Search for the Origin of Hematite at Meridiani Planum and Gusev Crater

NASA Astrophysics Data System (ADS)

Dreibus, G.; Brückner, J.; Jagoutz, E.

2005-05-01

The landscape in Meridiani Planum encountered by the Rover Opportunity is different to all previous Mars landing sites. While those locations look like typical unsorted alluvials, Meridiani Planum consists of sorted sands with aeolian features like small dunes and desert pavements in places. Chemical compositions of soils and rocks at Gusev crater and Meridiani Planum were measured by the Alpha Proton X-Ray Spectrometer (APXS) [1, 2]. At Meridiani Planum all soils and outcrops have a higher mean Fe/Si ratio of 0.75 compared to rocks and soils in Gusev crater with a mean Fe/Si of 0.57. The enrichment of Fe results from an admixture of hematite (Fe2O3) as determined in-situ by the Mössbauer spectrometer (MB) [3]. The formation of hematite is an indicator for aqueous activities under oxidizing conditions. The highest portion of this mineral was found in the spherical grains, also nicknamed `blueberries', which cover most place at the landing site. These spherules were also found in rock exposures in Eagle crater to about 2 % by volume and were interpreted as concretions that formed by precipitation from aqueous fluids inside sedimentary rocks [4]. At Gusev crater no hematite was observed until sol 90 except for layering on a rock. However, about three months later at the foot of the Columbia Hills the MB detected hematite in a rock, dubbed `Pot of Gold'. Our investigations of hematite bearing materials, measured by APXS, MB, and Microscopic Imager (MI) [5], provide an integrated view of different occurrences of hematite on the Martian surface. Ratios of Fe to Mn are compared with Fe concentrations for various soils and outcrops in Meridiani Planum and Gusev crater. Most samples cluster at a mean Fe/Mn ratio of about 50 and range in Fe from 12 to 17 wt. %. Exceptions are found for those Meridiani Planum soils that have very high Fe contents of about 26 wt. %, such as targets dubbed `JackRussell', `FredRipple', and `Berry Bowl full', all showing Fe/Mn ratios of about 110. Based on APXS measurements we cannot distinguish, whether spherules consist of pure hematite or carry a thin layer of hematite. All these high hematite bearing soils are top surface samples, while corresponding subsurface soil samples or soils disturbed by rover wheels have low hematite contents. The very high Fe/Mn ratios of three undisturbed samples together with very high hematite contents suggest the presence of a hematite-rich top layer irrespectively of shape and area coverage of spherules or fragments and could be interpreted as a surface coating similar to terrestrial surface coatings. In the hematite rich outcrops with the same Fe/Mn ratio as found for the soil samples the formation of the main portion of fine dispersed hematite must be an isochemical re-crystallization process under strongly oxidizing conditions. [1] Gellert, R. et al. (2004) Science, 305, 829-832. [2] Rieder, R. et al. (2004) Science, 306, 1746-1749. [3] Klingelhöfer, G. et al. (2004) Science, 306, 1740-1745. [4] Squyres, S, et al. (2004) Science, 306, 1698-1703. [5] Herkenhoff, K. E. et al. (2004) Science, 306, 1727-1730.

VNIR spectral features observed by the Mars Exploration Rover Opportunity in hematite-bearing materials at Meridiani Planum

NASA Astrophysics Data System (ADS)

Farrand, W. H.; Bell, J. F.; Morris, R. V.; Joliff, B. L.; Squyres, S. W.; Souza, P. A.

2004-12-01

The Mars Exploration Rover Opportunity was sent to Meridiani Planum based largely on MGS TES spectroscopic evidence of a large surface exposure of coarse grained gray hematite. The presence of hematite at Meridiani Planum has been confirmed through thermal infrared spectroscopy by the rover's Mini-TES instrument and by in-situ measurements by its Moessbauer (MB) spectrometer. Several types of hematite, as expressed by differences in MB spectral parameters, have been associated with various rocks and soils examined in Eagle crater and on the surrounding plains. The host materials include the small spherules (informally known as "blueberries") littering the floor of Eagle crater and the plains of Meridiani, the outcrop rock itself, specific types of soils, and two measurements on unique rocks in the Shoemaker's Patio area of Eagle crater. At the visible to near infrared (VNIR) wavelengths covered by the rover's multispectral Panoramic camera (Pancam), gray hematite is spectrally neutral. However, multispectral observations by Pancam of some of these hematite-bearing materials show discernable spectral features. Specifically, portions of the outcrop visible in the walls of Eagle crater display a strong 535 nm absorption feature. This feature resembles a similar feature in laboratory spectra of red hematite, but the characteristic 860 nm absorption of red hematite is either absent or is instead replaced by a longer wavelength absorption centered on Pancam's 900 nm channel. The blueberries display a deep and broad absorption centered on 900 nm and as well as an increase in reflectance in the 1009 nm band. The shape of the absorption feature in the blueberries is consistent with that seen in red hematite, but again the band minimum is displaced to a longer wavelength than would be expected for red hematite. The blueberries also lack the prominent absorption at the shortest wavelengths that would be expected of red hematite. The unique hematite-bearing (or coated) rocks at Shoemaker's Patio lack the very strong 535 nm band depth of other portions of the outcrop but still have a stronger 535 nm feature than most of the outcrop. Interestingly, VNIR spectra more consistent with that expected for red hematite have been found in cuttings released by grinding into outcrop by the rover's Rock Abrasion Tool. The cause of the observed spectral features in the portions of outcrop with strong 535 nm band depths and of the reddish rocks in the Shoemaker's Patio area is believed to be attributable either to red hematite mixed with other Fe3+ - bearing phases (such as jarosite and/or schwertmannite) or, at the longer wavelengths, with Fe2+ - bearing phases (such as pyroxenes). Determination of the nature of these iron-bearing materials will further elucidate the geologic, aqueous and diagenetic history of the rocks at Meridiani Planum.

A probable martian analogue in muttom in southern india

NASA Astrophysics Data System (ADS)

Wankhede, Tushar; Rajesh, V. J.; Charri, Abhishek

2012-07-01

Mars, a terrestrial planet fourth from the Sun in the solar system, is widely known as the red planet. The iron oxide sand/dust is predominant on its surface and gives the reddish appearance. Recent explorations have exposed abundance of haematite-rich loose materials in the surface of Mars especially at Meridiani Planum. Sedimentary structures like bedding, cross-bedding, ripple marks, gullies, mud cracks etc. are identified in this area. It is essential to look for some terrestrial analogues for the iron oxide rich sand/dust in order to explore their genetic mechanisms in Martian surface. Red sand beds occur above the crystalline basement or younger calcareous sandstone/limestone as isolated patches of partly indurated or unindurated dunes and sheets fringing the south western coastal lands of Tamil Nadu. Calcretes, source of carbonates, also occur at places within these red sand beds. Muttom soils are dark red in color on fresh surfaces. The red sand beds are dominated by iron-bearing minerals such as hematite and ilmenite. Local patches of heavy mineral deposition by the action of wind and water were also observed in the Muttom area. Preliminary spectral analyses confirmed the presence of iron bearing minerals like hematite and ilmenite which are also present in Mars. Many sedimentary structures like gullies, channels, polygonal mud cracks, erosion pits and dunes were present in Muttom area similar to those observed on Martian surface. Meridiani planum outcrops are composed of some siliciclastics grains, and hematite, and only few deposits on Earth match this description. The siliciclastics grains are primarily quartz grain coated with hematite. Quartz is also found in Muttom which, may have been transported by the action of wind while in the Mars siliciclastics is the alteration product of basalt. The structures are more or less similar to those observed at Meridiani Planum. Previous workers interpreted these red sands as `unique' formed either by a mixed beach and dune environment, or as similar to colluvium (formed by mass wasting and fluvial processes). Comparative studies between the red sand beds formations on Martian surface and southern Tamil Nadu can provide valuable insights on the origin, weathering pattern, tectonics and depositional environment of red sand beds in Mars.

Influence of surface morphology on the immersion mode ice nucleation efficiency of hematite particles

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Hoffmann, N.; Kiselev, A.; Dreyer, A.; Zhang, K.; Kulkarni, G.; Koop, T.; Möhler, O.

2014-03-01

In this paper, the effect of the morphological modification of aerosol particles with respect to heterogeneous ice nucleation is comprehensively investigated for laboratory-generated hematite particles as a model substrate for atmospheric dust particles. The surface-area-scaled ice nucleation efficiencies of monodisperse cubic hematite particles and milled hematite particles were measured with a series of expansion cooling experiments using the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud simulation chamber. Complementary offline characterization of physico-chemical properties of both hematite subsets were also carried out with scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, dynamic light scattering (DLS), and an electro-kinetic particle charge detector to further constrain droplet-freezing measurements of hematite particles. Additionally, an empirical parameterization derived from our laboratory measurements was implemented in the single-column version of the Community Atmospheric Model version 5 (CAM5) to investigate the model sensitivity in simulated ice crystal number concentration on different ice nucleation efficiencies. From an experimental perspective, our results show that the immersion mode ice nucleation efficiency of milled hematite particles is almost an order of magnitude higher at -35.2 °C < T < -33.5 °C than that of the cubic hematite particles, indicating a substantial effect of morphological irregularities on immersion mode freezing. Our modeling results similarly show that the increased droplet-freezing rates of milled hematite particles lead to about one order magnitude higher ice crystal number in the upper troposphere than cubic hematite particles. Overall, our results suggest that the surface irregularities and associated active sites lead to greater ice activation through droplet freezing.

Sorption of organic phosphates and its effects on aggregation of hematite nanoparticles in monovalent and bivalent solutions.

PubMed

Xu, Chen-Yang; Li, Jiu-Yu; Xu, Ren-Kou; Hong, Zhi-Neng

2017-03-01

Sorption of organic phosphates-myo-inositol hexakisphosphate (IHP) and glycerol phosphate (GP) and its effects on the early stage of hematite aggregation kinetics were investigated at different pH and electrolyte composition. KH 2 PO 4 (KP) was taken as an inorganic P source for comparison. Results indicated that for all types of P, the sorption amounts decreased with increasing solution pH. Sorption amount of IHP was almost two times that of KP, while those of GP and KP were close. Both organic P and inorganic P interacted with hematite via ligand exchange through their phosphate groups, which conveyed negative charges to mineral surface and significantly decreased the zeta potential of hematite. In Na + solution, critical coagulation concentrations (CCCs) of hematite suspensions increased with increasing P concentration and followed the order of KP < GP < IHP at pH 5.5. Compared with KP, the organic P could more effectively stabilize the hematite suspension not only through increasing the negative charges and electrostatic repulsive force, but also through steric repulsion between P-sorbed hematite nanoparticles. When the pH was increased from 5.5 to 10.0, the CCCs of the hematite suspensions with GP and IHP decreased mainly because of the great reductions in organic P sorption amounts and consequent decreases in electrostatic and steric repulsive forces. However, enhanced aggregation was observed in the presence of IHP at pH 4.5 and above in low Ca 2+ solutions. The precipitation of calcium phytate formed net-like structure, which served as bridges to bind hematite nanoparticles and resulted in enhanced aggregation. These results have important implications for assessing the fate and transport of organic P and hematite nanoparticles in soil and aquatic environments.

Hematite spherules at Meridiani: Results from MI, Mini-TES, and Pancam

NASA Astrophysics Data System (ADS)

Calvin, W. M.; Shoffner, J. D.; Johnson, J. R.; Knoll, A. H.; Pocock, J. M.; Squyres, S. W.; Weitz, C. M.; Arvidson, R. E.; Bell, J. F.; Christensen, P. R.; de Souza, P. A.; Farrand, W. H.; Glotch, T. D.; Herkenhoff, K. E.; Jolliff, B. L.; Knudson, A. T.; McLennan, S. M.; Rogers, A. D.; Thompson, S. D.

2008-12-01

We report on observations of hematite-bearing spherules at Meridiani Planum made using the Microscopic Imager (MI), Mini-Thermal Emission Spectrometer (Mini-TES), and Panoramic Camera (Pancam) instruments on the Mars Exploration Rover Opportunity. Spherules were observed on soil surfaces and in outcrop rocks, both on undisturbed surfaces and in abraded surfaces ground using the Rock Abrasion Tool (RAT). Spherule size and shape change little along the 850 m eastward traverse from Eagle Crater to Endurance Crater, but spherules decrease and then slightly increase in size along the 6 km traverse from Endurance south to Victoria Crater. Local populations range from submillimeters to several millimeters in diameter. An additional small diameter (100 μm) size population is possible. An increase in irregular shapes is found near Victoria Crater. This, combined with the size decrease south of Endurance, suggests either a changing depositional environment, or variation in the duration and timing of diagenetic events. The dominant smaller size population observed early in the mission in aeolian areas and ripple crests is observed as the primary size population in abraded outcrop farther south. This suggests that successively younger beds are exposed at the surface along the southward traverse. Stratigraphically higher units removed by erosion could be recorded by the present surface lag deposit. Coordinated systematic observations are used to determine optical and infrared hematite indices of the surface soils in Pancam and Mini-TES. In spite of the systematic variation seen in MI, both Pancam and Mini-TES indices are highly variable based on the local surface, and neither show systematic trends south of Endurance. The lack of a 390 cm-1 feature in Mini-TES spectra suggests concentric or radial interior structure within the spherules at scales too fine for MI to observe. Mini-TES does not detect any silicate component in the spherules. A bound water component in soils or in exchange with the atmosphere is observed. These spherules have been previously interpreted as concretions formed within what were once water-saturated, diagenetically altered ``dirty evaporate'' sandstone sediments. Our observations support this interpretation; however, no single terrestrial analog provides a model that can account for all attributes of the spherules on Mars.

Hematite spherules at Meridiani: results from MI, Mini-TES, and Pancam

USGS Publications Warehouse

Calvin, W.M.; Shoffner, J.D.; Johnson, J. R.; Knoll, A.H.; Pocock, J.M.; Squyres, S. W.; Weitz, C.M.; Arvidson, R. E.; Bell, J.F.; Christensen, P.R.; de Souza, P. A.; Farrand, W. H.; Glotch, T.D.; Herkenhoff, K. E.; Jolliff, B.L.; Knudson, A.T.; McLennan, S.M.; Rogers, A.D.; Thompson, S.D.

2008-01-01

We report on observations of hematite-bearing spherules at Meridiani Planum made using the Microscopic Imager (MI), Mini-Thermal Emission Spectrometer (Mini-TES), and Panoramic Camera (Pancam) instruments on the Mars Exploration Rover Opportunity. Spherules were observed on soil surfaces and in outcrop rocks, both on undisturbed surfaces and in abraded surfaces ground using the Rock Abrasion Tool (RAT). Spherule size and shape change little along the 850 m eastward traverse from Eagle Crater to Endurance Crater, but spherules decrease and then slightly increase in size along the 6 km traverse from Endurance south to Victoria Crater. Local populations range from submillimeters to several millimeters in diameter. An additional small diameter (100 μm) size population is possible. An increase in irregular shapes is found near Victoria Crater. This, combined with the size decrease south of Endurance, suggests either a changing depositional environment, or variation in the duration and timing of diagenetic events. The dominant smaller size population observed early in the mission in aeolian areas and ripple crests is observed as the primary size population in abraded outcrop farther south. This suggests that successively younger beds are exposed at the surface along the southward traverse. Stratigraphically higher units removed by erosion could be recorded by the present surface lag deposit. Coordinated systematic observations are used to determine optical and infrared hematite indices of the surface soils in Pancam and Mini-TES. In spite of the systematic variation seen in MI, both Pancam and Mini-TES indices are highly variable based on the local surface, and neither show systematic trends south of Endurance. The lack of a 390 cm?1 feature in Mini-TES spectra suggests concentric or radial interior structure within the spherules at scales too fine for MI to observe. Mini-TES does not detect any silicate component in the spherules. A bound water component in soils or in exchange with the atmosphere is observed. These spherules have been previously interpreted as concretions formed within what were once water-saturated, diagenetically altered ?dirty evaporate? sandstone sediments. Our observations support this interpretation; however, no single terrestrial analog provides a model that can account for all attributes of the spherules on Mars.

Metabolism, survival, and gene expression of Pseudomonas putida to hematite nanoparticles mediated by surface-bound humic acid

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

Ouyang, Kai; Walker, Sharon L.; Yu, Xiao-Ying

Natural organic matter (NOM) is likely to coat naturally occurring nanoparticles (NNPs) in the soil environment and poses distinct effects on the interaction between NPs and soil microorganisms, however such topic has not been well investigated. This study explored the influence of nanoparticle surface-bound humic acid (HA, as a model NOM) on the toxicity of hematite NPs (i.e., nano-Fe2O3) to Pseudomonas putida (P. putida). Results showed that nano-Fe2O3 could inhibit the bacterial growth with an IC50 of 23.58 mg L-1, while nanoparticle surface-bound HA could significantly alleviate the P. putida toxicity of nano-Fe2O3. IC50 of nano-Fe2O3 increased to 4774.23 mgmore » L-1 as a result of surface-saturation by HA. Co-precipitation experiment and transmission electron microscopy observation revealed that nanoparticle surface-bound HA prevented the adhesion of nano-Fe2O3 to the cells as well as limited cell internalization of nanoparticles due to the increased electrostatic repulsion. The generation of intracellular reactive oxygen species (ROS) was significantly limited by the nanoparticle surface-bound HA. The prevention of adhesion and inhibition of ROS generation could account for the HA-mitigated nanotoxicity. Interfacial interactions between hematite NPs and cell membrane were also evaluated on the basis of the Derjaguin–Landau–Verwey–Overbeek (DLVO) theory, and the magnitude of interaction energy barrier correlated well with the 48 h LC50 data of hematite NPs to P. putida. This result implies that metal oxide NPs with strong association with the cell surface might induce more severe cytotoxicity in microorganisms.« less

Liquid Adsorption of Organic Compounds on Hematite α-Fe2O3 Using ReaxFF.

PubMed

Chia, Chung-Lim; Avendaño, Carlos; Siperstein, Flor R; Filip, Sorin

2017-10-24

ReaxFF-based molecular dynamics simulations are used in this work to study the effect of the polarity of adsorbed molecules in the liquid phase on the structure and polarization of hematite (α-Fe 2 O 3 ). We compared the adsorption of organic molecules with different polarities on a rigid hematite surface and on a flexible and polarizable surface. We show that the displacements of surface atoms and surface polarization in a flexible hematite model are proportional to the adsorbed molecule's polarity. The increase in electrostatic interactions resulting from charge transfer in the outermost solid atoms in a flexible hematite model results in better-defined adsorbed layers that are less ordered than those obtained assuming a rigid solid. These results suggest that care must be taken when parametrizing empirical transferable force fields because the calculated charges on a solid slab in vacuum may not be representative of a real system, especially when the solid is in contact with a polar liquid.

Improved flotation performance of hematite fines using citric acid as a dispersant

NASA Astrophysics Data System (ADS)

Luo, Xi-mei; Yin, Wan-zhong; Sun, Chuan-yao; Wang, Nai-ling; Ma, Ying-qiang; Wang, Yun-fan

2016-10-01

In this study, citric acid was used as a dispersant to improve the flotation performance of hematite fines. The effect and mechanism of citric acid on the reverse flotation of hematite fines were investigated by flotation tests, sedimentation experiments, scanning electron microscopy (SEM), zeta-potential measurements, and X-ray photoelectron spectroscopy (XPS). The results of SEM analysis and flotation tests reveal that a strong heterocoagulation in the form of slime coating or coagulation in hematite fine slurry affects the beneficiation of hematite ores by froth flotation. The addition of a small amount of citric acid (less than 300 g/t) favorably affects the reverse flotation of hematite fines by improving particle dispersion. The results of sedimentation experiments, zeta-potential measurements, and XPS measurements demonstrate that citric acid adsorbs onto hematite and quartz surfaces via hydrogen bonding, thereby reducing the zeta potentials of mineral surfaces, strengthening the electrical double-layer repulsion between mineral particles, and dispersing the pulp particles.

Passivation of surface states of α-Fe2O3(0001) surface by deposition of Ga2O3 overlayers: A density functional theory study.

PubMed

Ulman, Kanchan; Nguyen, Manh-Thuong; Seriani, Nicola; Gebauer, Ralph

2016-03-07

There is a big debate in the community regarding the role of surface states of hematite in the photoelectrochemical water splitting. Experimental studies on non-catalytic overlayers passivating the hematite surface states claim a favorable reduction in the overpotential for the water splitting reaction. As a first step towards understanding the effect of these overlayers, we have studied the system Ga2O3 overlayers on hematite (0001) surfaces using first principles computations in the PBE+U framework. Our computations suggest that stoichiometric terminations of Ga2O3 overlayers are energetically more favored than the bare surface, at ambient oxygen chemical potentials. Energetics suggest that the overlayers prefer to grow via a layer-plus-island (Stranski-Krastanov) growth mode with a critical layer thickness of 1-2 layers. Thus, a complete wetting of the hematite surface by an overlayer of gallium oxide is thermodynamically favored. We establish that the effect of deposition of the Ga2O3 overlayers on the bare hematite surface is to passivate the surface states for the stoichiometric termination. For the oxygen terminated surface which is the most stable termination under photoelectrochemical conditions, the effect of deposition of the Ga2O3 overlayer is to passivate the hole-trapping surface state.

Frequency Dependent Susceptibility Analysis of Magnetic Carriers: Application to Fe-Oxides on Mars surface

NASA Astrophysics Data System (ADS)

Adachi, T.; Kletetschka, G.; Mikula, V.

2007-12-01

On Mars, Fe-oxides mineral phases (inferred/detected) are mainly magnetite, pyrrhotite, and hematite. Kletetschka et al., 2005 suggested that the grain size dependent potential may contribute to the Mars surface magnetic anomaly. Grain size of Fe-oxides may play a role for the magnetic signature and anomaly on Mars. According to Kletetschka et al., 2005, the larger the grain size, the larger the magnetization (in this case hematite's TRM). Weather they are magnetite, pyrrhotite or hematite, nano-phase or superparamagnetic grains may contribute to the absence of remanent magnetization on the surface of Mars. In this contribution we tackle how to resolve grain size variations by frequency dependent susceptibility measured on terrestrial hematite samples such as hemo-ilmenite from Allard Lake, Canada, Mars analogue concretions from Utah and Czech Republic, and hematite aggregates from Hawaii. The magnetic characteristics of hematite-goethite mineralogies of Utah and Czech concretions suggested (Adachi et al., 2007) that they contain super paramagnetic (SP) to single domain (SD) magnetic states. Coercivity spectra analysis from acquisition of isothermal remanent magnetization (IRM) data showed the distinct behaviors of hematite, goethite, and mixed composition of both. The estimated magnetic states are analyzed with the frequency-dependent susceptibility instrument (500-250,000 Hertz). The frequency- and size-dependent susceptibility for hematite, goethite, and magnetite are calibrated using the known size powdered (commercial) samples.

Impact of environmental conditions on aggregation kinetics of hematite and goethite nanoparticles

NASA Astrophysics Data System (ADS)

Xu, Chen-yang; Deng, Kai-ying; Li, Jiu-yu; Xu, Ren-kou

2015-10-01

Hematite and goethite nanoparticles were used as model minerals to investigate their aggregation kinetics under soil environmental conditions in the present study. The hydrodynamic diameters of hematite and goethite nanoparticles were 34.4 and 66.3 nm, respectively. The positive surface charges and zeta potential values for goethite were higher than for hematite. The effective diameter for goethite was much larger than for hematite due to anisotropic sticking of needle-shaped goethite during aggregation. Moreover, the critical coagulation concentration (CCC) values of nanoparticles in solutions of NaNO3, NaCl, NaF, and Na2SO4 were 79.2, 75.0, 7.8, and 0.5 mM for hematite and they were 54.7, 62.6, 5.5, and 0.2 mM for goethite, respectively. The disparity of anions in inducing hematite or goethite aggregation lay in the differences in interfacial interactions. NO3 - and Cl- could decrease the zeta potential and enhance aggregation mainly through increasing ionic strength and compressing electric double layers of hematite and goethite nanoparticles. F- and SO4 2- highly destabilized the suspensions of nanoparticles mainly through specific adsorption and then neutralizing the positive surface charges of nanoparticles. Specific adsorption of cations could increase positive surface charges and stabilize hematite and goethite nanoparticles. The Hamaker constants of hematite and goethite nanoparticles were calculated to be 2.87 × 10-20 and 2.29 × 10-20 J-1, respectively. The predicted CCC values based on DLVO theory were consistent well with the experimentally determined CCC values in NaNO3, NaCl, NaF, and Na2SO4 systems, which demonstrated that DLVO theory could successfully predict the aggregation kinetics even when specific adsorption of ions occurred.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Detection of Crystalline Hematite Mineralization on Mars by the Thermal Emission Spectrometer: Evidence for Near-surface Water

NASA Technical Reports Server (NTRS)

Christensen, P. R.; Bandfield, J. L.; Clark, R. N.; Edgett, K. S.; Hamilton, V. E.; Hoefen, T.; Kieffer, H. H.; Kuzmin, R. O.; Lane, M. D.; Malin, M. C.

1999-01-01

The Thermal Emission Spectrometer (TES) instrument on the Mars Global Surveyor (MGS) mission has discovered a remarkable accumulation of crystalline hematite ((alpha-Fe2O3) that covers an area with very sharp boundaries approximately 350 by 350-750 km in size centered near 2 S latitude between 0 and 5 W longitude (Sinus Meridiani). Crystalline hematite is uniquely identified by the presence of fundamental vibrational absorption features centered near 300, 450, and >525/cm, and by the absence of silicate fundamentals in the 1000/cm region. Spectral features resulting from atmospheric CO2, dust, and water ice were removed using a radiative transfer model. The spectral properties unique to Sinus Meridiani were emphasized by removing the average spectrum of the surrounding region. The depth and shape of the hematite fundamental bands show that the hematite is crystalline and relatively coarse grained (>5-10 micron). Diameters up to and greater than 100s of micrometers are permitted within the instrumental noise and natural variability of hematite spectra. Hematite particles <5-10 micron in diameter (either as an unpacked or hard-packed powders) fail to match the TES spectra. The spectrally-derived areal abundance of hematite varies with particle size from approximately 10% for particles >30 micron in diameter to 40-60% for unpacked 10 micron powders. The hematite in Sinus Meridiani is thus distinct from the fine-grained (diameter <5-10 micron), red, crystalline hematite considered, on the basis of visible, near-IR data, to be a minor spectral component in Martian bright regions like Olympus-Amazonis. Sinus Meridiani hematite is closely associated with a smooth, layered, friable surface that is interpreted to be sedimentary in origin. This material may be the uppermost surface in the region, indicating that it could be a late-stage sedimentary unit, or it could be a layered portion of the heavily cratered plains units. We consider five possible mechanisms for the formation of coarse-grained, crystalline hematite. These processes fall into two classes depending on whether they require a significant amount of near-surface water: (1) chemical precipitation that includes origin by (a) precipitation from oxygenated, Fe-rich water (iron formations), (b) hydrothermal extraction and crystal growth.

Lunar and Planetary Science XXXV: Mars: Surface Coatings, Mineralogy, and Surface Properties

NASA Technical Reports Server (NTRS)

2004-01-01

The session "Mars: Surface Coatings, Mineralogy, and Surface Properties" contained the following reports:High-Silica Rock Coatings: TES Surface-Type 2 and Chemical Weathering on Mars; Old Desert Varnish-like Coatings and Young Breccias at the Mars Pathfinder Landing Site; Analyses of IR-Stealthy and Coated Surface Materials: A Comparison of LIBS and Reflectance Spectra and Their Application to Mars Surface Exploration; Contrasting Interpretations of TES Spectra of the 2003 Rover:Opportunity-Landing Site: Hematite Coatings and Gray Hematite; A New Hematite Formation Mechanism for Mars; Geomorphic and Diagenetic Analogs to Hematite Regions on Mars: Examples from Jurassic Sandstones of Southern Utah, USA; The Geologic Record of Early Mars: A Layered, Cratered, and "Valley-"ed: Volume; A Simple Approach to Estimating Surface Emissivity with THEMIS; A Large Scale Topographic Correction for THEMIS Data; Thermophysical Properties of Meridiani Planum, Mars; Thermophysical and Spectral Properties of Gusev, the MER-Spirit Landing Site on Mars; Determining Water Content of Geologic Materials Using Reflectance Spectroscopy; and Global Mapping of Martian Bound Water at 6.1 Microns Based on TES Data: Seasonal Hydration.

Contact angle and detachment energy of shape anisotropic particles at fluid-fluid interfaces.

PubMed

Anjali, Thriveni G; Basavaraj, Madivala G

2016-09-15

The three phase contact angle of particles, a measure of its wettability, is an important factor that greatly influences their behaviour at interfaces. It is one of the principal design parameters for potential applications of particles as emulsion/foam stabilizers, functional coatings and other novel materials. In the present work, the effect of size, shape and surface chemistry of particles on their contact angle is investigated using the gel trapping technique, which facilitates the direct visualization of the equilibrium position of particles at interfaces. The contact angle of hematite particles of spherocylindrical, peanut and cuboidal shapes, hematite-silica core-shell and silica shells is reported at a single particle level. The spherocylindrical and peanut shaped particles are always positioned with their major axis parallel to the interface. However, for cuboidal particles at air-water as well as decane-water interfaces, different orientations namely - face-up, edge-up and the vertex-up - are observed. The influence of gravity on the equilibrium position of the colloidal particles at the interface is studied using the hematite-silica core-shell particles and the silica shells. The measured contact angle values are utilized in the calculations of the detachment and surface energies of the hematite particles adsorbed at the interface. Copyright © 2016 Elsevier Inc. All rights reserved.

Phosphate adsorption on hematite, kaolinite, and kaolinite-hematite (k-h) systems as described by a constant capacitance model

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

Ioannou, A.; Dimirkou, A.

1997-08-01

The constant capacitance model was used to describe phosphate adsorption on hematite, kaolinite, and a kaolinite-hematite system (k-h). The model assumes a ligand exchange mechanism and considers the charge on both adsorbate and adsorbent. The model is shown to provide a quantitative description of phosphate adsorption on these, including the effect of varying pH values. The computer program Ma-Za 2, a program that fits equilibrium constants to experimental data using an optimization technique, was used to obtain optimal values for the anion surface complexation constants on hematite, kaolinite, and a kaolinite-hematite system, while the PC program Ma-Za 1 in Q-Basicmore » language was used for the application of the constant capacitance model. The model represented adsorption of phosphate anions well over the entire pH range studied (3.8--9.0). The main advantage of the model is its ability to represent changes in anion adsorption occurring with changes in pH. Extension of the model to describe phosphate adsorption in a mixed system, such as the kaolinite-hematite system, using the surface protonation-dissociation constant of hematite was qualitatively successful. In mixed system the model reproduced the shape of the adsorption isotherms well over the pH range 3.8--9.0. However, phosphate adsorption was overestimated. The hematite and the kaolinite-hematite system were synthesized and identified by X-ray, NMR, and FT-IR spectroscopy.« less

Isothermal Oxidation of Magnetite to Hematite in Air and Cyclic Reduction/Oxidation Under Carbon Looping Combustion Conditions

NASA Astrophysics Data System (ADS)

Simmonds, Tegan; Hayes, Peter C.

2017-12-01

In the carbon looping combustion process the oxygen carrier is regenerated through oxidation in air; this process has been simulated by the oxidation of dense synthetic magnetite for selected temperatures and times. The oxidation of magnetite in air is shown to occur through the formation of dense hematite layers on the particle surface. This dense hematite forms through lath type shear transformations or solid-state diffusion through the product layer. Cyclic reduction in CO-CO2/oxidation in air of hematite single crystals has been carried out under controlled laboratory conditions at 1173 K (900 °C). It has been shown that the initial reduction step is critical to determining the product microstructure, which consists of gas pore dendrites in the magnetite matrix with blocky hematite formed on the pore surfaces. The progressive growth of the magnetite layer with the application of subsequent cycles appears to continue until no original hematite remains, after which physical disintegration of the particles takes place.

Hematite (U-Th)/He thermochronometry constrains intraplate strike-slip faulting on the Kuh-e-Faghan Fault, central Iran

NASA Astrophysics Data System (ADS)

Calzolari, Gabriele; Rossetti, Federico; Ault, Alexis K.; Lucci, Federico; Olivetti, Valerio; Nozaem, Reza

2018-03-01

The Kuh-e-Faghan strike-slip fault system (KFF), located to the northern edge of the Lut Block in central Iran, developed through a Neogene-Quaternary pulsed history of eastward fault propagation and fault-related exhumation. This system is a consequence of the residual stresses transmitted from the Arabia-Eurasia convergent plate boundary. Here we integrate structural and textural analysis with new and previously published apatite fission-track (AFT) and apatite (U-Th)/He (apatite He) results, chlorite thermomentry, and hematite (U-Th)/He data from hematite-coated brittle fault surfaces to constrain the timing of tectonic activity and refine patterns of late Miocene-Pliocene burial and exhumation associated with the propagation of the KFF. Twenty-nine hematite (U-Th)/He (hematite He) dates from three striated hematite coated slip surfaces from the KFF fault core and damage zone yield individual dates from 12-2 Ma. Petrographic analysis and chlorite thermometry of a polyphase, fossil fluid system in the KFF fault core document that fluid circulation and mineralization transitioned from a closed system characterized by pressure solution and calcite growth to an open system characterized by hot hydrothermal (T = 239 ± 10 °C) fluids and hematite formation. Hematite microtextures and grain size analysis reveal primary and secondary syntectonic hematite fabrics, no evidence of hematite comminution and similar hematite He closure temperatures ( 60-85 °C) in each sample. Integration of these results with thermal history modeling of AFT and apatite He data shows that KFF activity in the late Miocene is characterized by an early stage of fault nucleation, fluid circulation, hematite mineralization, and eastward propagation not associated with vertical movement that lasted from 12 to 7 Ma. Hematite He, AFT, and apatite He data track a second phase of fault system activity involving fault-related exhumation initiating at 7 Ma and continuing until present time. Our new data constrain the onset of the recognized Late Miocene-Pliocene tectonic reorganization in north-central Iran.

Facet-Dependent Cr(VI) Adsorption of Hematite Nanocrystals.

PubMed

Huang, Xiaopeng; Hou, Xiaojing; Song, Fahui; Zhao, Jincai; Zhang, Lizhi

2016-02-16

In this study, the adsorption process of Cr(VI) on the hematite facets was systematically investigated with synchrotron-based Cr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, density-functional theory calculation, and surface complexation models. Structural model fitting of EXAFS spectroscopy suggested that the interatomic distances of Cr-Fe were, respectively, 3.61 Å for the chromate coordinated hematite nanoplates with exposed {001} facets, 3.60 and 3.30 Å for the chromate coordinated hematite nanorods with exposed {001} and {110} facets, which were characteristic of inner-sphere complexation. In situ ATR-FTIR spectroscopy analysis confirmed the presence of two inner-sphere surface complexes with C3ν and C2ν symmetry, while the C3ν and C2ν species were assigned to monodentate and bidentate inner-sphere surface complexes with average Cr-Fe interatomic distances of 3.60 and 3.30 Å, respectively. On the basis of these experimental and theoretical results, we concluded that HCrO4(-) as dominated Cr(VI) species was adsorbed on {001} and {110} facets in inner-sphere monodentate mononuclear and bidentate binuclear configurations, respectively. Moreover, the Cr(VI) adsorption performance of hematite facets was strongly dependent on the chromate complexes formed on the hematite facets.

Surface complexation studied via combined grazing-incidence EXAFS and surface diffraction: Arsenate on hematite (0001) and (10-12)

USGS Publications Warehouse

Waychunas, G.; Trainor, T.; Eng, P.; Catalano, J.; Brown, G.; Davis, J.; Rogers, J.; Bargar, J.

2005-01-01

X-ray diffraction [crystal-truncation-rod (CTR)] studies of the surface structure of moisture-equilibrated hematite reveal sites for complexation not present on the bulk oxygen-terminated surface, and impose constraints on the types of inner-sphere sorption topologies. We have used this improved model of the hematite surface to analyze grazing-incidence EXAFS results for arsenate sorption on the c(0001) and r(10-12) surfaces measured in two electric vector polarizations. This work shows that the reconfiguration of the surface under moist conditions is responsible for an increased adsorption density of arsenate complexes on the (0001) surface relative to predicted ideal termination, and an abundance of "edge-sharing" bidentate complexes on both studied surfaces. We consider possible limitations on combining the methods due to differing surface sensitivities, and discuss further analysis possibilities using both methods. ?? Springer-Verlag 2005.

Ultrathin planar hematite film for solar photoelectrochemical water splitting

DOE PAGES

Liu, Dong; Bierman, David M.; Lenert, Andrej; ...

2015-10-08

Hematite holds promise for photoelectrochemical (PEC) water splitting due to its stability, low-cost, abundance and appropriate bandgap. However, it suffers from a mismatch between the hole diffusion length and light penetration length. We have theoretically designed and characterized an ultrathin planar hematite/silver nanohole array/silver substrate photoanode. Due to the supported destructive interference and surface plasmon resonance, photons are efficiently absorbed in an ultrathin hematite film. In conclusion, compared with ultrathin hematite photoanodes with nanophotonic structures, this photoanode has comparable photon absorption but with intrinsically lower recombination losses due to its planar structure and promises to exceed the state-of-the-art photocurrent ofmore » hematite photoanodes.« less

In situ spectroscopic evidence for neptunium(V)-carbonate inner-sphere and outer-sphere ternary surface complexes on hematite surfaces.

PubMed

Arai, Yuji; Moran, P B; Honeyman, B D; Davis, J A

2007-06-01

Np(V) surface speciation on hematite surfaces at pH 7-9 under pC2 = 10(-3.45) atm was investigated using X-ray absorption spectroscopy (XAS). In situ XAS analyses suggest that bis-carbonato inner-sphere and tris-carbonato outer-sphere ternary surface species coexist at the hematite-water interface at pH 7-8.8, and the fraction of outer-sphere species gradually increases from 27 to 54% with increasing pH from 7 to 8.8. The results suggest that the heretofore unknown Np(V)-carbonato ternary surface species may be important in predicting the fate and transport of Np(V) in the subsurface environment down gradient of high-level nuclear waste respositories.

Synergetic effect of Sn addition and oxygen-deficient atmosphere to fabricate active hematite photoelectrodes for light-induced water splitting

NASA Astrophysics Data System (ADS)

Freitas, Andre L. M.; Souza, Flavio L.

2017-11-01

This work describes the design of a microwave-assisted method using hydrothermal conditions to fabricate pure and Sn-doped hematite photoelectrodes with varied synthesis time and additional thermal treatment under air and N2 atmosphere. The hematite photoelectrode formed under N2 atmosphere, with Sn deposited on its surface—which is represented by material synthesized at 4 h —exhibits the highest performance. Hence, Sn addition followed by high temperature annealing conducted in an oxygen-deficient atmosphere seems to create oxygen vacancies, and to prevent the segregation of dopant to form the SnO2 phase at the hematite crystal surface, reducing its energy and suppressing the grain growth. The increased donor number density provided by the oxygen vacancies (confirmed by x-ray photoelectron data), and a possible reduction in the grain boundary energy or hematite crystal interface might favor charge separation, and increase the electron transfer through the hematite into the back contact (FTO substrate). In consequence, the light-induced water oxidation reaction efficiency of Sn-hematite photoelectrodes was significantly increased in comparison with pure ones, even though the vertical rod morphology was not preserved. This finding provides a novel insight into intentional Sn addition, revealing that dopant segregation at the hematite crystal surface (or at the grain boundaries) could—by increasing the electron mobility—be the more relevant factor in developing active hematite photoelectrodes than the control of columnar morphology.

In-situ deposition of hematite (α-Fe2O3) microcubes on cotton cellulose via hydrothermal method

NASA Astrophysics Data System (ADS)

Gili, M.; Latag, G.; Balela, M.

2018-03-01

Hematite microcubes with truncated edges have been successfully deposited on cotton cellulose via one-step hydrothermal process using anhydrous FeCl3 and glycine as Fe(III) precursor and chelating agent, respectively. The amount of glycine significantly affects the morphology and yield of hematite. The addition of 0.495 g of glycine to 50 ml of 0.1 M FeCl3 solution with 0.400 g of cotton resulted to hematite-deposited cellulose having ∼15% hematite content. The reduction of glycine to 0.247 g increased the amount of hematite on the surface of the cotton cellulose to ∼20% by weight. However, the hematite microcubes have a wide size distribution, with particle size in the range of 0.684 μm to 1.520 μm. Without glycine, hematite cannot be formed in the solution.

Spatial and spectral resolution of carbonaceous material from hematite (α-Fe2O3) using multivariate curve resolution-alternating least squares (MCR-ALS) with Raman microspectroscopic mapping: implications for the search for life on Mars.

PubMed

Smith, Joseph P; Smith, Frank C; Booksh, Karl S

2017-08-21

The search for evidence of extant or past life on Mars is a primary objective of both the upcoming Mars 2020 rover (NASA) and ExoMars 2020 rover (ESA/Roscosmos) missions. This search will involve the detection and identification of organic molecules and/or carbonaceous material within the Martian surface environment. For the first time on a mission to Mars, the scientific payload for each rover will include a Raman spectrometer, an instrument well-suited for this search. Hematite (α-Fe 2 O 3 ) is a widespread mineral on the Martian surface. The 2LO Raman band of hematite and the Raman D-band of carbonaceous material show spectral overlap, leading to the potential misidentification of hematite as carbonaceous material. Here we report the ability to spatially and spectrally differentiate carbonaceous material from hematite using multivariate curve resolution-alternating least squares (MCR-ALS) applied to Raman microspectroscopic mapping under both 532 nm and 785 nm excitation. For this study, a sample comprised of hematite, carbonaceous material, and substrate-adhesive epoxy in spatially distinct domains was constructed. Principal component analysis (PCA) reveals that both 532 nm and 785 nm excitation produce representative three-phase systems of hematite, carbonaceous material, and substrate-adhesive epoxy in the analyzed sample. MCR-ALS with Raman microspectroscopic mapping using both 532 nm and 785 nm excitation was able to resolve hematite, carbonaceous material, and substrate-adhesive epoxy by generating spatially-resolved chemical maps and corresponding Raman spectra of these spatially distinct chemical species. Moreover, MCR-ALS applied to the combinatorial data sets of 532 nm and 785 nm excitation, which contain hematite and carbonaceous material within the same locations, was able to resolve hematite, carbonaceous material, and substrate-adhesive epoxy. Using multivariate analysis with Raman microspectroscopic mapping, 785 nm excitation more effectively resolved hematite, carbonaceous material, and substrate-adhesive epoxy as compared to 532 nm excitation. To our knowledge, this is the first report of multivariate analysis methods, namely MCR-ALS, with Raman microspectroscopic mapping being employed to differentiate carbonaceous material from hematite. We have therefore provided an analytical methodology useful for the search for extant or past life on the surface of Mars.

Aqueous Chemical Modeling of Sedimentation on Early Mars with Application to Surface-Atmosphere Evolution

NASA Technical Reports Server (NTRS)

Catling, David C.

2004-01-01

This project was to investigate models for aqueous sedimentation on early Mars from fluid evaporation. Results focused on three specific areas: (1) First, a fluid evaporation model incorporating iron minerals was developed to compute the evaporation of a likely solution on early Mars derived from the weathering of mafic rock. (2) Second, the fluid evaporation model was applied to salts within Martian meteorites, specifically salts in the nakhlites and ALH84001. Evaporation models were found to be consistent with the mineralogy of salt assemblages-anhydrite, gypsum, Fe-Mg-Ca carbonates, halite, clays-- and the concentric chemical fractionation of Ca-to Mg-rich carbonate rosettes in ALH84001. We made progress in further developing our models of fluid concentration by contributing to updating the FREZCHEM model. (3) Third, theoretical investigation was done to determine the thermodynamics and kinetics involved in the formation of gray, crystalline hematite. This mineral, of probable ancient aqueous origin, has been observed in several areas on the surface of Mars by the Thermal Emission Spectrometer on Mars Global Surveyor. The "Opportunity" Mars Exploration Rover has also detected gray hematite at its landing site in Meridiani Planum. We investigated how gray hematite can be formed via atmospheric oxidation, aqueous precipitation and subsequent diagenesis, or hydrothermal processes. We also studied the geomorphology of the Aram Chaos hematite region using Mars Orbiter Camera (MOC) images.

Aggregation Kinetics of Hematite Particles in the Presence of Outer Membrane Cytochrome OmcA of Shewanella oneidenesis MR-1

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

Sheng, Anxu; Liu, Feng; Shi, Liang

2016-09-20

The aggregation behavior of 9, 36, and 112 nm hematite particles was studied in the presence of OmcA, a bacterial extracellular protein, in aqueous dispersions at pH 5.7 through time-resolved dynamic light scattering, electrophoretic mobility, and circular dichroism spectra, respectively. At low salt concentration, the attachment efficiencies of hematite particles in all sizes first increased, then decreased, and finally remained stable with the increase of OmcA concentration, indicating the dominant interparticle interaction changed along with the increase in the protein-to-particle ratio. Nevertheless, at high salt concentration, the attachment efficiencies of all hematite samples gradually decreased with increasing OmcA concentration, whichmore » can be attributed to increasing steric force. Additionally, the aggregation behavior of OmcA-hematite conjugates was more correlated to total particle-surface area than primary particle size. It was further established that OmcA could stabilize hematite nanoparticles more efficiently than bovine serum albumin (BSA), a model plasma protein, due to the higher affinity of OmcA to hematite surface. This study highlighted the effects of particle properties, solution conditions, and protein properties on the complicated aggregation behavior of protein-nanoparticle conjugates in aqueous environments.« less

Reductive Dissolution of Goethite and Hematite by Reduced Flavins

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

Shi, Zhi; Zachara, John M.; Wang, Zheming

2013-10-02

The abiotic reductive dissolution of goethite and hematite by the reduced forms of flavin mononucleotide (FMNH2) and riboflavin (RBFH2), electron transfer mediators (ETM) secreted by the dissimilatory iron-reducing bacterium Shewanella, was investigated under stringent anaerobic conditions. In contrast to the rapid redox reaction rate observed for ferrihydrite and lepidocrocite (Shi et al., 2012), the reductive dissolution of crystalline goethite and hematite was slower, with the extent of reaction limited by the thermodynamic driving force at circumneutral pH. Both the initial reaction rate and reaction extent increased with decreasing pH. On a unit surface area basis, goethite was less reactive thanmore » hematite between pH 4.0 and 7.0. AH2DS, the reduced form of the well-studied synthetic ETM anthraquinone-2,6-disulfonate (AQDS), yielded higher rates than FMNH2 under most reaction conditions, despite the fact that FMNH2 was a more effective reductant than AH2DS for ferryhydrite and lepidocrocite. Two additional model compounds, methyl viologen and benzyl viologen, were investigated under similar reaction conditions to explore the relationship between reaction rate and thermodynamic properties. Relevant kinetic data from the literature were also included in the analysis to span a broad range of half-cell potentials. Other conditions being equal, the surface area normalized initial reaction rate (ra) increased as the redox potential of the reductant became more negative. A non-linear, parabolic relationship was observed between log ra and the redox potential for eight reducants at pH 7.0, as predicted by Marcus theory for electron transfer. When pH and reductant concentration were fixed, log ra was positively correlated to the redox potential of four Fe(III) oxides over a wide pH range, following a non-linear parabolic relationship as well.« less

Effect of magnetic starch on the clarification of hematite tailings wastewater

NASA Astrophysics Data System (ADS)

Yue, Tao; Wu, Xiqing

2018-02-01

The magnetic starch solution, synthesized by mixing the caustic starch, the Fe2+ solution (in some cases containing the Zn2+, Cu2+, Mn2+ or Mg2+ ions) and H2O2 solution, was used as the flocculant to investigate its clarification effect on hematite tailings wastewater. Based on the clarification tests and adsorption analysis it was demonstrated that the magnetic starch produced better clarification effect than the caustic starch, and the adsorption of magnetic starch onto hematite tailings particles was also stronger than the caustic starch. AFM found that the magnetic interaction between magnetic seeds and hematite is characteristic of long range force and greatly strengthens the adsorption of magnetic seeds onto fine hematite for agglomeration. FTIR indicates the starch adsorbed onto the surfaces of hematite and magnetic seeds, thus acting as the bridging between hematite particles and magnetic seeds, resulting in an intensified coverage of the starch onto hematite and positive action in the clarification.

Surface Interrogation Scanning Electrochemical Microscopy for a Photoelectrochemical Reaction: Water Oxidation on a Hematite Surface.

PubMed

Kim, Jae Young; Ahn, Hyun S; Bard, Allen J

2018-03-06

To understand the pathway of a photoelectrochemical (PEC) reaction, quantitative knowledge of reaction intermediates is important. We describe here surface interrogation scanning electrochemical microscopy for this purpose (PEC SI-SECM), where a light pulse to a photoactive semiconductor film at a given potential generates intermediates that are then analyzed by a tip generated titrant at known times after the light pulse. The improvements were demonstrated for photoelectrochemical water oxidation (oxygen evolution) reaction on a hematite surface. The density of photoactive sites, proposed to be Fe 4+ species, on a hematite surface was successfully quantified, and the photoelectrochemical water oxidation reaction dynamics were elucidated by time-dependent redox titration experiments. The new configuration of PEC SI-SECM should find expanded usage to understand and investigate more complicated PEC reactions with other materials.

Topotaxial reactions during the genesis of oriented rutile/hematite intergrowths from Mwinilunga (Zambia)

NASA Astrophysics Data System (ADS)

Rečnik, Aleksander; Stanković, Nadežda; Daneu, Nina

2015-02-01

Oriented rutile/hematite intergrowths from Mwinilunga in Zambia were investigated by electron microscopy methods in order to resolve the complex sequence of topotaxial reactions. The specimens are composed of up to several-centimeter-large euhedral hematite crystals covered by epitaxially grown reticulated rutile networks. Following a top-down analytical approach, the samples were studied from their macroscopic crystallographic features down to subnanometer-scale analysis of phase compositions and occurring interfaces. Already, a simple morphological analysis indicates that rutile and hematite are met near the orientation relationship. However, a more detailed structural analysis of rutile/hematite interfaces using electron diffraction and high-resolution transmission electron microscopy (HRTEM) has shown that the actual relationship between the rutile and hosting hematite is in fact . The intergrowth is dictated by the formation of equilibrium interfaces leading to 12 possible directions of rutile exsolution within a hematite matrix and 144 different incidences between the intergrown rutile crystals. Analyzing the potential rutile-rutile interfaces, these could be classified into four classes: (1) non-crystallographic contacts at 60° and 120°, (2) {101} twins with incidence angles of 114.44° and their complementaries at 65.56°, (3) {301} twins at 54.44° with complementaries at 125.56° and (4) low-angle tilt boundaries at 174.44° and 5.56°. Except for non-crystallographic contacts, all other rutile-rutile interfaces were confirmed in Mwinilunga samples. Using a HRTEM and high-angle annular dark-field scanning TEM methods combined with energy-dispersive X-ray spectroscopy, we identified remnants of ilmenite lamellae in the vicinity of rutile exsolutions, which were an important indication of the high-T formation of the primary ferrian-ilmenite crystals. Another type of exsolution process was observed in rutile crystals, where hematite precipitates topotaxially exsolved from Fe-rich parts of rutile through intermediate Guinier-Preston zones, characterized by tripling the {101} rutile reflections. Unlike rutile exsolutions in hematite, hematite exsolutions in rutile form equilibrium interfaces. The overall composition of our samples indicates that the ratio between ilmenite and hematite in parent ferrian-ilmenite crystals was close to Ilm67Hem33, typical for Fe-Ti-rich differentiates of mafic magma. The presence of ilmenite lamellae indicates that the primary solid solution passed the miscibility gap at 900 °C. Subsequent exsolution processes were triggered by surface oxidation of ferrous iron and remobilization of cations within the common oxygen sublattice. Based on nanostructural analysis of the samples, we identified three successive exsolution processes: (1) exsolution of ilmenite lamellae from the primary ferrian-ilmenite crystals, (2) exsolution of rutile lamellae from ilmenite and (3) exsolution of hematite precipitates from Fe-rich rutile lamellae. All observed topotaxial reactions appear to be a combined function of temperature and oxygen fugacity, fO2.

Formation of environmentally persistent free radicals as the mechanism for reduced catechol degradation on hematite-silica surface under UV irradiation.

PubMed

Li, Hao; Pan, Bo; Liao, Shaohua; Zhang, Di; Xing, Baoshan

2014-05-01

Iron is rich in soils, and is recently reported to form stable complexes with organic free radicals, generating environmentally persistent free radicals (EPFRs). The observation may challenge the common viewpoint that iron is an effective catalyst to facilitate the degradation of various organic chemicals. But no study was specifically designed to investigate the possible inhibited degradation of organic chemicals because of the formation of EPFRs in dry environment. We observed that catechol degradation under UV irradiation was decreased over 20% in silica particles coated with 1% hematite in comparison to uncoated silica particles. Stabilized semiquinone or quinine and phenol radicals were involved in HMT-silica system. EPFR formation was thus the reason for the reduced catechol degradation on HMT-silica surface under UV irradiation at ambient temperature. EPFRs should be incorporated in the studies of organic contaminants geochemical behavior, and will be a new input in their environmental fate modeling. Copyright © 2014 Elsevier Ltd. All rights reserved.

Interaction of copper and fulvic acid at the hematite-water interface

NASA Astrophysics Data System (ADS)

Christl, Iso; Kretzschmar, Ruben

2001-10-01

The influence of surface-bound fulvic acid on the sorption of Cu(II) to colloidal hematite particles was studied experimentally and the results were compared with model calculations based on the linear additivity assumption. In the first step, proton and Cu binding to colloidal hematite particles and to purified fulvic acid was studied by batch equilibration and ion-selective electrode titration experiments, respectively. The sorption data for these binary systems were modeled with a basic Stern surface complexation model for hematite and the NICA-Donnan model for fulvic acid. In the second step, pH-dependent sorption of Cu and fulvic acid in ternary systems containing Cu, hematite, and fulvic acid in NaNO3 electrolyte solutions was investigated in batch sorption experiments. Sorption of fulvic acid to the hematite decreased with increasing pH (pH 3-10) and decreasing ionic strength (0.01-0.1 M NaNO3), while the presence of 22 μM Cu had a small effect on fulvic acid sorption, only detectable at low ionic strength (0.01 M). Sorption of Cu to the solid phase separated by centrifugation was strongly affected by the presence of fulvic acid. Below pH 6, sorption of Cu to the solid phase increased by up to 40% compared with the pure hematite. Above pH 6, the presence of fulvic acid resulted in a decrease in Cu sorption due to increasing concentrations of dissolved metal-organic complexes. At low ionic strength (0.01 M), the effects of fulvic acid on Cu sorption to the solid phase were more pronounced than at higher ionic strength (0.1 M). Comparison of the experimental data with model calculations shows that Cu sorption in ternary hematite-fulvic acid systems is systematically underestimated by up to 30% using the linear additivity assumption. Therefore, specific interactions between organic matter and trace metal cations at mineral surfaces must be taken into account when applying surface complexation models to soils or sediments which contain oxides and natural organic matter.

Surface catalysis of uranium(VI) reduction by iron(II)

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

Liger, E.; Charlet, L.; Van Cappellen, P.

1999-10-01

Colloidal hematite ({alpha}-Fe{sub 2}O{sub 3}) is used as model solid to investigate the kinetic effect of specific adsorption interactions on the chemical reduction of uranyl (U{sup VI}O{sub 2}{sup 2+}) by ferrous iron. Acid-base titrations and Fe(II) and uranyl adsorption experiments are performed on hematite suspensions, under O{sub 2}- and CO{sub 2}-free conditions. The results are explained in terms of a constant capacitance surface complexation model of the hematite-aqueous solution interface. Two distinct Fe(II) surface complexes are required to reproduce the data: ({equivalent{underscore}to}Fe{sup III}OFe{sup II}){sup +} (or {equivalent{underscore}to}Fe{sup III}OFe{sup II}(OH{sub 2}){sub n}{sup +}) and {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0} (or {equivalent{underscore}to}Fe{sup III}OFe{supmore » II}(OH{sub 2}){sub n{minus}1}OH{sup 0}). The latter complex represents a significant fraction of total adsorbed Fe(II) at pH {gt} 6.5. Uranyl binding to the hematite particles is characterized by a sharp adsorption edge between pH 4 and pH 5.5. Because of the absence of competing aqueous carbonate complexes, uranyl remains completely adsorbed at pH {gt} 7. A single mononuclear surface complex accounts for the adsorption of uranyl over the entire range of experimental conditions. Although thermodynamically feasible, no reaction between uranyl and Fe(II) is observed in homogeneous solution at pH 7.5, for periods of up to three days. In hematite suspensions, however, surface-bound uranyl reacts on a time scale of hours. Based on Fourier Transformed Infrared spectra, chemical reduction of U(VI) is inferred to be the mechanism responsible for the disappearance of uranyl. The kinetics of uranyl reduction are quantified by measuring the decrease with time of the concentration of U(VI) extractable from the hematite particles by NaHCO{sub 3}. In the presence of excess Fe(II), the initial rate of U(VI) reduction exhibits a first-order dependence on the concentration of adsorbed uranyl. The pseudo-first-order rate constant varies with pH (range, 6--7.5) and the total (dissolved + adsorbed) concentration of Fe(II) (range, 2--160 {micro}M). When analyzing the rate data in terms of the calculated surface speciation, the variability of the rate constant can be accounted for entirely by changes in the concentration of the Fe(II) monohydroxo surface complex {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0}. Therefore, the rate law is derived for the hematite-catalyzed reduction of uranyl by Fe(II), where the bimolecular rate constant {kappa} has a value of 399 {+-} 25 M{sup {minus}1} min{sup {minus}1} at 25 C. The hydroxo surface complex is the rate-controlling reductant species, because it provides the most favorable coordination environment in which electrons are removed from Fe(II). Natural particulate matter collected in the hypolimnion of a seasonally stratified lake also causes the rapid reduction of uranyl by Fe(II), Ferrihydrite, identified in the particulate matter by X-ray diffraction, is one possible mineral phase accelerating the reaction between U(VI) and Fe(II). At near-neutral pH and total Fe(II) levels less than 1 mM, the pseudo-first-order rate constants of chemical U(VI) reduction, measured in the presence of the hematite and lake particles, are of the same order of magnitude as the highest corresponding rate coefficients for enzymatic U(VI) reduction in bacterial cultures. Hence, based on the results of this study, surface-catalyzed U(VI) reduction by Fe(II) is expected to be a major pathway of uranium immobilization in a wide range of redox-stratified environments.« less

Trade-off between Zr Passivation and Sn Doping on Hematite Nanorod Photoanodes for Efficient Solar Water Oxidation: Effects of a ZrO2 Underlayer and FTO Deformation.

PubMed

Subramanian, Arunprabaharan; Annamalai, Alagappan; Lee, Hyun Hwi; Choi, Sun Hee; Ryu, Jungho; Park, Jung Hee; Jang, Jum Suk

2016-08-03

Herein we report the influence of a ZrO2 underlayer on the PEC (photoelectrochemical) behavior of hematite nanorod photoanodes for efficient solar water splitting. Particular attention was given to the cathodic shift in onset potential and photocurrent enhancement. Akaganite (β-FeOOH) nanorods were grown on ZrO2-coated FTO (fluorine-doped tin oxide) substrates. Sintering at 800 °C transformed akaganite to the hematite (α-Fe2O3) phase and induced Sn diffusion into the crystal structure of hematite nanorods from the FTO substrates and surface migration, shallow doping of Zr atoms from the ZrO2 underlayer. The ZrO2 underlayer-treated photoanode showed better water oxidation performance compared to the pristine (α-Fe2O3) photoanode. A cathodic shift in the onset potential and photocurrent enhancement was achieved by surface passivation and shallow doping of Zr from the ZrO2 underlayer, along with Sn doping from the FTO substrate to the crystal lattice of hematite nanorods. The Zr based hematite nanorod photoanode achieved 1 mA/cm(2) at 1.23 VRHE with a low turn-on voltage of 0.80 VRHE. Sn doping and Zr passivation, as well as shallow doping, were confirmed by XPS, Iph, and M-S plot analyses. Electrochemical impedance spectroscopy revealed that the presence of a ZrO2 underlayer decreased the deformation of FTO substrate, improved electron transfer at the hematite/FTO interface and increased charge-transfer resistance at the electrolyte/hematite interface. This is the first systematic investigation of the effects of Zr passivation, shallow doping, and Sn doping on hematite nanorod photoanodes through application of a ZrO2 underlayer on the FTO substrate.

Searching for an Improved Spectral Match to TES and IRIS Sinus Meridiani Spectra: Coatings and Cemented Materials

NASA Astrophysics Data System (ADS)

Kirkland, L. E.; Herr, K. C.; Adams, P. M.

2001-05-01

A region on Mars within Sinus Meridiani has been interpreted as a surface partially covered by coarse-grained (gray) hematite, using spectra measured by the 1996 Global Surveyor Thermal Emission Spectrometer (TES) [Lane et al., 1999; Christensen et al., 2000]. The band strengths recorded by TES of this region are consistent with either coarse-grained hematite, or cemented poorly crystalline or cemented fine-grained hematite. The band strengths are inconsistent with unconsolidated, poorly crystalline or fine-grained hematite, including nanophase hematite dust [Christensen et al., 2000]. Currently the gray hematite interpretation is based on bands centered near 22 and 33 microns. TES also records a band centered near 18 microns that was used in early hematite interpretations [Lane et al., 1999]. However, it was noted [Kirkland et al., 1999a] that the 18 micron band is too narrow in both TES and the 1971 Mariner Mars IRIS spectra to be a good match to typical spectra of well-crystalline hematite [e.g. Salisbury et al., 1991]. The 18 micron band is near the very strong 15 micron atmospheric CO2 band, but if anything the nearby CO2 band should cause the 18 micron band to appear wider, not narrower. In addition, the higher spectral resolution of IRIS allows improved separation of the bands [Kirkland et al., 1999b]. More recent publications no longer show the TES 18 micron band [e.g. Lane et al., 2000; Christensen et al., 2000], which temporarily resolved the issue. However, we feel it is important to understand why TES and IRIS spectra exhibit an 18 micron band that is too narrow to match typical spectra of coarse-grained hematite. Smooth-surfaced cemented (e.g. ferricrete) or coated materials (e.g. desert varnish) have spectral contrast that is consistent with the observed IRIS and TES band contrast. On Mars, one possible source for cemented material or coatings would be the nanophase hematite dust. Cemented materials may occur in bulk (e.g. duricrust or ferricrete), or as a thin coating (e.g. desert varnish). We have investigated the signatures of naturally occurring cemented materials that contain hematite, and found samples that exhibit 22 and 33 micron bands that are consistent with coarse-grained hematite signatures, and yet also exhibit narrower 18 micron bands. We are continuing to study the materials more in-depth to examine the variations in spectral shape, and to determine the cause of varied 18 micron band width. References. Christensen, P. R. et al., JGR 105, 9632, 2000. Kirkland, L., K. Herr, P. Forney, and J. Salisbury, LPSC XXX, abs. 1693 and oral presentation, 1999a. Kirkland, L., K. Herr, and P. Forney, 5th Internat'l Conf. on Mars, abs. 6174, 1999b. Lane, M., R. Morris, and P. Christensen, LPSC XXX, abs. 1469, 1999. Lane, M., R. Morris, and P. Christensen, LPSC XXXI, abs. 1140, 2000. Salisbury, J., L. Walter, N. Vergo, D. D'Aria, Infrared (2.1-25 micron) Spectra of Minerals, Johns Hopkins UP, 1991.

Alteration minerals in impact-generated hydrothermal systems - Exploring host rock variability

NASA Astrophysics Data System (ADS)

Schwenzer, Susanne P.; Kring, David A.

2013-09-01

Impact-generated hydrothermal systems have been previously linked to the alteration of Mars’ crust and the production of secondary mineral assemblages seen from orbit. The sensitivity of the resultant assemblages has not yet been evaluated as a function of precursor primary rock compositions. In this work, we use thermochemical modeling to explore the variety of minerals that could be produced by altering several known lithologies based on martian meteorite compositions. For a basaltic host rock lithology (Dhofar 378, Humphrey) the main alteration phases are feldspar, zeolite, pyroxene, chlorite, clay (nontronite, kaolinite), and hematite; for a lherzolithic host rock lithology (LEW 88516) the main alteration phases are amphibole, serpentine, chlorite, clay (nontronite, kaolinite), and hematite; and for an ultramafic host rock lithology (Chassigny) the main minerals are secondary olivine, serpentine, magnetite, quartz, and hematite. These assemblages and proportions of phases in each of those cases depend on W/R and temperature. Integrating geologic, hydrologic and alteration mineral evidence, we have developed a model to illustrate the distribution of alteration assemblages that occur in different levels of an impact structure. At the surface, hot, hydrous alteration affects the ejecta and melt sheet producing clay and chlorite. Deeper in the subsurface and depending on the permeability of the rock, a variety of minerals - smectite, chlorite, serpentine, amphiboles and hematite - are produced in a circulating hydrothermal system. These modeled mineral distributions should assist with interpretation of orbital observations and help guide surface exploration by rovers and sample return assets.

A 'Pot of Gold' Rich with Nuggets

NASA Technical Reports Server (NTRS)

2004-01-01

This close-up image taken by the Mars Exploration Rover Spirit highlights the nodular nuggets that cover the rock dubbed 'Pot of Gold.' These nuggets appear to stand on the end of stalk-like features. The surface of the rock is dotted with fine-scale pits. Data from the rover's scientific instruments have shown that Pot of Gold contains the mineral hematite, which can be formed with or without water.

Scientists are planning further observations of this rock, which they hope will yield more insight into the hematite's origins as well as how the enigmatic nuggets formed.

This image was taken by Spirit's microscopic imager on sol 162 (June 17, 2004). The observed area is 3 centimeters by 3 centimeters (1.2 inches by 1.2 inches)

A 'Pot of Gold' Rich with Nuggets (Sol 163-2)

NASA Technical Reports Server (NTRS)

2004-01-01

This close-up image taken by the Mars Exploration Rover Spirit highlights the nobular nuggets that cover the rock dubbed 'Pot of Gold.' These nuggets appear to stand on the end of stalk-like features. The surface of the rock is dotted with fine-scale pits. Data from the rover's scientific instruments have shown that Pot of Gold contains the mineral hematite, which can be formed with or without water.

Scientists are planning further observations of this rock, which they hope will yield more insight into the hematite's origins as well as how the enigmatic nuggets formed.

This image was taken by Spirit's microscopic imager on sol 163 (June 18, 2004). The observed area is 3 centimeters by 3 centimeters (1.2 inches by 1.2 inches).

A 'Pot of Gold' Rich with Nuggets (Sol 163)

NASA Technical Reports Server (NTRS)

2004-01-01

This close-up image taken by the Mars Exploration Rover Spirit highlights the nodular nuggets that cover the rock dubbed 'Pot of Gold.' These nuggets appear to stand on the end of stalk-like features. The surface of the rock is dotted with fine-scale pits. Data from the rover's scientific instruments have shown that Pot of Gold contains the mineral hematite, which can be formed with or without water.

Scientists are planning further observations of this rock, which they hope will yield more insight into the hematite's origins as well as how the enigmatic nuggets formed.

This image was taken by Spirit's microscopic imager on sol 163 (June 18, 2004). The observed area is 3 centimeters by 3 centimeters (1.2 inches by 1.2 inches).

Spontaneous Water Oxidation at Hematite (α-Fe2O3) Crystal Faces

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

Chatman, Shawn ME; Zarzycki, Piotr P.; Rosso, Kevin M.

2015-01-28

Hematite (α-Fe2O3) persists as a promising candidate for photoelectrochemical water splitting but a slow oxygen evolution reaction (OER) at its surfaces remains a limitation. Here we extend a series of studies that examine pH-dependent surface potentials and electron transfer properties of effectively perfect low-index crystal faces of hematite in contact with simple electrolyte. Zero resistance amperometry was performed in a two electrode configuration to quantify spontaneous dark current between hematite crystal face pairs (001)/(012), (001)/(113), and (012)/(113) at pH 3. Exponentially decaying currents initially of up to 200 nA were reported between faces over four minute experiments. Fourth order ZRAmore » kinetics indicated rate limitation by the OER for current that flows between (001)/(012) and (001)/(113) face pairs, with the (012) and (113) faces serving as the anodes when paired with (001). The cathodic partner reaction is reductive dissolution of the (001) face, converting surface Fe3+ to solubilized aqueous Fe2+, at a rate maintained by the OER at the anode. In contrast, OER rate limitation does not manifest for the (012)/(113) pair. The uniqueness of the (001) face is established in terms of a faster intrinsic ability to accept the protons required for the reductive dissolution reaction. OER rate limitation inversely may thus arise from sluggish kinetics of hematite surfaces to dispense with the protons that accompany the four-electron OER. The results are explained in terms of semi-quantitative energy band diagrams. The finding may be useful as a consideration for tailoring the design of polycrystalline hematite photoanodes that present multiple terminations to the interface with electrolyte.« less

Passivation of hematite nanorod photoanodes with a phosphorus overlayer for enhanced photoelectrochemical water oxidation

NASA Astrophysics Data System (ADS)

Xiong, Dehua; Li, Wei; Wang, Xiaoguang; Liu, Lifeng

2016-09-01

Hematite (i.e., α-Fe2O3) nanorod photoanodes passivated with a phosphorus overlayer have been fabricated by decomposing sodium hypophosphite (NaH2PO2) at a low temperature over the hematite nanorod surface. Extensive scanning electron microscopy, transmission electron microscopy, x-ray diffractometry and UV-vis spectroscopy characterizations confirm that conformal deposition of an amorphous phosphorus overlayer does not change the crystal structure, morphology, and optical absorption properties of hematite photoanodes. X-ray photoelectron spectroscopy reveals that phosphorus in the deposited overlayer exists in an oxidized state. Comprehensive steady-state polarization, transient photocurrent response, and impedance spectroscopy measurements as well as Mott-Schottky analysis manifest that the phosphorus overlayer is able to effectively passivate surface states and suppress electron-hole recombination, substantially enhancing the photocurrent for water oxidation. Combining the phosphorization treatment with two-step thermal activation, a photocurrent density of 1.1 mA cm-2 is achieved at 1.23 V versus reversible hydrogen electrode under illumination of 100 mW cm-2, ca 55 times higher than that of the non-activated pristine hematite photoanode measured under the same conditions. The simple and fast phosphorization strategy we present here can be readily applied to passivate surfaces of other semiconductor photoelectrodes to improve their photoelectrochemical performance.

Solution chemistry of carbonate minerals and its effects on the flotation of hematite with sodium oleate

NASA Astrophysics Data System (ADS)

Li, Dong; Yin, Wan-zhong; Xue, Ji-wei; Yao, Jin; Fu, Ya-feng; Liu, Qi

2017-07-01

The effects of carbonate minerals (dolomite and siderite) on the flotation of hematite using sodium oleate as a collector were investigated through flotation tests, supplemented by dissolution measurements, solution chemistry calculations, zeta-potential measurements, Fourier transform infrared (FTIR) spectroscopic studies, and X-ray photoelectron spectroscopy (XPS) analyses. The results of flotation tests show that the presence of siderite or dolomite reduced the recovery of hematite and that the inhibiting effects of dolomite were stronger. Dissolution measurements, solution chemistry calculations, and flotation tests confirmed that both the cations (Ca2+ and Mg2+) and CO3 2- ions dissolved from dolomite depressed hematite flotation, whereas only the CO3 2- ions dissolved from siderite were responsible for hematite depression. The zeta-potential, FTIR spectroscopic, and XPS analyses indicated that Ca2+, Mg2+, and CO3 2- (HCO3 -) could adsorb onto the hematite surface, thereby hindering the adsorption of sodium oleate, which was the main reason for the inhibiting effects of carbonate minerals on hematite flotation.

Experimental Constraints on Reconstruction of Archean Seawater Ni Isotopic Composition from Banded Iron Formations

NASA Astrophysics Data System (ADS)

Wang, S.; Wasylenki, L.

2016-12-01

Ni isotope systematics in banded iron formations (BIFs) potentially recorded the Ni isotopic composition of ancient seawater during the Precambrian Eon[1]. The use of BIFs as seawater proxies requires knowing how Ni isotopes fractionated during initial incorporation into iron-rich sediments and during early diagenesis. We conducted experiments to investigate Ni isotope behavior during coprecipitation with ferrihydrite and transformation of ferrihydrite to hematite. Ferrihydrite synthesis at neutral pH demonstrated that dissolved Ni was variably heavier than coprecipitated Ni (Δ60/58Ni = +0.08 to +0.50 ‰), in contrast to the constant offset observed earlier during adsorption to pre-existing ferrihydrite[2]. Experiments at lower pH (<7) yielded negative values of Δ60/58Ni ( -0.18 ‰), suggesting enrichment in heavier isotopes of structurally incorporated Ni relative to dissolved and adsorbed Ni, possibly due to the presence of a small amount of highly fractionated tetrahedral Ni2+ in the ferrihydrite structure. We model our results as equilibrium fractionation among three pools of Ni with systematically varied proportions. We synthesized hematite by transforming Ni-bearing ferrihydrite in aqueous solution at 100 °C and observed significant Ni release from solids (up to 60 %) as pH dropped from 7 to 4.5 - 5.5 during phase transformation. Rinsing hematite with acetic acid released very little Ni (presumably surface-adsorbed) compared to the amounts remaining in solid residues (presumably incorporated). We infer that Δ60/58Ni values (-0.04 to +0.77 ‰) observed in hematite experiments likely reflect Rayleigh fractionation between incorporated and dissolved Ni. The final hematite was slightly lighter than the ferrihydrite had been (by 0.08 ‰), indicating that this phase transformation results in very limited change in Ni isotopic composition, given current analytical uncertainty of ± 0.09 ‰. [1] Wasylenki and Wang (2016) Goldschmidt; [2] Wasylenki et al. (2015) ChemGeol.

Spherulitic (c-axis) Growth for Terrestrial (Mauna Kea, Hawaii) and Martian Hematite "blueberries"

NASA Technical Reports Server (NTRS)

Golden, D. C.; Ming, D. W.; Morris, R. V.

2006-01-01

Hematite concentrations observed by Thermal Emission Spectrometer (TES) onboard Mars Global Surveyor were considered a possible indicator for aqueous processes on Mars. Observations made by Opportunity show that the hematite at Meridiani Planum is present as spherules ( blueberries) and their fragments. The internal structure of the hematite spherules is not discernable at the resolution limit (approx.30 m/pixel) of Opportunity s Microscopic Imager (MI). A terrestrial analog for martian hematite spherules are spherules from hydrothermally altered and sulfate-rich tephra from the summit region of Mauna Kea volcano, Hawaii. The objective of this study is to determine the crystal growth fabric of the Mauna Kea hematite spherules using transmission electron microscopy (TEM) techniques and to relate that crystalline fabric to the observed TES signature of Meridiani Planum "blueberries." TEM analysis of Mauna Kea spherules exhibited a radial growth pattern consisting of "fibrous" hematite with the c-axis of hematite particles aligned along the elongation direction of the hematite fibers. The individual fibers appear to be made of coalesced nano-particles of hematite arranged with their c-axis oriented radially to form a spherical structure. Lattice fringes suggest long-range order across particles and along fibers. According to interpretations of thermal emission spectra for Meridian Planum hematite, the absence of a band at approx. 390/cm implies a geometry where c-face emission dominates. Because the c-face is perpendicular to the c-axis, this is precisely the geometry for the Mauna Kea spherules because the c-axis is aligned parallel to their radial growth direction. Therefore, we conclude as a working hypothesis that the martian spherules also have radial, c-axis growth pattern on a scale that is too small to be detected by the MER MI. Furthermore, by analogy with the Mauna Kea spherules, the martian blueberries could have formed during hydrothermal alteration of basaltic precursors under acid-sulfate conditions.

Particle size effect and the mechanism of hematite reduction by the outer membrane cytochrome OmcA of Shewanella oneidensis MR-1

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

Liu, Juan; Pearce, Carolyn I.; Shi, Liang

The cycling of iron at the Earth’s near surface is profoundly influenced by dissimilatory metal reducing microorganisms, and many studies have focused on unraveling electron transfer mechanisms between these bacteria and Fe(III)-(oxyhydr)oxides. However, these efforts have been complicated by the fact that these minerals often occur in the micro- to nanosize regime, and in relevant natural environments as well as in the laboratory are subject to aggregation. The nature of the physical interface between the cellular envelope, the outer-membrane cytochromes responsible for facilitating the interfacial electron transfer step, and these complex mineral particulates is thus difficult to probe. Previous studiesmore » using whole cells have reported reduction rates that do not correlate with particle size. In the present study we isolate the interaction between the decaheme outer-membrane cytochrome OmcA of Shewanella oneidensis and nanoparticulate hematite, examining the reduction rate as a function of particle size and reaction products through detailed characterization of the electron balance and the structure and valence of iron at particle surfaces. By comparison with abiotic reduction via the smaller molecule ascorbic acid, we show that the reduction rate is systematically controlled by the sterically accessible interfacial contact area between OmcA and hematite in particle aggregates; rates increase once pore throat sizes in aggregates become as large as OmcA. Simultaneous measure of OmcA oxidation against Fe(II) release shows a ratio of 1:10, consistent with a cascade OmcA oxidation mechanism heme by heme. X-ray absorption spectroscopies reveal incipient magnetite on the reacted surfaces of the hematite nanoparticles after reaction. The collective findings establish the importance of accessibility of physical contact between the terminal reductases and iron oxide surfaces, and through apparent consistency of observations help reconcile behavior reported at the larger more complex scale of whole cell studies.« less

Particle size effect and the mechanism of hematite reduction by the outer membrane cytochrome OmcA of Shewanella oneidensis MR-1

NASA Astrophysics Data System (ADS)

Liu, Juan; Pearce, Carolyn I.; Shi, Liang; Wang, Zheming; Shi, Zhi; Arenholz, Elke; Rosso, Kevin M.

2016-11-01

The cycling of iron at the Earth's near surface is profoundly influenced by dissimilatory metal reducing microorganisms, and many studies have focused on unraveling electron transfer mechanisms between these bacteria and Fe(III)-(oxyhydr)oxides. However, these efforts have been complicated by the fact that these minerals often occur in the micro- to nanosize regime, and in relevant natural environments as well as in the laboratory are subject to aggregation. The nature of the physical interface between the cellular envelope, the outer-membrane cytochromes responsible for facilitating the interfacial electron transfer step, and these complex mineral particulates is thus difficult to probe. Previous studies using whole cells have reported reduction rates that do not correlate with particle size. In the present study we isolate the interaction between the decaheme outer-membrane cytochrome OmcA of Shewanella oneidensis and nanoparticulate hematite, examining the reduction rate as a function of particle size and reaction products through detailed characterization of the electron balance and the structure and valence of iron at particle surfaces. By comparison with abiotic reduction via the smaller molecule ascorbic acid, we show that the reduction rate is systematically controlled by the sterically accessible interfacial contact area between OmcA and hematite in particle aggregates; rates increase once pore throat sizes in aggregates become as large as OmcA. Simultaneous measure of OmcA oxidation against Fe(II) release shows a ratio of 1:10, consistent with a cascade OmcA oxidation mechanism heme by heme. X-ray absorption spectroscopies reveal incipient magnetite on the reacted surfaces of the hematite nanoparticles after reaction. The collective findings establish the importance of accessibility of physical contact between the terminal reductases and iron oxide surfaces, and through apparent consistency of observations help reconcile behavior reported at the larger more complex scale of whole cell studies.

CO adsorption on small Au{sub n} (n = 1–4) structures supported on hematite. I. Adsorption on iron terminated α-Fe{sub 2}O{sub 3} (0001) surface

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

Pabisiak, Tomasz; Kiejna, Adam, E-mail: kiejna@ifd.uni.wroc.pl; Winiarski, Maciej J.

2016-01-28

This is the first of two papers dealing with the adsorption of Au and formation of Au{sub n} nanostructures (n = 1–4) on hematite (0001) surface and adsorption of CO thereon. The stoichiometric Fe-terminated (0001) surface of hematite was investigated using density functional theory in the generalized gradient approximation of Perdew-Burke-Ernzerhof (PBE) form with Hubbard correction U, accounting for strong electron correlations (PBE+U). The structural, energetic, and electronic properties of the systems studied were examined for vertical and flattened configurations of Au{sub n} nanostructures adsorbed on the hematite surfaces. The flattened ones, which can be viewed as bilayer-like structures, weremore » found energetically more favored than vertical ones. For both classes of structures the adsorption binding energy increases with the number of Au atoms in a structure. The adsorption of Au{sub n} induces charge rearrangement at the Au{sub n}/oxide contact which is reflected in work function changes. In most considered cases Au{sub n} adsorption increases the work function. A detailed analysis of the bonding electron charge is presented and the corresponding electron charge rearrangements at the contacts were quantified by a Bader charge analyses. The interaction of a CO molecule with the Au{sub n} nanostructures supported on α-Fe{sub 2}O{sub 3} (0001) and the oxide support was studied. It is found that the CO adsorption binding to the hematite supported Au{sub n} structures is more than twice as strong as to the bare hematite surface. Analysis of the Bader charges on the atoms showed that in each case CO binds to the most positively charged (cationic) atom of the Au{sub n} structure. Changes in the electronic structure of the Au{sub n} species and of the oxide support, and their consequences for the interactions with CO, are discussed.« less

Role of Outer Membrane C-Type Cytochromes MtrC and OmcA in Shewanella Oneidensis MR-1 Cell Production, Accumulation, and Detachment During Respiration on Hematite

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

Mitchell, Andrew C.; Peterson, L.; Reardon, Catherine L.

2012-07-01

Solid phase iron oxides are considered to be important terminal electron acceptors for microbial respiration in many anoxic environments. Besides the knowledge that cells attach to and reduce these substrates, other aspects of surface-associated cell behavior and the related cell surface components that influence cell-mineral interactions are not well understood. In the present study, wild-type cells of the dissimilatory iron-reducing bacterium Shewanella oneidensis MR-1 formed thin biofilms one-to-two cell layers in thickness when respiring on natural specular hematite under flow conditions similar to those which exist in aquatic sediments and subsurface environments. The distribution of cells within the biofilm indicatedmore » that direct contact was not required for electron transfer from cells to the mineral surface. Detached biomass in the form of single cells represented >99% of the surface-associated wild-type cell production from respiration on hematite over the biofilm life cycle. A mutant deficient in the outer membrane c35 type cytochrome OmcA, while still able to respire and replicate on hematite, established a lower steady-state cell density on the mineral surface than that of the wild-type strain. A mutant deficient in MtrC, another outer membrane c-type cytochrome, and a mutant deficient in both cytochromes were unable to reduce sufficient amounts of hematite to support detectable growth on the mineral surface. When considered in the context of previous work, the results support a growing body of evidence that the relative importance of OmcA and MtrC to cell respiration and replication depends on the form of iron oxide available as terminal electron acceptor.« less

Evidence for pigmentary hematite on Mars based on optical, magnetic, and Moessbauer studies of superparamagnetic (nanocrystalline) hematite

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Agresti, David G.; Newcomb, Jeffery A.; Shelfer, Tad D.; Lauer, Howard V., Jr.

1989-01-01

Samples containing variable amounts of superparamagnetic hematite (sp-Hm) were prepared by a method in which the sp-Hm particles were dispersed throughout larger particles of silica gel, and the optical and magnetic properties of these samples were compared with those of larger-diameter hematite (bulk-Hm). It is shown that the optical properties of sp-Hm are different from those of bulk-Hm. Implications of the results for mineralogical interpretations of spectral data for the Martian surface and its terrestrial analogues are discussed. It is concluded that features resulting from ferric iron in the Martian spectral data and the results of the Viking magnetic properties experiment are both consistent with hematite present as both sp-Hm and bulk-Hm; the hematite particles most likely occur in pigmentary form, i.e., as particles dispersed throughout the volume of a spectrally neutral material.

Cosmogenic 3He in hematite and goethite from Brazilian "canga" duricrust demonstrates the extreme stability of these surfaces

NASA Astrophysics Data System (ADS)

Shuster, David L.; Farley, Kenneth A.; Vasconcelos, Paulo M.; Balco, Greg; Monteiro, Hevelyn S.; Waltenberg, Kathryn; Stone, John O.

2012-05-01

Helium isotopes were measured in hematite and goethite samples from several lateritiric duricrusts (canga) developed on banded iron formations. These samples uniformly have high 3He concentrations which must arise from long periods of cosmic ray exposure. From coexisting phases from the Quadrilátero Ferrífero in east central Brazil, we determined the ratio of cosmogenic 3He in hematite to that of 21Ne in quartz to be 3.96 ± 0.19. Combined with best current estimates of the 21Ne production rate in quartz, this ratio implies a sea-level high latitude (SLHL) 3He production rate in hematite of 68.1 ± 8.1 atoms/g/yr; from the chemical composition we estimate the 3He production rate in goethite to be ~ 5% higher. We use these production rate estimates to interpret 3He concentrations measured in goethite and hematite from a ~ 10 m depth profile collected from a surface canga in Carajás, in the Amazon basin of Brazil. We find that the Carajás canga has experienced a very low rate of surface erosion (~ 0.16-0.54 m/Myr) over at least the last few millions of years. This iron-rich canga surface is remarkably resistant to erosion despite its location in a wet tropical environment. Details of the depth profile suggest that despite its stability, the canga has also been internally dynamic (translocation of material; solution and reprecipitation) over million-year timescales.

Inner-Helmholtz potential development at the hematite (α-Fe 2O 3) (0 0 1) surface

NASA Astrophysics Data System (ADS)

Boily, Jean-François; Chatman, Shawn; Rosso, Kevin M.

2011-08-01

Electric potentials of the (0 0 1) surface of hematite were measured as a function of pH and ionic strength in solutions of sodium nitrate and oxalic acid using the single-crystal electrode approach. The surface is predominantly charge-neutral in the pH 4-14 range, and develops a positive surface potential below pH 4 due to protonation of μ-OH 0 sites (p K1,1,0,int = -1.32). This site is resilient to deprotonation up to at least pH 14 (-p K-1,1,0,int ≫ 19). The associated Stern layer capacitance of 0.31-0.73 F/m 2 is smaller than typical values of powders, and possibly arises from a lower degree of surface solvation. Acid-promoted dissolution under elevated concentrations of HNO 3 etches the (0 0 1) surface, yielding a convoluted surface populated by -OH20.5+ sites. The resulting surface potential was therefore larger under these conditions than in the absence of dissolution. Oxalate ions also promoted (0 0 1) dissolution. Associated electric potentials were strongly negative, with values as large as -0.5 V, possibly from metal-bonded interactions with oxalate. The hematite surface can also acquire negative potentials in the pH 7-11 range due to surface complexation and/or precipitation of iron species (0.0038 Fe/nm 2) produced from acidic conditions. Oxalate-bearing systems also result in negative potentials in the same pH range, and may include ferric-oxalate surface complexes and/or surface precipitates. All measurements can be modeled by a thermodynamic model that can be used to predict inner-Helmholtz potentials of hematite surfaces.

Fine-grained Goethite as a Precursor for Martian Gray Hematite

NASA Technical Reports Server (NTRS)

Glotch, T. D.; Morris, R. V.; Sharp, T. G.; Christensen, P. R.

2003-01-01

Several isolated deposits of gray, crystalline hematite on Mars were discovered using data returned from the Thermal Emission Spectrometer (TES) instrument aboard the Mars Global Surveyor spacecraft. Christensen et al. provided five testable hypotheses regarding the formation of crystalline hematite on Mars: 1) low-temperature precipitation of Fe oxides/hydroxides from standing, oxygenated, Fe-rich water, followed by subsequent alteration to gray hematite, 2) low-temperature leaching of iron-bearing silicates and other materials leaving a Fe-rich residue laterite-style weathering) which is subsequently altered to gray hematite, 3) direct precipitation of gray hematite from Fe-rich circulating fluids of hydrothermal or other origin, 4) formation of gray hematitic surface coatings during weathering, and 5) thermal oxidation of magnetite-rich lavas. Since this initial work, several authors have examined the hematite deposits to determine their formation mechanism. Lane et al. cited the absence of a 390/ cm absorption in the martian hematite spectrum as evidence for platy hematite grains. Their model for the formation of the deposits includes deposition of any of a variety of iron oxides or oxyhydroxides by aqueous or hydrothermal fluids, burial and metamorphosis to gray platy hematite grains, and exhumation in recent times. Based on a detailed geomorphic examination of the Sinus Meridiani region, Hynek et al. conclude that the most likely method of hematite formation was either emplacement by a hydrothermal fluid or oxidation of a magnetite-rich pyroclastic deposit. Similarly, Arvidson et al., favor a model involving the alteration of pyroclastic deposits by aqueous or hydrothermal fluids. Finally, based on geochemical modeling and an examination of Aram Chaos, Catling and Moore favor emplacement by hydrothermal fluids with a minimum temperature of 100 C. Comparison of the average martian hematite spectrum measured by TES to hematite emissivity spectra for a variety of naturally occurring hematites shows small but potentially important differences. In particular, band shapes, positions and relative band emissivities of hematite spectra vary over the range of samples. These differences imply that the natural variability of thermal infrared hematite spectra has not been fully characterized, especially with respect to the reaction pathway and crystal structure.

Evidence for a Hematite Ore Body on Mars

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Lane, M. D.; Christensen, P. R.

2000-01-01

The Mars Global Surveyor (MGS) spacecraft was launched from Cape Kennedy in November 1996. MGS was put into orbit around Mars in September of 1997 and has since been sending back data from a suite of instruments, including the Thermal Emission Spectrometer (TES). The TES instrument is an interferometric spectrometer designed to map the surface mineralogy of Mars by measuring the midinfrared emitted radiation over the spectral region of about 1600 to 200 cm(exp -1) (about 6 to 50 microns). This mineralogically sensitive technique utilizes the characteristic intra- and inter-molecular vibrations of minerals that are manifested in the midinfrared spectra. These spectral "fingerprints" are unique because they are dependent upon chemical composition, crystal structure, crystal orientation, and other factors. Midinfrared spectral data received from the MGS-TES instrument have indicated the presence of a large deposit of hematite (alpha-Fe2O3) in Sinus Meridiani, Mars. This hematite ore body, that is accompanied by basalt, is really extensive, encompassing an area about 350 by 500 km. To better understand the geologic context of this large deposit, a detailed laboratory spectroscopic investigation was conducted using more than 20 hematite samples so that their spectra could be compared to the martian spectra. The samples included red and gray polycrystaline hand samples, gray single-crystal hand samples, and red and gray fine- and coarse-grained particulates. The laboratory analyses provided thermal emissivity spectra that, when compared to the hematite emissivity spectra from Mars, suggest the Sinus Meridiani hematite is possibly an exposure of oriented hematite grains. These grains are likely coarser that 10 microns (and may be much larger) and gray in color. The characteristic of oriented grains is suggested by the apparent crystal axis-dependence of the energy emitted from the surface of Mars. The strong degree of crystal alignment exhibited in the emissivity spectra of Mars suggests that these oriented hematite crystals most likely occur as bedrock of aligned specular hematite grains (possibly schistose in texture) or as a secondary coating on bedrock, rather than as discrete particles. We are investigating the nature of this vast hematite deposit in order to understand better the geologic setting and infer past conditions and geological evolution on Mars.

Evidence for a Hematite Ore Body on Mars

NASA Technical Reports Server (NTRS)

Lane, M. D.; Christensen, P. R.

2000-01-01

The Mars Global Surveyor (MGS) spacecraft was launched from Cape Kennedy in November 1996. MGS was put into orbit around Mars in September of 1997 and has since been sending back data from a suite of instruments, including the Thermal Emission Spectrometer (TES). The TES instrument is an interferometric spectrometer designed to map the surface mineralogy of Mars by measuring the midinfrared emitted radiation over the spectral region of approximately 1600 to 200 per centimeter (appjroximately 6 to 50 microns). This mineralogically sensitive technique utilizes the characteristic intra- and inter-molecular vibrations of minerals that are manifested in the midinfrared spectra. These spectral "fingerprints" are unique because they are dependent upon chemical composition, crystal structure, crystal orientation, and other factors. Midinfrared spectral data received from the MGS-TES instrument have indicated the presence of a large deposit of hematite (alpha-Fe2O3) in Sinus Meridiani, Mars. This hematite ore body, that is accompanied by basalt, is areally extensive, encompassing and area approximately 350 by 500 km. To better understand the geologic context of this large deposit, a detailed laboratory spectroscopic investigation was conducted using more than 20 hematite samples so that their spectra could be compared to the martian spectra. The samples included red and gray polycrystaline hand samples, gray single-crystal hand samples, and red and gray fine- and coarse-grained particulates. The laboratory analyses provided thermal emissivity spectra that, when compared to the hematite emissivity spectra from Mars, suggest the Sinus Meridiani hematite is possibly an exposure of oriented hematite grains. These grains are likely coarser that 10 microns (and may be much larger) and gray in color The characteristic of oriented grains is suggested by the apparent crystal axis-dependence of the energy emitted from the surface of Mars. The strong degree of crystal alignment exhibited in the emissivity spectra of Mars suggests that these oriented hematite crystals most likely occur as bedrock of aligned specular hematite grains (possibly schistose in texture) or as a secondary coating on bedrock, rather than as discrete particles. We are investigating the nature of this vast hematite deposit in order to understand better the geologic setting and infer past conditions and geological evolution on Mars.

The transformation of magnetite to hematite and its influence on the rheology of iron oxide rock

NASA Astrophysics Data System (ADS)

Lagoeiro, Leonardo; Barbosa, Paola; Goncalves, Fabio; Rodrigues, Carlos

2013-04-01

Phase transformation is an important process for strain localization after the initiation of ductile shear zones. In polyphase aggregates one important aspect to consider is likely to be the interconnectivity of weak phase after the transformation of the load-bearing framework grains. However the physical processes involved in that transition is not well understood, partially because the microstructures of the initial weakening are generally obliterated by subsequent deformation. Iron oxide-quartz rocks from paleoproterozoic Iron Formations in southern Brazil preserve microstructures that allow a good insight into the evolution of the deformation mechanisms and fabrics during the transition from a load-bearing framework (magnetite) to an interconnected weak phase (hematite). We conducted microstructural and textural analyses of aggregates of magnetite and hematite combining observations in an optical microscope and measurements in the electron back-scatter diffraction (EBSD). The samples were cut parallel to the mineral lineation (the X-axis) and perpendicular to the foliation. Our goal was to understand the evolution of fabric and texture of the iron oxide aggregates caused by the change in deformation behavior resulting from the phase transformation. The studied samples consist mainly of aggregates of magnetite and hematite in a varied proportions. Samples that preserve the early microstructures consist in aggregate of magnetite grains of varied sizes. The grains are partially transformed to hematite along {111} planes but no foliation is observed in the samples. Basically the samples consist of grains of irregular shapes and a weak or absent crystallographic preferred orientation. The newly transformed hematite crystals share the (0001) planes and directions <11-20> with planes {111} and directions <110> of magnetite grains. Other samples present relicts of initial magnetite grains surrounded by a matrix of tabular to platy hematite crystals. The matrix show a preferred orientation of hematite grains. Close to the magnetite, hematite crystals show crystallographic relationship similar to those observed inside the magnetite crystals showing a good match in crystallographic planes and directions. However away from the magnetite crystals hematite of the matrix tend to show a more independent crystallographic orientation with respect to the magnetite grains. The poles to the basal planes of hematite distributed in a small circle centered around the Z-axis and the crystallographic directions <11-20> spread in a wide angle along the foliation plane. In samples where no crystal of magnetite grains is observed only platy hematite with a strong shape preferred orientation occur. Their basal planes show a strong concentration around the foliation pole contrasting to the more dispersed distribution around the Z-axis found in the samples with magnetite relicts.The directions <11-20> also distributed along the foliation planes in platy hematite samples but with a narrower angles than those of samples with magnetite relicts. The progressive transformation of magnetite to hematite led to a change in the iron formation rock fabrics from an isotropic distribution of a load-supporting magnetite to an interconnected weak platy hematite forming a strongly anisotropic fabric. The hard magnetite behaves in a brittle manner with a very limited operation of slip along the main crystallographic planes. The microfracturing creates an easy path for oxidation and transformation of magnetite. The newly formed hematite grains behave in a ductile manner and form a matrix of strongly oriented crystals. The deformation mechanisms change from the microfracturing of the harder magnetite phase to a crystal plastic deformation of the softer hematite platy grains through slip along their basal planes.

Influence of Al substitution on magnetism and adsorption properties of hematite

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

Cao, Shanshan; Kang, Feifei; Yang, Xin

2015-08-15

A series of Al-substituted hematite was prepared. The structures and properties of as-prepared samples were characterized by various techniques. The magnetic property of the samples was determined and the adsorption of three dyes Acid Blue 74, Methylene Blue and Phenol Red onto the samples was investigated. The results showed that Al incorporation into the crystal structure of hematite occurs via isomorphous ionic substitution of Al for Fe. With increasing Al content, the particle size of samples decreases, the magnetization increases and the remanent magnetization remains unchanged. The coercivity of the samples increases with Al substitution up to n{sub Al}/n{sub Fe}more » 0.03, and then decreases as Al content further increases. Compared with Al-free hematite, Al-substituted samples exhibit better adsorption ability to all of the three dyes. The adsorption rates of the three dyes on the surface of Al substituted samples depend on the structure of dye, pH and Al content in hematite. - Graphical abstract: Effect of Al on the structure, magnetic properties and adsorption performance of hematite was investigated. - Highlights: • A series of Al-substituted α-Fe{sub 2}O{sub 3} was prepared. • Effect of Al content on the crystal structure and magnetic property of hematite was investigated. • Al-substituted hematite exhibits better adsorption ability than hematite.« less

In situ evidence for an ancient aqueous environment at Meridiani Planum, Mars.

PubMed

Squyres, S W; Grotzinger, J P; Arvidson, R E; Bell, J F; Calvin, W; Christensen, P R; Clark, B C; Crisp, J A; Farrand, W H; Herkenhoff, K E; Johnson, J R; Klingelhöfer, G; Knoll, A H; McLennan, S M; McSween, H Y; Morris, R V; Rice, J W; Rieder, R; Soderblom, L A

2004-12-03

Sedimentary rocks at Eagle crater in Meridiani Planum are composed of fine-grained siliciclastic materials derived from weathering of basaltic rocks, sulfate minerals (including magnesium sulfate and jarosite) that constitute several tens of percent of the rock by weight, and hematite. Cross-stratification observed in rock outcrops indicates eolian and aqueous transport. Diagenetic features include hematite-rich concretions and crystal-mold vugs. We interpret the rocks to be a mixture of chemical and siliciclastic sediments with a complex diagenetic history. The environmental conditions that they record include episodic inundation by shallow surface water, evaporation, and desiccation. The geologic record at Meridiani Planum suggests that conditions were suitable for biological activity for a period of time in martian history.

Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system

USGS Publications Warehouse

Lenhart, J.J.; Bargar, J.R.; Davis, J.A.

2001-01-01

Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb LIII-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 A??, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. ?? 2001 Academic Press.

Iron Oxide Films Prepared by Rapid Thermal Processing for Solar Energy Conversion

PubMed Central

Wickman, B.; Bastos Fanta, A.; Burrows, A.; Hellman, A.; Wagner, J. B.; Iandolo, B.

2017-01-01

Hematite is a promising and extensively investigated material for various photoelectrochemical (PEC) processes for energy conversion and storage, in particular for oxidation reactions. Thermal treatments during synthesis of hematite are found to affect the performance of hematite electrodes considerably. Herein, we present hematite thin films fabricated via one-step oxidation of Fe by rapid thermal processing (RTP). In particular, we investigate the effect of oxidation temperature on the PEC properties of hematite. Films prepared at 750 °C show the highest activity towards water oxidation. These films show the largest average grain size and the highest charge carrier density, as determined from electron microscopy and impedance spectroscopy analysis. We believe that the fast processing enabled by RTP makes this technique a preferred method for investigation of novel materials and architectures, potentially also on nanostructured electrodes, where retaining high surface area is crucial to maximize performance. PMID:28091573

On the influence of carbonate in mineral dissolution: I. The thermodynamics and kinetics of hematite dissolution in bicarbonate solutions at T = 25° C

NASA Astrophysics Data System (ADS)

Bruno, Jordi; Stumm, Werner; Wersin, Paul; Brandberg, Frederick

1992-03-01

We have studied the thermodynamics and kinetics of hematite dissolution in bicarbonate solutions under constant pCO 2. The solubility of hematite is increased in the presence of bicarbonate. We have established that the complexes responsible for this increase are FeOHCO 3 (aq) and Fe(CO 3) 2-. The stability constants of these complexes at the infinite dilution standard state are log β 11 = -3.83 ± 0.21 and log β 2 = 7.40 ± 0.11 , respectively (all errors are given at 2σ confidence level through this work). The rate of dissolution of hematite is enhanced in bicarbonate solutions. This rate of dissolution can be expressed as R diss = k 1[HCO 3-] 0.23 (mol m -2h -1), with k 1 = 1.42 10 -7h -1. The combination of the study of the surface complexation and kinetics of dissolution of hematite in bicarbonate solutions indicate that the dissolution of hematite is surface controlled and bicarbonate promoted. The rate of dissolution follows the expression R diss = k HCO 3-FeOH - HCO 3-}, where k HCO 3- = 1.1 10 -3 h -1. The implications of these findings in the oxic cycle of iron in natural waters are discussed, most importantly in order to explain the high-Fe(III) concentrations measured in groundwaters from the Poços de Caldas complex in Brazil.

Temperature-dependent infrared and calorimetric studies on arsenicals adsorption from solution to hematite nanoparticles

USDA-ARS?s Scientific Manuscript database

To address the lack of systematic and surface sensitive studies on the adsorption energetics of arsenic compounds on metal (oxyhydr)oxides, we conducted temperature-dependent ATR-FTIR studies for the adsorption of arsenate, monomethylarsonic acid, and dimethylarsinic acid on hematite nanoparticles a...

Surface Temperature Measurement Using Hematite Coating

NASA Technical Reports Server (NTRS)

Bencic, Timothy J. (Inventor)

2015-01-01

Systems and methods that are capable of measuring temperature via spectrophotometry principles are discussed herein. These systems and methods are based on the temperature dependence of the reflection spectrum of hematite. Light reflected from these sensors can be measured to determine a temperature, based on changes in the reflection spectrum discussed herein.

Synthesis and characterization of Sn-doped hematite as visible light photocatalyst

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

Cao, Zhiqin; School of Materials Science and Engineering, Pan Zhihua University, Pan Zhihua 617000; Qin, Mingli, E-mail: qinml@mater.ustb.edu.cn

2016-05-15

Highlights: • Sn-doped hematite nanoparticles are prepared by SCS in one step. • The Sn doping have the ability to inhibit particle growth of hematite. • Sn can enhance visible light harvesting and e{sup −}/h{sup +} separation. • Sn-doped hematite degrades MB under visible light effectively. • The products with 5 mol% Sn have the highest photocatalytic activity. - Abstract: Sn-doped hematite nanoparticles are prepared by solution combustion synthesis. The products are characterized with various analytical and spectroscopic techniques to determine their structural, morphological, light absorption and photocatalytic properties. The results reveal that all the samples consist of nanocrystalline hematitemore » with mesoporous structures, and Sn has the ability to inhibit the growth of hematite particle. Compared to pure hematite, the doped hematite samples with appropriate amount of Sn show better activities for degradation of methylene blue under visible light irradiation. The highest activity is observed for 5% Sn doped hematite and this product has long-term stability and no selectivity for dye degradation. The enhanced performance of 5% Sn doped hematite is ascribed to the smaller particle size, increased ability to absorb in visible light, efficient charge separation as well as improved e{sup −} transfer associated with the effects of appropriate amount of Sn doped sample.« less

Adsorption of bis(2-hydroxy-3-chloropropyl) dodecylamine on quartz surface and its implication on flotation

NASA Astrophysics Data System (ADS)

Liu, Wengang; Liu, Wenbao; Dai, Shujuan; Wang, Benying

2018-06-01

In order to clarify the effect of polar group modification on flotation performance of amine collector, flotation properties of quartz and hematite using bis(2-hydroxy-3-chloropropyl) dodecylamine (N23) as a collector were investigated. And the adsorption mechanism of N23 on quartz surface was established by zeta potential measurements, SEM/EDS measurements, and molecular structure analysis. Single mineral flotation results indicated that N23 showed stronger collecting ability on quartz and hematite than DDA-CH3COOH. However, starch could depress the flotation of hematite. Flotation recovery of 98.10% for quartz could be achieved, when N23 concentration was 43.33 mg/L and starch concentration was 16.67 mg/L at natural slurry pH. Separation of artificially mixed minerals of hematite and quartz was achieved effectively using N23 as the collector. The optimized separation result with 66.29% iron grade and 90.06% iron recovery in concentrate was obtained when slurry pH was 7.34 with 43.33 mg/L N23 and 23.33 mg/L starch. The interaction energies of N23 with mineral surface also showed well consistency with flotation results. SEM/EDS analyses and zeta potential measurements revealed that N23 could absorb on quartz surface in the forms of strong electrostatic and hydrogen bonding interaction. Compared with DDA, N23 had a higher HLB value and better water-solubility, which resulted in better dispersion in water and stronger adsorption on mineral surface.

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

Taylor, Sandra D.; Liu, Jia; Arey, Bruce W.

The distribution of iron resulting from the autocatalytic interaction of aqueous Fe(II) with the hematite (001) surface was directly mapped in three dimensions (3D) for the first time, using iron isotopic labelling and atom probe tomography (APT). Analyses of the mass spectrum showed that natural abundance ratios in 56Fe-dominant hematite are recovered at depth with good accuracy, whereas at the relict interface with 57Fe(II) solution evidence for hematite growth by oxidative adsorption of Fe(II) was found. 3D reconstructions of the isotope positions along the surface normal direction showed a zone enriched in 57Fe, which was consistent with an average netmore » adsorption of 3.2 – 4.3 57Fe atoms nm–2. Statistical analyses utilizing grid-based frequency distribution analyses show a heterogeneous, non-random distribution of oxidized Fe on the (001) surface, consistent with Volmer-Weber-like island growth. The unique 3D nature of the APT data provides an unprecedented means to quantify the atomic-scale distribution of sorbed 57Fe atoms and the extent of segregation on the hematite surface. This new ability to spatially map growth on single crystal faces at the atomic scale will enable resolution to long-standing unanswered questions about the underlying mechanisms for electron and atom exchange involved in a wide variety of redox-catalyzed processes at this archetypal and broadly relevant interface.« less

Probing size-dependent electrokinetics of hematite aggregates

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

Kedra-Królik, Karolina; Rosso, Kevin M.; Zarzycki, Piotr

Aqueous particle suspensions of many kinds are stabilized by the electrostatic potential developed at their surfaces from reaction with water and ions. An important and less well understood aspect of this stabilization is the dependence of the electrostatic surface potential on particle size. Surface electrostatics are typically probed by measuring particle electrophoretic mobilities and quantified in the electrokinetic potential (f), using commercially available Zeta Potential Analyzers (ZPA). Even though ZPAs provide frequency-spectra (histograms) of electrophoretic mobility and hydrodynamic diameter, typically only the maximal-intensity values are reported, despite the information in the remainder of the spectra. Here we propose a mappingmore » procedure that inter-correlates these histograms to extract additional insight, in this case to probe particle size-dependent electrokinetics. Our method is illustrated for a suspension of prototypical iron (III) oxide (hematite, a-Fe2O3). We found that the electrophoretic mobility and f-potential are a linear function of the aggregate size. By analyzing the distribution of surface site types as a function of aggregate size we show that site coordination increases with increasing aggregate diameter. This observation explains why the acidity of the iron oxide particles decreases with increasing particle size.« less

Plasma Generated Spherules

NASA Astrophysics Data System (ADS)

Ransom, C. J.

2005-04-01

Z-pinch plasma simulations have been performed that indicate the production of spherules under certain experimental parameters. (A. L. Peratt, private communication) While performing experiments dealing with the impact of plasma discharges on various materials, we observed that spherules were created at the surface of some of the materials. For specific materials and conditions, spherules were always produced. Both individual spherules and joined spherules were created. The size and shapes were nearly identical to items found by the Mars rover, Opportunity, and called ``blueberries.'' Sky & Telescope, June 2004, p. 20, among other sources indicated the blueberries were gray spherules composed of hematite. The experiments produced hematite spherules identical in appearance to those found on Mars. These experiments suggest how the newly discovered blueberries were formed on Mars while providing an explanation that does not depend on the presence of water.

Size-dependent structural transformations of hematite nanoparticles. 1. Phase transition.

PubMed

Chernyshova, I V; Hochella, M F; Madden, A S

2007-04-14

Using Fourier Transform InfraRed (FTIR) spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), and Transmission Electron Microscopy (TEM), we characterize the structure and/or morphology of hematite (alpha-Fe(2)O(3)) particles with sizes of 7, 18, 39 and 120 nm. It is found that these nanoparticles possess maghemite (gamma-Fe(2)O(3))-like defects in the near surface regions, to which a vibrational mode at 690 cm(-1), active both in FTIR and Raman spectra, is assigned. The fraction of the maghemite-like defects and the net lattice disorder are inversely related to the particle size. However, the effect is opposite for nanoparticles grown by sintering of smaller hematite precursors under conditions when the formation of a uniform hematite-like structure throughout the aggregate is restricted by kinetic issues. This means that not only particle size but also the growth kinetics determines the structure of the nanoparticles. The observed structural changes are interpreted as size-induced alpha-Fe(2)O(3)<-->gamma-Fe(2)O(3) phase transitions. We develop a general model that considers spinel defects and absorbed/adsorbed species (in our case, hydroxyls) as dominant controls on structural changes with particle size in hematite nanoparticles, including solid-state phase transitions. These changes are represented by trajectories in a phase diagram built in three phase coordinates-concentrations of spinel defects, absorbed impurities, and adsorbed species. The critical size for the onset of the alpha-->gamma phase transition depends on the particle environment, and for the dry particles used in this study is about 40 nm. The model supports the existence of intermediate phases (protohematite and hydrohematite) during dehydration of goethite. We also demonstrate that the hematite structure is significantly less defective when the nanoparticles are immersed in water or KBr matrix, which is explained by the effects of the electrochemical double layer and increased rigidity of the particle environment. Finally, we revise the problem of applicability of IR spectroscopy to the lattice vibrations of hematite nanoparticles, demonstrating that structural comparison of different samples is much more reliable if it is based on the E(u) band at about 460 cm(-1) and the spinel band at 690 cm(-1), instead of the A(2u)/E(u) band at about 550 cm(-1) used in previous work. The new methodology is applied to analysis of the reported IR spectra of Martian hematite.

Hematite-bearing materials surrounding Candor Mensa in Candor Chasma, Mars: Implications for hematite origin and post-emplacement modification

USGS Publications Warehouse

Fergason, Robin L.; Gaddis, Lisa R.; Rogers, A. D.

2014-01-01

The Valles Marineris canyon system on Mars is of enduring scientific interest in part due to the presence of interior mounds that contain extensive layering and water-altered minerals, such as crystalline gray hematite and hydrated sulfates. The presence of hematite and hydrated sulfate minerals is important because their host rock lithologies provide information about past environments that may have supported liquid water and may have been habitable. This work further defines the association and relationship between hematite-bearing materials and low albedo (presumably aeolian) deposits and layered materials, identifies physical characteristics that are strongly correlated with the presence of hematite, and refines hypotheses for the origin and post-emplacement modification (including transport) of these hematite-bearing and associated materials. There are only three regions surrounding Candor Mensa where hematite has been identified, even though morphologic properties are similar throughout the entire mensa. Three possible explanations for why hematite is only exposed in these regions include: (1) the topographic structure of the mensa walls concentrates hematite at the base of the layered deposits, influencing the ability to detect hematite from orbit; (2) the presence of differing amounts of “dark mantling material” and hematite-free erosional sediment; (3) the potential fracturing of the mensa and the influence of these structures on fluid flow and subsequent digenesis. The observations of hematite-bearing materials in this work support the hypothesis that hematite is eroding from a unit in the Candor Mensa interior layered deposits (ILD) and is being concentrated as a lag deposit adjacent to the lower layers of Candor Mensa and at the base in the form of dark aeolian material. Due to the similar geologic context associated with hematite-bearing and ILD materials throughout the Valles Marineris canyon system, the insight gained from studying these materials surrounding Candor Mensa can likely be applicable to similar layered deposits throughout Valles Marineris.

Effects of iron-containing minerals on hydrothermal reactions of ketones

NASA Astrophysics Data System (ADS)

Yang, Ziming; Gould, Ian R.; Williams, Lynda B.; Hartnett, Hilairy E.; Shock, Everett L.

2018-02-01

Hydrothermal organic transformations occurring in geochemical processes are influenced by the surrounding environments including rocks and minerals. This work is focused on the effects of five common minerals on reactions of a model ketone substrate, dibenzylketone (DBK), in an experimental hydrothermal system. Ketones play a central role in many hydrothermal organic functional group transformations, such as those converting hydrocarbons to oxygenated compounds; however, how these minerals control the hydrothermal chemistry of ketones is poorly understood. Under the hydrothermal conditions of 300 °C and 70 MPa for up to 168 h, we observed that, while quartz (SiO2) and corundum (Al2O3) had no detectable effect on the hydrothermal reactions of DBK, iron-containing minerals, such as hematite (Fe2O3), magnetite (Fe3O4), and troilite (synthetic FeS), accelerated the reaction of DBK by up to an order of magnitude. We observed that fragmentation products, such as toluene and bibenzyl, dominated in the presence of hematite or magnetite, while use of troilite gave primarily the reduction products, e.g., 1, 3-diphenyl-propane and 1, 3-diphenyl-2-propanol. The roles of the three iron minerals in these transformations were further explored by (1) control experiments with various mineral surface areas, (2) measuring H2 in hydrothermal solutions, and (3) determining hydrogen balance among the organic products. These results suggest the reactions catalyzed by iron oxides (hematite and magnetite) are promoted mainly by the mineral surfaces, whereas the sulfide mineral (troilite) facilitated the reduction of ketone in the reaction solution. Therefore, this work not only provides a useful chemical approach to study and uncover complicated hydrothermal organic-mineral interactions, but also fosters a mechanistic understanding of ketone reactions in the deep carbon cycle.

Direct electron-transfer conduits constructed at the interface between multicopper oxidase and nanocrystalline semiconductive Fe oxides

NASA Astrophysics Data System (ADS)

Nakamura, Ryuhei; Kamiya, Kazuhide; Hashimoto, Kazuhito

2010-10-01

Herein, the electron-transfer reactions occurring at the interface between bilirubin oxidase (BOD) and nanocrystalline hematite (α-Fe 2O 3) were characterized. Cyclic voltammograms indicated that BOD has an affinity for hematite surfaces and establishes a direct electron-transfer (DET) conduit between the primary electron acceptor T1 site and the conduction band of α-Fe 2O 3. DET was also confirmed photo-electrochemically, as cathodic photocurrents were generated when a nanocomposite of BOD and α-Fe 2O 3 was illuminated under oxygenated conditions. A proline residue displayed a high-binding affinity for hematite surfaces and is therefore likely part of an orientation-controlled motif which serves to locate BOD at the T1 site at a suitable distance for DET to α-Fe 2O 3.

Ab initio simulation of structure and surface energy of low-index surfaces of stoichiometric α-Fe2O3

NASA Astrophysics Data System (ADS)

Stirner, Thomas; Scholz, David; Sun, Jizhong

2018-05-01

The structure and surface energy of a series of low-index surfaces of stoichiometric α-Fe2O3 (hematite) are investigated using the periodic Hartree-Fock approach with an a posteriori correction of the correlation energy. The simulations show that, amongst the modeled facets, (01 1 bar2) and (0001) are the most stable surfaces of hematite, which is consistent with the fact that the latter are the dominant growth faces exposed on natural α-Fe2O3. The Fe-terminated (0001) surface is shown to exhibit a large relaxation of the surface atoms. It is argued that this arises mainly due to the fact that the surface cations are located opposite empty cation sites in the filled-filled-unfilled cation sequence along the c-axis. In contrast, the (01 1 bar2) plane cuts the crystal through a plane of empty cation sites, thus giving rise to relatively small relaxations and surface energies. The small relaxations and concomitant exposure of five-coordinate cation sites may be important for the catalytic activity of hematite. The simulations also show that the relative stability of the investigated surfaces changes after a full lattice relaxation with the (0001) and (11 2 bar6) facets relaxing disproportionately large. Wherever possible, the simulations are compared with previous simulation data and experimental results. A Wulff-Gibbs construction is also presented.

The role of the domain size and titanium dopant in nanocrystalline hematite thin films for water photolysis

DOE PAGES

Yan, Danhua; Tao, Jing; Kisslinger, Kim; ...

2015-10-13

Here we develop a novel technique for preparing high quality Ti-doped hematite thin films for photoelectrochemical (PEC) water splitting, through sputtering deposition of metallic iron films from an iron target embedded with titanium (dopants) pellets, followed by a thermal oxidation step that turns the metal films into doped hematite. It is found that the hematite domain size can be tuned from ~10 nm to over 100 nm by adjusting the sputtering atmosphere from more oxidative to mostly inert. The better crystallinity at a larger domain size ensures excellent PEC water splitting performance, leading to record high photocurrent from pure planarmore » hematite thin films on FTO substrates. Titanium doping further enhances the PEC performance of hematite photoanodes. The photocurrent is improved by 50%, with a titanium dopant concentration as low as 0.5 atom%. As a result, it is also found that the role of the titanium dopant in improving the PEC performance is not apparently related to the films’ electrical conductivity which had been widely believed, but is more likely due to the passivation of surface defects by the titanium dopants.« less

Helium diffusion parameters of hematite from a single-diffusion-domain crystal

NASA Astrophysics Data System (ADS)

Farley, K. A.

2018-06-01

This contribution reports new parameters for helium diffusion in hematite useful for interpretation of cosmogenic 3He and radiogenic 4He chronometry. Fragments of a coarse, euhedral single crystal of hematite from Minas Gerais, Brazil were subjected to bulk step-heating helium diffusion experiments after proton irradiation to make a uniform distribution of 3He. Aliquots of three different grain sizes ranging from ∼300 to ∼700 μm in equivalent-sphere radius yielded helium diffusion activation energies Ea ∼ 170 kJ/mol, very similar to previous estimates for Ea in hematite. Uniquely in this specimen, diffusivity varies with the dimensions of the analyzed fragments in precisely the fashion expected if the diffusion domain corresponds to the physical grain. This contrasts with previous studies that concluded that the analyzed hematites consist of polycrystalline aggregates in which helium migration is governed by the size distribution of the constituent crystallites. These new data permit a direct estimate of the helium diffusivity at infinite temperature for hematite of ln(Do) = -0.66 ± 0.35 in cm2/s. The major implication of the new diffusion parameters is that hematite is very retentive of helium even at very small crystal sizes. For example, a 20 nm radius hematite crystal, at the smallest end of the size range so far described in dated polycrystalline hematite specimens, will retain more than 99% of its ingrown He over 1 Myr at 30 °C, and more than 90% over 100 Myr. Under most conditions, hematite is close to quantitatively helium-retentive on the Earth's surface, simplifying radiogenic and cosmogenic helium dating of this phase. In a system cooling at 10 °C/Myr, the 20 nm hematite crystal has a He closure temperature of ∼70 °C, similar to a typical ∼100 μm apatite crystal. Helium is likely held tightly in hematite owing to its dense hexagonal closest packing structure and absence of migration-enhancing channels. The isostructural minerals corundum and ilmenite are likely to be similarly helium retentive.

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode.

PubMed

Shinde, Pravin S; Lee, Su Yong; Choi, Sun Hee; Lee, Hyun Hwi; Ryu, Jungho; Jang, Jum Suk

2016-08-31

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr(4+) ions from ZrO2 UL and Sn(4+) ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes.

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode

NASA Astrophysics Data System (ADS)

Shinde, Pravin S.; Lee, Su Yong; Choi, Sun Hee; Lee, Hyun Hwi; Ryu, Jungho; Jang, Jum Suk

2016-08-01

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr4+ ions from ZrO2 UL and Sn4+ ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes.

Design, Fabrication, and Characterization of Hematite (α-Fe2O3) Nanostructures

NASA Astrophysics Data System (ADS)

Jansi Rani, B.; Mageswari, R.; Ravi, G.; Ganesh, V.; Yuvakkumar, R.

2017-12-01

The influence of processing parameters on the physicochemical properties of hematite α-Fe2O3 nanostructures was investigated. X-ray diffraction results revealed the hematite phase rhombohedral structure. Scanning electron microscope results explored nanospheres, nanohexagonal platelets, nanoellipsoids, distorted nanocubes, and interconnected platelets nanostructures. Rhombohedral single-phase hematite was confirmed through five Raman active modes. 2 P 3/2 (1) → 2 P 1/2 transition in photoluminescence spectra and Fourier-transform infrared spectroscopy band observed at 555 cm-1 revealed the hematite formation. The highest specific capacitance value of 151.09 F/g for scan rate of 10 mV/s was obtained for the hydrothermal-assisted product using an Fe(NO3)2·9H2O precursor in KOH electrolyte solutions.

Identifying the role of cytochromes upon the attachment, growth and detachment of Shewanella oneidensis MR-1 on hematite during dissimilatory iron reduction under natural- flow conditions

NASA Astrophysics Data System (ADS)

Mitchell, A. C.; Geesey, G. G.

2006-12-01

Current understanding of bacterial respiration by dissimilatory iron (Fe) reduction is based primarily on studies of closed systems using soluble Fe(III). However, natural environments likely to support Fe reduction are typically open systems and contain Fe(III) primarily in the form of crystalline (hydr)oxides. Mechanisms by which electrons are transported between bacteria and mineral terminal electron acceptors (TEAs) under open system conditions are still poorly understood. However, a number of cytochromes have been identified as potentially playing a critical role in the electron transport system of some Fe reducing bacteria. Experiments were performed using (i) omcA, (ii) mtrC, or (iii) omcA and mtrC cytochrome deficient mutants of the Fe-reducing bacteria, Shewanella oneidensis MR-1, in transparent-window flow- reactors containing hematite as the only TEA. These were operated under defined hydrodynamic and anaerobic conditions. Cells expressed green fluorescent protein (gfp), allowing real time measurement of cells at the mineral surface by epifluorescence microscopy. Cytochromes which play a critical role in the anaerobic growth of S. Oneidensis by Fe reduction under open system natural-flow conditions could then be identified. Differences in the accumulation, maximum density, detachment and total production of surface-associated cells growing on hematite surfaces were apparent between the mutants, and between the mutants and the wild-type. Mutants deficient in cytochromes grew to a lower max density by up to 2 orders of magnitude than the wild-type, and exhibited no reduced Fe in the reactor effluent or at the surface of the hematite at the conclusion of the experiment, as revealed by X-Ray photoelectron spectroscopy (XPS). Therefore omcA and / or mtrC cytochromes appear critical for electron shuttling and anaerobic growth of S. Oneidensis on hematite under natural-flow conditions.

Hematite photoanode co-functionalized with self-assembling melanin and C-phycocyanin for solar water splitting at neutral pH

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

Schrantz, Krisztina; Wyss, Pradeep P.; Ihssen, Julian

2017-04-01

tNature provides functional units which can be integrated in inorganic solar cell materials, such as lightharvesting antenna proteins and photosynthetic molecular machineries, and thus help in advancing artifi-cial photosynthesis. Their integration needs to address mechanical adhesion, light capture, charge transferand corrosion resistance. We showed recently how enzymatic polymerization of melanin can immobi-lize the cyanobacterial light harvesting protein C-phycocyanin on the surface of hematite, a prospectivemetal oxide photoanode for solar hydrogen production by water splitting in photoelectrochemical cells.After the optimization of the functionalization procedure, in this work we show reproducible hydrogenproduction, measured parallel to the photocurrent on this bio-hybrid electrode inmore » benign neutral pHphosphate. Over 90% increase compared to the photocurrent of the pristine hematite could be achieved.The hydrogen evolution was monitored during the photoelectrochemical measurement in an improvedphotoelectrochemical cell. The C-phycocyanin-melanin coating on the hematite was shown to exhibit acomb-like fractal pattern. Raman spectroscopy supported the presence of the protein on the hematiteanode surface. The stability of the protein coating is demonstrated during the 2 h GC measurement andthe 24 h operando current density measurement« less

Adsorption of polyethyleneimine and polymethacrylic acid onto synthesized hematite.

PubMed

Chibowski, S; Patkowski, J; Grzadka, E

2009-01-01

An influence of different functional groups of polymer, its molecular weight, polydispersity ratio (M(w)/M(n)) and presence of impurities on its adsorption in different pH values (3, 6 and 9) onto synthesized hematite (Fe(2)O(3)) was measured. A structure of adsorbed macromolecules of PMA and PEI was obtained according to S-F theory. Two polymers were used: polymethacrylic acid (PMA) of 6500 and 75,100 molecular weight as well as polyethyleneimine (PEI) 25,000 commercial and fractionated. Electrokinetic properties of the interface oxide-polymer solution (surface charge density and zeta potential) were also measured as well as adsorption layer thicknesses (with use of viscosimetric measurements). Obtained data show, that all above-mentioned factors do influence not only the adsorption process itself but also a surface charge, zeta potential and structure of adsorbed polymer layers on polymer/hematite interface.

Molecular dynamics simulation of siderite-hematite-quartz flotation with sodium oleate

NASA Astrophysics Data System (ADS)

Li, Lixia; Hao, Haiqing; Yuan, Zhitao; Liu, Jiongtian

2017-10-01

Models of sodium oleate adsorption on siderite, hematite and quartz were investigated by molecular dynamic simulation, respectively. Surface energy was calculated to confirm the cleavage plan of hematite and quartz. Both natural cleavage plane of siderite and calculated plane were used to investigate the flotation of the three minerals. Based on the molecular simulation in solution with water as medium, adsorption quantity and interaction capability of oleate ions on the three minerals indicated that siderite could be collected efficiently by sodium oleate at neutral pH. Results of flotation experiments were further demonstrated by analysis of relative concentration of carbon atoms and oxygen atoms.

[Reduction of nitrobenzene by iron oxides bound Fe(II) system at different pH values].

PubMed

Luan, Fu-Bo; Xie, Li; Li, Jun; Zhou, Qi

2009-07-15

Batch tests were conducted to investigate the reductive transformation of nitrobenzene by goethite, hematite, magnetite and steel converter slag bound Fe(II) system. And the reduction mechanism was explored at different pH values. Experimental results showed that hematite, magnetite and steel converter slag could adsorb Fe(II) on surfaces and form iron oxides bound Fe(II) system at pH from 6.5 to 7.0. The systems had strong reductive capacity and could reduce nitrobenzene to aniline. The reduction efficiency of nitrobenzene in surface bound Fe(II) system followed the sequence of magnetite, hematite and steel converter slag from high to low. The reduction efficiency of hematite and magnetite system increased with pH increasing. While it was almost pH independent in steel converter slag system. Although goethite adsorbed most of Fe(II) in solution, the adsorbed Fe(II) had no reductive activity for nitrobenzene. At pH 6.0, small amount of Fe(II) was adsorbed on magnetite and hematite and the systems did not show reductive activity for nitrobenzene. However, steel converter slag could adsorb Fe(II) at pH 6.0 and reduction efficiency almost equaled to the value at pH 7.0. When pH was above 7.5, dissolved Fe(II) could be converted to Fe(OH)2 and the newly formed Fe(OH)2 became the main redactor in the system. Under alkali condition, the presence of iron oxides inhibited the reduction capacity of system.

Keepers of the Hematite

NASA Technical Reports Server (NTRS)

2004-01-01

This figure shows spectra taken by the Mars Exploration Rover Opportunity's Moessbauer spectrometer at various spots in 'Eagle Crater.' From top to bottom, the spectra represent soil measurements taken from the center of the crater and out to the rim. The top spectrum taken on sol 56 near the center of the crater shows a basaltic mineral composition and only minor amounts of hematite. Basalts are volcanic minerals and hematite is an iron-bearing mineral often formed in water. Moving closer to the rim, the spectra show increasing amounts of hematite with the 'Punaluu' site containing the highest amounts seen to date on Mars. Only minor basaltic components are seen in this sample.

The corresponding microscopic image of Punaluu shows a high density of 'blueberries,' indicating that these sphere-like grains are responsible for the observed high levels of hematite.

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.

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.

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode

PubMed Central

Shinde, Pravin S.; Lee, Su Yong; Choi, Sun Hee; Lee, Hyun Hwi; Ryu, Jungho; Jang, Jum Suk

2016-01-01

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr4+ ions from ZrO2 UL and Sn4+ ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes. PMID:27577967

Mineralogy and geochemistry of the Meridiani landing site as determined by the Mars Exploration Rover Opportunity

NASA Astrophysics Data System (ADS)

Calvin, W. M.; Athena Science Team

The Meridiani Planum landing site was selected based on a unique mineralogical signature (coarse hematite) observed from orbit, as well as suitability for rover landing and operations. On January 25th (UTC) the spacecraft executed a flawless landing, placing the rover Opportunity inside a small crater. Navigation and panorama camera images (Navcam and Pancam) returned during the first days on the surface set the initial exploration goals for the rover and the Athena Science Payload. Within the crater is a rock outcrop unlike anything previously observed from the surface of Mars. Color and textural variations were immediately evident both in the outcrop and in soils, especially in conjunction with the final rolling trajectory of the lander system and the airbag retraction. First observations by the Mini-Thermal Emission Spectrometer (Mini-TES) confirmed the spectral signature of coarse-grained hematite seen from orbit and found significant spatial variability in the strength of this feature. Pancam data confirm that the hematite rich regions do not have a strong color variation. The rover executed Alpha-Particle X-Ray Spectrometer (APXS) and Moessbauer (MB) measurements on the soil immediately after egress from the lander. Opportunity then approached one end of the outcrop, obtaining APXS, MB, Mini-TES and Pancam spectral data in addition to 30 micrometers per pixel images from the Microscopic Imager (MI). This site revealed the small unusual spherical grains, dubbed "blueberries" by the Team, that are eroding from the outcrop, and a higher sulfur content than all previous measurements on Mars. We then proceeded with a systematic survey of the outcrop in three stops, performing Mini-TES and Pancam at each stop. A traverse was made to an area more rich in hematite (as determined by Mini-TES) where a trench into the soil was performed with accompanying pre- and post-trench measurements by all spectral instruments. Opportunity then returned to a high-priority target in the center of the outcrop, called El Capitan, where distinct differences were noted in Pancam observations of the upper and lower units. As of the abstract deadline, the rover was performing a systematic survey on both the upper and lower units and preparing for the first use of the Rock Abrasion Tool (RAT) on the lower outcrop unit with spectral observations by all instruments before and after "ratting". Surveys of the magnets mounted on the rover deck provides information on accumulated atmospheric dust. A summary of the chemical and mineralogical signatures determined by these measurements as well as targets yet to be explored outside the crater will be presented at the Assembly.

Lepidocrocite to Maghemite to Hematite: A way to have Magnetic and Hematitic Martian Soil

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Golden, D. C.; Shelfer, Tad D.; Lauer, H. V., Jr.

1997-01-01

We examined decomposition products of lepidocrocite, which were produced by heating the phase in air at temperatures up to 525 C for 3 and 300 hr, by XRD, TEM, magnetic methods, and reflectance spectroscopy (visible and near-IR). Single-crystal lepidocrocite particles dehydroxilated to polycrystalline particles of disordered maghemite which subsequently transformed to polycrystalline particles of hematite. Essentially pure maghemite was obtained at 265 and 223 C for the 3 and 300 hr heating experiments, respectively. Its saturation magnetization (J(sub s)) and mass specific susceptibility are approximately 50 A(sq m)/kg and approximately 40 cubic micrometers/kg, respectively. Because hematite is spectrally dominant, spectrally-hematitic samples (i.e., characterized bv a minimum near 860 nm and a maximum near 750 nm) could also be strongly magnetic (J(sub s) up to approximately 30 A(sq m)/kg) from the masked maghemite component. TEM analyses showed that individual particles are polycrystalline with respect to both maghemite and hematite. The spectrally-hematitic and magnetic Mh+Hm particles can satisfy the spectral and magnetic constraints for Martian surface materials over a wide range of values of Mh/(Mh+Hm) and as either pure oxide powders or (within limits) as components of multiphase particles. These experiments are consistent with lepidocrocite as the precursor of Mh+Hm assemblages on Mars, but other phases (e.g., magnetite) that decompose to Mh and Hm are also possible precursors. Simulations done with a copy of the Mars Pathfinder Magnet Array showed that spectrally hematitic Mh+Hm powders having J(sub s) equal to 20.6 A(sq m)/kg adhered to all five magnets.

Synthesis of hematite and maghemite nanotubes and study of their applications in neuroscience and drug delivery

NASA Astrophysics Data System (ADS)

Chen, Linfeng; Xie, Jining; Aatre, Kiran R.; Yancey, Justin; Chetan, Sahitya; Srivatsan, Malathi; Varadan, Vijay K.

2011-04-01

This report discusses our work on synthesis of hematite and maghemite nanotubes, analysis of their biocompatibility with pheochromocytoma cells (PC12 cells), and study of their applications in the culture of dorsal root ganglion (DRG) neurons and the delivery of ibuprofen sodium salt (ISS) drug model. Two methods, template-assisted thermal decomposition method and hydrothermal method, were used for synthesizing hematite nanotubes, and maghemite nanotubes were obtained from the synthesized hematite nanotubes by thermal treatment. The crystalline, morphology and magnetic properties of the hematite and maghemite nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and vibrating sample magnetometer (VSM), respectively. The biocompatibility of the synthesized hematite nanotubes was confirmed by the survival and differentiation of PC12 cells in the presence of the hematite nanotubes coupled to nerve growth factor (NGF). To study the combined effects of the presence of magnetic nanotubes and external magnetic fields on neurite growth, laminin was coupled to hematite and maghemite nanotubes, and DRG neurons were cultured in the presence of the treated nanotubes with the application of external magnetic fields. It was found that neurons can better tolerate external magnetic fields when magnetic nanotubes were present. Close contacts between nanotubes and filopodia that were observed under SEM showed that the nanotubes and the growing neurites interacted readily. The drug loading and release capabilities of hematite nanotubes synthesized by hydrothermal method were tested by using ibuprofen sodium salt (ISS) as a drug model. Our experimental results indicate that hematite and maghemite nanotubes have good biocompatibility with neurons, could be used in regulating neurite growth, and are promising vehicles for drug delivery.

Confinement and surface effects on the physical properties of rhombohedral-shape hematite (α-Fe{sub 2}O{sub 3}) nanocrystals

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

Luna, Carlos, E-mail: carlos.lunacd@uanl.edu.mx; Cuan-Guerra, Aída D.; Barriga-Castro, Enrique D.

2016-08-15

Highlights: • Uniform rhombohedral hematite nanocrystals (RHNCs) have been obtained. • A detailed formation mechanism of these HNCS has been proposed. • Phonon confinement effects were revealed in the RHNCS vibrational bands. • Quantum confinement effects on the optical and electronic properties were found. - Abstract: Morphological, microstructural and vibrational properties of hematite (α-Fe{sub 2}O{sub 3}) nanocrystals with a rhombohedral shape and rounded edges, obtained by forced hydrolysis of iron(III) solutions under a fast nucleation, have been investigated in detail as a function of aging time. These studies allowed us to propose a detailed formation mechanism and revealed that thesemore » nanocrystals are composed of four {104} side facets, two {110} faces at the edges of the long diagonal of the nanocrystals and two {−441} facets as the top and bottom faces. Also, the presence of nanoscopic pores and fissures was evidenced. The vibrational bands of such nanocrystals were shifted to lower frequencies in comparison with bulk hematite ones as the nanocrystal size was reduced due to phonon confinement effects. Also, the indirect and direct transition band gaps displayed interesting dependences on the aging time arising from quantum confinement and surface effects.« less

Hematite-Ilmenite with Magnetite from the Ecstall Pluton, British Columbia: Single Crystal Magnetic Experiments

NASA Astrophysics Data System (ADS)

Scott, G. R.; Brownlee, S. J.; Feinberg, J. M.; Renne, P. R.

2008-12-01

Rocks provide a compound paleomagnetic signal from mixtures of various iron minerals with different grain sizes and magnetic stabilities. To unravel this complex signal, specific mineral phases with stable remanence can be individually examined as single crystals. In the case of the Ecstall Pluton (~91 Ma), intra-pluton discordance of paleomagnetic directions may be the result of post-crystallization deformation, or mineralogical changes caused by re-heating from the adjacent Quottoon Pluton (~52 Ma). In order to distinguish between these two hypotheses we conducted rock magnetic experiments on single crystals of finely-exsolved hematite-ilmenite along a transect approaching the Quottoon Pluton. Reflected light, and SEM observations show grains of hematite and ilmenite as the dominant Fe-oxide throughout the Ecstall. Nearest the Quottoon Pluton, the hematite-ilmenite grains exhibit the classic rutile blitz texture. The lamellar microstructure observed in the hematite-ilmenite grains, as well as the rutile blitz texture are linked to the thermal history of the Ecstall Pluton, and have important effects on the magnetic properties of these grains (i.e. lamellar magnetism). Our results include the magnetic unmixing of isothermal remanence magnetization (IRM) acquisition, First Order Reversal Curve (FORC) diagrams, temperature vs. remanence experiments (MPMS), and TEM studies. These data provide a spatially resolved record of rock magnetic variations across the Ecstall Pluton, showing evidence of thermally activated reduction of hematite to magnetite in samples within 13 km of the Quottoon Pluton. TEM analysis shows the magnetite is present as 20-50 nm-sized particles within hematite. This mineralogic change may be responsible for the variations in paleomagnetic directions across the Ecstall Pluton, and clear evidence for this reaction cannot be found by traditional rock characterization techniques, illustrating the need to couple detailed rock magnetic, paleomagnetic, and mineralogic analyses.

Hole transport in pure and doped hematite

NASA Astrophysics Data System (ADS)

Liao, Peilin; Carter, Emily A.

2012-07-01

Hematite (α-Fe2O3) is a promising candidate for use in photovoltaic (PV) and photoelectrochemical devices. Its poor conductivity is one major drawback. Doping hematite either p-type or n-type greatly enhances its measured conductivity and is required for potential p-n junctions in PVs. Here, we study hole transport in pure and doped hematite using an electrostatically embedded cluster model with ab initio quantum mechanics (unrestricted Hartree-Fock theory). Consistent with previous work, the model suggests that hole hopping is via oxygen anions for pure hematite. The activation energy for hole mobility is predicted to be at least 0.1 eV higher than the activation energy for electron mobility, consistent with the trend observed in experiments. We examine four dopants—magnesium(II), nickel(II), copper(II), and manganese(II/III) in direct cation substitution sites—to gain insight into the mechanism by which conductivity is improved. The activation energies are used to assess qualitative effects of different dopants. The hole carriers are predicted to be attracted to O anions near the dopants. The magnitude of the trapping effect is similar among the four dopants in their +2 oxidation states. The multivalent character of Mn doping facilitates local hole transport around Mn centers via a low-barrier O-Mn-O pathway, which suggests that higher hole mobility can be achieved with increasing Mn doping concentration, especially when a network of these low-barrier pathways is produced. Our results suggest that the experimentally observed conductivity increase in Mg-, Ni-, and Cu-doped p-type hematite is mostly due to an increase in hole carriers rather than improved mobility, and that Mg-, Ni-, and Cu-doping perform similarly, while the conductivity of Mn-doped hematite might be significantly improved in the high doping concentration limit.

Differential cellular responses in healthy mice and in mice with established airway inflammation when exposed to hematite nanoparticles

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

Gustafsson, Åsa, E-mail: asa.gustafsson@foi.se; Dept of Public Health and Clinical Medicine, Umeå University; Bergström, Ulrika

The aim of this study was to investigate the inflammatory and immunological responses in airways and lung-draining lymph nodes (LDLNs), following lung exposure to iron oxide (hematite) nanoparticles (NPs). The responses to the hematite NPs were evaluated in both healthy non-sensitized mice, and in sensitized mice with an established allergic airway disease. The mice were exposed intratracheally to either hematite NPs or to vehicle (PBS) and the cellular responses were evaluated on days 1, 2, and 7, post-exposure. Exposure to hematite NPs increased the numbers of neutrophils, eosinophils, and lymphocytes in the airways of non-sensitized mice on days 1 andmore » 2 post-exposure; at these time points the number of lymphocytes was also elevated in the LDLNs. In contrast, exposing sensitized mice to hematite NPs induced a rapid and unspecific cellular reduction in the alveolar space on day 1 post-exposure; a similar decrease of lymphocytes was also observed in the LDLN. The results indicate that cells in the airways and in the LDLN of individuals with established airway inflammation undergo cell death when exposed to hematite NPs. A possible explanation for this toxic response is the extensive generation of reactive oxygen species (ROS) in the pro-oxidative environment of inflamed airways. This study demonstrates how sensitized and non-sensitized mice respond differently to hematite NP exposure, and it highlights the importance of including individuals with respiratory disorders when evaluating health effects of inhaled nanomaterials. - Highlights: • Hematite NPs induce differential responses in airways of healthy and allergic mice. • Hematite induced an airway inflammation in healthy mice. • Hematite induced cellular reduction in the alveolus and lymph nodes of allergic mice. • Cell death is possible due to extensive pro-oxidative environment in allergic mice. • It is important to include sensitive individuals when valuing health effects of NPs.« less

Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite.

PubMed

Flynn, Elaine D; Catalano, Jeffrey G

2018-06-05

During biogeochemical iron cycling at redox interfaces, dissolved Fe(II) induces the recrystallization of Fe(III) oxides. Oxalate and other organic acids promote dissolution of these minerals and may also induce recrystallization. These processes may redistribute trace metals among the mineral bulk, mineral surface, and aqueous solution. However, the impact of interactions among organic acids, dissolved Fe(II), and iron oxide minerals on trace metal fate in such systems is unclear. The present study thus explores the effect of oxalate on Ni release from and incorporation into hematite and goethite in the absence and presence of Fe(II). When Ni is initially structurally incorporated into the iron oxides, both oxalate and dissolved Fe(II) promote the release of Ni to aqueous solution. When both species are present, their effects on Ni release are synergistic at pH 7 but inhibitory at pH 4, indicating that cooperative and competitive interactions vary with pH. In contrast, oxalate suppresses Ni incorporation into goethite and hematite during Fe(II)-induced recrystallization, decreasing the proportion of Ni substituting in a mineral structure by up to 36%. These observations suggest that at redox interfaces oxalate largely enhances trace metal mobility. In such settings, oxalate, and likely other organic acids, may thus enhance micronutrient availability and inhibit contaminant sequestration.

Magnetism of Al-substituted magnetite reduced from Al-hematite

NASA Astrophysics Data System (ADS)

Jiang, Zhaoxia; Liu, Qingsong; Zhao, Xiang; Roberts, Andrew P.; Heslop, David; Barrón, Vidal; Torrent, José

2016-06-01

Aluminum-substituted magnetite (Al-magnetite) reduced from Al-substituted hematite or goethite (Al-hematite or Al-goethite) is an environmentally important constituent of magnetically enhanced soils. In order to characterize the magnetic properties of Al-magnetite, two series of Al-magnetite samples were synthesized through reduction of Al-hematite by a mixed gas (80% CO2 and 20% CO) at 395°C for 72 h in a quartz tube furnace. Al-magnetite samples inherited the morphology of their parent Al-hematite samples, but only those transformed from Al-hematite synthesized at low temperature possessed surficial micropores, which originated from the release of structural water during heating. Surface micropores could thus serve as a practical fingerprint of fire or other high-temperature mineralogical alteration processes in natural environments, e.g., shear friction in seismic zones. In addition, Al substitution greatly affects the magnetic properties of Al-magnetite. For example, coercivity (Bc) increases with increasing Al content and then decreases slightly, while the saturation magnetization (Ms), Curie temperature (Tc), and Verwey transition temperature (Tv) all decrease with increasing Al content due to crystal defect formation and dilution of magnetic ions caused by Al incorporation. Moreover, different trends in the correlation between Tc and Bc can be used to discriminate titanomagnetite from Al-magnetite, which is likely to be important in environmental and paleomagnetic studies, particularly in soil.

Utilization of natural hematite as reactive barrier for immobilization of radionuclides from radioactive liquid waste.

PubMed

El Afifi, E M; Attallah, M F; Borai, E H

2016-01-01

Potential utilization of hematite as a natural material for immobilization of long-lived radionuclides from radioactive liquid waste was investigated. Hematite ore has been characterized by different analytical tools such as Fourier transformer infrared (FTIR), X-ray fluorescence (XRF), powder X-ray diffraction (XRD), thermogravimetry (TG) and differential thermal (DT) analysis, scanning electron microscopy (SEM) and BET-surface area. In this study, europium was used as REEs(III) and as a homolog of Am(III)-isotopes (such as (241)Am of 432.6 y, (242m)Am of 141 y and (243)Am of 7370 y). Micro particles of the hematite ore were used for treatment of radioactive waste containing (152+154)Eu(III). The results indicated that 96% (4.1 × 10(4) Bq) of (152+154)Eu(III) was efficiently retained onto hematite ore. Kinetic experiments indicated that the processes could be simulated by a pseudo-second-order model and suggested that the process may be chemisorption in nature. The applicability of Langmuir, Freundlich and Temkin models was investigated. It was found that Langmuir isotherm exhibited the best fit with the experimental results. It can be concluded that hematite is an economic and efficient reactive barrier for immobilization of long-lived radio isotopes of actinides and REEs(III). Copyright © 2015 Elsevier Ltd. All rights reserved.

Biosignatures Preservation Potential and Habitability in Phyllosilicates vs. Iron-rich Environments

NASA Astrophysics Data System (ADS)

Bonaccorsi, R.; Stoker, C. R.; McKay, C. P.; Science Team

2008-12-01

Phyllosilicates have been identified on the surface of Mars by the OMEGA-Mars/Express [e.g., 1], the Mars Reconnaissance Orbiter (MRO) instruments, i.e., HiRISE and CRISM, as well as inferred from rover observations in Gusev Crater [2]). A better understanding of the preservation potential and habitability in phyllosilicates and hematite-rich materials, achieved by studying analog sites, will therefore provide critical information in support of next decade missions landing site selection e.g., 2009 Mars Science Laboratory (MSL), the ESA Pasteur ExoMars. We present geochemical (d13C-org, d13N-tot, CN ratios) and microbiological proxies i.e., Adenosin-Triphosphate (ATP-based) and Limulus-Amebocite-Lysate (LAL-based biomass) from a suite of phyllosilicate and iron-rich environmental samples e.g., Rio Tinto (Spain), Death Valley (CA, USA), Atacama Desert (Chile), and the California coast. Phyllosilicates-rich zones (47-74wt.%) from the Rio Tinto (RT) region can preserve up to 10-time higher amount of organics (C-org = 0.23 wt.%) than the embedding hematite/goethite-rich (34-89 wt.%) rocks i.e., C-org: ~0.05 wt.% [4]. It is possible that under low pH and highly oxidizing conditions [e.g., 3] surface-derived organics are rapidly oxidized within the shallow hematite/goethite-rich materials, but preserved in phyllosilicates (smectites/illite) where conditions are more conducive [4]. ATP-based biomass was detected in some oxidized-rock samples where roots materials were present (750-1245 RLUs). Geochemical and microbiological analyses are underway to confirm the preservation/ habitability trends observed in the Rio Tinto near surface. Preliminary results suggest that oxidized, goethite-rich, sandstone (Purisima formation, CA) have higher ATP- and LAL-based (Gram negative) biomass contents i.e., 2.0 107 cell/g (35.05 EU/mL) and 3891 RLUs, than the overlying clays units i.e., 1.34 107 cell/g (22.0EU/mL) and 1143 RLUs. REFERENCES: [1] Bibring et al., 2006, Science 312:400-404; [2] Wang et al., 2006 JGR E02S16 Vol. 111; [3] Sumner, 2004, JGR, 109; [4] Bonaccorsi and Stoker, Astrobiology 2008; in press.

Experimental constraints on reconstruction of Archean seawater Ni isotopic composition from banded iron formations

NASA Astrophysics Data System (ADS)

Wang, Shui-Jiong; Wasylenki, Laura E.

2017-06-01

The Ni isotopic systematics in banded iron formations (BIFs) potentially recorded the Ni isotopic composition of ancient seawater over Precambrian geological history. However, the utility of BIFs as proxies requires quantitative knowledge of how Ni isotopes fractionated as dissolved Ni was initially incorporated into iron-rich sediments and how diagenesis may have affected the Ni isotopic systematics. Here we report results of synthesis experiments to investigate the behavior of Ni isotopes during Ni coprecipitation with ferrihydrite and then transformation of ferrihydrite to hematite. Ferrihydrite coprecipitation experiments at neutral pH demonstrated that the dissolved Ni was variably heavier than coprecipitated Ni (likely a mixture of surface-adsorbed and structurally incorporated Ni), with the isotope fractionation becoming larger as the fraction of Ni associated with solid increased (Δ60/58Nisolution-solid = +0.08 to +0.50‰). Further experiments at lower pH (3.7-6.7), in which structurally incorporated Ni likely dominated in solids, documented a decrease in Δ60/58Nisolution-solid from +0.44‰ to -0.18‰ as the pH decreased. The negative value for Δ60/58Nisolution-solid at low pH indicates the enrichment of heavier isotopes in incorporated Ni relative to dissolved and adsorbed Ni, possibly as a result of the presence of a small amount of tetrahedral Ni2+ in addition to octahedral Ni2+ in the ferrihydrite structure. The results of the ferrihydrite experiments thus reflect equilibrium isotope fractionation between three pools of Ni, with δ60/58Ni values in the order of incorporated > dissolved > adsorbed. Hematite was synthesized by transformation of Ni-bearing ferrihydrite in aqueous solution at ∼100 °C. A significant amount of Ni (up to 60%) was released (desorbed) from solids into solutions as pH dropped from ∼7 to 4.5-5.5 upon phase transformation. Rinsing of the synthesized hematite in 2 M acetic acid released only very small amounts of Ni (<4% of total Ni, presumably surface-adsorbed) that were isotopically heavier (δ60/58Ni = +0.11 ± 0.06‰) than the residues (presumably dominated by incorporated Ni), which had δ60/58Ni of -0.26 ± 0.07‰. The preference of lighter isotopes for the incorporated Ni relative to the surface-adsorbed Ni after phase transformation (most had been released into solution) is probably due to distortion of Nisbnd O octahedra in the hematite structure, with weaker Nisbnd O bond strengths on average. Hence, the more variable Δ60/58Nisolution-solid values (-0.04 to +0.77‰) observed in hematite experiments most likely reflect thermodynamically driven Rayleigh fractionation, with incorporated Ni unavailable to exchange with dissolved Ni due to continuous reduction in size of the highly reactive surface pool of Ni, through which all solid-solution exchange must occur. Overall, the synthesized hematite was isotopically lighter than the ferrihydrite by ∼0.08‰ in δ60/58Ni, which is however within the current analytical uncertainties (±0.09‰). This implies that earliest diagenesis of BIFs results in very limited change in the isotopic composition of solid-associated Ni. Our experimental results, although conducted in a very simple system that differs from Archean seawater, represent an important step toward reconstruction of the Ni isotopic composition of ancient seawater from Ni isotopic signatures in BIFs.

Soils of eagle crater and Meridiani Planum at the opportunity Rover landing site

USGS Publications Warehouse

Soderblom, L.A.; Anderson, R.C.; Arvidson, R. E.; Bell, J.F.; Cabrol, N.A.; Calvin, W.; Christensen, P.R.; Clark, B. C.; Economou, T.; Ehlmann, B.L.; Farrand, W. H.; Fike, D.; Gellert, Ralf; Glotch, T.D.; Golombek, M.P.; Greeley, R.; Grotzinger, J.P.; Herkenhoff, K. E.; Jerolmack, D.J.; Johnson, J. R.; Jolliff, B.; Klingelhofer, C.; Knoll, A.H.; Learner, Z.A.; Li, R.; Malin, M.C.; McLennan, S.M.; McSween, H.Y.; Ming, D. W.; Morris, R.V.; Rice, J. W.; Richter, L.; Rieder, R.; Rodionov, D.; Schroder, C.; Seelos, F.P.; Soderblom, J.M.; Squyres, S. W.; Sullivan, R.; Watters, W.A.; Weitz, C.M.; Wyatt, M.B.; Yen, A.; Zipfel, J.

2004-01-01

The soils at the Opportunity site are fine-grained basaltic sands mixed with dust and sulfate-rich outcrop debris. Hematite is concentrated in spherules eroded from the strata. Ongoing saltation exhumes the spherules and their fragments, concentrating them at the surface. Spherules emerge from soils coated, perhaps from subsurface cementation, by salts. Two types of vesicular clasts may represent basaltic sand sources. Eolian ripples, armored by well-sorted hematite-rich grains, pervade Meridiani Planum. The thickness of the soil on the plain is estimated to be about a meter. The flatness and thin cover suggest that the plain may represent the original sedimentary surface.

Pressure demagnetization of synthetic Al substituted hematite and its implications for planetary studies

NASA Astrophysics Data System (ADS)

Jiang, Zhaoxia; Rochette, Pierre; Liu, Qingsong; Gattacceca, Jérôme; Yu, Yongjae; Barrón, Vidal; Torrent, José

2013-11-01

Magnetic minerals can undergo high pressures during their formation and subsequent evolution, which can modify both their intrinsic magnetic properties and remanent magnetization. Aluminum-substituted hematite (Al-hematite) occurs in significant proportion in many soils and sediments, especially in temperate and warm areas. In this work we investigated the effect of high hydrostatic pressures on the magnetic remanence of two series of synthetic Al-hematites. A pressure of 1.44 GPa resulted in 50% reduction of the isothermal remanent magnetization (IRM), which was more effective than alternating field (AF) demagnetization with the largest peak field of 120 mT. In addition, repeated application of the same pressure leads to further demagnetization. Aluminum substitution may increase the resistance to the pressure effect by decreasing particle size and generating defects in magnetic lattices, which results in an increase in coercivity. Our study contributes to understanding the effects of pressure on rocks from the interior of Earth and other planets as well as shocked planetary surfaces, which is significant for future planetary studies.

Synthesis of goethite in solutions of artificial seawater and amino acids: a prebiotic chemistry study

NASA Astrophysics Data System (ADS)

Carneiro, Cristine E. A.; Ivashita, Flávio F.; de Souza, Ivan Granemann; de Souza, Cláudio M. D.; Paesano, Andrea; da Costa, Antonio C. S.; di Mauro, Eduardo; de Santana, Henrique; Zaia, Cássia T. B. V.; Zaia, Dimas A. M.

2013-04-01

This study investigated the synthesis of goethite under conditions resembling those of the prebiotic Earth. The artificial seawater used contains all the major elements as well as amino acids (α-Ala, β-Ala, Gly, Cys, AIB) that could be found on the prebiotic Earth. The spectroscopic methods (FT-IR, EPR, Raman), scanning electron microscopy (SEM) and X-ray diffraction showed that in any condition Gly and Cys favoured the formation of goethite, artificial seawater plus β-Ala and distilled water plus AIB favoured the formation of hematite and for the other synthesis a mixture of goethite and hematite were obtained. Thus in general no protein amino acids (β-Ala, AIB) favoured the formation of hematite. As shown by surface enhanced Raman spectroscopy (SERS) spectra the interaction between Cys and Fe3+ of goethite is very complex, involving decomposition of Cys producing sulphur, as well as interaction of carboxylic group with Fe3+. SERS spectra also showed that amino/CN and C-CH3 groups of α-Ala are interacting with Fe3+ of goethite. For the other samples the shifting of several bands was observed. However, it was not possible to say which amino acid groups are interacting with Fe3+. The pH at point of zero charge of goethites increased with artificial seawater and decreased with amino acids. SEM images showed when only goethite was synthesized the images of the samples were acicular and when only hematite was synthesized the images of the samples were spherical. SEM images for the synthesis of goethite with Cys were spherical crystal aggregates with radiating acicular crystals. The highest resonance line intensities were obtained for the samples where only hematite was obtained. Electron paramagnetic resonance (EPR) and Mössbauer spectra showed for the synthesis of goethite with artificial seawater an isomorphic substitution of iron by seawater cations. Mössbauer spectra also showed that for the synthesis goethite in distilled water plus Gly only goethite was synthesized and in artificial seawater plus Cys a doublet due to interaction of iron with artificial seawater/Cys was observed. It should be pointed out that EPR spectroscopy did not show the interaction of iron with artificial seawater/Cys.

Pyrite oxidation in the presence of hematite and alumina: I. Batch leaching experiments and kinetic modeling calculations.

PubMed

Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

2017-02-15

Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe 2 O 3 ) and alumina (α-Al 2 O 3 ) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe 2+ to Fe 3+ by dissolved O 2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.

Acid Sulfate Alteration on Mars

NASA Technical Reports Server (NTRS)

Ming, D. W.; Morris, R. V.

2016-01-01

A variety of mineralogical and geochemical indicators for aqueous alteration on Mars have been identified by a combination of surface and orbital robotic missions, telescopic observations, characterization of Martian meteorites, and laboratory and terrestrial analog studies. Acid sulfate alteration has been identified at all three landing sites visited by NASA rover missions (Spirit, Opportunity, and Curiosity). Spirit landed in Gusev crater in 2004 and discovered Fe-sulfates and materials that have been extensively leached by acid sulfate solutions. Opportunity landing on the plains of Meridiani Planum also in 2004 where the rover encountered large abundances of jarosite and hematite in sedimentary rocks. Curiosity landed in Gale crater in 2012 and has characterized fluvial, deltaic, and lacustrine sediments. Jarosite and hematite were discovered in some of the lacustrine sediments. The high elemental abundance of sulfur in surface materials is obvious evidence that sulfate has played a major role in aqueous processes at all landing sites on Mars. The sulfate-rich outcrop at Meridiani Planum has an SO3 content of up to 25 wt.%. The interiors of rocks and outcrops on the Columbia Hills within Gusev crater have up to 8 wt.% SO3. Soils at both sites generally have between 5 to 14 wt.% SO3, and several soils in Gusev crater contain around 30 wt.% SO3. After normalization of major element compositions to a SO3-free basis, the bulk compositions of these materials are basaltic, with a few exceptions in Gusev crater and in lacustrine mudstones in Gale crater. These observations suggest that materials encountered by the rovers were derived from basaltic precursors by acid sulfate alteration under nearly isochemical conditions (i.e., minimal leaching). There are several cases, however, where acid sulfate alteration minerals (jarosite and hematite) formed in open hydrologic systems, e.g., in Gale crater lacustrine mudstones. Several hypotheses have been suggested for the aqueous formation of sulfate-bearing phases under acidic conditions on the surface of Mars including (1) sulfuric acid weathering of basaltic materials; (2) oxidative weathering of ultramafic igneous rocks containing sulfides; (3) acid fog weathering of basaltic materials, and (4) near-neutral pH subsurface solutions rich in Fe2(+) that were rapidly oxidized to Fe3(+), which produced excess acidity as iron was oxidized on exposure to O2 or photo-oxidized by ultraviolet radiation at the martian surface. Next, we briefly describe evidence for these hypothesis.

Catechol degradation on hematite/silica-gas interface as affected by gas composition and the formation of environmentally persistent free radicals.

PubMed

Li, Hao; Guo, Huiying; Pan, Bo; Liao, Shaohua; Zhang, Di; Yang, Xikun; Min, Chungang; Xing, Baoshan

2016-04-15

Environmentally persistent free radicals (EPFRs) formed on a solid particle surface have received increasing attention because of their toxic effects. However, organic chemical fate regulated by EPFRs has rarely been investigated, and this information may provide the missing link in understanding their environmental behavior. Previous studies have suggested that the reduction of transition metals is involved in EPFRs formation. We thus hypothesize that an oxidative environment may inhibit EPFRs formation in particle-gas interface, which will consequently release free radicals and accelerate organic chemical degradation. Our result indicates that a 1% hematite coating on a silica surface inhibited catechol degradation in N2, especially at low catechol loadings on solid particles (SCT). However, under an O2 environment, catechol degradation decreased when SCT was <1 μg/mg but increased when SCT was >1 μg/mg. Stable organic free radicals were observed in the N2 system with g factors in the 2.0035-2.0050 range, suggesting the dominance of oxygen-centered free radicals. The introduction of O2 into the catechol degradation system substantially decreased the free radical signals and decreased the Fe(II) content. These results were observed in both dark and light irradiation systems, indicating the ubiquitous presence of EPFRs in regulating the fate of organic chemicals.

Catechol degradation on hematite/silica–gas interface as affected by gas composition and the formation of environmentally persistent free radicals

PubMed Central

Li, Hao; Guo, Huiying; Pan, Bo; Liao, Shaohua; Zhang, Di; Yang, Xikun; Min, Chungang; Xing, Baoshan

2016-01-01

Environmentally persistent free radicals (EPFRs) formed on a solid particle surface have received increasing attention because of their toxic effects. However, organic chemical fate regulated by EPFRs has rarely been investigated, and this information may provide the missing link in understanding their environmental behavior. Previous studies have suggested that the reduction of transition metals is involved in EPFRs formation. We thus hypothesize that an oxidative environment may inhibit EPFRs formation in particle-gas interface, which will consequently release free radicals and accelerate organic chemical degradation. Our result indicates that a 1% hematite coating on a silica surface inhibited catechol degradation in N2, especially at low catechol loadings on solid particles (SCT). However, under an O2 environment, catechol degradation decreased when SCT was <1 μg/mg but increased when SCT was >1 μg/mg. Stable organic free radicals were observed in the N2 system with g factors in the 2.0035–2.0050 range, suggesting the dominance of oxygen-centered free radicals. The introduction of O2 into the catechol degradation system substantially decreased the free radical signals and decreased the Fe(II) content. These results were observed in both dark and light irradiation systems, indicating the ubiquitous presence of EPFRs in regulating the fate of organic chemicals. PMID:27079263

Hybrid density functional theory band structure engineering in hematite

NASA Astrophysics Data System (ADS)

Pozun, Zachary D.; Henkelman, Graeme

2011-06-01

We present a hybrid density functional theory (DFT) study of doping effects in α-Fe2O3, hematite. Standard DFT underestimates the band gap by roughly 75% and incorrectly identifies hematite as a Mott-Hubbard insulator. Hybrid DFT accurately predicts the proper structural, magnetic, and electronic properties of hematite and, unlike the DFT+U method, does not contain d-electron specific empirical parameters. We find that using a screened functional that smoothly transitions from 12% exact exchange at short ranges to standard DFT at long range accurately reproduces the experimental band gap and other material properties. We then show that the antiferromagnetic symmetry in the pure α-Fe2O3 crystal is broken by all dopants and that the ligand field theory correctly predicts local magnetic moments on the dopants. We characterize the resulting band gaps for hematite doped by transition metals and the p-block post-transition metals. The specific case of Pd doping is investigated in order to correlate calculated doping energies and optical properties with experimentally observed photocatalytic behavior.

ChemCam passive reflectance spectroscopy of the Lubango, Okoruso, and Oudam drill targets in Gale Crater, Mars

NASA Astrophysics Data System (ADS)

Johnson, J. R.; Cloutis, E.; Fraeman, A.; Wiens, R. C.; Maurice, S.; Blaney, D. L.; Gasnault, O.

2016-12-01

The ChemCam laser-induced breakdown spectroscopy instrument on the MSL rover Curiosity was used in passive mode (without the laser) to obtain relative reflectance spectra (400-840 nm) of drill tailings and sieved dump piles associated with the targets Lubango, Okoruso, and Oudam between mission sols 1324-1369 near the base of Mt. Sharp. The Lubango and Okoruso drill holes were studied to compare the light-toned zones in the Stimson sandstone (Lubango; 61 wt % SiO2 from ChemCam LIBS data) with nearby unaltered materials (Okoruso; 42 wt % SiO2). Passive spectra of the Lubango tailings (derived from 1-2 cm near the surface) were 50% brighter than the sieved samples (obtained from >2 cm depths). All samples exhibited flat spectra with a slight decrease in reflectance toward the near-infrared. The presence of a weak band near 433 nm (from trace ferric materials such as ferric sulfate) was likely enhanced by the relatively transparent, silica-rich matrix. Lubango was spectrally similar to Greenhorn, another high-silica alteration zone observed in the Stimson unit (Sol 1139). Okoruso passive spectra exhibited flat but increasing reflectance towards the near-infrared with a minor downturn past 800 nm likely related to minor pyroxene. The spectra were darker than the Lubango sieved samples, with no evidence for a 433 nm band. They were similar to the spectra of Big Sky (the unaltered Stimson companion observation to Greenhorn). The Oudam drill tailings pile was observed at two locations: along its outer edge and at a more inward location. Both areas exhibited broad bands near 535 nm and 670 nm and a near-infrared dropoff consistent with hematite. Peak reflectances were near 785 nm for the edge sample but closer to 765 nm for the inner surface (similar to the hematite-bearing Confidence Hills sample from Sol 762). The difference likely results from the presence of other ferric materials in addition to hematite along the edge. This may indicate minor variations in oxidation state with depth in the drilled sampled.

Nature and origin of the hematite-bearing plains of Terra Meridiani based on analyses of orbital and Mars Exploration rover data sets

USGS Publications Warehouse

Arvidson, R. E.; Poulet, F.; Morris, R.V.; Bibring, J.-P.; Bell, J.F.; Squyres, S. W.; Christensen, P.R.; Bellucci, G.; Gondet, B.; Ehlmann, B.L.; Farrand, W. H.; Fergason, R.L.; Golombeck, M.; Griffes, J.L.; Grotzinger, J.; Guinness, E.A.; Herkenhoff, K. E.; Johnson, J. R.; Klingelhofer, G.; Langevin, Y.; Ming, D.; Seelos, K.; Sullivan, R.J.; Ward, J.G.; Wiseman, S.M.; Wolff, M.J.

2006-01-01

The ???5 km of traverses and observations completed by the Opportunity rover from Endurance crater to the Fruitbasket outcrop show that the Meridiani plains consist of sulfate-rich sedimentary rocks that are largely covered by poorly-sorted basaltic aeolian sands and a lag of granule-sized hematitic concretions. Orbital reflectance spectra obtained by Mars Express OMEGA over this region are dominated by pyroxene, plagioclase feldspar, crystalline hematite (i.e., concretions), and nano-phase iron oxide dust signatures, consistent with Pancam and Mini-TES observations. Mo??ssbauer Spectrometer observations indicate more olivine than observed with the other instruments, consistent with preferential optical obscuration of olivine features in mixtures with pyroxene and dust. Orbital data covering bright plains located several kilometers to the south of the landing site expose a smaller areal abundance of hematite, more dust, and a larger areal extent of outcrop compared to plains proximal to the landing site. Low-albedo, low-thermal-inertia, windswept plains located several hundred kilometers to the south of the landing site are predicted from OMEGA data to have more hematite and fine-grained olivine grains exposed as compared to the landing site. Low calcium pyroxene dominates spectral signatures from the cratered highlands to the south of Opportunity. A regional-scale model is presented for the formation of the plains explored by Opportunity, based on a rising ground water table late in the Noachian Era that trapped and altered local materials and aeolian basaltic sands. Cessation of this aqueous process led to dominance of aeolian processes and formation of the current configuration of the plains. Copyright 2006 by the American Geophysical Union.

A topological screening heuristic for low-energy, high-index surfaces

NASA Astrophysics Data System (ADS)

Sun, Wenhao; Ceder, Gerbrand

2018-03-01

Robust ab initio investigations of nanoparticle surface properties require a method to identify candidate low-energy surface facets a priori. By assuming that low-energy surfaces are planes with high atomic density, we devise an efficient algorithm to screen for low-energy surface orientations, even if they have high (hkl) miller indices. We successfully predict the observed low-energy, high-index { 10 12 bar } and { 10 1 bar 4 } surfaces of hematite α-Fe2O3, the {311} surfaces of cuprite Cu2O, and the {112} surfaces of anatase TiO2. We further tabulate candidate low-energy surface orientations for nine of the most common binary oxide structures. Screened surfaces are found to be generally applicable across isostructural compounds with varying chemistries, although relative surface energies between facets may vary based on the preferred coordination of the surface atoms.

Hematite-Rich Deposits in Capri Chasma

NASA Image and Video Library

2016-12-14

Capri Chasma is located in the eastern portion of the Valles Marineris canyon system, the largest known canyon system in the Solar System. Deeply incised canyons such as this are excellent targets for studying the Martian crust, as the walls may reveal many distinct types of bedrock. This section of the canyon was targeted by HiRISE based on a previous spectral detection of hematite-rich deposits in the area. Hematite, a common iron-oxide mineral, was first identified here by the Mars Global Surveyor Thermal Emission Spectrometer (TES). In this TES image, red pixels indicate higher abundances of hematite, while the blue and green pixels represent different types of volcanic rocks (e.g., basalt). Hematite in the Meridiani Planum region was also detected with the TES instrument (which we can see with the bright red spot on the Global TES mineral map). As a consequence, Meridiani Planum was the first landing site selected on Mars due to the spectral detection of a mineral that may have formed in the presence of liquid water. Shortly after landing, the Opportunity rover detected the presence of hematite in the form of concretions called "blueberries." The blueberries are found in association with layers of sulfate salt-rich rocks. The salts are hypothesized to have formed through the raising and lowering of the groundwater table. During one such an event, the rock altered to form the hematite-rich blueberries. As the rock was eroded away, the more resistant hematite-rich blueberries were plucked out and concentrated on the plains as a "lag" deposit. Martian blueberries are observed to be scattered across the plains of Meridiani along Opportunity's traverse from Eagle Crater to Endeavor Crater, where Opportunity continues to explore after its mission began over 10 years ago. This infrared-color image close-up highlights what is possibly the hematite-rich deposits nestled between different types of bedrock terraces in Capri Chasma. The bluish terrace is likely volcanic in origin, possibly basaltic, whereas the greenish rocks remain unidentified. The central reddish terrace is possibly where some of the hematite may be concentrated. The higher elevation terrace with the lighter-colored materials is likely a sulfate-rich rock (based on CRISM data in the area). Given the presence of both sulfate salts and hematite in this area, akin to the deposits and associations explored by the Opportunity rover in Meridiani Planum, it might be that these materials in Capri Chasma may share a similar origin. The yellow rectangular box shown on the TES spectral map outlines the corresponding location of the HiRISE image. Although the outline does not appear to contain a high hematite abundance, we note that the lower resolution of TES (about 3 to 6 kilometers per pixel) may exclude smaller exposures and finer sub-pixel details not-yet captured, but could be with HiRISE. A follow-up observation by the CRISM spectrometer may reveal additional details and a spectral signature for hematite in the vicinity at a finer resolution than TES. http://photojournal.jpl.nasa.gov/catalog/PIA21274

Differential cellular responses in healthy mice and in mice with established airway inflammation when exposed to hematite nanoparticles.

PubMed

Gustafsson, Åsa; Bergström, Ulrika; Ågren, Lina; Österlund, Lars; Sandström, Thomas; Bucht, Anders

2015-10-01

The aim of this study was to investigate the inflammatory and immunological responses in airways and lung-draining lymph nodes (LDLNs), following lung exposure to iron oxide (hematite) nanoparticles (NPs). The responses to the hematite NPs were evaluated in both healthy non-sensitized mice, and in sensitized mice with an established allergic airway disease. The mice were exposed intratracheally to either hematite NPs or to vehicle (PBS) and the cellular responses were evaluated on days 1, 2, and 7, post-exposure. Exposure to hematite NPs increased the numbers of neutrophils, eosinophils, and lymphocytes in the airways of non-sensitized mice on days 1 and 2 post-exposure; at these time points the number of lymphocytes was also elevated in the LDLNs. In contrast, exposing sensitized mice to hematite NPs induced a rapid and unspecific cellular reduction in the alveolar space on day 1 post-exposure; a similar decrease of lymphocytes was also observed in the LDLN. The results indicate that cells in the airways and in the LDLN of individuals with established airway inflammation undergo cell death when exposed to hematite NPs. A possible explanation for this toxic response is the extensive generation of reactive oxygen species (ROS) in the pro-oxidative environment of inflamed airways. This study demonstrates how sensitized and non-sensitized mice respond differently to hematite NP exposure, and it highlights the importance of including individuals with respiratory disorders when evaluating health effects of inhaled nanomaterials. Copyright © 2015 Elsevier Inc. All rights reserved.

In situ spectroscopic identification of neptunium(V) inner-sphere complexes on the hematite-water interface.

PubMed

Müller, Katharina; Gröschel, Annett; Rossberg, André; Bok, Frank; Franzen, Carola; Brendler, Vinzenz; Foerstendorf, Harald

2015-02-17

Hematite plays a decisive role in regulating the mobility of contaminants in rocks and soils. The Np(V) reactions at the hematite-water interface were comprehensively investigated by a combined approach of in situ vibrational spectroscopy, X-ray absorption spectroscopy and surface complexation modeling. A variety of sorption parameters such as Np(V) concentration, pH, ionic strength, and the presence of bicarbonate was considered. Time-resolved IR spectroscopic sorption experiments at the iron oxide-water interface evidenced the formation of a single monomer Np(V) inner-sphere sorption complex. EXAFS provided complementary information on bidentate edge-sharing coordination. In the presence of atmospherically derived bicarbonate the formation of the bis-carbonato inner-sphere complex was confirmed supporting previous EXAFS findings.1 The obtained molecular structure allows more reliable surface complexation modeling of recent and future macroscopic data. Such confident modeling is mandatory for evaluating water contamination and for predicting the fate and migration of radioactive contaminants in the subsurface environment as it might occur in the vicinity of a radioactive waste repository or a reprocessing plant.

Biogenic magnetite, detrital hematite, and relative paleointensity in Quaternary sediments from the Southwest Iberian Margin

NASA Astrophysics Data System (ADS)

Channell, J. E. T.; Hodell, D. A.; Margari, V.; Skinner, L. C.; Tzedakis, P. C.; Kesler, M. S.

2013-08-01

Magnetic properties of late Quaternary sediments on the SW Iberian Margin are dominated by bacterial magnetite, observed by transmission electron microscopy (TEM), with contributions from detrital titanomagnetite and hematite. Reactive hematite, together with low organic matter concentrations and the lack of sulfate reduction, lead to dissimilatory iron reduction and availability of Fe(II) for abundant magnetotactic bacteria. Magnetite grain-size proxies (κARM/κ and ARM/IRM) and S-ratios (sensitive to hematite) vary on stadial/interstadial timescales, contain orbital power, and mimic planktic δ18O. The detrital/biogenic magnetite ratio and hematite concentration are greater during stadials and glacial isotopic stages, reflecting increased detrital (magnetite) input during times of lowered sea level, coinciding with atmospheric conditions favoring hematitic dust supply. Magnetic susceptibility, on the other hand, has a very different response being sensitive to coarse detrital multidomain (MD) magnetite associated with ice-rafted debris (IRD). High susceptibility and/or magnetic grain-size coarsening, mark Heinrich stadials (HS), particularly HS2, HS3, HS4, HS5, HS6 and HS7, as well as older Heinrich-like detrital layers, indicating the sensitivity of this region to fluctuations in the position of the polar front. Relative paleointensity (RPI) records have well-constrained age models based on planktic δ18O correlation to ice-core chronologies, however, they differ from reference records (e.g. PISO) particularly in the vicinity of glacial maxima, mainly due to inefficient normalization of RPI records in intervals of enhanced hematite input.

Molecular dynamics studies of water deposition on hematite surfaces

NASA Astrophysics Data System (ADS)

Kvamme, Bjørn; Kuznetsova, Tatiana; Haynes, Martin

2012-12-01

The interest in carbon dioxide for enhanced oil recovery is increasing proportional to the decrease in naturally driven oil production and also due to the increasing demand for reduced emission of carbon dioxide to the atmosphere. Transport of carbon dioxide in offshore pipelines involves high pressure and low temperatures which may lead to the formation of hydrate between residual water dissolved in carbon dioxide. The critical question is whether the water at some condition of temperature and pressure will drop out as liquid droplets or as water adsorbed on the surfaces of the pipeline and then subsequently form hydrates heterogeneously. In this work we have used the 6-311G basis set with B3LYP to estimate the charge distribution of different sizes of hematite crystals. The obtained surface charge distribution were kept unchanged while the inner charge distribution where scaled so as to result in an overall neutral crystal. These rust particles were embedded in water and chemical potential for adsorbed water molecules were estimated through thermodynamic integration and compared to similar estimates for same size water cluster. Estimated values of water chemical potentials indicate that it is thermodynamically favorable for water to adsorb on hematite, and that evaluation of potential carbon dioxide hydrate formation conditions and kinetics should be based this sequence of processes.

Local electronic structure and photoelectrochemical activity of partial chemically etched Ti-doped hematite

NASA Astrophysics Data System (ADS)

Rioult, Maxime; Belkhou, Rachid; Magnan, Hélène; Stanescu, Dana; Stanescu, Stefan; Maccherozzi, Francesco; Rountree, Cindy; Barbier, Antoine

2015-11-01

The direct conversion of solar light into chemical energy or fuel through photoelectrochemical water splitting is promising as a clean hydrogen production solution. Ti-doped hematite (Ti:α-Fe2O3) is a potential key photoanode material, which despite its optimal band gap, excellent chemical stability, abundance, non-toxicity and low cost, still has to be improved. Here we give evidence of a drastic improvement of the water splitting performances of Ti-doped hematite photoanodes upon a HCl wet-etching. In addition to the topography investigation by atomic force microscopy, a detailed determination of the local electronic structure has been carried out in order to understand the phenomenon and to provide new insights in the understanding of solar water splitting. Using synchrotron radiation based spectromicroscopy (X-PEEM), we investigated the X-ray absorption spectral features at the L3 Fe edge of the as grown surface and of the wet-etched surface on the very same sample thanks to patterning. We show that HCl wet etching leads to substantial surface modifications of the oxide layer including increased roughness and chemical reduction (presence of Fe2 +) without changing the band gap. We demonstrate that these changes are profitable and correlated to the drastic changes of the photocatalytic activity.

In situ XAS study of CoBi modified hematite photoanodes.

PubMed

Xi, Lifei; Schwanke, Christoph; Zhou, Dong; Drevon, Dorian; van de Krol, Roel; Lange, Kathrin M

2017-11-21

Solar water splitting is a potentially scalable method to store solar energy in the form of renewable hydrogen gas. In this study, we demonstrate that the photoelectrochemical (PEC) performance of hematite photoanodes can be improved by modification with the oxygen evolution catalyst CoB i . The current density at 1.23 V of the pristine hematite under one sun is 0.88 mA cm -2 and it increases to 1.12 mA cm -2 after CoB i modification (∼27% improvement). The presence of a CoB i cocatalayst layer is proposed to improve the oxygen evolution reaction (OER) kinetics and also to prevent electron-hole recombination at the surface via passivating surface defects as well as suppressing the tunneling of electrons from the hematite core, thus improving the photocurrents and resulting in a negative shift of photocurrent onset potentials. These effects of CoB i modification are supported by experimental data obtained by performing electrochemical impedance spectroscopy (EIS), PEC and incident photon-to-current efficiency (IPCE) measurements. To investigate the electronic structure of the CoB i cocatalyst deposited on hematite, XPS and in situ X-ray absorption spectroscopy (XAS) are employed. Co K-edge spectra at different potentials and light conditions are recorded. This makes the present work different from most of the previous studies. Using a quantitative analysis method, information on the mean oxidation state of Co in the CoB i film under applied potential and illumination is revealed. We also compare different methods for determining the oxidation state from the edge position and find that the integral method and half height methods are most suitable. In summary, the present work underlines the improvement of the semiconductor/cocatalyst interface of oxygen evolving photoanodes and strengthens the importance of in situ XAS spectroscopy when studying catalysts. This study is the first report so far combining the studies of the PEC performance of a CoB i modified hematite nanorod array photoanode and in situ XAS at the Co K-edge.

Meridiani Planum Hematite Deposit: Potential for Preservation of Microfossils

NASA Technical Reports Server (NTRS)

Allen, C. C.; Westall, F.; Longazo, T. G.; Schelble, R. T.; Probst, L. W.; Flood, B. F.

2003-01-01

Christensen et al., using data from the Mars Global Surveyor Thermal Emission Spectrometer (TES), have identified gray crystalline hematite in a 350 km by 750 km region near Meridiani Planum. The deposit corresponds closely to the low-albedo highlands unit sm, mapped as a wind-eroded, ancient, subaqueous sedimentary deposit. Christensen et al. interpreted the Meridiani Planum deposit to be an in-place, rock-stratigraphic sedimentary unit characterized by smooth, friable layers composed primarily of basaltic sediments with approximately 10 to 15% crystalline gray hematite. The Meridiani Planum hematite deposit has recently been designated as the prime landing site for one of the two Mars Exploration Rover (MER) spacecraft. The MER landings are scheduled for January, 2004. Christensen et al. discussed five possible mechanisms for the formation of this deposit: direct precipitation from standing, oxygenated, Fe-rich water; precipitation from Fe-rich hydrothermal fluids; low-temperature dissolution and precipitation through mobile groundwater leaching; surface weathering and coatings; thermal oxidation of magnetite-rich lavas. Four of these mechanisms involve the interactions of rock with water, and thus have implications in the search for evidence of microbial life.

Controls on Fe(II)-Activated Trace Element Release from Goethite and Hematite

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

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-03-26

Electron transfer and atom exchange (ETAE) between aqueous Fe(II) and Fe(III) oxides induces surface growth and dissolution that affects trace element fate and transport. We have recently demonstrated Ni(II) cycling through goethite and hematite (adsorbed Ni incorporates into the mineral structure and preincorporated Ni releases to solution) during Fe(II)-Fe(III) ETAE. However, the chemical parameters affecting net trace element release remain unknown. Here, we examine the chemical controls on Ni(II) and Zn(II) release from Ni- and Zn-substituted goethite and hematite during reaction with Fe(II). Release follows a rate law consistent with surface reaction limited mineral dissolution and suggests that release occursmore » near sites of Fe(III) reductive dissolution during Fe(II)-Fe(III) ETAE. Metal substituent type affects reactivity; Zn release is more pronounced from hematite than goethite, whereas the opposite trend occurs for Ni. Buildup of Ni or Zn in solution inhibits further release but this resumes upon fluid exchange, suggesting that sustained release is possible under flow conditions. Mineral and aqueous Fe(II) concentrations as well as pH strongly affect sorbed Fe(II) concentrations, which directly control the reaction rates and final metal concentrations. Our results demonstrate that structurally incorporated trace elements are mobilized from iron oxides into fluids without abiotic or microbial net iron reduction. Such release may affect micronutrient availability, contaminant transport, and the distribution of redox-inactive trace elements in natural and engineered systems.« less

Effective aqueous arsenic removal using zero valent iron doped MWCNT synthesized by in situ CVD method using natural α-Fe2O3 as a precursor.

PubMed

Alijani, Hassan; Shariatinia, Zahra

2017-03-01

This research presents an efficient system for removing aqua's arsenic based on in situ zero valent iron doping onto multiwall carbon nanotube (MWCNT) through MWCNT growth onto the natural α-Fe 2 O 3 surface in chemical vapor deposition (CVD) reactor. The as-synthesized magnetic nanohybrid was characterized by XRD, VSM, FE-SEM and TEM techniques. The result of XRD analysis revealed that MWCNT has been successfully generated on the surface of zero valent iron. Moreover, the material showed good superparamagnetic characteristic to be employed as a magnetic adsorbent. The hematite, nanohybrid and its air oxidized form were used for removing aqueous arsenite and arsenate; however, non oxidized material exhibited greater efficiency for the analytes uptake. Equilibrium times were 60 and 90 min for arsenate and arsenite adsorption using nanohybrid and oxidized sorbent but the equilibrium time was 1320 min using hematite. The adsorption efficiencies of hematite and oxidized sorbent were 18, 74% and 26, 77% for arsenite and arsenate, respectively, at initial concentration of 10 mg L -1 . At this situation, the removal efficiencies were 96 and 98.5% for arsenite and arsenate adsorption using raw nanohybrid. Thermodynamic study was also performed and results indicated that arsenic adsorption onto nanohybrid and oxidized sorbent was spontaneous however hematite followed a nonspontaneous path for the arsenic removal. Copyright © 2016 Elsevier Ltd. All rights reserved.

Thermo-mechanical characterization of siliconized E-glass fiber/hematite particles reinforced epoxy resin hybrid composite

NASA Astrophysics Data System (ADS)

V. R., Arun prakash; Rajadurai, A.

2016-10-01

In this present work hybrid polymer (epoxy) matrix composite has been strengthened with surface modified E-glass fiber and iron(III) oxide particles with varying size. The particle sizes of 200 nm and <100 nm has been prepared by high energy ball milling and sol-gel methods respectively. To enhance better dispersion of particles and improve adhesion of fibers and fillers with epoxy matrix surface modification process has been done on both fiber and filler by an amino functional silane 3-Aminopropyltrimethoxysilane (APTMS). Crystalline and functional groups of siliconized iron(III) oxide particles were characterized by XRD and FTIR spectroscopy analysis. Fixed quantity of surface treated 15 vol% E-glass fiber was laid along with 0.5 and 1.0 vol% of iron(III) oxide particles into the matrix to fabricate hybrid composites. The composites were cured by an aliphatic hardener Triethylenetetramine (TETA). Effectiveness of surface modified particles and fibers addition into the resin matrix were revealed by mechanical testing like tensile testing, flexural testing, impact testing, inter laminar shear strength and hardness. Thermal behavior of composites was evaluated by TGA, DSC and thermal conductivity (Lee's disc). The scanning electron microscopy was employed to found shape and size of iron(III) oxide particles adhesion quality of fiber with epoxy matrix. Good dispersion of fillers in matrix was achieved with surface modifier APTMS. Tensile, flexural, impact and inter laminar shear strength of composites was improved by reinforcing surface modified fiber and filler. Thermal stability of epoxy resin was improved when surface modified fiber was reinforced along with hard hematite particles. Thermal conductivity of epoxy increased with increase of hematite content in epoxy matrix.

Principal Components Analysis of Reflectance Spectra from the Mars Exploration Rover Opportunity

NASA Technical Reports Server (NTRS)

Mercer, C. M.; Cohen, B. A.

2010-01-01

In the summer of 2007 a global dust storm on Mars effectively disabled Opportunity's Miniature Thermal Emission Spectrometer (Mini-TES), the primary instrument used by the Athena Science Team to identify locally unique rocks on the Martian surface. The science team needs another way to distinguish interesting rocks from their surroundings on a tactical timescale. This study was designed to develop the ability to identify locally unique rocks on the Martian surface remotely using the Mars Exploration Rovers' Panoramica Camera (PanCam) instrument. Meridiani bedrock observed by Opportunity is largely characterized by sulfate-rich sandstones and hematite spherules. Additionally, loose fragments of bedrock and "cobbles" of foreign origin collet on the surface, some of which are interpreted as meteorites.

Fate of Adsorbed U(VI) during Sulfidization of Lepidocrocite and Hematite

PubMed Central

2017-01-01

The impact on U(VI) adsorbed to lepidocrocite (γ-FeOOH) and hematite (α-Fe2O3) was assessed when exposed to aqueous sulfide (S(-II)aq) at pH 8.0. With both minerals, competition between S(-II) and U(VI) for surface sites caused instantaneous release of adsorbed U(VI). Compared to lepidocrocite, consumption of S(-II)aq proceeded slower with hematite, but yielded maximum dissolved U concentrations that were more than 10 times higher, representing about one-third of the initially adsorbed U. Prolonged presence of S(-II)aq in experiments with hematite in combination with a larger release of adsorbed U(VI), enhanced the reduction of U(VI): after 24 h of reaction about 60–70% of U was in the form of U(IV), much higher than the 25% detected in the lepidocrocite suspensions. X-ray absorption spectra indicated that U(IV) in both hematite and lepidocrocite suspensions was not in the form of uraninite (UO2). Upon exposure to oxygen only part of U(IV) reoxidized, suggesting that monomeric U(IV) might have become incorporated in newly formed iron precipitates. Hence, sulfidization of Fe oxides can have diverse consequences for U mobility: in short-term, desorption of U(VI) increases U mobility, while reduction to U(IV) and its possible incorporation in Fe transformation products may lead to long-term U immobilization. PMID:28121137

Active hematite concretion formation in modern acid saline lake sediments, Lake Brown, Western Australia

NASA Astrophysics Data System (ADS)

Bowen, Brenda Beitler; Benison, K. C.; Oboh-Ikuenobe, F. E.; Story, S.; Mormile, M. R.

2008-04-01

Concretions can provide valuable records of diagenesis and fluid-sediment interactions, however, reconstruction of ancient concretion-forming conditions can be difficult. Observation of modern hematite concretion growth in a natural sedimentary setting provides a rare glimpse of conditions at the time of formation. Spheroidal hematite-cemented concretions are actively precipitating in shallow subsurface sediments at Lake Brown in Western Australia. Lake Brown is a hypersaline (total dissolved solids up to 23%) and acidic (pH ˜ 4) ephemeral lake. The concretion host sediments were deposited between ˜ 1 and 3 ka, based on dating of stratigraphically higher and lower beds. These age constraints indicate that the diagenetic concretions formed < 3 ka, and field observations suggest that some are currently forming. These modern concretions from Lake Brown provide an example of very early diagenetic formation in acid and saline conditions that may be analogous to past conditions on Mars. Previously, the hematite concretions in the Burns formation on Mars have been interpreted as late stage diagenetic products, requiring long geologic time scales and multiple fluid flow events to form. In contrast, the Lake Brown concretions support the possibility of similar syndepositional to very early diagenetic concretion precipitation on Mars.

Possible mechanism for explaining the origin and size distribution of Martian hematite spherules

NASA Astrophysics Data System (ADS)

Misra, Anupam K.; Acosta-Maeda, Tayro E.; Scott, Edward R. D.; Sharma, Shiv K.

2014-03-01

Mysterious hematite spherules, also known as “blueberries”, observed at Meridiani Planum on Mars have been widely accepted as concretions which are formed by precipitation of aqueous fluids. One of the biggest mysteries is that all observed Martian blueberries are limited in size with maximum diameter of 6.2 mm. In contrast, terrestrial concretions are not size limited. In this article, we discuss significant differences between Martian blueberries and Earth concretion analogs. Puzzling observations from Mars Exploration Rovers Opportunity and Spirit suggest that the spherules may not be concretions but are cosmic spherules formed by ablation of meteorites. The perfect spherical shape of spherules, their observed size limit, and all other physical properties are easily explained by a meteorite ablation model. Evidence that some of these spherules are only few years old strongly constrains concretion and other growth mechanisms related to aqueous processes that require the existence of water on Mars in its recent history. The large number of hematite spherules in Meridiani Planum may be due to a big rare iron meteorite impact event in this region sometime in the past.

Principal Components Analysis of Reflectance Spectra Returned by the Mars Exploration Rover Opportunity

NASA Technical Reports Server (NTRS)

Mercer, C. M.; Cohen, Barbara A.

2010-01-01

The Mars Exploration Rover Opportunity has spent over six years exploring the Martian surface near its landing site at Meridiani Planum. Meridiani bedrock observed by the rover is largely characterized by sulfate-rich sandstones and hematite spherules, recording evidence of ancient aqueous environments [1]. The region is a deflationary surface, allowing hematite spherules, fragments of bedrock, and "cobbles" of foreign origin to collect loosely on the surface. These cobbles may be meteorites (e.g., Barberton, Heat Shield Rock, Santa Catarina) [2], or rock fragments of exotic composition derived from adjacent terranes or from the subsurface and delivered to Meridiani Planum as impact ejecta [3]. The cobbles provide a way to better understand Martian meteorites and the lithologic diversity of Meridiani Planum by examining the various rock types located there. In the summer of 2007, a global dust storm on Mars effectively disabled Opportunity's Miniature Thermal Emission Spectrometer (Mini-TES), which served as the Athena Science Team s primary tool for remotely identifying rocks of interest on a tactical timescale for efficient rover planning. While efforts are ongoing to recover use of the Mini-TES, the team is currently limited to identifying rocks of interest by visual inspection of images returned from Opportunity's Panoramic Camera (Pancam). This study builds off of previous efforts to characterize cobbles at Meridiani Planum using a database of reflectance spectra extracted from Pancam 13-Filter (13F) images [3]. We analyzed the variability of rock spectra in this database and identified physical characteristics of Martian rocks that could potentially account for the observed variance. By understanding such trends, we may be able to distinguish between rock types at Meridiani Planum and regain the capability to remotely identify locally unique rocks.

Linking interfacial chemistry of CO2 to surface structures of hydrated metal oxide nanoparticles: hematite.

PubMed

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

2013-05-14

A better understanding of interaction with dissolved CO2 is required to rationally design and model the (photo)catalytic and sorption processes on metal (hydr)oxide nanoparticles (NPs) in aqueous media. Using in situ FTIR spectroscopy, we address this problem for rhombohedral 38 nm hematite (α-Fe2O3) nanoparticles as a model. We not only resolve the structures of the adsorbed carbonate species, but also specify their adsorption sites and their location on the nanoparticle surface. The spectral relationships obtained present a basis for a new method of characterizing the microscopic structural and acid-base properties (related to individual adsorption sites) of hydrated metal (hydr)oxide NPs using atmospherically derived CO2 as a probe. Specifically, we distinguish two carbonate species suggesting two principally different adsorption mechanisms. One species, which is more weakly adsorbed, has an inner-sphere mononuclear monodentate structure which is formed by a conventional ligand-exchange mechanism. At natural levels of dissolved carbonate and pH from 3 to 11, this species is attached to the most acidic/reactive surface cations (surface states) associated with ferrihydrite-like surface defects. The second species, which is more strongly adsorbed, presents a mixed C and O coordination of bent CO2. This species uniquely recognizes the stoichiometric rhombohedral {104} facets in the NP texture. Like in gas phase, it is formed through the surface coordination of molecular CO2. We address how the adsorption sites hosting these two carbonate species are affected by the annealing and acid etching of the NPs. These results support the nanosize-induced phase transformation of hematite towards ferrihydrite under hydrous conditions, and additionally show that the process starts from the roughened areas of the facet intersections.

Role of background ions in guar gum adsorption on oxide minerals and kaolinite.

PubMed

Ma, Xiaodong; Pawlik, Marek

2007-09-15

Adsorption of guar gum onto alumina, titania (rutile), hematite, quartz, and kaolinite was investigated as a function of pH, ionic strength (from distilled water to saturated NaCl and KCl), and the type of background electrolyte (0.01 mol/L LiCl, NaCl, KCl, and CsCl). It was demonstrated that the adsorption density of the polymer does not depend on pH for any of the tested minerals, so only hydrogen bonding was identified as the dominant adsorption mechanism. The minerals could, however, be divided into two groups depending on the effect of the salt type on polymer adsorption. Guar gum adsorption onto quartz and kaolinite significantly increased in the presence of even a small amount of KCl, while NaCl equally enhanced guar gum adsorption on these two minerals only at concentrations approaching saturation. In contrast, no significant differences between the effects of KCl and NaCl on polysaccharide adsorption were observed on titania, alumina, and hematite. The results were correlated with the chaotropic (KCl) and kosmotropic (NaCl) properties of the background salts, and-based on a review of the available literature data-with the presence (quartz) or absence (titania, alumina, hematite) of an extensive hydration layer on the oxide surfaces. It was concluded that the main role of background ions in the studied systems was to control the stability of the interfacial water layer on oxide particles whose presence serves as a barrier to guar gum adsorption.

Astrobiology Investigations at a Martian Hematite Site

NASA Technical Reports Server (NTRS)

Allen, Carlton, C.; Westall, Frances; Schelble, Rachel T.

2001-01-01

Christensen et al, using data from the Mars Global Surveyor Thermal Emission Spectrometer (TES), have identified gray crystalline hematite in a 350 km by 750 km region near Sinus Meridiani. The deposit corresponds closely to the low-albedo highlands unit 'sm', mapped as a wind-eroded, ancient, subaqueous sedimentary deposit. Christensen et al interpreted the Sinus Meridiani deposit to be 'an in-place, rock-stratigraphic sedimentary unit characterized by smooth, friable layers composed primarily of basaltic sediments with approximately 10 to 15 % crystalline gray hematite.' Christensen et al discussed five possible mechanisms for the formation of this deposit: direct precipitation from standing, oxygenated, Fe-rich water; precipitation from Fe-rich hydrothermal fluids; low-temperature dissolution and precipitation through mobile groundwater leaching; surface weathering and coatings; thermal oxidation of magnetite-rich lavas. Four of these mechanisms involve the interactions of rock with water, and thus have implications in the search for evidence of microbial life.

On the Spectral Variance of MGS TES Spectra in the 300-500 cm-1 Range

NASA Astrophysics Data System (ADS)

Altieri, F.; Bellucci, G.

2001-11-01

The Thermal Emission Spectrometer (TES) aboard NASA mission Mars Global Surveyor (MGS) is collecting 200 - 1600 cm-1 thermal emission spectra since September 1997. The principal purpose of TES is to determine and map the Mars surface composition. Spectral features directly ascribable to surface minerals have been identified in the 300 - 500 cm-1 spectral range. Outcrops of hematite have been localized in Sinus Meridiani, Aram Chaos and Valles Marineris [1, 2] and areas with olivine have been individuated in Nili Fossae and in other limited regions [3]. On the other hand, TES spectra show, in general, significant variance between 300 and 500 cm-1; this variance is not directly attributable to surface mineralogical components. In this study we report some examples of spectra with typical hematite and olivine bands and spectra with a different spectral contrast. The spectral masking effect of a dust layer is suggested to explain this behaviour. Spectra characterized by hematite features have been localized also inside a crater near Baldet Crater. The MOC narrow-angle image M02-0039 acquired on the same area shows dark layers at the crater bottom. References: [1] Christensen P. R., et al., JGR, 105, 9623-9642, 2000. [2] Christensen P. R., et al., JGR, in press., 2001. [3] Hoefen T. M. and Clark R. N., LPS XXXII, 2049, 2001.

Aqueous history of Mars as inferred from landed mission measurements of rocks, soils, and water ice

NASA Astrophysics Data System (ADS)

Arvidson, Raymond E.

2016-09-01

The missions that have operated on the surface of Mars acquired data that complement observations acquired from orbit and provide information that would not have been acquired without surface measurements. Data from the Viking Landers demonstrated that soils have basaltic compositions, containing minor amounts of salts and one or more strong oxidants. Pathfinder with its rover confirmed that the distal portion of Ares Vallis is the site of flood-deposited boulders. Spirit found evidence for hydrothermal deposits surrounding the Home Plate volcanoclastic feature. Opportunity discovered that the hematite signature on Meridiani Planum as seen from orbit is due to hematitic concretions concentrated on the surface as winds eroded sulfate-rich sandstones that dominate the Burns formation. The sandstones originated as playa muds that were subsequently reworked by wind and rising groundwater. Opportunity also found evidence on the rim of the Noachian Endurance Crater for smectites, with extensive leaching along fractures. Curiosity acquired data at the base of Mount Sharp in Gale Crater that allows reconstruction of a sustained fluvial-deltaic-lacustrine system prograding into the crater. Smectites and low concentrations of chlorinated hydrocarbons have been identified in the lacustrine deposits. Phoenix, landing above the Arctic Circle, found icy soils, along with low concentrations of perchlorate salt. Perchlorate is considered to be a strong candidate for the oxidant found by the Viking Landers. It is also a freezing point depressant and may play a role in allowing brines to exist at and beneath the surface in more modern periods of time on Mars.

Iron oxide minerals in dust of the Red Dawn event in eastern Australia, September 2009

USGS Publications Warehouse

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 A.; Breit, George N.

2014-01-01

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.

Iron insertion and hematite segregation on Fe-doped TiO2 nanoparticles obtained from sol-gel and hydrothermal methods.

PubMed

Santos, Reginaldo da S; Faria, Guilherme A; Giles, Carlos; Leite, Carlos A P; Barbosa, Herbert de S; Arruda, Marco A Z; Longo, Claudia

2012-10-24

Iron-doped TiO(2) (Fe:TiO(2)) nanoparticles were synthesized by the sol-gel method (with Fe/Ti molar ratio corresponding to 1, 3, and 5%), followed by hydrothermal treatment, drying, and annealing. A similar methodology was used to synthesize TiO(2) and α-Fe(2)O(3) nanoparticles. For comparison, a mixture hematite/titania, with Fe/Ti = 4% was also investigated. Characterization of the samples using Rietveld refinement of X-ray diffraction data revealed that TiO(2) consisted of 82% anatase and 18% brookite; for Fe:TiO(2), brookite increased to 30% and hematite was also identified (0.5, 1.0, and 1.2 wt % for samples prepared with 1, 3, and 5% of Fe/Ti). For hematite/titania mixture, Fe/Ti was estimated as 4.4%, indicating the Rietveld method reliability for estimation of phase composition. Because the band gap energy, estimated as 3.2 eV for TiO(2), gradually ranged from 3.0 to 2.7 eV with increasing Fe content at Fe:TiO(2), it can be assumed that a Fe fraction was also inserted as dopant in the TiO(2) lattice. Extended X-ray absorption fine structure spectra obtained for the Ti K-edge and Fe K-edge indicated that absorbing Fe occupied a Ti site in the TiO(2) lattice, but hematite features were not observed. Hematite particles also could not be identified in the images obtained by transmission electron microscopy, in spite of iron identification by elemental mapping, suggesting that hematite can be segregated at the grain boundaries of Fe:TiO(2).

Two years at Meridiani Planum: Results from the opportunity rover

USGS Publications Warehouse

Squyres, S. W.; Knoll, A.H.; Arvidson, R. E.; Clark, B. C.; Grotzinger, J.P.; Jolliff, B.L.; McLennan, S.M.; Tosca, N.; Bell, J.F.; Calvin, W.M.; Farrand, W. H.; Glotch, T.D.; Golombek, M.P.; Herkenhoff, K. E.; Johnson, J. R.; Klingelhofer, G.; McSween, H.Y.; Yen, A. S.

2006-01-01

The Mars Exploration Rover Opportunity has spent more than 2 years exploring Meridiani Planum, traveling ???8 kilometers and detecting features that reveal ancient environmental conditions. These include well-developed festoon (trough) cross-lamination formed in flowing liquid water, strata with smaller and more abundant hematite-rich concretions than those seen previously, possible relict "hopper crystals" that might reflect the formation of halite, thick weathering rinds on rock surfaces, resistant fracture fills, and networks of polygonal fractures likely caused by dehydration of sulfate salts. Chemical variations with depth show that the siliciclastic fraction of outcrop rock has undergone substantial chemical alteration from a precursor basaltic composition. Observations from microscopic to orbital scales indicate that ancient Meridiani once had abundant acidic groundwater, arid and oxidizing surface conditions, and occasional liquid flow on the surface.

Thermodynamic Characterization of Iron Oxide-Aqueous Fe(2+) Redox Couples.

PubMed

Gorski, Christopher A; Edwards, Rebecca; Sander, Michael; Hofstetter, Thomas B; Stewart, Sydney M

2016-08-16

Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe2+ and Fe3+ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe2+ associated with iron oxide surfaces (i.e., oxide-associated Fe2+) often reduces oxidized contaminants much faster than aqueous Fe2+ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides—hematite and goethite—and aqueous Fe2+ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (EH) values in solutions containing these oxides at different pH values and aqueous Fe2+ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (EH0) values of 768 ± 1 mV for the aqueous Fe2+–goethite redox couple and 769 ± 2 mV for the aqueous Fe2+–hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering EH values of aqueous Fe3+/Fe2+ redox couples.

Properties of Martian Hematite at Meridiani Planum by Simultaneous Fitting of Mars Mossbauer Spectra

NASA Technical Reports Server (NTRS)

Agresti, D. G.; Fleischer, I.; Klingelhoefer, G.; Morris, R. V.

2010-01-01

Mossbauer spectrometers [1] on the two Mars Exploration Rovers (MERs) have been making measurements of surface rocks and soils since January 2004, recording spectra in 10-K-wide temperature bins ranging from 180 K to 290 K. Initial analyses focused on modeling individual spectra directly as acquired or, to increase statistical quality, as sums of single-rock or soil spectra over temperature or as sums over similar rock or soil type [2, 3]. Recently, we have begun to apply simultaneous fitting procedures [4] to Mars Mossbauer data [5-7]. During simultaneous fitting (simfitting), many spectra are modeled similarly and fit together to a single convergence criterion. A satisfactory simfit with parameter values consistent among all spectra is more likely than many single-spectrum fits of the same data because fitting parameters are shared among multiple spectra in the simfit. Consequently, the number of variable parameters, as well as the correlations among them, is greatly reduced. Here we focus on applications of simfitting to interpret the hematite signature in Moessbauer spectra acquired at Meridiani Planum, results of which were reported in [7]. The Spectra. We simfit two sets of spectra with large hematite content [7]: 1) 60 rock outcrop spectra from Eagle Crater; and 2) 46 spectra of spherule-rich lag deposits (Table 1). Spectra of 10 different targets acquired at several distinct temperatures are included in each simfit set. In the table, each Sol (martian day) represents a different target, NS is the number of spectra for a given sol, and NT is the number of spectra for a given temperature. The spectra are indexed to facilitate definition of parameter relations and constraints. An example spectrum is shown in Figure 1, together with a typical fitting model. Results. We have shown that simultaneous fitting is effective in analyzing a large set of related MER Mossbauer spectra. By using appropriate constraints, we derive target-specific quantities and the temperature dependence of certain parameters. By examining different fitting models, we demonstrate an improved fit for martian hematite modeled with two sextets rather than as a single sextet, and show that outcrop and spherule hematite are distinct. For outcrop, the weaker sextet indicates a Morin transition typical of well-crystallized and chemically pure hematite, while most of the outcrop hematite remains in a weakly ferromagnetic state at all temperatures. For spherule spectra, both sextets are consistent with weakly ferromagnetic hematite with no Morin transition. For both hematites, there is evidence for a range of particle sizes.

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.

Adhesion of Escherichia coli onto quartz, hematite and corundum: extended DLVO theory and flotation behavior.

PubMed

Farahat, Mohsen; Hirajima, Tsuyoshi; Sasaki, Keiko; Doi, Katsumi

2009-11-01

The adhesion of Escherichia coli onto quartz, hematite and corundum was experimentally investigated. A strain of E. coli was used that had the genes for expressing protein for silica precipitation. The maximum cell adhesion was observed at pH <4.3 for quartz and at pH 4.5-8.5 for corundum. For hematite, cell adhesion remained low at all pH values. The microbe-mineral adhesion was assessed by the extended DLVO theory approach. The essential parameters for calculation of microbe-mineral interaction energy (Hamaker constants and acid-base components) were experimentally determined. The extended DLVO approach could be used to explain the results of the adhesion experiments. The effect of E. coli on the floatability of three oxide minerals was determined and the results showed that E. coli can act as a selective collector for quartz at acidic pH values, with 90% of the quartz floated at 1.5 x 10(9)cells/ml. However, only 9% hematite and 30% corundum could be floated under similar conditions. By using E. coli and no reagents, it was possible to separate quartz from a hematite-quartz mixture with Newton's efficiency of 0.70. Removal of quartz from the corundum mixture was achieved by E. coli with Newton's efficiency of 0.62.

Direct measurement of hematite individual particle anisotropy: implications for inclination shallowing in red bed DRMs.

NASA Astrophysics Data System (ADS)

Bilardello, D.; Kodama, K. P.

2007-12-01

Methods to correct for the observed inclination shallowing in sedimentary rocks have been proposed that are based on either models of the geomagnetic field and the resulting directional distribution of paleomagnetic vectors or the magnetic anisotropy of the magnetic minerals carrying the remanence. One limitation of the anisotropy method for hematite-bearing red beds has been the isolation and determination of a rock's detrital hematite individual particle anisotropy. Up to now, our red bed inclination shallowing corrections have been dependent on estimates of hematite individual particle anisotropy using data fit to theoretical correction curves. We have developed a technique for preferentially extracting the detrital hematite particles in a sample in order to directly measure their individual particle anisotropy. The method involves crushing of the sample followed by ball milling and sieving to ensure that the rock particles are smaller than 4Φ. The resulting slurry was then placed in an ultrasonic cleaner for at least 24 hours and finally centrifuged at 1000 rpm for 20 minutes in order to separate the dense, gray iron oxide particles from the red pigmentary grains. The gray, iron oxide-rich slurry was collected by hand and circulated in a magnetic extraction apparatus. The magnetic separate was then collected over a period of two to three weeks. Small amounts of the magnetic separates where mixed in a slow-drying epoxy resin for 24 hours and placed in a DC magnetic field (100 mT to 180 mT) in order to align the grains. The bulk IRM anisotropy of the epoxy samples provides an average individual particle anisotropy for the magnetic grains. Separates were collected from samples of the Mauch Chunk Fm. of Pennsylvania, the Maringouin and the Shepody Fms of New Brunswick/ Nova Scotia and the Kapusaliang Fm. of northwestern China. IRM acquisitions experiments were performed in fields of up to 1.2 T in order to identify the magnetic mineralogies present. Remanence appears to be carried by a low coercivity phase (~50 mT) interpreted to be secondary magnetite and a higher coercivity phase (~350 mT) interpreted to be primary hematite for the Shepody and Maringouin Fms or just one high coercivity component (200- 250 mT) interpreted as primary hematite for the Mauch Chunk and Kapusaliang Fms. Hematite individual particle anisotropy was measured by imparting a 1.2 T IRM to the specimens in 9 different orientations followed by AF demagnetization at 100 mT. Calculated individual particle anisotropy values ranged between 1.28 and 1.45 with bulk anisotropies of ~$40%. Inclination corrections using the directly measured individual particle anisotropies indicate significant inclination shallowing for the Mauch Chunk and Kapusaliang Fms, while more moderate shallowing for the Maringouin and Shepody Fms. Curve fitting techniques with added constraints give a good first order approximation of the individual particle anisotropy, however direct measurement is preferable. The measured particle anisotropies for hematite are low and suggest that there is the potential for significant amounts of shallowing for a hematite DRM. This observation is consistent with redeposition experiments performed by Tauxe and Kent [1984] and the notion that depositional inclination of hematite may suffer from more shallowing than magnetite because of its lower spontaneous magnetization making it more affected by gravitational forces.

Constraints on iron sulfate and iron oxide mineralogy from ChemCam visible/near-infrared reflectance spectroscopy of Mt. Sharp basal units, Gale Crater, Mars

DOE PAGES

Johnson, Jeffrey R.; Bell, James F.; Bender, Steve; ...

2016-07-01

Relative reflectace point spectra (400–840 nm) were acquired by the Chemistry and Camera (ChemCam) instrument on the Mars Science Laboratory (MSL) rover Curiosity in passive mode (no laser) of drill tailings and broken rock fragments near the rover as it entered the lower reaches of Mt. Sharp and of landforms at distances of 2–8 km. Freshly disturbed surfaces are less subject to the spectral masking effects of dust, and revealed spectral features consistent with the presence of iron oxides and ferric sulfates. Here, we present the first detection on Mars of a ~433 nm absorption band consistent with small abundancesmore » of ferric sulfates, corroborated by jarosite detections by the Chemistry and Mineralogy (CheMin) X-ray diffraction instrument in the Mojave, Telegraph Peak, and Confidence Hills drilled samples. The disturbed materials near the Bonanza King region also exhibited strong 433 nm bands and negative near-infrared spectral slopes consistent with jarosite. ChemCam passive spectra of the Confidence Hills and Mojave drill tailings showed features suggestive of the crystalline hematite identified by CheMin analyses. The Windjana drill sample tailings exhibited flat, low relative reflectance spectra, explained by the occurrence of magnetite detected by CheMin. Passive spectra of Bonanza King were similar, suggesting the presence of spectrally dark and neutral minerals such as magnetite. Long-distance spectra of the “Hematite Ridge” feature (3–5 km from the rover) exhibited features consistent with crystalline hematite. The Bagnold dune field north of the Hematite Ridge area exhibited low relative reflectance and near-infrared features indicative of basaltic materials (olivine, pyroxene). Light-toned layers south of Hematite Ridge lacked distinct spectral features in the 400–840 nm region, and may represent portions of nearby clay minerals and sulfates mapped with orbital near-infrared observations. The presence of ferric sulfates such as jarosite in the drill tailings suggests a relatively acidic environment, likely associated with flow of iron-bearing fluids, associated oxidation, and/or hydrothermal leaching of sedimentary rocks. Combined with other remote sensing data sets, mineralogical constraints from ChemCam passive spectra will continue to play an important role in interpreting the mineralogy and composition of materials encountered as Curiosity traverses further south within the basal layers of the Mt. Sharp complex.« less

Constraints on iron sulfate and iron oxide mineralogy from ChemCam visible/near-infrared reflectance spectroscopy of Mt. Sharp basal units, Gale Crater, Mars

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

Johnson, Jeffrey R.; Bell, James F.; Bender, Steve

Relative reflectace point spectra (400–840 nm) were acquired by the Chemistry and Camera (ChemCam) instrument on the Mars Science Laboratory (MSL) rover Curiosity in passive mode (no laser) of drill tailings and broken rock fragments near the rover as it entered the lower reaches of Mt. Sharp and of landforms at distances of 2–8 km. Freshly disturbed surfaces are less subject to the spectral masking effects of dust, and revealed spectral features consistent with the presence of iron oxides and ferric sulfates. Here, we present the first detection on Mars of a ~433 nm absorption band consistent with small abundancesmore » of ferric sulfates, corroborated by jarosite detections by the Chemistry and Mineralogy (CheMin) X-ray diffraction instrument in the Mojave, Telegraph Peak, and Confidence Hills drilled samples. The disturbed materials near the Bonanza King region also exhibited strong 433 nm bands and negative near-infrared spectral slopes consistent with jarosite. ChemCam passive spectra of the Confidence Hills and Mojave drill tailings showed features suggestive of the crystalline hematite identified by CheMin analyses. The Windjana drill sample tailings exhibited flat, low relative reflectance spectra, explained by the occurrence of magnetite detected by CheMin. Passive spectra of Bonanza King were similar, suggesting the presence of spectrally dark and neutral minerals such as magnetite. Long-distance spectra of the “Hematite Ridge” feature (3–5 km from the rover) exhibited features consistent with crystalline hematite. The Bagnold dune field north of the Hematite Ridge area exhibited low relative reflectance and near-infrared features indicative of basaltic materials (olivine, pyroxene). Light-toned layers south of Hematite Ridge lacked distinct spectral features in the 400–840 nm region, and may represent portions of nearby clay minerals and sulfates mapped with orbital near-infrared observations. The presence of ferric sulfates such as jarosite in the drill tailings suggests a relatively acidic environment, likely associated with flow of iron-bearing fluids, associated oxidation, and/or hydrothermal leaching of sedimentary rocks. Combined with other remote sensing data sets, mineralogical constraints from ChemCam passive spectra will continue to play an important role in interpreting the mineralogy and composition of materials encountered as Curiosity traverses further south within the basal layers of the Mt. Sharp complex.« less

Enhancing electrical conductivity of room temperature deposited Sn-doped In2O3 thin films by hematite seed layers

NASA Astrophysics Data System (ADS)

Lohaus, Christian; Steinert, Céline; Deyu, Getnet; Brötz, Joachim; Jaegermann, Wolfram; Klein, Andreas

2018-04-01

Hematite Fe2O3 seed layers are shown to constitute a pathway to prepare highly conductive transparent tin-doped indium oxide thin films by room temperature magnetron sputtering. Conductivities of up to σ = 3300 S/cm are observed. The improved conductivity is not restricted to the interface but related to an enhanced crystallization of the films, which proceeds in the rhombohedral phase.

Mixed-valence iron minerals on Venus: Fe(2+)-Fe(3+) oxides and oxy-silicates formed by surface-atmosphere interactions

NASA Technical Reports Server (NTRS)

Burns, Roger G.; Straub, Darcy W.

1992-01-01

Inferences from these investigations are that Fe(3+)-bearing minerals such as hematite magnesioferrite, acmite, and epidote are thermodynamically unstable, and that magnetite is the predominant mixed-valence iron oxide mineral on venus. Recently, the Fe(2+)-Fe(3+) silicate mineral laihunite was proposed to be a reaction product of olivine with the venusian atmosphere. This possibility is discussed further here. We suggest that other mixed-valence Fe(2+)-Fe(3+)-Oz-OH(-) silicates could also result from surface-atmosphere interactions on Venus. Topics discussed include the following: (1) conversion of hematite to magnetite; (2) stability of laihunite; (3) the possible existence of oxy-amphiboles and oxy-micas on Venus; and (4) other mixed-valence Fe(2+)-Fe(3+) silicates likely to exist on Venus.

Computer modeling of adsorption and decomposition pathways of boundary-layer lubricants on clean aluminum(111) surface, and adhesive metal transfer at the aluminum/steel interface: The ab-initio study

NASA Astrophysics Data System (ADS)

Zhong, Jun

Density functional theory (DFT) is employed to study lubricant adsorption and decomposition pathways, and adhesive metal transfer on clean aluminum surfaces. In this dissertation, density functional theory (DFT-GGA) is used to investigate the optimal adsorption geometries and binding energies of vinyl-phosphonic and ethanoic acids on an A1(111) surface. Tri-bridged, bi-bridged and uni-dentate coordinations for adsorbates are examined to determine the optimal binding sites on the surface. An analysis of the charge density of states (DOS) of oxygen involved in reacting with aluminum ions reveals changes in the atomic bonding configuration. For these acid molecules, the favorable decomposition pathways lead to fragments of vinyl- and alkylchains bonding to the Al(111) surface with phosphorous and carbon ions. Final optimal decomposition geometries and binding energies for various decomposition stages are also discussed. In addition, ab-initio molecular dynamics (AIMD) is carried out to explore collisions of aliphatic lubricants like butanol-alcohol and butanoic-acid with the Al(111) surface. Simulation results indicate that functional oxygen groups on these molecules could react with the "islands of nascent aluminum" and oxidize the surface. Favorable decomposition pieces on the surface, which were corroborated with experiment and DFT calculations, are found to contribute to the effectiveness of a particular molecule for boundary thinfilm lubrication to reduce the wear of aluminum. Finally, ab-initio molecular dynamics is also applied to investigations of the interaction between aluminum and hematite surfaces with and without a vinyl-phosphonic acid (VPA) lubricant. Without the lubricant, hematite is found to react with Al strongly (thermit reaction). This removes relatively large fragments from the surface of the aluminum substrate when this substrate is rubbed with a harder steel-roller under an external shock contact-load exceeding the ability of the substrate to support the aluminum-oxide film. Adhesive wear is found to significantly raise the temperature of system. Addition of VPA lubricant is found to retard the reaction of hematite with aluminum by forming an effective barrier between the two surfaces.

Compositional Models of Hematite-Rich Spherules (Blueberries) at Meridiani Planum, Mars and Constraints on Their Formation

NASA Astrophysics Data System (ADS)

Schneider, A.; Mittlefehldt, D.

2006-10-01

The Mars Exploration Rover Opportunity discovered hematite-rich spherules (``blueberries'') believed to be diagenetic concretions formed in the bedrock in stagnant or slow-moving groundwater. These spherules likely precipitated from solution, but their origins are poorly understood. Three formation mechanisms are possible: inclusive, replacive and displacive. The first would result in a distinct spherule composition compared to the other two. We propose that chemical clues may help to constrain the nature of blueberry formation. We used Alpha Particle X-ray Spectrometer data for undisturbed soils that were blueberry-free and with visible blueberries at the surface in Microscopic Imager images. We made plots of the elements versus iron for the spherule-rich soils and compared them to a mixing line representative of a pure hematite end member spherule (called ``the zero model''). This modeled the replacive formation mechanism, in which pure hematite would replace all of the original material. If the spherules grew inclusively, chemical data should reflect a compositional component of the rock grains included during formation. Four models were developed to test for possible compositions of a rock component. These models could not easily explain the APXS data and thus demonstrate that the most plausible rock compositions are not components of blueberries.

Curiosity Checks Under the Dust on a Martian Rock

NASA Image and Video Library

2017-11-01

On a part of "Vera Rubin Ridge" where rover-team researchers sought to determine whether dust coatings are hiding rocks' hematite content, the Mast Camera (Mastcam) on NASA's Curiosity Mars rover took this image of a rock surface that had been brushed with the rover's Dust Removal Tool. The image is shown in the usual full color of featured Mastcam images: with a color adjustment similar to white balancing for approximating how the rocks and sand would appear under daytime lighting conditions on Earth. Sunlight on Mars is tinged by the dusty atmosphere and this adjustment helps geologists recognize color patterns they are familiar with on Earth. In this case, the purplish tint of the brushed area suggested fine-grained hematite. Bright lines within the rocks are fractures filled with calcium sulfate minerals. The brushed area is about 2.5 inches (6 centimeters) across. The image was taken on Sept. 17, 2017, during the 1,819th Martian day, or sol, of Curiosity's work on Mars. Mastcam also imaged this same scene using three special filters that help to identify hematite, an iron-oxide mineral that can provide information about ancient environmental conditions. A science-filters image identifies hematite in this brushed target even more clearly. https://photojournal.jpl.nasa.gov/catalog/PIA22067

The Influence Of Hydrothermal Alteration And Weathering On Rock Magnetic Properties Of Granites From The Eps-1 Drilling (soultz-sous-forÊts / France)

NASA Astrophysics Data System (ADS)

Just, J.; Schleicher, A.; Kontny, A.; de Wall, H.

The EPS-1 drilling in Soultz-sous-Forêts (Rhinegraben, France) recovered a core pro- file of Tertiary to Permo-Mesozoic sediments deposited on a Variscan granitic base- ment. Magnetic susceptibility (k) measurements on the core material revealed a con- tinous increase from the basement/cover boundary (kmean 0.4 x 10-3 SI) into the magnetite-bearing granite (kmean 13 x 10-3 SI) over a depth range of 1417 U 1555 m. Rock magnetic and mineralogic studies were performed for the fresh granite, the hydrothermally altered granite near a fault zone and the altered granite from the fossil land surface near the basement/cover boundary. The decrease in susceptibility can be correlated with a gradual decomposition of magnetite to hematite and an alteration of the matrix minerals feldspars, biotite and hornblende to clay minerals and carbon- ates. Along with this transition, characteristic rock magnetic signatures can be dis- criminated for different degrees of alteration. While temperature-dependent magnetic susceptibility k(T)-curves in fresh granites indicate a typical multidomain magnetite course with good reversibility, different types of irreversible courses are observed for the altered granite. However, hematite could not be identified in the k(T)-curves. Al- tered granite shows relatively weak magnetic behaviour in AF-demagnetisation exper- iments, untypical for hematite. The alteration of the fresh granite also causes a change in magnetic fabric parameter, especially of the anisotropy factor. The magnetic min- eralogy from the altered granite in respect to the changes in rock magnetic properties will be discussed.

New method for revealing dislocations in garnet: premelting decoration

NASA Astrophysics Data System (ADS)

Liu, Xiangwen; Xie, Zhanjun; Jin, Zhenmin; Li, Zhuoyue; Ao, Ping; Wu, Yikun

2018-05-01

Premelting decoration (PMD) of dislocation experiments was carried out on garnets at 1 atmosphere pressure and temperatures of 800-1000 °C. Numerous decorated lines were observed on the polished surface of heat-treated garnet grains. The results of scanning electron microscopy, laser Raman spectroscopy and transmission electron microscopy (TEM) analyses indicate that these decorated lines were generated by premelting reaction along the dislocation lines and subgrain boundaries. The constituents of decorated lines on the polished surface of garnet are hematite, magnetite, and melt. While, in the interior of garnet, their constituents changed to Al-bearing magnetite and melt. The dislocation density of a gem-quality megacrystal garnet grain by means of the PMD is similar to that obtained by TEM, which confirms that the PMD is a new reliable method for revealing dislocations in garnet. This method greatly reduces the cost and time involved in the observation of dislocation microstructures in deformed garnet.

CCl 4 chemistry on the magnetite selvedge of single-crystal hematite: competitive surface reactions

NASA Astrophysics Data System (ADS)

Adib, K.; Camillone, N., III; Fitts, J. P.; Rim, K. T.; Flynn, G. W.; Joyce, S. A.; Osgood, R. M., Jr.

2002-01-01

Temperature programmed reaction/desorption (TPR/D) studies were undertaken to characterize the surface chemistry which occurs between CCl 4 and the Fe 3O 4 (1 1 1) selvedge of single crystal α-Fe 2O 3 (0 0 0 1). Six separate desorption events are clearly observed and four desorbing species are identified: CCl 4, OCCl 2, C 2Cl 4 and FeCl 2. It is proposed that OCCl 2, CCl 4 and C 2Cl 4 are produced in reactions involving the same precursor, CCl 2. Three reaction paths compete for the CCl 2 precursor: oxygen atom abstraction (for OCCl 2), molecular recombinative desorption (for CCl 4) and associative desorption (for C 2Cl 4). During the TPR/D temperature ramp, the branching ratio is observed to depend upon temperature and the availability of reactive sites. The data are consistent with a rich site-dependent chemistry.

Enhanced photoelectrochemical performance of Ti-doped hematite thin films prepared by the sol-gel method

NASA Astrophysics Data System (ADS)

Lian, Xiaojuan; Yang, Xin; Liu, Shangjun; Xu, Ying; Jiang, Chunping; Chen, Jinwei; Wang, Ruilin

2012-01-01

Ti-doped α-Fe2O3 thin films were successfully prepared on FTO substrates by the sol-gel route. Hematite film was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy dispersive spectrometer (EDS). The XRD data showed α-Fe2O3 had a preferred (1 1 0) orientation which belonged to the rhombohedral system. Interestingly, the grains turned into worm-like shape after annealed at high temperature. The IPCE could reach 32.6% at 400 nm without any additional potential vs. SCE. Titanium in the lattice can affect the photo electro chemical performance positively by increasing the conductivity of the thin film. So the excited electrons and holes could live longer, rather than recombining with each other rapidly as undoped hematite. And the efficient carrier density on the Ti-doped anode surface was higher than the undoped anode, which contribute to the well PEC performance.

Hematite at Meridiani Planum and Gusev Crater as identified by the Moessbauer Spectrometer MIMOS II

NASA Astrophysics Data System (ADS)

Klingelhoefer, G.; Morris, R. V.; Rodionov, D.; Schroeder, C.; de Souza, P. A.; Yen, A.; Renz, F.; Wdowiak, T.

2004-12-01

The Moessbauer (MB) spectrometers on the MER rovers Opportunity and Spirit, which landed on Mars in January 2004, have identified the iron-containing mineral hematite (a-Fe2O3) at both landing sites. On Earth, hematite can occur either by itself or with other iron oxides as massive deposits, in veins , and as particles dispersed through a silicate or other matrix material. Hematite particle size can range from nanophase (superparamagnetic) to multidomain and particle shape ranges from equant to acicular to platy. Fine-grained hematite is red in color and is a pigmenting agent. Coarse-grained hematite can be spectrally neutral (gray) at visible wavelengths. Substitutional impurities, particularly Al, are common in hematite. Chemically pure, coarse-grained, and well-crystalline hematite has a magnetic transition (the Morin transition) at ~260 K. Moessbauer spectra, recorded as a function of temperature, provide a way to characterize Martian hematite with respect to some of the physical and chemical characteristics. At Meridiani Planum besides the iron-sulfate mineral jarosite also the Fe-oxide hematite has been identified by the Moessbauer spectrometer, mainly in three distinct types of reservoir: - outcrop matrix material dominated by the mineral jarosite in the MB spectrum, certain basaltic soils, and mm-sized spherules dubbed blueberries. Moessbauer spectra of each reservoir yield a distinct set of hyperfine parameters for hematite, suggesting different degrees of crystallinity and particle size. The hematite found by MB instrument MIMOS II in the outcrop material shows the Morin transition at relatively high temperatures (ca. 250 K) which is an indication of pure and well-crystallized hematite. The source of the hematite in the `Blueberries' as identified by Moessbauer spectroscopy, and also by MiniTES, is not known. These spherules, covering nearly the whole landing site area (Eagle crater, plains, Endurance crater), may be concretions formed in the outcrop involving aqueous processes. They are dispersed throughout the hematite containing jarositic outcrop material. According to Moessbauer analysis the dominating iron-bearing mineral in the spherules is hematite, and jarosite not been detected so far in significant amounts. But there are some places with hematite showing characteristics different from the hematite described above: (1) the soil at B023-HematiteSlope-Hema2 has some blueberries, but the MB did not seem to intercept any. The temperature dependence of its MB parameteres are different from those of blueberries. (2) B049-RasberryNewton-Filling shows a unique Hm MB signature, as well as (3) B051-RealSharksTooth-Enamel1. At Gusev Crater no widespread occurrence of hematite has been detected on the Gusev plains, although minor amounts of hematite were detected in an alteration rind on the rock Mazatzal at the rim of Bonneville crater. At the Columbia Hills, however, the MB instrument did find hematite in significant amounts in highly altered rocks, showing at the same time a significant decrease in the amount of olivine compared to typical basaltic rocks at Gusev crater.

Experimental and theoretical investigations of mercury adsorption on hematite (1-102) surfaces

NASA Astrophysics Data System (ADS)

Jung, J.; Wilcox, J.; Jew, A. D.; Rupp, E. C.; Brown, G. E.

2013-12-01

Fly ash is a primary byproduct of the coal combustion process. The release of fly ash into the environment and its use in consumer products are public health concerns because of the presence of toxic trace metals and metalloids, such as mercury (Hg), selenium (Se), and arsenic (As), which may exist as components of fly ash, partition onto fly ash as it cools, or is lost to the environment through smoke stacks in a vapor phase. Therefore, it is important to understand the components of fly ash and their interaction with trace metals. In this study, calculations using density functional theory (DFT) were carried out in conjunction with experimental studies to investigate the interaction between Hg and hematite, an important mineral component of fly ash. Our experimental study, designed to simulate Hg sorption in a coal-fired power plant exhaust system, involved exposure of the fine fraction of bituminous coal fly ash (≤ 0.1 μm) to methane combustion flue gas, supplemented with SO2, NOx, HCl, and Hg in a packed-bed reactor. Sorption reaction products were characterized by synchrotron-based x-ray fluorescence mapping (s-XRF), x-ray diffraction (XRD), and extended x-ray absorption fine structure (EXAFS) spectroscopy. Preliminary s-XRF results showed that Hg in the sample is correlated with Fe, S, Cl, Br, and to a lesser extent with Se and As. From the XRD analysis, the dominant mineral phases detected were quartz, iron oxide (hematite), and various sulfate-bearing cements. Based on the experimental results, DFT studies were carried out to investigate the adsorption of Hg on hematite (α-Fe2O3) (1-102) surfaces. The two α-Fe2O3 (1-102) surfaces modeled consisted of two different surface terminations: (1) M2-clean, which corresponds to the oxygen terminated r-cut surface with the first layer of cations removed and no hydroxyl group and (2) M2-OH2-OH which has bihydroxylated top oxygen atoms and a second layer of hydroxylated oxygen atoms. These surface terminations were selected because both surfaces are highly stable in the temperature range of flue gases. All calculations were conducted using the Vienna ab-initio simulation package (VASP). Probable adsorption sites of Hg on the two α-Fe2O3 surface terminations are suggested based on calculated adsorption energies. Additionally, Bader charge analysis was conducted to characterize the oxidation state of both Hg and Fe in the α-Fe2O3 surfaces. The layer spacing of the structure was also calculated in order to compare the surface geometry before and after Hg adsorption. Preliminary results indicate that the binding energy of Hg on the M2-clean surface is -0.102 eV and that mercury donates electrons to the O and Fe atoms in the top layer when it adsorbs onto the surface.

Hematite at Meridiani Planum and Gusev Crater as identified by the Moessbauer Spectrometer MIMOS II

NASA Technical Reports Server (NTRS)

Klingelhoefer, G.; Morris, R. V.; Rodionov, D.; Schroeder, C.; de Souza, P. A.; Yen, A.; Renz, F.; Wdowiak, T.

2006-01-01

The Moessbauer (MB) spectrometers on the MER rovers Opportunity and Spirit, which landed on Mars in January 2004, have identified the iron-containing mineral hematite (a-Fe2O3) at both landing sites. On Earth, hematite can occur either by itself or with other iron oxides as massive deposits, in veins , and as particles dispersed through a silicate or other matrix material. Hematite particle size can range from nanophase (superparamagnetic) to multidomain and particle shape ranges from equant to acicular to platy. Fine-grained hematite is red in color and is a pigmenting agent. Coarse-grained hematite can be spectrally neutral (gray) at visible wavelengths. Substitutional impurities, particularly Al, are common in hematite. Chemically pure, coarse-grained, and well-crystalline hematite has a magnetic transition (the Morin transition) at 260 K. Moessbauer spectra, recorded as a function of temperature, provide a way to characterize Martian hematite with respect to some of the physical and chemical characteristics. At Meridiani Planum besides the iron-sulfate mineral jarosite also the Fe-oxide hematite has been identified by the Moessbauer spectrometer, mainly in three distinct types of reservoir: - outcrop matrix material dominated by the mineral jarosite in the MB spectrum, certain basaltic soils, and mm-sized spherules dubbed blueberries. Moessbauer spectra of each reservoir yield a distinct set of hyperfine parameters for hematite, suggesting different degrees of crystallinity and particle size. The hematite found by MB instrument MIMOS II in the outcrop material shows the Morin transition at relatively high temperatures (ca. 250 K) which is an indication of pure and well-crystallized hematite. The source of the hematite in the Blueberries as identified by Moessbauer spectroscopy, and also by MiniTES, is not known. These spherules, covering nearly the whole landing site area (Eagle crater, plains, Endurance crater), may be concretions formed in the outcrop involving aqueous processes. They are dispersed throughout the hematite containing jarositic outcrop material. According to Moessbauer analysis the dominating iron-bearing mineral in the spherules is hematite, and jarosite not been detected so far in significant amounts. But there are some places with hematite showing characteristics different from the hematite described above: (1) the soil at B023_HematiteSlope_Hema2 has some blueberries, but the MB did not seem to intercept any. The temperature dependence of its MB parameters are different from those of blueberries. (2) B049_RasberryNewton_Filling shows a unique Hm MB signature, as well as (3) B051_RealSharksTooth_Enamel1.

Iron-tolerant Cyanobacteria as a Tool to Study Terrestrial and Extraterrestrial Iron Deposition

NASA Technical Reports Server (NTRS)

Brown, I. I.; Mummey, D.; Cooksey, K. E.; McKay, D. S.

2005-01-01

We are investigating biological mechanisms of terrestrial iron deposition as analogs for Martian hematite recently confirmed by. Possible terrestrial analogs include iron oxide hydrothermal deposits, rock varnish, iron-rich laterites, ferricrete soils, moki balls, and banded iron formations (BIFs). With the discovery of recent volcanic activity in the summit craters of five Martian volcanoes, renewed interest in the iron dynamics of terrestrial hydrothermal environments and associated microorganisms is warranted. In this study we describe a new genus and species of CB exhibiting elevated dissolved iron tolerance and the ability to precipitate hematite on the surface of their exopolymeric sheathes.

A comprehensive parameterization of heterogeneous ice nucleation of dust surrogate: laboratory study with hematite particles and its application to atmospheric models

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Paukert, M.; Steinke, I.; Zhang, K.; Kulkarni, G.; Hoose, C.; Schnaiter, M.; Saathoff, H.; Möhler, O.

2014-12-01

A new heterogeneous ice nucleation parameterization that covers a wide temperature range (-36 to -78 °C) is presented. Developing and testing such an ice nucleation parameterization, which is constrained through identical experimental conditions, is important to accurately simulate the ice nucleation processes in cirrus clouds. The ice nucleation active surface-site density (ns) of hematite particles, used as a proxy for atmospheric dust particles, were derived from AIDA (Aerosol Interaction and Dynamics in the Atmosphere) cloud chamber measurements under water subsaturated conditions. These conditions were achieved by continuously changing the temperature (T) and relative humidity with respect to ice (RHice) in the chamber. Our measurements showed several different pathways to nucleate ice depending on T and RHice conditions. For instance, almost T-independent freezing was observed at -60 °C < T < -50 °C, where RHice explicitly controlled ice nucleation efficiency, while both T and RHice played roles in other two T regimes: -78 °C < T < -60 °C and -50 °C < T < -36 °C. More specifically, observations at T lower than -60 °C revealed that higher RHice was necessary to maintain a constant ns, whereas T may have played a significant role in ice nucleation at T higher than -50 °C. We implemented the new hematite-derived ns parameterization, which agrees well with previous AIDA measurements of desert dust, into two conceptual cloud models to investigate their sensitivity to the new parameterization in comparison to existing ice nucleation schemes for simulating cirrus cloud properties. Our results show that the new AIDA-based parameterization leads to an order of magnitude higher ice crystal concentrations and to an inhibition of homogeneous nucleation in lower-temperature regions. Our cloud simulation results suggest that atmospheric dust particles that form ice nuclei at lower temperatures, below -36 °C, can potentially have a stronger influence on cloud properties, such as cloud longevity and initiation, compared to previous parameterizations.

Effect of Mineralogy on Dissolution and Speciation of Iron Containing Mineral Oxides in Atmospheric Aerosol Dust

NASA Astrophysics Data System (ADS)

Hettiarachchi, E.; Rubasinghege, G. R. S.; Reynolds, R. L.; Goldstein, H. L.; Moskowitz, B. M.

2017-12-01

Iron is one of the important trace elements for the life. Though it is the fourth most abundant element in the terrestrial crust, given higher pH ( 8.5) in the ocean, the direct dissolution of iron from the Earth crust is limited. Despite this limitation, ocean contains about 2 nM of dissolved iron that is 20-fold greater. Therefore, it is hypothesized most iron comes to the ocean via atmosphere, and dissolution occurs in the acidic atmospheric environments. The current work focuses on the effect of minerology on atmospheric processing of Fe-containing mineral dust using four authentic dust samples, collected from different parts of the world, along with three model systems, hematite (α-Fe2O3), magnetite (Fe3O4) and ilmenite (FeTiO3). Here, spectroscopic methods are combined with batch reactor studies to investigate total iron dissolution and speciation, with a specific focus on source material i.e. particle size, mineralogy, and environmental conditions, i.e. pH, temperature and solar flux. Our data suggests that the presence of Ti metal enhances the dissolution of iron regardless the total %Fe in the mineral. The surface area normalized total iron dissolution in ilmenite, under the dark conditions, in the presence of nitric acid (HNO3) is 3-fold higher than that of hematite. In authentic samples, similar effects were observed for samples containing %Ti. Further, 74% of the dissolved iron in ilmenite remained as Fe(II), bioavailable iron, whereas it was only 60% for magnetite and 8% for hematite. In this study, these results were used to interpret similar trends observed for authentic dust samples with high magnetite content. Thus, the findings of the current study highlight important, yet unconsidered, factors in the atmospheric processing of iron-containing mineral dust aerosol.

Effects of Dissolved Carbonate on Arsenate Adsorption and Surface Speciation at the Hematite-Water Interface

USGS Publications Warehouse

Arai, Y.; Sparks, D.L.; Davis, J.A.

2004-01-01

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite-water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [PCO2 = 10 -3.5 atm and ???0; CO2-free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L -1, [As(V)]0 = 1.5 mM and / = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L-1, [As(V)] 0 = 0.5 mM and / = 0.01 M NaCl], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems (PCO2 = 10-3.5 atm)than in the CO2-free argon system at pH 4-7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear (???2.8 A??) and bidentate binuclear (???3.3 A??) bonding at pH 4.5-8 and loading levels of 0.46-3.10 ??M m-2. Using the results of the pseudoequilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the PCO2 = 10-3.5 atm and the CO2-free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO2(g).

Hematite Reduction Buffers Acid Generation and Enhances Nutrient Uptake by a Fermentative Iron Reducing Bacterium, Orenia metallireducens Strain Z6.

PubMed

Dong, Yiran; Sanford, Robert A; Chang, Yun-Juan; McInerney, Michael J; Fouke, Bruce W

2017-01-03

Fermentative iron-reducing organisms have been identified in a variety of environments. Instead of coupling iron reduction to respiration, they have been consistently observed to use ferric iron minerals as an electron sink for fermentation. In the present study, a fermentative iron reducer, Orenia metallireducens strain Z6, was shown to use iron reduction to enhance fermentation not only by consuming electron equivalents, but also by generating alkalinity that effectively buffers the pH. Fermentation of glucose by this organism in the presence of a ferric oxide mineral, hematite (Fe 2 O 3 ), resulted in enhanced glucose decomposition compared with fermentation in the absence of an iron source. Parallel evidence (i.e., genomic reconstruction, metabolomics, thermodynamic analyses, and calculation of electron transfer) suggested hematite reduction as a proton-consuming reaction effectively consumed acid produced by fermentation. The buffering effect of hematite was further supported by a greater extent of glucose utilization by strain Z6 in media with increasing buffer capacity. Such maintenance of a stable pH through hematite reduction for enhanced glucose fermentation complements the thermodynamic interpretation of interactions between microbial iron reduction and other biogeochemical processes. This newly discovered feature of iron reducer metabolism also has significant implications for groundwater management and contaminant remediation by providing microbially mediated buffering systems for the associated microbial and/or chemical reactions.

Iron isotope fractionation during hydrothermal ore deposition and alteration

NASA Astrophysics Data System (ADS)

Markl, Gregor; von Blanckenburg, Friedhelm; Wagner, Thomas

2006-06-01

Iron isotopes fractionate during hydrothermal processes. Therefore, the Fe isotope composition of ore-forming minerals characterizes either iron sources or fluid histories. The former potentially serves to distinguish between sedimentary, magmatic or metamorphic iron sources, and the latter allows the reconstruction of precipitation and redox processes. These processes take place during ore formation or alteration. The aim of this contribution is to investigate the suitability of this new isotope method as a probe of ore-related processes. For this purpose 51 samples of iron ores and iron mineral separates from the Schwarzwald region, southwest Germany, were analyzed for their iron isotope composition using multicollector ICP-MS. Further, the ore-forming and ore-altering processes were quantitatively modeled using reaction path calculations. The Schwarzwald mining district hosts mineralizations that formed discontinuously over almost 300 Ma of hydrothermal activity. Primary hematite, siderite and sulfides formed from mixing of meteoric fluids with deeper crustal brines. Later, these minerals were partly dissolved and oxidized, and secondary hematite, goethite and iron arsenates were precipitated. Two types of alteration products formed: (1) primary and high-temperature secondary Fe minerals formed between 120 and 300 °C, and (2) low-temperature secondary Fe minerals formed under supergene conditions (<100 °C). Measured iron isotope compositions are variable and cover a range in δ56Fe between -2.3‰ and +1.3‰. Primary hematite ( δ56Fe: -0.5‰ to +0.5‰) precipitated by mixing oxidizing surface waters with a hydrothermal fluid that contained moderately light Fe ( δ56Fe: -0.5‰) leached from the crystalline basement. Occasional input of CO 2-rich waters resulted in precipitation of isotopically light siderite ( δ56Fe: -1.4 to -0.7‰). The difference between hematite and siderite is compatible with published Fe isotope fractionation factors. The observed range in isotopic compositions can be accounted for by variable fractions of Fe precipitating from the fluid. Therefore, both fluid processes and mass balance can be inferred from Fe isotopes. Supergene weathering of siderite by oxidizing surface waters led to replacement of isotopically light primary siderite by similarly light secondary hematite and goethite, respectively. Because this replacement entails quantitative transfer of iron from precursor mineral to product, no significant isotope fractionation is produced. Hence, Fe isotopes potentially serve to identify precursors in ore alteration products. Goethites from oolitic sedimentary iron ores were also analyzed. Their compositional range appears to indicate oxidative precipitation from relatively uniform Fe dissolved in coastal water. This comprehensive iron isotope study illustrates the potential of the new technique in deciphering ore formation and alteration processes. Isotope ratios are strongly dependent on and highly characteristic of fluid and precipitation histories. Therefore, they are less suitable to provide information on Fe sources. However, it will be possible to unravel the physico-chemical processes leading to the formation, dissolution and redeposition of ores in great detail.

The Opportunity Rover's Athena science investigation at Meridiani Planum, Mars

NASA Technical Reports Server (NTRS)

Squyres, S. W.; Arvidson, R. E.; Bell, J. F., III; Bruckner, J.; Cabrol, N. A.; Calvin, W.; Carr, M. H.; Christensen, P. R.; Clark, B. C.; Crumpler, L.;

The opportunity Rover's athena science investigation at Meridiani Planum, Mars

USGS Publications Warehouse

Squyres, S. W.; Arvidson, R. E.; Bell, J.F.; Brückner, J.; Cabrol, N.A.; Calvin, W.; Carr, M.H.; Christensen, P.R.; Clark, B. C.; Crumpler, L.; Des Marais, D.J.; D'Uston, C.; Economou, T.; Farmer, J.; Farrand, W.; Folkner, W.; Golombek, M.; Gorevan, S.; Grant, J. A.; Greeley, R.; Grotzinger, J.; Haskin, L.; Herkenhoff, K. E.; Hviid, S.; Johnson, J.; Klingelhofer, G.; Knoll, A.H.; Landis, G.; Lemmon, M.; Li, R.; Madsen, M.B.; Malin, M.C.; McLennan, S.M.; McSween, H.Y.; Ming, D. W.; Moersch, J.; Morris, R.V.; Parker, T.; Rice, J. W.; Richter, L.; Rieder, R.; Sims, M.; Smith, M.; Smith, P.; Soderblom, L.A.; Sullivan, R.; Wanke, H.; Wdowiak, T.; Wolff, M.; Yen, A.

2004-01-01

The Mars Exploration Rover Opportunity has investigated the landing site in Eagle crater and the nearby plains within Meridiani Planum. The soils consist of fine-grained basaltic sand and a surface lag of hematite-rich spherules, spherule fragments, and other granules. Wind ripples are common. Underlying the thin soil layer, and exposed within small impact craters and troughs, are flat-lying sedimentary rocks. These rocks are finely laminated, are rich in sulfur, and contain abundant sulfate salts. Small-scale cross-lamination in some locations provides evidence for deposition in flowing liquid water. We interpret the rocks to be a mixture of chemical and siliciclastic sediments formed by episodic inundation by shallow surface water, followed by evaporation, exposure, and desiccation. Hematite-rich spherules are embedded in the rock and eroding from them. We interpret these spherules to be concretions formed by postdepositional diagenesis, again involving liquid water.

Thermal Sensitivity of MD Hematite: Implication for Magnetic Anomalies

NASA Technical Reports Server (NTRS)

Kletetschka, Gunther; Wasilewski, Peter J.; Taylor, Patrick T.

1999-01-01

Magnetic remanence of crustal rocks can reside in three common rock-forming magnetic minerals: magnetite, pyrrhotite, and hematite. Thermoremanent magnetization (TRM) of magnetite and pyrrhotite is carried mostly by single domain (SD) grains. The TRM of hematite grains, however, is carried mostly by multidomain (NM) grains. This characteristic is illustrated by TRM acquisition curves for hematite of variable grainsizes. The transition between truly NM behavior and tendency towards SD behavior his been established between hematite grainsizes of 0. 1 and 0.05 mm. Coarse grainsize of lower crustal rocks and the large sensitivity of MD hematite grains to acquire TRM indicates that hematite could be a significant contributor to long-wavelength magnetic anomalies.

Transformation of goethite/ferrihydrite to hematite and maghemite under temperate humid conditions in Denmark

NASA Astrophysics Data System (ADS)

Nørnberg, P.; Finster, K.; Gunnlaugsson, H. P.; Jensen, S. K.; Merrison, J. P.; Vendelboe, A. L.

2012-04-01

At a number of sandy soil sites in Mid Jutland, Denmark, with iron content of 1-2%, very red spots (Munsell colour: dusky red 10R 3/4) of a few square meters are found. These spots are most likely due to burning events. After the fire ashes raised pH. This dispersed silt and clay size soil particles which were then transported with seepage water down into lower soil horizons. These particles contain hematite and maghemite due to influence of the fire. However, a long-standing unresolved question is how hematite and maghemite can also be present along with goethite and ferrihydrite, in the same geographical region, and in extended areas with high iron content (8-40 %) in the topsoil. Hematite and particularly maghemite would normally not be expected to form under the temperate humid Danish climate, but be interpreted as the result of high temperature as found in tropical regions or as seen in soils exposed to fire. The high iron content most likely has its origin in pyrite dissolution in top of the groundwater zone in deeper Miocene deposits. From there Fe2+ is brought to the surface by the groundwater, and in wells oxidized by meeting the atmosphere and precipitated as two line ferrihydrite. This is later transformed into goethite. However, along with these two minerals hematite and maghemite are present in the topsoil around the well area. Forest fires would be a likely explanation to the hematite and maghemite. But a body of evidence argues against these sites having been exposed to fire. 1) The pH in the topsoil is 3.6 - 4.8 and thus not raised by ashes. 2) No charcoal is present. 3) There is no indication of fire outside the high iron content areas. 4) Goethite is present along with hematite and maghemite in microparticles, and the mineralogical zonation produced in a forest fire is not seen. The natural sites contain a uniform mixture of goethite/ferrihydrite, hematite and maghemite down to 20 cm depth. An experimental forest fire left charcoal and ashes at the topsoil, produced high pH, mineral zonation and decreased organic matter content, all of which is in contrast to the natural sites. In the freshly precipitated iron materials iron oxidizers as Gallionella sp. were found, but also iron reducing Geobachter sp.were present. Microbial activity might have influenced the mineral transformations.

Feasibility of retrieving dust properties and total column water vapor from solar spectra measured using a lander camera on Mars

NASA Astrophysics Data System (ADS)

Manago, Naohiro; Noguchi, Katsuyuki; Hashimoto, George L.; Senshu, Hiroki; Otobe, Naohito; Suzuki, Makoto; Kuze, Hiroaki

2017-12-01

Dust and water vapor are important constituents in the Martian atmosphere, exerting significant influence on the heat balance of the atmosphere and surface. We have developed a method to retrieve optical and physical properties of Martian dust from spectral intensities of direct and scattered solar radiation to be measured using a multi-wavelength environmental camera onboard a Mars lander. Martian dust is assumed to be composed of silicate-like substrate and hematite-like inclusion, having spheroidal shape with a monomodal gamma size distribution. Error analysis based on simulated data reveals that appropriate combinations of three bands centered at 450, 550, and 675 nm wavelengths and 4 scattering angles of 3°, 10°, 50°, and 120° lead to good retrieval of four dust parameters, namely, aerosol optical depth, effective radius and variance of size distribution, and volume mixing ratio of hematite. Retrieval error increases when some of the observational parameters such as color ratio or aureole are omitted from the retrieval. Also, the capability of retrieving total column water vapor is examined through observations of direct and scattered solar radiation intensities at 925, 935, and 972 nm. The simulation and error analysis presented here will be useful for designing an environmental camera that can elucidate the dust and water vapor properties in a future Mars lander mission.

Annealing effect on the structural and dielectric properties of hematite nanoparticles

NASA Astrophysics Data System (ADS)

Kumar, Vijay; Chahal, Surjeet; Singh, Dharamvir; Kumar, Ashok; Kumar, Parmod; Asokan, K.

2018-05-01

In the present work, we have synthesized hematite (α-Fe2O3) nanoparticles by sol-gel method and sintered them at different temperatures (200 °C, 400 °C and 800 °C for six hours). The samples were then characterized using versatile characterization techniques such as X-ray diffraction (XRD), dielectric measurement and temperature dependent resistivity (RT) for their structural, dielectric and electrical properties. XRD measurements infer that intensity of peak increases with an increase in temperature resulting an increase in crystallite size. Temperature dependent resistivity also shows decrease in the resistivity of the samples. Furthermore, the dielectric measurements correspond to the increase in the dielectric constant. Based on these observations, it can be inferred that sintering temperature plays an important role in tailoring the various physical properties of hematite nanoparticles.

Point of zero potential of single-crystal electrode/inert electrolyte interface.

PubMed

Zarzycki, Piotr; Preočanin, Tajana

2012-03-15

Most of the environmentally important processes occur at the specific hydrated mineral faces. Their rates and mechanisms are in part controlled by the interfacial electrostatics, which can be quantitatively described by the point of zero potential (PZP). Unfortunately, the PZP value of specific crystal face is very difficult to be experimentally determined. Here we show that PZP can be extracted from a single-crystal electrode potentiometric titration, assuming the stable electrochemical cell resistivity and lack of specific electrolyte ions sorption. Our method is based on determining a common intersection point of the electrochemical cell electromotive force at various ionic strengths, and it is illustrated for a few selected surfaces of rutile, hematite, silver chloride, and bromide monocrystals. In the case of metal oxides, we have observed the higher PZP values than those theoretically predicted using the MultiSite Complexation Model (MUSIC), that is, 8.4 for (001) hematite (MUSIC-predicted ~6), 8.7 for (110) rutile (MUSIC-predicted ~6), and about 7 for (001) rutile (MUSIC-predicted 6.6). In the case of silver halides, the order of estimated PZP values (6.4 for AgCl<6.5 for AgBr) agrees well with sequence estimated from the silver halide solubility products; however, the halide anions (Cl(-), Br(-)) are attracted toward surface much stronger than the Ag(+) cations. The observed PZPs sequence and strong anions affinity toward silver halide surface can be correlated with ions hydration energies. Presented approach is the complementary one to the hysteresis method reported previously [P. Zarzycki, S. Chatman, T. Preočanin, K.M. Rosso, Langmuir 27 (2011) 7986-7990]. A unique experimental characterization of specific crystal faces provided by these two methods is essential in deeper understanding of environmentally important processes, including migration of heavy and radioactive ions in soils and groundwaters. Copyright © 2012 Elsevier Inc. All rights reserved.

The Search for Hesperian Organic Matter on Mars: Pyrolysis Studies of Sediments Rich in Sulfur and Iron.

PubMed

Lewis, James M T; Najorka, Jens; Watson, Jonathan S; Sephton, Mark A

2018-04-01

Jarosite on Mars is of significant geological and astrobiological interest, as it forms in acidic aqueous conditions that are potentially habitable for acidophilic organisms. Jarosite can provide environmental context and may host organic matter. The most common extraction technique used to search for organic compounds on the surface of Mars is pyrolysis. However, thermal decomposition of jarosite releases oxygen into pyrolysis ovens, which degrades organic signals. Jarosite has a close association with the iron oxyhydroxide goethite in many depositional/diagenetic environments. Hematite can form by dehydration of goethite or directly from jarosite under certain aqueous conditions. Goethite and hematite are significantly more amenable than jarosite for pyrolysis experiments employed to search for organic matter. Analysis of the mineralogy and organic chemistry of samples from a natural acidic stream revealed a diverse response for organic compounds during pyrolysis of goethite-rich layers but a poor response for jarosite-rich or mixed jarosite-goethite samples. Goethite units that are associated with jarosite, but do not contain jarosite themselves, should be targeted for organic detection pyrolysis experiments on Mars. These findings are extremely timely, as exploration targets for Mars Science Laboratory include Vera Rubin Ridge (formerly known as "Hematite Ridge"), which may have formed from goethite precursors. Key Words: Mars-Pyrolysis-Jarosite-Goethite-Hematite-Biosignatures. Astrobiology 18, 454-464.

Low-cost superior solid-state symmetric supercapacitors based on hematite nanocrystals.

PubMed

Peng, Shaomin; Yu, Lin; Lan, Bang; Sun, Ming; Cheng, Gao; Liao, Shuhuan; Cao, Han; Deng, Yulin

2016-11-22

We present a facile method for the fabrication of hematite nanocrystal-carbon cloth (Fe 2 O 3 -CC) composite. Hierarchical manganite is chosen as the sacrificial precursor, that does not contribute to the component of final iron oxide but can be in situ dissolved by the acid produced from the Fe 3+ hydrolysis. This method effectively enhances the specific surface area and conductivity of hematite (Fe 2 O 3 ) by attaching Fe 2 O 3 nanocrystals (around 5 nm) firmly on the surface of carbon fibers. The obtained Fe 2 O 3 -CC can be directly used as a binder-free electrode for a supercapacitor. Interestingly, the composite electrode exhibits synergistic electrochemical capacitance (electrochemical double-layer capacitance and pseudo-capacitance). It manifests a very high areal capacitance of 1.66 F cm -2 (1660 F g -1 ) at 2 mA cm -2 and excellent cycling performance at large current densities (88.6% retention at 30 mA cm -2 after 5000 cycles) in a three-electrode testing system, which is among the best performances reported in the literature. Importantly, when fabricated as a solid-state flexible symmetric supercapacitor it still shows a maximum energy density of 8.74 mW h cm -3 and power density of 253.9 mW cm -3 . Additionally, its good flexibility makes it suitable for portable devices.

Low-cost superior solid-state symmetric supercapacitors based on hematite nanocrystals

NASA Astrophysics Data System (ADS)

Peng, Shaomin; Yu, Lin; Lan, Bang; Sun, Ming; Cheng, Gao; Liao, Shuhuan; Cao, Han; Deng, Yulin

2016-12-01

We present a facile method for the fabrication of hematite nanocrystal-carbon cloth (Fe2O3-CC) composite. Hierarchical manganite is chosen as the sacrificial precursor, that does not contribute to the component of final iron oxide but can be in situ dissolved by the acid produced from the Fe3+ hydrolysis. This method effectively enhances the specific surface area and conductivity of hematite (Fe2O3) by attaching Fe2O3 nanocrystals (around 5 nm) firmly on the surface of carbon fibers. The obtained Fe2O3-CC can be directly used as a binder-free electrode for a supercapacitor. Interestingly, the composite electrode exhibits synergistic electrochemical capacitance (electrochemical double-layer capacitance and pseudo-capacitance). It manifests a very high areal capacitance of 1.66 F cm-2 (1660 F g-1) at 2 mA cm-2 and excellent cycling performance at large current densities (88.6% retention at 30 mA cm-2 after 5000 cycles) in a three-electrode testing system, which is among the best performances reported in the literature. Importantly, when fabricated as a solid-state flexible symmetric supercapacitor it still shows a maximum energy density of 8.74 mW h cm-3 and power density of 253.9 mW cm-3. Additionally, its good flexibility makes it suitable for portable devices.

Low Concentration Fe-Doped Alumina Catalysts Using Sol-Gel and Impregnation Methods: The Synthesis, Characterization and Catalytic Performance during the Combustion of Trichloroethylene.

PubMed

Maldonado, Carolina Solis; De la Rosa, Javier Rivera; Lucio-Ortiz, Carlos J; Hernández-Ramírez, Aracely; Barraza, Felipe F Castillón; Valente, Jaime S

2014-03-12

The role of iron in two modes of integration into alumina catalysts was studied at 0.39 wt% Fe and tested in trichloroethylene combustion. One modified alumina was synthesized using the sol-gel method with Fe added in situ during hydrolysis; another modification was performed using calcined alumina, prepared using the sol-gel method and impregnated with Fe. Several characterization techniques were used to study the level of Fe modification in the γ-Al₂O₃ phase formed and to correlate the catalytic properties during trichloroethylene (TCE) combustion. The introduction of Fe in situ during the sol-gel process influenced the crystallite size, and three iron species were generated, namely, magnetite, maghemite and hematite. The impregnated Fe-alumina formed hematite and maghemite, which were highly dispersed on the γ-Al₂O 3 surface. The X-ray photoelectron spectra (XPS), FT-IR and Mössbauer spectroscopy analyses revealed how Fe interacted with the γ-Al₂O₃ lattice in both catalysts. The impregnated Fe-catalyst showed the best catalytic performance compared to the catalyst that was Fe-doped in situ by the sol-gel method; both had better catalytic activity than pure alumina. This difference in activity was correlated with the accessibility of the reactants to the hematite iron species on the surface. The chlorine poisoning for all three catalysts was less than 1.8%.

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

NASA Technical Reports Server (NTRS)

Orenberg, J. B.; Handy, J.

1991-01-01

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

Compositional Constraints on Hematite-Rich Spherule (Blueberry) Formation at Meridiani Planum, Mars

NASA Technical Reports Server (NTRS)

Schneider, A. L.; Mittlefehldt, D. W.; Gellert, R.; Jolliff, B.

2007-01-01

Meridiani Planum was chosen as the landing site for the Mars Exploration Rover Opportunity partially based on Mars Global Surveyor Thermal Emission Spectrometer data indicating an abundance of hematite. Hematite often forms through processes that involve water, so the site was a promising one to determine whether conditions on Mars were ever suitable for life. Opportunity struck pay dirt; it s Miniature Thermal Emission Spectrometer (Mini-TES) and Mossbauer Spectrometer (MB) confirmed the presence of hematite in sulfate-rich sedimentary beds and in lag deposits. Meridiani Planum rocks contain three main components: silicate phases, sulfate and possibly chloride salts, and ferric oxide phases such as hematite. Primary igneous phases are at low abundance despite the basaltic origin of the protoliths. Jarosite, an alkali ferric sulfate, was identified by Mossbauer. Some of the hematite is contained in the spherules, and some resides in finer grains in outcrops. Mossbauer and Mini-TES data indicate that hematite is a dominant constituent of the spherules. Panoramic Camera (Pancam) and Microscopic Imager (MI) images of spherule interiors show that hematite is present throughout. The exact composition of the spherules is unknown. Mini-TES only identifies a hematite signature in the spherules; any other constituents have an upper limit of 5-10% .The MB data are consistent with the spherules being composed of only hematite.

Oxidation study by Mössbauer and optic microscopy of steels from boiler tubes used in sugar industry

NASA Astrophysics Data System (ADS)

Fajardo, M.; Pérez Alcázar, G. A.; Aguilar, Y.

1998-08-01

Optic microscopy and Mössbauer spectroscopy were used to study the fail and the inner rusted surface of two boiler tubes used in the sugar industry, respectively. The studied tubes, of the type ASTM A 192, were found to have cracks. By optic microscopy it was observed that the failure begins in the inner surface with circumferential cracking. Also, inside and around the surface close to the cracks a rusted layer was detected. Powder from these layers was collected for Mössbauer spectroscopy analysis. By this method the presence of two or three types of Fe oxides such as wüstite, magnetite and hematite, was proved. These results permit to conclude that the failure mechanism was the thermal fatigue due to a hot work in an O2 -rich vapor atmosphere. The rusted products are stable at high temperatures.

Tubular nanostructured materials for bioapplications

NASA Astrophysics Data System (ADS)

Xie, Jining; Chen, Linfeng; Srivatsan, Malathi; Varadan, Vijay K.

2009-03-01

Tubular nanomaterials possess hollow structures as well as high aspect ratios. In addition to their unique physical and chemical properties induced by their nanoscale dimensions, their inner voids and outer surfaces make them ideal candidates for a number of biomedical applications. In this work, three types of tubular nanomaterials including carbon nanotubes, hematite nanotubes, and maghemite nanotubes, were synthesized by different chemical techniques. Their structural and crystalline properties were characterized. For potential bioapplications of tubular nanomaterials, experimental investigations were carried out to demonstrate the feasibility of using carbon nanotubes, hematite nanotubes, and maghemite nanotubes in glucose sensing, neuronal growth, and drug delivery, respectively. Preliminary results show the promise of tubular nanomaterials in future biomedical applications.

Iron oxide minerals in dust-source sediments from the Bodélé Depression, Chad: Implications for radiative properties and Fe bioavailability of dust plumes from the Sahara

USGS Publications Warehouse

Moskowitz, Bruce M; Reynolds, Richard L.; Goldstein, Harland L.; Beroquo, Thelma; Kokaly, Raymond F.; Bristow, Charlie S

2016-01-01

Atmospheric mineral dust can influence climate and biogeochemical cycles. An important component of mineral dust is ferric oxide minerals (hematite and goethite) which have been shown to influence strongly the optical properties of dust plumes and thus affect the radiative forcing of global dust. Here we report on the iron mineralogy of dust-source samples from the Bodélé Depression (Chad, north-central Africa), which is estimated to be Earth’s most prolific dust producer and may be a key contributor to the global radiative budget of the atmosphere as well as to long-range nutrient transport to the Amazon Basin. By using a combination of magnetic property measurements, Mössbauer spectroscopy, reflectance spectroscopy, chemical analysis, and scanning electron microscopy, we document the abundance and relative amounts of goethite, hematite, and magnetite in dust-source samples from the Bodélé Depression. The partition between hematite and goethite is important to know to improve models for the radiative effects of ferric oxide minerals in mineral dust aerosols. The combination of methods shows (1) the dominance of goethite over hematite in the source sediments, (2) the abundance and occurrences of their nanosize components, and (3) the ubiquity of magnetite, albeit in small amounts. Dominant goethite and subordinate hematite together compose about 2% of yellow-reddish dust-source sediments from the Bodélé Depression and contribute strongly to diminution of reflectance in bulk samples. These observations imply that dust plumes from the Bodélé Depression that are derived from goethite-dominated sediments strongly absorb solar radiation. The presence of ubiquitous magnetite (0.002–0.57 wt%) is also noteworthy for its potentially higher solubility relative to ferric oxide and for its small sizes, including PM < 0.1 μm. For all examined samples, the average iron apportionment is estimated at about 33% in ferric oxide minerals, 1.4% in magnetite, and 65% in ferric silicates. Structural iron in clay minerals may account for much of the iron in the ferric silicates. We estimate that the mean ferric oxides flux exported from the Bodélé Depression is 0.9 Tg/yr with greater than 50% exported as ferric oxide nanoparticles (<0.1 μm). The high surface-to-volume ratios of ferric oxide nanoparticles once entrained into dust plumes may facilitate increased atmospheric chemical and physical processing and affect iron solubility and bioavailability to marine and terrestrial ecosystems.

Raw hematite based Fe(III) bio-reduction process for humified landfill leachate treatment.

PubMed

Li, Rui; Jiang, Yu; Xi, Beidou; Li, Mingxiao; Meng, Xiaoguang; Feng, Chuanping; Mao, Xuhui; Liu, Hongliang; Jiang, Yonghai

2018-05-03

Microorganisms from paddy soils and raw hematite are used for enhancing natural Fe(III) bio-reduction, in order to remove macromolecular organic pollutants from humified landfill leachate. Based on batch experiments, 60% of refractory organics can be adsorbed by hematite in 12 days. In the presence of Fe(III)-reducing bacteria, 489.60 ± 0.14 mg L -1 of dissolved organic matters can be degraded to 51.90 ± 3.96 mg L -1 within 50 days; twelve types of semi volatile organic compounds can be degraded; hereby, the reaction follows a first-order kinetics. Crystalline Fe(III) is transformed into the amorphous form and reduced to Fe(II), hydroquinone functional groups in the humic acid (HA) are transformed to quinone ones, and the formation of HA-hematite ligands is promoted. Comparing with most of the studies about electron shuttling of HA, the transformation of quinone in the HA to hydroquinone could not be observed in the present bio-system. Based on column evaluations, more than 93% of chemical oxygen demand (influent concentration of 658 ± 19 mg L -1 ) could be removed microbially under flow conditions, when the hydraulic retention time was 45 h. Raw hematite-based Fe(III) bio-reduction has a promising potential for the removal of humic and benzene series in humified landfill leachate. Copyright © 2018. Published by Elsevier B.V.

Solution deposited and modified iron oxide for enhanced solar water splitting

NASA Astrophysics Data System (ADS)

Abel, Anthony J.

Growing worldwide energy demand coupled with an increasing awareness of anthropogenic climate change has driven research into carbon-neutral and solar-derived energy sources. One attractive strategy is the storage of solar energy in the bonds of H2 formed by photoelectrochemical (PEC) water splitting. Hematite, an iron oxide, has been widely investigated as a candidate material for PEC water splitting due to its stability, non-toxicity, earth abundance and consequent low cost, and a theoretical 15% solar-to-hydrogen conversion efficiency. However, poor electrical properties and slow rates of the water oxidation reaction have limited its potential as an economical water splitting catalyst. Additionally, the most efficient hematite-based devices are fabricated via expensive, vacuum-phase techniques, limiting scalability to broad integration into the energy supply. In this thesis, I develop a new, solution-based deposition method for high quality, planar hematite thin films using successive ionic layer adsorption and reaction (SILAR). The constant geometry and tight control over layer thickness possible with SILAR makes these films ideal model systems to understand the two key steps of PEC water oxidation: charge separation and interfacial hole transfer. In Chapter 3, I report on facile annealing treatments to dope hematite with Ti and Sn, and I show that these impurity atoms at the hematite/electrolyte interface increase hole transfer efficiency from nearly 0 to above 60%. However, charge separation remains below 15% with these dopants incorporated via solid state diffusion, mainly due to low hole mobility. To overcome this associated small transport length, extremely thin hematite coatings were deposited on Sb:SnO2 monolayer inverse opal scaffolds. With this modified substrate, photocurrent increased proportionately to the surface area of the scaffold. While Chapter 3 discusses incorporation of dopants via solid state diffusion, Chapter 4 examines methods to incorporate Ti via modified SILAR solutions. With this method, hematite films with well-controlled, uniform doping profiles were successfully fabricated. An optimal Ti concentration of 4.2% in the film enabled a charge separation efficiency of >20%, and I show that holes generated within 3 nm of the depletion region are separated with unity efficiency. With the addition of an ultrathin FeOOH overlayer, hole transfer efficiency is increased to 100% as a result of an increased concentration of reactive holes at the hematite/electrolyte interface. These combined effects lead to photocurrents >0.85 mAcm-2 at 1.23 VRHE, which is competitive with champion planar films regardless of fabrication method. Importantly, the methods of fabrication and analysis described in this thesis are applicable to a wide range of materials for a variety of applications. The SILAR method can be applied to many compounds, provided their constituent atoms are soluble in liquid solvents. Additionally, the facile optical and electrochemical measurements used to analyze hematite in Chapters 3 and 4 can be readily adapted to other semiconductor materials with the aim of understanding their charge transport properties.

Discovery Served Up in a Bowl

NASA Technical Reports Server (NTRS)

2004-01-01

This image from the Mars Exploration Rover Opportunity's panoramic camera is an approximate true-color rendering of the exceptional rock called 'Berry Bowl' in the 'Eagle Crater' outcrop. The study of this 'blueberry-strewn' area and the identification of hematite as the major iron-bearing element within these sphere-like grains helped scientists confirm their hypothesis that the hematite in these martian spherules was deposited in water. To separately analyze the mineralogical content of three main features within this area -- blueberries, dust and rock -- it was important that the rock abrasion tool's brush was able to rest on a relatively berry-free spot. The rock's small size and crowd of berries made the 10-minute brushing a challenge to plan and execute. The successful brushing on the target whimsically referred to as 'Near Empty' on the rover's 48th sol on Mars left a dust-free impression for subsequent examination by the rover's spectrometers. No grinding was necessary on the rock because spectral data obtained on the dust-free surface were sufficient to verify that the rock's chemical composition differs significantly from the hematite-rich berries.

Magnetite-hematite transformation: correlation between natural and synthetic features

NASA Astrophysics Data System (ADS)

Barbosa, Paola F.; Lagoeiro, Leonardo; Scholz, Ricardo; Graça, Leonardo M.; Mohallem, Nelcy

2015-06-01

The iron-oxide system can be used as a marker of oxidized and reduced conditions in closed systems. However, natural rocks with iron oxide minerals also exhibit such reactions, although the natural system is typically open. To understand the behaviour of this natural system, some similarities were investigated, in terms of crystallographic textures, between the microstructures of two systems: natural open system and synthetic closed system of iron oxide phase transformation. Particular cases of phase transformation in iron oxide minerals, described as natural reactions of magnetite to hematite and synthetic reactions of hematite to magnetite, were chosen. It is observed, in both scenarios, that the transformation obeys the topotaxial and epitaxial relationship, which are well described for the iron oxide system. However, in natural open systems, the precipitation of a new phase during the in situ transformation modifies the microstructures and must be taken into account as an important factor to describe them.

Effect of surface site interactions on potentiometric titration of hematite (α-Fe2O3) crystal faces.

PubMed

Chatman, Shawn; Zarzycki, P; Preočanin, T; Rosso, K M

2013-02-01

Time dependent potentiometric pH titrations were used to study the effect of atomic scale surface structure on the protonation behavior of the structurally well-defined hematite/electrolyte interfaces. Our recently proposed thermodynamic model [1,25] was applied to measured acidimetric and alkalimetric titration hysteresis loops, collected from highly organized (001), (012), and (113) crystal face terminations using pH equilibration times ranging from 15 to 30 min. Hysteresis loop areas indicate that (001) faces equilibrate faster than the (012) and (113) faces, consistent with the different expected ensembles of singly-, doubly-, and triply-coordinated surface sites on each face. Strongly non-linear hysteretic pH-potential relationships were found, with slopes exceeding Nernstian, collectively indicating that protonation and deprotonation is much more complex than embodied in present day surface complexation models. The asymmetrical shape of the acidimetric and alkalimetric titration branches were used to illustrate a proposed steric "leaky screen" repulsion/trapping interaction mechanism that stems from high affinity singly-coordinated sites electrostatically and sterically screening lower affinity doubly- and triply-coordinated sites. Our data indicate that site interaction is the dominant phenomenon defining surface potential accumulation behavior on single crystal faces of metal oxide minerals. Copyright © 2012 Elsevier Inc. All rights reserved.

The TES Hematite-Rich Region in Sinus Meridiani: A Proposed Landing Site for the 2003 Rover

NASA Technical Reports Server (NTRS)

Christensen, Philip R.; Bandfield, Joshua; Hamilton, Victoria; Ruff, Steven; Morris, Richard; Lane, Melissa; Malin, Michael

2001-01-01

The Thermal Emission Spectrometer (TES) instrument on the Mars Global Surveyor (MGS) mission has identified an accumulation of crystalline hematite (alpha-Fe2O3) that covers an area with very sharp boundaries approximately 350 by 750 km in size centered near 2 S latitude between 0 and 8 W longitude (Sinus Meridiani). The depth and shape of the hematite fundamental bands in the TES spectra show that the hematite is relatively coarse grained (greater than 5-10 micrometers). The spectrally-derived areal abundance of hematite varies with particle size from approximately 10% for particles greater than 30 micrometers in diameter to 40-60% for unpacked 10 micrometer powders. The hematite in Sinus Meridiani is thus distinct from the fine-grained (diameter less than 5-10 micrometers), red, crystalline hematite considered, on the basis of visible and near-IR data, to be a minor spectral component in Martian bright regions. A global map of the hematite abundance has been constructed using TES data from the MGS mapping mission.

Subsurface Organics in Aseptic Cores From the MARTE Robotic Drilling Experiment: Ground truth and Contamination Issues

NASA Astrophysics Data System (ADS)

Bonaccorsi, R.; Stoker, C. R.

2006-12-01

The subsurface is the key environment for searching for life on planets lacking surface life. This includes the search for past/present life on Mars where possible subsurface life could exist [1]. The Mars-Analog-Rio-Tinto-Experiment (MARTE) performed a simulation of a Mars robotic drilling at the RT Borehole#7 Site ~6.07m, atop a massive-pyrite deposit from the Iberian Pyritic Belt. The RT site is considered an important analog of Sinus Meridiani on Mars, an ideal model analog for a subsurface Martian setting [2], and a relevant example of deep subsurface microbial community including aerobic and anaerobic chemoautotrophs [4-5]. Searching for microbes or bulk organics of biological origin in a subsurface sample from a planet is a key scientific objective of Robotic drilling missions. During the 2005 Field experiment 28 minicores were robotically handled and subsampled for life detection experiments under anti-contamination protocols. Ground truth included visual observation of cores and lab based Elemental and Isotope Ratios Mass Spectrometry analysis (EA-IRMS) of bulk organics in Hematite and Gohetite-rich gossanized tuffs, gossan and clay layers within 0-6m-depth. C-org and N-tot vary up to four orders of magnitude among the litter (~11Wt%, 0-1cm) and the mineralized (~3Wt%, 1-3cm) layers, and the first 6 m-depth (C-org=0.02-0.38Wt%). Overall, the distribution/ preservation of plant and soil-derived organics (d13C-org = 26 per mil to 24 per mil) is ten times higher (C-org=0.33Wt%) that in hematite-poor clays, or where rootlets are present, than in hematite- rich samples (C-org=<0.01Wt%). This is consistent with ATP assay (Lightning-MVP, Biocontrol) for total biomass in subsurface (Borehole#7 ~6.07m, ~avg. 153RLU) vs. surface soil samples (~1,500-81,449RLU) [5]. However, the in-situ ATP assay failed in detecting presence of roots during the in-situ life detection experiment. Furthermore, cm-sized roots were overlooked during remote observations. Finally, ATP Luminometry provided insights for potential contamination from core-handling and environmental dust loadings on cleaned/sterilized control surfaces (e.g., 6,782-36,243RLU/cm2). Cleanliness/sterility can be maintained by applying a simple sterile protocol under field conditions. Science results from this research will support future Astrobiology driven drilling mission planned on Mars. Specifically, ground truth offers relevant insights to assess strengths and limits of in-situ/remote observations vs. laboratory measurements. Results from this experiment will also aid the debate on advantages/ disadvantages of manned vs. robotic drilling missions on Mars or other planets. [1] Boston et al., 1997; [2] http://marte.arc.nasa.gov; [3] Stoker, C., et al., 2006 AbSciCon, [4] Stoker et al., submitted; [5] Bonaccorsi., et al., 2006 AbSciCon.

Morphology and Doping Engineering of Sn-Doped Hematite Nanowire Photoanodes.

PubMed

Li, Mingyang; Yang, Yi; Ling, Yichuan; Qiu, Weitao; Wang, Fuxin; Liu, Tianyu; Song, Yu; Liu, Xiaoxia; Fang, Pingping; Tong, Yexiang; Li, Yat

2017-04-12

High-temperature activation has been commonly used to boost the photoelectrochemical (PEC) performance of hematite nanowires for water oxidation, by inducing Sn diffusion from fluorine-doped tin oxide (FTO) substrate into hematite. Yet, hematite nanowires thermally annealed at high temperature suffer from two major drawbacks that negatively affect their performance. First, the structural deformation reduces light absorption capability of nanowire. Second, this "passive" doping method leads to nonuniform distribution of Sn dopant in nanowire and limits the Sn doping concentration. Both factors impair the electrochemical properties of hematite nanowire. Here we demonstrate a silica encapsulation method that is able to simultaneously retain the hematite nanowire morphology even after high-temperature calcination at 800 °C and improve the concentration and uniformity of dopant distribution along the nanowire growth axis. The capability of retaining nanowire morphology allows tuning the nanowire length for optimal light absorption. Uniform distribution of Sn doping enhances the donor density and charge transport of hematite nanowire. The morphology and doping engineered hematite nanowire photoanode decorated with a cobalt oxide-based oxygen evolution reaction (OER) catalyst achieves an outstanding photocurrent density of 2.2 mA cm -2 at 0.23 V vs Ag/AgCl. This work provides important insights on how the morphology and doping uniformity of hematite photoanodes affect their PEC performance.

The Rio Tinto Basin, Spain: Mineralogy, Sedimentary Geobiology, and Implications for Interpretation of Outcrop Rocks at Meridiani Planum, Mars

NASA Technical Reports Server (NTRS)

Fernandez-Remolar, David C.; Morris, Richard V.; Gruener, John E.; Amils, Ricardo; Knoll, Andrew H.

2005-01-01

Exploration by the NASA rover Opportunity has revealed sulfate- and hematite-rich sedimentary rocks exposed in craters and other surface features of Meridiani Planum, Mars. Modern, Holocene, and Plio-Pleistocene deposits of the Rio Tinto, southwestern Spain, provide at least a partial environmental analog to Meridiani Planum rocks, facilitating our understanding of Meridiani mineral precipitation and diagenesis, while informing considerations of martian astrobiology. Oxidation, thought to be biologically mediated, of pyritic ore bodies by groundwaters in the source area of the Rio Tinto generates headwaters enriched in sulfuric acid and ferric iron. Seasonal evaporation of river water drives precipitation of hydronium jarosite and schwertmannite, while (Mg,Al,Fe(sup 3+))-copiapite, coquimbite, gypsum, and other sulfate minerals precipitate nearby as efflorescences where locally variable source waters are brought to the surface by capillary action. During the wet season, hydrolysis of sulfate salts results in the precipitation of nanophase goethite. Holocene and Plio-Pleistocene terraces show increasing goethite crystallinity and then replacement of goethite with hematite through time. Hematite in Meridiani spherules also formed during diagenesis, although whether these replaced precursor goethite or precipitated directly from groundwaters is not known. The retention of jarosite and other soluble sulfate salts suggests that water limited the diagenesis of Meridiani rocks. Diverse prokaryotic and eukaryotic microorganisms inhabit acidic and seasonally dry Rio Tinto environments. Organic matter does not persist in Rio Tinto sediments, but biosignatures imparted to sedimentary rocks as macroscopic textures of coated microbial streamers, surface blisters formed by biogenic gas, and microfossils preserved as casts and molds in iron oxides help to shape strategies for astrobiological investigation of Meridiani outcrops.

A Case for Hydrothermal Gray Hematite in Aram Chaos

NASA Technical Reports Server (NTRS)

Catling, D. C.; Moore, J. M.

2003-01-01

The Thermal Emission Spectrometer (TES) on Mars Global Surveyor has detected deposits of coarsegrained, gray crystalline hematite in Sinus Meridiani, Aram Chaos, and Vallis Marineris [1]. Detailed features in the hematite spectral signature of the Sinus Meridiani region show that the spectrum is consistent with emission dominated by crystal c-faces of hematite, implying that the hematite is specular [2]. Gray specular hematite (also known as specularite ) is a particular gray crystalline form that has intergrown, hexagonal plates with a silvery metallic luster. We believe that the key to the origin of specularite is that it requires crystallization at temperatures in excess of about 100 C. In reviewing the occurrence of gray hematite on Earth, we find no exceptions to this warm temperature requirement [3]. Thermal crystallization on Mars could occur (1) as diagenesis at a depth of a few kilometers of sediments originally formed in lowtemperature waters, or (2) as direct precipitation from hydrothermal solution. Aram Chaos has unique chaotic terrain that offers more clues to the formation of the hematite than the relatively featureless flat terrain (as seen from orbit) of Sinus Meridiani. Aram Chaos provides the opportunity to look at a combination of TES data, Mars Orbiter Camera images, and Mars Orbiter Laser Altimeter (MOLA) topography. This combination of data suggests that high concentrations of hematite were formed in planar strata and have since been exposed by erosion of an overlying light-toned, caprock. Lesser concentrations of hematite are found adjacent to these strata at lower elevations, which we interpret as perhaps a lag deposit. The topography and the collapsed nature of the chaotic terrain favor a hydrothermally charged aquifer as the original setting where the hematite formed. An alternative sedimentary origin requires post-depositional burial to a depth of 3-5 km to induce thermally driven recrystallization of fine-grained iron oxides to coarse-grained hematite.

Red Marks the Spot

NASA Technical Reports Server (NTRS)

2004-01-01

This hematite abundance index map helps geologists choose hematite-rich locations to visit around Opportunity's landing site. Blue dots equal areas low in hematite and red dots equal areas high in hematite.

Why Hematite Geologists are eager to reach the hematite-rich area in the upper left to closely examine the soil, which may reveal secrets about how the hematite got to this location. Knowing how the hematite on Mars was formed may help scientists characterize the past environment and determine whether that environment provided favorable conditions for life.

The Plan Over the next few sols, engineers and scientists plan to drive Opportunity to the hematite-rich area then attempt a 'pre-trench' sequence, taking measurements with the Moessbauer spectrometer, alpha particle X-ray spectrometer and microscopic imager. Next, the plan is to trench the hematite rich area by spinning one wheel in place to 'dig' a shallow hole. Finally, scientists will aim the instrument arm back at the same area where it pre-trenched to get post-trench data with the same instruments to compare and contrast the levels of hematite and revel how deep the hematite lays in the dirt.

Index Map Details The hematite abundance index map was created using data from the miniature thermal emission instrument. The first layer is a mosaic of panoramic camera images taken prior to egress, when Opportunity was still on the lander. The colored dots represent data collected by the miniature thermal emission spectrometer on sol 11, after Opportunity had rolled off of the lander and the rover was located at the center of the blue semi-circle.

The spectrometer is located on the panoramic camera mast. On sol 11, it took a low-angle 180-degree panorama of the area in front of the rover, indicated by the blue shaded dots. The instrument then raised the angle of its field of view a few degrees higher to sweep around behind the rover, indicated by the red and yellow dots offset at the far sides of the image.

JPL, a division of the California Institute of Technology in Pasadena, manages the Mars Exploration Rover project for NASA's Office of Space Science, Washington, D.C.

Experimental evidence for ternary colloid-facilitated transport of Th(IV) with hematite (α-Fe2O3) colloids and Suwannee River fulvic acid.

PubMed

Emerson, Hilary P; Hickok, Katherine A; Powell, Brian A

2016-12-01

Previous field experiments have suggested colloid-facilitated transport via inorganic and organic colloids as the primary mechanism of enhanced actinide transport in the subsurface at former nuclear weapons facilities. In this work, research was guided by the hypothesis that humic substances can enhance tetravalent actinide (An(IV)) migration by coating and mobilizing natural colloids in environmental systems and increasing An(IV) sorption to colloids. This mechanism is expected to occur under relatively acidic conditions where organic matter can sorb and coat colloid surfaces and facilitate formation of ternary colloid-ligand-actinide complexes. The objective of this work was to examine Th transport through packed columns in the presence of hematite colloids and/or Suwannee River fulvic acid (SRFA). In the presence of SRFA, with or without hematite colloids, significant transport (>60% recovery within the effluent) of thorium occurred through quartz columns. It is notable that the SRFA contributed to increased transport of both Th and hematite colloids, while insignificant transport occurred in the absence of fulvic acid. Further, in the presence of a natural sandy sediment (as opposed to pure quartz), transport is negligible in the presence of SRFA due to interactions with natural, clay-sized sediment coatings. Moreover, this data shows that the transport of Th through quartz columns is enhanced in ternary Th-colloid-SRFA and binary Th-SRFA systems as compared to a system containing only Th. Copyright © 2016 Elsevier Ltd. All rights reserved.

Low Concentration Fe-Doped Alumina Catalysts Using Sol-Gel and Impregnation Methods: The Synthesis, Characterization and Catalytic Performance during the Combustion of Trichloroethylene

PubMed Central

Maldonado, Carolina Solis; De la Rosa, Javier Rivera; Lucio-Ortiz, Carlos J.; Hernández-Ramírez, Aracely; Castillón Barraza, Felipe F.; Valente, Jaime S.

2014-01-01

The role of iron in two modes of integration into alumina catalysts was studied at 0.39 wt% Fe and tested in trichloroethylene combustion. One modified alumina was synthesized using the sol-gel method with Fe added in situ during hydrolysis; another modification was performed using calcined alumina, prepared using the sol-gel method and impregnated with Fe. Several characterization techniques were used to study the level of Fe modification in the γ-Al2O3 phase formed and to correlate the catalytic properties during trichloroethylene (TCE) combustion. The introduction of Fe in situ during the sol-gel process influenced the crystallite size, and three iron species were generated, namely, magnetite, maghemite and hematite. The impregnated Fe-alumina formed hematite and maghemite, which were highly dispersed on the γ-Al2O3 surface. The X-ray photoelectron spectra (XPS), FT-IR and Mössbauer spectroscopy analyses revealed how Fe interacted with the γ-Al2O3 lattice in both catalysts. The impregnated Fe-catalyst showed the best catalytic performance compared to the catalyst that was Fe-doped in situ by the sol-gel method; both had better catalytic activity than pure alumina. This difference in activity was correlated with the accessibility of the reactants to the hematite iron species on the surface. The chlorine poisoning for all three catalysts was less than 1.8%. PMID:28788556

Potential-specific structure at the hematite-electrolyte interface

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

McBriarty, Martin E.; Stubbs, Joanne; Eng, Peter

The atomic-scale structure of interfaces between metal oxides and aqueous electrolytes controls their catalytic, geochemical, and corrosion behavior. Measurements that probe these interfaces in situ provide important details of ion and solvent arrangements, but atomically precise structural models do not exist for common oxide-electrolyte interfaces far from equilibrium. Using a novel cell, we measured the structure of the hematite (a-Fe 2O 3) (110more » $$\\bar{2}$$)-electrolyte interface under controlled electrochemical bias using synchrotron crystal truncation rod X ray scattering. At increasingly cathodic potentials, charge-compensating protonation of surface oxygen groups increases the coverage of specifically bound water while adjacent water layers displace outwardly and became disordered. Returning to open circuit potential leaves the surface in a persistent metastable protonation state. The flux of current and ions at applied potential is thus regulated by a unique interfacial electrolyte environment, suggesting that electrical double layer models should be adapted to the dynamically changing interfacial structure far from equilibrium.« less

Effects of atmospheric moisture on rock resistivity.

NASA Technical Reports Server (NTRS)

Alvarez, R.

1973-01-01

This study examines the changes in resistivity of rock samples as induced by atmospheric moisture. Experiments were performed on samples of hematitic sandstone, pyrite, and galena. The sandstone underwent a change in resistivity of four orders of magnitude when it was measured in a vacuum of 500 ntorr and in air of 37% relative humidity. Pyrite and galena showed no variations in resistivity when they were measured under the same conditions. These results, plus others obtained elsewhere, indicate that rocks of the resistive type are affected in their electrical properties by atmospheric moisture, whereas rocks of the conductive type are not. The experimental evidence obtained is difficult to reconcile with a model of aqueous electrolytic conduction on the sample surface. It is instead suggested that adsorbed water molecules alter the surface resistivity in a manner similar to that observed in semiconductors and insulators.

Curiosity's ChemCam Checks 'Christmas Cove' Colors

NASA Image and Video Library

2017-11-01

The Chemistry and Camera (ChemCam) instrument on NASA's Curiosity Mars rover examined a freshly brushed area on target rock "Christmas Cove" and found spectral evidence of hematite, an iron-oxide mineral. ChemCam sometimes zaps rocks with a laser, but can also be used, as in this case, in a "passive" mode. In this type of investigation, the instrument's telescope delivers to spectrometers the sunlight reflected from a small target point. The upper-left inset of this graphic is an image from ChemCam's Remote Micro-Imager with five labeled points that the instrument analyzed. The image covers an area about 2 inches (5 centimeters) wide, and the bright lines are fractures in the rock filled with calcium sulfate minerals. The five charted lines of the graphic correspond to those five points and show the spectrometer measurements of brightness at thousands of different wavelengths, from 400 nanometers (at the violet end of the visible-light spectrum) to 840 nanometers (in near-infrared). Sections of the spectrum measurements that are helpful for identifying hematite are annotated. These include a dip around 535 nanometers, the green-light portion of the spectrum at which fine-grained hematite tends to absorb more light and reflect less compared to other parts of the spectrum. That same green-absorbing characteristic of the hematite makes it appear purplish when imaged through special filters of Curiosity's Mast Camera and even in usual color images. The spectra also show maximum reflectance values near 750 nanometers, followed by a steep decrease in the spectral slope toward 840 nanometers, both of which are consistent with hematite. This ChemCam examination of Christmas Cove was part of an experiment to determine whether the rock had evidence of hematite under a tan coating of dust. The target area was brushed with Curiosity's Dust Removal Tool prior to these ChemCam passive observations on Sept. 17, 2017, during the 1,819th Martian day, or sol, of Curiosity's work on Mars. https://photojournal.jpl.nasa.gov/catalog/PIA22068

Nanostructured hematite for photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Ling, Yichuan

Solar water splitting is an environmentally friendly reaction of producing hydrogen gas. Since Honda and Fujishima first demonstrated solar water splitting in 1972 by using semiconductor titanium dioxide (TiO2) as photoanode in a photoelectrochemical (PEC) cell, extensive efforts have been invested into improving the solar-to-hydrogen (STH) conversion efficiency and lower the production cost of photoelectrochemical devices. In the last few years, hematite (alpha-Fe2O3) nanostructures have been extensively studied as photoanodes for PEC water splitting. Although nanostructured hematite can improve its photoelectrochemical water splitting performance to some extent, by increasing active sites for water oxidation and shortening photogenerated hole path length to semiconductor/electrolyte interface, the photoactivity of pristine hematite nanostructures is still limited by a number of factors, such as poor electrical conductivities and slow oxygen evolution reaction kinetics. Previous studies have shown that tin (Sn) as an n-type dopant can substantially enhance the photoactivity of hematite photoanodes by modifying their optical and electrical properties. In this thesis, I will first demonstrate an unintentional Sn-doping method via high temperature annealing of hematite nanowires grown on fluorine-doped tin oxide (FTO) substrate to enhance the donor density. In addition to introducing extrinsic dopants into semiconductors, the carrier densities of hematite can also be enhanced by creating intrinsic defects. Oxygen vacancies function as shallow donors for a number of hematite. In this regard, I have investigated the influence of oxygen content on thermal decomposition of FeOOH to induce oxygen vacancies in hematite. In the end, I have studied low temperature activation of hematite nanostructures.

A Ga2O3 underlayer as an isomorphic template for ultrathin hematite films toward efficient photoelectrochemical water splitting.

PubMed

Hisatomi, Takashi; Brillet, Jérémie; Cornuz, Maurin; Le Formal, Florian; Tétreault, Nicolas; Sivula, Kevin; Grätzel, Michael

2012-01-01

Hematite photoanodes for photoelectrochemical (PEC) water splitting are often fabricated as extremely-thin films to minimize charge recombination because of the short diffusion lengths of photoexcited carriers. However, poor crystallinity caused by structural interaction with a substrate negates the potential of ultrathin hematite photoanodes. This study demonstrates that ultrathin Ga2O3 underlayers, which were deposited on conducting substrates prior to hematite layers by atomic layer deposition, served as an isomorphic (corundum-type) structural template for ultrathin hematite and improved the photocurrent onset of PEC water splitting by 0.2 V. The benefit from Ga2O3 underlayers was most pronounced when the thickness of the underlayer was approximately 2 nm. Thinner underlayers did not work effectively as a template presumably because of insufficient crystallinity of the underlayer, while thicker ones diminished the PEC performance of hematite because the underlayer prevented electron injection from hematite to a conductive substrate due to the large conduction band offset. The enhancement of PEC performance by a Ga2O3 underlayer was more significant for thinner hematite layers owing to greater margins for improving the crystallinity of ultrathin hematite. It was confirmed that a Ga2O3 underlayer was applicable to a rough conducting substrate loaded with Sb-doped SnO2 nanoparticles, improving the photocurrent by a factor of 1.4. Accordingly, a Ga2O3 underlayer could push forward the development of host-guest-type nanocomposites consisting of highly-rough substrates and extremely-thin hematite absorbers.

Considering the formation of hematite spherules on Mars by freezing aqueous hematite nanoparticle suspensions

NASA Astrophysics Data System (ADS)

Sexton, M. R.; Elwood Madden, M. E.; Swindle, A. L.; Hamilton, V. E.; Bickmore, B. R.; Elwood Madden, A. S.

2017-04-01

The enigmatic and unexpected occurrence of coarse crystalline (gray) hematite spherules at Terra Meridiani on Mars in association with deposits of jarosite-rich sediments fueled a variety of hypotheses to explain their origin. In this study, we tested the hypothesis that freezing of aqueous hematite nanoparticle suspensions, possibly produced from low-temperature weathering of jarosite-bearing deposits, could produce coarse-grained hematite aggregate spherules. We synthesized four hematite nanoparticle suspensions with a range of sizes and morphologies and performed freezing experiments. All sizes of hematite nanoparticles rapidly aggregate during freezing. Regardless of the size or shape of the initial starting material, they rapidly collect into aggregates that are then too big to push in front of a stable advancing ice front, leading to incohesive masses of particles, rather than solid spherules. We also explored the effects of "seed" silicates, a matrix of sand grains, various concentrations of NaCl and CaCl2, and varying the freezing temperature on hematite nanoparticle aggregation. However, none of these factors resulted in mm-scale spherical aggregates. By comparing our measured freezing rates with empirical and theoretical values from the literature, we conclude that the spherules on Mars could not have been produced through the freezing of aqueous hematite nanoparticle suspensions; ice crystallization front instability disrupts the aggregation process and prevents the formation of mm-scale continuous aggregates.

Innovative Method for Separating Phosphorus and Iron from High-Phosphorus Oolitic Hematite by Iron Nugget Process

NASA Astrophysics Data System (ADS)

Han, Hongliang; Duan, Dongping; Wang, Xing; Chen, Siming

2014-10-01

This study puts forward a new method to separate phosphorus and iron from high-phosphorus oolitic hematite through iron nuggets process. Firstly, the physical, chemical, and microscopic characteristics of high-phosphorus oolitic hematite are investigated. Then, the reaction mechanisms of high-phosphorus hematite together with feasibility to separating phosphorus and iron by iron nugget process are discussed. Meanwhile, the experiments of high-phosphorus hematite used in rotary hearth furnace iron nugget processes are studied as well. The results indicate that the iron nugget process is a feasible and efficient method for iron and phosphorus separation of high-phosphorus oolitic hematite. The phosphorus content in iron nuggets is relatively low. Through the optimization of process parameters, the lowest of phosphorus in iron nuggets is 0.22 pct, the dephosphorization rate is above 86 pct, and the recovery of Fe is above 85 pct by the iron nugget process. This study aims to provide a theoretical and technical basis for economical and rational use of high-phosphorus oolitic hematite.

Incorporation of Uranium into Hematite during Crystallization from Ferrihydrite

PubMed Central

2014-01-01

Ferrihydrite was exposed to U(VI)-containing cement leachate (pH 10.5) and aged to induce crystallization of hematite. A combination of chemical extractions, TEM, and XAS techniques provided the first evidence that adsorbed U(VI) (≈3000 ppm) was incorporated into hematite during ferrihydrite aggregation and the early stages of crystallization, with continued uptake occurring during hematite ripening. Analysis of EXAFS and XANES data indicated that the U(VI) was incorporated into a distorted, octahedrally coordinated site replacing Fe(III). Fitting of the EXAFS showed the uranyl bonds lengthened from 1.81 to 1.87 Å, in contrast to previous studies that have suggested that the uranyl bond is lost altogether upon incorporation into hematite. The results of this study both provide a new mechanistic understanding of uranium incorporation into hematite and define the nature of the bonding environment of uranium within the mineral structure. Immobilization of U(VI) by incorporation into hematite has clear and important implications for limiting uranium migration in natural and engineered environments. PMID:24580024

Ferrix Chloride-Graphite Intercalation Compounds Prepared From Graphite Flouride

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1995-01-01

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 sp(sup 3) 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 sp(sup 2) electronic structure and are electrical conductors. They contain first-stage FeCl3 intercalated graphite. Some of the products contain FeCl2 (center dot) 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 disappearance 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 exposed to 800 C N2, in a quartz tube, they lost most of their halogen atoms and formed iron oxides (other than hematite), distributed evenly in or on the fiber.

Formation and alteration of airborne particles in the subway environment.

PubMed

Moreno, T; Querol, X; Martins, V; Minguillón, M C; Reche, C; Ku, L H; Eun, H R; Ahn, K H; Capdevila, M; de Miguel, E

2017-01-25

Most particles in the rail subway environment are sub-micron sized ferruginous flakes and splinters generated mechanically by frictional wear of brake pads, wheels and rails. To better understand the mechanisms of formation and the alteration processes affecting inhalable particles in subways, PM samples (1-2.5 μm and 2.5-10 μm) were collected in the Barcelona Metro and then studied under a scanning electron microscope. Most particles in these samples are hematitic (up to 88%), with relatively minor amounts of mineral matter (up to 9%) and sulphates (up to 5%). Detailed microscopy (using back scattered and TEM-DRX imaging) reveals how many of the metallic particles comprise the metallic Fe nucleus surrounded by hematite (Fe 2 O 3 ) and a coating of sulphate and chloride salts mixed with mineral matter (including Ca-carbonates, clay minerals and quartz). These observations record the emission of fine to ultrafine FePM by frictional wear at elevated temperatures that promote rapid partial (or complete) oxidation of the native metal. Water condensing on the PM surface during cooling leads to the adsorption of inorganic mineral particles that coat the iron oxide. The distinctively layered polymineralic structure that results from these processes is peculiar to particles generated in the subway environment and very different from PM typically inhaled outdoors.

Hematite mining in the ancient Americas: Mina Primavera, A 2,000 year old Peruvian mine

NASA Astrophysics Data System (ADS)

Vaughn, Kevin J.; Grados, Moises Linares; Eerkens, Jelmer W.; Edwards, Matthew J.

2007-12-01

Mina Primavera, a hematite (Fe2O3) mine located in southern Peru, was exploited beginning approximately 2,000 years ago by two Andean civilizations, the Nasca and Wari. Despite the importance of hematite in the material culture of the ancient Americas, few hematite mines have been reported in the New World literature and none have been reported for the Central Andes. An estimated 3,710 tonnes of hematite were extracted from the mine for over 1,400 years at an average rate of 2.65 tonnes per year, suggesting regular and extensive mining prior to Spanish conquest. The hematite was likely used as a pigment for painting pottery, and the mine demonstrates that iron ores were extracted extensively at an early date in the Americas.

Effects of annealing temperature on the physicochemical, optical and photoelectrochemical properties of nanostructured hematite thin films prepared via electrodeposition method

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

Phuan, Yi Wen; Chong, Meng Nan, E-mail: Chong.Meng.Nan@monash.edu; Sustainable Water Alliance, Advanced Engineering Platform, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway 46150 Selangor DE

2015-09-15

Highlights: • Nanostructured hematite thin films were synthesized via electrodeposition method. • Effects of annealing on size, grain boundary and PEC properties were examined. • Photocurrents generation was enhanced when the thin films were annealed at 600 °C. • The highest photocurrent density of 1.6 mA/cm{sup 2} at 0.6 V vs Ag/AgCl was achieved. - Abstract: Hematite (α-Fe{sub 2}O{sub 3}) is a promising photoanode material for hydrogen production from photoelectrochemical (PEC) water splitting due to its wide abundance, narrow band-gap energy, efficient light absorption and high chemical stability under aqueous environment. The key challenge to the wider utilisation of nanostructuredmore » hematite-based photoanode in PEC water splitting, however, is limited by its low photo-assisted water oxidation caused by large overpotential in the nominal range of 0.5–0.6 V. The main aim of this study was to enhance the performance of hematite for photo-assisted water oxidation by optimising the annealing temperature used during the synthesis of nanostructured hematite thin films on fluorine-doped tin oxide (FTO)-based photoanodes prepared via the cathodic electrodeposition method. The resultant nanostructured hematite thin films were characterised using field emission-scanning electron microscopy (FE-SEM) coupled with energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), UV-visible spectroscopy and Fourier transform infrared spectroscopy (FTIR) for their elemental composition, average nanocrystallites size and morphology; phase and crystallinity; UV-absorptivity and band gap energy; and the functional groups, respectively. Results showed that the nanostructured hematite thin films possess good ordered nanocrystallites array and high crystallinity after annealing treatment at 400–600 °C. FE-SEM images illustrated an increase in the average hematite nanocrystallites size from 65 nm to 95 nm when the annealing temperature was varied from 400 °C to 600 °C. As the crystallites size increases, the grain boundaries reduce and this suppresses the recombination rate of electron–hole pairs on the nanostructured hematite thin films. As a result, the measured photocurrent densities of nanostructured hematite thin films also increased. The highest measured photocurrent density of 1.6 mA/cm{sup 2} at 0.6 V vs Ag/AgCl in 1 M NaOH electrolyte was achieved for the nanostructured hematite thin film annealed at 600 °C. This study had confirmed that strong interdependencies exist between the average hematite nanocrystallites size and grain boundaries with annealing temperature on the eventual PEC water splitting performance of nanostructured hematite thin films. The annealed hematite thin films at a higher temperature will enhance the nanocrystals growth and thus, suppressing the electron–hole pairs recombination rate, lowering the grain boundary resistance and enabling higher photocurrent flow at the molecular level. As a result, the photocurrent density and thus, the overall PEC water splitting performance of the nanostructured hematite thin films are significantly enhanced.« less

Thermal Properties of Soils

DTIC Science & Technology

1981-12-01

plagio - clase feldspar and pyroxene. The tine fraction may Surface area and its effects contain the clay "sheet" minerals (i.e. kaolinite. illite...Pyroxene, Kaoliniwe Unified By By Ortho. Plagio . amphibole, Basic clay min. Hematite Soil Soil soil petrogr. X.ray clase clase and Igneous and clay and no

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Science-Filters Study of Martian Rock Sees Hematite

NASA Image and Video Library

2017-11-01

This false-color image demonstrates how use of special filters available on the Mast Camera (Mastcam) of NASA's Curiosity Mars rover can reveal the presence of certain minerals in target rocks. It is a composite of images taken through three "science" filters chosen for making hematite, an iron-oxide mineral, stand out as exaggerated purple. This target rock, called "Christmas Cove," lies in an area on Mars' "Vera Rubin Ridge" where Mastcam reconnaissance imaging (see PIA22065) with science filters suggested a patchy distribution of exposed hematite. Bright lines within the rocks are fractures filled with calcium sulfate minerals. Christmas Cove did not appear to contain much hematite until the rover team conducted an experiment on this target: Curiosity's wire-bristled brush, the Dust Removal Tool, scrubbed the rock, and a close-up with the Mars Hand Lens Imager (MAHLI) confirmed the brushing. The brushed area is about is about 2.5 inches (6 centimeters) across. The next day -- Sept. 17, 2017, on the mission's Sol 1819 -- this observation with Mastcam and others with the Chemistry and Camera (ChemCam showed a strong hematite presence that had been subdued beneath the dust. The team is continuing to explore whether the patchiness in the reconnaissance imaging may result more from variations in the amount of dust cover rather than from variations in hematite content. Curiosity's Mastcam combines two cameras: one with a telephoto lens and the other with a wider-angle lens. Each camera has a filter wheel that can be rotated in front of the lens for a choice of eight different filters. One filter for each camera is clear to all visible light, for regular full-color photos, and another is specifically for viewing the Sun. Some of the other filters were selected to admit wavelengths of light that are useful for identifying iron minerals. Each of the filters used for this image admits light from a narrow band of wavelengths, extending to only about 5 nanometers longer or shorter than the filter's central wavelength. Three observations are combined for this image, each through one of the filters centered at 751 nanometers (in the near-infrared part of the spectrum just beyond red light), 527 nanometers (green) and 445 nanometers (blue). Usual color photographs from digital cameras -- such as a Mastcam one of this same place (see PIA22067) -- also combine information from red, green and blue filtering, but the filters are in a microscopic grid in a "Bayer" filter array situated directly over the detector behind the lens, with wider bands of wavelengths. Mastcam's narrow-band filters used for this view help to increase spectral contrast, making blues bluer and reds redder, particularly with the processing used to boost contrast in each of the component images of this composite. Fine-grained hematite preferentially absorbs sunlight around in the green portion of the spectrum around 527 nanometers. That gives it the purple look from a combination of red and blue light reflected by the hematite and reaching the camera through the other two filters. https://photojournal.jpl.nasa.gov/catalog/PIA22066

Geological features indicative of processes related to the hematite formation in Meridiani Planum and Aram Chaos, Mars: a comparison with diagenetic hematite deposits in southern Utah, USA

NASA Astrophysics Data System (ADS)

Ormö, Jens; Komatsu, Goro; Chan, Marjorie A.; Beitler, Brenda; Parry, William T.

2004-10-01

In order to understand the formation of the few but large, hematite deposits on Mars, comparisons are often made with terrestrial hematite occurrences. In southern Utah, hematite concretions have formed within continental sandstones and are exposed as extensive weathered-out beds. The hematite deposits are linked to geological and geomorphological features such as knobs, buttes, bleached beds, fractures and rings. These terrestrial features are visible in aerial and satellite images, which enables a comparison with similar features occurring extensively in the martian hematite-rich areas. The combination of processes involved in the movement and precipitation of iron in southern Utah can provide new insights in the context of the hematite formation on Mars. Here we present a mapping of the analogue geological and geomorphological features in parts of Meridiani Planum and Aram Chaos. Based on mapping comparisons with the Utah occurrences, we present models for the formation of the martian analogues, as well as a model for iron transport and precipitation on Mars. Following the Utah model, high albedo layers and rings in the mapped area on Mars are due to removal or lack of iron, and precipitation of secondary diagenetic minerals as fluids moved up along fractures and permeable materials. Hematite was precipitated intraformationally where the fluid transporting the reduced iron met oxidizing conditions. Our study shows that certain geological/geomorphological features can be linked to the hematite formation on Mars and that pH differences could suffice for the transport of the iron from an orthopyroxene volcanoclastic source rock. The presence of organic compounds can enhance the iron mobilization and precipitation processes. Continued studies will focus on possible influence of biological activity and/or methane in the formation of the hematite concretions in Utah and on Mars.

Atomic-Scale Structure of the Hematite α-Fe2O3(11̅02) “R-Cut” Surface

PubMed Central

2017-01-01

The α-Fe2O3(11̅02) surface (also known as the hematite r-cut or (012) surface) was studied using low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), scanning tunneling microscopy (STM), noncontact atomic force microscopy (nc-AFM), and ab initio density functional theory (DFT)+U calculations. Two surface structures are stable under ultrahigh vacuum (UHV) conditions; a stoichiometric (1 × 1) surface can be prepared by annealing at 450 °C in ≈10–6 mbar O2, and a reduced (2 × 1) reconstruction is formed by UHV annealing at 540 °C. The (1 × 1) surface is close to an ideal bulk termination, and the undercoordinated surface Fe atoms reduce the surface bandgap by ≈0.2 eV with respect to the bulk. The work function is measured to be 5.7 ± 0.2 eV, and the VBM is located 1.5 ± 0.1 eV below EF. The images obtained from the (2 × 1) reconstruction cannot be reconciled with previously proposed models, and a new “alternating trench” structure is proposed based on an ordered removal of lattice oxygen atoms. DFT+U calculations show that this surface is favored in reducing conditions and that 4-fold-coordinated Fe2+ cations at the surface introduce gap states approximately 1 eV below EF. The work function on the (2 × 1) termination is 5.4 ± 0.2 eV. PMID:29492182

Ab initio simulations of water splitting on hematite

NASA Astrophysics Data System (ADS)

Seriani, Nicola

2017-11-01

In recent years, hematite has attracted great interest as a photocatalyst for water splitting, but many questions remain unanswered about the mechanisms and the main limiting factors. For this reason, density functional theory has been used to understand the optical, electronic and chemical properties of this material at an atomistic level. Bulk doping can be used to reduce the band gap, and to increase photoabsorption and charge mobility. Charge transport takes place through adiabatic polaron hopping. The stable (0 0 0 1) surface has a stoichiometric termination when exposed to oxygen, it becomes hydroxylated in water, and it has an oxygen-rich termination under illumination in a photoelectrochemical setup. On the oxygen-rich termination, surface states are present that might act as recombination centres for electrons and holes. On the contrary, on the hydroxylated termination surface states appear only on reaction intermediates. The intrinsic surface states disappear in the presence of an overlayer of gallium oxide. The reaction of water oxidation is assumed to proceed by four proton-coupled electron transfers and it is shown to involve a nucleophilic attack with the formation of an OOH group. Calculated overpotentials are in the range of 0.5-0.6 V. Open questions and future research directions are briefly discussed.

Spectral and magnetic properties of hematite Fe2O3 (001) surface: results from DFT+DMFT

NASA Astrophysics Data System (ADS)

Kabir, Alamgir; Turkowski, Volodymyr; Rahman, Talat S.

2015-03-01

It has been demonstrated that strong correlation effects may significantly modify the spectrum of a system, in particular leading to an increase of the bandgap and to a change in the orbital occupancies, which affects the magnetic properties of the system. With this in mind, we have examined the spectral and magnetic properties of the hematite Fe2O3 film system with (001) surface orientation by using the combined density functional theory (DFT) and dynamical mean-field theory (DMFT) approach. We pay special attention to the surface geometry and electronic structure, magnetization and magnetic anisotropy (MA) of the system by performing calculations at different values of the parameters for the local Coulomb repulsion and exchange energy. To calculate the MA of the system, we propose and apply a combined Bruno model within DMFT, and demonstrate that under-coordinated surface Fe atoms contribute significantly to the MA of the film. We also compare our results with the DFT+U solution and show that the dynamical effects taken into account by the DMFT significantly affect system properties, notably leading to a decrease of the atomic magnetic moments. Work supported in part by DOE Grant No. DOE-DE-FG02-07ER46354.

Initial results from the MER Athena science investigation

NASA Astrophysics Data System (ADS)

Squyres, S.; Athena Science Team

The Mars Exploration Rover Spirit landed in Gusev Crater on January 4 (UTC), 2004. It was followed 21 days later by the rover Opportunity, which landed on Meridiani Planum. The landing site at Gusev crater lies on a flat, rock-strewn plain. The rocks at the site are mostly angular, and some clearly appear to contain vesicles. The rock at Gusev that has been studied best to date has been named "Adirondack". Three sets of measurements have been made on Adirondack with the full set of payload instruments: one of the natural rock surface, one of the same location after being brushed by the RAT, and one of the same location after removal of 2-3 mm of rock by the RAT. The concentration of presumably dust-borne elements like sulfur and chlorine diminished significantly with brushing, and diminished dramatically with grinding. All of the observations of Adirondack are consistent with it being an essentially unweathered olivine and magnetite-bearing, low-silica basalt. The only soil at Gusev that has been investigated in detail so far is one dominated by fairly coarse (100-300 micron) grains that have the appearance and behavior of well-cemented agglomerates. APXS spectra of this soil are similar to those of soils found at the Viking and Pathfinder sites. Mössbauer spectra show two ferrous doublets and a ferric doublet, with the stronger ferrous doublet assigned to olivine. Mini-TES spectra have been acquired for soils surrounding the the Spirit landing site, and show spectra nearly identical to globally averaged soil viewed by the TES instrument on Mars Global Surveyor. This includes identification of a small amount (a few percent) of carbonate. The dominant rocks in the vicinity of the Spirit landing site at Gusev are clearly volcanic. Upcoming rover activities include a traverse to a nearby crater that is about 200 m in diameter and whose ejecta may include other non-volcanic geologic materials. The landing site at Meridiani Planum lies inside an impact crater that is roughly 20 meters in diameter. The lander came to rest on soil that fills most of the crater. An outcrop of layered bedrock is exposed on the crater wall. The landing site was selected partly because coarse gray hematite was expected to be present on the basis of orbital data. Mini-TES data have confirmed the presence of this hematite in the soil. The soil within the crater has several components. Microscopic images of undisturbed surface soil show that one component is fine (~100 micron) sand. Mössbauer spectra of the sand show two ferrous doublets (one of them due to olivine), a ferric doublet, and a weak magnetic sextet. APXS and Mini-TES data on this sand are consistent with a composition dominated by basalt. Another component of the soil consists of coarse (several mm) granules. These range in shape from subangular to rounded to remarkably spherical. In some locations, granules have been pressed down into the soil by the impact of the lander's airbags. At those locations the concentration of hematite as determined by Mini-TES is sharply reduced, suggesting that at least some of the granules are hematite-bearing. The bedrock outcrop is finely laminated, with typical layer thicknesses of only a few mm. The texture of the outcrop as viewed in miroscopic images suggests that it is fine-grained, with well-expressed structure that is revealed by varying degrees of mechanical abrasion of layers of varying induration. Initial APXS results on this fine-grained matrix suggest an unusual composition, including sulfur concentrations significantly higher than any observed elsewhere on Mars. Embedded within the outcrop and weathering out of it are highly spherical granules with diameters of several mm. The visible to near-IR spectral properties of these embedded spherical granules, as determined by Pancam, are distinctly different from those of the matrix in which they are embedded. The highest Mini-TES-derived concentrations of hematite are found in soil and possible rock units above the bedrock outcrop that have not been visited by the rover as of this writing. Future activities include climbing out of the crater and investigating this hematite-rich material.

Chemical and Mineralogical Characterization of a Hematite-bearing Ridge on Mauna Kea, Hawaii: A Potential Mineralogical Process Analog for the Mount Sharp Hematite Ridge

NASA Technical Reports Server (NTRS)

Graff, T. G.; Morris, R. V.; Ming, D. W.; Hamilton, J. C.; Adams, M.; Fraeman, A. A.; Arvidson, R. E.; Catalano, J. G.; Mertzman, S. A.

2014-01-01

The Mars Science Laboratory (MSL) rover Curiosity landed in Gale Crater in August 2012 and is currently roving towards the layered central mound known as Mount Sharp [1]. Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) hyperspectral data indicate Mount Sharp contains an 5 km stratigraphic sequence including Fe-Mg smectites, hematite, and hydrated sulfates in the lower layers separated by an unconformity from the overlying anhydrous strata [1,2,3]. Hematite was initially detected in CRISM data to occur in the lower sulfate layers on the north side of the mound [2]. [3] further mapped a distinct hematite detection occurring as part of a 200 m wide ridge that extends 6.5 km NE-SW, approximately parallel with the base of Mount Sharp. It is likely a target for in-situ analyses by Curiosity. We document here the occurrence of a stratum of hematite-bearing breccia that is exposed on the Puu Poliahu cinder cone near the summit of Mauna Kea volcano (Hawaii) (Fig.1). The stratum is more resistant to weathering than surrounding material, giving it the appearance of a ridge. The Mauna Kea hematite ridge is thus arguably a potential terrestrial mineralogical and process analog for the Gale Crater hematite ridge. We are acquiring a variety of chemical and mineralogical data on the Mauna Kea samples, with a focus on the chemical and mineralogical information already available or planned for the Gale hematite ridge.

Mineralogy at Meridiani Planum from the Mini-TES experiment on the opportunity rover

USGS Publications Warehouse

Christensen, P.R.; Wyatt, M.B.; Glotch, T.D.; Rogers, A.D.; Anwar, S.; Arvidson, R. E.; Bandfield, J.L.; Blaney, D.L.; Budney, C.; Calvin, W.M.; Fallacaro, A.; Fergason, R.L.; Gorelick, N.; Graff, T.G.; Hamilton, V.E.; Hayes, A.G.; Johnson, J. R.; Knudson, A.T.; McSween, H.Y.; Mehall, G.L.; Mehall, L.K.; Moersch, J.E.; Morris, R.V.; Smith, M.D.; Squyres, S. W.; Ruff, S.W.; Wolff, M.J.

2004-01-01

The Miniature Thermal Emission Spectrometer (Mini-TES) on Opportunity investigated the mineral abundances and compositions of outcrops, rocks, and soils at Meridiani Planum. Coarse crystalline hematite and olivine-rich basaltic sands were observed as predicted from orbital TES spectroscopy. Outcrops of aqueous origin are composed of 15 to 35% by volume magnesium and calcium sulfates [a high-silica component modeled as a combination of glass, feldspar, and sheet silicates (???20 to 30%)], and hematite; only minor jarosite is identified in Mini-TES spectra. Mini-TES spectra show only a hematite signature in the millimeter-sized spherules. Basaltic materials have more plagioclase than pyroxene, contain olivine, and are similar in inferred mineral composition to basalt mapped from orbit. Bounce rock is dominated by clinopyroxene and is close in inferred mineral composition to the basaltic martian meteorites. Bright wind streak material matches global dust. Waterlain rocks covered by unaltered basaltic sands suggest a change from an aqueous environment to one dominated by physical weathering.

Control of Earth-like magnetic fields on the transformation of ferrihydrite to hematite and goethite

PubMed Central

Jiang, Zhaoxia; Liu, Qingsong; Dekkers, Mark J.; Barrón, Vidal; Torrent, José; Roberts, Andrew P.

2016-01-01

Hematite and goethite are the two most abundant iron oxides in natural environments. Their formation is controlled by multiple environmental factors; therefore, their relative concentration has been used widely to indicate climatic variations. In this study, we aimed to test whether hematite and goethite growth is influenced by ambient magnetic fields of Earth-like values. Ferrihydrite was aged at 95 °C in magnetic fields ranging from ~0 to ~100 μT. Our results indicate a large influence of the applied magnetic field on hematite and goethite growth from ferrihydrite. The synthesized products are a mixture of hematite and goethite for field intensities <~60 μT. Higher fields favour hematite formation by accelerating ferrimagnetic ferrihydrite aggregation. Additionally, hematite particles growing in a controlled magnetic field of ~100 μT appear to be arranged in chains, which may be reduced to magnetite keeping its original configuration, therefore, the presence of magnetic particles in chains in natural sediments cannot be used as an exclusive indicator of biogenic magnetite. Hematite vs. goethite formation in our experiments is influenced by field intensity values within the range of geomagnetic field variability. Thus, geomagnetic field intensity could be a source of variation when using iron (oxyhydr-)oxide concentrations in environmental magnetism. PMID:27458091

Control of Earth-like magnetic fields on the transformation of ferrihydrite to hematite and goethite.

PubMed

Jiang, Zhaoxia; Liu, Qingsong; Dekkers, Mark J; Barrón, Vidal; Torrent, José; Roberts, Andrew P

2016-07-26

Hematite and goethite are the two most abundant iron oxides in natural environments. Their formation is controlled by multiple environmental factors; therefore, their relative concentration has been used widely to indicate climatic variations. In this study, we aimed to test whether hematite and goethite growth is influenced by ambient magnetic fields of Earth-like values. Ferrihydrite was aged at 95 °C in magnetic fields ranging from ~0 to ~100 μT. Our results indicate a large influence of the applied magnetic field on hematite and goethite growth from ferrihydrite. The synthesized products are a mixture of hematite and goethite for field intensities <~60 μT. Higher fields favour hematite formation by accelerating ferrimagnetic ferrihydrite aggregation. Additionally, hematite particles growing in a controlled magnetic field of ~100 μT appear to be arranged in chains, which may be reduced to magnetite keeping its original configuration, therefore, the presence of magnetic particles in chains in natural sediments cannot be used as an exclusive indicator of biogenic magnetite. Hematite vs. goethite formation in our experiments is influenced by field intensity values within the range of geomagnetic field variability. Thus, geomagnetic field intensity could be a source of variation when using iron (oxyhydr-)oxide concentrations in environmental magnetism.

In situ Ni-doping during cathodic electrodeposition of hematite for excellent photoelectrochemical performance of nanostructured nickel oxide-hematite p-n junction photoanode

NASA Astrophysics Data System (ADS)

Phuan, Yi Wen; Ibrahim, Elyas; Chong, Meng Nan; Zhu, Tao; Lee, Byeong-Kyu; Ocon, Joey D.; Chan, Eng Seng

2017-01-01

Nanostructured nickel oxide-hematite (NiO/α-Fe2O3) p-n junction photoanodes synthesized from in situ doping of nickel (Ni) during cathodic electrodeposition of hematite were successfully demonstrated. A postulation model was proposed to explain the fundamental mechanism of Ni2+ ions involved, and the eventual formation of NiO on the subsurface region of hematite that enhanced the potential photoelectrochemical water oxidation process. Through this study, it was found that the measured photocurrent densities of the Ni-doped hematite photoanodes were highly dependent on the concentrations of Ni dopant used. The optimum Ni dopant at 25 M% demonstrated an excellent photoelectrochemical performance of 7-folds enhancement as compared to bare hematite photoanode. This was attributed to the increased electron donor density through the p-n junction and thus lowering the energetic barrier for water oxidation activity at the optimum Ni dopant concentration. Concurrently, the in situ Ni-doping of hematite has also lowered the photogenerated charge carrier transfer resistance as measured using the electrochemical impedance spectroscopy. It is expected that the fundamental understanding gained through this study is helpful for the rational design and construction of highly efficient photoanodes for application in photoelectrochemical process.

Direct Solar Charging of an Organic–Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode

PubMed Central

Wedege, Kristina; Azevedo, João; Khataee, Amirreza

2016-01-01

Abstract The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone‐2,7‐disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide‐hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron–hole recombination. PMID:27151516

High Field Remagnetization of Hematite Concretions from Utah, USA and Czech Republic

NASA Astrophysics Data System (ADS)

Adachi, T.; Kletetschka, G.; Chan, M.; Mikula, V.; Adamovic, J.; Pruner, P.; Schnabl, P.; Wasilewski, P.

2007-03-01

Terrestrial hematite concretions of the Navajo Sandstone have been discussed as analogues to the blueberries on Mars. Magnetic investigation of terrestrial concretions showed unusual behavior of antiferromagnetic hematite-goethite composition that may mem

Artificial meteor ablation studies - Iron oxides.

NASA Technical Reports Server (NTRS)

Blanchard, M. B.

1972-01-01

Artificial meteor ablation was performed on natural minerals composed predominantly of magnetite and hematite by using an arc-heated plasma stream of air. Analysis indicates that most of the ablated debris was composed of two or more minerals. Wustite, a metastable mineral, was found to occur as a common product. The 'magnetite' sample, which was 80% magnetite, 14% hematite, 4% apatite, and 2% quartz, yielded ablated products consisting of more than 12 different minerals. Magnetite occurred in 91% of the specimens examined, hematite in 16%, and wustite in 30%. The 'hematite' sample, which was 96% hematite and 3% quartz, yielded ablated products consisting of more than 13 different minerals. Hematite occurred in 47% of the specimens examined, magnetite in 60%, and wustite in 28%. The more volatile elements (Si, P, and Cl) were depleted by about 50%. This study has shown that artificially created ablation products from iron oxides exhibit unique properties that can be used for identification.

Observations of rock spectral classes by the Opportunity rover's Pancam on northern Cape York and on Matijevic Hill, Endeavour Crater, Mars

NASA Astrophysics Data System (ADS)

Farrand, W. H.; Bell, J. F.; Johnson, J. R.; Rice, M. S.; Jolliff, B. L.; Arvidson, R. E.

2014-11-01

The Opportunity rover's exploration of the portion of the rim of Endeavour crater known as Cape York included examination of the sulfate-bearing Grasberg formation and the Matijevic Hill region. Multispectral visible and near-infrared (VNIR) Pancam observations were used to characterize reflectance properties of rock units. Using spectral end-member detection and classification approaches including a principal components/n-dimensional visualization, automatic sequential maximum angle convex cone method, and classification through hierarchical clustering, six main spectral classes of rock surfaces were identified: light-toned veins, Grasberg fm., the smectite-bearing Matijevic formation, the hematitic "blueberry" spherules, resistant spherules within the Matijevic fm. dubbed "newberries," and the Shoemaker formation impact breccia. Some of these could be divided into spectral subclasses. There were three types of veins: veins in the bench unit of Cape York, thinner veins in the Matijevic fm., and boxwork pattern-forming veins. The bench unit veins had higher 535 nm band depths than the other two vein subclasses and a steeper 934 to 1009 nm slope. The Grasberg fm. has VNIR spectral features that are interpreted to indicate higher fractions of red hematite than in the sulfate-bearing Burns Fm. The Matijevic fm. includes both light-toned, fine-grained matrix, and dark-toned veneers. The latter has a weak near-infrared absorption band centered near 950 nm consistent with nontronite. Observations of Rock Abrasion Tool brushed and ground newberries indicated that cuttings from the RAT grind had a longer wavelength reflectance maximum and deeper 535 nm band depth, consistent with more oxidized materials. Greater oxidation of cementing materials in the newberries is consistent with a diagenetic concretion origin.

Surface reactivity of mercury on the oxygen-terminated hematite(0001) surface: a first-principle study

NASA Astrophysics Data System (ADS)

Jung, J. E.; Wilcox, J.

2016-12-01

Hematite (α-Fe2O3) is a common mineral found in Earth's near-surface environment. Due to its nontoxicity, corrosion-resistance, and high thermal stability, α-Fe2O3 has attracted attentions as materials for various applications such as photocatalysts, gas sensors, as well as for the removal of heavy metals. In this study, α-Fe2O3 is chosen for potential mercury (Hg) sorbent in order to remove Hg from coal-fired power plants. Specifically, theoretical approaches using density functional theory (DFT) is used to understand surface reactivity of Hg on oxygen (O) terminated α-Fe2O3(0001) surface. The most probable adsorption sites of Hg, chlorine (Cl), and mercury chloride (HgCl) on the α-Fe2O3 surface are found based on adsorption energy calculations, and the oxidation states of the adsorbates are determined by Bader charge analysis. Additionally, projected density of states (PDOS) analysis characterizes the surface-adsorbate bonding mechanism. The results of adsorption energy calculation proposes that Hg physisorbs to the α-Fe2O3(0001) surface with adsorption energy of -0.278 eV, and the subsequent Bader charge analysis confirms that Hg is slightly oxidized. In addition, Cl introduced to the Hg-adsorbed surface strengthens Hg stability on the α-Fe2O3(0001) surface as evidenced by a shortened Hg-surface equilibrium distance. The PDOS analysis also suggests that Cl enhances the chemical bonding between the surface and the adsorbate, thereby increasing adsorption strength. In summary, α-Fe2O3 has ability to adsorb and oxidize Hg, and this reactivity is enhanced in the presence of Cl.

Biogenic catalysis of soil formation on Mars?

NASA Technical Reports Server (NTRS)

Bishop, J. L.

1998-01-01

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

Interaction of aromatic amines with iron oxides: implications for prebiotic chemistry.

PubMed

Shanker, Uma; Singh, Gurinder; Kamaluddin

2013-06-01

The interaction of aromatic amines (aniline, p-chloroaniline, p-toludine and p-anisidine) with iron oxides (goethite, akaganeite and hematite) has been studied. Maximum uptake of amines was observed around pH 7. The adsorption data obtained at neutral pH were found to follow Langmuir adsorption. Anisidine was found to be a better adsorbate probably due to its higher basicity. In alkaline medium (pH > 8), amines reacted on goethite and akaganeite to give colored products. Analysis of the products by GC-MS showed benzoquinone and azobenzene as the reaction products of aniline while p-anisidine afforded a dimer. IR analysis of the amine-iron oxide hydroxide adduct suggests that the surface acidity of iron oxide hydroxides is responsible for the interaction. The present study suggests that iron oxide hydroxides might have played a role in the stabilization of organic molecules through their surface activity and in prebiotic condensation reactions.

Spherulitic Growth of Hematite Under Hydrothermal Conditions: Insights into the Growth Mechanism of Hematite Spherules at Meridiani Planum Mars.

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Golden, D. C.; Morris, R. V.

2010-01-01

Hematite-rich spherules were discovered embedded in sulfate-rich outcrop rock and as lag deposits of whole and broken spherules by the Opportunity rover at Meridiani Planem [1-6]. The Mars Global Surveyor (MGS) Thermal Emission Spectrometer (TES), which has a wider spectral range compared to the Mars Exploration Rover Mini-TES, provided an important constraint that hematite-rich spherules are dominated by emission along the crystallographic c-axis [7-10]. We have previously synthesized hematite spherules whose mineralogic, chemical, and crystallographic properties are strikingly similar to those for the hematite-rich spherules at Meridiani Planum [11]. The spherules were synthesized in the laboratory along with hydronium jarosite and minor hydronium alunite from Fe-Al-Mg-S-Cl acid sulfate solutions under hydrothermal conditions. The reaction sequence was (1) precipitation of hydronium jarosite, (2) jarosite dissolution and precipitation of hematite spherules, and (3) precipitation of hydronium alunite upon depletion of hydronium jarosite. The spherules exhibit a radial growth texture with the crystallographic c-axis aligned along the radial direction, so that thermal emission spectra have no hematite emissivity minimum at approx.390/cm similar to the emission spectra returned by MGS TES. The objective of this paper is to expand on our initial studies [11] to examine the morphological evolution during growth of spherules starting from sub-micrometer crystals to spherules many orders of magnitude in size.

Detection of Gray Crystalline Hematite in the Aureum and Iani Chaos Layered Terrains

NASA Astrophysics Data System (ADS)

Glotch, T. D.; Rogers, D.; Christensen, P. R.

2005-12-01

Using the TES and THEMIS datasets, small hematite-rich deposits have been discovered in Aureum and Iani Chaos. The newly discovered hematite-rich deposits share several similarities with the deposit in Aram Chaos [1], including the occurrence of hematite in a friable layered unit, and the presence of a light-toned caprock. The presence of these units over a distance of several hundred kilometers in the equatorial latitudes of Mars may point to a preferred global mechanism for hematite formation. However, it is unclear how, if at all, these units are related to the hematite- and sulfate-rich unit in Meridiani Planum, which is substantially larger and older (by as much as 1 Ga) than the layered units seen in the equatorial chaotic terrains. Though the caprock units in Aram Chaos and Aureum Chaos are similar, the corresponding unit in Iani Chaos is morphologically different, exhibiting less of a cliff-forming erosional pattern. The hematite-rich units in Aram and Aureum Chaos lie stratigraphically below the light-toned caprock units. In Iani Chaos, the hematite deposit is coincident with the light-toned unit. Data returned from the Mars Express OMEGA instrument have shown the presence of hydrated sulfates in the hematite-rich units associated with Aram and Iani Chaos, although to date, no sulfate detection has been reported in Aureum Chaos [2]. The sequence of caprock and hematite units in Aram, Aureum, and Iani Chaos probably did not form coincidentally as part of an extensive regional layer, but instead formed by similar, but not identical, processes in their respective chaotic terrains. The presence of these units in chaotic terrains, which have been hypothesized to form by subsidence after the release of subsurface water, indicate that these units may have been deposited in an aqueous environment. By analogy to Meridiani Planum, later subsurface aqueous activity in the region of the chaotic terrains may have provided the necessary diagenetic conditions for the formation of hematite within the layered units. [1] Glotch and Christensen, J. Geophys. Res., in press. [2] Gendrin et al., 2005, Science, 307 p. 1587-1590

Effect of tetravalent dopants on hematite nanostructure for enhanced photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Subramanian, Arunprabaharan; Gracia-Espino, Eduardo; Annamalai, Alagappan; Lee, Hyun Hwi; Lee, Su Yong; Choi, Sun Hee; Jang, Jum Suk

2018-01-01

In this paper, the influence of tetravalent dopants such as Si4+, Sn4+, Ti4+, and Zr4+ on the hematite (α-Fe2O3) nanostructure for enhanced photoelectrochemical (PEC) water splitting are reported. The tetravalent doping was performed on hydrothermally grown akaganeite (β-FeOOH) nanorods on FTO (fluorine-doped tin-oxide) substrates via a simple dipping method for which the respective metal-precursor solution was used, followed by a high-temperature (800° C) sintering in a box furnace. The photocurrent density for the pristine (hematite) photoanode is ∼0.81 mA/cm2 at 1.23 VRHE, with an onset potential of 0.72 VRHE; however, the tetravalent dopants on the hematite nanostructures alter the properties of the pristine photoanode. The Si4+-doped hematite photoanode showed a slight photocurrent increment without a changing of the onset potential of the pristine photoanode. The Sn4+- and Ti4+-doped hematite photoanodes, however, showed an anodic shift of the onset potential with the photocurrent increment at a higher applied potential. Interestingly, the Zr4+-doped hematite photoanode exhibited an onset potential that is similar to those of the pristine and Si4+-doped hematite, but a larger photocurrent density that is similar to those of the Sn4+- and Ti4+-doped photoanodes was recorded. The photoactivity of the doped photoanodes at 1.23 VRHE follows the order Zr > Sn > Ti > Si. The onset-potential shifts of the doped photoanodes were investigated using the Ab initio calculations that are well correlated with the experimental data. X-ray diffraction (XRD) and scanning-electron microscopy (FESEM) revealed that both the crystalline phase of the hematite and the nanorod morphology were preserved after the doping procedure. X-ray photoelectron spectroscopy (XPS) confirmed the presence of the tetravalent dopants on the hematite nanostructure. The charge-transfer resistance at the various interfaces of the doped photoanodes was studied using impedance spectroscopy. The doping on the hematite photoanodes was confirmed using the Mott-Schottky (MS) analysis.

Iron oxide nanotubes synthesized via template-based electrodeposition

NASA Astrophysics Data System (ADS)

Lim, Jin-Hee; Min, Seong-Gi; Malkinski, Leszek; Wiley, John B.

2014-04-01

Considerable effort has been invested in the development of synthetic methods for the preparation iron oxide nanostructures for applications in nanotechnology. While a variety of structures have been reported, only a few studies have focused on iron oxide nanotubes. Here, we present details on the synthesis and characterization of iron oxide nanotubes along with a proposed mechanism for FeOOH tube formation. The FeOOH nanotubes, fabricated via a template-based electrodeposition method, are found to exhibit a unique inner-surface. Heat treatment of these tubes under oxidizing or reducing atmospheres can produce either hematite (α-Fe2O3) or magnetite (Fe3O4) structures, respectively. Hematite nanotubes are composed of small nanoparticles less than 20 nm in diameter and the magnetization curves and FC-ZFC curves show superparamagnetic properties without the Morin transition. In the case of magnetite nanotubes, which consist of slightly larger nanoparticles, magnetization curves show ferromagnetism with weak coercivity at room temperature, while FC-ZFC curves exhibit the Verwey transition at 125 K.Considerable effort has been invested in the development of synthetic methods for the preparation iron oxide nanostructures for applications in nanotechnology. While a variety of structures have been reported, only a few studies have focused on iron oxide nanotubes. Here, we present details on the synthesis and characterization of iron oxide nanotubes along with a proposed mechanism for FeOOH tube formation. The FeOOH nanotubes, fabricated via a template-based electrodeposition method, are found to exhibit a unique inner-surface. Heat treatment of these tubes under oxidizing or reducing atmospheres can produce either hematite (α-Fe2O3) or magnetite (Fe3O4) structures, respectively. Hematite nanotubes are composed of small nanoparticles less than 20 nm in diameter and the magnetization curves and FC-ZFC curves show superparamagnetic properties without the Morin transition. In the case of magnetite nanotubes, which consist of slightly larger nanoparticles, magnetization curves show ferromagnetism with weak coercivity at room temperature, while FC-ZFC curves exhibit the Verwey transition at 125 K. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06924a

Synthetic (Hydrothermal) Hematite-Rich Mars-Analog Spherules from Acid-Sulfate Brines: Implications for Formation and Diagenesis of Hematite Spherules in Outcrops at Meridiani Planum, Mars

NASA Technical Reports Server (NTRS)

Golden, D. C.; Ming, D. W.; Morris, R. V.; Graff, T. G.

2008-01-01

The Thermal Emission Spectrometer (TES) onboard the Mars Global Surveyor (MGS) orbiter discovered a large area at Meridiani Planum (MP) covered with the Fe-oxide hematite (alpha-Fe2O3) [1,2]. This discovery and favorable landing site characteristics led to selection of MP as the landing site for the Opportunity Mars Exploration Rover (MER) [3]. The Athena science payload onboard the Opportunity rover identified hematite-rich spherules (mean spherule diameter approx.4.2+/-0.8 mm) embedded in S-rich outcrop rock and also as lag deposits of whole and broken spherules [4,5,6,7,8,9]. Although the chemical and mineralogical compositions of spherules are not fully constrained, Moessbauer spectrometer (MB) Miniature Thermal Emission Spectrometer (Mini-TES) and chemical analyses from the Alpha Particle X-Ray Spectrometer (APXS) are consistent with a hematite mineralogical composition and an oxide bulk chemical composition consisting of Fe2O3. MGS-TES, also provides an important constraint that emission from the hematite-rich spherules is dominated by emission along the crystallographic c-axis [1,2,10,11]. The formation of hematite-rich spherules with similar chemical, mineralogical, morphological, and crystallographic properties to the MP spherules is rare on Earth, to date, only two natural analogs have been proposed; one from Utah (Navaho Concretions) and the other from Mauna Kea, Hawaii [12,13]. In this study, we synthesized in the laboratory hematite-rich spherules using conditions that may have existed on Early Mars [14] and compared their properties to those for MP hematite spherules of Mars and the analog spherules from Utah and Mauna Kea in order to assess their relative merit as MP hematite spherule analogs. Such comparisons yield clues to the formation pathway for MP spherules.

Hematite/silica nanoparticle bilayers on mica: AFM and electrokinetic characterization.

PubMed

Morga, Maria; Adamczyk, Zbigniew; Kosior, Dominik; Oćwieja, Magdalena

2018-06-06

Quantitative studies on self-assembled hematite/silica nanoparticle (NP) bilayers on mica were performed by applying scanning electron microscopy (SEM), atomic force microscopy (AFM), and streaming potential measurements. The coverage of the supporting hematite layers was adjusted by changing the bulk concentration of the suspension and the deposition time. The coverage was determined by direct enumeration of deposited particles from AFM images and SEM micrographs. Afterward, silica nanoparticle monolayers were assembled under diffusion-controlled transport. A unique functional relationship was derived connecting the silica coverage with the hematite precursor layer coverage. The formation of the hematite monolayer and the hematite/silica bilayer was also monitored in situ by streaming potential measurements. It was confirmed that the zeta potential of the bilayers was independent of the supporting layer coverage, exceeding 0.15. These measurements were theoretically interpreted in terms of the general electrokinetic model that allowed for deriving a formula for calculating nanoparticle coverage in the bilayers. Additionally, from desorption experiments, the interactions among hematite/silica particles in the bilayers were determined using DLVO theory. These results facilitate the development of a robust method of preparing nanoparticle bilayers with controlled properties, with potential applications in catalytic processes.

Use of interfacial layers to prolong hole lifetimes in hematite probed by ultrafast transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Paradzah, Alexander T.; Diale, Mmantsae; Maabong, Kelebogile; Krüger, Tjaart P. J.

2018-04-01

Hematite is a widely investigated material for applications in solar water oxidation due primarily to its small bandgap. However, full realization of the material continues to be hampered by fast electron-hole recombination rates among other weaknesses such as low hole mobility, short hole diffusion length and low conductivity. To address the problem of fast electron-hole recombination, researchers have resorted to growth of nano-structured hematite, doping and use of under-layers. Under-layer materials enhance the photo-current by minimising electron-hole recombination through suppressing of back electron flow from the substrate, such as fluorine-doped tin oxide (FTO), to hematite. We have carried out ultrafast transient absorption spectroscopy on hematite in which Nb2O5 and SnO2 materials were used as interfacial layers to enhance hole lifetimes. The transient absorption data was fit with four different lifetimes ranging from a few hundred femtoseconds to a few nanoseconds. We show that the electron-hole recombination is slower in samples where interfacial layers are used than in pristine hematite. We also develop a model through target analysis to illustrate the effect of under-layers on electron-hole recombination rates in hematite thin films.

Enhancing Hematite Photoanode Activity for Water Oxidation by Incorporation of Reduced Graphene Oxide.

PubMed

do Amaral Carminati, Saulo; Souza, Flavio L; Nogueira, Ana F

2016-01-04

Two effective methods to prepare reduced graphene oxide (rGO)/hematite nanostructured photoanodes and their photoelectrochemical characterization towards water splitting reactions are presented. First, graphene oxide (GO) is reduced to rGO using hydrazine in a basic solution containing tetrabutylammonium hydroxide (TBAOH), and then deposited over the nanostructured hematite photoanodes previously treated at 750 °C for 30 min. The second method follows the deposition of a paste containing a mixture of hematite nanoparticles and rGO sheets by the doctor-blade method, varying the rGO concentration. Since hematite suffers from low electron mobility, a low absorption coefficient, high recombination rates and slow reaction kinetics, the incorporation of rGO in the hematite can overcome such limitations due to graphene's exceptional properties. Using the first method, the rGO incorporation results in a photocurrent density increase from 0.56 to 0.82 mA cm(-2) at 1.23 VRHE. Our results indicate that the rGO incorporation in the hematite photoanodes shows a positive effect in the reduction of the electron-hole recombination rate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal Inertia, Albedo, and MOLA-derived Roughness for Terrains in the Terra Meridiani Area, Mars

NASA Technical Reports Server (NTRS)

Arvidson, R. E.; Deal, K.; Hynek, B. M.; Seelos, F. P., IV; Snider, N. O.; Mellon, M. T.; Garvin, J. B.

2002-01-01

Surface properties of layered deposits draped on dissected, cratered terrain in the Terra Meridiani area are analyzed using remote sensing data. The etched plains are cemented and differentially eroded, and the hematite plains are loose and drifting. Additional information is contained in the original extended abstract.

Kinetics of Photoelectrochemical Oxidation of Methanol on Hematite Photoanodes

PubMed Central

2017-01-01

The kinetics of photoelectrochemical (PEC) oxidation of methanol, as a model organic substrate, on α-Fe2O3 photoanodes are studied using photoinduced absorption spectroscopy and transient photocurrent measurements. Methanol is oxidized on α-Fe2O3 to formaldehyde with near unity Faradaic efficiency. A rate law analysis under quasi-steady-state conditions of PEC methanol oxidation indicates that rate of reaction is second order in the density of surface holes on hematite and independent of the applied potential. Analogous data on anatase TiO2 photoanodes indicate similar second-order kinetics for methanol oxidation with a second-order rate constant 2 orders of magnitude higher than that on α-Fe2O3. Kinetic isotope effect studies determine that the rate constant for methanol oxidation on α-Fe2O3 is retarded ∼20-fold by H/D substitution. Employing these data, we propose a mechanism for methanol oxidation under 1 sun irradiation on these metal oxide surfaces and discuss the implications for the efficient PEC methanol oxidation to formaldehyde and concomitant hydrogen evolution. PMID:28735533

Effect of cycled combustion ageing on a cordierite burner plate

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

Garcia, Eugenio; Gancedo, J. Ramon; Gracia, Mercedes, E-mail: rocgracia@iqfr.csic.es

2010-11-15

A combination of {sup 57}Fe-Moessbauer spectroscopy and X-ray Powder Diffraction analysis has been employed to study modifications in chemical and mechanical stability occurring in a cordierite burner aged under combustion conditions which simulate the working of domestic boilers. Moessbauer study shows that Fe is distributed into the structural sites of the cordierite lattice as Fe{sup 2+} and Fe{sup 3+} ions located mostly at octahedral sites. Ferric oxide impurities, mainly hematite, are also present in the starting cordierite material accounting for {approx_equal}40% of the total iron phases. From Moessbauer and X-ray diffraction data it can be deduced that, under the combustionmore » conditions used, new crystalline phases were formed, some of the substitutional Fe{sup 3+} ions existing in the cordierite lattice were reduced to Fe{sup 2+}, and ferric oxides underwent a sintering process which results in hematite with higher particle size. All these findings were detected in the burner zone located in the proximity of the flame and were related to possible chemical reactions which might explain the observed deterioration of the burner material. Research Highlights: {yields}Depth profile analyses used as a probe to understand changes in refractory structure. {yields}All changes take place in the uppermost surface of the burner, close to the flame. {yields}Reduction to Fe{sup 2+} of substitutional Fe{sup 3+} ions and partial cordierite decomposition. {yields}Heating-cooling cycling induces a sintering of the existing iron oxide particles. {yields}Chemical changes can explain the alterations observed in the material microstructure.« less

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

Decrease of dissolved sulfide in sewage by powdered natural magnetite and hematite.

PubMed

Zhang, Lehua; Verstraete, Willy; de Lourdes Mendoza, María; Lu, Zhihao; Liu, Yongdi; Huang, Guangtuan; Cai, Lankun

2016-12-15

Natural magnetite and hematite were explored to decrease sulfide in sewage, compared with iron salts (FeCl 3 and FeSO 4 ). A particle size of magnetite and hematite ranging from 45 to 60μm was used. The results showed that 40mgL -1 of powdered magnetite and hematite addition decreased the sulfide in sewage by 79%and 70%, respectively. The achieved decrease of sulfide production capacities were 197.3, 210.6, 317.6 and 283.3mgSg -1 Fe for magnetite, hematite, FeCl 3 and FeSO 4 at the optimal dosage of 40mgL -1 , respectively. Magnetite and hematite provided a higher decrease of sulfide production since more iron ions are capable of being released from the solid phase, not because of adsorption capacity of per gram iron. Besides, the impact on pH and oxidation-reduction potential (ORP) of hematite addition was negligible; while magnetite addition resulted in slight increase of 0.3-0.5 on pH and 10-40mV on ORP. Powdered magnetite and hematite thus appear to be suitable for sulfide decrease in sewage, for their sparing solubility, sustained-release, long reactive time in sewage as well as cost-effectiveness, compared with iron salts. Further investigation over long time periods under practical conditions are needed to evaluate the possible settlement in sewers and unwanted (toxic) metal elements presenting as impurities. Powdered magnetite and hematite were more cost-effective at only 30% costs of iron salts, such as FeCl 3 and FeSO 4 for decreasing sulfide production in sewage. Copyright © 2016. Published by Elsevier B.V.

An enigmatic source of hematitic carbonate beds containing vast amounts of iron oxidizers in a paleozoic metamorphic complex, South Hungary, Geresd-Hills, Ófalu.

NASA Astrophysics Data System (ADS)

Jáger, Viktor; Dabi, Gergely; Menyhárt, Adrienn

2013-04-01

Near the village of Ófalu, in the Geresd Hills, South Hungary, within the "Mecsekalja tectonic belt", low and intermediate grade paleozoic metamorphic complex (phyllite, gneiss) contains vein-like hematitic carbonate beds, up to 30 cm in thickness. The carbonate mineral is calcite. These hematitic carbonate beds cross-cut the foliation of the phyllite, and show no signs of any metamorphic alteration. In the studied section the red carbonate beds are associated with a vein system filled with multiple generations of vein carbonates(Dabi et al., 2011). The red carbonate beds contain a vaste number of twisted stalks of the iron oxidizing taxon of Gallionella. Rarely in some siliceous parts, Leptothrix-like microbial fossils can be found and these beds also contain numerous unidentifiable, hematitic foraminifers. According to ICP-AES measurements, the hematitic carbonate beds contains 8 % Fe, 0.86 % Mn and 0.12 % Ba. XRD and Raman measurements proved that the iron phase is hematite. The SEM observations revealed that the bacterial microfossils and foraminifers are built up of micron-submicron sized pseudohexagonal platy hematite. The bacterial microfossils of the Gallionella iron oxidizer are very well preserved and reaches about 80 µm length and about 2-3 µm width. The above observations raise the following issues: 1. how did these non metamorphic hematitic-carbonatic beds get inside into the metamorphic complex?, 2. what is the age of the formation of these beds?, and 3. what was the source of the iron? If we consider that the hematitic beds contain foraminifers and iron oxidizing bacteria, and no signs of metamorphic alteration nor foliations can be observed in these beds, the only answer for the first question is that the formations are fractures filled with lime-mud, i.e. neptunian dykes, which penetrated into the cracks of the phyllite. The presence of foraminifers and the geotectonic situation of the unit imply marine origin. Considering that these beds are neptunian dykes, their age must be younger than the paleozoic metamorphic event. They must be older than the Early Cretaceous dyke emplacement in the region, based on cross-cutting relation with limonite stained calcite veins, related to the volcanic activity (Dabi et al., 2011) In this region (Tisza-megaunit) continental rift-related alkali basaltic submarine volcanism was widespread during the Early Cretaceous epoch, when hypabyssal basaltic bodies (intrusive pillow basalts) intruded into unconsolidated sediments. Along these magmatic bodies low temperature hydrothermal circulation of seawater hydrolyzed basaltic glass and mafic minerals, and huge amount of Fe(II) was released and got into the lime mud that was saturated with anaerobic water, where iron oxidizing microorganisms thrived (Jáger et al., 2012).We propose a very similar paleoenvironmental model for Ófalu occurence, where low temperature, reductive iron-rich hydrothermal fluids penetrated soft sediments and contributed to the flourishing of iron-oxidizers. Due to subsequent tectonic events, these iron-rich sediments got into the fissures of the Ófalu metamorphic complex. This model is strenghtened by some borehole and outcrops where the Lower Cretaceous interpillow sediments and hyaloclastites rich in iron oxydes and intrusive pillow basalt can be found close to our investigated section. (Hetényi et al., 1976) This study was supported by the Developing Competitiveness of Universities in the South Transdanubian Region (SROP-4.2.1.B-10/2/KONV-2010-0002). Dabi, G., Siklósy, Z., Schubert, F., Bajnóczi, B., M. Tóth, T., 2011. The relevance of vein texture in understanding the past hydraulic behaviour of a crystalline rock mass: reconstruction of the palaeohydrology of the Mecsekalja Zone, South Hungary. Geofluids, 11, 309-327. Hetényi, R., Földi, M., Hámor, G., Nagy, I., Bilik, I., Jantsky, B. 1976. Magyarázó a Mecsek hegység földtani térképéhez 10 000-es sorozat. MÁFI Budapest (in hungarian). Jáger, V., Molnár, F., Buchs, D. & Koděra, P. 2012: The connection between iron ore formations and "mud-shrimp" colonizations around sunken wood debris and hydrothermal sediments in a Lower Cretaceous continental rift basin, Mecsek Mts., Hungary. — Earth-Science Reviews 114/3-4, 250-278.

Influence of organic surface coatings on the sorption of anticonvulsants on mineral surfaces.

PubMed

Qu, Shen; Cwiertny, David M

2013-10-01

Here, we explore the role that sorption to mineral surfaces plays in the fate of two commonly encountered effluent-derived pharmaceuticals, the anticonvulsants phenytoin and carbamazepine. Adsorption isotherms and pH-edge experiments are consistent with electrostatics governing anticonvulsant uptake on metal oxides typically found in soil and aquifer material (e.g., Si, Al, Fe, Mn, and Ti). Appreciable, albeit limited, adsorption was observed only for phenytoin, which is anionic above pH 8.3, on the iron oxides hematite and ferrihydrite. Adsorption increased substantially in the presence of cationic and anionic surfactants, species also commonly encountered in wastewater effluent. For carbamazepine, we propose the enhanced uptake results entirely from hydrophobic interactions with apolar tails of surfactant surface coatings. For phenytoin, adsorption also arises from the ability of surfactants to alter the net charge of the mineral surface and thereby further enhance favorable electrostatic interactions with its anionic form. Collectively, our results demonstrate that although pristine mineral surfaces are likely not major sinks for phenytoin and carbamazepine in the environment, their alteration with organic matter, particularly surfactants, can considerably increase their ability to retain these emerging pollutants in subsurface systems.

Hematite from Natural Iron Stones as Microwave Absorbing Material on X-Band Frequency Ranges

NASA Astrophysics Data System (ADS)

Zainuri, Mochamad

2017-05-01

This study has been investigated the effect of hematite as microwave absorbing materials (RAM) on X-Band frequency ranges. Hematite was succesfully processed by coprecipitation method and calcined at 500 °C for 5 hour. It was synthesized from natural iron stones from Tanah Laut, South Kalimantan, Indonesia. The products were characterized by X-ray diffraxtion (XRD), conductivity measurement, Vibrating Sample Magnetometer (VSM), and Vector Network Analyzer (VNA). The result was shown that hematite has conductivity value on (2.5-3).10-7 S/cm and be included as dielectric materials. The hysterisis curve was shown that hematite was a super paramagnetic materials. The product was mixed on paint with procentage 10% of total weight and coated on steel grade AH36 with spray methods. Then, the maximum of reflection loss on x - band’s frequency range (8,2-12,4) GHz was -7 dB on frequency of 10.5 GHz. It mean that almost 50% electromagnetic energy was absorbed by hematite.

Synthesis of nanocrystalline α-Fe2O3 by using thermal oxidation of Fe Films

NASA Astrophysics Data System (ADS)

Fortas, G.; Saidoun, I.; Abboud, H.; Gabouze, N.; Haine, N.; Manseri, A.; Zergoug, M.; Menari, H.; Sam, S.; Cheraga, H.; Bozetine, I.

2018-03-01

α-Fe2O3 hematite films were prepared by thermal oxidation from Fe films electroplated on silicon. Electrodeposition of Fe thin films was carried out from a sulfate bath containing an ammonium chloride complexing agent. The electrochemical study was performed by cyclic voltammetry. The SEM analysis of the films obtained at a -1.3 V constant polarization shows dendritic grains in the form of islet. The DRX spectra exhibit characteristic iron peaks according to the face centered cubic (Fcc) structure. These samples were annealed. At a temperature of 650 ° C, a single iron oxide phase was well formed, with the hematite structure. The SEM photos show a well-assembled columnar structure with formation of nanowires at the surface of the deposit. The absorbance spectra reveal an absorption features in the ultraviolet range

Direct Solar Charging of an Organic-Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode.

PubMed

Wedege, Kristina; Azevedo, João; Khataee, Amirreza; Bentien, Anders; Mendes, Adélio

2016-06-13

The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone-2,7-disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide-hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron-hole recombination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Overview of DAN/MSL water and chlorine measurements acquired in Gale area for four years of surface observations

NASA Astrophysics Data System (ADS)

Litvak, Maxim

2017-04-01

During more than 4 years MSL Curiosity rover (landed in Gale crater in August 2012) is traveling toward sedimentary layered mound deposited with phyllosilicates and hematite hydrated minerals. Curiosity already traversed more than 14 km and identified lacustrine deposits left from ancient lakes filled Gale area in early history of Mars. Along the traverse the Curiosity rover discovered unique signatures regarding how the Mars environment changed from ancient warm and wet conditions and probably habitable environment to the modern cold and dry climate. We have summarized numerous measurements from the Dynamic Albedo of Neutron (DAN) instrument on Curiosity rover to overview variations of subsurface bound water distribution from the wet to the dry locations, compared it with other MSL measurements and with possible distribution of hydrated minerals and sequence of geological units travelled by Curiosity. We have also performed joint analysis of water and chlorine distributions and compared bulk (down to 0.5 m depth) equivalent chlorine concentrations measured by DAN throughout the Gale area and APXS observations of corresponding local surface targets and drill fines.

Sorption of a nonionic surfactant Tween 80 by minerals and soils.

PubMed

Kang, Soyoung; Jeong, Hoon Young

2015-03-02

Batch experiments were conducted to evaluate Tween 80 sorption by oxides, aluminosilicates, and soils. For oxides, the sorption by silica and alumina follow linear isotherms, and that by hematite follows a Langmuir isotherm. Considering isotherm type and surface coverage, Tween 80 may partition into the silica/alumina-water interface, whereas it may bind to hematite surface sites. Among aluminosilicates, montmorillonite shows the greatest sorption due to the absorption of Tween 80 into interlayers. For other aluminosilicates, it sorbs to surfaces, with the sorption increasing as plagioclase

Scattering Properties of Large Irregular Cosmic Dust Particles at Visible Wavelengths

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

Escobar-Cerezo, J.; Palmer, C.; Muñoz, O.

The effect of internal inhomogeneities and surface roughness on the scattering behavior of large cosmic dust particles is studied by comparing model simulations with laboratory measurements. The present work shows the results of an attempt to model a dust sample measured in the laboratory with simulations performed by a ray-optics model code. We consider this dust sample as a good analogue for interplanetary and interstellar dust as it shares its refractive index with known materials in these media. Several sensitivity tests have been performed for both structural cases (internal inclusions and surface roughness). Three different samples have been selected tomore » mimic inclusion/coating inhomogeneities: two measured scattering matrices of hematite and white clay, and a simulated matrix for water ice. These three matrices are selected to cover a wide range of imaginary refractive indices. The selection of these materials also seeks to study astrophysical environments of interest such as Mars, where hematite and clays have been detected, and comets. Based on the results of the sensitivity tests shown in this work, we perform calculations for a size distribution of a silicate-type host particle model with inclusions and surface roughness to reproduce the experimental measurements of a dust sample. The model fits the measurements quite well, proving that surface roughness and internal structure play a role in the scattering pattern of irregular cosmic dust particles.« less

Hematite Spherules of Meridiani Planum: Implications for Aqueous History at the Site

NASA Astrophysics Data System (ADS)

Calvin, W. M.

2004-12-01

The thermal infrared spectral signature of bulk, grey hematite was the chemical "beacon" that focused the selection of Meridiani Planum as the landing site for the Mars Exploration Rover Opportunity, and aqueous processes were favored for its formation. Orbital data suggesting more bound water in accessory minerals at this location also supported this interpretation. After landing January 24, 2004, the Mini-TES instrument rapidly confirmed the thermal spectral signature of bulk hematite in soils on the plains surrounding Eagle crater and unevenly distributed within the crater. Observations within Eagle crater soon uncovered unusual spherical grains in abundance surrounding the outcrop and Microscopic Imager (MI) showed these grains eroding from within these rocks. They were dubbed "blueberries" by the team due to their spherical nature and their grey or blue appearance compared to their surroundings in various color composites of Pancam images. Extensive observations with the Mössbauer, Alpha-Particle X-ray Spectrometer (APXS) and Mini-TES instruments, especially of the "Berry Bowl" (i.e. with berries and adjacent berry-free rock), confirmed that these spherules are dominantly composed of hematite. Pancam spectra of individual spheres also match laboratory spectra of hematite. These spheres are found within and around outcrop rocks, across the plains of Meridiani, and rolling into the interior of Endurance crater. They are ubiquitous and remarkably even in size and tone. Grains are spherical to subspherical typically 2 to 6 mm in diameter. Opportunity has performed numerous operations with the Rock Abrasion Tool (RAT), and has sliced through individual spherules. The appearance after ratting shows limited or no interior structure and they remain uniformly grey in color. They can preserve scratches from the grinding wheel or become dislodged by ratting, indicating they are harder than the host rock. Several lines of evidence suggest the spheres are post-depositional diagenetic products. On Earth, oolitic iron occurs as concretions in Utah and in the Clinton Formation outcropping from New York into Alabama. Ferromanganese nodules occur in abundance on the modern sea floor and are found in the Great Lakes. Although diagenetic in origin, these terrestrial analogs have strong contrasts with what is observed on Mars, including diverse size, shape and composition of terrestrial samples, significant interior lamination and presence of nucleation centers that are lacking in the Martian spheres. The uniformity of composition and size of the Martian examples provide clues to the redox state of fluids at the time of formation and by analogy with seafloor nodules a rough estimate of the time required for growth.

Surface termination dependence of the reactivity of single crystal hematite with CCl 4

NASA Astrophysics Data System (ADS)

Camillone, Nicholas, III; Adib, Kaveh; Fitts, Jeffrey P.; Rim, Kwang T.; Flynn, George W.; Joyce, S. A.; Osgood, Richard M.

2002-06-01

We describe ultrahigh vacuum Auger electron spectrometric measurements of the uptake of chlorine following the room temperature exposure of single crystal hematite, α-Fe2O3, to CCl4. We compare the surface chemistry of two specific surface phases formed on the basal plane of α-Fe2O3: the Fe3O4(1 1 1)-(2×2) ;selvedge; and the α-Fe2O3/Fe1-xO ;biphase.; For Fe3O4(1 1 1)-(2×2) an estimated saturation level of Cl of ∼75% of a monolayer is readily attained. Carbon uptake is well below that expected for simple stoichiometric dissociative chemisorption, consistent with desorption of organic products during the surface reaction. Low energy electron diffraction measurements suggest that, dependent upon preparation procedures, at least two types of α-Fe2O3/Fe1-xO biphase structures can be formed. Surprisingly, upon exposure to CCl4, Cl uptake does not occur on either of these biphase surfaces, despite the fact that these surfaces are thought to have the same surface concentrations of iron and oxygen as Fe3O4(1 1 1). The dramatic difference between the reactivity of the Fe3O4 and biphase surfaces suggests that the active site for the dissociative adsorption of CCl4 on Fe3O4(1 1 1)-(2×2) comprises both an iron cation and an oxygen anion with a surface-normal-oriented dangling bond that is uncapped by iron cations. Electron stimulated and thermal desorption of Cl from the saturated Fe3O4(1 1 1)-(2×2) selvedge is also reported.

Visible-NIR Spectroscopic Evidence for the Composition of Low-Albedo Altered Soils on Mars

NASA Astrophysics Data System (ADS)

Murchie, S.; Merenyi, E.; Singer, R.; Kirkland, L.

1996-03-01

Spectroscopic studies of altered Martian soils at visible and at NIR wavelengths have generally supported the canonical model of the surface layer as consisting mostly of 2 components, bright red hematite-containing dust and dark gray pyroxene-containing sand. However several of the studies have also provided tantalizing evidence for distinct 1 micrometer Fe absorptions in discrete areas, particularly dark red soils which are hypothesized to consist of duricrust. These distinct absorptions have been proposed to originate from one or more non-hematitic ferric phases. We have tested this hypothesis by merging high spatial resolution visible- and NIR-wavelength data to synthesize composite 0.44-3.14 1lm spectra for regions of western Arabia and Margaritifer Terra. The extended wavelength coverage allows more complete assessment of ferric, ferrous, and H2O absorptions in both wavelength ranges. The composite data show that, compared to nearby bright red soil in Arabia, dark red soil in Oxia has a lower albedo, a more negative continuum slope, and a stronger 3 micrometer H2O absorption . However Fe absorptions are closely similar in position and depth. These results suggest that at least some dark red soils may differ from "normal" dust and mafic sand more in texture than in Fe mineralogy, although there appears to be enrichment in a water-containing phase and/or a dark, spectrally neutral phase. In contrast, there is clear evidence for enrichment of a low-albedo ferric mineral in dark gray soils composing Sinus Meridiani. These have visible- and NIR-wavelength absorptions consistent with crystalline hematite with relatively little pyroxene, plus a very weak 3 micrometer H2O absorption. These properties suggest a Ethology richer in crystalline hematite and less hydrated than both dust and mafic-rich sand.

Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes.

PubMed

Hegner, Franziska Simone; Cardenas-Morcoso, Drialys; Giménez, Sixto; López, Núria; Galan-Mascaros, Jose Ramon

2017-11-23

The realization of artificial photosynthesis may depend on the efficient integration of photoactive semiconductors and catalysts to promote photoelectrochemical water splitting. Many efforts are currently devoted to the processing of multicomponent anodes and cathodes in the search for appropriate synergy between light absorbers and active catalysts. No single material appears to combine both features. Many experimental parameters are key to achieve the needed synergy between both systems, without clear protocols for success. Herein, we show how computational chemistry can shed some light on this cumbersome problem. DFT calculations are useful to predict adequate energy-level alignment for thermodynamically favored hole transfer. As proof of concept, we experimentally confirmed the limited performance enhancement in hematite photoanodes decorated with cobalt hexacyanoferrate as a competent water-oxidation catalyst. Computational methods describe the misalignment of their energy levels, which is the origin of this mismatch. Photoelectrochemical studies indicate that the catalyst exclusively shifts the hematite surface state to lower potentials, which therefore reduces the onset for water oxidation. Although kinetics will still depend on interface architecture, our simple theoretical approach may identify and predict plausible semiconductor/catalyst combinations, which will speed up experimental work towards promising photoelectrocatalytic systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Proton transport, water uptake and hydrogen permeability of nanoporous hematite ceramic membranes

NASA Astrophysics Data System (ADS)

Colomer, M. T.

2011-10-01

For the first time, mesoporous acid-free hematite ceramic membranes have been studied as proton conductors. The xerogels after calcination at 300 °C for 1 h were mesoporous, as is mentioned above, with a BET surface area of 130 ± 2 m2 g-1, an average pore diameter of 3.8 nm and a pore volume of 0.149 ± 0.001 cc g-1. A sigmoidal dependence of the conductivity and the water uptake with the RH at a constant temperature was observed. The conductivity of the ceramic membranes increased linearly with temperature for all relative humidities studied. The highest value of proton conductivity was found to be 2.76 × 10-3 S cm-1 at 90 °C and 81% RH. According to the activation energy values, proton migration in this kind of materials could be dominated by the Grotthuss mechanism in the whole range of RH. The low cost and high hydrophilicity of these ceramic membranes make them potential substitutes for perfluorosulfonic polymeric membranes in proton exchange membrane (PEMFCs). In addition, since hydrogen permeability values are in the range of 10-9 to 10-10 mol cm-1 s Pa, in order to fabricate oxide-based PEMs that are capable of keeping streams of H2 and O2 from mixing, a separation layer with pore sizes <2 nm whose pores are filled with water will be needed.

Mineralogy at Gusev Crater and Meridiani Planum from the Moessbauer Spectrometers on the Mars Exploration Rovers

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Klingelhoefer, Goestar

2006-01-01

The Moessbauer spectrometers on the twin MER rovers Spirit and Opportunity have provided significant new information on the distribution of iron among its oxidation states, the identification of the mineralogical composition of iron-bearing phases, and the distribution of iron among those phases for rock and soil at Gusev Crater and Meridiani Planum. The plains of Gusev Crater are dominated by olivine-bearing basalt (approximately Fo(60)) and Fe(3+)/Fe(total)=0.1 - 0.5. The oxide mineral generally present is magnetite. In contrast, initial results for the Columbia Hills are consistent with the presence of hematite and a ferrous iron phase, possibly pyroxene. Gusev spectra also have a ferric doublet (not jarosite) that is tentatively associated with nano-phase ferric oxide. A wider diversity of material is present at Meridiani Planum. Significantly, jarosite-bearing outcrop is present throughout the region, with good exposures in impact craters such as Eagle and Endurance (Fe(3+)/Fe (total) approx. 0.9). The Moessbauer identification of jarosite (a hydroxyl-bearing sulfate mineral) is evidence for aqueous, acid-sulfate processes on Mars. Hematite is observed within the outcrop matrix and in the spheroidal particles (Blueberries) found within the outcrop and as a surface lag. An isolated rock (Bounce Rock) was the only sample at either landing site whose iron-bearing phase was dominated by pyroxene. The basaltic sand in the central portion of Eagle crater, in the intercrater plains, and between slabs of outcrop at both Eagle and Endurance craters is olivine-bearing basalt. The widespread occurrence of olivine-bearing basalt at both MER landing sites implies that physical, rather than chemical, weathering processes dominate at the surface of contemporary Mars.

New composite spectra of Mars, 0.4-5.7 μm

USGS Publications Warehouse

Erard, Stephane; Calvin, Wendy M.

1997-01-01

About 15 areas were observed in the equatorial regions of Mars by the infrared spectrometers IRS (Mariner 6 and 7) and ISM (Phobos-2). The comparison between the spectra shows a remarkable consistency between two data sets acquired 20 years apart and calibrated independently. This similarity demonstrates the accuracy of ISM calibration above 2 μm, except for a possible stray light contribution above 2.6 μm, on the order of ∼1–2% of the solar flux at 2.7 μm. Most differences in spectral shapes are related to differences in spectral/spatial resolution and viewing geometries. No important variation in surface properties is detected, except for a spot in southern Arabia Terra which has a much deeper hydration feature in IRS spectra; differences in viewing geometries and spatial resolutions do not seem to account for this difference that could result from shifting or dehydration of surface materials. Composite spectra of several types of bright and dark materials are computed by modeling the thermal emission and are completed with telescopic spectra in the visible range. Modeled reflectance in the 3.0–5.7 μm range is consistent with basalts and palagonites. The bright regions and analog palagonite spectra are different from hematite in this range, but resemble several phyllosilicates. We infer that (1) although hematite dominates the spectra in the 0.4- to 2.5-μm range, the silicate-clay host is spectrally active beyond 3 μm and can be identified from this domain; (2) phyllosilicates such as montmorillonite or smectite may be abundant components of the martian soils, although the domain below 3 μm lacks the characteristic features of the most usual terrestrial clay minerals.

Effect of aluminum substitution on the reflectance spectra of hematite

NASA Technical Reports Server (NTRS)

Morris, R. V.; Lauer, H. V., Jr.; Mendell, W. W.

1982-01-01

Hematite and aluminous hematite were synthesized and the diffuse reflectance spectra were recorded for the region between 0.35 and 1.20 microns. Results show that the near-IR based minimum for the aluminous hematite is shifted longward by about 0.02 microns and is much more shallow. Also, the aluminous specimen is considerably more reflective shortward of approximately 0.55 microns where the ferritic specimen is strongly absorbing. This is noteworthy since the visible slope and the red shoulder are often used in the construction of false color and band ratio images.

Hematite enhances the removal of Cr(VI) by Bacillus subtilis BSn5 from aquatic environment.

PubMed

Ma, Shuai; Song, Chang-Shun; Chen, Yuefang; Wang, Fei; Chen, Hui-Lun

2018-06-05

In the present study, we investigated the removal of Cr(VI) and the associated bacterial activity in the systems containing Bacillus subtilis BSn5 (B. subtilis BSn5) and hematite. The microcalorimetry was used to study the effect of hematite on the normal physiological functions of B. subtilis BSn5 towards the removal of Cr(VI) for the first time. The results of the heat flux and the sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) showed that hematite does not affect the normal physiological functions of B. subtilis BSn5, and can help the strains maintain their activity in the presence of Cr(VI). More importantly, the relative capacity and intensity of Cr(VI) and total Cr removal by B. subtilis BSn5 in the presence of hematite were higher than that in the absence of hematite. The enhancement effect could be associated with their mineral adsorption, biosorption, Fe(II) reduction, bioreduction and immobilization functions. This study demonstrates the possibility of reducing the toxicity of Cr(VI) and enhancing the Cr(VI) removal efficiency in contaminated environments using a combination of hematite and B. subtilis BSn5. Copyright © 2018 Elsevier Ltd. All rights reserved.

Oxygen vacancy doping of hematite analyzed by electrical conductivity and thermoelectric power measurements

NASA Astrophysics Data System (ADS)

Mock, Jan; Klingebiel, Benjamin; Köhler, Florian; Nuys, Maurice; Flohre, Jan; Muthmann, Stefan; Kirchartz, Thomas; Carius, Reinhard

2017-11-01

Hematite (α -F e2O3 ) is known for poor electronic transport properties, which are the main drawback of this material for optoelectronic applications. In this study, we investigate the concept of enhancing electrical conductivity by the introduction of oxygen vacancies during temperature treatment under low oxygen partial pressure. We demonstrate the possibility of tuning the conductivity continuously by more than five orders of magnitude during stepwise annealing in a moderate temperature range between 300 and 620 K. With thermoelectric power measurements, we are able to attribute the improvement of the electrical conductivity to an enhanced charge-carrier density by more than three orders of magnitude. We compare the oxygen vacancy doping of hematite thin films with hematite nanoparticle layers. Thereby we show that the dominant potential barrier that limits charge transport is either due to grain boundaries in hematite thin films or due to potential barriers that occur at the contact area between the nanoparticles, rather than the potential barrier within the small polaron hopping model, which is usually applied for hematite. Furthermore, we discuss the transition from oxygen-deficient hematite α -F e2O3 -x towards the magnetite F e3O4 phase of iron oxide at high density of vacancies.

Evolution and alteration in situ of a massive iron duricrust in Central Africa

NASA Astrophysics Data System (ADS)

Bitom, Dieudonné; Volkoff, Boris; Abossolo-Angue, Monique

2003-08-01

A soil sequence with iron duricrust is described in an area covered by tropical rain forest in South Cameroon. The dismantling of the iron duricrust is documented through a close observation of a soft duricrust, which corresponds to a transitional stage in the degradation of a massive iron duricrust into a loose nodular horizon. In the initial massive and hematitic duricrust, nodular shapes are progressively formed. The nodules and the internodular matrix remain hematitic. The internodular matrix undergoes goethitization and a pronounced deferruginisation before loosening; the primary structure of the iron duricrust is maintained, however, due to internodular bridges, relics of internodular matrix which escaped the process of goethitization. The iron is gradually released from these hematitic bridges, which become softer. This leads to the collapse of the initial structures of the iron duricrust and to the formation of a loose nodular material with a clayey matrix containing kaolinite and goethite. Many loose nodular horizons, which are found all over Central Africa, may have been formed by such alteration of a former iron duricrust.

Solventless synthesis, morphology, structure and magnetic properties of iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Das, Bratati; Kusz, Joachim; Reddy, V. Raghavendra; Zubko, Maciej; Bhattacharjee, Ashis

2017-12-01

In this study we report the solventless synthesis of iron oxide through thermal decomposition of acetyl ferrocene as well as its mixtures with maliec anhydride and characterization of the synthesized product by various comprehensive physical techniques. Morphology, size and structure of the reaction products were investigated by scanning electron microscopy, transmission electron microscopy and X-ray powder diffraction technique, respectively. Physical characterization techniques like FT-IR spectroscopy, dc magnetization study as well as 57Fe Mössbauer spectroscopy were employed to characterize the magnetic property of the product. The results observed from these studies unequivocally established that the synthesized materials are hematite. Thermal decomposition has been studied with the help of thermogravimetry. Reaction pathway for synthesis of hematite has been proposed. It is noted that maliec anhydride in the solid reaction environment as well as the gaseous reaction atmosphere strongly affect the reaction yield as well as the particle size. In general, a method of preparing hematite nanoparticles through solventless thermal decomposition technique using organometallic compounds and the possible use of reaction promoter have been discussed in detail.

Hematite-rich fracture fill at Meridiani Planum, Mars: Implications for fluid chemistry

NASA Astrophysics Data System (ADS)

Yen, Albert; Mittlefehldt, David; Morris, Richard; Gellert, Ralf

The Mars Exploration Rover Opportunity has been operating at the surface of Mars for over 2100 sols and has driven a distance of approximately 20 km. Throughout the traverse, outcrop rocks with margins and fracture fill resistant to erosion have been imaged and analyzed in detail by the Müssbauer (MB) spectrometer and the Alpha Particle X-ray Spectrometer (APXS). A recent APXS analysis of an outcrop block excavated by a young impact crater shows a coating with the highest concentration of iron measured by either rover, not including the iron-nickel meteorites. Texturally, this sample (referred to as "Chocolate Hills -Aloya") appears as a cemented collection of partially fragmented "blueberries." With the exception of an el-evated sulfur content, the elemental chemistry of this particular sample is entirely consistent with other analyses of hematite spherules at Merdiani Planum. As a result, it is difficult to determine whether this coating, which may have been filling a fracture in outcrop rocks prior to disruption by the impact, was simply an agglomeration of spherules or a result of a more complicated aqueous process. In contrast, a number of other fracture-filling exposures and erosion-resistant rinds have been analyzed by the APXS and MB instruments showing significant concentrations of iron in the form of hematite without the texture of spherule fragments. In one of these samples, a broken piece of fracture fill within Victoria crater referred to as "Dorsal," showed over 50% of the iron in hematite, the highest Mn concentration of any sample measured by the rovers, and elevated levels of Cl and Br. While the Fe:Mn ratio of the Dorsal analyses are comparable to that of Gusev and Meridiani basalts, it is clear that chemistry of this sample cannot be completely explained by a simple mixing of outcrop and blueberry compositions. A likely formation process for fracture fill and certain rinds involves the infiltration of iron-rich fluids post-dating the development of subsurface cracks. Mineral precipitates from these fluids resulted in hematite-rich zones within the outcrop rocks.

Spectral characterization and surface complexation modeling of low molecular weight organics on hematite nanoparticles: Role of electrolytes in the binding mechanism

USDA-ARS?s Scientific Manuscript database

Given the ubiquity of organic-metal oxide interfaces in environmental and medical systems, it is incumbent to obtain mechanistic details at the molecular level from experimental procedures that mimic real systems and conditions. We report herein the adsorption pH envelopes (range 9-5) and isotherms...

Hematitic concretions at Meridiani Planum, Mars: Their growth timescale and possible relationship with iron sulfates

NASA Astrophysics Data System (ADS)

Sefton-Nash, Elliot; Catling, David C.

2008-05-01

Using diffusion-based models for concretion growth, we calculate growth times of hematitic concretions that have been found in the Burns formation at Meridiani Planum, Mars, by NASA's Opportunity Mars Exploration Rover. Growth times of ~ 350-1900 terrestrial years are obtained for the observed size range of the concretions over a range of parameters representing likely diagenetic conditions and allowing for an iron source from diagenetic redistribution. This time scale is consistent with radiometric age constraints for the growth time of iron oxide concretions in sandy sediments of the acid-saline Lake Brown in Western Australia (< 3000 yr) reported elsewhere. We consider the source of the iron for Meridiani concretions by calculating the constraints on the supply of Fe 3+ to growing concretions from the dissolution and oxidation rates of iron minerals on early Mars. Mass balance arguments suggest that acid dissolution of jarosite ((H 3O,K)(Fe 3+3(OH) 6(SO 4) 2) and minor ferric sulfates is probably the most plausible dominant contributor to Fe 3+ in the concretions. Ferrous iron released from melanterite (Fe 2+SO 4·7H 2O) that is subsequently oxidized could also have been an important iron source if melanterite existed prior to diagenesis. Our conclusion that the iron is sourced from iron sulfates may explain the global observation from orbiters that grey crystalline hematite occurs in association with sulfate deposits.

A microbial-mineralization approach for syntheses of iron oxides with a high specific surface area.

PubMed

Yagita, Naoki; Oaki, Yuya; Imai, Hiroaki

2013-04-02

Of minerals and microbes: A microbial-mineralization-inspired approach was used to facilitate the syntheses of iron oxides with a high specific surface area, such as 253 m(2)g(-1) for maghemite (γ-Fe(2)O(3)) and 148 m(2)g(-1) for hematite (α-Fe(2)O(3)). These iron oxides can be applied to electrode material of lithium-ion batteries, adsorbents, and catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characteristics of the Ahmadabad hematite/barite deposit, Iran - studies of mineralogy, geochemistry and fluid inclusions

NASA Astrophysics Data System (ADS)

Babaei, Amir Haji; Ganji, Alireza

2018-03-01

The Ahmadabad hematite/barite deposit is located to the northeast of the city of Semnan, Iran. Geostructurally, this deposit lies between the Alborz and the Central Iran zones in the Semnan Subzone. Hematite-barite mineralisation occurs in the form of a vein along a local fault within Eocene volcanic host rocks. The Ahmadabad deposit has a simple mineralogy, of which hematite and barite are the main constituents, followed by pyrite and Fe-oxyhydroxides such as limonite and goethite. Based on textural relationships between the above-mentioned principal minerals, it could be deduced that there are three hydrothermal mineralisation stages in which pyrite, hematite and barite with primary open space filling textures formed under different hydrothermal conditions. Subsequently, in the supergene stage, goethite and limonite minerals with secondary replacement textures formed under oxidation surficial conditions. Microthermometric studies on barite samples show that homogenisation temperatures (TH) for primary fluid inclusions range from 142 to 256°C with a temperature peak between 200 and 220°C. Salinities vary from 3.62 to 16.70 NaCl wt% with two different peaks, including one of 6 to 8 NaCl wt% and another of 12 to 14 NaCl wt%. This indicates that two different hydrothermal waters, including basinal and sea waters, could have been involved in barite mineralisation. The geochemistry of the major and trace elements in the samples studied indicate a hydrothermal origin for hematite and barite mineralisation. Moreover, the Fe/Mn ratio (>10) and plots of hematite samples of Ahmadabad ores on Al-Fe-Mn, Fe-Mn-(Ni+Co+ Cu)×10, Fe-Mn-SiX2 and MnO/TiO2 - Fe2O3/TiO2 diagrams indicate that hematite mineralisation in the Ahmadabad deposit occurred under hydrothermal conditions. Furthermore, Ba and Sr enrichment, along with Pb, Zn, Hg, Cu and Sb depletion, in the barite samples of Ahmadabad ores are indicative of a low temperature hydrothermal origin for the deposit. A comparison of the ratios of LaN/YbN, CeN/YbN, TbN/LaN, SmN/NdN and parameters of Ce/Ce* and La/La* anomalies of the hematite, barite, host volcanic rocks and quartz latite samples to each other elucidate two important points: 1) the barite could have originated from volcanic host rocks, 2) the hematite could have originated from a quartz latite lithological unit. The chondrite normalised REE patterns of samples of hematite barite, volcanic host rocks and quartz latite imply that two different hydrothermal fluids could be proposed for hematite and barite mineralisation. The comparison between chondrite normalised REE patterns of Ahmadabad barite with oceanic origin barite and low temperature hydrothermal barite shows close similarities to the low temperature hydrothermal barite deposits.

Aircraft and ground measurements of dust aerosols over the west African coast in summer 2015 during ICE-D and AER-D

NASA Astrophysics Data System (ADS)

Liu, Dantong; Taylor, Jonathan W.; Crosier, Jonathan; Marsden, Nicholas; Bower, Keith N.; Lloyd, Gary; Ryder, Claire L.; Brooke, Jennifer K.; Cotton, Richard; Marenco, Franco; Blyth, Alan; Cui, Zhiqiang; Estelles, Victor; Gallagher, Martin; Coe, Hugh; Choularton, Tom W.

2018-03-01

During the summertime, dust from the Sahara can be efficiently transported westwards within the Saharan air layer (SAL). This can lead to high aerosol loadings being observed above a relatively clean marine boundary layer (MBL) in the tropical Atlantic Ocean. These dust layers can impart significant radiative effects through strong visible and IR light absorption and scattering, and can also have indirect impacts by altering cloud properties. The processing of the dust aerosol can result in changes in both direct and indirect radiative effects, leading to significant uncertainty in climate prediction in this region. During August 2015, measurements of aerosol and cloud properties were conducted off the coast of west Africa as part of the Ice in Cloud Experiment - Dust (ICE-D) and AERosol properties - Dust (AER-D) campaigns. Observations were obtained over a 4-week period using the UK Facility for Atmospheric Airborne Measurements (FAAM) BAe 146 aircraft based on Santiago Island, Cabo Verde. Ground-based observations were collected from Praia (14°57' N, 23°29' W; 100 m a.s.l.), also located on Santiago Island. The dust in the SAL was mostly sampled in situ at altitudes of 2-4 km, and the potential dust age was estimated by backward trajectory analysis. The particle mass concentration (at diameter d = 0.1-20 µm) decreased with transport time. Mean effective diameter (Deff) for supermicron SAL dust (d = 1-20 µm) was found to be 5-6 µm regardless of dust age, whereas submicron Deff (d = 0.1-1 µm) showed a decreasing trend with longer transport. For the first time, an airborne laser-induced incandescence instrument (the single particle soot photometer - SP2) was deployed to measure the hematite content of dust. For the Sahel-influenced dust in the SAL, the observed hematite mass fraction of dust (FHm) was found to be anti-correlated with the single scattering albedo (SSA, λ = 550 nm, for particles d < 2.5 µm); as potential dust age increased from 2 to 7 days, FHm increased from 2.5 to 4.5 %, SSA decreased from 0.97 to 0.93 and the derived imaginary part (k) of the refractive index at 550 nm increased from 0.0015 to 0.0035. However, the optical properties of Sahara-influenced plumes (not influenced by the Sahel) were independent of dust age and hematite content with SSA ˜ 0.95 and k ˜ 0.0028. This indicates that the absorbing component of dust may be source dependent, or that gravitational settling of larger particles may lead to a higher fraction of more absorbing clay-iron aggregates at smaller sizes. Mie calculation using the measured size distribution and size-resolved refractive indices of the absorbing components (black carbon and hematite) reproduces the measured SSA to within ±0.02 for SAL dust by assuming a goethite / hematite mass ratio of 2. Overall, hematite and goethite constituted 40-80 % of the absorption for particles d < 2.5 µm, and black carbon (BC) contributed 10-37 %. This highlights the importance of size-dependent composition in determining the optical properties of dust and also the contribution from BC within dust plumes.

Importance of a martian hematite site for astrobiology

NASA Technical Reports Server (NTRS)

Allen, C. C.; Westall, F.; Schelble, R. T.

2001-01-01

Defining locations where conditions may have been favorable for life is a key objective for the exploration of Mars. Of prime importance are sites where conditions may have been favorable for the preservation of evidence of prebiotic or biotic processes. Areas displaying significant concentrations of the mineral hematite (alpha-Fe2O3), recently identified by thermal emission spectrometry, may have significance in the search for evidence of extraterrestrial life. Since iron oxides can form as aqueous mineral precipitates, the potential exists to preserve microscopic evidence of life in iron oxide-depositing ecosystems. Terrestrial hematite deposits proposed as possible analogs for hematite deposits on Mars include massive (banded) iron formations, iron oxide hydrothermal deposits, iron-rich laterites and ferricrete soils, and rock varnish. We report the potential for long-term preservation of microfossils by iron oxide mineralization in specimens of the approximately 2,100-Ma banded iron deposit of the Gunflint Formation, Canada. Scanning and analytical electron microscopy reveals micrometer-scale rods, spheres, and filaments consisting predominantly of iron and oxygen with minor carbon. We interpret these objects as microbial cells permineralized by an iron oxide, presumably hematite. The confirmation of ancient martian microbial life in hematite deposits will require the return of samples to terrestrial laboratories. A hematite-rich deposit composed of aqueous iron oxide precipitates may thus prove to be a prime site for future sample return.

Magnetic analysis of commercial hematite, magnetite, and their mixtures

NASA Astrophysics Data System (ADS)

Ahmadzadeh, Mostafa; Romero, Camila; McCloy, John

2018-05-01

Magnetic techniques are suitable to detect iron oxides even in trace concentrations. However, since several iron oxides may be simultaneously present in natural and synthetic samples, mixtures of magnetic particles and magnetic interactions between grains can complicate magnetic signatures. Among the iron oxide minerals, hematite (α-Fe2O3) and magnetite (Fe3O4) are the most common. In this work, different commercial hematite powders, normally used as Fe precursor in laboratory synthesis of Fe-containing oxides, were characterized using X-ray diffractometry (XRD), scanning electron microscopy (SEM), and vibrating sample magnetometry (VSM). The effects of different concentrations of the hematite and magnetite on the magnetic properties of a set of mixtures (from 1 to 10 wt% magnetite) were then investigated by measuring the hysteresis loops, first order reversal curves (FORCs), thermal demagnetization, and isothermal remanent magnetization (IRM) curves. The three commercial hematite powders presented different magnetic behaviors mostly due to the effects of particle size. The magnetic results of mixtures reveal that it is very difficult to identify hematite magnetic signals by means of hysteresis loops, FORCs, or thermal demagnetization when even a small amount of magnetite (>5 wt%) is present due to magnetite's high specific magnetization. However, IRM was found to be a sensitive method to determine the presence of hematite when magnetite is simultaneously present as high as 10 wt%.

Late Carboniferous remagnetisation of Palaeozoic rocks in the NE Rhenish Massif, Germany

NASA Astrophysics Data System (ADS)

Zwing, A.; Bachtadse, V.; Soffel, H. C.

During stepwise thermal and alternating field demagnetisation experiments on Devonian and Lower Carboniferous carbonate and clastic rocks from the north-eastern part of the Rhenish Massif, Germany, three components of magnetisation (A, B, C) are identified. Component A is a recent viscous overprint that parallels the local present day geomagnetic field. Component B is mainly observed from 260 up to 550 °C during thermal demagnetisation and is carried by magnetite. In two localities, where red siltstones and red carbonate rocks were sampled, component B is stable up to 670 °C, indicating the presence of hematite. Three clusters of in situ B directions can be identified, which are controlled by the tectonic position of the sampling areas. These are from NW to SE: the Remscheid anticline (RA), the Lüdenscheid syncline (LS) and the Attendorn and Wittgenstein synclines (AS/WS). Standard and inclination-only fold tests, using parametric resampling, yield optimal statistical parameters at increasing amounts of untilting ranging from 0% in the South up to 57% in the North of the NE Rhenish Massif. Despite the variations in optimal untilting, the resulting site mean directions of component B do not differ significantly in inclination. These results are interpreted to reflect the acquisition of magnetisation during progressive northward migration of the deformation front in Late Carboniferous times. The resulting palaeolatitudes (RA: 1°S +2°-3°; LS: 2°S +3°-2°; AS/WS: 1°S +3°-4°) are in good agreement with the predicted position of the sampling area in the Late Carboniferous, as derived from a published Apparent Polar Wander Path for Baltica and Laurentia. The unblocking temperature spectra and the synfolding nature of B yield strong evidence that chemical processes, possibly driven by fluid migration during orogenesis, caused this remagnetisation. A third component C was observed in zones of tight folding with steeply dipping to overturned bedding planes and is dominantly carried by hematite. The resulting palaeolatitude (27°N +10°-8°) suggest a Late Triassic to Early Jurassic age of component C, which is interpreted to be caused by either hematite-bearing post-Variscan mineralisation or oxidising fluids percolating from the weathering surface and penetrating zones of enhanced permeability in the Mesozoic.

Structural evolution of the Mount Wall region in the Hamersley province, Western Australia and its control on hydrothermal alteration and formation of high-grade iron deposits

NASA Astrophysics Data System (ADS)

Dalstra, Hilke J.

2014-10-01

The discovery of two relatively small but high-grade iron ore deposits near Mt Wall, an intensely faulted part of the southwestern Hamersley province provides unique insights into the structural control on ore formation in this region. The deposits have many geological features typical of the high grade microplaty hematite group which also contains the much larger Mt Tom Price, Paraburdoo and Mt Whaleback deposits. The deposits are structurally controlled along early normal faults and contain abundant microplaty hematite and martite, and are largely confined to the Dales Gorge member of the Brockman Iron Formation. In addition to the microplaty hematite-martite ore, there are martite-goethite ores and rare magnetite-goethite or magnetite-hematite ores. Below the modern weathering surface, hydrothermally altered zones in wallrock BIF from the Lower Dales Gorge member contain magnetite, hematite and carbonate/talc bearing mineral assemblages. A staged ore genesis model involving early extension and fluid circulation along normal faults, hypogene silica leaching and carbonate alteration, followed by deep meteoric oxidation with microplaty hematite formation and finally weathering can explain most features of the Mt Wall deposits. The role of deformation was to provide pathways for mineralising fluids and initiate the seed points for the mineralised systems. High grade iron in the Wellthandalthaluna deposit is situated between the NW to NNW trending Boolgeeda Creek fault and a synthetic joining splay, the Northern fault. Both are high angle normal faults and formed during early extension in this part of the province. Faults are characterised by localised small scale deformation and brecciation, deep carbonate alteration and oxidation. Recent weathering has penetrated deeply into the fault zones, converting the carbonate-rich assemblages into goethite. Mineralisation in the Arochar deposit is situated in the overlap or relay zone between two segments of the Mt Wall fault zone, a moderately to steeply southerly dipping normal fault system which at Arochar is intruded by dolerite dykes. At both locations, the ore controlling faults are offset by later NW trending dextral and normal faults. Fault relay zones or fault splay zones were likely zones of increased permeability and fluid flow during fault development or reactivation and may also have been important in initiating mineralisation in larger deposits such as Mt Tom Price and Mt Whaleback. However structural controls on the largest iron ore deposits are often obscured due to the intensity and scale of ore development, whereas they are better preserved in the smaller deposits. Recognition that carbonate bearing protores at Mt Wall survived for nearly two billion years until intense recent weathering converted them to martite-goethite or magnetite-goethite ores may imply that more of the giant hematite-goethite deposits of the Hamersley province had hydrothermal precursors and were not formed by supergene processes alone.

Initial Results from the MER Athena Science Investigation at Gusev Crater and Meridiani Planum

NASA Astrophysics Data System (ADS)

Squyres, S.

2004-05-01

The Mars Exploration Rover Spirit landed in Gusev Crater on January 4 (UTC), 2004. It was followed 21 days later by the rover Opportunity, which landed on Meridiani Planum. The landing site at Gusev crater lies on a flat, rock-strewn plain. The rock at Gusev that has been studied best to date has been named Adirondack. In its surface texture, Adirondack appears to be dense, fine-grained and sand-blasted. Three sets of measurements have been made on Adirondack with the full set of payload instruments: one of the natural rock surface, one of the same location after being brushed by the RAT, and one of the same location after removal of 2-3 mm of rock by the RAT. The concentration of presumably dust-borne elements like sulfur and chlorine diminished significantly with brushing, and diminished dramatically with grinding. All of the observations of Adirondack are consistent with it being an essentially unweathered olivine and magnetite-bearing, low-silica basalt. The only soil at Gusev that has been investigated in detail so far is one dominated by fairly coarse (100-300 micron) grains that have the appearance and behavior of well-cemented agglomerates. APXS spectra of this soil are similar to those of soils found at the Viking and Pathfinder sites. Mössbauer spectra show two ferrous doublets and a ferric doublet, with the stronger ferrous doublet assigned to olivine. Mini-TES spectra have been acquired for soils surrounding the the Spirit landing site, and show spectra nearly identical to globally averaged soil viewed by the TES instrument on Mars Global Surveyor. This includes identification of a small amount (a few percent) of carbonate. The landing site at Meridiani Planum lies inside an impact crater that is roughly 20 meters in diameter. The lander came to rest on soil that fills most of the crater. An outcrop of layered bedrock is exposed on the crater wall. The landing site was selected partly because coarse gray hematite was expected to be present on the basis of orbital data. Mini-TES data have confirmed the presence of this hematite in the soil. The soil within the crater has several components. Microscopic images of undisturbed surface soil show that one component is fine (~100 micron) sand. Mössbauer spectra of the sand show two ferrous doublets (one of them due to olivine), a ferric doublet, and a weak magnetic sextet. APXS and Mini-TES data on this sand are consistent with a composition dominated by basalt. Another component of the soil consists of coarse (several mm) granules. These range in shape from subangular to rounded to remarkably spherical. In some locations, granules have been pressed down into the soil by the impact of the landers airbags. At those locations the concentration of hematite as determined by Mini-TES is sharply reduced, suggesting that at least some of the granules are hematite-bearing. The bedrock outcrop is finely laminated, with typical layer thicknesses of only a few mm. The texture of the outcrop as viewed in miroscopic images suggests that it is fine-grained, with well-expressed structure that is revealed by varying degrees of mechanical abrasion of layers of varying induration. Initial APXS results on this fine-grained matrix indicate sulfur concentrations significantly higher than any observed elsewhere on Mars. Embedded within the outcrop and weathering out of it are highly spherical granules with diameters of several mm. The visible to near-IR spectral properties of these embedded spherical granules, as determined by Pancam, are distinctly different from those of the matrix in which they are embedded.

Sedimentary Rocks and Evidence for Aqueous Environment on the Surface of Mars

NASA Astrophysics Data System (ADS)

Grotzinger, J. P.; Athena Science Team

2004-12-01

On January 24, 2004 the Mars Exploration Rover Opportunity landed at Meridiani Planum. The landing region lies on a broad, flat plain near the martian equator. The landing site itself is within an impact crater about 20 meters in diameter which exposes small rock outcrops along its northwestern rim. As of September 1, 2004, the Opportunity rover has explored the outcrops exposed within Eagle crater, along with much larger outcrops exposed almost continuously along the rim of Endurance crater, about 175 m in diameter and approximately 750 m away from Eagle crater. The intervening plains exposed additional outcrop within a regionally-pervasive fracture system, and within a smaller impact crater of just a few meters diameter. All outcrops studied to date from these differing localities indicate the presence of regionally extensive, lithified sedimentary materials consisting of fine-grained siliciclastic sediments derived from basaltic source rocks, admixed and cemented by abundant sulfate minerals and hematite. These include the hydrated sulphate mineral jarosite, in addition to Mg-sulphate. Cross-stratification provides evidence for both eolian and aqueous transport. Subsequent alteration of these rocks produced hematite-rich concretions and vuggy porosity that is pseudomorphic after probable sulphate evaporite minerals. These combined observations indicate episodic inundation by surface water to shallow depths, followed by evaporation, exposure and desiccation. Festoon cross-lamination provides evidence for inundation by water, the mineralogy and geochemistry indicate evaporation of water and precipitation of dissolved salts, and the planar to low-angle lamination and larger scale cross-bedding are consistent with sediment transport across a dry surface. Terrestrial analogs for such a suite of facies and surface processes include interdune depressions, playa lakes, and sabkhas adjacent to marginal seaways. The primary objective of the Mars Exploration Rover mission is to search for evidence in the martian geologic record of environmental conditions that might once have been suitable for life. The results obtained by the Athena Science Team demonstrate that liquid water, regarded as a key condition for life, was once abundant at Meridiani Planum. Because evaporite sediments can easily entomb micro-organisms, Meridiani Planum is a significant target for future landed or sample return missions aimed at life detection.

Natural attenuation of arsenic in the environment by immobilization in nanostructured hematite.

PubMed

Freitas, Erico T F; Montoro, Luciano A; Gasparon, Massimo; Ciminelli, Virginia S T

2015-11-01

Iron (hydr)oxides are known to play a major role in arsenic fixation in the environment. The mechanisms for long-term fixation into their crystal structure, however, remain poorly understood, especially arsenic partitioning behavior during transformation from amorphous to crystalline phases under natural conditions. In this study, these mechanisms are investigated in Fe-Al-oxisols exposed over a period of 10 years to a sulfide concentrate in tailings impoundments. The spatial resolution necessary to investigate the markedly heterogeneous nanoscale phases found in the oxisols was achieved by combining three different, high resolution electron microscopy techniques - Nano-Beam Electron Diffraction (NBD), Electron Energy-Loss Spectroscopy (EELS), and High Resolution Transmission Electron Microscopy (HRTEM). Arsenic (1.6±0.5 wt.%) was unambiguously and precisely identified in mesocrystals of Al-hematite with an As/Fe atomic ratio of 0.026±0.006. The increase in the c-axis (c=1.379±0.009 nm) compared to standard hematite (c=1.372 nm) is consistent with the presence of arsenic in the Al-hematite structure. The As-bearing Al-hematite is interpreted as a secondary phase formed from oxyhydroxides, such as ferrihydrite, during the long-term exposure to the sulfide tailings. The proposed mechanism of arsenic fixation in the Al-hematite structure involves adsorption onto Al-ferrihydrite nanoparticles, followed by Al-ferrihydrite aggregation by self-assembly oriented attachment and coalescence that ultimately produces Al-hematite mesocrystals. Our results illustrate for the first time the process of formation of stable arsenic bearing Al-hematite for the long-term immobilization of arsenic in environmental samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

Acquisition of chemical remanent magnetization during experimental ferrihydrite-hematite conversion in Earth-like magnetic field-implications for paleomagnetic studies of red beds

NASA Astrophysics Data System (ADS)

Jiang, Zhaoxia; Liu, Qingsong; Dekkers, Mark J.; Tauxe, Lisa; Qin, Huafeng; Barrón, Vidal; Torrent, José

2015-10-01

Hematite-bearing red beds are renowned for their chemical remanent magnetization (CRM). If the CRM was acquired substantially later than the sediment was formed, this severely compromises paleomagnetic records. To improve our interpretation of the natural remanent magnetization, the intricacies of the CRM acquisition process must be understood. Here, we contribute to this issue by synthesizing hematite under controlled 'Earth-like' field conditions (≲ 100 μ T). CRM was imparted in 90 oriented samples with varying inclinations. The final synthesis product appeared to be dominated by hematite with traces of ferrimagnetic iron oxides. When the magnetic field intensity is ≳ 40 μ T, the CRM records the field direction faithfully. However, for field intensities ≲ 40 μ T, the CRM direction may deviate considerably from that of the applied field during synthesis. The CRM intensity normalized by the isothermal remanent magnetization (CRM/IRM@2.5 T) increases linearly with the intensity of growth field, implying that CRM could potentially be useful for relative paleointensity studies if hematite particles of chemical origins have consistent properties. CRM in hematite has a distributed unblocking temperature spectrum from ∼200 to ∼650 °C, while hematite with a depositional remanent magnetization (DRM) has a more confined spectrum from ∼ 600to 680 °C because it is usually coarser-grained and more stoichiometric. Therefore, the thermal decay curves of CRM with their concave shape are notably different from their DRM counterparts which are convex. These differences together are suggested to be a potential discriminator of CRM from DRM carried by hematite in natural red beds, and of significance for the interpretation of paleomagnetic studies on red beds.

Thermodynamic and spectroscopic speciation to explain the blackening process of hematite formed by atmospheric SO2 impact: the case of Marcus Lucretius House (Pompeii).

PubMed

Maguregui, Maite; Knuutinen, Ulla; Martínez-Arkarazo, Irantzu; Castro, Kepa; Madariaga, Juan M

2011-05-01

After many decades exposed to a polluted environment, in some areas of Marcus Lucretius House, there are clear signs that plasters and hematite pigments are suffering deterioration. In the exhaustive analysis of the black layer covering the red pigment hematite it was possible to identify magnetite (Fe(3)O(4)) as responsible for the black colour, which always appears in combination with gypsum. Thermodynamic modelling stated that the presence of gypsum as well as the transformation of hematite into magnetite is a consequence of the attack of atmospheric SO(2).

Hydrothermal Synthesis of Hematite-Rich Spherules: Implications for Diagenesis and Hematite Spherule Formation in Outcrops at Meridiani Planum, Mars

NASA Technical Reports Server (NTRS)

Golden, D. C.; Ming, D. W.; Morris, R. V.; Graff, T. G.

2007-01-01

The Athena science payload onboard the Opportunity rover identified hematite-rich spherules (mean diameter of 4.2 +/- 0.8 mm) embedded in outcrops and occurring as lag deposits at Meridiani Planum. They have formed as diagenetic concretions from the rapid breakdown of pre-existing jarosite and other iron sulfates when chemically distinct groundwater passed through the sediments. Diagenetic, Fe-cemented concretions found in the Jurassic Navajo Formation, Utah and hematite-rich spherules found within sulfate-rich volcanic breccia on Mauna Kea volcano, Hawaii are possible terrestrial analogues for Meridiani spherules. The Navajo Formation concretions form in porous quartz arenite from the dissolution of iron oxides by reducing fluids and subsequent Fe precipitation to form spherical Fe- and Si-rich concretions. The Mauna Kea spherules form by hydrothermal, acid-sulfate alteration of basaltic tephra. The formation of hematite-rich spherules with similar chemical, mineralogical, and morphological properties to the Meridiani spherules is rare on Earth, so little is known about their formation conditions. In this study, we have synthesized in the laboratory hematite-rich spherules that are analogous in nearly all respects to the Meridiani spherules.

Morphology, stability, and X-ray absorption spectroscopic study of iron oxide (Hematite) nanoparticles prepared by micelle nanolithography

NASA Astrophysics Data System (ADS)

Bera, Anupam; Bhattacharya, Atanu; Tiwari, N.; Jha, S. N.; Bhattacharyya, D.

2018-03-01

Currently, considerable effort is being made towards synthesis and characterization of iron oxide nanoparticles. In this article, we report on the preparation and characterization of iron oxide nanoparticle (NP) arrays supported on natively oxidized Si(100) surface. The NPs are synthesized by reverse micelle nanolithography technique and are then deposited onto natively oxidized Si(100) surface via spin-coating. Plasma oxidation followed by high temperature annealing results in a unimodal size distribution of pseudohexagonally-ordered array of iron oxide NPs (with ∼14 nm mean diameter and ∼5 nm mean height). High temperature annealing does not fragment the NPs. Particles are sinter-resistant: the unimodal arrays are robust with respect to thermal treatment. X-ray absorption spectroscopy (XAS), including X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS), reveals that structure of the iron oxide particle resembles closely the hematite α-Fe2O3 structure. Furthermore, with the help of EXAFS spectra, we eliminate the possibility of γ-Fe2O3, Fe3O4, FeO and FeO(OH) structures for the NPs.

Authigenic magnetite formation from goethite and hematite and chemical remanent magnetization acquisition

NASA Astrophysics Data System (ADS)

Till, J. L.; Nowaczyk, N.

2018-06-01

The iron oxyhydroxide goethite is unstable at elevated temperatures and can transform to magnetite under reducing conditions. In this study, various heating experiments were conducted to simulate Fe-mineral transformations during pyrogenic or burial diagenesis alteration in the presence of organic matter. Thermomagnetic measurements, capsule heating experiments and thermochemical remanence acquisition measurements were performed to determine the effect of organic carbon additions on samples containing synthetic microcrystalline goethite, microcrystalline hematite or nanocrystalline goethite. Changes in magnetic properties with heating were monitored to characterize the magnetic behaviour of secondary magnetite and hematite formed during the experiments. Authigenic magnetite formed in all samples containing organic C, while goethite heated without organic C altered to poorly crystalline pseudomorphic hematite. The concentration of organic matter was found to have little influence on the rate or extent of reaction or on the characteristics of the secondary phases. Authigenic magnetite formed from microcrystalline goethite and hematite dominantly behaves as interacting single-domain particles, while nanophase goethite alters to a mixture of small single-domain and superparamagnetic magnetite. Authigenic magnetite and hematite both acquire a stable thermochemical remanence on heating to temperatures between 350 and 600 °C, although the remanence intensity acquired below 500 °C is much weaker than that at higher temperatures. Reductive transformation of fine-grained goethite or hematite is therefore a potential pathway for the production of authigenic magnetite and the generation of stable chemical remanence that may be responsible for remagnetization in organic-matter-bearing sedimentary rocks.

Controls on the Fate and Speciation of Np(V) During Iron (Oxyhydr)oxide Crystallization.

PubMed

Bots, Pieter; Shaw, Samuel; Law, Gareth T W; Marshall, Timothy A; Mosselmans, J Frederick W; Morris, Katherine

2016-04-05

The speciation and fate of neptunium as Np(V)O2(+) during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2(+) to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments.

The Search for Hesperian Organic Matter on Mars: Pyrolysis Studies of Sediments Rich in Sulfur and Iron

PubMed Central

Najorka, Jens; Watson, Jonathan S.; Sephton, Mark A.

2018-01-01

Abstract Jarosite on Mars is of significant geological and astrobiological interest, as it forms in acidic aqueous conditions that are potentially habitable for acidophilic organisms. Jarosite can provide environmental context and may host organic matter. The most common extraction technique used to search for organic compounds on the surface of Mars is pyrolysis. However, thermal decomposition of jarosite releases oxygen into pyrolysis ovens, which degrades organic signals. Jarosite has a close association with the iron oxyhydroxide goethite in many depositional/diagenetic environments. Hematite can form by dehydration of goethite or directly from jarosite under certain aqueous conditions. Goethite and hematite are significantly more amenable than jarosite for pyrolysis experiments employed to search for organic matter. Analysis of the mineralogy and organic chemistry of samples from a natural acidic stream revealed a diverse response for organic compounds during pyrolysis of goethite-rich layers but a poor response for jarosite-rich or mixed jarosite-goethite samples. Goethite units that are associated with jarosite, but do not contain jarosite themselves, should be targeted for organic detection pyrolysis experiments on Mars. These findings are extremely timely, as exploration targets for Mars Science Laboratory include Vera Rubin Ridge (formerly known as “Hematite Ridge”), which may have formed from goethite precursors. Key Words: Mars—Pyrolysis—Jarosite—Goethite—Hematite—Biosignatures. Astrobiology 18, 454–464. PMID:29298093

AMS Fabric of a CRM in Hematite-Bearing Samples: Evidence of DRMs in Natural Red Beds

NASA Astrophysics Data System (ADS)

Kodama, K. P.

2002-12-01

Anisotropy of magnetic susceptibility (AMS) and anisotropy of isothermal remanence (AIR) in red sedimentary rocks both typically show a bedding parallel foliation with minimum axes clustered perpendicular to the bedding plane. Our studies have observed this type of magnetic fabric in red bed units that have a range of ages and come from widespread localities. These units include the Mississippian Mauch Chunk Formation from the Appalachians, the Triassic Passaic Formation from the Newark basin in Pennsylvania, the Cretaceous Kapusaliang Formation from the Tarim basin in China, and the early Mesozoic Kayenta and Chinle Formations from the Colorado Plateau in southwestern North America. Bedding parallel foliations are also observed in magnetite-bearing rocks that carry a depositional remanence (DRM), suggesting the possibility of a DRM in red beds, even though the conventional wisdom is that they carry a post-depositional chemical remanent magnetization (CRM). Before the typical magnetic fabric of red beds can be used to indicate their type of remanence, we must determine what the magnetic fabric of a CRM looks like. For this reason, I conducted a series of hematite-growth experiments following the procedures outlined by Stokking and Tauxe (1987). I grew hematite in the laboratory on stacks of glass-fiber filter papers and in slurries of quartz and kaolinite. The hematite was grown from a ferric nitrate solution heated to 95° C for 8 hours. The samples were then dehydrated in a vacuum at room temperature for approximately 38 hours. It was possible to thermally demagnetize the eight filter paper samples to 350° C, but the six kaolinite-quartz samples were grown in plastic sample cubes and could only be thermally demagnetized to 150° C, enough to remove the thermoviscous magnetization acquired by the samples during the heating at 95° C. The mean CRM acquired by the red-brown magnetic phase grown in the experiments was within its alpha-95 of the steeply inclined (inclination=60°) ambient magnetic field. The kaolinite-quartz samples had a very scattered remanence, probably due to the physical disturbance of the samples upon the initial application of the vacuum. In both the filter paper and kaolinite-quartz experiments the AMS fabric of the CRM-carrying grains was foliated with the maximum and intermediate principal axes defining a great circle that passes through the mean CRM direction and is moderately inclined (approximately 45°) to the horizontal. The moderately inclined great circle defined by the maximum-intermediate principal axes is quite distinct from the horizontal maximum-intermediate axes observed in the natural red bed samples, despite red bed characteristic remanences that range from nearly horizontal (Passaic, Chinle, Kayenta) to as steep as 30° (Mauch Chunk, Kapusaliang). This observation suggests that red bed characteristic remanence is typically a DRM, rather than a CRM. This has implications for interpreting red bed remanence since DRMs in hematite-bearing red beds may have large inclination errors.

Mineralogical diversity (spectral reflectance and Moessbauer data) in compositionally similar impact melt rocks from Manicouagan Crater, Canada

NASA Technical Reports Server (NTRS)

Morris, R. V.; Bell, J. F., III; Golden, D. C.; Lauer, H. V., Jr.

1993-01-01

Meteoritic impacts under oxidizing surface conditions occur on both earth and Mars. Oxidative alteration of impact melt sheets is reported at several terrestrial impact structures including Manicouagan, West Clearwater Lake, and the Ries Basin. A number of studies have advocated that a significant fraction of Martian soil may consist of erosional products of oxidatively altered impact melt sheets. If so, the signature of the Fe-bearing mineralogies formed by the process may be present in visible and near infrared reflectivity data for the Martian surface. Of concern is what mineral assemblages form in impact melt sheets produced under oxidizing conditions and what their spectral signatures are. Spectral and Moessbauer data for 19 powder samples of impact melt rock from Manicouagan Crater are reported. Results show for naturally occurring materials that composite hematite-pyroxene bands have minima in the 910-nm region. Thus many of the anomalous Phobos-2 spectra, characterized by a shallow band minimum in the near-IR whose position varies between approximately 850 and 1000 nm, can be explained by assemblages whose endmembers (hematite and pyroxene) are accepted to be present on Mars. Furthermore, results show that a mineralogically diverse suite of rocks can be generated at essentially constant composition, which implies that variations in Martian surface mineralogy do not necessarily imply variations in chemical composition.

Early Mars may have had a methanol ocean

NASA Astrophysics Data System (ADS)

Tang, Yan; Chen, Qianwang; Huang, Yujie

2006-01-01

The detection of gray crystalline hematite deposits on Mars by Thermal Emission Spectrometer (TES) has been used to argue for the presence of liquid water on Mars in the distant past. By methanol-thermal treatment of anhydrous FeCl 3 at low temperatures (70-160 °C), crystalline gray hematite with layered structure was synthesized, based on this result an alternative explanation for the origin of martian hematite deposits is suggested. Methane could be abundant in the early martian atmosphere; process such as photochemical oxidation of methane could result in the formation of ocean or pool of organic compounds such as methanol, which provides an environment for the formation of large-scale hematite deposits on Mars.

The performance of hematite nanostructures in different humidity levels

NASA Astrophysics Data System (ADS)

Ahmad, W. R. W.; Mamat, M. H.; Zoolfakar, A. S.; Khusaimi, Z.; Yusof, M. M.; Ismail, A. S.; Saidi, S. A.; Rusop, M.

2018-05-01

In this study, hematite (α-Fe2O3) nanostructure were prepared in Schott vials on fluorine-doped tin oxide (FTO) coated glass substrate using the sonicated immersion method in aqueous solution with ferric chloride FeCl3ṡ6H2O as a precursor and urea NH2-CONH2 as a stabilizer. The samples were characterized for different level of humidity conditions within range 40% to 90% RH. Based on the results obtained, the hematite nanostructure exhibited good optical properties and virtuous sensor response with high sensitivity. The fabricated hematite nanostructure has revealed a good potential for humidity sensor application based on the results obtained under different levels of humidity.

Synthesis and photo-electrochemical properties of spinel-ferrite-coated hematite for solar water splitting

NASA Astrophysics Data System (ADS)

Selvaraj, Seenivasan; Moon, Hee; Kim, Do-Heyoung

2018-01-01

Photo-electrochemical water splitting with hematite photo-anodes under solar irradiation has attracted considerable attention as regards the production of renewable hydrogen energy. However, many challenges remain unresolved, as the full contribution of the catalytic over-layers has not been fully realized. Herein, we incorporate uniform spinel nickel-ferrite over-layers in hematite photo-anodes to obtain an improved understanding of the associated intrinsic changes. We achieve a 1.5-mA/cm2 photo-current density at 1.23 VRHE (RHE: reversible hydrogen electrode) under one-sun illumination conditions, along with a negative shift of 200 mV in the onset potential, for NiFe2O4-coated Sn-doped hematite photo-anodes. Fundamental electrochemical analyses clearly show that the shift in the onset potential is predominantly due to the enhanced photo-voltage development inside the hematite, rather than being purely caused by the interfacial kinetics. These insights reveal a new direction for fundamental research on photo-anodes towards fabrication of more efficient photo-anode systems.

MSL/Mastcam Multispectral Observations of Lower Mt. Sharp Units: Spectral Evidence of Distinct Alteration Environments

NASA Astrophysics Data System (ADS)

Wellington, D. F.; Bell, J. F., III; Johnson, J. R.; Fraeman, A. A.; Kinch, K. M.; Godber, A.; Rice, M. S.

2016-12-01

The Mars Science Laboratory Curiosity rover reached the lower units of Mt. Sharp in Gale Crater approximately two years ago. Along the traverse, Mastcam multispectral observations have documented the visible/near-IR spectral variability of drill tailings, bedrock, float rocks, fines, and other materials, recording a set of diverse reflectance properties in twelve unique filters over wavelengths 400-1100 nm. The most recent multi-filter images include new spectral diversity not encountered in near-field imaging acquired earlier in the mission. Since departing Marias Pass ( sol 1072), the rover has sampled material from the Stimson sandstone unit four times at two widely separated locations. These drill pairs were designed to investigate alteration regions visible as bright haloes bordering fractures in the bedrock. Drill fines and piles of dumped sample material from these sites (at Bridger Basin and on the Naukluft Plateau) were targeted for multispectral observations, which quantify the differences in overall reflectance and spectral shape between the unaltered Stimson material and the light-toned haloes. In the latter, high reflectances and relatively flat spectral shapes are consistent with interpretations of silica enrichment from other instruments. Mastcam spectra of the portions of the underlying Murray Formation (mudstone) that were encountered on first approach to the Bagnold dunes, and again upon exiting the Naukluft Plateau, are consistent with the presence of crystalline hematite. Variations in the relative strength of hematite absorption features in different locations may suggest possible differences in relative and/or absolute abundances of hematite of varying degrees of crystallinity. Dune materials have low reflectances with a broad, shallow absorption near 1-µm consistent with an olivine-bearing basaltic composition. We present these and other examples of spectral variability encountered by the rover during its ascent up the lower slopes of Mt. Sharp.

2015 Progress Report/July 2016: Iron Oxide Redox Transformation Pathways: The Bulk Electrical Conduction Mechanism

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

Scherer, Michelle M.; Rosso, Kevin M.

Despite decades of research on the reactivity and stable isotope properties of Fe oxides, the ability to describe the redox behavior of Fe oxides in the environment is still quite limited. This is due, in large part, to the analytical and spatial complexities associated with studying microscopic processes at the Fe oxide-water interface. This project had the long-term vision of filling this gap by developing a detailed understanding of the relationship between interfacial ET processes, surface structure and charge, and mineral semiconducting properties. We focused on the Fe(III)-oxides and oxyhydroxides because of their geochemical preponderance, versatility in synthesis of compositionally,more » structurally, and morphologically tailored phases, and because they are amenable to a wide range of surface and bulk properties characterization. In particular, reductive transformation of phases such as hematite (α-Fe 2O 3) and goethite (α-FeOOH) in aqueous solution can serve as excellent model systems for studies of electron conduction processes, as well as provide valuable insights into effect of nanoscale conductive materials on contaminant fate at DOE sites. More specifically, the goal of the Iowa component of this project was to use stable Fe isotope measurements to simultaneously measure isotope specific oxidation states and concentrations of Fe at the hematite-water and goethite-water interface. This work builds on our previous work where we used an innovative combination of 57Fe Mössbauer spectroscopy and high precision isotope ratio measurements (MC-ICP-MS) to probe the dynamics of the reaction of aqueous Fe(II) with goethite. Mössbauer spectroscopy detects 57Fe only among all other Fe isotopes and we have capitalized on this to spectroscopically demonstrate Fe(II)-Fe(III) electron transfer between sorbed Fe(II) and Fe(III) oxides (Handler, et al., 2009; Gorski, et al. 2010; Rosso et al., 2010). By combining the Mössbauer spectroscopy and stable isotopes measurements, we have been able to simultaneously track the oxidation state and isotope concentration of the bulk Fe oxide and aqueous Fe. One of our most compelling findings is that despite the apparent stability of the Fe(II)-goethite system, there is actually a tremendous amount of Fe atom cycling occurring between the aqueous phase and the bulk goethite as indicated by the isotopic composition of both phases approaching the mass balance average (Handler et al., 2009). How such extensive re-crystallization and Fe atom exchange can occur with no significant morphological change is a fascinating question. Based on previous work from PI Rosso’s group showing that a potential gradient across hematite crystal faces leads to conduction through hematite and growth and dissolution at separate crystal faces we proposed that a redox-driven recrystallization could be occurring that would explain the extensive mixing observed with the isotope data. From our previous studies utilizing Mössbauer spectroscopy, we know that sorption of Fe(II) onto goethite results in electron transfer between the sorbed Fe(II) and the structural Fe(III) in goethite. Oxidation of the sorbed Fe(II) produces growth of goethite on goethite (i.e., homoepitaxy), as well as injection of an electron into goethite. It is possible that electron transfer from sorbed Fe(II) occurs across a potential gradient, and that Fe(II) atoms are dissolved at a different location on the goethite surface. These newly-reduced Fe(II) atoms could then dissolve into the aqueous phase, exposing fresh Fe(III) goethite to the aqueous phase. Through a repeated series of these five steps of sorption–electron transfer–crystal growth–conduction– dissolution, a redox-driven conveyor belt, could be established that would allow all of the goethite to be eventually exposed to the aqueous phase and exchanged. This surface-mediated recrystallization process would result in similar Fe isotope distributions in the aqueous phase and goethite particle, as we have observed here. It would also result in a stable aqueous Fe(II) concentration, if there were equal rates of goethite growth and dissolution.« less

Effect of defects on the small polaron formation and transport properties of hematite from first-principles calculations

NASA Astrophysics Data System (ADS)

Smart, Tyler J.; Ping, Yuan

2017-10-01

Hematite (α-Fe2O3) is a promising candidate as a photoanode material for solar-to-fuel conversion due to its favorable band gap for visible light absorption, its stability in an aqueous environment and its relatively low cost in comparison to other prospective materials. However, the small polaron transport nature in α-Fe2O3 results in low carrier mobility and conductivity, significantly lowering its efficiency from the theoretical limit. Experimentally, it has been found that the incorporation of oxygen vacancies and other dopants, such as Sn, into the material appreciably enhances its photo-to-current efficiency. Yet no quantitative explanation has been provided to understand the role of oxygen vacancy or Sn-doping in hematite. We employed density functional theory to probe the small polaron formation in oxygen deficient hematite, N-doped as well as Sn-doped hematite. We computed the charged defect formation energies, the small polaron formation energy and hopping activation energies to understand the effect of defects on carrier concentration and mobility. This work provides us with a fundamental understanding regarding the role of defects on small polaron formation and transport properties in hematite, offering key insights into the design of new dopants to further improve the efficiency of transition metal oxides for solar-to-fuel conversion.

Hematite Versus Magnetite as the Signature for Planetary Magnetic Anomalies?

NASA Technical Reports Server (NTRS)

Kletetshka, Gunther; Taylor, Patrick T.; Wasilewski, Peter J.

1999-01-01

Crustal magnetic anomalies are the result of adjacent geologic units having contrasting magnetization. This magnetization arises from induction and/or remanence. In a planetary context we now know that Mars has significant crustal magnetic anomalies due to remanent magnetization, while the Earth has some anomalies where remanence can be shown to be important. This picture, however, is less clear because of the nature and the magnitude of the geomagnetic field which is responsible for superimposed induced magnetization. Induced magnetization assumes a magnetite source, because of its much greater magnetic susceptibility when compared with other magnetic minerals. We investigated the TRM (thermoremanent magnetization) acquisition of hematite, in weak magnetic fields up to 1 mT, to determine if the remanent and induced magnetization of hematite could compete with magnetite. TRM acquisition curves of magnetite and hematite show that multi-domain hematite reaches TRM saturation (0.3 - 0.4 A sq m/kg) in fields as low as 100 microT. However, multi-domain magnetite reaches only a few percent of its TRM saturation in a field of 100 microT (0.02 - 0.06 A sq m/kg). These results suggest that a mineral such as hematite and, perhaps, other minerals with significant remanence and minor induced magnetization may play an important role in providing requisite magnetization contrast. Perhaps, and especially for the Mars case, we should reevaluate where hematite and other minerals, with efficient remanence acquisition, exist in significant concentration, allowing a more comprehensive explanation of Martian anomalies and better insight into the role of remanent magnetization in terrestrial crustal magnetic anomalies.

Experimental evidence for non-redox transformations between magnetite and hematite under H 2-rich hydrothermal conditions

NASA Astrophysics Data System (ADS)

Otake, Tsubasa; Wesolowski, David J.; Anovitz, Lawrence M.; Allard, Lawrence F.; Ohmoto, Hiroshi

2007-05-01

Transformations of magnetite (Fe IIFe 2IIIO 4) to hematite (Fe 2IIIO 3) (and vice versa) have been thought by many scientists and engineers to require molecular O 2 and/or H 2. Thus, the presence of magnetite and/or hematite in rocks has been linked to a specific oxidation environment. However, the availability of reductants or oxidants in many geologic and industrial environments appears to have been too low to account for the transformations of iron oxides through redox reactions. Here, we report the results of hydrothermal experiments in mildly acidic and H 2-rich aqueous solutions at 150 °C, which demonstrate that transformations of magnetite to hematite, and hematite to magnetite, occur rapidly without involving molecular O 2 or H 2: Fe3O 4(Mt) + 2H (aq)+ ↔ Fe 2O 3(Hm) + Fe (aq)2+ + H 2O. The transformation products are chemically and structurally homogeneous, and typically occur as euhedral single crystals much larger than the precursor minerals. This suggests that, in addition to the expected release of aqueous ferrous species to solution, the transformations involve release of aqueous ferric species from the precursor oxides to the solution, which reprecipitate without being reduced by H 2. These redox-independent transformations may have been responsible for the formation of some iron oxides in natural systems, such as high-grade hematite ores that developed from Banded Iron Formations (BIFs), hematite-rich deposits formed on Mars, corrosion products in power plants and other industrial systems.

Peleolakes and impact basins in southern Arabia Terra, including Meridiani Planum: Implications for the formation of hematite deposits on Mars

USGS Publications Warehouse

Newsom, Horton E.; Barber, C.A.; Hare, T.M.; Schelble, R.T.; Sutherland, V.A.; Feldman, W.C.

2003-01-01

The hematite deposit in Meridiani Planum was selected for a Mars Exploration Rover (MER) landing site because water could be involved in the formation of hematite, and water is a key ingredient in the search for life. Our discovery of a chain of paleolake basins and channels along the southern margin of the hematite deposits in Meridiani Planum with the presence of the strongest hematite signature adjacent to a paleolake basin, supports the possible role of water in the formation of the hematite and the deposition of other layered materials in the region. The hematite may have formed by direct precipitation from lake water, as coatings precipitated from groundwater, or by oxidation of preexisting iron oxide minerals. The paleolake basins were fed by an extensive channel system, originating from an area larger than Texas and located south of the Schiaparelli impact basin. On the basis of stratigraphic relationships, the formation of channels in the region occurred over much of Mars' history, from before the layered materials in Meridiani Planum were deposited until recently. The location of the paleolake basins and channels is connected with the impact cratering history of the region. The earliest structure identified in this study is an ancient circular multiringed basin (800-1600 km diameter) that underlies the entire Meridiani Planum region. The MER landing site is located on the buried northern rim of a later 150 km diameter crater. This crater is partially filled with layered deposits that contained a paleolake in its southern portion. Copyright 2003 by the American Geophysical Union.

Thermodynamic properties of hematite — ilmenite — geikielite solid solutions

NASA Astrophysics Data System (ADS)

Ghiorso, Mark S.

1990-11-01

A solution model is developed for rhombohedral oxide solid solutions having compositions within the ternary system ilmenite [(Fe{2+/ s }Ti{4+/1- s }) A (Fe{2+/1- s }Ti{4+/s}) B O3]-geikielite [(Mg{2+/ t }Ti{4+/1- t }) A (Mg{2+/1- t }Ti{4+/ t }) B O3]-hematite [(Fe3+) A (Fe3+) B O3]. The model incorporates an expression for the configurational entropy of solution, which accounts for varying degrees of structural long-range order (0≤s, t≤1) and utilizes simple regular solution theory to characterize the excess Gibbs free energy of mixing within the five-dimensional composition-ordering space. The 13 model parameters are calibrated from available data on: (1) the degree of long-range order and the composition-temperature dependence of theRbar 3c - Rbar 3 transition along the ilmenite-hematite binary join; (2) the compositions of coexisting olivine and rhombohedral oxide solid solutions close to the Mg-Fe2+ join; (3) the shape of the miscibility gap along the ilmenite-hematite join; (4) the compositions of coexisting spinel and rhombohedral oxide solid solutions along the Fe2+-Fe3+ join. In the course of calibration, estimates are obtained for the reference state enthalpy of formation of ulvöspinel and stoichiometric hematite (-1488.5 and -822.0 kJ/mol at 298 K and 1 bar, respectively). The model involves no excess entropies of mixing nor does it incorporate ternary interaction parameters. The formulation fits the available data and represents an internally consistent energetic model when used in conjuction with the standard state thermodynamic data set of Berman (1988) and the solution theory for orthopyroxenes, olivines and Fe-Mg titanomagnetite-aluminate-chromate spinels developed by Sack and Ghiorso (1989, 1990a, b). Calculated activity-composition relations for the end-members of the series, demonstrate the substantial degree of nonideality associated with interactions between the ordered and disordered structures and the dominant influence of the miscibility gap across much of the ternary system. The predicted shape of the miscibility gap, and the orientation of tie-lines relating the compositions of coexisting phases, display the effects of coupling between the excess enthalpy of solution and the degree of long-range order. One limb of the miscibility gap follows the composititiontemperature surface corresponding to the ternaryRbar 3 - Rbar 3c second-order transition.

Unique Spectral Features Search In The 20 - 35 Micron Range of Mgs Tes Data

NASA Astrophysics Data System (ADS)

Altieri, F.; Bellucci, G.

TES is the Thermal Emission Spectrometer aboard the NASA mission Mars Global Surveyor (MGS) orbiting around Mars since September 1997. It is collecting 6 - 50 micron thermal emission spectra and one of its principal purposes is to determine and map the Mars surface composition. Spectral features directly ascribable to sur- face minerals have been identified in the 20 - 35 micron spectral range: deposits of crystalline gray hematite have been localized in three regions, Sinus Meridiani, Aram Chaos and Valles Marineris [1, 2], and outcrops of olivines have been individuated in Nili Fossae [3]. The crystalline gray hematite areas have been interpreted to be formed by aqueous mineralization, indicating that liquid water was stable near the Mars sur- face for a long period of time in some limited regions. On the other hand there is no evidence in TES data for large scale occurrences (< 10 km) of moderate-grained (> 50 micron) carbonates exposed at the surface at a detection limit of 10 % [2]. Mars thermal emission spectra show, in general, significant variance between 20 and 35 mi- cron. This variance is not directly attributable to surface mineralogical components for the difficulty of discriminating the contribute of atmospheric components: CO2 and water vapour gas, dust and water ice aerosols. Moreover, the dust layer deposited on the soil has a spectral masking effect, obscuring superficial signature related to smaller mineral deposit and making difficult their identification. In this study we report some examples of single TES spectra with typical hematite and olivine bands and spectra with other unique features in the 20 - 35 micron range likely related to superficial components. For some of them we have analysed how the spectral features change in two different Mars seasons. These single TES pixels could be best investigated by instruments with an higher spatial resolution, as THEMIS and OMEGA. References: [1] Christensen P. R., et al., JGR, 105, 9623-9642, 2000. [2] Christensen P. R., et al., JGR,106, 23823-23871, 2001. [3] Hoefen T. M. and Clark R. N., LPS XXXII, 2049, 2001.

Hematite-Rich Fracture Fill at Meridiani Planum, Mars: Implications for Fluid Chemistry

NASA Technical Reports Server (NTRS)

Yen, Albert; Mittlefehldt, David W.; Morris, Richard V.; Gellert, Ralf

2010-01-01

The Mars Exploration Rover Opportunity has been operating at the surface of Mars for over 2100 sols and has driven a distance of approximately 20 km. Throughout the traverse, outcrop rocks with margins and fracture fill resistant to erosion have been imaged and analyzed in detail by the Moessbauer (MB) spectrometer and the Alpha Particle X-ray Spectrometer (APXS). A recent APXS analysis of an outcrop block excavated by a young impact crater shows a coating with the highest concentration of iron measured by either rover, not including the iron-nickel meteorites. Texturally, this sample (referred to as "Chocolate Hills -Aloya") appears as a cemented collection of partially fragmented \\blueberries." With the exception of an elevated sulfur content, the elemental chemistry of this particular sample is entirely consistent with other analyses of hematite spherules at Merdiani Planum. As a result, it is difficult to determine whether this coating, which may have been filling a fracture in outcrop rocks prior to disruption by the impact, was simply an agglomeration of spherules or a result of a more complicated aqueous process. In contrast, a number of other fracture-filling exposures and erosion-resistant rinds have been analyzed by the APXS and MB instruments showing significant concentrations of iron in the form of hematite without the texture of spherule fragments. In one of these samples, a broken piece of fracture fill within Victoria crater referred to as "Dorsal," showed over 50% of the iron in hematite, the highest Mn concentration of any sample measured by the rovers, and elevated levels of Cl and Br. While the Fe:Mn ratio of the Dorsal analyses are comparable to that of Gusev and Meridiani basalts, it is clear that chemistry of this sample cannot be completely explained by a simple mixing of outcrop and blueberry compositions

The role of sedimentology, oceanography, and alteration on the δ56Fe value of the Sokoman Iron Formation, Labrador Trough, Canada

NASA Astrophysics Data System (ADS)

Raye, Urmidola; Pufahl, Peir K.; Kyser, T. Kurtis; Ricard, Estelle; Hiatt, Eric E.

2015-09-01

The Sokoman Formation is a ca. 100-m-thick succession of interbedded iron formation and fine-grained siliciclastics deposited at 1.88 Ga. Accumulation occurred on a dynamic paleoshelf where oxygen stratification, coastal upwelling of hydrothermally derived Fe and Si, microbial processes, tide and storm currents, diagenesis, and low-grade prehnite-pumpellyite metamorphism controlled lithofacies character and produced complex associations of multigenerational chert, hematite, magnetite, greenalite, stilpnomelane and Fe carbonate. Hematite-rich facies were deposited along suboxic segments of the coastline where photosynthetic oxygen oases impinged on the seafloor. Hematitic, cross-stratified grainstones were formed by winnowing and reworking of freshly precipitated Fe-(oxyhydr)oxide and opal-A by waves and currents into subaqueous dunes. Magnetite-rich facies contain varying proportions of greenalite and stilpnomelane and record deposition in anoxic middle shelf environments beneath an oxygen chemocline. Minor negative Ce anomalies in hematitic facies, but prominent positive Ce and Eu anomalies and high LREE/HREE ratios in magnetite-rich facies imply the existence of a weakly oxygenated surface ocean above anoxic bottom waters. The Fe isotopic composition of 31 whole rock (-0.46 ⩽ δ56Fe ⩽ 0.47‰) and 21 magnetite samples (-0.29 ⩽ δ56Fe ⩽ 0.22‰) from suboxic and anoxic lithofacies was controlled primarily by the physical oceanography of the paleoshelf. Despite low-grade metamorphism recorded by the δ18O values of paragenetically related quartz and magnetite, the Sokoman Formation preserves a robust primary Fe isotopic signal. Coastal upwelling is interpreted to have affected the isotopic equilibria between Fe2+aq and Fe-(oxyhydr)oxide in open marine versus coastal environments, which controlled the Fe isotopic composition of lithofacies. Unlike previous work that focuses on microbial and abiotic fractionation processes with little regard for paleoenvironment, our work demonstrates that depositional setting is paramount in governing the Fe isotopic composition of iron formations irrespective of what Fe-bearing minerals precipitated.

Empirical Analysis of the Photoelectrochemical Impedance Response of Hematite Photoanodes for Water Photo-oxidation.

PubMed

Klotz, Dino; Grave, Daniel A; Dotan, Hen; Rothschild, Avner

2018-03-15

Photoelectrochemical impedance spectroscopy (PEIS) is a useful tool for the characterization of photoelectrodes for solar water splitting. However, the analysis of PEIS spectra often involves a priori assumptions that might bias the results. This work puts forward an empirical method that analyzes the distribution of relaxation times (DRT), obtained directly from the measured PEIS spectra of a model hematite photoanode. By following how the DRT evolves as a function of control parameters such as the applied potential and composition of the electrolyte solution, we obtain unbiased insights into the underlying mechanisms that shape the photocurrent. In a subsequent step, we fit the data to a process-oriented equivalent circuit model (ECM) whose makeup is derived from the DRT analysis in the first step. This yields consistent quantitative trends of the dominant polarization processes observed. Our observations reveal a common step for the photo-oxidation reactions of water and H 2 O 2 in alkaline solution.

Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate

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

Flynn, Elaine D.; Catalano, Jeffrey G.

Iron oxides are ubiquitous in soils and sediments and play a critical role in the geochemical distribution of trace elements and heavy metals via adsorption and coprecipitation. The presence of organic acids may potentially alter how metals associate with iron oxide minerals through a series of cooperative or competitive processes: solution complexation, ternary surface complexation, and surface site competition. The macroscopic and molecular-scale effects of these processes were investigated for Ni adsorption to hematite and goethite at pH 7 in the presence of oxalate. The addition of this organic acid suppresses Ni uptake on both minerals. Aqueous speciation suggests thatmore » this is dominantly the result of oxalate complexing and solubilizing Ni. Comparison of the Ni surface coverage to the concentration of free (uncomplexed) Ni 2+ in solution suggests that the oxalate also alters Ni adsorption affinity. EXAFS and ATR-FTIR spectroscopies indicate that these changes in binding affinity are due to the formation of Ni–oxalate ternary surface complexes. These observations demonstrate that competition between dissolved oxalate and the mineral surface for Ni overwhelms the enhancement in adsorption associated with ternary complexation. Oxalate thus largely enhances Ni mobility, thereby increasing micronutrient bioavailability and inhibiting contaminant sequestration.« less

Μicro-Raman spectroscopy for the characterization of rock-art pigments from Abrigo del Águila (Badajoz - Spain)

NASA Astrophysics Data System (ADS)

Rosina, P.; Gomes, H.; Collado, H.; Nicoli, M.; Volpe, L.; Vaccaro, C.

2018-06-01

Micro-Raman spectroscopic technique allowed the characterization of organic and inorganic pigments of different colours sampled from a rock-art shelter named Abrigo del Aguila, located in the district of Badajoz, Cabeza del Buey (Extremadura - Spain). Micro-Raman analyses has been coupled with SEM observation and elemental analyses (EDS). The white and the black colours, used for non-representative figures, have been identified respectively as anatase and amorphous carbon, while two different type of red pigment has been found on figurative representations. The darker one, sampled, from a sun-figure, comprises an indeterminate organic compound beside of hematite. The second one, sampled from an anthropomorphic figure, is of a brilliant red and only hematite has been recognized in it.

Influence of kinetics on the determination of the surface reactivity of oxide suspensions by acid-base titration.

PubMed

Duc, M; Adekola, F; Lefèvre, G; Fédoroff, M

2006-11-01

The effect of acid-base titration protocol and speed on pH measurement and surface charge calculation was studied on suspensions of gamma-alumina, hematite, goethite, and silica, whose size and porosity have been well characterized. The titration protocol has an important effect on surface charge calculation as well as on acid-base constants obtained by fitting of the titration curves. Variations of pH versus time after addition of acid or base to the suspension were interpreted as diffusion processes. Resulting apparent diffusion coefficients depend on the nature of the oxide and on its porosity.

Curiosity at Vera Rubin Ridge: Testable Hypotheses, First Results, and Implications for Habitability

NASA Astrophysics Data System (ADS)

Fraeman, A.; Bedford, C.; Bridges, J.; Edgar, L. A.; Hardgrove, C.; Horgan, B. H. N.; Gabriel, T. S. J.; Grotzinger, J. P.; Gupta, S.; Johnson, J. R.; Rampe, E. B.; Morris, R. V.; Salvatore, M. R.; Schwenzer, S. P.; Stack, K.; Pinet, P. C.; Rubin, D. M.; Weitz, C. M.; Wellington, D. F.; Wiens, R. C.; Williams, A. J.; Vasavada, A. R.

2017-12-01

As of sol 1756, Curiosity was 250 meters from ascending Vera Rubin Ridge, a unique geomorphic feature preserved in the lower foothills of Aeolis Mons (informally known as Mt. Sharp) that is distinguishable from orbit. Vera Rubin Ridge (previously termed the Hematite Ridge) is characterized by a higher thermal inertia than the surrounding terrain, is comparatively resistant to erosion, and is capped with a hematite-bearing layer that is visible in 18 m/pixel CRISM data. A key hypothesis associated with this unit is that it represents a redox interface where ferrous iron oxidized and precipitated either as hematite or another ferric precursor. The Curiosity integrated payload is being used to determine the depositional environment(s), stratigraphic context and geochemical conditions associated with this interface, all of which will provide key insights into its past habitability potential and the relative timing of processes. Specifically, analysis of Curiosity data will address four major questions related to the history and evolution of ridge-forming strata: (1) What is the stratigraphic relationship between the units in the ridge and the Mt. Sharp group (see Grotzinger et al., 2015)? (2) What primary and secondary geologic processes deposited and modified the ridge units over time? (3) What is the nature and timing of the hematite precipitation environment, and how does it relate to similar oxidized phases in the Murray formation? (4) What are the implications for habitability and the preservation of organic molecules? Initial results of a systematic imaging campaign along the contact between the lower portion or the ridge and the Murray formation has revealed dm-scale cross bedding within the ridge stratigraphy, which provide clues about the depositional environments; these can be compared to suites of sedimentary structures within the adjacent Murray formation. Long distance ChemCam passive and Mastcam multispectral data show that hematite and likely other ferric phases are present in the upper ridge, consistent with orbital data. Curiosity will continue to take systematic observations that draw upon testable hypotheses about the ridge environments as the rover ascends Vera Rubin Ridge.

Synthesis, structural, optical and morphological characterization of hematite through the precipitation method: Effect of varying the nature of the base

NASA Astrophysics Data System (ADS)

Lassoued, Abdelmajid; Lassoued, Mohamed Saber; Dkhil, Brahim; Gadri, Abdellatif; Ammar, Salah

2017-08-01

Iron oxide (α-Fe2O3) nanoparticles were synthesized using the precipitation synthesis method focusing only on (FeCl3, 6H2O), NaOH, KOH and NH4OH as raw materials. The impact of varying the nature of the base on the crystalline phase, size and morphology of α-Fe2O3 products was explored. XRD spectra revealed that samples crystallize in the rhombohedral (hexagonal) system at 800 °C.The Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) were used to detect the morphology of synthesized nanoparticles and specify their sizes. However, the Fourier Transform Infra-Red (FT-IR) spectroscopy has permitted the observation of vibration band Fe-O. Raman spectroscopy was used not only to prove that we have synthesized hematite but also to identify their phonon modes. The Thermo Gravimetric Analysis (TGA) findings allow the thermal cycle determination of samples whereas Differential Thermal Analysis (DTA) findings allow the phase transition temperature identification. Besides, the optical investigation revealed that samples have an optical gap of about 2.1 eV. Findings highlight that the nature of the agent precipitant plays a significant role in the morphology of the products and the formation of the crystalline phase. Hematite synthesis with the base NH4OH brought about much stronger, sharper and wider diffraction peaks of α-Fe2O3. The morphology of samples are spherical with a size of about 61 nm while the size of the nanoparticles of hematite which we have synthesized with NaOH and KOH is respectively of the order of 82 and 79 nm.

High-coercivity, thermally stable and low unblocking temperature magnetic phase: Implications for Archeomagnetic studies

NASA Astrophysics Data System (ADS)

Hartmann, G. A.; Gallet, Y.; Trindade, R. I.; Genevey, A.; Berquo, T. S.; Neumann, R.; Le Goff, M.

2013-05-01

The thermoremanent magnetization in baked clay archeological materials provide very useful information on the time evolution of the Earth's magnetic field over the past few millennia. In these materials, a thermally stable magnetic phase characterized by high coercivities (>400 mT) and low unblocking temperatures (~200 degrees Celsius) has recently been recognized in European bricks, tiles, kilns and hearth samples. Both the identification and the origin of this phase remain, however, poorly constrained. The very same high-coercivity, thermally stable, low unblocking temperature (HCSLT) magnetic phase has been identified in Brazilian bricks fragments dated of the past five centuries. We report here a large set of measurements on a selected collection of samples showing variable contributions of the HCSLT phase. These measurements include low-field magnetic susceptibility vs. temperature curves, hysteresis loops, isothermal remanent magnetization (IRM) acquisition, thermal demagnetization of the three-axis IRM, first order reversal curves (FORC), low-temperature magnetization experiments (remanent magnetization curves and alternating current susceptibility), Mössbauer spectroscopy and X-ray diffraction. Results show the coexistence of low-coercivity magnetic minerals (magnetite and titanomagnetite) and high-coercivity minerals (hematite, HCSLT phase and, in some cases, goethite). We note that the HCSLT magnetic phase is always found in association with hematite. We further observe that the Mössbauer spectroscopy, X-ray diffraction spectra, and the FORC diagrams are also very similar to results previously obtained from annealed clays in which nontronite or iron-rich montmorillonite was transformed into Al-substituted hematite by heating. The HCSLT magnetic phase is thus confidently identified as being hematite with Al substitution. Moreover, considering the abundance of montmorillonite in clay mining settings, we suggest that the widespread occurrence of HCSLT in archeological materials predominantly originates from the transformation of iron-rich montmorillonite during the manufacturing (heating) process.

Structural and Magnetic Properties of Dilute Ca²⁺ Doped Iron Oxide Nanoparticles.

PubMed

Samar Layek; Rout, K; Mohapatra, M; Anand, S; Verma, H C

2016-01-01

Undoped and calcium substituted hematite (α-Fe₂O₃) nanoparticles are synthesized by surfactant-directed co-precipitation and post annealing method. The annealed nanoparticles were found to be in single phase in nature and crystallize in the rhombohedral structure with space group R3c as confirmed by Rietveld refinement of the X-ray diffraction (XRD) data. Average crystallite sizes are calculated to be 20 to 30 nm and 50 to 60 nm for the nanoparticles annealed at 400 and 600 °C respectively. Mössbauer spectra for all the nanoparticles could be fitted with a sextet corresponding to the single magnetic state of the iron atoms in its Fe³⁺ state in the hematite matrix. The FTIR and Raman spectra of all the samples correspond to specific modes of α-Fe₂O₃. UV-Vis spectra of annealed samples showed broad peaks in the range of 525-630 nm resulting from spin-forbidden ligand field transition together with the spin-flip transition among the 2t₂g states. The estimated band gap energies were in the range of 1.6 to 1.9 eV which are much lower than the reported values for nano hematite. From the room temperature magnetic hysteresis loop measurements, weak ferromagnetic behavior is observed in all undoped and Ca²⁺ doped hematite samples. Morin temperature (T(M)) is calculated to be 257 and 237 K for 1.45% doped samples with particle size 54 and 27 nm respectively. The sample with Ca content of 1.45 wt% when annealed at 400 °C showed that the particles were of different shapes which included both quasi spherical and rod shaped. On annealing the same sample at 600 °C, the nanorods collapsed to form bigger spherical and ellipsoidal particles.

Characterization of potential sources of magnetic anomalies within the crust in a tectonically active region: Amphibolites and migmatites from Potrillo Maar, New Mexico

NASA Technical Reports Server (NTRS)

Spear, F. S.; Padovanni, E.

1985-01-01

The purpose was to characterize the oxide mineralogy and petrology of samples collected from Potrillo Maar, New Mexico with the goal of explaining the magnetic anamoly that is observed over this region from remote sensing. Potrillo Maar is a diatreme that has brought rocks from all depths in the crust to the surface almost instantaneously. The samples are therefore thought to be representative of the crust as it exists today below this portion of the Rio Grande Rift. It is generally believed that oxide minerals (magnetite, hematite, etc.) are responsible for the magnetic signature of the crust. The samples from Portillo Maar therefore offer a unique opportunity to examine the magnetic mineralogy of the entire crust. The results indicate that the magnetic anamoly observed over Rio Grande Rift may be consequence of the tectonic activity that caused mylonitization of the rocks and allowed the infiltration of oxidizing fluids.

The different climatic response of pedogenic hematite and ferrimagnetic minerals: Evidence from particle-sized modern soils over the Chinese Loess Plateau

NASA Astrophysics Data System (ADS)

Gao, Xinbo; Hao, Qingzhen; Wang, Luo; Oldfield, Frank; Bloemendal, Jan; Deng, Chenglong; Song, Yang; Ge, Junyi; Wu, Haibin; Xu, Bing; Li, Fengjiang; Han, Long; Fu, Yu; Guo, Zhengtang

2018-01-01

In recent years, increasing interest in loess studies has focused on qualitative and quantitative paleoclimatic reconstruction using the imperfect antiferromagnetic mineral hematite. However, the linkage between the hematite formation and climatic variables remains controversial. Here we present the results of a comprehensive investigation of the magnetic properties and statistical analysis of a suite of clay and silt fractions of modern soil samples from 179 sites across the Chinese Loess Plateau (CLP) and adjacent regions. Our objective was to clarify the relationships between modern climatic variables and pedogenic hematite, as well as pedogenic ferrimagnetic minerals. First-order reversal curve measurements were also conducted on representative particle-sized subsamples from a N-S transect to understand the differences in magnetic mineralogy between the two fractions. Our results show that pipette extraction separates the fine-grained superparamagnetic (SP) and most of the single-domain (SD) magnetic grains into the clay fraction, and that the remaining silt fraction displays the magnetic properties of coarse pseudo-single domain (PSD) or a mixture of multidomain (MD)/PSD and a few SD particles. Only the pedogenic clay fraction shows a strong correlation with climatic variables. The application of redundancy analysis helps to distinguish the climate variables controlling the formation of ferrimagnetic minerals and hematite during pedogenesis. On the CLP, pedogenic ferrimagnetic minerals are sensitive to mean annual precipitation, while pedogenic hematite formation is preferentially dependent on mean annual temperature. The confirmation of the temperature-dependent nature of hematite on the CLP provides a new possibility for quantitatively reconstructing the paleotemperature history of Chinese loess/paleosol sequences.

The Different Climatic Response of Pedogenic Hematite and Ferrimagnetic Minerals: Evidence from Particle-Sized Modern Soils over the Chinese Loess Plateau

NASA Astrophysics Data System (ADS)

Gao, X.; Hao, Q.; Luo, W.; Oldfield, F.; Bloemendal, J.; Deng, C.; Song, Y.; Ge, J.; Wu, H.; Xu, B.; Li, F.; Han, L.; Fu, Y.; Guo, Z.

2017-12-01

In recent years, increasing interest in loess studies has focused on qualitative and quantitative paleoclimatic reconstruction using the imperfect antiferromagnetic mineral hematite. However, the linkage between the hematite formation and climatic variables remains controversial. Here we present the results of a comprehensive investigation of the magnetic properties and statistical analysis of a suite of clay and silt fractions of modern soil samples from 179 sites across the Chinese Loess Plateau (CLP) and adjacent regions. Our objective was to clarify the relationships between modern climatic variables and pedogenic hematite, as well as pedogenic ferrimagnetic minerals. First-order reversal curve measurements were also conducted on representative particle-sized subsamples from a N-S transect to understand the differences in magnetic mineralogy between the two fractions. Our results show that pipette extraction separates the fine-grained superparamagnetic (SP) and most of the single-domain (SD) magnetic grains into the clay fraction, and that the remaining silt fraction displays the magnetic properties of coarse pseudo-single domain (PSD) or a mixture of multidomain (MD)/PSD and a few SD particles. Only the pedogenic clay fraction shows a strong correlation with climatic variables. The application of redundancy analysis helps to distinguish the climate variables controlling the formation of ferrimagnetic minerals and hematite during pedogenesis. On the CLP, pedogenic ferrimagnetic minerals are sensitive to mean annual precipitation, while pedogenic hematite formation is preferentially dependent on mean annual temperature. The confirmation of the temperature-dependent nature of hematite on the CLP provides a new possibility for quantitatively reconstructing the paleotemperature history of Chinese loess/paleosol sequences.

Hematite Spherules in Basaltic Tephra Altered Under Aqueous, Acid-Sulfate Conditions on Mauna Kea Volcano, Hawaii: Possible Clues for the Occurrence of Hematite-Rich Spherules in the Burns Formation at Meridiani Planum, Mars

NASA Technical Reports Server (NTRS)

Morris, R. V.; Ming, D. W.; Graff, T. G.; Arvidson, R. E.; Bell, J. F., III; Squyres, S. W.; Mertzman, S. A.; Gruener, J. E.; Golden, D. C.; Robinson, G. A.

2005-01-01

Iron-rich spherules (>90% Fe2O3 from electron microprobe analyses) approx.10-100 microns in diameter are found within sulfate-rich rocks formed by aqueous, acid-sulfate alteration of basaltic tephra on Mauna Kea volcano, Hawaii. Although some spherules are nearly pure Fe, most have two concentric compositional zones, with the core having a higher Fe/Al ratio than the rim. Oxide totals less than 100% (93-99%) suggest structural H2O and/or /OH. The transmission Moessbauer spectrum of a spherule-rich separate is dominated by a hematite (alpha-Fe2O3) sextet whose peaks are skewed toward zero velocity. Skewing is consistent with Al(3+) for Fe(3+) substitution and structural H2O and/or /OH. The grey color of the spherules implies specular hematite. Whole-rock powder X-ray diffraction spectra are dominated by peaks from smectite and the hydroxy sulfate mineral natroalunite as alteration products and plagioclase feldspar that was present in the precursor basaltic tephra. Whether spherule formation proceeded directly from basaltic material in one event (dissolution of basaltic material and precipitation of hematite spherules) or whether spherule formation required more than one event (formation of Fe-bearing sulfate rock and subsequent hydrolysis to hematite) is not currently constrained. By analogy, a formation pathway for the hematite spherules in sulfate-rich outcrops at Meridiani Planum on Mars (the Burns formation) is aqueous alteration of basaltic precursor material under acid-sulfate conditions. Although hydrothermal conditions are present on Mauna Kea, such conditions may not be required for spherule formation on Mars if the time interval for hydrolysis at lower temperatures is sufficiently long.

Competitive sorption of carbonate and arsenic to hematite: combined ATR-FTIR and batch experiments.

PubMed

Brechbühl, Yves; Christl, Iso; Elzinga, Evert J; Kretzschmar, Ruben

2012-07-01

The competitive sorption of carbonate and arsenic to hematite was investigated in closed-system batch experiments. The experimental conditions covered a pH range of 3-7, arsenate concentrations of 3-300 μM, and arsenite concentrations of 3-200 μM. Dissolved carbonate concentrations were varied by fixing the CO(2) partial pressure at 0.39 (atmospheric), 10, or 100 hPa. Sorption data were modeled with a one-site three plane model considering carbonate and arsenate surface complexes derived from ATR-FTIR spectroscopy analyses. Macroscopic sorption data revealed that in the pH range 3-7, carbonate was a weak competitor for both arsenite and arsenate. The competitive effect of carbonate increased with increasing CO(2) partial pressure and decreasing arsenic concentrations. For arsenate, sorption was reduced by carbonate only at slightly acidic to neutral pH values, whereas arsenite sorption was decreased across the entire pH range. ATR-FTIR spectra indicated the predominant formation of bidentate binuclear inner-sphere surface complexes for both sorbed arsenate and sorbed carbonate. Surface complexation modeling based on the dominant arsenate and carbonate surface complexes indicated by ATR-FTIR and assuming inner-sphere complexation of arsenite successfully described the macroscopic sorption data. Our results imply that in natural arsenic-contaminated systems where iron oxide minerals are important sorbents, dissolved carbonate may increase aqueous arsenite concentrations, but will affect dissolved arsenate concentrations only at neutral to alkaline pH and at very high CO(2) partial pressures. Copyright © 2012 Elsevier Inc. All rights reserved.

In silico approach to investigating the adsorption mechanisms of short chain perfluorinated sulfonic acids and perfluorooctane sulfonic acid on hydrated hematite surface.

PubMed

Feng, Hongru; Lin, Yuan; Sun, Yuzhen; Cao, Huiming; Fu, Jianjie; Gao, Ke; Zhang, Aiqian

2017-05-01

Short chain perfluorinated sulfonic acids (PFSAs) that were introduced as alternatives for perfluorooctane sulfonic acid (PFOS) have been widely produced and used. However, few studies have investigated the environmental process of short chain PFSAs, and the related adsorption mechanisms still need to be uncovered. The water-oxide interface is one of the major environmental interfaces that plays an important role in affecting the adsorption behaviour and transport potential of the environmental pollutant. In this study, we performed molecular dynamics simulations and quantum chemistry calculations to investigate the adsorption mechanisms of five PFSAs and their adsorption on hydrated hematite surface as well. Different to the vertical configuration reported for PFOS on titanium oxide, all PFSAs share the same adsorption configuration as the long carbon chains parallel to the surface. The formation of hydrogen bonds between F and inter-surface H helps to stabilize the unique configuration. As a result, the sorption capacity increases with increasing C-F chain length. Moreover, both calculated adsorption energy and partial density of states (PDOS) analysis demonstrate a PFSAs adsorption mechanism in between physical and chemical adsorption because the hydrogen bonds formed by the overlap of F (p) orbital and H (s) orbital are weak intermolecular interactions while the physical adsorption are mainly ascribed to the electrostatic interactions. This massive calculation provides a new insight into the pollutant adsorption behaviour, and in particular, may help to evaluate the environmental influence of pollutants. Copyright © 2017. Published by Elsevier Ltd.

Glycine Polymerization on Oxide Minerals.

PubMed

Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

2017-06-01

It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

Copper(II) sorption onto goethite, hematite and lepidocrocite: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2004-06-01

We measured the adsorption of Cu(II) onto goethite (α-FeOOH), hematite (α-Fe 2O 3) and lepidocrocite (γ-FeOOH) from pH 2-7. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 complexes. These form inner-sphere complexes with the iron (hydr)oxide surfaces by corner-sharing with two or three edge-sharing Fe(O,OH) 6 polyhedra. Our interpretation of the EXAFS data is supported by ab initio (density functional theory) geometries of analogue Fe 2(OH) 2(H 2O) 8Cu(OH) 4and Fe 3(OH) 4(H 2O) 10Cu 2(OH) 6 clusters. We find no evidence for surface complexes resulting from either monodentate corner-sharing or bidentate edge-sharing between (CuO 4H n) n-6 and Fe(O,OH) 6 polyhedra. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed even though we are supersaturated with respect to CuO and Cu(OH) 2. Having identified the bidentate (FeOH) 2Cu(OH) 20 and tridentate (Fe 3O(OH) 2)Cu 2(OH) 30 surface complexes, we are able to fit the experimental copper(II) adsorption data to the reactions 3( FeOH)+2 Cu2++3 H2O=( Fe3O( OH) 2) Cu2( OH) 30+4 H+ and 2( FeOH)+ Cu2++2 H2O=( FeOH) 2Cu( OH) 20+2 H+. The two stability constants are similar for the three iron (hydr)oxide phases investigated.

Photoelectrochemical Performance of the Ag(III)-Based Oxygen-Evolving Catalyst.

PubMed

Sordello, Fabrizio; Ghibaudo, Manuel; Minero, Claudio

2017-07-19

We report the electrosynthesis of a water oxidation catalyst based on Ag oxides (AgCat). The deposited AgCat is composed of mixed valence crystalline Ag oxides with the presence of particle aggregates whose size is ∼1 μm. This catalyst, coupled with TiO 2 and hematite, and under photoelectrochemical conditions, substantially increases photocurrents in a wide range of applied potentials compared with bare and Co-Pi-modified photocatalysts. AgCat can sustain current densities comparable with other water oxidation catalysts. Dark bulk electrolysis demonstrated that AgCat is stable and can sustain high turnover number in operative conditions. Oxygen evolution from water occurs in mild conditions: pH = 2-13, room temperature and pressure, and moderate overpotentials (600 mV) compatible with the coupling with semiconducting oxides as sensitizers. Using hematite in sustained electrolysis O 2 production is significant, both in the dark and under irradiation, after an initial slow induction time in which modification of surface species occurs.

High Temperature and High Pressure Mixtures of Iron Oxides from the Impact Event at the Bee Bluff Crypto-Meteorite Impact Crater of South Texas

NASA Astrophysics Data System (ADS)

Graham, R. A.

2012-10-01

Disturbed geology within a several km diameter surface area of sedimentary Carrizo Sandstone near Uvalde, Texas, indicates the presence of a partially buried meteorite impact crater. Identification of its impact origin is supported by detailed studies but quartz grains recovered from distances of about100 km from the structure also show planar deformation features (PDFs). While PDFs are recognized as uniquely from impact processes, quantitative interpretation requires extension of Hugoniot materials models to more realistic grain-level, mixture models. Carrizo sandstone is a porous mixture of fine quartz and goethite. At impact pressures of tens of GPa, goethite separates into hematite and water vapor upon release of impact pressure. Samples from six different locations up to 50 km from the impact site preserve characteristic features resulting from mixtures of goethite, its water vapor, hematite and quartz. Spheroids resulting from local radial acceleration of mixed density, hot products are common at various sites. Local hydrodynamic instabilities cause similar effects.

A photoelectrochemical (PEC) study on graphene oxide based hematite thin films heterojunction (R-GO/Fe2O3)

NASA Astrophysics Data System (ADS)

Sharma, Poonam; Zachariah, Michael; Ehrman, Sheryl; Shrivastava, Rohit; Dass, Sahab; Satsangi, Vibha; Michael Zachariah, Sheryl Ehrman Collaboration; Rohit Shrivastava, Sahab Dass Collaboration; Vibha R Satsangi, Poonam Sharma Team

2013-03-01

Graphene has an excellent electronic conductivity, a high theoretical surface area of 2630 m2/g and excellent mechanical properties and, thus, is a promising component for high-performance electrode materials. Following this, GO has been used to modify the PEC response of photoactive material hematite thin films in PEC cell. A reduced graphene oxide/iron oxide (R-GO/Fe2O3) thin film structure has been successfully prepared on ITO by directly growing iron oxide particles on the thermally reduced graphene oxide sheets prepared from suspension of exfoliated graphene oxide. R-GO/Fe2O3 thin films were tested in PEC cell and offered ten times higher photocurrent density than pristine Fe2O3 thin film sample. XRD, SEM, EDS, UV-Vis, Mott-Schottky and Raman studies were carried out to study spectro-electrochemical properties. Enhanced PEC performance of these photoelectrodes was attributed to its porous morphology, improved conductivity upon favorable carrier transfer across the oxides interface.

Mars Hematite Site: Potential for Preservation of Microfossils

NASA Technical Reports Server (NTRS)

Allen, Carlton C.; Westall, Frances; Longazo, Teresa; Schelble, Rachel; Probst, Luke; Flood, Beverly

2003-01-01

Defining locations where conditions may have been favorable for life is a key objective for the exploration of Mars. Of prime importance are sites where conditions may have been favorable for the preservation of evidence of pre-biotic or biotic processes. Areas displaying significant concentrations of the mineral hematite (alpha-Fe2O3) have been identified from orbit by thermal emission spectrometry. The largest such deposit, in Sinus Meridiani, is a strong candidate landing site for one of the twin Mars Exploration Rovers, scheduled to launch in 2003. The Martian hematite site may have significance in the search for evidence of extraterrestrial life. Since iron oxides can form as aqueous mineral precipitates, the potential exists for preserving microscopic evidence of life in ecosystems that deposit iron oxides. Terrestrial hematite deposits proposed as possible analogs for the hematite sites on Mars include massive (banded) iron formations, iron oxide hydrothermal deposits, iron-rich laterites and ferricrete soils, and rock varnish. We are engaged in a systematic effort to document the evidence of life preserved in iron oxide deposits from each of these environments.

Evidence of synsedimentary microbial activity and iron deposition in ferruginous crusts of the Late Cenomanian Utrillas Formation (Iberian Basin, central Spain)

NASA Astrophysics Data System (ADS)

García-Hidalgo, José F.; Elorza, Javier; Gil-Gil, Javier; Herrero, José M.; Segura, Manuel

2018-02-01

Ferruginous sandstones and crusts are prominent sedimentary features throughout the continental (braided)-coastal siliciclastic (estuarine-tidal) wedges of the Late Cenomanian Utrillas Formation in the Iberian Basin. Crust types recognized are: Ferruginous sandy crusts (Fsc) with oxides-oxyhydroxides (hematite and goethite) concentrated on sandstone tops presenting a fibro-radial internal structure reminding organic structures that penetrate different mineral phases, suggesting the existence of bacterial activity in crust development; Ferruginous muddy crusts (Fmc) consisting of wavy, laminated, microbial mats, being composed mainly of hematite. On the other hand, a more dispersed and broader mineralization included as Ferruginous sandstones with iron oxides and oxyhydroxides (hematite and goethite) representing a limited cement phase on these sediments. The presence of microbial remains, ferruginous minerals, Microbially-induced sedimentary structures, microbial laminites and vertebrate tracks preserved due to the presence of biofilms suggest firstly a direct evidence of syn-depositional microbial activity in these sediments; and, secondly, that iron accumulation and ferruginous crusts development occurred immediately after deposition of the host, still soft sediments. Ferruginous crusts cap sedimentary cycles and they represent the gradual development of hard substrate conditions, and the development of a discontinuity surface at the top of the parasequence sets, related to very low sedimentary rates; the overlying sediments record subsequent flooding of underlying shallower environments; crusts are, consequently, interpreted as boundaries for these higher-order cycles in the Iberian Basin.

Formation of Hematite fine crystals by hydrothermal alteration of synthetic Martian basalt, static and fluid flow experiments

NASA Astrophysics Data System (ADS)

Kobayashi, K.; Isobe, H.

2011-12-01

Exploration made by Martian rovers and probes provided enormous information on the composition of the Martian surface materials. Origin and formation processes of the Martian surface materials should be various depending on topography and history of the Martian crust. Especially, iron minerals in the Martian soil should have essential role to characterize surface environment of the "red planet". In the present study, experimental reproduction of the Martian soil was carried out by hydrothermal alteration of the synthetic iron-rich basaltic rock. Experimental conditions for temperature and fluid composition followed Isobe and Yoshizawa (2010). Static alteration experiments are carried out at 100 °C and 150 °C, and mass ratio of the starting material to the pH1.0 sulfuric acid solution is 1:50. Run durations are 1, 2, 4 or 8 weeks. Appropriate mass of dry ice was sealed in the experimental vessels to expel atmospheric oxygen with CO2. For the static experiments, powdered starting materials were charged in PFA vial to keep textures of the run products. For the fluid flow experiments, we constructed closed loop with Teflon tube inclined approximately 45°. One of the vertical tube is charged with crushed synthetic basalt and heated approximately 150°C by aluminum block with ribbon heater. Surlfuric acid solution flows through the tube from bottom to top and cooled at the end of the aluminum block. Cooled solution returns to the bottom of the heated tube through another vertical tube without heating block. In the static condition run products, characteristic iron mineral particles are formed for 100°C and 150°C concordant with Isobe and Yoshizawa (2010). These iron minerals distributed not only inside the starting material powder but also on the surface of the reaction vessel and the PFA vial in the reactive solution. The surface of the reaction vessel shows orange and reddish color on 100°C and 150°C run products, respectively. By SEM observation, dissolution of melt and olivine grains were observed, and iron mineral particles substituted olivine partly. Diameters of the iron mineral particles are submicron to several micron meters at 100°C, and slowly increase with run durations and temperatures. In the fluid flow experiment, deposition of the characteristic iron minerals occur inside the heated tube. Distribution of iron minerals corresponds to temperature gradient and fluid flow direction. Iron minerals are partially covered by silica phase with submicron meters in thickness. The occurrence of the iron minerals in the run products of this study suggests that characteristic iron mineral fine particles including hematite and goethite were formed by acidic hydrothermal alteration of iron-rich basaltic rock even at remote region from the source materials.

Origin of Lamellar Magnetism (Invited)

NASA Astrophysics Data System (ADS)

McEnroe, S. A.; Robinson, P.; Fabian, K.; Harrison, R. J.

2010-12-01

The theory of lamellar magnetism arose through search for the origin of the strong and extremely stable remanent magnetization (MDF>100 mT) recorded in igneous and metamorphic rocks containing ilmenite with exsolution lamellae of hematite, or hematite with exsolution lamellae of ilmenite. Properties of rocks producing major remanent magnetic anomalies could not be explained by PM ilmenite or CAF hematite alone. Monte Carlo modeling of chemical and magnetic interactions in such intergrowths at high temperature indicated the presence of "contact layers" one cation layer thick at (001) interfaces of the two phases. Contact layers, with chemical composition different from layers in the adjacent phases, provide partial relief of ionic charge imbalance at interfaces, and can be common, not only in magnetic minerals. In rhombohedral Fe-Ti oxides, magnetic moments of 2 Fe2+Fe3+ contact layers (2 x 4.5µB) on both sides of a lamella, are balanced by the unbalanced magnetic moment of 1 Fe3+ hematite layer (1 x 5µB), to produce a net uncompensated ferrimagnetic "lamellar moment" of 4µB. Bulk lamellar moment is not proportional to the amount of magnetic oxide, but to the quantity of magnetically "in-phase" lamellar interfaces, with greater abundance and smaller thickness of lamellae, extending down to 1-2 nm. The proportion of "magnetically in-phase" lamellae relates to the orientation of (001) interfaces to the magnetizing field during exsolution, hence highest in samples with a strong lattice-preferred orientation of (001) parallel to the field during exsolution. The nature of contact layers, ~0.23 nm thick, with Fe2+Fe3+ charge ordering postulated by the Monte Carlo models, was confirmed by bond-valence and DFT calculations, and, their presence confirmed by Mössbauer measurements. Hysteresis experiments on hematite with nanoscale ilmenite at temperatures below 57 K, where ilmenite becomes AF, demonstrate magnetic exchange bias produced by strong coupling across phase interfaces. Interface coupling, with nominal magnetic moments perpendicular and parallel to (001), is facilitated by magnetic moments in hematite near interfaces that are a few degrees out of the (001) plane, proved by neutron diffraction experiments. When a ~b.y.-old sample, with a highly stable NRM, is ZF cooled below 57 K, it shows bimodal exchange bias, indicating the presence of two lamellar populations that are magnetically "out-of-phase", and incidentally proving the existence of lamellar magnetism. Lamellar magnetism may enhance the strength and stability of remanence in samples with magnetite or maghemite lamellae in pure hematite, or magnetite lamellae in ilmenite, where coarse magnetite or maghemite alone would be multi-domain. Here the "contact layers" should be a complex hybrid of 2/3-filled rhombohedral layers parallel to (001) and 3/4-filled cubic octahedral layers parallel to (111), with a common octahedral orientation confirmed by TEM observations. Here, because of different layer populations, the calculated lamellar moment may be higher than in the purely rhombohedral example.

Lead and Antimony Speciation in Shooting Range Soils: Molecular Scale Analysis, Temporal Trends and Mobility

DTIC Science & Technology

2017-11-20

35 Figure 25. Effects of saturation time on Pb concentrations as a function of soil type and column...36 Figure 26. Effects of saturation time on Sb concentrations as a function of soil type and column set (a...representation of the oxygen -terminated full layer termination surface of hematite ( ) (second octahedral layer and those beneath are not shown for clarity) ; (D

Highly mesoporous α-Fe2O3 nanostructures: preparation, characterization and improved photocatalytic performance towards Rhodamine B (RhB)

NASA Astrophysics Data System (ADS)

Bharathi, S.; Nataraj, D.; Mangalaraj, D.; Masuda, Y.; Senthil, K.; Yong, K.

2010-01-01

Single-crystalline porous hematite nanorods and spindle-like nanostructures were successfully synthesized by a low temperature reflux condensation method. Two different iron sources, namely, FeCl3·6H2O and Fe(NO3)3·9H2O, were hydrolyzed in the presence of urea to selectively prepare nanorods and spindle-like nanostructures. Initially, the akagenite phase was obtained by refluxing the precursor for 12 h and then the as-prepared akagenite nanostructures were transformed to porous hematite nanostructures upon calcination at 300 °C for 1 h. The shape and the aspect ratio of the 12 h refluxed sample was retained even after calcination and this shows the topotactic transformation of the nanostructure. TEM and HRTEM investigations have shown the porous nature of the prepared sample. Brunauer-Emmett-Teller and Barret-Joyner-Halenda measurements have shown a large surface area and distribution of mesopores in the nanorods sample. The photocatalytic activity of the prepared nanostructures towards RhB has reflected this variation in the pore size distribution and specific surface area, by showing a higher activity for the nanorods sample. Magnetic studies by VSM have shown a weak ferromagnetic behaviour in both the samples due to shape anisotropy.

Facile Synthesis of Ultrafine Hematite Nanowire Arrays in Mixed Water-Ethanol-Acetic Acid Solution for Enhanced Charge Transport and Separation.

PubMed

Wang, Jian; Wang, Menglong; Zhang, Tao; Wang, Zhiqiang; Guo, Penghui; Su, Jinzhan; Guo, Liejin

2018-04-18

Nanostructure engineering is of great significance for semiconductor electrode to achieve high photoelectrochemical performance. Herein, we report a novel strategy to fabricate ultrafine hematite (α-Fe 2 O 3 ) nanowire arrays in a mixed water-ethanol-acetic acid (WEA) solvent. To the best of our knowledge, this is the first report on direct growth of ultrafine (∼10 nm) α-Fe 2 O 3 nanowire arrays on fluorine-doped tin oxide substrates through solution-based fabrication process. The effect of WEA ratio on the morphology of nanowires has been systematically studied to understand the formation mechanism. Photoelectrochemical measurements were conducted on both Ti-treated α-Fe 2 O 3 nanowire and nanorod photoelectrodes. It reveals that α-Fe 2 O 3 nanowire electrode has higher photocurrent and charge separation efficiencies than nanorod electrode if the carrier concentration and space-charge carrier width are in the same order of magnitude. Normalized by electrochemically active surface area, the Ti-treated α-Fe 2 O 3 nanowire electrode obtains 6.4 times higher specific photocurrent density than nanorod electrode. This superiority of nanowires arises from the higher bulk and surface charge separation efficiencies, which could be partly attributed to reduced distance that holes must transfer to reach the semiconductor-liquid junction.

The nature of the Pt(111)/α -Fe2O3(0001) interfaces revealed by DFT calculations

NASA Astrophysics Data System (ADS)

Mahmoud, Agnes; Deleuze, Pierre-Marie; Dupont, Céline

2018-05-01

Density functional theory calculations are performed to give a thorough description of structural, energetic, and electronic properties of Pt(111)/α-Fe2O3(0001) systems by spin-polarized calculations, accounting for the on-site Coulomb interaction. Toward the better understanding of Pt(111)/α-Fe2O3(0001) interfaces, two terminations of α-Fe2O3(0001) surface, namely, the single Fe- and the O3-termination, are considered and coupled with the four possible (top, hcp, fcc, and bridge) sites on Pt(111). The effect of the strain on clean hematite surfaces due to the lattice mismatch between the substrate and the overlayer is included in the analysis. Among the possible adsorption configurations, bridge sites are unstable, while the most favorable configurations are the ones at hollow sites. The stability of the interfaces is not only influenced by the termination of the overlayer but also influenced by the degree of its structural relaxation and the relative position of the first layer of O atoms in hematite with respect to Pt. To elucidate the different nature of the two terminations of the overlayer on Pt, projected density of states and 3D charge density difference plots are also discussed.

Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

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

Taylor, S. D.; Becker, U.; Rosso, K. M.

This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed,more » such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis for experimental interrogation of this important process at mineral-water interfaces.« less

The Fe removal in pyrophyllite by physical method

NASA Astrophysics Data System (ADS)

Cho, Kanghee; Jo, Jiyu; Bak, GeonYeong; Choi, NagChoul; Park*, CheonYoung

2015-04-01

The presence of Fe in ingredient material such as limestone, borax and pyrophyllite can prevent their use mainly in the glass fiber manufacturing industry. The red to yellow pigmentation in pyrophyllite is mainly due to the associated oxides and sulfides of Fe such as hematite, pyrite, etc. The removal of Fe in the pyrophyllite was investigated using high frequency treatment and magnetic separation under various alumina grades in pyrophyllite. The hematite and pyrite were observed in the pyrophyllite from photomicrograph and XRD analysis results. On the decrease of Al2O3 content in pyrophyllite was showed that SiO2, Fe2O3 and TiO2 content were increased by XRF analysis. The high frequency treatment experiment for the pyrophyllite showed that the (1) pyrite phase was transformed hematite and magnetite, (2) mass loss of the sample by volatilization of included sulfur(S) in pyrite. The results of magnetic separation for treated sample by high frequency were identified that Fe removal percent were in the range of 97.6~98.8%. This study demonstrated that physical method (high frequency treatment and magnetic separation) was effective for the removal of Fe in pyrophyllite. This subject is supported by Korea Ministry of Environment(MOE) as "Advanced Technology Program for Environmental Industry".

Aqueous Alteration on Mars. Chapter 23

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Morris, Richard V.; Clark, Benton C.

2007-01-01

Aqueous alteration is the change in composition of a rock, produced in response to interactions with H2O-bearing ices, liquids, and vapors by chemical weathering. A variety of mineralogical and geochemical indicators for aqueous alteration on Mars have been identified by a combination of surface and orbital robotic missions, telescopic observations, characterization of Martian meteorites, and laboratory and terrestrial analog studies. Mineralogical indicators for aqueous alteration include goethite (lander), jarosite (lander), kieserite (orbiter), gypsum (orbiter) and other Fe-, Mg-, and Ca-sulfates (landers), halides (meteorites, lander), phyllosilicates (orbiter, meteorites), hematite and nanophase iron oxides (telescopic, orbiter, lander), and Fe-, Mg-, and Ca-carbonates (meteorites). Geochemical indicators (landers only) for aqueous alteration include Mg-, Ca-, and Fe-sulfates, halides, and secondary aluminosilicates such as smectite. Based upon these indicators, several styles of aqueous alteration have been suggested on Mars. Acid-sulfate weathering (e.g., formation of jarosite, gypsum, hematite, and goethite), may occur during (1) the oxidative weathering of ultramafic igneous rocks containing sulfides, (2) sulfuric acid weathering of basaltic materials, and (3) acid fog (i.e., vapors rich in H2SO4) weathering of basaltic or basaltic-derived materials. Near-neutral or alkaline alteration occurs when solutions with pH near or above 7 move through basaltic materials and form phases such as phyllosilicates and carbonates. Very low water:rock ratios appear to have been prominent at most of the sites visited by landed missions because there is very little alteration (leaching) of the original basaltic composition (i.e., the alteration is isochemical or in a closed hydrologic system). Most of the aqueous alteration appears to have occurred early in the history of the planet (3 to 4.5 billion years ago); however, minor aqueous alteration may be occurring at the surface even today (e.g., in thin films of water or by acid fog).

Chemical and Mineralogical Characterization of Acid-Sulfate Alteration of Basaltic Material on Mauna Kea Volcano, Hawaii: Jarosite and Hydrated Halloysite

NASA Technical Reports Server (NTRS)

Graff, Trevor G.; Morris, R. V.; Archilles C. N.; Agresti, D. G.; Ming, D. W.; Hamilton, J. C.; Mertzman, S. A.; Smith, J.

2012-01-01

Sulfates have been identified on the martian surface during robotic surface exploration and by orbital remote sensing. Measurements at Meridiani Planum (MP) by the Alpha-Particle X-ray Spectrometer (APXS) and Mossbauer (MB) instruments on the Mars Exploration Rover Opportunity document the presence of a ubiquitous sulfate-rich outcrop (20-40% SO3) that has jarosite as an anhydrous Fe3+-sulfate [1- 3]. The presence of jarosite implies a highly acidic (pH <3) formation environment [4]. Jarosite and other sulfate minerals, including kieserite, gypsum, and alunite have also been identified in several locations in orbital remote sensing data from the MEx OMEGA and MRO CRISM instruments [e.g. 5-8]. Acid sulfate weathering of basaltic materials is an obvious pathway for formation of sulfate-bearing phases on Mars [e.g. 4, 9, 10]. In order to constrain acid-sulfate pathways on Mars, we are studying the mineralogical and chemical manifestations of acid-sulfate alteration of basaltic compositions in terrestrial environments. We have previously shown that acidsulfate alteration of tephra under hydrothermal conditions on the Puu Poliahu cone (summit region of Mauna Kea volcano, Hawaii) resulted in jarosite and alunite as sulfate-bearing alteration products [11-14]. Other, more soluble, sulfates may have formed, but were leached away by rain and melting snow. Acidsulfate processes on Puu Poliahu also formed hematite spherules similar (except in size) to the hematite spherules observed at MP as an alteration product [14]. Phyllosilicates, usually smectite }minor kaolinite are also present as alteration products [13]. We discuss here an occurrence of acid-sulfate alteration on Mauna Kea Volcano (Hawaii). We report VNIR spectra (0.35-2.5 microns ASD spectrometer), Mossbauer spectra (MER-like ESPI backscatter spectrometer), powder XRD (PANalytical), and major element chemical compositions (XRF with LOI and Fe redox) for comparison to similar data acquired or to be acquired by MRO-CRISM and MEx OMEGA, MERMB, MSL-CheMin, and MER and MSL APXS, respectively.

Microbial Fossils Detected in Desert Varnish

NASA Technical Reports Server (NTRS)

Flood, B. E.; Allen, C.; Longazo, T.

2003-01-01

Mars Global Surveyor Thermal Emission Spectrometer data indicate regions with significant levels of hematite (_Fe2O3). Fe-oxides, like hematite, can form as aqueous mineral precipitates and as such may preserve microscopic fossils or other biosignatures. Several potential terrestrial analogues to martian hematite like hydrothermal vents have preserved microfossils. Microbial fossilization in Fe-oxides is often a function of biomineralization. For example, goethite (FeO2H) encrustation of fungal mycelia from the mid-Tertiary preserved fungal morphologies such that their genera could be determined.

Sorption specificity and desorption hysteresis of gibberellic acid on ferrihydrite compared to goethite, hematite, montmorillonite, and kaolinite.

PubMed

Zhang, Li; Liu, Fei; Chen, Liang

2017-08-01

The pesticide gibberellic acid (GA 3 ) is a potential endocrine disruptor and environmental toxin; therefore, research into its environmental fate is warranted. Batch studies were conducted to investigate the sorption and desorption characteristics of GA 3 on aquifer media. The results demonstrated special sorption characteristic of GA 3 on ferrihydrite compared to goethite, hematite, montmorillonite, and kaolinite, where the sorption kinetics of GA 3 on ferrihydrite was fitted well with the pseudo-second-order, Elovich, and intra-particle diffusion models. The sorption kinetics of GA 3 on ferrihydrite indicated an initial high sorption rate followed by a slow reaction process. The initial high GA 3 sorption rate may be related to electrostatic sorption and surface complexation reactions on the outer surfaces and at the macropore entrances of ferrihydrite. While the slow step was controlled by GA 3 diffusion into mesopore of ferrihydrite. Analysis of the desorption hysteresis indicated a high hysteresis index (HI) ranging from 0.68 to 17.32, and a low desorption percentage ranging from 18 to 48%. After sufficient desorption, the calculated maximum residual GA 3 quantity due to surface complexation reactions with the ferrihydrite coordinated unsaturated sites was 9.05 ± 0.12 mg g -1 . The calculated maximum quantity of GA 3 trapped within the mesopore was 16.23 ± 0.91 mg g -1 . Graphical Abstract Schematic overview of GA 3 sorption and desorption on five minerals in groundwater.

In vitro enzymatic reduction kinetics of mineral oxides by membrane fractions from Shewanella oneidensis MR-1

NASA Astrophysics Data System (ADS)

Ruebush, Shane S.; Icopini, Gary A.; Brantley, Susan L.; Tien, Ming

2006-01-01

This study documents the first example of in vitro solid-phase mineral oxide reduction by enzyme-containing membrane fractions. Previous in vitro studies have only reported the reduction of aqueous ions. Total membrane (TM) fractions from iron-grown cultures of Shewanella oneidensis MR-1 were isolated and shown to catalyze the reduction of goethite, hematite, birnessite, and ramsdellite/pyrolusite using formate. In contrast, nicotinamide adenine dinucleotide (NADH) and succinate cannot function as electron donors. The significant implications of observations related to this cell-free system are: (i) both iron and manganese mineral oxides are reduced by the TM fraction, but aqueous U(VI) is not; (ii) TM fractions from anaerobically grown, but not aerobically grown, cells can reduce the mineral oxides; (iii) electron shuttles and iron chelators are not needed for this in vitro reduction, documenting conclusively that reduction can occur by direct contact with the mineral oxide; (iv) electron shuttles and EDTA stimulate the in vitro Fe(III) reduction, documenting that exogenous molecules can enhance rates of enzymatic mineral reduction; and (v) multiple membrane components are involved in solid-phase oxide reduction. The membrane fractions, consisting of liposomes of cytoplasmic and outer membrane segments, contain at least 100 proteins including the enzyme that oxidizes formate, formate dehydrogenase. Mineral oxide reduction was inhibited by the addition of detergent Triton X-100, which solubilizes membranes and their associated proteins, consistent with the involvement of multiple electron carriers that are disrupted by detergent addition. In contrast, formate dehydrogenase activity was not inhibited by Triton X-100. The addition of anthraquinone-2,6-disulfonate (AQDS) and menaquinone-4 was unable to restore activity; however, menadione (MD) restored 33% of the activity. The addition of AQDS and MD to reactions without added detergent increased the rate of goethite reduction. The Michaelis-Menten Km values of 71 ± 22 m 2/L for hematite and 50 ± 16 m 2/L for goethite were calculated as a function of surface area of the two insoluble minerals. Vmax was determined to be 123 ± 14 and 156 ± 13 nmol Fe(II)/min/mg of TM protein for hematite and goethite, respectively. These values are consistent with in vivo rates of reduction reported in the literature. These observations are consistent with our conclusion that the enzymatic reduction of mineral oxides is an effective probe that will allow elucidation of molecular chemistry of the membrane-mineral interface where electron transfer occurs.

Trench Reveals Two Faces of Soils

NASA Technical Reports Server (NTRS)

2004-01-01

This approximate true-color image mosaic from the panoramic camera on the Mars Exploration Rover Opportunity shows a trench dug by the rover in the vicinity of the 'Anatolia' region. Two imprints from the rover's Mossbauer spectrometer instrument were left in the exposed soils. Detailed comparisons between soils exposed at the surface and those found at depth reveal that surface soils have higher levels of hematite while subsurface soils show fine particles derived from basalt. The trench is approximately 11 centimeters deep. This image was taken on sol 81 with the panoramic camera's 430-, 530- and 750-nanometer filters.

GIXAFS study of Fe3+ sorption and precipitation on natural quartz surfaces

USGS Publications Warehouse

Waychunas, G.; Davis, J.; Reitmeyer, R.

1999-01-01

Grazing-incidence EXAFS has been used to characterize the structure of Fe3+ sorbed onto natural single crystal quartz surfaces. Fe3+ sorption at ca. 5% monolayer coverage on a natural crystal allowed to equilibrate in air resulted in formation of hematite nuclei with strong texturing on r-and m-planes. EXAFS calculations suggests that both O and Fe backscattering is necessary to yield acceptable structural models, that about 50% of the sorbed iron resides in nuclei, and that the approximate dimensions of the nuclei can be estimated via Feff 7.0 calculations of various nuclei sizes and shapes.

Synthetic effect between iron oxide and sulfate mineral on the anaerobic transformation of organic substance.

PubMed

Chen, Tian-Hu; Wang, Jin; Zhou, Yue-Fei; Yue, Zheng-Bo; Xie, Qiao-Qin; Pan, Min

2014-01-01

Synthetic effect between sulfate minerals (gypsum) and iron oxide (hematite) on the anaerobic transformation of organic substance was investigated in the current study. The results showed that gypsum was completely decomposed while hematite was partially reduced. The mineral phase analysis results showed that FeS and CaCO3 was the major mineralization product. Methane generation process was inhibited and inorganic carbon contents in the precipitates were enhanced compared to the control without hematite and gypsum. The inorganic carbon content increased with the increasing of hematite dosages. Co-addition of sulfate minerals and iron oxide would have a potential application prospect in the carbon sequestration area and reduction of the greenhouse gas release. The results would also reveal the role of inorganic mineral in the global carbon cycle. Copyright © 2013 Elsevier Ltd. All rights reserved.

Photoelectrochemical water splitting with mesoporous hematite prepared by a solution-based colloidal approach.

PubMed

Sivula, Kevin; Zboril, Radek; Le Formal, Florian; Robert, Rosa; Weidenkaff, Anke; Tucek, Jiri; Frydrych, Jiri; Grätzel, Michael

2010-06-02

Sustainable hydrogen production through photoelectrochemical water splitting using hematite (alpha-Fe(2)O(3)) is a promising approach for the chemical storage of solar energy, but is complicated by the material's nonoptimal optoelectronic properties. Nanostructuring approaches have been shown to increase the performance of hematite, but the ideal nanostructure giving high efficiencies for all absorbed light wavelengths remains elusive. Here, we report for the first time mesoporous hematite photoelectodes prepared by a solution-based colloidal method which yield water-splitting photocurrents of 0.56 mA cm(-2) under standard conditions (AM 1.5G 100 mW cm(-2), 1.23 V vs reversible hydrogen electrode, RHE) and over 1.0 mA cm(-2) before the dark current onset (1.55 V vs RHE). The sintering temperature is found to increase the average particle size, and have a drastic effect on the photoactivity. X-ray photoelectron spectroscopy and magnetic measurements using a SQUID magnetometer link this effect to the diffusion and incorporation of dopant atoms from the transparent conducting substrate. In addition, examining the optical properties of the films reveals a considerable change in the absorption coefficient and onset properties, critical aspects for hematite as a solar energy converter, as a function of the sintering temperature. A detailed investigation into hematite's crystal structure using powder X-ray diffraction with Rietveld refinement to account for these effects correlates an increase in a C(3v)-type crystal lattice distortion to the improved optical properties.

The effect of precursor types on the magnetic properties of Y-type hexa-ferrite composite

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

Kim, Chin Mo; Na, Eunhye; Kim, Ingyu

2015-05-07

With magnetic composite including uniform magnetic particles, we expect to realize good high-frequency soft magnetic properties. We produced needle-like (α-FeOOH) nanoparticles with nearly uniform diameter and length of 20 and 500 nm. Zn-doped Y-type hexa-ferrite samples were prepared by solid state reaction method using the uniform goethite and non-uniform hematite (Fe{sub 2}O{sub 3}) with size of <1 μm, respectively. The micrographs observed by scanning electron microscopy show that more uniform hexagonal plates are observed in ZYG-sample (Zn-doped Y-type hexa-ferrite prepared with non-uniform hematite) than in ZYH-sample (Zn-doped Y-type hexa-ferrite prepared with uniform goethite). The permeability (μ′) and loss tangent (δ) atmore » 2 GHz are 2.31 and 0.07 in ZYG-sample and 2.0 and 0.07 in ZYH sample, respectively. We can observe that permeability and loss tangent are strongly related to the particle size and uniformity based on the nucleation, growth, and two magnetizing mechanisms: spin rotation and domain wall motion. The complex permeability spectra also can be numerically separated into spin rotational and domain wall resonance components.« less

Mineralogical and morphological constraints on the reduction of Fe(III) minerals by Geobacter sulfurreducens

NASA Astrophysics Data System (ADS)

Cutting, R. S.; Coker, V. S.; Fellowes, J. W.; Lloyd, J. R.; Vaughan, D. J.

2009-07-01

The biologically-mediated reduction of synthetic samples of the Fe(III)-bearing minerals hematite, goethite, lepidocrocite, feroxhyte, ford ferrihydrite, akaganeite and schwertmannite by Geobacter sulfurreducens has been investigated using microbiological techniques in conjunction with X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). This combination of approaches offers unique insights into the influence of subtle variations in the crystallinity of a given mineral on biogeochemical processes, and has highlighted the importance of (oxyhydr)oxide crystallite morphology in determining the changes occurring in a given mineral phase. Problems arising from normalising the biological Fe(III) reduction rates relative to the specific surface areas of the starting materials are also highlighted. These problems are caused primarily by particle aggregation, and compounded when using spectrophotometric assays to monitor reduction. For example, the initial rates of Fe(III) reduction observed for two synthetic feroxyhytes with different crystallinities (as shown by XRD and TEM studies) but almost identical surface areas, differ substantially. Both microbiological and high-resolution TEM studies show that hematite and goethite are susceptible to limited amounts of Fe(III) reduction, as evidenced by the accumulation of Fe(II) during incubation with G. sulfurreducens and the growth of nodular structures on crystalline goethite laths during incubation. Lepidocrocite and akaganeite readily transform into mixtures of magnetite and goethite, and XRD data indicate that the proportion of magnetite increases within the transformation products as the crystallinity of the starting material decreases. The presence of anthraquinone-2,6-disulfonate (AQDS) as an electron shuttle increases both the initial rate and longer term extent of biological Fe(III) reduction for all of the synthetic minerals examined. High-resolution XPS indicates subtle but measurable differences in the Fe(III):Fe(II) ratios at the mineral surfaces following extended incubation. For example, for a poorly crystalline schwertmannite, deconvolution of the Fe2p 3/2 peak suggests that the Fe(III):Fe(II) ratio of the near-surface regions varies from 1.0 in the starting material to 0.9 following 144 h of incubation with G.sulfurreducens, and to 0.75 following the same incubation period in the presence of 10 μM AQDS. These results have important implications for the biogeochemical cycling of iron.

Single-Cell Imaging and Spectroscopic Analyses of Cr(VI) Reduction on the Surface of Bacterial Cells

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

Wang, Yuanmin; Sevinc, Papatya C.; Belchik, Sara M.

2013-01-22

We investigate single-cell reduction of toxic Cr(VI) by the dissimilatory metal-reducing bacterium Shewanella oneidensis MR-1 (MR-1), an important bioremediation process, using Raman spectroscopy and scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDX). Our experiments indicate that the toxic and highly soluble Cr(VI) can be efficiently reduced to the less toxic and non-soluble Cr2O3 nanoparticles by MR-1. Cr2O3 is observed to emerge as nanoparticles adsorbed on the cell surface and its chemical nature is identified by EDX imaging and Raman spectroscopy. Co-localization of Cr2O3 and cytochromes by EDX imaging and Raman spectroscopy suggests a terminal reductase role for MR-1more » surface-exposed cytochromes MtrC and OmcA. Our experiments revealed that the cooperation of surface proteins OmcA and MtrC makes the reduction reaction most efficient, and the sequence of the reducing reactivity of the MR-1 is: wild type > single mutant @mtrC or mutant @omcA > double mutant (@omcA-@mtrC). Moreover, our results also suggest that the direct microbial Cr(VI) reduction and Fe(II) (hematite)-mediated Cr(VI) reduction mechanisms may co-exist in the reduction processes.« less

Iron Oxides of Mars: Evidence for Contemporary Weathering

NASA Technical Reports Server (NTRS)

Huguenin, R. L.

1985-01-01

Reflectance spectra of Mars were analyzed using a multiple high order derivative spectroscopy technique. Among the results of the analysis was the presence of suites of bands in each of the spectra that can be attributed to Fe(3e) phases. Several of the spectra contained bands that are very close to the band positions in the laboratory spectra of goethite, an hexagonal hydrated ferric oxide. Spectra of other areas showed absorption bands that were within 3% of the positions for hematite, and hexagonal close packed unhydrated Fe203. Remaining areas showed bands that are intermediate in position to the goethite and hematite bands, suggesting that there may be mixtures of goethite and hematite, and/or intermediate (partially dehydrated goethite) phases present in those areas. Both bright areas and dark areas showed suites of goethite bands and hematite bands, and there does not therefore appear to be a correlation with albedo. The areas that showed the goethite bands are, however, within zones of ongoing or historically frequent dust cloud activity, and the areas with the hematite bands were outside of the zones of frequent dust cloud activity. This suggests the possiblility that the more hydrated phase may occur within a mobile dust component.

Fluvial and Lacustrine Processes in Meridiani Planum and the Origin of the Hematite by Aqueous Alteration

NASA Technical Reports Server (NTRS)

Newsom, H. E.; Barber, C. A.; Schelble, R. T.; Hare, T. M.; Feldman, W. C.; Sutherland, V.; Livingston, A.; Lewis, K.

2003-01-01

The prime MER landing site in Meridiani Planum is located on layered materials, including hematite, whose origin as lacustrine or aeolian sediments, or volcanic materials is uncertain. Our detailed mapping of the region provides important constraints on the history of the region. Our mapping of the location of fluvial and lacustrine land forms in the region relative to the layered deposits provides new evidence of a long history of erosion and deposition as has long been noted . In addition, our detailed mapping of the southern boundary of the hematite deposit strongly supports an association between longlived fluvial channels and lacustrine basins and the strongest hematite signatures. This evidence supports an origin of the hematite deposits by interaction with water under ambient conditions in contrast to suggestions of hydrothermal processes due to volcanic or impact crater processes. An important part of the story is the evidence for the localization of the layered deposits due to topographic control induce by the presence of a large early basin we have identified that extends to the north-east of the landing site. Distribution of current channel networks, drainages,

Hematite Core Nanoparticles with Carbon Shell: Potential for Environmentally Friendly Production from Iron Mining Sludge

NASA Astrophysics Data System (ADS)

Stević, Dragana; Mihajlović, Dijana; Kukobat, Radovan; Hattori, Yoshiyuki; Sagisaka, Kento; Kaneko, Katsumi; Atlagić, Suzana Gotovac

2016-08-01

Hematite nanoparticles with amorphous, yet relatively uniform carbon shell, were produced based exclusively on the waste sludge from the iron mine as the raw material. The procedure for acid digestion-based purification of the sludge with the full recovery of acid vapors and the remaining non-toxic rubble is described. Synthesis of the hematite nanoparticles was performed by the arrested precipitation method with cationic surfactant. The particles were thoroughly characterized and the potential of their economical production for the battery industry is indicated.

Magnetic Properties of Iron Oxide Minerals in Atmospheric Dust and Source Sediments from Western US

NASA Astrophysics Data System (ADS)

Moskowitz, B. M.; Yauk, K.; Till, J. L.; Berquo, T. S.; Banerjee, S. K.; Reynolds, R. L.; Goldstein, H. L.

2011-12-01

Atmospheric dust contains iron oxide minerals that can play important roles in various physical and biological processes affecting atmospheric and surface temperatures, marine phytoplankton productivity, and human health. Iron oxide minerals in dust deposited on mountain snow cover are especially important because these minerals absorb solar and IR radiation leading to changes in albedo and affecting the timing and rate of spring and summer snowpack melting. As part of an ongoing project to study physical and chemical properties of dust from sources to sinks in the western US, we will describe one approach to characterize iron oxide mineralogy using magnetic property measurements and Mossbauer spectroscopy. Magnetic property measurements over a wide range of temperatures (2-300 K) and magnetic fields (0-5 T) are particularly sensitive to composition, particle size (from nanometer to micrometer), and concentration of iron oxide and oxyhydroxide minerals. The high sensitivity of magnetic measurements to target minerals allows the measurement of bulk samples preventing any aliasing of composition or grain size resulting from attempts at prior magnetic separation. In addition, different magnetic measurement protocols can isolate different particle-size assemblages and different compositions in multicomponent mixtures and help to identify dust-source areas. These techniques have been applied to dust deposited on snow (DOS) cover of the San Juan Mountains, Colorado (collected 2005-2010) and Wasatch Mountains, Utah (collected 2010) and possible dust-source sediments from the North American Great Basin and Colorado Plateau deserts. Results show that all samples contain a high coercivity phase consistent with hematite and/or goethite as the dominate ferric oxide mineral plus minor amounts of magnetite (<0.5 wt%). The presence of magnetite was determined from the detection of the characteristic Verwey transition (T=121 K) on low-temperature (< 300 K) remanence and susceptibility curves. Room temperature remanence parameters for the San Juan Mountains DOS fall into two discrete populations of hematite concentration ( x2 difference) but with similar spreads in magnetite concentrations (0.05-0.2%) within each group. Preliminary Mössbauer spectroscopy at 300 K for San Juan Mountains DOS indicates hematite as the sole magnetic phase with magnetite below the detection limits. However, spectra taken at 4.2 K show an increase in the hematite component and the appearance of goethite indicating superparamagnetism and nanoparticle size distribution for both phases. The lack of the Morin transition (T=263 K) for hematite on low-temperature remanence curves is also consistent with nanohematite as the main iron oxide phase in DOS from the San Juan Mountains.

Morphology evolution of single-crystalline hematite nanocrystals: magnetically recoverable nanocatalysts for enhanced facet-driven photoredox activity

NASA Astrophysics Data System (ADS)

Patra, Astam K.; Kundu, Sudipta K.; Bhaumik, Asim; Kim, Dukjoon

2015-12-01

We have developed a new green chemical approach for the shape-controlled synthesis of single-crystalline hematite nanocrystals in aqueous medium. FESEM, HRTEM and SAED techniques were used to determine the morphology and crystallographic orientations of each nanocrystal and its exposed facets. PXRD and HRTEM techniques revealed that the nanocrystals are single crystalline in nature; twins and stacking faults were not detected in these nanocrystals. The structural, vibrational, and electronic spectra of these nanocrystals were highly dependent on their shape. Different shaped hematite nanocrystals with distinct crystallographic planes have been synthesized under similar reaction conditions, which can be desired as a model for the purpose of properties comparison with the nanocrystals prepared under different reaction conditions. Here we investigated the photocatalytic performance of these different shaped-nanocrystals for methyl orange degradation in the presence of white light (λ > 420 nm). In this study, we found that the density of surface Fe3+ ions in particular facets was the key factor for the photocatalytic activity and was higher on the bitruncated-dodecahedron shape nanocrystals by coexposed {104}, {100} and {001} facets, attributing to higher catalytic activity. The catalytic activity of different exposed facet nanocrystals were as follows: {104} + {100} + {001} (bitruncated-dodecahedron) > {101} + {001} (bitruncated-octahedron) > {001} + {110} (nanorods) > {012} (nanocuboid) which provided the direct evidence of exposed facet-driven photocatalytic activity. The nanocrystals were easily recoverable using an external magnet and reused at least six times without significant loss of its catalytic activity.We have developed a new green chemical approach for the shape-controlled synthesis of single-crystalline hematite nanocrystals in aqueous medium. FESEM, HRTEM and SAED techniques were used to determine the morphology and crystallographic orientations of each nanocrystal and its exposed facets. PXRD and HRTEM techniques revealed that the nanocrystals are single crystalline in nature; twins and stacking faults were not detected in these nanocrystals. The structural, vibrational, and electronic spectra of these nanocrystals were highly dependent on their shape. Different shaped hematite nanocrystals with distinct crystallographic planes have been synthesized under similar reaction conditions, which can be desired as a model for the purpose of properties comparison with the nanocrystals prepared under different reaction conditions. Here we investigated the photocatalytic performance of these different shaped-nanocrystals for methyl orange degradation in the presence of white light (λ > 420 nm). In this study, we found that the density of surface Fe3+ ions in particular facets was the key factor for the photocatalytic activity and was higher on the bitruncated-dodecahedron shape nanocrystals by coexposed {104}, {100} and {001} facets, attributing to higher catalytic activity. The catalytic activity of different exposed facet nanocrystals were as follows: {104} + {100} + {001} (bitruncated-dodecahedron) > {101} + {001} (bitruncated-octahedron) > {001} + {110} (nanorods) > {012} (nanocuboid) which provided the direct evidence of exposed facet-driven photocatalytic activity. The nanocrystals were easily recoverable using an external magnet and reused at least six times without significant loss of its catalytic activity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06509g

The Role of Authigenic (pigment) Hematite in Controlling the Remanence, Rock Magnetic, and Magnetic Fabric Properties of Red Beds--If You Have Seen One Red Bed, You Certainly Have Not Seen Them All!

NASA Astrophysics Data System (ADS)

Geissman, J. W.

2014-12-01

Discussion continues on the relative role of authigenic (pigment) fine-grained hematite, relative to detrital, considerably coarser specular hematite (specularite) as a carrier of geologically meaningful remanence, as a determinant of rock magnetic properties, and as a contributor to magnetic fabrics in red beds. For one, many workers commonly assume that the laboratory unblocking temperature spectra (Tlub) of a red bed dominated by authigenic pigment does not reach the maximum Tlub as approximated by the Neel temperature (~948 K) because of the ultra fine grain size of the pigment. This issue was discussed as recently as the IRM Santa Fe meeting in late June, 2014. Many laboratories routinely utilize chemical demagnetization in concert with progressive thermal demagnetization to attempt to assess the relative role of pigment vs. detrital hematite. However, the utility of chemical demagnetization has been long challenged. In studying the anisotropy of magnetic susceptibility and remanence in red beds, recent work has considered separating the contributions of both types of hematite to the fabric signal. Three different red bed "types" (siltstones of the Triassic Chugwater Group, Gros Ventre Range, Wyoming; mudrocks of lowermost Triassic Quartermaster Formation, west Texas; and siltstones to medium sandstones of Upper Cretaceous age, northwest Vietnam) are used to evaluate the effects of varying contributions by pigment hematite to remanence, rock magnetic, and magnetic fabric properties. All rocks are well-characterized petrographically, so that the modal abundance of detrital oxides is known. The Chugwater siltstones are notable because of a relatively low Tlub spectra (below about 620o C), with no evidence of a low coercivity cubic phase. Rock magnetic and magnetic fabric properties are monitored as a function of progressive chemical demagnetization to further elucidate the role of hematite pigment in rocks that have contributed much to the paleomagnetic record of Earth.

Experimental Acid Weathering of Fe-Bearing Mars Analog Minerals and Rocks: Implications for Aqueous Origin of Hematite-Bearing Sediments in Meridiani Planum, Mars

NASA Technical Reports Server (NTRS)

Golden, D. C.; Koster, A. M.; Ming, D. W.; Morris, R. V.; Mertzman, S. A.

2011-01-01

A working hypothesis for Meridiani evaporite formation involves the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [1, 2]. However, there are no reported experimental studies for the formation of jarosite and gray hematite (spherules), which are characteristic of Meridiani rocks from Mars analog precursor minerals. A terrestrial analog for hematite spherule formation from basaltic rocks under acidic hydrothermal conditions has been reported [3], and we have previously shown that the hematite spherules and jarosite can be synthetically produced in the laboratory using Fe3+ -bearing sulfate brines under hydrothermal conditions [4]. Here we expand and extend these studies by reacting Mars analog minerals with sulfuric acid to form Meridiani-like rock-mineral compositions. The objective of this study is to provide environmental constraints on past aqueous weathering of basaltic materials on Mars.

Origins of chromite and magnetite in sedimentary rocks deposited in a shallow water environment in the 3.2 Ga Moodies Group, South Africa

NASA Astrophysics Data System (ADS)

Otake, T.; Sakamoto, Y.; Itoh, S.; Yurimoto, H.; Kakegawa, T.

2012-12-01

*Otake, T. totake@eng.hokudai.ac.jp Div. of Sustainable Resources Engineering, Hokkaido Univ., Sapporo, Japan Sakamoto, Y. yu.sakamoto12@gmail.com Dep. of Earth Science, Tohoku Univ., Sendai, Japan Itoh, S. sitoh@ep.sci.hokudai.ac.jp Dep. of Natural History Sciences, Hokkaido Univ., Sapporo, Japan Yurimoto. H. yuri@ep.sci.hokudai.ac.jp Dep. of Natural History Sciences, Hokkaido Univ., Sapporo, Japan Kakegawa, T. kakegawa@m.tohoku.ac.jp Dep. of Earth Science, Tohoku Univ., Sendai, Japan Geochemical data from ferruginous chemical sedimentary rocks (e.g., Banded Iron Formation: BIF) have been used to reconstruct the surface environments of early Earth. However, only a few studies have investigated the geochemical characteristics of BIFs deposited in a shallow water environment during the Archean, which may have differed from those deposited in a deep water environment. Therefore, we investigated geological, petrographic and geochemical characteristics of ferruginous rocks deposited in a shallow water environment in the Moodies group, in the Barberton Greenstone Belt, South Africa. We obtained ferruginous rock samples in the Moodies group from both an outcrop and underground gold mine, and compared the characteristics of these samples. The 70 sedimentary rock samples were divided into groups based on the dominant Fe minerals they contain: Hematite-rich jaspilite (HM group), Magnetite-rich iron formation/shale/sandstone (MT group), and Siderite-rich sandstone (SD group). Samples in the HM group are predominantly composed of fine-grained quartz (< 20 μm) and hematite (< 5 μm), which are interpreted to be chemical precipitates. Samples in the MT group contain quartz, magnetite, siderite, ankerite, chlorite, biotite and chromite. The grain size of magnetite is much larger (20-150 μm) than that of hematite in the HM group. The magnetite is interpreted as a secondary mineral transformed from hematite during early diagenesis. Results of in situ oxygen isotope analysis by SIMS showed that magnetite in the Moodies group has similar δ18O values to those in the least metamorphosed BIFs. All chromite observed in the MT group is overgrown by magnetite. Samples in the SD group contain quartz, siderite, chlorite, biotite, and chromite; the chromite is included in Mg-rich siderite or silicate minerals (e.g., chlorite and biotite). Oxygen isotope compositions indicate that chromite in both the MT and SD groups, was hydrothermally altered. Results of geochemical analyses of the bulk outcrop samples showed that FeTotal/Ti and Cr/Ti ratios of outcrop samples increase concordantly in the ferruginous zone, particularly in the MT group. The Cr/Ti ratios of the underground samples also increase with increasing the Fetotal/Ti ratios. On the other hand, Th/U ratios of both the outcrop and underground samples decrease with increasing FeTotal/Ti ratios. The correlations of Fetotal/Ti ratios with U/Th and Cr/Ti ratios indicate that dissolved Cr and U species in the ocean were coprecipitated with ferric (hydr)oxides during the formation of ferruginous rocks of the Moodies Group. These results suggest that Cr and U were chemically mobile, possibly as oxidized species, in the Earth's surface environment at ~3.2 Ga.

Hole localization in Fe2O3 from density functional theory and wave-function-based methods

NASA Astrophysics Data System (ADS)

Ansari, Narjes; Ulman, Kanchan; Camellone, Matteo Farnesi; Seriani, Nicola; Gebauer, Ralph; Piccinin, Simone

2017-08-01

Hematite (α -Fe2O3 ) is a promising photocatalyst material for water splitting, where photoinduced holes lead to the oxidation of water and the release of molecular oxygen. In this work, we investigate the properties of holes in hematite using density functional theory (DFT) calculations with hybrid functionals. We find that holes form small polarons and, depending on the fraction of exact exchange included in the PBE0 functional, the site where the holes localize changes from Fe to O. We find this result to be independent of the size and structure of the system: small Fe2O3 clusters with tetrahedral coordination, larger clusters with octahedral coordination, Fe2O3 (001) surfaces in contact with water, and bulk Fe2O3 display a very similar behavior in terms of hole localization as a function of the fraction of exact exchange. We then use wave-function-based methods such as coupled cluster with single and double excitations and Møller-Plesset second-order perturbation theory applied on a cluster model of Fe2O3 to shed light on which of the two solutions is correct. We find that these high-level quantum chemistry methods suggest holes in hematite are localized on oxygen atoms. We also explore the use of the DFT +U approach as a computationally convenient way to overcome the known limitations of generalized gradient approximation functionals and recover a gap in line with experiments and hole localization on oxygen in agreement with quantum chemistry methods.

A Hierarchical Z-Scheme α-Fe2 O3 /g-C3 N4 Hybrid for Enhanced Photocatalytic CO2 Reduction.

PubMed

Jiang, Zhifeng; Wan, Weiming; Li, Huaming; Yuan, Shouqi; Zhao, Huijun; Wong, Po Keung

2018-03-01

The challenge in the artificial photosynthesis of fossil resources from CO 2 by utilizing solar energy is to achieve stable photocatalysts with effective CO 2 adsorption capacity and high charge-separation efficiency. A hierarchical direct Z-scheme system consisting of urchin-like hematite and carbon nitride provides an enhanced photocatalytic activity of reduction of CO 2 to CO, yielding a CO evolution rate of 27.2 µmol g -1 h -1 without cocatalyst and sacrifice reagent, which is >2.2 times higher than that produced by g-C 3 N 4 alone (10.3 µmol g -1 h -1 ). The enhanced photocatalytic activity of the Z-scheme hybrid material can be ascribed to its unique characteristics to accelerate the reduction process, including: (i) 3D hierarchical structure of urchin-like hematite and preferable basic sites which promotes the CO 2 adsorption, and (ii) the unique Z-scheme feature efficiently promotes the separation of the electron-hole pairs and enhances the reducibility of electrons in the conduction band of the g-C 3 N 4 . The origin of such an obvious advantage of the hierarchical Z-scheme is not only explained based on the experimental data but also investigated by modeling CO 2 adsorption and CO adsorption on the three different atomic-scale surfaces via density functional theory calculation. The study creates new opportunities for hierarchical hematite and other metal-oxide-based Z-scheme system for solar fuel generation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance Optimization of Metallic Iron and Iron Oxide Nanomaterials for Treatment of Impaired Water Supplies

NASA Astrophysics Data System (ADS)

Xie, Yang

Iron nanomaterials including nanoscale zero valent iron (NZVI), NZVI-based bimetallic reductants (e.g., Pd/NZVI) and naturally occurring nanoscale iron mineral phases represent promising treatment tools for impaired water supplies. However, questions pertaining to fundamental and practical aspects of their reactivity may limit their performance during applications. For NZVI treatment of pollutant source zones, a major hurdle is its limited reactive lifetime. In Chapter 2, we report the longevity of NZVI towards 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA) and hexavalent chromium [Cr(VI)] in oxygen-free systems with various anionic co-solutes (e.g., Cl-, SO4 2-, ClO4-, HCO3 -, NO3-). Trends in longevity provide evidence that surface-associated Fe(II) species are responsible for Cr(VI) reduction, whereas 1,1,1,2-TeCA reduction depends on the accessibility of Fe(0) at the NZVI particle surface. In Chapter 3, we show that dithionite, previously utilized for in situ redox manipulation, can restore the reducing capacity of passivated NZVI treatment systems. Air oxidation of NZVI at pH ≥ 8 quickly exhausted reactivity despite a significant fraction of Fe(0) persisting in the particle core. Reduction of this passive layer by low dithionite concentrations restored suspension reactivity to levels of unaged NZVI, with multiple dithionite additions further improving pollutant removal. In Chapter 4, measurements of solvent kinetic isotope effects reveals that optimal Pd/NZVI reactivity results from accumulation of atomic hydrogen, which only occurs in NZVI-based systems due to their higher rates of corrosion. However, atomic hydrogen formation only occurs in aged Pd/NZVI suspensions for ˜2 weeks, after which any reactivity enhancement likely results from galvanic corrosion of Fe(0). Finally, the activity of hybrid nanostructures consisting of multi-walled carbon nanotubes decorated with of hematite nanoparticles (alphaFe 2O3/MWCNT) is explored in Chapter 5. Sorption of Cu(II) and Cr(VI) is enhanced in hybrid nanostructure systems beyond what would be expected from simple additive sorption capacities of their building blocks. The enhanced sorption capacity is in part derived from the greater surface area of hematite nanoparticles immobilized on MWCNTs relative to aggregated hematite suspensions. The hybrid alphaFe2O3/MWCNT may also exhibit unique surface chemistry, as supported by the tunable values of zeta potential measured as a function of the mass of alphaFe2O 3 deposited on the MWCNTs.

Prediction of iron oxide contents using diffuse reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Marques, José, Jr.; Arantes Camargo, Livia

2015-04-01

Determining soil iron oxides using conventional analysis is relatively unfeasible when large areas are mapped, with the aim of characterizing spatial variability. Diffuse reflectance spectroscopy (DRS) is rapid, less expensive, non-destructive and sometimes more accurate than conventional analysis. Furthermore, this technique allows the simultaneous characterization of many soil attributes with agronomic and environmental relevance. This study aims to assess the DRS capability to predict iron oxides content -hematite and goethite - , characterizing their spatial variability in soils of Brazil. Soil samples collected from an 800-hectare area were scanned in the visible and near-infrared spectral range. Moreover, chemometric calibration was obtained through partial least-squares regression (PLSR). Then, spatial distribution maps of the attributes were constructed using predicted values from calibrated models through geostatistical methods. The studied area presented soils with varied contents of iron oxides as examples for the Oxisols and Entisols. In the spectra of each soil is observed that the reflectance decreases with the content of iron oxides present in the soil. In soils with a high content of iron oxides can be observed more pronounced concavities between 380 and 1100 nm which are characteristic of the presence of these oxides. In soils with higher reflectance it were observed concavity characteristics due to the presence of kaolinite, in agreement with the low iron contents of those soils. The best accuracy of prediction models [residual prediction deviation (RPD) = 1.7] was obtained for goethite within the visible region (380-800 nm), and for hematite (RPD = 2.0) within the visible near infrared (380-2300 nm). The maps of goethite and hematite predicted showed the spatial distribution pattern similar to the maps of clay and iron extracted by dithionite-citrate-bicarbonate, being consistent with the iron oxide contents of soils present in the study area. These results confirm the value of DRS in the mapping of iron oxides in large areas at detailed scale.

Ferrihydrite Alteration to Magnetite, Maghemite and Hematite; Implications for Iron Oxides on Mars

NASA Technical Reports Server (NTRS)

Zent, A. P.; Bishop, J. L.; Mancinelli, R. L.; Olsen, M.; Wagner, P. A.

2000-01-01

Synthetic ferrihydrites have been altered to form magnetite, maghemite and hematite through low-temperature heating experiments (some with an organic reductant). Maghemite formed in this manner could become an indicator for Astrobiology on Mars.

Utah Marbles and Mars Blueberries: Comparitive Terrestrial Analogs for Hematite Concretions on Mars

NASA Astrophysics Data System (ADS)

Chan, M. A.; Beitler, B.; Parry, W. T.; Ormö, J.; Komatsu, G.

2005-03-01

Compelling comparisons show why Utah iron oxide-cemented "marbles" are a good analog for Mars hematite "blueberries". Terrestrial examples offer valuable models for interpreting the diagenetic history and importance of water on Mars.

A~comprehensive parameterization of heterogeneous ice nucleation of dust surrogate: laboratory study with hematite particles and its application to atmospheric models

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Paukert, M.; Steinke, I.; Zhang, K.; Kulkarni, G.; Hoose, C.; Schnaiter, M.; Saathoff, H.; Möhler, O.

2014-06-01

A new heterogeneous ice nucleation parameterization that covers a~wide temperature range (-36 to -78 °C) is presented. Developing and testing such an ice nucleation parameterization, which is constrained through identical experimental conditions, is critical in order to accurately simulate the ice nucleation processes in cirrus clouds. The surface-scaled ice nucleation efficiencies of hematite particles, inferred by ns, were derived from AIDA (Aerosol Interaction and Dynamics in the Atmosphere) cloud chamber measurements under water subsaturated conditions that were realized by continuously changing temperature (T) and relative humidity with respect to ice (RHice) in the chamber. Our measurements showed several different pathways to nucleate ice depending on T and RHice conditions. For instance, almost T-independent freezing was observed at -60 °C < T < -50 °C, where RHice explicitly controlled ice nucleation efficiency, while both T and RHice played roles in other two T regimes: -78 °C < T < -60 °C and -50 °C < T < -36 °C. More specifically, observations at T colder than -60 °C revealed that higher RHice was necessary to maintain constant ns, whereas T may have played a significant role in ice nucleation at T warmer than -50 °C. We implemented new ns parameterizations into two cloud models to investigate its sensitivity and compare with the existing ice nucleation schemes towards simulating cirrus cloud properties. Our results show that the new AIDA-based parameterizations lead to an order of magnitude higher ice crystal concentrations and inhibition of homogeneous nucleation in colder temperature regions. Our cloud simulation results suggest that atmospheric dust particles that form ice nuclei at lower temperatures, below -36 °C, can potentially have stronger influence on cloud properties such as cloud longevity and initiation when compared to previous parameterizations.

A Comprehensive Parameterization of Heterogeneous Ice Nucleation of Dust Surrogate: Laboratory Study with Hematite Particles and Its Application to Atmospheric Models

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

Hiranuma, Naruki; Paukert, Marco; Steinke, Isabelle

2014-12-10

A new heterogeneous ice nucleation parameterization that covers a wide temperature range (-36 °C to -78 °C) is presented. Developing and testing such an ice nucleation parameterization, which is constrained through identical experimental conditions, is critical in order to accurately simulate the ice nucleation processes in cirrus clouds. The surface-scaled ice nucleation efficiencies of hematite particles, inferred by n s, were derived from AIDA (Aerosol Interaction and Dynamics in the Atmosphere) cloud chamber measurements under water subsaturated conditions that were realized by continuously changing temperature (T) and relative humidity with respect to ice (RH ice) in the chamber. Our measurementsmore » showed several different pathways to nucleate ice depending on T and RH ice conditions. For instance, almost independent freezing was observed at -60 °C < T < -50 °C, where RH ice explicitly controlled ice nucleation efficiency, while both T and RH ice played roles in other two T regimes: -78 °C < T < -60 °C and -50 °C < T < -36 °C. More specifically, observations at T colder than -60 °C revealed that higher RHice was necessary to maintain constant n s, whereas T may have played a significant role in ice nucleation at T warmer than -50 °C. We implemented new n s parameterizations into two cloud models to investigate its sensitivity and compare with the existing ice nucleation schemes towards simulating cirrus cloud properties. Our results show that the new AIDA-based parameterizations lead to an order of magnitude higher ice crystal concentrations and inhibition of homogeneous nucleation in colder temperature regions. Our cloud simulation results suggest that atmospheric dust particles that form ice nuclei at lower temperatures, below -36 °C, can potentially have stronger influence on cloud properties such as cloud longevity and initiation when compared to previous parameterizations.« less

Hydrothermal and Diagenetic Mineralization on Mars

NASA Astrophysics Data System (ADS)

Ehlmann, B. L.; Quinn, D. P.

2015-12-01

Predicted by geophysical modeling, the mineraolgic record of early Mars groundwater has only recently been discovered. First, rover exploration in sedimentary basins reveals diagenesis. At Meridiani, sandstone porosity is occluded by precipitation of secondary sulfates, hematite, and silica. Multiple alteration episodes are indicated by crystal vugs, disruption of preexisting textures by hematite concretions, and grain coatings (e.g. McLennan et al., 2005). At Gale crater, raised ridges in mudstones, interpreted to be early diagenetic features, are crossed by later-emplaced hydrated calcium sulfate veins (e.g. Grotzinger et al., 2014). Waters in Gale were likely circumneutral while jarosite mineralogy at Meridiani implies acidic waters. Second, systems of raised ridges at 100-m scale are observed from orbit in multiple Martian sedimentary rock units. An outstanding example is sulfate-bearing sediments exhumed at the northern margin of the Syrtis Major lavas (e.g. Quinn & Ehlmann, 2015). Polygonal and with no clearly preferred orientation, the ridges rise 5-30 m above the surrounding terrain. Parallel light-toned grooves with dark interiors (indicative of isopachous fills) and jarosite in ridge mineralogy point to mineralization by acidic waters. Third, some mineral assemblages observed from orbit represent the products of subsurface aqueous alteration at elevated temperatures (Ehlmann et al., 2011). These are globally distributed, exposed in scarps and by impact cratering. Mineral assemblages variously include (a) serpentine and carbonate; (b) prehnite and chlorite, and (c) zeolites. Collectively, these datasets indicate that groundwaters were spatially widespread on ancient Mars, contributing to the sustenance of lakes and to the alteration of bedrock to >1 km depths. While the Martian surface may have always been relatively inhospitable, a warmer, wetter subsurface provided a long-term potentially habitable environment. Key outstanding questions remaining include groundwater sources, their composition and compositional variability, and subsurface transport distances. Continued exploration of Mars, combined with studies of analogous bedrock mineralization on Earth, will advance understanding of environments with liquid water during Mars' first billion years.

Mapping iron oxides and the color of Australian soil using visible-near-infrared reflectance spectra

NASA Astrophysics Data System (ADS)

Viscarra Rossel, R. A.; Bui, E. N.; de Caritat, P.; McKenzie, N. J.

2010-12-01

Iron (Fe) oxide mineralogy in most Australian soils is poorly characterized, even though Fe oxides play an important role in soil function. Fe oxides reflect the conditions of pH, redox potential, moisture, and temperature in the soil environment. The strong pigmenting effect of Fe oxides gives most soils their color, which is largely a reflection of the soil's Fe mineralogy. Visible-near-infrared (vis-NIR) spectroscopy can be used to identify and measure the abundance of certain Fe oxides in soil, and the visible range can be used to derive tristimuli soil color information. The aims of this paper are (1) to measure the abundance of hematite and goethite in Australian soils from their vis-NIR spectra, (2) to compare these results to measurements of soil color, and (3) to describe the spatial variability of hematite, goethite, and soil color and map their distribution across Australia. We measured the spectra of 4606 surface soil samples from across Australia using a vis-NIR spectrometer with a wavelength range of 350-2500 nm. We determined the Fe oxide abundance for each sample using the diagnostic absorption features of hematite (near 880 nm) and goethite (near 920 nm) and derived a normalized iron oxide difference index (NIODI) to better discriminate between them. The NIODI was generalized across Australia with its spatial uncertainty using sequential indicator simulation, which resulted in a map of the probability of the occurrence of hematite and goethite. We also derived soil RGB color from the spectra and mapped its distribution and uncertainty across the country using sequential Gaussian simulations. The simulated RGB color values were made into a composite true color image and were also converted to Munsell hue, value, and chroma. These color maps were compared to the map of the NIODI, and both were used to interpret our results. The work presented here was validated by randomly splitting the data into training and test data sets, as well as by comparing our results to existing studies on the distribution of Fe oxides in Australian soils.

Dust Removal Target on 'Vera Rubin Ridge'

NASA Image and Video Library

2017-11-01

This image from the Mars Hand Lens Imager (MAHLI) camera on NASA's Curiosity Mars rover shows effects of using the rover's wire-bristled Dust Removal Tool (DRT) on a rock target called "Christmas Cove." The tool brushed an area about 2.5 inches (6 centimeters) across on Sept. 16, 2017, during the 1,118th Martian day, or sol of Curiosity's work on Mars. MAHLI took this image later the same sol. Both DRT and MAHLI are on the turret of tools at the end of Curiosity's arm. The site is partway up "Vera Rubin Ridge" on lower Mount Sharp, in an area where reconnaissance imaging with science filters revealed variability in indications of the mineral hematite. Removing dust from part of the Christmas Cove target was part of an experiment to check whether dust is subduing the apparent indications of hematite in some of the area's bedrock. The brushed area's purplish tint in this MAHLI image, accentuated even more when observed with science filters of the rover's Mast Camera, is characteristic of fine-grained hematite. Brushing of this target also exposed details in the fine layering and bright veins within the bedrock of this part of Vera Rubin Ridge. The image is oriented so that sunlight comes from upper left. Layers are lower (older) toward lower right. https://photojournal.jpl.nasa.gov/catalog/PIA22064

Reactivity of Iron Bearing Minerals and CO 2 Sequestration: A Multi-­Disciplinary and Experimental Approach

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

Schoonen, Martin A.

2014-12-22

The reactivity of sandstones was studied under conditions relevant to the injection of supercritical carbon dioxide in the context of carbon geosequestration. The emphasis of the study was on the reactivity of iron-­bearing minerals when exposed to supercritical CO 2 (scCO 2) and scCO 2 with commingled aqueous solutions containing H 2S and/or SO 2. Flow through and batch experiments were conducted. Results indicate that sandstones, irrespective of their mineralogy, are not reactive when exposed to pure scCO2 or scCO 2 with commingled aqueous solutions containing H 2S and/or SO 2 under conditions simulating the environment near the injection pointmore » (flow through experiments). However, sandstones are reactive under conditions simulating the edge of the injected CO 2 plume or ahead of the plume (batch experiments). Sandstones containing hematite (red sandstone) are particularly reactive. The composition of the reaction products is strongly dependent on the composition of the aqueous phase. The presence of dissolved sulfide leads to the conversion of hematite into pyrite and siderite. The relative amount of the pyrite and siderite is influenced by the ionic strength of the solution. Little reactivity is observed when sulfite is present in the aqueous phase. Sandstones without hematite (grey sandstones) show little reactivity regardless of the solution composition.« less

Mineralogical effects of an experimental forest fire on a goethite/ferrihydrite soil - an attempt to solve the presence of hematite and maghemite in topsoils in a temperate region

NASA Astrophysics Data System (ADS)

Nørnberg, Per; Vendelboe, Anders L.; Gunnlaugsson, Haraldur P.; Merrison, Jonathan P.; Finster, Kai; Jensen, Svend K.

2010-05-01

Isolated soil spots, a few square metres in size, as red as Munsell colour 10R ¾ are found in Denmark. These spots are well known as places that have been exposed to fire. However, a long-standing unresolved puzzle is the presence of extended areas with high iron content (8-40 %) where goethite and ferrihydrite are present in the topsoil along with hematite and maghemite. Hematite and particularly maghemite would normally not be expected to occur under the temperate humid Danish climate, but be interpreted as the result of high temperature as found in tropical areas or after forest fires. However, a body of evidence argues against these sites having been exposed to fire. In an attempt to get closer to an explanation of this iron mineralogy, an experimental forest fire was produced. The results showed a clear mineralogical zonation down to 10 cm depth. This was not observed at the natural sites, which contained a uniform mixture of goethite/ferrihydrite, hematite and maghemite down to 20 cm depth. The experimental forest fire furthermore left charcoal and ashes at the topsoil, produced high pH and decreased organic matter content, all of which is in contrast to the natural sites. Physical and chemical date as well as XRD, Mössbauer spectroscopic data and TEM micrographs from the sites will be presented. The conclusion from this work is that the mineralogy of these sites is not consistent with exposure to fire, but may rather result from long term transformation within a reducing environment, possibly involving microorganisms. References: Nørnberg, P., Vendelboe, A.L., Gunnlaugsson, H.P., Merrison, J.P., Finster, K., Jensen, S.K. 2009 Mineralogy after an experimental forest fire on Quaternary soil goethite, compared with a hematite, maghemite, goethite containing topsoil. Clay Minerals, 44, 239-247. Nørnberg, P., Gunnlaugsson, H.P., Merrison, J.P., Vendelboe, A.L. 2009: Salten Skov I: A Martian dust analogue. Planetary and Space Science, 57, 628-631. Nørnberg, P., Schwertmann, U., Stanjek, C.B., An¬dersen, T., Gunnlaugsson, H.P. 2004: Mineralogy of Quaternary iron oxide rich formations in Denmark.Clay Minerals, 39, 85-98.

Kinetics of homogeneous and surface-catalyzed mercury(II) reduction by iron(II)

USGS Publications Warehouse

Amirbahman, Aria; Kent, Douglas B.; Curtis, Gary P.; Marvin-DiPasquale, Mark C.

2013-01-01

Production of elemental mercury, Hg(0), via Hg(II) reduction is an important pathway that should be considered when studying Hg fate in environment. We conducted a kinetic study of abiotic homogeneous and surface-catalyzed Hg(0) production by Fe(II) under dark anoxic conditions. Hg(0) production rate, from initial 50 pM Hg(II) concentration, increased with increasing pH (5.5–8.1) and aqueous Fe(II) concentration (0.1–1 mM). The homogeneous rate was best described by the expression, rhom = khom [FeOH+] [Hg(OH)2]; khom = 7.19 × 10+3 L (mol min)−1. Compared to the homogeneous case, goethite (α-FeOOH) and hematite (α-Fe2O3) increased and γ-alumina (γ-Al2O3) decreased the Hg(0) production rate. Heterogeneous Hg(0) production rates were well described by a model incorporating equilibrium Fe(II) adsorption, rate-limited Hg(II) reduction by dissolved and adsorbed Fe(II), and rate-limited Hg(II) adsorption. Equilibrium Fe(II) adsorption was described using a surface complexation model calibrated with previously published experimental data. The Hg(0) production rate was well described by the expression rhet = khet [>SOFe(II)] [Hg(OH)2], where >SOFe(II) is the total adsorbed Fe(II) concentration; khet values were 5.36 × 10+3, 4.69 × 10+3, and 1.08 × 10+2 L (mol min)−1 for hematite, goethite, and γ-alumina, respectively. Hg(0) production coupled to reduction by Fe(II) may be an important process to consider in ecosystem Hg studies.

Migration behavior of naturally occurring radionuclides at the Nopal I uranium deposit, Chihuahua, Mexico

NASA Astrophysics Data System (ADS)

Prikryl, James D.; Pickett, David A.; Murphy, William M.; Pearcy, English C.

1997-04-01

Oxidation of pyrite at the Nopal I uranium deposit, Peña Blanca district, Chihuahua, Mexico has resulted in the formation of Fe-oxides/hydroxides. Anomalous U concentrations (i.e. several hundred to several thousand ppm) measured in goethite, hematite, and amorphous Fe-oxyhydroxides in a major fracture that crosscuts the deposit and the absence of U minerals in the fracture suggest that U was retained during secondary mineral growth or sorbed on mineral surfaces. Mobilization and transport of U away from the deposit is suggested by decreasing U concentrations in fracture-infilling materials and in goethite and hematite with distance from the deposit. Greater than unity {234U}/{238U} activity ratios measured in fracture-infilling materials indicate relatively recent ( < 1 Ma) U uptake from fluids that carried excess 234U. Systematic decreases in {234U}/{238U} activity ratios of fracture materials with distance from the deposit suggest a multistage mobilization process, such as remobilization of U from 234U-enriched infill minerals or differential or diminished transport of U-bearing solutions containing excess 234U.

Facet-controlled synthesis of polyhedral hematite/carbon composites with enhanced photoactivity

NASA Astrophysics Data System (ADS)

Hu, Xiaoyi; Han, Sancan; Zhu, Yufang

2018-06-01

Much effort has been made to develop the semiconductor photocatalysis, but it is still challenging to fabricate low-cost and high-activity photocatalysts. In this study, Hematite (α-Fe2O3) with three kinds of morphologies including dodecahedron, tetrakaidecahedron and hexagonal nanoplates have been synthesized without any organic reagents. The photocatalytic performance reveals that the dodecahedron with exposed {1 0 1} facets is superior to the hexagonal nanoplates with predominant exposure of {0 0 1} facets in the case of similar BET surface area. For further enhancement of photocatalytic activity, carbon layer was coated on dodecahedral α-Fe2O3 through the self-polymerization of dopamine and following pyrolysis at 400 °C under Ar flow. Compared with the pristine dodecahedral α-Fe2O3, the α-Fe2O3/C composites exhibit stronger visible absorption, lower photoexcited electron-hole pairs recombination rate and better photodegradation activity. The photocatalytic performance showed the degradation rate of α-Fe2O3-D/4.5C is nearly 6 times higher than pristine α-Fe2O3, which have great potential for photocatalysis applications.

Formation and decomposition of siderite for CO2 treatment

NASA Astrophysics Data System (ADS)

Y Mora, E.; Sarmiento, A.; Vera, E.; Drozd, V.; Durigyn, A.; Saxena, S.

2017-12-01

In this research work, we studied the conditions for formation and decomposition of siderite FeCO3 from hematite Fe2O3 along with carbon dioxide CO2 at suitable thermodynamic conditions. As reductant agents were used mixtures of two elements, metallic iron and graphite. Best levels of carbonation were found in mixtures with bigger amounts of metallic iron. It was demonstrated that CO2 capture capacity by hematite depends of temperature, CO2 pressure, and reaction time. Temperatures between 100 and 150°C, pressures between 10 and 30bar and reaction times between 1 and 4h were adjusted for analyse the carbonation behaviour; siderite formation was improved by increases of these three variables. There was no carbonation without water in the mixtures, due to kinetic limitations. CO2 capture capacity was calculated from Rietveld refinement results. Using vacuum system and Dielectric Barrier Discharge, DBD plasma, the siderite was decomposed at 300°C, and 320°C respectively. Techniques as X-ray diffraction, and surface area analysis were employed to study the material.

Composition of Meridiani Hematite-rich Spherules: A Mass-Balance Mixing-Model Approach

NASA Astrophysics Data System (ADS)

Jolliff, B. L.; Athena Science Team

2005-03-01

A mass-balance model using APXS data and microscopic images indicates that the composition of spherules ("blueberries"), found at the Meridiani site by the Mars Exploration Rover Opportunity and thought to be concretions, contain ~45-60 wt% hematite.

Environmental magnetism of intertrapean Deccan deposits: unravelling local paleoenvironmental during Phase 1 and 2

NASA Astrophysics Data System (ADS)

Font, Eric; Adatte, Thierry; Ponte, Jorge; Fantasia, Alicia; Mirão, José; Samant, Bandana; Mohabey, Dhananjay; Florindo, Fabio

2014-05-01

The Deccan phase 2 is a crucial period caracterized by the rapid eruptions of huge volume of continental flood basalts correlated in age to the mass extinction of the Cretaceous-Paleogene boundary. However, local to global paleonvironmental changes during the Deccan Phase 2 are still baddly known. Here we provide new environmental magnetic data coupled to scanning electron microscopy of intertrapean deposits from the Deccan Volcanic Province (India) in order to unravel local paleoenvironmental conditions during periods of volcanic quiescence in the aftermath of the Deccan Phase 1 and Phase 2. Our results show that the magnetic mineralogy of these lacustrine and fluvial sediments is composed by several populations of iron oxides and sulphur, with a large range of grain size, probably resulting from different source of magnetic carriers (aeolian, detrital and bio-chemical). The number of magnetic phases identified using unmixing Isothermal Remanence Magnetic techniques is significantly higher (2 to 4) in the Podgavan section equivalent to Phase 2 than in the other studied sections, interpreted to result from higher weathering rates (acidity) by correlation with index of chemical alteration. Detailed scanning electron microscopy analysis of the Podgavan section reveal a complex mineralogy constituted by detrital magnetite, spherical and framboidal magnetite, microsphere of silicon, pyrrhotite, sylvite, manganese oxides and sporangiospores. A peculiar interval observed in the middle part of the Podgavan section, and corresponding to a thin interval of organic-rich clay capped by a thin oxidized level of reddish clays, show the presence of calcite needles and very fine hematite pigment. Hematite pigment are systematically associated to voids and form structures comparable to the blueberry hematite formed on mars. The abrupt transition from organic-rich levels (reducing conditions) to red hematitic clays (oxidation) suggests drastic and abrupt paleoenvironmental changes and acid conditions during the Deccan Phase 2. Keywords: Deccan, lacustrine sediments, environmental magnetism, acid rain, climate, weathering, volcanism.

Simulation of soil iron oxide production via alteration of ferrihydrite confirms direct formation of maghemite and partially oxidized magnetite—Implication for magnetic enhancement models

NASA Astrophysics Data System (ADS)

Banerjee, S. K.; Smale, J.; Bilardello, D.; Feinberg, J. M.; Soltis, J. A.

2016-12-01

In spite of the empirical success of the correlation between rainfall and magnetic mineral enhancement in soils across China, Russia and elsewhere, a generally acceptable model of enhancement has eluded our community. Recent field and laboratory studies demonstrate the importance of both strongly magnetic (magnetite, maghemite) as well as weakly magnetic (goethite, hematite) nano-phase minerals forming in response to rainfall and temperature. In particular, the ferrihydrite -> (hydro) maghemite -> hematite pathway of Torrent et al. (2003, et seq.) and formation of magnetite or hematite from nano-goethite under reducing or oxidizing atmosphere by Till et al. (2014) are particularly instructive. Here we report ferrihydrite alteration in constant pH=6.8 at 90°C even without the presence of any strongly adsorbing organic ligand. Aging of an initially pure 2-line ferrihydrite over 4 hours, and freeze-drying the specimens to prevent further alteration, produces small amounts of a mixture of maghemite, hematite and a small amount of partially oxidized magnetite, as identified by its isotropic point, detected by cooling an SIRM imparted at 300K. The details of the precise pathways of initial, intermediate and final products and their relative amounts are difficult to estimate in mixtures, but in future experiments we will attempt to do just that. However, since both the strongly and weakly magnetic products were formed from the same ferrihydrite starting material, it may not be necessary to assume that magnetite -> maghemite, or maghemite -> hematite, or hematite -> magnetite are unique pathways for production of magnetic enhancement in soils. Instead, it appears that multiple, simultaneously active pathways may allow ferrihydrite to directly produce weakly and strongly magnetic iron oxides in soil at the same near normal pH.

Growth of p-type hematite by atomic layer deposition and its utilization for improved solar water splitting.

PubMed

Lin, Yongjing; Xu, Yang; Mayer, Matthew T; Simpson, Zachary I; McMahon, Gregory; Zhou, Sa; Wang, Dunwei

2012-03-28

Mg-doped hematite (α-Fe(2)O(3)) was synthesized by atomic layer deposition (ALD). The resulting material was identified as p-type with a hole concentration of ca. 1.7 × 10(15) cm(-3). When grown on n-type hematite, the p-type layer was found to create a built-in field that could be used to assist photoelectrochemical water splitting reactions. A nominal 200 mV turn-on voltage shift toward the cathodic direction was measured, which is comparable to what has been measured using water oxidation catalysts. This result suggests that it is possible to achieve desired energetics for solar water splitting directly on metal oxides through advanced material preparations. Similar approaches may be used to mitigate problems caused by energy mismatch between water redox potentials and the band edges of hematite and many other low-cost metal oxides, enabling practical solar water splitting as a means for solar energy storage.

Transformation products of submicron-sized aluminum-substituted magnetite: Color and reductant solubility

NASA Technical Reports Server (NTRS)

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

1991-01-01

Magnetite, when present as fine particles, is soluble in acid ammonium oxalate (pH equals 3). However, the commonly used extractant for free iron oxides (i.e., citrate dithionite-bicarbonate (CDB) is not very effective in dissolving magnetite in soils and geologic materials. Upon oxidation, magnetite transforms to maghemite; at elevated temperatures, maghemite inverts to hematite. This transformation causes a change in color from black to red and may affect the reductant solubility as well. The objectives here were to examine the color and reflectance spectral characteristics of products during the transformation of magnetite to maghemite to hematite and to study the effect of Al-substitution in magnetite on the above process. Reductant solubility of Al-substituted magnetite, maghemite, and hematite was also studied. In summary, the transformation of magnetite to maghemite was accompanied by a change in color from black to red because of the oxidation of Fe2(+) to Fe3(+). The phase change maghemite to hematite had a relatively minor effect on the color and the reflectance spectra.

Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites.

PubMed

Nedim Ay, Ahmet; Konuk, Deniz; Zümreoglu-Karan, Birgul

2011-02-03

A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules.

Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites

PubMed Central

2011-01-01

A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules. PMID:21711652

Fractography, fluidity, and tensile properties of aluminum/hematite particulate composites

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

Sharma, S.C.; Girish, B.M.; Kamath, R.

1999-06-01

This paper examines the effect of hematite (iron oxide) particles on the fluidity of the molten composite as well as the tensile properties and fracture behavior of the solidified as-cast aluminum composites. The percentage of hematite in the composite was varied from 1 to 7% in steps of 2% by weight. The vortex method was employed to prepare the composites. It followed from the results obtained that the ultimate tensile strength and Young`s modulus of the composite increased while the liquid fluidity and solid ductility decreased with the increase in hematite content in the composite specimens. The fluidity of themore » liquid was greater in a metal mold than in a sand mold, and it decreased with an increase in reinforcing particle size and increased with pouring temperature. The presence of the reinforcing particles altered the fracture behavior of the solid composites considerably. Final fracture of the composite occurred due to the propagation of cracks through the matrix between the reinforcing particles.« less

(U/Th)-He dating of Fe- and Mn-oxide minerals from the Buckskin-Rawhide detachment fault: a new method to determine timing of faulting and fluid flow

NASA Astrophysics Data System (ADS)

Evenson, N. S.; Reiners, P. W.; Spencer, J. E.

2012-12-01

The Buckskin-Rawhide-Harcuvar detachment fault is one of the largest and youngest extensional detachment faults on Earth. It is also associated with abundant deposits of specular hematite with less common Pb, Zn, Ag, Au, and Mn mineralization. Mineralization is thought to be the result of movement of basin brines along the active detachment and subsidiary normal faults, with circulation driven by the heat of the uplifted footwall rocks of the Harcuvar metamorphic core complex. (U/Th)-He dating of specular hematite from the Buckskin-Rawhide detachment system, and Mn oxide minerals from syn-extensional clastic sedimentary rocks directly above the detachment fault, yield ages primarily between 16-10 Ma. These ages are consistent with low-temperature apatite (U/Th)-He and fission track cooling ages from the Rawhide Mountains and other ranges along the detachment. This suggests that Fe and Mn mineralization occurred during a period of rapid footwall exhumation that was underway by ~16 Ma. Aliquots from four hematite samples from the eastern Rawhide Mountains yielded weighted mean ages of 12.1 ± 0.24 Ma, 12.8 ± 0.15 Ma, 13.1 ± 0.17 Ma, and 13.8 ± 0.20 Ma (all uncertainties as 2-sigma standard error). These ages are similar to apatite (U/Th)-He and fission track ages of nearby samples, and display a SW to NE-younging trend when projected parallel to the extension direction, consistent with findings from previous low-T thermochronology studies. Three hematite samples from the western Rawhide and Buckskin Mountains yield more dispersed ages than samples in the eastern part of the core complex. Published apatite fission-track and (U/Th)-He dates from the Rawhide and Buckskin Mountains fall between 16-10 Ma. These ages are interpreted to represent the timing of final tectonic exhumation and fault-driven fluid circulation along the detachment. Average ages for one hematite sample fall in this age range, but one other is younger (9.5 Ma) and another is substantially older (35 Ma). The older age age may indicate the presence of excess He in fluid inclusions. The younger age could indicate that hydrothermal circulation outlasted exhumation by several million years, or other unknown complications to the system. (U/Th)-He analysis of two samples of manganese oxides from the Artillery Mountains yielded weighted mean ages of 13.8 ± 0.20 and 8.12 ± 0.13 Ma. Both ages are consistent with the age of host strata, and suggest that these dates record near-surface mineralization that occurred shortly after the syn-extension host sandstone and conglomerate were deposited. Our results suggest that hematite and manganese oxide (U/Th)-He systems can provide information about the timing of faulting and related fluid flow/mineralization events. With further development in this and other localities, these systems have the potential to provide valuable insights that until now have been difficult or impossible to obtain by other methods.

Reconstructing Holocene hematite and goethite variations in the Indus Canyon to trace changes in the Asian monsoon system

NASA Astrophysics Data System (ADS)

Koehler, Cornelia; Clift, Peter; Pressling, Nicola; Limmer, David; Giosan, Liviu; Tabrez, Ali

2010-05-01

In order to study Holocene Asian monsoon variations, we reconstructed changes in chemical weathering by examining sediments from the Indus Canyon. During the late Holocene, the Asian monsoon system had periods of high and low intensities that influenced the civilisations living in its realm. For example, the demise of the Harappan civilisation has been linked to a weakened monsoon system around 4 ka. The sediments in the Indus Canyon, which originate from the River Indus and its Himalayan tributaries, provide an ideal, natural environmental archive of the South Asian monsoon system. In order to investigate the alternation between arid and humid monsoonal climatic conditions, variations are traced using the magnetic minerals hematite and goethite, which form under distinct environmental conditions: goethite is stable under humid conditions, whereas hematite forms from the dehydration of goethite under arid conditions. The two minerals are characterised and quantified using environmental magnetic measurements, as well as diffuse reflectance spectrometry. Combining both approaches will enable us to reconstruct variations in chemical weathering over time. Furthermore, because this is governed by temperature and the availability of moisture, our weathering record will allow us to understand monsoon variability during the Holocene and test whether summer rain intensity has been decreasing in SW Asia since 8 ka. In addition, the multi-component analysis of colour reflectance spectra identifies different mineral components including hematite/goethite, clay mineral mixtures, calcite and organics. We will present our results from the multi-sensor core logger equipped with a Minolta spectrometer, measuring both magnetic susceptibility and the optical properties of the split sediment cores. Initial results indicate the presence of hematite and goethite in the sediment. There is an increasing hematite content up the cores, indicating an aridification trend during the Holocene. The sediments are further analysed using the environmental magnetic proxies NRM, ARM and IRM to fully understand the mineral magnetic variations and to quantify hematite and goethite contributions. This work plays an integral part of a larger scale palaeoenvironmental project on Indus Canyon sediments.

Organics-bearing Clays from the Rio Tinto (spain): A Novel Analog for the Phyllosilicates Outcrops Seen By Omega-mex

NASA Astrophysics Data System (ADS)

Bonaccorsi, Rosalba

2007-12-01

The Rio Tinto (RT) is considered an important analog of Sinus Meridiani on Mars and an ideal model analog for a subsurface Martian setting [1]. The RT system comprises the upper sequence of an acid rock drainage system where weathered iron -rich rocks, overlain a massive-pyrite deposit. The RT analog site is ideal for testing on the preservation of organics in hematite-rich vs. phyllosilicates-rich environments [3]. It is suggested here that RT near-surface rocks, which embed pockets of Clays, represent also a potential new model analog for the phyllosilicates-rich outcrops seen by OMEGA-MEx on the surface of Mars [5]. Results from the analysis of cores drilled under the 2005 Robotic experiment of the MARTE project (Borehole#7 Site 607cm) [2-3] are presented in this paper. Primary mineral assemblages include hematite, goethite, and Phyllosilicates e.g.,smectite, kaolinite, as quantified by X-ray diffraction [4]. Organic carbon is at low concentration (<0.05%) beneath the soil horizon in most cores dominated by iron minerals but is considerably higher in Phyllosilicate-rich levels i.e., 0.2-0.3Wt% at 385 -550 cm-depth [2-3]. Phyllosilicate-rich terrains have been identified OMEGA/MEx in the Nili Fossae, Mawrth Valles and Candor Chasma regions [e.g., 5]. These outcrops are surrounded by hematite-rich deposits, which are potentially barren in organics [6]. The potential of phyllosilicates to preserve higher amounts of organics/ biosignatures is well known for several Earth environments as well as the RT near subsurface. This potential brings a relevant element for the selection of candidate sites for the MSL mission [e.g., 1]. References: [1]Fernandez-Remolar et al.,2005 EPSL, 240,149-167; [2]Stoker et al., 2007; [3] Bonaccorsi et al., 2007; [4] Sutter et al., 2007 in Astrobiology,MARTE Spec. Issue; [5] Bibring et al., 2006, Science 312, 400-404; [6] Sumner, 2004, JGR 109. Anknowlegments: NASA-Postdoctoral-Program/C.Stoker, B.Sutter, A.F Davila and the MARTE team for valuable suggestions.

New Constraints on the Deposition and Alteration History of Mt. Sharp in Gale Crater, Mars

NASA Astrophysics Data System (ADS)

Rice, M. S.; Horgan, B. H. N.; Fraeman, A.; Ackiss, S. E.

2015-12-01

The Mars Science Laboratory (MSL) rover is currently investigating the lower stratigraphy of northwestern Mt. Sharp, the 5 km thick stack of layered rock that makes up the central mound of Gale Crater. Previous near-infrared spectral investigations from orbit using CRISM have shown that this portion of the mound exhibits a diverse mineralogy that may indicate changing aqueous environments on early Mars. The relationship of these mineralogic units to stratigraphic units across the full extent of Mt. Sharp is not well understood, although such relationships are key to interpreting the depositional and digenetic history. Here we present new mineral maps derived from CRISM data, as well as detailed stratigraphic columns from around the mound, and we use these new results to constrain hypotheses for the modes of aqueous alteration. Our new CRISM mineral maps are projected and co-registered to HiRISE imagery and DEMs, and include Fe/Mg-smectites, poly- and mono-hydrated sulfates, iron oxides, high-Ca pyroxene, and a ferrous phase with a strong red spectral slope between 1.1-1.8 μm, which is consistent with ferrous alteration phases like ferrous clays. This latter unit consistently overlies Fe/Mg-smectites in NW and SW Mt. Sharp, and is located in topographic benches that are either immediately stratigaphically above hematite-bearing ridges. The presence of ferrous alteration phases supports previous interpretations that hematite formed when an Fe2+-bearing fluid encountered an oxidizing environment. In this scenario, the reducing fluids were created by long-term oxygen limited alteration of Fe-bearing minerals in the near-surface. Downward movement of these fluids may have been limited by the underlying clay layer, forcing lateral flow. On emergence at the surface, the iron was oxidized by photochemical or other redox reactions. On Earth, similar pedogenic processes form hematite ironpans on slopes surrounding poorly-drained hilltops, as well as ancient banded iron formations in shallow coastal waters. The reducing environment inferred from the ferrous phases could be a site of high organic preservation potential, and the redox gradient inferred from the ferric/ferrous mineral relationship could have served as an energy source for chemolithotrophic microbes.

Temperature-Sensitive Coating Sensor Based on Hematite

NASA Technical Reports Server (NTRS)

Bencic, Timothy J.

2011-01-01

A temperature-sensitive coating, based on hematite (iron III oxide), has been developed to measure surface temperature using spectral techniques. The hematite powder is added to a binder that allows the mixture to be painted on the surface of a test specimen. The coating dynamically changes its relative spectral makeup or color with changes in temperature. The color changes from a reddish-brown appearance at room temperature (25 C) to a black-gray appearance at temperatures around 600 C. The color change is reversible and repeatable with temperature cycling from low to high and back to low temperatures. Detection of the spectral changes can be recorded by different sensors, including spectrometers, photodiodes, and cameras. Using a-priori information obtained through calibration experiments in known thermal environments, the color change can then be calibrated to yield accurate quantitative temperature information. Temperature information can be obtained at a point, or over an entire surface, depending on the type of equipment used for data acquisition. Because this innovation uses spectrophotometry principles of operation, rather than the current methods, which use photoluminescence principles, white light can be used for illumination rather than high-intensity short wavelength excitation. The generation of high-intensity white (or potentially filtered long wavelength light) is much easier, and is used more prevalently for photography and video technologies. In outdoor tests, the Sun can be used for short durations as an illumination source as long as the amplitude remains relatively constant. The reflected light is also much higher in intensity than the emitted light from the inefficient current methods. Having a much brighter surface allows a wider array of detection schemes and devices. Because color change is the principle of operation, the development of high-quality, lower-cost digital cameras can be used for detection, as opposed to the high-cost imagers needed for intensity measurements with the current methods. Alternative methods of detection are possible to increase the measurement sensitivity. For example, a monochrome camera can be used with an appropriate filter and a radiometric measurement of normalized intensity change that is proportional to the change coating temperature. Using different spectral regions yields different sensitivities and calibration curves for converting intensity change to temperature units. Alternatively, using a color camera, a ratio of the standard red, green, and blue outputs can be used as a self-referenced change. The blue region (less than 500 nm) does not change nearly as much as the red region (greater than 575 nm), so a ratio of color intensities will yield a calibrated temperature image. The new temperature sensor coating is easy to apply, is inexpensive, can contour complex shape surfaces, and can be a global surface measurement system based on spectrophotometry. The color change, or relative intensity change, at different colors makes the optical detection under white light illumination, and associated interpretation, much easier to measure and interpret than in the detection systems of the current methods.

Study of iron oxide nanoparticles in soil for remediation of arsenic

NASA Astrophysics Data System (ADS)

Shipley, Heather J.; Engates, Karen E.; Guettner, Allison M.

2011-06-01

There is a growing interest in the use of nanoparticles for environmental applications due to their unique physical and chemical properties. One possible application is the removal of contaminants from water. In this study, the use of iron oxide nanoparticles (19.3 nm magnetite and 37.0 nm hematite) were examined to remove arsenate and arsenite through column studies. The columns contained 1.5 or 15 wt% iron oxide nanoparticles and soil. Arsenic experiments were conducted with 1.5 wt% iron oxides at 1.5 and 6 mL/h with initial arsenate and arsenite concentrations of 100 μg/L. Arsenic release occurred after 400 PV, and 100% release was reached. A long-term study was conducted with 15 wt% magnetite nanoparticles in soil at 0.3 mL/h with an initial arsenate concentration of 100 μg/L. A negligible arsenate concentration occurred for 3559.6 pore volumes (PVs) (132.1 d). Eventually, the arsenate concentration reached about 20% after 9884.1 PV (207.9 d). A retardation factor of about 6742 was calculated indicating strong adsorption of arsenic to the magnetite nanoparticles in the column. Also, increased adsorption was observed after flow interruption. Other experiments showed that arsenic and 12 other metals (V, Cr, Co, Mn, Se, Mo, Cd, Pb, Sb, Tl, Th, U) could be simultaneously removed by the iron oxide nanoparticles in soil. Effluent concentrations were less than 10% for six out of the 12 metals. Desorption experiment showed partial irreversible sorption of arsenic to the iron oxide nanoparticle surface. Strong adsorption, large retardation factor, and resistant desorption suggest that magnetite and hematite nanoparticles have the potential to be used to remove arsenic in sandy soil possibly through in situ techniques.

Chemistry and Mineralogy of Martian Soils from In-Situ Analyses

NASA Astrophysics Data System (ADS)

Yen, A. S.

2017-12-01

In-situ analyses of typical martian soils by the Spirit, Opportunity and Curiosity rovers have shown remarkable planet-scale similarities in composition. The Alpha Particle X-ray Spectrometer data indicate that fine-grained, basaltic soils analyzed at Gusev Crater, Meridiani Planum and Gale Crater are nearly identical when cross-calibration uncertainties between the individual instruments are considered. Martian soils generally exhibit correlated increases in S, Cl and Zn with finer grain sizes, balanced by decreasing Si and Al from the feldspar component. The trends in S, Cl and Zn are consistent with condensates of volcanic exhalations and indicate minimal aqueous alteration of the soil samples after the accumulation of the volcanic volatiles. The mineralogy established by the CheMin X-ray diffractometer on the Curiosity rover show that soils are dominated by plagioclase feldspar, pyroxenes, olivine, and amorphous material. Minor phases include hematite, magnetite and anhydrite. These results are consistent with the Mössbauer spectrometer data from Spirit and Opportunity which indicate that the iron is contained in olivine, pyroxene, hematite, magnetite, and a nanophase ferric iron oxide/hydroxide. With the exception of the nanophase/amorphous component, typical martian soils are fundamentally basaltic in nature and remain relatively unaltered. Variations from typical basaltic soils have also been observed: Local contributions to the soil are evident in a number of samples which contain characteristic chemical signatures of nearby rocks. Larger sand grains on surfaces of aeolian bedforms have distinct compositions consistent with greater proportions of olivine, and in some cases, magnetite. Extensively altered fine-grained deposits dominated by sulfates and silica at Gusev Crater are distinct from basaltic soils and are consistent with fumarolic origins.

Synthesis of α-Fe2O3 and Fe-Mn Oxide Foams with Highly Tunable Magnetic Properties by the Replication Method from Polyurethane Templates

PubMed Central

Feng, Yuping; Fornell, Jordina; Zhang, Huiyan; Solsona, Pau; Barό, Maria Dolors; Suriñach, Santiago; Sort, Jordi

2018-01-01

Open cell foams consisting of Fe and Fe-Mn oxides are prepared from metallic Fe and Mn powder precursors by the replication method using porous polyurethane (PU) templates. First, reticulated PU templates are coated by slurry impregnation. The templates are then thermally removed at 260 °C and the debinded powders are sintered at 1000 °C under N2 atmosphere. The morphology, structure, and magnetic properties are studied by scanning electron microscopy, X-ray diffraction and vibrating sample magnetometry, respectively. The obtained Fe and Fe-Mn oxide foams possess both high surface area and homogeneous open-cell structure. Hematite (α-Fe2O3) foams are obtained from the metallic iron slurry independently of the N2 flow. In contrast, the microstructure of the FeMn-based oxide foams can be tailored by adjusting the N2 flow. While the main phases for a N2 flow rate of 180 L/h are α-Fe2O3 and FeMnO3, the predominant phase for high N2 flow rates (e.g., 650 L/h) is Fe2MnO4. Accordingly, a linear magnetization versus field behavior is observed for the hematite foams, while clear hysteresis loops are obtained for the Fe2MnO4 foams. Actually, the saturation magnetization of the foams containing Mn increases from 5 emu/g to 52 emu/g when the N2 flow rate (i.e., the amount of Fe2MnO4) is increased. The obtained foams are appealing for a wide range of applications, such as electromagnetic absorbers, catalysts supports, thermal and acoustic insulation systems or wirelessly magnetically-guided porous objects in fluids. PMID:29439450

Synthesis of α-Fe₂O₃ and Fe-Mn Oxide Foams with Highly Tunable Magnetic Properties by the Replication Method from Polyurethane Templates.

PubMed

Feng, Yuping; Fornell, Jordina; Zhang, Huiyan; Solsona, Pau; Barό, Maria Dolors; Suriñach, Santiago; Pellicer, Eva; Sort, Jordi

2018-02-11

Open cell foams consisting of Fe and Fe-Mn oxides are prepared from metallic Fe and Mn powder precursors by the replication method using porous polyurethane (PU) templates. First, reticulated PU templates are coated by slurry impregnation. The templates are then thermally removed at 260 °C and the debinded powders are sintered at 1000 °C under N₂ atmosphere. The morphology, structure, and magnetic properties are studied by scanning electron microscopy, X-ray diffraction and vibrating sample magnetometry, respectively. The obtained Fe and Fe-Mn oxide foams possess both high surface area and homogeneous open-cell structure. Hematite (α-Fe₂O₃) foams are obtained from the metallic iron slurry independently of the N₂ flow. In contrast, the microstructure of the FeMn-based oxide foams can be tailored by adjusting the N₂ flow. While the main phases for a N₂ flow rate of 180 L/h are α-Fe₂O₃ and FeMnO₃, the predominant phase for high N₂ flow rates (e.g., 650 L/h) is Fe₂MnO₄. Accordingly, a linear magnetization versus field behavior is observed for the hematite foams, while clear hysteresis loops are obtained for the Fe₂MnO₄ foams. Actually, the saturation magnetization of the foams containing Mn increases from 5 emu/g to 52 emu/g when the N₂ flow rate (i.e., the amount of Fe₂MnO₄) is increased. The obtained foams are appealing for a wide range of applications, such as electromagnetic absorbers, catalysts supports, thermal and acoustic insulation systems or wirelessly magnetically-guided porous objects in fluids.

A Bowl of Hematite-Rich 'Berries'

NASA Technical Reports Server (NTRS)

2004-01-01

This graph shows two spectra of outcrop regions near the Mars Exploration Rover Opportunity's landing site. The blue line shows data for a region dubbed 'Berry Bowl,' which contains a handful of the sphere-like grains dubbed 'blueberries.' The yellow line represents an area called 'Empty' next to Berry Bowl that is devoid of berries. Berry Bowl's spectrum still shows typical outcrop characteristics, but also exhibits an intense hematite signature, seen as a 'magnetic sextet.' Hematite is an iron-bearing mineral often formed in water. These spectra were taken by the rover's Moessbauer spectrometer on the 46th (Empty) and 48th (Berry Bowl) martian days, or sols, of its mission.

Iron Isotopes in Spherical Hematite and Goethite Concretions from the Navajo Sandstone (Utah, USA): A Prospective Study for "Martian Blueberries"

NASA Astrophysics Data System (ADS)

Busigny, V.; Dauphas, N.

2006-03-01

Iron isotopes of terrestrial hematite and goethite concretions provide clues on fluid transport, reservoir sizes, redox variations and biotic versus abiotic processes. This opens several avenues of research for future work on Martian blueberries.

Ultrafast transient absorption studies of hematite nanoparticles: the effect of particle shape on exciton dynamics.

PubMed

Fitzmorris, Bob C; Patete, Jonathan M; Smith, Jacqueline; Mascorro, Xiomara; Adams, Staci; Wong, Stanislaus S; Zhang, Jin Z

2013-10-01

Much progress has been made in using hematite (α-Fe2 O3 ) as a potentially practical and sustainable material for applications such as solar-energy conversion and photoelectrochemical (PEC) water splitting; however, recent studies have shown that the performance can be limited by a very short charge-carrier diffusion length or exciton lifetime. In this study, we performed ultrafast studies on hematite nanoparticles of different shapes to determine the possible influence of particle shape on the exciton dynamics. Nanorice, multifaceted spheroidal nanoparticles, faceted nanocubes, and faceted nanorhombohedra were synthesized and characterized by using SEM and XRD techniques. Their exciton dynamics were investigated by using femtosecond transient absorption (TA) spectroscopy. Although the TA spectral features differ for the four samples studied, their decay profiles are similar, which can be fitted with time constants of 1-3 ps, approximately 25 ps, and a slow nanosecond component extending beyond the experimental time window that was measured (2 ns). The results indicate that the overall exciton lifetime is weakly dependent on the shape of the hematite nanoparticles, even though the overall optical absorption and scattering are influenced by the particle shape. This study suggests that other strategies need to be developed to increase the exciton lifetime or to lengthen the exciton diffusion length in hematite nanostructures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Arsenic sorption by nanocrystalline magnetite: an example of environmentally promising interface with geosphere.

PubMed

Bujňáková, Z; Baláž, P; Zorkovská, A; Sayagués, M J; Kováč, J; Timko, M

2013-11-15

In this paper, the sorption of arsenic onto nanocrystalline magnetite mineral Fe3O4 was studied in a model system. Nanocrystalline magnetite was produced by mechanical activation in a planetary ball mill from natural microcrystalline magnetite. As a consequence of milling, the specific surface area increased from 0.1m(2)/g to 11.9 m(2)/g and the surface site concentration enhanced from 2.2 sites/nm(2) to 8.4 sites/nm(2). These changes in surface properties of magnetite lead to the enhancement of arsenic removal from model system. The best sorption ability was achieved with magnetite sample activated for 90 min. In this case the sample was able to absorb around 4 mg/g. The structural changes of magnetite were also observed and the new hematite phase was detected after 120 min of milling. A good correlation between the decreasing particle size, increasing specific surface area and reduction of saturation magnetization was found. In desorption study, KOH and NaOH were found as the best eluents where more than 70% of arsenic was released back into the solution. The principal novelty of the paper is that mineral magnetite, truly one nature's gift can be used after "smart" milling (mechanical activation) as an effective arsenic sorbent. Copyright © 2013 Elsevier B.V. All rights reserved.

Mössbauer spectroscopic studies on the iron forms of deep-sea sediments

NASA Astrophysics Data System (ADS)

Drodt, M.; Trautwein, A. X.; König, I.; Suess, E.; Koch, C. Bender

Mössbauer spectroscopy was applied to characterize the valence states Fe(II) and Fe(III) in sedimentary minerals from a core of the Peru Basin. The procedure in unraveling this information includes temperature-dependent measurements from 275 K to very low temperature (300 mK) in zero-field and also at 4.2 K in an applied field (up to 6.2 T) and by mathematical procedures (least-squares fits and spectral simulations) in order to resolve individual spectral components. The depth distribution of the amount of Fe(II) is about 11% of the total Fe to a depth of 19 cm with a subsequent steep increase (within 3 cm) to about 37%, after which it remains constant to the lower end of the sediment core (at about 40 cm). The steep increase of the amount of Fe(II) defines a redox boundary which coincides with the position where the tan/green color transition of the sediment occurs. The isomer shifts and quadrupole splittings of Fe(II) and Fe(III) in the sediment are consistent with hexacoordination by oxygen or hydroxide ligands as in oxide and silicate minerals. Goethite and traces of hematite are observed only above the redox boundary, with a linear gradient extending from about 20% of the total Fe close to the sediment surface to about zero at the redox boundary. The superparamagnetic relaxation behavior allows to estimate the order of magnitude for the size of the largest goethite and hematite particles within the particle-site distribution, e.g. 170 Å and 50 Å, respectively. The composition of the sediment spectra recorded at 300 mK in zero-field, apart from the contributions due to goethite and hematite, resembles that of the sheet silicates smectite, illite and chlorite, which have been identified as major constituents of the sediment in the <2 μm fraction by X-ray diffraction. The specific ``ferromagnetic'' type of magnetic ordering in the sediment, as detected at 4.2 K in an applied field, also resembles that observed in sheet silicates and indicates that both Fe(II) and Fe(III) are involved in magnetic ordering. This ``ferromagnetic'' behavior is probably due to the double-exchange mechanism known from other mixed-valence Fe(II)-Fe(III) systems. A significant part of the clay-mineral iron is redox sensitive. It is proposed that the color change of the sediment at the redox boundary from tan to green is related to the increase of Fe(II)-Fe(III) pairs in the layer silicates, because of the intervalence electron transfer bands which are caused by such pairs.

76 FR 60557 - Environmental Assessment and Finding of No Significant Impact for a License Amendment to...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-29

... Electric Company, LLC, Hematite Decommissioning Project, Hematite, MO AGENCY: Nuclear Regulatory Commission... (SNM) License number SNM-33, issued to Westinghouse Electric Company, LLC (WEC) to authorize... radioactively contaminated material by rail car to an offsite facility located in Idaho was also confirmed in...

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

PubMed

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

1999-04-25

Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite-rich chert stromatolite. Our research demonstrates that in situ Mossbauer spectroscopy can help determine whether hydrothermal mineral deposits exist on Mars, which is significant for exobiology because of the issue of whether that world ever had conditions conductive to the origin of life. As a useful tool for selection of samples suitable for transport to Earth, Mossbauer spectroscopy will not only serve geological interests but will also have potential for exopaleontology.

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

NASA Technical Reports Server (NTRS)

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

1999-01-01

Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite-rich chert stromatolite. Our research demonstrates that in situ Mossbauer spectroscopy can help determine whether hydrothermal mineral deposits exist on Mars, which is significant for exobiology because of the issue of whether that world ever had conditions conductive to the origin of life. As a useful tool for selection of samples suitable for transport to Earth, Mossbauer spectroscopy will not only serve geological interests but will also have potential for exopaleontology.

The nanosphere iron mineral(s) in Mars soil

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

The role of counter ions in nano-hematite synthesis: Implications for surface area and selenium adsorption capacity.

PubMed

Lounsbury, Amanda W; Yamani, Jamila S; Johnston, Chad P; Larese-Casanova, Philip; Zimmerman, Julie B

2016-06-05

Nano metal oxides are of interest for aqueous selenium (Se) remediation, and as such, nano-hematite (nα-Fe2O3) was examined for use as a Se adsorbent. The effect of surface area on adsorption was also studied. nα-Fe2O3 particles were synthesized from Fe(NO3)3 and FeCl3 via forced hydrolysis. The resulting particles have similar sizes, morphologies, aggregate size, pore size, and PZC. The nα-Fe2O3 from FeCl3 (nα-Fe2O3-C) differs from the nα-Fe2O3 from Fe(NO3)3 (nα-Fe2O3-N) with a ∼25±2m(2)/g greater surface area. Selenite Se(IV) adsorption capacity on nα-Fe2O3 has a qmax ∼17mg/g for the freeze-dried and re-suspended nα-Fe2O3. The Δqmax for nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension was 4.6mg/g. For selenate Se(VI), the freeze-dried and re-suspended particles realize a Δqmax= 1.5mg/g for nα-Fe2O3 from Fe(NO3)3 and FeCl3. The nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension demonstrated Se(VI) Δqmax=5.4mg/g. In situ ATR-FTIR isotherm measurements completed for Se(VI) at a pH 6 suggest that Se(VI) forms primarily outer-sphere complexes with nα-Fe2O3 synthesized from both salts. Copyright © 2016 Elsevier B.V. All rights reserved.

Light in the darkening on Naica gypsum crystals

NASA Astrophysics Data System (ADS)

Castillo-Sandoval, I.; Fuentes-Cobas, L. E.; Fuentes-Montero, M. E.; Esparza-Ponce, H. E.; Carreno-Márquez, J.; Reyes-Cortes, M.; Montero-Cabrera, M. E.

2015-07-01

Naica mine is located in a semi-desertic region at the central-south of Chihuahua State. The Cave of Swords was discovered in 1910 and the Cave of Crystals 90 years later at Naica mines. It is expected that during the last century the human presence has changed the microclimatic conditions inside the cave, resulting in the deterioration of the crystals and the deposition of impurities on gypsum surfaces. As a contribution to the clarification of the mentioned issues, the present work refers to the use of synchrotron radiation for the identification of phases on these surfaces. All the experiments were performed at the Stanford Synchrotron Radiation Lightsource. Grazing incidence X-ray diffraction (GIXRD) and radiography-aided X-ray diffraction (RAXRD) experiments were performed at beamline 11-3. X-Ray micro-fluorescence (μ-SXRF) and micro-X-ray absorption (μ-XANES) were measured at beamline 2-3. Representative results obtained may be summarized as follows: a) Gypsum, galena, sphalerite, hematite and cuprite at the surface of the gypsum crystals were determined. b) The samples micro-structure is affected by impurities. c) The elemental distributions and correlations (0.6-0.9) of Cu, K, Fe, Mn, Pb, Zn, Ca and S were identified by μ-SXRF. The correlations among elemental contents confirmed the phase identification, with the exception of manganese and potassium due to the amorphous nature of some impurity compounds in these samples. The compounds hematite (Fe2O3), β-MnO2, Mn2O3, MnO and/or MnCO3, PbS, PbCO3 and/or PbSO4, ZnO4, ZnS and/or smithsonite (ZnCO3), CuS + Cu Oxide were identified by XANES. Plausibly, these latter compounds do not form crystalline phases.

Composition and Mineralogy of Martian Soils

NASA Astrophysics Data System (ADS)

Bell, J. F.

2007-05-01

The soils of Mars--the fine-grained, porous, uppermost layer of the planet's regolith--appear to have been created by a combination of physical and chemical weathering processes that can provide insights about the evolution of the martian surface and climate. Remote sensing and in situ measurements and analyses of soils from five different landing sites have revealed both surprising similarities and important (sometimes unexpected) differences among soils across the planet. Among the similarities are the ubiquitous presence and homogeneity of "dust" at widely-separated landing sites. Dust is the finest-grained (less than 5 microns) fraction of the soil, and the fact that it is easily suspended and transported by dust devils and dust storms explains its ubiquity. The reddish color and small size of dust particles had been cited as evidence for its origin as perhaps physically or chemically comminuted and heavily-oxidized (ferric) secondary weathering products. New results from the MER Sprit and Opportunity missions, however, indicate that dust grains may instead be volumetrically mostly unoxidized (ferrous) material, with visual color properties imparted by only a thin rind or coating of ferric oxides/oxyhydroxides. Another fine-grained global-scale unit is dark, silt- to sand-sized soils that occur in dunes, drifts, and ripples. Dark sands exhibit rather homogeneous composition and mineralogy (dominated by olivine and pyroxene) across the landing sites, suggesting that they, too, are globally-transported materials. Examples of the kinds of variability detected in martian soils are the hematite-rich spherules, sulfur/jarosite-rich outcrop- derived soils, and basaltic clastic fragments encountered in Meridiani Planum, the hematite, goethite, and ferric- sulfate bearing soils encountered in Gusev crater, and crusted/armored soils and rinds encountered at both Viking and both MER sites. Much of the observed martian soil variability may result from the action of local-scale weathering processes and/or reflect the diversity of local precursor bedrock sources. This presentation will provide an overview of what we know about the composition and mineralogy of martian soils, will review current models for martian soil formation in light of the currently-available data, and will describe ways that these models might be tested with ongoing and future Mars surface exploration missions.

Martian Surface Mineralogy from Rovers with Spirit, Opportunity, and Curiosity

NASA Technical Reports Server (NTRS)

Morris, Richard V.

2016-01-01

Beginning in 2004, NASA has landed three well-instrumented rovers on the equatorial martian surface. The Spirit rover landed in Gusev crater in early January, 2004, and the Opportunity rover landed on the opposite side of Mars at Meridian Planum 21 days later. The Curiosity rover landed in Gale crater to the west of Gusev crater in August, 2012. Both Opportunity and Curiosity are currently operational. The twin rovers Spirit and Opportunity carried Mossbauer spectrometers to determine the oxidation state of iron and its mineralogical composition. The Curiosity rover has an X-ray diffraction instrument for identification and quantification of crystalline materials including clay minerals. Instrument suites on all three rovers are capable of distinguishing primary rock-forming minerals like olivine, pyroxene and magnetite and products of aqueous alteration in including amorphous iron oxides, hematite, goethite, sulfates, and clay minerals. The oxidation state of iron ranges from that typical for unweathered rocks and soils to nearly completely oxidized (weathered) rocks and soils as products of aqueous and acid-sulfate alteration. The in situ rover mineralogy also serves as ground-truth for orbital observations, and orbital mineralogical inferences are used for evaluating and planning rover exploration.

Adsorption and co-adsorption of graphene oxide and Ni(II) on iron oxides: A spectroscopic and microscopic investigation.

PubMed

Sheng, Guodong; Huang, Chengcai; Chen, Guohe; Sheng, Jiang; Ren, Xuemei; Hu, Baowei; Ma, Jingyuan; Wang, Xiangke; Huang, Yuying; Alsaedi, Ahmed; Hayat, Tasawar

2018-02-01

Graphene oxide (GO) may strongly interact with toxic metal ions and mineral particles upon release into the soil environment. We evaluated the mutual effects between GO and Ni (Ni(II)) with regard to their adsorption and co-adsorption on two minerals (goethite and hematite) in aqueous phase. Results indicated that GO and Ni could mutually facilitate the adsorption of each other on both goethite and hematite over a wide pH range. Addition of Ni promoted GO co-adsorption mainly due to the increased positive charge of minerals and cation-π interactions, while the presence of GO enhanced Ni co-adsorption predominantly due to neutralization of positive charge and strong interaction with oxygen-containing functional groups on adsorbed GO. Increasing adsorption of GO and Ni on minerals as they coexist may thus reduce their mobility in soil. Extended X-ray absorption fine structure (EXAFS) spectroscopy data revealed that GO altered the microstructure of Ni on minerals, i.e., Ni formed edge-sharing surface species (at R Ni-Fe ∼3.2 Å) without GO, while a GO-bridging ternary surface complexes (at R Ni-C ∼2.49 Å and R Ni-Fe ∼4.23 Å) was formed with GO. These findings improved the understanding of potential fate and toxicity of GO as well as the partitioning processes of Ni ions in aquatic and soil environments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hard templating ultrathin polycrystalline hematite nanosheets: effect of nano-dimension on CO2 to CO conversion via the reverse water-gas shift reaction.

PubMed

Fishman, Zachary S; He, Yulian; Yang, Ke R; Lounsbury, Amanda W; Zhu, Junqing; Tran, Thanh Minh; Zimmerman, Julie B; Batista, Victor S; Pfefferle, Lisa D

2017-09-14

Understanding how nano-dimensionality impacts iron oxide based catalysis is central to a wide range of applications. Here, we focus on hematite nanosheets, nanowires and nanoparticles as applied to catalyze the reverse water gas shift (RWGS) probe reaction. We introduce a novel approach to synthesize ultrathin (4-7 nm) hematite nanosheets using copper oxide nanosheets as a hard template and propose a reaction mechanism based on density functional theory (DFT) calculations. Hematite nanowires and nanoparticles were also synthesized and characterized. H 2 temperature programmed reduction (H 2 -TPR) and RWGS reactions were performed to glean insights into the mechanism of CO 2 conversion to CO over the iron oxide nanomaterials and were compared to H 2 binding energy calculations based on density functional theory. While the nanosheets did exhibit high CO 2 conversion, 28% at 510 °C, we found that the iron oxide nanowires had the highest CO 2 conversion, reaching 50% at 750 °C under atmospheric pressure. No products besides CO and H 2 O were detected.

Investigation of porosity and heterojunction effects of a mesoporous hematite electrode on photoelectrochemical water splitting.

PubMed

Liu, Jingling; Shahid, Muhammad; Ko, Young-Seon; Kim, Eunchul; Ahn, Tae Kyu; Park, Jong Hyeok; Kwon, Young-Uk

2013-06-28

In this paper, we report the porosity and heterojunction effects of hematite (α-Fe2O3) on the photoelectrochemical (PEC) water splitting properties. The worm-like mesoporous hematite thin films (MHFs) with a pore size of ~9 nm and a wall thickness of ~5 nm were successfully obtained through the self-assembly process. MHFs formed on FTO showed much better PEC properties than those of nonporous hematite thin films (NP-HF) owing to the suppression of charge recombination. The PEC data of MHFs under front and back illumination conditions indicated that the porous structure allows the diffusion of electrolyte deep inside the MHF increasing the number of holes to be utilized in the water oxidation reaction. A heterojunction structure was formed by introducing a thin layer of SnO2 (~15 nm in thickness) between the MHF and FTO for a dramatically enhanced PEC response, which is attributed to the efficient electron transfer. Our spectroscopic and electrochemical data show that the SnO2 layer functions as an efficient electron transmitter, but does not affect the recombination kinetics of MHFs.

Assessment of Mars Exploration Rover Landing Site Predictions

NASA Astrophysics Data System (ADS)

Golombek, M. P.

2005-05-01

Comprehensive analyses of remote sensing data during the 3-year effort to select the Mars Exploration Rover landing sites at Gusev crater and Meridiani Planum correctly predicted the safe and trafficable surfaces explored by the two rovers. Gusev crater was predicted to be a relatively low relief surface that was comparably dusty, but less rocky than the Viking landing sites. Available data for Meridiani Planum indicated a very flat plain composed of basaltic sand to granules and hematite that would look completely unlike any of the existing landing sites with a dark, low albedo surface, little dust and very few rocks. Orbital thermal inertia measurements of 315 J m-2 s-0.5 K-1 at Gusev suggested surfaces dominated by duricrust to cemented soil-like materials or cohesionless sand or granules, which is consistent with observed soil characteristics and measured thermal inertias from the surface. THEMIS thermal inertias along the traverse at Gusev vary from 285 at the landing site to 330 around Bonneville rim and show systematic variations that can be related to the observed increase in rock abundance (5-30%). Meridiani has an orbital bulk inertia of ~200, similar to measured surface inertias that correspond to observed surfaces dominated by 0.2 mm sand size particles. Rock abundance derived from orbital thermal differencing techniques suggested that Meridiani Planum would have very low rock abundance, consistent with the rock free plain traversed by Opportunity. Spirit landed in an 8% orbital rock abundance pixel, consistent with the measured 7% of the surface covered by rocks >0.04 m diameter at the landing site, which is representative of the plains away from craters. The orbital albedo of the Spirit traverse varies from 0.19 to 0.30, consistent with surface measurements in and out of dust devil tracks. Opportunity is the first landing in a low albedo portion of Mars as seen from orbit, which is consistent with the dark, dust-free surface and measured albedos. The close correspondence between surface characteristics inferred from orbital remote sensing data and that found at the landing sites argues that future efforts to select safe landing sites will be successful. Linking the five landing sites to their remote sensing signatures suggests that they span most of the important, likely safe surfaces available for landing on Mars.

Testing variations of the GW approximation on strongly correlated transition metal oxides: hematite (α-Fe2O3) as a benchmark.

PubMed

Liao, Peilin; Carter, Emily A

2011-09-07

Quantitative characterization of low-lying excited electronic states in materials is critical for the development of solar energy conversion materials. The many-body Green's function method known as the GW approximation (GWA) directly probes states corresponding to photoemission and inverse photoemission experiments, thereby determining the associated band structure. Several versions of the GW approximation with different levels of self-consistency exist in the field. While the GWA based on density functional theory (DFT) works well for conventional semiconductors, less is known about its reliability for strongly correlated semiconducting materials. Here we present a systematic study of the GWA using hematite (α-Fe(2)O(3)) as the benchmark material. We analyze its performance in terms of the calculated photoemission/inverse photoemission band gaps, densities of states, and dielectric functions. Overall, a non-self-consistent G(0)W(0) using input from DFT+U theory produces physical observables in best agreement with experiments. This journal is © the Owner Societies 2011

Simulation of reduction of iron-oxide-carbon composite pellets in a rotary hearth furnace

NASA Astrophysics Data System (ADS)

Halder, Sabuj

The primary motivation of this work is to evaluate a new alternative ironmaking process which involves the combination of a Rotary Hearth Furnace (RHF) with an iron bath smelter. This work is concerned primarily, with the productivity of the RHF. It is known that the reduction in the RHF is controlled by chemical kinetics of the carbon oxidation and wustite reduction reactions as well as by heat transfer to the pellet surface and within the pellet. It is heat transfer to the pellet which limits the number of layers of pellets in the pellet bed in the RHF and thus, the overall productivity. Different types of carbon like graphite, coal-char and wood charcoal were examined. Part of the research was to investigate the chemical kinetics by de-coupling it from the influence of heat and mass transfer. This was accomplished by carrying out reduction experiments using small iron-oxide-carbon powder composite mixtures. The reaction rate constants were determined by fitting the experimental mass loss with a mixed reaction model. This model accounts for the carbon oxidation by CO2 and wustite reduction by CO, which are the primary rate controlling surface-chemical reactions in the composite system. The reaction rate constants have been obtained using wustite-coal-char powder mixtures and wustite-wood-charcoal mixtures. The wustite for these mixtures was obtained from two iron-oxide sources: artificial porous analytical hematite (PAH) and hematite ore tailings. In the next phase of this study, larger scale experiments were conducted in a RHF simulator using spherical composite pellets. Measurement of the reaction rates was accomplished using off-gas analysis. Different combinations of raw materials for the pellets were investigated. These included artificial ferric oxide as well as naturally existing hematite and taconite ores. Graphite, coal-char and wood-charcoal were the reductants. Experiments were conducted using a single layer, a double layer and a triple layer of composite pellets to look into the different aspects associated with multi-layer reduction in the RHF. The reduced pellets were examined for morphology and phase distribution using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) analysis. Efforts were made to interpret the differences in the observed rates from one kind of pellet to the other on the grounds of chemical kinetics of the carbon oxidation and wustite reduction reactions and the issues of external and internal heat transport to and within the pellets. It was concluded from the experiments that in the ore containing pellets, wood-charcoal appeared to be a faster reductant than coal-char. However, in the PAH containing pellets, the reverse was found to be true. This is because of the internal heat transport limitations imposed by two factors (a) lower thermal conductivity of wood-charcoal in comparison to coal-char and (b) swelling of the PAH-Wood-Charcoal pellets during the initial heat-up stage. For the same type of reductant, hematite containing pellets were observed to reduce faster than taconite containing pellets. This is in accordance with the higher reducibility of hematite because of development of internal porosity due to cracking and fissure formation during the Fe2O3 to Fe 3O4 transformation stage. This is however, absent during the reduction of taconite, which is primarily Fe3O4. The PAH-Wood-Charcoal pellets were found to undergo significant amounts of swelling under low temperature conditions. This behavior of the PAH-Wood-Charcoal pellets of a certain layer impeded the external heat transport to the lower layer and consequently, resulted in a relatively lower reduction rate for a multi-layer bed. The volume change phenomena associated with the reduction of composites were also studied. Volume changes influence the external heat transport, especially to the lower layers of a multi-layer bed. The volume change of the different kinds of composite pellets was studied as a function of reduction temperature and time. Empirical correlations were developed associating the volume shrinkage to the fractional mass loss of the pellets. The estimation of the change in the amount of external heat transport with varying pellet sizes for a particular layer of a multi-layer bed was obtained by conducting heat transport tests using inert low carbon steel spheres. The experimental temperature data for the spheres of different layers was interpreted using a simple mathematical model. It was found through this exercise, that if the spheres of the top layer of the bed shrink by 30%, the external heat transfer to the second layer increases by almost 6 times. This is because of the decrease in the shielded area of the second layer due to the decreasing size of the top layer spheres. If the average degree of reduction targeted in a RHF is reduced from 95% to about 70% by coupling the RHF with a bath smelter, the productivity of the RHF can be enhanced by 1.5 to 2 times. The use of a 2 or 3 layer bed was found to be far superior to that of a single layer for higher productivities under the current experimental conditions. Sometimes, a 2 layer bed is more advantageous than a 3 layer bed, as was found to be the case with hematite-wood-charcoal pellets. The choice of the optimal number of layers depends upon several factors like pellet size, kind of pellet and shrinking characteristics of the pellet.

Geology of the Eymir iron mine, Edremit, Turkey

USGS Publications Warehouse

Jacobson, Herbert Samuel; Turet, Erdogan

1972-01-01

The Eymir mine near Edremit on Turkey's Aegean coast (long 27?30'E.,1at 39?36'N.) was investigated as part of the Maden Tetkik ve Arama Enstitutsu (MTA)-U. S. Geological Survey (USGS) mineral exploration and training project, for the purpose of increasing the known mineral reserves. Geologic mapping of the mine area indicates that hematite is restricted to argillized, silicified, and pyritized dacite and possibly andesite. Hematite is present as massive replacements, impregnations, disseminations, and fracture fillings. Most of the upper part of the iron deposit consists of a breccia composed mostly of silicifiled dacite fragments in a hematite matrix. The iron deposit was apparently formed in three steps: 1. Argillation, silicification, and pyritization of the andesitic lava and dacite units as a result of a regional intrusion. 2. Intrusion of the Dere Oren dacite stock, with associated faulting, fracturing, and breccia formation at the surface. 3. Deposition of hematite by oxidation of pyrite, and transfer of iron via fractures and faults by hydrothermal or meteoric fluids. The Eymir iron deposit is a blanketlike deposit on the crest of the Sivritepe-Eymir ridge. It is 1300 meters long, 80 to 450 meters wide, and has an average thickness of 18.6 meters. Drill holes in the deposit show the iron content to range from 32.0 to 57.6 percent, and to average 46.5 percent. Most of the gangue is silica, and an arsenic impurity averaging 0.39 percent is present. Most of the deposit cannot be utilized as iron ore because of low iron content, high silica content, and high arsenic content. Ore-dressing tests have shown that it is feasible to concentrate the low-grade material, producing a concentrate having increased iron content and reduced silica content. Tests have shown also that the arsenic content of the ore can be reduced substantially by sintering. Further tests and economic feasibility studies are necessary to determine whether an economic marketable iron ore can be produced. If such studies indicate the technical and economic feasibility of utilizing all the Eymir iron deposit, detailed additional studies are recommended including: 1. A detailed drilling and sampling program to include 60 drill holes averaging 40 meters in depth and detailed sampling of mine dumps. 2. Pilot-plant testing of concentration and sintering procedures. 3. A detailed pre-investment economic feasibility study.

Science Results from a Mars Drilling Simulation (Río Tinto, Spain) and Ground Truth for Remote Science Observations

NASA Astrophysics Data System (ADS)

Bonaccorsi, Rosalba; Stoker, Carol R.

2008-10-01

Science results from a field-simulated lander payload and post-mission laboratory investigations provided "ground truth" to interpret remote science observations made as part of the 2005 Mars Astrobiology Research and Technology Experiment (MARTE) drilling mission simulation. The experiment was successful in detecting evidence for life, habitability, and preservation potential of organics in a relevant astrobiological analogue of Mars. Science results. Borehole 7 was drilled near the Río Tinto headwaters at Peña de Hierro (Spain) in the upper oxidized remnant of an acid rock drainage system. Analysis of 29 cores (215 cm of core was recovered from 606 cm penetrated depth) revealed a matrix of goethite- (42-94%) and hematite-rich (47-87%) rocks with pockets of phyllosilicates (47-74%) and fine- to coarse-grained loose material. Post-mission X-ray diffraction (XRD) analysis confirmed the range of hematite:goethite mixtures that were visually recognizable (˜1:1, ˜1:2, and ˜1:3 mixtures displayed a yellowish-red color whereas 3:1 mixtures displayed a dark reddish-brown color). Organic carbon was poorly preserved in hematite/goethite-rich materials (Corg <0.05 wt %) beneath the biologically active organic-rich soil horizon (Corg ˜3-11 wt %) in contrast to the phyllosilicate-rich zones (Corg ˜0.23 wt %). Ground truth vs. remote science analysis. Laboratory-based analytical results were compared to the analyses obtained by a Remote Science Team (RST) using a blind protocol. Ferric iron phases, lithostratigraphy, and inferred geologic history were correctly identified by the RST with the exception of phyllosilicate-rich materials that were misinterpreted as weathered igneous rock. Adenosine 5‧-triphosphate (ATP) luminometry, a tool available to the RST, revealed ATP amounts above background noise, i.e., 278-876 Relative Luminosity Units (RLUs) in only 6 cores, whereas organic carbon was detected in all cores. Our manned vs. remote observations based on automated acquisitions during the project provide insights for the preparation of future astrobiology-driven Mars missions.

Science results from a Mars drilling simulation (Río Tinto, Spain) and ground truth for remote science observations.

PubMed

Bonaccorsi, Rosalba; Stoker, Carol R

2008-10-01

Science results from a field-simulated lander payload and post-mission laboratory investigations provided "ground truth" to interpret remote science observations made as part of the 2005 Mars Astrobiology Research and Technology Experiment (MARTE) drilling mission simulation. The experiment was successful in detecting evidence for life, habitability, and preservation potential of organics in a relevant astrobiological analogue of Mars. SCIENCE RESULTS: Borehole 7 was drilled near the Río Tinto headwaters at Peña de Hierro (Spain) in the upper oxidized remnant of an acid rock drainage system. Analysis of 29 cores (215 cm of core was recovered from 606 cm penetrated depth) revealed a matrix of goethite- (42-94%) and hematite-rich (47-87%) rocks with pockets of phyllosilicates (47-74%) and fine- to coarse-grained loose material. Post-mission X-ray diffraction (XRD) analysis confirmed the range of hematite:goethite mixtures that were visually recognizable (approximately 1:1, approximately 1:2, and approximately 1:3 mixtures displayed a yellowish-red color whereas 3:1 mixtures displayed a dark reddish-brown color). Organic carbon was poorly preserved in hematite/goethite-rich materials (C(org) <0.05 wt %) beneath the biologically active organic-rich soil horizon (C(org) approximately 3-11 wt %) in contrast to the phyllosilicate-rich zones (C(org) approximately 0.23 wt %). GROUND TRUTH VS. REMOTE SCIENCE ANALYSIS: Laboratory-based analytical results were compared to the analyses obtained by a Remote Science Team (RST) using a blind protocol. Ferric iron phases, lithostratigraphy, and inferred geologic history were correctly identified by the RST with the exception of phyllosilicate-rich materials that were misinterpreted as weathered igneous rock. Adenosine 5'-triphosphate (ATP) luminometry, a tool available to the RST, revealed ATP amounts above background noise, i.e., 278-876 Relative Luminosity Units (RLUs) in only 6 cores, whereas organic carbon was detected in all cores. Our manned vs. remote observations based on automated acquisitions during the project provide insights for the preparation of future astrobiology-driven Mars missions.

Accurate determination of the charge transfer efficiency of photoanodes for solar water splitting.

PubMed

Klotz, Dino; Grave, Daniel A; Rothschild, Avner

2017-08-09

The oxygen evolution reaction (OER) at the surface of semiconductor photoanodes is critical for photoelectrochemical water splitting. This reaction involves photo-generated holes that oxidize water via charge transfer at the photoanode/electrolyte interface. However, a certain fraction of the holes that reach the surface recombine with electrons from the conduction band, giving rise to the surface recombination loss. The charge transfer efficiency, η t , defined as the ratio between the flux of holes that contribute to the water oxidation reaction and the total flux of holes that reach the surface, is an important parameter that helps to distinguish between bulk and surface recombination losses. However, accurate determination of η t by conventional voltammetry measurements is complicated because only the total current is measured and it is difficult to discern between different contributions to the current. Chopped light measurement (CLM) and hole scavenger measurement (HSM) techniques are widely employed to determine η t , but they often lead to errors resulting from instrumental as well as fundamental limitations. Intensity modulated photocurrent spectroscopy (IMPS) is better suited for accurate determination of η t because it provides direct information on both the total photocurrent and the surface recombination current. However, careful analysis of IMPS measurements at different light intensities is required to account for nonlinear effects. This work compares the η t values obtained by these methods using heteroepitaxial thin-film hematite photoanodes as a case study. We show that a wide spread of η t values is obtained by different analysis methods, and even within the same method different values may be obtained depending on instrumental and experimental conditions such as the light source and light intensity. Statistical analysis of the results obtained for our model hematite photoanode show good correlation between different methods for measurements carried out with the same light source, light intensity and potential. However, there is a considerable spread in the results obtained by different methods. For accurate determination of η t , we recommend IMPS measurements in operando with a bias light intensity such that the irradiance is as close as possible to the AM1.5 Global solar spectrum.

Iron oxide and hydroxide precipitation from ferrous solutions and its relevance to Martian surface mineralogy

NASA Technical Reports Server (NTRS)

Posey-Dowty, J.; Moskowitz, B.; Crerar, D.; Hargraves, R.; Tanenbaum, L.

1986-01-01

Experiments were performed to examine if the ubiquitousness of a weak magnetic component in all Martian surface fines tested with the Viking Landers can be attributed to ferric iron precipitation in aqueous solution under oxidizing conditions at neutral pH. Ferrous solutions were mixed in deionized water and various minerals were added to separate liquid samples. The iron-bearing additives included hematite, goethite, magnetite, maghemite, lepidocrocite and potassium bromide blank at varying concentrations. IR spectroscopic scans were made to identify any precipitates resulting from bubbling oxygen throughout the solutions; the magnetic properties of the precipitates were also examined. The data indicated that the lepidocrocite may have been preferentially precipitated, then aged to maghemite. The process would account for the presumed thin residue of maghemite on the present Martian surface, long after abundant liquid water on the Martian surface vanished.

Density functional theory study of phase stability and defect thermodynamics in iron-oxyhydroxide mineral materials

NASA Astrophysics Data System (ADS)

Pinney, Nathan Douglas

Due to their high surface area and reactivity toward a variety of heavy metal and oxyanion species of environmental concern, Fe-(oxyhydr)oxide materials play an important role in the geochemical fate of natural and anthropogenic contaminants in soils, aquifers and surface water environments worldwide. In this research, ab initio simulations describe the bulk structure, magnetic properties, and relative phase stability of major Fe-(oxyhydr)oxide materials, including hematite, goethite, lepidocrocite, and ferrihydrite.These bulk models are employed in further studies of point defect and alloy/dopant thermodynamics in these materials, allowing construction of a phase stability model that better replicates the structure and composition of real materials. Li + adsorption at the predominant goethite (101) surface is simulated using ab initio methods, offering energetic and structural insight into the binding mechanisms of metal cations over a range of surface protonation conditions.

Evidence for an 800 km Diameter Impact Structure in Meridiani Planum and Associated Channels and Basins: A Connection with the Origin of the Hematite Deposits?

NASA Technical Reports Server (NTRS)

Newsom, H. E.; Barber, C. A.; Schelble, R. T.; Hare, T. M.; Feldman, W. C.; Sutherland, V.; Gordon, H.; Thorsos, I. E.; Livingston, A.; Lewis, K.

2003-01-01

Topographic evidence for the existence of an early 800 km diameter multi-ringed impact structure, and evidence for fluvial and lacustrine environments in Meridiani Planum suggests a connection with the origin of the hematite deposits present in the region.

The "Rust" Challenge: On the Correlations between Electronic Structure, Excited State Dynamics, and Photoelectrochemical Performance of Hematite Photoanodes for Solar Water Splitting.

PubMed

Grave, Daniel A; Yatom, Natav; Ellis, David S; Toroker, Maytal Caspary; Rothschild, Avner

2018-03-05

In recent years, hematite's potential as a photoanode material for solar hydrogen production has ignited a renewed interest in its physical and interfacial properties, which continues to be an active field of research. Research on hematite photoanodes provides new insights on the correlations between electronic structure, transport properties, excited state dynamics, and charge transfer phenomena, and expands our knowledge on solar cell materials into correlated electron systems. This research news article presents a snapshot of selected theoretical and experimental developments linking the electronic structure to the photoelectrochemical performance, with particular focus on optoelectronic properties and charge carrier dynamics. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Overview of the Opportunity Mars Exploration Rover Mission to Meridiani Planum: Eagle Crater to Purgatory Ripple

NASA Astrophysics Data System (ADS)

Squyres, S. W.; Arvidson, R. E.; Bollen, D.; Bell, J. F.; Brückner, J.; Cabrol, N. A.; Calvin, W. M.; Carr, M. H.; Christensen, P. R.; Clark, B. C.; Crumpler, L.; Des Marais, D. J.; d'Uston, C.; Economou, T.; Farmer, J.; Farrand, W. H.; Folkner, W.; Gellert, R.; Glotch, T. D.; Golombek, M.; Gorevan, S.; Grant, J. A.; Greeley, R.; Grotzinger, J.; Herkenhoff, K. E.; Hviid, S.; Johnson, J. R.; Klingelhöfer, G.; Knoll, A. H.; Landis, G.; Lemmon, M.; Li, R.; Madsen, M. B.; Malin, M. C.; McLennan, S. M.; McSween, H. Y.; Ming, D. W.; Moersch, J.; Morris, R. V.; Parker, T.; Rice, J. W.; Richter, L.; Rieder, R.; Schröder, C.; Sims, M.; Smith, M.; Smith, P.; Soderblom, L. A.; Sullivan, R.; Tosca, N. J.; Wänke, H.; Wdowiak, T.; Wolff, M.; Yen, A.

2006-12-01

The Mars Exploration Rover Opportunity touched down at Meridiani Planum in January 2004 and since then has been conducting observations with the Athena science payload. The rover has traversed more than 5 km, carrying out the first outcrop-scale investigation of sedimentary rocks on Mars. The rocks of Meridiani Planum are sandstones formed by eolian and aqueous reworking of sand grains that are composed of mixed fine-grained siliciclastics and sulfates. The siliciclastic fraction was produced by chemical alteration of a precursor basalt. The sulfates are dominantly Mg-sulfates and also include Ca-sulfates and jarosite. The stratigraphic section observed to date is dominated by eolian bedforms, with subaqueous current ripples exposed near the top of the section. After deposition, interaction with groundwater produced a range of diagenetic features, notably the hematite-rich concretions known as ``blueberries.'' The bedrock at Meridiani is highly friable and has undergone substantial erosion by wind-transported basaltic sand. This sand, along with concretions and concretion fragments eroded from the rock, makes up a soil cover that thinly and discontinuously buries the bedrock. The soil surface exhibits both ancient and active wind ripples that record past and present wind directions. Loose rocks on the soil surface are rare and include both impact ejecta and meteorites. While Opportunity's results show that liquid water was once present at Meridiani Planum below and occasionally at the surface, the environmental conditions recorded were dominantly arid, acidic, and oxidizing and would have posed some significant challenges to the origin of life.

Thermal Analyses of Apollo Lunar Soils Provide Evidence for Water in Permanently Shadowed Areas

NASA Technical Reports Server (NTRS)

Cooper, Bonnie L.; Smith, M. C.; Gibson, E. K.

2011-01-01

Thermally-evolved-gas analyses were performed on the Apollo lunar soils shortly after their return to Earth [1-8]. The analyses revealed the presence of water evolving at temperatures above 200 C. Of particular interest are samples that were collected from permanently-shadowed locations (e.g., under a boulder) with a second sample collected in nearby sunlight, and pairs in which one was taken from the top of a trench, and the second was taken at the base of the trench, where the temperature would have been -10 to -20 C prior to the disturbance [9]. These samples include 63340/63500, 69941/69961, and 76240/76280. At the time that this research was first reported, the idea of hydrated minerals on the lunar surface was somewhat novel. Nevertheless, goethite was observed in lunar breccias from Apollo 14 [10], and it was shown that goethite, hematite and magnetite could originate in an equilibrium assemblage of lunar rocks

iron phase control during pressure leaching at elevated temperature

NASA Astrophysics Data System (ADS)

Fleuriault, Camille

Iron is a common contaminant encountered in most metal recovery operations, and particularly hydrometallurgical processes. For example, the Hematite Process uses autoclaves to precipitate iron oxide out of the leaching solution, while other metals are solubilized for further hydrometallurgical processing. In some cases, Basic Iron Sulfate (BIS) forms in place of hematite. The presence of BIS is unwanted in the autoclave discharge because it diminishes recovery and causes environmental matters. The focus of this master thesis is on the various iron phases forming during the pressure oxidation of sulfates. Artificial leaching solutions were produced from CuSO4, FeSO4 and H2SO4 in an attempt to recreate the matrix composition and conditions used for copper sulfides autoclaving. The following factors were investigated in order to determine which conditions hinder the formation of BIS: initial free acidity (5 -- 98 g/L), initial copper concentration (12.7 -- 63.5 g/L), initial iron concentration (16.7 -- 30.7 g/L) and initial iron oxidation state. There were three solid species formed in the autoclave: hematite, BIS and hydronium jarosite. The results show that free acid is the main factor influencing the composition of the residue. At an initial concentration of 22.3 g/L iron and no copper added, the upper limit for iron oxide formation is 41 g/L H2SO4. The increase of BIS content in the residue is not gradual and occurs over a change of a few grams per liter around the aforementioned limit. Increasing copper sulfate concentration in the solution hinders the formation of BIS. At 63.5g/L copper, the upper free acidity limit is increased to 61g/L. This effect seems to be related to the buffering action of copper sulfate, decreasing the overall acid concentration and thus extending the stability range of hematite. The effect of varying iron concentration on the precipitate chemistry is unclear. At high iron levels, the only noticeable effect was the inhibition of jarosite. The results were reported within a Cu-Fe-S ternary system and modeled. The modeling confirmed the experimental observations with the exception that increasing iron concentrations seem to promote BIS stability.

One Martian Year of in Situ Chemistry by the APXS on Board the Mars Exploration Rover Opportunity at Meridiani Planum

NASA Astrophysics Data System (ADS)

Brueckner, J.; Dreibus, G.; Gellert, R.; Clark, B. C.; Klingelhoefer, G.; Lugmair, G.; Ming, D.; Rieder, R.; Waenke, H.; Yen, A.; Zipfel, J.

2005-12-01

Two in-situ instruments, the Alpha Particle X-ray Spectrometer (APXS) and the Moessbauer Spectrometer (MB), gathered geochemical and mineralogical data along the traverse of the Mars Exploration Rover Opportunity at Meridiani Planum. Eagle crater, the landing site of the rover, contains undisturbed soils that resemble those at Gusev crater; however, the Fe, Ni, and Cr contents and Fe/Si ratios of Meridiani soils are higher than those of Gusev soils. The enrichment of Fe results from an admixture of the mineral hematite as determined by MB. This mineral occurs as a finely disseminated component of the outcrop rocks as well as in mm- to several mm-sized spherules, nicknamed blueberries, which are spread at the landing site and along the several kilometers traverse to the Erebus crater. The formation of hematite is typically an indicator for aqueous activity under oxidizing conditions. Light-toned layered outcrops were discovered in Eagle crater and later in other craters, as well as along the rover's traverse. Most of these undisturbed rock surfaces have a factor of 2 to 3 higher S concentrations compared to the soils. In Eagle crater, ground rock surfaces (exposed by the Rock Abrasion Tool, or RAT) showed even higher S contents of up to 9.5 weight percent. Assuming all SO3 is bound to Mg and Ca sulfates and, according to MB data, to ferric sulfates, mainly jarosite, these rocks contain about 40 weight percent sulfates. High concentrations of Br were discovered in some soils excavated with the rover wheels and rocks ground with the RAT. The high abundances of S and Br in these rocks point to ancient occurrence of acidified water and the formation of brines, which could have been occasionally evaporated. Small quantities of the hematite-rich spherules (ca. 2 volume percent) were found in the rocks of Eagle crater. The acidic conditions during the formation of the hematitic spherules in the rocks as concretions allowed co-precipitation of Fe2O3 and NiO but no MnO. When the rover was climbing into Endurance crater, a full stratigraphic sequence was measured with APXS and MB. Large enrichments of Cl were not accompanied by Br and S. The major elements varied within small ranges except for lower layers, where Mg is depleted together with S but Si and Al are enriched. Two rocks on the plains, analyzed by APXS and MB, are related to known meteorite classes: 'Bounce Rock' is similar in chemistry and mineralogy to basaltic shergottites, a subgroup of martian meteorites, whereas 'Heat Shield Rock' with high Fe and Ni concentrations is an iron meteorite. On the rover's journey from Endurance crater to Erebus crater, light-toned rocks were encountered whose chemical compositions resemble those of the well-known rocks of Eagle and Endurance craters, indicating that the sulfur-rich deposits occur on a scale exceeding several kilometers, consistent with evidence from orbital spacecraft.

Paleomagnetic evidence that the central block of Salinia (California) is not a far-traveled terrane

USGS Publications Warehouse

Whidden, K.J.; Lund, S.P.; Bottjer, D.J.; Champion, D.; Howell, D.G.

1998-01-01

New paleomagnetic results from Late Cretaceous (75-85 m.y.) red beds on the central block of Salinia indicate that Salinia was located within 6?? (in latitude) of its current cratonal North American position during the Late Cretaceous (after correction for Neogene San Andreas Fault transport). The red beds formed as alluvial-fan overbank deposits with hematite cement deposited directly on Salinian granites in the La Panza Range. Paleomagnetic analysis shows two components of magnetization in the red beds, a low-blocking-temperature present-day overprint residing in goethite and a high-blocking-temperature (>600??) component residing in hematite. The hematite magnetization is a chemical remanent magnetization which formed soon after deposition during pedogenesis. The bedding-corrected hematite remanence contains a magnetic polarity stratigraphy with antipodal normal and reversed directions. Twenty-three Class I sites (??95 < 20??) have an average hematite direction with inclination = 54.4?? and declination = 18.2?? (??95 = 6.1??) after structural correction. These paleomagnetic data suggest that Salinia resided at about 35??N latitude during the Late Cretaceous, within 6?? of its current location adjacent to cratonal North America. By contrast, a summary of paleomagnetic data from the Peninsular Ranges terrane and the Sur-Obispo terrane, which are currently outboard of Salinia, shows northward transport of these terranes of 12,.o\\ to 22?? relative to their current locations in North America since the Cretaceous. The offsets increase systematically away from the craton with the most outboard Sur-Obispo terrane (which is composed of accretionary prism and distal forearc material) showing the largest degree of northward translation.

Mineral Mapping Using AVIRIS Data at Ray Mine, AZ

NASA Technical Reports Server (NTRS)

McCubbin, Ian; Lang, Harold; Green, Robert O.; Roberts, Dar

1998-01-01

Imaging Spectroscopy enables the identification and mapping of surface mineralogy over large areas. This study focused on assessing the utility of Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) data for environmental impact analysis over the Environmental Protection Agency's (EPA) high priority Superfund site Ray Mine, AZ. Using the Spectral Angle Mapper (SAM) algorithm to analyze AVIRIS data makes it possible to map surface materials that are indicative of acid generating minerals. The improved performance of the AVIRIS sensor since 1996 provides data with sufficient signal to noise ratio to characterize up to 8 image endmembers. Specifically we employed SAM to map minerals associated with mine generated acid waste, namely jarositc, goethite, and hematite, in the presence of a complex mineralogical background.

Spectral Mapping of Interior Layered Deposits of Western Candor Chasma by CRISM

NASA Astrophysics Data System (ADS)

Murchie, S.; Roach, L.; Milliken, R.; Seelos, F.; Wiseman, S.; Humm, D.; Mustard, J.; Bibring, J.; CRISM Team

2007-12-01

Western Candor Chasma contains a 3 km-thick sequence of interior layered deposits (ILDs) that may have been emplaced by sedimentary deposition subsequent to formation of Valles Marineris. Proposed genetic mechanisms include subaerial fluvial deposition or volcanism, accumulation of airfall dust, lacustrine evaporite precipitation, hydrovolcanism, or alternatively deep erosion of the chasma wall materials. Observations by the Mars Express/OMEGA spectrometer showed that the ILDs contain both monohydrated and polyhydrated sulfates in close spatial association with fine-grained ferric oxides having distinctive visible-infrared absorptions (Gendrin et al. 2005a,b). In general, OMEGA data also suggest that monohydrated sulfates are associated with steeper slopes and higher albedos than are polyhydrated sulfates (Mangold 2006). CRISM has observed the ILDs in western Candor using both its 200 m/pixel global mapping mode and targeted observations at 20 or 40 m/pixel. CRISM data show spatial heterogeneity in spectral properties to the spatial resolution limit of the instrument. Both monohydrated sulfates (indicated by 2130- and 2400-nm absorptions) and polyhydrated sulfates (indicated by 1450-, 1940-, and 2420-nm absorptions) are evident at all elevations in the ILDs. Polyhydrate signatures occur on intermediate-albedo, relatively intact exposures of stratified material and are rare, but not absent, in nearby erosional debris. Typically the polyhydrate outcrops are low-sloped and form erosion-resistant cap rocks. The monohydrated sulfate also occurs in intermediate- to high-albedo outcrops, but is more commonly distributed as dark, erosional debris on ledges and in depressions that has been modified by wind to form dunes. Only in rare cases can the dark debris be associated with a discrete, dark source layer. The erosional debris exhibits enhancements in sulfate absorptions as well as in 530-, 660-, and 860- to 900-nm absorptions due to ferric iron minerals; different debris deposits have band centers consistent with hematite and with one or more non- hematitic phases. To the spatial resolution limit of CRISM, there is no evidence for comparable sulfate- or ferric- containing materials in the chasma walls, whose spectra are instead dominated by high-Ca pyroxene. Preliminary interpretations of the CRISM data covering western Candor Chasma include: (a) the ILDs have a lithology distinct from the chasma walls; (b) interbedded layers weather to form surfaces with distinct absorptions due to polyhydrated and monohydrated sulfates; (c) the difference in sulfate absorptions may be attributable to deposition of different phases in response to environmental changes or to preferential dehydration / rehydration of sulfate phases in some exposures; and (d) enhancement of ferric iron absorptions in erosional debris is consistent with abrasion generating more optically active, finer-grained particles, possibly from gray hematite- bearing, sulfate-rich layers. An outstanding issue is whether the dark erosional debris is derived locally from thin, poorly resolved layers, is transported tens of kilometers from common sources, or represents a dark component that is sorted from higher-albedo source layers. References: A. Gendrin et al., Science 307, 1587-1591 (2005a); A. Gendrin et al., Lunar and Planetary Science XXXVI, 1378 (2005b); N. Mangold et al., in Martian Sulfates as Recorders of Atmospheric-Fluid-Rock Interactions, 7039 (2006).

Bedded jaspers of the Ordovician Løkken ophiolite, Norway: seafloor deposition and diagenetic maturation of hydrothermal plume-derived silica-iron gels

USGS Publications Warehouse

Grenne, Tor; Slack, John F.

2003-01-01

The jaspers are interpreted to record colloidal fallout from one or more hydrothermal plumes, followed by maturation (ageing) of an Si-Fe-oxyhydroxide gel, on and beneath the Ordovician sea floor. Small hematitic filaments in the jaspers reflect bacteria-catalysed oxidation of Fe2+ within the plume. The larger tubular filaments resulted from either microbial activity or inorganic self-organized mineral growth of Fe-oxyhydroxide within the Si-Fe-oxyhydroxide gel after deposition on the sea floor, prior to more advanced maturation of the gel as represented by the spheroidal and botryoidal silica-hematite textures. Bleaching and hematite±epidote growth are interpreted to reflect heat and fluids generated during deposition of basaltic sheet flows on top of the gels.

Elucidating ultrafast electron dynamics at surfaces using extreme ultraviolet (XUV) reflection-absorption spectroscopy.

PubMed

Biswas, Somnath; Husek, Jakub; Baker, L Robert

2018-04-24

Here we review the recent development of extreme ultraviolet reflection-absorption (XUV-RA) spectroscopy. This method combines the benefits of X-ray absorption spectroscopy, such as element, oxidation, and spin state specificity, with surface sensitivity and ultrafast time resolution, having a probe depth of only a few nm and an instrument response less than 100 fs. Using this technique we investigated the ultrafast electron dynamics at a hematite (α-Fe2O3) surface. Surface electron trapping and small polaron formation both occur in 660 fs following photoexcitation. These kinetics are independent of surface morphology indicating that electron trapping is not mediated by defects. Instead, small polaron formation is proposed as the likely driving force for surface electron trapping. We also show that in Fe2O3, Co3O4, and NiO, band gap excitation promotes electron transfer from O 2p valence band states to metal 3d conduction band states. In addition to detecting the photoexcited electron at the metal M2,3-edge, the valence band hole is directly observed as transient signal at the O L1-edge. The size of the resulting charge transfer exciton is on the order of a single metal-oxygen bond length. Spectral shifts at the O L1-edge correlate with metal-oxygen bond covalency, confirming the relationship between valence band hybridization and the overpotential for water oxidation. These examples demonstrate the unique ability to measure ultrafast electron dynamics with element and chemical state resolution using XUV-RA spectroscopy. Accordingly, this method is poised to play an important role to reveal chemical details of previously unseen surface electron dynamics.

Pyrite Stability Under Venus Surface Conditions

NASA Astrophysics Data System (ADS)

Kohler, E.; Craig, P.; Port, S.; Chevrier, V.; Johnson, N.

2015-12-01

Radar mapping of the surface of Venus shows areas of high reflectivity in the Venusian highlands, increasing to 0.35 ± 0.04 to 0.43 ± 0.05 in the highlands from the planetary average of 0.14 ± 0.03. Iron sulfides, specifically pyrite (FeS2), can explain the observed high reflectivity. However, several studies suggest that pyrite is not stable under Venusian conditions and is destroyed on geologic timescales. To test the stability of pyrite on the Venusian surface, pyrite was heated in the Venus simulation chamber at NASA Goddard Space Flight Center to average Venusian surface conditions, and separately to highland conditions under an atmosphere of pure CO2 and separately under an atmosphere of 96.5% CO2, 3.5% N2 and 150 ppm SO2. After each run, the samples were weighed and analyzed using X-Ray Diffraction (XRD) to identify possible phase changes and determine the stability of pyrite under Venusian surface conditions. Under a pure CO2 atmosphere, the Fe in pyrite oxidizes to form hematite which is more stable at higher temperatures corresponding to the Venusian lowlands. Magnetite is the primary iron oxide that forms at lower temperatures corresponding to the radar-bright highlands. Our experiments also showed that the presence of atmospheric SO2 inhibits the oxidation of pyrite, increasing its stability under Venusian conditions, especially those corresponding to the highlands. This indicates that the relatively high level of SO2 in the Venusian atmosphere is key to the stability of pyrite, making it a possible candidate for the bright radar signal in the Venusian highlands.

Minerals associated with biofilms occurring on exposed rock in a granitic underground research laboratory.

PubMed

Brown, D A; Kamineni, D C; Sawicki, J A; Beveridge, T J

1994-09-01

The concept of disposal of nuclear fuel waste in crystalline rock requires the effects of microbial action to be investigated. The Underground Research Laboratory excavated in a pluton of the Canadian Shield provides a unique opportunity to study these effects. Three biofilms kept moist by seepage through fractures in granitic rock faces of the Underground Research Laboratory have been examined. The biofilms contained a variety of gram-negative and gram-positive morphotypes held together by an organic extracellular matrix. Nutrient levels in the groundwater were low, but energy-dispersive X-ray spectroscopy has shown biogeochemical immobilization of several elements in the biofilms; some of these elements were concentrated from extremely dilute environmental concentrations, and all elements were chemically complexed together to form amorphous or crystalline fine-grained minerals. These were seen by transmission electron microscopy to be both associated with the surfaces of the bacteria and scattered throughout the extracellular matrix, suggesting their de novo development through bacterial surface-mediated nucleation. The biofilm consortia are thought to concentrate elements both by passive sorption and by energy metabolism. By Mössbauer spectroscopy and X-ray diffraction, one of the biofilms showed that iron was both oxidized and precipitated as ferrihydrite or hematite aerobically and reduced and precipitated as siderite anaerobically. We believe that some Archean banded-iron formations could have been formed in a manner similar to this, as it would explain the deposition of hematite and siderite in close proximity. This biogeochemical development of minerals may also affect the transport of material in waste disposal sites.

Minerals Associated with Biofilms Occurring on Exposed Rock in a Granitic Underground Research Laboratory

PubMed Central

Brown, D. Ann; Kamineni, D. Choudari; Sawicki, Jerzy A.; Beveridge, Terry J.

1994-01-01

The concept of disposal of nuclear fuel waste in crystalline rock requires the effects of microbial action to be investigated. The Underground Research Laboratory excavated in a pluton of the Canadian Shield provides a unique opportunity to study these effects. Three biofilms kept moist by seepage through fractures in granitic rock faces of the Underground Research Laboratory have been examined. The biofilms contained a variety of gram-negative and gram-positive morphotypes held together by an organic extracellular matrix. Nutrient levels in the groundwater were low, but energy-dispersive X-ray spectroscopy has shown biogeochemical immobilization of several elements in the biofilms; some of these elements were concentrated from extremely dilute environmental concentrations, and all elements were chemically complexed together to form amorphous or crystalline fine-grained minerals. These were seen by transmission electron microscopy to be both associated with the surfaces of the bacteria and scattered throughout the extracellular matrix, suggesting their de novo development through bacterial surface-mediated nucleation. The biofilm consortia are thought to concentrate elements both by passive sorption and by energy metabolism. By Mössbauer spectroscopy and X-ray diffraction, one of the biofilms showed that iron was both oxidized and precipitated as ferrihydrite or hematite aerobically and reduced and precipitated as siderite anaerobically. We believe that some Archean banded-iron formations could have been formed in a manner similar to this, as it would explain the deposition of hematite and siderite in close proximity. This biogeochemical development of minerals may also affect the transport of material in waste disposal sites. Images PMID:16349374

VNIR multispectral observations of rocks at Cape York, Endeavour crater, Mars by the Opportunity rover's Pancam

NASA Astrophysics Data System (ADS)

Farrand, William H.; Bell, James F.; Johnson, Jeffrey R.; Rice, Melissa S.; Hurowitz, Joel A.

2013-07-01

From its arrival at the portion of the rim of Endeavour crater known informally as Cape York, the Mars Exploration Rover Opportunity has made numerous visible and near infrared (VNIR) multispectral observations of rock surfaces. This paper describes multispectral observations from Opportunity's arrival at Cape York to its winter-over location at Greeley Haven. Averages of pixels from the Pancam's left and right eyes were joined to form 11 point spectra from numerous observations and were examined via a number of techniques. These included principal components analysis, a sequential maximum angle convex cone approach, examination of spectral parameters, and a hierarchical clustering approach. The end result of these analyses was the determination of six primary spectral (PS) classes describing spectrally unique materials observed on Cape York. These classes consisted of a "standard" outcrop spectrum that was observed on the clasts and matrix comprising the upper unit of the Shoemaker formation, a class representing rock surfaces exposed around Odyssey crater and typified by the rocks of the Tisdale series, pebbles occurring in and weathered out of the upper unit of the Shoemaker formation that appear red in 1009, 904, 754 nm color composites, patches on Tisdale rocks exhibiting a 864 nm band minimum that were spectrally anomalous in root mean square error images derived from spectral mixture analyses, clasts with a high 904 nm band depth occurring in the Greeley Haven location, and gypsum veins typified by the vein Homestake. Comparisons of three of these classes that had well defined band minima between 800 and 1009 nm with spectral library spectra of ferrous silicates and ferric oxide, oxyhydroxide and ferric sulfate minerals indicated tentative matches of the "red" pebbles with orthopyroxenes, of the spectrally anomalous 864 nm band minimum material with hematite or ferric sulfates, and of the high 904 nm band depth material with an orthopyroxene-clinopyroxene mixture. The spectral properties of rock surfaces on Cape York are distinct from those of Burns Formation outcrops observed on the Meridiani Plains. The Cape York outcrop is Noachian in age and study of these materials provides insight into less acidic environmental conditions extant before the formation of the Burns Formation.

Hematite (α-Fe2O3) - A potential Ce4+ carrier in red mud.

PubMed

Bolanz, Ralph M; Kiefer, Stefan; Göttlicher, Jörg; Steininger, Ralph

2018-05-01

Cerium is the most abundant rare earth element (REE) within the waste product of alumina production (red mud), but its speciation in this complex material is still barely understood. Previous studies showed evidence for a correlation between Ce and the main constituent of red mud, iron oxides, which led us to investigate the most abundant iron oxide in red mud, hematite, as possible carrier phase for Ce. Synthetic hematite can incorporate up to 1.70±0.01wt% Ce, which leads to a systematical increase of all unit cell parameters. Investigations by extended X-ray absorption fine structure spectroscopy suggest an incorporation of Ce 4+ O 6 into the hematite structure by a novel atomic arrangement, fundamentally different from the close-range order around Fe 3+ in hematite. Samples of red mud were taken in Lauta (Saxony), Germany and analyzed by powder X-ray diffraction, inductively coupled plasma mass and optical emission spectrometry, electron microprobe analysis and X-ray absorption near-edge structure spectroscopy. Red mud samples consist of hematite (Fe 2 O 3 ) (34-58wt%), sodalite (Na 8 Al 6 Si 6 O 24 Cl 2 ) (4-30wt%), gibbsite (Al(OH) 3 ) (0-25wt%), goethite (FeOOH) (10-23wt%), böhmite (AlOOH) (0-11wt%), rutile (TiO 2 ) (4-8wt%), cancrinite (Na 6 Ca 2 Al 6 Si 6 O 24 (CO 3 ) 2 ) (0-5wt%), nordstrandite (Al(OH) 3 ) (0-5wt%) and quartz (SiO 2 ) (0-4wt%). While the main elemental composition is Fe>Al>Na>Ti>Ca (Si not included), the average concentration of REE is 1109±6mg/kg with an average Ce concentration of 464±3mg/kg. The main carrier of Ce was located in the Fe-rich fine-grained fraction of red mud (0.10wt% Ce 2 O 3 ), while other potential Ce carriers like monazite, lead oxides, secondary Ce-minerals and particles of potentially anthropogenic origin are of subordinated relevance. Cerium in red mud occurs predominantly as Ce 4+ , which further excludes Ce 3+ minerals as relevant sources. Copyright © 2017. Published by Elsevier B.V.

Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

PubMed

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite and also to sulfates, and at 250 °C mainly to magnetite instead of pyrite, associated to the same ferric oxides/hydroxides and sulfates. Some examples of geological terrains, such as Mawrth Vallis on Mars, the Tagish Lake meteorite and hydrothermal venting fields, where hydrolysis/oxidation of ferromagnesian silicates and iron(II)-monosulfides may occur, are discussed. Considering the evolution of rocks during their interaction with water, in the absence of oxygen and in radiolyzed water, with hydrothermal release of H 2 and the plausible associated formation of components of life, geobiotropic signatures are proposed. They are mainly Fe(III)-phyllosilicates, magnetite, ferric trihydroxide, goethite/lepidocrocite, hematite, but not pyrite.

Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

NASA Astrophysics Data System (ADS)

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite and also to sulfates, and at 250 °C mainly to magnetite instead of pyrite, associated to the same ferric oxides/hydroxides and sulfates. Some examples of geological terrains, such as Mawrth Vallis on Mars, the Tagish Lake meteorite and hydrothermal venting fields, where hydrolysis/oxidation of ferromagnesian silicates and iron(II)-monosulfides may occur, are discussed. Considering the evolution of rocks during their interaction with water, in the absence of oxygen and in radiolyzed water, with hydrothermal release of H2 and the plausible associated formation of components of life, geobiotropic signatures are proposed. They are mainly Fe(III)-phyllosilicates, magnetite, ferric trihydroxide, goethite/lepidocrocite, hematite, but not pyrite.

Isolating the anisotropy of the characteristic remanence-carrying hematite grains: a first multispecimen approach

NASA Astrophysics Data System (ADS)

Bilardello, Dario

2015-08-01

Separating the contribution of different hematite coercivity grains to the magnetic fabric is a standing problem in rock magnetism because of the common occurrence of thermochemical alterations when measuring the anisotropy of thermal remanence. A technique that eliminates this bias is presented, which is useful when there is a need to separate the fabric of detrital from pigmentary hematite, for example. The method is based on stepwise thermal demagnetization of saturation isothermal remanent magnetizations (IRMs) applied orthogonally on three sister specimens, allowing calculation of the anisotropy tensor from the three components of each demagnetized IRM vector, avoiding the necessity of having to apply IRMs to thermochemically altered specimens. Vector subtraction allows determining the anisotropy tensor for specific unblocking-temperature ranges. The anisotropies of the pigmentary, specular and total hematite of the Mauch Chunk Formation red beds of Pennsylvania have been measured from an oriented block sample and results are compared to previous anisotropy measurements performed using the high-field anisotropy of isothermal remanence technique (hf-AIR), which measures total undifferentiated hematite. Experiments were conducted using non-saturating 1 T and fully saturating 5.5 T fields: both experimental sets seem capable of measuring the orientation of the specularite anisotropy principal axes, but 5.5 T are needed to capture the orientation of the higher coercivity pigmentary grains. The magnitudes of the principal axes, instead, are only faithfully measured using 5.5 T fields and yield somewhat higher anisotropies than those measured by hf-AIR. The fundamental requirement for this technique is homogeneous material among the three sister specimens, which is a significant limitation; homogeneity tests allow assessment of applicability of the method and reliability of the results.

Deposition and disinfection of Escherichia coli O157:H7 on naturally occurring photoactive materials in a parallel plate chamber†

PubMed Central

Taylor, Alicia A.; Chowdhury, Indranil; Gong, Amy S.; Cwiertny, David M.; Walker, Sharon L.

2014-01-01

Dissolved organic matter in combination with iron oxides has been shown to facilitate photochemical disinfection through the production of reactive oxygen species (ROS) under UV and visible light. However, due to the extremely short lifetime of these radicals, the disinfection effciency is limited by the successful transport of ROS to bacterial surfaces. This study was designed to quantitatively investigate three collector surfaces with various potentials to produce ROS [bare quartz, hematite (α-Fe2O3) coated quartz, and Suwannee River humic acid (SRHA)] and the effects of extracellular polymeric substance (EPS) (full or partial coating) and solution chemistry (ionic strength, IS) on the interactions between bacteria and the ROS-producing substrates. With few exceptions, bacterial deposition studies in a parallel plate (PP) flow chamber have revealed increasing cell adhesion with IS. Furthermore, interactions between collector surfaces and cells can be explained by electrostatic forces, with negatively charged SRHA reducing and positively charged α-Fe2O3 enhancing bacterial deposition significantly. Increased deposition was also observed with full EPS content, indicating the ability of EPS to facilitate interaction between cells and surfaces in the aquatic environment. In complementary disinfection studies conducted with simulated light, viability loss was observed for cells fully coated with EPS when attached to α-Fe2O3 under all IS conditions. Based upon our prior study in which EPS was found to not inhibit hydroxyl radical activity toward bacteria, we proposed that EPS might therefore promote disinfection by facilitating cell attachment to ROS-producing surfaces where higher concentrations of ROS are expected at closer proximities to reactive substrates (e.g., SRHA and α-Fe2O3). Our findings on the mechanism and controlling factors of cell interactions with photoactive substrates provide insight as to the role of ionic strength in photochemical disinfection processes. PMID:24362649

Mineral Precipitation in Porous Media: Laboratory Diffusion Experiments as Analogues for Concretion Formation in Utah and on Mars

NASA Astrophysics Data System (ADS)

Barge, L. M.; Petruska, J.; Potter, S.; Cho, J.; Chan, M.; Nealson, K.

2007-12-01

We present results of laboratory gel diffusion experiments designed to simulate the precipitation of iron minerals in natural systems. Liesegang bands and crystals of various iron minerals were formed in aqueous gels, "mini- concretions" of mineral precipitate were formed in both sand and a sand/agarose mixture, and the formation of hollow mineral spheres was observed in gel precipitation experiments where organics were introduced. These mineral structures are analogous to concretion forms observed in the Navajo Sandstone region of Utah, which have been suggested as terrestrial analogs for the "blueberry" hematite concretions on Mars. Iron mineral precipitates (perhaps with a gel precursor) occur in many forms in the Navajo Sandstone, including "mini- concretions" (solid concretions 1-2 mm in diameter), "rind-like" concretions (hollow spheres of hematite several cm in diameter, surrounding a region of sandstone), and Liesegang banding (banded patterns that form at reaction fronts through diffusion of ions from one reservoir to another). On Mars only small (4-5mm) and mini-concretions (~ 1mm) have been observed; Liesegang bands or large rind-like concretions have not yet been discovered. The varying conditions that give rise to each of these mineral structures in the laboratory indicate that the small, spheroidal types of iron precipitates found in the Utah and Martian environments may be diagnostic of the diffusion medium, presence of organics, and characteristics of fluid in that region.

Role of outer membrane c-type cytochromes MtrC and OmcA in Shewanella oneidensis MR-1 cell production, accumulation and detachment during respiration on hematite

USDA-ARS?s Scientific Manuscript database

The iron-reducing bacterium Shewanella oneidensis MR-1 has the capacity to contribute to iron cycling over the long term by respiring on crystalline iron oxides such as hematite when poorly crystalline phases are depleted. The ability of outer membrane cytochromes OmcA and MtrC of MR-1 to bind to an...

Synthesis and characterization of goethite and goethite-hematite composite: experimental study and literature survey.

PubMed

Kosmulski, Marek; Maczka, Edward; Jartych, Elzbieta; Rosenholm, Jarl B

2003-03-19

Aging of synthetic goethite at 140 degrees C overnight leads to a composite material in which hematite is detectable by Mössbauer spectroscopy, but X-ray diffraction does not reveal any hematite peaks. The pristine point of zero charge (PZC) of synthetic goethite was found at pH 9.4 as the common intersection point of potentiometric titration curves at different ionic strengths and the isoelectric point (IEP). For the goethite-hematite composite, the common intersection point (pH 9.4), and the IEP (pH 8.8) do not match. The electrokinetic potential of goethite at ionic strengths up to 1 mol dm(-3) was determined. Unlike metal oxides, for which the electrokinetic potential is reversed to positive over the entire pH range at sufficiently high ionic strength, the IEP of goethite is rather insensitive to the ionic strength. A literature survey of published PZC/IEP values of iron oxides and hydroxides indicated that the average PZC/IEP does not depend on the degree of hydration (oxide or hydroxide). Our material showed a higher PZC and IEP than most published results. The present results confirm the allegation that electroacoustic measurements produce a higher IEP than the average IEP obtained by means of classical electrokinetic methods.

MOLA-Based Landing Site Characterization

NASA Technical Reports Server (NTRS)

Duxbury, T. C.; Ivanov, A. B.

2001-01-01

The Mars Global Surveyor (MGS) Mars Orbiter Laser Altimeter (MOLA) data provide the basis for site characterization and selection never before possible. The basic MOLA information includes absolute radii, elevation and 1 micrometer albedo with derived datasets including digital image models (DIM's illuminated elevation data), slopes maps and slope statistics and small scale surface roughness maps and statistics. These quantities are useful in downsizing potential sites from descent engineering constraints and landing/roving hazard and mobility assessments. Slope baselines at the few hundred meter level and surface roughness at the 10 meter level are possible. Additionally, the MOLA-derived Mars surface offers the possibility to precisely register and map project other instrument datasets (images, ultraviolet, infrared, radar, etc.) taken at different resolution, viewing and lighting geometry, building multiple layers of an information cube for site characterization and selection. Examples of direct MOLA data, data derived from MOLA and other instruments data registered to MOLA arc given for the Hematite area.

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.

Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System.

PubMed

Lavrynenko, O M; Pavlenko, O Yu; Shchukin, Yu S

2016-12-01

The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are formed on the steel surface. Mixed LDHs keep stability against further oxidation and complicate the obtaining of spinel ferrite nanoparticles. Thermal treatment of mixed LDHs among other mineral phases formed via the rotation-corrosion dispergation process at certain temperatures permits to obtain homogenous nanoparticles of spinel ferrites as well as maghemite or hematite doped by 3d-metal cations.

Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System

NASA Astrophysics Data System (ADS)

Lavrynenko, O. M.; Pavlenko, O. Yu; Shchukin, Yu S.

2016-02-01

The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are formed on the steel surface. Mixed LDHs keep stability against further oxidation and complicate the obtaining of spinel ferrite nanoparticles. Thermal treatment of mixed LDHs among other mineral phases formed via the rotation-corrosion dispergation process at certain temperatures permits to obtain homogenous nanoparticles of spinel ferrites as well as maghemite or hematite doped by 3d-metal cations.

Desert Varnish - Preservation of Biofabrics/Implcations for Mars

NASA Technical Reports Server (NTRS)

Probst, Luke W.; Allen, Carlton C.; Thomas-Keprta, Kathie L.; Clemett, Simon J.; Longazo, Teresa G.; Nelman-Gonzalez, Mayra A.; Sams, Clarence

2002-01-01

Desert varnish is the orange to dark brown rind that accumulates on exposed rock surfaces in many arid environments. Samples from the Sonoran Desert of Arizona are composed predominantly of clays (illite, smectite) and Mn- and Fe- oxides (birnessite, hematite). Features that appear to be single organisms are found within the varnish and at the rock-varnish interface. Many of these features are embedded in films that strongly resemble the water-rich extracellular polysaccharides produced by diverse microorganisms. Most common are rod-shaped celllike objects, 0.5-2 microns in the longest dimension, located within the varnish coatings. Some of these objects are shown to contain amines by fluorescence microscopy. The rod-shaped objects are observed in various states of degradation, as indicated by C and S abundances. Rods with higher C and S abundances appear less degraded than those with lower concentrations of these two elements. Regions rich in apparent microbes are present, while other regions display Mn- and Fe-rich mineral fabrics with microbe-sized voids and no obvious cells. These textures are interpreted as biofabrics, preserved by the precipitation of Mn and Fe minerals. We are researching the preservation of biofabrics by desert varnish in Earth's geological record. Rock coatings may similarly preserve evidence of microbial life on the hyper-arid surface of Mars.

Rapid electron exchange between surface-exposed bacterial cytochromes and Fe(III) minerals

PubMed Central

White, Gaye F.; Shi, Zhi; Shi, Liang; Wang, Zheming; Dohnalkova, Alice C.; Marshall, Matthew J.; Fredrickson, James K.; Zachara, John M.; Butt, Julea N.; Richardson, David J.; Clarke, Thomas A.

2013-01-01

The mineral-respiring bacterium Shewanella oneidensis uses a protein complex, MtrCAB, composed of two decaheme cytochromes, MtrC and MtrA, brought together inside a transmembrane porin, MtrB, to transport electrons across the outer membrane to a variety of mineral-based electron acceptors. A proteoliposome system containing a pool of internalized electron carriers was used to investigate how the topology of the MtrCAB complex relates to its ability to transport electrons across a lipid bilayer to externally located Fe(III) oxides. With MtrA facing the interior and MtrC exposed on the outer surface of the phospholipid bilayer, the established in vivo orientation, electron transfer from the interior electron carrier pool through MtrCAB to solid-phase Fe(III) oxides was demonstrated. The rates were 103 times higher than those reported for reduction of goethite, hematite, and lepidocrocite by S. oneidensis, and the order of the reaction rates was consistent with those observed in S. oneidensis cultures. In contrast, established rates for single turnover reactions between purified MtrC and Fe(III) oxides were 103 times lower. By providing a continuous flow of electrons, the proteoliposome experiments demonstrate that conduction through MtrCAB directly to Fe(III) oxides is sufficient to support in vivo, anaerobic, solid-phase iron respiration. PMID:23538304

Mechanical, structural and dissolution properties of heat treated thin-film phosphate based glasses

NASA Astrophysics Data System (ADS)

Stuart, Bryan W.; Gimeno-Fabra, Miquel; Segal, Joel; Ahmed, Ifty; Grant, David M.

2017-09-01

Here we show the deposition of 2.7 μm thick phosphate based glass films produced by magnetron sputtering, followed by post heat treatments at 500 °C. Variations in degradation properties pre and post heat treatment were attributed to the formation of Hematite crystals within a glass matrix, iron oxidation and the depletion of hydrophilic P-O-P bonds within the surface layer. As deposited and heat treated coatings showed interfacial tensile adhesion in excess of 73.6 MPa; which surpassed ISO and FDA requirements for HA coatings. Scratch testing of coatings on polished substrates revealed brittle failure mechanisms, amplified due to heat treatment and interfacial failure occurring from 2.3 to 5.0 N. Coatings that were deposited onto sandblasted substrates to mimic commercial implant surfaces, did not suffer from tensile cracking or trackside delamination showing substantial interfacial improvements to between 8.6 and 11.3 N. An exponential dissolution rate was observed from 0 to 2 h for as deposited coatings, which was eliminated via heat treatment. From 2 to 24 h ion release rates ordered P > Na > Mg > Ca > Fe whilst all coatings exhibited linear degradation rates, which reduced by factors of 2.4-3.0 following heat treatments.

Reduced partition function ratios of iron and oxygen in goethite

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

Blanchard, M.; Dauphas, N.; Hu, M. Y.

2015-02-01

First-principles calculations based on the density functional theory (DFT) with or without the addition of a Hubbard U correction, are performed on goethite in order to determine the iron and oxygen reduced partition function ratios (beta-factors). The calculated iron phonon density of states (pDOS), force constant and beta-factor are compared with reevaluated experimental beta-factors obtained from Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements. The reappraisal of old experimental data is motivated by the erroneous previous interpretation of the low- and high-energy ends of the NRIXS spectrum of goethite and jarosite samples (Dauphas et al., 2012). Here the NRIXS data aremore » analyzed using the SciPhon software that corrects for non-constant baseline. New NRIXS measurements also demonstrate the reproducibility of the results. Unlike for hematite and pyrite, a significant discrepancy remains between DFT, NRIXS and the existing Mossbauer-derived data. Calculations suggest a slight overestimation of the NRIXS signal possibly related to the baseline definition. The intrinsic features of the samples studied by NRIXS and Mossbauer spectroscopy may also contribute to the discrepancy (e. g., internal structural and/or chemical defects, microstructure, surface contribution). As for oxygen, DFT results indicate that goethite and hematite have similar beta-factors, which suggests almost no fractionation between the two minerals at equilibrium.« less

Production of mineral aggregates in quartz tumbling experiments

NASA Astrophysics Data System (ADS)

Nørnberg, Per; Finster, Kai; Pall Gunnlaugsson, Haraldur; Knak Jensen, Svend; Merrison, Jonathan Peter

2013-04-01

Introduction Tumbling experiments with quartz sand with the purpose of tracing the effect of broken bonds in mineral surfaces resulted in an unexpected production of aggregates. These aggregates are a few microns in diameter, spherical and resembling tiny white "snowballs." Particle comminution by aeolian and other natural weathering processes are known in soil science and is often seen as an increase of fine particles towards the top of soil profiles (Nørnberg, P. 1987, 1988, 2002, J.S. Wright 2007). When mineral grains collide in aeolian processes they break up along weakness zones in the crystal lattice. This mechanism causes broken bonds between atoms in the crystal lattice and results in reactive groups in the mineral surface. This mechanism provides the background for experiments to investigate the oxidation processes of magnetite on the planet Mars. The primary magnetic iron oxide phase on Mars is to day known to be magnetite and the colour of the dust on Mars is most likely due to hematite. To investigate if the oxidation process could take place without going over dissolution and precipitation in water, experiments with tumbling of quartz grains in sealed glass containers along with magnetite were started. The idea was that activated bonds at the surface of quartz could oxidize magnetite and convert it to hematite over time. This proved to be the case (Merrison, J.P. et al. 2010). However, in these experiments we observed the formation of the white aggregates which has been the subject of the study that we present here. Results of tumbling experiments Commercially available quarts (Merck) was sieved to obtain the fraction between 125 and 1000 µm. This fraction was tumbled in glass containers for months and resulted in production of a significant amount of fine grained material (Merrison, J.P et al. 2010). A part of this fine fraction consists of the "snowball"-like aggregates which is a fragile element with relatively high specific surface. The physical properties of these structures will be discussed in this paper. Nørnberg, P. 1977: Soil Profile Development in Sands of Varying Age in Vendsyssel, Denmark. Catena, 4, 165-179. Nørnberg, P. 1980: Mineralogy of a podzol formed in sandy materials in Northern Denmark. Geoderma, 24, 25-43. Nørnberg, P. 2002: Particle comminution and aeolian addition in young dune sand soils. Transactions, 17th World Congress of Soil Science, Bangkok, Thailand, Symp. 25, pp. 9. Janet S. Wright, Janet S. 2007: An overview of the role of weathering in the production of quartz silt Sedimentary Geology, 202, 337-351 Merrison, J.P., Gunnlaugsson, H.P., Nørnberg, P., Jensen, A.E., Rasmussen, K.R. 2007: Determination of the Wind Induced Detachment Threshold for Granular Material on Mars using Wind Tunnel Simulations. Icarus, 191, 568-580.

Formation of albitite-hosted uranium within IOCG systems: the Southern Breccia, Great Bear magmatic zone, Northwest Territories, Canada

NASA Astrophysics Data System (ADS)

Montreuil, Jean-François; Corriveau, Louise; Potter, Eric G.

2015-03-01

Uranium and polymetallic U mineralization hosted within brecciated albitites occurs one kilometer south of the magnetite-rich Au-Co-Bi-Cu NICO deposit in the southern Great Bear magmatic zone (GBMZ), Canada. Concentrations up to 1 wt% U are distributed throughout a 3 by 0.5 km albitization corridor defined as the Southern Breccia zone. Two distinct U mineralization events are observed. Primary uraninite precipitated with or without pyrite-chalcopyrite ± molybdenite within magnetite-ilmenite-biotite-K-feldspar-altered breccias during high-temperature potassic-iron alteration. Subsequently, pitchblende precipitated in earthy hematite-specular hematite-chlorite veins associated with a low-temperature iron-magnesium alteration. The uraninite-bearing mineralization postdates sodic (albite) and more localized high-temperature potassic-iron (biotite-magnetite ± K-feldspar) alteration yet predates potassic (K-feldspar), boron (tourmaline) and potassic-iron-magnesium (hematite ± K-feldspar ± chlorite) alteration. The Southern Breccia zone shares attributes of the Valhalla (Australia) and Lagoa Real (Brazil) albitite-hosted U deposits but contains greater iron oxide contents and lower contents of riebeckite and carbonates. Potassium, Ni, and Th are also enriched whereas Zr and Sr are depleted with respect to the aforementioned albitite-hosted U deposits. Field relationships, geochemical signatures and available U-Pb dates on pre-, syn- and post-mineralization intrusions place the development of the Southern Breccia and the NICO deposit as part of a single iron oxide alkali-altered (IOAA) system. In addition, this case example illustrates that albitite-hosted U deposits can form in albitization zones that predate base and precious metal ore zones in a single IOAA system and become traps for U and multiple metals once the tectonic regime favors fluid mixing and oxidation-reduction reactions.

Magnetic analyses of soils from the Wind River Range, Wyoming, constrain rates and pathways of magnetic enhancement for soils from semiarid climates

NASA Astrophysics Data System (ADS)

Quinton, Emily E.; Dahms, Dennis E.; Geiss, Christoph E.

2011-07-01

In order to constrain the rate of magnetic enhancement in soils, we investigated modern soils from five fluvial terraces in the eastern Wind River Range, Wyoming. Profiles up to 1.2 m deep were sampled in 5-cm intervals from hand-dug pits or natural riverbank exposures. Soils formed in fluvial terraces correlated to the Sacajawea Ridge (730-610 ka BP), Bull Lake (130-100 ka BP) and Pinedale-age (˜20 ka BP) glacial advances. One soil profile formed in Holocene-age sediment. Abundance, mineralogy, and grain size of magnetic minerals were estimated through magnetic measurements. Magnetic enhancement of the A-horizon as well as an increase in fine-grained magnetic minerals occurred mostly in Bull Lake profiles but was absent from the older profile. Such low rates of magnetic enhancement may limit the temporal resolution of paleosol-based paleoclimate reconstructions in semiarid regions even where high sedimentation rates result in multiple paleosols. A loss of ferrimagnetic and an increase in antiferromagnetic minerals occurred with age. Our findings suggest either the conversion of ferrimagnetic minerals to weakly magnetic hematite with progressing soil age, or the presence of ferrimagnetic minerals as an intermediate product of pedogenesis. Absolute and relative hematite abundance increase with age, making both useful proxies for soil age and the dating of regional glacial deposits. All coercivity proxies are consistent with each other, which suggests that observed changes in HIRM and S-ratio are representative of real changes in hematite abundance rather than shifts in coercivity distributions, even though the modified L-ratio varies widely.

Spin Crossover and the Magnetic P- T Phase Diagram of Hematite at High Hydrostatic Pressures and Cryogenic Temperatures

NASA Astrophysics Data System (ADS)

Gavriliuk, A. G.; Struzhkin, V. V.; Mironovich, A. A.; Lyubutin, I. S.; Troyan, I. A.; Chow, P.; Xiao, Y.

2018-02-01

The magnetic properties of the α-Fe2O3 hematite at a high hydrostatic pressure have been studied by synchrotron Mössbauer spectroscopy (nuclear forward scattering (NFS)) on iron nuclei. Time-domain NFS spectra of hematite have been measured in a diamond anvil cell in the pressure range of 0-72 GPa and the temperature range of 36-300 K in order to study the magnetic properties at a phase transition near a critical pressure of 50 GPa. In addition, Raman spectra at room temperature have been studied in the pressure range of 0-77 GPa. Neon has been used as a pressure-transmitting medium. The appearance of an intermediate electronic state has been revealed at a pressure of 48 GPa. This state is probably related to the spin crossover in Fe3+ ions at their transition from the high-spin state (HS, S = 5/2) to a low-spin one (LS, S = 1/2). It has been found that the transient pressure range of the HS-LS crossover is extended from 48 to 55 GPa and is almost independent of the temperature. This surprising result differs fundamentally from other cases of the spin crossover in Fe3+ ions observed in other crystals based on iron oxides. The transition region of spin crossover appears because of thermal fluctuations between HS and LS states in the critical pressure range and is significantly narrowed at cooling because of the suppression of thermal excitations. The magnetic P- T phase diagram of α-Fe2O3 at high pressures and low temperatures in the spin crossover region has been constructed according to the results of measurements.

Mineralogy and autoradiography of selected mineral-spring precipitates in the Western United States

USGS Publications Warehouse

Bove, Dana; Felmlee, J.K.

1982-01-01

X-ray diffaction analysis of 236 precipitate or sediment samples from 97 mineral-spring sites in nine Western States showed the presence of 25 minerals, some precipitated and some detrital. Calcite and (or) aragonite are the most common of all the precipitated minerals. Gypsum and (or) anhydrite, as well as barite and native sulfur, are less common but are also believed to be precipitated minerals. Precipitated manganese and iron oxides, including romanechite, manganite, pyrolusite, goethite, and hematite, were found in some of the samples. Various salts of sodium, including halite and thenardite, were also identified. Dolomite and an unknown type of siliceous material are present in some of the samples and were possibly precipitated at the spring sites. Quartz, feldspar, and mica are present in many of the samples and are believed to be detrital contaminants. An autoradiographic and thin section study of 11 samples from nine of the most radioactive spring sites showed the radioactivity, which is due primarily to radium, to be directly associated with mineral phases containing barium, manganese, iron, and (or) calcium as major constituents. Furthermore, the radioactivity has an exclusive affinity for the manganese-bearing minerals, which in these samples contain a substantial amount of barium, even if calcite or iron oxides are present. Where calcite predominates and manganese- and barium-bearing minerals are absent, the radioactivity shows a close association with the iron oxides present, especially hematite, but also shows a moderate association with the calcite and (or) aragonite cementing phases. In other samples composed predominantly of calcite but lacking iron oxides, the radioactivity is preferentially associated with an early stage of calcite development and is considerably lower in the later cementing stages. The radioactivity observed in all these samples is believed to be caused by radium substituting for barium in mineral lattices, filling irregularities in other crystal structures, or adsorbing on the surfaces of precipitated molecules.

The role of biomineralization in microbiologically influenced corrosion

NASA Technical Reports Server (NTRS)

Little, B.; Wagner, P.; Hart, K.; Ray, R.; Lavoie, D.; Nealson, K.; Aguilar, C.

1998-01-01

Synthetic iron oxides (goethite, alpha-FeO.OH; hematite, Fe2O3; and ferrihydrite, Fe(OH)3) were used as model compounds to simulate the mineralogy of surface films on carbon steel. Dissolution of these oxides exposed to pure cultures of the metal-reducing bacterium, Shewanella putrefaciens, was followed by direct atomic absorption spectroscopy measurement of ferrous iron coupled with microscopic analyses using confocal laser scanning and environmental scanning electron microscopies. During an 8-day exposure the organism colonized mineral surfaces and reduced solid ferric oxides to soluble ferrous ions. Elemental composition, as monitored by energy dispersive x-ray spectroscopy, indicated mineral replacement reactions with both ferrihydrite and goethite as iron reduction occurred. When carbon steel electrodes were exposed to S. putrefaciens, microbiologically influenced corrosion was demonstrated electrochemically and microscopically.

Phyllosilicate and sulfate-hematite deposits within Miyamoto crater in Southern Sinus Meridiani, Mars

USGS Publications Warehouse

Wiseman, S.M.; Arvidson, R. E.; Andrews-Hanna, J. C.; Clark, R.N.; Lanza, N.L.; des Marais, D.; Marzo, G.A.; Morris, R.V.; Murchie, S.L.; Newsom, Horton E.; Noe Dobrea, E.Z.; Ollila, A.M.; Poulet, F.; Roush, T.L.; Seelos, F.P.; Swayze, G.A.

2008-01-01

Orbital topographic, image, and spectral data show that sulfate- and hematite-bearing plains deposits similar to those explored by the MER rover Opportunity unconformably overlie the northeastern portion of the 160 km in diameter Miyamoto crater. Crater floor materials exhumed to the west of the contact exhibit CRISM and OMEGA NIR spectral signatures consistent with the presence of Fe/Mg-rich smectite phyllosilicates. Based on superposition relationships, the phyllosilicate-bearing deposits formed either in-situ or were deposited on the floor of Miyamoto crater prior to the formation of the sulfate-rich plains unit. These findings support the hypothesis that neutral pH aqueous conditions transitioned to a ground-water driven acid sulfate system in the Sinus Meridiani region. The presence of both phyllosilicate and sulfate- and hematite-bearing deposits within Miyamoto crater make it an attractive site for exploration by future rover missions. Copyright 2008 by the American Geophysical Union.

Strontium-Doped Hematite as a Possible Humidity Sensing Material for Soil Water Content Determination

PubMed Central

Tulliani, Jean-Marc; Baroni, Chiara; Zavattaro, Laura; Grignani, Carlo

2013-01-01

The aim of this work is to study the sensing behavior of Sr-doped hematite for soil water content measurement. The material was prepared by solid state reaction from commercial hematite and strontium carbonate heat treated at 900 °C. X-Ray diffraction, scanning electron microscopy and mercury intrusion porosimetry were used for microstructural characterization of the synthesized powder. Sensors were then prepared by uniaxially pressing and by screen-printing, on an alumina substrate, the prepared powder and subsequent firing in the 800–1,000 °C range. These sensors were first tested in a laboratory apparatus under humid air and then in an homogenized soil and finally in field. The results evidenced that the screen printed film was able to give a response for a soil matric potential from about 570 kPa, that is to say well below the wilting point in the used soil. PMID:24025555

Light in the darkening on Naica gypsum crystals

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

Castillo-Sandoval, I.; Fuentes-Cobas, L. E.; Esparza-Ponce, H. E.

2015-07-23

Naica mine is located in a semi-desertic region at the central-south of Chihuahua State. The Cave of Swords was discovered in 1910 and the Cave of Crystals 90 years later at Naica mines. It is expected that during the last century the human presence has changed the microclimatic conditions inside the cave, resulting in the deterioration of the crystals and the deposition of impurities on gypsum surfaces. As a contribution to the clarification of the mentioned issues, the present work refers to the use of synchrotron radiation for the identification of phases on these surfaces. All the experiments were performedmore » at the Stanford Synchrotron Radiation Lightsource. Grazing incidence X-ray diffraction (GIXRD) and radiography-aided X-ray diffraction (RAXRD) experiments were performed at beamline 11-3. X-Ray micro-fluorescence (μ-SXRF) and micro-X-ray absorption (μ-XANES) were measured at beamline 2-3. Representative results obtained may be summarized as follows: a) Gypsum, galena, sphalerite, hematite and cuprite at the surface of the gypsum crystals were determined. b) The samples micro-structure is affected by impurities. c) The elemental distributions and correlations (0.6-0.9) of Cu, K, Fe, Mn, Pb, Zn, Ca and S were identified by μ-SXRF. The correlations among elemental contents confirmed the phase identification, with the exception of manganese and potassium due to the amorphous nature of some impurity compounds in these samples. The compounds hematite (Fe{sub 2}O{sub 3}), β-MnO{sub 2}, Mn{sub 2}O{sub 3}, MnO and/or MnCO{sub 3}, PbS, PbCO{sub 3} and/or PbSO4, ZnO{sub 4}, ZnS and/or smithsonite (ZnCO{sub 3}), CuS + Cu Oxide were identified by XANES. Plausibly, these latter compounds do not form crystalline phases.« less

Mechanisms of iron-silica aqueous interaction and the genesis of Precambrian iron formation

NASA Astrophysics Data System (ADS)

Chemtob, S. M.; Catalano, J. G.; Moynier, F.; Pringle, E. A.

2015-12-01

Iron formations (IFs), Fe- and Si-rich chemical sediments common in Precambrian successions, preserve key information about the compositional, biological, and oxidative evolution of the Precambrian ocean. Stable Si isotopes (δ30Si) of IF have been used to infer paleo-oceanic composition, and secular variations in δ30Si may reflect ancient biogeochemical cycles. The δ30Si of primary Fe-Si precipitates that formed IF depends not only on the δ30Si of aqueous silica but also on the precipitation mechanism. Multiple formation mechanisms for these primary precipitates are plausible. Aqueous Si may have adsorbed on newly precipitated iron oxyhydroxide surfaces; alternatively, Fe and Si may have coprecipitated as a single phase. Here we explore variations in the Si isotope fractionation factor (ɛ) with Fe-Si aqueous interaction mechanism (adsorption vs. coprecipitation). In adsorption experiments, sodium silicate solutions (pH 8.1, 125-2000 µM Si) were reacted with iron oxide particles (hematite, ferrihydrite, goethite, and magnetite) for 24 to 72 hours. Resultant solutions had δ30Si between 0 and +6‰. Calculated ɛ varied significantly with oxide mineralogy and morphology. For ferrihydrite, ɛ = -1.7‰; for hematite, ɛ = -2 to -5‰, depending on particle morphology. Apparent ɛ decreased upon surface site saturation, implying a smaller isotope effect for polymeric Si adsorption than monomeric adsorption. In coprecipitation experiments, solutions of Na-silicate and Fe(II) chloride (0.4-10 mM) were prepared anaerobically, then air-oxidized for 3 days to induce precipitation. At low Si concentrations, magnetite formed; near silica saturation, lepidocrocite and ferrihydrite formed. The Si isotope fractionation factor for coprecipitation was within the range of ɛ observed for adsorption (ɛ = -2.3 ± 1.0‰). These results indicate that the mechanism of Fe-Si interaction affects ɛ, presumably due to varying silicate coordination environments. These isotopic analyses will be paired with Si K-edge and Fe K-edge X-ray absorption spectra of the solids to illustrate how Si bonding environment affects ɛ. Effective reconstruction of paleo-oceanic δ30Si may require additional constraints on the relative importance of Si adsorption and Fe-Si coprecipitation in the production of IF primary precipitates.

Evidence for Aqueously Precipitated Sulfates in Northeast Meridiani Using THEMIS and TES Data

NASA Technical Reports Server (NTRS)

Lane, Melissa D.

2005-01-01

Recently aqueously deposited sulfate-rich bedrock was found at the MER-B Meridiani landing site [1]. Additional sulfate was observed from orbit by the Mars Express OMEGA instrument [2]. In this work, I present midinfrared spectral evidence (using THEMIS and TES) for sulfate in and around a channel deposit that lies to the northeast of the hematite- strewn plains of Meridiani at approx.2degN, 1degW (Fig. 1).

Visible and near-infrared multispectral analysis of rocks at Meridiani Planum, Mars, by the Mars Exploration Rover Opportunity

USGS Publications Warehouse

Farrand, W. H.; Bell, J.F.; Johnson, J. R.; Jolliff, B.L.; Knoll, A.H.; McLennan, S.M.; Squyres, S. W.; Calvin, W.M.; Grotzinger, J.P.; Morris, R.V.; Soderblom, J.; Thompson, S.D.; Watters, W.A.; Yen, A. S.

2007-01-01

Multispectral measurements in the visible and near infrared of rocks at Meridiani Planum by the Mars Exploration Rover Opportunity's Pancam are described. The Pancam multispectral data show that the outcrops of the Burns formation consist of two main spectral units which in stretched 673, 535, 432 nm color composites appear buff- and purple-colored. These units are referred to as the HFS and LFS spectral units based on higher and lower values of 482 to 535 nm slope. Spectral characteristics are consistent with the LFS outcrop consisting of less oxidized, and the HFS outcrop consisting of more oxidized, iron-bearing minerals. The LFS surfaces are not as common and appear, primarily, at the distal ends of outcrop layers and on steep, more massive surfaces, locations that are subject to greater eolian erosion. Consequently, the HFS surfaces are interpreted as a weathering rind. Further inherent spectral differences between layer's and between different outcrop map units, both untouched and patches abraded by the rover's Rock Abrasion Tool, are also described. Comparisons of the spectral parameters of the Meridiani outcrop with a set of laboratory reflectance measurements of Fe3+-bearing minerals show that the field of outcrop measurements plots near the fields of hematite, ferrihydrite, poorly crystalline goethite, and schwertmannite. Rind and fracture fill materials, observed intermittently at outcrop exposures, are intermediate in their spectral character between both the HFS and LFS spectral classes and other, less oxidized, surface materials (basaltic sands, spherules, and cobbles). Copyright 2007 by the American Geophysical Union.

Monazite, iron oxide and barite exsolutions in apatite aggregates from CCSD drillhole eclogites and their geological implications

NASA Astrophysics Data System (ADS)

Sun, Xiaoming; Tang, Qian; Sun, Weidong; Xu, Li; Zhai, Wei; Liang, Jinlong; Liang, Yeheng; Shen, Kun; Zhang, Zeming; Zhou, Bing; Wang, Fangyue

2007-06-01

We have identified abundant exsolutions in apatite aggregates from eclogitic drillhole samples of the Chinese Continental Scientific Drilling (CCSD) project. Electron microscope and laser Raman spectroscopy analyses show that the apatite is fluorapatite, whereas exsolutions that can be classified into four types: (A) platy to rhombic monazite exsolutions; (B) needle-like hematite exsolutions; (C) irregular magnetite and hematite intergrowths; and (D) needle-like strontian barite exsolutions. The widths and lengths of type A monazite exsolutions range from about 6-10 μm (mostly 6 μm) and about 50-75 μm, respectively. Type B exsolutions are parallel with the C axis of apatite, with widths ranging from 0.5 to 2 μm, with most around 1.5 μm, and lengths that vary dramatically from 6 to 50 μm. Type C exsolutions are also parallel with the C axis of apatite, with lengths of ˜30-150 μm and widths of ˜10 to 50 μm. Type D strontian barite exsolutions coexist mostly with type B hematite exsolutions, with widths of about 9 μm and lengths of about 60-70 μm. Exsolutions of types B, C and D have never been reported in apatites before. Most of the exsolutions are parallel with the C axis of apatite, implying that they were probably exsolved at roughly the same time. Dating by the chemical Th-U-total Pb isochron method (CHIME) yields an U-Pb isochron age of 202 ± 28 Ma for monazite exsolutions, suggesting that these exsolutions were formed during recrystallization and retrograde metamorphism of the exhumed ultrahigh pressure (UHP) rocks. Quartz veins hosting apatite aggregates were probably formed slightly earlier than 202 Ma. Abundant hematite exsolutions, as well as coexistence of magnetite/hematite and barite/hematite in the apatite, suggest that the oxygen fugacity of apatite aggregates is well above the sulfide-sulfur oxide buffer (SSO). Given that quartz veins host these apatite aggregates, they were probably deposited from SiO 2-rich hydrous fluids formed during retrogression of the subducted slab. Such SiO 2-rich hydrous fluids may act as an oxidizing agent, a feasible explanation for the high oxygen fugacity in convergent margin systems.

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

PubMed

Gilbert, Benjamin; Katz, Jordan E; Huse, Nils; Zhang, Xiaoyi; Frandsen, Cathrine; Falcone, Roger W; Waychunas, Glenn A

2013-10-28

An emerging area in chemical science is the study of solid-phase redox reactions using ultrafast time-resolved spectroscopy. We have used molecules of the photoactive dye 2',7'-dichlorofluorescein (DCF) anchored to the surface of iron(III) oxide nanoparticles to create iron(II) surface atoms via photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(III) oxide nanoparticles has not been reported. We addressed this topic by performing femtosecond transient absorption (TA) measurements of aqueous suspensions of uncoated and DCF-sensitized iron oxide and oxyhydroxide nanoparticles, and an aqueous iron(III)-dye complex. Following light absorption, excited state relaxation times of the dye of 115-310 fs were found for all samples. Comparison between TA dynamics on uncoated and dye-sensitized hematite nanoparticles revealed the dye de-excitation pathway to consist of a competition between electron and energy transfer to the nanoparticles. We analyzed the TA data for hematite nanoparticles using a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye-oxide energy transfer is energetically forbidden) even though the acceptor states are different. Comparison of the alignment of the excited states of the dye and the unoccupied states of these oxides showed that the dye injects into acceptor states of different symmetry (Ti t2gvs. Fe eg).

Ancient Aqueous Conditions on Mars as Inferred from Spirit and Opportunity Rover Data

NASA Astrophysics Data System (ADS)

Arvidson, R. E.

2017-12-01

The Spirit and Opportunity rover missions have added significantly to our understanding of the availability of surface and subsurface waters on Mars over a range of timescales, from the Noachian Period until the present. The most important discoveries from Spirit's traverses and measurements are focused around Home Plate in the Noachian-aged Columbia Hills, Gusev Crater. Home Plate is postulated to be a largely eroded volcanoclastic construct. Spirit's wheels excavated a variety of hydrated sulfate minerals and iron oxides just beneath the surface in the vicinity of Home Plate, likely reworked hydrothermal deposits. Spirit also explored silica-rich deposits found adjacent to Home Plate of likely hydrothermal origin, perhaps deposited as sinters. Opportunity's exploration of the Burns formation sulfate-rich sandstones that underlie Meridiani Planum provided the key observations to infer an origin as sulfate-rich muds accumulating in shallow, ephemeral lakes during the late Noachian to early Hesperian Periods. Fluvial and aeolian activity reworked the muds into sandstones, to be later cemented and altered by rising groundwaters. Opportunity's exploration of the Noachian-aged 22 km diameter Endeavour Crater, combined with mineral mapping using Mars Reconnaissance Orbiter CRISM hyperspectral data, led to the discovery and characterization of ferric smectite-bearing layered outcrops and Al-rich smectites in fractures, both in the Matijevic formation that underlies Endeavour's ejecta (Shoemaker formation). In addition, Opportunity observations led to the discovery and characterization of: (a) extensive Ca sulfate veins in the above mentioned formations and in the overlying Grasberg formation, (b) Shoemaker formation rocks excavated from a soil-filled fracture coated by sulfates and Mn oxides, and (c) extensive Fe-Mg smectites in outcrops and strings of hematite-rich pebbles in sulfate-rich soil-filled fractures in Marathon Valley. Spirit and Opportunity observations thus add to the mounting evidence for significant subsurface aqueous alteration along fractures, in addition to the sustained presence of surface water during the Noachian to early Hesperian Eras.

The choice of iron-containing filling for composite radioprotective material

NASA Astrophysics Data System (ADS)

Matyukhin, P. V.

2018-03-01

The paper presents the data the composition of modern composite building materials including materials which in addition to high physical-mechanical have radio-protective properties. The article presents infrared researches and differential thermal data of fine-grained magnetite and hematite beneficiated iron-ore concentrates. The choice of the most suitable filling for new composite radio-protective building material engineering and development was made basing on the magnetite and hematite data presented in the paper.

Designing New Materials for Converting Solar Energy to Fuels via Quantum Mechanics

DTIC Science & Technology

2014-07-11

dopants can also be exploited to increase charge carrier concentration without creating traps and hence improve the conductivity of these materials...e.g., Mn(II) in hematite for hole transport, Y(III) in MnO:ZnO for electron transport). • We discovered that dopants derived from covalent oxides...e.g., Si from silica, as a dopant in hematite) can also be used to increase charge carrier density without creating traps. Charge carriers stay

Modification of the Magnetic Properties of α-Fe2O3 Powders by Ultrasonic Processing

NASA Astrophysics Data System (ADS)

Stolyar, S. V.; Bayukov, O. A.; Iskhakov, R. S.; Yaroslavtsev, R. N.; Ladygina, V. P.

2017-12-01

Hematite (α-Fe2O3) powders after ultrasonic treatment (UST) in the regime of cavitation in aqueous suspension and in that with an organic component (albumin protein) have been studied by Mössbauer spectroscopy and ferromagnetic resonance techniques. It is established that the UST in aqueous hematite suspensions with albumin results in the formation of a new magnetic phase with parameters coinciding with those of the α-Fe metallic phase.

Effect of Cr2O3 addition on the oxidation induration mechanism of Hongge vanadium titanomagnetite pellets

NASA Astrophysics Data System (ADS)

Li, Wei; Wang, Nan; Fu, Gui-qin; Chu, Man-sheng; Zhu, Miao-yong

2018-04-01

As part of a research project to develop a novel clean smelting process for the comprehensive utilization of Hongge vanadium titanomagnetite (HVTM), in this study, the effect of Cr2O3 addition on the oxidation induration mechanism of HVTM pellets (HVTMPs) was investigated in detail. The results showed that the compressive strength of the HVTMPs was greatly weakened by the Cr2O3 addition, mainly because of a substantial increase in the porosity of the HVTMPs. The Cr2O3 addition marginally affected the phase composition but greatly affected the microstructural changes of the HVTMPs. Increased amounts of Cr2O3 resulted in a decrease in the uniform distribution of the hematite grains and in an increase in the Fe-Cr solid solutions (Fe1.2Cr0.8O3 and Fe0.7Cr1.3O3) embedded in the hematite grains. Moreover, the compact hematite was destroyed by forming a dispersed structure and the hematite recrystallization was hindered during the oxidation induration, which adversely affected the compressive strength. On the basis of these results, a schematic was formulated to describe the oxidation induration mechanism with different amounts of added Cr2O3. This study provides theoretical and technical foundations for the effective production of HVTMPs and a reference for chromium-bearing minerals.

Structural, optical, magnetic and electrical properties of hematite (α-Fe2O3) nanoparticles synthesized by two methods: polyol and precipitation

NASA Astrophysics Data System (ADS)

Mansour, Houda; Letifi, Hanen; Bargougui, Radhouane; De Almeida-Didry, Sonia; Negulescu, Beatrice; Autret-Lambert, Cécile; Gadri, Abdellatif; Ammar, Salah

2017-12-01

Hematite (α-Fe2O3) nanoparticles have been successfully synthesized via two methods: (1) polyol and (2) precipitation in water. The influence of synthesis methods on the crystalline structure, morphological, optical, magnetic and electrical properties were investigated using X-ray diffraction, RAMAN spectroscopy, scanning electron microscopy, transmission electron microscopy, UV-visible diffuse reflectance spectroscopy (UV-vis DRS), superconducting quantum interference device and impedance spectroscopy. The structural properties showed that the obtained hematite α-Fe2O3 nanoparticles with two preparation methods exhibit hexagonal phase with high crystallinity and high-phase stability at room temperature. It was found that the average hematite nanoparticle size is estimated to be 36.86 nm for the sample synthesized by precipitation and 54.14 nm for the sample synthesized by polyol. Moreover, the optical properties showed that the band gap energy value of α-Fe2O3 synthesized by precipitation (2.07 eV) was higher than that of α-Fe2O3 synthesized by polyol (1.97 eV) and they showed a red shift to the visible region. Furthermore, the measurements of magnetic properties indicated a magnetization loop typical of ferromagnetic systems at room temperature. Measurements of electrical properties show higher dielectric permittivity (5.64 × 103) and relaxation phenomenon for α-Fe2O3 issued from the precipitation method than the other sample.

Structural and magnetic properties of the products of the transformation of ferrihydrite: Effect of cobalt dications

NASA Astrophysics Data System (ADS)

Camacho, K. I.; Pariona, N.; Martinez, A. I.; Baggio-Saitovitch, E.; Herrera-Trejo, M.; Perry, Dale L.

2017-05-01

The effect of cobalt dications on the transformation of 2-line ferrihydrite (2LF) has been studied. The products of the transformation reaction were characterized by X-ray diffraction, Mössbauer spectroscopy (MS), transmission electron microscopy (TEM), magnetometry, and first-order reversal curve (FORC) diagrams. It was found that the concentration of cobalt dications plays an important role on the structural and magnetic properties of the products; i.e., for low cobalt concentrations, cobalt-substituted hematite is formed, while higher concentrations promote the formation of cobalt-substituted magnetite. Structural results revealed that formation of other iron oxide polymorphs is avoided and residual 2LF is always present in the final products. In this way, hematite/2LF and magnetite/2LF nanocomposites were formed. For all the samples, magnetic measurements yielded non-saturated hysteresis loops at a maximum field of 12 kOe. For cobalt-substituted hematite/2LF samples, FORC diagrams revealed the presence of multiple single-domain (SD) components which generate interaction coupling between SD with low and high coercivity. Moreover, for cobalt-substituted magnetite/2LF samples, the FORC diagrams revealed the components of wasp-waist hysteresis loops which consist of mixtures of SD and superparamagnetic particles. One of the goals of the present study is the rigorous, experimental documentation of ferrihydrite/hematite mixtures as a function of reaction conditions for use as analytical standards research.

Multistep Reduction Kinetics of Fine Iron Ore with Carbon Monoxide in a Micro Fluidized Bed Reaction Analyzer

NASA Astrophysics Data System (ADS)

Chen, Hongsheng; Zheng, Zhong; Chen, Zhiwei; Yu, Wenzhou; Yue, Junrong

2017-04-01

The reduction kinetics of Brazilian hematite by CO is investigated in a Micro Fluidized Bed Reaction Analyzer (MFBRA) using an analyzing method based on Johnson-Mehl-Avrami (JMA) model at temperatures of 973 K (700 °C), 1023 K (750 °C), 1073 K (800 °C), and 1123 K (850 °C). The solid products at different reduction stages are evaluated by SEM/EDS and XRD technologies. Results indicate that the reduction process is better to be discussed in terms of a parallel reaction model that consists of the reactions of hematite to wüstite and wüstite to iron, rather than a stepwise route. Meanwhile, the controlling mechanism of the reduction process is found to vary with temperature and the degree of conversion. The overall process is controlled by the gas-solid reaction occurring at the iron/wüstite interface in the initial stages, and then is limited by the nucleation of wüstite, and finally shifts to diffusion control. Moreover, the reactions of hematite to wüstite and wüstite to iron take place simultaneously but with different time dependences, and the apparent activation energies of hematite to wüstite and wüstite to iron are determined as 83.61 and 80.40 KJ/mol, respectively.

Structural, optical and morphological characterization of Cu-doped α-Fe2O3 nanoparticles synthesized through co-precipitation technique

NASA Astrophysics Data System (ADS)

Lassoued, Abdelmajid; Lassoued, Mohamed Saber; Dkhil, Brahim; Gadri, Abdellatif; Ammar, Salah

2017-11-01

Pure and copper (Cu concentration varying from 2 to 8%) doped hematite (α-Fe2O3) nanocrystals were synthesized through co-precipitation method using simple equipment. X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Fourier Transform Infra-Red (FT-IR), Raman spectroscopy, Differential Thermal Analysis (DTA), Thermo Gravimetric Analysis (TGA) and Ultraviolet-Visible (UV-Vis) techniques were used to characterize the synthesized samples. XRD measurements confirm that all the prepared nanocrystals consist only in nanocrystalline hematite phase. These results along with TEM and SEM show that the size of the nanoparticles decreases with Cu-doping down to 21 nm. FT-IR confirm the phase purity of the nanoparticles synthesized. The Raman spectroscopy was used not only to prove that we synthesized pure and Cu-doped hematite but also to identify their phonon modes. The TGA showed three mass losses, whereas DTA resulted in three endothermic peaks. The UV-Vis absorption measurements confirm that the decrease of particle size is accompanied by a decrease in the band gap value from 2.12 eV for pure α-Fe2O3 down to 1.91 eV for 8% Cu-doped α-Fe2O3. 8% Cu-doped hematite had the smallest size, the best crystallinity and the lowest band gap.

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

Martinson, A. B. F.; DeVries, M. J.; Libera, J. A.

Growing interest in Fe{sub 2}O{sub 3} as a light harvesting layer in solar energy conversion devices stems from its unique combination of stability, nontoxicity, and exceptionally low material cost. Unfortunately, the known methods for conformally coating high aspect ratio structures with Fe{sub 2}O{sub 3} leave a glaring gap in the technologically relevant temperature range of 170-350 C. Here, we elucidate a self-limiting atomic layer deposition (ALD) process for the growth of hematite, {alpha}-Fe{sub 2}O{sub 3}, over a moderate temperature window using ferrocene and ozone. At 200 C, the self-limiting growth of Fe{sub 2}O{sub 3} is observed at rates up tomore » 1.4 {angstrom}/cycle. Dense and robust thin films grown on both fused quartz and silicon exhibit the expected optical bandgap (2.1 eV). In situ mass spectrometric analysis reveals the evolution of two distinct cyclic reaction products during the layer-by-layer growth. The readily available and relatively high vapor pressure iron precursor is utilized to uniformly coat a high surface area template with aspect ratio 150.« less

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

Martinson, Alex B.F.; DeVries, Michael J.; Libera, J. A.

Growing interest in Fe 2O 3 as a light harvesting layer in solar energy conversion devices stems from its unique combination of stability, nontoxicity, and exceptionally low material cost. Unfortunately, the known methods for conformally coating high aspect ratio structures with Fe 2O 3 leave a glaring gap in the technologically relevant temperature range of 170-350 °C. Here, we elucidate a self-limiting atomic layer deposition (ALD) process for the growth of hematite, α-Fe 2O 3, over a moderate temperature window using ferrocene and ozone. At 200 °C, the self-limiting growth of Fe 2O 3 is observed at rates up tomore » 1.4 Å/cycle. Dense and robust thin films grown on both fused quartz and silicon exhibit the expected optical bandgap (2.1 eV). In situ mass spectrometric analysis reveals the evolution of two distinct cyclic reaction products during the layer-by-layer growth. The readily available and relatively high vapor pressure iron precursor is utilized to uniformly coat a high surface area template with aspect ratio ~150.« less

Characterizing Martian Soils: Correlating Orbital Observations with Chemistry and Mineralogy from Landed Missions

NASA Astrophysics Data System (ADS)

Bishop, J. L.

2010-12-01

Great advances have been achieved recently in our understanding of the surface of Mars at global scales from orbital missions and at local scales from landed missions. This presentation seeks to provide links between the chemistry and mineralogy observed by landed missions with remote detections of minerals from orbit. Spectral data from CRISM, OMEGA and TES characterize a mostly basaltic planet with some outcrops of hematite, clays, sulfates and carbonates at the surface. Recent alteration of these rocks to form soils has likely been dominated by physical processes; however, martian soils probably also contain relicts of early alteration involving aqueous processes. Clays, hydroxides, sulfates, carbonates and perchlorates are examples of surface components that may have formed early in the planet’s history in the presence of liquid water. Some of these minerals have not been detected in the soil, but all have likely contributed to the current soil composition. The grain size, shape, chemistry, mineralogy, and magnetic properties of Martian soils are similar to altered volcanic ash found at many analog sites on Earth. Reflectance and emission spectra of some of these analog soils are consistent with the basic soil spectral properties observed from orbit. The cemented soil units observed by rovers may have formed through interaction of the soil grains with salts, clays, and hydroxides. Lab experiments have shown that cementing of analog grains darkens the VN reflectance, which could explain the low reflectance of Martian soils compared to analog sites. Reflectance spectra of an analog soil mixture containing altered ash and sulfate are shown in Figure 1. A pellet was made by adding water and allowing the sample to dry in air. Finally, the pellet was crushed and ground again to <125 µm. Both the dried pellet spectrum and the crushed pellet spectrum are darker than the original spectrum of the same composition. Erosion and weathering are likely the dominant processes forming the soils on Mars. However, reaction of surface grains with sulfates and perchlorates probably also influenced the soil grains. The perchlorates found by Phoenix are a strong oxidant. Consideration is being given to the interactions of perchlorates with minerals identified in surface rocks (pyroxene, olivine, feldspar, phyllosilicate, iron oxides, sulfate, silica, carbonate) and how perchlorates might be contributing to soil formation from these minerals and what their spectral properties might be.

Lunar and Planetary Science XXXV: Weird Martian Minerals: Complex Mars Surface Processes

NASA Technical Reports Server (NTRS)

2004-01-01

The session "Complex Mars Surface" included the following reports:A Reappraisal of Adsorbed Superoxide Ion as the Cause Behind the Reactivity of the Martian Soils; Sub-Surface Deposits of Hydrous Silicates or Hydrated Magnesium Sulfates as Hydrogen Reservoirs near the Martian Equator: Plausible or Not?; Thermal and Evolved Gas Analysis of Smectites: The Search for Water on Mars; Aqueous Alteration Pathways for K, Th, and U on Mars; Temperature Dependence of the Moessbauer Fraction in Mars-Analog Minerals; Acid-Sulfate Vapor Reactions with Basaltic Tephra: An Analog for Martian Surface Processes; Iron Oxide Weathering in Sulfuric Acid: Implications for Mars; P/Fe as an Aquamarker for Mars; Stable Isotope Composition of Carbonates Formed in Low-Temperature Terrestrial Environments as Martian Analogs; Can the Phosphate Sorption and Occlusion Properties Help to Elucidate the Genesis of Specular Hematite on the Mars Surface?; Sulfate Salts, Regolith Interactions, and Water Storage in Equatorial Martian Regolith; Potential Pathways to Maghemite in Mars Soils: The Key Role of Phosphate; and Mineralogy, Abundance, and Hydration State of Sulfates and Chlorides at the Mars Pathfinder Landing Site.

Rodolicoite and grattarolaite, intermediates in the thermal transformation of synthetic P-doped ferrihydrite

NASA Astrophysics Data System (ADS)

Pieczara, Gabriela; Borkiewicz, Olaf; Manecki, Maciej

2017-04-01

Rodolicoite FePO4 and grattarolaite Fe3PO7, naturally occurring anhydrous iron(III) phosphates have been identified in coal samples derived from Santa Barbara lignite mine, as final products of the progressive thermal conversion and oxidation of vivianite Fe32+(PO4)2•8H2O to amorphous phase [1]. In natural environment however, the conversion steps of amorphous phase into these nanominerals are extremely difficult to identify. We propose to fill this gap by utilizing the nanoparticles of synthetic P-doped ferrihydrite Fe5HO8•4H2O as a source of amorphous hydrated iron(III) phosphate. This phase, at certain conditions, undergoes thermal conversion to rodolicoite and grattarolaite. Synthetic anhydrous iron(III) phosphate analogs of berlinite AlPO4 and α- quartz, particularly rodolicoite, receive a lot of attention in mineral sciences partly because of their geologic importance and partly because of their prospective applications as raw material for lithium iron phosphate batteries LiFePO4[2]. In this case, potential presence of impurities and intermediates during thermal synthesis or oxidation steps of rodolicoite is inexpedient. Thus, the main goal of this research was to characterize the products of thermal transformation of P-doped ferrihydrite. Ferrihydrite synthesized in the presence of phosphate PO43- was used. P-ferrihydrites were synthesized by precipitation from aqueous solutions of Fe2(SO4)3 and K2HPO4 at pH 8.2. The thermal transformation experiments were carried out using ferrihydrites with various P/Fe ratios (0.00, 0.20, 0.50 and 1.00) at various heating temperatures. All samples were characterized by XRD, FTIR, SEM and differential thermal analysis prior and after the experiments. The results indicate that the presence of phosphate not only stabilizes the structure of ferrihydrite but also controls its thermal transformation to hematite α-Fe2O3 in more complex manner. Pure ferrihydrite transforms immediately to hematite at the temperature below 500˚ C. When ferrihydrite with P/Fe=0.20 and P/Fe=0.50 was annealed, the presence of tetragonal maghemite γ-Fe2O3 was detected between 650 and 700˚ C, followed by formation of hematite α-Fe2O3 at higher temperatures. Hematite is accompanied with small amounts of trigonal rodolicoite FePO4 which forms between 800 and 900˚ C. This intermediate phase is not very stable and completely vanishes in the sample of P/Fe=0.20 at temperatures above 900˚ C (transforms into hematite). In contrast, a further increase in temperature of the sample of P/Fe=0.50 causes formation of hematite associated with grattarolaite Fe3PO7. Thermal transformation of ferrihydrite containing the highest-P ratio (P/Fe=1.00) results in the formation of rodolicoite and hematite at 700˚ C, grattarolaite at 800˚ C, and a mixture of two anhydrous phosphates with hematite around 1000˚ C. This project is financed by AGH research grant no. 15.11.140.831 and partly by the Polish National Science Centre under the research project awarded by the decision no. 2015/19/N/ST10/01516. References: [1] Cipriani C, Mellini M, Pratesi G, Viti C (1997) EJM. 9, pp. 1101-1106. [2] Zhu Y, Tang S, Shi H, Hu H (2014) Ceram. Int. 40, pp. 2685-2690.

Hematite-coated microfossils: primary ecological fingerprint or taphonomic oddity of the Paleoproterozoic?

PubMed

Shapiro, R S; Konhauser, K O

2015-05-01

Microfossils belonging to the 1.88-billion-year-old 'Gunflint-biota' are preserved as carbonaceous and hematitic filaments and spheres that are believed to represent ancient chemolithoautotrophic Fe(II) oxidizing bacteria that grew above a chemocline where ferruginous seawater upwelled into shallow, oxygenated waters. This 'biological' model posits that hematite formed during burial from dewatering of the precursor ferric oxyhydroxides that encrusted Fe(II)-oxidizing bacteria. Here, we present an alternate 'taphonomic' model in which iron-rich groundwaters discharged into buried stromatolites; thus, the mineralization reactions are more informative of diagenetic processes than they are for primary marine conditions. We sampled centimeter-scale columnar stromatolites from both the lower and upper stromatolite horizons of the Biwabik and Gunflint formations, across a range of metamorphic gradients including unaltered to prehnite-pumpellyite taconite, supergene altered ore, and amphibolite-pyroxene grade contact-metamorphic zones. Fossils are rare to very rare and comprise curved filaments that exist in clusters with similar orientations. The filaments from throughout the Biwabik are similar to well-preserved carbonaceous Gunflintia from Ontario. Spheres of Huroniospora are also found in both formations. Microfossils from the least altered sections are preserved as carbon. Prehnite-pumpellyite samples are composed of either carbon or hematite (Fe2 O3 ). Within the contact aureole, filaments are densely coated by magnetite (Fe3 O4 ); the highest grade samples are secondarily oxidized to martite. The consistency in stromatolite microstructure and lithofacies throughout the metamorphic grades suggests they formed under similar environmental conditions. Post-depositional alteration led to replacement of the carbon by iron oxide. The facies association, filament distribution, and lack of branching and attached spherical cells argue against Gunflintia being a direct analogue to common marine, chemolithoautotrophic Fe(II)-oxidizing bacteria. Instead, we propose that the presence of hematite-coated microfossils is a reflection of taphonomic processes and does not necessarily reflect the byproduct of an original microbial ecosystem. © 2015 John Wiley & Sons Ltd.

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

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

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

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

Laser treatment of a neodymium magnet and analysis of surface characteristics

NASA Astrophysics Data System (ADS)

Yilbas, B. S.; Ali, H.; Rizwan, M.; Kassas, M.

2016-08-01

Laser treatment of neodymium magnet (Nd2Fe14B) surface is carried out under the high pressure nitrogen assisting gas. A thin carbon film containing 12% WC carbide particles with 400 nm sizes are formed at the surface prior to the laser treatment process. Morphological and metallurgical changes in the laser treated layer are examined using the analytical tools. The corrosion resistance of the laser treated surface is analyzed incorporating the potentiodynamic tests carried out in 0.05 M NaCl+0.1 M H2SO4 solution. The friction coefficient of the laser treated surface is measured using the micro-scratch tester. The wetting characteristics of the treated surface are assessed incorporating the sessile water drop measurements. It is found that a dense layer consisting of fine size grains and WC particles is formed in the surface region of the laser treated layer. Corrosion resistance of the surface improves significantly after the laser treatment process. Friction coefficient of laser treated surface is lower than that of the as received surface. Laser treatment results in superhydrophobic characteristics at the substrate surface. The formation of hematite and grain size variation in the treated layer slightly lowers the magnetic strength of the laser treated workpiece.

A Wind Dependent Desert Aerosol Model: Radiative Properties

DTIC Science & Technology

1988-04-19

Source Regions and Transport Characteristics 5 2.2 Size Distributions 6 2.3 Composition 8 2.4 Effects of Wind 10 2.5 Indices of Refraction 12 2.5.1 An...Hematite Concentrations of 0, 5, and 10 %, (a) O-Ray and (b) E-Ray 44 8 . Imaginary Part of the Index of Refraction for Sand Having Hematite...rarbonaceous Material 31 8 . Indices of Refraction "or Ammonium Sulfate 32 9. Indices of Refraction for the 0-Ray of Quartz 35 10 . Indices of Refraction for the

Au nanorice assemble electrolytically into mesostars.

PubMed

Bardhan, Rizia; Neumann, Oara; Mirin, Nikolay; Wang, Hui; Halas, Naomi J

2009-02-24

Star-shaped mesotructures are formed when an aqueous suspension of Au nanorice particles, which consist of prolate hematite cores and a thin Au shell, is subjected to an electric current. The nanorice particles assemble to form hyperbranched micrometer-scale mesostars. To our knowledge, this is the first reported observation of nanoparticle assembly into larger ordered structures under the influence of an electrochemical process (H(2)O electrolysis). The assembly is accompanied by significant modifications in the morphology, dimensions, chemical composition, crystallographic structure, and optical properties of the constituent nanoparticles.

Final Technical Report. Reactivity of Iron-Bearing Minerals and CO 2 Sequestration and Surface Chemistry of Pyrite. An Interdisciplinary Approach

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

Strongin, Daniel

2014-12-31

Over the course of the scientific program, two areas of research were pursued: reactions of iron oxides with supercritical CO 2 and sulfide and surface reactivity of pyrite. The latter area of interest was to understand the chemistry that results when supercritical CO 2 (scCO 2 ) with H 2 S and/or SO 2 in deep saline formations (DFS) contacts iron bearing minerals. Understanding the complexities the sulfur co-injectants introduce is a critical step in developing CO 2 sequestration as a climate-mitigating strategy. The research strategy was to understand macroscopic observations of this chemistry with anmore » atomic/molecular level view using surface analytical techniques. Research showed that the exposure of iron (oxyhdr)oxides (which included ferrihydrite, goethite, and hematite) to scCO 2 in the presence of sulfide led to reactions that formed siderite (FeCO 3). The results have important implications for the sequestration of CO 2 via carbonation reactions in the Earth’s subsurface. An earlier area of focus in the project was to understand pyrite oxidation in microscopic detail. This understanding was used to understand macroscopic observations of pyrite reactivity. Results obtained from this research led to a better understanding how pyrite reacts in a range of chemical environments. Geochemical and modern surface science techniques were used to understand the chemistry of pyrite in important environmental conditions. The program relied on a strong integration the results of these techniques to provide a fundamental understanding to the macroscopic chemistry exhibited by pyrite in the environment. Major achievements during these studies included developing an understanding of the surface sites on pyrite that controlled its reactivity under oxidizing conditions. In particular sulfur anion vacancies and/or ferric sites were sites of reactivity. Studies also showed that the adsorption of phospholipid on the surface to selectively suppress the reactivity of these sites could of potential importance for suppressing acid mine drainage in the environment (a problem common to coal-mining sites). Biotic studies showed that microbial activity that promotes the oxidation of pyrite to produce AMD could also be suppressed by the adsorption of phospholipid.« less

Aqueous geochemistry on Mars: Possible clues from salts and clays in SNC meteorites

NASA Technical Reports Server (NTRS)

Gooding, James L.

1992-01-01

All subgroups of the shergottite, nakhlite, and chassignite (SNC) meteorites contain traces of water precipitated minerals that include various combinations of carbonates, sulfates, halides, ferric oxides, and aluminosilicate clays of preterrestrial origin. Oxygen three-isotope analysis of thermally extracted bulk water has confirmed that at least some of the water in SNC's is, indeed, extraterrestrial. A mixture of aqueous precipitates found in the SNC's, comprising smectite, illite, and gypsum (with minor halite +/- calcite and hematite), provides a self-consistent, though not unique, model for the bulk elemental composition of surface sediments at the Viking Lander sites. Therefore, if the salts and clays in SNC's are truly linked to aqueous alteration and soil formation on Mars, then the suite of SNC secondary minerals might provide the best currently available insight into near-surface martian chemistry.

Pore and Continuum Scale Study of the Effect of Subgrid Transport Heterogeneity on Redox Reaction Rates

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

Liu, Yuanyuan; Liu, Chongxuan; Zhang, Changyong

2015-08-01

A micromodel system with a pore structure for heterogeneous flow and transport was used to investigate the effect of subgrid transport heterogeneity on redox reaction rates. Hematite reductive dissolution by injecting a reduced form of flavin mononucleotide (FMNH2) at variable flow rates was used as an example to probe the variations of redox reaction rates in different subgrid transport domains. Experiments, pore-scale simulations, and macroscopic modeling were performed to measure and simulate in-situ hematite reduction and to evaluate the scaling behavior of the redox reaction rates from the pore to macroscopic scales. The results indicated that the measured pore-scale ratesmore » of hematite reduction were consistent with the predictions from a pore scale reactive transport model. A general trend is that hematite reduction followed reductant transport pathways, starting from the advection-dominated pores toward the interior of diffusion-dominated domains. Two types of diffusion domains were considered in the micromodel: a micropore diffusion domain, which locates inside solid grains or aggregates where reactant transport is limited by diffusion; and a macropore diffusion domain, which locates at wedged, dead-end pore spaces created by the grain-grain contacts. The rate of hematite reduction in the advection-dominated domain was faster than those in the diffusion-controlled domains, and the rate in the macropore diffusion domain was faster than that in the micropore domain. The reduction rates in the advection and macropore diffusion domains increased with increasing flow rate, but were affected by different mechanisms. The rate increase in the advection domain was controlled by the mass action effect as a faster flow supplied more reactants, and the rate increase in the macropore domain was more affected by the rate of mass exchange with the advection domain, which increased with increasing flow rate. The hematite reduction rate in the micropore domain was, however, not affected by the flow rate because molecular diffusion limits reductant supply to the micropore domain interior. Domain-based macroscopic models were evaluated to scale redox reaction rates from the pore to macroscopic scales. A single domain model, which ignores subgrid transport heterogeneity deviated significantly from the pore-scale results. Further analysis revealed that the rate expression for hematite reduction was not scalable from the pore to porous media using the single domain model. A three-domain model, which effectively considers subgrid reactive diffusion in the micropore and macropore domains, significantly improved model description. Overall this study revealed the importance of subgrid transport heterogeneity in the manifestation of redox reaction rates in porous media and in scaling reactions from the pore to porous media. The research also supported that the domain-based scaling approach can be used to directly scale redox reactions in porous media with subgrid transport heterogeneity.« less

Study on Reduction Kinetics of Briquettes of Hematite Fines with Boiler Grade Coal and Coke Dust in Two Different Forms: Intermixing and Multilayered

NASA Astrophysics Data System (ADS)

Roy, Gopal Ghosh; Sarkar, Bitan Kumar; Chaudhuri, Mahua Ghosh; Mitra, Manoj Kumar; Dey, Rajib

2017-10-01

An attempt has been made to utilise hematite ore fines in the form of briquettes with two different form of mixing i.e. intermixing and multilayered by means of carbothermal reduction along with boiler grade coal and coke dust. The influence of reduction temperature (1323, 1373 and 1423 K) and reduction time (10, 20, 30, 45 and 60 min) has been investigated in detail and the reduced briquettes are characterised by XRD, SEM analyses. The reducibility of intermixing briquettes is found to be higher for multilayered briquettes. In addition, isothermal kinetic study has also been carried out for both intermixing and multilayered briquettes. The activation energy for intermixing briquettes are evaluated to be 125.88 kJ/mol for the initial stage of reaction (CG3 controlled mechanism) and 113.11 kJ/mol for the later part of reaction (D3 controlled mechanism), respectively. In case of multilayered briquettes, the corresponding activation energy is found to be 235.59 kJ/mol for reaction (CG3 controlled mechanism). These results corroborate the observed better reducibility of the intermixing briquettes over multilayered briquettes.

Investigation of structural, morphological, luminescent and thermal properties of combusted aluminium-based iron oxide

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

Shinde, S.S.; Rajpure, K.Y., E-mail: rajpure@yahoo.co

Nanocomposites of aluminium integrated hematite {alpha}-Fe{sub 2}O{sub 3} are synthesized by combustion route using aqueous solutions of AR grade ferric trichloride and aluminium nitrate as precursors. The influence of aluminium incorporation on to the morphology, XPS, photoluminescence and thermal properties has been investigated. The FESEM and AFM micrographs depict that the samples are compact and have homogeneously distributed grains of varying sizes ({approx}20-60 nm). Chemical composition and valence states of constituent elements in hematite are analyzed by XPS. In room temperature photoluminescence (PL) study, we observed strong violet emission around 436 nm without any deep-level emission and a small PLmore » FWHM indicating that the concentrations of defects are responsible for deep-level emissions. The specific heat and thermal conductivity study shows the phonon conduction behavior is dominant. We studied interparticle interactions using complex impedance spectroscopy. We report a new potential candidate for its possible applications in optoelectronics and magnetic devices. -- Graphical abstract: Frequency and temperature dependent interparticle interactions like grains, grain boundary effects using complex impedance spectroscopy of pure and 10 at% Al:Fe{sub 2}O{sub 3} have been studied. Display Omitted« less

Venus Surface Composition Constrained by Observation and Experiment

NASA Astrophysics Data System (ADS)

Gilmore, Martha; Treiman, Allan; Helbert, Jörn; Smrekar, Suzanne

2017-11-01

New observations from the Venus Express spacecraft as well as theoretical and experimental investigation of Venus analogue materials have advanced our understanding of the petrology of Venus melts and the mineralogy of rocks on the surface. The VIRTIS instrument aboard Venus Express provided a map of the southern hemisphere of Venus at ˜1 μm allowing, for the first time, the definition of surface units in terms of their 1 μm emissivity and derived mineralogy. Tessera terrain has lower emissivity than the presumably basaltic plains, consistent with a more silica-rich or felsic mineralogy. Thermodynamic modeling and experimental production of melts with Venera and Vega starting compositions predict derivative melts that range from mafic to felsic. Large volumes of felsic melts require water and may link the formation of tesserae to the presence of a Venus ocean. Low emissivity rocks may also be produced by atmosphere-surface weathering reactions unlike those seen presently. High 1 μm emissivity values correlate to stratigraphically recent flows and have been used with theoretical and experimental predictions of basalt weathering to identify regions of recent volcanism. The timescale of this volcanism is currently constrained by the weathering of magnetite (higher emissivity) in fresh basalts to hematite (lower emissivity) in Venus' oxidizing environment. Recent volcanism is corroborated by transient thermal anomalies identified by the VMC instrument aboard Venus Express. The interpretation of all emissivity data depends critically on understanding the composition of surface materials, kinetics of rock weathering and their measurement under Venus conditions. Extended theoretical studies, continued analysis of earlier spacecraft results, new atmospheric data, and measurements of mineral stability under Venus conditions have improved our understanding atmosphere-surface interactions. The calcite-wollastonite CO2 buffer has been discounted due, among other things, to the rarity of wollastonite and instability of carbonate at the Venus surface. Sulfur in the Venus atmosphere has been shown experimentally to react with Ca in surface minerals to produce anhydrite. The extent of this SO2 buffer is constrained by the Ca content of surface rocks and sulfur content of the atmosphere, both of which are likely variable, perhaps due to active volcanism. Experimental work on a range of semiconductor and ferroelectric minerals is placing constraints on the cause(s) of Venus' anomalously radar bright highlands.

Continual model of magnetic dynamics for antiferromagnetic particles in analyzing size effects on Morin transition in hematite nanoparticles

NASA Astrophysics Data System (ADS)

Mishchenko, I.; Chuev, M.; Kubrin, S.; Lastovina, T.; Polyakov, V.; Soldatov, A.

2018-05-01

Alternative explanation to the effect of disappearance of the Morin transition on hematite nanoparticles with their size decreasing is proposed basing on an idea of the predominant role of the shape anisotropy for nanosize particles. Three types of the magnetic structure of hematite nanoparticles with various sizes are found by Mössbauer spectroscopy: coexistence of the well-pronounced antiferromagnetic and weakly ferromagnetic phases for particles with average diameters of about 55 nm, non-uniform distribution of the magnetization axes which concentrate on the vicinity of the basal plane (111) for prolonged particles with cross sections of about 20 nm, and uniform distribution of the easy axes in regard to the crystalline directions for 3-nm particles. Description of the temperature evolution of experimental data within novel model of the magnetic dynamics for antiferromagnetic particles which accounts the exchange, relativistic, and anisotropy interactions is provided, and the structural as well as energy characteristics of the studied systems are reconstructed.

Remote Detection and Mapping of Supergene Iron Oxides in the Cripple Creek Mining District, Colorado

NASA Technical Reports Server (NTRS)

Taranik, D. L.; Kruse, F. A.; Goetz, A. F. H.; Atkinson, W. W.

1990-01-01

The Geophysical and Environmental Research Imaging Spectrometer (GERIS) was flown over the Cripple Creek mining district in south-central Colorado to improve the geological understanding of the district. As part of the study, an airborne mapping technique was developed for the discrimination of the ferric iron minerals hematite, goethite, and jarosite, minerals often important indicators of the distribution of economic mineralization. A software technique was developed which uses the binary encoding of spectral slopes to identify the mineral hematite from the group goethite/jarosite. Mixtures of hematite and goethite can also be detected with GERIS data. The study included district-wide field mapping and spectral measurements to evaluate the accuracy of the image classifications. The ARC/INFO geographic information system (GIS) was a useful tool which allowed quantitative comparison of the field mapping and GERIS image data sets. The study results demonstrate the ability to discriminate individual iron minerals using imaging spectroscopy, and the development of a rapid mapping technique useful in the reconnaissance stage of minerals exploration.

Copahue Volcano: A Modern Terrestrial Analog for the Opportunity Landing Site?

NASA Astrophysics Data System (ADS)

Varekamp, Johan C.

2004-10-01

The Opportunity Rover on Mars encountered an environment that contained grey hematite (specularite) and jarosite, with structures indicative of flowing water. Less firm evidence suggests the presence of gypsum as well, and the environment is overall rich in S, Cl, and Br (NASA news releases, 2004). Such a suite of minerals may form from an iron- and sulfate-rich brine, either through evaporation, cooling or changes in redox conditions (see Hynek et al. [2002] and Christensen et al. [2001], for a discussion of the extent and possible origins of the Mars hematite deposits). On Earth, such an association of minerals is not very common, but is found in alteration zones with fumarolic activity in some volcanic craters. The condensation or dissolution in meteoric waters of S-rich volcanic gases creates acid fluids in the surficial environment that leach rock-forming elements (RFEs) from the surrounding rocks, forming large, bleached areas of mineralizations of hematite, cristobalite, and gypsum, occasionally with zones rich in alunite or jarosite.

Morphology and orientational behavior of silica-coated spindle-type hematite particles in a magnetic field probed by small-angle X-ray scattering.

PubMed

Reufer, Mathias; Dietsch, Hervé; Gasser, Urs; Hirt, Ann; Menzel, Andreas; Schurtenberger, Peter

2010-04-15

Form factor and magnetic properties of silica-coated spindle-type hematite nanoparticles are determined from SAXS measurements with applied magnetic field and magnetometry measurements. The particle size, polydispersity and porosity are determined using a core-shell model for the form factor. The particles are found to align with their long axis perpendicular to the applied field. The orientational order is determined from the SAXS data and compared to the orientational order obtained from magnetometry. The direct access to both, the orientational order of the particles, and the magnetic moments allow one to determine the magnetic properties of the individual spindle-type hematite particles. We study the influence of the silica coating on the magnetic properties and find a fundamentally different behavior of silica-coated particles. The silica coating reduces the effective magnetic moment of the particles. This effect is enhanced with field strength and can be explained by superparamagnetic relaxation in the highly porous particles.

Evaluation of the mercaptobenzothiazole degradation by combined adsorption process and Fenton reaction using iron mining residue.

PubMed

Martins, Adriana Lau da Silva; Teixeira, Luís Alberto César; da Fonseca, Fabiana Valéria; Yokoyama, Lídia

2017-08-01

The present study investigated the degradation of mercaptobenzothiazole (MBT), evaluating homogeneous and heterogeneous systems. An iron mineral residue from the desliming step of iron mining was used as a source in the Fenton-like reaction (advanced oxidation process). A granulometric analysis of the residue was performed and yielded fractions with high hematite (Fe 2 O 3 ) and low quartz content in sieves from 74 to below 44 mm. In this particle size range, the hematite content from 58.9% to 67.4% and the Brunauer-Emmett-Teller area from 0.1345 to 1.3137 m 2  g -1 were obtained. The zeta potential curves as a function of pH were obtained for the residue, the MBT solution and mixtures thereof. The adsorption of MBT in the residue and its degradation through the Fenton-like reaction were investigated. Adsorption tests and the Fenton-like reaction were carried out, where the MBT species and the residue are oppositely charged, yielding, respectively, 10% MBT adsorption on the surface of the residue and 100% MBT degradation by the Fenton-like reaction at pH 3, hydrogen peroxide concentration of 25 mg L -1 , residue concentration of 3 g L -1 , 200 rpm and 25°C, from a 100 mg L -1 MBT solution. MBT degradation was found to occur mainly by the heterogeneous Fenton-like process.

Prediction of erodibility in Oxisols using iron oxides, soil color and diffuse reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Arantes Camargo, Livia; Marques, José, Jr.

2015-04-01

The prediction of erodibility using indirect methods such as diffuse reflectance spectroscopy could facilitate the characterization of the spatial variability in large areas and optimize implementation of conservation practices. The aim of this study was to evaluate the prediction of interrill erodibility (Ki) and rill erodibility (Kr) by means of iron oxides content and soil color using multiple linear regression and diffuse reflectance spectroscopy (DRS) using regression analysis by least squares partial (PLSR). The soils were collected from three geomorphic surfaces and analyzed for chemical, physical and mineralogical properties, plus scanned in the spectral range from the visible and infrared. Maps of spatial distribution of Ki and Kr were built with the values calculated by the calibrated models that obtained the best accuracy using geostatistics. Interrill-rill erodibility presented negative correlation with iron extracted by dithionite-citrate-bicarbonate, hematite, and chroma, confirming the influence of iron oxides in soil structural stability. Hematite and hue were the attributes that most contributed in calibration models by multiple linear regression for the prediction of Ki (R2 = 0.55) and Kr (R2 = 0.53). The diffuse reflectance spectroscopy via PLSR allowed to predict Interrill-rill erodibility with high accuracy (R2adj = 0.76, 0.81 respectively and RPD> 2.0) in the range of the visible spectrum (380-800 nm) and the characterization of the spatial variability of these attributes by geostatistics.

Analysis of Red Pigments from the Neolithic sites of Çatalhöyük in Turkey and Sheikh-e Abad in Iran

NASA Astrophysics Data System (ADS)

Anderson, Emma; Almond, Matthew J.; Matthews, Wendy; Cinque, Gianfelice; Frogley, Mark D.

2014-10-01

Samples containing red pigment have been collected from two different archaeological sites dating to the Neolithic (Çatalhöyük in Turkey and Sheikh-e Abad in Iran) and have been analysed by a range of techniques. Sub-samples were examined by IR spectroscopy and X-ray diffraction, whilst thin sections were studied using optical polarising microscopy, synchrotron based IR microscopy and environmental scanning electron microscopy with energy dispersive X-ray analysis. Thin layers of red paint in a wall painting from Çatalhöyük were found to contain ochre (hematite and clay) as well as an unexpected component, grains of red and colourless obsidian, which have not been identified in any previous studies of the wall paintings at Çatalhöyük. These small grains of obsidian may have improved the reflective properties of the paint and made the artwork more vivid in the darkness of the buildings. Analysis of a roughly shaped ball of red sediment found on a possible working surface at Sheikh-e Abad revealed that the cause of the red colouring was the mineral hematite, which was probably from a source of terra rossa sediment in the local area. The results of this work suggest it is unlikely that this had been altered by the Neolithic people through mixing with other minerals.

An investigation of reaction parameters on geochemical storage of non-pure CO2 streams in iron oxides-bearing formations

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

Garcia, Susana; Liu, Q.; Bacon, Diana H.

2014-08-26

Hematite deposit that is the main FeIII-bearing mineral in sedimentary red beds was proposed as a potential host repository for converting CO2 into carbonate minerals such as siderite (FeCO3), when CO2–SO2 gas mixtures are co-injected. This work investigated CO2 mineral trapping using hematite and sensitivity of the reactive systems to different parameters, including particle size, gas composition, temperature, pressure, and solid-to-liquid ratio. Experimental and modelling studies of hydrothermal experiments were conducted, which emulated a CO2 sequestration scenario by injecting CO2-SO2 gas streams into a NaCl-NaOH brine hosted in iron oxide-containing aquifer. This study provides novel information on the mineralogical changesmore » and fluid chemistry derived from the co-injection of CO2-SO2 gas mixtures in hematite deposit. It can be concluded that the amount of siderite precipitate depends primarily on the SO2 content of the gas stream. Increasing SO2 content in the system could promote the reduction of Fe3+ from the hematite sample to Fe2+, which will be further available for its precipitation as siderite. Moreover, siderite precipitation is enhanced at low temperatures and high pressures. The influence of the solid to liquid ratio on the overall carbonation reaction suggests that the conversion increases if the system becomes more diluted.« less

On the origin of an unusual dependence of (bio)chemical reactivity of ferric hydroxides on nanoparticle size.

PubMed

Chernyshova, I V; Ponnurangam, S; Somasundaran, P

2010-11-14

Application of in situ UV-Vis absorption spectroscopy and ex situ X-ray photoelectron spectroscopy (XPS) makes it possible to resolve the controversies about the electronic properties of hematite (α-Fe(2)O(3)) nanoparticles (NPs) and, on this basis, to rationalize the unusual dependence of aquatic (bio)chemistry of these NPs on NP size. 2-Line ferrihydrite (FH) is also included in the study as the end polymorph of the size-driven phase transformation of hematite NPs in aqueous media. It is shown that the absorption edge of all NPs studied is due to the direct O 2p-Fe 3d charge transfer (CT) process, while a manifold of weak bands superimposed onto two main p-d CT bands is attributed to the d-d ligand field transitions. The band gap decreases from 2.95 to 2.18 eV with increasing NP size from 7 nm to 120 nm. This effect is attributed to restoration of hematite lattice structure, which ultimately results in an increase in the O 2p-Fe 3d hybridization, stabilization of the valence band, and delocalization of valence electrons, as confirmed by XPS. Finally, we show that the optical effects such as the Mie resonance significantly distort absorption spectra of hematite NPs larger than ∼120 nm. Possible impacts of these findings on (photo)catalytic and biochemical properties of ferric (hydr)oxide NPs are discussed.

Pu'u Poli'ahu, Mauna Kea: A Possible Analog for the Hematite Bearing Layer Located in Gale Crater, Mars.

NASA Technical Reports Server (NTRS)

Adams, M. E.

2014-01-01

Hyperspectral data detected by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) on board Mars Reconnaissance Orbiter (MRO) indicated the presence of a hematite bearing ridge on Mount Sharp situated in the Gale Crater, Mars. [Fraeman]. The presence of this mineral in high concentrations is indicative of possible aqueous origins. [Fraeman] In 2012, Curiosity Rover landed in Gale Crater on Mars. Curiosity's mission is to determine Mars' habitability and is equipped with an advanced suite of scientific instruments that are capable of conducting analyses on rocks and soil. The hematite bearing ridge on Mount Sharp is thought to be a good candidate of study for Curiosity. To better understand this type of terrain, the study of analog sites similar in geologic setting is of great importance. One site thought to be a comparable analog is a cinder cone called Pu'u Poli'ahu located on the summit of Mauna Kea, Hawai?i. Poli'ahu is unique among the tephra cones of Mauna Kea because it is thought to have formed in subaqueous conditions approximately 170,000 to 175,000 years ago. [Porter] Consequently located on the inner flanks of Poli'ahu is a rock outcrop that contains hematite. Samples were collected from the outcrop and characterized using the following instruments: Digital Microscope, Panalytical X-ray diffraction (XRD), and scanning electron microscope (SEM). The initial preparation of the rocks involved documenting each sample by creating powdered samples, thick sections, and photo documentation.