function as an electron shuttle during microbial iron reduction and as an indicator of pe. Iron reduction was measured with time, and the resulting solids were analyzed by X-ray diffraction, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) with energy-dispersive X-ray spectroscopy (EDS) and selected area electron diffraction (SAED). In HCO 3- buffered medium with AQDS, HFO was rapidly and extensively reduced, and the resulting solids were dominated by ferrous carbonate (siderite). Ferrous phosphate (vivianite) was also present in HCO 3- medium containing P, and fine-grained magnetite was present as a minor phase in HCO 3- medium with or without P. In the PIPES-buffered medium, the rate and extent of reduction was strongly influenced by AQDS and P. With AQDS, HFO was rapidly converted to highly crystalline magnetite whereas in its absence, magnetite mineralization was slower and the final material less crystalline. In PIPES with both P and AQDS, a green rust type compound [Fe (6-x)IIFe xIII(OH) 12] x+[(A 2-) x/2 · yH 2O] x- was the dominant solid phase formed; in the absence of AQDS a poorly crystalline product was observed. The measured pe and nature of the solids identified were consistent with thermodynamic considerations. The composition of aqueous media in which microbial iron reduction occurred strongly impacted the rate and extent of iron reduction and the nature of the reduced solids. This, in turn, can provide a feedback control mechanism on microbial metabolism. Hence, in sediments where geochemical conditions promote magnetite formation, two-thirds of the Fe(III) will be sequestered in a form that may not be available for anaerobic bacterial respiration.

  6. Immobilization of strontium during iron biomineralization coupled to dissimilatory hydrous ferric oxide reduction

    NASA Astrophysics Data System (ADS)

    Roden, Eric E.; Leonardo, Michael R.; Ferris, F. Grant

    2002-09-01

    The potential for incorporation of strontium (Sr) into biogenic Fe(II)-bearing minerals formed during microbial reduction of synthetic hydrous ferric oxide (HFO) was investigated in circumneutral bicarbonate-buffered medium containing SrCl 2 at concentrations of 10 ?M, 100 ?M, or 1.0 mM. CaCl 2 (10 mM) was added to some experiments to simulate a Ca-rich groundwater. In Ca-free systems, 89 to 100% of total Sr was captured in solid-phase compounds formed during reduction of 30 to 40 mmol Fe(III) L -1 over a 1-month period. A smaller fraction of total Sr (25 to 34%) was incorporated into the solid phase in cultures amended with 10 mM CaCl 2. X-ray diffraction identified siderite and ferroan ankerite as major end products of HFO reduction in Ca-free and Ca-amended cultures, respectively. Scanning electron microscopy-energy dispersive x-ray spectroscopy revealed the presence of Sr associated with carbonate phases. Selective extraction of HFO reduction end products indicated that 46 to 100% of the solid-phase Sr was associated with carbonates. The sequestration of Sr into carbonate phases in the Ca-free systems occurred systematically according to a heterogeneous (Doerner-Hoskins) partition coefficient (D D-H) of 1.81 ± 0.15. This D D-H value was 2 to 10 times higher than values determined for incorporation of Sr (10 ?M) into FeCO 3(s) precipitated abiotically at rates comparable to or greater than rates observed during HFO reduction, and fivefold higher than theoretical partition coefficients for equilibrium Fe(Sr)CO 3 solid solution formation. Surface complexation and entrapment of Sr by rapidly growing siderite crystals (and possibly other biogenic Fe(II) solids) provides an explanation for the intensive scavenging of Sr in the Ca-free systems. The results of abiotic siderite precipitation experiments in the presence and absence of excess Ca indicate that substitution of Ca for Sr at foreign element incorporation sites (mass action effect) on growing FeCO 3(s) surfaces can account for the inhibition of Sr incorporation into the siderite component of ankerite formed in the Ca-amended HFO reduction experiments. Likewise, substitution of Fe(II) for Sr may explain the absence of major Sr partitioning into the calcite component of ankerite. The findings indicate that under appropriate conditions, sequestration of metals in siderite produced during bacterial Fe(III) oxide reduction may provide a mechanism for retarding the migration of Sr and other divalent metal contaminants in anaerobic, carbonate-rich sedimentary environments.

  7. Kinetic study of the oxidation of complex nickeliferous sulfide ore in aqueous ferric sulfate. [Pentlandite

    SciTech Connect

    Chang, Q.Z.; Bautista, R.G.

    1984-01-01

    The kinetics of leaching the nickel, cobalt, and copper from the minerals pyrrhotite and pentlandite by ferric ion in a naturally occurring complex nickeliferous sulfide ore are presented. The kinetic results from these experiments can be represented in one equation with two unknowns (pyrrhotite and pentlandite minerals). Knowledge of the mineral-ferric ion reaction allows the separate determination of the leaching rates of nickel, cobalt, and copper from either the pyrrhotite or pentlandite mineral. This work has more practical significance in hydrometallurgical processing compared to data obtained using mixtures of pure nickel sulfide, cobalt sulfide, and copper sulfide.

  8. 21 CFR 73.1298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...) Identity. (1) The color additive ferric ammonium ferrocyanide is the blue pigment obtained by oxidizing... product is filtered, washed, and dried. The pigment consists principally of ferric ammonium...

  9. 21 CFR 73.1298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...) Identity. (1) The color additive ferric ammonium ferrocyanide is the blue pigment obtained by oxidizing... product is filtered, washed, and dried. The pigment consists principally of ferric ammonium...

  10. 21 CFR 73.1298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...) Identity. (1) The color additive ferric ammonium ferrocyanide is the blue pigment obtained by oxidizing... product is filtered, washed, and dried. The pigment consists principally of ferric ammonium...

  11. 21 CFR 73.1298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...) Identity. (1) The color additive ferric ammonium ferrocyanide is the blue pigment obtained by oxidizing... product is filtered, washed, and dried. The pigment consists principally of ferric ammonium...

  12. 21 CFR 73.1298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...) Identity. (1) The color additive ferric ammonium ferrocyanide is the blue pigment obtained by oxidizing... product is filtered, washed, and dried. The pigment consists principally of ferric ammonium...

  13. 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.

  14. Rational design of interfacial properties of ferric (hydr)oxide nanoparticles by adsorption of fatty acids from aqueous solutions.

    PubMed

    Ponnurangam, Sathish; Chernyshova, Irina V; Somasundaran, Ponisseril

    2012-07-24

    Notwithstanding the great practical importance, still open are the questions how, why, and to what extent the size, morphology, and surface charge of metal (hydr)oxide nanoparticles (NPs) affect the adsorption form, adsorption strength, surface density, and packing order of organic (bio)molecules containing carboxylic groups. In this article, we conclusively answer these questions for a model system of ferric (hydr)oxide NPs and demonstrate applicability of the established relationships to manipulating their hydrophobicity and dispersibility. Employing in situ Fourier transform infrared (FTIR) spectroscopy and adsorption isotherm measurements, we study the interaction of 150, 38, and 9 nm hematite (?-Fe(2)O(3)) and ?4 nm 2-line ferrihydrite with sodium laurate (dodecanoate) in water. We discover that, independent of morphology, an increase in size of the ferric (hydr)oxide NPs significantly improves their adsorption capacity and affinity toward fatty acids. This effect favors the formation of bilayers, which in turn promotes dispersibility of the larger NPs in water. At the same time, the local order in self-assembled monolayer (SAM) strongly depends on the morphological compatibility of the NP facets with the geometry-driven well-packed arrangements of the hydrocarbon chains as well as on the ratio of the chemisorbed to the physically adsorbed carboxylate groups. Surprisingly, the geometrical constraints can be removed, and adsorption capacity can be increased by negatively polarizing the NPs due to promotion of the outer-sphere complexes of the fatty acid. We interpret these findings and discuss their implications for the nanotechnological applications of surface-functionalized metal (hydr)oxide NPs. PMID:22694303

  15. Visible Wavelength Spectroscopy of Ferric Minerals: A Key Tool for Identification of Ancient Martian Aqueous Environments

    NASA Technical Reports Server (NTRS)

    Murchie, Scott L.; Bell, J. F., III; Morris, Richard V.

    2000-01-01

    The mineralogic signatures of past aqueous alteration of a basaltic Martian crust may include iron oxides and oxyhydroxides, zeolites, carbonates, phyllosilicates, and silica. The identities, relative abundances, and crystallinities of the phases formed in a particular environment depend on physicochemical conditions. At one extreme, hot spring environments may be characterized by smectite-chlorite to talc-kaolinite silicate assemblages, plus crystalline ferric oxides dominated by hematite. However, most environments, including cold springs, pedogenic layers, and ponded surface water, are expected to deposit iron oxides and oxyhydroxides, carbonates, and smectite-dominated phyllosilicates. A substantial fraction of the ferric iron is expected to occur in nanophase form, with the exact mineralogy strongly influenced by Eh-pH conditions. Detection of these phases has been an objective of a large body of terrestrial telescopic, Mars orbital, and landed spectral investigations and in situ compositional measurements. However, clear identifications of many of these phases is lacking. Neither carbonate nor silica has been unequivocally detected by any method. Although phyllosilicates may occur near the limit of detection by remote sensing, in general they appear to occur in only poorly crystalline form. In contrast, compelling evidence for ferric iron minerals has been gathered by recent telescopic investigations, the Imager for Mars Pathfinder (IMP), and the Thermal Emission Spectrometer (TES) on the Mars Global Surveyor (MGS). These data yield two crucial findings: (1) In the global, high spatial resolution TES data set, highly crystalline ferric iron (as coarse-grained 'gray' hematite) has been recognized but with only very limited spatial occurrence and (2) Low-resolution telescopic reflectance spectroscopy, very limited orbital reflectance spectroscopy, and landed multispectral imaging provide strong indications that at least two broad classes of ferric iron minerals are commonplace in non-dust covered regions.

  16. doi:10.1016/S0016-7037(03)00096-6 ATR-FTIR spectroscopic studies of boric acid adsorption on hydrous ferric oxide

    E-print Network

    Sparks, Donald L.

    .S. states (Keren and Bingham, 1985). Most of the research of boron chemistry by soil chemists has provided information about the sorption of boron on soils and soil components. In all cases, researchers have noted on hydrous ferric oxide DEREK PEAK,1, * GEORGE W. LUTHER, III,2 and DONALD L. SPARKS 3 1 Department of Soil

  17. Fayalite Oxidation Processes: Experimental Evidence for the Stability of Pure Ferric Fayalite?

    NASA Technical Reports Server (NTRS)

    Martin, A. M.; Righter, K.; Keller, L. P.; Medard, E.; Devouard, B.; Rahman, Z.

    2011-01-01

    Olivine is one of the most important minerals in Earth and planetary sciences. Fayalite Fe2(2+)SiO4, the ferrous end-member of olivine, is present in some terrestrial rocks and primitive meteorites (CV3 chondrites). A ferric fayalite (or ferri-fayalite), Fe(2+) Fe2(3+)(SiO4)2 laihunite, has been reported in Earth samples (magnetite ore, metamorphic and volcanic rocks...) and in Martian meteorites (nakhlites). Laihunite was also synthesized at 1 atmosphere between 400 and 700 C. We show evidence for the stability of a pure ferrifayalite end-member and for potential minerals with XFe(3+) between 2/3 and 1.

  18. Biodiesel synthesis catalyzed by transition metal oxides: ferric-manganese doped tungstated/molybdena nanoparticle catalyst.

    PubMed

    Alhassan, Fatah Hamid; Rashid, Umer; Taufiq-Yap, Yun Hin

    2015-01-01

    The solid acid Ferric-manganese doped tungstated/molybdena nananoparticle catalyst was prepared via impregnation reaction followed by calcination at 600°C for 3 h. The characterization was done using X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), X-ray fluorescence (XRF), Transmission electron microscope (TEM) and Brunner-Emmett-Teller surface area measurement (BET). Moreover, dependence of biodiesel yield on the reaction variables such as the reaction temperature, catalyst loading, as well as molar ratio of methanol/oil and reusability were also appraised. The catalyst was reused six times without any loss in activity with maximum yield of 92.3% ±1.12 achieved in the optimized conditions of reaction temperature of 200°C; stirring speed of 600 rpm, 1:25 molar ratio of oil to alcohol, 6 % w/w catalyst loading as well as 8 h as time of the reaction. The fuel properties of WCOME's were evaluated, including the density, kinematic viscosity, pour point, cloud point and flash point whereas all properties were compared with the limits in the ASTM D6751 standard. PMID:25492234

  19. 21 CFR 73.1298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...The color additive ferric ammonium ferrocyanide is the blue pigment obtained by oxidizing under acidic conditions with sodium...The oxidized product is filtered, washed, and dried. The pigment consists principally of ferric ammonium ferrocyanide...

  20. 21 CFR 73.1298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...The color additive ferric ammonium ferrocyanide is the blue pigment obtained by oxidizing under acidic conditions with sodium...The oxidized product is filtered, washed, and dried. The pigment consists principally of ferric ammonium ferrocyanide...

  1. 21 CFR 73.1298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...The color additive ferric ammonium ferrocyanide is the blue pigment obtained by oxidizing under acidic conditions with sodium...The oxidized product is filtered, washed, and dried. The pigment consists principally of ferric ammonium ferrocyanide...

  2. 21 CFR 73.1298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...The color additive ferric ammonium ferrocyanide is the blue pigment obtained by oxidizing under acidic conditions with sodium...The oxidized product is filtered, washed, and dried. The pigment consists principally of ferric ammonium ferrocyanide...

  3. 21 CFR 73.1298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...The color additive ferric ammonium ferrocyanide is the blue pigment obtained by oxidizing under acidic conditions with sodium...The oxidized product is filtered, washed, and dried. The pigment consists principally of ferric ammonium ferrocyanide...

  4. Amperometric determination of acetylcholine-A neurotransmitter, by chitosan/gold-coated ferric oxide nanoparticles modified gold electrode.

    PubMed

    Chauhan, Nidhi; Pundir, C S

    2014-11-15

    An amperometric acetylcholine biosensor was constructed by co-immobilizing covalently, a mixture of acetylcholinesterase (AChE) and choline oxidase (ChO) onto nanocomposite of chitosan (CHIT)/gold-coated ferric oxide nanoparticles (Fe@AuNPs) electrodeposited onto surface of a Au electrode and using it as a working electrode, Ag/AgCl as reference electrode and Pt wire as auxiliary electrode connected through potentiostat. The biosensor is based on electrochemical measurement of H2O2 generated from oxidation of choline by immobilized ChO, which in turn is produced from hydrolysis of acetylcholine by immobilized AChE. The biosensor exhibited optimum response within 3s at +0.2V, pH 7.0 and 30°C. The enzyme electrode had a linear working range of 0.005-400 µM, with a detection limit of 0.005 µM for acetylcholine. The biosensor measured plasma acetylcholine in apparently healthy and persons suffering from Alzheimer's disease. The enzyme electrode was unaffected by a number of serum substances but lost 50% of its initial activity after its 100 uses over a period of 3 months, when stored at 4°C. PMID:24836212

  5. Nitrogen Requirement of Iron-Oxidizing Thiobacilli for Acidic Ferric Sulfate Regeneration

    PubMed Central

    Tuovinen, Olli H.; Panda, Fern A.; Tsuchiya, Henry M.

    1979-01-01

    Ammonium was shown to be a limiting nutrient for iron oxidation in cultures of Thiobacillus ferrooxidans. In addition, one strain was also able to assimilate nitrate, but not nitrite, for growth and coupled iron oxidation. Some amino acids (0.5 mM) were tested as a source of nitrogen; none clearly stimulated bacterial activity and inhibition was commonly encountered. Complex nitrogenous compounds were inhibitory at high concentrations (0.1 to 0.5%, wt/vol) and, at low concentrations, some clearly stimulated the bacterial iron oxidation in ammonium-limited cultures. Enhancement of iron oxidation by these compounds was also observed in ammonium-unlimited cultures, suggesting their possible role in providing trace nutrients and possibly carbon for the bacteria. PMID:16345391

  6. Ascorbic acid inhibits ferric nitrilotriacetate induction of ornithine decarboxylase, DNA synthesis, oxidative stress, and hepatotoxicity in rats.

    PubMed

    Ansar, S; Iqbal, M

    2015-11-01

    Ascorbic acid (AA) is a naturally occurring phenolic compound with antioxidant properties used in food, cosmetics, and pharmaceutical products. In this study, the effect of AA on ferric nitrilotriacetate (Fe-NTA)-induced hepatotoxicity in rats has been examined. Fe-NTA alone enhances ornithine decarboxylase activity to 4.5-fold and tritiated thymidine incorporation in DNA to 3.6-fold in livers compared with the corresponding saline-treated controls. The enhanced ornithine decarboxylase activity and DNA synthesis showed a reduction to 3.02- and 1.88-fold, respectively, at a higher dose of 2 mg AA per day per animal, compared with the Fe-NTA-treated groups. Fe-NTA treatment also enhanced the hepatic microsomal lipid peroxidation to 1.7-fold compared to saline-treated controls. These changes were reversed significantly in animals receiving pretreatment of AA. The present data shows that AA can reciprocate the toxic effects of Fe-NTA and can serve as a potent chemopreventive agent to suppress oxidant-induced tissue injury and hepatotoxicity in rats. PMID:23863956

  7. Novel approach to zinc removal from circum-neutral mine waters using pelletised recovered hydrous ferric oxide.

    PubMed

    Mayes, William M; Potter, Hugh A B; Jarvis, Adam P

    2009-02-15

    Data are presented which evaluate the performance of a pilot-scale treatment system using pelletised hydrous ferric oxide (HFO; a waste stream from coal mine water treatment) as a high surface area sorbent for removing zinc (Zn) from a metal mine water discharge in the North Pennines Orefield, UK. Over a 10-month period the system removed Zn at mean area- and volume-adjusted removal rates of 3.7 and 8.1gm(-3)day(-1), respectively, with a mean treatment efficiency of 32% at a low mean residence time of 49min. There were seasonal effects in Zn removal owing to establishment and dieback of algae in the treatment tank. This led to increased Zn uptake in early summer months followed by slight Zn release upon algae senescence. In addition to these biosorptive processes, the principal sinks for Zn appear to be (1) sorption onto the HFO surface, and (2) precipitation with calcite-dominated secondary minerals. The latter were formed as a product of dissolution of portlandite in the cement binder and calcium recarbonation. Further optimisation of the HFO pelletisation process holds the possibility for providing a low-cost, low footprint treatment option for metal rich mine waters, in addition to a valuable after-use for recovered HFO from coal mine water treatment facilities. PMID:18583040

  8. Mercury (II) reduction and co-precipitation of metallic mercury on hydrous ferric oxide in contaminated groundwater.

    PubMed

    Richard, Jan-Helge; Bischoff, Cornelia; Ahrens, Christian G M; Biester, Harald

    2016-01-01

    Mercury (Hg) speciation and sorption analyses in contaminated aquifers are useful for understanding transformation, retention, and mobility of Hg in groundwater. In most aquifers hydrous ferric oxides (HFOs) are among the most important sorbents for trace metals; however, their role in sorption or mobilization of Hg in aquifers has been rarely analyzed. In this study, we investigated Hg chemistry and Hg sorption to HFO under changing redox conditions in a highly HgCl2-contaminated aquifer (up to 870?gL(-1) Hg). Results from aqueous and solid phase Hg measurements were compared to modeled (PHREEQC) data. Speciation analyses of dissolved mercury indicated that Hg(II) forms were reduced to Hg(0) under anoxic conditions, and adsorbed to or co-precipitated with HFO. Solid phase Hg thermo-desorption measurements revealed that between 55 and 93% of Hg bound to HFO was elemental Hg (Hg(0)). Hg concentrations in precipitates reached more than 4 weight %, up to 7000 times higher than predicted by geochemical models that do not consider unspecific sorption to and co-precipitation of elemental Hg with HFO. The observed process of Hg(II) reduction and Hg(0) formation, and its retention and co-precipitation by HFO is thought to be crucial in HgCl2-contaminated aquifers with variable redox-conditions regarding the related decrease in Hg solubility (factor of ~10(6)), and retention of Hg in the aquifer. PMID:26352645

  9. The formation, structure, and ageing of As-rich hydrous ferric oxide at the abandoned Sb deposit Pezinok (Slovakia)

    NASA Astrophysics Data System (ADS)

    Majzlan, Juraj; Lalinská, Bronislava; Chovan, Martin; Jurkovi?, L.'ubomír; Milovská, Stanislava; Göttlicher, Jörg

    2007-09-01

    The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold ˜380,000 m 3 of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 ± 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS 2; arsenopyrite, FeAsS; berthierite, FeSb 2S 4) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ ?-XANES experiments indicate that As in the weathering rims is fully oxidized (As 5+). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As 2O 5 and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate-binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As 5+. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe-Fe pairs at a distance of 3.3-3.5 Å, that is, increasing polymerization of the iron octahedra to form larger units with fewer adsorption sites. Therefore, although ferrihydrite is an excellent material for capturing arsenic, its use as a medium for a long-term storage of As has to be considered with a great caution because it will tend to release arsenic as it ages.

  10. The Formation, Structure, and Ageing of As-Rich Hydrous Ferric Oxide at the Abandoned Sb Deposit Pezinok (Slovakia)

    SciTech Connect

    Majzlan,J.; Lalinska, B.; Chovan, M.; Jurkovic, L.; Milovska, S.; Gottlicher, J.

    2007-01-01

    The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold {approx}380,000 m{sup 3} of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 {+-} 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS{sub 2}; arsenopyrite, FeAsS; berthierite, FeSb{sub 2}S{sub 4}) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ {mu}-XANES experiments indicate that As in the weathering rims is fully oxidized (As{sup 5+}). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As{sub 2}O{sub 5} and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate-binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As{sup 5+}. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe-Fe pairs at a distance of 3.3-3.5 {angstrom}, that is, increasing polymerization of the iron octahedra to form larger units with fewer adsorption sites. Therefore, although ferrihydrite is an excellent material for capturing arsenic, its use as a medium for a long-term storage of As has to be considered with a great caution because it will tend to release arsenic as it ages.

  11. [Effect of hydrogen peroxide and hydrated ferric oxides on the metabolism of soil microflora].

    PubMed

    Imshenetski?, A A; Murzakov, B G; Evdokimova, M D; Dorofeeva, I K

    1979-01-01

    The effect of hydrogen peroxide and the mineral limonite on the rate of microbial processes was studied in poor and rich soils. The dynamics of CO2 evolution can be registered upon addition of hydrogen peroxide to chernozem samples, which confirms the existence of metabolism of soil microorganisms. In experiments with desert soil, the evolution of O2 increases rather than that of CO2, which is probably due to an increase in the number of microorganisms producing catalase. Limonite stimulates the metabolic activity of microrganisms. The cultural and morphological properties of microflora are described, which are typical of soils incubated in the presence of limonite and hydrogen peroxide. This work supports the conclusion that, theoretically, the ground of Mars may contain microorganisms which have adapted, in the course of evolution, to high concentrations of hydrogen peroxide and hydrated iron oxides (of the limonite type) in the surrounding medium. PMID:502913

  12. 21 CFR 184.1297 - Ferric chloride.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...from iron and chlorine or from ferric oxide and hydrogen chloride. The pure material occurs as hydroscopic, hexagonal, dark crystals. Ferric chloride hexahydrate (iron (III) chloride hexahydrate, FeC13 . 6H2 0, CAS Reg. No. 10025-77-1)...

  13. Interactions between substrates and the haem-bound nitric oxide of ferric and ferrous bacterial nitric oxide synthases

    PubMed Central

    Chartier, François J. M.; Couture, Manon

    2006-01-01

    We report here the resonance Raman spectra of the FeIII–NO and FeII–NO complexes of the bacterial NOSs (nitric oxide synthases) from Staphylococcus aureus and Bacillus subtilis. The haem–NO complexes of these bacterial NOSs displayed Fe–N–O frequencies similar to those of the mammalian NOSs, in presence and absence of L-arginine, indicating that haem-bound NO and L-arginine had similar haem environments in bacterial and mammalian NOSs. The only notable difference between the two types of NOS was the lack of change in Fe–N–O frequencies of the FeIII–NO complexes upon (6R) 5,6,7,8-tetrahydro-L-biopterin binding to bacterial NOSs. We report, for the first time, the characterization of NO complexes with NOHA (N?-hydroxy-L-arginine), the substrate used in the second half of the catalytic cycle of NOSs. In the FeIII–NO complexes, both L-arginine and NOHA induced the Fe–N–O bending mode at nearly the same frequency as a result of a steric interaction between the substrates and the haem-bound NO. However, in the FeII–NO complexes, the Fe–N–O bending mode was not observed and the ?Fe?NO mode displayed a 5 cm?1 higher frequency in the complex with NOHA than in the complex with L-arginine as a result of direct interactions that probably involve hydrogen bonds. The different behaviour of the substrates in the FeII–NO complexes thus reveal that the interactions between haem-bound NO and the substrates are finely tuned by the geometry of the Fe-ligand structure and are relevant to the use of the FeII–NO complex as a model of the oxygenated complex of NOSs. PMID:16970546

  14. Sodium Ferric Gluconate Injection

    MedlinePLUS

    Sodium ferric gluconate injection is used to treat iron-deficiency anemia (a lower than normal number of ... are also receiving the medication epoetin (Epogen, Procrit). Sodium ferric gluconate injection is in a class of ...

  15. 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.

  16. Heterogeneous catalytic ozonation of biologically pretreated Lurgi coal gasification wastewater using sewage sludge based activated carbon supported manganese and ferric oxides as catalysts.

    PubMed

    Zhuang, Haifeng; Han, Hongjun; Hou, Baolin; Jia, Shengyong; Zhao, Qian

    2014-08-01

    Sewage sludge of biological wastewater treatment plant was converted into sewage sludge based activated carbon (SBAC) with ZnCl? as activation agent, which supported manganese and ferric oxides as catalysts (including SBAC) to improve the performance of ozonation of real biologically pretreated Lurgi coal gasification wastewater. The results indicated catalytic ozonation with the prepared catalysts significantly enhanced performance of pollutants removal and the treated wastewater was more biodegradable and less toxic than that in ozonation alone. On the basis of positive effect of higher pH and significant inhibition of radical scavengers in catalytic ozonation, it was deduced that the enhancement of catalytic activity was responsible for generating hydroxyl radicals and the possible reaction pathway was proposed. Moreover, the prepared catalysts showed superior stability and most of toxic and refractory compounds were eliminated at successive catalytic ozonation runs. Thus, the process with economical, efficient and sustainable advantages was beneficial to engineering application. PMID:24907577

  17. Development of Surface Complexation Models of Cr(VI) Adsorption on Soils, Sediments and Model Mixtures of Kaolinite, Montmorillonite, ?-Alumina, Hydrous Manganese and Ferric Oxides and Goethite

    SciTech Connect

    Koretsky, Carla

    2013-11-29

    Hexavalent chromium is a highly toxic contaminant that has been introduced into aquifers and shallow sediments and soils via many anthropogenic activities. Hexavalent chromium contamination is a problem or potential problem in the shallow subsurface at several DOE sites, including Hanford, Idaho National Laboratory, Los Alamos National Laboratory and the Oak Ridge Reservation (DOE, 2008). To accurately quantify the fate and transport of hexavalent chromium at DOE and other contaminated sites, robust geochemical models, capable of correctly predicting changes in chromium chemical form resulting from chemical reactions occurring in subsurface environments are needed. One important chemical reaction that may greatly impact the bioavailability and mobility of hexavalent chromium in the subsurface is chemical binding to the surfaces of particulates, termed adsorption or surface complexation. Quantitative thermodynamic surface complexation models have been derived that can correctly calculate hexavalent chromium adsorption on well-characterized materials over ranges in subsurface conditions, such pH and salinity. However, models have not yet been developed for hexavalent chromium adsorption on many important constituents of natural soils and sediments, such as clay minerals. Furthermore, most of the existing thermodynamic models have been developed for relatively simple, single solid systems and have rarely been tested for the complex mixtures of solids present in real sediments and soils. In this study, the adsorption of hexavalent chromium was measured as a function of pH (3-10), salinity (0.001 to 0.1 M NaNO3), and partial pressure of carbon dioxide(0-5%) on a suite of naturally-occurring solids including goethite (FeOOH), hydrous manganese oxide (MnOOH), hydrous ferric oxide (Fe(OH)3), ?-alumina (Al2O3), kaolinite (Al2Si2O5(OH)4), and montmorillonite (Na3(Al, Mg)2Si4O10(OH)2?nH2O). The results show that all of these materials can bind substantial quantities of hexavalent chromium, especially at low pH. Unexpectedly, experiments with the clay minerals kaolinite and montmorillonite suggest that hexavalent chromium may interact with these solids over much longer periods of time than expected. Furthermore, hexavalent chromium may irreversibly bind to these solids, perhaps because of oxidation-reduction reactions occurring on the surfaces of the clay minerals. More work should be done to investigate and quantify these chemical reactions. Experiments conducted with mixtures of goethite, hydrous manganese oxide, hydrous ferric oxide, ?-alumina, montmorillonite and kaolinite demonstrate that it is possible to correctly predict hexavalent chromium binding in the presence of multiple minerals using thermodynamic models derived for the simpler systems. Further, these models suggest that of the six solid considered in this study, goethite is typically the solid to which most of the hexavalent chromium will bind. Experiments completed with organic-rich and organic-poor natural sediments demonstrate that in organic-rich substrates, organic matter is likely to control uptake of the hexavalent chromium. The models derived and tested in this study for hexavalent chromium binding to ?-alumina, hydrous manganese oxide, goethite, hydrous ferric oxide and clay minerals can be used to better predict changes in hexavalent chromium bioavailability and mobility in contaminated sediments and soils.

  18. 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.

  19. Nuclear fuel elements made from nanophase materials

    DOEpatents

    Heubeck, Norman B. (Schenectady, NY)

    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.

  20. Low electrical potential anode modified with Fe/ferric oxide and its application in marine benthic microbial fuel cell with higher voltage and power output

    NASA Astrophysics Data System (ADS)

    Fu, Yubin; Xu, Qian; Zai, Xuerong; Liu, Yuanyuan; Lu, Zhikai

    2014-01-01

    Low voltage and power output limit the widespread application of marine benthic microbial fuel cell (BMFCs). To increase the cell power, a Fe/Ferric oxide modified anode fabricating by electrolytic deposition is reported here. The novel anode has a lower surface contact angle and higher wettability, which favors the adhesion of bacteria. It is firstly demonstrated that the electrical potential of the modified anode is about -775 mV, much lower than that of the plain graphite (about -450 mV). Open circuit potential of BMFC with the modified anode is about 1050 ± 50 mV, while the potential for the plain cells is only 700 ± 50 mV. In comparison with the plain graphite, the modified anode presents a 393-fold exchange current density and a higher kinetic activity. The output power reaches 7.4 × 10-2 mW cm-2, 17.4-fold higher than that of the plain graphite. A composite mechanism of both chemical and microbial enhancement of the modified anode is proposed to explain its excellent electrochemical performance. The modified anode has potential for high-power output cell and novel voltage-booster design to make the BMFC utilization feasibility.

  1. 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 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/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.

  2. Combined Hydrous Ferric Oxide and Quaternary Ammonium Surfactant Tailoring of Granular Activated Carbon for Concurrent Arsenate and Perchlorate Removal

    SciTech Connect

    Jang, M.; Cannon, F; Parette, R; Yoon, S; Chen, W

    2009-01-01

    Activated carbon was tailored with both iron and quaternary ammonium surfactants so as to concurrently remove both arsenate and perchlorate from groundwater. The iron (hydr)oxide preferentially removed the arsenate oxyanion but not perchlorate; while the quaternary ammonium preferentially removed the perchlorate oxyanion, but not the arsenate. The co-sorption of two anionic oxyanions via distinct mechanisms has yielded intriguing phenomena. Rapid small-scale column tests (RSSCTs) with these dually prepared media employed synthetic waters that were concurrently spiked with arsenate and perchlorate; and these trial results showed that the quaternary ammonium surfactants enhanced arsenate removal bed life by 25-50% when compared to activated carbon media that had been preloaded merely with iron (hydr)oxide; and the surfactant also enhanced the diffusion rate of arsenate per the Donnan effect. The authors also employed natural groundwater from Rutland, MA which contained 60 microg/L As and traces of silica, and sulfate; and the authors spiked this with 40 microg/L perchlorate. When processing this water, activated carbon that had been tailored with iron and cationic surfactant could treat 12,500 bed volumes before 10 microg/L arsenic breakthrough, and 4500 bed volumes before 6 microg/L perchlorate breakthrough. Although the quaternary ammonium surfactants exhibited only a slight capacity for removing arsenate, these surfactants did facilitate a more favorably positively charged avenue for the arsenate to diffuse through the media to the iron sorption site (i.e. via the Donnan effect).

  3. Formation, reactivity, and aging of ferric oxide particles formed from Fe(II) and Fe(III) sources: Implications for iron bioavailability in the marine environment

    NASA Astrophysics Data System (ADS)

    Bligh, Mark W.; Waite, T. David

    2011-12-01

    Freshly formed amorphous ferric oxides (AFO) in the water column are potentially highly reactive, but with reactivity declining rapidly with age, and have the capacity to partake in reactions with dissolved species and to be a significant source of bioavailable iron. However, the controls on reactivity in aggregated oxides are not well understood. Additionally, the mechanism by which early rapid aging occurs is not clear. Aging is typically considered in terms of changes in crystallinity as the structure of an iron oxide becomes more stable and ordered with time thus leading to declining reactivity. However, there has been recognition of the role that aggregation can play in determining reactivity, although it has received limited attention. Here, we have formed AFO in seawater in the laboratory from either an Fe(II) or Fe(III) source to produce either AFO(II) or AFO(III). The changes in reactivity of these two oxides following formation was measured using both ligand-promoted dissolution (LPD) and reductive dissolution (RD). The structure of the two oxides was examined using light scattering and X-ray adsorption techniques. The dissolution rate of AFO(III) was greater than that of AFO(II), as measured by both dissolution techniques, and could be attributed to both the less ordered molecular structure and smaller primary particle size of AFO(III). From EXAFS analysis shortly (90 min) following formation, AFO(II) and AFO(III) were shown to have the same structure as aged lepidocrocite and ferrihydrite respectively. Both oxides displayed a rapid decrease in dissolution rate over the first hours following formation in a pattern that was very similar when normalised. The early establishment and little subsequent change of crystal structure for both oxides undermined the hypothesis that increasing crystallinity was responsible for early rapid aging. Also, an aging model describing this proposed process could only be fitted to the data with kinetic parameters that were inconsistent with such a mechanism. The similar aging patterns and existence of diffusion limited cluster aggregation (DLCA) suggested that loss of Fe centre accessibility due to aggregation is the likely cause of early rapid aging of AFO. A simple model describing the loss of surface area during the aggregate growth, measured using dynamic light scattering (DLS), produced aging patterns that matched the reactivity loss of AFO(III) measured using RD but not LPD. The difference between the two measures of dissolution rate could not be explained, but indicated that different measures of reactivity respond differentially to various parameters controlling reactivity. Analysis of aggregate structure using aggregation kinetics and static light scattering (SLS) suggested that restructuring during aggregation was occurring at an aggregate level for AFO(III), but only minimally so for AFO(II). While our investigations support the contention that aggregation is responsible for early rapid aging, the role of aggregate structure is remains unclear.

  4. Ferric Tourmaline from Mexico.

    PubMed

    Mason, B; Donnay, G; Hardie, L A

    1964-04-01

    Dark brown crystals, up to 10 mm long, occur in rhyolite at Mexquitic, San Luis Potosi, Mexico. They are short prismatic, showing {1120}, {3030}, {1011}, {0221}, with c/a 0.4521, measured with a goniometer, and distinct {1120} cleavage. With an unusual combination of cell dimensions, high density, high refractive indices, and extreme birefringence, this tourmaline falls outside the known elbaite-schorl and schorl-dravite series. A chemical analysis, recalculated on the basis of cell volume and density, gives close to the theoretical 150 atoms per cell, whether the iron is ferrous or ferric, but the physical properties indicate a ferric tourmaline. PMID:17729799

  5. 21 CFR 73.1299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...1299 Ferric ferrocyanide. (a) Identity. (1) The color additive ferric ferrocyanide is a ferric hexacyanoferrate pigment characterized by the structual formula Fe4 [Fe(CN)6 ]3 ·XH2 O, which may contain small amounts of ferric...

  6. 21 CFR 73.1299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...1299 Ferric ferrocyanide. (a) Identity. (1) The color additive ferric ferrocyanide is a ferric hexacyanoferrate pigment characterized by the structual formula Fe4 [Fe(CN)6 ]3 ·XH2 O, which may contain small amounts of ferric...

  7. 21 CFR 184.1301 - Ferric phosphate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...2013-04-01 2013-04-01 false Ferric phosphate. 184.1301 Section 184.1301 Food and...Substances Affirmed as GRAS § 184.1301 Ferric phosphate. (a) Ferric phosphate (ferric orthophosphate, iron (III)...

  8. 21 CFR 184.1301 - Ferric phosphate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...2012-04-01 2012-04-01 false Ferric phosphate. 184.1301 Section 184.1301 Food and...Substances Affirmed as GRAS § 184.1301 Ferric phosphate. (a) Ferric phosphate (ferric orthophosphate, iron (III)...

  9. 21 CFR 184.1301 - Ferric phosphate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...2011-04-01 2011-04-01 false Ferric phosphate. 184.1301 Section 184.1301 Food and...Substances Affirmed as GRAS § 184.1301 Ferric phosphate. (a) Ferric phosphate (ferric orthophosphate, iron (III)...

  10. 21 CFR 184.1301 - Ferric phosphate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...2010-04-01 2009-04-01 true Ferric phosphate. 184.1301 Section 184.1301 Food and...Substances Affirmed as GRAS § 184.1301 Ferric phosphate. (a) Ferric phosphate (ferric orthophosphate, iron (III)...

  11. Staff Scientist Center for Nanophase Materials Sciences

    E-print Network

    Pennycook, Steve

    1 Jihua Chen Staff Scientist Center for Nanophase Materials Sciences Oak Ridge National Laboratory Scientist, Center for Nanophase Materials Sciences (CNMS), Oak Ridge National Laboratory (ORNL) 2009. Government Agency, and iii. New Meetings #12;2 2012 Session Chair, "Low-Voltage Electron Microscopy

  12. Center for Nanophase Materials Sciences Strategic Plan

    E-print Network

    Center for Nanophase Materials Sciences Strategic Plan 2015­2019 October 2014 #12;#12;iii CONTENTS ................................................................... 5 3. Integration into ORNL Missions: Neutron Sciences, Materials by Design, Imaging ................ 6 The Link to Neutron Sciences

  13. Microwave polyol process for metal nanophases

    NASA Astrophysics Data System (ADS)

    Komarneni, Sridhar; Katsuki, Hiroaki; Li, Dongsheng; Bhalla, Amar S.

    2004-04-01

    The microwave-assisted polyol process was investigated for the synthesis of several nanophase metals under different conditions in the temperature range of 100 to 200 °C. Nanophase Ag metal particle synthesis using ethylene glycol (EG) was carried out at 100 and 150 °C in the presence of polyvinyl pyrrolidone (PVP), dodecyl amine (DDA), oleic acid (OA) or trioctylphosphine (TOP) to determine whether particle size and shape can be controlled. The Ag particle size was changed with different capping agents. The use of PVP led to well defined Ag nanoparticles in the range of about 30-50 nm. Morphologically well defined nanophase metals of Fe, Co and Ni were produced in the presence of both PVP and DDA, while the use of just PVP or PVP and TOP did not yield such particles. The results presented here show that a variety of well defined nanophase metals can be produced by using the microwave-polyol process and optimizing the metal capping agents.

  14. Defect Clustering and Nano-Phase Structure Characterization of Multi-Component Rare Earth Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

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

    2003-01-01

    Advanced oxide thermal barrier coatings have been developed by incorporating multi-component rare earth oxide dopants into zirconia-yttria to effectively promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nano-scale phases within the coating systems. The presence of these nano-sized defect clusters has found to significantly reduce the coating intrinsic thermal conductivity, improve sintering resistance, and maintain long-term high temperature stability. In this paper, the defect clusters and nano-structured phases, which were created by the addition of multi-component rare earth dopants to the plasma-sprayed and electron-beam physical vapor deposited thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The defect cluster size, distribution, crystallographic and compositional information were investigated using high-resolution TEM lattice imaging, selected area diffraction (SAD), electron energy-loss spectroscopy (EELS) and energy dispersive spectroscopy (EDS) analysis techniques. The results showed that substantial defect clusters were formed in the advanced multi-component rare earth oxide doped zirconia- yttria systems. The size of the oxide defect clusters and the cluster dopant segregation was typically ranging from 5 to 50 nm. These multi-component dopant induced defect clusters are an important factor for the coating long-term high temperature stability and excellent performance.

  15. Defect Clustering and Nano-Phase Structure Characterization of Multi-Component Rare Earth Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

    Advanced oxide thermal barrier coatings have been developed by incorporating multi- component rare earth oxide dopants into zirconia-yttria to effectively promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nano-scale phases within the coating systems. The presence of these nano-sized defect clusters has found to significantly reduce the coating intrinsic thermal conductivity, improve sintering resistance, and maintain long-term high temperature stability. In this paper, the defect clusters and nano-structured phases, which were created by the addition of multi-component rare earth dopants to the plasma- sprayed and electron-beam physical vapor deposited thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The defect cluster size, distribution, crystallographic and compositional information were investigated using high-resolution TEM lattice imaging, selected area diffraction (SAD), and energy dispersive spectroscopy (EDS) analysis techniques. The results showed that substantial defect clusters were formed in the advanced multi-component rare earth oxide doped zirconia-yttria systems. The size of the oxide defect clusters and the cluster dopant segregation was typically ranging fiom 5 to 50 nm. These multi-component dopant induced defect clusters are an important factor for the coating long-term high temperature stability and excellent performance.

  16. Nanophase materials assembled from clusters

    SciTech Connect

    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 and 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.

  17. Calorimetry of Nanophases of Macromolecules

    NASA Astrophysics Data System (ADS)

    Wunderlich, Bernhard

    2007-06-01

    The thermodynamic description of polymeric systems is summarized based on 50 years of gathering experimental information with adiabatic, differential-scanning, and temperature-modulated calorimetry. This experience has led to a description of macro- to micro- to nano-phases with macromolecules able to traverse the phase boundaries and decouple at the surfaces, resulting in different thermodynamic properties for the separated parts of the molecule. A typical thermodynamic characterization of semicystalline polymers is that of a globally metastable system with locally reversible processes. Unique phenomena in polymers include the ability of semicrystalline polymers to undergo cold crystallization and molecular nucleation, possess thermally generated point defects and rigid-amorphous fractions, and have amorphous to mesophasic to crystalline macroconformations with glass, ordering, and disordering transitions in all three structures. To describe such multifaceted systems, special combinations of equilibrium, and irreversible thermodynamics as well as statistical and quantum mechanics are necessary. Only then is it possible to handle violations of phase rules, changes of properties when approaching nanophase dimensions, local reversibility, and enthalpy relaxation. The enthalpy relaxation in polymers originates in the cooperativeness of conformational motion and the interferences of processes of different time scales. The experiments to identify the effects of the different molecular motions from typical vibrational time scales of picoseconds to cooperative, large-amplitude rearrangements of up to megaseconds span heating rates of thousands of K·s-1 with superfast chip calorimeters to many hours for slow, quasi-isothermal analysis by temperature-modulated differential scanning calorimetry (TMDSC). Selected examples of this far-reaching thermal characterization will be presented.

  18. 21 CFR 184.1297 - Ferric chloride.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ferric chloride. 184.1297 Section 184.1297 Food... Specific Substances Affirmed as GRAS § 184.1297 Ferric chloride. (a) Ferric chloride (iron (III) chloride... hydrogen chloride. The pure material occurs as hydroscopic, hexagonal, dark crystals. Ferric...

  19. 21 CFR 184.1297 - Ferric chloride.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ferric chloride. 184.1297 Section 184.1297 Food... Specific Substances Affirmed as GRAS § 184.1297 Ferric chloride. (a) Ferric chloride (iron (III) chloride... hydrogen chloride. The pure material occurs as hydroscopic, hexagonal, dark crystals. Ferric...

  20. 21 CFR 184.1301 - Ferric phosphate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ferric phosphate. 184.1301 Section 184.1301 Food... Specific Substances Affirmed as GRAS § 184.1301 Ferric phosphate. (a) Ferric phosphate (ferric orthophosphate, iron (III) phosphate, FePO4·xH2O, CAS Reg. No. 10045-86-0) is an odorless, yellowish-white...

  1. 21 CFR 184.1301 - Ferric phosphate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ferric phosphate. 184.1301 Section 184.1301 Food... Specific Substances Affirmed as GRAS § 184.1301 Ferric phosphate. (a) Ferric phosphate (ferric orthophosphate, iron (III) phosphate, FePO4·xH2O, CAS Reg. No. 10045-86-0) is an odorless, yellowish-white...

  2. 21 CFR 184.1301 - Ferric phosphate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ferric phosphate. 184.1301 Section 184.1301 Food... Specific Substances Affirmed as GRAS § 184.1301 Ferric phosphate. (a) Ferric phosphate (ferric orthophosphate, iron (III) phosphate, FePO4·xH2O, CAS Reg. No. 10045-86-0) is an odorless, yellowish-white...

  3. 21 CFR 184.1301 - Ferric phosphate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ferric phosphate. 184.1301 Section 184.1301 Food... Specific Substances Affirmed as GRAS § 184.1301 Ferric phosphate. (a) Ferric phosphate (ferric orthophosphate, iron (III) phosphate, FePO4·xH2O, CAS Reg. No. 10045-86-0) is an odorless, yellowish-white...

  4. 21 CFR 184.1297 - Ferric chloride.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ferric chloride. 184.1297 Section 184.1297 Food... Specific Substances Affirmed as GRAS § 184.1297 Ferric chloride. (a) Ferric chloride (iron (III) chloride... hydrogen chloride. The pure material occurs as hydroscopic, hexagonal, dark crystals. Ferric...

  5. ESTCP DEMONSTRATION OF A BIOAVAILABLE FERRIC IRON TEST KIT

    EPA Science Inventory

    Bioavailable ferric iron (BAFeIII) is used by iron-reducing bacteria as an electron acceptor during the oxidation of various organic contaminants such as vinyl chloride and benzene. Quantification of BAFeIII is important with respect to characterizing candidate natural attenuati...

  6. DEMONSTRATION OF A BIOAVAILABLE FERRIC IRON TEST KIT

    EPA Science Inventory

    Bioavailable ferric iron (BAFeIII) is used by iron-reducing bacteria as an electron acceptor during the oxidation of various organic contaminants such as vinyl chloride and benzene. Quantification of BAFeIII is important with respect to characterizing candidate natural attenuati...

  7. Reflectance spectroscopy of ferric sulfate-bearing montmorillonites as Mars soil analog materials

    NASA Technical Reports Server (NTRS)

    Bishop, J. L.; Pieters, C. M.; Burns, R. G.; Edwards, J. O.; Mancinelli, R. L.; Froschl, H.

    1995-01-01

    Spectroscopic analyses have shown that smectites enhanced in the laboratory with additional ferric species exhibit important similarities to those of the soils on Mars. Ferrihydrite in these chemically treated smectites has features in the visible to near-infrared region that resemble the energies and band strengths of features in reflectance spectra observed for several bright regions on Mars. New samples have been prepared with sulfate as well, because S was found by Viking to be a major component in the surface material on Mars. A suite of ferrihydrite-bearing and ferric sulfate-bearing montmorillonites, prepared with variable Fe3+ and S concentrations and variable pH conditions, has been analyzed using reflectance spectroscopy in the visible and infrared regions, Mossbauer spectroscopy at room temperature and 4 K, differential thermal analysis, and X-ray diffraction. These analyses support the formation of ferrihydrite of variable crystallinity in the ferrihydrite-bearing montmorillonites and a combination of schwertmannite and ferrihydrite in the ferric sulfate-bearing montmorillonites. Small quantities of poorly crystalline or nanophase forms of other ferric materials may also be present in these samples. The chemical formation conditions of the ferrihydrite-bearing and ferric sulfate-bearing montmorillonites influence the character of the low temperature Mossbauer sextets and the visible reflectance spectra. An absorption minimum is observed at 0.88-0.89 micrometers in spectra of the ferric sulfate-bearing samples, and at 0.89-0.92 micrometers in spectra of the ferrihydrate-bearing montmorillonites. Mossbauer spectra of the ferric sulfate-bearing montmorillonites indicate variable concentrations of ferrihydrite and schwertmannite in the interlaminar spaces and along grain surfaces. Dehydration under reduced atmospheric pressure conditions induces a greater effect on the adsorbed and interlayer water in ferrihydrite-bearing montmorillonite than on the water in ferric sulfate-bearing montmorillonite. Reflectance spectra of ferric sulfate-bearing montmorillonite include a strong 3-micrometers band that is more resistant to dry atmospheric conditions than the 3-micrometers band in spectra of similarly prepared ferrihydrite-bearing montmorillonites.

  8. Adhesion of Pseudomonas fluorescens onto nanophase materials

    NASA Astrophysics Data System (ADS)

    Webster, Thomas J.; Tong, Zonghua; Liu, Jin; Banks, M. Katherine

    2005-07-01

    Nanobiotechnology is a growing area of research, primarily due to the potentially numerous applications of new synthetic nanomaterials in engineering/science. Although various definitions have been given for the word 'nanomaterials' by many different experts, the commonly accepted one refers to nanomaterials as those materials which possess grains, particles, fibres, or other constituent components that have one dimension specifically less than 100 nm. In biological applications, most of the research to date has focused on the interactions between mammalian cells and synthetic nanophase surfaces for the creation of better tissue engineering materials. Although mammalian cells have shown a definite positive response to nanophase materials, information on bacterial interactions with nanophase materials remains elusive. For this reason, this study was designed to assess the adhesion of Pseudomonas fluorescens on nanophase compared to conventional grain size alumina substrates. Results provide the first evidence of increased adhesion of Pseudomonas fluorescens on alumina with nanometre compared to conventional grain sizes. To understand more about the process, polymer (specifically, poly-lactic-co-glycolic acid or PLGA) casts were made of the conventional and nanostructured alumina surfaces. Results showed similar increased Pseudomonas fluorescens capture on PLGA casts of nanostructured compared to conventional alumina as on the alumina itself. For these reasons, a key material property shown to enhance bacterial adhesion was elucidated in this study for both polymers and ceramics: nanostructured surface features.

  9. 21 CFR 582.5304 - Ferric pyrophosphate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5304 Ferric pyrophosphate. (a) Product. Ferric pyrophosphate. (b) Conditions of use....

  10. 21 CFR 582.5304 - Ferric pyrophosphate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5304 Ferric pyrophosphate. (a) Product. Ferric pyrophosphate. (b) Conditions of use....

  11. 21 CFR 184.1304 - Ferric pyrophosphate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... GRAS § 184.1304 Ferric pyrophosphate. (a) Ferric pyrophosphate (iron (III) pyrophosphate, Fe4(P207)3·x... nutrient supplement as defined in § 170.3(o)(20) of this chapter, with no limitation other than...

  12. 21 CFR 582.5301 - Ferric phosphate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5301 Ferric phosphate. (a) Product. Ferric phosphate. (b) Conditions of use....

  13. 21 CFR 582.5304 - Ferric pyrophosphate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5304 Ferric pyrophosphate. (a) Product. Ferric pyrophosphate. (b) Conditions of...

  14. 21 CFR 582.5301 - Ferric phosphate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5301 Ferric phosphate. (a) Product. Ferric phosphate. (b) Conditions of use....

  15. 21 CFR 582.5301 - Ferric phosphate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5301 Ferric phosphate. (a) Product. Ferric phosphate. (b) Conditions of use....

  16. 21 CFR 582.5301 - Ferric phosphate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Nutrients and/or Dietary Supplements 1 § 582.5301 Ferric phosphate. (a) Product. Ferric phosphate. (b) Conditions of use....

  17. 21 CFR 582.5301 - Ferric phosphate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Ferric phosphate. 582.5301 Section 582.5301 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5301 Ferric phosphate. (a) Product. Ferric phosphate. (b) Conditions of use....

  18. 21 CFR 582.5301 - Ferric phosphate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Ferric phosphate. 582.5301 Section 582.5301 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5301 Ferric phosphate. (a) Product. Ferric phosphate. (b) Conditions of use....

  19. 21 CFR 582.5301 - Ferric phosphate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Ferric phosphate. 582.5301 Section 582.5301 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5301 Ferric phosphate. (a) Product. Ferric phosphate. (b) Conditions of use....

  20. 21 CFR 582.5301 - Ferric phosphate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Ferric phosphate. 582.5301 Section 582.5301 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5301 Ferric phosphate. (a) Product. Ferric phosphate. (b) Conditions of use....

  1. 21 CFR 582.5301 - Ferric phosphate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Ferric phosphate. 582.5301 Section 582.5301 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5301 Ferric phosphate. (a) Product. Ferric phosphate. (b) Conditions of use....

  2. Hydrogen Reduction of Ferric Ions for Use in Copper Electrowinning

    SciTech Connect

    Karl S. Noah; Debby F. Bruhn; John E. Wey; Robert S. Cherry

    2005-01-01

    The conventional copper electrowinning process uses the water hydrolysis reaction as the anodic source of electrons. However this reaction generates acid mist and requires large quantities of energy. In order to improve energy efficiency and avoid acid mist, an alternative anodic reaction of ferrous ion oxidation has been proposed. This reaction does not involve evolution of acid mist and can be carried out at a lower cell voltage than the conventional process. However, because ferrous ions are converted to ferric ions at the anode in this process, there is a need for reduction of ferric ions to ferrous ions to continue this process. The most promising method for this reduction is the use of hydrogen gas since the resulting byproduct acid can be used elsewhere in the process and, unlike other reductants, hydrogen does not introduce other species that need subsequent removal. Because the hydrogen reduction technology has undergone only preliminary lab scale testing, additional research is needed to evaluate its commercial potential. Two issues for this research are the potentially low mass transfer rate of hydrogen into the electrolyte stream because of its low solubility in water, and whether other gaseous reductants less expensive than hydrogen, such as natural gas or syngas, might work. In this study various reductants were investigated to carry out the reduction of ferric ions to ferrous ions using a simulated electrolyte solution recycled through a trickle bed reactor packed with catalyst. The gases tested as reductants were hydrogen, methane, carbon monoxide, and a 50/50 mixture of H2 and CO. Nitrogen was also tested as an inert control. These gases were tested because they are constituents in either natural gas or syngas. The catalysts tested were palladium and platinum. Two gas flow rates and five electrolyte flow rates were tested. Pure hydrogen was an effective reductant of ferric ion. The rates were similar with both palladium and platinum. The ferric iron reduction increased with both the flow rate of gas as well as the liquid flow rate (up to ~0.1 g/L/min). Pure carbon monoxide also reduced the ferric ion, but at a rate about one tenth that of pure hydrogen at similar conditions. The syngas mixture of equimolar hydrogen and carbon monoxide reacted at a rate intermediate between each gas as a pure stream (up to ~ 0.06 g/L/min). This gas mixture shows that some form of unpurified reformer gas could be used to reduce the ferric ion in the electrolyte solution. Nitrogen was inert causing very little to no reduction of ferric ion.

  3. Functionally Graded Nanophase Beryllium/Carbon Composites

    NASA Technical Reports Server (NTRS)

    Choi, Michael K.

    2003-01-01

    Beryllium, beryllium alloys, beryllium carbide, and carbon are the ingredients of a class of nanophase Be/Be2C/C composite materials that can be formulated and functionally graded to suit a variety of applications. In a typical case, such a composite consists of a first layer of either pure beryllium or a beryllium alloy, a second layer of B2C, and a third layer of nanophase sintered carbon derived from fullerenes and nanotubes. The three layers are interconnected through interpenetrating spongelike structures. These Be/Be2C/C composite materials are similar to Co/WC/diamond functionally graded composite materials, except that (1) W and Co are replaced by Be and alloys thereof and (2) diamond is replaced by sintered carbon derived from fullerenes and nanotubes. (Optionally, one could form a Be/Be2C/diamond composite.) Because Be is lighter than W and Co, the present Be/Be2C/C composites weigh less than do the corresponding Co/WC/diamond composites. The nanophase carbon is almost as hard as diamond. WC/Co is the toughest material. It is widely used for drilling, digging, and machining. However, the fact that W is a heavy element (that is, has high atomic mass and mass density) makes W unattractive for applications in which weight is a severe disadvantage. Be is the lightest tough element, but its toughness is less than that of WC/Co alloy. Be strengthened by nanophase carbon is much tougher than pure or alloy Be. The nanophase carbon has an unsurpassed strength-to-weight ratio. The Be/Be2C/C composite materials are especially attractive for terrestrial and aerospace applications in which there are requirements for light weight along with the high strength and toughness of the denser Co/WC/diamond materials. These materials could be incorporated into diverse components, including cutting tools, bearings, rocket nozzles, and shields. Moreover, because Be and C are effective as neutron moderators, Be/Be2C/C composites could be attractive for some nuclear applications.

  4. Method of treating inflammatory diseases using a radiolabeled ferric hydroxide calloid

    DOEpatents

    Atcher, Robert W. (Chicago, IL); Hines, John J. (Glen Ellyn, IL)

    1992-01-01

    A ferric hydroxide colloid having an alpha-emitting radionuclide essentially on the outer surfaces and a method of forming same. The method includes oxidizing a ferrous hydroxide to ferric hydroxide in the presence of a preselected radionuclide to form a colloid having the radionuclide on the outer surface thereof, and thereafter washing the colloid, and suspending the washed colloid in a suitable solution. The labelled colloid is useful in cancer therapy and for the treatment of inflamed joints.

  5. 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.; DesMarais, D. J.; Downs, R. T.; Farmer, J. D.; Morookian, J. M.; Morrison, S. M.; Sarrazin, P.; Spanovich, N.; Stolper, E. M.; Treiman, A. H.; Vaniman, D. T.; Yen, A. S.

    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 the Rocknest samples.

  6. 21 CFR 73.2299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2299 Ferric ferrocyanide. (a) Identity and... coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in...

  7. 21 CFR 73.2299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2299 Ferric ferrocyanide. (a) Identity and... coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in...

  8. 21 CFR 73.2299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2299 Ferric ferrocyanide. (a) Identity and... coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in...

  9. 21 CFR 73.2299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2299 Ferric ferrocyanide. (a) Identity and... coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in...

  10. 21 CFR 73.2299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2299 Ferric ferrocyanide. (a) Identity and... coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in...

  11. Hydrolysis of ferric chloride in solution

    SciTech Connect

    Lussiez, G.; Beckstead, L.

    1996-11-01

    The Detox{trademark} process uses concentrated ferric chloride and small amounts of catalysts to oxidize organic compounds. It is under consideration for oxidizing transuranic organic wastes. Although the solution is reused extensively, at some point it will reach the acceptable limit of radioactivity or maximum solubility of the radioisotopes. This solution could be cemented, but the volume would be increased substantially because of the poor compatibility of chlorides and cement. A process has been developed that recovers the chloride ions as HCl and either minimizes the volume of radioactive waste or permits recycling of the radioactive chlorides. The process involves a two-step hydrolysis at atmospheric pressure, or preferably under a slight vacuum, and relatively low temperature, about 200{degrees}C. During the first step of the process, hydrolysis occurs according to the reaction below: FeCl{sub 3 liquid} + H{sub 2}O {r_arrow} FeOCl{sub solid} + 2 HCl{sub gas} During the second step, the hot, solid, iron oxychloride is sprayed with water or placed in contact with steam, and hydrolysis proceeds to the iron oxide according to the following reaction: 2 FeOCl{sub solid} + H{sub 2}O {r_arrow} Fe{sub 2}O{sub 3 solid} + 2 HCl{sub gas}. The iron oxide, which contains radioisotopes, can then be disposed of by cementation or encapsulation. Alternately, these chlorides can be washed off of the solids and can then either be recycled or disposed of in some other way.

  12. Spectrophotometric Ferric Ion Biosensor From Pseudomonas fluorescens Culture

    E-print Network

    Mittal, Aditya

    ARTICLE Spectrophotometric Ferric Ion Biosensor From Pseudomonas fluorescens Culture Varun Gupta Engineering and Biotechnology, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India broth supernatant as a robust ferric ions biosensor. For characterizing the ferric ions biosensor, we

  13. 21 CFR 184.1301 - Ferric phosphate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...O, CAS Reg. No. 10045-86-0) is an odorless, yellowish-white to buff-colored powder and contains from one to four molecules of water of hydration. It is prepared by reaction of sodium phosphate with ferric chloride or ferric citrate....

  14. Is superplasticity in the future of nanophase materials

    SciTech Connect

    Siegel, R.W.

    1990-07-01

    The ultrafine grain sizes and high diffusivities in nanophase materials assembled from atomic clusters suggest that these materials may have a strong tendency toward superplastic mechanical behavior. Both small grain size and enhanced diffusivity can be expected to lead to increased diffusional creep rates as well as to a significantly greater propensity for grain boundary sliding. Recent mechanical properties measurements at room temperature on nanophase Cu, Pd, and TiO{sub 2}, however, give no indications of superplasticity. Nonetheless, significant ductility has been clearly demonstrated in these studies of both nanophase ceramics and metals. The synthesis of cluster-assembled nanophase materials is described and the salient features of what is known of their structure and mechanical properties is reviewed. Finally, the answer to the question posed in the title is addressed. 34 refs., 6 figs.

  15. Hematite, pyroxene, and phyllosilicates on Mars: Implications from oxidized impact melt rocks from Manicouagan Crater, Quebec, Canada

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.; Golden, D. C.; Bell, James F., III; Lauer, H. V., Jr.

    1995-01-01

    Visible and near-IR reflectivity, Mossbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to 15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250 C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration (Fe(3+)/Fe(sub tot)) and ranged from approx. 1000 nm (high-Ca pyroxene) to approx. 850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900-920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the 850 and 1000 nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900-920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250 C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relatively high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from analyses of soil at the two Viking landing sites.

  16. Hematite, pyroxene, and phyllosilicates on Mars: Implications from oxidized impact melt rocks from Manicouagan Crater, Quebec, Canada

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.; Golden, D. C.; Bell, James F., III; Lauer, H. V., Jr.

    1995-01-01

    Visible and near-IR refectivity, Moessbauer, and X ray diffraction data were obtained on powders of impact melt rock from the Manicouagan Impact Crater located in Quebec, Canada. The iron mineralogy is dominated by pyroxene for the least oxidized samples and by hematite for the most oxidized samples. Phyllosilicate (smectite) contents up to approximately 15 wt % were found in some heavily oxidized samples. Nanophase hematite and/or paramagnetic ferric iron is observed in all samples. No hydrous ferric oxides (e.g., goethite, lepidocrocite, and ferrihydrite) were detected, which implies the alteration occurred above 250 C. Oxidative alteration is thought to have occurred predominantly during late-stage crystallization and subsolidus cooling of the impact melt by invasion of oxidizing vapors and/or solutions while the impact melt rocks were still hot. The near-IR band minimum correlated with the extent of aleration Fe(3+)/Fe(sub tot) and ranged from approximately 1000 nm (high-Ca pyroxene) to approximately 850 nm (bulk, well-crystalline hematite) for least and most oxidized samples, respectively. Intermediate band positions (900-920 nm) are attributed to low-Ca pyroxene and/or a composite band from hematite-pyroxene assemblages. Manicouagan data are consistent with previous assignments of hematite and pyroxene to the approximately 850 and approximately 1000nm bands observed in Martian reflectivity spectra. Manicouagan data also show that possible assignments for intermediate band positions (900-920 nm) in Martian spectra are pyroxene and/or hematite-pyroxene assemblages. By analogy with impact melt sheets and in agreement with observables for Mars, oxidative alteration of Martian impact melt sheets above 250 C and subsequent erosion could produce rocks and soils with variable proportions of hematite (both bulk and nanophase), pyroxene, and phyllosilicates as iron-bearing mineralogies. If this process is dominant, these phases on Mars were formed rapidly at relativly high temperatures on a sporadic basis throughout the history of the planet. The Manicouagan samples also show that this mineralogical diversity can be accomplished at constant chemical composition, which is also indicated for Mars from the analyses of soil at the two Viking landing sites.

  17. Hydrogen Storage in Nano-Phase Diamond at High Temperature and Its Release

    SciTech Connect

    Tushar K Ghosh

    2008-10-13

    The objectives of this proposed research were: 91) Separation and storage of hydrogen on nanophase diamonds. It is expected that the produced hydrogen, which will be in a mixture, can be directed to a nanophase diamond system directly, which will not only store the hydrogen, but also separate it from the gas mixture, and (2) release of the stored hydrogen from the nanophase diamond.

  18. Transparent monolithic metal ion containing nanophase aerogels

    SciTech Connect

    Risen, W. M., Jr.; Hu, X.; Ji, S.; Littrell, K.

    1999-12-01

    The formation of monolithic and transparent transition metal containing aerogels has been achieved through cooperative interactions of high molecular weight functionalized carbohydrates and silica precursors, which strongly influence the kinetics of gelation. After initial gelation, subsequent modification of the ligating character of the system, coordination of the group VIII metal ions, and supercritical extraction afford the aerogels. The structures at the nanophase level have been probed by photon and electron transmission and neutron scattering techniques to help elucidate the basis for structural integrity together with the small entity sizes that permit transparency in the visible range. They also help with understanding the chemical reactivities of the metal-containing sites in these very high surface area materials. These results are discussed in connection with new reaction studies.

  19. Superhard nanophase materials for rock drilling applications

    SciTech Connect

    Sadangi, R.K.; Voronov, O.A.; Tompa, G.S.; Kear, B.H.

    1997-12-31

    Diamond Materials Incorporated is developing new class of superhard materials for rock drilling applications. In this paper, we will describe two types of superhard materials, (a) binderless polycrystalline diamond compacts (BPCD), and (b) functionally graded triphasic nanocomposite materials (FGTNC). BPCDs are true polycrystalline diamond ceramic with < 0.5 wt% binders and have demonstrated to maintain their wear properties in a granite-log test even after 700{degrees}C thermal treatment. FGTNCs are functionally-graded triphasic superhard material, comprising a nanophase WC/Co core and a diamond-enriched surface, that combine high strength and toughness with superior wear resistance, making FGTNC an attractive material for use as roller cone stud inserts.

  20. 21 CFR 184.1298 - Ferric citrate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Reg. No. 2338-05-8) is prepared from reaction of citric acid with ferric hydroxide. It is a compound of indefinite ratio of citric acid and iron. (b) The ingredient must be of a purity suitable for...

  1. 21 CFR 184.1298 - Ferric citrate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... Reg. No. 2338-05-8) is prepared from reaction of citric acid with ferric hydroxide. It is a compound of indefinite ratio of citric acid and iron. (b) The ingredient must be of a purity suitable for...

  2. 21 CFR 184.1298 - Ferric citrate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... prepared from reaction of citric acid with ferric hydroxide. It is a compound of indefinite ratio of citric acid and iron. (b) The ingredient must be of a purity suitable for its intended use. (c) In...

  3. 21 CFR 184.1298 - Ferric citrate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... Reg. No. 2338-05-8) is prepared from reaction of citric acid with ferric hydroxide. It is a compound of indefinite ratio of citric acid and iron. (b) The ingredient must be of a purity suitable for...

  4. 21 CFR 73.2299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION...specifications. The color additive ferric ferrocyanide shall...amounts consistent with good manufacturing practice. (c) Labeling. The color additive and any mixture...

  5. 21 CFR 73.2299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION...specifications. The color additive ferric ferrocyanide shall...amounts consistent with good manufacturing practice. (c) Labeling. The color additive and any mixture...

  6. 21 CFR 73.2299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2299 Ferric ferrocyanide. (a...ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in amounts...

  7. 21 CFR 73.2299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2299 Ferric ferrocyanide. (a...ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in amounts...

  8. 21 CFR 73.2299 - Ferric ferrocyanide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2299 Ferric ferrocyanide. (a...ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in amounts...

  9. Superhard nanophase cutter materials for rock drilling applications

    SciTech Connect

    Voronov, O.; Tompa, G.; Sadangi, R.; Kear, B.; Wilson, C.; Yan, P.

    2000-06-23

    The Low Pressure-High Temperature (LPHT) System has been developed for sintering of nanophase cutter and anvil materials. Microstructured and nanostructured cutters were sintered and studied for rock drilling applications. The WC/Co anvils were sintered and used for development of High Pressure-High Temperature (HPHT) Systems. Binderless diamond and superhard nanophase cutter materials were manufactured with help of HPHT Systems. The diamond materials were studied for rock machining and drilling applications. Binderless Polycrystalline Diamonds (BPCD) have high thermal stability and can be used in geothermal drilling of hard rock formations. Nanophase Polycrystalline Diamonds (NPCD) are under study in precision machining of optical lenses. Triphasic Diamond/Carbide/Metal Composites (TDCC) will be commercialized in drilling and machining applications.

  10. Ferric chloride graphite intercalation compounds prepared from graphite fluoride

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh

    1994-01-01

    The reaction between graphite fluoride and ferric chloride was observed in the temperature range of 300 to 400 C. The graphite fluorides used for this reaction have an sp3 electronic structure and are electrical insulators. They can be made by fluorinating either carbon fibers or powder having various degrees of graphitization. Reaction is fast and spontaneous and can occur in the presence of air. The ferric chloride does not have to be predried. The products have an sp2 electronic structure and are electrical conductors. They contain first stage FeCl3 intercalated graphite. Some of the products contain FeCl2*2H2O, others contain FeF3 in concentrations that depend on the intercalation condition. The graphite intercalated compounds (GIC) deintercalated slowly in air at room temperature, but deintercalated quickly and completely at 370 C. Deintercalation is accompanied by the disappearing of iron halides and the formation of rust (hematite) distributed unevenly on the fiber surface. When heated to 400 C in pure N2 (99.99 vol %), this new GIC deintercalates without losing its molecular structure. However, when the compounds are heated to 800 C in quartz tube, they lost most of its halogen atoms and formed iron oxides (other than hematite), distributed evenly in or on the fiber. This iron-oxide-covered fiber may be useful in making carbon-fiber/ceramic-matrix composites with strong bonding at the fiber-ceramic interface.

  11. Iron metabolism in aerobes: managing ferric iron hydrolysis and ferrous iron autoxidation

    PubMed Central

    Kosman, Daniel J.

    2012-01-01

    Aerobes and anaerobes alike express a plethora of essential iron enzymes; in the resting state, the iron atom(s) in these proteins are in the ferrous state. For aerobes, ferric iron is the predominant environmental valence form which, given ferric iron’s aqueous chemistry, occurs as ‘rust’, insoluble, bio-inert polymeric ferric oxide that results from the hydrolysis of [Fe(H2O)6]3+. Mobilizing this iron requires bio-ferrireduction which in turn requires managing the rapid autoxidation of the resulting FeII which occurs at pH > 6. This review examines the aqueous redox chemistry of iron and the mechanisms evolved in aerobes to suppress the ‘rusting out’ of FeIII and the ROS-generating autoxidation of FeII so as to make this metal ion available as the most ubiquitous prosthetic group in metallobiology. PMID:23264695

  12. 21 CFR 73.1025 - Ferric ammonium citrate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... Section 73.1025 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF...ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1025 Ferric ammonium...complex chelates prepared by the interaction of ferric hydroxide with...

  13. Post.Doc Researcher Center for Nanophase Materials Sciences

    E-print Network

    Pennycook, Steve

    Youjun He Post.Doc Researcher Center for Nanophase Materials Sciences Oak Ridge National Laboratory National Laboratory. Post. Doc Researcher. 2010, 08-2011, 12 University of California, Los Angeles. Post. Doc Researcher. Research Synopsis: 1. Conjugated Polymer Donor Materials for Polymeric Solar Cell

  14. Postdoctoral Research Associate Center for Nanophase Materials Sciences

    E-print Network

    Pennycook, Steve

    1 Hui Wang Postdoctoral Research Associate Center for Nanophase Materials Sciences Oak Ridge Michigan Technological University Materials Science and Engineering Ph.D., 2013 Research Interests Science and Engineering B.S., 2006 Shandong University Materials Science and Engineering M.S., 2009

  15. 21 CFR 184.1298 - Ferric citrate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ferric citrate. 184.1298 Section 184.1298 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of Specific Substances Affirmed as GRAS §...

  16. Modeling ferrous ferric iron chemistry with application to martian surface geochemistry

    NASA Astrophysics Data System (ADS)

    Marion, Giles M.; Kargel, Jeffrey S.; Catling, David C.

    2008-01-01

    The Mars Global Surveyor, Mars Exploration Rover, and Mars Express missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major recent mission findings are the presence of jarosite (a ferric sulfate salt), which requires formation from an acid-sulfate brine, and the occurrence of hematite and goethite on Mars. Recent ferric iron models have largely focused on 25 °C, which is a major limitation for models exploring the geochemical history of cold bodies such as Mars. Until recently, our work on low-temperature iron-bearing brines involved ferrous but not ferric iron, also obviously a limitation. The objectives of this work were to (1) add ferric iron chemistry to an existing ferrous iron model (FREZCHEM), (2) extend this ferrous/ferric iron geochemical model to lower temperatures (<0 °C), and (3) use the reformulated model to explore ferrous/ferric iron chemistries on Mars. The FREZCHEM model is an equilibrium chemical thermodynamic model parameterized for concentrated electrolyte solutions using the Pitzer approach for the temperature range from <-70 to 25 °C and the pressure range from 1 to 1000 bars. Ferric chloride and sulfate mineral parameterizations were based, in part, on experimental data. Ferric oxide/hydroxide mineral parameterizations were based exclusively on Gibbs free energy and enthalpy data. New iron parameterizations added 23 new ferrous/ferric minerals to the model for this Na-K-Mg-Ca-Fe(II)-Fe(III)-H-Cl-SO 4-NO 3-OH-HCO 3-CO 3-CO 2-O 2-CH 4-H 2O system. The model was used to develop paragenetic sequences for Rio Tinto waters on Earth and a hypothetical Martian brine derived from acid weathering of basaltic minerals. In general, model simulations were in agreement with field evidence on Earth and Mars in predicting precipitation of stable iron minerals such as jarosites, goethite, and hematite. In addition, paragenetic simulations for Mars suggest that other iron minerals such as lepidocrocite, schwertmannite, ferricopiapite, copiapite, and bilinite may also be present on the surface of Mars. Evaporation or freezing of the Martian brine led to similar mineral precipitates. However, in freezing, compared to evaporation, the following key differences were found: (1) magnesium sulfates had higher hydration states; (2) there was greater total aqueous sulfate (SO 4T = SO 4 + HSO 4) removal; and (3) there was a significantly higher aqueous Cl/SO 4T ratio in the residual Na-Mg-Cl brine. Given the similarities of model results to observations, alternating dry/wet and freeze/thaw cycles and brine migration could have played major roles in vug formation, Cl stratification, and hematite concretion formation on Mars.

  17. 21 CFR 582.5306 - Ferric sodium pyrophosphate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Ferric sodium pyrophosphate. 582.5306 Section 582.5306 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED... Dietary Supplements 1 § 582.5306 Ferric sodium pyrophosphate. (a) Product. Ferric sodium pyrophosphate....

  18. Design of bulk nanocrystalline tungsten alloys via nano-phase separation sintering

    E-print Network

    Park, Mansoo, Ph. D. Massachusetts Institute of Technology

    2015-01-01

    An accelerated sintering method called 'nano-phase separation sintering' is developed, with specific applicability to nanostructured tungsten alloys. Nanocrystalline tungsten alloys containing minority additions of chromium ...

  19. Understanding Arsenate Reaction Kinetics with Ferric Hydroxides

    PubMed Central

    Farrell, James; Chaudhary, Binod K.

    2015-01-01

    Understanding arsenic reactions with ferric hydroxides is important in understanding arsenic transport in the environment and in designing systems for removing arsenic from potable water. Many experimental studies have shown that the kinetics of arsenic adsorption on ferric hydroxides is biphasic, where a fraction of the arsenic adsorption occurs on a time scale of seconds while full equilibrium may require weeks to attain. This research employed density functional theory modeling in order to understand the mechanisms contributing to biphasic arsenic adsorption kinetics. The reaction energies and activation barriers for three modes of arsenate adsorption to ferric hydroxides were calculated. Gibbs free energies of reaction depended on the net charge of the complexes, which is a function of the system pH value. Physical adsorption of arsenate to ferric hydroxide proceeded with no activation barrier, with Gibbs free energies of reaction ranging from ?21 to ?58 kJ/mol. The highest Gibbs free energies of reaction for physical adsorption resulted from negative charge assisted hydrogen bonding between H atoms on the ferric hydroxide and O atoms in arsenate. The conversion of physically adsorbed arsenate into monodentate surface complexes had Gibbs free energies of activation ranging from 62 to 73 kJ/mol, and Gibbs free energies of reaction ranging from ?23 to ?38 kJ/mol. The conversion of monodentate surface complexes to bidentate, binuclear complexes had Gibbs free energies of activation ranging from 79 to 112 kJ/mol, and Gibbs free energies of reaction ranging from ?11 to ?55 kJ/mol. For release of arsenate from uncharged bidentate complexes, energies of activation as high as 167 kJ/mol were encountered. Increasingly negative charges on the complexes lowered the activation barriers for desorption of arsenate, and in complexes with ?2 charges, the highest activation barrier was 65 kJ/mol. This study shows that the slow kinetics associated with arsenic adsorption and desorption can be attributed to the high Gibbs free energies of activation for forming and breaking bonds with the ferric hydroxide. PMID:23806140

  20. Three paradoxes of ferric enterobactin uptake.

    PubMed

    Klebba, Phillip E

    2003-09-01

    Bacteria elaborate iron chelators that scavenge iron from the environment, including their human and animal hosts, and iron acquisition is a determinant of pathogenicity. One such iron chelate, the siderophore ferric enterobactin, enters Gram-negative bacteria through the FepA protein of the outer membrane. The ferric enterobactin transport process is a high-affinity, multi-specific, multi-component, energy dependent reaction, that is a paradigm of ligand-gated transport: FeEnt binding activates FepA to transport competency. On the basis of the FepA, FhuA, FecA and BtuB crystal structures, and in light of recent molecular biological, biochemical, and biophysical findings, this review considers the mechanism of ferric enterobactin uptake. The discussion focuses on three preeminent questions about the transport reaction: the function of the N-terminal globular domain that resides within the FepA channel, the mechanistic contributions of TonB to the activities of ligand-gated porins, and the energy dependence of metal transport reactions through the OM bilayer. Available data points to the idea that the N-terminal globular domains of these receptor proteins dynamically exit their pores during transport, creating a suction-force that pulls ligands through the surface loops into the periplasm. The functions of TonB and energy in these processes remain unknown. PMID:12957833

  1. 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.

  2. Sinter-forging of nanophase TiO sub 2

    SciTech Connect

    Uchic, M.; Hofler, H.J.; Flick, W.J.; Tao, R.; Averback, R.S. . Dept. of Materials Science and Engineering); Kurath, P. . Dept. of Mechanical Engineering)

    1992-03-01

    Considerable effort has been directed in recent years to developing ceramic materials that can be both sintered to full density at low temperatures and processed by superplastic forming. One strategy for achieving this goal has been to reduce the particle size of the starting powder, and by anaphase processing, particles of sizes less than {approx}10 nm can now be realized. Indeed, recent studies on nanophase ceramics have demonstrated that sintering temperatures can be reduced dramatically and that nanophase ceramics have excellent potential for superplastic forming. Nevertheless, the grain growth that occurs during the processing of these new materials restricts their applicability. In nanophase (n-) TiO{sub 2}, some progress in controlling grain size has been achieved by using dopants or hot pressing. Sinter-forging offers another means to achieve this goal, although this method has been applied mostly to materials with larger grains. Studies of sinter-forging are also useful for elucidating the mechanisms of sintering and creep in ceramic materials. In the present paper, the authors examine the characteristics of sinter-forging in n-TiO{sub 2}. Only limited studies of sinter-forging have thus far been performed on well characterized powders of comparable size, and even these had a somewhat larger grain size.

  3. Ferric carboxymaltose: a review of its use in iron deficiency.

    PubMed

    Keating, Gillian M

    2015-01-01

    Ferric carboxymaltose (Ferinject(®), Injectafer(®)) is an intravenous iron preparation approved in numerous countries for the treatment of iron deficiency. A single high dose of ferric carboxymaltose (up to 750 mg of iron in the US and 1,000 mg of iron in the EU) can be infused in a short time frame (15 min). Consequently, fewer doses of ferric carboxymaltose may be needed to replenish iron stores compared with some other intravenous iron preparations (e.g. iron sucrose). Ferric carboxymaltose improved self-reported patient global assessment, New York Heart Association functional class and exercise capacity in patients with chronic heart failure and iron deficiency in two randomized, placebo-controlled trials (FAIR-HF and CONFIRM-HF). In other randomized controlled trials, ferric carboxymaltose replenished iron stores and corrected anaemia in various populations with iron-deficiency anaemia, including patients with chronic kidney disease, inflammatory bowel disease or heavy uterine bleeding, postpartum iron-deficiency anaemia and perioperative anaemia. Intravenous ferric carboxymaltose was generally well tolerated, with a low risk of hypersensitivity reactions. It was generally better tolerated than oral ferrous sulfate, mainly reflecting a lower incidence of gastrointestinal adverse effects. The most common laboratory abnormality seen in ferric carboxymaltose recipients was transient, asymptomatic hypophosphataemia. The higher acquisition cost of ferric carboxymaltose appeared to be offset by lower costs for other items, with the potential for cost savings. In conclusion, ferric carboxymaltose is an important option for the treatment of iron deficiency. PMID:25428711

  4. 40 CFR 415.380 - Applicability; description of the ferric chloride production subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...Applicability; description of the ferric chloride production subcategory. 415.380...MANUFACTURING POINT SOURCE CATEGORY Ferric Chloride Production Subcategory § 415.380 Applicability; description of the ferric chloride production subcategory. The...

  5. 40 CFR 415.380 - Applicability; description of the ferric chloride production subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...Applicability; description of the ferric chloride production subcategory. 415.380...MANUFACTURING POINT SOURCE CATEGORY Ferric Chloride Production Subcategory § 415.380 Applicability; description of the ferric chloride production subcategory. The...

  6. 40 CFR 415.380 - Applicability; description of the ferric chloride production subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...Applicability; description of the ferric chloride production subcategory. 415.380...MANUFACTURING POINT SOURCE CATEGORY Ferric Chloride Production Subcategory § 415.380 Applicability; description of the ferric chloride production subcategory. The...

  7. 40 CFR 415.380 - Applicability; description of the ferric chloride production subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...Applicability; description of the ferric chloride production subcategory. 415.380...MANUFACTURING POINT SOURCE CATEGORY Ferric Chloride Production Subcategory § 415.380 Applicability; description of the ferric chloride production subcategory. The...

  8. 40 CFR 415.380 - Applicability; description of the ferric chloride production subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...Applicability; description of the ferric chloride production subcategory. 415.380...MANUFACTURING POINT SOURCE CATEGORY Ferric Chloride Production Subcategory § 415.380 Applicability; description of the ferric chloride production subcategory. The...

  9. 46 CFR 151.50-75 - Ferric chloride solution.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride...

  10. 46 CFR 151.50-75 - Ferric chloride solution.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride...

  11. 46 CFR 151.50-75 - Ferric chloride solution.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ...Shipping 5 2012-10-01 2012-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping...MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride solution. A containment system (cargo tank...

  12. 46 CFR 151.50-75 - Ferric chloride solution.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ...Shipping 5 2014-10-01 2014-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping...MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride solution. A containment system (cargo tank...

  13. 46 CFR 151.50-75 - Ferric chloride solution.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ...Shipping 5 2013-10-01 2013-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping...MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride solution. A containment system (cargo tank...

  14. 46 CFR 151.50-75 - Ferric chloride solution.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ...Shipping 5 2010-10-01 2010-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping...MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride solution. A containment system (cargo tank...

  15. 46 CFR 151.50-75 - Ferric chloride solution.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ...Shipping 5 2011-10-01 2011-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping...MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride solution. A containment system (cargo tank...

  16. 46 CFR 151.50-75 - Ferric chloride solution.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride...

  17. 46 CFR 151.50-75 - Ferric chloride solution.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride...

  18. 46 CFR 151.50-75 - Ferric chloride solution.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride...

  19. Energy transduction by anaerobic ferric iron respiration in Thiobacillus ferrooxidans

    SciTech Connect

    Pronk, J.T.; Liem, K.; Bos, P.; Kuenen, J.G. )

    1991-07-01

    Formate-grown cells of the obligately chemolithoautotrophic acidophile Thiobacillus ferrooxidans were capable of formate- and elemental sulfur-dependent reduction of ferric iron under anaerovic conditions. Under aerobic conditions, both oxygen and ferric iron could be simultaneously used as electron acceptors. To investigate whether anaerobic ferric iron respiration by T. ferrooxidans is an energy-transducing process, uptake of amino acids was studied. Glycine uptake by starved cells did not occur in the absence of an electron donor, neither under aerobic conditions nor under anaerobic conditions. Uptake of glycine could be driven by formate- and ferrous iron-dependent oxygen uptake. Under anaerobic conditions, ferric iron respiration with the electron donors formate and elemental sulfur could energize glycine uptake. Glycine uptake was inhibited by the uncoupler 2,4-dinitrophenol. The results indicate that anaerobic ferric iron respiration can contribute to the energy budget of T. ferrooxidans.

  20. Anacardic acids and ferric ion chelation.

    PubMed

    Tsujimoto, Kazuo; Hayashi, Akio; Ha, Tae Joung; Kubo, Isao

    2007-01-01

    6-Pentadeca(e)nylsalicylic acids isolated from the cashew Anacardium occidentale L. (Anacardiaceae), commonly known as anacardic acids, inhibited the linoleic acid peroxidation catalyzed by soybean lipoxygenase-1 (EC 1.13.11.12, type 1) competitively without prooxidant effects. Their parent compound, salicylic acid, did not have this inhibitory activity up to 800 pm, indicating that the pentadeca(e)nyl group is an essential element to elicit the activity. The inhibition is attributed to its ability to chelate iron in the enzyme. Thus, anacardic acids chelate iron in the active site of the enzyme and then the hydrophobic tail portion slowly begins to interact with the hydrophobic domain close to the active site. Formation of the anacardic acids-ferric ion complex was detected in the ratio of 2:1 as the base peak in the negative ion electrospray ionization mass spectrometry. Hence, anacardic acids inhibit both Eox and Ered forms. PMID:18069245

  1. Nickel hydroxide and other nanophase cathode materials for rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Reisner, David E.; Salkind, Alvin J.; Strutt, Peter R.; Xiao, T. Danny

    The staff of US Nanocorp, Inc. are developing unique nanostructured materials for a wide range of applications in the areas of energy storage (batteries and ultracapacitors) and energy conversion (fuel cells and thermoelectric) devices. Many of the preparations of these materials exploit a wet synthesis process (patent pending) that is scaleable to large volume manufacturing and anticipated to be low in cost. Specifically, both the ?-form of nickel hydroxide and the hollandite form of manganese dioxide have been synthesized. The hexagonal Ni(OH) 2 is anticipated to significantly boost energy densities in nickel-alkaline batteries, including nickel/cadmium, nickel/metal hydride and nickel/zinc. The nanophase MnO 2 microstructure exhibits an unusual tunnelled tubular geometry within a 'bird's nest' superstructure, and is expected to be of interest as an intercalation cathode material in lithium-ion systems as well as a catalyst for fuel cells. Characterization of these materials has been by the techniques of high resolution SEM and TEM, as well as XRD. Both Hg porosimetry and BET surface measurements for conventional and spherical nickel hydroxides are summarized. Pore distribution and electrochemical activity for the nanophase materials will be examined in the future.

  2. 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. PMID:25128452

  3. Ferric chloride based downstream process for microalgae based biodiesel production.

    PubMed

    Seo, Yeong Hwan; Sung, Mina; Kim, Bohwa; Oh, You-Kwan; Kim, Dong Yeon; Han, Jong-In

    2015-04-01

    In this study, ferric chloride (FeCl3) was used to integrate downstream processes (harvesting, lipid extraction, and esterification). At concentration of 200 mg/L and at pH 3, FeCl3 exhibited an expected degree of coagulation and an increase in cell density of ten times (170 mg/10 mL). An iron-mediated oxidation reaction, Fenton-like reaction, was used to extract lipid from the harvested biomass, and efficiency of 80% was obtained with 0.5% H2O2 at 90 °C. The iron compound was also employed in the esterification step, and converted free fatty acids to fatty acid methyl esters under acidic conditions; thus, the fatal problem of saponification during esterification with alkaline catalysts was avoided, and esterification efficiency over 90% was obtained. This study clearly showed that FeCl3 in the harvesting process is beneficial in all downstream steps and have a potential to greatly reduce the production cost of microalgae-originated biodiesel. PMID:25647024

  4. Immobilization of arsenite and ferric iron by Acidithiobacillus ferrooxidans and its relevance to acid mine drainage.

    PubMed

    Duquesne, K; Lebrun, S; Casiot, C; Bruneel, O; Personné, J-C; Leblanc, M; Elbaz-Poulichet, F; Morin, G; Bonnefoy, V

    2003-10-01

    Weathering of the As-rich pyrite-rich tailings of the abandoned mining site of Carnoulès (southeastern France) results in the formation of acid waters heavily loaded with arsenic. Dissolved arsenic present in the seepage waters precipitates within a few meters from the bottom of the tailing dam in the presence of microorganisms. An Acidithiobacillus ferrooxidans strain, referred to as CC1, was isolated from the effluents. This strain was able to remove arsenic from a defined synthetic medium only when grown on ferrous iron. This A. ferrooxidans strain did not oxidize arsenite to arsenate directly or indirectly. Strain CC1 precipitated arsenic unexpectedly as arsenite but not arsenate, with ferric iron produced by its energy metabolism. Furthermore, arsenite was almost not found adsorbed on jarosite but associated with a poorly ordered schwertmannite. Arsenate is known to efficiently precipitate with ferric iron and sulfate in the form of more or less ordered schwertmannite, depending on the sulfur-to-arsenic ratio. Our data demonstrate that the coprecipitation of arsenite with schwertmannite also appears as a potential mechanism of arsenite removal in heavily contaminated acid waters. The removal of arsenite by coprecipitation with ferric iron appears to be a common property of the A. ferrooxidans species, as such a feature was observed with one private and three collection strains, one of which was the type strain. PMID:14532077

  5. Immobilization of Arsenite and Ferric Iron by Acidithiobacillus ferrooxidans and Its Relevance to Acid Mine Drainage

    PubMed Central

    Duquesne, K.; Lebrun, S.; Casiot, C.; Bruneel, O.; Personné, J.-C.; Leblanc, M.; Elbaz-Poulichet, F.; Morin, G.; Bonnefoy, V.

    2003-01-01

    Weathering of the As-rich pyrite-rich tailings of the abandoned mining site of Carnoulès (southeastern France) results in the formation of acid waters heavily loaded with arsenic. Dissolved arsenic present in the seepage waters precipitates within a few meters from the bottom of the tailing dam in the presence of microorganisms. An Acidithiobacillus ferrooxidans strain, referred to as CC1, was isolated from the effluents. This strain was able to remove arsenic from a defined synthetic medium only when grown on ferrous iron. This A. ferrooxidans strain did not oxidize arsenite to arsenate directly or indirectly. Strain CC1 precipitated arsenic unexpectedly as arsenite but not arsenate, with ferric iron produced by its energy metabolism. Furthermore, arsenite was almost not found adsorbed on jarosite but associated with a poorly ordered schwertmannite. Arsenate is known to efficiently precipitate with ferric iron and sulfate in the form of more or less ordered schwertmannite, depending on the sulfur-to-arsenic ratio. Our data demonstrate that the coprecipitation of arsenite with schwertmannite also appears as a potential mechanism of arsenite removal in heavily contaminated acid waters. The removal of arsenite by coprecipitation with ferric iron appears to be a common property of the A. ferrooxidans species, as such a feature was observed with one private and three collection strains, one of which was the type strain. PMID:14532077

  6. The crystal chemistry of ferric oxyhydroxyapatite.

    PubMed

    Low, H R; Phonthammachai, N; Maignan, A; Stewart, G A; Bastow, T J; Ma, L L; White, T J

    2008-12-15

    Ferric hydroxyapatites (Fe-HAp) and oxyapatites (Fe-OAp) of nominal composition [Ca(10-x)Fe(x)(3+)][(PO(4))(6)][(OH)(2-x)O(x)] (0 < or = x < or = 0.5) were synthesized from a coprecipitated precursor calcined under flowing nitrogen. The solid solubility of iron was temperature-dependent, varying from x = 0.5 after firing at 600 degrees C to x approximately 0.2 at 1000 degrees C, beyond which Fe-OAp was progressively replaced by tricalcium phosphate (Fe-TCP). Crystal size (13-116 nm) was controlled by iron content and calcination temperature. Ferric iron replaces calcium by two altervalent mechanisms in which carbonate and oxygen are incorporated as counterions. At low iron loadings, carbonate predominantly displaces hydroxyl in the apatite channels (Ca(2+) + OH(-) --> Fe(3+) + CO(3)(2-)), while at higher loadings, "interstitial" oxygen is tenanted in the framework (2Ca(2+) + (vac) --> 2Fe(3+) + O(2+)). Although Fe(3+) is smaller than Ca(2+), the unit cell dilates as iron enters apatite, providing evidence of oxygen injection that converts PO(4) tetrahedra to PO(5) trigonal bipyramids, leading to the crystal chemical formula [Ca(10-x)Fe(x)][(PO(4))(6-x/2)(PO(5))(x/2)][(OH)(2-y)O(2y)] (x < or = 0.5). A discontinuity in unit cell expansion at x approximately 0.2 combined with a substantial reduction of the carbonate FTIR fingerprint shows that oxygen infusion, rather than tunnel hydroxyl displacement, is dominant beyond this loading. This behavior is in contrast to ferrous-fluorapatite where Ca(2+) --> Fe(2+) aliovalent replacement does not require oxygen penetration and the cell volume contracts with iron loading. All of the materials were paramagnetic, but at low iron concentrations, a transition arising from crystallographic modification or a change in spin ordering is observed at 90 K. The excipient behavior of Fe-OAp was superior to that of HAp and may be linked to the crystalline component or mediated by a ubiquitous nondiffracting amorphous phase. Fe-HAp and Fe-OAp are not intrinsically suitable magnetic agents for drug delivery but may be useful in reactive cements that promote osteoblast proliferation. PMID:19007209

  7. Comparing polyaluminum chloride and ferric chloride for antimony removal.

    PubMed

    Kang, Meea; Kamei, Tasuku; Magara, Yasumoto

    2003-10-01

    Antimony has been one of the contaminants required to be regulated, however, only limited information has been collected to date regarding antimony removal by polyaluminium chloride (PACl) and ferric chloride (FC). Accordingly, the possible use of coagulation by PACl or FC for antimony removal was investigated. Jar tests were used to determine the effects of solution pH, coagulant dosage, and pre-chlorination on the removal of various antimony species. Although high-efficiency antimony removal by aluminum coagulation has been expected because antimony is similar to arsenic in that both antimony and arsenic are a kind of metalloid in group V of the periodic chart, this study indicated: (1) removal density (arsenic or antimony removed per mg coagulant) for antimony by PACl was about one forty-fifth as low as observed for As(V); (2) although the removal of both Sb(III) and Sb(V) by coagulation with FC was much higher than that of PACl, a high coagulant dose of 10.5mg of FeL(-1) at optimal pH of 5.0 was still not sufficient to meet the standard antimony level of 2 microg as SbL(-1) for drinking water when around 6 microg as SbL(-1) were initially present. Consequently, investigation of a more appropriate treatment process is necessary to develop economical Sb reduction; (3) although previous studies concluded that As(V) is more effectively removed than As(III), this study showed that the removal of Sb(III) by coagulation with FC was much more pronounced than that of Sb(V); (4) oxidation of Sb(III) with chlorine decreased the ability of FC to remove antimony. Accordingly, natural water containing Sb(III) under anoxic condition should be coagulated without pre-oxidation. PMID:12946899

  8. 21 CFR 73.2298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION...specifications. The color additive ferric ammonium ferrocyanide...amounts consistent with good manufacturing practice. (c) Labeling. The color additive and any mixture...

  9. 21 CFR 73.2298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION...specifications. The color additive ferric ammonium ferrocyanide...amounts consistent with good manufacturing practice. (c) Labeling. The color additive and any mixture...

  10. 21 CFR 73.2298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2298 Ferric ammonium ferrocyanide. (a... ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the...

  11. 21 CFR 73.2298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2298 Ferric ammonium ferrocyanide. (a... ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the...

  12. 21 CFR 73.2298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2298 Ferric ammonium ferrocyanide. (a... ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the...

  13. 21 CFR 73.2298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2298 Ferric ammonium ferrocyanide. (a... ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the...

  14. 21 CFR 73.2298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2298 Ferric ammonium ferrocyanide. (a... ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the...

  15. 21 CFR 73.2298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2298 Ferric ammonium ferrocyanide...ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in amounts...

  16. 21 CFR 73.2298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2298 Ferric ammonium ferrocyanide...ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in amounts...

  17. 21 CFR 73.2298 - Ferric ammonium ferrocyanide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2298 Ferric ammonium ferrocyanide...ferrocyanide is safe for use in coloring externally applied cosmetics, including cosmetics applied to the area of the eye, in amounts...

  18. Radiolytic formation of ferrous and ferric ions in carbon steel - deaerated water system

    NASA Astrophysics Data System (ADS)

    ?uba, Václav; Silber, Rostislav; Mú?ka, Viliam; Pospíšil, Milan; Neufuss, Sob?slav; Bárta, Jan; Vokál, Antonín

    2011-03-01

    The influence of gamma irradiation on the formation of Fe ions was investigated with respect to the expected ingress of groundwater into the disposal site with spent nuclear fuel containers. Deaerated conditions were ensured by working in an inert atmosphere. The kinetics of Fe 2+ and Fe 3+ formation in the presence of ionizing radiation was studied. Radiation increases the amount of corrosion products; it affects their composition mainly via radiation oxidation of ferrous to ferric ions. Characterization of crystalline solid corrosion products using X-ray powder diffraction was performed. Predominantly magnetite and lepidocrocite were found in solid phase.

  19. Magnetic phases in lunar fines - Metallic Fe or ferric oxides.

    NASA Technical Reports Server (NTRS)

    Tsay, F.-D.; Manatt, S. L.; Chan, S. I.

    1973-01-01

    The ferromagnetic resonance observed for the Apollo 11 and 12 lunar fines is characterized by an asymmetric lineshape with a narrower appearance on the high field side. This asymmetry together with an anisotropy energy which varies from +640 to +500 G over the temperature range of 80 to 298 K indicate that the ferromagnetic resonance arises from metallic Fe having the body-centered cubic structure and not from hematite, magnetite or other Fe(3+) ions in magnetite-like phases. The g-value, the lineshape asymmetry, and the temperature dependence of the linewidth for the Apollo 14 and 15 fines as reported by other workers are found to be essentially similar to those observed for the Apollo 11 and 12 fines.

  20. High Strain Rate Response of Sandwich Composites with Nanophased Cores

    NASA Astrophysics Data System (ADS)

    Mahfuz, Hassan; Uddin, Mohammed F.; Rangari, Vijaya K.; Saha, Mrinal C.; Zainuddin, Shaik; Jeelani, Shaik

    2005-05-01

    Polyurethane foam materials have been used as core materials in a sandwich construction with S2-Glass/SC-15 facings. The foam material has been manufactured from liquid polymer precursors of polyurethane. The precursors are made of two components; part-A (diphenylmethane diisocyanate) and part-B (polyol). In one set of experiments, part-A was mixed with part-B to manufacture the foam. In another set, TiO2 nanoparticles have been dispersed in part-A through ultrasonic cavitation technique. The loading of nanoparticles was 3% by weight of the total polymer precursor. The TiO2 nanoparticles were spherical in shape, and were about 29 nm in diameter. Sonic cavitation was carried out with a vibrasound liquid processor at 20 kHz frequency with a power intensity of about 100 kW/m2. The two categories of foams manufactured in this manner were termed as neat and nanophased. Sandwich composites were then fabricated using these two categories of core materials using a co-injection resin transfer molding (CIRTM) technique. Test samples extracted from the panel were subjected to quasi-static as well as high strain rate loadings. Rate of loading varied from 0.002 s-1 to around 1300 s-1. It has been observed that infusion of nanoparticles had a direct correlation with the cell geometry. The cell dimensions increased by about 46% with particle infusion suggesting that nanoparticles might have worked as catalysts during the foaming process. Correspondingly, enhancement in thermal properties was also noticed especially in the TGA experiments. There was also a significant improvement in mechanical properties due to nanoparticle infusion. Average increase in sandwich strength and energy absorption with nanophased cores was between 40 60% over their neat counterparts. Details of manufacturing and analyses of thermal and mechanical tests are presented in this paper.

  1. Hydrogen and Ferric Iron in Mars Materials

    NASA Technical Reports Server (NTRS)

    Dyar, Melinda D.

    2004-01-01

    Knowledge of oxygen and hydrogen fugacity is of paramount importance in constraining phase equilibria and crystallization processes of melts, as well as understanding the partitioning of elements between the cope and silicate portions of terrestrial planets. H and Fe(3+) must both be analyzed in order to reconstruct hydrogen and oxygen fugacities on Mars. To date, SIMS data have elucidated D/H and H contents of hydrous phases in SNC meteorites, but until now anhydrous martian minerals have not been systematically examined for trace hydrogen. Ferric iron has been quantified using XANES in many martian phases, but integrated studies of both Fe(3+) and H on the same spots are really needed to address the H budget. Finally, the effects of shock on both Fe(3+) and H in hydrous and anhydrous phases must be quantified. Thus, the overall goal of this research was to understand the oxygen and hydrogen fugacities under which martian samples crystallized. In this research one-year project, we approached this problem by 1) characterizing Fe(3+) and H contents of SNC meteorites using both bulk (Mossbauer spectroscopy and uranium extraction, respectively) and microscale (synchrotron micro-XANES and SIMS) methods; 2) relating Fe(3+) and H contents of martian minerals to their oxygen and hydrogen fugacities through analysis of experimentally equilibrated phases (for pyroxene) and through study of volcanic rocks in which the oxygen and hydrogen fugacities can be independently constrained (for feldspar); and 3) studying the effects of shock processes on Fe(3+) and H contents of the phases of interest. Results have been used to assess quantitatively the distribution of H and Fe(3+) among phases in the martian interior, which will better constrain the geodynamic processes of the interior, as well as the overall hydrogen and water budgets on Mars. There were no inventions funded by this research.

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

    E-print Network

    Downs, Robert T.

    -scale mineraloids that are amorphous or have short-range atomic order and result from incipient chemical weathering chemical weathering at Gale crater? To help answer this question, we synthesized a variety of nanophaseDetecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane

  3. Evidence of the direct involvement of the substrate TCP radical in functional switching from oxyferrous O2 carrier to ferric peroxidase in the dual-function hemoglobin/dehaloperoxidase from Amphitrite ornata.

    PubMed

    Sun, Shengfang; Sono, Masanori; Du, Jing; Dawson, John H

    2014-08-01

    The coelomic O2-binding hemoglobin dehaloperoxidase (DHP) from the sea worm Amphitrite ornata is a dual-function heme protein that also possesses a peroxidase activity. Two different starting oxidation states are required for reversible O2 binding (ferrous) and peroxidase (ferric) activity, bringing into question how DHP manages the two functions. In our previous study, the copresence of substrate 2,4,6-trichlorophenol (TCP) and H2O2 was found to be essential for the conversion of oxy-DHP to enzymatically active ferric DHP. On the basis of that study, a functional switching mechanism involving substrate radicals (TCP(•)) was proposed. To further support this mechanism, herein we report details of our investigations into the H2O2-mediated conversion of oxy-DHP to the ferric or ferryl ([TCP] < [H2O2]) state triggered by both biologically relevant [TCP and 4-bromophenol (4-BP)] and nonrelevant (ferrocyanide) compounds. At <50 ?M H2O2, all of these conversion reactions are completely inhibited by ferric heme ligands (KCN and imidazole), indicating the involvement of ferric DHP. Furthermore, the spin-trapping reagent 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) effectively inhibits the TCP/4-BP (but not ferrocyanide)-triggered conversion of oxy-DHP to ferric DHP. These results and O2 concentration-dependent conversion rates observed in this study demonstrate that substrate TCP triggers the conversion of oxy-DHP to a peroxidase by TCP(•) oxidation of the deoxyferrous state. TCP(•) is progressively generated, by increasingly produced amounts of ferric DHP, upon H2O2 oxidation of TCP catalyzed initially by trace amounts of ferric enzyme present in the oxy-DHP sample. The data presented herein further address the mechanism of how the halophenolic substrate triggers the conversion of hemoglobin DHP into a peroxidase. PMID:24972312

  4. Use of ferric sulfate: acid media for the desulfurization of model compounds of coal. [Dibenzothiophene, diphenyl sulfide, di-n-butyl sulfide

    SciTech Connect

    Clary, L.R.; Vermeulen, T.; Lynn, S.

    1980-12-01

    The objective of this work has been to investigate the ability of ferric sulfate-acid leach systems to oxidize the sulfur in model compounds of coal. Ferric iron-acid leach systems have been shown to be quite effective at removal of inorganic sulfur in coal. In this study, the oxidative effect of ferric iron in acid-leach systems was studied using dibenzothiophene, diphenyl sulfide, and di-n-butyl sulfide as models of organic sulfur groups in coal. Nitrogen and oxygen, as well as various transition metal catalysts and oxidants, were utilized in this investigation. Dibenzothiophene was found to be quite refractory to oxidation, except in the case where metavanadate was added, where it appears that 40% oxidation to sulfone could have occurred per hour at 150/sup 0/C and mild oxygen pressure. Diphenyl sulfide was selectively oxidized to sulfoxide and sulfone in an iron and oxygen system. Approximately 15% conversion to sulfone occurred per hour under these conditions. Some of the di-n-butyl sulfide was cracked to 1-butene and 1-butanethiol under similar conditions. Zinc chloride and ferric iron were used at 200/sup 0/C in an attempt to desulfonate dibenzothiophene sulfone, diphenyl sulfone, and di-n-butyl sulfone. Di-n-butyl sulfone was completely desulfurized on one hour and fragmented to oxidized parafins, while dibenzothiophene sulfone and diphenyl sulfone were unaffected. These results suggest that an iron-acid leach process could only selectively oxidize aryl sulfides under mild conditions, representing only 20% of the organic sulfur in coal (8% of the total sulfur). Removal through desulfonation once selective sulfur oxidation had occurred was only demonstrated for alkyl sulfones, with severe oxidation of the fragmented paraffins also occurring in one hour.

  5. Nanophase Fe alloys consolidated to full density from mechanically milled powders

    SciTech Connect

    He, L.; Allard, L. F.; Breder, K.; Ma, E.

    2000-04-01

    Nanophase elemental Fe powders prepared by mechanical milling were sinter forged to full density with an average grain size in the nanophase range (below 100 nm). If Cu additions are introduced during milling to form supersaturated solid solutions (Fe{sub 85}Cu{sub 15} and Fe{sub 60}Cu{sub 40}), grain sizes can be easily controlled to below 50 nm after consolidation. For Fe-Cu, it was observed that atomic level alloying between the two elements during milling was very helpful for obtaining a homogeneous microstructure and nanocrystalline grain/domain sizes in the consolidated product. The advantages of using sinter forging (upset die forging), as well as the role of the Cu addition, in the retention of nanocrystalline grain sizes are discussed. The consolidated Fe alloys exhibit very high strength under compression, further demonstrating that low populations of flaws and nanophase grain structures were attained in the consolidated products. (c) 2000 Materials Research Society.

  6. Preparation of nanophase M-type ferrite and its laser-attenuated characteristics

    NASA Astrophysics Data System (ADS)

    Liu, Xiang-Cui; Cheng, Xiang; Zhang, Liang; Liu, Jian-Hui; Du, Gui-Ping

    2011-07-01

    By citrate sol-gel auto-combustion method, the nanophase M-type planar hexagonal ferrite is prepared. The transmission electron microscopy (TEM), X-ray diffraction (XRD) and thermal analysis are used to study the grain size, phase composition, microstructure and crystallization process. The results show that the nanophase M-type Sr-ferrite prepared by this method is single, and its grain size is smaller than 100 nm. Moreover, most of the grains present hexagonal sheet shape. Tests are carried out for its attenuation to 1.06 ?m laser. It is found that the extinction capability of the nanophase M-type Sr-ferrite smoke is good, and its mass extinction coefficient is 1.628 m2/g.

  7. Bacterial Formation of As(V) and As(III) Ferric Oxyhydroxides in Acid Mine Drainage.

    NASA Astrophysics Data System (ADS)

    Morin, G.; Juillot, F.; Lebrun, S.; Casiot, C.; Elbaz-Poulichet, F.; Bruneel, O.; Personne, J.; Leblanc, M.; Ildefonse, P.; Calas, G.

    2002-12-01

    The oxidation of dissolved Fe(II) which is often promoted by acidophilic bacteria in acid mine drainage (AMD) and some hot springs, leads to the precipitation of Fe(III) oxy-hydroxides which incorporate toxic elements within their structure or adsorb them at their surface, thus limiting their mobility. In such complex natural systems, synchrotron-based techniques as X-ray absorption spectroscopy offer the opportunity to monitor surface/solution interactions as well as redox changes affecting the mobility and toxicity of trace elements as arsenic. Spatial and seasonal variations of the (bio-) oxidation of Fe(II) and As(III), and the subsequent precipitation of As-Fe gels, were followed by XANES, XRD, and SEM along the CarnoulŠs AMD (Gard, France). Chemical and mineralogical data collected on sediments, stromatolite, and bioassay samples showed that some indigenous bacteria living in the As-rich CarnoulŠs water ([As] = up to 350 mg.l-1) play an important role in the nature and composition of the solid phases that sequester arsenic at the site. The formation of nano-crystalline and amorphous As(III) ferric oxy-hydroxides has been related to the presence of bacteria able to oxidize Fe(II) but not As(III), which are only present in winter in the upstream area. A rare ferric arsenite sulfate oxy-hydroxide mineral was discovered in this context. Other types of bacteria, occurring in the downstream area whatever the season, are able to catalyze As(III) to As(V) oxidation and, provided that enough Fe(II) oxidizes, promote the formation of amorphous As(V) rich ferric oxy-hydroxides. These bacterially mediated reactions significantly reduce the concentration of dissolved As(III), which is more toxic and mobile than As(V), and might thus be helpful for designing As-removal processes. This work was supported by the French PEVS and ACI Ecologie Quantitative Programs and the PIRAMID EC program. ?Deceased, 26 October 1999 Juillot F., Ildefonse Ph., Morin G., Calas G., De Kersabiec A.M. and Benedetti M. Applied Geochemistry 8, 1031-1048 (1999). Morin G., Lecocq D., Juillot F., Ildefonse Ph., Calas Bull. Soc. Géol. Fr. 173, 281-291 (2002). Morin G., Juillot F., Casiot C., Bruneel O., Personné J-C., Elbaz-Poulichet F., Leblanc M., Ildefonse P. and Calas G. Environ. Sci. Technol (in review.)

  8. Optimization of ferric hydroxide coprecipitation process for selenium removal from petroleum refinery stripped four water

    SciTech Connect

    Gerhardt, M.B.; Marrs, D.R.; Roehl, R.

    1996-12-31

    Iron coprecipitation was used in bench-scale tests to remove selenium from stripped sour water generated by two petroleum refineries. Chlorine dioxide and hydrogen peroxide were found to convert selenocyanate in the stripped sour water to selenite, which can be removed by iron coprecipitation. An iodometric titration procedure was developed to determine the required oxidant dose. Iron coprecipitation reduced selenium concentrations by 40 to 99 percent in stripped sour water after chlorine dioxide pretreatment Removal was less effective with hydrogen peroxide as the oxidant: total selenium concentrations were reduced by 28 to 92 percent in stripped sour water after hydrogen peroxide pretreatment. Highest removals were obtained at the highest oxidant and iron doses. Sludges produced in coprecipitation tests were hazardous under California regulations. Ozone oxidized selenocyanate but prevented ferric hydroxide precipitation or coagulation. Air was ineffective at selenocyanate oxidation. Repeatedly contacting iron hydroxide with stripped sour water pretreated with hydrogen peroxide, in a simulation of a countercurrent adsorption process, increased the selenium adsorbed on the solids from 32 to 147 pg selenium per mg of iron, but some of the adsorbed selenite was oxidized to selenate and desorbed back into solution.

  9. Statistics of sub-Poissonian nucleation in a nanophase

    NASA Astrophysics Data System (ADS)

    Glas, Frank

    2014-09-01

    We develop a fully analytical calculation of the sub-Poissonian statistics resulting from the temporal anticorrelation of the nucleation events in a supersaturated nanophase, such as occurs in particular during vapor-liquid-solid growth of nanowires [F. Glas, J. C. Harmand, and G. Patriarche, Phys. Rev. Lett. 104, 135501 (2010), 10.1103/PhysRevLett.104.135501]. The sequence of nucleation events is modeled as a stochastic Markov process. The deviation from Poisson statistics is quantified by a single parameter ?, namely the ratio of the nucleation probabilities immediately after and before nucleation. We first determine self-consistently, by using q-calculus, the densities of probability of the nucleation probability, both when nucleation occurs and at an arbitrary instant. We then derive the probability for having a given number of nucleations in any given time interval. The distribution of these probabilities shows a marked narrowing with respect to Poisson statistics, in agreement with our previous experiments. We calculate explicitly the standard deviation of this distribution, which quickly saturates as the length of the time interval increases. Finally, we compute the distribution of the waiting times between nucleations. We discuss how the computed quantities vary with parameter ?. The results are in complete agreement with our numerical simulations. Somewhat surprisingly, a marked narrowing of the distribution of the numbers of nucleations occurring in fixed time intervals appears as fully compatible with a very broad distribution of waiting times.

  10. Surface Enthalpies of Nanophase ZnO with Different Morphologies

    SciTech Connect

    Zhang, Peng; Xu, Fen; Navrotsky, Alexandra; Lee, Jong Soo; Kim, Sangtae; Liu, Jun

    2007-11-13

    A direct calorimetric measurement of the dependence of the surface enthalpy of nanophase ZnO on morphology is reported. Nanoparticles, nanoporous composites, nanorods, and nanotetrapods were prepared with various sizes and their surface enthalpies were derived from their drop solution enthalpies in molten sodium molybdate. Water adsorption calorimetry for nanoparticles and nanorods was carried out to characterize the stabilization effect of surface hydration. The surface enthalpies of hydrated surfaces for nanoparticles, nanoporous composites, nanorods and nanotetrapods are 1.31±0.07, 1.42±0.21, 5.19±0.56, and 5.77±2.50 J/m2, respectively, while those of the anhydrous surfaces are 2.55±0.23, 2.74±0.16, 6.67±0.56, and 7.28±2.50 J/m2. The surface enthalpies of nanoparticles are the same as those of nanoporous composites, and are much lower than those of nanorods and nanotetrapods, which are also close to each other. The dependence of surface enthalpy on morphology is discussed in terms of exposed surface structures. This is the first time that calorimetry on nanocrystalline powders bas been able to detect differences in surface energetics of materials having different morphologies.

  11. 21 CFR 184.1296 - Ferric ammonium citrate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ferric ammonium citrate. 184.1296 Section 184.1296 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of Specific Substances Affirmed as GRAS...

  12. 21 CFR 184.1296 - Ferric ammonium citrate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... prepared by the reaction of ferric hydroxide with citric acid, followed by treatment with ammonium..., approximately 9 percent ammonia, and 65 percent citric acid and occurs as reddish brown or garnet red scales or..., approximately 7.5 percent ammonia, and 75 percent citric acid and occurs as thin transparent green scales,...

  13. 21 CFR 184.1296 - Ferric ammonium citrate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... citrate (iron (III) ammonium citrate) is prepared by the reaction of ferric hydroxide with citric acid... 18.5 percent iron, approximately 9 percent ammonia, and 65 percent citric acid and occurs as reddish... composed of 14.5 to 16 percent iron, approximately 7.5 percent ammonia, and 75 percent citric acid...

  14. 21 CFR 184.1296 - Ferric ammonium citrate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... citrate (iron (III) ammonium citrate) is prepared by the reaction of ferric hydroxide with citric acid... 18.5 percent iron, approximately 9 percent ammonia, and 65 percent citric acid and occurs as reddish... composed of 14.5 to 16 percent iron, approximately 7.5 percent ammonia, and 75 percent citric acid...

  15. 21 CFR 184.1296 - Ferric ammonium citrate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... citrate (iron (III) ammonium citrate) is prepared by the reaction of ferric hydroxide with citric acid... 18.5 percent iron, approximately 9 percent ammonia, and 65 percent citric acid and occurs as reddish... composed of 14.5 to 16 percent iron, approximately 7.5 percent ammonia, and 75 percent citric acid...

  16. Hydrolysis of ferric ion in water and conformational equilibrium

    E-print Network

    Martin, R L E; Pratt, L R; Martin, Richard L.; Pratt, Lawrence R.

    1998-01-01

    Reported here are results of theoretical calculations on the hexaaquoferric complex and deprotonated products to investigate the molecular mechanisms of hydrolysis of ferric ion in water. The combination of density functional electronic structure techniques and a dielectric continuum model for electrostatic solvation applied to the Fe(H$_2$O)$_6

  17. 40 CFR 415.380 - Applicability; description of the ferric chloride production subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... ferric chloride production subcategory. 415.380 Section 415.380 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Ferric Chloride Production Subcategory § 415.380 Applicability; description of the ferric chloride production subcategory. The provisions of this subpart are applicable to discharges and to...

  18. 40 CFR 415.380 - Applicability; description of the ferric chloride production subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... ferric chloride production subcategory. 415.380 Section 415.380 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Ferric Chloride Production Subcategory § 415.380 Applicability; description of the ferric chloride production subcategory. The provisions of this subpart are applicable to discharges and to...

  19. 40 CFR 180.1191 - Ferric phosphate; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Ferric phosphate; exemption from the... Exemptions From Tolerances § 180.1191 Ferric phosphate; exemption from the requirement of a tolerance. An..., ferric phosphate (FePO4, CAS No. 11045-86-0) in or on all food commodities....

  20. 40 CFR 180.1191 - Ferric phosphate; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Ferric phosphate; exemption from the... Exemptions From Tolerances § 180.1191 Ferric phosphate; exemption from the requirement of a tolerance. An..., ferric phosphate (FePO4, CAS No. 11045-86-0) in or on all food commodities....

  1. 40 CFR 180.1191 - Ferric phosphate; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Ferric phosphate; exemption from the... Exemptions From Tolerances § 180.1191 Ferric phosphate; exemption from the requirement of a tolerance. An..., ferric phosphate (FePO4, CAS No. 11045-86-0) in or on all food commodities....

  2. 40 CFR 180.1191 - Ferric phosphate; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Ferric phosphate; exemption from the... Exemptions From Tolerances § 180.1191 Ferric phosphate; exemption from the requirement of a tolerance. An..., ferric phosphate (FePO4, CAS No. 11045-86-0) in or on all food commodities....

  3. 40 CFR 180.1191 - Ferric phosphate; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Ferric phosphate; exemption from the... Exemptions From Tolerances § 180.1191 Ferric phosphate; exemption from the requirement of a tolerance. An..., ferric phosphate (FePO4, CAS No. 11045-86-0) in or on all food commodities....

  4. 40 CFR 415.380 - Applicability; description of the ferric chloride production subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... ferric chloride production subcategory. 415.380 Section 415.380 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Ferric Chloride Production Subcategory § 415.380 Applicability; description of the ferric chloride production subcategory. The provisions of this subpart are applicable to discharges and to...

  5. 40 CFR 415.380 - Applicability; description of the ferric chloride production subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... ferric chloride production subcategory. 415.380 Section 415.380 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Ferric Chloride Production Subcategory § 415.380 Applicability; description of the ferric chloride production subcategory. The provisions of this subpart are applicable to discharges and to...

  6. 40 CFR 415.380 - Applicability; description of the ferric chloride production subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... ferric chloride production subcategory. 415.380 Section 415.380 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Ferric Chloride Production Subcategory § 415.380 Applicability; description of the ferric chloride production subcategory. The provisions of this subpart are applicable to discharges and to...

  7. 40 CFR 180.1191 - Ferric phosphate; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...2013-07-01 2013-07-01 false Ferric phosphate; exemption from the requirement of a...From Tolerances § 180.1191 Ferric phosphate; exemption from the requirement of a...of the biochemical pesticide, ferric phosphate (FePO4 , CAS No....

  8. 40 CFR 180.1191 - Ferric phosphate; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...2014-07-01 2014-07-01 false Ferric phosphate; exemption from the requirement of a...From Tolerances § 180.1191 Ferric phosphate; exemption from the requirement of a...of the biochemical pesticide, ferric phosphate (FePO4 , CAS No....

  9. 40 CFR 180.1191 - Ferric phosphate; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...2012-07-01 2012-07-01 false Ferric phosphate; exemption from the requirement of a...From Tolerances § 180.1191 Ferric phosphate; exemption from the requirement of a...of the biochemical pesticide, ferric phosphate (FePO4 , CAS No....

  10. 40 CFR 180.1191 - Ferric phosphate; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...2010-07-01 2010-07-01 false Ferric phosphate; exemption from the requirement of a...From Tolerances § 180.1191 Ferric phosphate; exemption from the requirement of a...of the biochemical pesticide, ferric phosphate (FePO4 , CAS No....

  11. 40 CFR 180.1191 - Ferric phosphate; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...2011-07-01 2011-07-01 false Ferric phosphate; exemption from the requirement of a...From Tolerances § 180.1191 Ferric phosphate; exemption from the requirement of a...of the biochemical pesticide, ferric phosphate (FePO4 , CAS No....

  12. Ferric sulfate as pulpotomy agent in primary teeth: twenty month clinical follow-up.

    PubMed

    Ibricevic, H; al-Jame, Q

    2000-01-01

    Seventy primary molar teeth, carious exposed, symptom free, without any sign of root resorption in children aged from 3 to 6 years (main age 4.3 yr) were treated with conventional pulpotomy procedures. Ferric sulfate 15.5% solution (applied for 15 second for 35 teeth) and formocresol solution (five minute procedure of Buckley's formula for next 35 teeth) have been used as pulpotomy agents. In both groups, pulp stumps were covered with zinc-oxide eugenol paste. Permanent restorations were stainless steel crowns. Clinical check up was every three-months and radiographic follow-up time was six and twenty months after treatment. Our results within this period revealed 100% clinical success rate in both groups. Radiographic success rate was in both groups 97.2%, while in 2.8% cases has shown internal root resorption. On the basis of these results, we can recommend ferric sulfate as a pulpotomy agent in primary teeth in substitution for formocresol at the moment. PMID:11314410

  13. Pre-terrestrial oxidation products in carbonaceous meteorites identified by Mossbauer spectroscopy

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.; Fisher, Duncan S.

    1991-01-01

    The occurrence of ferric bearing assemblages, comprising phyllosilicates, oxide hydroxides and magnetite, in carbonaceous chondrites (CC) indicates that these meteorites underwent pre-terrestrial, sub-aqueous oxidation reactions. Reported here are results of a Mossbauer spectral study of a suite of CC demonstrating that a variety of ferrous and ferric bearing phases may be distinguished in different classes of this meteorite type.

  14. Synthesis, processing, and deformation of bulk nanophase Fe-28Al-2Cr intermetallic

    NASA Astrophysics Data System (ADS)

    Jain, M.; Christman, T.

    1994-06-01

    Nanophase Fe-28Al-2Cr powder was obtained by ball milling and consolidated by shock wave compaction. Fully-dense well-bonded compacts were produced with a diameter of 32 mm and a thickness approximately = 6 mm. The grain size in the compacts was approximately = 80 nm. In tension, the nanophase intermetallic is brittle with a failure strength (sigma(sub f) = 0.65 GPa) comparable to a coarse-grained intermetallic with similar composition. In compression, the nanophase material exhibits superplastic-like flow during room temperature quasistatic deformation to true strains greater than 1.4. The compressive flow strength is 2.1 GPa and no macroscopic strain hardening is observed. This behavior is compared to the coarse-grained material that has a yield strength of 0.25 GPa, displays significant work hardening and little tension-compression anisotropy. TEM examination of the nanophase material before and after deformation shows a refinement of the microstructure during deformation. The microstructure refines to approximately 10 nm grains surrounded by amorphous material.

  15. Synthesis, processing, and deformation of bulk nanophase Fe-28Al-2Cr intermetallic

    SciTech Connect

    Jain, M.; Christman, T. . W.M. Keck Lab. of Engineering Materials)

    1994-06-01

    Nanophase Fe-28Al-2Cr powder was obtained by ball milling and consolidated by shock wave compaction. Fully-dense well-bonded compacts were produced with a diameter of 32 mm and a thickness of [approx]6 mm. The grain size in the compacts was [approx]80 nm. In tension, the nanophase intermetallic is brittle with a failure strength ([sigma][sub f] = 0.65 GPa) comparable to a coarse-grained intermetallic with similar composition. In compression, the nanophase material exhibits superplastic-like flow during room temperature quasistatic deformation to true strains greater than 1.4. The compressive flow strength is 2.1 GPa and no macroscopic strain hardening is observed. This behavior is compared to the coarse-grained material that has a yield strength of 0.25 GPa, displays significant work hardening and little tension-compression anisotropy. TEM examination of the nanophase material before and after deformation shows a refinement of the microstructure during deformation. The microstructure refines to [approx]10 nm grains surrounded by amorphous material.

  16. Bacillus cereus iron uptake protein fishes out an unstable ferric citrate trimer

    PubMed Central

    Fukushima, Tatsuya; Sia, Allyson K.; Allred, Benjamin E.; Nichiporuk, Rita; Zhou, Zhongrui; Andersen, Ulla N.; Raymond, Kenneth N.

    2012-01-01

    Citrate is a common biomolecule that chelates Fe(III). Many bacteria and plants use ferric citrate to fulfill their nutritional requirement for iron. Only the Escherichia coli ferric citrate outer-membrane transport protein FecA has been characterized; little is known about other ferric citrate-binding proteins. Here we report a unique siderophore-binding protein from the Gram-positive pathogenic bacterium Bacillus cereus that binds multinuclear ferric citrate complexes. We have demonstrated that B. cereus ATCC 14579 takes up 55Fe radiolabeled ferric citrate and that a protein, BC_3466 [renamed FctC (ferric citrate-binding protein C)], binds ferric citrate. The dissociation constant (Kd) of FctC at pH 7.4 with ferric citrate (molar ratio 1:50) is 2.6 nM. This is the tightest binding observed of any B. cereus siderophore-binding protein. Nano electrospray ionization–mass spectrometry (nano ESI-MS) analysis of FctC and ferric citrate complexes or citrate alone show that FctC binds diferric di-citrate, and triferric tricitrate, but does not bind ferric di-citrate, ferric monocitrate, or citrate alone. Significantly, the protein selectively binds triferric tricitrate even though this species is naturally present at very low equilibrium concentrations. PMID:23027976

  17. Bacillus cereus iron uptake protein fishes out an unstable ferric citrate trimer.

    PubMed

    Fukushima, Tatsuya; Sia, Allyson K; Allred, Benjamin E; Nichiporuk, Rita; Zhou, Zhongrui; Andersen, Ulla N; Raymond, Kenneth N

    2012-10-16

    Citrate is a common biomolecule that chelates Fe(III). Many bacteria and plants use ferric citrate to fulfill their nutritional requirement for iron. Only the Escherichia coli ferric citrate outer-membrane transport protein FecA has been characterized; little is known about other ferric citrate-binding proteins. Here we report a unique siderophore-binding protein from the gram-positive pathogenic bacterium Bacillus cereus that binds multinuclear ferric citrate complexes. We have demonstrated that B. cereus ATCC 14579 takes up (55)Fe radiolabeled ferric citrate and that a protein, BC_3466 [renamed FctC (ferric citrate-binding protein C)], binds ferric citrate. The dissociation constant (K(d)) of FctC at pH 7.4 with ferric citrate (molar ratio 1:50) is 2.6 nM. This is the tightest binding observed of any B. cereus siderophore-binding protein. Nano electrospray ionization-mass spectrometry (nano ESI-MS) analysis of FctC and ferric citrate complexes or citrate alone show that FctC binds diferric di-citrate, and triferric tricitrate, but does not bind ferric di-citrate, ferric monocitrate, or citrate alone. Significantly, the protein selectively binds triferric tricitrate even though this species is naturally present at very low equilibrium concentrations. PMID:23027976

  18. Factors influencing the mechanism of surfactant catalyzed reaction of vitamin C-ferric chloride hexahydrate system

    NASA Astrophysics Data System (ADS)

    Farrukh, Muhammad Akhyar; Kauser, Robina; Adnan, Rohana

    2013-09-01

    The kinetics of vitamin C by ferric chloride hexahydrate has been investigated in the aqueous ethanol solution of basic surfactant viz. octadecylamine (ODA) under pseudo-first order conditions. The critical micelle concentration (CMC) of surfactant was determined by surface tension measurement. The effect of pH (2.5-4.5) and temperature (15-35°C) in the presence and absence of surfactant were investigated. Activation parameters, ? E a, ? H #, ? S #, ? G ?, for the reaction were calculated by using Arrhenius and Eyring plot. Surface excess concentration (?max), minimum area per surfactant molecule ( A min), average area occupied by each molecule of surfactant ( a), surface pressure at the CMC (?max), Gibb's energy of micellization (? G M°), Gibb's energy of adsorption (? G ad°), were calculated. It was found that the reaction in the presence of surfactant showed faster oxidation rate than the aqueous ethanol solution. Reaction mechanism has been deduced in the presence and absence of surfactant.

  19. Ferric-Thiolate Bond Dissociation Studied with Electronic Structure Calculations.

    PubMed

    Arantes, Guilherme Menegon; Field, Martin J

    2015-10-01

    The stability and reactivity of iron-sulfur clusters are fundamental properties for the biological function of these prosthetic groups. Here, we investigate the ferric-thiolate bond dissociation of model iron-sulfur tetrahedral complexes with high-level ab initio multiconfigurational electronic structure calculations. We find that the reaction mechanism is homolytic with a spin-crossing from the sextet state in the reactant to quartet state in the product. We also compare several density functionals and semiempirical configuration interaction with the high-level ab initio results to find an accurate but computationally more efficient method to describe the reaction. The functionals M06 and those based on the OPTX exchange functional show the best performance and may reasonably describe the various electron correlation effects involved in ferric-thiolate bond dissociation. PMID:26351881

  20. Paracoccidioides spp. ferrous and ferric iron assimilation pathways

    PubMed Central

    Bailão, Elisa Flávia L. C.; Lima, Patrícia de Sousa; Silva-Bailão, Mirelle G.; Bailão, Alexandre M.; Fernandes, Gabriel da Rocha; Kosman, Daniel J.; Soares, Célia Maria de Almeida

    2015-01-01

    Iron is an essential micronutrient for almost all organisms, including fungi. Usually, fungi can uptake iron through receptor-mediated internalization of a siderophore or heme, and/or reductive iron assimilation (RIA). Traditionally, the RIA pathway consists of ferric reductases (Fres), ferroxidase (Fet3) and a high-affinity iron permease (Ftr1). Paracoccidioides spp. genomes do not present an Ftr1 homolog. However, this fungus expresses zinc regulated transporter homologs (Zrts), members of the ZIP family of membrane transporters that are able in some organisms to transport zinc and iron. A 2,3,5-triphenyltetrazolium chloride (TTC)-overlay assay indicates that both Pb01 and Pb18 express a ferric reductase activity; however, 59Fe uptake assays indicate that only in Pb18 is this activity coupled to a reductase-dependent iron uptake pathway. In addition, Zrts are up-regulated in iron deprivation, as indicated by RNAseq and qRT-PCR using Pb01 transcripts. RNAseq strategy also demonstrated that transcripts related to siderophore uptake and biosynthesis are up-regulated in iron-deprived condition. The data suggest that the fungus could use both a non-classical RIA, comprising ferric reductases and Fe/Zn permeases (Zrts), and siderophore uptake pathways under iron-limited conditions. The study of iron metabolism reveals novel surface molecules that could function as accessible targets for drugs to block iron uptake and, consequently, inhibit pathogen's proliferation. PMID:26441843

  1. The effect of ferric iron concentration on lower mantle phase assemblage: Implications for mantle convection

    NASA Astrophysics Data System (ADS)

    Gu, T.; McCammon, C. A.; Lee, K. K. M.

    2014-12-01

    Earth's mantle connects the atmosphere with the deep interior through convection thus setting up a gradient of oxidation: currently the atmosphere is ~20% oxygen, while the core is mostly metallic iron. As the atmosphere has changed composition throughout Earth history, the redox evolution has proven to be critical to Earth's evolution and the origin of life. Despite its importance, the redox state of Earth's mantle is largely an enigma and its effect on composition, phase relations and the physicochemical properties of the mantle phases is controversial. It is expected that oxygen fugacity of the mantle decreases with increasing depth. However, some experiments show an increase in the ferric iron (Fe3+) concentration in Mg-silicate perovskite (bridgmanite)—the most abundant mineral in the Earth—with accompanying metallic Fe, and suggest that the trend in iron oxidation state is opposite. In this study, we take two samples of nearly identical bulk composition [enstatite chondrite composition (Javoy, 1995: Mg/Si ~0.77, Fe/Si ~0.26)] that only differ in the relative abundance of Fe3+ to the same synthesis conditions in a laser-heated diamond-anvil cell (LHDAC). We find that despite similar starting bulk compositions and synthesis conditions (lower mantle conditions: ~30-90 GPa, 1900-2300 K), different assemblages are synthesized due to differing ferric iron content. For a more reduced (lower Fe3+/?Fe) composition, we find Al2O3 forms its own phase separate from the dominant Mg-silicate perovskite phase, in contrast to a more Al-rich Mg-silicate perovskite-dominated assemblage for a more oxidized starting composition. The density of the reduced composition is found to be 1-1.5% denser than the more oxidized sample. This implies that as a single composition is taken deeper in to the mantle, where it is more reducing, may become denser than if the redox state remained constant. This redox-induced density difference could potentially cause sluggish convection due to the increased density in Earth's lower mantle and lead to a more oxidized upper mantle and more reduced lower mantle.

  2. Nanophase Carbonates on Mars: Implications for Carbonate Formation and Habitability

    NASA Technical Reports Server (NTRS)

    Archer, P. Douglas, Jr.; Lauer, H. Vern; Ming, Douglas W.; Niles, Paul B.; Morris, Richard V.; Rampe, Elizabeth B.; Sutter, Brad

    2014-01-01

    Despite having an atmosphere composed primarily of CO2 and evidence for abundant water in the past, carbonate minerals have only been discovered in small amounts in martian dust [1], in outcrops of very limited extent [2, 3], in soils in the Northern Plains (the landing site of the 2007 Phoenix Mars Scout Mission) [4] and may have recently been detected in aeolian material and drilled and powdered sedimentary rock in Gale Crater (the Mars Science Laboratory [MSL] landing site) [5]. Thermal analysis of martian soils by instruments on Phoenix and MSL has demonstrated a release of CO2 at temperatures as low as 250-300 degC, much lower than the traditional decomposition temperatures of calcium or magnesium carbonates. Thermal decomposition temperature can depend on a number of factors such as instrument pressure and ramp rate, and sample particle size [6]. However, if the CO2 released at low temperatures is from carbonates, small particle size is the only effect that could have such a large impact on decomposition temperature, implying the presence of extremely fine-grained (i.e., "nanophase" or clay-sized) carbonates. We hypothesize that this lower temperature release is the signature of small particle-sized (clay-sized) carbonates formed by the weathering of primary minerals in dust or soils through interactions with atmospheric water and carbon dioxide and that this process may persist under current martian conditions. Preliminary work has shown that clay-sized carbonate grains can decompose at much lower temperatures than previously thought. The first work took carbonate, decomposed it to CaO, then flowed CO2 over these samples held at temperatures >100 degC to reform carbonates. Thermal analysis confirmed that carbonates were indeed formed and transmission electron microsopy was used to determine crystal sized were on the order of 10 nm. The next step used minerals such as diopside and wollastonite that were sealed in a glass tube with a CO2 and H2O source. After reacting these materials for a number of hours, thermal analysis demonstrated the formations of carbonates that decomposed at temperatures as low as 500 degC [7]. Further work is underway to carry out the weathering process under more Mars-like conditions (low pressure and low temperature) to determine if the carbonate decomposition temperature can be shifted to even lower temperatures, consistent with what has been detected by thermal analysis instruments on Mars.

  3. Deposition rates of oxidized iron on Mars

    NASA Technical Reports Server (NTRS)

    Burns, R. G.

    1993-01-01

    The reddened oxidized surface of Mars is indicative of temporal interactions between the Martian atmosphere and its surface. During the evolution of the Martian regolith, primary ferromagnesian silicate and sulfide minerals in basaltic rocks apparently have been oxidized to secondary ferric-bearing assemblages. To evaluate how and when such oxidized deposits were formed on Mars, information about the mechanisms and rates of chemical weathering of Fe(2+)-bearing minerals has been determined. In this paper, mechanisms and rates of deposition of ferric oxide phases on the Martian surface are discussed.

  4. 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.

  5. Nanophase Magnetite and Pyrrhotite in ALH84001 Martian Meteorite: Evidence for an Abiotic Origin

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

    The nanophase magnetite crystals in the black rims of pancake-shaped carbonate globules of the Martian meteorite ALH84001 have been studied extensively because of the claim by McKay et al.that they are biogenic in origin. A subpopulation of these magnetite crystals are reported to conform to a unique elongated shape called "truncated hexa-octahedral" or "THO" by Thomas-Keprta et al. They claim these THO magnetite crystals can only be produced by living bacteria thus forming a biomarker in the meteorite. In contrast, thermal decomposition of Fe-rich carbonate has been suggested as an alternate hypothesis for the elongated magnetite formation in ALH84001 carbonates. The experimental and observational evidence for the inorganic formation of nanophase magnetite and pyrrhotite in ALH84001 by decomposition of Fe-rich carbonate in the presence of pyrite are provided.

  6. Preparation of silica nanospheres and porous polymer membranes with controlled morphologies via nanophase separation

    NASA Astrophysics Data System (ADS)

    Lee, Jung-Pil; Choi, Sinho; Park, Soojin

    2012-08-01

    We successfully synthesized two different structures, silica nanospheres and porous polymer membranes, via nanophase separation, based on a sol-gel process. Silica sol, which was in situ polymerized from tetraorthosilicate, was used as a precursor. Subsequently, it was mixed with a polymer that was used as a matrix component. It was observed that nanophase separation occurred after the mixing of polymer with silica sol and subsequent evaporation of solvents, resulting in organizing various structures, from random network silica structures to silica spheres. In particular, silica nanospheres were produced by manipulating the mixing ratio of polymer to silica sol. The size of silica beads was gradually changed from micro- to nanoscale, depending on the polymer content. At the same time, porous polymer membranes were generated by removing the silica component with hydrofluoric acid. Furthermore, porous carbon membranes were produced using carbon source polymer through the carbonization process.

  7. Prevention of Acid Mine Drainage Through Complexation of Ferric Iron by Soluble Microbial Growth Products

    NASA Astrophysics Data System (ADS)

    Pandey, S.; Yacob, T. W.; Silverstein, J.; Rajaram, H.; Minchow, K.; Basta, J.

    2011-12-01

    Acid mine drainage (AMD) is a widespread environmental problem with deleterious impacts on water quality in streams and watersheds. AMD is generated largely by the oxidation of metal sulfides (i.e. pyrite) by ferric iron. This abiotic reaction is catalyzed by conversion of ferrous to ferric iron by iron and sulfur oxidizing microorganisms. Biostimulation is currently being investigated as an attempt to inhibit the oxidation of pyrite and growth of iron oxidizing bacteria through addition of organic carbon. This may stimulate growth of indigenous communities of acidophilic heterotrophic bacteria to compete for oxygen. The goal of this research is to investigate a secondary mechanism associated with carbon addition: complexation of free Fe(III) by soluble microbial growth products (SMPs) produced by microorganisms growing in waste rock. Exploratory research at the laboratory scale examined the effect of soluble microbial products (SMPs) on the kinetics of oxidation of pure pyrite during shaker flask experiments. The results confirmed a decrease in the rate of pyrite oxidation that was dependent upon the concentration of SMPs in solution. We are using these data to verify results from a pyrite oxidation model that accounts for SMPs. This reactor model involves differential-algebraic equations incorporating total component mass balances and mass action laws for equilibrium reactions. Species concentrations determined in each time step are applied to abiotic pyrite oxidation rate expressions from the literature to determine the evolution of total component concentrations. The model was embedded in a parameter estimation algorithm to determine the reactive surface area of pyrite in an abiotic control experiment, yielding an optimized value of 0.0037 m2. The optimized model exhibited similar behavior to the experiment for this case; the root mean squared of residuals for Fe(III) was calculated to be 7.58 x 10-4 M, which is several orders of magnitude less than the actual Fe(III) concentrations. The model was refined to include Fe(III)-SMP complexes, but these are not well documented and vary depending upon the nature and origin of the growth products. Well known chelating agents form predictable complexes with Fe(III) iron through documented complexation reactions. If chelation of soluble Fe(III) by SMPs is similar to such a chelator, the latter may be used as a basis to parameterize inhibition of pyrite oxidation due to complexation of Fe(III) by SMPs. Fe(III) complexation by known ligands or SMPs may adequately be represented by a bulk complex whose stability constant reflects the extent to which free Fe(III) is diminished. The stability constant may differ among the different SMPs experiments depending upon their origin but can be optimized for each case using inverse modeling techniques. We present results from these inverse modeling exercises to demonstrate the validity of using bulk Fe(III)-SMP complexes to explain inhibition of pyrite oxidation in the presence of SMPs. Our results will facilitate the design of in-situ carbon addition strategies by determining organic carbon dose intensity and application frequency required to effectively mitigate impacts on receiving water quality.

  8. Ferric and cobaltous hydroacid complexes for forward osmosis (FO) processes.

    PubMed

    Ge, Qingchun; Fu, Fengjiang; Chung, Tai-Shung

    2014-07-01

    Cupric and ferric hydroacid complexes have proven their advantages as draw solutes in forward osmosis in terms of high water fluxes, negligible reverse solute fluxes and easy recovery (Ge and Chung, 2013. Hydroacid complexes: A new class of draw solutes to promote forward osmosis (FO) processes. Chemical Communications 49, 8471-8473.). In this study, cobaltous hydroacid complexes were explored as draw solutes and compared with the ferric hydroacid complex to study the factors influencing their FO performance. The solutions of the cobaltous complexes produce high osmotic pressures due to the presence of abundant hydrophilic groups. These solutes are able to dissociate and form a multi-charged anion and Na(+) cations in water. In addition, these complexes have expanded structures which lead to negligible reverse solute fluxes and provide relatively easy approaches in regeneration. These characteristics make the newly synthesized cobaltous complexes appropriate as draw solutes. The FO performance of the cobaltous and ferric-citric acid (Fe-CA) complexes were evaluated respectively through cellulose acetate membranes, thin-film composite membranes fabricated on polyethersulfone supports (referred as TFC-PES), and polybenzimidazole and PES dual-layer (referred as PBI/PES) hollow fiber membranes. Under the conditions of DI water as the feed and facing the support layer of TFC-PES FO membranes (PRO mode), draw solutions at 2.0 M produced relatively high water fluxes of 39-48 LMH (L m(-2) hr(-1)) with negligible reverse solute fluxes. A water flux of 17.4 LMH was achieved when model seawater of 3.5 wt.% NaCl replaced DI water as the feed and 2.0 M Fe-CA as the draw solution under the same conditions. The performance of these hydroacid complexes surpasses those of the synthetic draw solutes developed in recent years. This observation, along with the relatively easy regeneration, makes these complexes very promising as a novel class of draw solutes. PMID:24768702

  9. Iron Amendment and Fenton Oxidation of MTBE-Spent Granular Activated Carbon

    EPA Science Inventory

    Fenton-driven regeneration of Methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) involves Fe amendment to the GAC to catalyze H2O2 reactions and to enhance the rate of MTBE oxidation and GAC regeneration. Four forms of iron (ferric sulfate, ferric chloride, fer...

  10. Intravenous ferric carboxymaltose for the treatment of iron deficiency anemia

    PubMed Central

    Friedrisch, João Ricardo; Cançado, Rodolfo Delfini

    2015-01-01

    Nutritional iron deficiency anemia is the most common deficiency disorder, affecting more than two billion people worldwide. Oral iron supplementation is usually the first choice for the treatment of iron deficiency anemia, but in many conditions, oral iron is less than ideal mainly because of gastrointestinal adverse events and the long course needed to treat the disease and replenish body iron stores. Intravenous iron compounds consist of an iron oxyhydroxide core, which is surrounded by a carbohydrate shell made of polymers such as dextran, sucrose or gluconate. The first iron product for intravenous use was the high molecular weight iron dextran. However, dextran-containing intravenous iron preparations are associated with an elevated risk of anaphylactic reactions, which made physicians reluctant to use intravenous iron for the treatment of iron deficiency anemia over many years. Intravenous ferric carboxymaltose is a stable complex with the advantage of being non-dextran-containing and a very low immunogenic potential and therefore not predisposed to anaphylactic reactions. Its properties permit the administration of large doses (15 mg/kg; maximum of 1000 mg/infusion) in a single and rapid session (15-minute infusion) without the requirement of a test dose. The purpose of this review is to discuss some pertinent issues in relation to the history, pharmacology, administration, efficacy, and safety profile of ferric carboxymaltose in the treatment of patients with iron deficiency anemia. PMID:26670403

  11. The stability of oxyamphiboles: Existence of Ferric-bearing minerals under the reducing conditions on the surface of Venus

    NASA Technical Reports Server (NTRS)

    Straub, Darcy W.; Burns, Roger G.

    1993-01-01

    An enigma of Venusian mineralogy is the suggestion that Fe(3+)-bearing minerals exist under the reducing conditions of the Venusian atmosphere. Analysis of the spectrophotometric data from the Venera 13 and 14 missions, combined with the laboratory reflectance spectral measurements of oxidized basalts at elevated temperatures, led to the suggestion that metastable hematite might exist on Venus. Heating experiments at 475 C when f(sub O2) approximately 10(exp -24) demonstrated that the hematite to magnetite conversion is rapid indicating metastable hematite is not present on Venus. In addition to hematite, several other ferric oxide and silicate minerals have been proposed to occur on Venus, including laihunite or ferrifayalite, Fe(3+)-bearing tephroite, oxyamphiboles, and oxybiotites. Heating experiments performed on these Fe(3+)-bearing minerals under temperature-f(sub O2) conditions existing on Venus suggest that only oxyamphiboles and oxybiotites may be stable on the surface of Venus.

  12. Presence of an iron-rich nanophase material in the upper layer of the Cretaceous-Tertiary boundary clay

    NASA Astrophysics Data System (ADS)

    Wdowiak, Thomas J.; Armendarez, Lawrence P.; Agresti, David G.; Wade, Manson L.; Wdowiak, Suzanne Y.; Claeys, Philippe; Izett, Glenn

    2001-01-01

    We report new geochemical evidence from ten Cretaceous-Tertiary boundary sites in North America and Europe, indicating the presence of a material remnant of a large asteroid or comet that struck the Earth at 65.0 Ma. Mössbauer spectroscopic data reveals that a ubiquitous iron-rich nanophase material exists at the uppermost part of the K-T boundary layer in the Western Hemisphere and in Europe in marine and continental fine-grained sedimentary rock. The high surface-to-volume ratio of nanophase material suggests that it may be the carrier of the iridium abundance enhancement that marks the K-T boundary. Even more provocative is the possibility that the discovered nanophase material is, for the most part, composed of the vaporized impactor after the impact-generated high-temperature vapor plume rose and cooled above the atmosphere.

  13. QTL analysis of ferric reductase activity in the model legume lotus japonicus

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Physiological and molecular studies have demonstrated that iron accumulation from the soil into Strategy I plants can be limited by ferric reductase activity. An initial study of Lotus japonicus ecotypes Miyakojima MG-20 and Gifu B-129 identified significant leaf chlorosis and ferric reductase activ...

  14. Application of granular ferric hydroxides for removal elevated concentrations of arsenic from mine waters

    NASA Astrophysics Data System (ADS)

    Szlachta, Ma?gorzata; W?odarczyk, Pawe?; Wójtowicz, Patryk

    2015-04-01

    Arsenic is naturally occurring element in the environment. Over three hundred minerals are known to contain some form of arsenic and among them arsenopyrite is the most common one. Arsenic-bearing minerals are frequently associated with ores containing mined metals such as copper, tin, nickel, lead, uranium, zinc, cobalt, platinum and gold. In the aquatic environment arsenic is typically present in inorganic forms, mainly in two oxidation states (+5, +3). As(III) is dominant in more reduced conditions, whereas As(V) is mostly present in an oxidizing environment. However, due to certain human activities the elevated arsenic levels in aquatic ecosystems are arising to a serious environmental problem. High arsenic concentrations found in surface and groundwaters, in some regions originate from mining activities and ore processing. Therefore, the major concern of mining industry is to maintain a good quality of effluents discharged in large volumes. This requires constant monitoring of effluents quality that guarantee the efficient protection of the receiving waters and reacting to possible negative impact of contamination on local communities. A number of proven technologies are available for arsenic removal from waters and wastewaters. In the presented work special attention is given to the adsorption method as a technically feasible, commonly applied and effective technique for the treatment of arsenic rich mine effluents. It is know that arsenic has a strong affinity towards iron rich materials. Thus, in this study the granular ferric hydroxides (CFH 12, provided by Kemira Oyj, Finland) was applied to remove As(III) and As(V) from aqueous solutions. The batch adsorption experiments were carried out to assess the efficiency of the tested Fe-based material under various operating parameters, including composition of treated water, solution pH and temperature. The results obtained from the fixed bed adsorption tests demonstrated the benefits of applying granular ferric hydroxides for treatment As-contaminated waters. This research is a part of the study supported by the National Centre for Research and Development grant (2014-2017) "Sustainable and responsible supply of primary resources - SUSMIN" (http://projects.gtk.fi/susmin), within the EU ERA-NET ERA-MIN program.

  15. The antagonism of tetracycline and ferric iron in vivo.

    PubMed

    Miles, A A; Maskell, J P

    1985-08-01

    To test the hypothesis that the in-vivo antibiotic action of tetracycline might be affected by ferric iron and the enhancement of infection by ferric iron by tetracycline, the actions of intraperitoneal antibiotic and local ferric ammonium citrate, given separately and together, were measured in the dorsal skin of guinea-pigs bearing lesions due to staphylococci, streptococci, a Proteus sp., an Erysipelothrix sp., Clostridium perfringens, Pseudomonas aeruginosa, Aeromonas hydrophila and Klebsiella pneumoniae. Tetracycline, given in two intraperitoneal doses of 25 mg/kg at 0 and 2 h after intracutaneous challenge, maintained plasma concentrations of 4-6 micrograms/ml for more than the first 4 h of infection, after which the local lesions had become largely insusceptible to the antibiotic. The intracutaneous injection of Fe 10 micrograms in a volume of 0.1 ml containing the bacteria was sufficient to enhance infection by those strains susceptible to this effect. The in-vivo efficacy of tetracycline was not always related to low MIC; a low MIC was sometimes associated with little action and a high MIC with moderate action. Sixteen organisms were tested. The iron diminished the tetracycline effect only feebly with one staphylococcal strain and the strain of E. rhusiopathiae. In only one case, with a strain of Proteus sp., was the tetracycline action grossly diminished. On the other hand, tetracycline diminished the enhancement effect of iron moderately with three strains of staphylococci and one strain each of K. pneumoniae, P. aeruginosa and C. perfringens, and strongly with two strains of staphylococci, a group-C streptococcus and one strain each of K. pneumoniae, E. rhusiopathiae and A. hydrophila. It is evident that the diminution of tetracycline action by moderate excess of readily available Fe , whether endogenous or administered, is an unlikely event (three instances among the 16 tested) whereas the diminution of the infection-enhancing effect of iron by tetracycline is much more likely (12 instances among the 16). Insofar as a decrease in iron available for enhancement of infection is valid evidence of a diminution of the iron available for necessary physiological processes of the subject treated, our results suggest that these processes might be affected by tetracycline. PMID:4020849

  16. Transcriptional regulation by Ferric Uptake Regulator (Fur) in pathogenic bacteria

    PubMed Central

    Troxell, Bryan; Hassan, Hosni M.

    2013-01-01

    In the ancient anaerobic environment, ferrous iron (Fe2+) was one of the first metal cofactors. Oxygenation of the ancient world challenged bacteria to acquire the insoluble ferric iron (Fe3+) and later to defend against reactive oxygen species (ROS) generated by the Fenton chemistry. To acquire Fe3+, bacteria produce low-molecular weight compounds, known as siderophores, which have extremely high affinity for Fe3+. However, during infection the host restricts iron from pathogens by producing iron- and siderophore-chelating proteins, by exporting iron from intracellular pathogen-containing compartments, and by limiting absorption of dietary iron. Ferric Uptake Regulator (Fur) is a transcription factor which utilizes Fe2+ as a corepressor and represses siderophore synthesis in pathogens. Fur, directly or indirectly, controls expression of enzymes that protect against ROS damage. Thus, the challenges of iron homeostasis and defense against ROS are addressed via Fur. Although the role of Fur as a repressor is well-documented, emerging evidence demonstrates that Fur can function as an activator. Fur activation can occur through three distinct mechanisms (1) indirectly via small RNAs, (2) binding at cis regulatory elements that enhance recruitment of the RNA polymerase holoenzyme (RNAP), and (3) functioning as an antirepressor by removing or blocking DNA binding of a repressor of transcription. In addition, Fur homologs control defense against peroxide stress (PerR) and control uptake of other metals such as zinc (Zur) and manganese (Mur) in pathogenic bacteria. Fur family members are important for virulence within bacterial pathogens since mutants of fur, perR, or zur exhibit reduced virulence within numerous animal and plant models of infection. This review focuses on the breadth of Fur regulation in pathogenic bacteria. PMID:24106689

  17. [Stabilization of Cadmium Contaminated Soils by Ferric Ion Modified Attapulgite (Fe/ATP)--Characterizations and Stabilization Mechanism].

    PubMed

    Rong, Yang; Li, Rong-bo; Zhou, Yong-li; Chen, Jing; Wang, Lin-ling; Lu, Xiao-hua

    2015-08-01

    Ferric ion modified attapulgite (Fe/ATP) was prepared by impregnation and its structure and morphology were characterized. The toxicity characteristic leaching procedure (TCLP) was used to evaluate the effect of Cadmium( Cd) stabilization in soil with the addition of attapulgite (ATP) and Fe/ATP. The stabilization mechanism of Cd was further elucidated by comparing the morphologies and structure of ATP and Fe/ATP before and after Cd adsorption. Fe/ATP exhibited much better adsorption capacity than ATP, suggesting different adsorption mechanisms occurred between ATP and Fe/ATP. The leaching concentrations of Cd in soil decreased by 45% and 91% respectively, with the addition of wt. 20% ATP and Fe/ATP. The former was attributed to the interaction between Cd2 and --OH groups by chemical binding to form inner-sphere complexes in ATP and the attachment between Cd2+ and the defect sites in ATP framework. Whereas Cd stabilization with Fe/ATP was resulted from the fact that the active centers (--OH bonds or O- sites) on ATP could react with Fe3+ giving Fe--O--Cd-- bridges, which helped stabilize Cd in surface soil. What'more, the ferric oxides and metal hydroxides on the surface of ATP could interact with Cd, probably by the formation of cadmium ferrite. In conclusion, Fe/ATP, which can be easily prepared, holds promise as a potential low-cost and environmental friendly stabilizing agent for remediation of soil contaminated with heavy metals. PMID:26592037

  18. Formation of ferric iron crusts in Quaternary sediments of Lake Baikal, Russia, and implications for paleoclimate

    USGS Publications Warehouse

    Deike, R.G.; Granina, L.; Callender, E.; McGee, J.J.

    1997-01-01

    Phosphate-bearing, ferric iron and siliceous crusts ranging in age from Recent to approximately 65,000 yr B.P. are observed in sediments of Lake Baikal. In younger sediments the crusts are at the base of a spectrum of secondary iron and manganese oxides that accumulate near the sediment/water interface in the zone of positive oxidation potential beneath an oxygenated water column. In areas where the average Quaternary sedimentation rates have been slow (e.g. 0.026 mm/yr), the crusts are more common, and span a wider range of ages. No crusts have been found where the Quaternary sedimentation mode has been deltaic and rapid (0.15 mm/yr). Independent core correlation based on magnetic properties of the sediment suggests that crusts can be correlated over most of Academician Ridge, an area that is particularly sensitive to climatic events affecting the concentration of suspended sediment. These crusts may be indicative of periods of low suspended sediment concentration, which occur during sustained transitions from glacial periods of high detrital input, to interglacial periods of high diatom sedimentation. The crusts are dominated by iron-rich and siliceous amorphous mineral phases, with an FeO:SiO2 by weight of 3:1. Regardless of age or location in the lake the Fe phase always includes Ca, P and Mn. Extensive microprobe data for these four elements recast as normalized elemental weight percent reveal linear trends of Ca:P and Fe:P. With increasing P, Ca also increases such that the two elements maintain a linear relationship passing very close to the origin and with a mean molar Ca:P=0.3 (too low for well-characterized apatite). Conversely, with increasing P, Fe decreases (mean molar Fe:P=3.4). There is no correlation between Mn and P. Molar Fe:P ratios for vivianite (an Fe(II) phosphate mineral observed in sediments closely below some crusts) are clustered around a stoichiometric composition. The covariant increase in Ca:P and the corresponding decrease in Fe:P may be explained by: (1) coupled adsorption of aqueous Ca and P by a colloidal ferric hydrous oxide; (2) loss of Fe from a Ca-P-Fe phase; or (3) oxidation of vivianite to a metastable mineral phase that gradually loses Ca and gains Fe. The first explanation is favored, because there is no petrographic evidence for either the existence of an originating Ca-P-Fe phase, or, for the oxidation of vivianite. Further, it is suggested that by continually equalizing surface charge, Ca allows more phosphate to be adsorbed leading to thicker crusts and longer preservation after burial.

  19. Multidomain human peroxidasin 1 is a highly glycosylated and stable homotrimeric high spin ferric peroxidase.

    PubMed

    Soudi, Monika; Paumann-Page, Martina; Delporte, Cedric; Pirker, Katharina F; Bellei, Marzia; Edenhofer, Eva; Stadlmayr, Gerhard; Battistuzzi, Gianantonio; Boudjeltia, Karim Zouaoui; Furtmüller, Paul G; Van Antwerpen, Pierre; Obinger, Christian

    2015-04-24

    Human peroxidasin 1 (hsPxd01) is a multidomain heme peroxidase that uses bromide as a cofactor for the formation of sulfilimine cross-links. The latter confers critical structural reinforcement to collagen IV scaffolds. Here, hsPxd01 and various truncated variants lacking nonenzymatic domains were recombinantly expressed in HEK cell lines. The N-glycosylation site occupancy and disulfide pattern, the oligomeric structure, and unfolding pathway are reported. The homotrimeric iron protein contains a covalently bound ferric high spin heme per subunit with a standard reduction potential of the Fe(III)/Fe(II) couple of -233 ± 5 mV at pH 7.0. Despite sequence homology at the active site and biophysical properties similar to human peroxidases, the catalytic efficiency of bromide oxidation (kcat/KM(app)) of full-length hsPxd01 is rather low but increased upon truncation. This is discussed with respect to its structure and proposed biosynthetic function in collagen IV cross-linking. PMID:25713063

  20. NOM removal by adsorption onto granular ferric hydroxide: Equilibrium, kinetics, filter and regeneration studies.

    PubMed

    Genz, Arne; Baumgarten, Benno; Goernitz, Mandy; Jekel, Martin

    2008-01-01

    Adsorption onto granular ferric hydroxide (GFH) with subsequent in-situ regeneration is studied as a new process for natural organic matter (NOM) removal from groundwater. Adsorbent equilibrium loadings of 10-30 mgDOC g(-1)GFH(-1) are obtained, whereas the non-adsorbable DOC fraction amounts to 1.5 mgL(-1) for all investigated groundwaters. The larger and UV-active NOM fractions (mainly fulvic acids) are well adsorbed while the smaller molecular fractions are poorly or not adsorbed. However, kinetic studies show that the smaller and medium-sized fulvic acids are removed first. The equilibrium is strongly dependent on pH but only weakly on ionic strength, pointing to ligand exchange as the dominant adsorption mechanism. With regard to NOM structure, prerequisites for adsorption onto GFH are both a minimum number of functional groups and a molecular size small enough to enter the GFH pores. NOM breakthrough curves are successfully simulated using the LDF model (homogeneous surface diffusion model (HSDM) with linear driving force approach for surface diffusion) and experimentally determined mass transfer coefficients. Regeneration of loaded GFH is possible either by use of NaOH or oxidatively by H(2)O(2). The optimal quantities and concentrations are determined. PMID:17681584

  1. The role of the crystallization temperature on the nanophase structure evolution of poly[(R)-3-hydroxybutyrate].

    PubMed

    Righetti, Maria Cristina; Tombari, Elpidio; Di Lorenzo, Maria Laura

    2013-10-10

    The nanophase structure of semicrystalline polymers, which determines the mechanical, thermal, and gas permeability behavior, can be quantified by thermal methods. A detailed investigation of the nanophase structure of poly[(R)-3-hydroxybutyrate] (PHB) was performed under conditions of isothermal, quasi-isothermal, and nonisothermal crystallizations. The experimental analyses revealed that the establishment of the nanophase rigid amorphous fraction (RAF) in PHB depends on the temperature at which crystallization occurs. The RAF grows in parallel with the crystal phase during quasi-isothermal crystallization at 30 °C, whereas during nonisothermal crystallization at higher temperatures, RAF starts to develop at 70 °C, in correspondence with the final stages of the crystallization process. The influence of crystallization temperature on the nanophase structure was rationalized taking into account the effect of the mobility of the entangled chain segments during the phase transition. The melting behavior was found to change after isothermal crystallization at 70 °C, revealing that complete RAF mobilization is achieved approximately at this temperature. The temperature of 70 °C could be the limit for the formation and the disappearance of rigid amorphous fraction in the PHB analyzed in the present study. PMID:24020615

  2. 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(?-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(?-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). PMID:23768062

  3. Laboratory Simulation of Space Weathering: ESR Measurements of Nanophase Metallic Iron in Laser-irradiated Olivine and Pyroxene Samples

    NASA Technical Reports Server (NTRS)

    Kurahashi, E.; Yamanaka, C.; Nakamura, K.; Sasaki, S.

    2003-01-01

    S-type asteroids are believed to be parent bodies of ordinary chondrites. Although both S-type asteroids and ordinary chondrites contain the same mineral assemblage, mainly olivine and pyroxene, the reflectance spectra of the asteroids exhibit more overall depletion (darkening) and reddening, and more weakening of absorption bands relative to the meteorites. This spectral mismatch is explained by space weathering process, where high-velocity dust particle impacts should change the optical properties of the uppermost regolith surface of asteroids. In order to simulate the space weathering, we irradiated nanosecond pulse laser beam onto pellet samples of olivine (8.97wt% FeO) and pyroxene (enstatite: 9.88wt% FeO, hypersthene: 16.70wt%). We got spectral changes in our samples similar to that by space weathering on asteroids and confirmed nanophase alpha-metallic iron particles, which were theoretically predicted, not only on olivine but also on pyroxene samples by Transmission Electron Microscopy (TEM). Nanophase metallic iron particles were widely scattered throughout the amorphous rims developed along the olivine grains, whereas they were embedded in aggregates of amorphous in enstatite samples. Recently, we also measured laser-irradiated samples by ESR (Electron Spin Resonance). Strong ESR signals, characteristic to nanophase iron particles, are observed on irradiated olivine samples. In this paper, we report the quantities of nanophase metallic iron particles in pyroxene samples by ESR observations in addition to olivine samples.

  4. Heavy metal phosphate nanophases in silica: influence of radiolysis probed via f-electron state properties

    SciTech Connect

    Beitz, James V. . E-mail: beitz@anl.gov; Williams, C.W.; Hong, K.-S.; Liu, G.K.

    2005-02-15

    We have assessed the feasibility of carrying out time- and wavelength-resolved laser-induced fluorescence measurements of radiation damage in glassy silica. The consequences of alpha decay of Es-253 in LaPO{sub 4} nanophases embedded in silica were probed based on excitation of 5f states of Cm{sup 3+}, Bk{sup 3+}, and Es{sup 3+} ions. The recorded emission spectra and luminescence decays showed that alpha decay of Es-253 ejected Bk-249 decay daughter ions into the surrounding silica and created radiation damage within the LaPO{sub 4} nanophases. This conclusion is consistent with predictions of an ion transport code commonly used to model ion implantation. Luminescence from the {sup 6}D{sub 7/2} state of Cm{sup 3+}was used as an internal standard. Ion-ion energy transfer dominated the dynamics of the observed emitting 5f states and strongly influenced the intensity of observed spectra. In appropriate sample materials, laser-induced fluorescence provides a powerful method for fundamental investigation of alpha-induced radiation damage in silica.

  5. 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.

  6. Enhanced organic pollutant removal influenced by activated-ferric-sludge.

    PubMed

    Xu, G R; Tang, J H; Li, G B; Spinosa, L

    2014-01-01

    The primary goal of this study was to compare the pollutant removal efficiency of the reactivated activated-ferric-sludge (AFS) with that of the activated sludge (AS). Most tested organic pollutants were preferably removed by reactivated AFS. The optimal reactivated conditions for AFS were a reactivation time of 3 h, pH of 5-9, AFS dose of 5 g/L and dissolved oxygen of 2-6 mg/L. The results revealed a positive correlation between microbial activity and the removal efficiency of organic pollutants, with a higher microbial activity being associated with a better removal efficiency of organic pollutants. Additionally, variations in extracellular polymeric substances were found to be crucial to the microbial activity and adsorption capacity of reactivated AFS. After reactivation, reactivated AFS was superior to AS for the removal ofmost pollutants. Finally, the mechanism of AFS reactivation was investigated. Overall, the results of the present study demonstrate that reactivated AFS has the potential for widespread application in the removal of organic pollutants during the wastewater treatment process. PMID:25145208

  7. Exfoliation of Hexagonal Boron Nitride via Ferric Chloride Intercalation

    NASA Technical Reports Server (NTRS)

    Hung, Ching-cheh; Hurst, Janet; Santiago, Diana; Rogers, Richard B.

    2014-01-01

    Sodium fluoride (NaF) was used as an activation agent to successfully intercalate ferric chloride (FeCl3) into hexagonal boron nitride (hBN). This reaction caused the hBN mass to increase by approx.100 percent, the lattice parameter c to decrease from 6.6585 to between 6.6565 and 6.6569 ?, the x-ray diffraction (XRD) (002) peak to widen from 0.01deg to 0.05deg of the full width half maximum value, the Fourier transform infrared (FTIR) spectrum's broad band (1277/cm peak) to change shape, and new FTIR bands to emerge at 3700 to 2700 and 1600/cm. This indicates hBN's structural and chemical properties are significantly changed. The intercalated product was hygroscopic and interacted with moisture in the air to cause further structural and chemical changes (from XRD and FTIR). During a 24-h hold at room temperature in air with 100 percent relative humidity, the mass increased another 141 percent. The intercalated product, hydrated or not, can be heated to 750 C in air to cause exfoliation. Exfoliation becomes significant after two intercalation-air heating cycles, when 20-nm nanosheets are commonly found. Structural and chemical changes indicated by XRD and FTIR data were nearly reversed after the product was placed in hydrochloric acid (HCl), resulting in purified, exfoliated, thin hBN products.

  8. Ferric Phosphate Hydroxide Microstructures Affect Their Magnetic Properties

    PubMed Central

    Zhao, Junhong; Zhang, Youjuan; Run, Zhen; Li, Pengwei; Guo, Qifei; Pang, Huan

    2015-01-01

    Uniformly sized and shape-controlled nanoparticles are important due to their applications in catalysis, electrochemistry, ion exchange, molecular adsorption, and electronics. Several ferric phosphate hydroxide (Fe4(OH)3(PO4)3) microstructures were successfully prepared under hydrothermal conditions. Using controlled variations in the reaction conditions, such as reaction time, temperature, and amount of hexadecyltrimethylammonium bromide (CTAB), the crystals can be grown as almost perfect hyperbranched microcrystals at 180?°C (without CTAB) or relatively monodisperse particles at 220?°C (with CTAB). The large hyperbranched structure of Fe4(OH)3(PO4)3 with a size of ?19??m forms with the “fractal growth rule” and shows many branches. More importantly, the magnetic properties of these materials are directly correlated to their size and micro/nanostructure morphology. Interestingly, the blocking temperature (TB) shows a dependence on size and shape, and a smaller size resulted in a lower TB. These crystals are good examples that prove that physical and chemical properties of nano/microstructured materials are related to their structures, and the precise control of the morphology of such functional materials could allow for the control of their performance. PMID:26246988

  9. Iron fortification of flour with a complex ferric orthophosphate

    SciTech Connect

    Hallberg, L.; Rossander-Hulthen, L.; Gramatkovski, E.

    1989-07-01

    The unexpectedly low bioavailability in humans of elemental iron powder prompted us to search for other Fe compounds suitable for Fe fortification of flour that fulfill the two requirements of insolubility in water (due to high water content of flour) and good bioavailability in humans. Systematic studies of compatibility, solubility, and bioavailability led to this study of a microcrystalline complex ferric orthophosphate (CFOP), Fe/sub 3/H/sub 8/(NH/sub 4/)-(PO/sub 4/)6.6H/sub 2/O, a well-defined compound. This compound was labeled with /sup 59/Fe, and the native Fe in meals was labeled with /sup 55/FeCl3. The ratio of absorbed /sup 59/Fe to absorbed /sup 55/Fe is a direct measure of the fraction of CFOP that joins the nonheme Fe pool and that is made potentially available for absorption. The relative bioavailability of CFOP varied from 30% to 60% when labeled wheat rolls were served with different meals. The CFOP meets practical requirements of an Fe fortificant for flour well, with regard to both compatibility and bioavailability in humans.

  10. Method for preventing the precipitation of ferric compounds during the acid treatment of wells

    SciTech Connect

    Crowe, C.W.; Maddin, C.M.

    1986-03-04

    A method is described for preventing the undesirable formation and precipitation of ferric compounds from a spent threatment acid containing dissolved iron following an acidizing treatment of subterranean formations surrounding a wellbore. The method consists of adding to the treatment acid prior to contact with the formation an amount of ascorbic acid and/or erythorbic acid, and/or a soluble salt of the acid, sufficient to prevent the formation and precipitation of ferric compounds from the treatment acid upon spending.

  11. Total X-ray scattering, EXAFS, and Mössbauer spectroscopy analyses of amorphous ferric arsenate and amorphous ferric phosphate

    NASA Astrophysics Data System (ADS)

    Mikutta, Christian; Schröder, Christian; Marc Michel, F.

    2014-09-01

    Amorphous ferric arsenate (AFA, FeAsO4·xH2O) is an important As precipitate in a range of oxic As-rich environments, especially acidic sulfide-bearing mine wastes. Its structure has been proposed to consist of small polymers of single corner-sharing FeO6 octahedra (rFe-Fe ?3.6 Å) to which arsenate is attached as a monodentate binuclear 2C complex (‘chain model’). Here, we analyzed the structure of AFA and analogously prepared amorphous ferric phosphates (AFP, FePO4·xH2O) by a combination of high-energy total X-ray scattering, Fe K-edge X-ray absorption spectroscopy, and 57Fe Mössbauer spectroscopy. Pair distribution function (PDF) analysis of total X-ray scattering data revealed that the coherently scattering domain size of AFA and AFP is about 8 Å. The PDFs of AFA lacked Fe-Fe pair correlations at r ?3.6 Å indicative of single corner-sharing FeO6 octahedra, which strongly supports a local scorodite (FeAsO4·2H2O) structure. Likewise, the PDFs and Fe K-edge extended X-ray absorption fine structure data of AFP were consistent with a local strengite (FePO4·2H2O) structure of isolated FeO6 octahedra being corner-linked to PO4 tetrahedra (rFe-P = 3.25(1) Å). Mössbauer spectroscopy analyses of AFA and AFP indicated a strong superparamagnetism. While AFA only showed a weak onset of magnetic hyperfine splitting at 5 K, magnetic ordering of AFP was completely absent at this temperature. Mössbauer spectroscopy may thus offer a convenient way to identify and quantify AFA and AFP in mineral mixtures containing poorly crystalline Fe(III)-oxyhydroxides. In summary, our results imply a close structural relationship between AFA and AFP and suggest that these amorphous materials serve as templates for the formation of scorodite and strengite (phosphosiderite) in strongly acidic low-temperature environments.

  12. Stabilisation of Fe2O3-rich Perovskite Nanophase in Epitaxial Rare-earth Doped BiFeO3 Films.

    PubMed

    Zhang, Huairuo; Reaney, Ian M; Marincel, Daniel M; Trolier-McKinstry, Susan; Ramasse, Quentin M; MacLaren, Ian; Findlay, Scott D; Fraleigh, Robert D; Ross, Ian M; Hu, Shunbo; Ren, Wei; Rainforth, W Mark

    2015-01-01

    Researchers have demonstrated that BiFeO3 exhibits ferroelectric hysteresis but none have shown a strong ferromagnetic response in either bulk or thin film without significant structural or compositional modification. When remanent magnetisations are observed in BiFeO3 based thin films, iron oxide second phases are often detected. Using aberration-corrected scanning transmission electron microscopy, atomic resolution electron energy loss spectrum-mapping and quantitative energy dispersive X-ray spectroscopy analysis, we reveal the existence of a new Fe2O3-rich perovskite nanophase, with an approximate formula (Fe0.6Bi0.25Nd0.15)(3+) Fe(3+)O3, formed within epitaxial Ti and Nd doped BiFeO3 perovskite films grown by pulsed laser deposition. The incorporation of Nd and Bi ions on the A-site and coherent growth with the matrix stabilise the Fe2O3-rich perovskite phase and preliminary density functional theory calculations suggest that it should have a ferrimagnetic response. Perovskite-structured Fe2O3 has been reported previously but never conclusively proven when fabricated at high-pressure high-temperature. This work suggests the incorporation of large A-site species may help stabilise perovskite-structured Fe2O3. This finding is therefore significant not only to the thin film but also to the high-pressure community. PMID:26272264

  13. Stabilisation of Fe2O3-rich Perovskite Nanophase in Epitaxial Rare-earth Doped BiFeO3 Films

    NASA Astrophysics Data System (ADS)

    Zhang, Huairuo; Reaney, Ian M.; Marincel, Daniel M.; Trolier-McKinstry, Susan; Ramasse, Quentin M.; MacLaren, Ian; Findlay, Scott D.; Fraleigh, Robert D.; Ross, Ian M.; Hu, Shunbo; Ren, Wei; Mark Rainforth, W.

    2015-08-01

    Researchers have demonstrated that BiFeO3 exhibits ferroelectric hysteresis but none have shown a strong ferromagnetic response in either bulk or thin film without significant structural or compositional modification. When remanent magnetisations are observed in BiFeO3 based thin films, iron oxide second phases are often detected. Using aberration-corrected scanning transmission electron microscopy, atomic resolution electron energy loss spectrum-mapping and quantitative energy dispersive X-ray spectroscopy analysis, we reveal the existence of a new Fe2O3-rich perovskite nanophase, with an approximate formula (Fe0.6Bi0.25Nd0.15)3+ Fe3+O3, formed within epitaxial Ti and Nd doped BiFeO3 perovskite films grown by pulsed laser deposition. The incorporation of Nd and Bi ions on the A-site and coherent growth with the matrix stabilise the Fe2O3-rich perovskite phase and preliminary density functional theory calculations suggest that it should have a ferrimagnetic response. Perovskite-structured Fe2O3 has been reported previously but never conclusively proven when fabricated at high-pressure high-temperature. This work suggests the incorporation of large A-site species may help stabilise perovskite-structured Fe2O3. This finding is therefore significant not only to the thin film but also to the high-pressure community.

  14. Stabilisation of Fe2O3-rich Perovskite Nanophase in Epitaxial Rare-earth Doped BiFeO3 Films

    PubMed Central

    Zhang, Huairuo; Reaney, Ian M.; Marincel, Daniel M.; Trolier-McKinstry, Susan; Ramasse, Quentin M.; MacLaren, Ian; Findlay, Scott D.; Fraleigh, Robert D.; Ross, Ian M.; Hu, Shunbo; Ren, Wei; Mark Rainforth, W.

    2015-01-01

    Researchers have demonstrated that BiFeO3 exhibits ferroelectric hysteresis but none have shown a strong ferromagnetic response in either bulk or thin film without significant structural or compositional modification. When remanent magnetisations are observed in BiFeO3 based thin films, iron oxide second phases are often detected. Using aberration-corrected scanning transmission electron microscopy, atomic resolution electron energy loss spectrum-mapping and quantitative energy dispersive X-ray spectroscopy analysis, we reveal the existence of a new Fe2O3-rich perovskite nanophase, with an approximate formula (Fe0.6Bi0.25Nd0.15)3+ Fe3+O3, formed within epitaxial Ti and Nd doped BiFeO3 perovskite films grown by pulsed laser deposition. The incorporation of Nd and Bi ions on the A-site and coherent growth with the matrix stabilise the Fe2O3-rich perovskite phase and preliminary density functional theory calculations suggest that it should have a ferrimagnetic response. Perovskite-structured Fe2O3 has been reported previously but never conclusively proven when fabricated at high-pressure high-temperature. This work suggests the incorporation of large A-site species may help stabilise perovskite-structured Fe2O3. This finding is therefore significant not only to the thin film but also to the high-pressure community. PMID:26272264

  15. Formation of Metallic Nanophases in Polymeric Matrices for Space Applications

    NASA Technical Reports Server (NTRS)

    Orwoll, Robert A.; Thompson, David W.

    1999-01-01

    There are a select number of polyimides which are soluble in organic media. Incorporation of hexafluoroisopropylidene groups is a route to achieving solubility. Such fluorinated polyimides have desirable properties for processing and electronic purposes; however, they often have linear coefficients of thermal expansion (CTE) which are well above those for metals and inorganic oxides or ceramics with which they might be bonded. We have developed a synthesis of composite inorganic-polyimide films using diaquotris(2,4-pentane-dionato)lanthanam(III) as the inorganic precursor and two soluble polyimides formed from 2,2-bis(3,4- dicarboxyphenyl)hexafluoro-propane (6FDA) and 1,3-bis(3-aminophenoxy)benzene (APB) or 2,2-bis[4-(4-aminophenoxy)phenyllhexafluoropropane (4-BDAF). A primary goal of our work was to control the linear CTE in these fluorinated polymer composites without adversely affecting mechanical or other thermal properties.

  16. Nanophase separation in monomolecularly thin water-ethanol films controlled by graphene.

    PubMed

    Severin, N; Gienger, J; Scenev, V; Lange, P; Sokolov, I M; Rabe, J P

    2015-02-11

    Control over nanoscale patterning of ultrathin molecular films plays an important role both in natural as well as artificial nanosystems. Here we report on nanophase separated patterns of water and ethanol within monomolecularly thin films confined between the cleavage plane of mica and single or a few layers of graphene. Employing scanning force microscopy of the graphene layers conforming to the molecular films we quantify the patterns using the ethanol-water cross correlation and the autocorrelation of domain wall directions. They reveal that lateral pattern dimensions grow and the domain walls stiffen upon increasing the thickness of the graphene multilayers. We attribute the control of the patterns through the graphene layers to the competition between the mechanical deformation energy of the graphene sheets and the electrostatic repulsion of dipoles normal to the interface. The latter results from charge transfer between graphene and the molecules confined between mica and graphene. PMID:25615007

  17. The Optical Properties of Nanophase Iron: Investigation of a Space Weathering Analog

    NASA Technical Reports Server (NTRS)

    Noble, S. K.; Pieters, C. M.; Keller, L. P.

    2003-01-01

    It is known that space weathering, in particular the nanophase iron (npFe(sup 0)) created via vapor and/or sputter deposition, has distinct and predictable effects on the optical properties of lunar soils. In addition to the attenuation of absorption bands, weathering introduces a characteristic continuum which is controlled by the amount of npFe(sup 0) present. The shape of this continuum may also be controlled by the size of the npFe(sup 0) grains. It is thought that small npFe(sup 0) grains result in reddening, while larger grains only darken the material. To investigate this phenomenon we have created a lunar weathering analog by impregnating silica gel powders with npFe(sup 0) following the methods presented.

  18. Quantitative determination of cesium binding to ferric hexacyanoferrate: Prussian blue.

    PubMed

    Faustino, Patrick J; Yang, Yongsheng; Progar, Joseph J; Brownell, Charles R; Sadrieh, Nakissa; May, Joan C; Leutzinger, Eldon; Place, David A; Duffy, Eric P; Houn, Florence; Loewke, Sally A; Mecozzi, Vincent J; Ellison, Christopher D; Khan, Mansoor A; Hussain, Ajaz S; Lyon, Robbe C

    2008-05-12

    Ferric hexacyanoferrate (Fe4III[FeII(CN)6]3), also known as insoluble Prussian blue (PB) is the active pharmaceutical ingredient (API) of the drug product, Radiogardase. Radiogardase is the first FDA approved medical countermeasure for the treatment of internal contamination with radioactive cesium (Cs) or thallium in the event of a major radiological incident such as a "dirty bomb". A number of pre-clinical and clinical studies have evaluated the use of PB as an investigational decorporation agent to enhance the excretion of metal cations. There are few sources of published in vitro data that detail the binding capacity of cesium to insoluble PB under various chemical and physical conditions. The study objective was to determine the in vitro binding capacity of PB APIs and drug products by evaluating certain chemical and physical factors such as medium pH, particle size, and storage conditions (temperature). In vitro experimental conditions ranged from pH 1 to 9, to cover the range of pH levels that PB may encounter in the gastrointestinal (GI) tract in humans. Measurements of cesium binding were made between 1 and 24h, to cover gastric and intestinal tract residence time using a validated atomic emission spectroscopy (AES) method. The results indicated that pH, exposure time, storage temperature (affecting moisture content) and particle size play significant roles in the cesium binding to both the PB API and the drug product. The lowest cesium binding was observed at gastric pH of 1 and 2, whereas the highest cesium binding was observed at physiological pH of 7.5. It was observed that dry storage conditions resulted in a loss of moisture from PB, which had a significant negative effect on the PB cesium binding capacity at time intervals consistent with gastric residence. Differences were also observed in the binding capacity of PB with different particle sizes. Significant batch to batch differences were also observed in the binding capacity of some PB API and drug products. Our results suggest that certain physiochemical properties affect the initial binding capacity and the overall binding capacity of PB APIs and drug products during conditions that simulated gastric and GI residence time. These physiochemical properties can be utilized as quality attributes to monitor and predict drug product quality under certain manufacturing and storage conditions and may be utilized to enhance the clinical efficacy of PB. PMID:18242038

  19. Ferric ion mediated photodecomposition of aqueous perfluorooctane sulfonate (PFOS) under UV irradiation and its mechanism.

    PubMed

    Jin, Ling; Zhang, Pengyi; Shao, Tian; Zhao, Shiliang

    2014-04-30

    Perfluorooctane sulfonate (PFOS) recently has received much attention due to its global distribution, environmental persistence and bioaccumulation. The methods for PFOS decomposition are very limited due to its inertness. In this report we first found the photodecomposition of PFOS under UV was greatly accelerated by addition of ferric ions. In the presence of ferric ion (100 ?M), PFOS (20 ?M) decreased to below the detection limit within 48 h, with the rate constant of 1.67 d(-1), which was 50 times higher than that by direct photolysis (0.033 d(-1)). Besides fluoride and sulfate ions, C2-C8 perfluorocarboxylic acids (PFCAs) were identified as the main intermediates. It was found that addition of PFOS into the FeCl3 aqueous solution led to reduction of UV absorption, and the presence of ferric ion reduced the response of PFOS as analyzed by UPLC-MS/MS, which indicated that PFOS formed a complex with ferric ion. The ESR detection indicated that the electronic state of Fe(3+)-PFOS complex changed during reaction. And the role of oxygen and hydroxyl radical on the defluorination of PFOS was investigated. Accordingly the mechanism for PFOS photodecomposition in the presence of ferric ion was proposed. PMID:24583810

  20. Folding process of silk fibroin induced by ferric and ferrous ions

    NASA Astrophysics Data System (ADS)

    Ji, Dan; Deng, Yi-Bin; Zhou, Ping

    2009-12-01

    Bombyx mori silk fiber has useful mechanical properties largely due to a high content of ordered ?-sheet crystallites separated by non-crystalline spacers. Metallic ions present in the silk dope in nature could affect the ?-sheet content. In this work, we used solid-state 13C NMR, EPR and Raman spectroscopy to investigate how the ferric/ferrous ions affect the folding process of the silk fibroin. NMR and Raman results indicate that ferric and ferrous ions have different effects on the secondary structure of silk fibroin. Ferric ions can induce a conformation change from helix to ?-sheet form in silk fibroin when their concentration exceeds a critical value, while ferrous ions cannot. EPR results indicate that the ferric ions bound with silk fibroin have a high-spin state ( S = 5/2) with g-value of g1 = 1.950, g2 = 1.990 and g3 = 1.995, zero-field splitting interaction D of 1.2-2 cm -1, and symmetric character of E/ D = 1/3, resulting in an effective g-value of g' = 4.25. The hydrophilic spacer GTGSSGFGPYVAN(H)GGYSGYEYAWSSESDFGT in the heavy chain of silk fibroin is likely to be involved in the binding of ferric ions, and His, Asn and Tyr residues are considered as the potential binding sites.

  1. Evaluation of Ferric and Ferrous Iron Therapies in Women with Iron Deficiency Anaemia

    PubMed Central

    Berber, Ilhami; Erkurt, Mehmet Ali; Aydogdu, Ismet; Kuku, Irfan

    2014-01-01

    Introduction. Different ferric and ferrous iron preparations can be used as oral iron supplements. Our aim was to compare the effects of oral ferric and ferrous iron therapies in women with iron deficiency anaemia. Methods. The present study included 104 women diagnosed with iron deficiency anaemia after evaluation. In the evaluations performed to detect the aetiology underlying the iron deficiency anaemia, it was found and treated. After the detection of the iron deficiency anaemia aetiology and treatment of the underlying aetiology, the ferric group consisted of 30 patients treated with oral ferric protein succinylate tablets (2 × 40?mg elemental iron/day), and the second group consisted of 34 patients treated with oral ferrous glycine sulphate tablets (2 × 40?mg elemental iron/day) for three months. In all patients, the following laboratory evaluations were performed before beginning treatment and after treatment. Results. The mean haemoglobin and haematocrit increases were 0.95?g/dL and 2.62% in the ferric group, while they were 2.25?g/dL and 5.91% in the ferrous group, respectively. A significant difference was found between the groups regarding the increase in haemoglobin and haematocrit values (P < 0.05). Conclusion. Data are submitted on the good tolerability, higher efficacy, and lower cost of the ferrous preparation used in our study. PMID:25006339

  2. Nitrosative Stress and Apoptosis by Intravenous Ferumoxytol, Iron Isomaltoside 1000, Iron Dextran, Iron Sucrose, and Ferric Carboxymaltose in a Nonclinical Model.

    PubMed

    Toblli, J E; Cao, G; Giani, J F; Dominici, F P; Angerosa, M

    2015-07-01

    Iron is involved in the formation as well as in the scavenging of reactive oxygen and nitrogen species. Thus, iron can induce as well as inhibit both oxidative and nitrosative stress. It also has a key role in reactive oxygen and nitrogen species-mediated apoptosis. We assessed the differences in tyrosine nitration and caspase 3 expression in the liver, heart, and kidneys of rats treated weekly with intravenous ferumoxytol, iron isomaltoside 1000, iron dextran, iron sucrose and ferric carboxymaltose (40?mg iron/kg body weight) for 5 weeks. Nitrotyrosine was quantified in tissue homogenates by Western blotting and the distribution of nitrotyrosine and caspase 3 was assessed in tissue sections by immunohistochemistry. Ferric carboxymaltose and iron sucrose administration did not result in detectable levels of nitrotyrosine or significant levels of caspase 3?vs. control in any of the tissue studied. Nitrotyrosine and caspase 3 levels were significantly (p<0.01) increased in all assessed organs of animals treated with iron dextran and iron isomaltoside 1000, as well as in the liver and kidneys of ferumoxytol-treated animals compared to isotonic saline solution (control). Nitrotyrosine and caspase 3 levels were shown to correlate positively with the amount of Prussian blue-detectable iron(III) deposits in iron dextran- and iron isomaltoside 1000-treated rats but not in ferumoxytol-treated rats, suggesting that iron dextran, iron isomaltoside 1000 and ferumoxytol induce nitrosative (and oxidative) stress as well as apoptosis via different mechanism(s). PMID:25050519

  3. Nanophasic biodegradation enhances the durability and biocompatibility of magnesium alloys for the next-generation vascular stents

    NASA Astrophysics Data System (ADS)

    Mao, Lin; Shen, Li; Niu, Jialin; Zhang, Jian; Ding, Wenjiang; Wu, Yu; Fan, Rong; Yuan, Guangyin

    2013-09-01

    Biodegradable metal alloys emerge as a new class of biomaterials for tissue engineering and medical devices such as cardiovascular stents. Deploying biodegradable materials to fabricate stents not only obviates a second surgical intervention for implant removal but also circumvents the long-term foreign body effect of permanent implants. However, these materials for stents suffer from an un-controlled degradation rate, acute toxic responses, and rapid structural failure presumably due to a non-uniform, fast corrosion process. Here we report that highly uniform, nanophasic degradation is achieved in a new Mg alloy with unique interstitial alloying composition as the nominal formula Mg-2.5Nd-0.2Zn-0.4Zr (wt%, hereafter, denoted as JDBM). This material exhibits highly homogeneous nanophasic biodegradation patterns as compared to other biodegradable metal alloy materials. Consequently it has significantly reduced degradation rate determined by electrochemical characterization. The in vitro cytotoxicity test using human vascular endothelial cells indicates excellent biocompatibility and potentially minimal toxic effect on arterial vessel walls. Finally, we fabricated a cardiovascular stent using JDBM and performed in vivo long-term assessment via implantation of this stent in an animal model. The results confirmed the reduced degradation rate in vivo, excellent tissue compatibility and long-term structural and mechanical durability. Thus, this new Mg-alloy with highly uniform nanophasic biodegradation represents a major breakthrough in the field and a promising material for manufacturing the next generation biodegradable vascular stents.

  4. Microbial acquisition of iron from ferric iron bearing minerals

    SciTech Connect

    Hersman, L.E.; Sposito, G.

    1998-12-31

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Iron is a universal requirement for all life forms. Although the fourth most abundant element in the geosphere, iron is virtually insoluble at physiological pH in oxidizing environments, existing mainly as very insoluble oxides and hydroxides. Currently it is not understood how iron is solubilized and made available for biological use. This research project addressed this topic by conducting a series of experiments that utilized techniques from both soil microbiology and mineral surface geochemistry. Microbiological analysis consisted of the examination of metabolic and physiological responses to mineral iron supplements. At the same time mineral surfaces were examined for structural changes brought about by microbially mediated dissolution. The results of these experiments demonstrated that (1) bacterial siderophores were able to promote the dissolution of iron oxides, (2) that strict aerobic microorganisms may use anaerobic processes to promote iron oxide dissolution, and (3) that it is possible to image the surface of iron oxides undergoing microbial dissolution.

  5. Chemical evolution. XL - Clay-mediated oxidation of diaminomaleonitrile

    NASA Technical Reports Server (NTRS)

    Ferris, J. P.; Hagan, W. J., Jr.; Alwis, K. W.; Mccrea, J.

    1982-01-01

    The inhibition of the oligomerization of HCN by montmorillonite clays is shown to be caused by oxidation of diaminomaleonitrile (DAMN) by ferric ion in the clay lattice, with ferrous ion and oxalic acid the reaction products. It is demonstrated that diiminosuccinonitrile is the initial reaction product and is rapidly hydrolized to oxalic acid and HCN. The same oxidative transformations are effected by ferric ion bound to Dowex 50, ferric ion in solution, and Ni(NH3)6(2+). The rate of reaction of DAMN indicates no catalytic role for the clay in the oxidation of DAMN, and little reaction of the latter was observed with montmorillonite in which the bulk of the iron was in the divalent state. The possible significance of these redox reactions to chemical evolution is discussed.

  6. The oxidizing power of illinois coal. I. The reaction with titanous chloride

    USGS Publications Warehouse

    Yoke, G.R.; Harman, C. Alex

    1941-01-01

    Illinois coals which have been exposed to air or oxygen show a small but definite ability to oxidize titanous chloride. This oxidizing power is gained very rapidly when freshly ground coal is exposed to air. Neither the magnitude nor the rapid increase of this oxidizing power can be accounted for entirely by the presence or the formation of soluble ferric compounds in the coal.

  7. Suboxic Deposition of Ferric Iron by Bacteria in Opposing Gradients of Fe(II) and Oxygen at Circumneutral pH

    PubMed Central

    Sobolev, Dmitri; Roden, Eric E.

    2001-01-01

    The influence of lithotrophic Fe(II)-oxidizing bacteria on patterns of ferric oxide deposition in opposing gradients of Fe(II) and O2 was examined at submillimeter resolution by use of an O2 microelectrode and diffusion microprobes for iron. In cultures inoculated with lithotrophic Fe(II)-oxidizing bacteria, the majority of Fe(III) deposition occurred below the depth of O2 penetration. In contrast, Fe(III) deposition in abiotic control cultures occurred entirely within the aerobic zone. The diffusion microprobes revealed the formation of soluble or colloidal Fe(III) compounds during biological Fe(II) oxidation. The presence of mobile Fe(III) in diffusion probes from live cultures was verified by washing the probes in anoxic water, which removed ca. 70% of the Fe(III) content of probes from live cultures but did not alter the Fe(III) content of probes from abiotic controls. Measurements of the amount of Fe(III) oxide deposited in the medium versus the probes indicated that ca. 90% of the Fe(III) deposited in live cultures was formed biologically. Our findings show that bacterial Fe(II) oxidation is likely to generate reactive Fe(III) compounds that can be immediately available for use as electron acceptors for anaerobic respiration and that biological Fe(II) oxidation may thereby promote rapid microscale Fe redox cycling at aerobic-anaerobic interfaces. PMID:11229928

  8. Experimental Spinel Standards for Ferric Iron (Fe3+) Determination During Peridotite Partial Melting

    NASA Astrophysics Data System (ADS)

    Wenz, M. D.; Sorbadere, F.; Rosenthal, A.; Frost, D. J.; McCammon, C. A.

    2014-12-01

    The presence of ferric iron (Fe3+) in the mantle plays a significant role in the oxygen fugacity (fO2) of the Earth's interior. This has a wide range of implications for Earth related processes ranging from the composition of the atmosphere to magmatic phase relations during melting and crystallization processes [1]. A major source of Earth's mantle magmas is spinel peridotite. Despite its low abundance, spinel (Fe3+/?Fe = 15-34%, [2]) is the main contributor of Fe3+to the melt upon partial melting. Analyses of Fe3+ on small areas of spinel and melt are required to study the Fe3+ behavior during partial melting of spinel peridotite. Fe K-edge X-ray Absorption Near Edge Structure (XANES) combines both high precision and small beam size, but requires standards with a wide range of Fe3+ content to obtain good calibration. Glasses with varying Fe3+ content are easily synthesized [3, 4]. Spinel, however, presents a challenge for experimental standards due to the low diffusion of Cr and Al preventing compositional homogeneity. Natural spinel standards are often used, but only cover a narrow Fe3+ range. Thus, there is a need for better experimental spinel standards over a wider range of fO2. Our study involves making experimental mantle spinels with variable Fe3+ content. We used a sol-gel auto-combustion method to synthesize our starting material [5]. FMQ-2, FMQ+0, and air fO2 conditions were established using a gas mixing furnace. Piston cylinder experiments were performed at 1.5GPa, and 1310 -1370°C to obtain solid material for XANES. To maintain distinct oxidizing conditions, three capsules were used: graphite for reduced, Re for intermediate and AuPd for oxidized conditions. The spinels were analyzed by Mössbauer spectroscopy. Fe3+/?Fe ranged from 0.3 to 0.6. These values are consistent with the Fe edge position obtained using XANES analyses, between 7130 and 7132 eV, respectively. Our spinels are thus suitable standards for Fe3+ measurements in peridotite systems and can be used to determine Fe3+/?Fe ratio of spinel during magma genesis from a peridotite source. [1] Canil et al. (1994), EPSL 123, 205-220. [2] Frost & McCammon (2008), Annu Rev Earth Planet Sci 36, 389-420. [3] Cottrell & Kelley (2011), EPSL 305, 270-282. [4] Falloon et al. (2008) J. Petrol. 49, 591-613. [5] Vader et al. (2013), J mater Sci 25, 765-771.

  9. Effects of phosphate and silicate on the transformation of hydroxycarbonate green rust to ferric oxyhydroxides

    NASA Astrophysics Data System (ADS)

    Feng, Xionghan; Wang, Xiaoming; Zhu, Mengqiang; Koopal, Luuk K.; Xu, Huanhuan; Wang, Yan; Liu, Fan

    2015-12-01

    Hydroxycarbonate green rust (GR1(CO32-)) was prepared by oxidation of aerated aqueous suspensions of Fe(II) hydroxide, and the presence of light promoted the transformation of GR1(CO32-) by dissolved O2 at pH 7.8 and 25 °C. Further transformation of GR1(CO32-) in the light was conducted in the presence of orthophosphate (P) or silicate (Si) anions, followed by solution analysis and solid product characterization using X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR). Results show that both P and Si anions significantly affect the transformation of GR1(CO32-) through adsorption on the intermediate products. The time required for complete GR1(CO32-) transformation and the phases, crystallinity and morphology of the transformation products all depend on the Fe/anion molar ratio. When compared to the control, the transformation can be promoted by low Si concentrations but retarded by P. With decreasing Fe/P ratio, the products change from acicular goethite (absence of P) to tabular lepidocrocite (Fe/P: 120-48) and to mixed phases of platelets of ferric GR1(CO32-) (EX-GR1) and minor ferrihydrite (Fe/P: 24-3). In terms of Si, the products are goethites when the Fe/Si ratio of 48-12, and with increasing ratio, the goethite crystallinity and particle size decrease and the morphology changes from acicular (absence of Si) to plate-like or isodimensional particles. The goethite morphology at low Fe/Si ratios is comparable to natural goethite samples commonly found in soils. At Fe/Si = 3, the products are EX-GR1 platelets with minor ferrihydrite coexisting. The likely pathway of the oxidative GR1(CO32-) transformation in the control system and in the presence of low concentrations of Si (Fe/Si ? 12) is GR1(CO32-) ? amorphous ?-FeOOH-like phase ? ?-FeOOH via a dissolution-oxidation-precipitation mechanism. In addition, Fe(II) released during dissolution of GR1(CO32-) is adsorbed on the products and the transformation of the ?-FeOOH-like phase to goethite is catalyzed by the adsorbed Fe(II). For the P system, the released Fe(II) forms ternary surface complexes with P on the mineral surfaces without any catalytic role, leading to the formation of lepidocrocite at low P concentrations. Clearly, the oxidative transformation of green rust to various crystalline iron oxyhydroxides depends on the type and concentration (Fe/anion molar ratio) of co-existing anions. This study also suggests that the natural goethite formed by Fe(II) oxidation in the form of plate-like or isodimensional particles is most likely related to the ubiquitous presence of silicates in soil environments.

  10. DBAR investigation on films of polypyrrole incorporated polyvinylalcohol doped with ferric chloride

    NASA Astrophysics Data System (ADS)

    Lobo, Blaise; Baraker, B. M.; Hammannavar, P. B.; Bhajantri, R. F.; Ranganath, M. R.; Hurkadli, M.; Ravindrachary, V.

    2015-06-01

    Flexible films of pyrrole(Py) sorbed, ferric chloride (FeCl3) doped polyvinylalcohol(PVA) were prepared by solution casting. The films were characterized by XRD, UV-Visible spectrometry, Thermal Analysis (DSC, DTA/TGA), FTIR and electrical measurements. In this paper, the results of Doppler Broadening of Annihilation Radiation (DBAR) spectra in the doping range, from 4 wt% up to 18 wt%, are discussed. The XRD and DSC scans complement the DBAR results. The computed S- parameter and W -parameter reflect changes in the degree of crystallinity and the average crystallite size, respectively, of polypyrrole(PPy) incorporated PVA samples doped with ferric chloride.

  11. Effects of melt composition on Fe3+/Fe2+ in silicate melts: a step to model ferric/ferrous ratio in multicomponent systems

    NASA Astrophysics Data System (ADS)

    Borisov, Alexander; Behrens, Harald; Holtz, Francois

    2015-02-01

    The effect of Al2O3, MgO and total iron on the ferric/ferrous ratio in silicate melts was investigated in model silicate melts in the temperature range 1400-1550 °C at 1 atm total pressure. The experiments were done mostly in air and partially in pure CO2. It is demonstrated that an increase in Al2O3 concentration in a basaltic melt results in a moderate decrease of Fe3+/Fe2+ ratio. In contrast, the increase in Al2O3 in more silicic melts results in a much more pronounced decrease of Fe3+/Fe2+ ratio. The increase of MgO concentration in a basaltic melt results in a moderate increase of Fe3+/Fe2+ ratio but has a negligible effects in more silicic melts. The different behavior of Al2O3 and MgO in basaltic and more silicic melts indicates that at constant T- fO2 conditions, the effects of melt composition on ferric/ferrous ratio cannot be predicted accurately as a function of ? d i X i where d i are fixed empirical coefficients and X i are mole fractions of the main oxide component in silicate melts. We suggest an alternative approach which accounts for the interaction of cations in complex silicate melts. Based on the data obtained in this study, an equation predicting the ferric/ferrous ratio of ultramafic to silicic melts at air conditions with changing SiO2, TiO2, Al2O3, total iron, MgO and P2O5 is proposed.

  12. 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 discovered the presence of abundant np-Fe(sup 0) particles in the glass patinas coating most soil particles. Therefore, the correlation of glass content and magnetic susceptibility can be explained by the presence of the np-Feo particles in glass: small particles contain relatively more np-Fe(sup 0) as glass coatings because the surface area versus mass ratio of the grain size is so increased. The magnetic properties of lunar soil are important in dust mitigation on the Moon (Taylor et al. 2005). Thus material simulating this property is important for testing mitigation methods using electromagnetic field. This np- Fe(sup 0) also produces a unique energy coupling to normal microwaves, such as present in kitchen microwave ovens. Effectively, a portion of lunar soil placed in a normal 2.45 GHz oven will melt at greater than 1200 C before your tea will boil at 100 C, a startling and new discovery reported by Taylor and Meek (2004, 2005). Several methods have been investigated in attempts to make nanophase-sized Feo dispersed within silicate glass; like in the lunar glass. We have been successful in synthesizing such a product and continue to improve on our recipe. We have performed extensive experimentation on this subject to date. Ultimately it will probably be necessary to add this np-Fe(sup 0) bearing silicate glass to lunar soil stimulant, like JSC-1, to actually produce the desired magnetic and microwave coupling properties for use in appropriate ISRU experimentation.

  13. Perturbation-Response Scanning Reveals Ligand Entry-Exit Mechanisms of Ferric Binding Protein

    E-print Network

    Yanikoglu, Berrin

    , Turkey Abstract We study apo and holo forms of the bacterial ferric binding protein (FBP) which exhibits dynamics simulations. We find that the residue-by-residue displacements between the apo and the holo forms of the residues of the apo form. However, once the stabilizing ligand (Fe) is integrated to the system in holo FBP

  14. Microdetermination of proteins by resonance light scattering technique based on aggregation of ferric nanoparticles

    NASA Astrophysics Data System (ADS)

    Shu-hong, Zhang; Yong-shan, Fan; Shuo, Feng; Yun-feng, Zhang

    2009-05-01

    A new method for protein determination is presented that allows measurement of proteins at nanogram levels with simple procedure. The method applies a resonance light scattering (RLS) technique, but based on aggregation of ferric nanoparticles on protein template instead of the usual interaction of organic days with proteins. By mixing ferric colloid with sodium cacodylate buffer solution, ferric nanoparticles can be obtained in the size of about 5 nm and kept their positive charges in a wide range of pH 1.8-7.6. The ferric nanoparticles can interact with proteins to form particular aggregates and thus result in strong and stable RLS. Under optimal conditions (wavelength of 451 nm and pH 7.4), few substances interfere with this assay. The detection limitation of bovine serum albumin (BSA) is 6.6 ng/mL and the linear range is 20-700 ng/mL. This method gives almost identical responses for BSA, human serum albumin (HSA) and ?-globulin (?-G), and can be used for the determination of total proteins in human serum with satisfactory results.

  15. A novel electrochemical process for the recovery and recycling of ferric chloride from precipitation sludge.

    PubMed

    Mejia Likosova, E; Keller, J; Poussade, Y; Freguia, S

    2014-03-15

    During wastewater treatment and drinking water production, significant amounts of ferric sludge (comprising ferric oxy-hydroxides and FePO4) are generated that require disposal. This practice has a major impact on the overall treatment cost as a result of both chemical addition and the disposal of the generated chemical sludge. Iron sulfide (FeS) precipitation via sulfide addition to ferric phosphate (FePO4) sludge has been proven as an effective process for phosphate recovery. In turn, iron and sulfide could potentially be recovered from the FeS sludge, and recycled back to the process. In this work, a novel process was investigated at lab scale for the recovery of soluble iron and sulfide from FeS sludge. Soluble iron is regenerated electrochemically at a graphite anode, while sulfide is recovered at the cathode of the same electrochemical cell. Up to 60 ± 18% soluble Fe and 46 ± 11% sulfide were recovered on graphite granules for up-stream reuse. Peak current densities of 9.5 ± 4.2 A m(-2) and minimum power requirements of 2.4 ± 0.5 kWh kg Fe(-1) were reached with real full strength FeS suspensions. Multiple consecutive runs of the electrochemical process were performed, leading to the successful demonstration of an integrated process, comprising FeS formation/separation and ferric/sulfide electrochemical regeneration. PMID:24397913

  16. TRANSFORMATION AND MOBILIZATION OF ARSENIC ADSORBED ON GRANULAR FERRIC HYDROXIDE UNDER BIO-REDUCTIVE CONDITIONS

    EPA Science Inventory

    Biotic and abiotic reduction of arsenic (V) and iron (III) influences the partioning of arsenic (As) between the solid and aqueous phases in soils, sediments and wastes. In this study, laboratory experiments on arsenic adsorbed on granular ferric hydroxide (GFH) was performed to ...

  17. Identification and Characterization of a Novel Ferric Reductase from the Hyperthermophilic Archaeon Archaeoglobus fulgidus*

    E-print Network

    Schroeder, Imke

    activity in its soluble protein fraction. The correspond- ing enzyme, which constitutes about 0(P)H:flavin oxi- doreductase. The enzyme exhibits a temperature opti- mum of 88 °C. When incubated at 85 °C, the ferric re- ductase consists of a single subunit with a Mr of 18,000. The Mr of the native enzyme

  18. Ferric reductase activity and PsFRO1 sequence variation in pisum sps

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Physiological studies in pea (Pisum sativum) suggest that the reduction of iron (Fe) is the rate-limiting physiological process in Fe acquisition by dicotyledonous plants. Previous molecular work suggests that ferric reductase activity is regulated at both the transcriptional and post-translational ...

  19. MOLECULAR AND PHENOTYPIC CHARACTERIZATION OF TRANSGENIC SOYBEAN EXPRESSING THE ARABIDOPSIS FERRIC CHELATE REDUCTASE GENE, FRO2

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soybean (Glycine max Merr.) production is reduced under iron-limiting calcareous soils throughout the upper Midwest regions of the U.S. Soybean like other dicotyledonous plants responds to iron-limiting environments by induction of an active proton pump, a ferric iron reductase and a Fe transporter....

  20. ELECTRODE MEASUREMENT OF REDOX POTENTIAL IN ANAEROBIC FERRIC/FERROUS CHLORIDE SYSTEMS

    EPA Science Inventory

    The behaviour of two inert redox electrodes (Pt and wax-impregnated graphite) was investigated in anaerobic ferrous and ferric chloride solutions in order to establish if these electrodes respond to the Fe3+/Fe2+ couple in a Nernstian manner. A new method fo...

  1. ELECTRODE MEASUREMENT OF REDOX POTENTIAL IN ANAEROBIC FERRIC/FERROUS CHLORIDE SYSTEMS

    EPA Science Inventory

    The behavior of two inert redox electrodes (Pt and wax-impregnated graphite) was investigated in anaerobic ferrous and ferric chloride solutions in order to establish if these electrodes respond to the FE3/Fe2+ couple in a Nernstian nanner. ew method for determining dissolved fer...

  2. ANALYSIS OF FERRIC AND FERROUS IONS IN SOIL EXTRACTS BY ION CHROMATOGRAPHY

    EPA Science Inventory

    A method using ion chromatography (IC) for the analysis of ferrous (Fe 2+) and ferric (Fe 3+) ions in soil extracts has been developed. This method uses an ion exchange column with detection at 520 nm after post-column derivatization. Selectivity is achieved by using an anionic...

  3. 40 CFR 180.1302 - Sodium Ferric Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance. 180.1302 Section 180.1302 Protection of... Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance. An exemption from the requirement of a tolerance is established for residues of sodium ferric EDTA in or on all food commodities when applied as...

  4. 40 CFR 180.1302 - Sodium Ferric Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance. 180.1302 Section 180.1302 Protection of... Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance. An exemption from the requirement of a tolerance is established for residues of sodium ferric EDTA in or on all food commodities when applied as...

  5. 40 CFR 180.1302 - Sodium Ferric Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance. 180.1302 Section 180.1302 Protection of... Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance. An exemption from the requirement of a tolerance is established for residues of sodium ferric EDTA in or on all food commodities when applied as...

  6. 40 CFR 180.1302 - Sodium Ferric Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance. 180.1302 Section 180.1302 Protection of... Ethylenediaminetetraacetate (EDTA); exemption from the requirement of a tolerance. An exemption from the requirement of a tolerance is established for residues of sodium ferric EDTA in or on all food commodities when applied as...

  7. Martian weathering/alteration scenarios from spectral studies of ferric and ferrous minerals

    NASA Technical Reports Server (NTRS)

    Bell, James F., III; Adams, John B.; Morris, Richard V.

    1992-01-01

    We review the major aspects of our current knowledge of martian ferric and ferrous mineralogy based on the available ground-based telescopic and spacecraft data. What we know and what we don't know are used to constrain various weathering/alteration models and to identify key future measurements and techniques that can distinguish between these models.

  8. Mineralogy at Gusev Crater from the Mossbauer spectrometer on the Spirit Rover

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Klingelhofer, G.; Bernhardt, B.; Schroder, C.; Rodionov, D. S.; De Souza, P. A. Jr; Yen, A.; Gellert, R.; Evlanov, E. N.; Foh, J.; Kankeleit, E.; Gutlich, P.; Ming, D. W.; Renz, F.; Wdowiak, T.; Squyres, S. W.; Arvidson, R. E.

    2004-01-01

    Mossbauer spectra measured on Mars by the Spirit rover during the primary mission are characterized by two ferrous iron doublets (olivine and probably pyroxene) and a ferric iron doublet (tentatively associated to nanophase ferric iron oxide). Two sextets resulting from nonstoichiometric magnetite are also present, except for a coating on the rock Mazatzal, where a hematite-like sextet is present. Greater proportions of ferric-bearing phases are associated with undisturbed soils and rock surfaces as compared to fresh rock surfaces exposed by grinding. The ubiquitous presence of olivine in soil suggests that physical rather than chemical weathering processes currently dominate at Gusev crater.

  9. Accessible and green manufacturing of magnetite (ferrous ferric oxide) nanocrystals and their use in magnetic separations

    NASA Astrophysics Data System (ADS)

    Yavuz, Cafer Tayyar

    This work describes the first size dependent magnetic separation in nanoscale. Magnetite (Fe3O4) nanocrystals of high quality and uniform size were synthesized with monodispersity below 10%. Magnetite nanocrystals of 4 nm to 33 nm (average diameter) were produced. Batch synthesis was shown to go up to 20 grams which is more than 10 times of a standard nanocrystal synthesis, without loosing the quality and monodispersity. Reactor design for mass (1 gram per hour) production of magnetite nanocrystals is reported for the first time. The cost of a kg of lab purity magnetite nanocrystals was shown to be 2600. A green synthesis that utilizes rust and edible oils was developed. The cost of a kg was brought down to 22. Size dependency of magnetism was shown in nanoscale for the first time. Reversible aggregation theory was developed to explain the low field magnetic separation and solution behavior of magnetite nanocrystals. Arsenic was removed from drinking water with magnetite nanocrystals 200 times better than commercial adsorbents. Silica coating was successfully applied to enable the known silica related biotechnologies. Magnetite-silica nanoshells were functionalized with amino groups. For the first time, silver was coated on the magnetite-silica nanoshells to produce triple multishells. Anti-microbial activity of multishells is anticipated.

  10. Side chain crystallization and non-equilibrium phenomena in nanophase separated poly(3-alkyl thiophenes)

    NASA Astrophysics Data System (ADS)

    Pankaj, Shireesh; Beiner, Mario

    2010-06-01

    A series of regio-random poly(3-alkyl thiophenes) containing C = 6-12 carbon atoms per side chain is studied using shear, calorimetry and x-ray scattering methods. Dynamic and structural data indicate a nanophase separation of thiophene main chains and alkyl groups. Alkyl nanodomains of size of 1-3 nm are formed as indicated by pre-peaks in scattering data at 0.2Å-1?q?0.6Å-1. Apart from the conventional ? relaxation, an additional ?PE process appears at low temperatures reflecting an independent dynamics within the alkyl nanodomains. The influence of slow side chain crystallization and densification processes during physical aging below Tg on the relaxation behavior is studied. Long term experiments show that short alkyl groups do not crystallize, whereas for longer alkyl groups, side chain crystallization is occurring but hindered by immobile and rigid main chains. Slow side chain crystallization processes are indicated in poly(3-decyl thiophene) and poly(3-dodecyl thiophene) by melting peaks in DSC scans, a decreasing ?PE intensity and an increase in the plateau modulus. Isothermal crystallization experiments on these samples show that the alkyl groups can exist in different polymorphic states.

  11. 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

  12. 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 ?. 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, ? \\lt 0.0701 u (b) transition regime, 0.0701 u?slant ? ?slant 0.0916 u and (c) thick coating regime, ? \\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 ? \\lt 7.0 \\text{nm} transition regime, 7.0\\lt? \\lt 9.2 \\text{nm} and thick coating, ? \\gt 9.2 \\text{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 components can have substantial effects upon aggregation for concentrations less than 1%.

  13. Primary Ferric Iron-Bearing Rhönite in Plutonic Igneous Angrite NWA 4590: Implications for Redox Conditions on the Angrite Parent Body

    NASA Astrophysics Data System (ADS)

    Kuehner, S. M.; Irving, A. J.

    2007-12-01

    Northwest Africa 4590 is a heterogeneous olivine gabbro with cumulate texture composed of Al-Ti-rich clinopyroxene, pure anorthite, Ca-rich olivine, kirschsteinite and ulvöspinel, with accessory troilite, merrillite, Ca silicophosphate, kamacite and glasses [1]. Rhönite now has been identified in this specimen (for the first time in any angrite) as (1) a large (0.65 mm long), blocky, anhedral grain adjacent to anorthite, kirschsteinite and troilite, (2) ca. 15 micron grains along grain boundaries of the major phases (in one case in contact with clinopyroxene and metal), and (3) ca. 30 micron grains within melt inclusions and veins composed of kirschsteinite, olivine, anorthite, troilite, hercynite and glass. The rhönite is nearly opaque in transmitted light, with a deep cinnamon-red color on thin grain edges. The average composition of the largest grain is (in wt.%): SiO2 23.6, TiO2 9.9, Al2O3 16.3, Cr2O3 0.1, FeOt 33.6, MnO 0.14, MgO 3.5, CaO 13.1. Stoichiometry (14 cations, 20 oxygen atoms) requires about 12% of the total iron to be in the ferric state, resulting in the nominal formula: (Ca2.01Mn0.02)(Fe2+3.55Fe3+0.45Mg0.75Al0.12Cr0.15)Ti0.9 5(Si3.37Al2.63)O20 In the co-existing ulvöspinel about 18% of the iron must be ferric to achieve charge balance; likewise, Fe-Ti spinel coexisting with metal in Angra dos Reis contains ferric iron [2]. In contrast, the spinel (Cr-pleonaste) in metal-rich angrite NWA 2999 is stoichiometric without any apparent ferric iron. The coexistence of ferric iron- bearing silicate and oxide phases with Fe metal implies that the oxygen fugacity during crystallization of NWA 4590 was somewhat more oxidizing than that of the IW buffer. Compositions of primary (pre-exsolution) olivine and kirschsteinite in NWA 4590 record a minimum magmatic temperature of 910-950°C, based on the solvus of [3]. Previous experimental studies [4] also imply that other metal-bearing plutonic (AdoR, LEW 86010) and quench-textured (LEW 87051) angrites equilibrated at oxygen fugacities near QFM - 2 log units and relatively high temperatures. Although not previously known from angrites, rhönite has been reported from terrestrial alkalic rocks, CV chondrites and a lunar mare basalt [5]. [1] Irving A. et al. (2006) EOS, Trans. AGU 87, #P51E-1245; Kuehner S. and Irving A. (2007) LPS XXXVIII, #1344 [2] Prinz M. et al. (1977) EPSL 35, 317-330 [3] Mukhopadhyay D. and Lindsley D. (1983) Amer. Mineral. 68, 1089-1094 [4] Jurewicz A. et al. (1991) Science 252, 695-698; McKay G. et al. (1994) GCA 58, 2911-2919 [5] Treiman A. (2007) LPS XXXVIII, #1244.

  14. Name: Ilia N. Ivanov Position Title: R&D Staff, CNMS, and Center for Nanophase Materials Sciences Adjunct Professor, University of TN-Knoxville

    E-print Network

    Pennycook, Steve

    International School for Business in Industry and Sciences, 1993 Russian University of Chemical Technology BName: Ilia N. Ivanov Position Title: R&D Staff, CNMS, and Center for Nanophase Materials Sciences. of Material Sciences and Technologies, University of Tennessee-Knoxville 1998­2001 Postdoctoral Research

  15. Energy cascades, excited state dynamics, and photochemistry in cob(III)alamins and ferric porphyrins.

    PubMed

    Rury, Aaron S; Wiley, Theodore E; Sension, Roseanne J

    2015-03-17

    Porphyrins and the related chlorins and corrins contain a cyclic tetrapyrrole with the ability to coordinate an active metal center and to perform a variety of functions exploiting the oxidation state, reactivity, and axial ligation of the metal center. These compounds are used in optically activated applications ranging from light harvesting and energy conversion to medical therapeutics and photodynamic therapy to molecular electronics, spintronics, optoelectronic thin films, and optomagnetics. Cobalt containing corrin rings extend the range of applications through photolytic cleavage of a unique axial carbon-cobalt bond, permitting spatiotemporal control of drug delivery. The photochemistry and photophysics of cyclic tetrapyrroles are controlled by electronic relaxation dynamics including internal conversion and intersystem crossing. Typically the electronic excitation cascades through ring centered ??* states, ligand to metal charge transfer (LMCT) states, metal to ligand charge transfer (MLCT) states, and metal centered states. Ultrafast transient absorption spectroscopy provides a powerful tool for the investigation of the electronic state dynamics in metal containing tetrapyrroles. The UV-visible spectrum is sensitive to the oxidation state, electronic configuration, spin state, and axial ligation of the central metal atom. Ultrashort broadband white light probes spanning the range from 270 to 800 nm, combined with tunable excitation pulses, permit the detailed unravelling of the time scales involved in the electronic energy cascade. State-of-the-art theoretical calculations provide additional insight required for precise assignment of the states. In this Account, we focus on recent ultrafast transient absorption studies of ferric porphyrins and corrin containing cob(III)alamins elucidating the electronic states responsible for ultrafast energy cascades, excited state dynamics, and the resulting photoreactivity or photostability of these compounds. Iron tetraphenyl porphyrin chloride (Fe((III))TPPCl) exhibits picosecond decay to a metal centered d ? d* (4)T state. This state decays on a ca. 16 ps time scale in room temperature solution but persists for much longer in a cryogenic glass. The photoreactivity of the (4)T state may lead to novel future applications for these compounds. In contrast, the nonplanar cob(III)alamins contain two axial ligands to the central cobalt atom. The upper axial ligand can be an alkyl group as in the two biologically active coenzymes or a nonalkyl ligand such as -CN in cyanocobalamin (vitamin B12) or -OH in hydroxocobalamin. The electronic structure, energy cascade, and bond cleavage of these compounds is sensitive to the details of the axial ligand. Nonalkylcobalamins exhibit ultrafast internal conversion to a low-lying state of metal to ligand or ligand to metal charge transfer character. The compounds are generally photostable with ground state recovery complete on a time scale of 2-7 ps in room temperature aqueous solution. Alkylcobalamins exhibit ultrafast internal conversion to an S1 state of d/? ? ?* character. Most compounds undergo bond cleavage from this state with near unit quantum yield within ?100 ps. Recent theoretical calculations provide a potential energy surface accounting for these observations. Conformation dependent mixing of the corrin ? and cobalt d orbitals plays a significant role in the observed photochemistry and photophysics. PMID:25741574

  16. Nanocrystalline Complex Oxides Prepared by Mechanochemical Reactions

    SciTech Connect

    Sepelak, V.; Bergmann, I.; Indris, S.; Subrt, J.; Heitjans, P.; Becker, K.-D.

    2010-07-13

    The preparation of complex oxides by the conventional solid-state (ceramic) route requires a number of stages, including homogenization of the powder precursors, compaction of the reactants, and finally prolonged heat treatment at considerably elevated temperatures under controlled oxygen fugacity. One goal of modern materials research and development has been to identify simpler processing schemes that do not rely upon high-temperature treatments for inducing solid-state reactions. At present, mechanochemical methods become widely used for the preparation of nanocrystalline materials due to their relative simplicity and availability. In this work, selected examples of the preparation of nanoscale complex oxides via single-step mechanochemical routes are presented. Nuclear spectroscopic methods are employed to follow the mechanically induced formation of nanooxides and to characterize the nonequilibrium structural state of the resulting nanophases at the atomic level.

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

    PubMed

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

    2015-08-30

    Abiotic oxidation of Fe(II) is a common pathway in the formation of Fe (hydr)oxides under natural conditions, however, little is known regarding the presence of arsenate on this process. In hence, the effect of arsenate on the precipitation of Fe (hydr)oxides during the oxidation of Fe(II) is investigated. Formation of arsenic-containing Fe (hydr)oxides is constrained by pH and molar ratios of As:Fe during the oxidation Fe(II). At pH 6.0, arsenate inhibits the formation of lepidocrocite and goethite, while favors the formation of ferric arsenate with the increasing As:Fe ratio. At pH 7.0, arsenate promotes the formation of hollow-structured Fe (hydr)oxides containing arsenate, as the As:Fe ratio reaches 0.07. Arsenate effectively inhibits the formation of magnetite at pH 8.0 even at As:Fe ratio of 0.01, while favors the formation of lepidocrocite and green rust, which can be latterly degenerated and replaced by ferric arsenate with the increasing As:Fe ratio. This study indicates that arsenate and low pH value favor the slow growth of dense-structured Fe (hydr)oxides like spherical ferric arsenate. With the rapid oxidation rate of Fe(II) at high pH, ferric (hydr)oxides prefer to precipitate in the formation of loose-structured Fe (hydr)oxides like lepidocrocite and green rust. PMID:25855615

  18. Determination of iron-ligand bond lengths in ferric and ferrous horse heart cytochrome c using multiple-scattering analyses of XAFS data

    SciTech Connect

    Cheng, M.C.; Rich, A.M.; Armstrong, R.S.; Ellis, P.J.; Lay, P.A.

    1999-12-13

    Cytochrome c (cyt c) is a small heme protein (MW 12 384) that functions as a biological electron-transfer agent. It consists of a single polypeptide chain and a prosthetic heme group and provides a pathway for the transfer of electrons from cyt c reductase to cyt c oxidase in the mitochondrial respiratory chain (oxidative phosphorylation). The protein participates in oxidation-reduction reactions with the heme iron alternating between the oxidized (ferric, Fe{sup III}) state and the reduced (ferrous, Fe{sup II}) state. X-ray absorption fine structure (XAFS) data were obtained from frozen aqueous solutions (10 K) of horse heart ferri- and ferrocyt c. Models of the structure about the Fe center were refined to optimize the fit between the observed XAFS in the range 0 {le} k {le} 16.3 {angstrom}{sup {minus}1} and the XAFS calculated using both single-scattering (SS) and multiple-scattering (MS) calculations. The bond lengths obtained are more accurate and precise than those determined previously for cyt c from various species using X-ray crystallography. The Fe-N bond lengths are 1.98--1.99 {angstrom} for both oxidation states of cyt c. The Fe-S bond of derricyt c (2.33 {angstrom}) is significantly longer than that of ferrocyt c (2.29 {angstrom}). The small changes in the bond lengths are consistent with the small reorganizational energy required for the fast electron-transfer reaction of cyt c.

  19. Chemical Precipitation Synthesis of Ferric Chloride Doped Zinc Sulphide Nanoparticles and Their Characterization Studies

    E-print Network

    Theivasanthi, T; Alagar, M; 10.7598/cst2013.207

    2013-01-01

    Nanoparticles of Ferric Chloride doped ZnS has been synthesized by simple chemical precipitation method and characterized by XRD, SEM, UV-Vis analysis, Differential Thermal Analysis, Thermo Gravimetric Analysis and Differential Scanning Calorimetry. XRD patterns of the samples reveal particle size, specific surface area and the formation of cubic structure. The SEM images show that the cauliflower likes structure. Optical band gap values have been obtained from UV-Vis absorption spectra. It has also been found that energy band gap (Eg) increases with the increase in molar concentration of reactant solution. Thermal analysis measurement of the prepared sample shows that the thermal stability of pure ZnS is decreased due to increase in Ferric Chloride concentration. Undoped ZnS is more thermal stable when compared to FeCl3 doped ZnS.

  20. Influence of carboxymethyl dextran and ferric citrate on the adhesion of CHO cells on microcarriers.

    PubMed

    Landauer, Karlheinz; Wiederkum, Susanne; Dürrschmid, Markus; Klug, Helga; Simic, Gordana; Blüml, Gerald; Doblhoff-Dier, Otto

    2003-01-01

    Due to the inherent risks of animal-derived raw materials, the biopharmaceutical industry has an increasing demand for serum-free and protein-free media for industrial cell culture bioprocesses. The absence of serum often changes the characteristics of mammalian cells, especially growth, productivity, and adherence properties. This study is mainly focused on the influence of media additives on cell adherence characteristics. An array of different carboxymethyl dextrans and different ferric citrate concentrations was tested with a number of CHO clones, using standard cell culture Roux-flasks and Cytoline 1 macroporous microcarriers. A prototype mixing system with controlled shear force input was developed as a screening system for adherence characteristics. The results of this evaluation revealed a negatively correlated dose-dependent influence on adhesion for ferric citrate. It was also found that certain carboxymethyl dextrans are capable of increasing the adherence on Roux-flasks and microcarriers. PMID:12573002

  1. Ferric sulfates on Mars: A combined mission data analysis of salty soils at Gusev crater and laboratory experimental investigations

    E-print Network

    on the stability field and phase transition pathway of typical ferric sulfates, we suggest that the strong materials, e.g., phyllosilicatebearing deposits [Bishop et al., 2008; Ehlmann et al., 2008a; Mustard et al

  2. Thermoreversible Transition between Nanophase- and Macrophase-Separation from Block Supramacromolecules via Hydrogen Bonding in an Ionic Liquid

    NASA Astrophysics Data System (ADS)

    Noro, Atsushi; Yamagishi, Hajime; Matsushita, Yushu

    2010-03-01

    We investigate thermoreversible transition between nanophase- and macrophase-separation from block supramacromolecules in an ionic liquid induced by association-dissociation of two macromolecules with hydrogen bonding end-linkers, where supramacromolecules are termed as supramolecular assembly of macromolecules via non-covalent bonding. A thermally stable ionic liquid with negligible vapor pressure, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, was used as a solvent to attain the molecular mobility of the system under better control. Two macromolecular building blocks were prepared: one is a poly(trimethoxystyrene) with a small end-linker of poly(hydroxystyrene) (Mn = 53k) and the other is a poly(butyl acrylate) with a small end-linker of poly(vinylpyridine) (Mn = 54k), both of which dissolve in the ionic liquid. Phenol should be hydrogen-bonded with pyridine. Nanophase-separated structure was observed in the ionic liquid solution of the blend by small-angle X-ray scattering at 30 ^oC, because of the formation of block supramacromolecules. But there are no scattering peaks above 90 ^oC in X-ray profiles: The sample is causing macrophase separation. It has also been found that the formation of supramacromolecules is thermoreversible due to hydrogen bonding.

  3. 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. PMID:18259645

  4. 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.

  5. The determination of ferric iron in plants by HPLC using the microbial iron chelator desferrioxamine E.

    PubMed

    Fernández, Victoria; Winkelmann, Günther

    2005-02-01

    Common methods for plant iron determination are based on atomic absorption spectroscopy, radioactive measurements or extraction with subsequent spectrophotometry. However, accuracy is often a problem due to background, contamination and interfering compounds. We here describe a novel method for the easy determination of ferric iron in plants by chelation with a highly effective microbial siderophore and separation by high performance liquid chromatography (HPLC). After addition of colourless desferrioxamine E (DFE) to plant fluids, the soluble iron is trapped as a brown-red ferrioxamine E (FoxE) complex which is subsequently separated by HPLC on a reversed phase column. The formed FoxE complex can be identified due to its ligand-to-metal charge transfer band at 435 nm. Alternatively, elution of both, DFE and FoxE can be followed as separate peaks at 220 nm wavelength with characteristic retention times. The extraordinarily high stability constant of DFE with ferric iron of K = 10(32) enables extraction of iron from a variety of ferrous and ferric iron compounds and allows quantitation after separation by HPLC without interference by coloured by-products. Thus, iron bound to protein, amino acids, citrate and other organic acid ligands and even insoluble ferric hydroxides and phosphates can be solubilized in the presence desferrioxamine E. The "Ferrioxamine E method" can be applied to all kinds of plant fluids (apoplasmic, xylem, phloem, intracellular) either at physiological pH or even at acid pH values. The FoxE complex is stable down to pH 1 allowing protein removal by perchloric acid treatment and HPLC separation in the presence of trifluoroacetic acid containing eluents. PMID:15865410

  6. Repeat radiation synovectomy with dysprosium 165-ferric hydroxide macroaggregates in rheumatoid knees unresponsive to initial injection

    SciTech Connect

    Vella, M.; Zuckerman, J.D.; Shortkroff, S.; Venkatesan, P.; Sledge, C.B.

    1988-06-01

    Because of failure to fully respond to an initial intraarticular injection of dysprosium 165-ferric hydroxide macroaggregates, 17 patients with seropositive rheumatoid arthritis underwent repeat radiation synovectomy using this agent. Of the 13 patients who were evaluated 1 year later, 54% (7 knees) had good results, 31% (4 knees) had fair results, and 15% (2 knees) had poor results. The initial lack of significant benefit from radiation synovectomy did not appear to preclude a favorable response to a second injection.

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

    EPA Science Inventory

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

  8. Ferric Iron Precipitation in the Nagahama Bay, Satsuma Iwo-Jima Island, Kagoshima

    NASA Astrophysics Data System (ADS)

    Nagata, T.; Kiyokawa, S.; Ikehara, M.; Oguri, K.; Goto, S.; Ito, T.; Yamaguchi, K. E.; Ueshiba, T.

    2010-12-01

    Satsuma-Iwojima island is active volcanic island and 6 x 3 km in size, located 38km south of Kyushu island, Japan. The reddish brown water along the coast of the Iwo-dake volcano at the center of the island formed by neutralization through mixing of shallow hydrothermal fluid and seawater. The reddish brown water contains reddish ferrihydrite (Fe3+) that is derived from oxidation of Fe2+ from acidic hot spring (Shikaura and Tazaki, 2001). In the Nagahama Bay with its opening to the south, red-colored Fe-rich water is affected by tidal current, but sedimentation of the ferric hydroxide is confirmed to occur in the ocean bottom (Ninomiya and Kiyokawa, 2009). Here we focus other lines of evidence from long term observations and meteorological records as important factor to form thick iron rich sediments. Meteorological and stationary observations: We used weather record in the Satsuma Iwo-jima and cross-checked with stationary observations, which enabled us to observe color changes of the surface of Nagahama Bay. It was made clear that north wind condition in the Nagahama Bay resulted in changes of the color of its surface, from red to green, by intrusion of ocean water coming from outside. Long term temperature monitoring: The temperature of seawater in the Nagahama Bay fluctuated synchronically with the air temperature. But that of hot spring water rather remained constant regardless of the seasonal change. We observed that seawater temperature in the Nagahama Bay is low at high tide and high at low tide, and the rage of temperature change is maximum at the spring tide and minimum at the neap tide. In other words, the amount of discharge of hot spring and that of seawater inflow vary inversely. Core sample: In the Nagahama Bay, iron rich sediments that is more than 1 m thick were identified. The core sample shows lithology as following; upper part, 10-20cm thick, formed loose Fe-rich deposit, lower portion formed alteration of weakly consolidated Fe-rich orange-colored mud, the organic-rich black mud and volcanic ash layers. The basal part has distinctive pink ash layer, which was identified as 1997 volcanic activity. Therefore, the core samples have records of the past 12 years and show average deposition rate of 8cm/year. Sediment trap: There accumulated 7.5cm-thick materials, dominated by ferrihydrite, during the 82 days experiment (2009/July/12~Oct./03). Sedimentation rate is 2.8cm/month (33.3cm/year). Estimated deposition rate of the core sample is 8cm/year. These differences suggest that about three-forth of Fe-hydroxide formed the Nagahama Bay would have been flashed to the open ocean by tidal and storm effects. These lines of evidence suggest that neap tide supports relatively quiet and has enough supply of hot spring into seawater and south wind works as a cap. The fine-grained iron Fe-hydroxide in the Nagahama Bay is provided and deposited at neap tide and south wind condition.

  9. Super adsorption capability from amorphousization of metal oxide nanoparticles for dye removal

    NASA Astrophysics Data System (ADS)

    Li, L. H.; Xiao, J.; Liu, P.; Yang, G. W.

    2015-03-01

    Transitional metal oxide nanoparticles as advanced environment and energy materials require very well absorption performance to apply in practice. Although most metal oxides are based on crystalline, high activities can also be achieved with amorphous phases. Here, we reported the adsorption behavior and mechanism of methyl blue (MB) on the amorphous transitional metal oxide (Fe, Co and Ni oxides) nanoparticles, and we demonstrated that the amorphousization of transitional metal oxide (Fe, Co and Ni oxides) nanoparticles driven by a novel process involving laser irradiation in liquid can create a super adsorption capability for MB, and the maximum adsorption capacity of the fabricated NiO amorphous nanostructure reaches up to 10584.6 mgg-1, the largest value reported to date for all MB adsorbents. The proof-of-principle investigation of NiO amorphous nanophase demonstrated the broad applicability of this methodology for obtaining new super dyes adsorbents.

  10. Super adsorption capability from amorphousization of metal oxide nanoparticles for dye removal

    PubMed Central

    Li, L. H.; Xiao, J.; Liu, P.; Yang, G. W.

    2015-01-01

    Transitional metal oxide nanoparticles as advanced environment and energy materials require very well absorption performance to apply in practice. Although most metal oxides are based on crystalline, high activities can also be achieved with amorphous phases. Here, we reported the adsorption behavior and mechanism of methyl blue (MB) on the amorphous transitional metal oxide (Fe, Co and Ni oxides) nanoparticles, and we demonstrated that the amorphousization of transitional metal oxide (Fe, Co and Ni oxides) nanoparticles driven by a novel process involving laser irradiation in liquid can create a super adsorption capability for MB, and the maximum adsorption capacity of the fabricated NiO amorphous nanostructure reaches up to 10584.6?mgg?1, the largest value reported to date for all MB adsorbents. The proof-of-principle investigation of NiO amorphous nanophase demonstrated the broad applicability of this methodology for obtaining new super dyes adsorbents. PMID:25761448

  11. Resonant Inelastic X-ray Scattering on Ferrous and Ferric Bis-imidazole Porphyrin and Cytochrome c: Nature and Role of the Axial Methionine–Fe Bond

    PubMed Central

    2015-01-01

    Axial Cu–S(Met) bonds in electron transfer (ET) active sites are generally found to lower their reduction potentials. An axial S(Met) bond is also present in cytochrome c (cyt c) and is generally thought to increase the reduction potential. The highly covalent nature of the porphyrin environment in heme proteins precludes using many spectroscopic approaches to directly study the Fe site to experimentally quantify this bond. Alternatively, L-edge X-ray absorption spectroscopy (XAS) enables one to directly focus on the 3d-orbitals in a highly covalent environment and has previously been successfully applied to porphyrin model complexes. However, this technique cannot be extended to metalloproteins in solution. Here, we use metal K-edge XAS to obtain L-edge like data through 1s2p resonance inelastic X-ray scattering (RIXS). It has been applied here to a bis-imidazole porphyrin model complex and cyt c. The RIXS data on the model complex are directly correlated to L-edge XAS data to develop the complementary nature of these two spectroscopic methods. Comparison between the bis-imidazole model complex and cyt c in ferrous and ferric oxidation states show quantitative differences that reflect differences in axial ligand covalency. The data reveal an increased covalency for the S(Met) relative to N(His) axial ligand and a higher degree of covalency for the ferric states relative to the ferrous states. These results are reproduced by DFT calculations, which are used to evaluate the thermodynamics of the Fe–S(Met) bond and its dependence on redox state. These results provide insight into a number of previous chemical and physical results on cyt c. PMID:25475739

  12. Synthesis and XRD/PL Studies of Pure and Sb2O3 Doped ZnO Nanophases

    SciTech Connect

    Boulares, N.; Guergouri, K.; Tabet, N.; Monty, C.

    2007-08-22

    Pure and Sb2O3 (0 to 5% molar fraction) doped ZnO nanophases were synthesized using a sublimation-condensation method in a solar furnace. The initial and final powders were characterized by X-ray diffraction (XRD) and photoluminescence (PL) techniques. XRD results showed no significant change in the lattice parameters and the presence of a new phase Zn7O2Sb12 in the highly doped micropowders but not in the nanopowders. The photoluminescence spectra showed a strong donor-acceptor pair (DAP) emission in the pure untreated ZnO micropowder which is drastically reduced in pure and doped nanopowders. The donor-bound excitonic band (DX) includes three well resolved peaks in the PL spectra of the doped micropowders while the spectra of doped nanopowders showed a broader band. Furthermore, the free exciton emission was absent in all doped samples.

  13. Analysis of the ferric citrate transport gene promoter of Escherichia coli.

    PubMed

    Enz, Sabine; Mahren, Susanne; Menzel, Claudia; Braun, Volkmar

    2003-04-01

    FecI, an extracytoplasmic-function sigma factor, is required for initiation of transcription of the ferric citrate transport genes. A mutational analysis of the fecA promoter revealed that the nonconserved -10 region and a downstream regulatory element are important for fecA promoter activity. However, nucleotide substitutions in the well-conserved -35 region also have an effect on the fecA promoter activity. Titration of FecI suggests that the FecI-RNA polymerase holoenzyme does not bind strongly to the downstream regulatory element, which is therefore probably involved in a subsequent step of transcription initiation. PMID:12644513

  14. Surface topology of the Escherichia coli K-12 ferric enterobactin receptor.

    PubMed Central

    Murphy, C K; Kalve, V I; Klebba, P E

    1990-01-01

    Monoclonal antibodies (MAb) were raised to the Escherichia coli K-12 ferric enterobactin receptor, FepA, and used to identify regions of the polypeptide that are involved in interaction with its ligands ferric enterobactin and colicins B and D. A total of 11 distinct FepA epitopes were identified. The locations of these epitopes within the primary sequence of FepA were mapped by screening MAb against a library of FepA::PhoA fusion proteins, a FepA deletion mutant, and proteolytically modified FepA. These experiments localized the 11 epitopes to seven different regions within the FepA polypeptide, including residues 2 to 24, 27 to 37, 100 to 178, 204 to 227, 258 to 290, 290 to 339, and 382 to 400 of the mature protein. Cell surface-exposed epitopes of FepA were identified and discriminated by cytofluorimetry and by the ability of MAb that recognize them to block the interaction of FepA with its ligands. Seven surface epitopes were defined, including one each in regions 27 to 37, 204 to 227, and 258 to 290 and two each in regions 290 to 339 and 382 to 400. One of these, within region 290 to 339, was recognized by MAb in bacteria containing intact (rfa+) lipopolysaccharide (LPS); all other surface epitopes were susceptible to MAb binding only in a strain containing a truncated (rfaD) LPS core, suggesting that they are physically shielded by E. coli K-12 LPS core sugars. Antibody binding to FepA surface epitopes within region 290 to 339 or 382 to 400 inhibited killing by colicin B or D and the uptake of ferric enterobactin. In addition to the FepA-specific MAb, antibodies that recognized other outer membrane components, including Cir, OmpA, TonA, and LPS, were identified. Immunochemical and biochemical characterization of the surface structures of FepA and analysis of its hydrophobicity and amphilicity were used to generate a model of the ferric enterobactin receptor's transmembrane strands, surface peptides, and ligand-binding domains. Images PMID:2139651

  15. Carboxylate free ?-oxo bridged ferric wheel with a record exchange coupling.

    PubMed

    Ahmed, Naushad; Upadhyay, Apoorva; Rajeshkumar, Thayalan; Vaidya, Shefali; Schnack, Jürgen; Rajaraman, Gopalan; Shanmugam, Maheswaran

    2015-10-27

    A novel oxo-bridged, carboxylate free 'ferric wheel' was isolated with the molecular formula [Fe(?-O)4(L(2-))8] (). Magnetic susceptibility measurements suggest that the Fe(iii) ions are coupled antiferromagnetically and magnetic data modelling yields J1 = -26.4 cm(-1), J2 = -170 cm(-1) which are rationalized by DFT calculation. The exchange value for of -170 cm(-1) (Fe-O(oxo)-Fe) is the largest exchange value known compared to any homometallic or heterometallic wheel reported to date. PMID:26479520

  16. [Topography structure and flocculation mechanism of polymeric phosphate ferric sulfate (PPFS)].

    PubMed

    Zheng, Huai-li; Zhang, Hui-qin; Jiang, Shao-jie; Li, Fang; Jiao, Shi-jun; Fang, Hui-li

    2011-05-01

    Characteristics of polymeric phosphate ferric sulfate (PPFS) were investigated using FTIR (Fourier transform infrared spectrometer), XRD (X-ray diffraction) and SEM (scanning electron microscope) in the present study. The formed PPFS structure and morphology were stereo meshwork, which was clustered and close to coral reef, synthesis of high charge density, bioactive polyhydroxy and mixed polynuclear complex PPFS. The results showed that charge neutralization of PPFS had not played a decisive role in the coagulation beaker test and the zeta potential proved that PPFS was largely affected by bridging and netting sweep. Therefore, the coagulation mechanisms of PPFS were mainly composed of charge neutralization, adsorption bridging and netting sweep mechanisms. PMID:21800611

  17. Structure and energetics of solvated ferrous and ferric ions: Car-Parrinello molecular dynamics in the DFT+U formalism

    E-print Network

    P. H. -L. Sit; Matteo Cococcioni; Nicola Marzari

    2007-01-12

    We implemented a rotationally-invariant Hubbard U extension to density-functional theory in the Car-Parrinello molecular dynamics framework, with the goal of bringing the accuracy of the DFT+U approach to finite-temperature simulations, especially for liquids or solids containing transition-metal ions. First, we studied the effects on the Hubbard U on the static equilibrium structure of the hexa-aqua ferrous and ferric ions, and the inner-sphere reorganization energy for the electron-transfer reaction between aqueous ferrous and ferric ions. It is found that the reorganization energy is increased, mostly as a result of the Fe-O distance elongation in the hexa-aqua ferrous ion. Second, we performed a first-principles molecular dynamics study of the solvation structure of the two aqueous ferrous and ferric ions. The Hubbard term is found to change the Fe-O radial distribution function for the ferrous ion, while having a negligible effect on the aqueous ferric ion. Moreover, the frequencies of vibrations between Fe and oxygen atoms in the first-solvation shell are shown to be unaffected by the Hubbard corrections for both ferrous and ferric ions.

  18. Car–Parrinello molecular dynamics in the DFT + U formalism: Structure and energetics of solvated ferrous and ferric ions

    SciTech Connect

    Sit, P H L.; Cococcioni, Matteo; Marzari, Nicola N.

    2007-09-01

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. We implemented a rotationally-invariant Hubbard U extension to density-functional theory in the Car–Parrinello molecular dynamics framework, with the goal of bringing the accuracy of the DFT + U approach to finite-temperature simulations, especially for liquids or solids containing transition-metal ions. First, we studied the effects on the Hubbard U on the static equilibrium structure of the hexaaqua ferrous and ferric ions, and the inner-sphere reorganization energy for the electron-transfer reaction between aqueous ferrous and ferric ions. It is found that the reorganization energy is increased, mostly as a result of the Fe–O distance elongation in the hexa-aqua ferrous ion. Second, we performed a first-principles molecular dynamics study of the solvation structure of the two aqueous ferrous and ferric ions. The Hubbard term is found to change the Fe–O radial distribution function for the ferrous ion, while having a negligible effect on the aqueous ferric ion. Moreover, the frequencies of vibrations between Fe and oxygen atoms in the first-solvation shell are shown to be unaffected by the Hubbard corrections for both ferrous and ferric ions.

  19. Ferric citrate.

    PubMed

    Cada, Dennis J; Cong, Jasen; Baker, Danial E

    2015-02-01

    Each month, subscribers to The Formulary Monograph Service receive 5 to 6 well-documented monographs on drugs that are newly released or are in late phase 3 trials. The monographs are targeted to Pharmacy & Therapeutics Committees. Subscribers also receive monthly 1-page summary monographs on agents that are useful for agendas and pharmacy/nursing in-services. A comprehensive target drug utilization evaluation/medication use evaluation (DUE/MUE) is also provided each month. With a subscription, the monographs are sent in print and are also available on-line. Monographs can be customized to meet the needs of a facility. A drug class review is now published monthly with The Formulary Monograph Service. Through the cooperation of The Formulary, Hospital Pharmacy publishes selected reviews in this column. For more information about The Formulary Monograph Service, call The Formulary at 800-322-4349. The February 2015 monograph topics are netupitant/palonosetron, naltrxone SR/bupropion SR, nintedanib, pirfenidone, and ivabradine. The Safety MUE is on netupitant/palonosetron. PMID:25717210

  20. Six-coordinate ferric porphyrins containing bidentate N-t-butyl-N-nitrosohydroxylaminato ligands: structure, magnetism, IR spectroelectrochemisty, and reactivity.

    PubMed

    Xu, Nan; Christian, Jonathan H; Dalal, Naresh S; Abucayon, Erwin G; Lingafelt, Colin; Powell, Douglas R; Richter-Addo, George B

    2015-11-18

    NONOates (diazeniumdiolates) containing the [X{N2O2}](-) functional group are frequently employed as nitric oxide (NO) donors in biology, and some NONOates have been shown to bind to metalloenzymes. We report the preparation, crystal structures, detailed magnetic behavior, redox properties, and reactivities of the first isolable alkyl C-NONOate complexes of heme models, namely (OEP)Fe(?(2)-ON(t-Bu)NO) () and (TPP)Fe(?(2)-ON(t-Bu)NO) () (OEP = octaethylporphyrinato dianion, TPP = tetraphenylporphyrinato dianion). The compounds display the unusual NONOate O,O-bidentate binding mode for porphyrins, resulting in significant apical Fe displacements (+0.60 Å for , and +0.69 Å for ) towards the axial ligands. Magnetic susceptibility and magnetization measurements made from 1.8-300 K at magnetic fields from 0.02 to 5 T, yielded magnetic moments of 5.976 and 5.974 Bohr magnetons for and , respectively, clearly identifying them as high-spin (S = 5/2) ferric compounds. Variable-frequency (9.4 GHz and 34.5 GHz) EPR measurements, coupled with computer simulations, confirmed the magnetization results and yielded more precise values for the spin Hamiltonian parameters: gavg = 2.00 ± 0.03, |D| = 3.89 ± 0.09 cm(-1), and E/D = 0.07 ± 0.01 for both compounds, where D and E are the axial and rhombic zero-field splittings. IR spectroelectrochemistry studies reveal that the first oxidations of these compounds occur at the porphyrin macrocycles and not at the Fe-NONOate moieties. Reactions of and with a histidine mimic (1-methylimidazole) generate RNO and NO, both of which may bind to the metal center if sterics allow, as shown by a comparative study with the Cupferron complex (T(p-OMe)PP)Fe(?(2)-ON(Ph)NO). Protonation of and yields N2O as a gaseous product, presumably from the initial generation of HNO that dimerizes to the observed N2O product. PMID:26530148

  1. Iron sucrose and ferric carboxymaltose: no correlation between physicochemical stability and biological activity.

    PubMed

    Praschberger, Monika; Haider, Kathrin; Cornelius, Carolin; Schitegg, Markus; Sturm, Brigitte; Goldenberg, Hans; Scheiber-Mojdehkar, Barbara

    2015-02-01

    Intravenous iron preparations, like iron sucrose (IS) and ferric carboxymaltose (FCM) differ in their physicochemical stability. Thus differences in storage and utilization can be expected and were investigated in a non-clinical study in liver parenchyma HepG2-cells and THP-1 macrophages as models for toxicological and pharmacological target cells. HepG2-cells incorporated significant amounts of IS, elevated the labile iron pool (LIP) and ferritin and stimulated iron release. HepG2-cells had lower basal cellular iron and ferritin content than THP-1 macrophages, which showed only marginal accumulation of IS and FCM. However, FCM increased the LIP up to twofold and significantly elevated ferritin within 24 h in HepG2-cells. IS and FCM were non-toxic for HepG2-cells and THP-1 macrophages were more sensitive to FCM compared to IS at all concentrations tested. In a cell-free environment redox-active iron was higher with IS than FCM. Biostability testing via assessment of direct transfer to serum transferrin did not reflect the chemical stability of the complexes (i.e., FCM > IS). Effect of vitamin C on mobilisation to transferrin was an increase with IS and interestingly a decrease with FCM. In conclusion, FCM has low bioavailability for liver parenchyma cells, therefore liver iron deposition is unlikely. Ascorbic acid reduces transferrin-chelatable iron from ferric carboxymaltose, thus effects on hepcidin expression should be investigated in clinical studies. PMID:25326244

  2. The ferric fluosilicate leaching of lead concentrates; Part 1: Kinetic studies

    SciTech Connect

    Chen, A.A.; Dreisinger, D.B. )

    1994-08-01

    Under the current pressure of strict environmental regulations, lead producers are seeking more efficient ways to produce lead. A new hydrometallurgical leaching process, which dissolves lead concentrates with acidified ferric fluosilicate solution, has been investigated for the selective extraction of lead and zinc from lead concentrates containing galena. The leaching of the Pine Point lead concentrate by ferric fluosilicate solutions was studied under various experimental conditions in the temperature range 20 C to 95 C. Temperature had a pronounced effect on the dissolution of the concentrates. The rates of lead leaching are very rapid over the temperature range 38 C to 95 C. The kinetics of zinc extraction are much lower than those of lead extraction. The reaction rates for the dissolution of galena were found to be controlled by surface chemical reaction. The apparent activation energy of the leaching reaction was calculated to be 62.1 kJ/mol. The initial concentrations of Pb[sup 2+], H[sup +], and Fe[sup 3+] in the lixiviant do not have a significant effect on the rate or extent of lead extraction under the experimental conditions in this study.

  3. [Mechanism of groundwater As(V) removal with ferric flocculation and direct filtration].

    PubMed

    Kang, Ying; Duan, Jin-Ming; Jing, Chuan-Yong

    2015-02-01

    The As removal process and mechanism from groundwater using ferric flocculation-direct filtration system was investigated using batch, field pilot tests, extended X-ray absorption fine structure ( EXAFS) spectroscopy, and charge-distribution multisite complexation (CD-MUSIC) model. The results showed that arsenate [As(V)] was the dominant As species in the groundwater with a concentration of 40 ?g x L(-1). The treatment system could supply 64 984 L As-safe drinking water (< 10 ?g L(-1)) using Fe 1.5 mg x L(-1). Toxicity characteristic leaching procedure (TCLP) demonstrated that the leachate As was 3.4 ?g x L(-1), much lower than the EPA regulatory concentration (5 mg x L(-1)). EXAFS and CD-MUSIC model indicated that As(V) was adsorbed onto ferric hydroxide via bidentate binuclear complexes in the pH range of 3 to 9.5, while formation of precipitate with Ca or Mg dominated the As removal at pH > 9.5. PMID:26031078

  4. Histoplasma capsulatum secreted ?-glutamyltransferase reduces iron by generating an efficient ferric reductant

    PubMed Central

    Zarnowski, Robert; Cooper, Kendal G.; Brunold, Laura Schmitt; Calaycay, Jimmy; Woods, Jon P.

    2008-01-01

    Summary The intracellular fungal pathogen Histoplasma capsulatum (Hc) resides in mammalian macrophages and causes respiratory and systemic disease. Iron limitation is an important host antimicrobial defense, and iron acquisition is critical for microbial pathogenesis. Hc displays several iron acquisition mechanisms, including secreted glutathione-dependent ferric reductase activity (GSH-FeR). We purified this enzyme from culture supernatant and identified a novel extracellular iron reduction strategy involving ?-glutamyltransferase (Ggt1) activity. The 320-kDa complex was composed of glycosylated protein subunits of about 50 and 37 kDa. The purified enzyme exhibited ?-glutamyl transfer activity as well as iron reduction activity in the presence of glutathione. We cloned and manipulated expression of the encoding gene. Overexpression or RNAi silencing affected both GGT and GSH-FeR activities concurrently. Enzyme inhibition experiments showed the activity is complex and involves two reactions. First, Ggt1 initiates enzymatic breakdown of GSH by cleavage of the ?-glutamyl bond and release of cysteinylglycine. Second, the thiol group of the released dipeptide reduces ferric to ferrous iron. A combination of kinetic properties of both reactions resulted in efficient iron reduction over a broad pH range. Our findings provide novel insight into Hc iron acquisition strategies and reveal a unique aspect of Ggt1 function in this dimorphic mycopathogen. PMID:18761625

  5. Synovectomy of the rheumatoid knee using intra-articular injection of dysprosium-165-ferric hydroxide macroaggregates

    SciTech Connect

    Sledge, C.B.; Zuckerman, J.D.; Shortkroff, S.; Zalutsky, M.R.; Venkatesan, P.; Snyder, M.A.; Barrett, W.P.

    1987-09-01

    One hundred and eleven patients who had seropositive rheumatoid arthritis and persistent synovitis of the knee were treated with intra-articular injection of 270 millicuries of dysprosium-165 bound to ferric hydroxide macroaggregates. A two-year follow-up was available for fifty-nine of the treated knees. Thirty-nine had a good result; nine, a fair result; and eleven, a poor result. Of the twenty-five knees that had Stage-I radiographic changes, nineteen had a good result. Of the thirty-four knees that had Stage-II radiographic changes, twenty showed a good result. Systemic spread of the radioactivity from the injected joint was minimum. The mean whole-body dose was calculated to be 0.3 rad and that to the liver twenty-four hours after injection, 3.2 rads. The results indicated that dysprosium-165-ferric hydroxide macroaggregate is an effective agent for performing radiation synovectomy, particularly in knees that have Stage-I radiographic changes. Because of the minimum rate of systemic spread of the dysprosium-165, it offers a definite advantage over agents that previously have been used.

  6. Treatment of rheumatoid synovitis of the knee with intraarticular injection of dysprosium 165-ferric hydroxide macroaggregates

    SciTech Connect

    Sledge, C.B.; Zuckerman, J.D.; Zalutsky, M.R.; Atcher, R.W.; Shortkroff, S.; Lionberger, D.R.; Rose, H.A.; Hurson, B.J.; Lankenner, P.A. Jr.; Anderson, R.J.

    1986-02-01

    One hundred eight knees of 93 patients with seropositive rheumatoid arthritis and persistent synovitis of the knee were treated with an intraarticular injection of 270 mCi of dysprosium 165 bound to ferric hydroxide macroaggregate. Leakage of radioactivity from the injected joint was minimal. Mean leakage to the venous blood 3 hours after injection was 0.11% of the injected dose; this corresponds to a mean whole body dose of 0.2 rads. Mean leakage to the liver 24 hours after injection was 0.64% of the injected dose; this corresponds to a mean liver dose of 3.2 rads. In 7 additional patients examined, there was negligible or near negligible activity found in the draining inguinal lymph nodes. One-year followup was possible for 74 knees (63 patients). Sixty-one percent of the knees had good results, 23% had fair results, and 16% had poor results. There was a direct correlation between the radiographic stage and response to treatment. In knees with stage I radiographic changes, 72% showed good results; 93% showed improvement. In knees with stage II changes, 59% showed good results; 81% showed improvement. These preliminary results indicate that dysprosium 165-ferric hydroxide macroaggregate is an effective agent for radiation synovectomy. The low leakage rates observed offer a definite advantage over agents previously used.

  7. A Silica/Fly Ash-Based Technology for Controlling Pyrite Oxidation

    SciTech Connect

    V. P. Evangelou

    1997-04-14

    The purpose of our studies during this past six-month period was to evaluate the surface properties of iron-oxide-silicate coatings. The specific objectives were (a) to evaluate the mechanisms and ability of hydrous ferric oxide (HFO) to adsorb silica (Si); (b) to evaluate the effects of Si on the bulk and surface properties of HFO; and (c) to evaluate the effect of Si on heavy-metal adsorption properties by iron-oxides.

  8. Effect of ionic strength on ligand exchange kinetics between a mononuclear ferric citrate complex and siderophore desferrioxamine B

    NASA Astrophysics Data System (ADS)

    Ito, Hiroaki; Fujii, Manabu; Masago, Yoshifumi; Waite, T. David; Omura, Tatsuo

    2015-04-01

    The effect of ionic strength (I) on the ligand exchange reaction between a mononuclear ferric citrate complex and the siderophore, desferrioxamine B (DFB), was examined in the NaCl concentration range of 0.01-0.5 M, particularly focusing on the kinetics and mechanism of ligand exchange under environmentally relevant conditions. Overall ligand exchange rate constants were determined by spectrophotometrically measuring the time course of ferrioxamine B formation at a water temperature of 25 °C, pH 8.0, and citrate/Fe molar ratios of 500-5000. The overall ligand exchange rate decreased by 2-11-fold (depending on the citrate/Fe molar ratios) as I increased from approximately 0.01 to 0.5 M. In particular, a relatively large decrease was observed at lower I (<0.1 M). A ligand exchange model describing the effect of I on the ligand exchange rate via disjunctive and adjunctive pathways was developed by considering the pseudo-equilibration of ferric citrate complexes and subsequent ferrioxamine formation on the basis of the Eigen-Wilkins metal-ligand complexation theory. The model and experimental data consistently suggest that the adjunctive pathway (i.e., direct association of DFB with ferric mono- and di-citrate complexes following dissociation of citrate from the parent complexes) dominates in ferrioxamine formation under the experimental conditions used. The model also predicts that the higher rate of ligand exchange at lower I is associated with the decrease in the ferric dicitrate complex stability because of the relatively high electrical repulsion between ferric monocitrate and free citrate at lower I (note that the reactivity of ferric dicitrate with DFB is smaller than that for the monocitrate complex). Overall, the findings of this study contribute to the understanding of the potential effect of I on ligand exchange kinetics in natural waters and provide fundamental knowledge on iron transformation and bioavailability.

  9. Catalytic performance and deactivation of precipitated iron catalyst for selective oxidation of hydrogen sulfide to elemental sulfur in the waste gas streams from coal gasification

    SciTech Connect

    Mashapa, T.N.; Rademan, J.D.; van Vuuren, M.J.J.

    2007-09-15

    The selective oxidation of hydrogen sulfide to elemental sulfur, using a commercial, precipitated silica promoted ferric oxide based catalyst, was investigated in laboratory and pilot-plant reactors. Low levels of hydrogen sulfide (1-3 vol%) can be readily removed, but a continuous slow decrease in catalyst activity was apparent. X-ray photoelectron spectroscopy showed that the loss of activity was due to the formation of ferrous sulfate, which is known to be less active than the ferric oxide. In addition, studies using a model feed showed that the propene and HCN impurities in the plant feed stocks also act as potent catalyst poisons.

  10. Shallow-water hydrothermal system and sedimentation of the ferric deposit in the Nagahama-bay, Satsuma Iwo-jima Island

    NASA Astrophysics Data System (ADS)

    Ninomiya, T.; Kiyokawa, S.; Koge, S.; Oguri, K.; Yamaguchi, K. E.; Ito, T.; Ikehara, M.

    2008-12-01

    Satsuma Iwo-jima Island, located 40km south of Kyushu, Japan, has characteristic hydrothermal activities surrounding its active volcano Iwo-dake. Along the shoreline, hydrothermal fluids discharge and they cause discoloration of the seawater. At Nagahama-bay, iron ion in carbonated spring is oxidized to iron hydroxide precipitate by mixing with the sea water and the water takes on red color(Kamada, 1964). To understand the relationships among the ferric deposits, hydrothermal ventings, and the sea tide in the bay, we conducted the following studies; (a) naked eye observation at seafloor by SCUBA diving and the measurements of temperature and sediment distributions, (b) time-series in situ observation of the sesafloor by OGURI-View system (an automatic underwater digital camera system; Oguri et al., 2006), (c) time-series observation of color changes in the surface water by automatic acquisition system modified from OGURI-View, (d) geochemical analysis of the sea water collected in spring and fall 2007 and summer 2008, (e) coring to find the components in the sediment, and (f) six months-long sediment trap to estimate total mass flux in the bay. On the seafloor, numerous hot vents were found in the eastern part of the bay at 4m in depth. Soft sediment was also formed around the vents up to 1.5m thick. Temperature of the surface sediment ranged from 30 to 55 degree Celsius; the highest temperature was observed near those vents. The time-series images taken by OGURI-View system showed that turbidness of the bottom of the sea water changed daily. The turbidity data in the bay indicated that their daily changes occurred by tidal currents and sometimes by unusual mixing induced by strong typhoon. The sediment of 83cm core sample consisted of clay-sized reddish ferric oxides, quartz, volcanic ashes, rock fragments, and very fine to fine sand. From the sediment trap experiment, total mass accumulation rate was estimated to 0.12-0.18g/cm2/day. This high rate may be one factor contributing to the thick sediment.

  11. Identification of an additional ferric-siderophore uptake gene clustered with receptor, biosynthesis, and fur-like regulatory genes in fluorescent Pseudomonas sp. strain M114.

    PubMed Central

    O'Sullivan, D J; Morris, J; O'Gara, F

    1990-01-01

    Five cosmid clones with insert sizes averaging 22.6 kilobases (kb) were isolated after complementation of 22 Tn5-induced Sid- mutants of Pseudomonas sp. strain M114. One of these plasmids (pMS639) was also shown to encode ferric-siderophore receptor and dissociation functions. The receptor gene was located on this plasmid since introduction of the plasmid into three wild-type fluorescent pseudomonads enabled them to utilize the ferric-siderophore from strain M114. The presence of an extra iron-regulated protein in the outer membrane profile of one of these strains was detected by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. A ferric-siderophore dissociation gene was attributed to pMS639 since it complemented the ferric-siderophore uptake mutation in strain M114FR2. This mutant was not defective in the outer membrane receptor for ferric-siderophore but apparently accumulated ferric-siderophore internally. Since ferric-citrate alleviated the iron stress of the mutant, there was no defect in iron metabolism subsequent to release of iron from the ferric-siderophore complex. Consequently, this mutant was defective in ferric-siderophore dissociation. A fur-like regulatory gene also present on pMS639 was subcloned to a 7.0-kb BglII insert of pCUP5 and was located approximately 7.3 kb from the receptor region. These results established that the 27.2-kb insert of pMS639 encoded at least two siderophore biosynthesis genes, ferric-siderophore receptor and dissociation genes, and a fur-like regulatory gene from the biocontrol fluorescent Pseudomonas sp. strain M114. Images PMID:2143887

  12. Ferric iron content of ferropericlase as a function of composition, oxygen fugacity, temperature and pressure: Implications for redox conditions during

    E-print Network

    and pressure: Implications for redox conditions during diamond formation in the lower mantle Kazuhiko Otsuka a ferropericlase diffusion lower mantle diamond a b s t r a c t We investigated the ferric iron (Fe3þ stability limit of diamond in mantle peridotite at the top of the lower mantle at adiabatic or slightly

  13. Comparative Evaluation of Aluminum Sulfate and Ferric Sulfate-Induced Coagulations as Pretreatment of Microfiltration for Treatment of Surface Water

    PubMed Central

    Song, Yali; Dong, Bingzhi; Gao, Naiyun; Deng, Yang

    2015-01-01

    Two coagulants, aluminum sulfate and ferric chloride, were tested to reduce natural organic matter (NOM) as a pretreatment prior to polyvinylidene fluoride (PVDF) microfiltration (MF) membranes for potable water treatment. The results showed that the two coagulants exhibited different treatment performance in NOM removal. Molecular weight (MW) distributions of NOM in the tested surface raw water were concentrated at 3–5 kDa and approximately 0.2 kDa. Regardless of the coagulant species and dosages, the removal of 0.2 kDa NOM molecules was limited. In contrast, NOM at 3–5 kDa were readily removed with increasing coagulant dosages. In particular, aluminum sulfate favorably removed NOM near 5 kDa, whereas ferric chloride tended to reduce 3 kDa organic substances. Although aluminum sulfate and ferric chloride could improve the flux of the ensuing MF treatment, the optimal coagulant dosages to achieve effective pretreatment were different: 2–30 mg/L for aluminum sulfate and >15 mg/L for ferric chloride. The scanning electron microscope (SEM) image of the membrane-filtered coagulated raw water showed that coagulation efficiency dramatically affected membrane flux and that good coagulation properties can reduce membrane fouling. PMID:26075726

  14. Comparative Evaluation of Aluminum Sulfate and Ferric Sulfate-Induced Coagulations as Pretreatment of Microfiltration for Treatment of Surface Water.

    PubMed

    Song, Yali; Dong, Bingzhi; Gao, Naiyun; Deng, Yang

    2015-06-01

    Two coagulants, aluminum sulfate and ferric chloride, were tested to reduce natural organic matter (NOM) as a pretreatment prior to polyvinylidene fluoride (PVDF) microfiltration (MF) membranes for potable water treatment. The results showed that the two coagulants exhibited different treatment performance in NOM removal. Molecular weight (MW) distributions of NOM in the tested surface raw water were concentrated at 3-5 kDa and approximately 0.2 kDa. Regardless of the coagulant species and dosages, the removal of 0.2 kDa NOM molecules was limited. In contrast, NOM at 3-5 kDa were readily removed with increasing coagulant dosages. In particular, aluminum sulfate favorably removed NOM near 5 kDa, whereas ferric chloride tended to reduce 3 kDa organic substances. Although aluminum sulfate and ferric chloride could improve the flux of the ensuing MF treatment, the optimal coagulant dosages to achieve effective pretreatment were different: 2-30 mg/L for aluminum sulfate and >15 mg/L for ferric chloride. The scanning electron microscope (SEM) image of the membrane-filtered coagulated raw water showed that coagulation efficiency dramatically affected membrane flux and that good coagulation properties can reduce membrane fouling. PMID:26075726

  15. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate

    E-print Network

    Alvarez, Pedro J.

    , chelated ferric iron or nitrate Marcio L.B. Da Silva1 , Graciela M.L. Ruiz-Aguilar2 & Pedro J.J. Alvarez1­Fe(III) or nitrate to enhance the biodegradation of BTEX and ethanol mixtures. The rapid biodegradation of ethanol­Fe(III) or nitrate suppressed methanogenesis and significantly increased BTEX biodegradation efficiencies. Nev

  16. Ferric Perchlorate Promoted Reaction of [60]Fullerene with N-Sulfonyl Aldimines: Synthesis and Functionalization of Fulleroxazolidines.

    PubMed

    Liu, Tong-Xin; Li, Fa-Bao; Zhou, Dian-Bing; Wang, Guan-Wu

    2015-12-18

    The rare fulleroxazolidines 2 were successfully synthesized by the facile ferric perchlorate promoted reaction of [60]fullerene with various N-sulfonyl aldimines 1. Further functionalization of fulleroxazolidines by arenes in the presence of boron trifluoride afforded 1,4-bisarylation products 4. A possible reaction mechanism for the formation of the fulleroxazolidines is proposed. PMID:26595850

  17. Managing hyperphosphatemia in patients with chronic kidney disease on dialysis with ferric citrate: latest evidence and clinical usefulness

    PubMed Central

    Fadem, Stephen Z.; Kant, Kotagal S.; Bhatt, Udayan; Sika, Mohammed; Lewis, Julia B.; Negoi, Dana

    2015-01-01

    Ferric citrate is a novel phosphate binder that allows the simultaneous treatment of hyperphosphatemia and iron deficiency in patients being treated for end-stage renal disease with hemodialysis (HD). Multiple clinical trials in HD patients have uniformly and consistently demonstrated the efficacy of the drug in controlling hyperphosphatemia with a good safety profile, leading the US Food and Drug Administration in 2014 to approve its use for that indication. A concurrent beneficial effect, while using ferric citrate as a phosphate binder, is its salutary effect in HD patients with iron deficiency being treated with an erythropoietin-stimulating agent (ESA) in restoring iron that becomes available for reversing chronic kidney disease (CKD)-related anemia. Ferric citrate has also been shown in several studies to diminish the need for intravenous iron treatment and to reduce the requirement for ESA. Ferric citrate is thus a preferred phosphate binder that helps resolve CKD-related mineral bone disease and iron-deficiency anemia. PMID:26336594

  18. Spin state transitions upon visible and infrared excitation of ferric MbN3

    NASA Astrophysics Data System (ADS)

    Helbing, Jan

    2012-03-01

    When azide binds to ferric Myoglobin it forms either a low-spin or a high-spin complex, which give rise to two well-separated asymmetric stretch bands of the ligand. Both electronic excitation of the Q-band and vibrational excitation of N3- in the mid-IR lead to a similar ultrafast population redistribution in favor of the high spin configuration, which is characterized by a 8° reorientation of the ligand transition dipole moment. The more stable low spin complex subsequently re-emerges with a 18 ps time-constant. It is argued that the observed spin state changes are caused by the participation of low-lying electronic excitations in the cooling process of heme.

  19. Structure and kinetics of formation of catechol complexes of ferric soybean lipoxygenase-1

    SciTech Connect

    Nelson, M.J.; Brennan, B.A.; Chase, D.B. |

    1995-11-21

    Ferric soybean lipoxygenase forms stable complexes with 4-substituted catechols. The structure of the complex between the enzyme and 3,4-dihydroxybenzonitrile has been studied by resonance Raman, electron paramagnetic resonance, visible, and X-ray spectroscopies. It is a bidentate iron-catecholate complex with at least one water ligand. The kinetics of formation of complexes between lipoxygenase and 3,4-dihydroxybenzonitrile and 3,4-dihydroxyacetophenone have been studied by stopped-flow spectroscopy. The data are consistent with two kinetically distinct, reversible steps. The pH dependence of the first step suggests that the substrate for the reaction is the catechol monoanion. When these results are combined, plausible mechanisms for the complexation reaction are suggested. 51 refs., 12 figs., 2 tabs.

  20. Authigenic vivianite in Potomac River sediments: control by ferric oxy-hydroxides.

    USGS Publications Warehouse

    Hearn, P.P.; Parkhurst, D.L.; Callender, E.

    1983-01-01

    Sand-size aggregates of vivianite crystals occur in the uppermost sediments of the Potomac River estuary immediately downstream from the outfall of a sewage treatment plant at the southernmost boundary of the District of Columbia, USA. They are most abundant in a small area of coarse sand (dredge spoil) which contrasts with the adjacent, much finer sediments. The sewage outfall supplies both reducing conditions and abundant phosphate. Analyses and calculations indicate that the pore waters in all the adjacent sediments are supersaturated with respect to vivianite. Its concentration in the coarse sand is attributed to the absence there of amorphous ferric oxyhydroxides, which are present in the finer sediments and preferentially absorb the phosphate ion. -H.R.B.

  1. Concerted loop motion triggers induced fit of FepA to ferric enterobactin

    PubMed Central

    Smallwood, Chuck R.; Jordan, Lorne; Trinh, Vy; Schuerch, Daniel W.; Gala, Amparo; Hanson, Mathew; Shipelskiy, Yan; Majumdar, Aritri; Newton, Salete M.C.

    2014-01-01

    Spectroscopic analyses of fluorophore-labeled Escherichia coli FepA described dynamic actions of its surface loops during binding and transport of ferric enterobactin (FeEnt). When FeEnt bound to fluoresceinated FepA, in living cells or outer membrane fragments, quenching of fluorophore emissions reflected conformational motion of the external vestibular loops. We reacted Cys sulfhydryls in seven surface loops (L2, L3, L4, L5, L7 L8, and L11) with fluorophore maleimides. The target residues had different accessibilities, and the labeled loops themselves showed variable extents of quenching and rates of motion during ligand binding. The vestibular loops closed around FeEnt in about a second, in the order L3 > L11 > L7 > L2 > L5 > L8 > L4. This sequence suggested that the loops bind the metal complex like the fingers of two hands closing on an object, by individually adsorbing to the iron chelate. Fluorescence from L3 followed a biphasic exponential decay as FeEnt bound, but fluorescence from all the other loops followed single exponential decay processes. After binding, the restoration of fluorescence intensity (from any of the labeled loops) mirrored cellular uptake that depleted FeEnt from solution. Fluorescence microscopic images also showed FeEnt transport, and demonstrated that ferric siderophore uptake uniformly occurs throughout outer membrane, including at the poles of the cells, despite the fact that TonB, its inner membrane transport partner, was not detectable at the poles. PMID:24981231

  2. Viscosity of liquid ferric sulfate solutions and application to the formation of gullies on Mars

    NASA Astrophysics Data System (ADS)

    Chevrier, Vincent F.; Ulrich, Richard; Altheide, Travis S.

    2009-06-01

    We studied the viscosity of ferric sulfate Fe2(SO4)3 solutions as a model for low-temperature liquids on the surface of Mars and their implication in the formation of gullies. Viscosity varies with temperature and concentration, ranging from 7.0 × 10-3 Pa s for 38.8 wt % at 285.15 K to 4.6 Pa s for 58.2 wt % at 260.15 K. Using the experimental results, we built a semiempirical equation of viscosity as a function of temperature and salt concentration, which was combined with a numerical model to estimate the effect of these solutions on the formation of gullies. Calculated fluid velocities ranged from 0.5 to 14 m s-1, in accordance with estimates from image analyses. Turbulent flow occurs in the majority of the conditions and is characterized by a constant velocity (˜8.5 m s-1). At very low temperature and high concentration, the laminar regime shows reduced velocities (down to ˜0.5 m s-1). In between, a transitional regime presents high velocities, up to 14 m s-1. Using the velocities, we determined the size threshold for boulders to be moved by the liquid flow. Depending on the regime, boulders of diameter inferior to 3 m (turbulent), 4 m (transition), and down to 0.5 m (laminar) are displaced. Since laminar flow occurs only in an extremely limited range of conditions, for low temperatures (<240 K) and supersaturated solutions, the abundance of small boulders (˜0.5 m) in gully channels requires lower velocities and higher viscosities than ferric sulfate solution or any other water-based liquid can reach. This suggests an important participation of debris mixed with the liquid phase.

  3. Variation of the oxidation state of verdoheme in the heme oxygenase reaction

    SciTech Connect

    Gohya, Tomohiko; Sato, Michihiko; Zhang Xuhong; Migita, Catharina T.

    2008-11-14

    Heme oxygenase (HO) converts hemin to biliverdin, CO, and iron applying molecular oxygen and electrons. During successive HO reactions, two intermediates, {alpha}-hydroxyhemin and verdoheme, have been generated. Here, oxidation state of the verdoheme-HO complexes is controversial. To clarify this, the heme conversion by soybean and rat HO isoform-1 (GmHO-1 and rHO-1, respectively) was compared both under physiological conditions, with oxygen and NADPH coupled with ferredoxin reductase/ferredoxin for GmHO-1 or with cytochrome P450 reductase for rHO-1, and under a non-physiological condition with hydrogen peroxide. EPR measurements on the hemin-GmHO-1 reaction with oxygen detected a low-spin ferric intermediate, which was undetectable in the rHO-1 reaction, suggesting the verdoheme in the six-coordinate ferric state in GmHO-1. Optical absorption measurements on this reaction indicated that the heme degradation was extremely retarded at verdoheme though this reaction was not inhibited under high-CO concentrations, unlike the rHO-1 reaction. On the contrary, the Gm and rHO-1 reactions with hydrogen peroxide both provided ferric low-spin intermediates though their yields were different. The optical absorption spectra suggested that the ferric and ferrous verdoheme coexisted in reaction mixtures and were slowly converted to the ferric biliverdin complex. Consequently, in the physiological oxygen reactions, the verdoheme is found to be stabilized in the ferric state in GmHO-1 probably guided by protein distal residues and in the ferrous state in rHO-1, whereas in the hydrogen peroxide reactions, hydrogen peroxide or hydroxide coordination stabilizes the ferric state of verdoheme in both HOs.

  4. 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.

  5. Reaction of nitric oxide with heme proteins and model compounds of hemoglobin

    SciTech Connect

    Sharma, V.S.; Traylor, T.G.; Gardiner, R.; Mizukami, H.

    1987-06-30

    Rates for the reaction of nitric oxide with several ferric heme proteins and model compounds have been measured. The NO combination rates are markedly affected by the presence or absence of distal histidine. Elephant myoglobin in which the E7 distal histidine has been replaced by glutamine reacts with NO 500-1000 times faster than do the native hemoglobins or myoglobins. By contrast, there is not difference in the CO combination rate constants of sperm whale and elephant myoglobins. Studies on ferric model compounds for the R and T states of hemoglobin indicate that their NO combination rate constants are similar to those observed for the combination of CO with the corresponding ferro derivatives. The last observation suggests that the presence of an axial water molecule at the ligand binding site of ferric hemoglobin A prevents it from exhibiting significant cooperativity in its reactions with NO.

  6. Isolation of microorganisms involved in reduction of crystalline iron(III) oxides in natural environments

    PubMed Central

    Hori, Tomoyuki; Aoyagi, Tomo; Itoh, Hideomi; Narihiro, Takashi; Oikawa, Azusa; Suzuki, Kiyofumi; Ogata, Atsushi; Friedrich, Michael W.; Conrad, Ralf; Kamagata, Yoichi

    2015-01-01

    Reduction of crystalline Fe(III) oxides is one of the most important electron sinks for organic compound oxidation in natural environments. Yet the limited number of isolates makes it difficult to understand the physiology and ecological impact of the microorganisms involved. Here, two-stage cultivation was implemented to selectively enrich and isolate crystalline iron(III) oxide reducing microorganisms in soils and sediments. Firstly, iron reducers were enriched and other untargeted eutrophs were depleted by 2-years successive culture on a crystalline ferric iron oxide (i.e., goethite, lepidocrocite, hematite, or magnetite) as electron acceptor. Fifty-eight out of 136 incubation conditions allowed the continued existence of microorganisms as confirmed by PCR amplification. High-throughput Illumina sequencing and clone library analysis based on 16S rRNA genes revealed that the enrichment cultures on each of the ferric iron oxides contained bacteria belonging to the Deltaproteobacteria (mainly Geobacteraceae), followed by Firmicutes and Chloroflexi, which also comprised most of the operational taxonomic units (OTUs) identified. Venn diagrams indicated that the core OTUs enriched with all of the iron oxides were dominant in the Geobacteraceae while each type of iron oxides supplemented selectively enriched specific OTUs in the other phylogenetic groups. Secondly, 38 enrichment cultures including novel microorganisms were transferred to soluble-iron(III) containing media in order to stimulate the proliferation of the enriched iron reducers. Through extinction dilution-culture and single colony isolation, six strains within the Deltaproteobacteria were finally obtained; five strains belonged to the genus Geobacter and one strain to Pelobacter. The 16S rRNA genes of these isolates were 94.8–98.1% identical in sequence to cultured relatives. All the isolates were able to grow on acetate and ferric iron but their physiological characteristics differed considerably in terms of growth rate. Thus, the novel strategy allowed to enrich and isolate novel iron(III) reducers that were able to thrive by reducing crystalline ferric iron oxides. PMID:25999927

  7. Isolation of microorganisms involved in reduction of crystalline iron(III) oxides in natural environments.

    PubMed

    Hori, Tomoyuki; Aoyagi, Tomo; Itoh, Hideomi; Narihiro, Takashi; Oikawa, Azusa; Suzuki, Kiyofumi; Ogata, Atsushi; Friedrich, Michael W; Conrad, Ralf; Kamagata, Yoichi

    2015-01-01

    Reduction of crystalline Fe(III) oxides is one of the most important electron sinks for organic compound oxidation in natural environments. Yet the limited number of isolates makes it difficult to understand the physiology and ecological impact of the microorganisms involved. Here, two-stage cultivation was implemented to selectively enrich and isolate crystalline iron(III) oxide reducing microorganisms in soils and sediments. Firstly, iron reducers were enriched and other untargeted eutrophs were depleted by 2-years successive culture on a crystalline ferric iron oxide (i.e., goethite, lepidocrocite, hematite, or magnetite) as electron acceptor. Fifty-eight out of 136 incubation conditions allowed the continued existence of microorganisms as confirmed by PCR amplification. High-throughput Illumina sequencing and clone library analysis based on 16S rRNA genes revealed that the enrichment cultures on each of the ferric iron oxides contained bacteria belonging to the Deltaproteobacteria (mainly Geobacteraceae), followed by Firmicutes and Chloroflexi, which also comprised most of the operational taxonomic units (OTUs) identified. Venn diagrams indicated that the core OTUs enriched with all of the iron oxides were dominant in the Geobacteraceae while each type of iron oxides supplemented selectively enriched specific OTUs in the other phylogenetic groups. Secondly, 38 enrichment cultures including novel microorganisms were transferred to soluble-iron(III) containing media in order to stimulate the proliferation of the enriched iron reducers. Through extinction dilution-culture and single colony isolation, six strains within the Deltaproteobacteria were finally obtained; five strains belonged to the genus Geobacter and one strain to Pelobacter. The 16S rRNA genes of these isolates were 94.8-98.1% identical in sequence to cultured relatives. All the isolates were able to grow on acetate and ferric iron but their physiological characteristics differed considerably in terms of growth rate. Thus, the novel strategy allowed to enrich and isolate novel iron(III) reducers that were able to thrive by reducing crystalline ferric iron oxides. PMID:25999927

  8. Characterization of N-diethylnitrosamine-initiated and ferric nitrilotriacetate-promoted renal cell carcinoma experimental model and effect of a tamarind seed extract against acute nephrotoxicity and carcinogenesis.

    PubMed

    Vargas-Olvera, Chabetty Y; Sánchez-González, Dolores Javier; Solano, José D; Aguilar-Alonso, Francisco A; Montalvo-Muñoz, Fernando; Martínez-Martínez, Claudia María; Medina-Campos, Omar N; Ibarra-Rubio, María Elena

    2012-10-01

    Renal cell carcinoma (RCC), the commonest malignancy in adult kidney, lacks of early signs, resulting often in metastasis at first diagnosis. N-Diethylnitrosamine (DEN)-initiated and ferric nitrilotriacetate (FeNTA)-promoted RCC may be a useful experimental model, but it is not well characterized. In this study, histological alterations and oxidative stress markers were analyzed at different times throughout RCC development, histological subtype was re-evaluated in the light of current classification, and a tamarind seed extract (TSE) effect was examined. Male Wistar rats experimental groups were control, TSE, DEN, DEN+FeNTA, and TSE+DEN+FeNTA. TSE was given 2 weeks before DEN administration (200 mg/kg) and throughout the experiment. Fourteen days after DEN treatment, two FeNTA doses (9 mg Fe/kg) for acute nephrotoxicity study, and increasing FeNTA doses (3-9 mg Fe/kg) twice a week for 16 weeks for carcinogenesis protocol, were administered. In acute study, necrosis and renal failure were observed and TSE ameliorated them. Throughout carcinogenesis protocol, preneoplastic lesions were observed since 1 month of FeNTA treatment, which were more evident at 2 months, when also renal cysts and RCC were already detected. RCC tumors were obtained without changes in renal function, and clear cell histological subtype was identified in all cases. 4-Hydroxy-2-nonenal and 3-nitro-L: -tyrosine levels increased progressively throughout protocol. TSE decreased both oxidative stress markers and, although there was no statistical difference, it delayed RCC progress and decreased its incidence (21 %). This study brings an insight of the time course events in this carcinogenesis model, identifies clear cell subtype and establishes TSE renoprotective effects. PMID:22761015

  9. Comparison of the Hemostatic Activity of Quercus persica Jaub. & Spach. (Oak) With Ferric Sulfate in Bony Crypts.

    PubMed

    Nabavizadeh, Mohammad Reza; Zargaran, Arman; Moazami, Fariborz; Askari, Fatemeh; Sahebi, Safoora; Farhadpoor, Alireza; Faridi, Pouya

    2016-01-01

    Effective tissue hemostasis in periapical surgical site is important in the procedures. Plants with large amount of tannins may act as a local hemostatic agent. We aimed to compare the hemostatic effect of the extract of Quercus persica with one of the common hemostatic material used in periapical surgery. Six standardized bone holes were prepared in the calvaria of 5 Burgundy rabbits. Two hemostatic medicaments were tested for their hemostatic effect and were compared with control defects: Group 1, cotton pellet soaked in 15.5% ferric sulfate solution; Group 2, cotton pellet soaked in pure ethanolic extract of Q. persica. Bleeding score between the groups was compared. The ferric sulfate group exhibited significantly less bleeding than the other 2 groups. Q. persica was found to cause more hemostasis than the control group at 4 and 5 minutes but there were no significant differences between normal saline and Q. persica extract in bleeding control. PMID:26130010

  10. The Enzyme-mimic Activity of Ferric Nano-Core Residing in Ferritin and Its Biosensing Applications

    SciTech Connect

    Tang, Zhiwen; Wu, Hong J.; Zhang, Youyu; Li, Zhaohui; Lin, Yuehe

    2011-11-15

    Ferritins are nano-scale globular protein cages encapsulating a ferric core. They widely exist in animals, plants, and microbes, playing indispensable roles in iron homeostasis. Interestingly, our study clearly demonstrates that ferritin has an enzyme-mimic activity derived from its ferric nano-core, but not the protein cage. Further study revealed that the mimic-enzyme activity of ferritin is more thermally stable and pH-tolerant compared with horseradish peroxidase. Considering the abundance of ferritin in numerous organisms, this finding may indicate a new role of ferritin in antioxidant and detoxification metabolisms. In addition, as a natural protein-caged nanoparticle with an enzyme-mimic activity, ferritin is readily conjugated with biomolecules to construct nano-biosensors, thus holds promising potential for facile and biocompatible labeling for sensitive and robust bioassays in biomedical applications.

  11. Spectral study of the interaction between 2-pyridinecarbaldehyde-p-phenyldihydrazone and ferric iron and its analytical application

    NASA Astrophysics Data System (ADS)

    Zhou, Quanying; Liu, Weizhou; Chang, Lin; Chen, Fang

    2012-06-01

    The synthesis and spectral characterization of a schiff base, 2-pyridinecarbaldehyde-p-phenylenedihydrazone (short for 2PC-PPH), were described. It was found that ferric ion (Fe3+) could selectively quench the fluorescence of 2PC-PPH, whereas many other metal ions, such as Mn2+, Zn2+, Cu2+, K+, Al3+, Ca2+, Ni2+, Co2+, Cr3+ and Fe2+, could not quench its fluorescence. Based on this, a sensitive method for ferric ion selective detection was established. Under the optimum conditions, the decreasing fluorescence intensity of 2PC-PPH is proportional to the concentration of Fe3+ within the range of 6.0 × 10-7-1.0 × 10-5 mol L-1. The detection limit (3?) for Fe3+ determination is 3.6 × 10-7 mol L-1. The proposed method was successfully applied to determine iron in tea and milk powder.

  12. Synthetic analogues of [Fe4S4(Cys)3(His)] in hydrogenases and [Fe4S4(Cys)4] in HiPIP derived from all-ferric [Fe4S4{N(SiMe3)2}4].

    PubMed

    Ohki, Yasuhiro; Tanifuji, Kazuki; Yamada, Norihiro; Imada, Motosuke; Tajima, Tomoyuki; Tatsumi, Kazuyuki

    2011-08-01

    The all-ferric [Fe(4)S(4)](4+) cluster [Fe(4)S(4){N(SiMe(3))(2)}(4)] 1 and its one-electron reduced form [1](-) serve as convenient precursors for the synthesis of 31-site differentiated [Fe(4)S(4)] clusters and high-potential iron-sulfur protein (HiPIP) model clusters. The reaction of 1 with four equivalents (equiv) of the bulky thiol HSDmp (Dmp = 2,6-(mesityl)(2)C(6)H(3), mesityl = 2,4,6-Me(3)C(6)H(2)) followed by treatment with tetrahydrofuran (THF) resulted in the isolation of [Fe(4)S(4)(SDmp)(3)(THF)(3)] 2. Cluster 2 contains an octahedral iron atom with three THF ligands, and its Fe(S)(3)(O)(3) coordination environment is relevant to that in the active site of substrate-bound aconitase. An analogous reaction of [1](-) with four equiv of HSDmp gave [Fe(4)S(4)(SDmp)(4)](-) 3, which models the oxidized form of HiPIP. The THF ligands in 2 can be replaced by tetramethyl-imidazole (Me(4)Im) to give [Fe(4)S(4)(SDmp)(3)(Me(4)Im)] 4 modeling the [Fe(4)S(4)(Cys)(3)(His)] cluster in hydrogenases, and its one-electron reduced form [4](-) was synthesized from the reaction of 3 with Me(4)Im. The reversible redox couple between 3 and [3](-) was observed at E(1/2) = -820 mV vs. Ag/Ag(+), and the corresponding reversible couple for 4 and [4](-) is positively shifted by +440 mV. The cyclic voltammogram of 3 also exhibited a reversible oxidation couple, which indicates generation of the all-ferric [Fe(4)S(4)](4+) cluster, [Fe(4)S(4)(SDmp)(4)]. PMID:21768339

  13. Decomposition of a Mixed-Valence [2Fe-2S] Cluster to Linear Tetra-Ferric and Ferrous Clusters

    PubMed Central

    Saouma, Caroline T.; Kaminsky, Werner; Mayer, James M.

    2012-01-01

    Despite the ease of preparing di-ferric [2Fe-2S] clusters, preparing stable mixed-valence analogues remains a challenge, as these clusters have limited thermal stability. Herein we identify two decomposition products of the mixed-valence thiosalicylate-ligated [2Fe-2S] cluster, [Fe2S2(SArCOO)2]3? ((SArCOO)2? = thiosalicylate). PMID:23976815

  14. Process for the synthesis of nanophase dispersion-strengthened aluminum alloy

    DOEpatents

    Barbour, John C. (Albuquerque, NM); Knapp, James Arthur (Albuquerque, NM); Follstaedt, David Martin (Albuquerque, NM); Myers, Samuel Maxwell (Albuquerque, NM)

    1998-12-15

    A process for fabricating dispersion-strengthened ceramic-metal composites is claimed. The process comprises in-situ interaction and chemical reaction of a metal in gaseous form with a ceramic producer in plasma form. Such composites can be fabricated with macroscopic dimensions. Special emphasis is placed on fabrication of dispersion-strengthened aluminum oxide-aluminum composites, which can exhibit flow stresses more characteristic of high strength steel.

  15. Ferric Chloride-induced Thrombosis Mouse Model on Carotid Artery and Mesentery Vessel.

    PubMed

    Bonnard, Thomas; Hagemeyer, Christoph E

    2015-01-01

    Severe thrombosis and its ischemic consequences such as myocardial infarction, pulmonary embolism and stroke are major worldwide health issues. The ferric chloride injury is now a well-established technique to rapidly and accurately induce the formation of thrombi in exposed veins or artery of small and large diameter. This model has played a key role in the study of the pathophysiology of thrombosis, in the discovery and validation of novel antithrombotic drugs and in the understanding of the mechanism of action of these new agents. Here, the implementation of this technique on a mesenteric vessel and carotid artery in mice is presented. The method describes how to label circulating leukocytes and platelets with a fluorescent dye and to observe, by intravital microscopy on the exposed mesentery, their accumulation at the injured vessel wall which leads to the formation of a thrombus. On the carotid artery, the occlusion caused by the clot formation is measured by monitoring the blood flow with a Doppler probe. PMID:26167713

  16. Safety and Efficacy of Ferric Carboxymaltose in Anemic Pregnant Women: A Retrospective Case Control Study

    PubMed Central

    Pels, Anouk; Ganzevoort, Wessel

    2015-01-01

    Background. Anemia during pregnancy is commonly caused by iron deficiency and can have severe consequences for both the mother and the developing fetus. The aim of this retrospective study was to assess the safety and efficacy of intravenous ferric carboxymaltose (FCM) in pregnant women. Methods. All women treated with FCM for anemia during pregnancy between 2010 and 2012 at our institution were included. A matched control group was selected, including women who either were nonanemic or had anemia but were not considered for intravenous iron. Main outcome measures were maternal safety and pregnancy outcomes. Results. The study included 128 patients (FCM: 64; control: 64). Median FCM dose was 1000?mg and median gestational age at the time of first treatment was 34 weeks and 6 days. Median Hb increased from 8.4?g/dL (interquartile range 7.7; 8.9?g/dL) at the first FCM administration to 10.7?g/dL (9.8; 11.5?g/dL; n = 46 with available Hb at delivery) at the time of delivery, achieving levels similar to those in the control group (10.8?g/dL [9.8; 11.8?g/dL; n = 48]). No treatment-related adverse events were reported and no statistically significant differences in pregnancy outcomes were observed between groups. Conclusions. Within the limitations of this case control study, FCM was a safe and efficient treatment of anemia during pregnancy.

  17. Mechanistic insights into metal ion activation and operator recognition by the ferric uptake regulator.

    PubMed

    Deng, Zengqin; Wang, Qing; Liu, Zhao; Zhang, Manfeng; Machado, Ana Carolina Dantas; Chiu, Tsu-Pei; Feng, Chong; Zhang, Qi; Yu, Lin; Qi, Lei; Zheng, Jiangge; Wang, Xu; Huo, XinMei; Qi, Xiaoxuan; Li, Xiaorong; Wu, Wei; Rohs, Remo; Li, Ying; Chen, Zhongzhou

    2015-01-01

    Ferric uptake regulator (Fur) plays a key role in the iron homeostasis of prokaryotes, such as bacterial pathogens, but the molecular mechanisms and structural basis of Fur-DNA binding remain incompletely understood. Here, we report high-resolution structures of Magnetospirillum gryphiswaldense MSR-1 Fur in four different states: apo-Fur, holo-Fur, the Fur-feoAB1 operator complex and the Fur-Pseudomonas aeruginosa Fur box complex. Apo-Fur is a transition metal ion-independent dimer whose binding induces profound conformational changes and confers DNA-binding ability. Structural characterization, mutagenesis, biochemistry and in vivo data reveal that Fur recognizes DNA by using a combination of base readout through direct contacts in the major groove and shape readout through recognition of the minor-groove electrostatic potential by lysine. The resulting conformational plasticity enables Fur binding to diverse substrates. Our results provide insights into metal ion activation and substrate recognition by Fur that suggest pathways to engineer magnetotactic bacteria and antipathogenic drugs. PMID:26134419

  18. Overproduction in Escherichia coli and Characterization of a Soybean Ferric Leghemoglobin Reductase.

    PubMed Central

    Ji, L.; Becana, M.; Sarath, G.; Shearman, L.; Klucas, R. V.

    1994-01-01

    We previously cloned and sequenced a cDNA encoding soybean ferric leghemoglobin reductase (FLbR), an enzyme postulated to play an important role in maintaining leghemoglobin in a functional ferrous state in nitrogen-fixing root nodules. This cDNA was sub-cloned into an expression plasmid, pTrcHis C, and overexpressed in Escherichia coli. The recombinant FLbR protein, which was purified by two steps of column chromatography, was catalytically active and fully functional. The recombinant FLbR cross-reacted with antisera raised against native FLbR purified from soybean root nodules. The recombinant FLbR, the native FLbR purified from soybean (Glycine max L.) root nodules, and dihydrolipoamide dehydrogenases from pig heart and yeast had similar but not identical ultraviolet-visible absorption and fluorescence spectra, cofactor binding, and kinetic properties. FLbR shared common structural features in the active site and prosthetic group binding sites with other pyridine nucleotide-disulfide oxidoreductases such as dihydrolipoamide dehydrogenases, but displayed different microenvironments for the prosthetic groups. PMID:12232320

  19. Resolving the multifaceted mechanisms of the ferric chloride thrombosis model using an interdisciplinary microfluidic approach.

    PubMed

    Ciciliano, Jordan C; Sakurai, Yumiko; Myers, David R; Fay, Meredith E; Hechler, Beatrice; Meeks, Shannon; Li, Renhao; Dixon, J Brandon; Lyon, L Andrew; Gachet, Christian; Lam, Wilbur A

    2015-08-01

    The mechanism of action of the widely used in vivo ferric chloride (FeCl3) thrombosis model remains poorly understood; although endothelial cell denudation is historically cited, a recent study refutes this and implicates a role for erythrocytes. Given the complexity of the in vivo environment, an in vitro reductionist approach is required to systematically isolate and analyze the biochemical, mass transfer, and biological phenomena that govern the system. To this end, we designed an "endothelial-ized" microfluidic device to introduce controlled FeCl3 concentrations to the molecular and cellular components of blood and vasculature. FeCl3 induces aggregation of all plasma proteins and blood cells, independent of endothelial cells, by colloidal chemistry principles: initial aggregation is due to binding of negatively charged blood components to positively charged iron, independent of biological receptor/ligand interactions. Full occlusion of the microchannel proceeds by conventional pathways, and can be attenuated by antithrombotic agents and loss-of-function proteins (as in IL4-R/Iba mice). As elevated FeCl3 concentrations overcome protective effects, the overlap between charge-based aggregation and clotting is a function of mass transfer. Our physiologically relevant in vitro system allows us to discern the multifaceted mechanism of FeCl3-induced thrombosis, thereby reconciling literature findings and cautioning researchers in using the FeCl3 model. PMID:25931587

  20. Investigations of the Low Frequency Modes of Ferric Cytochrome c Using Vibrational Coherence Spectroscopy

    PubMed Central

    2015-01-01

    Femtosecond vibrational coherence spectroscopy is used to investigate the low frequency vibrational dynamics of the electron transfer heme protein, cytochrome c (cyt c). The vibrational coherence spectra of ferric cyt c have been measured as a function of excitation wavelength within the Soret band. Vibrational coherence spectra obtained with excitation between 412 and 421 nm display a strong mode at ?44 cm–1 that has been assigned to have a significant contribution from heme ruffling motion in the electronic ground state. This assignment is based partially on the presence of a large heme ruffling distortion in the normal coordinate structural decomposition (NSD) analysis of the X-ray crystal structures. When the excitation wavelength is moved into the ?421–435 nm region, the transient absorption increases along with the relative intensity of two modes near ?55 and 30 cm–1. The intensity of the mode near 44 cm–1 appears to minimize in this region and then recover (but with an opposite phase compared to the blue excitation) when the laser is tuned to 443 nm. These observations are consistent with the superposition of both ground and excited state coherence in the 421–435 nm region due to the excitation of a weak porphyrin-to-iron charge transfer (CT) state, which has a lifetime long enough to observe vibrational coherence. The mode near 55 cm–1 is suggested to arise from ruffling in a transient CT state that has a less ruffled heme due to its iron d6 configuration. PMID:24823442

  1. Time-dependence of ferric reducing antioxidant power (FRAP) index in Chilean apples and berries.

    PubMed

    Henríquez, Carolina; López-Alarcón, Camilo; Gómez, Maritza; Lutz, Mariane; Speisky, Hernán

    2011-09-01

    We hypothesize that the Ferric Reducing Antioxidant Power (FRAP) assay that follows the reaction of Fe(3+)-TPTZ at 593 nm underestimates the antioxidant capacity of fruits, since the standardized time of the reaction (4 min) is not enough to titrate all the reducing compounds available. We measured FRAP, total phenolics and anthocyanins content in a variety of Chilean berry fruits (blueberries, blackberries, raspberries and strawberries) and apples (cv. Fuji, Granny Smith, Pink Lady, Red Delicious and Royal Gala). Taking into account the dependence of FRAP on the time course of the reaction, we propose to measure FRAP indexes after 1 min (FRAP-1), 30 min (FRAP-30) and 120 min (FRAP-120) of incubation. Most fruit extracts showed significant correlations between the antioxidant capacity and the incubation time, although in some cases the FRAP indexes did not correlate with the total phenolics and/or anthocyanins content. In fact, in apples and berries the correlation between anthocyanins content and FRAP indexes decreased with the incubation time. It is concluded that the fruit extracts analyzed require an incubation period higher than the established in the original experimental protocol to reach the equilibrium, due to the presence of a complex mixture of antioxidant compounds. In addition, a kinetic profile should be realized in each sample studied to establish the most suitable incubation period to titrate all the reactive antioxidant species. PMID:22696902

  2. Mechanistic insights into metal ion activation and operator recognition by the ferric uptake regulator

    PubMed Central

    Deng, Zengqin; Wang, Qing; Liu, Zhao; Zhang, Manfeng; Machado, Ana Carolina Dantas; Chiu, Tsu-Pei; Feng, Chong; Zhang, Qi; Yu, Lin; Qi, Lei; Zheng, Jiangge; Wang, Xu; Huo, XinMei; Qi, Xiaoxuan; Li, Xiaorong; Wu, Wei; Rohs, Remo; Li, Ying; Chen, Zhongzhou

    2015-01-01

    Ferric uptake regulator (Fur) plays a key role in the iron homeostasis of prokaryotes, such as bacterial pathogens, but the molecular mechanisms and structural basis of Fur–DNA binding remain incompletely understood. Here, we report high-resolution structures of Magnetospirillum gryphiswaldense MSR-1 Fur in four different states: apo-Fur, holo-Fur, the Fur–feoAB1 operator complex and the Fur–Pseudomonas aeruginosa Fur box complex. Apo-Fur is a transition metal ion-independent dimer whose binding induces profound conformational changes and confers DNA-binding ability. Structural characterization, mutagenesis, biochemistry and in vivo data reveal that Fur recognizes DNA by using a combination of base readout through direct contacts in the major groove and shape readout through recognition of the minor-groove electrostatic potential by lysine. The resulting conformational plasticity enables Fur binding to diverse substrates. Our results provide insights into metal ion activation and substrate recognition by Fur that suggest pathways to engineer magnetotactic bacteria and antipathogenic drugs. PMID:26134419

  3. Adsorption of phosphonate antiscalant from reverse osmosis membrane concentrate onto granular ferric hydroxide.

    PubMed

    Boels, Luciaan; Keesman, Karel J; Witkamp, Geert-Jan

    2012-09-01

    Adsorptive removal of antiscalants offers a promising way to improve current reverse osmosis (RO) concentrate treatment processes and enables the reuse of the antiscalant in the RO desalination process. This work investigates the adsorption and desorption of the phosphonate antiscalant nitrilotris(methylenephosphonic acid) (NTMP) from RO membrane concentrate onto granular ferric hydroxide (GFH), a material that consists predominantly of akaganéite. The kinetics of the adsorption of NTMP onto GFH was predicted fairly well with two models that consider either combined film-pore or combined film-surface diffusion as the main mechanism for mass transport. It is also demonstrated that NTMP is preferentially adsorbed over sulfate by GFH at pH 7.85. The presence of calcium causes a transformation in the equilibrium adsorption isotherm from a Langmuir type to a Freundlich type with much higher adsorption capacities. Furthermore, calcium also increases the rate of adsorption substantially. GFH is reusable after regeneration with sodium hydroxide solution, indicating that NTMP can be potentially recovered from the RO concentrate. This work shows that GFH is a promising adsorbent for the removal and recovery of NTMP antiscalant from RO membrane concentrates. PMID:22873428

  4. Impaired myelination and reduced brain ferric iron in the mouse model of mucolipidosis IV.

    PubMed

    Grishchuk, Yulia; Peña, Karina A; Coblentz, Jessica; King, Victoria E; Humphrey, Daniel M; Wang, Shirley L; Kiselyov, Kirill I; Slaugenhaupt, Susan A

    2015-12-01

    Mucolipidosis type IV (MLIV) is a lysosomal storage disease caused by mutations in the MCOLN1 gene, which encodes the lysosomal transient receptor potential ion channel mucolipin-1 (TRPML1). MLIV causes impaired motor and cognitive development, progressive loss of vision and gastric achlorhydria. How loss of TRPML1 leads to severe psychomotor retardation is currently unknown, and there is no therapy for MLIV. White matter abnormalities and a hypoplastic corpus callosum are the major hallmarks of MLIV brain pathology. Here, we report that loss of TRPML1 in mice results in developmental aberrations of brain myelination as a result of deficient maturation and loss of oligodendrocytes. Defective myelination is evident in Mcoln1(-/-) mice at postnatal day 10, an active stage of postnatal myelination in the mouse brain. Expression of mature oligodendrocyte markers is reduced in Mcoln1(-/-) mice at postnatal day 10 and remains lower throughout the course of the disease. We observed reduced Perls' staining in Mcoln1(-/-) brain, indicating lower levels of ferric iron. Total iron content in unperfused brain is not significantly different between Mcoln1(-/-) and wild-type littermate mice, suggesting that the observed maturation delay or loss of oligodendrocytes might be caused by impaired iron handling, rather than by global iron deficiency. Overall, these data emphasize a developmental rather than a degenerative disease course in MLIV, and suggest that there should be a stronger focus on oligodendrocyte maturation and survival to better understand MLIV pathogenesis and aid treatment development. PMID:26398942

  5. Characterization of ferric and ferrous iron transport systems in Vibrio cholerae.

    PubMed

    Wyckoff, Elizabeth E; Mey, Alexandra R; Leimbach, Andreas; Fisher, Carolyn F; Payne, Shelley M

    2006-09-01

    Vibrio cholerae has multiple iron acquisition systems, including TonB-dependent transport of heme and of the catechol siderophore vibriobactin. Strains defective in both of these systems grow well in laboratory media and in the infant mouse intestine, indicating the presence of additional iron acquisition systems. Previously uncharacterized potential iron transport systems, including a homologue of the ferrous transporter Feo and a periplasmic binding protein-dependent ATP binding cassette (ABC) transport system, termed Fbp, were identified in the V. cholerae genome sequence. Clones encoding either the Feo or the Fbp system exhibited characteristics of iron transporters: both repressed the expression of lacZ cloned under the control of a Fur-regulated promoter in Escherichia coli and also conferred growth on a Shigella flexneri mutant that has a severe defect in iron transport. Two other ABC transporters were also evaluated but were negative by these assays. Transport of radioactive iron by the Feo system into the S. flexneri iron transport mutant was stimulated by the reducing agent ascorbate, consistent with Feo functioning as a ferrous transporter. Conversely, ascorbate inhibited transport by the Fbp system, suggesting that it transports ferric iron. The growth of V. cholerae strains carrying mutations in one or more of the potential iron transport genes indicated that both Feo and Fbp contribute to iron acquisition. However, a mutant defective in the vibriobactin, Fbp, and Feo systems was not attenuated in a suckling mouse model, suggesting that at least one other iron transport system can be used in vivo. PMID:16952942

  6. Passive immunization by recombinant ferric enterobactin protein (FepA) from Escherichia coli O157

    PubMed Central

    Larrie-Bagha, Seyed Mehdi; Rasooli, Iraj; Mousavi-Gargari, Seyed Latif; Rasooli, Zohreh; Nazarian, Shahram

    2013-01-01

    Background and Objectives Enterohemorrhagic Escherichia coli (EHEC) O157:H7 has been recognized as a major food borne pathogen responsible for frequent hemorrhagic colitis and hemolytic uremic syndrome in humans. Cattle are important reservoirs of E. coli O157:H7, in which the organism colonizes the intestinal tract and is shed in the feces. Objective Vaccination of cattle has significant potential as a pre-harvest intervention strategy for E. coli O157:H7. The aim of this study was to evaluate active and passive immunization against E. coli O157:H7 using a recombinant protein. Materials and Methods The recombinant FepA protein induced by IPTG was purified by nickel affinity chromatography. Antibody titre was determined by ELISA in FepA immunized rabbits sera. Sera collected from vaccinated animals were used for bacterial challenge in passive immunization studies. Results The results demonstrate that passive immunization with serum raised against FepA protects rabbits from subsequent infection. Conclusion Significant recognition by the antibody of ferric enterobactin binding protein may lead to its application in the restriction of Enterobacteriaceae propagation. PMID:23825727

  7. Leaching of arsenic from granular ferric hydroxide residuals under mature landfill conditions.

    PubMed

    Ghosh, Amlan; Mukiibi, Muhammed; Sáez, A Eduardo; Ela, Wendell P

    2006-10-01

    Most arsenic bearing solid residuals (ABSR) from water treatment will be disposed in nonhazardous landfills. The lack of an appropriate leaching test to predict arsenic mobilization from ABSR creates a need to evaluate the magnitude and mechanisms of arsenic release under landfill conditions. This work studies the leaching of arsenic and iron from a common ABSR, granular ferric hydroxide, in a laboratory-scale column that simulates the biological and physicochemical conditions of a mature, mixed solid waste landfill. The column operated for approximately 900 days and the mode of transport as well as chemical speciation of iron and arsenic changed with column age. Both iron and arsenic were readily mobilized under the anaerobic, reducing conditions. During the early stages of operation, most arsenic and iron leaching (80% and 65%, respectively) was associated with suspended particulate matter, and iron was lost proportionately faster than arsenic. In later stages, while the rate of iron leaching declined, the arsenic leaching rate increased greater than 7-fold. The final phase was characterized by dissolved species leaching. Future work on the development of standard batch leaching tests should take into account the dominant mobilization mechanisms identified in this work: solid associated transport, reductive sorbent dissolution, and microbially mediated arsenic reduction. PMID:17051802

  8. Mechanistic insights into metal ion activation and operator recognition by the ferric uptake regulator

    NASA Astrophysics Data System (ADS)

    Deng, Zengqin; Wang, Qing; Liu, Zhao; Zhang, Manfeng; Machado, Ana Carolina Dantas; Chiu, Tsu-Pei; Feng, Chong; Zhang, Qi; Yu, Lin; Qi, Lei; Zheng, Jiangge; Wang, Xu; Huo, Xinmei; Qi, Xiaoxuan; Li, Xiaorong; Wu, Wei; Rohs, Remo; Li, Ying; Chen, Zhongzhou

    2015-07-01

    Ferric uptake regulator (Fur) plays a key role in the iron homeostasis of prokaryotes, such as bacterial pathogens, but the molecular mechanisms and structural basis of Fur-DNA binding remain incompletely understood. Here, we report high-resolution structures of Magnetospirillum gryphiswaldense MSR-1 Fur in four different states: apo-Fur, holo-Fur, the Fur-feoAB1 operator complex and the Fur-Pseudomonas aeruginosa Fur box complex. Apo-Fur is a transition metal ion-independent dimer whose binding induces profound conformational changes and confers DNA-binding ability. Structural characterization, mutagenesis, biochemistry and in vivo data reveal that Fur recognizes DNA by using a combination of base readout through direct contacts in the major groove and shape readout through recognition of the minor-groove electrostatic potential by lysine. The resulting conformational plasticity enables Fur binding to diverse substrates. Our results provide insights into metal ion activation and substrate recognition by Fur that suggest pathways to engineer magnetotactic bacteria and antipathogenic drugs.

  9. Evaluation of formocresol, calcium hydroxide, ferric sulfate, and MTA primary molar pulpotomies

    PubMed Central

    Yildiz, Esma; Tosun, Gul

    2014-01-01

    Objective: The aim of this study is to evaluate four different pulpotomy medicaments in primary molars. Materials and Methods: A total of 147 primary molars with deep caries were treated with four different pulpotomy medicaments (FC: formocresol, FS: ferric sulfate, CH: calcium hydroxide, and MTA: mineral trioxide aggregate) in this study. The criteria for tooth selection for inclusion were no clinical and radiographic evidence of pulp pathology. During 30 months of follow-up at 6-month intervals, clinical and radiographic success and failures were recorded. The differences between the groups were statistically analyzed using the Chi-square test and Kaplan-Meier analysis. Results: At 30 months, clinical success rates were 100%, 95.2%, 96.4%, and 85% in the FC, FS, MTA, and CH groups, respectively. In radiographic analysis, the MTA group had the highest (96.4%), and the CH group had the lowest success rate (85%). There were no clinical and radiographic differences between materials (P > 0.05). Conclusions: Although there were no differences between materials, only in the CH group did three teeth require extraction due to further clinical symptoms of radiographic failures during the 30-month follow-up period. None of the failed teeth in the other groups required extraction during the 30-month follow-up period. PMID:24966776

  10. Thermodynamics of Manganese Oxides at Bulk and Nanoscale: Phase Formation, Transformation, Oxidation-Reduction, and Hydration

    NASA Astrophysics Data System (ADS)

    Birkner, Nancy R.

    Natural manganese oxides are generally formed in surficial environments that are near ambient temperature and water-rich, and may be exposed to wet-dry cycles and a variety of adsorbate species that influence dramatically their level of hydration. Manganese oxide minerals are often poorly crystalline, nanophase, and hydrous. In the near-surface environment they are involved in processes that are important to life, such as water column oxygen cycling, biomineralization, and transport of minerals/nutrients through soils and water. These processes, often involving transformations among manganese oxide polymorphs, are governed by a complex interplay between thermodynamics and kinetics. Manganese oxides are also used in technology as catalysts, and for other applications. The major goal of this dissertation is to examine the energetics of bulk and nanophase manganese oxide phases as a function of particle size, composition, and surface hydration. Careful synthesis and characterization of manganese oxide phases with different surface areas provided samples for the study of enthalpies of formation by high temperature oxide melt solution calorimetry and of the energetics of water adsorption on their surfaces. These data provide a quantitative picture of phase stability and how it changes at the nanoscale. The surface energy of the hydrous surface of Mn3O4 is 0.96 +/- 0.08 J/m2, of Mn2O3 is 1.29 +/- 0.10 J/m2, and of MnO2 is 1.64 +/- 0.10 J/m2. The surface energy of the anhydrous surface of Mn3O4 is 1.62 +/- 0.08 J/m 2, of Mn2O3 is 1.77 +/- 0.10 J/m 2, and of MnO2 is 2.05 +/- 0.10 J/m2. Supporting preliminary findings (Navrotsky et al., 2010), the spinel phase (Mn3O4) has a lower surface energy (more stabilizing) than bixbyite, while the latter has a smaller surface energy than pyrolusite. These differences significantly change the positions in oxygen fugacity---temperature space of the redox couples Mn3O4-Mn2O 3 and Mn2O3-MnO2 favoring the lower surface enthalpy phase (the spinel Mn3O4) for smaller particle size and in the presence of surface hydration. Chemisorption of water onto anhydrous nanophase Mn2O 3 surfaces promotes rapidly reversible redox phase changes at room temperature as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Water adsorption microcalorimetry (in situ) at room temperature measured the strongly exothermic integral enthalpy of water adsorption (-103.5 kJ/mol) and monitored the energetics of the redox phase transformation. Hydration-driven redox transformation of anhydrous nanophase Mn(III) 2O3, (high surface enthalpy of anhydrous surfaces 1.77 +/- 0.10 J/m2) to Mn(II,III)3O4 (lower surface enthalpy 0.96 +/- 0.08 J/m2) occurred during the first few doses of water vapor. Surface reduction of nanoparticle bixbyite (Mn 2O3) to hausmannite (Mn3O4) occurs under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Layered structure manganese oxides contain alkali or alkaline earth cations and water, are generally fine-grained, and have considerable thermodynamic stability. The surface enthalpies (SE) of layered and tunnel structure complex manganese oxides are significantly lower than those of the binary manganese oxide phases. The SE for hydrous surfaces and overall manganese average oxidation state (AOS) (value in parentheses) are: cryptomelane 0.77 +/- 0.10 J/m 2 (3.78), sodium birnessite 0.69 +/- 0.13 J/m2 (3.56), potassium birnessite 0.55 +/- 0.11 J/m2 (3.52), and calcium birnessite 0.41 +/- 0.11 J/m2 (3.50). Surface enthalpies of hydrous surfaces of the calcium manganese oxide nanosheets are: deltaCa 0.39MnO2.3nH2O 0.75 +/- 0.10 J/m2 (3.89) and deltaCa0.43MnO2.3nH2O 0.57 +/- 0.12 J/m2 (3.68). The surface enthalpy of the complex manganese oxides appears to decrease with decreasing manganese average oxidation state, that is, with greater mixed valence manganese (Mn 3+/4+). Low surface energy suggests loose binding of H2O on the internal and external surfaces and may be critical to catalysis in bo

  11. Synthesis of Fullerene-Fused Dioxanes/Dioxepanes: Ferric Perchlorate-Mediated One-Step Reaction of [60]Fullerene with Diols.

    PubMed

    Zhang, Xiao-Feng; Li, Fa-Bao; Wu, Jun; Shi, Ji-Long; Liu, Zhan; Liu, Li

    2015-06-19

    The facile one-step reaction of [60]fullerene with various diols in the presence of ferric perchlorate afforded a series of rare fullerene-fused dioxanes/dioxepanes. Nevertheless, the reaction of [60]fullerene with diethylene glycol, triethylene glycol, and tripropylene glycol promoted by ferric perchlorate unexpectedly generated fullerene-fused dioxanes instead of the anticipated fullerene-fused crown ethers. A plausible reaction mechanism is proposed to explain the formation of fullerene-fused dioxane/dioxepane products. PMID:25996442

  12. Ferric Maltol Is Effective in Correcting Iron Deficiency Anemia in Patients with Inflammatory Bowel Disease: Results from a Phase-3 Clinical Trial Program

    PubMed Central

    Ahmad, Tariq; Tulassay, Zsolt; Baumgart, Daniel C.; Bokemeyer, Bernd; Büning, Carsten; Howaldt, Stefanie; Stallmach, Andreas

    2014-01-01

    Background: Iron deficiency anemia (IDA) is frequently seen in inflammatory bowel disease. Traditionally, oral iron supplementation is linked to extensive gastrointestinal side effects and possible disease exacerbation. This multicenter phase-3 study tested the efficacy and safety of ferric maltol, a complex of ferric (Fe3+) iron with maltol (3-hydroxy-2-methyl-4-pyrone), as a novel oral iron therapy for IDA. Methods: Adult patients with quiescent or mild-to-moderate ulcerative colitis or Crohn's disease, mild-to-moderate IDA (9.5–12.0 g/dL and 9.5–13.0 g/dL in females and males, respectively), and documented failure on previous oral ferrous products received oral ferric maltol capsules (30 mg twice a day) or identical placebo for 12 weeks according to a randomized, double-blind, placebo-controlled study design. The primary efficacy endpoint was change in hemoglobin (Hb) from baseline to week 12. Safety and tolerability were assessed. Results: Of 329 patients screened, 128 received randomized therapy (64 ferric maltol-treated and 64 placebo-treated patients) and comprised the intent-to-treat efficacy analysis: 55 ferric maltol patients (86%) and 53 placebo patients (83%) completed the trial. Significant improvements in Hb were observed with ferric maltol versus placebo at weeks 4, 8, and 12: mean (SE) 1.04 (0.11) g/dL, 1.76 (0.15) g/dL, and 2.25 (0.19) g/dL, respectively (P < 0.0001 at all time-points; analysis of covariance). Hb was normalized in two-thirds of patients by week 12. The safety profile of ferric maltol was comparable with placebo, with no impact on inflammatory bowel disease severity. Conclusions: Ferric maltol provided rapid clinically meaningful improvements in Hb and showed a favorable safety profile, suggesting its possible use as an alternative to intravenous iron in IDA inflammatory bowel disease. PMID:25545376

  13. TRANSFORMATION OF NITROSOBENZENES AND HYDROXYLANILINES BY FE (II) SPECIES: ELUCIDATION OF MECHANISM, EFFECT OF FERRIC OXIDES AND PH

    EPA Science Inventory

    The purpose of this work was to (i) study the effect of structure composition on the reactivity of a series of N-hydroxylaniline and nitrosobenzene compounds toward their reduction by Fe(II) species, (ii) evaluate the usefulness of several chemical parameters for predicting the r...

  14. TRANSFORMATION OF NITROSOBENZENES AND HYDROXYLANILINES BY FE II SPECIES: ELUCIDATION OF MECHANISM, EFFECT OF FERRIC OXIDES AND PH

    EPA Science Inventory

    Nitrosobenzenes, the first intermediates in the reduction of nitrobenzenes, were reduced by Fe(II) solutions as well as by Fe(II)-treated goethite suspensions (Fe(II)/G). Results indicate a reactivity trend in which electron-withdrawing groups in the para position increased the ...

  15. Insights into solar photo-Fenton reaction parameters in the oxidation of a sanitary landfill leachate at lab-scale.

    PubMed

    Silva, Tânia F C V; Ferreira, Rui; Soares, Petrick A; Manenti, Diego R; Fonseca, Amélia; Saraiva, Isabel; Boaventura, Rui A R; Vilar, Vítor J P

    2015-12-01

    This work evaluates the effect of the main photo-Fenton (PF) reaction variables on the treatment of a sanitary landfill leachate collected at the outlet of a leachate treatment plant, which includes aerated lagooning followed by aerated activated sludge and a final coagulation-flocculation step. The PF experiments were performed in a lab-scale compound parabolic collector (CPC) photoreactor using artificial solar radiation. The photocatalytic reaction rate was determined while varying the total dissolved iron concentration (20-100 mg Fe(2+)/L), solution pH (2.0-3.6), operating temperature (10-50 °C), type of acid used for acidification (H2SO4, HCl and H2SO4 + HCl) and UV irradiance (22-68 W/m(2)). This work also tries to elucidate the role of ferric hydroxides, ferric sulphate and ferric chloride species, by taking advantage of ferric speciation diagrams, in the efficiency of the PF reaction when applied to leachate oxidation. The molar fraction of the most photoactive ferric species, FeOH(2+), was linearly correlated with the PF pseudo-first order kinetic constants obtained at different solution pH and temperature values. Ferric ion speciation diagrams also showed that the presence of high amounts of chloride ions negatively affected the PF reaction, due to the decrease of ferric ions solubility and scavenging of hydroxyl radicals for chlorine radical formation. The increment of the PF reaction rates with temperature was mainly associated with the increase of the molar fraction of FeOH(2+). The optimal parameters for the photo-Fenton reaction were: pH = 2.8 (acidification agent: H2SO4); T = 30 °C; [Fe(2+)] = 60 mg/L and UV irradiance = 44 WUV/m(2), achieving 72% mineralization after 25 kJUV/L of accumulated UV energy and 149 mM of H2O2 consumed. PMID:26342264

  16. The Porphyromonas gingivalis Ferric Uptake Regulator Orthologue Binds Hemin and Regulates Hemin-Responsive Biofilm Development

    PubMed Central

    Seers, Christine A.; Mitchell, Helen L.; Catmull, Deanne V.; Glew, Michelle D.; Heath, Jacqueline E.; Tan, Yan; Khan, Hasnah S. G.; Reynolds, Eric C.

    2014-01-01

    Porphyromonas gingivalis is a Gram-negative pathogen associated with the biofilm-mediated disease chronic periodontitis. P. gingivalis biofilm formation is dependent on environmental heme for which P. gingivalis has an obligate requirement as it is unable to synthesize protoporphyrin IX de novo, hence P. gingivalis transports iron and heme liberated from the human host. Homeostasis of a variety of transition metal ions is often mediated in Gram-negative bacteria at the transcriptional level by members of the Ferric Uptake Regulator (Fur) superfamily. P. gingivalis has a single predicted Fur superfamily orthologue which we have designated Har (heme associated regulator). Recombinant Har formed dimers in the presence of Zn2+ and bound one hemin molecule per monomer with high affinity (Kd of 0.23 µM). The binding of hemin resulted in conformational changes of Zn(II)Har and residue 97Cys was involved in hemin binding as part of a predicted -97C-98P-99L- hemin binding motif. The expression of 35 genes was down-regulated and 9 up-regulated in a Har mutant (ECR455) relative to wild-type. Twenty six of the down-regulated genes were previously found to be up-regulated in P. gingivalis grown as a biofilm and 11 were up-regulated under hemin limitation. A truncated Zn(II)Har bound the promoter region of dnaA (PGN_0001), one of the up-regulated genes in the ECR455 mutant. This binding decreased as hemin concentration increased which was consistent with gene expression being regulated by hemin availability. ECR455 formed significantly less biofilm than the wild-type and unlike wild-type biofilm formation was independent of hemin availability. P. gingivalis possesses a hemin-binding Fur orthologue that regulates hemin-dependent biofilm formation. PMID:25375181

  17. Computational methods for intramolecular electron transfer in a ferrous-ferric iron complex.

    PubMed

    Zarzycki, Piotr; Kerisit, Sebastien; Rosso, Kevin

    2011-09-01

    The limitations of common theoretical and molecular computational approaches for predicting electron transfer quantities were assessed, using an archetypal bridged ferrous-ferric electron transfer system in aqueous solution. The basis set effect on the magnitude of the electronic coupling matrix element computed using the quasi-diabatic method was carefully examined, and it was found that the error related to a poor basis set could exceed the thermal energy at room temperature. A range of approaches to determining the external (solvent) reorganization energy were also investigated. Significant improvements from the Marcus continuum model can be obtained by including dipolar Born-Kirkwood-Onsager correction. In this regard, we also found that Klamt's Conductor-Like Screening Model (COSMO) yields estimations of the external reorganization energy similar to those obtained with explicit solvent molecular dynamics simulations if the fast-frequency modes are neglected, which makes it an attractive alternative to laborious umbrella sampling simulations. By using the COSMO model, we also confirm that a decrease in curvature of the potential energy surface is a manifestation of the dielectric saturation observed in the first solvation layer. The linearity of solvent response to the charge redistribution was assessed by analyzing the energy gap autocorrelation function as well as the solvent density and dipole moment fluctuations. Molecular dynamics was also used to evaluate the sign and magnitude of the solvent reorganization entropy and to determine its effect on the predicted electron transfer rate. Finally, we present a simple way of estimating the vibration frequency along the reaction coordinate, which also enables prediction of the mass-dependent isotopic signature of electron transfer reactions. PMID:21696749

  18. Opsonic activity of serum and whey from cows immunized with the ferric citrate receptor.

    PubMed

    Wise, A J; Hogan, J S; Takemura, K; Smith, K L

    2003-01-01

    The effects of immunizing dairy cows with the ferric citrate receptor, FecA, on the opsonic activity of serum and whey were measured in a phagocytosis assay. Fifteen cows were assigned to five blocks of three cows based on date of expected parturition. Cows within a block were randomly assigned to one of three treatments: 1) FecA immunization, 2) immunization with a commercially available Escherichia coli J5 bacterin, and 3) unimmunized controls. Cows were challenged at approximately 21 DIM by intramammary infusion of E. coli 727 into one mammary quarter. Escherichia coli 727 were opsonized for the phagocytosis assay with either 10% heat-inactivated serum or 50% heat-inactivated whey collected from each cow at calving, immediately before challenge and 7 d after challenge. Cows immunized with FecA or the E. coli J5 bacterin had increased IgG titers against FecA and E. coli 727 compared with unimmunized control cows. However, sera and whey collected from cows immunized with FecA did not enhance opsonization of E. coli 727 compared with sera and whey from control cows. Immunization with the E. coli J5 bacterin increased opsonization of sera greater than immunization with FecA. Immunoglobulin M antibody titer against E. coli 727 in whey and phagocytic indexes were positively correlated. The phagocytic index of whey immediately before challenge and 7 d after challenge were negatively associated with peak bacterial counts in mammary quarters challenged with E. coli 727. Results of the current trial suggest that the immune response resulting from immunization with FecA did not enhance opsonization and in vitro phagocytosis of E. coli 727. PMID:12613859

  19. Ferric Uptake Regulator and Its Role in the Pathogenesis of Nontypeable Haemophilus influenzae

    PubMed Central

    Santana, Estevan A.; Szelestey, Blake R.; Newsom, David E.; White, Peter; Mason, Kevin M.

    2013-01-01

    Nontypeable Haemophilus influenzae (NTHi) is a commensal microorganism of the human nasopharynx, and yet is also an opportunistic pathogen of the upper and lower respiratory tracts. Host microenvironments influence gene expression patterns, likely critical for NTHi persistence. The host sequesters iron as a mechanism to control microbial growth, and yet iron limitation influences gene expression and subsequent production of proteins involved in iron homeostasis. Careful regulation of iron uptake, via the ferric uptake regulator Fur, is essential in multiple bacteria, including NTHi. We hypothesized therefore that Fur contributes to iron homeostasis in NTHi, is critical for bacterial persistence, and likely regulates expression of virulence factors. Toward this end, fur was deleted in the prototypic NTHi clinical isolate, 86-028NP, and we assessed gene expression regulated by Fur. As expected, expression of the majority of genes that encode proteins with predicted roles in iron utilization was repressed by Fur. However, 14 Fur-regulated genes encode proteins with no known function, and yet may contribute to iron utilization or other biological functions. In a mammalian model of human otitis media, we determined that Fur was critical for bacterial persistence, indicating an important role for Fur-mediated iron homeostasis in disease progression. These data provide a profile of genes regulated by Fur in NTHi and likely identify additional regulatory pathways involved in iron utilization. Identification of such pathways will increase our understanding of how this pathogen can persist within host microenvironments, as a common commensal and, importantly, as a pathogen with significant clinical impact. PMID:23381990

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

    PubMed Central

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

    2013-01-01

    Iron-reducing bacteria (FeRB) play key roles in anaerobic metal and carbon cycling and carry out biogeochemical transformations that can be harnessed for environmental bioremediation. A subset of FeRB require direct contact with Fe(III)-bearing minerals for dissimilatory growth, yet these bacteria must move between mineral particles. Furthermore, they proliferate in planktonic consortia during biostimulation experiments. Thus, a key question is how such organisms can sustain growth under these conditions. Here we characterized planktonic microbial communities sampled from an aquifer in Rifle, Colorado, USA, close to the peak of iron reduction following in situ acetate amendment. Samples were cryo-plunged on site and subsequently examined using correlated two- and three-dimensional cryogenic transmission electron microscopy (cryo-TEM) and scanning transmission X-ray microscopy (STXM). The outer membranes of most cells were decorated with aggregates up to 150?nm in diameter composed of ?3?nm wide amorphous, Fe-rich nanoparticles. Fluorescent in situ hybridization of lineage-specific probes applied to rRNA of cells subsequently imaged via cryo-TEM identified Geobacter spp., a well-studied group of FeRB. STXM results at the Fe L2,3 absorption edges indicate that nanoparticle aggregates contain a variable mixture of Fe(II)–Fe(III), and are generally enriched in Fe(III). Geobacter bemidjiensis cultivated anaerobically in the laboratory on acetate and hydrous ferric oxyhydroxides also accumulated mixed-valence nanoparticle aggregates. In field-collected samples, FeRB with a wide variety of morphologies were associated with nano-aggregates, indicating that cell surface Fe(III) accumulation may be a general mechanism by which FeRB can grow while in planktonic suspension. PMID:23038172

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

    SciTech Connect

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

    2013-02-04

    Iron-reducing bacteria (FeRB) play key roles in anaerobic metal and carbon cycling and carry out biogeochemical transformations that can be harnessed for environmental bioremediation. A subset of FeRB require direct contact with Fe(III) bearing minerals for dissimilatory growth, yet these bacteria must move between mineral particles. Further, they proliferate in planktonic consortia during biostimulation experiments. Thus, a key question is how such organisms can sustain growth under these conditions. Here we characterized planktonic microbial communities sampled from an aquifer in Rifle, Colorado, USA close to the peak of iron reduction following in situ acetate amendment. Samples were cryo-plunged on site and subsequently examined using correlated 2- and 3- dimensional cryogenic transmission electron microscopy (cryo-TEM) and scanning transmission X-ray microscopy (STXM). Most cells had their outer membranes decorated with up to 150 nm diameter aggregates composed of a few nm wide amorphous, Fe-rich nanoparticles. Fluorescent in situ hybridization of lineage-specific probes applied to rRNA of cells subsequently imaged via cryo-TEM identified Geobacter spp., a well studied group of FeRB. STXM results at the Fe L2,3 absorption edges indicate that nanoparticle aggregates contain a variable mixture of Fe(II)-Fe(III), and are generally enriched in Fe(III). Geobacter bemidjiensis cultivated anaerobically in the laboratory on acetate and hydrous ferric oxyhydroxides also accumulated mixed valence nanoparticle aggregates. In field-collected samples, FeRB with a wide variety of morphologies were associated with nano-aggregates, indicating that cell-surface Fe(III) accumulation may be a general mechanism by which FeRB can grow while in planktonic suspension.

  2. Growth, spectroscopic and physicochemical properties of bis mercury ferric chloride tetra thiocyanate: a nonlinear optical crystal.

    PubMed

    Ramesh, V; Shihabuddeen Syed, A; Jagannathan, K; Rajarajan, K

    2013-05-01

    Single crystal of bis mercury ferric chloride tetra thiocyanate [Hg2FeCl3(SCN)4; (MFCTC)] was grown from ethanol-water (3:1) mixed solvent using slow evaporation solvent technique (SEST) for the first time. The cell parameters of the grown crystal were confirmed by single crystal XRD. The coordination of transition metal ions with the SCN ligand is well-identified using FT-IR spectral analysis. The chemical composition of MFCTC was confirmed using CHNS elemental test. The ESR spectral profile of MFCTC was recorded from 298 K to 110K, which strongly suggests the incorporation of Fe(3+) ion and its environment with respect to SCN ligand. The HPLC chromatogram of MFCTC highlights the purity of the compound. The UV-Vis-NIR studies revealed the ultra violet cut-off wavelength of MFCTC in ethanol as 338 nm. The dielectric constant and dielectric loss of the sample were studied as a function of frequency and temperature. The TGA-DTA and DSC thermal analysis show that the sample is thermally stable up to 234.31 °C, which is comparatively far better than the thermal stability of Hg3CdCl2(SCN)6; (171.3 °C) and other metal-organic coordination complex crystals such as CdHg(SCN)4 (198.5 °C), Hg(N2H4CS)4Mn(SCN)4 (199.06 °C) and Hg(N2H4CS)4Zn(SCN)4 (185 °C). The SHG conversion efficiency of MFCTC is found to be higher than KDP. PMID:23501934

  3. Direct measurements of the outer membrane stage of ferric enterobactin transport: postuptake binding.

    PubMed

    Newton, Salete M; Trinh, Vy; Pi, Hualiang; Klebba, Phillip E

    2010-06-01

    When Gram-negative bacteria acquire iron, the metal crosses both the outer membrane (OM) and the inner membrane, but existing radioisotopic uptake assays only measure its passage through the latter bilayer, as the accumulation of the radionuclide in the cytoplasm. We devised a methodology that exclusively observes OM transport and used it to study the uptake of ferric enterobactin (FeEnt) by Escherichia coli FepA. This technique, called postuptake binding, revealed previously unknown aspects of TonB-dependent transport reactions. The experiments showed, for the first time, that despite the discrepancy in cell envelope concentrations of FepA and TonB ( approximately 35:1), all FepA proteins were active and equivalent in FeEnt uptake, with a maximum turnover number of approximately 5/min. FepA-mediated transport of FeEnt progressed through three distinct phases with successively decreasing rates, and from its temperature dependence, the activation energy of the OM stage was 33-35 kcal/mol. The accumulation of FeEnt in the periplasm required the binding protein and inner membrane permease components of its overall transport system; postuptake binding assays on strains devoid of FepB, FepD, or FepG did not show uptake of FeEnt through the OM. However, fluorescence labeling data implied that FepA was active in the DeltafepB strain, suggesting that FeEnt entered the periplasm but then leaked out. Further experiments confirmed this futile cycle; cells without FepB transported FeEnt across the OM, but it immediately escaped through TolC. PMID:20335169

  4. Optimizing iron delivery in the management of anemia: patient considerations and the role of ferric carboxymaltose

    PubMed Central

    Toblli, Jorge Eduardo; Angerosa, Margarita

    2014-01-01

    With the challenge of optimizing iron delivery, new intravenous (iv) iron–carbohydrate complexes have been developed in the last few years. A good example of these new compounds is ferric carboxymaltose (FCM), which has recently been approved by the US Food and Drug Administration for the treatment of iron deficiency anemia in adult patients who are intolerant to oral iron or present an unsatisfactory response to oral iron, and in adult patients with non-dialysis-dependent chronic kidney disease (NDD-CKD). FCM is a robust and stable complex similar to ferritin, which minimizes the release of labile iron during administration, allowing higher doses to be administered in a single application and with a favorable cost-effective rate. Cumulative information from randomized, controlled, multicenter trials on a diverse range of indications, including patients with chronic heart failure, postpartum anemia/abnormal uterine bleeding, inflammatory bowel disease, NDD-CKD, and those undergoing hemodialysis, supports the efficacy of FCM for iron replacement in patients with iron deficiency and iron-deficiency anemia. Furthermore, as FCM is a dextran-free iron–carbohydrate complex (which has a very low risk for hypersensitivity reactions) with a small proportion of the reported adverse effects in a large number of subjects who received FCM, it may be considered a safe drug. Therefore, FCM appears as an interesting option to apply high doses of iron as a single infusion in a few minutes in order to obtain the quick replacement of iron stores. The present review on FCM summarizes diverse aspects such as pharmacology characteristics and analyzes trials on the efficacy/safety of FCM versus oral iron and different iv iron compounds in multiple clinical scenarios. Additionally, the information on cost effectiveness and data on change in quality of life are also discussed. PMID:25525337

  5. Ferric Citrate Reduces Intravenous Iron and Erythropoiesis-Stimulating Agent Use in ESRD.

    PubMed

    Umanath, Kausik; Jalal, Diana I; Greco, Barbara A; Umeukeje, Ebele M; Reisin, Efrain; Manley, John; Zeig, Steven; Negoi, Dana G; Hiremath, Anand N; Blumenthal, Samuel S; Sika, Mohammed; Niecestro, Robert; Koury, Mark J; Ma, Khe-Ni; Greene, Tom; Lewis, Julia B; Dwyer, Jamie P

    2015-10-01

    Ferric citrate (FC) is a phosphate binder with shown efficacy and additional effects on iron stores and use of intravenous (iv) iron and erythropoiesis-stimulating agents (ESAs). We provide detailed analyses of changes in iron/hematologic parameters and iv iron/ESA use at time points throughout the active control period of a phase 3 international randomized clinical trial. In all, 441 subjects were randomized (292 to FC and 149 to sevelamer carbonate and/or calcium acetate [active control (AC)]) and followed for 52 weeks. Subjects on FC had increased ferritin and transferrin saturation (TSAT) levels compared with subjects on AC by week 12 (change in ferritin, 114.1±29.35 ng/ml; P<0.001; change in TSAT, 8.62%±1.57%; P<0.001). Change in TSAT plateaued at this point, whereas change in ferritin increased through week 24, remaining relatively stable thereafter. Subjects on FC needed less iv iron compared with subjects on AC over 52 weeks (median [interquartile range] dose=12.9 [1.0-28.9] versus 26.8 [13.4-47.6] mg/wk; P<0.001), and the percentage of subjects not requiring iv iron was higher with FC (P<0.001). Cumulative ESA over 52 weeks was lower with FC than AC (median [interquartile range] dose=5303 [2023-9695] versus 6954 [2664-12,375] units/wk; P=0.04). Overall, 90.3% of subjects on FC and 89.3% of subjects on AC experienced adverse events. In conclusion, treatment with FC as a phosphate binder results in increased iron parameters apparent after 12 weeks and reduces iv iron and ESA use while maintaining hemoglobin over 52 weeks, with a safety profile similar to that of available binders. PMID:25736045

  6. Method for fluorination of uranium oxide

    DOEpatents

    Petit, George S. (Oak Ridge, TN)

    1987-01-01

    Highly pure uranium hexafluoride is made from uranium oxide and fluorine. The uranium oxide, which includes UO.sub.3, UO.sub.2, U.sub.3 O.sub.8 and mixtures thereof, is introduced together with a small amount of a fluorine-reactive substance, selected from alkali chlorides, silicon dioxide, silicic acid, ferric oxide, and bromine, into a constant volume reaction zone. Sufficient fluorine is charged into the zone at a temperature below approximately 0.degree. C. to provide an initial pressure of at least approximately 600 lbs/sq. in. at the ambient atmospheric temperature. The temperature is then allowed to rise in the reaction zone until reaction occurs.

  7. Method for catalyzing oxidation/reduction reactions of simple molecules

    SciTech Connect

    Bicker, D.; Bonaventura, J.

    1988-06-14

    A method for oxidizing carbon monoxide to carbon dioxide is described comprising: (1) contacting, together, carbon monoxide, a nitrogen-containing chelating agent and water; wherein the chelating agent is at least one member selected from the group consisting of methmeoglobin bound to a support, ferric hemoglobin bound to a support, iron-containing porphyrins bound to a support, and sperm whale myoglobin bound to a support, wherein the support is glass, a natural fiber, a synthetic fiber, a gel, charcoal, carbon ceramic material, a metal oxide, a synthetic polymer, a zeolite, a silica compound of an alumina compound; and (2) obtaining carbon dioxide.

  8. Sickle Cell Hemoglobin in the Ferryl State Promotes ?Cys-93 Oxidation and Mitochondrial Dysfunction in Epithelial Lung Cells (E10).

    PubMed

    Kassa, Tigist; Jana, Sirsendu; Strader, Michael Brad; Meng, Fantao; Jia, Yiping; Wilson, Michael T; Alayash, Abdu I

    2015-11-13

    Polymerization of intraerythrocytic deoxyhemoglobin S (HbS) is the primary molecular event that leads to hemolytic anemia in sickle cell disease (SCD). We reasoned that HbS may contribute to the complex pathophysiology of SCD in part due to its pseudoperoxidase activity. We compared oxidation reactions and the turnover of oxidation intermediates of purified human HbS and HbA. Hydrogen peroxide (H2O2) drives a catalytic cycle that includes the following three distinct steps: 1) initial oxidation of ferrous (oxy) to ferryl Hb; 2) autoreduction of the ferryl intermediate to ferric (metHb); and 3) reaction of metHb with an additional H2O2 molecule to regenerate the ferryl intermediate. Ferrous and ferric forms of both proteins underwent initial oxidation to the ferryl heme in the presence of H2O2 at equal rates. However, the rate of autoreduction of ferryl to the ferric form was slower in the HbS solutions. Using quantitative mass spectrometry and the spin trap, 5,5-dimethyl-1-pyrroline-N-oxide, we found more irreversibly oxidized ?Cys-93in HbS than in HbA. Incubation of the ferric or ferryl HbS with cultured lung epithelial cells (E10) induced a drop in mitochondrial oxygen consumption rate and impairment of cellular bioenergetics that was related to the redox state of the iron. Ferryl HbS induced a substantial drop in the mitochondrial transmembrane potential and increases in cytosolic heme oxygenase (HO-1) expression and mitochondrial colocalization in E10 cells. Thus, highly oxidizing ferryl Hb and heme, the product of oxidation, may be central to the evolution of vasculopathy in SCD and may suggest therapeutic modalities that interrupt heme-mediated inflammation. PMID:26396189

  9. Enhancement of a solar photo-Fenton reaction with ferric-organic ligands for the treatment of acrylic-textile dyeing wastewater.

    PubMed

    Soares, Petrick A; Batalha, Mauro; Souza, Selene M A Guelli U; Boaventura, Rui A R; Vilar, Vítor J P

    2015-04-01

    Literature describes a kinetic mineralization profile for most of acrylic-textile dyeing wastewaters using a photo-Fenton reaction characterized by a slow degradation process and high reactants consumption. This work tries to elucidate that the slow decay on DOC concentration is associated with the formation of stable complexes between Fe(3+) and textile auxiliary products, limiting the photoreduction of Fe(3+). This work also evaluates the enhancement of a solar photo-Fenton reaction through the use of different ferric-organic ligands applied to the treatment of a simulated acrylic-textile dyeing wastewater, as a pre-oxidation step to enhance its biodegradability. The photo-Fenton reaction was negatively affected by two dyeing auxiliary products: i) Sera(®) Tard A-AS, a surfactant mainly composed of alkyl dimethyl benzyl ammonium chloride and ii) Sera(®) Sperse M-IW, a dispersing agent composed of polyglycol solvents. The catalytic activity of the organic ligands toward the ferrous-catalysed system followed this order: Fe(III)-Oxalate > Fe(III)-Citrate > Fe(III)-EDDS, and all were better than the traditional photo-Fenton reaction. Different design parameters such as iron concentration, pH, temperature, flow conditions, UV irradiance and H2O2 addition strategy and dose were evaluated. The ferrioxalate induced photo-Fenton process presented the best results, achieving 87% mineralization after 9.3 kJUV L(-1) and allowing to work until near neutral pH values. As expected, the biodegradability of the textile wastewater was significantly enhanced during the photo-Fenton treatment, achieving a value of 73%, consuming 32.4 mM of H2O2 and 5.7 kJUV L(-1). PMID:25618444

  10. Iron uptake by Escherichia coli cultured with antibodies from cows immunized with high-affinity ferric receptors.

    PubMed

    Wolf, S L; Hogan, J S; Smith, K L

    2004-07-01

    The synergistic effects of immunoglobulin G (IgG) from cows vaccinated with ferric citrate receptor (FecA) and IgG from cows vaccinated with ferric enterobactin receptor (FepA) were measured in an in vitro iron uptake assay. Serum was isolated and pooled within treatment from five cows each vaccinated with FepA or FecA or not vaccinated. Immunoglobulin G was isolated by ammonium sulfate precipitation and protein G affinity chromatography. Six Escherichia coli isolates from bovine intramammary infections were cultured in an iron-depleted medium to induce high-affinity iron acquisition systems and, in iron-depleted conditions, to specifically induce the expression of FecA. The bacterial cells were mixed with either 3 or 6 mg/mL of purified IgG and 55Fe. The radioactivity of 55Fe taken up by the bacterial cells was measured by a liquid scintillation counter after 5-, 10-, and 15-min incubations at 37 degrees C. The combination of anti-FecA IgG and anti-FepA IgG reduced 55Fe uptake compared with either anti-FecA or anti-FepA alone. Iron uptake was reduced more by anti-FecA IgG than by anti-FepA IgG when the ferric citrate system was induced. Reduction of iron uptake did not differ between anti-FepA alone and anti-FecA alone when citrate was absent from the medium. PMID:15328222

  11. Comparative evaluation of Ferric Sulfate, Electrosurgical and Diode Laser on human primary molars pulpotomy: an “in-vivo” study

    PubMed Central

    Yadav, P; Indushekar, KR; Saraf, BG; Sheoran, N; Sardana, D

    2014-01-01

    Background and aims: Despite modern advances in the prevention of dental caries and increased understanding of the importance of maintaining the natural primary dentition, many teeth are still lost prematurely. This can lead to malocclusion with aesthetic, phonetic and functional problems that may be transient or permanent. Therefore, maintaining the integrity and health of the oral tissues is the primary objective of pulp treatment. Pulpotomy has remained an acceptable and mainstay treatment in preserving the vitality of primary tooth and prolonging its life till the permanent successor erupts. Various materials and techniques are available for pulpotomy on primary molars; all with some advantages and disadvantages. The present study was carried out on 45 primary molars to evaluate and compare the clinical and radiographic success of diode laser, electrosurgical and ferric sulfate pulpotomy over a period of 9 months. Materials (Subjects) and Methods: The forty five primary molars were randomly and equally divided into three treatment groups which were as follows: Group A: 15 primary molars treated with 15.5% Ferric sulfate Group B: 15 primary molars treated with electrosurgical unit and Group C: 15 primary molars treated with diode laser. All teeth in three categories were followed up clinically and radiographically at 1, 3, 6 and 9 months post treatment and the findings were recorded on the prepared proforma Results: Clinically, 86.6% success rate was found in ferric sulfate group whereas 100% success rate was found in electrosurgical and diode laser groups. Radiographically, 80% success rate was found in all the three groups at the end of 9 months with internal resorption being the most common cause of failure after pulpotomy. Conclusions: Thus, electrosurgery and diode lasers appear to be acceptable alternative to pharmacotherapeutic pulpotomy agents. PMID:24771970

  12. The role of rare-earth dopants in nanophase zirconia catalysts for automotive emission control.

    SciTech Connect

    Loong, C.-K.; Ozawa, M.

    1999-07-16

    Rare earth (RE) modification of automotive catalysts (e.g., ZrO{sub 2}) for exhaust gas treatment results in outstanding improvement of the structural stability, catalytic functions and resistance to sintering at high temperatures. Owing to the low redox potential of nonstoichiometric CeO{sub 2}, oxygen release and intake associated with the conversion between the 3+ and 4+ oxidation states of the Ce ions in Ce-doped ZrO{sub 2} provide the oxygen storage capacity that is essentially to effective catalytic functions under dynamic air-to-fuel ratio cycling. Doping tripositive RE ions such as La and Nd in ZrO{sub 2}, on the other hand, introduces oxygen vacancies that affect the electronic and ionic conductivity. These effects, in conjunction with the nanostructure and surface reactivity of the fine powders, present a challenging problem in the development of better ZrO{sub 2}-containing three-way catalysts. We have carried out in-situ small-to-wide angle neutron diffraction at high temperatures and under controlled atmospheres to study the structural phase transitions, sintering behavior, and Ce{sup 3+} {leftrightarrow} Ce{sup 4+} redox process. We found substantial effects due to RE doping on the nature of aggregation of nanoparticles, defect formation, crystal phase transformation, and metal-support interaction in ZrO{sub 2} catalysts for automotive emission control.

  13. Assessment of mapping exposed ferrous and ferric iron compounds using Skylab-EREP data. [Pisgah Crater, California

    NASA Technical Reports Server (NTRS)

    Vincent, R. (principal investigator); Wagner, H.; Pillars, W.; Bennett, C.

    1976-01-01

    The author has identified the following significant results. The S190B color photography is as useful as LANDSAT data for the mapping of color differences in the rocks and soils of the terrain. An S192 ratio of 0.79 - 0.89 and 0.93 - 1.05 micron bands produced an apparently successful delineation of ferrous, ferric, and other materials, in agreement with theory and ratio code studies. From an analysis of S191 data, basalt and dacite were separated on the basis of differences in spectral emissivity in the 8.3 - 12 micron region.

  14. Ibuprofen Impairs Allosterically Peroxynitrite Isomerization by Ferric Human Serum Heme-Albumin*

    PubMed Central

    Ascenzi, Paolo; di Masi, Alessandra; Coletta, Massimo; Ciaccio, Chiara; Fanali, Gabriella; Nicoletti, Francesco P.; Smulevich, Giulietta; Fasano, Mauro

    2009-01-01

    Human serum albumin (HSA) participates in heme scavenging; in turn, heme endows HSA with myoglobin-like reactivity and spectroscopic properties. Here, the allosteric effect of ibuprofen on peroxynitrite isomerization to NO3? catalyzed by ferric human serum heme-albumin (HSA-heme-Fe(III)) is reported. Data were obtained at 22.0 °C. HSA-heme-Fe(III) catalyzes peroxynitrite isomerization in the absence and presence of CO2; the values of the second order catalytic rate constant (kon) are 4.1 × 105 and 4.5 × 105 m?1 s?1, respectively. Moreover, HSA-heme-Fe(III) prevents peroxynitrite-mediated nitration of free added l-tyrosine. The pH dependence of kon (pKa = 6.9) suggests that peroxynitrous acid reacts preferentially with the heme-Fe(III) atom, in the absence and presence of CO2. The HSA-heme-Fe(III)-catalyzed isomerization of peroxynitrite has been ascribed to the reactive pentacoordinated heme-Fe(III) atom. In the absence and presence of CO2, ibuprofen impairs dose-dependently peroxynitrite isomerization by HSA-heme-Fe(III) and facilitates the nitration of free added l-tyrosine; the value of the dissociation equilibrium constant for ibuprofen binding to HSA-heme-Fe(III) (L) ranges between 7.7 × 10?4 and 9.7 × 10?4 m. Under conditions where [ibuprofen] is ?L, the kinetics of HSA-heme-Fe(III)-catalyzed isomerization of peroxynitrite is superimposable to that obtained in the absence of HSA-heme-Fe(III) or in the presence of non-catalytic HSA-heme-Fe(III)-cyanide complex and HSA. Ibuprofen binding impairs allosterically peroxynitrite isomerization by HSA-heme-Fe(III), inducing the hexacoordination of the heme-Fe(III) atom. These results represent the first evidence for peroxynitrite isomerization by HSA-heme-Fe(III), highlighting the allosteric modulation of HSA-heme-Fe(III) reactivity by heterotropic interaction(s), and outlining the role of drugs in modulating HSA functions. The present results could be relevant for the drug-dependent protective role of HSA-heme-Fe(III) in vivo. PMID:19734142

  15. Effect of ferric oxyhydroxide grain coatings on the transport of bacteriophage PRD1 and Cryptosporidium parvum oocysts in saturated porous media

    USGS Publications Warehouse

    Abudalo, R.A.; Bogatsu, Y.G.; Ryan, J.N.; Harvey, R.W.; Metge, D.W.; Elimelech, M.

    2005-01-01

    To test the effect of geochemical heterogeneity on microorganism transport in saturated porous media, we measured the removal of two microorganisms, the bacteriophage PRD1 and oocysts of the protozoan parasite Cryptosporidium parvum, in flow-through columns of quartz sand coated by different amounts of a ferric oxyhydroxide. The experiments were conducted over ranges of ferric oxyhydroxide coating fraction of ?? = 0-0.12 for PRD1 and from ?? = 0-0.32 for the oocysts at pH 5.6-5.8 and 10-4 M ionic strength. To determine the effect of pH on the transport of the oocysts, experiments were also conducted over a pH range of 5.7-10.0 at a coating fraction of ?? = 0.04. Collision (attachment) efficiencies increased as the fraction of ferric oxyhydroxide coated quartz sand increased, from ?? = 0.0071 to 0.13 over ?? = 0-0.12 for PRD1 and from ?? = 0.059 to 0.75 over ?? = 0-0.32 for the oocysts. Increasing the pH from 5.7 to 10.0 resulted in a decrease in the oocyst collision efficiency as the pH exceeded the expected point of zero charge of the ferric oxyhydroxide coatings. The collision efficiencies correlated very well with the fraction of quartz sand coated by the ferric oxyhydroxide for PRD1 but not as well for the oocysts. ?? 2005 American Chemical Society.

  16. A least-squares error minimization approach in the determination of ferric ion diffusion coefficient of Fricke-infused dosimeter gels

    SciTech Connect

    Tseng, Y.J.; Huang, S.-C.; Chu, W.C.

    2005-04-01

    A least-squares error minimization approach was adopted to assess ferric ion diffusion coefficient of Fricke-agarose gels. Ferric ion diffusion process was modeled as a Gaussian-shaped degradation kernel operating on an initial concentration distribution. Diffusion coefficient was iteratively determined by minimizing the error function defined as the difference between the theoretically calculated and the experimentally measured dose distributions. A rapid MR image-based differential gel dosimetry technique that time resolves the evolution of the ferric ion diffusion process minimizes smearing of the dose distribution. Our results showed that for a Fricke-agarose gel contained 1 mM ammonium ferrous sulfate, 1% agarose, 1 mM sodium chloride, and 50 mM sulfuric acid, its ferric ion diffusion coefficient is (1.59{+-}0.28)x10{sup -2} cm{sup 2} h{sup -1} at room temperature. This value falls within the 1.00-2.00x10{sup -2} cm{sup 2} h{sup -1} range previously reported under varying gelling ingredients and concentrations. This method allows a quick, nondestructive evaluation of the ferric ion diffusion coefficient that can be used in conjunction with the in situ gel dosimetry experiment to provide a practical diffusion characterization of the dosimeter gel.

  17. Influence of organic matter on the transport of Cryptosporidium parvum oocysts in a ferric oxyhydroxide-coated quartz sand saturated porous medium

    USGS Publications Warehouse

    Abudalo, R.A.; Ryan, J.N.; Harvey, R.W.; Metge, D.W.; Landkamer, L.

    2010-01-01

    To assess the effect of organic matter on the transport of Cryptosporidium parvum oocysts in a geochemically heterogeneous saturated porous medium, we measured the breakthrough and collision efficiencies of oocysts as a function of dissolved organic matter concentration in a flow-through column containing ferric oxyhydroxide-coated sand. We characterized the surface properties of the oocysts and ferric oxyhydroxide-coated sand using microelectrophoresis and streaming potential, respectively, and the amount of organic matter adsorbed on the ferric oxyhydroxide-coated sand as a function of the concentration of dissolved organic matter (a fulvic acid isolated from Florida Everglades water). The dissolved organic matter had no significant effect on the zeta potential of the oocysts. Low concentrations of dissolved organic matter were responsible for reversing the charge of the ferric oxyhydroxide-coated sand surface from positive to negative. The charge reversal and accumulation of negative charge on the ferric oxyhydroxide-coated sand led to increases in oocyst breakthrough and decreases in oocyst collision efficiency with increasing dissolved organic matter concentration. The increase in dissolved organic matter concentration from 0 to 20 mg L-1 resulted in a two-fold decrease in the collision efficiency. ?? 2009 Elsevier Ltd.

  18. Oxidative Dissolution of Arsenopyrite by Mesophilic and Moderately Thermophilic Acidophiles †

    PubMed Central

    Tuovinen, Olli H.; Bhatti, Tariq M.; Bigham, Jerry M.; Hallberg, Kevin B.; Garcia, Oswaldo; Lindström, E. Börje

    1994-01-01

    The purpose of this work was to determine solution- and solid-phase changes associated with the oxidative leaching of arsenopyrite (FeAsS) by Thiobacillus ferrooxidans and a moderately thermoacidophilic mixed culture. Jarosite [KFe3(SO4)2(OH)6], elemental sulfur (S0), and amorphous ferric arsenate were detected by X-ray diffraction as solid-phase products. The oxidation was not a strongly acid-producing reaction and was accompanied by a relatively low redox level. The X-ray diffraction lines of jarosite increased considerably when ferrous sulfate was used as an additional substrate for T. ferroxidans. A moderately thermoacidophilic mixed culture oxidized arsenopyrite faster at 45°C than did T. ferroxidans at 22°C, and the oxidation was accompanied by a nearly stoichiometric release of Fe and As. The redox potential was initially low but subsequently increased during arsenopyrite oxidation by the thermoacidophiles. Jarosite, S0, and amorphous ferric arsenate were also formed under these conditions. PMID:16349379

  19. Equilibrium between ferrous and ferric iron when subjected to an alternating current

    E-print Network

    Robinson, James Gordon

    1915-01-01

    ) Oxidation. Current .75 amp. Trial Temp. Time KMK04 cc oxidized fo oxidation 1 0 25.58 0 0 2 - 60-70 2 24.92 , 66 2.58 3 68-76 5 24.18 1.40 5.44 4 70-80 10 23.97 1.61 6.30 5 60-81 20 22.82 2;76 10.80 6 52-80 30 20.32 5.26 20.57 7 56-79 40 19*50 6....5 amp. Trial Time cc oxidized $ oxidized 1 5 1.44 5.7 2 50 4.89 19.4 3 165 8.34 33.1 Table 5 (b) Reduction * Trial Time cc reduced $ reduced 1 2 #70 2.79 2 5 2.84 U. 3 J. 3 10 3.62 14.4 4 20 5.89 23.4 5 30 6.45 25.6 6 40 A 9.14 36.4 7 50 12...

  20. Simultaneous X-ray and neutron diffraction Rietveld refinements of nanophase iron substituted hydroxyapatite

    NASA Astrophysics Data System (ADS)

    Kyriacou, Andreas

    The effect of Fe substitution on the crystal structure of hydroxyapatite (HAp) is studied by applying simultaneous Rietveld refinements of powder x-ray and neutron diffraction patterns. Fe is one of the trace elements replacing Ca in HAp, which is the major mineral phase in bones and teeth. The morphology and magnetic properties of the Fe-HAp system are also studied by transmission electron microscopy and magnetization measurements. Samples of Ca(5-x)Fex(PO4)3OH with 0 ? x ? 0.3 were prepared. Single phase HAp was identified in x-ray diffraction patterns (XRD) of samples with x < 0.1 inferring that the solubility limits are less than 0.1. Hematite (alpha-Fe2O3) is identified as a secondary phase for higher Fe content. The refined parameters show that Fe is incorporated in the HAp structure by replacing Ca in the two crystallographic sites with a preference at the Ca2 site. This preference explains the small effect of the Fe substitution on the lattice constants of HAp. The overall decrease of the lattice constants is explained by the ionic size difference of Ca and Fe. The increasing trend of the a-lattice constant with x in the Fe substituted samples is attributed to a lattice relaxation caused by the substitution of the 4- and 6-fold Fe at the 7- and 9-fold Ca1 and Ca2 sites. This Ca local geometry reduction is indicated by a slight increase of the Ca1-O3 and Ca2-O1 bond lengths. Above the solubility limit x = 0.05, the Fe is partitioned in and out of the HAp structure with increasing nominal Fe content x. The excess Fe is oxidized to hematite. The TEM analysis and magnetic measurements support the results of the simultaneous Rietveld refinements. The TEM images show no significant effect on the morphology and size of the HAp particles upon Fe incorporation. The particles are either spheres or short rods of dimensions 20--60 nm. Hematite particles are imaged in the samples with x exceeding the solubility limit. These particles are spheres, about 15 nm in diameter and are more resistant to electron beam damage. Magnetic measurements reveal a transition of the diamagnetic pure HAp to paramagnetic Fe substituted HAp.

  1. Ferrous iron oxidation by anoxygenic phototrophic bacteria

    NASA Astrophysics Data System (ADS)

    Widdel, Friedrich; Schnell, Sylvia; Heising, Silke; Ehrenreich, Armin; Assmus, Bernhard; Schink, Bernhard

    1993-04-01

    NATURAL oxidation of ferrous to ferric iron by bacteria such as Thiobacillus ferrooxidans or Gallionella ferruginea1, or by chemical oxidation2,3 has previously been thought always to involve molecular oxygen as the electron acceptor. Anoxic photochemical reactions4-6 or a photobiological process involving two photosystems7-9 have also been discussed as mechanisms of ferrous iron oxidation. The knowledge of such processes has implications that bear on our understanding of the origin of Precambrian banded iron formations10-14. The reducing power of ferrous iron increases dramatically at pH values higher than 2-3 owing to the formation of ferric hydroxy and oxyhydroxy compounds1,2,15 (Fig. 1). The standard redox potential of Fe3+/Fe2+ (E0 = +0.77 V) is relevant only under acidic conditions. At pH 7.0, the couples Fe(OH)3/Fe2+ (E'0 = -0.236V) or Fe(OH)3 + HCO-3FeCO3 (E'0 = +0.200 V) prevail, matching redox potentials measured in natural sediments9,16,17. It should thus be possible for Fe(n) around pH 7.0 to function as an electron donor for anoxygenic photosynthesis. The midpoint potential of the reaction centre in purple bacteria is around +0.45 V (ref. 18). Here we describe purple, non-sulphur bacteria that can indeed oxidize colourless Fe(u) to brown Fe(in) and reduce CO2 to cell material, implying that oxygen-independent biological iron oxidation was possible before the evolution of oxygenic photosynthesis.

  2. Role for the outer membrane ferric siderophore receptor PupB in signal transduction across the bacterial cell envelope.

    PubMed Central

    Koster, M; van Klompenburg, W; Bitter, W; Leong, J; Weisbeek, P

    1994-01-01

    The outer membrane protein PupB of Pseudomonas putida WCS358 facilitates transport of iron complexed to the siderophores pseudobactin BN8 and pseudobactin BN7 into the cell. Its synthesis is induced by the presence of these specific siderophores under iron limitation. The signal transduction pathway regulating siderophore-dependent expression of pupB was shown to consist of two regulatory proteins, PupI and PupR, and the PupB receptor itself. Mutational analysis of the regulatory genes suggested that PupI acts as a positive regulator of pupB transcription, whereas PupR modifies PupI activity dependent on the presence of pseudobactin BN8. PupI and PupR do not share homology with the classical bacterial two-component systems but display significant similarity to the FecI and FecR proteins of Escherichia coli involved in regulation of ferric dicitrate transport. The function of the PupB receptor in pupB regulation was studied by the use of chimeric receptor proteins composed of PupB and the ferric pseudobactin 358 receptor PupA. This experiment revealed that PupB is involved in the initiation of the signal transduction pathway, implying a so far unique role for an outer membrane protein in signal transduction. Images PMID:8026465

  3. Survey of ferric reductase transcription and activity in Pisum sativum accessions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Iron (Fe) is an essential element for the growth of plants. While Fe is not limiting in most soils (it makes up approximately 5% of total soil minerals), Fe availability to plants in aerated, calcareous soils near neutral or basic pH can be severely limited as Fe oxidizes to form less soluble ferri...

  4. BIOGEOCHEMICAL PROCESSES CONTROLLING ARSENIC SPECIATION AND BIOTRANSFORMATION IN GRANULAR FERRIC HYDROXIDE COATED SAND

    EPA Science Inventory

    Arsenic mobilization from solid phase Fe (III) hydroxides is an issue of concern, as water-borne arsenic can migrate into pristine environments, endangering aquatic and human life. In general, metal oxide (hydroxides) exerts a dominating effect on the fate and transport of arseni...

  5. Copper Oxide Nanoparticles Induce Autophagic Cell Death in A549 Cells

    PubMed Central

    Zhao, Yan; Guo, Feng; Jiang, Chengyu

    2012-01-01

    Metal oxide nanoparticles (NPs) are among the most highly produced nanomaterials, and have many diverse functions in catalysis, environmental remediation, as sensors, and in the production of personal care products. In this study, the toxicity of several widely used metal oxide NPs such as copper oxide, silica, titanium oxide and ferric oxide NPs, were evaluated In vitro. We exposed A549, H1650 and CNE-2Z cell lines to metal oxide NPs, and found CuO NPs to be the most toxic, SiO2 mild toxic, while the other metal oxide NPs had little effect on cell viability. Furthermore, the autophagic biomarker LC3-II significantly increased in A549 cells treated with CuO NPs, and the use of the autophagy inhibitors wortmannin and 3-methyladenin significantly improved cell survival. These results indicate that the cytoxicity of CuO NPs may involve the autophagic pathway in A549 cells. PMID:22916263

  6. Structure and reactivity of As(III)- and As(V)-rich schwertmannites and amorphous ferric arsenate sulfate from the Carnoulès acid mine drainage, France: Comparison with biotic and abiotic model compounds and implications for As remediation

    NASA Astrophysics Data System (ADS)

    Maillot, Fabien; Morin, Guillaume; Juillot, Farid; Bruneel, Odile; Casiot, Corinne; Ona-Nguema, Georges; Wang, Yuheng; Lebrun, Sophie; Aubry, Emmanuel; Vlaic, Gilberto; Brown, Gordon E.

    2013-03-01

    Poorly ordered nanocrystalline hydroxysulfate minerals of microbial origin, such as schwertmannite, Fe8O8(OH)6SO4, are important arsenic scavengers in sulfate-rich acid mine drainage (AMD) environments. However, despite the fact that As(III) and As(V) have been shown to sorb on schwertmannite, little is known about the actual mechanism of arsenic scavenging processes after microbial Fe(II) oxidation in AMD environments. The major focus of the present study is to determine the molecular-level structure of poorly ordered As(III) and As(V) bearing Fe oxyhydroxysulfate minerals from the Carnoulès AMD, France, which exhibits exceptional As(III) concentrations. Powder X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy were used to compare field samples with a large set of synthetic analogs prepared via biotic or abiotic pathways, with As/Fe ratios typical of minerals and mineraloids ranging from nanocrystalline schwertmannite to amorphous hydroxysulfate compounds. Our results yield further evidence for the poisoning effect of As(V) in limiting the nucleation of schwertmannite. For initial dissolved As(V)/Fe(III) molar ratios ?0.2, amorphous Fe(III)-As(V) hydroxysulfate forms, with a local structure consistent with that of amorphous ferric arsenate. EXAFS data for this amorphous material are consistent with corner-sharing FeO6 octahedra to which AsO4 tetrahedra attach via double-corner 2C linkages. For As(V)/Fe(III) molar ratios lower than 0.2, As(V) binds to schwertmannite via 2C surface complexes. In contrast with the As(V)-containing samples, As(III) has a lower affinity for schwertmannite following its nucleation, as this mineral phase persists up to an initial As(III)/Fe(III) molar ratio of 0.6. EXAFS data indicate that during the precipitation process, As(III) forms dominantly 2C surface complexes on schwertmannite surfaces, likely on the sides of double-chains of Fe(III)(O,OH)6 octahedra, with a smaller proportion of edge-sharing 2E surface complexes at the apexes of these chains. Importantly, dissolved As(V) concentrations in contact with As(V)-schwertmannite or ferric arsenate were found to be ˜10 times lower than dissolved As(III) concentrations in contact with As(III)-schwertmannite for similar As/Fe ratios in the solid phase. Consequently, remediation of As-rich AMD environments is greatly improved by oxidation of As(III) to As(V).

  7. Extraction of copper from an oxidized (lateritic) ore using bacterially catalysed reductive dissolution.

    PubMed

    Nancucheo, Ivan; Grail, Barry M; Hilario, Felipe; du Plessis, Chris; Johnson, D Barrie

    2014-01-01

    An oxidized lateritic ore which contained 0.8 % (by weight) copper was bioleached in pH- and temperature-controlled stirred reactors under acidic reducing conditions using pure and mixed cultures of the acidophilic chemolithotrophic bacterium Acidithiobacillus ferrooxidans. Sulfur was provided as the electron donor for the bacteria, and ferric iron present in goethite (the major ferric iron mineral present in the ore) acted as electron acceptor. Significantly more copper was leached by bacterially catalysed reductive dissolution of the laterite than in aerobic cultures or in sterile anoxic reactors, with up to 78 % of the copper present in the ore being extracted. This included copper that was leached from acid-labile minerals (chiefly copper silicates) and that which was associated with ferric iron minerals in the lateritic ore. In the anaerobic bioreactors, soluble iron in the leach liquors was present as iron (II) and copper as copper (I), but both metals were rapidly oxidized (to iron (III) and copper (II)) when the reactors were aerated. The number of bacteria added to the reactors had a critical role in dictating the rate and yield of copper solubilised from the ore. This work has provided further evidence that reductive bioprocessing, a recently described approach for extracting base metals from oxidized deposits, has the potential to greatly extend the range of metal ores that can be biomined. PMID:24687752

  8. Performance evaluation of ALCAN-AASF50-ferric coated activated alumina and granular ferric hydroxide (GFH) for arsenic removal in the presence of competitive ions in an active well :Kirtland field trial - initial studies.

    SciTech Connect

    Neidel, Linnah L.; Krumhansl, James Lee; Siegel, Malcolm Dean; Khandaker, Nadim Reza

    2006-01-01

    This report documents a field trial program carried out at Well No.15 located at Kirtland Air Force Base, Albuquerque, New Mexico, to evaluate the performance of two relatively new arsenic removal media, ALCAN-AASF50 (ferric coated activated alumina) and granular ferric hydroxide (US Filter-GFH). The field trial program showed that both media were able to remove arsenate and meet the new total arsenic maximum contaminant level (MCL) in drinking water of 10 {micro}g/L. The arsenate removal capacity was defined at a breakthrough effluent concentration of 5 {micro}g/L arsenic (50% of the arsenic MCL of 10 {micro}g/L). At an influent pH of 8.1 {+-} 0.4, the arsenate removal capacity of AASF50 was 33.5 mg As(V)/L of dry media (29.9 {micro}g As(V)/g of media on a dry basis). At an influent pH of 7.2 {+-} 0.3, the arsenate removal capacity of GFH was 155 mg As(V)/L of wet media (286 {micro}g As(V)/g of media on a dry basis). Silicate, fluoride, and bicarbonate ions are removed by ALCAN AASF50. Chloride, nitrate, and sulfate ions were not removed by AASF50. The GFH media also removed silicate and bicarbonate ions; however, it did not remove fluoride, chloride, nitrate, and sulfate ions. Differences in the media performance partly reflect the variations in the feed-water pH between the 2 tests. Both the exhausted AASF50 and GFH media passed the Toxicity Characteristic Leaching Procedure (TCLP) test with respect to arsenic and therefore could be disposed as nonhazardous waste.

  9. Spin-state crossover and hyperfine interactions of ferric iron in MgSiO$_3$ perovskite

    E-print Network

    Hsu, Han; Cococcioni, Matteo; Wentzcovitch, Renata M

    2011-01-01

    Using density functional theory plus Hubbard $U$ calculations, we show that the ground state of (Mg,Fe)(Si,Fe)O$_3$ perovskite, a major mineral phase in the Earth's lower mantle, has high-spin ferric iron ($S=5/2$) at both the dodecahedral (A) and octahedral (B) site. As the pressure increases, the B-site iron undergoes a spin-state crossover to the low-spin state ($S=1/2$), while the A-site iron remains in the high-spin state. Our calculation shows that the B-site spin-state crossover in the pressure range of 40-70 GPa is accompanied by a noticeable volume reduction and an increase in quadrupole splitting, consistent with recent X-ray diffraction and M\\"ossbauer spectroscopy measurements. The volume reduction leads to a significant softening in the bulk modulus, which suggests a possible source of seismic velocity anomalies in the lower mantle.

  10. Breadboard wash water renovation system. [using ferric chloride and ion exchange resins to remove soap and dissolved salts

    NASA Technical Reports Server (NTRS)

    1978-01-01

    A total wash water renovation system concept was developed for removing objectionable materials from spacecraft wash water in order to make the water reusable. The breadboard model system described provides for pretreatment with ferric chloride to remove soap by chemical precipitation, carbon adsorption to remove trace dissolved organics, and ion exchange for removal of dissolved salts. The entire system was put into continuous operation and carefully monitored to assess overall efficiency and equipment maintenance problems that could be expected in actual use. In addition, the capacity of the carbon adsorbers and the ion-exchange resin was calculated and taken into consideration in the final evaluation of the system adequacy. The product water produced was well within the Tentative Wash Water Standards with regard to total organic carbon, conductivity, urea content, sodium chloride content, color, odor, and clarity.

  11. Efficacy of immunization with ferric citrate receptor FecA from Escherichia coli on induced coliform mastitis.

    PubMed

    Takemura, K; Hogan, J S; Lin, J; Smith, K L

    2002-04-01

    The effects of immunization with the ferric citrate receptor FecA on antibody responses and on experimentally induced mastitis following intramammary challenge were investigated. Twenty-one cows were assigned to seven blocks of three cows based on expected parturition. Cows within block were randomly assigned to one of three treatments: 1) FecA immunization, 2) Escherichia coli J5 immunization, and 3) unimmunized controls. Challenge was by infusion of approximately 60 cfu of E. coli 727 into one uninfected mammary gland between 13 and 31 d after parturition. Cows within block were challenged on the same day. Cows immunized with FecA had higher immunoglobulin (Ig)G titers against FecA in serum and in mammary secretions at calving, immediately before challenge, and 7 d after challenge than did cows immunized with E. coli J5 or control cows. Immunization with FecA also increased IgG titers against whole-cell E. coli 727 in serum and in mammary secretions at calving. Serum IgM titers against FecA were higher in FecA immunized cows than in other treatment groups immediately before challenge. Bacterial counts in milk, duration of bacterial isolation in milk, rectal temperature, and milk somatic cell counts following intramammary challenge were similar among treatments. Milk production and dry matter intake did not differ among treatments. The ferric citrate receptor FecA was immunogenic in cows, but immunization had minimal effect on the clinical severity of experimentally induced E. coli mastitis. PMID:12018422

  12. Physico-chemical properties of the new generation IV iron preparations ferumoxytol, iron isomaltoside 1000 and ferric carboxymaltose.

    PubMed

    Neiser, Susann; Rentsch, Daniel; Dippon, Urs; Kappler, Andreas; Weidler, Peter G; Göttlicher, Jörg; Steininger, Ralph; Wilhelm, Maria; Braitsch, Michaela; Funk, Felix; Philipp, Erik; Burckhardt, Susanna

    2015-08-01

    The advantage of the new generation IV iron preparations ferric carboxymaltose (FCM), ferumoxytol (FMX), and iron isomaltoside 1000 (IIM) is that they can be administered in relatively high doses in a short period of time. We investigated the physico-chemical properties of these preparations and compared them with those of the older preparations iron sucrose (IS), sodium ferric gluconate (SFG), and low molecular weight iron dextran (LMWID). Mössbauer spectroscopy, X-ray diffraction, and Fe K-edge X-ray absorption near edge structure spectroscopy indicated akaganeite structures (?-FeOOH) for the cores of FCM, IIM and IS, and a maghemite (?-Fe2O3) structure for that of FMX. Nuclear magnetic resonance studies confirmed the structure of the carbohydrate of FMX as a reduced, carboxymethylated, low molecular weight dextran, and that of IIM as a reduced Dextran 1000. Polarography yielded significantly different fingerprints of the investigated compounds. Reductive degradation kinetics of FMX was faster than that of FCM and IIM, which is in contrast to the high stability of FMX towards acid degradation. The labile iron content, i.e. the amount of iron that is only weakly bound in the polynuclear iron core, was assessed by a qualitative test that confirmed decreasing labile iron contents in the order SFG ? IS > LMWID ? FMX ? IIM ? FCM. The presented data are a step forward in the characterization of these non-biological complex drugs, which is a prerequisite to understand their cellular uptake mechanisms and the relationship between the structure and physiological safety as well as efficacy of these complexes. PMID:25801756

  13. Groundwater arsenic removal by coagulation using ferric(III) sulfate and polyferric sulfate: A comparative and mechanistic study.

    PubMed

    Cui, Jinli; Jing, Chuanyong; Che, Dongsheng; Zhang, Jianfeng; Duan, Shuxuan

    2015-06-01

    Elevated arsenic (As) in groundwater poses a great threat to human health. Coagulation using mono- and poly-Fe salts is becoming one of the most cost-effective processes for groundwater As removal. However, a limitation comes from insufficient understanding of the As removal mechanism from groundwater matrices in the coagulation process, which is critical for groundwater treatment and residual solid disposal. Here, we overcame this hurdle by utilizing microscopic techniques to explore molecular As surface complexes on the freshly formed Fe flocs and compared ferric(III) sulfate (FS) and polyferric sulfate (PFS) performance, and finally provided a practical solution in As-geogenic areas. FS and PFS exhibited a similar As removal efficiency in coagulation and coagulation/filtration in a two-bucket system using 5mg/L Ca(ClO)2. By using the two-bucket system combining coagulation and sand filtration, 500 L of As-safe water (<10 ?g/L) was achieved during five treatment cycles by washing the sand layer after each cycle. Fe k-edge X-ray absorption near-edge structure (XANES) and As k-edge extended X-ray absorption fine structure (EXAFS) analysis of the solid residue indicated that As formed a bidentate binuclear complex on ferrihydrite, with no observation of scorodite or poorly-crystalline ferric arsenate. Such a stable surface complex is beneficial for As immobilization in the solid residue, as confirmed by the achievement of much lower leachate As (0.9 ?g/L-0.487 mg/L) than the US EPA regulatory limit (5 mg/L). Finally, PFS is superior to FS because of its lower dose, much lower solid residue, and lower cost for As-safe drinking water. PMID:26040730

  14. Induction of hepatic and renal metallothionein synthesis by ferric nitrilotriacetate in mice: the role of MT as an antioxidant

    SciTech Connect

    Min, Kyong-Son . E-mail: min@nutr.kobegakuin.ac.jp; Morishita, Fumio; Tetsuchikawahara, Noriko; Onosaka, Satomi

    2005-04-01

    Metallothionein (MT) demonstrates strong antioxidant properties, yet the physiological relevance of its antioxidant action is not clear. Injection of mice with ferric nitrilotriacetate (Fe-NTA) caused a dose-dependent increase in hepatic and renal MT. Fe-NTA caused a greater increase in hepatic and renal MT concentration (2.5- and 4-fold) compared with FeCl{sub 3} at the same dose of ferric ion. MT mRNA levels were markedly elevated in both of tissues. Thiobarbituric acid (TBA) values in both tissues reached a maximum after 2-4 h. The MT concentrations were significantly increased after 2-4 h in liver and after 8-16 h in kidneys. Plasma concentrations of cytokines such as IL-6 and TNF{alpha} were elevated by 4 h; IL-6 levels were 24 times higher after Fe-NTA than that after injection of FeCl{sub 3}. Pretreatment of mice with ZnSO{sub 4} attenuated nephrotoxicity induced by Fe-NTA after 2 h, but was not effective 4 h after injection. After a Fe-NTA injection, a loss of Cd-binding properties of preinduced MT was observed only in kidneys of Zn-pretreated mice but not in liver. Treatment with BSO, glutathione (GSH) depletor, intensified a loss of its Cd-binding properties after a Fe-NTA injection. These results indicate that induction of MT synthesis may result from reactive oxygen species (ROS) generated by Fe-NTA, and MT may act in vivo as a complementary antioxidant.

  15. Identification of a positively charged platform in Staphylococcus aureus HtsA that is essential for ferric staphyloferrin A transport.

    PubMed

    Cooper, John D; Hannauer, Mélissa; Marolda, Cristina L; Briere, Lee-Ann K; Heinrichs, David E

    2014-08-12

    In response to iron starvation, Staphylococcus aureus secretes both staphyloferrin A and staphyloferrin B, which are high-affinity iron-chelating molecules. The structures of both HtsA and SirA, the ferric-staphyloferrin A [Fe(III)-SA] and ferric-staphyloferrin B [Fe(III)-SB] receptors, respectively, have recently been determined. The structure of HtsA identifies a novel form of ligand entrapment composed of many positively charged residues. Through ionic interactions, the binding pocket appears highly adapted for the binding of the highly anionic siderophore SA. However, biological validation of the importance of the nine SA-interacting residues (six arginines, one tyrosine, one histidine, and one lysine) has not been previously performed. Here, we mutated each of the Fe(III)-SA-interacting residues in HtsA and found that substitutions R104A, R126A, H209A, R306A, and R306K resulted in a reduction of binding affinity of HtsA for Fe(III)-SA. While mutation of almost all proposed ligand-interacting residues decreased the ability of S. aureus cells to transport (55)Fe(III)-SA, S. aureus expressing HtsA R104A, R126A, R306A, and R306K showed the greatest transport defects and were incapable of growth in iron-restricted growth media in a SA-dependent manner. These three residues cluster together and, relative to other residues in the binding pocket, move very little between the apo and closed holo structures. Their essentiality for receptor function, together with structural information, suggests that they form a positively charged platform that is required for initial contact with the terminal carboxyl groups of the two citrates in the Fe(III)-SA complex. This is a likely mechanism by which HtsA discerns iron-bound SA from iron-free SA. PMID:25050909

  16. Influence of oxidizing or reducing agents on gastrointestinal absorption of U, Pu, Am, Cm and Pm by rats.

    PubMed

    Sullivan, M F; Ruemmler, P S; Ryan, J L; Buschbom, R L

    1986-02-01

    Absorption of 233U, 238Pu, 241Am, and 244Cm from the gastrointestinal (GI) tract was measured in rats, fed ad libitum or fasted, that were gavaged with solutions containing ferric iron, ferrous iron, iron powder, quinhydrone or ascorbic acid. Absorption and retention of all of these actinides was increased substantially by fasting and by the addition of mild oxidizing agents, ferric iron and quinhydrone. In contrast, absorption and retention were decreased to below the fasted level by all the reducing agents except ascorbic acid, which caused diarrhea and an increase in absorption. Absorption of the lanthanide element 147Pm from the intestine of fasted rats was also increased by ferric iron. Some of these actinide elements are polyvalent and are, in some cases, known to be absorbed from the GI tract more readily in their higher oxidation states. This suggested an oxidation-reduction mechanism for the effect of fasting and the action of the chemical agents used. However, the improbability that either 241Am(III) 244Cm(III) or 147Pm is converted to a different oxidation state under these conditions makes that mechanism unlikely. Other explanations are suggested. PMID:3005196

  17. Remote sensing of ferric iron minerals as guides for gold exploration

    NASA Technical Reports Server (NTRS)

    Taranik, Dan L.; Kruse, Fred A.; Goetz, Alexander F. H.; Atkinson, William W.

    1991-01-01

    The relationship between the surficial iron mineralogy and economic mineralization is investigated, using data from an airborne imaging spectrometer (the 63-channel Geophysical and Environmental Research Imaging Spectrometer) to map the distribution of iron minerals in the Cripple Creek mining district in Colorado. The airborne image data were coregistered with the field map data for the distribution of iron oxides in the district, in a geographic information computer system, in order to compare their information content. It is shown that the remote imagery was able to uniquely identify the mineral hematite, a mixture of goethite/jarosite, and a mixture of hematite/goethite.

  18. Carbon monoxide-driven reduction of ferric heme and heme proteins.

    PubMed

    Bickar, D; Bonaventura, C; Bonaventura, J

    1984-09-10

    Oxidized cytochrome c oxidase in a carbon monoxide atmosphere slowly becomes reduced as shown by changes in its visible spectra and its reactivity toward oxygen. The "auto-reduction" of cytochrome c oxidase by this procedure has been used to prepare mixed valence hybrids. We have found that this process is a general phenomenon for oxygen-binding heme proteins, and even for isolated hemin in basic aqueous solution. This reductive reaction may have physiological significance. It also explains why oxygen-binding heme proteins become oxidized much more slowly and appear to be more stable when they are kept under a CO atmosphere. Oxidized alpha and beta chains of human hemoglobin become reduced under CO much more slowly than does cytochrome c oxidase, where the CO-binding heme is coupled with another electron accepting metal center. By observing the reaction in both the forward and reverse direction, we have concluded that the heme is reduced by an equivalent of the water-gas shift reaction (CO + H2O----CO2 + 2e- + 2H+). The reaction does not require molecular oxygen. However, when the CO-driven reduction of cytochrome c oxidase occurs in the presence of oxygen, there is a competition between CO and oxygen for the reduced heme and copper of cytochrome alpha 3. Under certain conditions when both CO and oxygen are present, a peroxide adduct derived from oxygen reduction can be observed. This "607 nm complex," described in 1981 by Nicholls and Chanady (Nicholls, P., and Chanady, G. (1981) Biochim. Biophys. Acta 634, 256-265), forms and decays with kinetics in accord with the rate constants for CO dissociation, oxygen association and reduction, and dissociation of the peroxide adduct. In the absence of oxygen, if a mixture of cytochrome c and cytochrome c oxidase is incubated under a CO atmosphere, auto-reduction of the cytochrome c as well as of the cytochrome c oxidase occurs. By our proposed mechanism this involves a redistribution of electrons from cytochrome alpha 3 to cytochrome alpha and cytochrome c. PMID:6088517

  19. Copper Oxide Nanoparticles Induce Oxidative Stress and Cytotoxicity in Airway Epithelial Cells

    PubMed Central

    Fahmy, Baher; Cormier, Stephania A.

    2009-01-01

    Metal oxide nanoparticles are often used as industrial catalysts and elevated levels of these particles have been clearly demonstrated at sites surrounding factories. To date, limited toxicity data on metal oxide nanoparticles are available. To understand the impact of these airborne pollutants on the respiratory system, airway epithelial (HEp-2) cells were exposed to increasing doses of silicon oxide (SiO2), ferric oxide (Fe2O3) and copper oxide (CuO) nanoparticles, the leading metal oxides found in ambient air surrounding factories. CuO induced the greatest amount of cytotoxicity in a dose dependent manner; while even high doses (400 µg/cm2) of SiO2 and Fe2O3 were non-toxic to HEp-2 cells. Although all metal oxide nanoparticles were able to generate ROS in HEp-2 cells, CuO was better able to overwhelm antioxidant defenses (e.g. catalase and glutathione reductase). A significant increase in the level of 8-isoprostanes and in the ratio of GSSG to total glutathione in cells exposed to CuO suggested that ROS generated by CuO induced oxidative stress in HEp-2 cells. Co-treatment of cells with CuO and the antioxidant resveratrol increased cell viability suggesting that oxidative stress may be the cause of the cytotoxic effect of CuO. These studies demonstrated that there is a high degree of variability in the cytotoxic effects of metal oxides, that this variability is not due to the solubility of the transition metal, and that this variability appears to involve sustained oxidative stress possibly due to redox cycling. PMID:19699289

  20. Design Insights for Tuning the Electrocatalytic Activity of Perovskite Oxides for the Oxygen Evolution Reaction

    SciTech Connect

    Malkhandi, S; Trinh, P; Manohar, AK; Manivannan, A; Balasubramanian, M; Prakash, GKS; Narayanan, SR

    2015-04-16

    Rechargeable metal-air batteries and water electrolyzers based on aqueous alkaline electrolytes hold the potential to be sustainable solutions to address the challenge of storing large amounts of electrical energy generated from solar and wind resources. For these batteries and electrolyzers to be economically viable, it is essential to have efficient, durable, and inexpensive electrocatalysts for the oxygen evolution reaction. In this article, we describe new insights for predicting and tuning the activity of inexpensive transition metal oxides for designing efficient and inexpensive electrocatalysts. We have focused on understanding the factors determining the electrocatalytic activity for oxygen evolution in a strong alkaline medium. To this end, we have conducted a systematic investigation of nanophase calcium-doped lanthanum cobalt manganese oxide, an example of a mixed metal oxide that can be tuned for its electrocatalytic activity by varying the transition metal composition. Using X-ray absorption spectroscopy (XANES), X-ray photoelectron spectroscopy (XPS), electrochemical polarization experiments, and analysis of mechanisms, we have identified the key determinants of electrocatalytic activity. We have found that the Tafel slopes are determined by the oxidation states and the bond energy of the surface intermediates of Mn-OH and Co-OH bonds while the catalytic activity increased with the average d-electron occupancy of the sigma* orbital of the M-OH bond. We anticipate that such understanding will be very useful in predicting the behavior of other transition metal oxide catalysts.

  1. Rapid oxidation and immobilization of arsenic by contact glow discharge plasma in acidic solution.

    PubMed

    Jiang, Bo; Hu, Ping; Zheng, Xing; Zheng, Jingtang; Tan, Minghui; Wu, Mingbo; Xue, Qinzhong

    2015-04-01

    Arsenic is a priority pollutant in aquatic ecosystem and therefore the remediation of arsenic-bearing wastewater is an important environmental issue. This study unprecedentedly reported simultaneous oxidation of As(III) and immobilization of arsenic can be achieved using contact glow discharge process (CGDP). CGDP with thinner anodic wire and higher energy input were beneficial for higher As(V) production efficiency. Adding Fe(II) in CGDP system significantly enhanced the oxidation rate of As(III) due to the generations of additional OH and Fe(IV) species, accompanied with which arsenic can be simultaneously immobilized in one process. Arsenic immobilization can be favorably obtained at solution pH in the range of 4.0-6.0 and Fe(II) concentration from 250 to 1000 ?M. The presence of organics (i.e., oxalic acid, ethanol and phenol) retarded the arsenic immobilization by scavenging OH or complexing Fe(III) in aqueous solution. On the basis of these results, a mechanism was proposed that the formed ionic As(V) rapidly coprecipitated with Fe(III) ions or was adsorbed on the ferric oxyhydroxides with the formation of amorphous ferric arsenate-bearing ferric oxyhydroxides. This CGDP-Fenton system was of great interest for engineered systems concerned with the remediation of arsenic containing wastewater. PMID:25600320

  2. Literature review for oxalate oxidation processes and plutonium oxalate solubility

    SciTech Connect

    Nash, C. A.

    2015-10-01

    A literature review of oxalate oxidation processes finds that manganese(II)-catalyzed nitric acid oxidation of oxalate in precipitate filtrate is a viable and well-documented process. The process has been operated on the large scale at Savannah River in the past, including oxidation of 20 tons of oxalic acid in F-Canyon. Research data under a variety of conditions show the process to be robust. This process is recommended for oxalate destruction in H-Canyon in the upcoming program to produce feed for the MOX facility. Prevention of plutonium oxalate precipitation in filtrate can be achieved by concentrated nitric acid/ferric nitrate sequestration of oxalate. Organic complexants do not appear practical to sequester plutonium. Testing is proposed to confirm the literature and calculation findings of this review at projected operating conditions for the upcoming campaign.

  3. Lipid extraction from microalgae cell using persulfate-based oxidation.

    PubMed

    Seo, Yeong Hwan; Sung, Mina; Oh, You-Kwan; Han, Jong-In

    2016-01-01

    In this study, persulfate, a solid-type oxidant, was adopted as a substitute for hydrogen peroxide in extracting lipid from microalgae biomass. Microalgae cells were concentrated at pH 3 and with 200mg/L of ferric chloride, conditions which can activate oxidants such as hydrogen peroxide and persulfate. At a persulfate concentration of 2mM and a reaction temperature of 90°C, exceedingly high extraction efficiency over 95% was obtained, which was higher than with 0.5% hydrogen peroxide at the same temperature. This result showed that persulfate is sufficiently powerful and incomparably cheap enough to replace the potent yet expensive oxidant. It appears that combining iron-based coagulation and persulfate-based lipid extraction is indeed a competitive approach that can possibly lighten the process burden for the microalgae-derived biodiesel production. PMID:26614226

  4. Complex Effects of Alumina/Silica on Ferric/Ferrous Iron in Earth's Lower Mantle

    NASA Astrophysics Data System (ADS)

    Dorfman, S. M.; Potapkin, V.; Kupenko, I.; Chumakov, A. I.; Nabiei, F.; Magrez, A.; Dubrovinsky, L. S.; McCammon, C. A.; Gillet, P.

    2014-12-01

    The electronic states of Fe in silicates are key to the chemistry, physical properties and dynamics of Earth's mantle. In the lower mantle's dominant phase, perovskite-structured (Mg,Fe)SiO3, recently named bridgmanite, and its deep lower mantle polymorph, post-perovskite, Fe can occupy either cation site and multiple valence and spin states. In addition, studies of Fe2+-bearing starting materials at lower mantle conditions have observed oxidation to Fe3+ in the synthesized silicate, either by a disproportionation, Fe2+ = Fe3+ + Fe metal, or possibly reduction of the high-pressure cell. The incorporation of Al in lower mantle silicates has been observed to promote higher Fe3+/?Fe. Due to this complexity, electronic states of Fe in lower mantle silicates are controversial. We used energy-domain synchrotron Mössbauer spectroscopy at ESRF beamline ID18 to examine spin and valence states of bridgmanite and post-perovskite synthesized from Fe2+-rich compositions with and without Al. 57Fe-enriched starting materials (Mg0.5Fe0.5)SiO3 pyroxene and Fe2.8Al2.2Si3.0O12 almandine-composition glass were pressurized in an NaCl medium in the laser-heated diamond anvil cell to up to 170 GPa. Bridgmanite was synthesized at 75-99 GPa and 2000-2500 K. Post-perovskite was synthesized at 149-160 GPa and 2500-3000 K. The observed quadrupole splitting (QS) and center shift (CS) are consistent with dominant Fe2+ for all compositions and do not show higher Fe3+/?Fe with higher Al-content. The dominant doublet at lower mantle pressures exhibits QS=3.6-4.2 mm/s and CS=0.9-1.1 mm/s, similar to previous observations of high or intermediate spin Fe2+. A second high-spin Fe2+ doublet is observed at QS=2.2-3.3 mm/s and CS=0.8-1.2 mm/s. A minor high-spin Fe3+ doublet is fit to QS~1.2 mm/s and CS=0.3-0.5 mm/s. For the Al-bearing bridgmanite, ambient spectra before and after synthesis contain no more than ~10% Fe3+/?Fe, indicating no disproportionation or oxidation of Fe2+. In contrast, previous studies of Al-bearing bridgmanite observed ~50% Fe3+/?Fe. This difference may reflect the high Si-content of the starting material and balance of Al between the Si-site and Mg-site. The effects of Al on oxidation potential of Fe in bridgmanite and the lower mantle oxygen fugacity must also be assessed as a function of Si-content and Si/Al ratio.

  5. Modeling the Nanophase Structural Dynamics of Phenylated Sulfonated Poly Ether Ether Ketone Ketone (Ph-SPEEKK) Membranes as a Function of Hydration

    SciTech Connect

    Lins, Roberto D.; Devanathan, Ramaswami; Dupuis, Michel

    2011-03-03

    Solvated phenylated sulfonated poly ether ether ketone ketone (Ph-SPEEKK) membranes in the presence of hydronium ions were modeled by classical molecular dynamics simulations. The characterization of the nanophase structure and dynamics of such membranes was carried out as a function of the water content lambda, where lambda is the number of water molecules per sulfonate group, for lambda values of 3.5, 6, 11, 25, and 40. Analysis of pair correlation functions supports the experimental observation of membrane swelling upon hydration as well the increase in water and hydronium ion diffusion with increasing lambda. While the average number of hydrogen bonds between hydronium ions and sulfonate groups is dramatically affected by the hydration level, the average lifetime of the hydrogen bonds remains essentially constant. The membrane is found to be relatively rigid and its overall flexibility shows little dependence on water content. Compared to Nafion, water and ion diffusion coefficients are considerably smaller at lower hydration levels and room temperature. However, at higher lambda values of 25 and 40 these coefficients are comparable to those in Nafion at a lambda value of 16. This study also shows that water diffusion in Ph-SPEEKK membranes at low hydration levels can be significantly improved by raising the temperature with important implications for proton conductivity.

  6. Simultaneous photoreduction and microbial oxidation of iron in a stream in the New Jersey Pinelands

    SciTech Connect

    Not Available

    1986-07-01

    Photoreduction of ferric to ferrous iron was determined in water held in bottles placed in a New Jersey Pinelands stream, although concentrations of ferrous iron in the stream itself remained below detection (15 ng ml/sup -1/). The low ambient levels of ferrous iron apparently resulted from the action of iron-oxidizing microorganisms in water and soil, as shown by a temperature optimum for, and by the inhibitory effect of sterilization upon, the disappearance of ferrous iron. Measurements of /sup 14/CO/sub 2/ incorporation into soil organic matter indicated that the iron-oxidizing microorganisms were not chemolithoautotrophs, but might have been iron-depositing bacteria or chemolithoheterotrophs.

  7. Sampling the oxidative weathering products and the potentially acidic permafrost on Mars

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.

    1988-01-01

    Large areas of Mars' surface are covered by oxidative weathering products containing ferric and sulfate ions having analogies to terrestrial gossans derived from sulfide mineralization associated with iron-rich basalts. Chemical weathering of such massive and disseminated pyrrhotite-pentlandite assemblages and host basaltic rocks in the Martian environment could have produced metastable gossaniferous phases (limonite containing poorly crystalline hydrated ferric sulfates and oxyhydroxides, clay silicates and opal). Underlying groundwater, now permafrost on Mars, may still be acidic due to incomplete buffering reactions by wall-rock alteration of unfractured host rock. Such acidic solutions stabilize temperature-sensitive complex ions and sols which flocculate to colloidal precipitates at elevated temperatures. Sampling procedures of Martian regolith will need to be designed bearing in mind that the frozen permafrost may be corrosive and be stabilizing unique complex ions and sols of Fe, Al, Mg, Ni and other minor elements.

  8. Occurrence and regulation of the ferric citrate transport system in Escherichia coli B, Klebsiella pneumoniae, Enterobacter aerogenes, and Photorhabdus luminescens.

    PubMed

    Mahren, Susanne; Schnell, Heidrun; Braun, Volkmar

    2005-11-01

    In Escherichia coli K-12, transcription of the ferric citrate transport genes fecABCDE is initiated by binding of diferric dicitrate to the outer membrane protein FecA which elicits a signaling cascade from the cell surface to the cytoplasm. The FecI sigma factor is only active in the presence of FecR, which transfers the signal across the cytoplasmic membrane. In other bacteria, fecIRA homologues control iron transport gene transcription by siderophores other than citrate. However, in most cases, the FecI homologues are active in the absence of the FecR homologues, which might function as anti-sigma factors. Since not all E. coli strains contain a fec system, we determined the occurrence of fec genes in selected Enterobacteriaceae and the dependence of FecI activity on FecR. Incomplete FecIRA systems were chromosomally encoded in Enterobacter aerogenes strains and plasmid-encoded in K. pneumoniae. E. coli B, Photorhabdus luminescens and one of three Klebsiella pneumoniae strains had a functional FecIRA regulatory system as in E. coli K-12. The cytoplasmic N-terminal FecR fragments caused constitutive FecI activity in the absence of ferric citrate. The PCR-generated mutant FecI(D40G) was inactive and FecI(S15P) was partially active. FecR of E. coli K-12 activated FecI of all tested strains except FecI encoded on the virulence plasmid pLVPK of K. pneumoniae, which differed from E. coli K-12 FecI by having mutations in region 4, which is important for interaction with FecR. The C-terminally truncated FecR homologue of pLVPK was inactive. pLVPK-encoded FecA contains a 38-residue sequence in front of the signal sequence that did not prevent processing and proper integration of FecA into the outer membrane of E. coli and lacks the signaling sequence required for transcription initiation of the fec transport genes, making it induction-incompetent but transport-competent. The evidence indicates that fecIRABCDE genes are acquired by horizontal DNA transfer and can undergo debilitating mutations. PMID:16193283

  9. Spectral Behavior of Hematite at Visible/Near Infrared and Midinfrared Wavelengths

    NASA Technical Reports Server (NTRS)

    Lane, Melissa D.; Christensen, Philip R.

    1999-01-01

    The oxide mineral hematite alpha-Fe2O3) is present on Mars as evidenced by spectroscopy using visible/near infrared (VNIR) and midinfrared (MIR) wavelengths. The physical nature of this surficial hematite varies from fine-grained, crystalline red hematite (red-Hm) in certain martian bright regions, to coarser-grained, crystalline gray hematite (gray-Hm) in the Sinus Meridiani equatorial site discovered in the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) data. The VNIR spectra require that the red hematite is present in amounts subordinate to a second ferric pigment, which accounts for the general shape and position of the martian ferric absorption edge. By analogy with palagonitic tephra and synthetic samples, the pigment is a nanophase ferric oxide, possibly nanophase hematite (np-Hm). The purpose of this abstract is to document the physicospectral properties of hematite in the VNIR (0.35 to 2.2 microns) and MIR (5 to 25 microns) with respect to the terms "nanophase" and "crystalline", "red" and "gray", and "fine-grained" and "coarse-grained". We will show that different "types" of hematite (no-, red-, and gray-Hm) have different spectral responses in the VNIR and MIR regions and that these differences are important for inferring the types of hematite and their relative proportions from remotely sensed spectra of Mars. Because hematite is an alteration product that forms through many different geologic processes, determination of the type of hematite provides important clues about the style and diversity of martian weathering processes.

  10. Spectral Behavior of Hematite at Visible/Near Infrared and Midinfrared Wavelengths

    NASA Technical Reports Server (NTRS)

    Lane, M. D.; Morris, R. V.; Christensen, P. R.

    1999-01-01

    The oxide mineral hematite alpha-Fe2O3) is present on Mars as evidenced by spectroscopy using visible/near infrared (VNIR) and midinfrared (MIR) wavelengths. The physical nature of this surficial hematite varies from fine-grained, crystalline red hematite (red-Hm) in certain martian bright regions, to coarser-grained, crystalline gray hematite (gray-Hm) in the Sinus Meridiani equatorial site discovered in the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) data. The VNIR spectra require that the red hematite is present in amounts subordinate to a second ferric pigment, which accounts for the general shape and position of the martian ferric absorption edge. By analogy with palagonitic tephra and synthetic samples, the pigment is a nanophase ferric oxide, possibly nanophase hematite (np-Hm). The purpose of this abstract is to document the physicospectral properties of hematite in the VNIR (0.35 to 2.2 mm) and MIR (5 to 25 mm) with respect to the terms "nanophase" and "crystalline", "red" and "gray", and "fine-grained" and "coarse-grained". We will show that different "types" of hematite (np-, red-, and gray-Hm) have different spectral responses in the VNIR and MIR regions and that these differences are important for inferring the types of hematite and their relative proportions from remotely sensed spectra of Mars. Because hematite is an alteration product that forms through many different geologic processes, determination of the type of hematite provides important clues about the style and diversity of martian weathering processes. Additional information is contained in the original extended abstract.

  11. The ferric uptake regulator of Helicobacter pylori: a critical player in the battle for iron and colonization of the stomach

    PubMed Central

    Pich, Oscar Q; Merrell, D Scott

    2013-01-01

    Helicobacter pylori is arguably one of the most successful pathogens; it colonizes the stomachs of more than half of the human population. Colonization and persistence in such an inhospitable niche requires the presence of exquisite adaptive mechanisms. One of the proteins that contributes significantly to the remarkable adaptability of H. pylori is the ferric uptake regulator (Fur), which functions as a master regulator of gene expression. In addition to genes directly related to iron homeostasis, Fur controls expression of several enzymes that play a central role in metabolism and energy production. The absence of Fur leads to severe H. pylori colonization defects and, accordingly, several Fur-regulated genes have been shown to be essential for colonization. Moreover, proteins encoded by Fur-regulated genes have a strong impact on redox homeostasis in the stomach and are major determinants of inflammation. In this review, we discuss the main roles of Fur in the biology of H. pylori and highlight the importance of this regulatory protein in the infectious process. PMID:23701330

  12. Growth responses of Escherichia coli to immunoglobulin G from cows immunized with ferric citrate receptor, FecA.

    PubMed

    Takemura, K; Hogan, J S; Smith, K L

    2004-02-01

    Effects of purified immunoglobulin (Ig) G from cows immunized with ferric citrate receptor, FecA, on the in vitro growth of Escherichia coli were investigated. Twenty-one cows were assigned to one of 3 treatments: 1) FecA immunization, 2) E. coli J5 bacterin immunization, and 3) unimmunized control. FecA was derived from E. coli UT5600/pSV66. Immunoglobulin G was purified from pooled colostral whey for each treatment group. The IgG from FecA immunized cows had higher titers against FecA compared with other treatment groups. Bacterial isolates tested were 14 E. coli from intramammary infections and E. coli UT5600/pSV66. Iron depletion decreased the growth of E. coli compared with growth in Fe-replete medium. The presence of IgG further decreased the growth compared with the growth under iron restriction alone. Bacterial growth did not differ among IgG sources nor between IgG concentrations. Replenishing media with exogenous iron overrode the inhibitory effects of the Fe-depletion and IgG. Vaccinating cows with FecA had little effect on the growth inhibitory properties of IgG toward E. coli mastitis isolates cultured in Fe-deplete media. PMID:14762074

  13. Non-Transferrin-Bound Iron (NTBI) Uptake by T Lymphocytes: Evidence for the Selective Acquisition of Oligomeric Ferric Citrate Species

    PubMed Central

    Arezes, Joao; Costa, Monica; Vieira, Ines; Dias, Vera; Kong, Xiao L.; Fernandes, Rui; Vos, Matthijn; Carlsson, Anna; Rikers, Yuri; Porto, Graça; Rangel, Maria; Hider, Robert C.; Pinto, Jorge P.

    2013-01-01

    Iron is an essential nutrient in several biological processes such as oxygen transport, DNA replication and erythropoiesis. Plasma iron normally circulates bound to transferrin. In iron overload disorders, however, iron concentrations exceed transferrin binding capacity and iron appears complexed with low molecular weight molecules, known as non-transferrin-bound iron (NTBI). NTBI is responsible for the toxicity associated with iron-overload pathologies but the mechanisms leading to NTBI uptake are not fully understood. Here we show for the first time that T lymphocytes are able to take up and accumulate NTBI in a manner that resembles that of hepatocytes. Moreover, we show that both hepatocytes and T lymphocytes take up the oligomeric Fe3Cit3 preferentially to other iron-citrate species, suggesting the existence of a selective NTBI carrier. These results provide a tool for the identification of the still elusive ferric-citrate cellular carrier and may also open a new pathway towards the design of more efficient iron chelators for the treatment of iron overload disorders. PMID:24278199

  14. Shock Experiments on Basalt - Ferric Sulfate Mixes at 21 GPa & 49 GPa and their Relevance to Martian Meteorite Impact Glasses

    NASA Technical Reports Server (NTRS)

    Rao, M. N.; Ross, D. K.; See, T. H.; Nyquist, L. E.; Sutton, S.; Asimow, P.

    2013-01-01

    Large abundance of Martian atmospheric gases and neutron-induced isotopic excesses as well as Rb-Sr isotopic variations determined in some impact glasses in basaltic shergottites (e.g., Shergotty #DBS, Zagami #H1 and EET79001 #27, #8 and #104) provide definitive evidence for the occurrence of a Martian regolith component in their constituent mineral assemblages. Some of these glass-es, known as gas-rich impact-melts (GRIM), contain numerous micron-sized iron sulfide blebs along with minor amounts of iron sulfate particulates. As these GRIM glasses contain a Martian regolith component and as iron sulfates (but not sulfides) are found to occur abundantly on the Mars surface, we suggested that the sulfide blebs in GRIMs were likely generated by shock-reduction of the parental iron sulfate bearing regolith material that had been incorporated into the cavities/crevices of basaltic host rock prior to the impact event on Mars. To test whether the sulfates could be reduced to sulfides by impact shock, we carried out laboratory shock experiments on a basalt plus ferric sulfate mixture at 49 GPa at the Caltech Shock Wave Laboratory and at 21 GPa at Johnson Space Center (JSC) Experimental Impact Laboratory. The experimental details and the preliminary results for the Caltech 49 GPa experiment were presented at LPSC last year. Here, we report the results for the 21 GPa experiment at JSC and compare these results to obtain further insight into the mechanism of the bleb formation in the GRIM glasses.

  15. The ferric uptake regulator of Helicobacter pylori: a critical player in the battle for iron and colonization of the stomach.

    PubMed

    Pich, Oscar Q; Merrell, D Scott

    2013-06-01

    Helicobacter pylori is arguably one of the most successful pathogens; it colonizes the stomachs of more than half of the human population. Colonization and persistence in such an inhospitable niche requires the presence of exquisite adaptive mechanisms. One of the proteins that contributes significantly to the remarkable adaptability of H. pylori is the ferric uptake regulator (Fur), which functions as a master regulator of gene expression. In addition to genes directly related to iron homeostasis, Fur controls expression of several enzymes that play a central role in metabolism and energy production. The absence of Fur leads to severe H. pylori colonization defects and, accordingly, several Fur-regulated genes have been shown to be essential for colonization. Moreover, proteins encoded by Fur-regulated genes have a strong impact on redox homeostasis in the stomach and are major determinants of inflammation. In this review, we discuss the main roles of Fur in the biology of H. pylori and highlight the importance of this regulatory protein in the infectious process. PMID:23701330

  16. Floc properties of polyaluminum ferric chloride in water treatment: The effect of Al/Fe molar ratio and basicity.

    PubMed

    Cao, Baichuan; Gao, Baoyu; Wang, Mengmeng; Sun, Xiaomei; Wang, Jin

    2015-11-15

    Producing flocs with desired properties is significant for contaminants removal in water treatment works. In this study, an inorganic composite coagulant, polyaluminum ferric chloride (PAFC), was prepared and used in surface water treatment, and the influence of Al/Fe molar ratio and basicity (B) on floc properties was investigated. The contribution of metal species analysis showed a competition relationship between Al and Fe in the pre-hydrolysis, while the monomeric contents decreased with the increase of B value. The investigation of floc properties was conducted on a laser scattering instrument, in terms of floc size, strength, recovery capacity and fractal dimension (Df). The largest floc size and the highest growth rate was achieved when Al/Fe=7:1 and B=1.5. Floc formed at the Al/Fe ratios of 5:1 and 7:1 were considered to be more compact. Meanwhile, the Df value increased when B value was increased. At Al/Fe=7:1 and B=1.5, strongest flocs were obtained. During the breakage period, the Df value increased. As lower shear was replaced, the floc size decreased continuously, with a further increase of Df value. However, after breakage at higher shear, all of the PAFC flocs showed capacity for regrowth and loose structures were formed. PMID:26232731

  17. Expression profiling of the Arabidopsis ferric chelate reductase (FRO) gene family reveals differential regulation by iron and copper.

    PubMed

    Mukherjee, Indrani; Campbell, Nathan H; Ash, Joshua S; Connolly, Erin L

    2006-05-01

    The Arabidopsis FRO2 gene encodes the iron deficiency-inducible ferric chelate reductase responsible for reduction of iron at the root surface; subsequent transport of iron across the plasma membrane is carried out by a ferrous iron transporter (IRT1). Genome annotation has identified seven additional FRO family members in the Arabidopsis genome. We used real-time RT-PCR to examine the expression of each FRO gene in different tissues and in response to iron and copper limitation. FRO2 and FRO5 are primarily expressed in roots while FRO8 is primarily expressed in shoots. FRO6 and FRO7 show high expression in all the green parts of the plant. FRO3 is expressed at high levels in roots and shoots, and expression of FRO3 is elevated in roots and shoots of iron-deficient plants. Interestingly, when plants are Cu-limited, the expression of FRO6 in shoot tissues is reduced. Expression of FRO3 is induced in roots and shoots by Cu-limitation. While it is known that FRO2 is expressed at high levels in the outer layers of iron-deficient roots, histochemical staining of FRO3-GUS plants revealed that FRO3 is predominantly expressed in the vascular cylinder of roots. Together our results suggest that FRO family members function in metal ion homeostasis in a variety of locations in the plant. PMID:16362328

  18. The crystal structures of the ferric and ferrous forms of the heme complex of HmuO, a heme oxygenase of Corynebacterium diphtheriae.

    PubMed

    Hirotsu, Shoko; Chu, Grace C; Unno, Masaki; Lee, Dong-Sun; Yoshida, Tadashi; Park, Sam-Yong; Shiro, Yoshitsugu; Ikeda-Saito, Masao

    2004-03-19

    Crystal structures of the ferric and ferrous heme complexes of HmuO, a 24-kDa heme oxygenase of Corynebacterium diphtheriae, have been refined to 1.4 and 1.5 A resolution, respectively. The HmuO structures show that the heme group is closely sandwiched between the proximal and distal helices. The imidazole group of His-20 is the proximal heme ligand, which closely eclipses the beta- and delta-meso axis of the porphyrin ring. A long range hydrogen bonding network is present, connecting the iron-bound water ligand to the solvent water molecule. This enables proton transfer from the solvent to the catalytic site, where the oxygen activation occurs. In comparison to the ferric complex, the proximal and distal helices move closer to the heme plane in the ferrous complex. Together with the kinked distal helix, this movement leaves only the alpha-meso carbon atom accessible to the iron-bound dioxygen. The heme pocket architecture is responsible for stabilization of the ferric hydroperoxo-active intermediate by preventing premature heterolytic O-O bond cleavage. This allows the enzyme to oxygenate selectively at the alpha-meso carbon in HmuO catalysis. PMID:14645223

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

    SciTech Connect

    Stengl, Vaclav; Houskova, Vendula; Bakardjieva, Snejana; Murafa, Nataliya; Marikova, Monika; Oplustil, Frantisek; Nemec, Tomas

    2010-11-15

    Zirconium doped nano dispersive oxides of Fe, Al and Zn were prepared by a homogeneous hydrolysis of the respective sulfate salts with urea in aqueous solutions. Synthesized metal oxide hydroxides were characterized using Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX). These oxides were taken for an experimental evaluation of their reactivity with sulfur mustard (HD or bis(2-chloroethyl)sulfide), soman (GD or (3,3'-Dimethylbutan-2-yl)-methylphosphonofluoridate) and VX agent (S-[2-(diisopropylamino)ethyl]-O-ethyl-methylphosphonothionate). The presence of Zr{sup 4+} dopant can increase both the surface area and the surface hydroxylation of the resulting doped oxides, decreases their crystallites' sizes thereby it may contribute in enabling the substrate adsorption at the oxide surface thus it can accelerate the rate of degradation of warfare agents. Addition of Zr{sup 4+} converts the product of the reaction of ferric sulphate with urea from ferrihydrite to goethite. We found out that doped oxo-hydroxides Zr-FeO(OH) - being prepared by a homogeneous hydrolysis of ferric and zirconium oxo-sulfates mixture in aqueous solutions - exhibit a comparatively higher degradation activity towards chemical warfare agents (CWAs). Degradation of soman or VX agent on Zr-doped FeO(OH) containing ca. 8.3 wt.% of zirconium proceeded to completion within 30 min.

  20. Ferric Iron Concentrations in Silicate Glasses: a Mössbauer and XAS Study

    NASA Astrophysics Data System (ADS)

    Dyar, M. D.; McCanta, M. C.

    2014-12-01

    Fe2+/Fe3+ ratios of volcanic materials on a planet reflect oxidation of the magma source region and the additional effects of magma interaction with the near surface environment. Synchrotron X-ray absorption spectroscopy (XAS) enables measurement of Fe2+/Fe3+ ratios in situ at micro-scales on standard thin sections. Because melt composition and structure affect Fe3+/?Fe, XAS measurements of unknowns require calibration standards with like compositions. To address this need, a suite of 33 synthetic glass standards covering a wide range of geologically-relevant compositions was generated under four varying fO2conditions. Runs were conducted in a 1-atm gas mixing furnace using the Pt (fO2 ? QFM) or Re (fO2 < QFM) wire-loop technique. Air, MH (CO2), QFM, and IW were used to equilibrate each composition, with fO2 values fixed by gas mixing or use of a solid buffer. Samples were then prepared for Mössbauer and XAS analyses, with Fe2+/Fe3+values from the former used to calibrate the latter using a multivariate model. XAS data were acquired both at NSLS beamline x26a and at the GSECARS beamline (13-ID) at APS. Over the compositional range from andesite (7.1-11.8 wt.% FeO and 53.6-55.9 wt. SiO2) to basaltic andesite (4.6-7.9 wt.% FeO and 58.8-62.4 wt. SiO2) to basalt (6.8-11.0 wt.% FeO and 47.9-50.7 wt. SiO2), Fe3+ contents of glasses equilibrated at each buffer are comparable, as expected. Those samples equilibrated in air are ~89±2% Fe3+, in CO2, ~77±3 Fe3+, and in QFM and IW, ~11±4% Fe3+. Predictive models (e.g., Kilinc et al., 1983) suggest that the increased SiO2 concentrations in dacites and rhyolites result in increased Fe3+ at higher fO2s (Figure 1). Our data support this prediction; e.g., dacites with 67.1-71.6 wt.% SiO2 at IW are 20±10%Fe3+. Once synthesized and characterized, these equilibrated glasses will form the basis for multivariate analysis of XAS spectra that will provide a broad calibration for measuring Fe3+ in silicate glasses at any synchrotron facility.

  1. Observational evidence of crystalline iron oxides on Mars

    SciTech Connect

    Bell, J.F. III; McCord, T.B.; Owensby, P.D. )

    1990-08-30

    Visible to near-IR (0.4-1.0 {mu}m) spectral reflectance observations of Mars during the 1988 opposition were performed at Mauna Kea Observatory using a circular variable filter spectrometer at a spectral resolution R = {lambda}/{Delta}{lambda} {approx} 80. On August 13 and 14 1988, UT, 41 regions 500-600 km in diameter were observed on Mars. The data have been reduced both to reflectance relative to solar analog (Mars/16 Cyg B) and to relative reflectance (spot/spot). The spectra show the strong near-UV reflectance dropoff characteristic of Mars as well as absorptions at 0.62-0.72 {mu}m and 0.81-0.94 {mu}m both seen here clearly for the first time. These absorption features are interpreted as Fe{sup 3+} electronic transition bands that indicate the presence of crystalline ferric oxide or hydroxide minerals on the Martian surface. Comparison of these data with laboratory spectra obtained by other workers supports the conclusion that a single iron oxide phase, most likely hematite, could account for all of the observed spectral behavior of the Martian surface soils and airborne dust in the 0.4-1.0 {mu}m region. This possibility must be reconciled with data from other possible spectral analogs and other wavelength regions as well as geochemical and mineral stability considerations to arrive at a more complete understanding of the role of ferric minerals in Martian surface mineralogy and weathering.

  2. Sites of interaction between the FecA and FecR signal transduction proteins of ferric citrate transport in Escherichia coli K-12.

    PubMed

    Enz, Sabine; Brand, Heidi; Orellana, Claudia; Mahren, Susanne; Braun, Volkmar

    2003-07-01

    Transcription of the fecABCDE ferric citrate transport genes of Escherichia coli K-12 is initiated by a signaling cascade from the cell surface into the cytoplasm. FecR receives the signal in the periplasm from the outer membrane protein FecA loaded with ferric citrate, transmits the signal across the cytoplasmic membrane, and converts FecI in the cytoplasm to an active sigma factor. In this study, it was shown through the use of a bacterial two-hybrid system that, in the periplasm, the C-terminal FecR(237-317) fragment interacts with the N-terminal FecA(1-79) fragment. In the same C-terminal region, amino acid residues important for the interaction of FecR with FecA were identified by random and site-directed mutagenesis. They were preferentially located in and around a leucine motif (residues 247 to 268) which was found to be highly conserved in FecR-like proteins. The degree of residual binding of FecR mutant proteins to FecA was correlated with the degree of transcription initiation in response to ferric citrate in the culture medium. Three randomly generated inactive FecR mutants, FecR(L254E), FecR(L269G), and FecR(F284L), were suppressed to different degrees by the mutants FecA(G39R) and FecR(D43E). One FecR mutant, FecR (D138E, V197A), induced fecA promoter-directed transcription constitutively in the absence of ferric citrate and bound more strongly than wild-type FecR to FecA. The data showed that FecR interacts in the periplasm with FecA to confer ferric citrate-induced transcription of the fec transport genes and identified sites in FecR and FecA that are important for signal transduction. PMID:12813067

  3. Iron oxide minerals in dust of the Red Dawn event in eastern Australia, September 2009

    NASA Astrophysics Data System (ADS)

    Reynolds, Richard L.; Cattle, Stephen R.; Moskowitz, Bruce M.; Goldstein, Harland L.; Yauk, Kimberly; Flagg, Cody B.; Berquó, Thelma S.; Kokaly, Raymond F.; Morman, Suzette; Breit, George N.

    2014-12-01

    Iron oxide minerals typically compose only a few weight percent of bulk atmospheric dust but are important for potential roles in forcing climate, affecting cloud properties, influencing rates of snow and ice melt, and fertilizing marine phytoplankton. Dust samples collected from locations across eastern Australia (Lake Cowal, Orange, Hornsby, and Sydney) following the spectacular "Red Dawn" dust storm on 23 September 2009 enabled study of the dust iron oxide assemblage using a combination of magnetic measurements, Mössbauer spectroscopy, reflectance spectroscopy, and scanning electron microscopy. Red Dawn was the worst dust storm to have hit the city of Sydney in more than 60 years, and it also deposited dust into the Tasman Sea and onto snow cover in New Zealand. Magnetization measurements from 20 to 400 K reveal that hematite, goethite, and trace amounts of magnetite are present in all samples. Magnetite concentrations (as much as 0.29 wt%) were much higher in eastern, urban sites than in western, agricultural sites in central New South Wales (0.01 wt%), strongly suggesting addition of magnetite from local urban sources. Variable temperature Mössbauer spectroscopy (300 and 4.2 K) indicates that goethite and hematite compose approximately 25-45% of the Fe-bearing phases in samples from the inland sites of Orange and Lake Cowal. Hematite was observed at both temperatures but goethite only at 4.2 K, thereby revealing the presence of nanogoethite (less than about 20 nm). Similarly, hematite particulate matter is very small (some of it d < 100 nm) on the basis of magnetic results and Mössbauer spectra. The degree to which ferric oxide in these samples might absorb solar radiation is estimated by comparing reflectance values with a magnetic parameter (hard isothermal remanent magnetization, HIRM) for ferric oxide abundance. Average visible reflectance and HIRM are correlated as a group (r2 = 0.24), indicating that Red Dawn ferric oxides have capacity to absorb solar radiation. Much of this ferric oxide occurs as nanohematite and nanogoethite particles on surfaces of other particulate matter, thereby providing high surface area to enhance absorption of solar radiation. Leaching of the sample from Orange in simulated human-lung fluid revealed low bioaccessibility for most metals.

  4. Rates of oxidative weathering on the surface of Mars

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.

    1992-01-01

    Implicit in the mnemonic 'MSATT' (Mars surface and atmosphere through time) is that rates of surface processes on Mars through time should be investigated, including studies of the kinetics and mechanism of oxidative weathering reactions occurring in the Martian regolith. Such measurements are described. Two major elements analyzed in the Viking Lander XRF experiment that are most vulnerable to atmospheric oxidation are iron and sulfur. Originally, they occurred as Fe(2+)-bearing silicate and sulfide minerals in basaltic rocks on the surface of Mars. However, chemical weathering reactions through time have produced ferric- and sulfate-bearing assemblages now visible in the Martian regolith. Such observations raise several question about: (1) when the oxidative weathering reactions took place on Mars; (2) whether or not the oxidized regolith is a fossilized remnant of past weathering processes; (3) deducting chemical interactions of the ancient Martian atmosphere with its surface from surviving phases; (4) possible weathering reactions still occurring in the frozen regolith; and (5) the kinetics and mechanism of past and present-day oxidative reactions on Mars. These questions may be addressed experimentally by studying reaction rates of dissolution and oxidation of basaltic minerals, and by identifying reaction products forming on the mineral surfaces. Results for the oxidation of pyrrhotite and dissolved ferrous iron are reported.

  5. Effect of immunoglobulin G from cows immunized with ferric citrate receptor (FecA) on iron uptake by Escherichia coli.

    PubMed

    Takemura, K; Hogan, J S; Smith, K L

    2003-01-01

    The effects of immunoglobulin (Ig) G from cows immunized with the ferric citrate receptor (FecA) on iron uptake by Escherichia coli were investigated. Receptor FecA was purified from E. coli UT5600/pSV66. Cows were immunized with 400 microg purified FecA three times at 21 d intervals during late lactation and the nonlactating period. Immunoglobulin G was purified by protein G affinity chromatography from colostral whey from cows immunized with FecA and from unimmunized control cows. The purified IgG from FecA immunized cows had higher IgG titers against FecA compared with control IgG. Fifteen E. coli isolated from intramammary infections and E. coli UT5600/pSV66 were grown in an iron-depleted medium containing 1 mM citrate to induce FecA. The bacterial cells were mixed with 0, 2, and 4 mg/ml purified IgG, and 55Fe was added to the assay. After 5, 10, and 15 min incubations at 37 degrees C, samples were passed through 0.45-pm pore size filters. Filters were washed with saline three times, and the radioactivity of 55Fe taken up by the bacterial cells on the filters was measured by a liquid scintillation counter. The measurements were expressed as numbers of 55Fe atoms per colony-forming unit and transformed to log10. The assay was repeated three times for each isolate in a partially balanced incomplete block design. The presence of IgG decreased 55Fe uptake by E. coli mastitis isolates and E. coli UT5600/pSV66. Anti-FecA IgG reduced 55Fe uptake by E. coli greater than IgG from unimmunized cows. PMID:12613857

  6. Effects of suspended particles on the rate of mass transfer to a rotating disk electrode. [Ferric cyanide

    SciTech Connect

    Roha, D.J.

    1981-06-01

    Limiting currents for the reduction of ferric cyanide at a rotating disk were determined in the presence of 0 to 40 percent by volume of spherical glass beads. Experiments were conducted with six different particle diameters, and with rotation speeds in the range of 387 to 270 rpm, usong both a 0.56 cm and a 1.41 cm radius disk electrode. It was established that at a given rpm upon addition of glass beads in the limiting current, i/sub L/, may increase to more than three times its value without solids. This increase in limiting current density is greater at high rotation speeds and with the larger disk electrode. i/sub L/ as a function of particle diameter yields at maximum at approx. 10 ..mu..m. Two mass transfer models are offered to explain this behavior, both of which assume that the beads are in contact with the disk electrode and moving parallel to its surface. In the surface renewal model it is assumed that complete mixing takes place with the passage of each bead and the boundary layer is replaced with fresh bulk solution. While with the particle film model it is assumed the bead and a clinging film of fluid rotate together. The film promotes mass transfer by alternately absorbing and desorbing the diffusing species. The particle film model best explains the observed behavior of the limiting current density. Calculations of stirring power required verses i/sub L/ observed, show that adding beads to increase i/sub L/ consumes less additional power than simply increasing the rotation speed alone and even permits a decrease in the amount of stirring energy required per unit reactant consumed, at limiting current conditions.

  7. Ligand-Induced Structural Changes in the Escherichia coli Ferric Citrate Transporter Reveal Modes for Regulating Protein-Protein Interactions

    PubMed Central

    Mokdad, Audrey; Herrick, Dawn Z.; Kahn, Ali K.; Andrews, Emily; Kim, Miyeon; Cafiso, David S.

    2012-01-01

    Outer-membrane TonB-dependent transporters, such as the Escherichia coli ferric citrate transporter FecA, interact with the inner-membrane protein TonB through an energy-coupling segment termed the Ton box. In FecA, which regulates its own transcription, the Ton box is preceded by an N-terminal extension that interacts with the inner membrane protein FecR. Here, site-directed spin labeling was used to examine the structural basis for transcriptional signaling and Ton box regulation in FecA. EPR spectroscopy indicates that regions of the N-terminal domain are in conformational exchange, consistent with its role as a protein binding element; however, the local fold and dynamics of the domain are not altered by substrate or TonB. Distance restraints derived from pulse EPR were used to generate models for the position of the extension in the apo, substrate- and TonB-bound states. In the apo state, this domain is positioned at the periplasmic surface of FecA, where it interacts with the Ton box and blocks access of the Ton box to the periplasm. Substrate addition rotates the transcriptional domain and exposes the Ton box, leading to a disorder transition in the Ton box that may facilitate interactions with TonB. When a soluble fragment of TonB is bound to FecA, the transcriptional domain is displaced to one edge of the barrel, consistent with a proposed ?-strand exchange mechanism. However, neither substrate nor TonB displace the N-terminus further into the periplasm. This result suggests that the intact TonB system mediates both signaling and transport by unfolding portions of the transporter. PMID:22982293

  8. Ferric pyrophosphate citrate (Triferic™) administration via the dialysate maintains hemoglobin and iron balance in chronic hemodialysis patients

    PubMed Central

    Fishbane, Steven N.; Singh, Ajay K.; Cournoyer, Serge H.; Jindal, Kailash K.; Fanti, Paolo; Guss, Carrie D.; Lin, Vivian H.; Pratt, Raymond D.; Gupta, Ajay

    2015-01-01

    Background Administration of ferric pyrophosphate citrate (FPC, Triferic™) via hemodialysate may allow replacement of ongoing uremic and hemodialysis-related iron losses. FPC donates iron directly to transferrin, bypassing the reticuloendothelial system and avoiding iron sequestration. Methods Two identical Phase 3, randomized, placebo-controlled trials (CRUISE 1 and 2) were conducted in 599 iron-replete chronic hemodialysis patients. Patients were dialyzed with dialysate containing 2 µM FPC-iron or standard dialysate (placebo) for up to 48 weeks. Oral or intravenous iron supplementation was prohibited, and doses of erythropoiesis-stimulating agents were held constant. The primary efficacy end point was the change in hemoglobin (Hgb) concentration from baseline to end of treatment (EoT). Secondary end points included reticulocyte hemoglobin content (CHr) and serum ferritin. Results In both trials, Hgb concentration was maintained from baseline to EoT in the FPC group but decreased by 0.4 g/dL in the placebo group (P < 0.001, combined results; 95% confidence interval [CI] 0.2–0.6). Placebo treatment resulted in significantly larger mean decreases from baseline in CHr (?0.9 pg versus ?0.4 pg, P < 0.001) and serum ferritin (?133.1 µg/L versus ?69.7 µg/L, P < 0.001) than FPC treatment. The proportions of patients with adverse and serious adverse events were similar in both treatment groups. Conclusions FPC delivered via dialysate during hemodialysis replaces iron losses, maintains Hgb concentrations, does not increase iron stores and exhibits a safety profile similar to placebo. FPC administered by hemodialysis via dialysate represents a paradigm shift in delivering maintenance iron therapy to hemodialysis patients. PMID:26175145

  9. Ligand-induced structural changes in the Escherichia coli ferric citrate transporter reveal modes for regulating protein-protein interactions.

    PubMed

    Mokdad, Audrey; Herrick, Dawn Z; Kahn, Ali K; Andrews, Emily; Kim, Miyeon; Cafiso, David S

    2012-11-01

    Outer-membrane TonB-dependent transporters, such as the Escherichia coli ferric citrate transporter FecA, interact with the inner-membrane protein TonB through an energy-coupling segment termed the Ton box. In FecA, which regulates its own transcription, the Ton box is preceded by an N-terminal extension that interacts with the inner-membrane protein FecR. Here, site-directed spin labeling was used to examine the structural basis for transcriptional signaling and Ton box regulation in FecA. EPR spectroscopy indicates that regions of the N-terminal domain are in conformational exchange, consistent with its role as a protein binding element; however, the local fold and dynamics of the domain are not altered by substrate or TonB. Distance restraints derived from pulse EPR were used to generate models for the position of the extension in the apo, substrate-, and TonB-bound states. In the apo state, this domain is positioned at the periplasmic surface of FecA, where it interacts with the Ton box and blocks access of the Ton box to the periplasm. Substrate addition rotates the transcriptional domain and exposes the Ton box, leading to a disorder transition in the Ton box that may facilitate interactions with TonB. When a soluble fragment of TonB is bound to FecA, the transcriptional domain is displaced to one edge of the barrel, consistent with a proposed ?-strand exchange mechanism. However, neither substrate nor TonB displaces the N-terminus further into the periplasm. This result suggests that the intact TonB system mediates both signaling and transport by unfolding portions of the transporter. PMID:22982293

  10. In Vivo Evaluation of the Treatment Outcome of Pulpotomy in Primary Molars Using Diode Laser, Formocresol, and Ferric Sulphate

    PubMed Central

    Tanboga, Ilknur

    2014-01-01

    Abstract Objective: The purpose of this study was to assess whether the diode laser (DL) pulpotomy method is a suitable alternative to formocresol (FC) and ferric sulphate (FS) pulpotomies in human primary teeth. Background data: Pulpotomy is the amputation of infected coronal pulp to maintain radicular pulp vitality and function. Although FC is regarded as the gold standard for pulpotomy in primary teeth, concerns about its safety have been reported. Lasers are an effective nonpharmacological alternative for treating pulp in children. Methods: This study included 120 primary molars in 58 children 5–9 years of age who underwent an identical conventional pulpotomy technique; the molars were allocated to FC, FS, and DL groups. After removal of the coronal tissue, complete hemostasis of the remaining pulp in the DL group was achieved by DL at 1.5 W, 30?Hz, and 50?mJ, with a 10?sec exposure time. For the FC group, diluted FC (1:5 Buckley's formocresol) was used for 5?min., and for the FS group, a 15.5% FS solution was used for 15?sec. Treatments in all groups were completed with stainless steel crowns and monitored clinically and radiographically at 1, 3, 6, 9, and 12 months. Results: The clinical success rates at 12 months were 97%, 95%, and 100%, whereas the radiographic success rates were 87%, 79%, and 75%, for the FC, FS and DL groups, respectively. The differences in the results were not statistically significant according to the ?2 test (p>0.05). Conclusions: DL pulpotomy offers a high clinical success rate, however considering radiographic success rate, it may not replace traditional FC and FS pulpotomies in primary molars. PMID:24717147

  11. Amorphous iron-(hydr) oxide networks at liquid/vapor interfaces: In situ X-ray scattering and spectroscopy studies

    SciTech Connect

    Wang, W.; Pleasants, J.; Bu, W.; Park, R.Y.; Kuzmenko, I.; Vaknin, D.

    2012-06-23

    Surface sensitive X-ray reflectivity (XR), fluorescence (XF), and grazing incidence X-ray diffraction (GIXD) experiments were conducted to determine the accumulation of ferric iron Fe (III) or ferrous iron Fe (II) under dihexadecyl phosphate (DHDP) or arachidic acid (AA) Langmuir monolayers at liquid/vapor interfaces. Analysis of the X-ray reflectivity and fluorescence data of monolayers on the aqueous subphases containing FeCl3 indicates remarkably high levels of surface-bound Fe (III) in number of Fe3þ ions per molecule (DHDP or AA) that exceed the amount necessary to neutralize a hypothetically completely deprotonated monolayer (DHDP or AA). These results suggest that nano-scale iron (hydr) oxide complexes (oxides, hydroxides or oxyhydroxides) bind to the headgroups and effectively overcompensate the maximum possible charges at the interface. The lack of evidence of in-plane ordering in GIXD measurements and strong effects on the surface-pressure versus molecular area isotherms indicate that an amorphous network of iron (hydr) oxide complexes contiguous to the headgroups is formed. Similar experiments with FeCl2 generally resulted with the oxidation of Fe (II)–Fe (III) which consequently leads to ferric Fe (III) complexes binding albeit with less iron at the interface. Controlling the oxidation of Fe (II) changes the nature and amount of binding significantly. The implications to biomineralization of iron (hydr) oxides are briefly discussed.

  12. Red Dawn: Characterizing Iron Oxide Minerals in Atmospheric Dust

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    Atmospheric dust is comprised of many components including small amounts of iron oxide minerals. Although the iron oxides make up a small weight percent of the bulk dust, they are important because of their roles in ocean fertilization, controls on climate, and as a potential health hazard to humans. Here we report on the iron oxide mineralogy in dust from a large dust storm, dubbed Red Dawn, which engulfed eastern Australia along a 3000 km front on 23 September 2009. Red Dawn originated from the lower Lake Eyre Basin of South Australia, western New South Wales (NSW) and southwestern Queensland and was the worst dust storm to have hit the city of Sydney in more than 60 years. Dust samples were collected from various locations across eastern Australia (Lake Cowal, Orange, Hornsby, Sydney) following the Red Dawn event. Our dust collection provides a good opportunity to study the physical and mineralogical properties of iron oxides from Red Dawn using a combination of reflectance spectroscopy, Mössbauer spectroscopy (MB), and magnetic measurements. Magnetization measurements from 20-400 K reveal that magnetite/maghemite, hematite and goethite are present in all samples with magnetite occurring in trace amounts (< 0.5wt%). However, the amount of magnetite/maghemite even in trace concentrations generally increases from Lake Cowal from west to east (0.01 to 0.29 wt%), with highest magnetite contents in the urban-Sydney sites. These observations indicate the additions of magnetite from local urban sources. Variable temperature Mössbauer spectroscopy (300 K and 4.2 K) indicate that goethite and hematite compose approximately 25-45 % of the Fe-bearing phases in the Orange and Lake Cowal samples. Goethite is more abundant than hematite in the Lake Cowal samples whereas the opposite is observed for Orange. Hematite is observed at both temperatures but goethite only at 4.2 K. The identification of goethite in Mössbauer analyses at low-temperature but not at room temperature indicates the presence of nanogoethite and small particle sizes (< 30 nm). Magnetization experiments indicates that some of the nanogoethite has remanence blocking temperatures above 300 K (and hence larger particle sizes) but it must be a small fraction of the total grain distribution considering that goethite was not indicated at 300 K with Mössbauer. Likewise, Mössbauer spectra indicate that the hematite component is still above the Morin transition (TM=265 K) and in its canted antiferromagnetic state even at 4.2 K. Suppression of the Morin transition in hematite can occur due to reduced crystallinity, cation substitution (e.g., Ti4+, Al 3+), or small particle effects (d< 100 nm). Finally, we compared reflectance with a magnetic parameter (hard isothermal remanent magnetization, HIRM) for ferric oxide abundance to assess the degree to which ferric oxide in these samples might absorb solar radiation. In samples for which both parameters were obtained, HIRM and average reflectance over the visible wavelengths are correlated as a group (r2=0.24). These results indicate that the ferric oxide minerals in Red Dawn dust absorb solar radiation. Much of this ferric oxide occurs likely as grain coatings of nanohematite and nanogoethite, thereby providing high surface area to enhance absorption of solar radiation.

  13. Metal Oxide Decomposition In Hydrothermal Alkaline Sodium Phosphate Solutions

    SciTech Connect

    S.E. Ziemniak

    2003-09-24

    Alkaline hydrothermal solutions of sodium orthophosphate (2.15 < Na/P < 2.75) are shown to decompose transition metal oxides into two families of sodium-metal ion-(hydroxy)phosphate compounds. Equilibria for these reactions are quantified by determining phosphate concentration-temperature thresholds for decomposition of five oxides in the series: Ti(IV), Cr(III), Fe(III, II), Ni(II) and Zn(II). By application of a computational chemistry method General Utility Lattice Program (GULP), it is demonstrated that the unique non-whole-number Na/P molar ratio of sodium ferric hydroxyphosphate is a consequence of its open-cage structure in which the H{sup +} and excess Na{sup +} ions are located.

  14. Structure of Oxidized Alpha-Haemoglobin Bound to AHSP Reveals a Protective Mechanism for HAEM

    SciTech Connect

    Feng,L.; Zhou, S.; Gu, L.; Gell, D.; MacKay, J.; Weiss, M.; Gow, A.; Shi, Y.

    2005-01-01

    The synthesis of hemoglobin A (HbA) is exquisitely coordinated during erythrocyte development to prevent damaging effects from individual {alpha}- and {beta}-subunits. The {alpha}-hemoglobin-stabilizing protein (AHSP) binds {alpha}-hemoglobin ({alpha}Hb), inhibits the ability of {alpha}Hb to generate reactive oxygen species and prevents its precipitation on exposure to oxidant stress. The structure of AHSP bound to ferrous {alpha}Hb is thought to represent a transitional complex through which {alpha}Hb is converted to a non-reactive, hexacoordinate ferric form. Here we report the crystal structure of this ferric {alpha}Hb-AHSP complex at 2.4 Angstrom resolution. Our findings reveal a striking bis-histidyl configuration in which both the proximal and the distal histidines coordinate the haem iron atom. To attain this unusual conformation, segments of {alpha}Hb undergo drastic structural rearrangements, including the repositioning of several {alpha}-helices. Moreover, conversion to the ferric bis-histidine configuration strongly and specifically inhibits redox chemistry catalysis and haem loss from {alpha}Hb. The observed structural changes, which impair the chemical reactivity of haem iron, explain how AHSP stabilizes {alpha}Hb and prevents its damaging effects in cells.

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

    SciTech Connect

    Nowack, B.; Sigg, L.

    1997-03-01

    The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA > CaEDTA > PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced. 35 refs., 11 figs., 4 tabs.

  16. Pseudopotentials for quantum Monte Carlo calculations of transition metal oxides

    NASA Astrophysics Data System (ADS)

    Krogel, Jaron; Santana, Juan; Kent, Paul; Reboredo, Fernando

    2015-03-01

    Quantum Monte Carlo calculations of transition metal oxides are partially limited by the availability of high quality pseudopotentials that are both accurate in QMC and compatible with major electronic structure codes, e.g. by not being overly hard in the standard planewave basis. Following insight gained from recent GW calculations, a set of neon core pseudopotentials with small cutoff radii have been created for the early transition metal elements Sc to Zn within the local density approximation of DFT. The pseudopotentials have been tested for energy consistency within QMC by calculating the first through fourth ionization potentials of the isolated transition metal (TM) atoms and the binding curve of each TM-O dimer. The vast majority of the ionization potentials fall within 0.3 eV of the experimental values, with exceptions occurring mainly for atoms with multiple unpaired d electrons where multireference effects are the strongest. The equilibrium bond lengths of the dimers are within 1% of experimental values and the binding energy errors are typically less than 0.3 eV. Given the uniform treatment of the core, the larger deviations occasionally observed may primarily reflect the limitations of a Slater-Jastrow trial wavefunction. This work is supported by the Materials Sciences & Engineering Division of the Office of Basic Energy Sciences, U.S. DOE. Research by PRCK was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

  17. Piezoelectric force microscopy of crystalline oxide-semiconductor heterostructures

    NASA Astrophysics Data System (ADS)

    Marshall, Matthew S. J.; Reiner, James W.; Kumah, Divine; Maksymovych, Peter; Baddorf, Art P.; Ahn, Charles; Walker, Fred J.

    2011-03-01

    Coupling the properties of a ferroelectric material to a semiconductor has been pursued for decades. Epitaxial, coherently strained thin films of ferroelectric BaTiO3 can be grown on germanium with out-of-plane polarization using molecular beam epitaxy (MBE). Similarly, epitaxial thin films of SrTiO3 can be grown on Si with some indication that these films can be ferroelectric. In this work, we use oxide MBE to grow epitaxial films of SrTiO3 and BaTiO3 on Si and Ge, respectively, and we use both ambient and ultrahigh vacuum (UHV) piezoelectric force microscopy (PFM) to study the question of ferroelectricity in these systems. We find that the modulation of the PFM amplitude for thin films of SrTiO3 (6 uc. and 25 uc) on Si is the result of an electrostatic mechanism that can be traced back to tip-induced or as-grown defects in the film. These results are compared to results on thin films of BaTiO3 on Ge. A portion of this research was conducted at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, U.S. Dept. of Energy.

  18. Magnesium Oxide

    MedlinePLUS

    Magnesium is an element your body needs to function normally. Magnesium oxide may be used for different reasons. Some ... to relieve heartburn, sour stomach, or acid indigestion. Magnesium oxide also may be used as a laxative ...

  19. Structural evidence for iron-free citrate and ferric citrate binding to the TonB-dependent outer membrane transporter FecA.

    PubMed

    Yue, Wyatt W; Grizot, Sylvestre; Buchanan, Susan K

    2003-09-12

    Escherichia coli possesses a TonB-dependent transport system, which exploits the iron-binding capacity of citrate and its natural abundance. Here, we describe three structures of the outer membrane ferric citrate transporter FecA: unliganded and complexed with iron-free or diferric dicitrate. We show the structural mechanism for discrimination between the iron-free and ferric siderophore: the binding of diferric dicitrate, but not iron-free dicitrate alone, causes major conformational rearrangements in the transporter. The structure of FecA bound with iron-free dicitrate represents the first structure of a TonB-dependent transporter bound with an iron-free siderophore. Binding of diferric dicitrate to FecA results in changes in the orientation of the two citrate ions relative to each other and in their interactions with FecA, compared to the binding of iron-free dicitrate. The changes in ligand binding are accompanied by conformational changes in three areas of FecA: two extracellular loops, one plug domain loop and the periplasmic TonB-box motif. The positional and conformational changes in the siderophore and transporter initiate two independent events: ferric citrate transport into the periplasm and transcription induction of the fecABCDE transport genes. From these data, we propose a two-step ligand recognition event: FecA binds iron-free dicitrate in the non-productive state or first step, followed by siderophore displacement to form the transport-competent, diferric dicitrate-bound state in the second step. PMID:12948487

  20. Microbial reduction of ferric iron oxyhydroxides as a way for remediation of grey forest soils heavily polluted with toxic metals by infiltration of acid mine drainage

    NASA Astrophysics Data System (ADS)

    Georgiev, Plamen; Groudev, Stoyan; Spasova, Irena; Nicolova, Marina

    2015-04-01

    The abandoned uranium mine Curilo is a permanent source of acid mine drainage (AMD) which steadily contaminated grey forest soils in the area. As a result, the soil pH was highly acidic and the concentration of copper, lead, arsenic, and uranium in the topsoil was higher than the relevant Maximum Admissible Concentration (MAC) for soils. The leaching test revealed that approximately half of each pollutant was presented as a reducible fraction as well as the ferric iron in horizon A was presented mainly as minerals with amorphous structure. So, the approach for remediation of the AMD-affected soils was based on the process of redoxolysis carried out by iron-reducing bacteria. Ferric iron hydroxides reduction and the heavy metals released into soil solutions was studied in the dependence on the source of organic (fresh or silage hay) which was used for growth and activity of soil microflora, initial soil pH (3.65; 4.2; and 5.1), and the ion content of irrigation solutions. The combination of limestone (2.0 g/ kg soil), silage addition (at rate of 45 g dry weight/ kg soil) in the beginning and reiterated at 6 month since the start of soil remediation, and periodical soil irrigation with slightly acidic solutions containing CaCl2 was sufficient the content of lead and arsenic in horizon A to be decreased to concentrations similar to the relevant MAC. The reducible, exchangeable, and carbonate mobile fractions were phases from which the pollutants was leached during the applied soil remediation. It determined the higher reduction of the pollutants bioavailability also as well as the process of ferric iron reduction was combined with neutralization of the soil acidity to pH (H2O) 6.2.

  1. FhuD1, a Ferric Hydroxamate-binding Lipoprotein in Staphylococcus aureus - A case of gene duplication and lateral transfer

    SciTech Connect

    Sebulsky, M. Tom; Speziali, Craig D.; Shilton, Brian H.; Edgell, David R.

    2010-11-16

    Staphylococcus aureus can utilize ferric hydroxamates as a source of iron under iron-restricted growth conditions. Proteins involved in this transport process are: FhuCBG, which encodes a traffic ATPase; FhuD2, a post-translationally modified lipoprotein that acts as a high affinity receptor at the cytoplasmic membrane for the efficient capture of ferric hydroxamates; and FhuD1, a protein with similarity to FhuD2. Gene duplication likely gave rise to fhuD1 and fhuD2. While the genomic locations of fhuCBG and fhuD2 in S. aureus strains are conserved, both the presence and the location of fhuD1 are variable. The apparent redundancy of FhuD1 led us to examine the role of this protein. We demonstrate that FhuD1 is expressed only under conditions of iron limitation through the regulatory activity of Fur. FhuD1 fractions with the cell membrane and binds hydroxamate siderophores but with lower affinity than FhuD2. Using small angle x-ray scattering, the solution structure of FhuD1 resembles that of FhuD2, and only a small conformational change is associated with ferrichrome binding. FhuD1, therefore, appears to be a receptor for ferric hydroxamates, like FhuD2. Our data to date suggest, however, that FhuD1 is redundant to FhuD2 and plays a minor role in hydroxamate transport. However, given the very real possibility that we have not yet identified the proper conditions where FhuD1 does provide an advantage over FhuD2, we anticipate that FhuD1 serves an enhanced role in the transport of untested hydroxamate siderophores and that it may play a prominent role during the growth of S. aureus in its natural environments.

  2. Ethylene Oxide

    Cancer.gov

    At room temperature, ethylene oxide is a flammable colorless gas with a sweet odor. It is used primarily to produce other chemicals, including antifreeze. In smaller amounts, ethylene oxide is used as a pesticide and a sterilizing agent. The ability of ethylene oxide to damage DNA makes it an effective sterilizing agent but also accounts for its cancer-causing activity.

  3. Understanding Surface Processes on Mars Through Study of Iron Oxides/Oxyhydroxides: Clues to Surface Alteration and Aqueous Processes

    NASA Technical Reports Server (NTRS)

    Bishop, J. L.; Mancinelli, R. L.; Dyar, M. D.; Parente, M.; Drief, A.; Lane, M. D.; Murad, E.

    2006-01-01

    We are performing oxidation and reduction reactions on hydrated ferric oxide minerals in order to investigate how these might alter under a variety of conditions on the surface of Mars. Preliminary experiments on ferrihydrite and goethite showed that heating these minerals in a dry oxidizing environment produces fine-grained hematite, while heating these minerals in a reducing environment produces fine-grained magnetite. Under Mars-like oxidation levels this magnetite then oxidizes to maghemite. These reactions are dependent on the presence of water and organic material that can act as a reductant. We are using reflectance and Mossbauer spectroscopy to characterize the reaction products and TEM to analyze the sample texture. Our preliminary results indicate that magnetite and maghemite could be formed in the soil on Mars from ferrihydrite and goethite if organics were present on early Mars.

  4. The impact of intravenous ferric carboxymaltose on renal function: an analysis of the FAIR-HF study

    PubMed Central

    Ponikowski, Piotr; Filippatos, Gerasimos; Colet, Josep Comin; Willenheimer, Ronnie; Dickstein, Kenneth; Lüscher, Thomas; Gaudesius, Giedrius; von Eisenhart Rothe, Barbara; Mori, Claudio; Greenlaw, Nicola; Ford, Ian; Macdougall, Iain; Anker, Stefan D

    2015-01-01

    Aims Anaemia and iron deficiency are constituents of the cardio-renal syndrome in chronic heart failure (CHF). We investigated the effects of i.v. iron in iron-deficient CHF patients on renal function, and the efficacy and safety of this therapy in patients with renal dysfunction. Methods and results The FAIR-HF trial randomized 459 CHF patients with iron deficiency (ferritin <100 µg/L, or between 100 and 299 µg/L if transferrin saturation was <20%): 304 to i.v. ferric carboxymaltose (FCM) and 155 to placebo, and followed-up for 24 weeks. Renal function was assessed at baseline and at weeks 4, 12, and 24, using the estimated glomerular filtration rate (eGFR, mL/min/1.73 m2), calculated from the Chronic Kidney Disease Epidemiology Collaboration (CKD–EPI) formula. At baseline, renal function was similar between groups (62.4 ± 20.6 vs. 62.9 ± 23.4 mL/min/1.73 m2, FCM vs. placebo). Compared with placebo, treatment with FCM was associated with an increase in eGFR [treatment effect: week 4, 2.11 ± 1.21 (P = 0.082); week 12, 2.41 ± 1.33 (P = 0.070); and week 24, 2.98 ± 1.44 mL/min/1.73 m2 (P = 0.039)]. This effect was seen in all pre-specified subgroups (P > 0.20 for interactions). No interaction between the favourable effects of FCM and baseline renal function was seen for the primary endpoints [improvement in Patient Global Assessment (P = 0.43) and NYHA class (P = 0.37) at 24 weeks]. Safety and adverse event profiles were similar in patients with baseline eGFR <60 and ?60 mL/min/1.73 m2. Conclusions Treatment of iron deficiency in CHF patients with i.v. FCM was associated with an improvement in renal function. FCM therapy was effective and safe in CHF patients with renal dysfunction. PMID:25683972

  5. Coordinated analyses of orbital and spirit rover data to characterize surface materials on the cratered plains of Gusev Crater, Mars

    USGS Publications Warehouse

    Lichtenberg, K.A.; Arvidson, R.E.; Poulet, F.; Morris, R.V.; Knudson, A.; Bell, J.F.; Bellucci, G.; Bibring, J.-P.; Farrand, W.H.; Johnson, J.R.; Ming, D.W.; Pinet, P.C.; Rogers, A.D.; Squyres, S.W.

    2007-01-01

    Comparison of the Mars Exploration Rover Spirit's Pancam (0.4 to 1.0 ??m) and Mars Express Observatoire pour la Mineralogie l'Eau, les Glaces et l'Activite?? (OMEGA) (0.4 to 2.5 ??m) spectral reflectance data over Spirit's traverses shows that Gusev cratered plains are dominated by nanophase ferric-oxide-rich dust covering weakly altered basaltic sands. This interpretation is also consistent with both observations from OMEGA data covering plains beyond the traverse region and interpretations of data from the other payload instruments on the Spirit Rover. OMEGA observations of relatively low albedo regions where dust has presumably been stripped by dust devils show negative spectral reflectance slopes from 1.5 to 2.5 ??m and moderately masked spectral features which are indicative of olivine or pyroxene. High-albedo regions north and south of the Spirit landing site have flat spectral reflectance slopes and few spectral features, although all spectra have a nanophase ferric-oxide absorption edge between 0.4 and 0.75 ??m. Comparison of THEMIS-derived thermal inertia values with OMEGA-derived spectral parameters shows that although the dust cover can be optically thick (0.4 to 2.5 ??m wavelength region) in some areas, it is not thick enough (???1 cm) to mask the thermal inertia of the underlying substrate for areas included in this study. Copyright 2007 by the American Geophysical Union.

  6. Oxidative Transformations of Ferrous Iron-Bearing Smecitites: Routes to Martian Nontronites

    NASA Astrophysics Data System (ADS)

    Beehr, A. R.; Catalano, J. G.

    2011-12-01

    Data collected by the OMEGA spectrometer and the CRISM instrument indicate the presence of iron-bearing phyllosilicates on Mars' surface. Identified species include chlorite, saponite (Mg-rich smectite), and nontronite (Fe(III)-bearing smectite). The observed phyllosilicates occur in units that were deposited during the Noachian, which is thought to have had chemically reducing and alkaline conditions. Phyllosilicates are expected aqueous weathering products of basaltic minerals; the aqueous activity may have occurred episodically and hydrothermally, or as prolonged, low temperature alteration. Aqueous alkaline and reducing conditions favor the initial formation of ferrous iron-bearing phyllosilicates; subsequent surface alteration events are required to have oxidized these units into ferric smectites. Understanding the formation and oxidation of ferrous phyllosilicates can offer insight into the early Martian environment by allowing us to determine by what mechanism the oxidation occurred. We have investigated chemical and structural changes that occur upon oxidation of a synthetic ferrous saponite to determine the conditions under which such a process can produce nontronite or other ferric smectites. Both H2O2 and NO3- were used as oxidants. Hydrogen peroxide is likely the dominant oxidant currently present on Mars and nitrate is a plausible oxidant produced through photochemical processes. Deposition of photochemical nitrate is observed in the Antarctic dry valleys where it co-occurs with perchlorate, which was recently identified in Martian soil by the Phoenix lander. The initial ferrous saponite contains Fe(II) in the octahedral sheet. X-ray absorption spectroscopy (XAS) indicates that in the presence of a 1m nitrate solution under hydrothermally conditions the ferrous saponite undergoes oxidation to an Fe(III)-bearing phyllosilicate. Similar oxidation is not observed at 22°C, but this appears to be a kinetic phenomenon as oxidation is thermodynamically favorable. In contrast, exposure to hydrogen peroxide causes significant oxidation regardless of temperature. However, oxidation at 22°C produces a poorly crystalline material lacking substantial structural Fe. Recrystallization upon aging under mild hydrothermal conditions (150°C) produces an Fe(III)-bearing phyllosilicate. X-ray diffraction indicates that this oxidized phyllosilicate is a 2:1 clay with lattice parameters similar to nontronite. XAS demonstrates that this oxidized clay contains Fe in similar local coordiation environments as two nontronite standards, NAu-2 and SWa-1. In both systems the need for hydrothermal aging to produce a nontronite-like clay likely reflects the slow rate of crystallization of smectites at room temperature on laboratory timescales rather than changes in their favorabtility of formation. Oxidation of ferrous smectites formed through weathering of basalt under reducing conditions is thus a viable formation pathway for the observed Martian nontronites.

  7. Competitive Inhibition of Ferrous Iron Oxidation by Thiobacillus ferrooxidans by Increasing Concentrations of Cells

    PubMed Central

    Suzuki, Isamu; Lizama, Hector M.; Tackaberry, Patrick D.

    1989-01-01

    The oxidation of ferrous iron (Fe2+) to ferric iron (Fe3+) with dioxygen (O2) by various strains of Thiobacillus ferrooxidans was studied by measuring the rate of O2 consumption at various Fe2+ concentrations and cell concentrations. The apparent Km values for Fe2+ remained constant at different cell concentrations of laboratory strains ATCC 13661 and ATCC 19859 but increased with increasing cell concentrations of mine isolates SM-4 and SM-5. The latter results are explained by the competitive inhibition of the Fe2+-binding site of a cell by other cells in the reaction mixture. Possible mechanisms involving cell surface properties are discussed. PMID:16347904

  8. Characterization of Jarosite Formed upon Bacterial Oxidation of Ferrous Sulfate in a Packed-Bed Reactor †

    PubMed Central

    Grishin, Sergei I.; Bigham, Jerry M.; Tuovinen, Olli H.

    1988-01-01

    A packed-bed bioreactor with activated-carbon particles as a carrier matrix material inoculated with Thiobacillus ferrooxidans was operated at a pH of 1.35 to 1.5 to convert ferrous sulfate to ferric sulfate. Despite the low operating pH, trace amounts of precipitates were produced in both the reactor and the oxidized effluent. X-ray diffraction and chemical analyses indicated that the precipitates were well-ordered potassium jarosite. The chemical analyses also revealed a relative deficiency of Fe and an excess of S in the reactor sample compared with the theoretical composition of potassium jarosite. Images PMID:16347799

  9. Antigenic homology of the inducible ferric citrate receptor (FecA) of coliform bacteria isolated from herds with naturally occurring bovine intramammary infections.

    PubMed

    Lin, J; Hogan, J S; Smith, K L

    1999-11-01

    Expression of ferric citrate receptor FecA by Escherichia coli and Klebsiella pneumoniae isolated from bovine mastitis was investigated. Transformant E. coli UT5600/pSV66, which produces large quantities of FecA in the presence of citrate, was constructed. The FecA of E. coli UT5600/pSV66 was purified by preparative sodium dodecyl sulfate-polyacrylamide gel electrophoresis and used to prepare polyclonal antiserum in rabbits. All coliform isolates of E. coli (n = 18) and K. pneumoniae (n = 17) from naturally occurring bovine intramammary infections in five herds induced iron-regulated outer membrane proteins when grown in Trypticase soy broth containing 200 microM alpha-alpha'-dipyridyl and 1 mM citrate. Polyclonal antiserum against FecA was used in conjunction with an immunoblot technique to determine the degree of antigenic homology of FecA among isolates. In the presence of citrate, each isolate expressed FecA that reacted with the anti-FecA polyclonal antiserum. The molecular mass of FecA ( approximately 80.5 kDa) was also highly conserved among isolates. Therefore, the ferric citrate iron transport may be induced in coliform bacteria and utilized to acquire iron in milk for survival and growth. The FecA is an attractive vaccine component for controlling coliform mastitis during the lactation period. PMID:10548594

  10. Efficacy and Safety of Intravenous Ferric Carboxymaltose in Geriatric Inpatients at a German Tertiary University Teaching Hospital: A Retrospective Observational Cohort Study of Clinical Practice

    PubMed Central

    Bach, Matthias; Geisel, Tabea; Martin, Julia; Schulze, Bettina; Schaefer, Roland; Virgin, Garth; Stein, Juergen

    2015-01-01

    Current iron supplementation practice in geriatric patients is erratic and lacks evidence-based recommendations. Despite potential benefits in this population, intravenous iron supplementation is often withheld due to concerns regarding pharmacy expense, perceived safety issues, and doubts regarding efficacy in elderly patients. This retrospective, observational cohort study aimed to evaluate the safety and efficacy of intravenous ferric carboxymaltose (FCM, Ferinject) in patients aged >75 years with iron deficiency anaemia (IDA). Within a twelve-month data extraction period, the charts of 405 hospitalised patients aged 65–101 years were retrospectively analysed for IDA, defined according to WHO criteria for anaemia (haemoglobin: <13.0?g/dL (m)/<12.0?g/dL (f)) in conjunction with transferrin saturation <20%. Of 128 IDA patients screened, 51 (39.8%) received intravenous iron. 38 patient charts were analysed. Mean cumulative dose of intravenous FCM was 784.4 ± 271.7?mg iron (1–3 infusions). 18 patients (47%) fulfilled treatment response criteria (?1.0?g/dL increase in haemoglobin between baseline and hospital discharge). AEs were mild/moderate, most commonly transient increases of liver enzymes (n = 5/13.2%). AE incidence was comparable with that observed in patients <75 years. No serious AEs were observed. Ferric carboxymaltose was well tolerated and effective for correction of Hb levels and iron stores in this cohort of IDA patients aged over 75 years. PMID:26236500

  11. From the periplasmic signaling domain to the extracellular face of an outer membrane signal transducer of Pseudomonas aeruginosa: crystal structure of the ferric pyoverdine outer membrane receptor.

    PubMed

    Wirth, Christophe; Meyer-Klaucke, Wolfram; Pattus, Franc; Cobessi, David

    2007-04-27

    The pyoverdine outer membrane receptor, FpvA, from Pseudomonas aeruginosa translocates ferric pyoverdine across the outer membrane through an energy consuming mechanism using the proton motive force and the TonB-ExbB-ExbD energy transducing complex from the inner membrane. We solved the crystal structure of the full-length FpvA bound to iron-pyoverdine at 2.7 A resolution. Signal transduction to an anti-sigma protein of the inner membrane and to TonB-ExbB-ExbD involves the periplasmic domain, which displays a beta-alpha-beta fold composed of two alpha-helices sandwiched by two beta-sheets. One iron-pyoverdine conformer is bound at the extracellular face of FpvA, revealing the conformer selectivity of the binding site. The loop that contains the TonB box, involved in interactions with TonB, and connects the signaling domain to the plug domain of FpvA is not defined in the electron density following the binding of ferric pyoverdine. The high flexibility of this loop is probably necessary for signal transduction through the outer membrane. PMID:17349657

  12. High affinity (/sup 3/H). beta. -Alanine uptake by scar margins of ferric chloride-induced epileptogenic foci in rat isocortex

    SciTech Connect

    Robitaille, Y.; Sherwin, A.

    1984-07-01

    Cortical astrocytes of normal mammalian brain are endowed with a high affinity uptake system for ..beta..-Alanine which is competitively inhibited by gamma aminobutyric acid (GABA), a neurotransmitter strongly implicated in epileptogenesis. The authors evaluated (/sup 3/H) ..beta..-Alanine uptake by reactive astrocytes proliferating within scar of epileptogenic foci induced in rat motor cortex by microinjections of 100 mM ferric chloride. Following in vitro incubation of scar tissue with (/sup 3/H) ..beta..-Alanine, ultrastructural morphometry of grain patterns at 5, 30 and 120 days post injection revealed early and significant grain count increases over astroglial processes, predominantly those related to perivascular glial end-feet. Astrocytic cell body and endothelial cell counts showed a more gradual and stepwise increase. Similar data were obtained by comparing visual and edited mean astrocytic grain counts. These results suggest that the enhanced uptake of reactive astrocytes may reflect a marked decrease of inhibitory GABAergic neurons within ferric chloride-induced scars. 7 figures, 1 table.

  13. Dissolution of iron(III)(HYDR)oxides by metal-EDTA-complexes

    SciTech Connect

    Nowack, B.; Sigg, L.

    1996-10-01

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

  14. Interactions between the outer membrane ferric citrate transporter FecA and TonB: studies of the FecA TonB box.

    PubMed

    Ogierman, Monica; Braun, Volkmar

    2003-03-01

    Both induction of transcription of the ferric citrate transport genes and transport of ferric citrate by the Escherichia coli outer membrane receptor FecA require energy derived from the proton motive force (PMF) of the inner membrane. The energy is transduced to FecA by the inner membrane complex, TonB, ExbB, and ExbD. Region 160 of TonB and the conserved TonB box of other TonB-dependent receptors are implicated as sites of interaction. In the present study, the postulated TonB box (D(80)A(81)L(82)T(83)V(84)) of FecA was deleted in frame, with a subsequent loss of both FecA functions. DALTV of FecA could be functionally replaced with the core TonB boxes of FhuA (DTITV) and FepA (DTIVV). Each residue of the TonB box of FecA was sequentially replaced with cysteine residues, and only the D80C replacement showed a loss (reduction) of both FecA functions. A physical interaction between TonB and FecA was demonstrated using both in vivo site-specific disulfide bond cross-linking and nonspecific formaldehyde (FA) cross-linking. Pairwise combinations of FecA (DALTV)/Cys substitutions were cross-linked via disulfide bond formation with TonBQ160C, TonBQ162C, and TonBY163C. Unexpectedly, this cross-linking was not enhanced by substrate (ferric citrate). In contrast, the TonB-FecA interaction was enhanced by ferric citrate in the FA-cross-linking assay. Energy derived from the PMF was not required for the TonB-FecA interaction in either the disulfide- or FA-cross-linking assay. TonB/CysExbB/ExbD(D25N) was still able to cross-link with the FecA (DALTV)/Cys derivatives in a tonB tolQ background, even though ExbD25N renders the TonB/ExbBD complex nonfunctional (V. Braun, S. Gaisser, C. Herrmann, K. Kampfenkel, H. Killmann, and I. Traub, J. Bacteriol. 178:2836-2845, 1996). TonB cross-linked to FecA via FA was not inhibited by either carbonylcyanide-m-chlorophenylhydrazone or 1 mM 2,4-dinitrophenol, which dissipate the electrochemical potential of the cytoplasmic membrane and disrupt both FecA functions. The studies shown here demonstrate the significance of the TonB box for FecA functions and are consistent with the view that it is the structure and not the sequence of the TonB box that is important for activity. Demonstrated here for the first time is the physical interaction of TonB and FecA, which is enhanced by ferric citrate. PMID:12618451

  15. Cell Adhesion of Shewanella Oneidensis to Iron Oxide Minerals: Effect of Different Single Crystal Faces

    SciTech Connect

    Neal, Andrew L.; Bank, Tracy L.; Hochella Jr., Michael F.; Rosso, Kevin M.

    2005-12-02

    The results of experiments designed to test the hypothesis that near-surface molecular structure of iron oxide minerals influences adhesion of dissimilatory iron reducing bacteria are presented. These experiments involved the measurement, using atomic force microscopy, of interaction forces generated between Shewanella oneidensis MR-1 cells and single crystal growth faces of iron oxide minerals. Significantly different adhesive force was measured between cells and the (001) face of hematite, and the (100) and (111) faces of magnetite. A role for electrostatic interactions is apparent. The trend in relative forces of adhesion generated at the mineral surfaces is in agreement with predicted ferric site densities published previously. These results suggest that near-surface structure does indeed influence initial cell attachment to iron oxide surfaces; whether this is mediated via specific cell surface-mineral surface interactions or by more general interfacial phenomena remains untested.

  16. Environmental Factors Affecting Ammonium Oxidation Under Iron Reducing Conditions

    NASA Astrophysics Data System (ADS)

    Jaffe, P. R.; Huang, S.; Ruiz-Urigüen, M.

    2014-12-01

    Ammonium (NH4+) oxidation coupled to iron (Fe) reduction in the absence of oxygen and nitrate/nitrite (NO3-/NO2-) has been reported by several investigators and referred to as Feammox. Feammox is a biological reaction, where Fe(III) is the electron acceptor, which is reduced to Fe(II), and NH4+ is the electron donor, which is oxidized to NO2-. Through a 180-day anaerobic incubation experiment, and using PCR-DGGE, 454-pyosequecing and qPCR analysis, we have shown that an Acidimicrobiaceae bacterium A6, a previously unreported species in the Acidimicrobiaceae family, might be either responsible or plays a key role in the Feammox process, We have enriched these Feammox bacteria (65.8% in terms of cell numbers) in a membrane reactor, and isolated the pure Acidimicrobiaceae bacterium A6 strain in an autotrophic medium. In samples collected and then incubated from a series of local wetland-, upland-, as well as storm-water detention pond-sediments, Feammox activity was only detected in acidic soil environments that contain Fe oxides. Using primers we developed for this purpose, Acidimicrobiaceae bacterium A6 was detected in all incubations where Feammox was observed. Anaerobic incubations of Feammox enrichment cultures adjusted to different pH, revealed that the optimal pH for Feammox is 4 ~ 5, and the reaction does not proceed when pH > 7. Feammox was still proceeding at pH as low as 2. In Feammox culture amended with different Fe(III) sources, Feammox reaction proceeded only when Fe oxides (ferrihydrite or goethite ) were supplied, whereas samples incubated with ferric chloride or ferric citrate showed no measurable NH4+ oxidation. Furthermore, we have also determined from incubation experiments conducted with a temperature gradient (10 ~ 35?), that the Feammox process was active when the temperature is above 15?, and the optimal temperature is 20?. Incubations of enrichment culture with 79% Feammox bacteria appeared to remove circa 8% more NH4+ at 20ºC than at 35ºC. This is in contrast to anammox, another anaerobic ammonium oxidation pathway, for which optimal NH4+ oxidation is at temperatures ~ 30ºC. Hence, a Feammox-based process is an attractive candidate for wastewater treatment that could result in further energy savings, by requiring no aeration or heating of the wastewater in temperate climates.

  17. Elucidating the Role of the Proximal Cysteine Hydrogen Bonding Network in Ferric Cytochrome P450cam and corresponding mutants using Magnetic Circular Dichroism Spectroscopy†

    PubMed Central

    Galinato, Mary Grace I.; Spolitak, Tatyana; Ballou, David P.; Lehnert, Nicolai

    2011-01-01

    Although there has been extensive research on various Cytochrome P450s, especially Cyt P450cam, there is much to be learned about the mechanism of how its functional unit, a heme b ligated by an axial cysteine, is finely tuned for catalysis by its second coordination sphere. Here we study how the hydrogen bonding network affects the proximal cysteine and the Fe-S(Cys) bond in ferric Cyt P450cam. This is accomplished using low-temperature magnetic circular dichroism (MCD) spectroscopy on wild-type (wt) Cyt P450cam, and on the mutants Q360P (pure ferric high-spin at low temperature) and L358P with which the “Cys pocket” has been altered (by removing amino acids involved in the hydrogen bonding network), and Y96W (pure ferric low-spin). The MCD spectrum of Q360P reveals fourteen electronic transitions between 15200 and 31050 cm-1. Variable-temperature variable-field (VTVH) saturation curves were used to determine the polarizations of these electronic transitions, with respect to in-plane (xy) and out-of-plane (z) polarization relative to the heme. The polarizations, oscillator strengths, and TD-DFT calculations were then used to assign the observed electronic transitions. In the lower energy region, prominent bands at 15909 and 16919 cm-1 correspond to porphyrin (P) ? Fe charge transfer (CT) transitions. The band at 17881 cm-1 has distinct sulfur S(?)? Fe CT contributions. The Q band is observed as a pseudo A-term (derivative shape) at 18604 and 19539 cm-1. In the case of the Soret band, the negative component of the expected pseudo A-term is split into two features due to mixing with another ? ? ?* and potentially a P ? Fe CT excited state. These features are observed at 23731, 24859, and 25618 cm-1. Most importantly, the broad, prominent band at 28570 cm-1 is assigned to the S(?)? Fe CT transition, whose intensity is generated through a multitude of CT transitions with strong iron character. For wt, Q360P, and L358P, this band occurs at 28724, 28570, and 28620 cm-1, respectively. The small shift of this feature upon altering the hydrogen bonds to the proximal cysteine indicates that the role of the Cys pocket is not primarily for electronic fine tuning of the sulfur donor strength, but is more for stabilizing the proximal thiolate against external reactants (NO, O2, H3O+), and for properly positioning cysteine to coordinate to the iron center. This aspect is discussed in detail. PMID:21158478

  18. Synthesis and interfacing of biocompatible iron oxide nanoparticles through the ferroxidase activity of Helicobacter Pylori ferritin.

    PubMed

    Lee, I-Liang; Li, Pei-Shan; Yu, Wei-Lin; Shen, Hsin-Hsin

    2012-12-01

    Ferritin is an iron storage protein that is often used to coat metallic nanoparticles, such as iron oxide nanoparticles (IONPs). However, the synthesis and biocompatibility of ferritin-coated IONPs remain unclear. Therefore, this study reports the synthesis of a ferritin gene cloned and expressed from Helicobacter pylori (HPFn). The ferroxidase activity of the synthase HPFn was used for the de novo synthesis of HPFn-coated IONPs under mild conditions. Gel filtration chromatography and transmission electron microscopy analyses demonstrated that the core-shell structure of both the 5.0 nm IONP nanocore and the 12.4 nm HPFn shell were correctly assembled. The cellular uptake of mouse macrophage cells (RAW 264.7 cells) has shown that only a few HPFn-coated IONPs (3%) were taken up after 24 h of incubation. This study compares the biocompatibility of HPFn-coated IONPs, superparamagnetic iron oxide nanoparticles (SPIOs) and ferric salt (ferric ammonium citrate) in respect to cell growth inhibition, reactive oxygen species generation and pro-inflammatory cytokine TNF-? release. Assessment results showed that the responses elicited by HPFn-coated IONPs were similar to those elicited by SPIO treatment but milder than those elicited by ferric salt treatment. This accounts for the notion that ferritin-coated IONPs are biocompatible iron agents. These findings show that the ferroxidase activity of ferritin can be used to synthesize biocompatible IONPs. The favorable properties of HPFn-coated IONPs suggest that they can be used as a non-macrophage contrast agent through further surface conjugation. PMID:23013844

  19. Microbially catalyzed nitrate-dependent oxidation of biogenic solid-phase Fe(II) compounds.

    PubMed

    Weber, K A; Picardal, F W; Roden, E E

    2001-04-15

    The potential for microbially catalyzed NO3(-)-dependent oxidation of solid-phase Fe(II) compounds was examined using a previously described autotrophic, denitrifying, Fe(II)-oxidizing enrichment culture. The following solid-phase Fe(II)-bearing minerals were considered: microbially reduced synthetic goethite, two different end products of microbially hydrous ferric oxide (HFO) reduction (biogenic Fe3O4 and biogenic FeCO3), chemically precipitated FeCO3, and two microbially reduced iron(III) oxide-rich subsoils. The microbially reduced goethite, subsoils, and chemically precipitated FeCO3 were subject to rapid NO3(-)-dependent Fe(II) oxidation. Significant oxidation of biogenic Fe3O4 was observed. Very little biogenic FeCO3 was oxidized. No reduction of NO3- or oxidation of Fe(II) occurred in pasteurized cultures. The molar ratio of NO3- reduced to Fe(II) oxidized in cultures containing chemically precipitated FeCO3, and one of the microbially reduced subsoils approximated the theoretical stoichiometry of 0.2:1. However, molar ratios obtained for oxidation of microbially reduced goethite, the other subsoil, and the HFO reduction end products did not agree with this theoretical value. These discrepancies may be related to heterotrophic NO3- reduction coupled to oxidation of dead Fe(III)-reducing bacterial biomass. Our findings demonstrate that microbally catalyzed NO3(-)-dependent Fe(II) oxidation has the potential to significantly accelerate the oxidation of solid-phase Fe(II) compounds by oxidized N species. This process could have an important influence on the migration of contaminant metals and radionuclides in subsurface environments. PMID:11329715

  20. Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals

    USGS Publications Warehouse

    Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

    2009-01-01

    Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.