Direct photo-oxidation of methane to methanol over a mono-iron hydroxyl site
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Controlled Solidification of Liquids Within the SFC Primary Phase Field of the “Fe{sub 2}O{sub 3}”-CaO-SiO{sub 2} System in Air
To provide fundamental information on the phases and microstructures formed during sintering, a liquid with a bulk composition within the silico ferrite of calcium (SFC) primary phase field in the ternary “Fe{sub 2}O{sub 3}”-CaO-SiO{sub 2} system in air was solidified at a controlled rate. Samples of a bulk composition with a CaO/SiO{sub 2} ratio of 4.00 and 69.24 wt pct Fe{sub 2}O{sub 3}, were cooled from 1623 K (1350 °C) at 2 K/s, with samples quenched at temperatures between 1513 K (1240 °C) to 1453 K (1180 °C). The silico ferrite of calcium and aluminium I (SFCA-I) and Ca{sub 7.2}Fe{sub 0.8}{sup 2+}Fe{sub 30}{sup 3+}O{sub 53} phases were observed to form an intergrowth (‘SFC-I’) rather than the anticipated SFC phase. Solidification was found to occur in three stages, Liquid + ‘SFC-I’, Liquid + ‘SFC-I’ + C{sub 2}S + CF{sub 2}, and C{sub 2}S + CF{sub 2} + CF, where C{sub 2}S denotes dicalcium silicate, CF denotes calcium ferrite and CF{sub 2} denotes calcium diferrite. The phases formed and the solidification sequence differ from those predicted under equilibrium and Scheil–Gulliver Cooling. Although not directly applicable to industrial operations, this research clearly shows that the formation of both the SFCA and SFCA-I phase in iron ore sinters is controlled by kinetic processes rather than equilibrium conditions.
36 MATERIALS SCIENCE↗
Research on mechanisms of alloy strengthening 1 - Alloy strengthening by fine oxide particle dispersion. 2 - The splat cooling process for alloy development Semiannual report
Iron alloy strengthening by fine beryllium oxide particle dispersion, and fracture and tensile deformation of dispersioned strengthened alloys
Grant, N. J.↗
Reactive Fe anode for electrolytic reduction of solid metal oxide in molten LiCl-Li 2 O
Iron metal was investigated for use as a consumable anode for electrolytic reduction of solid metal oxides in molten LiCl-Li 2 O (2.0 - 2.4 wt%). Tests were performed where the potential of Fe anodes was increased incrementally from 0.1 to 1.0 V (vs Ni/NiO). Oxide formation on the anode started at a potential of 0.4 V and was identified as FeO via X-ray diffraction. In the absence of a pre-formed oxide layer, severe attack of the anode started at a potential of 0.7 V and was accompanied by an increase in Fe concentration in the salt. When an oxide layer was allowed to form on the anode, the Fe concentration did not increase in the salt. O 2 was detected in the headspace gas at an anode potential of 1.0 V only when an oxide layer was present on the anode. Finally, the results of this study support the idea that an inexpensive sacrificial anode could be an ideal replacement for expensive Pt that is currently widely used for this process.
36 MATERIALS SCIENCE↗
Ultraviolet Photooxidation of Smectite-Bound Fe(II) and Implications for the Origin of Martian Nontronites
Clay minerals detected with orbital and in situ instruments in ancient Martian terrains constrain Mars' climate and aqueous alteration history. Early in its history, Mars experienced an atmospheric redox change and iron-bearing clay minerals may preserve the effects of that transition. Ferrous smectites, the thermodynamically predicted product of chemical weathering of basalts under anoxic conditions, may have undergone oxidation by exposure to chemical oxidants in the atmosphere or regolith, or by direct photooxidation at the surface. To assess these potential oxidation pathways, ferrous trioctahedral smectites of varying initial iron content were synthesized and subjected to oxidation by ultraviolet (UV) irradiation. Experimental UV irradiation under an anoxic atmosphere equivalent to approximately 7 years of flux on the Martian surface caused partial oxidation of smectite-bound Fe (Fe 3+ /ΣFe = 16–18%) and octahedral sheet contraction. Metal-OH vibrational bands in visible/near infrared (VNIR) reflectance spectra of oxidized smectites changed in band depth and asymmetry with higher iron content. X-ray diffraction patterns of UV irradiated samples indicate the formation of a mixed di- and trioctahedral smectite or a secondary nontronite phase, possibly on the surfaces of higher iron content smectites. Furthermore, these experiments suggest that UV irradiation is able to oxidize structurally bound iron in smectites without the presence of other chemical oxidants. Photooxidation may have influenced the mineralogy, both syndepositionally and postdepositionally, of Martian alteration assemblages formed near the surface and this process needs not be limited to one part of their formation history.
58 GEOSCIENCES↗
Electrolytic Coagulant Generation for Treating Flowback and Produced Water for Reuse
This research investigated a novel electrochemical process for producing a ferric iron coagulant for use in treating flowback and produced water (FPW) from hydraulic fracturing and oil production operations. The electrolytic coagulant generation (ECG) system uses an electrochemical cell to produce acid and base from oilfield brine solutions. The acid is used to dissolve scrap iron to provide a Fe 3+ coagulating agent, and the base is used to neutralize the treated water. The costs for generating the ferric iron coagulant were determined as a function of current density and feed water salinity. The process was shown to be effective for removing colloidal bentonite particles from brine solutions. Here, the process has several advantages over conventional electrocoagulation using iron anodes, including: the ability to treat anoxic waters, elimination of electrode fouling, lower cost for the coagulant, and the ability to deliver Fe 3+ doses greater than 1 mM, since it is not limited by the amount of dissolved oxygen required to oxidize ferrous to ferric iron.
54 ENVIRONMENTAL SCIENCES↗
Evaluation of Tribocharged Electrostatic Beneficiation of Lunar Simulant in Lunar Gravity
The lunar regolith has high concentrations of aluminum, silicon, calcium, iron, sodium, and titanium oxides. Liberation of these metals would provide necessary materials for structural and building material fabrication, spare part, machine and tool production, and construction and site preparation in-situ on the moon or other extraterrestrial body (Rao et al 1979). Ilmenite (FeTi03) is a mineral of interest on the moon as a source of iron, titanium, and oxygen (Cameron 1992, Zhao and Shadman 1993) and therefore enrichment of this mineral in the feedstock before processing would be a considerable advantage in reducing energy requirements to process regolith. Not only for construction materials, but shipping oxygen and water from earth is weight prohibitive, and so investigations into the potential production of oxygen from the oxides of lunar regolith are a major research initiative by NASA (Sibille et al. 2009, Moscatello et al. 2009). In this paper, the results of electrostatic beneficiation of two sets of lunar simulants on two different reduced gravity flight series are presented.
Quinn, Jacqueline W.↗
Kinetic Studies of Iron Deposition Catalyzed by Recombinant Human Liver Heavy, and Light Ferritins and Azotobacter Vinelandii Bacterioferritin Using O2 and H2O2 as Oxidants
The discrepancy between predicted and measured H2O2 formation during iron deposition with recombinant heavy human liver ferritin (rHF) was attributed to reaction with the iron protein complex [Biochemistry 40 (2001) 10832-10838]. This proposal was examined by stopped-flow kinetic studies and analysis for H2O2 production using (1) rHF, and Azotobacter vinelandii bacterial ferritin (AvBF), each containing 24 identical subunits with ferroxidase centers; (2) site-altered rHF mutants with functional and dysfunctional ferroxidase centers; and (3) rccombinant human liver light ferritin (rLF), containing 110 ferroxidase center. For rHF, nearly identical pseudo-first-order rate constants of 0.18 per second at pH 7.5 were measured for Fe(2+) oxidation by both O2 and H2O2, but for rLF, the rate with O2 was 200-fold slower than that for H2O2 (k-0.22 per second). A Fe(2+)/O2 stoichiometry near 2.4 was measured for rHF and its site altered forms, suggesting formation of H2O2. Direct measurements revealed no H2O2 free in solution 0.5-10 min after all Fe(2+) was oxidized at pH 6.5 or 7.5. These results are consistent with initial H2O2 formation, which rapidly reacts in a secondary reaction with unidentified solution components. Using measured rate constants for rHF, simulations showed that steady-state H2O2 concentrations peaked at 14 pM at approx. 600 ms and decreased to zero at 10-30 s. rLF did not produce measurable H2O2 but apparently conducted the secondary reaction with H2O2. Fe(2+)/O2 values of 4.0 were measured for AvBF. Stopped-flow measurements with AvBF showed that both H2O2 and O2 react at the same rate (k=0.34 per second), that is faster than the reactions with rHF. Simulations suggest that AvBF reduces O2 directly to H2O without intermediate H2O2 formation.
Bunker, Jared↗
Cationic Effect of Ferrous Ions on Sulfide Capacity of CaO-Fe{sub t}O-Al{sub 2}O{sub 3}-SiO{sub 2} Slag System
The cationic effect of ferrous ions on the sulfide capacity of CaO-Fe{sub t}O-Al{sub 2}O{sub 3}-SiO{sub 2} slags was studied from the viewpoint of the ionic structure in the slag using micro-Raman spectroscopy. In the cation-excess region (M{sup 2+}/2(Fe{sup 3+} + Al{sup 3+}) > 1.0), the sulfide capacity was directly proportional to the basicity of the slags, owing to the S{sup 2−} stabilizing effect of excess cations. However, in the cation-deficient region (M{sup 2+}/2(Fe{sup 3+} + Al{sup 3+}) < 1.0), the sulfide capacity was independent of the basicity of the slags owing to the deficiency of cations required for charge compensation with Al{sup 3+} and Fe{sup 3+}. The cation-substitution effect on the sulfide capacity of the CaO-rich slags (Fe{sub t}O/(Fe{sub t}O + CaO < 0.5) exhibited a linear relationship with the Fe{sup 2+} content because Fe{sup 2+} had a stronger affinity with S{sup 2−} compared to that with Ca{sup 2+}. However, in the Fe{sub t}O-rich slags (Fe{sub t}O/(Fe{sub t}O + CaO > 0.5), the sulfide capacity decreased with the increase of the Fe{sup 2+} content owing to the Q{sup n} unit affinity of the Fe{sup 2+} ion. The sulfide capacity was determined by the competition between the Q{sup n} unit affinity and stability of the S{sup 2−} ion, depending on the type of cation. Therefore, the partial covalent bonding between the M{sup 2+} cations (M: Ca, Fe) and aluminosilicate affected the ionic interactions with the S{sup 2−} ions.
36 MATERIALS SCIENCE↗
Comparison of the earliest NC and CC planetesimals: Evidence from ungrouped iron meteorites
Isotope anomalies in meteorites reveal a fundamental dichotomy between Non-Carbonaceous- (NC) and Carbonaceous-type (CC) planetary bodies. Until now, this dichotomy is established for the major meteorite groups, representing about 36 distinct parent bodies. Ungrouped meteorites represent an even larger number of additional parent bodies, but whether they conform to the overall NC-CC dichotomy is unknown. Here, the genetics and chronology of 26 ungrouped iron meteorites are considered through nucleosynthetic Mo and radiogenic W isotopic compositions. Secondary cosmic ray-induced modifications of these isotope compositions are corrected using Pt isotope measurements on the same samples. We find that all of the ungrouped irons have Mo isotope anomalies within the range of the major meteorite groups and confirm the NC-CC dichotomy for Mo, where NC and CC meteorites define two distinct, subparallel s-process mixing lines. All ungrouped NC irons fall on the NC-line, which is now precisely defined for 41 distinct parent bodies. The ungrouped CC irons show scatter around the CC-line indicative of small r-process Mo heterogeneities among these samples. These r-process Mo isotope variations correlate with O isotope anomalies, most likely reflecting mixing of CI chondrite-like matrix, chondrule precursors, and Ca-Al-rich inclusions. This implies that CC iron meteorite parent bodies accreted the same nebular components as the later-formed carbonaceous chondrites. The Hf-W model ages of core formation for the ungrouped irons overlap with those of the iron meteorite groups from each reservoir and reveal a narrow age peak at ∼3.3 Ma after Ca-Al-rich inclusions for the CC irons. By contrast, the NC irons display more variable ages, including younger ages indicative of impact-induced melting events, which seem absent among the CC irons. This is attributed to the more fragile and porous nature of the CC bodies, making impact-induced melting on their surfaces difficult. The chemical characteristics of all iron meteorites together reveal slightly more oxidizing conditions during core formation for CC compared to NC irons. More strikingly, strong depletions in moderately volatile elements, typical of many iron meteorite parent bodies, predominantly occur among CC irons, for reasons that remain unclear at present.
Chondrite components↗
Moessbauer spectrometer for mineralogical analysis of the Mars surface: Moessbauer source considerations
Development of space rocketry and cosmic instrument making has made it possible to create interplanetary stations to be sent to the solar system bodies. In the last decade of the century the planet Mars will be in the focus of planetary science problems. Russia, USA (the NASA) and Europe (the ESA) plan to do a new step in the study of the planetary system by spacecraft missions to Mars. One part of the programs of these missions is Martian surface measurements of iron, which is a dominant element in both the Martian soil and rocks (about 13 percent by weight). The chemistry of iron in space is strongly coupled to the chemistry of abundant elements (to begin with hydrogen, carbon, oxygen) and it is this coupling of chemical cycles of abundant elements that gives us the possibility of understanding some features of the chemical evolution of matter. In this connection of extremely great importance for the understanding of the evolution of the solar system are the oxidation state of the iron and its mineral composition of the Mars surface. Being highly successful, the Viking landers had no instrumentation to answer these questions. Such instrumentation has to be specifically sensitive to mineralogy. For this purpose the back scattering Moessbauer spectrometer (MS-96) was proposed to be installed on a rover to be launched on board the Russian spacecraft Mars-96 mission to Mars. Due to power and mass restrictions three systems of the device MS-96 (velocity transducer, detector and electronic components) have been extremely miniaturized in comparison to a standard system. In this paper we intend to place for consideration a radioactive source to find out what characteristics it should have to be suitable for purposes of the experiment.
Evlanov, E. N.↗
Friction and Wear of Iron in Corrosive Media
Friction and wear experiments were conducted with elemental iron exposed to various corrosive media including two acids, base, and a salt. Studies involved various concentrations of nitric and sulfuric acids, sodium hydroxide, and sodium chloride. Load and reciprocating sliding speed were kept constant. With the base NaOH an increase in normality beyond 0.01 N resulted in a decrease in both friction and wear. X-ray photoelectron spectroscopy (XPS) analysis of the surface showed a decreasing concentration of ferric oxide (Fe2O3) on the iron surface with increasing NaOH concentration. With nitric acid (HNO3) friction decreased in solutions to 0.05 N, beyond which no further change in friction was observed. The concentration of Fe2O3 on the surface continued to increase with increasing normality. XPS analysis revealed the presence of sulfates in addition of Fe2O3 on surfaces exposed to sulfuric acid and iron chlorides but no sodium on surfaces exposed to NaCl.
Rengstorff, G. W. P.↗
Prebiotic Polymer Synthesis and the Origin of Glycolytic Metabolism
Our research resulted in several discoveries which contributed to understanding the origin and operation of life. (1) Most importantly, we discovered a new pathway of prebiotic amino acid synthesis in which formaldehyde and glycolaldehyde (formose reaction substrates) react with ammonia to give alanine and homoserine in the presence of thiol catalysts. The thiol-dependent synthesis of amino acids undoubtedly occurs via amino acid thioester intermediates capable of forming peptides. This 'one-pot' reaction system operates under mild aqueous conditions, and like modern amino acid biosynthesis, uses sugar intermediates which are converted to amino acids by energy-yielding redox disproportionation. Preliminary evidence suggests that this type of process can be "evolved" by a serial transfer methods that lead to enrichment of autocatalytic molecules. (2) We established that prebiotic peptide polymers can be made by condensation of amino acid thioesters (homocysteine thiolactone and S-(N-beta-orotidyl- diaminopropionic acid) ethanethiol), and that prebiotic polydisulfide polymers can be generated by oxidation of dithiols with iron(III) in minerals. (3) In our analysis of metabolism we discovered the primary energy source of biosynthesis -- chemical energy made available by the redox disproportionation of substrate carbon groups. We concluded that the energy and reactivity of sugars make them the optimal substrate for the origin and operation of terrestrial (or extraterrestrial) life. (4) Since it is likely that the use of optimal sugar substrates in biosynthesis sets the average oxidation number of functional biocarbon throughout the Universe near 0.0 (the reduction level of formaldehyde), we proposed that a line(s) in the microwave spectrum of formaldehyde could be rationally selected as a frequency for interstellar communication that symbolizes life. (5) Finally, in preparation for the analysis of Martian meteorite samples, we upgraded our HPLC system to one femtomole sensitivity, and developed a new electrophoretic method of sample preparation for HPLC analysis of the meteoritic amino acids. In a sample of the KT boundary layer from Sussex Wyoming, we found about 300 picomoles per gram of meteoritic alpha-aminoisobutyric acid per gram of KT layer.
Weber, Arthur L.↗
Role of the Oxide Support on the Structural and Chemical Evolution of Fe Catalysts during the Hydrogenation of CO 2
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia
Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.
NASA Program Exobiology↗
Garnet crystallization does not drive oxidation at arcs
Arc magmas, the building blocks of continental crust, are depleted in total iron (Fe), have higher ratios of oxidized Fe to total Fe (Fe 3+ /∑Fe), and record higher oxygen fugacities ( f O 2 ’s) compared with magmas erupted at mid-ocean ridges. Garnet crystallization could explain these observations if garnet removes substantial amounts of Fe 2+ , but not Fe 3+ , from magma, yet this model for continental crust generation has never been tested experimentally. Analysis of garnets and melts in laboratory experiments show that the compatibilities of Fe 2+ and Fe 3+ in garnet are of similar magnitudes. Our results indicate that fractional crystallization of garnet-bearing cumulates will remove 22 % of total Fe from primary arc basalts but negligibly alter the Fe 3+ /∑Fe ratio and f O 2 of the melt. Garnet crystallization is unlikely to be responsible for the relatively oxidized nature of basaltic arc magmas or the Fe-depletion trend observed in continental crust.
Science & Technology - Other Topics↗
Comparing the reaction profiles of single iron catalytic sites in enzymes and in reticular frameworks for methane-to-methanol oxidation
The design of synthetic inorganic catalysts mimicking the first coordination spheres of enzymatic cofactors often results in lower yields and selectivity than their biological counterparts. In this study, we exploit Kohn-Sham density functional methods to compare the reaction profiles of four single iron-based catalysts for the direct oxidation of methane to methanol: two biomimetic models based on two enzymes (cytochrome P450 and taurine dioxygenase [TauD]) and two synthetic reticular frameworks (iron-BEA zeolite and tri-iron oxo-center-based metal-organic framework). Both the biomimetic and inorganic catalysts show almost zero selectivity toward methanol for methane conversions >1% at ambient temperature. Furthermore, this study highlights that iron’s first coordination shell can influence selectivity toward methanol but to a limited extent. In the absence of methanol protection strategies, high selectivity can be reached only by mimicking the reaction microenvironment of enzymes beyond the first coordination shell of iron.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Development of rapidly solidified oxidation resistant alloys
The development of iron-base alloys that contain low concentrations of expensive and/or strategic metals, but that are very resistant to oxidation at elevated tempratures was investigated. Rapid solidification processing was employed to make alloys that are uniform in composition, that comprise very fine grains 10 microns and that contain a uniform dispersion of very fine ( 0.5 microns) nonmetallic inclusions. Each of these factors contribute to the oxidation behavior of alloys. The compositional and processing variables that yield the optimum oxidation resistance are described.
Yurek, G. J.↗