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At least 361 records · Page 20

Microbial Sulfate Reduction Measured by an Automated Electrical Impedance Technique

Electrical impedance measurements are used to investigate the rates of sulfate reduction by pure cultures of and sediments containing sulfur-reducing bacteria. Changes in the electrical impedance ratios of pure cultures of Desulfovibrio aestuarii and samples of reduced sediments from San Francisco Bay were measured by a Bactometer 32, and sulfate reduction was followed by measuring the incorporation of (S-35) sulfate into metal sulfides. The growth of the bacteria in pure culture is found to result in an increase of 0.2200 in the impedance ratio within 24 h, accompanied by increases in protein, ATP, sulfide and absorptance at 660 nm, all of which are inhibited by the addition of molybdate. Similar responses were observed in the sediments, although impedance ratio responses were not completely inhibited upon the addition of molybdate, due to the presence of nonsulfate-respiring microorganisms. Experiments conducted with sterile media and autoclaved sediments indicate that the presence of H2S together with iron is responsible for the impedance effect, and sulfate reduction rates ranging between 0.85 and 1.78 mmol/l per day are estimated for the sediments by the impedance technique.

Oremland, R. S.↗

Spectroscopy and crystallography define carotenoid oxygenases as a new subclass of mononuclear non-heme Fe II enzymes

Carotenoid cleavage dioxygenases (CCDs) are non-heme Fe II enzymes that catalyze the oxidative cleavage of alkene bonds in carotenoids, stilbenoids, and related compounds. How these enzymes control the reaction of dioxygen (O 2 ) with their alkene substrates is unclear. Here, we apply spectroscopy in conjunction with X-ray crystallography to define the iron coordination geometry of a model CCD, CAO1 (Neurospora crassa carotenoid oxygenase 1), in its resting state and following substrate binding and coordination sphere substitutions. Resting CAO1 exhibits a five-coordinate (5C), square pyramidal Fe II center that undergoes steric distortion toward a trigonal bipyramidal geometry in the presence of piceatannol. Titrations with the O 2 -analog, nitric oxide, show a >100-fold increase in iron–nitric oxide affinity upon substrate binding, defining a crucial role for the substrate in activating the Fe II site for O 2 reactivity. The importance of the 5C Fe II structure for reactivity was probed through mutagenesis of the second-sphere Thr151 residue of CAO1, which occludes ligand binding at the sixth coordination position. A T151G substitution resulted in the conversion of the iron center to a six-coordinate state and a 135-fold reduction in apparent catalytic efficiency toward piceatannol compared with the wildtype enzyme. Substrate complexation resulted in partial six-coordinate to 5C conversion, indicating solvent dissociation from the iron center. Additional substitutions at this site demonstrated a general functional importance of the occluding residue within the CCD superfamily. Taken together, these data suggest an ordered mechanism of CCD catalysis occurring via substrate-promoted solvent replacement by O 2 . CCDs thus represent a new class of mononuclear non-heme Fe II enzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observations of Two Non-Standard Grain Components

We discuss evidence for two non-standard grain components: small conglomerates and astronomical iron. The small conglomerates are small, temperature fluctuating grains made up of loosely bound 12 micron emitters (either PAH's or dielectrics). When these grains are exposed to strong UV radiation fields they break apart into smaller pieces. For high UV radiation regimes, such as H II regions, conglomerate grains best explain the reduction of 25 micron emission relative to 12 micron. Astronomical iron was originally proposed for isolated cirrus clouds in order to account for the strength of the 60 micron emission. Within the diffuse ISM, these grains emit at a relatively high equilibrium temperature of 50 K. Our analysis of IRAS data shows the presence of a strong 60 micron emitter in the Lambda Orionis H II region and a component within the Rosette Nebula emitting primarily at 25 micron. Both of these observations can be accommodated by the presence of iron grains within the H II regions.

Shipman, R. F.↗

Vapor-Phase Fabrication and Condensed-Phase Application of a MOF-Node-Supported Iron Thiolate Photocatalyst for Nitrate Conversion to Ammonium

Herein we describe a method for synthesizing a nitrate reduction catalyst within a metal organic framework (MOF). The MOF NU-1000, a zirconium-based mesoporous material, is exposed by using atomic layer deposition (ALD) to a vaporous iron amidinate coordination complex and subsequently a dodecanethiol ligand to synthesize an iron thiolate cluster grafted on the zirconium oxide nodes. Structural identification of the cluster is conducted through X-ray absorption spectroscopy (XAS) and differential envelope density (DED) analyses. Once submerged in an aqueous solution containing nitrate (30 ppm of N) and irradiated with light, the MOF/iron thiolate cluster assembly can photochemically transform the nitrate to ammonium ions. We suggest that sequential, self-limiting, atomic (metal ion), and molecular (ligand) deposition onto the reactive nodes of chemically and thermally stable MOFs could prove to be a versatile and attractive method for obtaining nature-inspired chemical catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Red blood cell and iron metabolism during space flight

Space flight anemia is a widely recognized phenomenon in astronauts. Reduction in circulating red blood cells and plasma volume results in a 10% to 15% decrement in circulatory volume. This effect appears to be a normal physiologic adaptation to weightlessness and results from the removal of newly released blood cells from the circulation. Iron availability increases, and (in the few subjects studied) iron stores increase during long-duration space flight. The consequences of these changes are not fully understood.

STS Shuttle Project↗

Spectroscopic Characterization of an Eight‐Iron Nitrogenase Cofactor Precursor that Lacks the “9 th Sulfur”

Abstract Nitrogenases catalyze the reduction of N 2 to NH 4 + at its cofactor site. Designated the M‐cluster, this [MoFe 7 S 9 C( R ‐homocitrate)] cofactor is synthesized via the transformation of a [Fe 4 S 4 ] cluster pair into an [Fe 8 S 9 C] precursor (designated the L‐cluster) prior to insertion of Mo and homocitrate. We report the characterization of an eight‐iron cofactor precursor (designated the L*‐cluster), which is proposed to have the composition [Fe 8 S 8 C] and lack the “9 th sulfur” in the belt region of the L‐cluster. Our X‐ray absorption and electron spin echo envelope modulation (ESEEM) analyses strongly suggest that the L*‐cluster represents a structural homologue to the l ‐cluster except for the missing belt sulfur. The absence of a belt sulfur from the L*‐cluster may prove beneficial for labeling the catalytically important belt region, which could in turn facilitate investigations into the reaction mechanism of nitrogenases.

Jasniewski, Andrew J.↗

Nonbiological fractionation of iron isotopes

Laboratory experiments demonstrate that iron isotopes can be chemically fractionated in the absence of biology. Isotopic variations comparable to those seen during microbially mediated reduction of ferrihydrite are observed. Fractionation may occur in aqueous solution during equilibration between inorganic iron complexes. These findings provide insight into the mechanisms of iron isotope fractionation and suggest that nonbiological processes may contribute to iron isotope variations observed in sediments.

NASA Discipline Exobiology↗

Development of molecular cluster models to probe pyrite surface reactivity

Abstract The recent discovery that anaerobic methanogens can reductively dissolve pyrite and utilize dissolution products as a source of iron and sulfur to meet their biosynthetic demands for these elements prompted the development of atomic‐scale nanoparticle models, as maquettes of reactive surface sites, for describing the fundamental redox steps that take place at the mineral surface during reduction. The given report describes our computational approach for modeling n (FeS 2 ) nanoparticles originated from mineral bulk structure. These maquettes contain a comprehensive set of coordinatively unsaturated Fe (II) sites that are connected via a range of persulfide (S 2 2− ) ligation. In addition to the specific maquettes with n = 8, 18, and 32 FeS 2 units, we established guidelines for obtaining low‐energy structures by considering the pattern of ionic, covalent, and magnetic interactions among the metal and ligand sites. The developed models serve as computational nano‐reactors that can be used to describe the reductive dissolution mechanism of pyrite to better understand the reactive sites on the mineral, where microbial extracellular electron‐transfer reactions can occur.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of a possible solar-wind darkening of the lunar surface by photoelectron spectroscopy.

Detailed sequential study by photoelectron spectroscopy of the change in valence states of iron in Fe2O3, Fe3O4, FeO, and Fe foil samples, showing that chemical reduction does take place on the sample surface when argon ion bombardment occurs. These spectra give evidence that, after prolonged ion bombardment, the surface of all four samples consisted predominantly of iron in the metallic state. Argon ion sputtering of 15 silicate and oxide samples under similar experimental conditions produced surface darkening only in samples containing iron. Monitoring of the photoelectron peak of carbon during the experiment indicates that ion-bombardment darkening is not due to the buildup of hydrocarbon surface contaminants in the oil-free high-vacuum system used by the authors. On the basis of these studies, it is concluded that solar-wind bombardment should be included as one of the possible mechanisms for producing darkening of the lunar surface.

Yin, L. I.↗

Phonon dispersion throughout the iron spin crossover in ferropericlase

Ferropericlase (Fp), (Mg 1– x Fex)O, is the second most abundant phase in the Earth's lower mantle. At relevant pressure-temperature conditions, iron in Fp undergoes a high spin (HS), $\textit{S}$ = 2, to low spin (LS), $\textit{S}$ = 0, state change. The nature of this phenomenon is quite well understood now, but there are still basic questions regarding the structural stability and the existence of soft phonon modes during this iron state change. General theories exist to explain the volume reduction, the significant thermoelastic anomalies, and the broad nature of this HS-LS crossover. These theories make extensive use of the quasiharmonic approximation. Therefore, dynamical and structural stability is essential to their validity. Here, we investigate the vibrational spectrum of Fp throughout this spin crossover using ab initio density-functional theory $+U_{sc}$ calculations. We address vibrational modes associated with isolated and (second-)nearest-neighbor iron ions undergoing the HS-LS state change. As expected, acoustic modes of this solid solution are resilient, while optical modes are the most affected. In this work, we show that there are no soft phonon modes across this HS-LS crossover, and Fp is dynamically stable at all relevant pressures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Small, Untethered, Mobile Robots for Inspecting Gas Pipes

Small, untethered mobile robots denoted gas-pipe explorers (GPEXs) have been proposed for inspecting the interiors of pipes used in the local distribution natural gas. The United States has network of gas-distribution pipes with a total length of approximately 109 m. These pipes are often made of iron and steel and some are more than 100 years old. As this network ages, there is a need to locate weaknesses that necessitate repair and/or preventive maintenance. The most common weaknesses are leaks and reductions in thickness, which are caused mostly by chemical reactions between the iron in the pipes and various substances in soil and groundwater. At present, mobile robots called pigs are used to inspect and clean the interiors of gas-transmission pipelines. Some carry magnetic-flux-leakage (MFL) sensors for measuring average wall thicknesses, some capture images, and some measure sizes and physical conditions. The operating ranges of pigs are limited to fairly straight sections of wide transmission- type (as distinguished from distribution- type) pipes: pigs are too large to negotiate such obstacles as bends with radii comparable to or smaller than pipe diameters, intrusions of other pipes at branch connections, and reductions in diameter at valves and meters. The GPEXs would be smaller and would be able to negotiate sharp bends and other obstacles that typically occur in gas-distribution pipes.

Wilcox, Brian↗

Chemical-Biological Cyclic Process for Hexavalent Chromium Reduction to Trivalent Chromium in Aqueous Medium - 20224

Conventional treatment of chromium contamination focuses on immobilization of the highly toxic and water-soluble form Cr(VI), by reducing it to the relatively less toxic and less mobile trivalent form, Cr(III), using reducing compounds like ferrous sulfate or ferrous iron, Fe(II). The Cr(VI) also respond to biodegradation and subsequent reduction. During the reduction reaction, Fe(II) is oxidized to ferric, Fe(III), which, being at the highest oxidation state, has no ability to reduce Cr(VI), and therefore remediation process terminates. The good news is that metal-reducing bacteria, S. oneidensis MR-1, can regenerate Fe(II) from Fe(III) with the help of an organic electron donor in an appropriate bacterial media. Thus, in the Cr(VI) chemical remediation process, Fe(II) to Fe(III) conversion is reversed by the biological process, regenerating Fe(II) and the Cr(VI) chemical reduction process continues in a cyclic fashion. This study presents the results of regeneration of Fe(II) from fresh Fe(III) as well as from the reaction products of Cr(VI) and Fe(II). Both fresh Fe(III) and reaction product Fe(III) exhibited the same reduction behavior. Fe(II) production increased with the increase of initial concentration of Fe(III), resulting in 87.5% Fe(II) regeneration. The extent of Fe(III) reduction (Fe(II)t/Fe(III)0.hour) was 21 times higher than the extent of Cr(VI) reduction (Cr(VI)t/Cr(VI)0.hour) by S. oneidensis MR-1. In a cyclic process of sequential Cr(VI) addition, the amount of Fe(II) regeneration decreased with the increase in cycle number, a fixed quantity of starting S. oneidensis MR-1 could regenerate Fe(II) at least five times in a ten-hour period. More importantly, regenerated Fe(II) instantly reduced Cr(VI) to Cr(III). So, Fe(II) regeneration with metal-reducing bacteria has a good potential for application in groundwater and wastewater remediation in reducing Cr(VI) to Cr(III). As a comparison of chemical to biological transformation, chemical transformation of Cr(VI) by Fe(II) was almost 600 times greater than that of biological transformation. Therefore a chemical-biological cyclic process offers potential applications for remediation of groundwater and hexavalent chromium contaminated waste sites. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Structural and Reactivity Effects of Secondary Metal Doping into Iron-Nitrogen-Carbon Catalysts for Oxygen Electroreduction

While improved activity was recently reported for bimetallic iron-metal-nitrogen-carbon (FeMNC) catalysts for the oxygen reduction reaction (ORR) in acid medium, the nature of active sites and interactions between the two metals are poorly understood. Here, FeSnNC and FeCoNC catalysts were structurally and catalytically compared to their parent FeNC and SnNC catalysts. While CO cryo-chemisorption revealed a twice lower site density of M-N x sites for FeSnNC and FeCoNC relative to FeNC and SnNC, the mass activity of both bimetallic catalysts is 50–100% higher than that of FeNC due to a larger turnover frequency in the bimetallic catalysts. Electron microscopy and X-ray absorption spectroscopy identified the coexistence of Fe-N x and Sn-N x or Co-N x sites, while no evidence was found for binuclear Fe-M-N x sites. 57 Fe Mössbauer spectroscopy revealed that the bimetallic catalysts feature a higher D 1 /D 2 ratio of the spectral signatures assigned to two distinct Fe-N x sites, relative to the FeNC parent catalyst. Furthermore, the addition of the secondary metal favored the formation of D 1 sites, associated with the higher turnover frequency.

36 MATERIALS SCIENCE↗

Texturing and residual stress in metals as a result of sliding

Pole figures of the texturing produced by friction in the alloys Cu - 10 at. % Sn, Cu - 10 at. % Si, 440 C stainless steel, and AISI 52100 bearing steel were obtained with an energy-dispersive X-ray diffractometer. While the texturing behavior of these alloys is generally similar to that of pure metals, the 52100 steel and the Cu5Si phase of Cu - 10 at. % Si show no texturing at the loads and speeds used in this experiment. Photographic methods were used in an attempt to measure the uniform residual stress in the wear tracks produced on some pure metals. The stress in copper and iron was, however, below the limit of detectability - about 4.3 x 10 to the 7th power N/sq m (6000 psi). Line broadening under all test conditions in the case of copper and at high load and speed conditions in iron is attributed, at least in part, to the reduction of crystallite size and, perhaps, to nonuniform residual stress, as well.

Wheeler, D. R.↗

The Redox Flow System for solar photovoltaic energy storage

The interfacing of a Solar Photovoltaic System and a Redox Flow System for storage was workable. The Redox Flow System, which utilizes the oxidation-reduction capability of two redox couples, in this case iron and titanium, for its storage capacity, gave a relatively constant output regardless of solar activity so that a load could be run continually day and night utilizing the sun's energy. One portion of the system was connected to a bank of solar cells to electrochemically charge the solutions, while a separate part of the system was used to electrochemically discharge the stored energy.

Odonnell, P.↗

Workshop on Oxygen in Asteroids and Meteorites

Contents include the following: Constraints on the detection of solar nebula's oxidation state through asteroid observation. Oxidation/Reduction Processes in Primitive Achondrites. Low-Temperature Chemical Processing on Asteroids. On the Formation Location of Asteroids and Meteorites. The Spectral Properties of Angritic Basalts. Correlation Between Chemical and Oxygen Isotopic Compositions in Chondrites. Effect of In-Situ Aqueous Alteration on Thermal Model Heat Budgets. Oxidation-Reduction in Meteorites: The Case of High-Ni Irons. Ureilite Atmospherics: Coming up for Air on a Parent Body. High Temperature Effects Including Oxygen Fugacity, in Pre-Planetary and Planetary Meteorites and Asteroids. Oxygen Isotopic Variation of Asteroidal Materials. High-Temperature Chemical Processing on Asteroids: An Oxygen Isotope Perspective. Oxygen Isotopes and Origin of Opaque Assemblages from the Ningqiang Carbonaceous Chondrite. Water Distribution in the Asteroid Belt. Comparative Planetary Mineralogy: V Systematics in Planetary Pyroxenes and fo 2 Estimates for Basalts from Vesta.

Source record↗

Studying the Iron Line Complex in the Bright Seyfert Galaxy NGC 5506

This grant was to support the reduction and analysis of our approved XMM observation of the nearby Seyfert 2 galaxy NGC 5506. The observation has been carried out simultaneously with a BeppoSAX observation of the same source. The proposal was aimed to study in detail the Compton reflection component and the complex Iron K line of this source, combining the still unique capability of BeppoSAX in hard X-rays (to strongly constrain the reflection component, and then the intrinsic nuclear continuum), and the sensitivity of XMM at the energy of the Iron Line complex. NGC 5506 is one of the brightest AGN in hard X-rays and has been intensively studied in the past. GINGA detected the complex iron line as well as the reflection component. Both ASCA (spectroscopically) and Rossi-XTE (through variability analysis) suggested that the FeK line is complex, possibly made up of several distinct components. The centroid of the FeK complex in a subsequent BeppoSAX observation was bluer than the 6.4 keV energy of the relatively low-ionization iron Kalpha transition. NGC 5506 has been observed simultaneously by NewtonXMM and BeppoSAX on February 2-3 2001. we have reduced and analyzed both the NewtonXMM and the BeppoSAX data, and have written and published a paper on our results (appeared in Volume 377 (page 31) of A&A-Letters). Our main results can be summarized as follows: (a) we confirm that the FeK line is complex, and for the first time disentangle its components: we find that at least two components made up the FeK complex, one neutral and narrow, at 6.4 keV (rest energy), and another one either broader and highly ionized, at about 6.7 keV (rest frame), or, in turn, made up of two narrow and unresolved components from the He-like and the H-like ions of Fe; (b) the two possible solution for the high-ionization Fe-K component, are statistically indistinguishable. However, physically, a blend of two narrow lines from photoionized matter seems to be preferable to emission of a relativistically broadened line from an ionized accretion disk; (c) The bulk of the Compton reflection continuum originates in neutral matter, and is therefore associated with the narrow FeK line at 6.4 keV: they are most likely emitted by distant matter.

Nicastro, Fabrizio↗

Strategies for the Photoreduction of Tc-99 Pertechnetate to Low-Valent Tc by Keggin Polyoxometalates

Technetium-99 (half-life of 2.1 × 10 5 yrs, β max = 0.29 MeV) is a hazardous radiological contaminant, which, in its predominant form of pertechnetate (TcO 4 – ), is highly mobile in the environment. Most strategies for the removal of pertechnetate from the environment involve uptake and/or absorption of pertechnetate using resins, clays, cationic metal-organic frameworks and even thorium borate ceramic like materials. Alternative approaches have involved the reduction and subsequent sequestration of lower valent technetium species using iron, sulfides, or iron sulfides. Here, our lab has explored this strategy using the lacunary alpha-2 Wells–Dawson polyoxometalate (α 2 -[P 2 W 17 O 61 ] 10– ) to both reduce and sequester lower valent technetium, and we have reported on the ligand features that stabilize the reduced species. In this work we investigate the potential of “plenary” Keggin POMs (XW 12 O 40 n – ) (X = P, Si, Al, n = 3, 4, 5, respectively) to both reduce TcO 4 – and stabilize the reduced Tc species. Specifically, we report on the mechanism by which the reduction of technetium occurs and find that PW 12 , SiW 12 , and AlW 12 promote the reduction of TcO 4 – to lower valent states. X-ray absorption spectroscopy was used to confirm a combination of Tc IV {in the form of TcO 2 · 2H 2 O and Tc 2 (µ-O) 2 4+ } and Tc V , which is subsequently complexed into a POM defect as a Tc V =O species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗