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Sample records for zn-rich phyllosilicate zn-layered

  1. Formation of Zn-rich phyllosilicate, Zn-layered double hydroxide and hydrozincite in contaminated calcareous soils

    Energy Technology Data Exchange (ETDEWEB)

    Jacquat, Olivier; Voegelin, Andreas; Villard, Andre; Marcus, Matthew A.; Kretzschmar, Ruben

    2007-10-15

    Recent studies demonstrated that Zn-phyllosilicate- and Zn-layered double hydroxide-type (Zn-LDH) precipitates may form in contaminated soils. However, the influence of soil properties and Zn content on the quantity and type of precipitate forming has not been studied in detail so far. In this work, we determined the speciation of Zn in six carbonate-rich surface soils (pH 6.2 to 7.5) contaminated by aqueous Zn in the runoff from galvanized power line towers (1322 to 30090 mg/kg Zn). Based on 12 bulk and 23 microfocused extended X-ray absorption fine structure (EXAFS) spectra, the number, type and proportion of Zn species were derived using principal component analysis, target testing, and linear combination fitting. Nearly pure Zn-rich phyllosilicate and Zn-LDH were identified at different locations within a single soil horizon, suggesting that the local availabilities of Al and Si controlled the type of precipitate forming. Hydrozincite was identified on the surfaces of limestone particles that were not in direct contact with the soil clay matrix. With increasing Zn loading of the soils, the percentage of precipitated Zn increased from {approx}20% to {approx}80%, while the precipitate type shifted from Zn-phyllosilicate and/or Zn-LDH at the lowest studied soil Zn contents over predominantly Zn-LDH at intermediate loadings to hydrozincite in extremely contaminated soils. These trends were in agreement with the solubility of Zn in equilibrium with these phases. Sequential extractions showed that large fractions of soil Zn ({approx}30% to {approx}80%) as well as of synthetic Zn-kerolite, Zn-LDH, and hydrozincite spiked into uncontaminated soil were readily extracted by 1 M NH{sub 4}NO{sub 3} followed by 1 M NH{sub 4}-acetate at pH 6.0. Even though the formation of Zn precipitates allows for the retention of Zn in excess to the adsorption capacity of calcareous soils, the long-term immobilization potential of these precipitates is limited.

  2. The effect of ZnS segregation on Zn-rich CZTS thin film solar cells

    International Nuclear Information System (INIS)

    Li, Wei; Chen, Jian; Yan, Chang; Hao, Xiaojing

    2015-01-01

    Highlights: • Secondary phase segregation in CZTS based solar cells has been studied by TEM. • A “Zn layer exchange” behaviour was found in sulphurisation of Zn/SnCu stacked layers. • XAS reveals a large spike-like CBO (>0.86 eV) between CZTS and ZnS. • Larger ZnS secondary phase proportion increases solar cell’s V oc but limits J sc . - Abstract: Analysis of ZnS segregation behaviour and its influence on the device performance has been made on the Zn-rich Cu 2 ZnSnS 4 thin film solar cells. Cross-sectional transmission electron microscopy images reveal that ZnS is the main secondary phase in the Cu 2 ZnSnS 4 layer obtained from a sulphurised Zn/CuSn metallic stack. The excess Zn diffuses from back contact region to top surface of Cu 2 ZnSnS 4 layer accumulating in the form of ZnS. The solar cell with a higher Zn concentration shows a large quantity of isolated ZnS grains at Cu 2 ZnSnS 4 top surface which is close to CdS/Cu 2 ZnSnS 4 heterojunction interface. Soft X-ray absorption spectroscopy indicates a large spike-like conduction band offset between Cu 2 ZnSnS 4 and ZnS. Consequently, such much ZnS precipitates would increase series resistance and generate lower short-circuit current and external quantum efficiency. However, appropriate amount of ZnS at the space charge region of the solar cell has beneficial effects by reducing the heterojunction interface recombination. Therefore, an improved open-circuit voltage and a higher shunt resistance are achieved. This paper provides a possible method to intentionally segregate ZnS at the space charge region by depositing the Zn layer at the bottom of co-sputtered CuSn layer. Although it is difficult to synthesis a pure phase Cu 2 ZnSnS 4 absorber, we can utilise the ZnS secondary phase to improve the Cu 2 ZnSnS 4 solar performance by controlling the Zn-excess amount

  3. Distribution of phyllosilicates on Ceres

    Science.gov (United States)

    Ammannito, Eleonora; De Sanctis, Maria Cristina; Ciarniello, Mauro; Frigeri, Alessandro; Giacomo Carrozzo, Filippo; Combe, Jean Philippe; Ehlmann, Bethany; Marchi, Simone; McSween, Hap Y.; Raponi, Andrea; Castillo-Rogez, Julie C.; Toplis, Michael J.; Tosi, Federico; Longobardo, Andrea; Palomba, Ernesto; Pieters, Carle M.; Raymond, Carol A.; Schenk, Paul; Zambon, Francesca; Russell, Christopher T.

    2016-04-01

    Studies of the dwarf planet Ceres using ground-based and orbiting telescopes proposed a variety of possible surficial composition including water in clay minerals [1], ammoniated phyllosilicates [2], or a mixture of brucite, Mg2CO3 and iron-rich serpentine [3, 4]. But the lack of spectral data in the 2.5 to 2.9 μm interval has precluded definitive identifications. The Dawn spacecraft has been acquiring spectra of the surface of Ceres since January 2015 [5, 6, 7]. The average thermally corrected reflectance spectrum of Ceres shows that the 2.6-4.2μm region is characterized by a broad asymmetric feature, characteristic of H2O/OH bearing materials, with several distinct narrower absorption bands [8]. This spectrum is compatible with the presence on the surface of a mixture of ammoniated-phyllosilicates, Mg-phyllosilicates, carbonates, and dark materials [8]. A strong 2.7-μm absorption dominates the overall spectral properties, and it has been attributed to OH-stretching vibrations in phyllosilicates [9] while the weaker 3.05 μm absorption has been attributed to the presence of NH4+ in phyllosilicates [10]. The spectral parameters of the absorption features at 2.7 and 3.05 μm have been computed to study their position and intensity. The computed spectral position of both absorption features is remarkably homogeneous. The average values are 2.727±0.005 and 3.061±0.005 μm respectively. Since the position of both features is sensitive to the chemical composition of the phyllosilicates, we conclude that the composition of phyllosilicates does not significantly change across the mapped portion of Ceres' surface. The computed values are indicative of Mg-OH phases, like antigorite (Mg-serpentine) or saponite (Mg-smectite) [9]. The presence of Mg-, rather than Fe-serpentine on Ceres may be interpreted as an indication that alteration had been extensive, while the lack of geochemical variation indicates that this is true throughout the exposed upper layer with no

  4. From cobalt and zinc adsorption on hectorite and quartz to phyllosilicates heterogeneous nucleation

    International Nuclear Information System (INIS)

    Schlegel, Michel

    1999-01-01

    The sorption mechanism and the crystallochemical environment of divalent Co and Zn on hectorite, a magnesian smectite, and quartz are investigated by combined kinetics chemical studies and polarized-EXAFS (P-EXAFS) spectroscopy. At high ionic strength (0.3 M NaNO 3 ), pH 6.5, and a sorbate/hectorite ratio of ∼50 μmol/g, Zn and Co adsorb via a pH-dependent mechanism. This sorption process coincides with an initial excess release of protons and Mg in the supernatant, and with a long term inhibition of hectorite dissolution. Sorbate cations form mononuclear surface complexes in the continuity of the magnesian octahedral sheet of the clay structure. At low ionic strength, Zn and Co initially sorb rapidly by cation exchange, and form outer-sphere surface complexes. Following this fast sorption process, sorbed ions are progressively transferred from interlayer exchange sites to layer edges sites, where they form inner-sphere surface complexes. Cation exchange sites thus act as transient cationic buffer. At pH 7.3, high ionic strength and sorbate/hectorite ratio (1480 μmol/g), the amplitude and kinetics of Zn sorption depend on the concentration of dissolved Si, [Si]. At [Si] = 30-60 μmol/L, Zn forms small polynuclear complexes of 2-3 atoms located in structural continuity of hectorite octahedral sheets. At [Si] ≅ 540 μmol L -1 , hetero-nucleation and growth of a Zn-rich phyllosilicate occurs in structural continuity of hectorite layers. EXAFS spectra of Co-sorbed quartz first indicate formation of large Co octahedral sheets. However, close examination of atomic contributions revealed that these sheets are connected to Si tetrahedral sheets, meaning that the sorption of Co on quartz leads to the neo-formation of phyllosilicate. The mechanism of this neo-formation is discussed. (author) [fr

  5. Phyllosilicates and Amorphous Gel in the Nakhlites

    Science.gov (United States)

    Hicks, L. J.; Bridges, J. C.; Gurman, S. J.

    2013-09-01

    Previous studies of the nakhlite martian meteorites have revealed hydrothermal minerals present within the fractures of the olivine minerals and the mesostasis. The olivine fractures of the Lafayette nakhlite reveal variations with initial deposits of siderite on the fracture walls, followed by crystalline phyllosilicates (smectite), and finishing with a rapidly cooled amorphous silicate gel within the central regions of the fractures. The mesostasis fractures of Lafayette also contain a crystalline phyllosilicate (serpentine). The amorphous gel is the most abundant secondary phase within the fractures of the other nakhlites [1, 2]. By studying nine nakhlite samples, including Lafayette, Governador Valadares, Nakhla, Y-000593, Y-000749, Miller-Range 03346, NWA 817, NWA 998, and NWA 5790, our aim is to constrain the identity of the phyllosilicate secondary phase minerals found throughout the nakhlite martian meteorites. This is achieved using methods including Electron Probe Micro-analysis (EPMA); X-ray Absorption Near-Edge Structure (Fe-K XANES) spectroscopy measured using Beamline I-18 at the Diamond Light Source synchrotron; and the use of Transmission Electron Microscopy (TEM) at the University of Leicester for High-Resolution (HR) imaging and Selected Area Electron Diffraction (SAED). BF studying nine nakhlite samples, including Lafayette, Governador Valadares, Nakhla, Y-000593, Y-000749, Miller-Range 03346, NWA 817, NWA 998, and NWA 5790, our aim is to constrain the identity of the phyllosilicate secondary phase minerals found throughout the nakhlite martian meteorites. This is achieved using methods including Electron Probe Micro-analysis (EPMA); X-ray Absorption Near-Edge Structure (Fe-K XANES) spectroscopy measured using Beamline I-18 at the Diamond Light Source synchrotron; and the use of Transmission Electron Microscopy (TEM) at the University of Leicester for High-Resolution (HR) imaging and Selected Area Electron Diffraction (SAED).

  6. Noachian and more recent phyllosilicates in impact craters on Mars.

    Science.gov (United States)

    Fairén, Alberto G; Chevrier, Vincent; Abramov, Oleg; Marzo, Giuseppe A; Gavin, Patricia; Davila, Alfonso F; Tornabene, Livio L; Bishop, Janice L; Roush, Ted L; Gross, Christoph; Kneissl, Thomas; Uceda, Esther R; Dohm, James M; Schulze-Makuch, Dirk; Rodríguez, J Alexis P; Amils, Ricardo; McKay, Christopher P

    2010-07-06

    Hundreds of impact craters on Mars contain diverse phyllosilicates, interpreted as excavation products of preexisting subsurface deposits following impact and crater formation. This has been used to argue that the conditions conducive to phyllosilicate synthesis, which require the presence of abundant and long-lasting liquid water, were only met early in the history of the planet, during the Noachian period (> 3.6 Gy ago), and that aqueous environments were widespread then. Here we test this hypothesis by examining the excavation process of hydrated minerals by impact events on Mars and analyzing the stability of phyllosilicates against the impact-induced thermal shock. To do so, we first compare the infrared spectra of thermally altered phyllosilicates with those of hydrated minerals known to occur in craters on Mars and then analyze the postshock temperatures reached during impact crater excavation. Our results show that phyllosilicates can resist the postshock temperatures almost everywhere in the crater, except under particular conditions in a central area in and near the point of impact. We conclude that most phyllosilicates detected inside impact craters on Mars are consistent with excavated preexisting sediments, supporting the hypothesis of a primeval and long-lasting global aqueous environment. When our analyses are applied to specific impact craters on Mars, we are able to identify both pre- and postimpact phyllosilicates, therefore extending the time of local phyllosilicate synthesis to post-Noachian times.

  7. Supercritical CO2 uptake by nonswelling phyllosilicates.

    Science.gov (United States)

    Wan, Jiamin; Tokunaga, Tetsu K; Ashby, Paul D; Kim, Yongman; Voltolini, Marco; Gilbert, Benjamin; DePaolo, Donald J

    2018-01-30

    Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2 , can increase CO 2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism. Copyright © 2018 the Author(s). Published by PNAS.

  8. Examination of Phyllosilicate-bearing Materials in the Vicinity of the Nili Fossae Using Thermal Infrared Data

    Science.gov (United States)

    McDowell, M. L.; Hamilton, V. E.

    2007-07-01

    We examine THEMIS and TES TIR data in areas OMEGA identified as containing phyllosilicates to better understand the spectral characteristics of phyllosilicate-bearing materials and reliable TES detection limits for modeled phyllosilicate abundances.

  9. Phyllosilicate Detection and Uncertainty from Thermal Infrared Data in the Vicinity of the Nili Fossae

    Science.gov (United States)

    McDowell, M. L.; Hamilton, V. E.

    2007-03-01

    We examine TIR data from THEMIS and TES in areas identified by OMEGA as containing phyllosilicates. Our investigation will help to constrain phyllosilicate detection limits in TES data and likely surface abundances on Mars.

  10. Ultraviolet electroluminescence from Au/MgO/MgxZn1−xO heterojunction diodes and the observation of Zn-rich cluster emission

    International Nuclear Information System (INIS)

    Liu, C.Y.; Xu, H.Y.; Sun, Y.; Zhang, C.; Ma, J.G.; Liu, Y.C.

    2014-01-01

    In this work, ultraviolet (UV) electroluminescence (EL) is achieved from Au/MgO/Mg x Zn 1−x O heterojunction diodes. The EL mechanism and laser forming process are discussed based on the energy band diagram, impact-ionization process and disordered optical structure. For ZnO and low Mg-content MgZnO devices, their EL spectra show single near-band-edge (NBE) emission. While in high Mg-content MgZnO devices, the emission from self-formed Zn-rich MgZnO clusters is observed and also contribute to the UV EL band. These Zn-rich clusters can act as thermally-stable luminescence centers, suggesting a promising route for developing MgZnO-based UV light-emitting devices. -- Highlights: • A series of Au/MgO/Mg x Zn 1−x O heterojunction diodes with multiple Mg compositions are fabricated and ultraviolet electroluminescence is achieved. • EL mechanism and laser forming process are discussed based on energy band diagram, impact-ionization process and disordered optical structure. • The transition from spontaneous to stimulated emission is observed in these heterojunctions, and the lasing mode is random laser. • In high Mg-content MgZnO devices, the emission from self-formed Zn-rich clusters is observed, which are thermally stable luminescence centers

  11. Preparation and structural characterization of zwitterionic surfactant intercalated into NiZn-layered hydroxide salts

    Science.gov (United States)

    Liu, Jiexiang; Wang, Jianlong; Zhang, Xiaoguang; Fang, Binbin; Hu, Pan; Zhao, Xuyang

    2015-10-01

    Three zwitterionic surfactants, dodecyl dimethyl carboxylbetaine (DCB), dodecyl dimethyl sulfobetaine (DSB) and N-dodecyl-β-aminoprpionate (DAP), intercalated into NiZn-layered hydroxide salts (NZL-DCB, NZL-DSB and NZL-DAP) were synthesized by the coprecipitation method. The effect of surfactant content, pH, temperature and time of hydrothermal treatment on preparation was investigated and discussed. The NZL-DCB, NZL-DSB and NZL-DAP were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry analysis and differential thermal analysis (TGA/DTA). The results showed that basal spacings of NZL-DCB, NZL-DSB and NZL-DAP were around 3.45, 3.68 and 3.94 nm, respectively. DCB, DSB and DAP probably form an overlapped bilayer in the gallery. TGA/DTA data indicated that NZL-DCB, NZL-DSB and NZL-DAP displayed three loss weight stages: loss of adsorbed and structural water, dehydroxylation of matrix and decomposition of nitrate ions, decomposition and combustion of surfactants. Furthermore, chemical analysis data, BET surface area and scanning electron microscopic (SEM) were also measured and analyzed.

  12. Structural and Dynamical Properties of 2:1 Phyllosilicates Edges and Nanoparticles

    Science.gov (United States)

    Newton, A. G.; Sposito, G.

    2012-12-01

    Classical mechanics simulations of bulk 2:1 phyllosilicate minerals provide atomic scale perspectives of the macroscopic sorption and diffusion phenomena in interlayer nanopores. An equivalent perspective of these interfacial phenomena in macropores bounded by the edges of stacked phyllosilicate particles is not possible due to the absence of a forcefield for the edges of phyllosilicate minerals. A valid forcefield to describe the phyllosilicate edge is essential to link the quantum and continuum mechanical models. The inherently disordered edge of 2:1 phyllosilicate minerals and rarity of well-crystallized samples further complicates the task of validating a forcefield for the phyllosilicate edge. Periodic bond chain theory identifies three tetrahedral-octahedral-tetrahedral (TOT) structures that parallel the edge faces of pseudohexagonal phyllosilicate particles. These TOT structures are the basis of atomistic models of the dominant edge interface and nanoparticles. The CLAYFF forcefield describes all pairwise atomic interactions with only minimal partial charge adjustments to maintain model neutrality, where necessary. Atomistic simulations in the isobaric-isothermal ensemble at nanosecond timescales predict equilibrium edge structures and dynamical properties of the aqueous interface. The CLAYFF forcefield and the limited adjustments to parameters predict edge and particle structures that are consistent with the results of ab initio MD simulations, support macroscopic observations of phyllosilicate reactivity, and provide legitimacy for disordered models of 2:1 phyllosilicates. The heterogeneous edge structures can be explained by the chemistry of the octahedral cation and surface charge anisotropy. In the plane of the octahedral sheet, the cations of the octahedral layer can assume four-, five-, and six-coordinate polyhedral geometries at the edge interface. These disordered edge structures create alternate alignments in the tetrahedral sheet. The structural

  13. Intercalation of Molybdate Ions into Ni/Zn Layered Double Hydroxide Salts: Synthesis, Characterization, and Preliminary Catalytic Activity in Methyl Transesterification of Soybean Oil

    OpenAIRE

    Colombo, Kamila; Maruyama, Swami A.; Yamamoto, Carlos I.; Wypych, Fernando

    2017-01-01

    This study reports the synthesis and characterization of a Ni/Zn layered double hydroxide salt intercalated with acetate ions and the subsequent replacement of the acetate ions with molybdate ions via an ion exchange reaction, conducted at two different pH values. Regardless of the pH employed during the synthesis, the basal spacing in the Ni/Zn layered double hydroxide salt decreased from 13.08 Å to approximately 9.5 Å, which agreed with intercalation of hydrated molybdate anions. The non-ca...

  14. Compositional and structural characterisation of Ni-phyllosilicates in hydrous silicate type Ni-laterite deposits

    OpenAIRE

    Villanova de Benavent, Cristina

    2015-01-01

    Ni-bearing Mg-phyllosilicates (commonly known as garnierites) are significant ore minerals in many Ni-laterite deposits worldwide. However, the characterisation of these mineral phases is complex, as well as their classification and nomenclature, due to their fine-grained nature, low crystallinity and frequent occurrence as mixtures. The aim of this study is to shed some light to the nature of the Ni-bearing Mg-phyllosilicates occurring at the Falcondo Ni-laterite. In this deposit, these ...

  15. Biotite Comminution in Phyllosilicate Rich Mylonites: Microstructural and Nanostructural Observations

    Science.gov (United States)

    Aslin, J.; Mariani, E.; Dawson, K.

    2017-12-01

    Micas are one of the most important mineral groups with regard to the strength and rheology of the Earth's crust. This is a result of their distinct weakness relative to other silicate phases coupled with their generally high abundance at mid-crustal conditions. Despite this, relatively little is known regarding the mechanisms of viscous deformation in micas. The samples used in this study were collected from the Cossato-Mergozzo-Brissago (C-M-B) line, an amphibolite facies mylonitic shear zone in Northern Italy. The granitoid and metasedimentary protoliths of this 100 -150 m wide shear zone ensure a high but variable phyllosilicate content within predominantly quartzofelspathic lithologies. Initial microstructural analysis using optical and scanning electron microscopy (SEM) reveals a significant change in biotite deformation behaviour with increasing strain. At low strains kinking and basal glide dominate, however at higher strain biotite undergoes a dramatic grain size reduction which is at first concentrated along grain edges and kink band boundaries but later involves the entire grain. In the highest strain samples examined, biotite only survives as a component of a very fine grained matrix. In contrast, muscovite, also present in these rocks, remains coarse, forming kinked and bent mica fish even to high strains. The comminution of biotite is of critical importance to the microstructural evolution of these mylonites as it facilitates the development of an interconnected network of fine and potentially very weak grains. However, the mechanism responsible is not clear. We use transmission electron microscopy (TEM) to observe and characterise the intracrystalline structure of the biotite in these samples both prior to and after this grain size reduction has taken place. A better understanding of the nano-scale microstructures produced by natural deformation in micas will aid in determining the mechanisms which control the way these important crustal minerals

  16. Implications of Martian Phyllosilicate Formation Conditions to the Early Climate on Mars

    Science.gov (United States)

    Bishop, J. L.; Baker, L.; Fairén, A. G.; Michalski, J. R.; Gago-Duport, L.; Velbel, M. A.; Gross, C.; Rampe, E. B.

    2017-12-01

    We propose that short-term warmer and wetter environments, occurring sporadically in a generally cold early Mars, enabled formation of phyllosilicate-rich outcrops on the surface of Mars without requiring long-term warm and wet conditions. We are investigating phyllosilicate formation mechanisms including CO2 and H2O budgets to provide constraints on the early martian climate. We have evaluated the nature and stratigraphy of phyllosilicate-bearing surface units on Mars based on i) phyllosilicate-forming environments on Earth, ii) phyllosilicate reactions in the lab, and iii) modeling experiments involving phyllosilicates and short-range ordered (SRO) materials. The type of phyllosilicates that form on Mars depends on temperature, water/rock ratio, acidity, salinity and available ions. Mg-rich trioctahedral smectite mixtures are more consistent with subsurface formation environments (crustal, hydrothermal or alkaline lakes) up to 400 °C and are not associated with martian surface environments. In contrast, clay profiles dominated by dioctahedral Al/Fe-smectites are typically formed in subaqueous or subaerial surface environments. We propose models describing formation of smectite-rich outcrops and laterally extensive vertical profiles of Fe/Mg-smectites, sulfates, and Al-rich clay assemblages formed in surface environments. Further, the presence of abundant SRO materials without phyllosilicates could mark the end of the last warm and wet episode on Mars supporting smectite formation. Climate Implications for Early Mars: Clay formation reactions proceed extremely slowly at cool temperatures. The thick smectite outcrops observed on Mars through remote sensing would require standing water on Mars for hundreds of millions of years if they formed in waters 10-15 °C. However, warmer temperatures could have enabled faster production of these smectite-rich beds. Sporadic warming episodes to 30-40 °C could have enabled formation of these smectites over only tens or

  17. Reactivity of iron-rich phyllosilicates with uranium and chromium through redox transition zones

    International Nuclear Information System (INIS)

    Burgos, William D.

    2016-01-01

    This project performed thermodynamic, kinetic, and mineral structural studies on the reactivity of phyllosilicate Fe(II/III) with metal-reducing bacteria, and with two important poly-valent DOE contaminants (chromium and uranium) that show high mobility in their oxidized state. We focused on Fe-bearing phyllosilicates because these are important components of the reactive, fines fraction of Hanford, Oak Ridge, and Idaho National Laboratory sediments. Iron-bearing phyllosilicates strongly influence the redox state and mobility of Cr and U because of their limited hydraulic conductivity, high specific surface area, and redox reactivity. This was a collaborative project between Penn State (W.D. Burgos - PI), Miami University (H. Dong - Co-PI), and Argonne National Laboratory (K. Kemner and M. Boyanov - Co-PIs). Penn State and Miami University were funded together but separately from ANL. This report summarizes research findings and publications produced by Penn State and Miami University.

  18. Reactivity of iron-rich phyllosilicates with uranium and chromium through redox transition zones

    Energy Technology Data Exchange (ETDEWEB)

    Burgos, William D. [Pennsylvania State Univ., University Park, PA (United States)

    2016-09-01

    This project performed thermodynamic, kinetic, and mineral structural studies on the reactivity of phyllosilicate Fe(II/III) with metal-reducing bacteria, and with two important poly-valent DOE contaminants (chromium and uranium) that show high mobility in their oxidized state. We focused on Fe-bearing phyllosilicates because these are important components of the reactive, fines fraction of Hanford, Oak Ridge, and Idaho National Laboratory sediments. Iron-bearing phyllosilicates strongly influence the redox state and mobility of Cr and U because of their limited hydraulic conductivity, high specific surface area, and redox reactivity. This was a collaborative project between Penn State (W.D. Burgos – PI), Miami University (H. Dong – Co-PI), and Argonne National Laboratory (K. Kemner and M. Boyanov – Co-PIs). Penn State and Miami University were funded together but separately from ANL. This report summarizes research findings and publications produced by Penn State and Miami University.

  19. Emplacement of Widespread Fe/Mg Phyllosilicate Layer in West Margaritifer Terra, Mars

    Science.gov (United States)

    Seelos, K. D.; Maxwell, R. E.; Seelos, F. P.; Buczkowski, D.; Viviano-Beck, C. E.

    2017-12-01

    West Margaritifer Terra is located at the eastern end of Valles Marineris at the complex intersection of chaos terrains, cratered highlands, and multiple generations of outflow channels. Adjacent regions host layered phyllosilicates thought to indicate early Mars pedogenic and/or ground water-based alteration (e.g., Le Deit et al., 2012), and indeed, hydrologic modeling supports prolonged aqueous activity in the Noachian and Hesperian eras (Andrews-Hanna and Lewis, 2011). The remnant high-standing plateaus in West Margaritifer (0-15°S, 325-345°E) host numerous phyllosilicate-bearing outcrops as well and are the focus of this study. Here, we performed a systematic mapping and characterization of mineralogy and morphology of these deposits in order to assess similarity to other layered phyllosilicates and evaluate potential formation mechanisms. Utilizing multiple remote sensing datasets, we identified three types of phyllosilicate exposures distributed throughout the region: 1) along upper chaos fracture walls, 2) in erosional windows on the plains, and 3) in crater walls and ejecta. Outcrops are spectrally indicative of Fe/Mg smectite (most similar to saponite) and only rare, isolated occurrences of Al-phyllosilicate were observed. Morphologically, the layer is a few to 10 m thick, light-toned, polygonally fractured at decameter scales, and vertical subparallel banding is evident in places. These characteristics were used along with spatial distribution, elevation, and geologic context to evaluate 4 potential formation mechanisms: fluvio-lacustrine, pedogenesis, diagenesis, and hydrothermal alteration. We find that the widespread distribution and spectral homogeneity of the layer favors formation via groundwater alteration and/or pedogenic weathering. This is consistent with interpretations of similar layered phyllosilicates in NW Noachis Terra and the Valles Marineris plains to the west, and significantly extends the area over which these aqueous processes

  20. Characterizing the Phyllosilicate Component of the Sheepbed Mudstone in Gale Crater, Mars Using Laboratory XRD and EGA

    Science.gov (United States)

    Rampe, E. B.; Morris, R. V.; Ming, D. W.; Archer, P. D.; Bish, D. L.; Chipera, S. J.; Vaniman, D. T.; Blake, D. F.; Bristow, T. F.; Sutter, B.; hide

    2014-01-01

    The Curiosity rover investigated the mineralogy of the Sheepbed mudstone member of the Yellowknife Bay formation in Gale crater. Data from the Chemistry and Mineralogy (CheMin) X-ray diffractometer (XRD) helped identify phyllosilicates in the two drilled samples, John Klein and Cumberland. These patterns showed peaks at low angles, consistent with (001) peaks in 2:1 swelling phyllosilicates [1]. Evolved gas analyses (EGA) by the Sample Analysis at Mars (SAM) instrument of these samples confirmed the presence of phyllosilicates through the release of H2O at high temperatures, consistent with dehydroxylation of octahedral OH in phyllosilicates [2]. CheMin data for the phyllosilicates at John Klein and Cumberland show that they are structurally similar in that their (02l) peaks are near 22.5 deg 2theta, suggesting both samples contain trioctahedral 2:1 phyllosilicates [1]. However, the positions of the (001) peaks differ: the phyllosilicate at John Klein has its (001) peak at 10 Angstroms, whereas the phyllosilicate at Cumberland has an (001) peak at 14 Angstroms. Such differences in (001) dspacings can be ascribed to the type of cation in the interlayer site [3]. For example, large monovalent cations (e.g., K(+)) have low hydration energies and readily lose their H2O of hydration, whereas small divalent cations (e.g., Mg(2+)) have high energies of hydration and retain H2O in the phyllosilicate interlayers [3,4]. The goal of this study is to determine whether differences in the interlayer cation composition can explain the CheMin data from John Klein and Cumberland and to use this knowledge to better understand phyllosilicate formation mechanisms.

  1. Atomic-scale structures of interfaces between phyllosilicate edges and water

    NARCIS (Netherlands)

    Liu, X.; Lu, X.; Meijer, E.J.; Wang, R.; Zhou, H.

    2012-01-01

    We report first-principles molecular dynamics (FPMD) studies on the structures of interfaces between phyllosilicate edges and water. Using FPMD, the substrates and solvents are simulated at the same first-principles level, and the thermal motions are sampled via molecular dynamics. Both the neutral

  2. Stepped fans and facies-equivalent phyllosilicates in Coprates Catena, Mars

    Science.gov (United States)

    Grindrod, P. M.; Warner, N. H.; Hobley, D. E. J.; Schwartz, C.; Gupta, S.

    2018-06-01

    Stepped fan deposits and phyllosilicate mineralogies are relatively common features on Mars but have not previously been found in association with each other. Both of these features are widely accepted to be the result of aqueous processes, but the assumed role and nature of any water varies. In this study we have investigated two stepped fan deposits in Coprates Catena, Mars, which have a genetic link to light-toned material that is rich in Fe-Mg phyllosilicate phases. Although of different sizes and in separate, but adjacent, trough-like depressions, we identify similar features at these stepped fans and phyllosilicates that are indicative of similar formation conditions and processes. Our observations of the overall geomorphology, mineralogy and chronology of these features are consistent with a two stage formation process, whereby deposition in the troughs first occurs into shallow standing water or playas, forming fluvial or alluvial fans that terminate in delta deposits and interfinger with interpreted lacustrine facies, with a later period of deposition under sub-aerial conditions, forming alluvial fan deposits. We suggest that the distinctive stepped appearance of these fans is the result of aeolian erosion, and is not a primary depositional feature. This combined formation framework for stepped fans and phyllosilicates can also explain other similar features on Mars, and adds to the growing evidence of fluvial activity in the equatorial region of Mars during the Hesperian and Amazonian.

  3. B_2S_2O_9. A boron sulfate with phyllosilicate topology

    International Nuclear Information System (INIS)

    Logemann, Christian; Wickleder, Mathias S.

    2013-01-01

    The condensation of [BO_4] and [SO_4] tetrahedra in the first binary boron sulfate B_2S_2O_9, leads to a structure with typical layered phyllosilicate topology. The compound is obtained from the hydrolysis of B(OH)_3 and HSO_3Cl. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Isolation of phyllosilicate-iron redox cycling microorganisms from an illite-smectite rich hydromorphic soil.

    Science.gov (United States)

    Shelobolina, Evgenya; Konishi, Hiromi; Xu, Huifang; Benzine, Jason; Xiong, Mai Yia; Wu, Tao; Blöthe, Marco; Roden, Eric

    2012-01-01

    The biogeochemistry of phyllosilicate-Fe redox cycling was studied in a Phalaris arundinacea (reed canary grass) dominated redoximorphic soil from Shovelers Sink, a small glacial depression near Madison, WI. The clay size fraction of Shovelers Sink soil accounts for 16% of the dry weight of the soil, yet contributes 74% of total Fe. The dominant mineral in the clay size fraction is mixed layer illite-smectite, and in contrast to many other soils and sediments, Fe(III) oxides are present in low abundance. We examined the Fe biogeochemistry of Shovelers Sink soils, estimated the abundance of Fe redox cycling microorganisms, and isolated in pure culture representative phyllosilicate-Fe oxidizing and reducing organisms. The abundance of phyllosilicate-Fe reducing and oxidizing organisms was low compared to culturable aerobic heterotrophs. Both direct isolation and dilution-to-extinction approaches using structural Fe(II) in Bancroft biotite as a Fe(II) source, and O(2) as the electron acceptor, resulted in recovery of common rhizosphere organisms including Bradyrhizobium spp. and strains of Cupriavidus necator and Ralstonia solanacearum. In addition to oxidizing biotite and soluble Fe(II) with O(2), each of these isolates was able to oxidize Fe(II) in reduced NAu-2 smectite with [Formula: see text] as the electron acceptor. Oxidized NAu-2 smectite or amorphous Fe(III) oxide served as electron acceptors for enrichment and isolation of Fe(III)-reducing microorganisms, resulting in recovery of a strain related to Geobacter toluenoxydans. The ability of the recovered microorganisms to cycle phyllosilicate-Fe was verified in an experiment with native Shovelers Sink clay. This study confirms that Fe in the native Shovelers Sink clay is readily available for microbial redox transformation and can be cycled by the Fe(III)-reducing and Fe(II)-oxidizing microorganisms recovered from the soil.

  5. Thermodynamics of low-temperature phyllosilicates: from a macroscopic perspective towards achieving atomistic simulation

    International Nuclear Information System (INIS)

    Dubacq, B.

    2008-12-01

    Phyllosilicates are important minerals in metamorphic petrology as well as in waste storage sites where clays are extensively used. Despite this fact, there is no thermodynamic model allowing to describe and to predict properly the behaviour of clay minerals (for example variation of volume with dehydration) and their phase relations with other minerals in metamorphic conditions. Inversely, the thermodynamic models of phengites are well constrained at high pressure and temperature but do not allow accurate thermo-barometric estimations at temperatures less than about 350 C. In this study, we propose two new thermodynamic models for smectites, illites, mixed-layers illites / smectites and phengites. With these models, it is possible to predict the composition of stable clays at low temperature and to estimate the pressure and temperature of crystallisation of di-octahedral aluminous phyllosilicates. These models take into consideration the hydration state of clay minerals as a function of pressure, temperature and water activity. The thermodynamic properties of solid solutions and hydrated mica-like end-members have been estimated in order to reproduce experimental results of i) clay dehydration, ii) nature of stable phases, iii) calorimetric measurements, as well as known (or estimated with independent methods) pressure-temperature conditions of crystallization of phyllosilicates analyses, from diagenesis conditions to ultra - high - pressure / temperature conditions. Phase diagrams have been computed with these models in simple systems. Conditions of crystallization of phyllosilicates have been estimated on many samples, including electron microprobe compositional maps. We investigated several approaches to estimate thermodynamic properties of minerals. All these methods revealed to be insufficiently accurate to estimate standard enthalpy of formation; calculated enthalpies of formation can not be directly used for thermo-barometric estimations. However, we

  6. Fe-phyllosilicate redox cycling organisms from a redox transition zone in Hanford 300 Area sediments

    Directory of Open Access Journals (Sweden)

    Jason eBenzine

    2013-12-01

    Full Text Available Microorganisms capable of reducing or oxidizing structural iron (Fe in Fe-bearing phyllosilicate minerals were enriched and isolated from a subsurface redox transition zone at the Hanford 300 Area site in eastern Washington, USA. Both conventional and in situ i-chip enrichment strategies were employed. One Fe(III-reducing Geobacter (G. bremensis strain R1, Deltaproteobacteria and six Fe(II phyllosilicate-oxidizing isolates from the Alphaproteobacteria (Bradyrhizobium japonicum strains 22, is5, and in8p8, Betaproteobacteria (Cupriavidus necator strain A5-1, Dechloromonas agitata strain is5, and Actinobacteria (Nocardioides sp. strain in31 were recovered. The G. bremensis isolate grew by oxidizing acetate with the oxidized form of NAu-2 smectite as the electron acceptor. The Fe(II-oxidizers grew by oxidation of chemically reduced smectite as the energy source with nitrate as the electron acceptor. The Bradyrhizobium isolates could also carry out aerobic oxidation of biotite. This is the first report of the recovery of a Fe(II-oxidizing Nocardioides, and to date only one other Fe(II-oxidizing Bradyrhizobium is known. The 16S rRNA gene sequences of the isolates were similar to ones found in clone libraries from Hanford 300 sediments and groundwater, suggesting that such organisms may be present and active in situ. Whole genome sequencing of the isolates is underway, the results of which will enable comparative genomic analysis of mechanisms of extracellular phyllosilicate Fe redox metabolism, and facilitate development of techniques to detect the presence and expression of genes associated with microbial phyllosilicate Fe redox cycling in sediments.

  7. Mineralogy and thermodynamic properties of magnesium phyllosilicates formed during the alteration of a simplified nuclear glass

    Energy Technology Data Exchange (ETDEWEB)

    Debure, Mathieu, E-mail: m.debure@brgm.fr [CEA, DEN, DTCD, SECM, F-30207 Bagnols-sur-Ceze (France); MINES-ParisTech, PSL Research University, Centre de Géosciences, 77305 Fontainebleau (France); De Windt, Laurent [MINES-ParisTech, PSL Research University, Centre de Géosciences, 77305 Fontainebleau (France); Frugier, Pierre; Gin, Stéphane [CEA, DEN, DTCD, SECM, F-30207 Bagnols-sur-Ceze (France); Vieillard, Philippe [IC2MP-CNRS-UMR 7285, 5 Ave. Albert Turpain TSA 51106, 86073 Poitiers Cedex 09 (France)

    2016-07-15

    The precipitation of crystallized magnesium phyllosilicates generally sustains the alteration rate of nuclear waste containment glass. However, glass alteration slows down to a residual rate as soon as Mg disappears from the solution. The identification of the phyllosilicates formed is therefore crucial for modeling the long-term behavior of nuclear glass. This study deals with batch alteration of the simplified nuclear glass ISG in presence of magnesium, and the characterization of the secondary phases. Morphological, chemical and structural analyses (MET, EDX, XRD) were performed to determine the nature and structure of the precipitated phases identified as trioctahedral smectites. Analyses conducted on the secondary phases proved the presence of Al, Na and Ca in the Mg-phyllosilicate phases. Such elements had been suspected but never quantitatively measured. The experimental results were then used to determine the thermodynamic solubility constants for each precipitated secondary phase at various temperatures. The calculated values were consistent with those available for sodium and magnesium saponites in the existing thermodynamic databases. - Highlights: • The international simple glass dissolution rate increases in presence of magnesium. • Mg added in solution combines with Si from glass to yield trioctahedral smectites. • Their calculated logK are close to smectite thermodynamic constants reported in databases. • It confirms assumptions on Mg-silicates phases made in previous geochemical modeling.

  8. Characterization of phyllosilicates observed in the central Mawrth Vallis region, Mars, their potential formational processes, and implications for past climate

    Science.gov (United States)

    McKeown, N.K.; Bishop, J.L.; Noe Dobrea, E.Z.; Ehlmann, B.L.; Parente, M.; Mustard, J.F.; Murchie, S.L.; Swayze, G.A.; Bibring, J.-P.; Silver, E.A.

    2009-01-01

    Mawrth Vallis contains one of the largest exposures of phyllosilicates on Mars. Nontronite, montmorillonite, kaolinite, and hydrated silica have been identified throughout the region using data from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM). In addition, saponite has been identified in one observation within a crater. These individual minerals are identified and distinguished by features at 1.38-1.42, ???1.91, and 2.17-2.41 ??m. There are two main phyllosilicate units in the Mawrth Vallis region. The lowermost unit is nontronite bearing, unconformably overlain by an Al-phyllosilicate unit containing montmorillonite plus hydrated silica, with a thin layer of kaolinite plus hydrated silica at the top of the unit. These two units are draped by a spectrally unremarkable capping unit. Smectites generally form in neutral to alkaline environments, while kaolinite and hydrated silica typically form in slightly acidic conditions; thus, the observed phyllosilicates may reflect a change in aqueous chemistry. Spectra retrieved near the boundary between the nontronite and Al-phyllosilicate units exhibit a strong positive slope from 1 to 2 ??m, likely from a ferrous component within the rock. This ferrous component indicates either rapid deposition in an oxidizing environment or reducing conditions. Formation of each of the phyllosilicate minerals identified requires liquid water, thus indicating a regional wet period in the Noachian when these units formed. The two main phyllosilicate units may be extensive layers of altered volcanic ash. Other potential formational processes include sediment deposition into a marine or lacustrine basin or pedogenesis. Copyright 2009 by the American Geophysical Union.

  9. Contemporaneous deposition of phyllosilicates and sulfates: Using Australian acidic saline lake deposits to describe geochemical variability on Mars

    Science.gov (United States)

    Baldridge, A.M.; Hook, S.J.; Crowley, J.K.; Marion, G.M.; Kargel, J.S.; Michalski, J.L.; Thomson, B.J.; de Souza, Filho C.R.; Bridges, N.T.; Brown, A.J.

    2009-01-01

    Studies of the origin of the Martian sulfate and phyllosilicate deposits have led to the hypothesis that there was a marked, global-scale change in the Mars environment from circum-neutral pH aqueous alteration in the Noachian to an acidic evaporitic system in the late Noachian to Hesperian. However, terrestrial studies suggest that two different geochemical systems need not be invoked to explain such geochemical variation.Western Australian acidic playa lakes have large pH differences separated vertically and laterally by only a few tens of meters, demonstrating how highly variable chemistries can coexist over short distances in natural environments. We suggest diverse and variable Martian aqueous environments where the coetaneous formation of phyllosilicates and sulfates at the Australian sites are analogs for regions where phyllosilicates and sulfates coexist on Mars. In these systems, Fe and alkali earth phyllosilicates represent deep facies associated with upwelling neutral to alkaline groundwater, whereas aluminous phyllosilicates and sulfates represent near-surface evaporitic facies formed from more acidic brines. Copyright 2009 by the American Geophysical Union.

  10. Physical Diversity of Phyllosilicate Deposits at the MSL Candidate Landing Sites

    Science.gov (United States)

    Fergason, R. L.

    2008-12-01

    The identification of phyllosilicates on Mars implies aqueous activity at the time of their formation and is important for understanding the history of Martian water and the past habitability of Mars. In addition, a significant fraction of the global water budget of Mars may be locked into clay mineral deposits within the Martian crust. As a result, six out of seven final landing sites being considered for the Mars Science Laboratory are sites where phyllosilicates have been identified in CRISM and OMEGA data. The physical characteristics of these materials, as identified using thermal inertia data, are an important component for understanding the geologic history of these deposits. Thermal inertia values provide information regarding effective particle size and help to constrain the possible presence of duricrust, rocks, and exposed bedrock at these locations. These identified physical characteristics suggest the degree of resistivity to erosion, which has implications for the post-emplacement modification of these deposits. At the aforementioned six locations (Nili Fossae Trough, Holden Crater, Mawrth Vallis, Miyamoto crater, southern Meridiani Planum, and Gale crater) the physical properties were quantified using THEMIS-derived thermal inertia data to characterize the physical properties at each site and identify the presence or absence of physical diversity among these materials. I identified a wide range of surface properties at these locations ranging from indurated surfaces intermixed with unconsolidated aeolian material (thermal inertia of 150-460 J m-2 K-1 s- 1/2) at Mawrth Vallis, to exposures of in-place bedrock and the presence of rocky material (thermal inertia exceeding 800 J m-2 K-1 s-1/2) in Gale crater. In addition, the surface texture and morphologic features observed in high-resolution visible images (such as narrow-angle MOC, HiRISE, and CTX) are dissimilar across these phyllosilicate exposures, and confirm the interpretation of thermal inertia

  11. Adsorption of nucleotides onto ferromagnesian phyllosilicates: Significance for the origin of life

    Science.gov (United States)

    Pedreira-Segade, Ulysse; Feuillie, Cécile; Pelletier, Manuel; Michot, Laurent J.; Daniel, Isabelle

    2016-03-01

    The concentration of prebiotic organic building blocks may have promoted the formation of biopolymers in the environment of the early Earth. We therefore studied the adsorption of RNA monomers AMP, GMP, CMP, and UMP, and DNA monomers dGMP, dCMP, and TMP, on minerals that were abundant in the early Earth environment as the result of aqueous or hydrothermal alteration of the primitive oceanic crust. We focused our study on swelling clays, i.e. nontronite and montmorillonite, and non-swelling phyllosilicates, i.e. pyrophyllite, chlorite, lizardite and chrysotile suspended in an aqueous saline solution analog to seawater. In this reference study, adsorption experiments were carried out under standard conditions of pressure and temperature and controlled pH. Under such conditions, this work is also relevant to the preservation of nucleic acids in Fe-Mg-rich terrestrial and Martian soils. We compared the adsorption of the different monomers on individual minerals, as well as the adsorption of single monomers on the whole suite of minerals. We found that DNA monomers adsorb much more strongly than RNA monomers, and that any monomer containing the G nucleobase adsorbed more strongly than one containing the C nucleobase. At high surface loadings (greater than about 1 mM monomer in aqueous solution) we also found a dramatic increase in the slope of adsorption isotherm on the swelling clays, leading to large increases in the amounts adsorbed. Data were processed in order to understand the adsorption mechanism of nucleotides onto mineral surfaces. We infer that all nucleotides behave as homologous molecules in regard to their adsorption onto the studied mineral surfaces. At low to moderate surface loadings, their adsorption is best explained by a single mechanism common to the suite of minerals of the present study. At pH 7, adsorption certainly proceeds by ligand exchange between the phosphate group and the hydroxyls of the broken edges of phyllosilicates leading to the

  12. Evaluation of phyllosilicates as a buffer component in the disposal of nuclear fuel waste

    International Nuclear Information System (INIS)

    Oscarson, D.W.; Cheung, S.C.H.

    1983-12-01

    The disposal concept now being assessed in the Canadian Nuclear Fuel Waste Management program entails the emplacement of containers with used fuel or fuel recycle waste deep in a stable plutonic formation, possibly in the Canadian Shield. One of the engineered barriers to radionuclide movement from the waste containers to the biosphere is a buffer material placed between the containers and the surrounding rock mass. An effective buffer material should have a combination of the following properties: low hydraulic conductivity and diffusivity for water and dissolved chemical species, a high sorption capacity for radionuclides, high thermal conductivity, sufficient physical strength to support the waste containers, and long-term stability under the conditions existing in a disposal vault. This report evaluates phyllosilicates for their effectiveness as potential buffer components. It concludes that bentonite, because of its high swelling potential, low hydraulic conductivity, low effective porosity, and high sorption capacity for many radionuclides, would be the most effective phyllosilicate for use as a buffer component

  13. Microbial reductive transformation of phyllosilicate Fe(III) and U(VI) in fluvial subsurface sediments.

    Science.gov (United States)

    Lee, Ji-Hoon; Fredrickson, James K; Kukkadapu, Ravi K; Boyanov, Maxim I; Kemner, Kenneth M; Lin, Xueju; Kennedy, David W; Bjornstad, Bruce N; Konopka, Allan E; Moore, Dean A; Resch, Charles T; Phillips, Jerry L

    2012-04-03

    The microbial reduction of Fe(III) and U(VI) was investigated in shallow aquifer sediments collected from subsurface flood deposits near the Hanford Reach of the Columbia River in Washington State. Increases in 0.5 N HCl-extractable Fe(II) were observed in incubated sediments and (57)Fe Mössbauer spectroscopy revealed that Fe(III) associated with phyllosilicates and pyroxene was reduced to Fe(II). Aqueous uranium(VI) concentrations decreased in subsurface sediments incubated in sulfate-containing synthetic groundwater with the rate and extent being greater in sediment amended with organic carbon. X-ray absorption spectroscopy of bioreduced sediments indicated that 67-77% of the U signal was U(VI), probably as an adsorbed species associated with a new or modified reactive mineral phase. Phylotypes within the Deltaproteobacteria were more common in Hanford sediments incubated with U(VI) than without, and in U(VI)-free incubations, members of the Clostridiales were dominant with sulfate-reducing phylotypes more common in the sulfate-amended sediments. These results demonstrate the potential for anaerobic reduction of phyllosilicate Fe(III) and sulfate in Hanford unconfined aquifer sediments and biotransformations involving reduction and adsorption leading to decreased aqueous U concentrations.

  14. Interaction of divalent cations with basal planes and edge surfaces of phyllosilicate minerals: muscovite and talc.

    Science.gov (United States)

    Yan, Lujie; Masliyah, Jacob H; Xu, Zhenghe

    2013-08-15

    Smooth basal plane and edge surfaces of two platy phyllosilicate minerals (muscovite and talc) were prepared successfully to allow accurate colloidal force measurement using an atomic force microscope (AFM), which allowed us to probe independently interactions of divalent cations with phyllosilicate basal planes and edge surfaces. The Stern potential of basal planes and edge surfaces was obtained by fitting the measured force profiles with the classical DLVO theory. The fitted Stern potential of the muscovite basal plane became less negative with increasing Ca(2+) or Mg(2+) concentration but did not reverse its sign even at Ca(2+) or Mg(2+) concentrations up to 5 mM. In contrast, the Stern potential of the muscovite edge surface reversed at Ca(2+) or Mg(2+) concentrations as low as 0.1 mM. The Stern potential of the talc basal plane became less negative with 0.1 mM Ca(2+) addition and nearly zero with 1 mM Ca(2+) addition. The Stern potential of talc edge surface became reversed with 0.1 mM Ca(2+) or 1 mM Mg(2+) addition, showing not only a different binding mechanism of talc basal planes and edge surfaces with Ca(2+) and Mg(2+), but also different binding mechanism between Ca(2+) and Mg(2+) ions with basal planes and edge surfaces. Copyright © 2013 Elsevier Inc. All rights reserved.

  15. Preferred orientation of phyllosilicates: Comparison of fault gouge, shale and schist

    International Nuclear Information System (INIS)

    Wenk, Hans-Rudolf; Kanitpanyacharoen, Waruntorn; Voltolini, Marco

    2010-01-01

    Samples of fault gouge from the San Andreas Fault drill hole (SAFOD), a shale from the North Sea sedimentary basin and schists from metamorphic rocks in the Alps have been analyzed with high energy synchrotron X-rays to determine preferred orientation of mica and clay minerals. The method relies on obtaining 2D diffraction images which are then processed with the crystallographic Rietveld method, implemented in the software MAUD, allowing for deconvolution of phases and extraction of their orientation distributions. It is possible to distinguish between detrital illite/muscovite and authigenic illite/smectite, kaolinite and chlorite, and muscovite and biotite, with strongly overlapping peaks in the diffraction pattern. The results demonstrate that phyllosilicates show large texture variations in various environments, where different mechanisms produce the rock microfabrics: fault gouge fabrics are quite weak and asymmetric with maxima for (001) in the range of 1.5-2.5 multiples of random distribution (m.r.d.). This is attributed to heterogeneous deformation with randomization, as well as dissolution-precipitation reactions. Shale fabrics have maxima ranging from 3 to 9 m.r.d. and this is due to sedimentation and compaction. The strongest fabrics were observed in metamorphic schists (10-14 m.r.d.) and developed by deformation as well as recrystallization in a stress field. In the analyzed samples, fabrics of co-existing quartz are weak. All phyllosilicate textures can be explained by orientation of (001) platelets, with no additional constraints on a-axes.

  16. Aminopropyl-modified magnesium-phyllosilicates: layered solids with tailored interlayer access and reactivity.

    Science.gov (United States)

    Ferreira, Ricardo B; da Silva, César R; Pastore, Heloise O

    2008-12-16

    Despite its wide application, the synthesis of aminopropyl-modified magnesium-phyllosilicates was known only in the case where every silicon atom bore an organic pending group. This paper shows the preparation of aminopropyl-modified talc where tailored amounts of silicon atoms are bound to an aminopropyl group. The decrease in the concentration of the organoamino group leaves a proportional concentration of interlayer SiOH groups that can be used to react with other silylation agents. The amino group reacts with CO2, forming a carbamate functionality; it seems that the presence of this group avoids delamination in water as performed for the parent compound. Bearing in mind that the aminopropyl group can be changed by other groups, the present synthesis strategy demonstrates ways to produce solids with controlled surface properties with interlayer amino and SiOH groups in variable concentrations, allowing formation of several other interlayer functionalities.

  17. Removal of malachite green by adsorption and precipitation using aminopropyl functionalized magnesium phyllosilicate

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Young-Chul [Department of Chemical and Biomolecular Engineering (BK21 Program), KAIST, 335 Gwahak-ro, Yuseong-gu, Daejeon 305-701 (Korea, Republic of); Kim, Eui Jin [Department of Chemical and Biochemical Engineering, Chosun University, Seosuk-dong, Dong-gu, Gwangju 501-759 (Korea, Republic of); Yang, Ji-Won [Department of Chemical and Biomolecular Engineering (BK21 Program), KAIST, 335 Gwahak-ro, Yuseong-gu, Daejeon 305-701 (Korea, Republic of); Shin, Hyun-Jae, E-mail: shinhj@chosun.ac.kr [Department of Chemical and Biochemical Engineering, Chosun University, Seosuk-dong, Dong-gu, Gwangju 501-759 (Korea, Republic of)

    2011-08-15

    Highlights: {yields} Preparation of aminopropyl functionalized magnesium phyllosilicate (AMP clay). {yields} Characterization of AMP clay and AMP clay-malachite green (MG) mixture. {yields} Novel precipitation mechanism including MG fading plus collapsed AMP clay. {yields} Adsorption kinetics and thermodynamics of MG using AMP clay. - Abstract: We report a method for the removal of malachite green (MG) by adsorption and precipitation using nano-sized aminopropyl functionalized magnesium phyllosilicate (AMP) clay. MG, which is used in aquaculture and fisheries, is a carcinogenic and mutagenic compound. In response to these health risks, many efforts have been focused on adsorption of MG onto various adsorbents, which is a versatile and widely used technique for removing MG from water. Herein, we describe the adsorption and precipitation of MG using AMP clay, as well as the alkaline fading phenomenon of MG. In this study, prepared AMP clay and the precipitate product after the reaction of MG-AMP clay mixture were characterized. In addition, adsorption isotherms and kinetics, as well as thermodynamic studies are presented. Based on the results, we suggest a macro- and microscopic removal mechanism for the adsorption and precipitation of MG using AMP clay. An AMP clay dosage of 0.1 mg mL{sup -1} exhibited a maximum removal capacity of 334.80 mg g{sup -1} and 81.72% MG removal efficiency. With further increases of the AMP clay dosage, removal capacity by AMP clay gradually decreased; at dosage above 0.2 mg mL{sup -1} of AMP clay, the removal efficiency reached 100%.

  18. Removal of malachite green by adsorption and precipitation using aminopropyl functionalized magnesium phyllosilicate

    International Nuclear Information System (INIS)

    Lee, Young-Chul; Kim, Eui Jin; Yang, Ji-Won; Shin, Hyun-Jae

    2011-01-01

    Highlights: → Preparation of aminopropyl functionalized magnesium phyllosilicate (AMP clay). → Characterization of AMP clay and AMP clay-malachite green (MG) mixture. → Novel precipitation mechanism including MG fading plus collapsed AMP clay. → Adsorption kinetics and thermodynamics of MG using AMP clay. - Abstract: We report a method for the removal of malachite green (MG) by adsorption and precipitation using nano-sized aminopropyl functionalized magnesium phyllosilicate (AMP) clay. MG, which is used in aquaculture and fisheries, is a carcinogenic and mutagenic compound. In response to these health risks, many efforts have been focused on adsorption of MG onto various adsorbents, which is a versatile and widely used technique for removing MG from water. Herein, we describe the adsorption and precipitation of MG using AMP clay, as well as the alkaline fading phenomenon of MG. In this study, prepared AMP clay and the precipitate product after the reaction of MG-AMP clay mixture were characterized. In addition, adsorption isotherms and kinetics, as well as thermodynamic studies are presented. Based on the results, we suggest a macro- and microscopic removal mechanism for the adsorption and precipitation of MG using AMP clay. An AMP clay dosage of 0.1 mg mL -1 exhibited a maximum removal capacity of 334.80 mg g -1 and 81.72% MG removal efficiency. With further increases of the AMP clay dosage, removal capacity by AMP clay gradually decreased; at dosage above 0.2 mg mL -1 of AMP clay, the removal efficiency reached 100%.

  19. B{sub 2}S{sub 2}O{sub 9}. A boron sulfate with phyllosilicate topology

    Energy Technology Data Exchange (ETDEWEB)

    Logemann, Christian; Wickleder, Mathias S. [Carl von Ossietzky University, Institute for Chemistry, Oldenburg (Germany)

    2013-12-23

    The condensation of [BO{sub 4}] and [SO{sub 4}] tetrahedra in the first binary boron sulfate B{sub 2}S{sub 2}O{sub 9}, leads to a structure with typical layered phyllosilicate topology. The compound is obtained from the hydrolysis of B(OH){sub 3} and HSO{sub 3}Cl. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Improved cell disruption of Pichia pastoris utilizing aminopropyl magnesium phyllosilicate (AMP) clay.

    Science.gov (United States)

    Kim, Sun-Il; Wu, Yuanzheng; Kim, Ka-Lyun; Kim, Geun-Joong; Shin, Hyun-Jae

    2013-06-01

    An efficient method for Pichia cell disruption that employs an aminopropyl magnesium phyllosilicate (AMP) clay-assisted glass beads mill is presented. AMP clay is functionalized nanocomposite resembling the talc parent structure Si8Mg6O20(OH)4 that has been proven to permeate the bacterial membrane and cause cell lysis. The recombinant capsid protein of cowpea chlorotic mottle virus (CCMV) expressed in Pichia pastoris GS115 was used as demonstration system for their ability of self-assembly into icosahedral virus-like particles (VLPs). The total protein concentration reached 4.24 mg/ml after 4 min treatment by glass beads mill combined with 0.2 % AMP clay, which was 11.2 % higher compared to glass beads mill only and the time was half shortened. The stability of purified CCMV VLPs illustrated AMP clay had no influence on virus assembly process. Considering the tiny amount added and simple approach of AMP clay, it could be a reliable method for yeast cell disruption.

  1. Transmutation effects on long-term Cs retention in phyllosilicate minerals from first principles.

    Science.gov (United States)

    Sassi, Michel; Okumura, Masahiko; Machida, Masahiko; Rosso, Kevin M

    2017-10-11

    The accidental release and incorporation of radiocesium into soil minerals represents a massive environmental, technical and social challenge. Accurately forecasting the evolving distribution and fate of long- and medium-lived isotopes such as 137 Cs and 134 Cs over decadal time scales is essential. The cesium cation has long been modeled as a strongly and selectively sorbed species into clay mineral interlayers; however, because of the time scales involved by the radioisotopes half-lives, the effects of radioactive decay on Cs retention have been unknown. We report density functional theory (DFT) simulations of transmutation effects of radiocesium on long-term Cs retention in phlogopite. The calculations show that the progressive appearance of daughter product Ba 2+ is accompanied by a proportional increase in thermodynamic driving force to preferentially discharge remaining Cs, both radioactive and stable, back into aqueous solution. Based on thermodynamic analysis, the findings indicate that radiocesium transmutation provides a mean to weaken the binding of Cs in phyllosilicate minerals, therefore potentially involving a premature re-release of Cs back into the environment. In the case where radiogenic Ba 2+ ions accumulate in the mineral, collateral effects would ultimately be an increase in the overall interlayer binding energy and a lower resorption capacity.

  2. Dispersion of phyllosilicates in aqueous suspensions: role of the nature and amount of surfactant.

    Science.gov (United States)

    Houta, Nadia; Lecomte-Nana, Gisèle-Laure; Tessier-Doyen, Nicolas; Peyratout, Claire

    2014-07-01

    The present work aims at investigating the effect of pH values and additives on the dispersion of two 1:1 dioctahedral phyllosilicates in the presence of water. Two model clays are used for this purpose, BIP kaolin and NZCC halloysite, presenting the same surface chemistry but different morphologies. The effect of sodium hexametaphosphate, sodium silicate and sodium carbonate is discussed. Kaolin and halloysite powders were first characterized using X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. Subsequently, suspensions containing 8 mass% of each clay were prepared with or without additives. Experimental measurements regarding the pH values, the zeta potential and the rheological behavior were performed to determine the most suitable additive. Results show that the conformation of halloysite particles changes regarding pH values of suspensions and is strongly related to the surface charges of these particles. At their natural pH values, halloysite and kaolin suspensions exhibit zeta potentials equal to -50 and -20 mV respectively. This trend indicates that halloysite-based suspensions are well dispersed compared to kaolin-based suspensions. Sodium hexametaphosphate is the most suitable dispersant for both clays. The rheological characterization regarding further applications in casting process indicates a shear-thinning behavior for all studied compositions. Copyright © 2014 Elsevier Inc. All rights reserved.

  3. In Situ XRD Studies of ZnO/GaN Mixtures at High Pressure and High Temperature: Synthesis of Zn-Rich (Ga1-xZnx)(N1-xOx) Photocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, J.A.; Chen, H.; Wang, L.; Bai, J.; Hanson, J.C.; Warren, J.B.; Muckerman, J.T.; Fujita, E.

    2010-02-04

    The high-pressure, high-temperature conditions for the synthesis of Zn-rich (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions from mixtures of ZnO/GaN were explored using synchrotron-based in situ time-resolved X-ray diffraction (XRD). Following a new synthetic path, (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions with a Zn content up to 75% were prepared for the first time. The structures of the (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions were characterized by XRD and X-ray absorption fine structure (XAFS) analyses and were in excellent agreement with the predictions of density functional calculations. These materials adopt a wurtzite crystal structure with metal-N or metal-O bond distances in the range of 1.95-1.98 {angstrom}. Although the (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions seem to be stable over the full range of compositions, no ideal solid solution formation was observed. In all cases, the lattice parameters were larger than those of ideal solid solutions. The variation of the lattice parameter c showed an upward double bowing curve, as was predicted by theoretical calculations. Also, no ideal behavior was observed in the electronic properties of the (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions. X-ray absorption spectra at the Zn and Ga K-edges of the (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) systems showed significant electronic perturbations with respect to ZnO and GaN. The synthesized (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solution with a Zn content of 50% displayed the ability to absorb visible light well above 500 nm. This material has a great potential for splitting water under visible light irradiation. The availability of (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions with a high Zn content opens the door to fully explore the application of these materials in photocatalysis.

  4. In Situ XRD Studies of ZnO/GaN Mixtures at High Pressure and High Temperature: Synthesis of Zn-Rich (Ga1-xZnx)(N1-xOx) Photocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chen, H.; Wang, L; Bai, J; Hanson, J; Warren, J; Muckerman, J; Fujita, E; Rodriguez, J

    2010-01-01

    The high-pressure, high-temperature conditions for the synthesis of Zn-rich (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions from mixtures of ZnO/GaN were explored using synchrotron-based in situ time-resolved X-ray diffraction (XRD). Following a new synthetic path, (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions with a Zn content up to {approx}75% were prepared for the first time. The structures of the (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions were characterized by XRD and X-ray absorption fine structure (XAFS) analyses and were in excellent agreement with the predictions of density functional calculations. These materials adopt a wurtzite crystal structure with metal-N or metal-O bond distances in the range of 1.95-1.98 {angstrom}. Although the (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions seem to be stable over the full range of compositions, no ideal solid solution formation was observed. In all cases, the lattice parameters were larger than those of ideal solid solutions. The variation of the lattice parameter c showed an upward double bowing curve, as was predicted by theoretical calculations. Also, no ideal behavior was observed in the electronic properties of the (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions. X-ray absorption spectra at the Zn and Ga K-edges of the (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) systems showed significant electronic perturbations with respect to ZnO and GaN. The synthesized (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solution with a Zn content of 50% displayed the ability to absorb visible light well above 500 nm. This material has a great potential for splitting water under visible light irradiation. The availability of (Ga{sub 1-x}Zn{sub x})(N{sub 1-x}O{sub x}) solid solutions with a high Zn content opens the door to fully explore the application of these materials in photocatalysis.

  5. Surface materials map of Afghanistan: carbonates, phyllosilicates, sulfates, altered minerals, and other materials

    Science.gov (United States)

    Kokaly, Raymond F.; King, Trude V.V.; Hoefen, Todd M.; Dudek, Kathleen B.; Livo, Keith E.

    2012-01-01

    This map shows the distribution of selected carbonates, phyllosilicates, sulfates, altered minerals, and other materials derived from analysis of HyMap imaging spectrometer data of Afghanistan. Using a NASA (National Aeronautics and Space Administration) WB-57 aircraft flown at an altitude of ~15,240 meters or ~50,000 feet, 218 flight lines of data were collected over Afghanistan between August 22 and October 2, 2007. The HyMap data were converted to apparent surface reflectance, then further empirically adjusted using ground-based reflectance measurements. The reflectance spectrum of each pixel of HyMap data was compared to the spectral features of reference entries in a spectral library of minerals, vegetation, water, ice, and snow. This map shows the spatial distribution of minerals that have diagnostic absorption features in the shortwave infrared wavelengths. These absorption features result primarily from characteristic chemical bonds and mineralogical vibrations. Several criteria, including (1) the reliability of detection and discrimination of minerals using the HyMap spectrometer data, (2) the relative abundance of minerals, and (3) the importance of particular minerals to studies of Afghanistan's natural resources, guided the selection of entries in the reference spectral library and, therefore, guided the selection of mineral classes shown on this map. Minerals occurring abundantly at the surface and those having unique spectral features were easily detected and discriminated. Minerals having similar spectral features were less easily discriminated, especially where the minerals were not particularly abundant and (or) where vegetation cover reduced the absorption strength of mineral features. Complications in reflectance calibration also affected the detection and identification of minerals.

  6. Pharmaceutical grade phyllosilicate dispersions: the influence of shear history on floc structure.

    Science.gov (United States)

    Viseras, C; Meeten, G H; Lopez-Galindo, A

    1999-05-10

    The effect of mixing conditions on the flow curves of some clay-water dispersions was studied. Two Spanish fibrous phyllosilicates (sepiolite from Vicálvaro and palygorskite from Turón) and a commercial bentonite (Bentopharm Copyright, UK) were selected as model clays. The disperse systems were made up using a rotor-stator mixer working at two different mixing rates (1000 and 8000 rpm), for periods of 1 and 10 min. Rheological measurements were taken and the corresponding flow curves obtained immediately after interposition and then after a period of 24 h under low shear caused by a roller apparatus. Aqueous sepiolite dispersions showed the highest viscosity and were easily interposed, whereas palygorskite dispersions were more difficult to obtain, resulting in low to medium viscosity gels. Bentonite dispersions provided medium viscosity systems, which greatly increased their viscosity after the low shear treatment (as a result of swelling), whereas the viscosity of the fibrous clays stayed at approximately the same values or even decreased. A linear relation was found between mixing energy and apparent viscosity in the bentonite systems, while apparent viscosity in the sepiolite samples was related to mixing power, with minor influence of mixing times. All the systems studied had thixotropic behaviour, changing from clearly positive to even negative thixotropy in some palygorskite systems. Finally, we studied the effect of drastic pH changes on the system structure. Results showed that rheological properties were highly sensitive to pH in the fibrous dispersions, but less sensitive behaviour was found in the laminar clay systems. Copyright.

  7. Some features associated with organosilane groups grafted by the sol-gel process onto synthetic talc-like phyllosilicate.

    Science.gov (United States)

    Sales, José A A; Petrucelli, Giovanni C; Oliveira, Fernando J V E; Airoldi, Claudio

    2006-05-01

    Two new lamellar inorganic-organic magnesium silicates have been successfully synthesized by using sol-gel based processes under mild temperature conditions. The talc-organosilicates derived using two silylating agents as the silicon source, (i) 3-chloropropyltrimethoxysilane, and (ii) from the attachment of 5-amino-1,3,4-thiadiazole-2-thiol molecule to this precursor agent, yielded PhMg-Cl and PhMg-Tz phyllosilicates. These organoclays were characterized through elemental analyses, infrared spectroscopy, X-ray diffractometry, surface area, thermogravimetry, and carbon and silicon solid state nuclear magnetic resonance spectroscopy. The results confirmed the presence of organic moieties covalently bonded to the inorganic silicon sheet network of the 2:1 class of phyllosilicates, with a density of organic molecules of 6.6+/-0.1 and 2.7+/-0.2 mmol g(-1) anchored on the inorganic layer and with interlayer distances of 1158 and 1628 pm, respectively. The nuclear magnetic resonances results in the solid state are in agreement with the sequence of carbons distributed in the pendant chains of the original silylating agents and the silicon bonded to oxygen atoms or carbon atoms of the inorganic sheets, as expected for the organically functionalized phyllosilicates. The enhanced potential of the new compound PhMg-Tz as a multi property material was explored in adsorbing cations from aqueous solution. The basic sulfur and nitrogen centers attached to the pendant chains inside the lamellar cavity can coordinate mercury, by presenting an isotherm saturated at 0.19 mmol g(-1) of this heavy metal. The functionality of this organoclay-like material expresses its potential for heavy cation removal from an ecosystem.

  8. Characterizing the Phyllosilicates and Amorphous Phases Found by MSL Using Laboratory XRD and EGA Measurements of Natural and Synthetic Materials

    Science.gov (United States)

    Rampe, Elizabeth B.; Morris, Richard V.; Chipera, Steve; Bish, David L.; Bristow, Thomas; Archer, Paul Douglas; Blake, David; Achilles, Cherie; Ming, Douglas W.; Vaniman, David; hide

    2013-01-01

    The Curiosity Rover landed on the Peace Vallis alluvial fan in Gale crater on August 5, 2012. A primary mission science objective is to search for past habitable environments, and, in particular, to assess the role of past water. Identifying the minerals and mineraloids that result from aqueous alteration at Gale crater is essential for understanding past aqueous processes at the MSL landing site and hence for interpreting the site's potential habitability. X-ray diffraction (XRD) data from the CheMin instrument and evolved gas analyses (EGA) from the SAM instrument have helped the MSL science team identify phases that resulted from aqueous processes: phyllosilicates and amorphous phases were measure in two drill samples (John Klein and Cumberland) obtained from the Sheepbed Member, Yellowknife Bay Fm., which is believed to represent a fluvial-lacustrine environment. A third set of analyses was obtained from scoop samples from the Rocknest sand shadow. Chemical data from the APXS instrument have helped constrain the chemical compositions of these secondary phases and suggest that the phyllosilicate component is Mg-enriched and the amorphous component is Fe-enriched, relatively Si-poor, and S- and H-bearing. To refine the phyllosilicate and amorphous components in the samples measured by MSL, we measured XRD and EGA data for a variety of relevant natural terrestrial phyllosilicates and synthetic mineraloids in laboratory testbeds of the CheMin and SAM instruments. Specifically, Mg-saturated smectites and vermiculites were measured with XRD at low relative humidity to understand the behavior of the 001 reflections under Mars-like conditions. Our laboratory XRD measurements suggest that interlayer cation composition affects the hydration state of swelling clays at low RH and, thus, the 001 peak positions. XRD patterns of synthetic amorphous materials, including allophane, ferrihydrite, and hisingerite were used in full-pattern fitting (FULLPAT) models to help

  9. Terrestrial analogs for interpretation of infrared spectra from the Martian surface and subsurface: Sulfate, nitrate, carbonate, and phyllosilicate-bearing Atacama Desert soils

    Science.gov (United States)

    Sutter, B.; Dalton, J. B.; Ewing, S. A.; Amundson, R.; McKay, C. P.

    2007-10-01

    Hyperarid (Mars soils have similar sulfate concentrations; possess phyllosilicates (e.g., smectite) and minor carbonate. Nitrate has not been detected on Mars, but its presence has been proposed. The similar compositions of Atacama and Mars soils have prompted the visible-infrared (0.35-25 μm) investigation of Atacama soils as Mars analogs. Results from this work determined the best infrared features for detecting sulfate, nitrate, carbonate, and phyllosilicate on Mars. The fundamental region (>6.5 μm) was not suited for salt and phyllosilicate detection because of overlapping spectra from primary silicates (e.g., feldspar), water and carbon dioxide. The visible near-infrared (0.35-2.5 μm) region was suited for detecting carbonate, nitrate, gypsum water of hydration, and phyllosilicate hydroxyls without interference from primary silicates. However, gypsum water of hydration features can obscure phyllosilicate hydroxyl, carbonate and nitrate, features if gypsum levels are high. Overtone/combination absorption features in the midinfrared were determined to be the best indicators of sulfate (4.48-4.70 μm), nitrate (4.12 μm), and carbonate (3.98 μm) because interferences from overlapping primary silicate and water features are not present in this region. Interferences from CO2 and thermal emission effects in the overtone/combination region are possible but may be minimized by corrective techniques. Infrared analysis of Atacama Desert soils can provide insight into the spectral search of sulfate, nitrate, carbonate, and phyllosilicate containing soils on Mars.

  10. Exploring the potential of phyllosilicate minerals as potassium fertilizers using sodium tetraphenylboron and intensive cropping with perennial ryegrass

    Science.gov (United States)

    Li, Ting; Wang, Huoyan; Wang, Jing; Zhou, Zijun; Zhou, Jianmin

    2015-01-01

    In response to addressing potassium (K) deficiency in soil and decreasing agricultural production costs, the potential of K-bearing phyllosilicate minerals that can be directly used as an alternative K source has been investigated using sodium tetraphenylboron (NaTPB) extraction and an intensive cropping experiment. The results showed that the critical value of K-release rate and leaf K concentration was 3.30 g kg−1 h−1 and 30.64 g (kg dry matter)−1, respectively under the experimental conditions. According to this critical value, the maximum amount of released K that could be utilized by a plant with no K deficiency symptoms was from biotite (27.80 g kg−1) and vermiculite (5.58 g kg−1), followed by illite, smectite and muscovite with 2.76, 0.88 and 0.49 g kg−1, respectively. Ryegrass grown on phlogopite showed K deficiency symptoms during the overall growth period. It is concluded that biotite and vermiculite can be directly applied as a promising and sustainable alternative to the use of classical K fertilizers, illite can be utilized in combination with soluble K fertilizers, whereas muscovite, phlogopite and smectite may not be suitable for plant growth. Further field experiments are needed to assess the use of these phyllosilicate minerals as sources of K fertilizer. PMID:25782771

  11. Grain size-dependent strength of phyllosilicate-rich gouges in the shallow crust: Insights from the SAFOD site

    Science.gov (United States)

    Phillips, Noah John; White, Joseph Clancy

    2017-07-01

    The San Andreas Fault Observatory at Depth (SAFOD) drilling project directly sampled a transitional (between creeping and locked) segment of the San Andreas Fault at 2.7 km depth. At the site, changes in strain rate occur between periods of coseismic slip (>10-7 s-1) and interseismic creep (10-10 s-1) over decadal scales ( 30 years). Microstructural observations of core retrieved from the SAFOD site show throughgoing fractures and gouge-rich cores within the fractures, evidence of predominantly brittle deformation mechanisms. Within the gouge-rich cores, strong phases show evidence of deformation by pressure solution once the grain size is reduced to a critical effective grain size. Models of pressure solution-accommodated creep for quartz-phyllosilicate mixtures indicate that viscous weakening of quartz occurs during the interseismic period once a critical effective grain size of 1 μm is achieved, consistent with microstructural observations. This causes pronounced weakening, as the strength of the mixture is then controlled by the frictional properties of the phyllosilicate phases. These results have pronounced implications for the internal deformation of fault zones in the shallow crust, where at low strain rates, deformation is accommodated by both viscous and brittle deformation mechanisms. As strain rates increase, the critical effective grain size for weakening decreases, localizing deformation into the finest-grained gouges until deformation can no longer be accommodated by viscous processes and purely brittle failure occurs.

  12. Influence of iron-bearing phyllosilicates on the dechlorination kinetics of 1,1,1-trichloroethane in Fe(II)/cement slurries.

    Science.gov (United States)

    Jung, Bahngmi; Batchelor, Bill

    2007-07-01

    This study examines the effect of iron-bearing phyllosilicates on dechlorination rates of chlorinated aliphatic hydrocarbons (CAHs) in iron-based degradative solidification/stabilization (DS/S-Fe(II)). Laboratory batch experiments were conducted to evaluate dechlorination rates of 1,1,1-trichloroethane (1,1,1-TCA) in a mixture solution of Fe(II), cement and three different iron-bearing phyllosilicates (biotite, vermiculite, and montmorillonite). A first-order rate model was generally used to describe the dechlorination kinetics and the rate constants were dependent on soil mineral type (biotite, vermiculite, and montmorillonite), Fe(II) dose, and the mass ratio of cement to soil mineral. The pseudo-first-order rate constant for montmorillonite was lower than that for biotite and vermiculite by factors of 11-27 when the mass ratio of cement to phyllosilicates was fixed at one. The presence of biotite and vermiculite increase and the presence of montmorillonite decrease the degradation rate that would be observed in their absence. The effect of cement/mineral ratio on rate constants with three different soil minerals indicates that biotite was more reactive than the other two phyllosilicates. This may be due to high accessible natural Fe(II) content in biotite. Montmorillonite appears to inhibit dechlorination by either inactivating Fe(II) by ion exchange or by physically blocking active sites on cement hydration products.

  13. Early phyllosilicates formed by alteration of R7T7 glass in water at 250 deg C

    International Nuclear Information System (INIS)

    Vernaz, E.; Dussossoy, J.L.; Caurel, J.; Crovisier, J.L.

    1991-01-01

    T7T7 glass samples have been altered during periods of one and seven days at 250 deg C in distilled water. Ultramicrotomic thin sections were performed in the outermost part of the glass for a study under analytical transmission electron microscope. After one day the alteration layer is about 5 μm thick. It is made up of sheeted silicated particles, tentatively identified as septechlorite (7 A intervals) mixed with an intercrystalline amorphous matrix of different composition. After seven days the alteration layer is about 11 μm thick. It is made up of sheeted silicated particles of smectite type (10 A intervals). No 7 A particles were found in the seven days sample. This study illustrates the capacity of poorly crystalline phyllosilicates to adapt to the chemical changes in solution. 15 refs., 4 tabs., 2 plates

  14. 3-aminopropyl functionalized magnesium phyllosilicate as an organoclay based drug carrier for improving the bioavailability of flurbiprofen

    Directory of Open Access Journals (Sweden)

    Yang L

    2013-10-01

    Full Text Available Liang Yang,1 Soo-Kyung Choi,2 Hyun-Jae Shin,2 Hyo-Kyung Han1 1College of Pharmacy, Dongguk University-Seoul, Siksa-dong, Ilsan-Donggu, Goyang, Gyunggi-do, Korea; 2Department of Chemical and Biochemical Engineering, Chosun University, Gwangju, Korea Abstract: This study aimed to develop an oral delivery system using clay-based organic–inorganic hybrid materials to improve the bioavailability of the drug, flurbiprofen, which is poorly soluble in water. 3-aminopropyl functionalized magnesium phyllosilicate (AMP clay was synthesized by a one-pot direct sol-gel method, and then flurbiprofen (FB was incorporated into AMP clay (FB-AMP at different drug/clay ratios. The structural characteristics of AMP and FB-AMP formulation were confirmed by X-ray diffraction, Fourier transform infrared spectroscopy, and transmission electron microscopy. Among tested formulations, FB-AMP(3, dramatically increased the dissolution of FB and achieved rapid and complete drug release within 2 hours. More than 60% of FB was released from FB-AMP(3 after 30 minutes; the drug was completely dissolved in the water within 2 hours. Under the acidic condition (pH 1.2, FB-AMP(3 also increased the dissolution of FB by up to 47.1% within 1 hour, which was three-fold higher than that of untreated FB. Furthermore, following an oral administration of FB-AMP(3 to Sprague-Dawley rats, the peak plasma concentration and area under the plasma concentration-time curve of FB increased two-fold, and the time to reach the peak plasma concentration was shortened compared with that in the untreated FB. This result suggests that the oral drug delivery system using clay-based organic–inorganic hybrid material might be useful to improve the bioavailability of FB. Keywords: poorly water-soluble drugs, aminopropyl functionalized magnesium phyllosilicate, organic clay, oral bioavailability

  15. 3-aminopropyl functionalized magnesium phyllosilicate as an organoclay based drug carrier for improving the bioavailability of flurbiprofen.

    Science.gov (United States)

    Yang, Liang; Choi, Soo-Kyung; Shin, Hyun-Jae; Han, Hyo-Kyung

    2013-01-01

    This study aimed to develop an oral delivery system using clay-based organic-inorganic hybrid materials to improve the bioavailability of the drug, flurbiprofen, which is poorly soluble in water. 3-aminopropyl functionalized magnesium phyllosilicate (AMP clay) was synthesized by a one-pot direct sol-gel method, and then flurbiprofen (FB) was incorporated into AMP clay (FB-AMP) at different drug/clay ratios. The structural characteristics of AMP and FB-AMP formulation were confirmed by X-ray diffraction, Fourier transform infrared spectroscopy, and transmission electron microscopy. Among tested formulations, FB-AMP(3), dramatically increased the dissolution of FB and achieved rapid and complete drug release within 2 hours. More than 60% of FB was released from FB-AMP(3) after 30 minutes; the drug was completely dissolved in the water within 2 hours. Under the acidic condition (pH 1.2), FB-AMP(3) also increased the dissolution of FB by up to 47.1% within 1 hour, which was three-fold higher than that of untreated FB. Furthermore, following an oral administration of FB-AMP(3) to Sprague-Dawley rats, the peak plasma concentration and area under the plasma concentration-time curve of FB increased two-fold, and the time to reach the peak plasma concentration was shortened compared with that in the untreated FB. This result suggests that the oral drug delivery system using clay-based organic-inorganic hybrid material might be useful to improve the bioavailability of FB.

  16. Phyllosilicate weathering pathways in chlorite-talc bearing soil parent materials, D.R. Congo: early findings.

    Science.gov (United States)

    Dumon, Mathijs; Oostermeyer, Fran; Timmermans, Els; De Meulemeester, Aschwin; Mees, Florias; Van Driessche, Isabel; Erens, Hans; Bazirake Mujinya, Basile; Van Ranst, Eric

    2015-04-01

    The study of the formation and transformation of clay minerals is of the upmost importance to understand soil formation and to adjust land-use management to the land surface conditions. These clay minerals determine to a large extent the soil physical and chemical properties. It is commonly observed that over time the mineralogy of any parent material is transformed to a simple assemblage composed mostly of Al and Fe oxides and low-activity clays, e.g. kaolinite. This is especially obvious in the humid tropics, which have been protected from glacial erosion, allowing deep, highly weathered soils to form. Despite the abundant presence of kaolinite in these soils, its formation pathways are still under debate: either neoformation by dissolution-crystallisation reactions or solid-state transformation of 2:1 phyllosilicates. To elucidate this, weathering sequences in a unique 40 m core taken below a termite mound, reaching a talc-chlorite bearing substrate in the Lubumbashi area, Katanga, DR Congo are being investigated in detail using a.o. quantitative X-ray diffraction analysis, chemical characterization, micromorphology and µXRF-scanning with the main objective to improve the understanding of the formation pathways of kaolinite subgroup minerals in humid tropical environments. Based on an initial characterization of the core, two zones of interest were selected for more detailed analysis, for which the early findings will be presented. The first zone extends from ca. 9 m to 11 m below the surface is dominated by kaolinite but shows early traces of primary talc and micas. The second zone extends from 34 to 36 m below the surface and contains large amounts of chlorite, with smaller amounts of talc, micas and kaolinite.

  17. Investigating α-particle radiation damage in phyllosilicates using synchrotron microfocus-XRD/XAS: implications for geological disposal of nuclear waste

    Science.gov (United States)

    Bower, W. R.; Pearce, C. I.; Pimblott, S. M.; Haigh, S. J.; Mosselmans, J. F. W.; Pattrick, R. A. D.

    2014-12-01

    The response of mineral phases to the radiation fields that will be experienced in a geological disposal facility (GDF) for nuclear waste is poorly understood. Phyllosilicates are critical phases in a GDF with bentonite clay as the backfill of choice surrounding high level wastes in the engineered barrier, and clays and micas forming the most important reactive component of potential host rocks. It is essential that we understand changes in mineral properties and behaviour as a result of damage from both α and γ radiation over long timescales. Radiation damage has been demonstrated to affect the physical integrity and oxidation state1 of minerals which will also influence their ability to react with radionuclides. Using the University of Manchester's newly commissioned particle accelerator at the Dalton Cumbrian Facility, UK, model phyllosilicate minerals (e.g. biotite, chlorite) were irradiated with high energy (5MeV) alpha particles at controlled dose rates. This has been compared alongside radiation damage found in naturally formed 'radiohalos' - spherical areas of discolouration in minerals surrounding radioactive inclusions, resulting from alpha particle penetration, providing a natural analogue to study lattice damage under long term bombardment1,2. Both natural and artificially irradiated samples have been analysed using microfocus X-ray absorption spectroscopy and high resolution X-ray diffraction mapping on Beamline I18 at Diamond Light Source; samples were probed for redox changes and long/short range disorder. This was combined with lattice scale imaging of damage using HR-TEM (TitanTM Transmission Electron Microscope). The results show aberrations in lattice parameters as a result of irradiation, with multiple damage-induced 'domains' surrounded by amorphous regions. In the naturally damaged samples, neo-formed phyllosilicate phases are shown to be breakdown products of highly damaged regions. A clear reduction of the Fe(III) component has been

  18. Equilibrium chemistry down to 100 K. Impact of silicates and phyllosilicates on the carbon to oxygen ratio

    Science.gov (United States)

    Woitke, P.; Helling, Ch.; Hunter, G. H.; Millard, J. D.; Turner, G. E.; Worters, M.; Blecic, J.; Stock, J. W.

    2018-06-01

    We have introduced a fast and versatile computer code, GGCHEM, to determine the chemical composition of gases in thermo-chemical equilibrium down to 100 K, with or without equilibrium condensation. We have reviewed the data for molecular equilibrium constants, kp(T), from several sources and discussed which functional fits are most suitable for low temperatures. We benchmarked our results against another chemical equilibrium code. We collected Gibbs free energies, ΔGf⊖, for about 200 solid and liquid species from the NIST-JANAF database and the geophysical database SUPCRTBL. We discussed the condensation sequence of the elements with solar abundances in phase equilibrium down to 100 K. Once the major magnesium silicates Mg2SiO4[s] and MgSiO3[s] have formed, the dust to gas mass ratio jumps to a value of about 0.0045 which is significantly lower than the often assumed value of 0.01. Silicate condensation is found to increase the carbon to oxygen ratio (C/O) in the gas from its solar value of 0.55 up to 0.71, and, by the additional intake of water and hydroxyl into the solid matrix, the formation of phyllosilicates at temperatures below 400 K increases the gaseous C/O further to about 0.83. Metallic tungsten (W) is the first condensate found to become thermodynamically stable around 1600-2200 K (depending on pressure), several hundreds of Kelvin before subsequent materials such as zirconium dioxide (ZrO2) or corundum (Al2O3) can condense. We briefly discuss whether tungsten, despite its low abundance of 2 × 10-7 times the silicon abundance, could provide the first seed particles for astrophysical dust formation. GGCHEM code is publicly available at http://https://github.com/pw31/GGchemTable D.1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/614/A1

  19. Híbridos inorgânico-orgânicos derivados da reação de filossicatos com organossilanos Inorganic-organic hybrids derived from the reaction of phyllosilicates with organosilanes

    Directory of Open Access Journals (Sweden)

    Maria Gardênnia da Fonseca

    2003-10-01

    Full Text Available Silylation reactions involving hydroxylated surfaces are an important route for synthesis of new materials that could present selected properties, for application in different areas such as catalysis, chromatography, adsorption and electrochemistry. An overview of many synthetic routes, comprising organosilanes to yield phyllosilicates is now presented.

  20. Use of phyllosilicates in electrochemical devices: possible use of sepiolite as a support of catalysts in direct alcohol fuel cells (DAFC)

    International Nuclear Information System (INIS)

    Parra-Silva, J.; Silva, A.C.; Mello-Castanho, S.R.H.; Cerpa, A.

    2014-01-01

    Direct alcohol Fuel cells (DAFC) are interesting to use Brazil for reasons of fuel logistics and availability. The catalysts used in these devices to promote the oxidation of alcohol at the anode need to be fixed on a substrate which must provide high specific surface area, porosity, chemical and thermal resistance, this target can be achieved with the characteristics sepiolite. This paper proposes sepiolite as catalyst support for DAFC. Sepiolite is a phyllosilicate with double layered tetrahedral silicon cells and fibrillar structure. Catalysts (Pt / Sb / Sn) were prepared by cation substitution method and tested by cyclic voltammetry. Techniques as XRD and FT-IR were also used for characterizing materials. Was obtained up to 35 mA / g (Pt) peak current (redox ethanol) indicating the possibility of sepiolite technology development to use un proposed purpose. (author)

  1. Mineralogical, chemical, organic and microbial properties of subsurface soil cores from Mars Desert Research Station (Utah, USA): Phyllosilicate and sulfate analogues to Mars mission landing sites

    Science.gov (United States)

    Stoker, Carol R.; Clarke, Jonathan; Direito, Susana O. L.; Blake, David; Martin, Kevin R.; Zavaleta, Jhony; Foing, Bernard

    2011-07-01

    We collected and analysed soil cores from four geologic units surrounding Mars Desert Research Station (MDRS) Utah, USA, including Mancos Shale, Dakota Sandstone, Morrison formation (Brushy Basin member) and Summerville formation. The area is an important geochemical and morphological analogue to terrains on Mars. Soils were analysed for mineralogy by a Terra X-ray diffractometer (XRD), a field version of the CheMin instrument on the Mars Science Laboratory (MSL) mission (2012 landing). Soluble ion chemistry, total organic content and identity and distribution of microbial populations were also determined. The Terra data reveal that Mancos and Morrison soils are rich in phyllosilicates similar to those observed on Mars from orbital measurements (montmorillonite, nontronite and illite). Evaporite minerals observed include gypsum, thenardite, polyhalite and calcite. Soil chemical analysis shows sulfate the dominant anion in all soils and SO4>>CO3, as on Mars. The cation pattern Na>Ca>Mg is seen in all soils except for the Summerville where Ca>Na. In all soils, SO4 correlates with Na, suggesting sodium sulfates are the dominant phase. Oxidizable organics are low in all soils and range from a high of 0.7% in the Mancos samples to undetectable at a detection limit of 0.1% in the Morrison soils. Minerals rich in chromium and vanadium were identified in Morrison soils that result from diagenetic replacement of organic compounds. Depositional environment, geologic history and mineralogy all affect the ability to preserve and detect organic compounds. Subsurface biosphere populations were revealed to contain organisms from all three domains (Archaea, Bacteria and Eukarya) with cell density between 3.0×106 and 1.8×107 cells ml-1 at the deepest depth. These measurements are analogous to data that could be obtained on future robotic or human Mars missions and results are relevant to the MSL mission that will investigate phyllosilicates on Mars.

  2. Spitzer IRS Spectroscopy of the 10 Myr-Old EF Cha Debris Disk: Evidence for Phyllosilicate-Rich Dust in the Terrestrial Zone

    Science.gov (United States)

    Currie, Thayne; Lisse, Carey M.; Sicillia-Aguilar, Aurora; Rieke, George H.; Su, Kate Y. L.

    2011-01-01

    We describe Spitzer IRS spectroscopic observations of the approx. 10 Myr-old star, EF Chao Compositional modeling of the spectra from 5 micron to 35 micron confirms that it is surrounded by a luminous debris disk with L(sub D)/L(sub *) approx. 10(exp -3), containing dust with temperatures between 225 K and 430 K characteristic of the terrestrial zone. The EF Cha spectrum shows evidence for many solid-state features, unlike most cold, low-luminosity debris disks but like some other 10-20 Myr-old luminous, warm debris disks (e.g. HD 113766A). The EF Cha debris disk is unusually rich in a species or combination of species whose emissivities resemble that of finely-powdered, laboratory-measured phyllosilicate species (talc, saponite, and smectite), which are likely produced by aqueous alteration of primordial anhydrous rocky materials. The dust and, by inference, the parent bodies of the debris also contain abundant amorphous silicates and metal sulfides, and possibly water ice. The dust's total olivine to pyroxene ratio of approx. 2 also provides evidence of aqueous alteration. The large mass volume of grains with sizes comparable to or below the radiation blow-out limit implies that planetesimals may be colliding at a rate high enough to yield the emitting dust but not so high as to devolatize the planetesimals via impact processing. Because phyllosilicates are produced by the interactions between anhydrous rock and warm, reactive water, EF Cha's disk is a likely signpost for water delivery to the terrestrial zone of a young planetary system.

  3. Experimental and numerical study of the stability of phyllosilicates in a strong thermal gradient. Test in the geothermal site of Soultz-sous-Forets

    International Nuclear Information System (INIS)

    Baldeyrou-Bailly, A.

    2003-01-01

    Thermodynamic data of hydrated phyllosilicates, in particular clay minerals are not well known. The stability fields of these minerals are not well determined; following some authors they even do not exist. We have developed an experimental approach, in which a sequence of local equilibrium states between a fluid and minerals take place in a closed gold cell along a strong thermal gradient. The experiments were conducted in the chemical systems: Mg-Al-Si-H 2 O (MASH), K-Al-Si-H 2 O (KASH), and K-Mg-Al-Si-H 2 O (KMASH). The sequences of crystallization observed along the thermal gradient are the same if one exchanges the position of the cells containing the initial reacting materials with respect to the thermal gradient end-members. The crystallization sequences correspond to local equilibrium states. Following the temperature increase (from 200 to 350 C) one observes the following sequences: di-octahedral smectite? tri-octahedral smectite; kaolinite? donbassite? tri-octahedral chlorite; smectite? illite? muscovite; or even kaolinite? illite + smectite? donbassite; commonly observed in hydrothermal systems. They allow to develop a thermodynamic model for hydrated phyllosilicates, taking into account their hydration state as a function of temperature. This model shows the stability fields of clay minerals between 200 and 350 C.The chemical and mineralogical dynamics showed in these experimental systems has been applied to predict the possible dissolutions and/or precipitations which may take place between the circulated hot fluid and the geothermal granitic reservoir in the geothermal system at Soultz-sous-Forets. These processes may affect the duration of the geothermal reservoir, as a function of evolution in the morphology of the porosity. Our experimental approach shows that feldspars and smectites are forming the major part of the total volume of silicates which may precipitate in addition to carbonates already described in previous studies. (author)

  4. Hyperspectral surface materials map of quadrangle 3564, Jowand (405) and Gurziwan (406) quadrangles, Afghanistan, showing carbonates, phyllosilicates, sulfates, altered minerals, and other materials

    Science.gov (United States)

    Kokaly, Raymond F.; King, Trude V.V.; Hoefen, Todd M.; Livo, Keith E.; Johnson, Michaela R.; Giles, Stuart A.

    2013-01-01

    This map shows the spatial distribution of selected carbonates, phyllosilicates, sulfates, altered minerals, and other materials derived from analysis of airborne HyMap™ imaging spectrometer (hyperspectral) data of Afghanistan collected in late 2007. The map is one in a series of U.S. Geological Survey/Afghanistan Geological Survey quadrangle maps covering Afghanistan. Flown at an altitude of 50,000 feet (15,240 meters (m)), the HyMap™ imaging spectrometer measured reflected sunlight in 128 channels, covering wavelengths between 0.4 and 2.5 μm. The data were georeferenced, atmospherically corrected and converted to apparent surface reflectance, empirically adjusted using ground-based reflectance measurements, and combined into a mosaic with 23-m pixel spacing. Variations in water vapor and dust content of the atmosphere, in solar angle, and in surface elevation complicated correction; therefore, some classification differences may be present between adjacent flight lines. The reflectance spectrum of each pixel of HyMap™ imaging spectrometer data was compared to the reference materials in a spectral library of minerals, vegetation, water, and other materials. Minerals occurring abundantly at the surface and those having unique spectral features were easily detected and discriminated, while minerals having slightly different compositions but similar spectral features were less easily discriminated; thus, some map classes consist of several minerals having similar spectra, such as “Epidote or chlorite.” A designation of “Not classified” was assigned to the pixel when there was no match with reference spectra.

  5. Rb-Sr and K-Ar age of globular phyllosilicates and biostratigraphy of the Riphean deposits of the Olenek Uplift (North Siberia)

    Science.gov (United States)

    Zaitseva, T. S.; Gorokhov, I. M.; Semikhatov, M. A.; Ivanovskaya, T. A.; Kuznetsov, A. B.; Dorzhieva, O. V.

    2017-11-01

    This work presents results of the complex mineralogical, geochemical, and isotope-geochronological investigation of globular dioctahedral 2: 1 phyllosilicates (GPS) of the illite-glauconite series from the Riphean sequences of the Olenek Uplift. It is established that GPS (glauconite, Al-glauconite, Fe-illite) in deposits of the Arymass, Debengda, and Khaipakh formations are represented by mixed-layer varieties of two types: (1) with relatively low (cell of minerals varies from 9.18 to 9.72 Å. The Rb-Sr age dating of GPS was first carried out in combination with the calculation of theoretical pattern of the cation distribution in the mineral structure and comparison of the calculation results obtained with the Mössbauer and IR spectroscopy data. This approach is based on the assumption that development and evolution of isotope systems in GPS are synchronous with the evolution of the crystalline structure of the mineral at various stages of the geological and geochemical history of the development of sedimentary units. Analysis of the obtained data allows us to state that the structural features of the Riphean GPS from the Olenek section reflect the early diagenetic stages of the formation of the minerals studied. The 87Sr/86Sr initial ratios in the studied sediments are consistent with the range of variations in this ratio in the Middle Riphean Ocean (0.7049-0.7061). The Rb-Sr and K-Ar ages of the GPS of the Arymass (1305 ± 8 and 1302 Ma, respectively), Debengda (1265 ± 12 and 1284 ± 22 Ma), and Khaipakh (1172 ± 18 and 1112 ± 24 Ma) formations in the Olenek Uplift section are close to the accumulation time of corresponding deposits and, correspondingly, have significance for stratigraphic correlations.

  6. Intercalation of vanadate in Ni, Zn layered hydroxyacetates

    International Nuclear Information System (INIS)

    Rojas, Ricardo; Barriga, Cristobalina; Ulibarri, M.A.; Rives, Vicente

    2004-01-01

    Interlayer acetate anions in layered double hydroxyacetates of Ni 2+ and Zn 2+ have been exchanged by oxovanadates following three synthetic routes (at 60 deg. C, under hydrothermal conditions and after preswelling with caprylate anions) and different pH; direct exchange at room temperature was not successful. Complete exchange was achieved under adequated conditions, and the precise nature of the interlayer anion depends on the pH during exchange: at low pH (4.5), the presence of α-VO 3 chains, with anchoring (grafting) of the species to the hydroxide layers, is proposed. At higher pH (9.5) V 2 O 7 4- species are present in the interlayer. Thermal decomposition of these vanadate-intercalated products leads to formation of orthorhombic Ni 2+ and Zn 2+ vanadates, together with NiO

  7. Synthesis in fluoride medium and characterisation of Montmorillonite type Photoelasticity. Structural study by X-ray Absorption and nuclear magnetic resonance spectroscopies; Synthese en milieu fluore et caracterisation de phyllosilicates de type montmorillonite. etude structurale par spectroscopies d'absorption des rayons x et de resonance magnetique nucleaire

    Energy Technology Data Exchange (ETDEWEB)

    Reinholdt, M.

    2001-12-15

    The aim of this work is to synthesize and characterise montmorillonite type phyllosilicates and to study the distribution of the metal elements in the structure. First, generalities about phyllosilicates are introduced. A particular attention is given to (2:1) di-octahedral phyllosilicates and especially to montmorillonite. The different methods of the synthesis of this mineral are reviewed. The method of hydrothermal synthesis in fluoride medium and the techniques used to characterize the materials (XRD, TGA-DTA, chemical analyses) are then described. The descriptions of solid state NMR and EXAFS are particularly developed. Next, a systematic study of the synthetic products is realised for two systems MO-Al{sub 2}O{sub 3}-SiO{sub 2} (M = Mg or Zn). The compositions of hydrogel are based on a theoretical formula of montmorillonite: Na{sub 2x}[Al{sub 2(1-x)}M{sub 2x}-vacancy]Si{sub 4}O{sub 10}OH{sub 2} (x represents the octahedral layer charge). A montmorillonite type phyllosilicate is obtained for 0.10 {<=} x {<=} 0.25 in the MgO-Al{sub 2}O{sub 3}-SiO{sub 2} system and for x = 0.10 in the ZnO-Al{sub 2}O{sub 3}-SiO{sub 2} system. Besides the Mg/Al substitutions in the octahedral sheet, Al/Si substitutions in the tetrahedral sheet are observed by {sup 29}Si and {sup 27}Al NMR. The {sup 19}F NMR shows a clustering of the octahedral elements in (Mg)phyllosilicate. Then, the parameters of the synthesis of (Mg)phyllosilicate are introduced. Kaolinite is observed as an intermediary phase during the crystallisation. The optimal pH is found between 5.0 and 5.5. The presence of a little amount of F- is necessary (0.05 {<=} F/SiO{sub 2} {<=} 0.10). Tetrahedral substitutions are fewer with the use of Na{sup +} as compensating cation. Finally, Zn and Mg K-edges EXAFS show a distortion of the layer and a clustering of the octahedral elements for the (Zn)phyllosilicate. A quantitative {sup 27}Al MAS-NMR method is elaborated which allows to determine both total amount of aluminium

  8. Thesis for being entitled to lead research work[Structure organization and changes in phyllosilicate clays]; Memoire presente en vue de l'obtention de L'Habilitation a Diriger des Recherches

    Energy Technology Data Exchange (ETDEWEB)

    Muller, F

    2004-11-15

    The study of the properties of clay minerals such as the di-octahedral phyllosilicates requires a multi-scale analysis of their features. The results that are presented here concern both the local scale (intern structure organisation of the sheet and the cation-sheet interaction) and the semi-local scale featuring the sheet piling up. Various investigation means have been used: X-ray and infra-red absorption, X-ray diffraction, small angle X-ray scattering, electron diffraction on selected spots and adequate simulation methods. The firs part is dedicated to order-disorder relationship in the organization of major octahedral cations (Al, Fe, Mg). The cation distribution is not due to random but is organized in domains that can be mono-cationic (Fe or Al) or mixed, in the latter case the trend is to promote the mixing of charges losses. The second part is devoted to the study of structure transformations induced by thermal and hydro-thermal treatments. Models for the cationic migration inside octahedral layers are proposed to explain structural changes. The composition and cationic distribution of octahedral layers play an important role in the process. In the case of smectite, treatments are responsible for the increase of disorder in the sheet distribution and for the decrease in hydration properties of some sheets.

  9. Bound magnetic polaron in Zn-rich cobalt-doped ZnSe nanowires

    Science.gov (United States)

    Hou, Lipeng; Pan, Longfei; Liang, Bianbian; Liu, Yuting; Zhang, Li; Bukhtiar, Arfan; Shi, Lijie; Liu, Ruibin; Zou, Bingsuo

    2018-02-01

    The micro-luminescence spectra of the diluted magnetic semiconductor (DMS) can reflect the spin-exciton interaction and related relaxation process. Here the micro-photoluminescence (micro-PL) spectra and PL lifetime measurements have been done on an individual ferromagnetic (FM)-coupled cobalt (Co) doped zinc selenide (ZnSe) nanowire. There occurs a double-peak profile in its near bandedge emission spectrum: the first peak is from free exciton (FX) and the second comes from magnetic polaron (MP). In their temperature dependent PL spectra, the MP emission peak demonstrates obviously temperature-independent behavior, in contrast to the behaviors of FX and reported exciton MP in nanobelt. It is found that in this Co(II) doped ZnSe nanowires, this MP’s temperature-independent emission is related to the coupling between exciton and a FM nanocluster (↑↑↓). The nanocluster is likely due to the interaction of Se vacancies of the wide bandgap semiconductors with the antiferromagnetic (AFM) arrangement transition metal (TM) ions in these Se-deficient Co doped ZnSe nanowires. These results reflect that the AFM coupling TM ions pair can give rise to FM behavior with the involvement of positive charge defect, also indicating that the micro-luminescence detection can be used to study the magnetic coupling in DMS.

  10. Nanoconfined water in magnesium-rich phyllosilicates.

    Energy Technology Data Exchange (ETDEWEB)

    Nenoff, Tina Maria; Durkin, Justin S.; Daemen, Luke L. (Los Alamos National Laboratory, Los Alamos, NM); Ockwig, Nathan W.; Cygan, Randall Timothy; Greathouse, Jeffery A.

    2009-10-01

    Inelastic neutron scattering, density functional theory, ab initio molecular dynamics, and classical molecular dynamics were used to examine the behavior of nanoconfined water in palygorskite and sepiolite. These complementary methods provide a strong basis to illustrate and correlate the significant differences observed in the spectroscopic signatures of water in two unique clay minerals. Distortions of silicate tetrahedra in the smaller-pore palygorskite exhibit a limited number of hydrogen bonds having relatively short bond lengths. In contrast, without the distorted silicate tetrahedra, an increased number of hydrogen bonds are observed in the larger-pore sepiolite with corresponding longer bond distances. Because there is more hydrogen bonding at the pore interface in sepiolite than in palygorskite, we expect librational modes to have higher overall frequencies (i.e., more restricted rotational motions); experimental neutron scattering data clearly illustrates this shift in spectroscopic signatures. Distortions of the silicate tetrahedra in these minerals effectively disrupts hydrogen bonding patterns at the silicate-water interface, and this has a greater impact on the dynamical behavior of nanoconfined water than the actual size of the pore or the presence of coordinatively-unsaturated magnesium edge sites.

  11. Use of phyllosilicates in electrochemical devices: possible use of sepiolite as a support of catalysts in direct alcohol fuel cells (DAFC); Utilizacao de filosilicatos em dispositivos eletroquimicos: possivel uso da sepiolita como suporte de catalisadores em celulas a combustivel com uso direto de etanol (DAFC)

    Energy Technology Data Exchange (ETDEWEB)

    Parra-Silva, J.; Silva, A.C.; Mello-Castanho, S.R.H. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Cerpa, A. [Universidad Europea de Madrid, Madrid (Spain)

    2014-07-01

    Direct alcohol Fuel cells (DAFC) are interesting to use Brazil for reasons of fuel logistics and availability. The catalysts used in these devices to promote the oxidation of alcohol at the anode need to be fixed on a substrate which must provide high specific surface area, porosity, chemical and thermal resistance, this target can be achieved with the characteristics sepiolite. This paper proposes sepiolite as catalyst support for DAFC. Sepiolite is a phyllosilicate with double layered tetrahedral silicon cells and fibrillar structure. Catalysts (Pt / Sb / Sn) were prepared by cation substitution method and tested by cyclic voltammetry. Techniques as XRD and FT-IR were also used for characterizing materials. Was obtained up to 35 mA / g (Pt) peak current (redox ethanol) indicating the possibility of sepiolite technology development to use un proposed purpose. (author)

  12. Microwave assisted organic modification and surface functionalization of Phyllosilicates

    CSIR Research Space (South Africa)

    Kesavan Pillai, Sreejarani

    2012-11-01

    Full Text Available decoration of raw montmorillonite clays with metal (Ag, Fe) nano-particles. The composites were characterized by transmission electron microscopy; x-ray diffraction; energy dispersive x-ray spectroscopy and Fourier transform infrared spectroscopy. Compared...

  13. Mineralogy and geochemistry of Zn-rich mine-drainage precipitates from an MgO passive treatment system by synchrotron-based X-ray analysis.

    Science.gov (United States)

    Pérez-López, Rafael; Macías, Francisco; Caraballo, Manuel A; Nieto, José Miguel; Román-Ross, Gabriela; Tucoulou, Rémi; Ayora, Carlos

    2011-09-15

    Synchrotron radiation-induced micro-X-ray analysis were applied to characterize the newly formed phases that precipitate in a passive treatment system using magnesium oxide to remove high concentrations of zinc (ca. 440 mg/L) and other minor metals from neutral pretreated waters in the Iberian Pyrite Belt (SW Iberian Peninsula). Micro-X-ray fluorescence (μ-XRF) maps of polished samples were used to find spatial correlations among metals, pinpointing zones of interest where micro-X-ray diffraction (μ-XRD) data were exploited to identify the mineral phases responsible for metal retention. This coupled technique identified hydrozincite (Zn(5)(CO(3))(2)(OH)(6)) and minor loseyite ((Mn,Zn)(7)(CO(3))(2)(OH)(10)) as the mineral sinks for Zn and also other potentially toxic elements such as Co and Ni. Although hydrozincite retains traces of Mn, this metal is mainly retained by precipitation of loseyite. The precipitation of zinc hydroxy-carbonates and their ability to uptake other metals (Mn, Co, and Ni) is hence of potential interest not only for the treatment of contaminated waters but also for the generation of a solid waste that could be exploited as a new Zn economic resource.

  14. Distribution and Influence of Iron Phases on the Physico-Chemical Properties of Phyllosilicates

    Institute of Scientific and Technical Information of China (English)

    MERVAT SAID HASSAN; SAYED MAHMOUD SALEM

    2002-01-01

    Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD, DTA, dissolution analysis (DCB), IR, Mossbauer and X-band Electron Spin Resonance (ESR) spectroscopies. The purity of the samples and the degree of structural order were determined by XRD. The location of Fe in the octahedral sheet is characterized by absorption bands at ~875 cm-1 assigned as Al-OH-Fe which is present after chemical dissolution of free iron. The Mossbauer spectra of these clays show two doublets with isomer shift and quadrupole splitting typical of octahedral coordinated Fe3+, in addition to third doubler with hyperfine parameter typical of Fe2+ in the spectra of Abu-Had kaolinite (H) sample. 6-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples. Goethite was confirmed by both IR and DTA. Multiple nature of ESR of these clays suggested structural Fe in distorted octahedral symmetry and as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activation of investigated montmorillonite samples by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles. This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure. However, extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand, amounts and site occupation of Fe associated with kaolinite samples show a negative correlation with the parameters used to describe the degree of crystalline perfection, color, brightness and vitrification range of these kaolinite samples.

  15. Distribution and Influence of Iron Phases the Physico—Chemical Properties of Phyllosilicates

    Institute of Scientific and Technical Information of China (English)

    MERVATSAIDHASSAN; SAYEDMAHMOUDSALEM

    2001-01-01

    Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD,DTA,dissolution analysis(DCB),IR,Moessbauer and X-ray Electron Spin Resonance(ESR) spectroscopes.The purity of the samples and the degree of their structural order were determined by XRD.The location of Fe in the octahedral sheet is characterized by absorption bands at-875cm-1 assigned as Al-OH-Fe which persist after chemical dissolution of free iron.The Moessbauer spectra of these clays show two doublets with isomer shift and quadrupole splitting typical of octahedrally coordinated Fe3+,in addition to third doublet with hyperfine parameter typical of Fe2+ in the spectra of Abu-Had kaolinite (H) sample.Six-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples.Goethite was confirmed by both IR and DTA.Multiple nature of ESR of these clays suggested structural Fe in distorted octahedral symmetry as well as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activation of the investigated montmorillonite samplas by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles.This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure.However,extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand,the amount and site occupation of Fe associated with kaolinite samples show an inverse correlation with the parameters used to describe the degree of crystallinity perfection,color,brightness and vitrification range of these kaolinite samples.

  16. Distribution and Influence of Iron Phases on the Physico-Chemical Properties of Phyllosilicates

    Institute of Scientific and Technical Information of China (English)

    MERVAT SAID HASSAN; SAYED MAHMOUD SALEM

    2001-01-01

    Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD, DTA, dissolution analysis (DCB), IR, Mossbauer and X-ray Electron Spin Resonance (ESR) spectroscopes. The purity of the samples and the degree of their structural order were determined by XRD. The location of Fe in the octahedral sheet is characterized by absorption bands at ~875cm-1 assigned as Al-OH-Fe which persist after chemical dissolution of free iron. The Mossbauer spectra of these clays show two doublets with isomer shift and quadrupole splitting typical of octahedrally coordinated Fe3 + , in addition to third doublet with hyperfine parameter typical of Fe2+ in the spectra of Abu-Had kaolinite (H) sample. Six-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples. Goethite was confirmed by both IR and DTA. Multiple nature of ESR of these clays suggested structural Fe in distorted octahedral symmetry as well as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activation of the investigated montmorillonite samples by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles. This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure. However, extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand, the amount and site occupation of Fe associated with kaolinite samples show an inverse correlation with the parameters used to describe the degree of crystallinity perfection, color, brightness and vitrification range of these kaolinite samples.

  17. Distribution and Influence of Iron Phases on the Physico—Chemical Properties of Phyllosilicates

    Institute of Scientific and Technical Information of China (English)

    MERVATSAIDHASSAN; SAYEDMAHMOUDSALEM

    2002-01-01

    Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD,DTA,dissolution analysis(DCB),IR,Moessbauer and X-band Electron Spin Resonance(ESR) spectroscopies.The purity of the samples and the degree of structural order were determined by XRD.The location of Fe in the octahedral sheet is characterized by absorption bands at-875cm-1 assigned as Al-OH-Fe which is present after chemical dissolution of free iron.The Moessbauer spectra of these clays sow two doublets with isomer shift and quadrupole splitting typical of octahedral coordinated Fe3+,in addition to third doubler with hyperfine parameter typical of Fe2+ in the spectra of Abu-Had kaolinite (H)sample.6-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples.Goethite was confirmed by both IR and DTA.Multiple nature of ESR of these clays suggested structural Fe in distorted octaedral symmetry and as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activaiton of investigated montmorillonite samples by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles.This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure.However,extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand,amounts and site occupation of Fe associated with kaolinite samples show a negative correlation with the parameters used to describe the degree of crystalline perfection,color,brightness and vitrification range of these kaolinite samples.

  18. Transmission Electron Microscope Observations of Phyllosilicate Development During Experimental Aqueous Alteration of Allende

    Science.gov (United States)

    Jones, C. L.; Brearley, A. J.

    2000-01-01

    Samples of Allende have been altered hydrothermally under oxidizing conditions at 200 C. TEM studies show that within 30 days evidence of replacement of matrix olivines by fine-grained serpentine is present and by 90 days complete alteration of many grains has occurred.

  19. Self-organized crystallization mechanism of non-equilibrium 2:1 type phyllosilicate systems

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The crystallization mechanism of 2:1 type regular interstratified minerals is investigated in views of non-equilibrium thermodynamics. The structural chemistry of relative layers and their interstratified combinations is analyzed and six kinds of non-equilibrium chemical systems have been induced. The universal laws of chemical reactions which happened in the interface region of these non-equilibrium systems have been summarized. From these laws, two reaction systems crystallizing out Tosudite and Rectorite respectively have been recovered. The kinetic model of chemical reactions has been developed by means of the mass conservation law. The oscillatory solution showing regular interstratified features has also been obtained numerically. These results indicate that the difference in original chemical composition among systems can affect the chemical connotation of reactants, intermediate products and resultants, and the flow chart of chemical reaction, but cannot change their crystallization behavior of network-forming cations, bigger and smaller network-modifying cations during crystallization. Hence, their kinetic model reflecting the universal crystallization law of these cations is just the same. These systems will crystallize out regular interstratified minerals at suitable parameters, which always exist as domain with nanometer-sized in thickness and can be called the self-organized ordering structure.

  20. In Situ Analysis of Martian Phyllosilicates Using the Chemin Minerological Instrument on Mars Science Laboratory

    Science.gov (United States)

    Blake, David F.

    2008-01-01

    The CheMin minerological instrument on Mars Science Laboratory (MSL'09) [1] will return quantitive Xray diffraction data (XRD) and quantative X-ray fluorescence data (XRF;14

  1. Magnetic characterization of Fe nanoparticles dispersed in phyllosilicate type silicon oxide

    Energy Technology Data Exchange (ETDEWEB)

    Sagredo, V [Lab. de Magnetismo, Fac. de Ciencias, Universidad de Los Andes, Merida 5101 (Venezuela, Bolivarian Republic of); Pena, O [Sciences Chimiques de Rennes, UMR 6226, Universite de Rennes 1, 35042, Rennes (France); Torres, T E [Instituto de Nanociencia de Aragon, Universidad de Zaragoza (Spain); Loaiza-Gil, A; Villarroel, M; Cruz, M de la; J, Balbuena, E-mail: sagredo@ula.v [Lab. de Cinetica y Catalisis, Fac. de Ciencias, Universidad de Los Andes, Merida (Venezuela, Bolivarian Republic of)

    2010-01-01

    We present the magnetic properties of silica-supported metal (Fe,catalyst) nanoparticles synthesized by precipitation of metal nitrate in ammonia-based medium. Our goal is the study of possible metal-support interactions in the nanoporous catalyst. The temperature dependence of the magnetization for all samples display spin-glass like behavior below c.a. 11-12 K, with clear Curie-Weiss dependence in the high-temperature regime. Spin-glass-like behavior was inferred from dynamic AC susceptibility data after analyzing the frequency-dependence of the in-phase component {chi}'(f) by the expression W = {Delta}T{sub f}/[T{sub f} {Delta}log(f)] = 3.0 x 10{sup -3}. We found that the magnetic behavior of the catalyst is drastically affected by the existence of interactions between the metal and the support.

  2. Dispersion de phyllosilicates et processus de frittage de céramiques silicatées

    OpenAIRE

    Houta , Nadia

    2015-01-01

    This thesis is devoted to improve both densification and stress to rupture values of silicate ceramics mainly elaborated from kaolin. This improvement is achieved by replacing a proportion of kaolin by halloysite. Indeed, this way also allows to highlight the influence of the shape of particles and their organization on microstructural properties. First, the dispersion of suspensions containing only kaolin or a mixture of kaolin and halloysite was optimized by reducing the size of agglomerate...

  3. Giant increase of optical transparency for Zn-rich CaxZn1-xO on Al2O3 (0 0 0 1) grown by pulsed laser deposition

    Science.gov (United States)

    Albrithen, H. A.; El-Naggar, A. M.; Ozga, K.; Alshahrani, H.; Alanazi, A.; Alfaifi, E.; Labis, J.; Alyamani, A.; Albadri, A.; Alkahtani, M. H.; Alahmed, Z. A.; Jedryka, J.; Fedorchuk, A. O.

    2016-02-01

    In this study, CaxZn1-xO high quality films with different Ca ratios (from 0% to 10%) were grown on Al2O3 (0 0 0 1) substrates by pulsed laser deposition for the first time. The optical properties for the grown films were studied over a wide spectral range from 200 to 3300 nm using the reflectance and transmittance spectrum. It was found that the calculated optical energy gap values increases from 3.275 to about 3.340 eV with increasing Ca concentrations from 0% to 10%. This opens a new stage in the study of the high quality optical films. The stoichiometry of the films was achieved using targets of the same intended film ratio. Two sample sets were grown at 650 °C, one set with argon gas background at 10 mTorr and the other one without any intentionally introduced gases. The structural properties for the grown films were studied using X-ray Diffraction. It was clear that by increasing Ca, the lattice parameter c is decreased and 2θ was shifted towards higher values from, while the FWHM was increased. These results indicated that the film crystallinity degrades as Ca content in the films increased.

  4. Specific Features of Profile Distribution and Crystallochemistry of Phyllosilicates in Soils of the Cisbaikal Forest-Steppe

    Science.gov (United States)

    Chizhikova, N. P.; Gamzikov, G. P.; Chechetko, E. S.

    2018-01-01

    The mineralogical composition of agrogray, dark gray, and agro-dark gray soils (Luvic Greyzemic Retic Phaeozems); agro-dark gray residual-calcareous soils (Calcaric Cambic Phaeozems); clay-illuvial agrochernozems (Luvic Chernic Phaeozems); and agrochernozems with migrational-mycelial carbonates (Haplic Chernozems) developed in the forest-steppe of Central Siberia within the Irkutsk Depression has been studied. The clay (smectite, vermiculite, and chlorite; the proportions between them change within the soil profiles. The clay fraction also contains hydromicas, kaolinite, chlorite, and some admixture of the fine-dispersed quartz. Each type of the soils is characterized by its own distribution pattern of clay material with specific alternation of layers in the mixed-layer formations. Mixed-layer minerals of the chlorite-vermiculite type predominate in the upper horizons of texture-differentiated soils. Down the soil profile, the content of mixed-layer mica-smectitic minerals increases. In the clay fraction of arable dark gray-humus soils with residual carbonates, the distribution of the clay fraction and major mineral phases in the soil profile is relatively even. An increased content of well-crystallized kaolinite is typical of these soils. The parent material of agrochernozems has a layered character: the upper horizons are generally depleted of clay, and the middle-profile and lower horizons are characterized by the considerable kaolinite content. In general, the clay material of soils of the Tulun-Irkutsk forest-steppe differs considerably from the clay material of foreststeppe soils developed from loesslike and mantle loams in the European part of Russia. In particular, this difference is seen in the proportions between major mineral phases and between biotitic and muscovitic components, as well as in the degree of crystallinity and behavior of kaolinite and chlorite.

  5. Faults, fluids and friction : Effect of pressure solution and phyllosilicates on fault slip behaviour, with implications for crustal rheology

    NARCIS (Netherlands)

    Bos, B.

    2000-01-01

    In order to model the mechanics of motion and earthquake generation on large crustal fault zones, a quantitative description of the rheology of fault zones is prerequisite. In the past decades, crustal strength has been modeled using a brittle or frictional failure law to represent fault slip at

  6. Faults, fluids and friction : effect of pressure solution and phyllosilicates on fault slip behaviour, with implications for crustal rheology

    NARCIS (Netherlands)

    Bos, B.

    2000-01-01

    In order to model the mechanics of motion and earthquake generation on large crustal fault zones, a quantitative description of the rheology of fault zones is prerequisite. In the past decades, crustal strength has been modeled using a brittle or frictional failure law to represent fault slip

  7. Oxygen isotope fractionation effects in soil water via interaction with cations (Mg, Ca, K, Na) adsorbed to phyllosilicate clay minerals

    Science.gov (United States)

    Oerter, Erik; Finstad, Kari; Schaefer, Justin; Goldsmith, Gregory R.; Dawson, Todd; Amundson, Ronald

    2014-07-01

    In isotope-enabled hydrology, soil and vadose zone sediments have been generally considered to be isotopically inert with respect to the water they host. This is inconsistent with knowledge that clay particles possessing an electronegative surface charge and resulting cation exchange capacity (CEC) interact with a wide range of solutes which, in the absence of clays, have been shown to exhibit δ18O isotope effects that vary in relation to the ionic strength of the solutions. To investigate the isotope effects caused by high CEC clays in mineral-water systems, we created a series of monominerallic-water mixtures at gravimetric water contents ranging from 5% to 32%, consisting of pure deionized water of known isotopic composition with homoionic (Mg, Ca, Na, K) montmorillonite. Similar mixtures were also created with quartz to determine the isotope effect of non-, or very minimally-, charged mineral surfaces. The δ18O value of the water in these monominerallic soil analogs was then measured by isotope ratio mass spectrometry (IRMS) after direct headspace CO2 equilibration. Mg- and Ca-exchanged homoionic montmorillonite depleted measured δ18O values up to 1.55‰ relative to pure water at 5% water content, declining to 0.49‰ depletion at 30% water content. K-montmorillonite enriched measured δ18O values up to 0.86‰ at 5% water content, declining to 0.11‰ enrichment at 30% water. Na-montmorillonite produces no measureable isotope effect. The isotope effects observed in these experiments may be present in natural, high-clay soils and sediments. These findings have relevance to the interpretation of results of direct CO2-water equilibration approaches to the measurement of the δ18O value of soil water. The adsorbed cation isotope effect may bear consideration in studies of pedogenic carbonate, plant-soil water use and soil-atmosphere interaction. Finally, the observed isotope effects may prove useful as molecular scale probes of the nature of mineral-water interactions.

  8. Mineralogical, chemical, organic and microbial properties of subsurface soil cores from Mars Desert Research Station (Utah, USA): Phyllosilicate and sulfate analogues to Mars mission landing sites

    NARCIS (Netherlands)

    Stoker, C.R.; Clarke, J.; Oliveira Lebre Direito, M.S.; Martin, K.; Zavaleta, J.; Blake, D.; Foing, B.H.

    2011-01-01

    We collected and analysed soil cores from four geologic units surrounding Mars Desert Research Station (MDRS) Utah, USA, including Mancos Shale, Dakota Sandstone, Morrison formation (Brushy Basin member) and Summerville formation. The area is an important geochemical and morphological analogue to

  9. Seismic velocity anisotropy of phyllosilicate-rich rocks: characteristics inferred from experimental and crack-model studies of biotite-rich schist

    Science.gov (United States)

    Nishizawa, O.; Kanagawa, K.

    2010-07-01

    Seismic velocity anisotropy of biotite schist (30 per cent-mode biotite) was measured under confining pressures up to 150 MPa. The rock shows weak orthotropy which was altered from transverse isotropy (TI) generated by biotite-preferred orientation. The orthotropy was caused by microfolding in the rock. The velocity increase under confining pressure indicates that most crack planes are aligned parallel to the cleavage planes (silicate sheet) of the oriented biotite minerals. The anisotropy of the rock is basically TI due to both the aligned biotite minerals and cracks, which have a common symmetry axis. We found that other sheet silicate-rich rocks have a similar anisotropy with the biotite schist, in which the TI-type anisotropy is characterized by the slow P- and S-wave velocities along the symmetry axis. This is caused by the preferred orientation of sheet silicate minerals and the extremely slow P- and S-wave velocities along the axis perpendicular to the silicate sheet compared to the directions along the silicate sheet. When rock contains a large percentage of highly oriented sheet silicates, the fast and slow shear waves exchange their polarities at some off-symmetry axis directions, indicating that the qS-wave (quasi-S wave) velocity exceeds the SH-wave velocity. The phase velocity distribution of qS wave shows an asymmetry with respect to the angle from the symmetry axis, which is characterized by a bulge in this distribution located near the symmetric axis. This is inherent to most sheet silicate minerals. When crack density of aligned cracks increases, the P-wave velocity along the symmetry axis decreases considerably. The qS-wave phase velocity in the off-axis directions also decreases, in accordance with the decrease of the P velocity along the symmetry axis. The asymmetry of the qS-wave phase velocity distribution increases as the P-wave velocity decreases along the symmetry axis. This relationship can be well understood by means of Berryman's extended Thomsen approach.

  10. Changes in zinc speciation with mine tailings acidification in a semi-arid weathering environment

    Science.gov (United States)

    Hayes, Sarah M.; O’Day, Peggy A.; Webb, Sam M.; Maier, Raina M.; Chorover, Jon

    2011-01-01

    High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semi-arid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6,000 to 450 mg kg−1) and plant-available (590 to 75 mg kg−1) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and micro-focused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn0.8talc), Zn sorbed to ferrihydrite (ZnadsFeOx), and zinc sulfate (ZnSO4·7H2O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly-crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Micro-scale analyses identified hetaerolite (ZnMn2O4), hemimorphite (Zn4Si2O7(OH)2·H2O) and sphalerite (ZnS) as minor phases. Bulk and micro-focused spectroscopy complement the chemical extraction results and highlight the importance of using a multi-method approach to interrogate complex tailings systems. PMID:21761897

  11. Changes in zinc speciation with mine tailings acidification in a semiarid weathering environment.

    Science.gov (United States)

    Hayes, Sarah M; O'Day, Peggy A; Webb, Sam M; Maier, Raina M; Chorover, Jon

    2011-09-01

    High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semiarid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6000 to 450 mg kg(-1)) and plant-available (590 to 75 mg kg(-1)) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and microfocused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn(0.8)talc), Zn sorbed to ferrihydrite (Zn(adsFeOx)), and zinc sulfate (ZnSO(4) · 7H(2)O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Microscale analyses identified hetaerolite (ZnMn(2)O(4)), hemimorphite (Zn(4)Si(2)O(7)(OH)(2) · H(2)O) and sphalerite (ZnS) as minor phases. Bulk and microfocused spectroscopy complement the chemical extraction results and highlight the importance of using a multimethod approach to interrogate complex tailings systems.

  12. Apports des phyllosilicates dans la différenciation entre altération hypogène et altération supergène dans le basalte triasique du Moyen Atlas (Maroc)Contribution of phyllosilicates to distinguish between hypogene alteration and weathering in Triassic basalt from Middle Atlas (Morocco)

    Science.gov (United States)

    Dekayir, Abdelilah; Danot, Michel; Allali, Nabil

    2002-09-01

    Triassic basalt of the Middle Atlas has been subject to metamorphic transformation then weathering. Occurrence in both metabasalt and saprolite of ubiquitous clay minerals, such as smectite and mixed layers chlorite-smectite, makes it difficult to distinguish between the two alteration facies and explains the interest of complementary sources of information. In the Bhallil weathering profile, petrographical and mineralogical analyses of primary igneous minerals and their alteration products coupled with Fe oxidation state determination in clay fractions allow to identify three alteration facies: ( i) metamorphic basalt, where iron occurs mainly as the ferrous form; ( ii) the lower part of saprolite, where iron is partially oxidized to its ferric form; ( iii) the upper part of saprolite, where iron is completely oxidized. To cite this article: A. Dekayir et al., C. R. Geoscience 334 (2002) 877-884.

  13. Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale Crater, Mars

    NARCIS (Netherlands)

    Ming, D.W.; Archer Jr., P.D.; Glavin, D.P.; Eigenbrode, J.L.; Franz, H.B.; Sutter, B.; Brunner, A.E.; Stern, J.C.; Freissinet, C.; McAdam, A.C.; Mahaffy, P.R.; Cabane, M.; Coll, P.; Campbell, J.L.; Atreya, S.K.; Niles, P.B.; Bell III, J.F.; Bish, D.L.; Brinckerhoff, W.B.; Buch, A.; Conrad, P.G.; Des Marais, D.J.; Ehlmann, B.L.; Fairén, A.G.; Farley, K.; Flesch, G.J.; Francois, P.; Gellert, R.; Grant, J.A.; Grotzinger, J.P.; Gupta, S.; Herkenhoff, K.E.; Hurowitz, J.A.; Leshin, L.A.; Lewis, K.W.; McLennan, S.M.; Miller, K.E.; Moersch, J.; Morris, R.V.; Navarro-González, R.; Pavlov, A.A.; Perrett, G.M.; Pradler, I.; Squyres, S.W.; Summons, R.E.; Steele, A.; Stolper, E.M.; Sumner, D.Y.; Szopa, C.; Teinturier, S.; Trainer, M.G.; Treiman, A.H.; Vaniman, D.T.; Vasavada, A.R.; Webster, C.R.; Wray, J.J.; Yingst, R.A.; MSL Science Team, the|info:eu-repo/dai/nl/292012217

    2014-01-01

    H2O, CO2, SO2, O2, H2, H2S, HCl, chlorinated hydrocarbons, NO, and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H2O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and

  14. R Raman Spectroscopy and Petrology of Antarctic CR Chondrites: Comparison with Other Carbonaceous Chondrites

    Science.gov (United States)

    Komatsu, M.; Fagan, T. J.; Yamaguchi, A.; Mikouchi, T.; Zolensky, M. E.; Yasutake, M.

    2015-01-01

    In Renazzo-like carbonaceous (CR) chondrites, abundant original Fe,Ni-metal is preserved in chrondules, but the matrix is characterized by fine-grained magnetite with phyllosilicate. This combination of reduced Fe in chrodrules with oxidized Fe and phyllosilicate in the matrix has been attributed to aqueous alteration of matrix at relatively low temperatures.

  15. In-situ TEM studies of nanostructured thermoelectric materials: An application to Mg-doped Zn4Sb3 alloy

    DEFF Research Database (Denmark)

    Ngo, Duc-The; Le, Hung Thanh; Ngo, Nong Van

    2018-01-01

    material have been dynamically captured as a function of temperature from 300 K to 573 K. On heating, we have observed clearly precipitation and growth of a Zn-rich secondary phase as nanoinclusions in the matrix of primary Zn4Sb3 phase. Elemental mapping by STEM-EDX spectroscopy reveals enrichment of Zn...

  16. Growth of zinc oxide nanostructures

    Indian Academy of Sciences (India)

    temperature of 400◦C by unbalanced magnetron sputtering and PLD techniques. Alternately a simple chemical route .... Zn layer was very critical and nanowhiskers did not form when the thicknesses was more than 20 nm. Furthermore, the ... crystallites are much smaller than incident λ. Also this mode is present between.

  17. Corrosion Performance of Composite Galvanic Coatings with Variable Concentration of Polymeric Nanoaggregates and/or Cr(III) Conversion Layers

    NARCIS (Netherlands)

    Koleva, D.A.; Taheri, P.; Tsvetkova, N.; Boshkov, N.; Van Breugel, K.; De Wit, J.H.W.; Mol, J.M.C.

    2011-01-01

    This paper reports on the corrosion performance of composite zinc layers (~ 8µm) on a steel substrate, considering the influence of nano-aggregates and Cr(III) conversion layers, compared to control (only Zn layers) conditions. The main factors, influencing the corrosion performance of Zn in this

  18. Bulk rock elastic moduli at high pressures, derived from the mineral textures and from extrapolated laboratory data

    International Nuclear Information System (INIS)

    Ullemeyer, K; Keppler, R; Lokajíček, T; Vasin, R N; Behrmann, J H

    2015-01-01

    The elastic anisotropy of bulk rock depends on the mineral textures, the crack fabric and external parameters like, e.g., confining pressure. The texture-related contribution to elastic anisotropy can be predicted from the mineral textures, the largely sample-dependent contribution of the other parameters must be determined experimentally. Laboratory measurements of the elastic wave velocities are mostly limited to pressures of the intermediate crust. We describe a method, how the elastic wave velocity trends and, by this means, the elastic constants can be extrapolated to the pressure conditions of the lower crust. The extrapolated elastic constants are compared to the texture-derived ones. Pronounced elastic anisotropy is evident for phyllosilicate minerals, hence, the approach is demonstrated for two phyllosilicate-rich gneisses with approximately identical volume fractions of the phyllosilicates but different texture types. (paper)

  19. Smectites on Cape York, Matijevic Hill, Mars, Observed and Characterized by Crism and Opportunity

    Science.gov (United States)

    Arvidson, R.; Bennett, K.; Catalano, J.; Fraeman, A.; Gellert, R.; Guinness, E.; Morris, R.; Murchie, S.; Smith, M.; Squyres, S.; hide

    2013-01-01

    Opportunity has conducted an extensive "walk-about" and set of in-situ measurements on strata exposed on the inboard side of Cape York, a segment of the dissected rim of the Noachian-age approx.22 km wide Endeavour crater [1] (Fig. 1). The specific region for the observations (Matijevic Hill) was chosen based on along track oversampled (ATO) CRISM hyperspectral observations (processed to 5 m/pixel) that showed the presence of exposures of Fe/Mg smectite phyllosilicates. We describe the first ground-based observations of phyllosilicates on Mars and discuss implications based on the combined CRISM and Opportunity measurements.

  20. Structural investigation of ZnO:Al films deposited on the Si substrates by radio frequency magnetron sputtering

    International Nuclear Information System (INIS)

    Chen, Y.Y.; Yang, J.R.; Cheng, S.L.; Shiojiri, M.

    2013-01-01

    ZnO:Al films 400 nm thick were prepared on (100) Si substrates by magnetron sputtering. Energy dispersive X-ray spectroscopy and transmission electron microscopy (TEM) revealed that in the initial stage of the deposition, an amorphous silicon oxide layer about 4 nm thick formed from damage to the Si substrate due to sputtered particle bombardment and the incorporation of Si atoms with oxygen. Subsequently, a crystalline Si (Zn) layer about 30 nm thick grew on the silicon oxide layer by co-deposition of Si atoms sputtered away from the substrate with Zn atoms from the target. Finally, a ZnO:Al film with columnar grains was deposited on the Si (Zn) layer. The sputtered particle bombardment greatly influenced the structure of the object films. The (0001) lattice fringes of the ZnO:Al film were observed in high-resolution TEM images, and the forbidden 0001 reflection spots in electron diffraction patterns were attributed to double diffraction. Therefore, the appearance of the forbidden reflection did not imply any ordering of Al atoms and/or O vacancies in the ZnO:Al film. - Highlights: • ZnO:Al films were deposited on (100) Si substrate using magnetron sputtering. • An amorphous silicon oxide layer with a thickness of 4 nm was formed on Si substrate. • Crystalline Si (Zn) layer about 30 nm thick grew on amorphous silicon oxide layer. • ZnO:Al film comprising columnar grains was deposited on the Si(Zn) layer. • Lattice image of the ZnO:Al film has been interpreted

  1. SORPTION AND ABIOTIC REDOX TRANSFORMATION OF NITROBENZENE AT THE SMECTITE-WATER INTERFACE

    Science.gov (United States)

    The effect of the redox state of structural Fe on the surface reactivity of iron-bearing phyllosilicates in aqueous suspension was investigated using a molecular probe. For this purpose the structural Fe in montmorillonite and ferruginous smectite was chemically reduced by sodium...

  2. Studying nanostructure gradients in injection-molded polypropylene/montmorillonite composites by microbeam small-angle x-ray scattering

    DEFF Research Database (Denmark)

    Stribeck, Norbert; Schneider, Konrad; Zeinolebadi, Ahmad

    2014-01-01

    The core–shell structure in oriented cylindrical rods of polypropylene (PP) and nanoclay composites (NCs) from PP and montmorillonite (MMT) is studied by microbeam small-angle x-ray scattering (SAXS). The structure of neat PP is almost homogeneous across the rod showing regular semicrystalline......-shaped phyllosilicate filler particles....

  3. The case of the lacking carbonates and the emergence of early life on mars

    NARCIS (Netherlands)

    Fernández-Remolar, David Carlos; Sánchez-Román, Mónica; Amils, Ricardo

    2010-01-01

    The mineralogical characterization of Mars by different exploration missions, provides a new image of the earliest conditions that prevailed on the planet surface. The detection of extensive deposits of phyllosillicates has been considered to be as a result of the production of hydrated silicates

  4. The Mawrth Vallis region of Mars: A potential landing site for the Mars Science Laboratory (MSL) mission.

    Science.gov (United States)

    Michalski, Joseph R; Jean-PierreBibring; Poulet, François; Loizeau, Damien; Mangold, Nicolas; Dobrea, Eldar Noe; Bishop, Janice L; Wray, James J; McKeown, Nancy K; Parente, Mario; Hauber, Ernst; Altieri, Francesca; Carrozzo, F Giacomo; Niles, Paul B

    2010-09-01

    The primary objective of NASA's Mars Science Laboratory (MSL) mission, which will launch in 2011, is to characterize the habitability of a site on Mars through detailed analyses of the composition and geological context of surface materials. Within the framework of established mission goals, we have evaluated the value of a possible landing site in the Mawrth Vallis region of Mars that is targeted directly on some of the most geologically and astrobiologically enticing materials in the Solar System. The area around Mawrth Vallis contains a vast (>1 × 10⁶ km²) deposit of phyllosilicate-rich, ancient, layered rocks. A thick (>150 m) stratigraphic section that exhibits spectral evidence for nontronite, montmorillonite, amorphous silica, kaolinite, saponite, other smectite clay minerals, ferrous mica, and sulfate minerals indicates a rich geological history that may have included multiple aqueous environments. Because phyllosilicates are strong indicators of ancient aqueous activity, and the preservation potential of biosignatures within sedimentary clay deposits is high, martian phyllosilicate deposits are desirable astrobiological targets. The proposed MSL landing site at Mawrth Vallis is located directly on the largest and most phyllosilicate-rich deposit on Mars and is therefore an excellent place to explore for evidence of life or habitability.

  5. Ultra-thin clay layers facilitate seismic slip in carbonate faults.

    Science.gov (United States)

    Smeraglia, Luca; Billi, Andrea; Carminati, Eugenio; Cavallo, Andrea; Di Toro, Giulio; Spagnuolo, Elena; Zorzi, Federico

    2017-04-06

    Many earthquakes propagate up to the Earth's surface producing surface ruptures. Seismic slip propagation is facilitated by along-fault low dynamic frictional resistance, which is controlled by a number of physico-chemical lubrication mechanisms. In particular, rotary shear experiments conducted at seismic slip rates (1 ms -1 ) show that phyllosilicates can facilitate co-seismic slip along faults during earthquakes. This evidence is crucial for hazard assessment along oceanic subduction zones, where pelagic clays participate in seismic slip propagation. Conversely, the reason why, in continental domains, co-seismic slip along faults can propagate up to the Earth's surface is still poorly understood. We document the occurrence of micrometer-thick phyllosilicate-bearing layers along a carbonate-hosted seismogenic extensional fault in the central Apennines, Italy. Using friction experiments, we demonstrate that, at seismic slip rates (1 ms -1 ), similar calcite gouges with pre-existing phyllosilicate-bearing (clay content ≤3 wt.%) micro-layers weaken faster than calcite gouges or mixed calcite-phyllosilicate gouges. We thus propose that, within calcite gouge, ultra-low clay content (≤3 wt.%) localized along micrometer-thick layers can facilitate seismic slip propagation during earthquakes in continental domains, possibly enhancing surface displacement.

  6. The direct transformation of ethanol to ethyl acetate over Cu/SiO2 ...

    Indian Academy of Sciences (India)

    Cu/SiO2 catalysts that contain copper phyllosilicate, were successfully ... of attention because both components are simple, non- .... bate on a Micromeritics ASAP 2010 system at liquid- ... The reactor was. Page 3. Direct transformation of ethanol to ethyl acetate. 1015 connected to gas chromatography using a six-port high.

  7. Iron alteration minerals in the visible and near-infrared spectra of low-albedo asteroids

    Science.gov (United States)

    Vilas, Faith; Jarvis, Kandy S.; Gaffey, Michael J.

    1994-01-01

    Absorption features centered near 0.60-0.65 and 0.80-0.90 micrometers have been identified in the spectra of five low-albedo main-belt and outer-belt asteroids. These absorption features are attributed respectively to the (6)A(sub 1) goes to (4)T(sub 2)(G) and (6)A(sub 1) goes to (4)T(sub 1)(G) charge transfer transitions in minerals such as goethite, hematite, and jarosite that are products of the aqueous alteration of anhydrous silicates. A shoulder near 0.63 micrometers has also been identified in the absorption feature centered near 0.7 micrometers attributed to oxidized iron in phyllosilicates found predominantly in C- and G-class asteroids reflectance spectra. The coexistence of iron oxides with phyllosilicates in asteroids believed to have undergone aqueous alteration would be expected based upon analogy with terrestrial aqueous alteration and the observed mineralogy of carbonaceous chondrites. The number of low-albedo asteroids having only iron alteration absorption features compared to the number of low-albedo asteroids having spectral characteristics indicative of phyllosilicates is small. Either the conditions under which these asteroids formed are rare, or the iron alteration minerals could be formed in the interiors of objects where phyllosilicates dominate the surface mineralogy.

  8. Electronic and elemental properties of the Cu{sub 2}ZnSn(S,Se){sub 4} surface and grain boundaries

    Energy Technology Data Exchange (ETDEWEB)

    Haight, Richard; Shao, Xiaoyan; Wang, Wei; Mitzi, David B. [IBM T. J. Watson Research Center, P.O. Box 218, Yorktown Hts., New York 10598 (United States)

    2014-01-20

    X-ray and femtosecond UV photoelectron spectroscopy, secondary ion mass spectrometry and photoluminescence imaging were used to investigate the electronic and elemental properties of the CZTS,Se surface and its oxides. Oxide removal reveals a very Cu poor and Zn rich surface relative to bulk composition. O and Na are observed at the surface and throughout the bulk. Upward bending of the valence bands indicates the presence of negative charge in the surface region and the Fermi level is found near the band gap center. The presence of point defects and the impact of these findings on grain boundary properties will be described.

  9. Electronic and elemental properties of the Cu2ZnSn(S,Se)4 surface and grain boundaries

    International Nuclear Information System (INIS)

    Haight, Richard; Shao, Xiaoyan; Wang, Wei; Mitzi, David B.

    2014-01-01

    X-ray and femtosecond UV photoelectron spectroscopy, secondary ion mass spectrometry and photoluminescence imaging were used to investigate the electronic and elemental properties of the CZTS,Se surface and its oxides. Oxide removal reveals a very Cu poor and Zn rich surface relative to bulk composition. O and Na are observed at the surface and throughout the bulk. Upward bending of the valence bands indicates the presence of negative charge in the surface region and the Fermi level is found near the band gap center. The presence of point defects and the impact of these findings on grain boundary properties will be described

  10. Electronic and elemental properties of the Cu2ZnSn(S,Se)4 surface and grain boundaries

    Science.gov (United States)

    Haight, Richard; Shao, Xiaoyan; Wang, Wei; Mitzi, David B.

    2014-01-01

    X-ray and femtosecond UV photoelectron spectroscopy, secondary ion mass spectrometry and photoluminescence imaging were used to investigate the electronic and elemental properties of the CZTS,Se surface and its oxides. Oxide removal reveals a very Cu poor and Zn rich surface relative to bulk composition. O and Na are observed at the surface and throughout the bulk. Upward bending of the valence bands indicates the presence of negative charge in the surface region and the Fermi level is found near the band gap center. The presence of point defects and the impact of these findings on grain boundary properties will be described.

  11. Annealing in sulfur of CZTS nanoparticles deposited through doctor blading

    DEFF Research Database (Denmark)

    Engberg, Sara Lena Josefin; Crovetto, Andrea

    of the main limitations for this approach, and (2) grain boundaries and defects are believed to be a site for recombination that limit the efficiency. Annealing in vacuum and/or nitrogen atmosphere facilitates grain growth and improves the electronic properties. Conventionally selenization shows the best...... results, however sulfurization has the advantage of being less toxic. In this work, nanocrystals of CZTS with a targeted Cu-poor/Zn-rich composition are synthesized through a hot-injection method with oleylamine as the solvent. The nanocrystal inks are deposited through doctor blading in octanethiol...

  12. Ultra-precision machining induced phase decomposition at surface of Zn-Al based alloy

    International Nuclear Information System (INIS)

    To, S.; Zhu, Y.H.; Lee, W.B.

    2006-01-01

    The microstructural changes and phase transformation of an ultra-precision machined Zn-Al based alloy were examined using X-ray diffraction and back-scattered electron microscopy techniques. Decomposition of the Zn-rich η phase and the related changes in crystal orientation was detected at the surface of the ultra-precision machined alloy specimen. The effects of the machining parameters, such as cutting speed and depth of cut, on the phase decomposition were discussed in comparison with the tensile and rolling induced microstrucutural changes and phase decomposition

  13. Draa Sfar, Morocco: A Visean (331 Ma) pyrrhotite-rich, polymetallic volcanogenic massive sulphide deposit in a Hercynian sediment-dominant terrane

    OpenAIRE

    Marcoux , Eric; Belkabir , Abdelhay; Gibson , Harold L.; Lentz , David; Ruffet , Gilles

    2008-01-01

    International audience; Draa Sfar is a Visean, stratabound, volcanogenic massive sulphide ore deposit hosted by a Hercynian carbonaceous, black shale-rich succession of the Jebilet terrane, Morocco. The ore deposit contains 10 Mt grading 5.3 wt.% Zn, 2 wt.% Pb, and 0.3 wt.% Cu within two main massive sulphides orebodies, Tazakourt (Zn-rich) and Sidi M'Barek (Zn–Cu rich). Pyrrhotite is by far the dominant sulphide (70 to 95% of total sulphides), sphalerite is fairly abundant, chalcopyrite and ...

  14. Mineralogy of Fluvio-Lacustrine Sediments Investigated by Curiosity During the Prime Mission: Implications for Diagenesis

    Science.gov (United States)

    Rampe, Elizabeth B.; Morris, R. V.; Bish, D. L.; Vaniman, D. T.; Bristow, T. F.; Chipera, S. J.; Blake, D. F.; Ming, D. W.; Farmer, J. D.; Morrison, S. M.; hide

    2014-01-01

    The Mars Science Laboratory rover Curiosity investigated sedimentary rocks that were deposited in a diversity of fluvio-lacustrine settings. The entire science payload was employed to characterize the mineralogy and chemistry of the Sheepbed mudstone at Yellowknife Bay and the Windjana sandstone at the Kimberley. Data from the CheMin instrument, a transmission Xray diffractometer, were used to determine the quantitative mineralogy of both samples. The Sheepbed mudstone contains detrital basaltic minerals, calcium sulfates, iron oxides or hydroxides, iron sulfides, trioctahedral smectite, and amorphous material. The mineral assemblage and chemical data from APXS suggest that the trioctahedral smectite and magnetite formed authigenically as a result of alteration of olivine. The apparent lack of higher-grade phyllosilicates (e.g., illite and chlorite) and the presence of anhydrite indicate diagenesis at 50- 80 ºC. The mineralogy of the Windjana sandstone is different than the Sheepbed mudstone. Windjana contains significant abundances of K-feldspar, low- and high-Ca pyroxenes, magnetite, phyllosilicates, and amorphous material. At least two distinct phyllosilicate phases exist: a 10 Å phase and a component that is expanded with a peak at 11.8 Å. The identity of the expanded phase is currently unknown, but could be a smectite with interlayer H2O, and the 10 Å phase could be illite or collapsed smectite. Further work is necessary to characterize the phyllosilicates, but the presence of illite could suggest that Windjana experienced burial diagenesis. Candidates for the cementing agents include fine-grained phyllosilicates, Fe-oxides, and/or amorphous material. Interpretations of CheMin data from the Windjana sandstone are ongoing at the time of writing, but we will present an estimate of the composition of the amorphous material from mass balance calculations using the APXS bulk chemistry and quantitative mineralogy from CheMin.

  15. First-principles calculations of vacancy formation in In-free photovoltaic semiconductor Cu2ZnSnSe4

    International Nuclear Information System (INIS)

    Maeda, Tsuyoshi; Nakamura, Satoshi; Wada, Takahiro

    2011-01-01

    To quantitatively evaluate the formation energies of Cu, Zn, Sn, and Se vacancies in kesterite-type Cu 2 ZnSnSe 4 (CZTSe), first-principles pseudopotential calculations using plane-wave basis functions were performed. The formation energies of neutral Cu, Zn, Sn and Se vacancies were calculated as a function of the atomic chemical potentials of constituent elements. The obtained results were as follows: (1) the formation energy of Cu vacancy was generally smaller than those of the other Zn, Sn and Se vacancies, (2) under the Cu-poor and Zn-rich condition, the formation energy of Cu vacancy was particularly low, (3) the formation energy of Zn vacancy greatly depended on the chemical potentials of the constituent elements and under the Zn-poor and Se-rich condition, the formation energy of Zn vacancy was smaller than that of Cu vacancy, and (4) the formation energy of Sn vacancy did not greatly depend on the chemical potentials of the constituent elements and was much larger than those of Cu, Zn, and Se vacancies. These results indicate that Cu vacancy is easily formed under Cu-poor and Zn-rich conditions, but Zn vacancy is easily formed under the Zn-poor and Se-rich conditions.

  16. Cu2ZnSnS4 thin films grown by flash evaporation and subsequent annealing in Ar atmosphere

    International Nuclear Information System (INIS)

    Caballero, R.; Izquierdo-Roca, V.; Merino, J.M.; Friedrich, E.J.; Climent-Font, A.; Saucedo, E.; 2UB, Departament d'Electrònica, Universitat de Barcelona, C. Martí i Franquès 1, E-08028 Barcelona (Spain))" data-affiliation=" (IREC, Catalonia Institute for Energy Research, C. Jardins de les Dones de Negre 1, Sant Adriá del Besòs, E-08930 Barcelona (Spain); IN2UB, Departament d'Electrònica, Universitat de Barcelona, C. Martí i Franquès 1, E-08028 Barcelona (Spain))" >Pérez-Rodríguez, A.; León, M.

    2013-01-01

    A study of Cu 2 ZnSnS 4 thin films grown by flash evaporation and subsequently annealed in Ar atmosphere has been carried out. Prior to thin film deposition, Cu 2 ZnSnS 4 bulk compounds with stoichiometric and Zn-rich compositions were synthesized as evaporation sources. The characteristics of the bulk compounds and thin films were investigated by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and elastic back scattering. Cu 2 ZnSnS 4 deposited films contain lower concentrations of Zn than the bulk compounds used as evaporation sources, which is related to a preferential Zn re-evaporation during the deposition process. The desired kesterite composition for solar cell applications was achieved by using a Zn-rich compound as the evaporation source plus a thermal treatment at 620 °C in Ar atmosphere. - Highlights: ► Cu 2 ZnSnS 4 (CZTS) thin films by flash evaporation + annealing in Ar atmosphere ► Difficulty of growing a single phase kesterite material ► X-ray diffraction and Raman spectroscopy to identify the different phases ► Importance of the starting film composition to get the desired CZTS material ► Annealing treatment to obtain the optimum material to be used for CZTS solar cells

  17. Cu{sub 2}ZnSnS{sub 4} thin films grown by flash evaporation and subsequent annealing in Ar atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Caballero, R., E-mail: raquel.caballero@uam.es [Universidad Autónoma de Madrid, Departamento de Física Aplicada, M12, C/Francisco Tomás y Valiente 7, E-28049 Madrid (Spain); Izquierdo-Roca, V. [IREC, Catalonia Institute for Energy Research, C. Jardins de les Dones de Negre 1, Sant Adriá del Besòs, E-08930 Barcelona (Spain); Merino, J.M.; Friedrich, E.J. [Universidad Autónoma de Madrid, Departamento de Física Aplicada, M12, C/Francisco Tomás y Valiente 7, E-28049 Madrid (Spain); Climent-Font, A. [Universidad Autónoma de Madrid, Departamento de Física Aplicada, M12, C/Francisco Tomás y Valiente 7, E-28049 Madrid (Spain); CMAM, Universidad Autónoma de Madrid, C/Faraday 3, E-28049, Madrid (Spain); Saucedo, E. [IREC, Catalonia Institute for Energy Research, C. Jardins de les Dones de Negre 1, Sant Adriá del Besòs, E-08930 Barcelona (Spain); Pérez-Rodríguez, A. [IREC, Catalonia Institute for Energy Research, C. Jardins de les Dones de Negre 1, Sant Adriá del Besòs, E-08930 Barcelona (Spain); IN" 2UB, Departament d' Electrònica, Universitat de Barcelona, C. Martí i Franquès 1, E-08028 Barcelona (Spain); León, M. [Universidad Autónoma de Madrid, Departamento de Física Aplicada, M12, C/Francisco Tomás y Valiente 7, E-28049 Madrid (Spain)

    2013-05-01

    A study of Cu{sub 2}ZnSnS{sub 4} thin films grown by flash evaporation and subsequently annealed in Ar atmosphere has been carried out. Prior to thin film deposition, Cu{sub 2}ZnSnS{sub 4} bulk compounds with stoichiometric and Zn-rich compositions were synthesized as evaporation sources. The characteristics of the bulk compounds and thin films were investigated by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and elastic back scattering. Cu{sub 2}ZnSnS{sub 4} deposited films contain lower concentrations of Zn than the bulk compounds used as evaporation sources, which is related to a preferential Zn re-evaporation during the deposition process. The desired kesterite composition for solar cell applications was achieved by using a Zn-rich compound as the evaporation source plus a thermal treatment at 620 °C in Ar atmosphere. - Highlights: ► Cu{sub 2}ZnSnS{sub 4} (CZTS) thin films by flash evaporation + annealing in Ar atmosphere ► Difficulty of growing a single phase kesterite material ► X-ray diffraction and Raman spectroscopy to identify the different phases ► Importance of the starting film composition to get the desired CZTS material ► Annealing treatment to obtain the optimum material to be used for CZTS solar cells.

  18. Volatile and Organic Compositions of Sedimentary Rocks in Yellowknife Bay, Gale Crater, Mars

    Science.gov (United States)

    Ming, D. W.; Archer, P. D.; Glavin, D. P.; Eigenbrode, J. L.; Franz, H. B.; Sutter, B.; Brunner, A. E.; Stern, J. C.; Freissinet, C.; McAdam, A. C.; Mahaffy, P. R.; Cabane, M.; Coll, P.; Campbell, J. L.; Atreya, S. K.; Niles, P. B.; Bell, J. F.; Bish, D. L.; Brinckerhoff, W. B.; Buch, A.; Conrad, P. G.; Des Marais, D. J.; Ehlmann, B. L.; Fairén, A. G.; Farley, K.; Flesch, G. J.; Francois, P.; Gellert, R.; Grant, J. A.; Grotzinger, J. P.; Gupta, S.; Herkenhoff, K. E.; Hurowitz, J. A.; Leshin, L. A.; Lewis, K. W.; McLennan, S. M.; Miller, K. E.; Moersch, J.; Morris, R. V.; Navarro-González, R.; Pavlov, A. A.; Perrett, G. M.; Pradler, I.; Squyres, S. W.; Summons, R. E.; Steele, A.; Stolper, E. M.; Sumner, D. Y.; Szopa, C.; Teinturier, S.; Trainer, M. G.; Treiman, A. H.; Vaniman, D. T.; Vasavada, A. R.; Webster, C. R.; Wray, J. J.; Yingst, R. A.; Kemppinen, Osku; Bridges, Nathan; Johnson, Jeffrey R.; Minitti, Michelle; Cremers, David; Edgar, Lauren; Farmer, Jack; Godber, Austin; Wadhwa, Meenakshi; Wellington, Danika; McEwan, Ian; Newman, Claire; Richardson, Mark; Charpentier, Antoine; Peret, Laurent; King, Penelope; Blank, Jennifer; Weigle, Gerald; Schmidt, Mariek; Li, Shuai; Milliken, Ralph; Robertson, Kevin; Sun, Vivian; Baker, Michael; Edwards, Christopher; Ehlmann, Bethany; Griffes, Jennifer; Newcombe, Megan; Pilorget, Cedric; Rice, Melissa; Siebach, Kirsten; Stack, Katie; Brunet, Claude; Hipkin, Victoria; Léveillé, Richard; Marchand, Geneviève; Sánchez, Pablo Sobrón; Favot, Laurent; Cody, George; Flückiger, Lorenzo; Lees, David; Nefian, Ara; Martin, Mildred; Gailhanou, Marc; Westall, Frances; Israël, Guy; Agard, Christophe; Baroukh, Julien; Donny, Christophe; Gaboriaud, Alain; Guillemot, Philippe; Lafaille, Vivian; Lorigny, Eric; Paillet, Alexis; Pérez, René; Saccoccio, Muriel; Yana, Charles; Armiens-Aparicio, Carlos; Rodríguez, Javier Caride; Blázquez, Isaías Carrasco; Gómez, Felipe Gómez; Gómez-Elvira, Javier; Hettrich, Sebastian; Malvitte, Alain Lepinette; Jiménez, Mercedes Marín; Martínez-Frías, Jesús; Martín-Soler, Javier; Martín-Torres, F. Javier; Jurado, Antonio Molina; Mora-Sotomayor, Luis; Caro, Guillermo Muñoz; López, Sara Navarro; Peinado-González, Verónica; Pla-García, Jorge; Manfredi, José Antonio Rodriguez; Romeral-Planelló, Julio José; Fuentes, Sara Alejandra Sans; Martinez, Eduardo Sebastian; Redondo, Josefina Torres; Urqui-O'Callaghan, Roser; Mier, María-Paz Zorzano; Chipera, Steve; Lacour, Jean-Luc; Mauchien, Patrick; Sirven, Jean-Baptiste; Manning, Heidi; Hayes, Alexander; Joseph, Jonathan; Sullivan, Robert; Thomas, Peter; Dupont, Audrey; Lundberg, Angela; Melikechi, Noureddine; Mezzacappa, Alissa; DeMarines, Julia; Grinspoon, David; Reitz, Günther; Prats, Benito; Atlaskin, Evgeny; Genzer, Maria; Harri, Ari-Matti; Haukka, Harri; Kahanpää, Henrik; Kauhanen, Janne; Kemppinen, Osku; Paton, Mark; Polkko, Jouni; Schmidt, Walter; Siili, Tero; Fabre, Cécile; Wilhelm, Mary Beth; Poitrasson, Franck; Patel, Kiran; Gorevan, Stephen; Indyk, Stephen; Paulsen, Gale; Schieber, Juergen; Gondet, Brigitte; Langevin, Yves; Geffroy, Claude; Baratoux, David; Berger, Gilles; Cros, Alain; d'Uston, Claude; Forni, Olivier; Gasnault, Olivier; Lasue, Jérémie; Lee, Qiu-Mei; Maurice, Sylvestre; Meslin, Pierre-Yves; Pallier, Etienne; Parot, Yann; Pinet, Patrick; Schröder, Susanne; Toplis, Mike; Lewin, Éric; Brunner, Will; Heydari, Ezat; Achilles, Cherie; Oehler, Dorothy; Coscia, David; Israël, Guy; Dromart, Gilles; Robert, François; Sautter, Violaine; Le Mouélic, Stéphane; Mangold, Nicolas; Nachon, Marion; Stalport, Fabien; Raulin, François; Cameron, James; Clegg, Sam; Cousin, Agnès; DeLapp, Dorothea; Dingler, Robert; Jackson, Ryan Steele; Johnstone, Stephen; Lanza, Nina; Little, Cynthia; Nelson, Tony; Wiens, Roger C.; Williams, Richard B.; Jones, Andrea; Kirkland, Laurel; Baker, Burt; Cantor, Bruce; Caplinger, Michael; Davis, Scott; Duston, Brian; Edgett, Kenneth; Fay, Donald; Hardgrove, Craig; Harker, David; Herrera, Paul; Jensen, Elsa; Kennedy, Megan R.; Krezoski, Gillian; Krysak, Daniel; Lipkaman, Leslie; Malin, Michael; McCartney, Elaina; McNair, Sean; Nixon, Brian; Posiolova, Liliya; Ravine, Michael; Salamon, Andrew; Saper, Lee; Stoiber, Kevin; Supulver, Kimberley; Van Beek, Jason; Van Beek, Tessa; Zimdar, Robert; French, Katherine Louise; Iagnemma, Karl; Miller, Kristen; Goesmann, Fred; Goetz, Walter; Hviid, Stubbe; Johnson, Micah; Lefavor, Matthew; Lyness, Eric; Breves, Elly; Dyar, M. Darby; Fassett, Caleb; Blake, David F.; Bristow, Thomas; Edwards, Laurence; Haberle, Robert; Hoehler, Tori; Hollingsworth, Jeff; Kahre, Melinda; Keely, Leslie; McKay, Christopher; Wilhelm, Mary Beth; Bleacher, Lora; Choi, David; Dworkin, Jason P.; Floyd, Melissa; Garvin, James; Harpold, Daniel; Jones, Andrea; Martin, David K.; Raaen, Eric; Smith, Michael D.; Tan, Florence; Meyer, Michael; Posner, Arik; Voytek, Mary; Anderson, Robert C.; Aubrey, Andrew; Beegle, Luther W.; Behar, Alberto; Blaney, Diana; Brinza, David; Calef, Fred; Christensen, Lance; Crisp, Joy A.; DeFlores, Lauren; Feldman, Jason; Feldman, Sabrina; Jun, Insoo; Keymeulen, Didier; Maki, Justin; Mischna, Michael; Morookian, John Michael; Parker, Timothy; Pavri, Betina; Schoppers, Marcel; Sengstacken, Aaron; Simmonds, John J.; Spanovich, Nicole; Juarez, Manuel de la Torre; Yen, Albert; Cucinotta, Francis; Jones, John H.; Rampe, Elizabeth; Nolan, Thomas; Fisk, Martin; Radziemski, Leon; Barraclough, Bruce; Bender, Steve; Berman, Daniel; Dobrea, Eldar Noe; Tokar, Robert; Williams, Rebecca M. E.; Cleghorn, Timothy; Huntress, Wesley; Manhès, Gérard; Hudgins, Judy; Olson, Timothy; Stewart, Noel; Sarrazin, Philippe; Vicenzi, Edward; Wilson, Sharon A.; Bullock, Mark; Ehresmann, Bent; Hamilton, Victoria; Hassler, Donald; Peterson, Joseph; Rafkin, Scot; Zeitlin, Cary; Fedosov, Fedor; Golovin, Dmitry; Karpushkina, Natalya; Kozyrev, Alexander; Litvak, Maxim; Malakhov, Alexey; Mitrofanov, Igor; Mokrousov, Maxim; Nikiforov, Sergey; Prokhorov, Vasily; Sanin, Anton; Tretyakov, Vladislav; Varenikov, Alexey; Vostrukhin, Andrey; Kuzmin, Ruslan; Clark, Benton; Wolff, Michael; Botta, Oliver; Drake, Darrell; Bean, Keri; Lemmon, Mark; Schwenzer, Susanne P.; Anderson, Ryan B.; Lee, Ella Mae; Sucharski, Robert; Hernández, Miguel Ángel de Pablo; Ávalos, Juan José Blanco; Ramos, Miguel; Kim, Myung-Hee; Malespin, Charles; Plante, Ianik; Muller, Jan-Peter; Ewing, Ryan; Boynton, William; Downs, Robert; Fitzgibbon, Mike; Harshman, Karl; Morrison, Shaunna; Dietrich, William; Kortmann, Onno; Palucis, Marisa; Williams, Amy; Lugmair, Günter; Wilson, Michael A.; Rubin, David; Jakosky, Bruce; Balic-Zunic, Tonci; Frydenvang, Jens; Jensen, Jaqueline Kløvgaard; Kinch, Kjartan; Koefoed, Asmus; Madsen, Morten Bo; Stipp, Susan Louise Svane; Boyd, Nick; VanBommel, Scott; Jacob, Samantha; Owen, Tobias; Rowland, Scott; Atlaskin, Evgeny; Savijärvi, Hannu; Boehm, Eckart; Böttcher, Stephan; Burmeister, Sönke; Guo, Jingnan; Köhler, Jan; García, César Martín; Mueller-Mellin, Reinhold; Wimmer-Schweingruber, Robert; Bridges, John C.; McConnochie, Timothy; Benna, Mehdi; Bower, Hannah; Blau, Hannah; Boucher, Thomas; Carmosino, Marco; Elliott, Harvey; Halleaux, Douglas; Rennó, Nilton; Wong, Michael; Pepin, Robert; Elliott, Beverley; Spray, John; Thompson, Lucy; Gordon, Suzanne; Newsom, Horton; Ollila, Ann; Williams, Joshua; Vasconcelos, Paulo; Bentz, Jennifer; Nealson, Kenneth; Popa, Radu; Kah, Linda C.; Tate, Christopher; Day, Mackenzie; Kocurek, Gary; Hallet, Bernard; Sletten, Ronald; Francis, Raymond; McCullough, Emily; Cloutis, Ed; ten Kate, Inge Loes; Kuzmin, Ruslan; Arvidson, Raymond; Fraeman, Abigail; Scholes, Daniel; Slavney, Susan; Stein, Thomas; Ward, Jennifer; Berger, Jeffrey; Moores, John E.

    2014-01-01

    H2O, CO2, SO2, O2, H2, H2S, HCl, chlorinated hydrocarbons, NO, and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H2O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and amorphous materials. Thermal decomposition of carbonates and combustion of organic materials are candidate sources for the CO2. Concurrent evolution of O2 and chlorinated hydrocarbons suggests the presence of oxychlorine phase(s). Sulfides are likely sources for sulfur-bearing species. Higher abundances of chlorinated hydrocarbons in the mudstone compared with Rocknest windblown materials previously analyzed by Curiosity suggest that indigenous martian or meteoritic organic carbon sources may be preserved in the mudstone; however, the carbon source for the chlorinated hydrocarbons is not definitively of martian origin.

  19. Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale crater, Mars

    Science.gov (United States)

    Ming, D. W.; Archer, P.D.; Glavin, D.P.; Eigenbrode, J.L.; Franz, H.B.; Sutter, B.; Brunner, A.E.; Stern, J.C.; Freissinet, C.; McAdam, A.C.; Mahaffy, P.R.; Cabane, M.; Coll, P.; Campbell, J.L.; Atreya, S.K.; Niles, P.B.; Bell, J.F.; Bish, D.L.; Brinckerhoff, W.B.; Buch, A.; Conrad, P.G.; Des Marais, D.J.; Ehlmann, B.L.; Fairén, A.G.; Farley, K.; Flesch, G.J.; Francois, P.; Gellert, Ralf; Grant, J. A.; Grotzinger, J.P.; Gupta, S.; Herkenhoff, K. E.; Hurowitz, J.A.; Leshin, L.A.; Lewis, K.W.; McLennan, S.M.; Miller, Karl E.; Moersch, J.; Morris, R.V.; Navarro- González, R.; Pavlov, A.A.; Perrett, G.M.; Pradler, I.; Squyres, S. W.; Summons, Roger E.; Steele, A.; Stolper, E.M.; Sumner, D.Y.; Szopa, C.; Teinturier, S.; Trainer, M.G.; Treiman, A.H.; Vaniman, D.T.; Vasavada, A.R.; Webster, C.R.; Wray, J.J.; Yingst, R.A.

    2014-01-01

    H2O, CO2, SO2, O2, H2, H2S, HCl, chlorinated hydrocarbons, NO, and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H2O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and amorphous materials. Thermal decomposition of carbonates and combustion of organic materials are candidate sources for the CO2. Concurrent evolution of O2 and chlorinated hydrocarbons suggests the presence of oxychlorine phase(s). Sulfides are likely sources for sulfur-bearing species. Higher abundances of chlorinated hydrocarbons in the mudstone compared with Rocknest windblown materials previously analyzed by Curiosity suggest that indigenous martian or meteoritic organic carbon sources may be preserved in the mudstone; however, the carbon source for the chlorinated hydrocarbons is not definitively of martian origin.

  20. Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale crater, Mars.

    Science.gov (United States)

    Ming, D W; Archer, P D; Glavin, D P; Eigenbrode, J L; Franz, H B; Sutter, B; Brunner, A E; Stern, J C; Freissinet, C; McAdam, A C; Mahaffy, P R; Cabane, M; Coll, P; Campbell, J L; Atreya, S K; Niles, P B; Bell, J F; Bish, D L; Brinckerhoff, W B; Buch, A; Conrad, P G; Des Marais, D J; Ehlmann, B L; Fairén, A G; Farley, K; Flesch, G J; Francois, P; Gellert, R; Grant, J A; Grotzinger, J P; Gupta, S; Herkenhoff, K E; Hurowitz, J A; Leshin, L A; Lewis, K W; McLennan, S M; Miller, K E; Moersch, J; Morris, R V; Navarro-González, R; Pavlov, A A; Perrett, G M; Pradler, I; Squyres, S W; Summons, R E; Steele, A; Stolper, E M; Sumner, D Y; Szopa, C; Teinturier, S; Trainer, M G; Treiman, A H; Vaniman, D T; Vasavada, A R; Webster, C R; Wray, J J; Yingst, R A

    2014-01-24

    H2O, CO2, SO2, O2, H2, H2S, HCl, chlorinated hydrocarbons, NO, and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H2O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and amorphous materials. Thermal decomposition of carbonates and combustion of organic materials are candidate sources for the CO2. Concurrent evolution of O2 and chlorinated hydrocarbons suggests the presence of oxychlorine phase(s). Sulfides are likely sources for sulfur-bearing species. Higher abundances of chlorinated hydrocarbons in the mudstone compared with Rocknest windblown materials previously analyzed by Curiosity suggest that indigenous martian or meteoritic organic carbon sources may be preserved in the mudstone; however, the carbon source for the chlorinated hydrocarbons is not definitively of martian origin.

  1. Aqueous alteration detection in Tikhonravov crater, Mars

    Science.gov (United States)

    Mancarella, F.; Fonti, S.; Alemanno, G.; Orofino, V.; Blanco, A.

    2018-03-01

    The existence of a wet period lasting long enough to allow the development of elementary forms of life on Mars has always been a very interesting issue. Given this perspective, the research for geological markers of such occurrences has been continually pursued. Once a favorable site is detected, effort should be spent to get as much information as possible aimed at a precise assessment of the genesis and evolution of the areas showing the selected markers. In this work, we discuss the recent finding of possible deposits pointing to the past existence of liquid water in Tikhonravov crater located in Arabia Terra. Comparison of CRISM spectra and those of laboratory minerals formed by aqueous alteration has led us to the conclusion that the studied areas within the impact crater host phyllosilicates deposits. In addition, analysis of the CRISM spectra has resulted in the tentative identification of carbonates mixed with phyllosilicates.

  2. Looking Towards Curiosity's Canyon Path: a 4 km Sequence of Gully, Debris Deposits, and Fan/Deltas Which are Bordered by a Sloping Bedform-Capped Plain and Crossed by Lake Shorelines

    Science.gov (United States)

    Dietrich, W. E.; Palucis, M. C.; Parker, T.; Rubin, D.; dePablo, M. A.; Oehler, D. Z.; Bridges, N. T.

    2014-01-01

    The Curiosity Rover is headed towards layered outcrops that appear to be rich in phyllosilicates and sulphates with the expectation of an eventual ascent up Mt. Sharp. One likely will take the rover up a well-defined canyon. Inspection of CTX and HiRISE imagery and topography (5 m contour intervals) reveal a rich geomorphic sequence that may be encountered during the journey.

  3. Archaeometric investigation and evaluation of the decay of ceramic materials from the church of Santa Maria del Carmine in Pavia, Italy

    OpenAIRE

    Setti, M.; Lanfranchi, A.; Cultrone, G.; Marinoni, L.

    2012-01-01

    We performed an archaeometric study of the ceramic materials from the façade of the church of Santa Maria del Carmine in Pavia (Italy). We obtained useful information about the firing temperatures, the provenance of raw materials and the type of oven used. The ceramics used in the façade are mineralogically rich in quartz, feldspar and phyllosilicates, and newly formed calcium silicate phases were detected in some samples. Microtextural observations revealed the presence of incipient reaction...

  4. Estudio arqueométrico y evaluación del deterioro de los materiales cerámicos de la fachada de la iglesia de Santa Maria del Carmine (Pavía, Italia)

    OpenAIRE

    Setti, M.; Lanfranchi, A.; Cultrone, G.; Marinoni, L.

    2012-01-01

    We performed an archaeometric study of the ceramic materials from the façade of the church of Santa Maria del Carmine in Pavia (Italy). We obtained useful information about the firing temperatures, the provenance of raw materials and the type of oven used. The ceramics used in the façade are mineralogically rich in quartz, feldspar and phyllosilicates, and newly formed calcium silicate phases were detected in some samples. Microtextural observations revealed the presence of incipient reaction...

  5. Characterization and modeling of major constituent equilibrium chemistry of a blended cement mortar

    International Nuclear Information System (INIS)

    Arnold, J.; Kosson, D. S.; Brown, K. G.; Garrabrants, A. C.; Meeussen, J. C. L.; Van Der Sloot, H. A.

    2013-01-01

    Cementitious materials containing ground granulated iron blast furnace slag and coal combustion fly ash as admixtures are being used extensively for nuclear waste containment applications. Whereas the solid phases of ordinary Portland cement (OPC) have been studied in great detail, the chemistry of cement, fly ash and slag blends has received relatively less study. Given that OPC is generally more reactive than slag and fly ash, the mineralogy of OPC provides a logical starting point for describing the major constituent chemistry of blended cement mortars. To this end, a blended cement mortar containing Portland cement, granulated blast furnace slag, fly ash and quartz sand was modeled using a set of solid phases known to form in hydrated OPC with the geochemical speciation solver LeachXS/ORCHESTRA. Comparison of modeling results to the experimentally determined pH-dependent batch leaching concentrations (USEPA Method 1313) indicates that major constituent concentrations are described reasonably well with the Portland cement mineral set; however, modeled and measured aluminum concentrations differ greatly. Scanning electron microscopic analysis of the mortar reveals the presence of Al-rich phyllosilicate minerals heretofore unreported in similar cementitious blends: kaolinite and potassic phyllosilicates similar in composition to illite and muscovite. Whereas the potassic phyllosilicates are present in the quartz sand aggregate, the formation of kaolinite appears to be authigenic. The inclusion of kaolinite in speciation modeling provides a substantially improved description of the release of Al and therefore, suggests that the behavior of phyllosilicate phases may be important for predicting long-term physico-chemical behavior of such systems. (authors)

  6. Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated martian surface ultraviolet radiation conditions.

    Science.gov (United States)

    Poch, Olivier; Jaber, Maguy; Stalport, Fabien; Nowak, Sophie; Georgelin, Thomas; Lambert, Jean-François; Szopa, Cyril; Coll, Patrice

    2015-03-01

    Most of the phyllosilicates detected at the surface of Mars today are probably remnants of ancient environments that sustained long-term bodies of liquid water at the surface or subsurface and were possibly favorable for the emergence of life. Consequently, phyllosilicates have become the main mineral target in the search for organics on Mars. But are phyllosilicates efficient at preserving organic molecules under current environmental conditions at the surface of Mars? We monitored the qualitative and quantitative evolutions of glycine, urea, and adenine in interaction with the Fe(3+)-smectite clay nontronite, one of the most abundant phyllosilicates present at the surface of Mars, under simulated martian surface ultraviolet light (190-400 nm), mean temperature (218 ± 2 K), and pressure (6 ± 1 mbar) in a laboratory simulation setup. We tested organic-rich samples that were representative of the evaporation of a small, warm pond of liquid water containing a high concentration of organics. For each molecule, we observed how the nontronite influences its quantum efficiency of photodecomposition and the nature of its solid evolution products. The results reveal a pronounced photoprotective effect of nontronite on the evolution of glycine and adenine; their efficiencies of photodecomposition were reduced by a factor of 5 when mixed at a concentration of 2.6 × 10(-2) mol of molecules per gram of nontronite. Moreover, when the amount of nontronite in the sample of glycine was increased by a factor of 2, the gain of photoprotection was multiplied by a factor of 5. This indicates that the photoprotection provided by the nontronite is not a purely mechanical shielding effect but is also due to stabilizing interactions. No new evolution product was firmly identified, but the results obtained with urea suggest a particular reactivity in the presence of nontronite, leading to an increase of its dissociation rate.

  7. Surface clay formation during short-term warmer and wetter conditions on a largely cold ancient Mars

    Science.gov (United States)

    Bishop, Janice L.; Fairén, Alberto G.; Michalski, Joseph R.; Gago-Duport, Luis; Baker, Leslie L.; Velbel, Michael A.; Gross, Christoph; Rampe, Elizabeth B.

    2018-03-01

    The ancient rock record for Mars has long been at odds with climate modelling. The presence of valley networks, dendritic channels and deltas on ancient terrains points towards running water and fluvial erosion on early Mars1, but climate modelling indicates that long-term warm conditions were not sustainable2. Widespread phyllosilicates and other aqueous minerals on the Martian surface3-6 provide additional evidence that an early wet Martian climate resulted in surface weathering. Some of these phyllosilicates formed in subsurface crustal environments5, with no association with the Martian climate, while other phyllosilicate-rich outcrops exhibit layered morphologies and broad stratigraphies7 consistent with surface formation. Here, we develop a new geochemical model for early Mars to explain the formation of these clay-bearing rocks in warm and wet surface locations. We propose that sporadic, short-term warm and wet environments during a generally cold early Mars enabled phyllosilicate formation without requiring long-term warm and wet conditions. We conclude that Mg-rich clay-bearing rocks with lateral variations in mixed Fe/Mg smectite, chlorite, talc, serpentine and zeolite occurrences formed in subsurface hydrothermal environments, whereas dioctahedral (Al/Fe3+-rich) smectite and widespread vertical horizonation of Fe/Mg smectites, clay assemblages and sulphates formed in variable aqueous environments on the surface of Mars. Our model for aluminosilicate formation on Mars is consistent with the observed geological features, diversity of aqueous mineralogies in ancient surface rocks and state-of-the-art palaeoclimate scenarios.

  8. Phase formation during corrosion experiments with two simulated borosilicate nuclear waste glasses

    International Nuclear Information System (INIS)

    Haaker, R.F.

    1985-10-01

    Corrosion products resulting from the reaction of simulated high-level radioactive waste glasses with various solutions have been identified. At 200degC, in saturated NaCl, a degree of reaction of 10 g C31-3 glass or 2.6 g SON 68 glass per liter of solution was obtained. Analcime, vermiculite (a phyllosilicate) and a 2:1 zinc silicate are the major silica containing alteration products for the C31-3 glass. Analcime was the only silicate alteration product which could be identified for SON 68 glass. C31-3 glass appeared to be less reactive with a quinary brine containing Mg ++ than with NaCl. With the quinary brine, montmorillonite (a phyllosilicate) was the predominant silica containing alteration product. Hydrotalcite (a Mg-Al hydroxysulfate) and montmorillonite were the major Al-containing phases. A phyllosilicate, probably montmorillonite, was observed to form during the reaction of SON 68 glass with quinary brine. With either glass, modified NaCl brines which contained small amounts of MgCl 2 seem to have the effect of decreasing the amount of analcime and increasing the amount of phyllosilicate which is formed. In the case of C31-3 glass, there is approximately enough Mg, Al and Zn to precipitate most of the leached Si; measured Si concentrations remain well below that expected for amorphous silica. SON 68 glass has less Zn, Al and Mg than C31-3 glass and much higher Si concentrations of the leachates. (orig./RB)

  9. Test and Delivery of the Chemin Mineralogical Instrument for Mars Science Laboratory

    Science.gov (United States)

    Blake, D. F.; Vaniman, D.; Anderson, R.; Bish, D.; Chipera, S.; Chemtob, S.; Crisp, J.; DesMarais, D. J.; Downs, R.; Feldman, S.; hide

    2010-01-01

    The CheMin mineralogical instrument on MSL will return quantitative powder X-ray diffraction data (XRD) and qualitative X-ray fluorescence data (XRF; 14phyllosilicate identification, could be detected.

  10. Evidence of relationships between texture and structure in smectite systems by small angle synchrotron X ray scattering

    International Nuclear Information System (INIS)

    Pons, Charles-Henri

    1980-01-01

    Phyllosilicates are major constituents of soils, and their partially swelled or dispersed states play an important role in sedimentary geology, in soil science, in biochemistry, and also in various technological applications (drilling sludge, oil synthesis catalysts). Properties of these systems are also in direct relationship with problems such as fixation of pollutants by soil (pesticides, heavy metals, radioactive materials, so on). After having recalled works performed during the past forty years on water-smectite dispersions to define prevailing factors of processes of formation of colloidal states, the author presents the different phyllosilicates which have been studied, and recalls the determining factors of inflation and dispersion mechanisms. Then, he recalls methods of interpretation of X diffraction diagrams and of small angle scattering. He reports the detailed study of the inflation mechanism in the case of montmorillonite- Na, and discusses results obtained with other phyllosilicates or with other cations than sodium. In appendix, the author reports the study of bi-ionic (Na-Ca) montmorillonite suspensions prepared by two different methods. He also discusses the method of interpretation of neutron small angle scattering which had been used on similar systems, and shows why this method leads to questionable conclusions

  11. On-Going Laboratory Efforts to Quantitatively Address Clay Abundance on Mars

    Science.gov (United States)

    Roush, Ted L.; Bishop, Janice L.; Brown, Adrian J.; Blake, David F.; Bristow, Thomas F.

    2012-01-01

    Data obtained at visible and near-infrared wavelengths by OMEGA on MarsExpress and CRISM on MRO provide definitive evidence for the presence of phyllosilicates and other hydrated phases on Mars. A diverse range of both Fe/Mg-OH and Al-OH-bearing phyllosilicates were identified including the smectites, nontronite, saponite, and montmorillonite. In order to constrain the abundances of these phyllosilicates spectral analyses of mixtures are needed. We report on our on-going effort to enable the quantitative evaluation of the abundance of hydrated-hydroxylated silicates when they are contained in mixtures. We include two component mixtures of hydrated/hydroxylated silicates with each other and with two analogs for other martian materials; pyroxene (enstatite) and palagonitic soil (an alteration product of basaltic glass). For the hydrated-hydroxylated silicates we include saponite and montmorillonite (Mg- and Al- rich smectites). We prepared three size separates of each end-member for study: 20-45, 63-90, and 125-150 µm. As the second phase of our effort we used scanning electron microscopy imaging and x-ray diffraction to characterize the grain size distribution, and structural nature, respectively, of the mixtures. Visible and near-infrared reflectance spectra of the 63-90 micrometers grain size of the mixture samples are shown in Figure 1. We discuss the results of our measurements of these mixtures.

  12. Hydrothermal alteration of deep fractured granite: Effects of dissolution and precipitation

    Science.gov (United States)

    Nishimoto, Shoji; Yoshida, Hidekazu

    2010-03-01

    This paper investigates the mineralogical effects of hydrothermal alteration at depth in fractures in granite. A fracture accompanied by an alteration halo and filled with clay was found at a depth of 200 m in a drill core through Toki granite, Gifu, central Japan. Microscopic observation, XRD, XRF, EPMA and SXAM investigations revealed that the microcrystalline clays consist of illite, quartz and pyrite and that the halo round the fracture can be subdivided into a phyllic zone adjacent to the fracture, surrounded by a propylitic zone in which Fe-phyllosilicates are present, and a distinctive outer alteration front characterized by plagioclase breakdown. The processes that result in these changes took place in three successive stages: 1) partial dissolution of plagioclase with partial chloritization of biotite; 2) biotite dissolution and precipitation of Fe-phyllosilicate in the dissolution pores; 3) dissolution of K-feldspar and Fe-phyllosilicate, and illite precipitation associated with development of microcracks. These hydrothermal alterations of the granite proceed mainly by a dissolution-precipitation process resulting from the infiltration of hydrothermal fluid along microcracks. Such infiltration causes locally high mobility of Al and increases the ratio of fluid to rock in the alteration halo. These results contribute to an understanding of how granitic rock becomes altered in orogenic fields such as the Japanese island arc.

  13. The central uplift of Ritchey crater, Mars

    Science.gov (United States)

    Ding, Ning; Bray, Veronica J.; McEwen, Alfred S.; Mattson, Sarah S.; Okubo, Chris H.; Chojnacki, Matthew; Tornabene, Livio L.

    2015-01-01

    Ritchey crater is a ∼79 km diameter complex crater near the boundary between Hesperian ridged plains and Noachian highland terrain on Mars (28.8°S, 309.0°E) that formed after the Noachian. High Resolution Imaging Science Experiment (HiRISE) images of the central peak reveal fractured massive bedrock and megabreccia with large clasts. Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) spectral analysis reveals low calcium pyroxene (LCP), olivine (OL), hydrated silicates (phyllosilicates) and a possible identification of plagioclase bedrock. We mapped the Ritchey crater central uplift into ten units, with 4 main groups from oldest and originally deepest to youngest: (1) megabreccia with large clasts rich in LCP and OL, and with alteration to phyllosilicates; (2) massive bedrock with bright and dark regions rich in LCP or OL, respectively; (3) LCP and OL-rich impactites draped over the central uplift; and (4) aeolian deposits. We interpret the primitive martian crust as igneous rocks rich in LCP, OL, and probably plagioclase, as previously observed in eastern Valles Marineris. We do not observe high-calcium pyroxene (HCP) rich bedrock as seen in Argyre or western Valles Marineris. The association of phyllosilicates with deep megabreccia could be from impact-induced alteration, either as a result of the Richey impact, or alteration of pre-existing impactites from Argyre basin and other large impacts that preceded the Ritchey impact, or both.

  14. The central uplift of Ritchey crater, Mars

    Science.gov (United States)

    Ding, Ning; Bray, Veronica J.; McEwen, Alfred S.; Mattson, Sarah S.; Okubo, Chris H.; Chojnacki, Matthew; Tornabene, Livio L.

    2015-05-01

    Ritchey crater is a ∼79 km diameter complex crater near the boundary between Hesperian ridged plains and Noachian highland terrain on Mars (28.8°S, 309.0°E) that formed after the Noachian. High Resolution Imaging Science Experiment (HiRISE) images of the central peak reveal fractured massive bedrock and megabreccia with large clasts. Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) spectral analysis reveals low calcium pyroxene (LCP), olivine (OL), hydrated silicates (phyllosilicates) and a possible identification of plagioclase bedrock. We mapped the Ritchey crater central uplift into ten units, with 4 main groups from oldest and originally deepest to youngest: (1) megabreccia with large clasts rich in LCP and OL, and with alteration to phyllosilicates; (2) massive bedrock with bright and dark regions rich in LCP or OL, respectively; (3) LCP and OL-rich impactites draped over the central uplift; and (4) aeolian deposits. We interpret the primitive martian crust as igneous rocks rich in LCP, OL, and probably plagioclase, as previously observed in eastern Valles Marineris. We do not observe high-calcium pyroxene (HCP) rich bedrock as seen in Argyre or western Valles Marineris. The association of phyllosilicates with deep megabreccia could be from impact-induced alteration, either as a result of the Richey impact, or alteration of pre-existing impactites from Argyre basin and other large impacts that preceded the Ritchey impact, or both.

  15. Influence of iron redox transformations on plutonium sorption to sediments

    Energy Technology Data Exchange (ETDEWEB)

    Hixon, A.E.; Powell, B.A. [Environmental Engineering and Earth Sciences, Clemson Univ., Clemson, SC (United States); Hu, Y.J.; Nitsche, H. [Dept. of Chemistry, Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab., Berkeley, CA (United States); Kaplan, D.I. [Savannah River National Lab., Aiken, SC (United States); Kukkadapu, R.K.; Qafoku, O. [Pacific Northwest National Lab., Richland, WA (United States)

    2010-07-01

    Plutonium subsurface mobility is primarily controlled by its oxidation state, which in turn is loosely coupled to the oxidation state of iron in the system. Experiments were conducted to examine the effect of sediment iron mineral composition and oxidation state on plutonium sorption and reduction. A pH 6.3 vadose zone sediment containing iron oxides and iron-containing phyllosilicates was treated with various complexants (ammonium oxalate) and reductants (hydroxylamine hydrochloride and dithionite-citrate-bicarbonate (DCB)) to selectively leach and/or reduce iron oxide and phyllosilicate/clay Fe(III). {sup 57}Fe-Moessbauer spectroscopy was used to identify initial iron mineral composition of the sediment and monitor dissolution and reduction of iron oxides and reduction of phyllosilicate Fe(III). {sup 57}Fe-Moessbauer spectroscopy showed that the Fe-mineral composition of the untreated sediment is: 25-30% hematite, 60-65% small-particle/Al-goethite, and < 10% Fe(III) in phyllosilicate; there was no detectable Fe(II). Upon reduction with a strong chemical reductant (dithionite-citrate-bicarbonate buffer), much of the hematite and goethite was removed. Partial reduction of phyllosilicate Fe(III) was evident in the sediments subjected to DCB treatment. Sorption of Pu(V) was monitored over one week for the untreated and each of five treated sediment fractions. Plutonium oxidation state speciation in the aqueous and solid phases was monitored using solvent extraction, coprecipitation, and XANES. The rate of sorption appears to correlate with the fraction of Fe(II) in the sediment (untreated or treated). Pu(V) was the only oxidation state measured in the aqueous phase, irrespective of treatment, whereas Pu(IV) and much smaller amounts of Pu(V) and Pu(VI) were measured in the solid phase. Surface-mediated reduction of Pu(V) to Pu(IV) occurred in treated and untreated sediment samples; Pu(V) remained on untreated sediment surface for two days before reducing to Pu

  16. Fe and O EELS Studies of Ion Irradiated Murchison CM2 Carbonaceous Chondrite Matrix

    Science.gov (United States)

    Keller, L. P.; Christofferson, R.; Dukes, C. A.; Baragiola, R. A.; Rahman, Z.

    2015-01-01

    Introduction: The physical and chemical response of hydrated carbonaceous chondrite materials to space weathering processes is poorly understood. Improving this understanding is a key part of establishing how regoliths on primitive carbonaceous asteroids respond to space weathering processes, knowledge that supports future sample return missions (Hayabusa 2 and OSIRISREx) that are targeting objects of this type. We previously reported on He+ irradiation of Murchison matrix and showed that the irradiation resulted in amorphization of the matrix phyllosilicates, loss of OH, and surface vesiculation. Here, we report electron energy-loss spectroscopy (EELS) measurements of the irradiated material with emphasis on the Fe and O speciation. Sample and Methods: A polished thin section of the Murchison CM2 carbonaceous chondrite was irradiated with 4 kilovolts He(+) (normal incidence) to a total dose of 1 x 10(exp 18) He(+) per square centimeter. We extracted thin sections from both irradiated and unirradiated regions in matrix using focused ion beam (FIB) techniques with electron beam deposition for the protective carbon strap to minimize surface damage artifacts from the FIB milling. The FIB sections were analyzed using a JEOL 2500SE scanning and transmission electron microscope (STEM) equipped with a Gatan Tridiem imaging filter. EELS spectra were collected from 50 nanometer diameter regions with an energy resolution of 0.7 electronvolts FWHM at the zero loss. EELS spectra were collected at low electron doses to minimize possible artifacts from electron-beam irradiation damage. Results and Discussion: Fe L (sub 2,3) EELS spectra from matrix phyllosilicates in CM chondrites show mixed Fe(2+)/Fe(3+) oxidation states with Fe(3+)/Sigma Fe approximately 0.5. Fe L(sub 2,3) spectra from the irradiated/ amorphized matrix phyllosilicates show higher Fe(2+)/Fe(3+) ratios compared to spectra obtained from pristine material at depths beyond the implantation/amorphization layer. We

  17. Organic carbon characteristics in density fractions of soils with contrasting mineralogies

    Science.gov (United States)

    Yeasmin, Sabina; Singh, Balwant; Johnston, Cliff T.; Sparks, Donald L.

    2017-12-01

    This study was aimed to evaluate the role of minerals in the preservation of organic carbon (OC) in different soil types. Sequential density fractionation was done to isolate particulate organic matter (POM, 2.6 g cm-3) from four soils, i.e., a Ferralsol, a Luvisol, a Vertisol and a Solonetz. Organic matter (OM) in the density fractions was characterised using diffuse reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and mass spectroscopy in the original states (i.e., without any chemical pre-treatment), and after 6% sodium hypochlorite (NaOCl) and 10% hydrofluoric acid (HF) treatments. The NaOCl oxidation resistant fraction was considered as a relatively stable pool of OC and the HF soluble fraction was presumed as the mineral bound OC. Phyllosilicate-dominated soils, i.e., Vertisol, Luvisol and Solonetz, contained a greater proportion of POM than Fe and Al oxide-dominated Ferralsol. Wider C:N ratio and lower δ13C and δ15N in POM suggest the dominance of labile OC in this fraction and this was also supported by a greater proportion of NaOCl oxidised OC in the same fraction that was enriched with aliphatic C. The sequential density fractionation method effectively isolated OM into three distinct groups in the soils: (i) OM associated with Fe and Al oxides (>1.8 g cm-3 in the Ferralsol); (ii) OM associated with phyllosilicates (1.8-2.6 g cm-3) and (iii) OM associated with quartz and feldspar (>2.6 g cm-3) in the other three soils. Greater oxidation resistance, and more dissolution of OC during the HF treatment in the Fe and Al oxides dominated fractions suggest a greater potential of these minerals to protect OC from oxidative degradation as compared to the phyllosilicates, and quartz and feldspar matrices. OM associated with Fe and Al oxides was predominantly aromatic and carboxylate C. Decreased C:N ratio in the NaOCl oxidation resistant OM and HF soluble OM of phyllosilicates, and quartz and feldspars dominant fractions

  18. Deformation mechanisms in the San Andreas Fault zone - a comparison between natural and experimentally deformed microstructures

    Science.gov (United States)

    van Diggelen, Esther; Holdsworth, Robert; de Bresser, Hans; Spiers, Chris

    2010-05-01

    The San Andreas Fault (SAF) in California marks the boundary between the Pacific plate and the North American plate. The San Andreas Fault Observatory at Depth (SAFOD) is located 9 km northwest of the town of Parkfield, CA and provide an extensive set of samples through the SAF. The SAFOD drill hole encountered different lithologies, including arkosic sediments from the Salinian block (Pacific plate) and claystones and siltstones from the Great Valley block (North American plate). Fault deformation in the area is mainly by a combination of micro-earthquakes and fault creep. Deformation of the borehole casing indicated that the SAFOD drill hole cross cuts two actively deforming strands of the SAF. In order to determine the deformation mechanisms in the actively creeping fault segments, we have studied thin sections obtained from SAFOD phase 3 core material using optical and electron microscopy, and we have compared these natural SAFOD microstructures with microstructures developed in simulated fault gouges deformed in laboratory shear experiments. The phase 3 core material is divided in three different core intervals consisting of different lithologies. Core interval 1 consists of mildly deformed Salinian rocks that show evidence of cataclasis, pressure solution and reaction of feldspar to form phyllosilicates, all common processes in upper crustal rocks. Most of Core interval 3 (Great Valley) is also only mildly deformed and very similar to Core interval 1. Bedding and some sedimentary features are still visible, together with limited evidence for cataclasis and pressure solution, and reaction of feldspar to form phyllosilicates. However, in between the relatively undeformed rocks, Core interval 3 encountered a zone of foliated fault gouge, consisting mostly of phyllosilicates. This zone is correlated with one of the zones of localized deformation of the borehole casing, i.e. with an actively deforming strand of the SAF. The fault gouge zone shows a strong, chaotic

  19. LED Die-Bonded on the Ag/Cu Substrate by a Sn-BiZn-Sn Bonding System

    Science.gov (United States)

    Tang, Y. K.; Hsu, Y. C.; Lin, E. J.; Hu, Y. J.; Liu, C. Y.

    2016-12-01

    In this study, light emitting diode (LED) chips were die-bonded on a Ag/Cu substrate by a Sn-BixZn-Sn bonding system. A high die-bonding strength is successfully achieved by using a Sn-BixZn-Sn ternary system. At the bonding interface, there is observed a Bi-segregation phenomenon. This Bi-segregation phenomenon solves the problems of the brittle layer-type Bi at the joint interface. Our shear test results show that the bonding interface with Bi-segregation enhances the shear strength of the LED die-bonding joints. The Bi-0.3Zn and Bi-0.5Zn die-bonding cases have the best shear strength among all die-bonding systems. In addition, we investigate the atomic depth profile of the deposited Bi-xZn layer by evaporating Bi-xZn E-gun alloy sources. The initial Zn content of the deposited Bi-Zn alloy layers are much higher than the average Zn content in the deposited Bi-Zn layers.

  20. Ultrafast carrier dynamics in band edge and broad deep defect emission ZnSe nanowires

    Science.gov (United States)

    Othonos, Andreas; Lioudakis, Emmanouil; Philipose, U.; Ruda, Harry E.

    2007-12-01

    Ultrafast carrier dynamics of ZnSe nanowires grown under different growth conditions have been studied. Transient absorption measurements reveal the dependence of the competing effects of state filling and photoinduced absorption on the probed energy states. The relaxation of the photogenerated carriers occupying defect states in the stoichiometric and Se-rich samples are single exponentials with time constants of 3-4ps. State filling is the main contribution for probe energies below 1.85eV in the Zn-rich grown sample. This ultrafast carrier dynamics study provides an important insight into the role that intrinsic point defects play in the observed photoluminescence from ZnSe nanowires.

  1. ZnTe Amorphous Semiconductor Nanowires Array Electrodeposited into Polycarbonate Membrane Thin Films

    International Nuclear Information System (INIS)

    Ohgai, T; Ikeda, T; Ohta, J

    2013-01-01

    ZnTe amorphous semiconductor nanowires array was electrodeposited into the nanochannels of ion-track etched polycarbonate membrane thin films from acidic aqueous solution at 313 K. ZnTe electrodeposits with Zn-rich composition was obtained over the wide range of cathode potential from −0.8 V to −1.1 V and the growth rate of ZnTe amorphous nanowires was around 3 nm.sec −1 at the cathode potential of −0.8 V. Cylindrical shape of the nanowires was precisely transferred from the nanochannels and the aspect ratio reached up to ca. 40. ZnTe amorphous phase electrodeposited at 313 K was crystallized by annealing at 683 K and the band gap energy of ZnTe crystalline phase reached up to ca. 2.13 eV.

  2. Surface characterization of ZnO nanorods grown by chemical bath deposition

    Energy Technology Data Exchange (ETDEWEB)

    Mbulanga, C.M., E-mail: crispin.mbulanga@nmmu.ac.za [Department of Physics, Nelson Mandela Metropolitan University, P.O. Box 77000, Port Elizabeth 6031 (South Africa); Urgessa, Z.N.; Tankio Djiokap, S.R.; Botha, J.R. [Department of Physics, Nelson Mandela Metropolitan University, P.O. Box 77000, Port Elizabeth 6031 (South Africa); Duvenhage, M.M.; Swart, H.C. [Department of Physics, University of the Free State, P.O Box 77000, Bloemfontein ZA9300 (South Africa)

    2016-01-01

    The surface composition of as-grown and annealed ZnO nanorods (ZNs) grown by a two-step chemical bath deposition method is investigated by the following surface-sensitive techniques: Time-of-Flight Secondary Ion Mass Spectroscopy (TOF-SIMS), X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES). The presence of H on the surface and throughout the entire thickness of ZNs is confirmed by TOF-SIMS. Based on TOF-SIMS results, the O2 XPS peak mostly observable at ~531.5 is assigned to O bound to H. Furthermore, it is found that the near surface region of as-grown ZNs is Zn-rich, and annealing at high temperature (~850 °C) removes H-related defects from the surface of ZNs and affect the balance of zinc and oxygen concentrations.

  3. Defect properties of Sn- and Ge-doped ZnTe: suitability for intermediate-band solar cells

    Science.gov (United States)

    Flores, Mauricio A.

    2018-01-01

    We investigate the electronic structure and defect properties of Sn- and Ge- doped ZnTe by first-principles calculations within the DFT+GW formalism. We find that ({{{Sn}}}{{Zn}}) and ({{{Ge}}}{{Zn}}) introduce isolated energy levels deep in the band gap of ZnTe, derived from Sn-5s and Ge-4s states, respectively. Moreover, the incorporation of Sn and Ge on the Zn site is favored in p-type ZnTe, in both Zn-rich and Te-rich environments. The optical absorption spectra obtained by solving the Bethe-Salpeter equation reveals that sub-bandgap absorptance is greatly enhanced due to the formation of the intermediate band. Our results suggest that Sn- and Ge-doped ZnTe would be a suitable material for the development of intermediate-band solar cells, which have the potential to achieve efficiencies beyond the single-junction limit.

  4. ZnSe thin films by chemical bath deposition method

    Energy Technology Data Exchange (ETDEWEB)

    Lokhande, C.D.; Patil, P.S.; Tributsch, H. [Hahn-Meitner-Institute, Bereich Physikalische Chemie, Abt. CS, Glienicker Strasse-100, D-14109 Berlin (Germany); Ennaoui, A. [Hahn-Meitner-Institute, Bereich Physikalische Chemie, Abt. CG, Glienicker Strasse-100, D-14109 Berlin (Germany)

    1998-09-04

    The ZnSe thin films have been deposited onto glass substrates by the simple chemical bath deposition method using selenourea as a selenide ion source from an aqueous alkaline medium. The effect of Zn ion concentration, bath temperature and deposition time period on the quality and thickness of ZnSe films has been studied. The ZnSe films have been characterized by XRD, TEM, EDAX, TRMC (time-resolved microwave conductivity), optical absorbance and RBS techniques for their structural, compositional, electronic and optical properties. The as-deposited ZnSe films are found to be amorphous, Zn rich with optical band gap, Eg, equal to 2.9 eV

  5. Early-stage precipitation in Al-Zn-Mg-Cu alloy (7050)

    International Nuclear Information System (INIS)

    Sha Gang; Cerezo, Alfred

    2004-01-01

    GP zone and metastable η ' formation during the early-stage precipitation of a 7050 Al alloy aged at 121 deg. C has been investigated using transmission electron microscopy, together with 3-dimensional atom probe analysis (of the chemistry and morphology) of individual precipitates. Small Mg-rich clusters (GPI zones) are found in the alloy after short ageing times at 121 deg. C, together with larger GPI zones (Zn/Mg=1.0). Zn-rich η ' platelets are seen to form mainly between 30 and 240 min ageing, coexisting with larger GPI zones. A significant fraction of elongated clusters have also been observed over this period of ageing. The dominant mechanism for η ' formation at this stage is shown to be by transformation of small GPI zones, via these elongated clusters and not by nucleation on larger zones

  6. Novel Vacuum System for In-Situ Characterization of Fluorescence Properties of Thin Films

    Science.gov (United States)

    Onozuka, Kohei; Iwata, Nobuyuki; Yamamoto, Hiroshi

    We constructed a novel vacuum system in which the cathode luminescence properties of as-prepared films can be measured in-situ. It has been observed that the Zn-Ga-O films deposited on 500°C ITO by sputtering emits light with wavelength of about 500 nm from an ultra thin Zn-rich layer formed near film surface. The luminescence induced by irradiation of electrons has also been observed for the first time in the organic bilayered TPD/Alq3 films prepared in thermal evaporation. Its wavelength blue-shifts by about 120 nm in comparison with the electroluminescence of the same materials. The developed vacuum system is useful to characterize various thin films.

  7. The 480 deg. C and 405 deg. C isothermal sections of the phase diagram of Fe-Zn-Si ternary system

    Energy Technology Data Exchange (ETDEWEB)

    Wang Jianhua [Institute of Materials Research, School of Mechanical Engineering, Xiangtan University, Hunan 411105 (China)]. E-mail: super_wang111@hotmail.com; Su Xuping [Institute of Materials Research, School of Mechanical Engineering, Xiangtan University, Hunan 411105 (China); Yin Fucheng [Institute of Materials Research, School of Mechanical Engineering, Xiangtan University, Hunan 411105 (China); Li Zhi [Institute of Materials Research, School of Mechanical Engineering, Xiangtan University, Hunan 411105 (China); Zhao Manxiu [Institute of Materials Research, School of Mechanical Engineering, Xiangtan University, Hunan 411105 (China)

    2005-08-16

    The 480 deg. C and 405 deg. C isothermal sections of the Fe-Zn-Si ternary phase diagram have been determined experimentally using scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS) and X-ray diffractometry. The research of the work has concentrated on the Zn-rich corner, which is relevant to general galvanizing. The present studies have confirmed the existence of equilibrium state between the liquid, the {zeta} phase and the FeSi phase at the 480 deg. C isothermal section. There exist some changes in the phase relationships compared with the isothermal section at 450 deg. C. Experimental results indicate that Si solubility in all four Zn-Fe compounds is also limited at 480 deg. C and 405 deg. C.

  8. 450 {sup o}C isothermal section of the Fe-Zn-Si ternary phase diagram

    Energy Technology Data Exchange (ETDEWEB)

    Su, Xuping [Inst. of Materials Research, School of Mechanical Engineering, Xiangtan Univ., Xiangtan, Hunan (China); Univ. of Toronto, Dept. of Materials Science and Engineering, Toronto, Ontario (Canada); Tang, Nai-Yong [Cominco Ltd., Product Technology Centre, Mississauga, Ontario (Canada); Toguri, J.M. [Univ. of Toronto, Dept. of Materials Science and Engineering, Toronto, Ontario (Canada)

    2001-07-01

    The 450 {sup o}C isothermal section of the Fe-Zn-Si ternary phase diagram has been determined experimentally using optical microscopy, scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS) and X-ray diffractometry. The focus of the work has been concentrated on the Zn-rich corner which is relevant to general galvanizing. The present study has confirmed the existence of the equilibrium state between the liquid, the {zeta} phase and the FeSi phase. This three phase equilibrium state prevents the equilibrium between the liquid and the {delta} phase suggested by some researchers. Experimental results indicate that Si solubility in all four binary Zn-Fe compounds is limited. The Fe solubility in molten Zn was found to decrease with increasing Si content in the melt. The liquid phase boundary was determined using a model based phenomenological approach. (author)

  9. Element enrichment and U-series isotopic characteristics of the hydrothermal sulfides at Jade site in the Okinawa Trough

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The geochemical and U-series isotopic characteristics of hydrothermal sulfide samples from the Jade site (127°04.5′E, 27°15′N, water depth 1300-1450 m) at Jade site in the Okinawa Trough were analyzed. In the hydrothermal sulfide samples bearing sulfate (samples HOK1 and HOK2), the LREEs are relatively enriched. All the hydrothermal sulfide samples except HOK1 belong to Zn-rich hydrothermal sulfide. In comparison with Zn-rich hydrothermal sulfides from other fields, the contents of Zn, Pb, Ag, Cd, Au and Hg are higher, the contents of Fe, Al, Cr, Co, Ni, Sr, Te, Cs, Ti and U lower, and the 210Pb radioactivity ratios and 210Pb/Pb ratios very low. In the hydrothermal sulfide mainly composed of sphalerite, the correlations between rare elements Hf and U, and Hf and Mn as well as that between dispersive elements Ga and Zn, are strongly positive; also the contents of Au and Ag are related to Fe-sulfide, because the low temperature promotes enrichment of Au and Ag. Meanwhile, the positive correlations between Fe and Bi and between Zn and Cd are not affected by the change of mineral assemblage. Based on the 210Pb/Pb ratios of hydrothermal sulfide samples (3.99×10-5-5.42×10?5), their U isotopic composition (238U content 1.15-2.53 ppm, 238U activity 1.07-1.87 dpm/g, 234U activity 1.15-2.09 dpm/g and 234U/238U ratio 1.07-1.14) and their 232Th and 230Th contents are at base level, and the chronological age of hydrothermal sulfide at Jade site in the Okinawa Trough is between 200 and 2000 yr.

  10. Evolution of Thermoelectric Properties of Zn4Sb3 Prepared by Mechanical Alloying and Different Consolidation Routes

    Directory of Open Access Journals (Sweden)

    Pee-Yew Lee

    2018-05-01

    Full Text Available In this research, a method combining the mechanical alloying with the vacuum sintering or hot pressing was adopted to obtain the compact of β-Zn4Sb3. Pure zinc and antimony powders were used as the starting material for mechanical alloying. These powders were mixed in the stoichiometry ratio of 4 to 3, or more Zn-rich. Single phase Zn4Sb3 was produced using a nominally 0.6 at. % Zn rich powder. Thermoelectric Zn4Sb3 bulk specimens have been fabricated by vacuum sintering or hot pressing of mechanically alloyed powders at various temperatures from 373 to 673 K. For the bulk specimens sintering at high temperature, phase transformation of β-Zn4Sb3 to ZnSb and Sb was observed due to Zn vaporization. However, single-phase Zn4Sb3 bulk specimens with 97.87% of theoretical density were successfully produced by vacuum hot pressing at 473 K. Electric resistivity, Seebeck coefficient, and thermal conductivity were evaluated for the hot pressed specimens from room temperature to 673 K. The results indicate that the Zn4Sb3 shows an intrinsic p-type behavior. The increase of Zn4Sb3 phase ratio can increase Seebeck coefficient but decrease electric conductivity. The maximum power factor and figure of merit (ZT value were 1.31 × 10−3 W/mK2 and 0.81 at 600 K, respectively. The ZT value was lower than that reported in the available data for materials prepared by conventional melt growth and hot pressed methods, but higher than the samples fabricated by vacuum melting and heat treatment techniques.

  11. First-principles research on the optical and electrical properties and mechanisms of In-doped ZnO

    Science.gov (United States)

    Hou, Qingyu; Xi, Dongmin; Li, Wenling; Jia, Xiaofang; Xu, Zhenchao

    2018-05-01

    The absorption spectra and conductivity of In-doped ZnO still exhibit differences. To resolve this contradiction, the ZnO supercell models with different In doping amounts and the Zn0.9375In0.0625(Zni)0.0625O supercell model were both constructed. When the geometrical structure of all the models was optimized, the GGA + U and GGA used to calculate the energy. In the range of In doping used in this study, the formation energy of In-doped ZnO under Zn-rich conditions is lower than that under O-rich conditions, thereby implying a more stability of In-doped ZnO under Zn-rich than that under O-rich. With the increased In doping content, the volume and the formation energy of the doped system increase, the doped systems become unstable, and doping becomes difficult. Furthermore, the band gaps are narrowed, and the red shift of absorption spectrum is enhanced. In the In doping amount ranging within 0.01389-0.05556, the electron effective mass decreases first and subsequently increases, and the electron concentration increases. The mobility and conductivity also increase first and subsequently decrease. These results are in accordance with the experimental results. The volume of Zn0.9375In0.0625(Zni)0.0625O with the coexistence of In replacing Zn and interstitial Zn is large. The band gap is widened and the absorption spectrum is blue-shifted in the UV region.

  12. Experimental Alteration of Basalt to Support Interpretation of Remote Sensing and In Situ Meausrements from Mars

    Science.gov (United States)

    Bell, M. S.

    2014-01-01

    Major occurrences of hydrous alteration minerals on Mars have been found in Noachian impact craters formed in basaltic targets and detected using visible/near infrared (VNIR) spectroscopy. Until recently phyllosilicates were detected only in craters in the southern hemisphere [1, 2]. However, it has been reported that at least nine craters in the northern plains apparently excavated thick layers of lava and sediment to expose phyllosilicates [3] as well. The MER (Mars Exploration Rovers) rovers previously reported results of in situ measurement indicating the presence of alteration minerals on Mars [4,5] and it was recently reported that the Mars Curiosity rover has detected alteration phases in situ at Yellowknife Bay in Gale crater as well [6,7]. An important discovery for Mars geochronology is that the Chemistry and Mineralogy (CheMin) x-ray diffraction (XRD) instrument on Curiosity detected phyllosilicates indicating that phyllosilicate formation on Mars extended beyond the Noachian Epoch [8]. These discoveries indicate that Mars was globally altered by water in the past but does not constrain formation conditions for alteration phase occurrences, which have important implications for the evolution of the surface and the biological potential on Mars. Understanding the alteration assemblages produced by a range of conditions is vital for the interpretation of phyllosilicate spectral signatures as well as in situ measurements and to decipher the environment and evolution of early Mars. The martian surface has been intensely altered by meteorite impacts whose effects include brecciation and melting of target materials as well as the initiation of hydrothermal circulation in a hydrous target [9,10,11,12]. Impact effects may facilitate aqueous alteration of a basaltic target because the rate of silicate dissolution is a function of the degree of crystallinity, surface area, and temperature. The resultant alteration mineralogies from shocked basaltic target material

  13. Field- to nano-scale evidence for weakening mechanisms along the fault of the 2016 Amatrice and Norcia earthquakes, Italy

    Science.gov (United States)

    Smeraglia, Luca; Billi, Andrea; Carminati, Eugenio; Cavallo, Andrea; Doglioni, Carlo

    2017-08-01

    In August and October 2016, two normal fault earthquakes (Mw 6.0 and Mw 6.5, respectively) struck the Amatrice-Norcia area in the central Apennines, Italy. The mainshocks nucleated at depths of 7-9 km with the co-seismic slip propagating upward along the Mt. Gorzano Fault (MGF) and Mt. Vettore Fault System (MVFS). To recognize possible weakening mechanisms along the carbonate-hosted seismogenic faults that generated the Amatrice-Norcia earthquakes, the fresh co-seismic fault exposure (i.e., "nastrino") exposed along the Mt. Vettoretto Fault was sampled and analyzed. This exposed fault belongs to the MVFS and was exhumed from 2-3 km depth. Over the fresh fault surface, phyllosilicates concentrated and localized along mm- to μm-thick layers, and truncated clasts and fluid-like structures were found. At the nano-scale, instead of their common platy-lamellar crystallographic texture, the analyzed phyllosilicates consist of welded nm-thick nanospherules and nanotubes similar to phyllosilicates deformed in rotary shear apparatus at seismic velocities or altered under high hydrothermal temperatures (> 250 °C). Moreover, the attitude of the Mt. Vettoretto Fault and its kinematics inferred from exposed slickenlines are consistent with the co-seismic fault and slip vectors obtained from the focal mechanisms computed for the 2016 mainshocks. All these pieces of evidence suggest that the Mt. Vettoretto Fault slipped seismically during past earthquakes and that co-seismic slip was assisted and facilitated at depths of synoptic picture of co-seismic processes and weakening mechanisms that may occur in carbonate-hosted seismogenic faults.

  14. Isotope tracing ({sup 29}Si and {sup 18}O) of the alteration mechanisms of the French glass 'SON68' used for the storage of nuclear waste; Tracage isotopique ({sup 29}Si and {sup 18}O) des mecanismes de l'alteration du verre de confinement des dechets nucleaires: 'SON68'

    Energy Technology Data Exchange (ETDEWEB)

    Valle, N

    2001-07-01

    This study aims to enhance our understanding of the mechanisms of aqueous corrosion of the glasses used for the storage of nuclear waste. Glass samples 'SON68', doped with a different rare earth element (La, Ce or Nd), were altered simultaneously with water enriched in {sup 29}Si and {sup 18}O, throughout a period of 20 months. The aim of such isotope tracing was (i) to follow the 'real' exchanges between glass and solution and (ii) to understand the reactions involving Si-O bonds in the leached layer during alteration. Leachates were analyzed by ICP-MS and -AES, and elemental and isotopic variations in the altered glass layer were measured by ion-probe, using a depth profiling technique. Elemental analyses enabled the distribution of the elements in the two layers of altered glass (phyllosilicates and gel) to be established, and the results reveal a selective partitioning of elements between the two layers. Isotopic analyses of altered layers and leachates allowed phyllosilicates to be distinguished from gel, and suggest two different mechanisms of formation. Whilst phyllosilicates grow on the surface of the glass by a mechanism of precipitation, gel is formed by a succession of hydrolysis / condensation reactions taking place mainly at the gel / pristine glass interface. This gel is formed by the in situ rearrangement of hydrated species, without reaching equilibrium with the solution. Moreover, an experimental technique has been developed enabling one to trace the transport of silicon from the solution into the altered glasses, under an isotopic gradient. Diffusion profiles, obtained by ion-probe, have been modeled and have allowed the determination of the apparent silicon diffusion coefficient (DSi) in gels. Therefore, our experiments have permitted the quantification of the influence of both the alteration conditions (dynamic or static tests) and the solution composition on the value of DSi. (author)

  15. Discovery of jarosite within the Mawrth Vallis region of Mars: Implications for the geologic history of the region

    Science.gov (United States)

    Farrand, W. H.; Glotch, T.D.; Rice, J. W.; Hurowitz, J.A.; Swayze, G.A.

    2009-01-01

    Analysis of visible to near infrared reflectance data from the MRO CRISM hyperspectral imager has revealed the presence of an ovoid-shaped landform, approximately 3 by 5 km in size, within the layered terrains surrounding the Mawrth Vallis outflow channel. This feature has spectral absorption features consistent with the presence of the ferric sulfate mineral jarosite, specifically a K-bearing jarosite (KFe3(SO4)2(OH)6). Terrestrial jarosite is formed through the oxidation of iron sulfides in acidic environments or from basaltic precursor minerals with the addition of sulfur. Previously identified phyllosilicates in the Mawrth Vallis layered terrains include a basal sequence of layers containing Fe-Mg smectites and an upper set of layers of hydrated silica and aluminous phyllosilicates. In terms of its fine scale morphology revealed by MRO HiRISE imagery, the jarosite-bearing unit has fracture patterns very similar to that observed in Fe-Mg smectite-bearing layers, but unlike that observed in the Al-bearing phyllosilicate unit. The ovoid-shaped landform is situated in an east-west bowl-shaped depression superposed on a north sloping surface. Spectra of the ovoid-shaped jarosite-bearing landform also display an anomalously high 600 nm shoulder, which may be consistent with the presence of goethite and a 1.92 ??m absorption which could indicate the presence of ferrihydrite. Goethite, jarosite, and ferrihydrite can be co-precipitated and/or form through transformation of schwertmannite, both processes generally occurring under low pH conditions (pH 2-4). To date, this location appears to be unique in the Mawrth Vallis region and could represent precipitation of jarosite in acidic, sulfur-rich ponded water during the waning stages of drying. ?? 2009 Elsevier Inc. All rights reserved.

  16. Very low-temperature metamorphism in Ordovician metasedimentary rocks above and below the Sardic unconformity, SW Sardinia, Italy

    Science.gov (United States)

    Franceschelli, M.; Battaglia, S.; Cruciani, G.; Pasci, S.; Puxeddu, M.

    2017-03-01

    In the Iglesiente region, the Cabitza and Monte Argentu Formations are separated by an angular unconformity known as the Sardic unconformity. This is related to an early Ordovician mild compressional phase, known as the "Sardic phase". The pelitic samples from the structurally lower Cabitza Formation consist of alternating reddish phyllosilicate-rich and whitish phyllosilicate-poor, sialic layers, whose S0 bedding plane is parallel to a pre-Variscan S1P schistosity overprinted by the Variscan S1V schistosity. Pelitic samples from the Monte Argentu Formation are characterized by a Variscan S1V axial plane schistosity. Samples from the two formations consist of quartz and phyllosilicates. The latter are potassic white mica, chlorite, paragonite, locally kaolinite, and pyrophyllite. The illite crystallinity values determined for the Cabitza samples are 0.25-0.31, with an average of 0.29; meanwhile, the Monte Argentu samples produce values of 0.33-0.38, with an average of 0.35. The chlorite crystallinity and b0 of potassic white mica values show greater heterogeneity in the Cabitza than the Monte Argentu samples. The b0 values and P-T pseudosections allow us to confirm that there is no significant difference in the P-T metamorphism conditions between the Cabitza and Monte Argentu samples. The Iglesiente region, which is considered to be the rift zone behind the Middle Ordovician Sarcidano-Barbagia volcanic arc, underwent the "Sardic phase", giving rise to E-W folds. These were first overprinted by weak E-W, and then by stronger N-S-oriented Variscan deformation events.

  17. Isotope tracing (29Si and 18O) of the alteration mechanisms of the French glass 'SON68' used for the storage of nuclear waste

    International Nuclear Information System (INIS)

    Valle, N.

    2001-01-01

    This study aims to enhance our understanding of the mechanisms of aqueous corrosion of the glasses used for the storage of nuclear waste. Glass samples 'SON68', doped with a different rare earth element (La, Ce or Nd), were altered simultaneously with water enriched in 29 Si and 18 O, throughout a period of 20 months. The aim of such isotope tracing was (i) to follow the 'real' exchanges between glass and solution and (ii) to understand the reactions involving Si-O bonds in the leached layer during alteration. Leachates were analyzed by ICP-MS and -AES, and elemental and isotopic variations in the altered glass layer were measured by ion-probe, using a depth profiling technique. Elemental analyses enabled the distribution of the elements in the two layers of altered glass (phyllosilicates and gel) to be established, and the results reveal a selective partitioning of elements between the two layers. Isotopic analyses of altered layers and leachates allowed phyllosilicates to be distinguished from gel, and suggest two different mechanisms of formation. Whilst phyllosilicates grow on the surface of the glass by a mechanism of precipitation, gel is formed by a succession of hydrolysis / condensation reactions taking place mainly at the gel / pristine glass interface. This gel is formed by the in situ rearrangement of hydrated species, without reaching equilibrium with the solution. Moreover, an experimental technique has been developed enabling one to trace the transport of silicon from the solution into the altered glasses, under an isotopic gradient. Diffusion profiles, obtained by ion-probe, have been modeled and have allowed the determination of the apparent silicon diffusion coefficient (DSi) in gels. Therefore, our experiments have permitted the quantification of the influence of both the alteration conditions (dynamic or static tests) and the solution composition on the value of DSi. (author)

  18. Discovery of jarosite within the Mawrth Vallis region of Mars: Implications for the geologic history of the region

    Science.gov (United States)

    Farrand, William H.; Glotch, Timothy D.; Rice, James W.; Hurowitz, Joel A.; Swayze, Gregg A.

    2009-12-01

    Analysis of visible to near infrared reflectance data from the MRO CRISM hyperspectral imager has revealed the presence of an ovoid-shaped landform, approximately 3 by 5 km in size, within the layered terrains surrounding the Mawrth Vallis outflow channel. This feature has spectral absorption features consistent with the presence of the ferric sulfate mineral jarosite, specifically a K-bearing jarosite (KFe 3(SO 4) 2(OH) 6). Terrestrial jarosite is formed through the oxidation of iron sulfides in acidic environments or from basaltic precursor minerals with the addition of sulfur. Previously identified phyllosilicates in the Mawrth Vallis layered terrains include a basal sequence of layers containing Fe-Mg smectites and an upper set of layers of hydrated silica and aluminous phyllosilicates. In terms of its fine scale morphology revealed by MRO HiRISE imagery, the jarosite-bearing unit has fracture patterns very similar to that observed in Fe-Mg smectite-bearing layers, but unlike that observed in the Al-bearing phyllosilicate unit. The ovoid-shaped landform is situated in an east-west bowl-shaped depression superposed on a north sloping surface. Spectra of the ovoid-shaped jarosite-bearing landform also display an anomalously high 600 nm shoulder, which may be consistent with the presence of goethite and a 1.92 μm absorption which could indicate the presence of ferrihydrite. Goethite, jarosite, and ferrihydrite can be co-precipitated and/or form through transformation of schwertmannite, both processes generally occurring under low pH conditions (pH 2-4). To date, this location appears to be unique in the Mawrth Vallis region and could represent precipitation of jarosite in acidic, sulfur-rich ponded water during the waning stages of drying.

  19. Crystallite size distribution of clay minerals from selected Serbian clay deposits

    Directory of Open Access Journals (Sweden)

    Simić Vladimir

    2006-01-01

    Full Text Available The BWA (Bertaut-Warren-Averbach technique for the measurement of the mean crystallite thickness and thickness distributions of phyllosilicates was applied to a set of kaolin and bentonite minerals. Six samples of kaolinitic clays, one sample of halloysite, and five bentonite samples from selected Serbian deposits were analyzed. These clays are of sedimentary volcano-sedimentary (diagenetic, and hydrothermal origin. Two different types of shape of thickness distribution were found - lognormal, typical for bentonite and halloysite, and polymodal, typical for kaolinite. The mean crystallite thickness (T BWA seams to be influenced by the genetic type of the clay sample.

  20. The Mineralogy and Geochemistry of Manganese Nodules From the Southern Ocean

    Science.gov (United States)

    1968-02-01

    viii Figure Page 17. Distribution of Values for the Ratio of Peak Areas 3.2 R Plagio lase-Phillipsite + 9.7 Todorokite / 3.34 § Quartz in Concretions...noted anorthoclase and plagio - clase both on the Rise crest and on the flanks. From their data they were able to delineate a province of acidic vol...peak shouldering on the 3.2 plagio - clase peak may have been caused by prehnite. Minor phyllosilicates Illite/muscovite, chlorite, and talc/pyrophyllite

  1. Uranyl adsorption at clay mineral surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Roesch, N. [Technische Univ. Muenchen (Germany). Fachgebiet Theoretische Chemie

    2016-11-01

    This first systematic survey of actinide adsorption at complex clay mineral surfaces, which provided new insights at the atomic level, is currently being extended to neptunyl NpO{sub 2}{sup +} and more complex minerals, like iron-substituted phyllosilicates. In this way we examine if the concepts developed so far can be applied more generally to support the interpretation of pertinent experiments. A further facet of these studies is to account also for the dynamic nature of the mineral/water interface by means of exemplary dynamic simulations.

  2. Year-round variations in the fluvial transport load of particulate 137Cs in a forested catchment affected by the Fukushima Daiichi Nuclear Power Plant accident

    International Nuclear Information System (INIS)

    Takeshi Matsunaga; Takahiro Nakanishi; Mariko Atarashi-Andoh; Erina Takeuchi; Kotomi Muto; Katsunori Tsuduki; Syusaku Nishimura; Jun Koarashi; Shigeyoshi Otosaka; Tsutomu Sato

    2016-01-01

    Particulate 137 Cs was collected from stream water for 2 years to assess the long-term trend of 137 Cs discharge from a forest after the Fukushima Nuclear Power Plant accident. A seasonal increase in the fluvial transport load of particulate 137 Cs in suspended solids (SS) was observed in July-October when rainfall was abundant. The 137 Cs load was controlled by the SS load. This control was attributed to cesium affinity for phyllosilicate clay minerals as verified by the low extractability of particulate 137 Cs. These findings indicate the fluvial particulate 137 Cs load is significantly related to the climate and geomorphological features of Japan. (author)

  3. Hints of Habitable Environments on Mars Challenge Our Studies of Mars-Analog Sites on Earth

    Science.gov (United States)

    desMarais, David J

    2009-01-01

    Life as we know it requires water with a chemical activity (alpha) >or approx.0.6 and sources of nutrients and useful energy. Some biota can survive even if favorable conditions occur only intermittently, but the minimum required frequency of occurrences is poorly understood. Recent discoveries have vindicated the Mars exploration strategy to follow the water. Mars Global Surveyor s Thermal Emission Spectrometer (TES) found coarse-grained hematite at Meridiani Planum. Opportunity rover confirmed this and also found evidence of ancient sulfate-rich playa lakes and near-surface groundwater. Elsewhere, TES found evidence of evaporitic halides in topographic depressions. But alpha might not have approached 0.6 in these evaporitic sulfate- and halide-bearing waters. Mars Express (MEX) and Mars Reconnaissance Orbiter (MRO) found extensive sulfate evaporites in Meridiani and Valles Marineris. MEX found phyllosilicates at several sites, most notably Mawrth Valles and Nili Fossae. MRO's CRISM near-IR mapper extended the known diversity and geographic distribution of phyllosilicates to include numerous Noachian craters. Phyllosilicates typically occur at the base of exposed ancient rock sections or in sediments in early Hesperian craters. It is uncertain whether the phyllosilicates developed in surface or subsurface aqueous environments and how long aqueous conditions persisted. Spirit rover found remarkably pure ferric sulfate, indicating oxidation and transport of Fe and S, perhaps in fumaroles or hot springs. Spirit also found opaline silica, consistent with hydrothermal activity. CRISM mapped extensive silica deposits in the Valles Marineris region, consistent with aqueous weathering and deposition. CRISM also found ultramafic rocks and magnesite at Nili Fossae, consistent with serpentinization, a process that can sustain habitable environments on Earth. The report of atmospheric methane implies subsurface aqueous conditions. A working hypothesis is that aqueous

  4. Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated Mars surface UV radiation conditions

    Science.gov (United States)

    Poch, Olivier; Dequaire, Tristan; Stalport, Fabien; Jaber, Maguy; Lambert, Jean-François; Szopa, Cyril; Coll, Patrice

    2015-04-01

    The search for organic carbon-containing molecules at the surface of Mars, as clues of past habitability or remnants of life, is a major scientific goal for Mars exploration. Several lines of evidence, including the detection of phyllosilicates, suggest that early Mars offered favorable conditions for long-term sustaining of water. As a consequence, we can assume that in those days, endogenous chemical processes, or even primitive life, may have produced organic matter on Mars. Moreover, exogenous delivery from small bodies or dust particles is likely to have brought fresh organic molecules to the surface of Mars up today. Organic matter is therefore expected to be present at the surface/subsurface of the planet. But the current environmental conditions at the surface - UV radiation, oxidants and energetic particles - generate physico-chemical processes that may affect organic molecules. On the other hand, on Earth, phyllosilicates are known to accumulate and preserve organic matter. But are phyllosilicates efficient at preserving organic molecules under the current environmental conditions at the surface of Mars? We have monitored the qualitative and quantitative evolutions of glycine, urea and adenine interacting with the Fe3+-smectite clay nontronite, one of the most abundant phyllosilicates present at the surface of Mars, under simulated Martian surface ultraviolet light (190-400 nm), mean temperature (218 ± 2 K) and pressure (6 ± 1 mbar) in a laboratory simulation setup. We have tested organic-rich samples which may be representative of the evaporation of a warm little pond of liquid water having concentrated organics on Mars. For each molecule, we have observed how the nontronite influences the quantum efficiency of its photodecomposition and the nature of its solid evolution products. The results reveal a pronounced photoprotective effect of nontronite on the evolution of glycine and adenine: their efficiencies of photodecomposition are reduced by a factor

  5. The Nature of C Asteroid Regolith Revealed from the Jbilet Winselwan CM Chondrite

    Science.gov (United States)

    Zolensky, Michael; Mikouchi, Takashi; Hagiya, Kenji; Ohsumi, Kazumasa; Komatsu, Mutsumi; Chan, Queenie H. S.; Le, Loan; Kring, David; Cato, Michael; Fagan, Amy L.

    2016-01-01

    C-class asteroids frequently exhibit reflectance spectra consistent with thermally metamorphosed carbonaceous chondrites, or a mixture of phyllosilicate-rich material along with regions where they are absent. One particularly important example appears to be asteroid 162173 Ryugu, the target of the Hayabusa 2 mission, although most spectra of Ryugu are featureless, suggesting a heterogeneous regolith. Here we explore an alternative cause of dehydration of regolith of C-class asteroids - impact shock melting. Impact shock melting has been proposed to ex-plain some mineralogical characteristics of CB chondrites, but has rarely been considered a major process for hydrous carbonaceous chondrites.

  6. How the Assumed Size Distribution of Dust Minerals Affects the Predicted Ice Forming Nuclei

    Science.gov (United States)

    Perlwitz, Jan P.; Fridlind, Ann M.; Garcia-Pando, Carlos Perez; Miller, Ron L.; Knopf, Daniel A.

    2015-01-01

    The formation of ice in clouds depends on the availability of ice forming nuclei (IFN). Dust aerosol particles are considered the most important source of IFN at a global scale. Recent laboratory studies have demonstrated that the mineral feldspar provides the most efficient dust IFN for immersion freezing and together with kaolinite for deposition ice nucleation, and that the phyllosilicates illite and montmorillonite (a member of the smectite group) are of secondary importance.A few studies have applied global models that simulate mineral specific dust to predict the number and geographical distribution of IFN. These studies have been based on the simple assumption that the mineral composition of soil as provided in data sets from the literature translates directly into the mineral composition of the dust aerosols. However, these tables are based on measurements of wet-sieved soil where dust aggregates are destroyed to a large degree. In consequence, the size distribution of dust is shifted to smaller sizes, and phyllosilicates like illite, kaolinite, and smectite are only found in the size range 2 m. In contrast, in measurements of the mineral composition of dust aerosols, the largest mass fraction of these phyllosilicates is found in the size range 2 m as part of dust aggregates. Conversely, the mass fraction of feldspar is smaller in this size range, varying with the geographical location. This may have a significant effect on the predicted IFN number and its geographical distribution.An improved mineral specific dust aerosol module has been recently implemented in the NASA GISS Earth System ModelE2. The dust module takes into consideration the disaggregated state of wet-sieved soil, on which the tables of soil mineral fractions are based. To simulate the atmospheric cycle of the minerals, the mass size distribution of each mineral in aggregates that are emitted from undispersed parent soil is reconstructed. In the current study, we test the null

  7. Long-term product consistency test of simulated 90-19/Nd HLW glass

    International Nuclear Information System (INIS)

    Gan, X.Y.; Zhang, Z.T.; Yuan, W.Y.; Wang, L.; Bai, Y.; Ma, H.

    2011-01-01

    Chemical durability of 90-19/Nd glass, a simulated high-level waste (HLW) glass in contact with the groundwater was investigated with a long-term product consistency test (PCT). Generally, it is difficult to observe the long term property of HLW glass due to the slow corrosion rate in a mild condition. In order to overcome this problem, increased contacting surface (S/V = 6000 m -1 ) and elevated temperature (150 o C) were employed to accelerate the glass corrosion evolution. The micro-morphological characteristics of the glass surface and the secondary minerals formed after the glass alteration were analyzed by SEM-EDS and XRD, and concentrations of elements in the leaching solution were determined by ICP-AES. In our experiments, two types of minerals, which have great impact on glass dissolution, were found to form on 90-19/Nd HLW glass surface when it was subjected to a long-term leaching in the groundwater. One is Mg-Fe-rich phyllosilicates with honeycomb structure; the other is aluminosilicates (zeolites). Mg and Fe in the leaching solution participated in the formation of phyllosilicates. The main components of phyllosilicates in alteration products of 90-19/Nd HLW glass are nontronite (Na 0.3 Fe 2 Si 4 O 10 (OH) 2 .4H 2 O) and montmorillonite (Ca 0.2 (Al,Mg) 2 Si 4 O 10 (OH) 2 .4H 2 O), and those of aluminosilicates are mordenite ((Na 2 ,K 2 ,Ca)Al 2 Si 10 O 24 .7H 2 O)) and clinoptilolite ((Na,K,Ca) 5 Al 6 Si 30 O 72 .18H 2 O). Minerals like Ca(Mg)SO 4 and CaCO 3 with low solubility limits are prone to form precipitant on the glass surface. Appearance of the phyllosilicates and aluminosilicates result in the dissolution rate of 90-19/Nd HLW glass resumed, which is increased by several times over the stable rate. As further dissolution of the glass, both B and Na in the glass were found to leach out in borax form.

  8. Rare Earth Elements: A Tool for Understanding the Behaviour of Trivalent Actinides in the Geosphere

    International Nuclear Information System (INIS)

    Buil, Belen; Gomez, Paloma; Garralon, Antonio; Turrero, M. Jesus

    2007-01-01

    Rare earth element (REE) concentrations have been determined in groundwaters, granite and fracture fillings in a restored uranium mine. The granitoids normalized REE patterns of groundwaters show heavy rare earth elements (HREE)-enrichment and positive Eu anomalies. This suggests that the REE are fractionated during leaching from the source rocks by groundwaters. Preferential leaching of HREE would be consistent with the greater stability of their aqueous complexes compared to those of the light rare earth elements (LREE), together with the dissolution of certain fracture filling minerals, dissolution/alteration of phyllosilicates and colloidal transport. (authors)

  9. Distribución de facies recientes en los fondos de la Bahía de Cádiz

    OpenAIRE

    Gutiérrez Mas, José Manuel; Achab, M.; Parrado Román, J. M.; Moral Cardona, J. P.; Sánchez Bellón, A.; González Caballero, J. L.; López Aguayo, F.

    1996-01-01

    Thè distribution of fàcies in thè bottoms ofthe Bay of Cadiz is studied in a preliminary phase of a wider study about the sedimentary èxchange between the continent and continental margin. Two sectors are distinguished, the inner one is clayely-muddy and the external one is sandy showing the grain size distribution the main transport path ofthe ebb tidal current and of those generated by the stórm wa ve. The quartz is majority in sandy areas and phyllosilicates in muddy sectors. The day fract...

  10. Electrodeposition of nanostructured Sn-Zn coatings

    Science.gov (United States)

    Salhi, Y.; Cherrouf, S.; Cherkaoui, M.; Abdelouahdi, K.

    2016-03-01

    The electrodeposition of Sn-Zn coating at ambient temperature was investigated. The bath consists of metal salts SnCl2·2H2O and ZnSO4·7H2O and sodium citrate (NaC6H5Na3O7·2H2O) as complexing agent. To prevent precipitation, the pH is fixed at 5. Reducing tin and zinc through Sncit2- and ZnHcit- complex respectively is confirmed by the presence of two cathodic peaks on the voltammogram. The kinetic of tin (II) reduction process is limited by the SnCit2- dissociation. The SEM and TEM observations have showed that the coating consists of a uniform Sn-Zn layer composed of fine grains on which tin aggregates grow up. XRD revealed peaks corresponding to the hexagonal Zn phase and the tetragonal β-Sn phase.

  11. Controlling interface oxygen for forming Ag ohmic contact to semi-polar (1 1 -2 2) plane p-type GaN

    Science.gov (United States)

    Park, Jae-Seong; Han, Jaecheon; Seong, Tae-Yeon

    2014-11-01

    Low-resistance Ag ohmic contacts to semi-polar (1 1 -2 2) p-GaN were developed by controlling interfacial oxide using a Zn layer. The 300 °C-annealed Zn/Ag samples showed ohmic behavior with a contact resistivity of 6.0 × 10-4 Ω cm2 better than that of Ag-only contacts (1.0 × 10-3 Ω cm2). The X-ray photoemission spectroscopy (XPS) results showed that annealing caused the indiffusion of oxygen at the contact/GaN interface, resulting in the formation of different types of interfacial oxides, viz. Ga-oxide and Ga-doped ZnO. Based on the XPS and electrical results, the possible mechanisms underlying the improved electrical properties of the Zn/Ag samples are discussed.

  12. The corrosion behaviour of galvanized steel in cooling tower water containing a biocide and a corrosion inhibitor.

    Science.gov (United States)

    Minnoş, Bihter; Ilhan-Sungur, Esra; Çotuk, Ayşın; Güngör, Nihal Doğruöz; Cansever, Nurhan

    2013-01-01

    The corrosion behaviour of galvanized steel in cooling tower water containing a biocide and a corrosion inhibitor was investigated over a 10-month period in a hotel. Planktonic and sessile numbers of sulphate reducing bacteria (SRB) and heterotrophic bacteria were monitored. The corrosion rate was determined by the weight loss method. The corrosion products were analyzed by energy dispersive X-ray spectroscopy and X-ray diffraction. A mineralized, heterogeneous biofilm was observed on the coupons. Although a biocide and a corrosion inhibitor were regularly added to the cooling water, the results showed that microorganisms, such as SRB in the mixed species biofilm, caused corrosion of galvanized steel. It was observed that Zn layers on the test coupons were completely depleted after 3 months. The Fe concentrations in the biofilm showed significant correlations with the weight loss and carbohydrate concentration (respectively, p < 0.01 and p < 0.01).

  13. Low-cost zinc-plated photoanode for fabric-type dye-sensitized solar cells

    Science.gov (United States)

    Kong, Lingfeng; Bao, Yunna; Guo, Wanwan; Cheng, Li; Du, Jun; Liu, Renlong; Wang, Yundong; Fan, Xing; Tao, Changyuan

    2016-02-01

    Fabric-type flexible solar cells have been recently proposed as a very promising power source for wearable electronics. To increase the photocurrent of fabric-type flexible solar cells, low-cost zinc-plated wire and mesh photoanodes are assembled for the first time through a mild wet process. Given the protection of the compact protection layer, the DSSC device could benefit from the low work function of Zn and self-repairing behavior on the Zn/ZnO interface. An evident current increase by ∼6 mA/cm2 could be observed after coating a layer of metal Zn on various metal substrates, such as traditional stainless steel wire. Given the self-repairing behavior on Zn/ZnO interface, the Zn layer can help to improve the interfacial carrier transfer, leading to better photovoltaic performance, for both liquid-type and solid-type cells.

  14. Detection and context of hydrated mineralogy in the Tyrrhena Terra region, Mars

    Science.gov (United States)

    den Haan, J.; Zegers, T. E.; van Ruitenbeek, F. J. A.; van der Werff, H. M. A.; Rossi, A.

    2008-09-01

    Introduction The discovery of phyllosilicates on Mars [1] has had major implications on the perceived geologic and climatologic evolution of Mars [2]. Not only do phyllosilicates represent a `wet' period on Mars, they might also represent a potentially favorable environment for life. The phyllosilicates have so far exclusively been found in or close to ancient Noachian highland terrain. Those phyllosilicate deposits studied (e.g. [3]) show a clear association between hydrated mineralogy and heavily eroded and crater-saturated outcrops. Phyllosilicates on Earth are associated with a wide variety of geological processes (volcanism, metamorphism, hydrothermal alteration, sedimentation). The occurrence of phyllosilicates on Mars may be equally diverse in nature. To be able to place constraints on the early Martian environment, the processes by which these phyllosilicates formed need to be reconstructed. To derive this information from individual phyllosilicate deposits, it is necessary to interpret their composition in relation to their geological context and relative time relationships. We conducted such an integrated hyperspectral and geological study of the Tyrrhena Terra region. Data products ad methods HRSC data products (both image at 12 m/pixel and stereo-derived DTMs) are used for examining geologic cross-cutting relationships, geomorphologic landforms and visual determination of unit boundaries. Odyssey THEMIS nighttime TIR images are analyzed for spatial variations in thermal inertia. Where available, HRSC is supplemented by higher-resolution visible observations of CTX or MOC. Hyperspectral analysis is conducted using data from the OMEGA hyperspectral instrument. In order to batch-process large amounts of OMEGA data, an IDL/ENVI tool was developed on top of the existing SOFT04, distributed by PSA. The applied atmospheric correction assumes that atmospheric contributions are multiplicative, and follow a power-law distribution with altitude [4]. The ratio of

  15. The Mineralogical and Chemical Case for Habitability at Yellowknife Bay, Gale Crater, Mars

    Science.gov (United States)

    Blake, David Frederick; Vaniman, David; Grotzinger, John P.; Conrad, Pamela Gales; Ming, Douglas W.; Bish, David L.; Farmer, Jack D.; Bristow, Thomas

    2013-01-01

    Sediments of the Yellowknife Bay formation (Gale crater) include the Sheepbed member, a mudstone cut by light-toned veins. Two drill samples, John Klein and Cumberland, were collected and analyzed by the CheMin XRD/XRF instrument and the Sample Analysis at Mars (SAM) evolved gas and isotopic analysis suite of instruments. Drill cuttings were also analyzed by the Alpha Particle X-ray Spectrometer (APXS) for bulk composition. The CheMin XRD analysis shows that the mudstone contains basaltic minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe-oxide/hydroxides, Fe-sulfides, amorphous materials, and trioctahedral phyllosilicates. SAM evolved gas analysis of higher-temperature OH matches the CheMin XRD estimate of 20% clay minerals in the mudstone. The light-toned veins contain Ca-sulfates; anhydrite and bassanite are detected by XRD but gypsum is also indicated from Mastcam spectral mapping. These sulfates appear to be almost entirely restricted to late-diagenetic veins. The sulfate content of the mudstone matrix itself is lower than other sediments analyzed on Mars. The presence of phyllosilicates indicates that the activity of water was high during their formation and/or transport and deposition (should they have been detrital). Lack of chlorite places limits on the maximum temperature of alteration (likely habitable environment: Aqueous deposition at clement conditions of P, T, pH, Eh and ionic strength, plus the availability of sources of chemical energy.

  16. Influence of mineral characteristics on the retention of low molecular weight organic compounds: a batch sorption-desorption and ATR-FTIR study.

    Science.gov (United States)

    Yeasmin, Sabina; Singh, Balwant; Kookana, Rai S; Farrell, Mark; Sparks, Donald L; Johnston, Cliff T

    2014-10-15

    Batch experiments were conducted to evaluate the sorption-desorption behaviour of (14)C-labelled carboxylic acids (citric and oxalic) and amino acids (glutamic, alanine, phenylalanine and lysine) on pure minerals (kaolinite, illite, montmorillonite, ferrihydrite and goethite). The sorption experiments were complemented by ATR-FTIR spectroscopy to gain possible mechanistic insight into the organic acids-mineral interactions. In terms of charge, the organic solutes ranged from strongly negative (i.e., citric) to positively charged solutes (i.e., lysine); similarly the mineral phases also ranged from positively to negatively charged surfaces. In general, sorption of anionic carboxylic and glutamic acids was higher compared to the other compounds (except lysine). Cationic lysine showed a stronger affinity to permanently charged phyllosilicates than Fe oxides. The sorption of alanine and phenylalanine was consistently low for all minerals, with relatively higher sorption and lower desorption of phenylalanine than alanine. Overall, the role of carboxylic functional groups for the sorption and retention of these carboxylic and amino acids on Fe oxides (and kaolinite) and of amino group on 2:1 phyllosilicates was noticeable. Mineral properties (surface chemistry, specific surface area), chemistry of the organic compounds (pKa value, functional groups) and the equilibrium pH of the system together controlled the differences in sorption-desorption patterns. The results of this study aid to understand the effects of mineralogical and chemical factors that affect naturally occurring low molecular weight organic compounds sorption under field conditions. Copyright © 2014 Elsevier Inc. All rights reserved.

  17. Molecular investigation on the binding of Cd(II) by the binary mixtures of montmorillonite with two bacterial species

    Energy Technology Data Exchange (ETDEWEB)

    Du, Huihui; Qu, ChenChen; Liu, Jing; Chen, Wenli; Cai, Peng; Shi, Zhihua; Yu, Xiao-Ying; Huang, Qiaoyun

    2017-10-01

    Bacteria and phyllosilicate commonly coexist in the natural environment, producing various bacteria–clay complexes that are capable of immobilizing heavy metals, such as cadmium, via adsorption. However, the molecular binding mechanisms of heavy metals on these complex aggregates still remain poorly understood. This study investigated Cd adsorption on Gram-positive B. subtilis, Gram-negative P. putida and their binary mixtures with montmorillonite (Mont) using the Cd K-edge x-ray absorption spectroscopy (XAS) and isothermal titration calorimetry (ITC). We observed a lower adsorptive capacity for P. putida than B. subtilis, whereas P. putida–Mont and B. subtilis–Mont mixtures showed nearly identical Cd adsorption behaviors. EXAFS fits and ITC measurements demonstrated more phosphoryl binding of Cd in P. putida. The decreased coordination of C atoms around Cd and the reduced adsorption enthalpies and entropies for the binary mixtures compared to that for individual bacteria suggested that the bidentate Cd-carboxyl complexes in pure bacteria systems were probably transformed into monodentate complexes that acted as ionic bridging structure between bacteria and motmorillonite. This study clarified the binding mechanism of Cd at the bacteria–phyllosilicate interfaces from a molecular and thermodynamic view, which has an environmental significance for predicting the chemical behavior of trace elements in complex mineral–organic systems.

  18. Surface Mineralogy Mapping of Ceres from the Dawn Mission

    Science.gov (United States)

    McCord, T. B.; Zambon, F.

    2017-12-01

    Ceres' surface composition is of special interest because it is a window into the interior state and the past evolution of this dwarf planet. Disk-integrated telescopic spectral observations indicated that Ceres' surface is hydroxylated, similar to but not exactly the same as some of the carbonaceous chondrite classes of meteorites. Furthermore, Ceres' bulk density is low, indicating significant water content. The Dawn mission in orbit around Ceres, provided a new and larger set of observations on the mineralogy, molecular and elemental composition, and their distributions in association with surface features and geology. A set of articles was prepared, from which this presentation is derived, that is the first treatment of the entire surface composition of Ceres using the complete High Altitude Mapping Orbit (HAMO) Dawn Ceres data set and the calibrations from all the Dawn instruments. This report provides a current and comprehensive view of Ceres' surface composition and integrates them into general conclusions. Ceres' surface composition shows a fairly uniform distribution of NH4- and Mg-phyllosilicates, carbonates, mixed with a dark component. The widespread presence of phyllosilicates, and salts on Ceres' surface is indicative of the presence of aqueous alteration processes, which involved the whole dwarf planet. There is also likely some contamination by low velocity infall, as seen on Vesta, but it is more difficult to distinguish this infall from native Ceres material, unlike for the Vesta case.

  19. Mid-IR Spectra of Refractory Minerals Relevant to Comets

    Science.gov (United States)

    Jauhari, Shekeab

    2008-09-01

    On 4 July 2005 the Spitzer Space Telescope obtained mid-IR ( 5-40 µm) spectra of the ejecta from the hypervelocity impact of the Deep Impact projectile with comet 9P/Tempel 1. Spectral modeling demonstrates that there are abundant minerals present in the ejecta including Ca/Fe/Mg-rich silicates, carbonates, phyllosilicates, water ice, amorphous carbon, and sulfides [1]. However, precise mineralogical identifications are hampered by the lack of comprehensive 5 - 40 µm spectral measurements of the emissivity for a broad compositional range of these materials. Here, we present our initial results for 2 - 50 µm transmission spectra and absorption constants for materials relevant to comets, including pyrrhotite, pyrite, and several phyllosilicate (clay) minerals. Measuring the transmission of materials over the full spectral range sensitive by Spitzer requires grinding the minerals into submicron powders and then mixing them with KBr (for the 1-25 um region) and polyethylene (16-50 um region) to form pellets. Transmission measurements of sub-micron sulfides are particularly difficult to obtain because the minerals oxidize rapidly upon grinding and subsequent handling unless special care is taken. A detailed description of our sample preparation and measurement technique will be provided to assist other researchers in their attempts to acquire similar spectra. References: [1] Lisse, C.M. et al., Science 313, 635 - 640 (2006)

  20. Zeolites on Mars: Possible environmental indicators in soils and sediments

    International Nuclear Information System (INIS)

    Ming, D.W.; Gooding, J.L.

    1988-01-01

    Weathering products should serve as indicators of weathering environments and may provide the best evidence of the nature of climate change on Mars. No direct mineralogical measurements of Martian regolith were performed by the Viking missions, but the biology and X-ray fluorescence experiments provided some information on the physiochemical properties of Martian regolith. Most post-Viking studies of candidate weathering products have emphasized phyllosilicates and Fe-oxides; zeolites are potentially important, but overlooked, candidate Martian minerals. Zeolites would be important on Mars for three different reasons. First, they are major sinks of atmospheric gases and, per unit mass, are stronger and more efficient sorbents than are phyllosilicates. Secondly, they can be virtually unique sorbents and shelters for organic compounds and possible catalysts for organic-based reactions. Finally, their exchangeable ions are good indicators of the chemical properties of solutions with which they have communicated. Accordingly, the search for information on past compositions of the Martian atmosphere and hydrosphere should find zeolites to be rich repositories

  1. Visible and Near-IR Reflectance Spectra for Smectite, Sulfate And Perchlorate under Dry Conditions for Interpretation of Martian Surface Mineralogy

    Science.gov (United States)

    Morris, R.V.; Ming, W.; Golden, D.C.; Arvidson, R.E.; Wiseman, S.M.; Lichtenberg, K.A.; Cull, S.; Graff, T.G.

    2009-01-01

    Visible and near-IR (VNIR) spectral data for the martian surface obtained from orbit by the MRO-CRISM and OMEGA instruments are interpreted as having spectral signatures of H2O/OH-bearing phases, including smectites and other phyllosilicates, sulfates, and high-SiO2 phases [e.g., 1-4]. Interpretations of martian spectral signatures are based on and constrained by spectra that are obtained in the laboratory on samples with known mineralogical compositions and other physicochemical characteristics under, as appropriate, Mars-like environmental conditions (e.g., temperature, pressure, and humidity). With respect to environmental conditions, differences in the absolute concentration of atmospheric H2O can effect the hydration state and therefore the spectra signatures of smectite phyllosilicates (solvation H2O) and certain sulfates (hydration H2O) [e.g., 5-7]. We report VNIR spectral data acquired under humid (laboratory air) and dry (dry N2 gas) environments for two natural smectites (nontronite API-33A and saponite SapCa-1) to characterize the effect of solvation H2O on spectral properties. We also report spectral data for the thermal dehydration products of (1) melanterite (FeSO4.7H2O) in both air and dry N2 gas and (2) Mg-perchlorate (Mg(ClO4)2.6H2O) in dry N2 environments. Spectral measurements for samples dehydrated in dry N2 were made without exposing them to humid laboratory air.

  2. Elemental and isotopic (Si-{sup 29} and O-{sup 18}) tracing of glass alteration mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Verney-Carron, A.; Libourel, G.; Deloule, E. [CNRS, Ctr Rech Petrog and Geochim, UPR 2300, F-54501 Vandoeuvre Les Nancy (France); Valle, N. [Ctr Rech Publ Gabriel Lippmann, Dept Sci and Anal Mat, L-4422 Belvaux (Luxembourg); Sterpenich, J. [Univ H Poincare, G2R, CNRS, UMR 7566, F-54501 Vandoeuvre Les Nancy (France); Jollivet, P. [CEA Marcoule, DEN, Lab Comportement Long Terme, F-30207 Bagnols Sur Ceze (France)

    2010-07-01

    To better understand glass alteration mechanisms, especially alteration layers formation, leaching experiments of a borosilicate glass (SON68) doped with a different rare earth element (La, Ce, or Nd) with solutions rich in {sup 29}Si and {sup 18}O were carried out. The coupled analyses of glass, alteration products, and solution led to a complete elemental and isotopic ({sup 29}Si and {sup 18}O) budget. They revealed different behaviours of elements that depend not only on their structural role in the glass, but also on their affinity for alteration products (gel, phyllosilicates, phosphates). However, analyses of both glass and solution are not sufficient to describe the real exchanges occurring between glass and solution. The use of {sup 29}Si and {sup 18}O tracers gives new insights on the formation of alteration layers. During alteration the phyllosilicates records the isotopic variations of the leaching solution. Their isotopic signatures highlight a mechanism of dissolution/precipitation, which implies equilibrium between the secondary phases and the solution. On the other hand the gel isotopic signature, that is intermediate between the glass and the solution, substantiates the hypothesis that the gel is formed by hydrolysis/condensation reactions. This mechanism can thus explain the influence of the gel formation conditions (alteration conditions, solution saturation) on the structure (reorganisation) and texture (porosity) of this layer and on its protective effect. These hydrolysis/condensation reactions are also certainly involved in the aluminosilicate glass alteration and in the formation of palagonite. (authors)

  3. Oxo Crater on (1) Ceres: Geological History and the Role of Water-ice

    Energy Technology Data Exchange (ETDEWEB)

    Nathues, A.; Platz, T.; Hoffmann, M.; Thangjam, G.; Le Corre, L.; Reddy, V. [Max Planck Institute for Solar System Research, Justus-von-Liebig-Weg 3, D-37077 Goettingen (Germany); Cloutis, E. A.; Applin, D. M. [University of Winnipeg, Winnipeg, MB R3B 2E9 (Canada); Mengel, K. [IELF, TU Clausthal, Adolph-Roemer-Straße 2A, D-38678 Clausthal-Zellerfeld (Germany); Protopapa, S. [University of Maryland, Department of Astronomy, College Park, MD 20742 (United States); Takir, D. [SETI Institute, Mountain View, CA 94043 (United States); Preusker, F. [German Aerospace Center (DLR), Institute of Planetary Research, D-12489 Berlin (Germany); Schmidt, B. E. [Georgia Institute of Technology, Atlanta, GA (United States); Russell, C. T., E-mail: nathues@mps.mpg.de [Institute of Geophysics and Planetary Physics, Dept. of Earth, Planetary and Space Sciences, University of California Los Angeles, Los Angeles, CA (United States)

    2017-09-01

    Dwarf planet Ceres (∅ ∼ 940 km) is the largest object in the main asteroid belt. Investigations suggest that Ceres is a thermally evolved, volatile-rich body with potential geological activity, a body that was never completely molten, but one that possibly partially differentiated into a rocky core and an ice-rich mantle, and may contain remnant internal liquid water. Thermal alteration and the infall of exogenic material contribute to producing a (dark) carbonaceous chondritic-like surface containing ammoniated phyllosilicates. Here we report imaging and spectroscopic analyses of data on the bright Oxo crater derived from the Framing Camera and the Visible and Infrared Spectrometer on board the Dawn spacecraft. We confirm that the transitional complex crater Oxo (∅ ∼ 9 km) exhibits exposed surface water-ice. We show that this water-ice-rich material is associated exclusively with two lobate deposits at pole-facing scarps, deposits that also contain carbonates and admixed phyllosilicates. Due to Oxo’s location at −4802 m below the cerean reference ellipsoid and its very young age of only 190 ka (1 σ : +100 ka, −70 ka), Oxo is predestined for ongoing water-ice sublimation.

  4. R7T7 glass alteration mechanism in an aqueous closed system: understanding and modelling the long term alteration kinetic

    International Nuclear Information System (INIS)

    Chave, T.

    2007-10-01

    The long term alteration rate of the French R7T7 nuclear glass has been investigated since many years because it will define the overall resistance of the radionuclide containment matrix. Recent studies have shown that the final rate remains constant or is slightly decreasing with time. It never reaches zero. Though this residual rate is very low, only 5 nm per year at 50 C, it would be the dominant alteration phenomenon in a geological repository. Two mechanisms are suggested for explaining such behaviour: diffusion in solution of elements from glass through an amorphous altered layer and precipitation of neo-formed phases. The diffusion processes are in agreement with a solid state diffusion mechanism and can lead to secondary phase precipitation due to solution concentration increases. Observed phases are mainly phyllosilicates and zeolites, in specific conditions. Phyllosilicates are expected to maintain the residual kinetic rate whereas alteration resumption could be observed in presence of zeolites at very high pH or temperature (10.5 at 90 C or temperature above 150 C). Both diffusion and neo-formed phase precipitation have been investigated in order to better understand their impact on the residual alteration rate and have then been modelled by a calculation code, coupling chemistry and transport, in order to be able to better anticipate the long term behaviour of the glass R7T7 in an aqueous closed system. (author)

  5. Identification of Zn-Bearing Micas and Clays from the Cristal and Mina Grande Zinc Deposits (Bongará Province, Amazonas Region, Northern Peru

    Directory of Open Access Journals (Sweden)

    Giuseppe Arfè

    2017-11-01

    Full Text Available Zn-bearing phyllosilicates are common minerals in nonsulfide Zn deposits, but they seldom represent the prevailing economic species. However, even though the presence of Zn-bearing clays is considered as a disadvantage in mineral processing, their characteristics can give crucial information on the genesis of the oxidized mineralization. This research has been carried out on the Mina Grande and Cristal Zn-sulfide/nonsulfide deposits, which occur in the Bongará district (Northern Peru. In both of the deposits, Zn-bearing micas and clays occur as an accessory to the ore minerals. The XRD analyses and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS investigations revealed that the Zn-bearing micas that are occurring in both deposits mostly consist of I/S mixed layers of detrital origin, which have been partly altered or overprinted by sauconite during the supergene alteration of sulfides. Sporadic hendricksite was also identified in the Cristal nonsulfide mineral assemblage, whereas at Mina Grande, the fraipontite-zaccagnaite (3R-polytype association was detected. The identified zaccagnaite polytype suggests that both fraipontite and zaccagnaite are genetically related to weathering processes. The hendricksite detected at Cristal is a product of hydrothermal alteration, which is formed during the emplacement of sulfides. The complex nature of the identified phyllosilicates may be considered as evidence of the multiple processes (hydrothermal and supergene that occurred in the Bongará district.

  6. Mineralogy of the clay fraction of soils from the moray cusco archaeological site: a study by energy dispersive X-ray fluorescence, X-ray diffractometry and Mössbauer spectroscopy

    International Nuclear Information System (INIS)

    Cerón Loayza, María L.; Bravo Cabrejos, Jorge A.; Mejía Santillán, Mirian E.

    2011-01-01

    The purpose of this work is to report the advances in the elemental and structural characterization of the clay fraction of soils from the terraces of the Moray Archaeological site, located 38 km north of the city of Cusco, Cusco Region. One sample was collected from each of the twelve terraces of this site and its clay fraction was separated by sedimentation. Previously the pH of the raw samples was measured resulting that all of the samples were from alkaline to strongly alkaline. Energy dispersive X-ray fluorescence (EDXRF) was used for the elemental characterization, and X-ray diffractometry (XRD) and transmission Mössbauer spectroscopy (TMS), using the γ 14.4 keV nuclear resonance transition in 57 Fe, were used for the structural characterization of the clays and clay minerals present in each sample. The EDXRF analyses of all the samples show the presence of relatively high concentrations of sulfur in some of the samples and relatively high concentrations of calcium in all of the samples, which may be related to the high alkalinity of the samples. By XRD it is observed the presence of quartz, calcite, gypsum, cronstedtite, 2:1 phyllosilicates, and iron oxides. The mineralogical analysis of Fe by TMS shows that it is present in the form of hematite and occupying Fe 2 +  and Fe 3 +  sites in phyllosilicates, cronstedtite, and other minerals not yet identified.

  7. Mineralogy of the clay fraction of soils from the moray cusco archaeological site: a study by energy dispersive X-ray fluorescence, X-ray diffractometry and Moessbauer spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ceron Loayza, Maria L., E-mail: malucelo@hotmail.com; Bravo Cabrejos, Jorge A.; Mejia Santillan, Mirian E. [Universidad Nacional Mayor de San Marcos, Laboratorio de Analisis de Suelos, Laboratorio de Espectroscopia Moessbauer, Facultad de Ciencias Fisicas (Peru)

    2011-11-15

    The purpose of this work is to report the advances in the elemental and structural characterization of the clay fraction of soils from the terraces of the Moray Archaeological site, located 38 km north of the city of Cusco, Cusco Region. One sample was collected from each of the twelve terraces of this site and its clay fraction was separated by sedimentation. Previously the pH of the raw samples was measured resulting that all of the samples were from alkaline to strongly alkaline. Energy dispersive X-ray fluorescence (EDXRF) was used for the elemental characterization, and X-ray diffractometry (XRD) and transmission Moessbauer spectroscopy (TMS), using the {gamma} 14.4 keV nuclear resonance transition in {sup 57}Fe, were used for the structural characterization of the clays and clay minerals present in each sample. The EDXRF analyses of all the samples show the presence of relatively high concentrations of sulfur in some of the samples and relatively high concentrations of calcium in all of the samples, which may be related to the high alkalinity of the samples. By XRD it is observed the presence of quartz, calcite, gypsum, cronstedtite, 2:1 phyllosilicates, and iron oxides. The mineralogical analysis of Fe by TMS shows that it is present in the form of hematite and occupying Fe{sup 2 + } and Fe{sup 3 + } sites in phyllosilicates, cronstedtite, and other minerals not yet identified.

  8. R7T7 glass alteration mechanism in an aqueous closed system: understanding and modelling the long term alteration kinetic; Etude des mecanismes d'alteration par l'eau du verre R7T7 en milieu confine: comprehension et modelisation de la cinetique residuelle

    Energy Technology Data Exchange (ETDEWEB)

    Chave, T

    2007-10-15

    The long term alteration rate of the French R7T7 nuclear glass has been investigated since many years because it will define the overall resistance of the radionuclide containment matrix. Recent studies have shown that the final rate remains constant or is slightly decreasing with time. It never reaches zero. Though this residual rate is very low, only 5 nm per year at 50 C, it would be the dominant alteration phenomenon in a geological repository. Two mechanisms are suggested for explaining such behaviour: diffusion in solution of elements from glass through an amorphous altered layer and precipitation of neo-formed phases. The diffusion processes are in agreement with a solid state diffusion mechanism and can lead to secondary phase precipitation due to solution concentration increases. Observed phases are mainly phyllosilicates and zeolites, in specific conditions. Phyllosilicates are expected to maintain the residual kinetic rate whereas alteration resumption could be observed in presence of zeolites at very high pH or temperature (10.5 at 90 C or temperature above 150 C). Both diffusion and neo-formed phase precipitation have been investigated in order to better understand their impact on the residual alteration rate and have then been modelled by a calculation code, coupling chemistry and transport, in order to be able to better anticipate the long term behaviour of the glass R7T7 in an aqueous closed system. (author)

  9. Mineral Trends in Early Hesperian Lacustrine Mudstone at Gale Crater, Mars

    Science.gov (United States)

    Rampe, E. B.; Ming, D. W.; Grotzinger, J. P.; Morris, R. V.; Blake, D. F.; Vaniman, D. T.; Bristow, T. F.; Morrison, S. M.; Yen, A. S.; Chipera, S. J.; hide

    2017-01-01

    The Mars Science Laboratory Curiosity rover landed in Gale crater in August 2012 to study the layered sediments of lower Aeolis Mons (i.e., Mount Sharp), which have signatures of phyllosilicates, hydrated sulfates, and iron oxides in orbital visible/near-infrared observations. The observed mineralogy within the stratigraphy, from phyllosilicates in lower units to sulfates in higher units, suggests an evolution in the environments in which these secondary phases formed. Curiosity is currently investigating the sedimentary structures, geochemistry, and mineralogy of the Murray formation, the lowest exposed unit of Mount Sharp. The Murray formation is dominated by laminated lacustrine mudstone and is approx.200 m thick. Curiosity previously investigated lacustrine mudstone early in the mission at Yellowknife Bay, which represents the lowest studied stratigraphic unit. Here, we present the minerals identified in lacus-trine mudstone from Yellowknife Bay and the Murray formation. We discuss trends in mineralogy within the stratigraphy and the implications for ancient lacustrine environments, diagenesis, and sediment sources.

  10. On crystallization of polypropylene on atomically flat silicate substrate and relationship to mechanical properties

    International Nuclear Information System (INIS)

    Huang, H.Z.; Yuan, Q.; Misra, R.D.K.

    2011-01-01

    Research highlights: → Phyllosilicate was used to probe the nucleation and chain organization in thin films. → Crystal morphology was altered from leaf-like structure to fully developed spherulites. → The lamellae structure changed from well-oriented to cross-hatched implying epitaxial growth. → The good interfacial bonding favored by epitaxial crystallization is beneficial for toughness. - Abstract: Phyllosilicates including mica offer one of the easiest methods to obtain atomically flat surface of macroscopic size by cleavage. Thus, thin films of polypropylene crystallized at different pressure and as a function of polypropylene concentration were investigated. The objective was to probe the nucleation and chain organization in thin films on basal plane surface from the view point of relating the nucleation and growth process to the intergallery space between the clay layers. The crystal morphology was altered from leaf-like structure at high undercooling to fully developed spherulites at low undercooling. Furthermore, the lamellae structure change from well-oriented to cross-hatched with increase in the crystallization pressure was indicative of epitaxial growth between polymer matrix and mica surface. The possible epitaxial mechanism is discussed here. The study provides a method to explore the macro- and microstructure of polymer and epitaxy between polymer matrix and inorganic particle surface. The good interfacial bonding favored by epitaxial crystallization is beneficial for toughness.

  11. Alteration of Basaltic Glass to Mg/Fe-Smectite under Acidic Conditions: A Potential Smectite Formation Mechanism on Mars

    Science.gov (United States)

    Peretyazhko, Tanya; Sutter, Brad; Ming, Douglas W.

    2014-01-01

    Phyllosilicates of the smectite group including Mg- and Fe-saponite and Fe(III)-rich nontronite have been identified on Mars. Smectites are believed to be formed under neutral to alkaline conditions that prevailed on early Mars. This hypothesis is supported by the observation of smectite and carbonate deposits in Noachian terrain on Mars. However, smectite may have formed under mildly acidic conditions. Abundant smectite formations have been detected as layered deposits hundreds of meters thick in intracrater depositional fans and plains sediments, while no large deposits of carbonates are found. Development of mildly acidic conditions at early Mars might allow formation of smectite but inhibit widespread carbonate precipitation. Little is known regarding the mechanisms of smectite formation from basaltic glass under acidic conditions. The objective of this study was to test a hypothesis that Mars-analogue basaltic glass alters to smectite minerals under acidic conditions (pH 4). The effects of Mg and Fe concentrations and temperature on smectite formation from basaltic glass were evaluated. Phyllosilicate synthesis was performed in batch reactors (Parr acid digestion vessel) under reducing hydrothermal conditions at 200 C and 100 C. Synthetic basaltic glass with a composition similar to that of the Gusev crater rock Adirondack (Ground surface APXS measurement) was used in these experiments. Basaltic glass was prepared by melting and quenching procedures. X-ray diffraction (XRD) analysis indicated that the synthesized glass was composed of olivine, magnetite and X-ray amorphous phase. Samples were prepared by mixing 250 mg Adirondack with 0.1 M acetic acid (final pH 4). In order to study influence of Mg concentration on smectite formation, experiments were performed with addition of 0, 1 and 10 mM MgCl2. After 1, 7 and 14 day incubations the solution composition was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the altered glass and formed

  12. Insights into fluid flow and environmental conditions present in deep-sea hydrothermal vent deposits from measurements of permeability and porosity

    Science.gov (United States)

    Gribbin, J. L.; Zhu, W.; Tivey, M. K.

    2008-12-01

    Evolution of permeability-porosity relationships (EPPRs) of different seafloor vent deposit sample types provide crucial information about how fluid flows within the deposits. In this study, we conducted permeability and porosity measurements on a wide range of vent sample types recovered from many different active seafloor vent fields. The sample set includes chalcopyrite-lined black smoker chimneys, Zn-rich diffusing spires (including white smokers), flanges/slabs/crusts (i.e., plate-like deposits that overlie pooled fluid), massive anhydrite, and cores recovered from the sides of vent structures. Using a probe permeameter, permeability measurements were systematically taken of each sample along several orientations. The measured permeability ranges over 6 orders of magnitude from 10-14 to 10-8 m2. Our data indicate that in general massive anhydrite samples are the least permeable with a mean at ~10-13 m2 and the samples from Zn-rich diffusing spires that were actively venting when collected are the most permeable with a mean at ~10-11 m2. With a mean at 10-11.5 m2, permeability data of flanges/slabs/crusts span over 4 orders of magnitude from 10-13 to 10-9 m2, the largest spread among all sample types tested. Permeability values of the outer portions of relict spires, ranging from ~10-13 m2 to 10-9.5 m2, displayed clear anisotropic trends: permeability along the radial directions is higher than that along the axial direction. Black smokers exhibit a strong layered heterogeneity, where inner chalcopyrite linings were significantly less permeable than outermost layers. To conduct porosity and directional permeability measurements, cylindrical cores will be taken from these vent samples. We will examine whether different sample types, or portions of samples, exhibit distinct permeability-porosity relationships, and will then use micro-structural observations of the cores to examine chimney growth processes (e.g., mineral deposition or cracking) that likely result

  13. Variation of mineralogy and organic material during the early stages of aqueous activity recorded in Antarctic micrometeorites

    Science.gov (United States)

    Noguchi, T.; Yabuta, H.; Itoh, S.; Sakamoto, N.; Mitsunari, T.; Okubo, A.; Okazaki, R.; Nakamura, T.; Tachibana, S.; Terada, K.; Ebihara, M.; Imae, N.; Kimura, M.; Nagahara, H.

    2017-07-01

    Micrometeorites (MMs) recovered from surface snow near the Dome Fuji Station, Antarctica are almost free from terrestrial weathering and contain very primitive materials, and are suitable for investigation of the evolution and interaction of inorganic and organic materials in the early solar system. We carried out a comprehensive study on seven porous and fluffy MMs [four Chondritic porous (CP) MMs and three fluffy fine-grained (Fluffy Fg) MMs] and one fine-grained type 1 (Fg C1) MM for comparison with scanning electron microscope, transmission electron microscope, X-ray absorption near-edge structure analysis, and secondary ion mass spectrometer. They show a variety of early aqueous activities. Four out of the seven CP MMs contain glass with embedded metal and sulfide (GEMS) and enstatite whiskers/platelets and do not have hydrated minerals. Despite the same mineralogy, organic chemistry of the CP MMs shows diversity. Two of them contain considerable amounts of organic materials with high carboxyl functionality, and one of them contains nitrile (Ctbnd N) and/or nitrogen heterocyclic groups with D and 15N enrichments, suggesting formation in the molecular cloud or a very low temperature region of the outer solar system. Another two CP MMs are poorer in organic materials than the above-mentioned MMs. Organic material in one of them is richer in aromatic C than the CP MMs mentioned above, being indistinguishable from those of hydrated carbonaceous chondrites. In addition, bulk chemical compositions of GEMS in the latter organic poor CP MMs are more homogeneous and have higher Fe/(Si + Mg + Fe) ratios than those of GEMS in the former organic-rich CP MMs. Functional group of the organic materials and amorphous silicate in GEMS in the organic-poor CP MMs may have transformed in the earliest stage of aqueous alteration, which did not form hydrated minerals. Three Fluffy Fg MMs contain abundant phyllosilicates, showing a clear evidence of aqueous alteration

  14. An in-situ X-ray diffraction study on the electrochemical formation of PtZn alloys on Pt(1 1 1) single crystal electrode

    Energy Technology Data Exchange (ETDEWEB)

    Drnec, J., E-mail: drnec@esrf.fr [ESRF, Grenoble (France); Bizzotto, D. [Department of Chemistry, AMPEL, University of British Columbia, Vancouver, BC (Canada); Carlà, F. [ESRF, Grenoble (France); Fiala, R. [Charles University, Faculty of Mathematics and Physics, Prague (Czech Republic); Sode, A. [Ruhr-Universität Bochum, Bochum (Germany); Balmes, O.; Detlefs, B.; Dufrane, T. [ESRF, Grenoble (France); Felici, R., E-mail: felici@esrf.fr [ESRF, Grenoble (France)

    2015-11-01

    Highlights: • PtZn electrochemical alloying is observed on single crystal Pt electrodes. • In-situ X-ray characterization during alloy formation and dissolution is provided. • Structural model of the surface during alloying and dissolution is discussed. • X-ray based techniques can be used in in-operando studies of bimetallic fuel cell catalysts. - Abstract: The electrochemical formation and dissolution of the oxygen reduction reaction (ORR) PtZn catalyst on Pt(1 1 1) surface is followed by in-situ X-ray diffraction (XRD) and X-ray reflectivity (XRR) measurements. When the crystalline Pt surface is polarized to sufficiently negative potential values, with respect to an Ag/AgCl|KCl reference electrode, the electrodeposited zinc atoms diffuse into the bulk and characteristic features are observed in the X-ray patterns. The surface structure and composition during deposition and dissolution is determined from analysis of XRR curves and measurements of crystal truncation rods. Thin Zn-rich surface layer is present during the alloy formation while a Zn-depleted layer forms during dissolution.

  15. Synthesis of (Ga 1–x Zn x )(N 1–x O x ) with Enhanced Visible-Light Absorption and Reduced Defects by Suppressing Zn Volatilization

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Dennis P.; Skrabalak, Sara E.

    2016-04-18

    (Ga1–x)(N1–x O x) (GZNO) particles with enhanced optical absorption were synthesized by topotactic transformation of Zn2+/Ga3+ layered double hydroxides. This outcome was achieved by suppressing Zn volatilization during nitridation by maintaining a low partial pressure of O2 (pO2). Zn-rich (x > 1/3) variants of GZNO were achieved and compared to those prepared by conventional ammonoylsis conditions. The optical absorption and structural properties of these samples were compared to those prepared in the absence of O2 by diffuse-reflectance spectroscopy and powder X-ray diffraction methods. Notably, suppression of Zn volatilization leads to smaller-band-gap materials (2.30 eV for x = 0.42 versus 2.71 eV for x = 0.21) and reduced structural defects. This synthetic route and set of characterizations provide useful structure–property studies of GZNO and potentially other oxynitrides of interest as photocatalysts.

  16. Structure and optical properties of cored wurtzite (Zn,Mg)O heteroepitaxial nanowires

    International Nuclear Information System (INIS)

    Heo, Y.W.; Abernathy, C.; Pruessner, K.; Sigmund, W.; Norton, D.P.; Overberg, M.; Ren, F.; Chisholm, M.F.

    2004-01-01

    The synthesis, structure, and optical properties of one-dimensional heteroepitaxial cored (Zn,Mg)O semiconductor nanowires grown by a catalyst-driven molecular beam epitaxy technique are discussed. The structures form spontaneously in a Zn, Mg and O 2 /O 3 flux, consisting of a single crystal, Zn-rich Zn 1-x Mg x O(x 1-y Mg y O(y>>0.02) sheath. High resolution Z-contrast scanning transmission electron microscopy shows core diameters as small as 4 nm. The cored structure forms spontaneously under constant flux due to a bimodal growth mechanism in which the core forms via bulk like vapor-liquid-solid growth, while the outer sheath grows as a heteroepitaxial layer. Temperature-dependent photoluminescence shows a slight blueshift in the near band edge peak, which is attributed to a few percent Mg doping in the nanoscale ZnO core. The catalyst-driven molecular beam epitaxy technique provides for site-specific nanorod growth on arbitrary substrates

  17. Tuning the nanostructures and optical properties of undoped and N-doped ZnO by supercritical fluid treatment

    Science.gov (United States)

    Li, Yaping; Wang, Hui-Qiong; Chu, Tian-Jian; Li, Yu-Chiuan; Li, Xiaojun; Liao, Xiaxia; Wang, Xiaodan; Zhou, Hua; Kang, Junyong; Chang, Kuan-Chang; Chang, Ting-Chang; Tsai, Tsung-Ming; Zheng, Jin-Cheng

    2018-05-01

    Treatment of ZnO films in a supercritical fluid (SCF) has been reported to improve the performance of devices in which the treated ZnO films are incorporated; however, the mechanism of this improvement remains unclear. In this paper, we study the transformation of the surface morphologies and emission properties of ZnO films before and after SCF treatment, establishing the relationship between the treated and untreated structures and thereby enabling tuning of the catalytic or opto-electronic performance of ZnO films or ZnO-film-based devices. Both undoped and N-doped ZnO nanostructures generated by SCF treatment of films are investigated using techniques to characterize their surface morphology (scanning electron microscopy (SEM) and atomic force microscopy (AFM)) as well as room-temperature photoluminescence (RT-PL) spectroscopy. The water-mixed supercritical CO2 (W-SCCO2) technology was found to form nanostructures in ZnO films through a self-catalyzed process enabled by the Zn-rich conditions in the ZnO films. The W-SCCO2 was also found to promote the inhibition of defect luminescence by introducing -OH groups onto the films. Two models are proposed to explain the effects of the treatment with W-SCCO2. This work demonstrates that the W-SCCO2 technology can be used as an effective tool for the nanodesign and property enhancement of functional metal oxides.

  18. Intrinsic point defects in off-stoichiometric Cu2ZnSnSe4: A neutron diffraction study

    Science.gov (United States)

    Gurieva, Galina; Valle Rios, Laura Elisa; Franz, Alexandra; Whitfield, Pamela; Schorr, Susan

    2018-04-01

    This work is an experimental study of intrinsic point defects in off-stoichiometric kesterite type CZTSe by means of neutron powder diffraction. We revealed the existence of copper vacancies (VCu), various cation anti site defects (CuZn, ZnCu, ZnSn, SnZn, and CuZn), as well as interstitials (Cui, Zni) in a wide range of off-stoichiometric polycrystalline powder samples synthesized by the solid state reaction. The results show that the point defects present in off-stoichiometric CZTSe agree with the off-stoichiometry type model, assuming certain cation substitutions accounting for charge balance. In addition to the known off-stoichiometry types A-H, new types (I-L) have been introduced. For the very first time, a correlation between the chemical composition of the CZTSe kesterite type phase and the occurring intrinsic point defects is presented. In addition to the off-stoichiometry type specific defects, the Cu/Zn disorder is always present in the CZTSe phase. In Cu-poor/Zn-rich CZTSe, a composition considered as the one that delivers the best photovoltaic performance, mainly copper vacancies, ZnCu and ZnSn anti sites are present. Also, this compositional region shows the lowest degree of Cu/Zn disorder.

  19. The influence of the precursor compositional ratio on Cu2ZnSnS4 films prepared by using sulfurization of the metallic precursor

    Science.gov (United States)

    Amal, Muhamad I.; Kim, Kyoo Ho

    2013-12-01

    Cu2ZnSnS4 (CZTS) films were prepared by using the sulfurization of sputtered metallic precursors. The compositional ratio of the CZTS films was slightly different compared to their initial metallic precursors due to elemental loss during annealing. The Cu/(Zn+Sn) ratio for the CZTS-1, CZTS-2 and CZTS-3 films were 0.91, 1.06 and 1.21, respectively. In addition, all films had a compositional ratio of Zn/Sn >1. The grain sizes of the CZTS films increased with increasing Cu ratio. X-ray diffraction and Raman spectroscopy showed that the CZTS films with an excess of copper and zinc had secondary phases of Cu2SnS3 and ZnS. The optical band gap and absorption coefficient for all CZTS films in the range of the experimental compositions were calculated to be 1.5 eV and >104 cm-1, respectively. The presence of secondary phases related to compositional ratio in the CZTS films influenced the electrical properties. The CZTS-1 film with a Cu-poor and Zn-rich composition whose a carrier concentration, an electrical mobility, and a resistivity values were 2.29 × 1018 cm-3, 10.29 cm2 V-1 s-1, 3.16 Ω cm, is the most suitable for solar-cell applications.

  20. Morphology and the structure of quasicrystal phase in as-cast and melt-spun Mg-Zn-Y-Zr alloys

    International Nuclear Information System (INIS)

    Tang, Y.L.; Zhao, D.S.; Shen, N.F.

    1993-01-01

    During recent years, many researchers have investigated the experimental and theoretical aspects of quasicrystal materials. In some Mg alloys (Mg 32 Al 17 Zn 32 , Mg 32 (Al,Zn) 49 , Mg 32 (Al,Zn,Cu) 49 , Mg 4 CuAl 6 and Ga 16 Mg 32 Zn 52 ), icosahedral quasicrystals (IQC) have been found. However, most of the quasicrystals in these alloys were formed under a rapid solidification condition. In the recent study on Mg-Zn-(Zr,Y) as-cast alloys, the authors identified a new Mg-rich and a Zn-rich IQC by X-ray diffraction (XRD) and electron microscopy (EM). The discovery of Mg-Zn-Y IQC is of interest because it formed in an as-cast ingot and did not contain the element Al, which is the major constituent of nearly all IQC forming alloys reported. Also, analyses on IQC in as-cast and RS Mg alloys with the composition have not previously been carried out. In this paper, TEM and XRD investigations were completed on IQC formed in a Mg-Zn-Y-Zr cast ingot and melt-spun ribbons for microstructure comparison

  1. Preparation and oxidation resistance of single crystalline β-Zn{sub 4}Sb{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Hong-xia; Deng, Shu-ping [Education Ministry Key Laboratory of Renewable Energy Advanced Materials and Manufacturing Technology, Yunnan Normal University, Kunming 650500 (China); Li, De-cong [Photoelectric Engineering College, Yunnan Open University, Kunming 650500 (China); Shen, Lan-xian; Cheng, Feng; Wang, Jin-song [Education Ministry Key Laboratory of Renewable Energy Advanced Materials and Manufacturing Technology, Yunnan Normal University, Kunming 650500 (China); Deng, Shu-kang, E-mail: skdeng@126.com [Education Ministry Key Laboratory of Renewable Energy Advanced Materials and Manufacturing Technology, Yunnan Normal University, Kunming 650500 (China)

    2016-11-01

    This study prepared a Zn-rich single crystal β-Zn{sub 4}Sb{sub 3} using a Sn flux method based on the stoichiometric ratios of Zn{sub 4.4}Sb{sub 3}Sn{sub 3}. The oxidation resistance of the sample was determined by exploring the effects of heat treatment in air on electrical transport properties and thermal stability, which is of practical importance in the application of the material at high temperatures. Results showed that the prepared sample possessed high electrical transport properties, with a high power factor of 1.67×10{sup −3} W m{sup −1} K{sup −2} at 563 K. The heat treatment in air weakened the electrical conductivity of the single crystalline β-Zn{sub 4}Sb{sub 3}, whereas the Seebeck coefficients were rarely independent of the annealing condition. Eventually, the power factor obtained after the first heating at 523 K for 4 h became comparable to that of the as-prepared sample, although it decreased after the second heating at 573 K for 5 h. Nevertheless, the single crystalline β-Zn{sub 4}Sb{sub 3} still possessed a good thermal stability after the heat treatment process.

  2. The effects of Pantoea sp. strain Y4-4 on alfalfa in the remediation of heavy-metal-contaminated soil, and auxiliary impacts of plant residues on the remediation of saline-alkali soils.

    Science.gov (United States)

    Li, Shuhuan; Wang, Jie; Gao, Nanxiong; Liu, Lizhu; Chen, Yahua

    2017-04-01

    The plant-growth-promoting rhizobacterium (PGPR) Y4-4 was isolated from plant rhizosphere soil and identified as Pantoea sp. by 16S rRNA sequence analysis. The effects of strain Y4-4 on alfalfa grown in heavy-metals-contaminated soil was investigated using a pot experiment. In a Cu-rich environment, the shoot dry mass and total dry mass of plants inoculated with strain Y4-4 increased by 22.6% and 21%, and Cu accumulation increased by 15%. In a Pb-Zn-rich environment, the shoot dry mass and total dry mass of plants inoculated with strain Y4-4 increased by 23.4% and 22%, and Zn accumulation increased by 30.3%. In addition, the salt tolerance and biomass of wheat seedlings could be improved by applying strain Y4-4 mixed with plant residue as a result of the Cu-rich plant residues providing copper nutrition to wheat. This study offers an efficient PGPR with strong salt tolerance and a safe strategy for the post-treatment of plant residue.

  3. Biosourced Polymetallic Catalysis: A Surprising and Efficient Means to Promote the Knoevenagel Condensation

    Directory of Open Access Journals (Sweden)

    Pierre-Alexandre Deyris

    2018-03-01

    Full Text Available Zn hyperaccumulator (Arabidobsis halleri and Zn accumulator Salix “Tordis” (Salix schwerinii × Salix viminalis have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore a novel methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the use of polymetallic salts derived from plants as bio-based catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FT-IR in order to precise the chemical composition, structure, and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to usual catalysts such as zinc (II chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis.

  4. Biosourced polymetallic catalysis: A surprising and efficient means to promote the Knoevenagel condensation

    Science.gov (United States)

    Deyris, Pierre-Alexandre; Bert, Valérie; Diliberto, Sébastien; Boulanger, Clotilde; Petit, Eddy; Legrand, Yves-Marie; Grison, Claude

    2018-03-01

    Zn hyperaccumulator (Arabidobsis halleri) and Zn accumulator Salix ‘Tordis’ (Salix schwerinii x S. viminalis) have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore an innovative methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the direct use of polymetallic salts derived from plants as “Lewis acid” catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, XRD, FT-IR in order to elucidate the chemical composition, structure and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to conventional catalysts such as zinc (II) chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis.

  5. Electrophoretic deposition of Cu2ZnSn(S0.5Se0.5)4 films using solvothermal synthesized nanoparticles

    Science.gov (United States)

    Badkoobehhezaveh, Amir Masoud; Abdizadeh, Hossein; Golobostanfard, Mohammad Reza

    2018-01-01

    In this paper, a simple, practical, and fast solvothermal route is presented for synthesizing the Cu2ZnSn(S0.5Se0.5)4 nanoparticles (CZTSSe). In this method, the precursors were dissolved in triethylenetetramine and placed in an autoclave at 240 °C for 1 h under controlled pressure and constant stirring. After washing the samples for several times with absolute ethanol, the obtained CZTSSe nanoparticles were successfully deposited on fluorine doped tin oxide substrates by convenient electrophoretic deposition (EPD) using colloidal nanoparticles. The most appropriate parameters for EPD of pre-synthesized CZTSSe nanoparticles which result in proper surface properties, controlled thickness, and high film quality are investigated by adjusting applied voltage, pH, and deposition time. X-ray diffraction pattern and Raman spectroscopy of the pre-synthesized nanoparticles show kesterite structure formation. The particle size of the CZTSSe nanoparticles is in the range of 100 to 400 nm and for some agglomerates, it is about 2 µm confirmed by scanning electron microscope. The deposited film with optimized parameter has acceptable quality without any crack in it with the thickness of about 4-5 µm. Energy-dispersive X-ray spectroscopy confirms that the chemical composition of the samples is in near stoichiometric Cu-poor and Zn-rich region, which guarantees the p-type character of the film. The diffuse reflectance spectroscopy also demonstrates that the optical band gap of the sample is about 1.2 eV.

  6. Cu{sub 2}ZnSnS{sub 4} thin film solar cells from electroplated precursors: Novel low-cost perspective

    Energy Technology Data Exchange (ETDEWEB)

    Ennaoui, A. [Helmholtz-Zentrum Berlin fuer Materialien und Energie GmbH, Solar Energy Division, Glienickerstrasse 100, D-14109 Berlin (Germany)], E-mail: ennaoui@helmholtz-berlin.de; Lux-Steiner, M.; Weber, A.; Abou-Ras, D.; Koetschau, I.; Schock, H.-W. [Helmholtz-Zentrum Berlin fuer Materialien und Energie GmbH, Solar Energy Division, Glienickerstrasse 100, D-14109 Berlin (Germany); Schurr, R.; Hoelzing, A.; Jost, S.; Hock, R. [Crystallography and Structural Physics, University of Erlangen-Nuernberg, Staudtstrasse 3, D-91058 Erlangen (Germany); Voss, T.; Schulze, J.; Kirbs, A. [Atotech Deutschland GmbH, Erasmusstr. 20, D-10553 Berlin (Germany)

    2009-02-02

    Thin-film solar cells based on Cu{sub 2}ZnSnS{sub 4} (CZTS) absorbers were fabricated successfully by solid-state reaction in H{sub 2}S atmosphere of electrodeposited Cu-Zn-Sn precursors. These ternary alloys were deposited in one step from a cyanide-free alkaline electrolyte containing Cu(II), Zn (II) and Sn (IV) metal salts on Mo-coated glass substrates. The solar cell was completed by a chemical bath-deposited CdS buffer layer and a sputtered i-ZnO/ZnO:Al bilayer. The best solar cell performance was obtained with Cu-poor samples. A total area (0.5 cm{sup 2}) efficiency of 3.4% is achieved (V{sub oc} = 563 mV, j{sub sc} = 14.8 mA/cm{sup 2}, FF = 41%) with a maximum external quantum efficiency (EQE) of 80%. The estimated band-gap energy from the external quantum efficiency (EQE) measurements is about 1.54 eV. Electron backscatter-diffraction maps of cross-section samples revealed CZTS grain sizes of up to 10 {mu}m. Elemental distribution maps of the CZTS absorber show Zn-rich precipitates, probably ZnS, and a Zn-poor region, presumably Cu{sub 2}SnS{sub 3}, close to the interface Mo/CZTS.

  7. Cu2ZnSnS4 thin film solar cells from electroplated precursors: Novel low-cost perspective

    International Nuclear Information System (INIS)

    Ennaoui, A.; Lux-Steiner, M.; Weber, A.; Abou-Ras, D.; Koetschau, I.; Schock, H.-W.; Schurr, R.; Hoelzing, A.; Jost, S.; Hock, R.; Voss, T.; Schulze, J.; Kirbs, A.

    2009-01-01

    Thin-film solar cells based on Cu 2 ZnSnS 4 (CZTS) absorbers were fabricated successfully by solid-state reaction in H 2 S atmosphere of electrodeposited Cu-Zn-Sn precursors. These ternary alloys were deposited in one step from a cyanide-free alkaline electrolyte containing Cu(II), Zn (II) and Sn (IV) metal salts on Mo-coated glass substrates. The solar cell was completed by a chemical bath-deposited CdS buffer layer and a sputtered i-ZnO/ZnO:Al bilayer. The best solar cell performance was obtained with Cu-poor samples. A total area (0.5 cm 2 ) efficiency of 3.4% is achieved (V oc = 563 mV, j sc = 14.8 mA/cm 2 , FF = 41%) with a maximum external quantum efficiency (EQE) of 80%. The estimated band-gap energy from the external quantum efficiency (EQE) measurements is about 1.54 eV. Electron backscatter-diffraction maps of cross-section samples revealed CZTS grain sizes of up to 10 μm. Elemental distribution maps of the CZTS absorber show Zn-rich precipitates, probably ZnS, and a Zn-poor region, presumably Cu 2 SnS 3 , close to the interface Mo/CZTS

  8. Preparation and photocatalytic activity of ZnO/Fe{sub 2}O{sub 3} nanotube composites

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yanjun; Sun, Li; Wu, Jiagen; Fang, Ting; Cai, Ran; Wei, Ang, E-mail: wei1177@126.com

    2015-04-15

    Highlights: • ZnO/Fe{sub 2}O{sub 3} tubular structure was prepared via photochemical deposition at RT. • The composites show a great improvement in photocatalytic characteristics. • The possible reasons of photocatalytic performance of composites were researched. • The formation mechanism of ZnO/Fe{sub 2}O{sub 3} tubular structure was discussed. - Abstract: Fe{sub 2}O{sub 3} nanoparticles were grown on ZnO nanorods (NRs) to form ZnO/Fe{sub 2}O{sub 3} nanotube (NT) composites via photochemical deposition under ultraviolet light irradiation at a room temperature. Fe{sup 3+} ions in the solution preferentially adhere to the metastable Zn-rich (0 0 0 1) polar surfaces in ZnO NRs, which leading to the formation of ZnO/Fe{sub 2}O{sub 3} NTs. ZnO/Fe{sub 2}O{sub 3} NT nanocomposites show a great improvement in photocatalytic characteristics compared with the bare ZnO NRs. It can be inferred that the enhanced photocatalytic performance of ZnO/Fe{sub 2}O{sub 3} is benefit from the synergistic effect of ZnO and Fe{sub 2}O{sub 3} semiconductors.

  9. Wetting and premelting of triple junctions and grain boundaries in the Al-Zn alloys

    International Nuclear Information System (INIS)

    Straumal, B.; Kogtenkova, O.; Protasova, S.; Mazilkin, A.; Zieba, P.; Czeppe, T.; Wojewoda-Budka, J.; Faryna, M.

    2008-01-01

    Phase transitions in grain boundaries (GBs) and GB triple junctions (TJs) can change drastically the properties of polycrystals. The GB and TJ wetting phase transition can occur in the two-phase area of the bulk phase diagram where the liquid and solid phases are in equilibrium. The GB and TJ wetting tie-lines can continue in one-phase area of the bulk phase diagram as a GB or TJ solidus line. This line represents the GB or TJ premelting phase transition. The structure and composition of grain boundaries and GB triple junctions were studied by high-resolution electron microscopy and analytical transmission electron microscopy in the Al-5 at.% Zn polycrystals and by differential scanning calorimetry (DSC) in the Al-7.5 at.% Zn polycrystals. Between bulk solidus and GB or TJ solidus the metastable Zn-rich β m -phase was observed in the GB triple junctions of quenched samples. This phase appears neither in the samples annealed above the bulk solidus nor in those annealed below the GB solidus. Zn-content in this β m -phase corresponds to that of bulk liquidus. This is a structural indication that if the melt wets the GBs or TJs, the GB (or TJ) solidus line appears in the bulk phase diagram, and the liquid-like phase exists in GBs and TJs between bulk solidus and GB (or TJ) solidus lines. The structural observation of this phase is also supported by our data obtained by means of DSC

  10. Preparation of Cu{sub 2}ZnSnS{sub 4} thin films by sulfurization of co-electroplated Cu-Zn-Sn precursors

    Energy Technology Data Exchange (ETDEWEB)

    Araki, Hideaki; Kubo, Yuki; Jimbo, Kazuo; Maw, Win Shwe; Katagiri, Hironori; Yamazaki, Makoto; Oishi, Koichiro; Takeuchi, Akiko [Nagaoka National College of Technology, 888 Nishikatakai, Nagaoka, Niigata 940-8532 (Japan)

    2009-05-15

    Cu{sub 2}ZnSnS{sub 4} (CZTS) thin films were prepared by sulfurization of electrodeposited Cu-Zn-Sn precursors. The Cu-Zn-Sn precursors were deposited on Mo-coated glass substrates in a one-step process from an electrolyte containing copper (II) sulfate pentahydrate, zinc sulfate heptahydrate, tin (II) chloride dehydrate and tri-sodium citrate dehydrate. The precursors were sulfurized by annealing with sulfur at temperatures of 580 C and 600 C in an N{sub 2} atmosphere. X-ray diffraction peaks attributable to CZTS were detected in the sulfurized films. Photovoltaic cells with the structure glass/Mo/CZTS/ CdS/ZnO:Al/Al were fabricated using the CZTS films by sulfurizing the electrodeposited precursors. The best photovoltaic cell performance was obtained with Zn-rich samples. An open-circuit voltage of 540 mV, a short-circuit current of 12.6 mA/cm{sup 2} and an efficiency of 3.16% were achieved. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  11. Zinc isotopic composition of particulate matter generated during the combustion of coal and coal + tire-derived fuels

    Science.gov (United States)

    Borrok, D.M.; Gieré, R.; Ren, M.; Landa, E.R.

    2010-01-01

    Atmospheric Zn emissions from the burning of coal and tire-derived fuel (TDF) for power generation can be considerable. In an effort to lay the foundation for tracking these contributions, we evaluated the Zn isotopes of coal, a mixture of 95 wt % coal + 5 wt % TDF, and the particulate matter (PM) derived from their combustion in a power-generating plant. The average Zn concentrations and δ(66)Zn were 36 mg/kg and 183 mg/kg and +0.24‰ and +0.13‰ for the coal and coal + TDF, respectively. The δ(66)Zn of the PM sequestered in the cyclone-type mechanical separator was the lightest measured, -0.48‰ for coal and -0.81‰ for coal+TDF. The δ(66)Zn of the PM from the electrostatic precipitator showed a slight enrichment in the heavier Zn isotopes relative to the starting material. PM collected from the stack had the heaviest δ(66)Zn in the system, +0.63‰ and +0.50‰ for the coal and coal + TDF, respectively. Initial fractionation during the generation of a Zn-rich vapor is followed by temperature-dependent fractionation as Zn condenses onto the PM. The isotopic changes of the two fuel types are similar, suggesting that their inherent chemical differences have only a secondary impact on the isotopic fractionation process.

  12. The effect of Ag and Ca additions on the age hardening response of Mg–Zn alloys

    International Nuclear Information System (INIS)

    Bhattacharjee, T.; Mendis, C.L.; Oh-ishi, K.; Ohkubo, T.; Hono, K.

    2013-01-01

    The effect of sole and combined additions of Ag and Ca in enhancing the age hardening response in a Mg–2.4Zn (at%) alloy have been studied by systematic microstructure investigations using transmission electron microscopy (TEM) and three dimensional atom probe (3DAP). In the early aging stage of a Mg–2.4Zn–0.1Ag–0.1Ca (at%) alloy at 160 °C, Zn-rich Guinier Preston (G.P.) zones form with Ag and Ca enrichment. Further aging lead to the formation of fine β′ 1 precipitates with Ag and Ca enrichment. We confirmed that the G.P. zones do not form in the Mg–2.4Zn (at%) binary alloy at 160 °C, but form after a prolonged aging at 70 °C. This suggests that the combined addition of Ag and Ca shifts the metastable solvus for the G.P. zones to a higher temperature, thereby making it possible to form G.P. zones even at the artificial aging temperature of 160 °C. Since G.P. zones act as nucleation sites for the β′ 1 precipitates, the peak-aged microstructure is refined substantially by the addition of Ag and Ca

  13. ZnO Nanowires Synthesized by Vapor Phase Transport Deposition on Transparent Oxide Substrates

    Directory of Open Access Journals (Sweden)

    Taylor Curtis

    2010-01-01

    Full Text Available Abstract Zinc oxide nanowires have been synthesized without using metal catalyst seed layers on fluorine-doped tin oxide (FTO substrates by a modified vapor phase transport deposition process using a double-tube reactor. The unique reactor configuration creates a Zn-rich vapor environment that facilitates formation and growth of zinc oxide nanoparticles and wires (20–80 nm in diameter, up to 6 μm in length, density <40 nm apart at substrate temperatures down to 300°C. Electron microscopy and other characterization techniques show nanowires with distinct morphologies when grown under different conditions. The effect of reaction parameters including reaction time, temperature, and carrier gas flow rate on the size, morphology, crystalline structure, and density of ZnO nanowires has been investigated. The nanowires grown by this method have a diameter, length, and density appropriate for use in fabricating hybrid polymer/metal oxide nanostructure solar cells. For example, it is preferable to have nanowires no more than 40 nm apart to minimize exciton recombination in polymer solar cells.

  14. Effect of nano Ni additions on the structure and properties of Sn-9Zn and Sn-Zn-3Bi solders in Au/Ni/Cu ball grid array packages

    Energy Technology Data Exchange (ETDEWEB)

    Gain, Asit Kumar [Department of Electronic Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong (Hong Kong); Chan, Y.C. [Department of Electronic Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong (Hong Kong)], E-mail: eeycchan@cityu.edu.hk; Yung, Winco K.C. [Department of Industrial and Systems Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon (Hong Kong)

    2009-05-25

    The effect of nano Ni additions in Sn-9Zn and Sn-8Zn-3Bi solders on their interfacial microstructures and shear loads with Au/Ni/Cu pad metallization in ball grid array (BGA) applications were investigated. After the addition of nano Ni powder in Sn-based lead-free solders, there were no significant changes in the interfacial microstructure. But, in the solder region a very fine Zn-rich phase was observed. Also on the fracture surfaces a fine Zn-Ni compound was found. After the addition of nano Ni powder in Sn-based solders, the shear loads were increased due to a refinement of the microstructure and in addition, ductile fracture surfaces were clearly observed. The shear loads of the plain Sn-9Zn and Sn-8Zn-3Bi solders after one reflow cycle were about 1798 g and 2059 g, respectively. After the addition of nano Ni powder, their loads were about 2172 g and 2212 g, respectively, after one reflow cycle and their shear loads after eight reflow cycles were about 2099 g and 2081 g, respectively.

  15. Effect of nano Ni additions on the structure and properties of Sn-9Zn and Sn-Zn-3Bi solders in Au/Ni/Cu ball grid array packages

    International Nuclear Information System (INIS)

    Gain, Asit Kumar; Chan, Y.C.; Yung, Winco K.C.

    2009-01-01

    The effect of nano Ni additions in Sn-9Zn and Sn-8Zn-3Bi solders on their interfacial microstructures and shear loads with Au/Ni/Cu pad metallization in ball grid array (BGA) applications were investigated. After the addition of nano Ni powder in Sn-based lead-free solders, there were no significant changes in the interfacial microstructure. But, in the solder region a very fine Zn-rich phase was observed. Also on the fracture surfaces a fine Zn-Ni compound was found. After the addition of nano Ni powder in Sn-based solders, the shear loads were increased due to a refinement of the microstructure and in addition, ductile fracture surfaces were clearly observed. The shear loads of the plain Sn-9Zn and Sn-8Zn-3Bi solders after one reflow cycle were about 1798 g and 2059 g, respectively. After the addition of nano Ni powder, their loads were about 2172 g and 2212 g, respectively, after one reflow cycle and their shear loads after eight reflow cycles were about 2099 g and 2081 g, respectively.

  16. Effect of Cooling Rate on the Microstructure of Al-Zn Alloys with Addition of Silicon as Nanocomposite

    Directory of Open Access Journals (Sweden)

    S. García-Villarreal

    2013-01-01

    Full Text Available Al-43.5Zn-1.5Si (wt% alloys are widely used as coatings on steel substrates. This kind of coatings is manufactured by hot-dip process, in which Si is added as solid particles or master alloy. The role of Si during formation of the coating is to control the metallurgical reactions between solid steel and liquid Al-Zn-Si alloy initially forming an AlZnFeSi intermetallic layer and next the excess of Si forms intermetallic compounds, which grows over this alloy layer, segregates into the Zn rich interdendritic regions, and solidifies as eutectic reaction product as massive particles with needle like morphology. Therefore, during the experimental procedure is very difficult to control the final morphology and distribution of the silicon phase. The acicular morphology of this phase greatly affects the mechanical properties of the alloy because it acts as stress concentrators. When the coated steel sheet is subjected to bending, the coating presents huge cracks due to the presence of silicon phase. Therefore, the aim of the paper was to propose a new methodology to control the silicon phase through its addition to Al-Zn alloy as nanocomposite and additionally determine the effect of cooling rate (between 10 and 50°Cs−1 on the solidification microstructure and mechanical properties of Al-Zn alloy.

  17. Broad range tuning of structural and optical properties of Znx Mg1−x O nanostructures grown by vapor transport method

    International Nuclear Information System (INIS)

    Vanjaria, Jignesh V; Azhar, Ebraheem Ali; Yu, Hongbin

    2016-01-01

    One-dimensional (1D) Zn x Mg 1−x O nanomaterials have drawn global attention due to their remarkable chemical and physical properties, and their diverse current and future technological applications. In this work, 1D ZnMgO nanostructures with different magnesium concentrations and different morphologies were grown directly on zinc oxide-coated silicon substrates by thermal evaporation of zinc oxide, magnesium boride and graphite powders. Highly well-defined Mg-rich ZnMgO nanorods with a rock salt structure and Zn-rich ZnMgO nanostructures with a wurtzite structure have been deposited individually by careful optimization of the source mixture and process parameters. Structural and optical properties of the deposited products were studied by scanning electron microscopy, energy dispersive x-ray spectroscopy, x-ray diffraction, and Raman spectroscopy. Cathodoluminescence measurements demonstrate strong dominant peaks at 3.3 eV in Mg poor ZnMgO nanostructures and 4.8 eV in Mg rich nanostructures implying that the ZnMgO nanostructures can be used for the fabrication of deep UV optoelectronic devices. A mechanism for the formation and achieved diverse morphology of the ZnMgO nanostructures was proposed based on the characterization results. (paper)

  18. Particulate matter analysis at elementary schools in Curitiba, Brazil.

    Science.gov (United States)

    Avigo, Devanir; Godoi, Ana F L; Janissek, Paulo R; Makarovska, Yaroslava; Krata, Agnieszka; Potgieter-Vermaak, Sanja; Alfoldy, Balint; Van Grieken, René; Godoi, Ricardo H M

    2008-06-01

    The particulate matter indoors and outdoors of the classrooms at two schools in Curitiba, Brazil, was characterised in order to assess the indoor air quality. Information concerning the bulk composition was provided by energy-dispersive x-ray fluorescence (EDXRF). From the calculated indoor/outdoor ratios and the enrichment factors it was observed that S-, Cl- and Zn-rich particles are of concern in the indoor environment. In the present research, the chemical compositions of individual particles were quantitatively elucidated, including low-Z components like C, N and O, as well as higher-Z elements, using automated electron probe microanalysis low Z EPMA. Samples were further analysed for chemical and morphological aspects, determining the particle size distribution and classifying them according to elemental composition associations. Five classes were identified based on major elemental concentrations: aluminosilicate, soot, organic, calcium carbonate and iron-rich particles. The majority of the respirable particulate matter found inside of the classroom was composed of soot, biogenic and aluminosilicate particles. In view of the chemical composition and size distribution of the aerosol particles, local deposition efficiencies in the human respiratory system were calculated revealing the deposition of soot at alveolar level. The results showed that on average 42% of coarse particles are deposited at the extrathoracic level, whereas 24% are deposited at the pulmonary region. The fine fraction showed a deposition rate of approximately 18% for both deposition levels.

  19. Food-chain transfer of cadmium and zinc from contaminated Urtica dioica to Helix aspersa and Lumbricus terrestris.

    Science.gov (United States)

    Sinnett, Danielle E; Hodson, Mark E; Hutchings, Tony R

    2009-08-01

    The present study examines the potential of Urtica dioica as an ecologically relevant species for use in ecotoxicological testing. It is prevalent in degraded ecosystems and is a food source for invertebrates. Urtica dioica grown in hydroponic solutions containing from less than 0.003 to 5.7 mg Cd/L or from 0.02 to 41.9 mg Zn/L accumulated metals resulting in leaf tissue concentrations in the range of 0.10 to 24.9 mg Cd/kg or 22.5 to 2,772.0 mg Zn/kg. No toxicological effects were apparent except at the highest concentrations tested, suggesting that this species may be an important pathway for transfer of metals to primary plant consumers. Helix aspersa and Lumbricus terrestris were fed the Cd- and Zn-rich leaves of U. dioica for six and four weeks, respectively. Cadmium and Zn body load increased with increasing metal concentration in the leaves (p nettle leaves with concentrations of approximately 23 mg Cd/kg and 3,400 mg Zn/kg. Models demonstrate that L. terrestris Cd tissue concentrations (r2 = 0.74, p < 0.001) and H. aspersa Zn tissue concentrations (r(2) = 0.69, p < 0.001) can be estimated from concentrations of Cd and Zn within the leaves of U. dioica and suggest that reasonably reproducible results can be obtained using these species for ecotoxicological testing.

  20. Mechanism of formation of perovskite phase and dielectric properties of Pb(Zn,Mg)1/3Nb2/3O3 ceramics prepared by columbite precursor routes

    International Nuclear Information System (INIS)

    Jang, H.M.; Cho, S.R.; Lee, K.M.

    1995-01-01

    The mechanism of formation of the perovskite phase and the dielectric properties of Pb(Zn,Mg) 1/3 Nb 2/3 O 3 (PZMN) ceramics were examined using two different types of columbite precursors, (Mg,Zn)Nb 2 O 6 (MZN) and MgNb 2 O 6 + ZnNb 2 O 6 (MN + ZN). The formation of perovskite phase in the PbO + MN + ZN system is characterized by an initial rapid formation of Mg-rich perovskite phase, followed by a sluggish formation of Zn-rich perovskite phase. On the other hand, due to the formation of pyrochlore phase of mixed divalent cations Pb 2-x (Zn,Mg) y Nb 2-y O 7-x-3y/2 , the pyrochlore/perovskite transformation in the PbO + MZN system proceeded uniformly with a spatial homogeneity. Further analysis suggested that the formation of perovskite phase is a diffusion-controlled process. The degree of diffuseness of the rhombohedral/cubic phase transition (DPT) is higher in the PbO + MN + ZN system than in the PbO + MZN specimen for T > T max (temperature of the dielectric permittivity maximum), indicating a broadened compositional distribution of the B-site cations in the PbO + MN + ZN system

  1. Action of a clay suspension on an Fe(0) surface under anoxic conditions: Characterization of neoformed minerals at the Fe(0)/solution and Fe(0)/atmosphere interfaces

    International Nuclear Information System (INIS)

    Le Pape, Pierre; Rivard, Camille; Pelletier, Manuel; Bihannic, Isabelle; Gley, Renaud; Mathieu, Sandrine; Salsi, Lise; Migot, Sylvie; Barres, Odile; Villiéras, Frédéric; Michau, Nicolas

    2015-01-01

    Highlights: • Immersion of an Fe(0) foil in a clay suspension at 90 °C and in anoxic conditions. • Magnetite was observed on the atmospheric part. • Iron-rich 7 Å serpentines were observed on the clay suspension part. • A gradient in serpentine cristallochemistry was observed. • A pure Fe–Si phyllosilicate was identified at the Fe(0)/clay suspension contact. - Abstract: To better understand the reaction mechanisms involved at the Fe(0)/clay minerals interface, we investigate in the present study the reaction between an Fe(0) surface and a clay suspension extracted from the Callovo-Oxfordian claystone (COx). Batch experiments were carried out under anoxic conditions in sealed autoclave, at 90 °C to mimic predicted radioactive waste disposal conditions. An Fe(0) foil was introduced into the autoclave so that the lower part of the foil was immersed in the clay suspension while the upper part was contacted with the atmosphere of the experimental setup. After two months, the mineralogical deposits that precipitated at the surface of the Fe(0) foil were analyzed using multiple techniques, namely X-ray diffraction (XRD), scanning/transmission electron microscopy associated to microanalysis (SEM/TEM–EDXS), and micro-spectroscopic measurements (μ-FTIR and μ-Raman). Both parts of the Fe(0) foil were then shown to react: magnetite was the main resulting mineral formed at the Fe(0) surface in the atmospheric conditions whereas serpentine 1:1 phyllosilicates were the main end-products in the clay suspension. The analyses performed on the immersed part of the foil revealed a spatial heterogeneity in both serpentine cristallochemistry and morphology, with a gradient from the Fe(0) contact point toward the clay suspension. A pure Fe–Si phyllosilicate ring was observed at the direct contact point with the Fe(0) foil and a progressive incorporation of Al instead of Fe into the clay phases was identified as deposit thickness increased from the Fe(0) surface to

  2. Evolution of organic matter in Orgueil, Murchison and Renazzo during parent body aqueous alteration: In situ investigations

    Science.gov (United States)

    Le Guillou, Corentin; Bernard, Sylvain; Brearley, Adrian J.; Remusat, Laurent

    2014-04-01

    Chondrites accreted the oldest solid materials in the solar system including dust processed in the protoplanetary disk and diverse organic compounds. After accretion, asteroidal alteration may have impacted organic particles in various ways. To constrain these processes, we conducted a comprehensive study of organics disseminated within the matrices of the three carbonaceous chondrite falls, Renazzo (CR2), Murchison (CM2) and Orgueil (CI). By combining synchrotron-based STXM and TEM analyses on FIB sections of samples previously characterized by NanoSIMS, we investigated the influence of aqueous alteration on the morphology, isotopic signature, molecular structure, spatial distribution, and mineralogical environment of the organic matter within the matrices. Two different populations of materials are distinguishable: sub-micrometric individual grains, likely dominated by insoluble compounds and diffuse organic matter, finely interspersed within phyllosilicates and/or (amorphous) nanocarbonates at the nanometer scale. We suggest that this latter component, which is depleted in aromatics and enriched in carboxylic functional groups, may be dominated by soluble compounds. Organic matter in Renazzo (CR) mainly consists of chemically-homogeneous individual grains surrounded by amorphous and nanocrystalline phyllosilicates. Evidence of connectivity between organic grains and fractures indicates that redistribution has occurred: some areas containing diffuse organic matter can be observed. This diffuse organic component is more abundant in Murchison (CM) and Orgueil (CI). This is interpreted as resulting from fluid transport at the micrometer scale and encapsulation within recrystallized alteration phases. In contrast to Renazzo, organic grains in Murchison and Orgueil display strong chemical heterogeneities, likely related to chemical evolution during aqueous alteration. The observations suggest that the altering fluid was a brine with elevated concentrations of both

  3. Controllable hydrothermal synthesis of Ni/H-BEA with a hierarchical core-shell structure and highly enhanced biomass hydrodeoxygenation performance.

    Science.gov (United States)

    Ma, Bing; Cui, Huimei; Wang, Darui; Wu, Peng; Zhao, Chen

    2017-05-11

    Ni based catalysts are wildly used in catalytic industrial processes due to their low costs and high activities. The design of highly hierarchical core-shell structured Ni/HBEA is achieved using a sustainable, simple, and easy-tunable hydrothermal synthesis approach using combined NH 4 Cl and NH 3 ·H 2 O as a co-precipitation agent at 120 °C. Starting from a single-crystalline hierarchical H + -exchanged beta polymorph zeolite (HBEA), the adjustment of the precipitate conditions shows that mixed NH 4 Cl and NH 3 ·H 2 O precipitates with proper concentrations are vital in the hydrothermal synthesis for preserving a good crystalline morphology of HBEA and generating abundant highly-dispersed Ni nanoparticles (loading: 41 wt%, 5.9 ± 0.7 nm) encapsulated onto/into the support. NH 4 Cl solution without an alkali is unable to generate abundant Ni nanoparticles from Ni salts under the hydrothermal conditions, whereas NH 3 ·H 2 O seriously damages the pore structure. After studying the in situ changes in infrared, X-ray diffractometry, temperature-programmed reduction, and scanning electron microscopy measurements, as well as variations in the filtrate pH, Si/Al ratios, and solid sample Ni loading, a two-step dissolution-recrystallization process is proposed. The process consists of Si dissolution and no change in elemental Al, and after the dissolved Si(iv) concentrations have promoted Ni phyllosilicate nanosheet solubility, further growth of multilayered Ni phyllosilicate nanosheets commences. The precursor Ni phyllosilicate is changeable between Ni 3 Si 2 O 5 (OH) 4 and Ni 3 Si 4 O 10 (OH) 2 , because of competition in kinetically-favored and thermodynamically-controlled species caused by different basic agents. The superior catalytic performance is demonstrated in the metal/acid catalyzed biomass derived bulky stearic acid hydrodeoxygenation with 90% octadecane selectivity and a promising rate of 54 g g -1 h -1 , which highly excels the reported rates catalyzed by

  4. Laboratory experiments on ammoniated clay minerals with relevance for asteroid (1) Ceres

    Science.gov (United States)

    De Angelis, Simone; Stefani, Stefania; De Sanctis, Maria Cristina; Piccioni, Giuseppe; Ammannito, Eleonora

    2017-04-01

    Recent observations with VIR spectrometer onboard Dawn spacecraft [1] have suggested the presence of ammoniated phyllosilicates widespread on the surface of asteroid (1) Ceres [2,3]. The global surface composition of Ceres as suggested by VIR average infrared spectrum in the 1-4 micron range appears to be due to a mixture of NH4-bearing phyllosilicates, serpentine, carbonates and a dark absorbing phase (magnetite or amorphous carbon) [2]. An absorption feature occurring near 3.1 micron in the average spectrum is considered the main evidence for the presence of NH4-bearing phase; nevertheless in the past several authors tried to explain this feature, as observed with telescopic spectra, invoking the presence of brucite, cronstedtite, water ice or clays [4]. In this project we are carrying out laboratory experiments with the aim of studying ammoniated phyllosilicates in the visible-infrared range. A suite of 9 clay minerals has been used for this study, including illite, nontronite and montmorillonite. In order to produce the ammoniated species we followed a modified procedure based on the one described in Bishop et al. (2002) [5]. All minerals were reduced in fine grain size (features, appearing at different wavelengths near 2, 3, 6 and 7 micron. In some cases the spectral shape of already existent absorption bands resulted deeply modified. A few species did not show the appearance of new features. These results suggest that NH4+ ions fix in various ways in different minerals. Nontronite and montmorillonite appear to be the best candidates, among the studied suite, to be used in future laboratory reproduced analog mixtures. [1] Russell C.T. et al., 2004, Planetary and Space Science, 52, 465-489 [2] De Sanctis M.C. et al., 2015, Nature, 528, 241-244 [3] Ammannito E. et al., 2016, Science, vol.353, issue 6303 [4] Rivkin A.S. et al., 2011, Space Science Reviews, 163, 95-116 [5] Bishop J.L. et al., 2002, Planetary and Space Science, 50, 11-19

  5. Alteration hydrothermale et deformation ductile des roches volcaniques acides associees au gisement sulfure de draa sfar (Jebilet Centrales, Maroc

    Directory of Open Access Journals (Sweden)

    Zinbi, Y.

    2005-12-01

    Full Text Available The volcanics and volcanoclastic rocks of Draa Sfar (Central Jebilet, Moroccan hercynian belt are affected by ductile stress and hydrothermal alteration accompanied by a weak degree of metamorphism (greenschist facies. Some N-S oriented shearing zones, affect locally these formations while being the site of an important hydrothermal activity. The consequences of these transformations from a non to slightly- deformed rhyodacite, show that through these ductile shearing zones: (1 the mineralogical assemblage of hydrothermal alteration is essentially formed by chlorite, sericite, quartz and magnetite; (2 the gradual increase of the alteration indexes is accompanied by the destruction of the phenocrists and the recrystallization of the matrix by phyllosilicates and quartz; (3 the progressive transfer of material is more intense in the more deformed zones where the values of Ti, Al and Zr remain constant. These shearing zones played a very important role in the circulation of fluids and the transformation of the rhyodacite of Draa Sfar.Les roches volcaniques et volcanoclastiques de Draa Sfar (Jebilet centrales, Maroc hercynien sont affectées par une déformation ductile accompagnée d’un métamorphisme de faible degré (faciès schistes verts et d’une altération hydrothermale. Des zones de cisaillement de direction N-S, ont affecté localement ces formations tout en étant vecteurs d’une importante activité hydrothermale. Le suivi de ces transformations à partir de la rhyodacite non ou peu déformée, montre qu’à travers ces zones de cisaillements ductiles : (1 l’assemblage minéralogique d’altération hydrothermale est formé essentiellement de chlorite, de séricite, de quartz et de magnétite ; (2 l’augmentation graduelle des indices d’altération s’exprime par la destruction des phénocristaux au profit d’une matrice recristallisée en phyllosilicates et quartz ; (3 le transfert progressif de la matière est plus intense

  6. Preliminary results on the influence of mineralogy on the turnover rates of SOM from different Hungarian soils

    Science.gov (United States)

    Zacháry, Dóra; Szalai, Zoltán; Jakab, Gergely; Németh, Tibor; Sipos, Péter; Filep, Tibor

    2016-04-01

    Fine textured soils generally considered containing more microbial biomass, and having a lower rate of biomass turnover and organic matter decomposition than coarse textured soils. In spite of this, several recent studies have shown contradicting trends. For example, the relative importance of different clay minerals for stabilizing SOM remains an open question. The aim of this study is to evaluate soil mineralological effect on the turnover of SOM by identifying and quantifying soil phyllosilicates. Our samples are derived from C3 forests and C3 croplands from different sites of Hungary. C4 maize residues are added to the soils in order to get natural 13C enrichment as tracer for the young carbon. Bulk samples of the soils from 0 to 20 cm depth were collected. The samples were dried at room temperature and preincubated in the dark for 4 months at 20 °C. The basic soil properties (pH, cation exchange capacity) were analysed after 2 mm sieving and homogenization. The amount of total C and N in the soils and maize residues were analysed using NDIR-chemiluminescent analyzer (Tekmar Dohrman Apollo 9000N). Particle size distribution was determined by laser diffraction (Fritsch Analysette MicroTec 22 plus) and particle imaging method (Malvern Morphologi G3-ID). The mineralological composition of the samples was determined by X-ray diffraction (Philips PW 1730 X-ray diffractometer). Moist soil equivalent to 400 g dry soil mixed with 2 g maize leaves is kept in air tight glass chambers for 183 days at 20°C. The leaves had previously been dried at 60 °C, were cut into pieces and sieved through a 2 mm mesh. The evolved CO2 is trapped by 10 mL 2 M NaOH, which is exchanged on day 1, 3, 5, 7, 10, 14, 21, 28 and subsequently every 31 days. The fractional abundance of 13C of the soils, the plant material and the evolved CO2 is measured with isotope ratio mass spectrometer (Thermo Scientific Delta V IRMS). Our work show the preliminary results on the link between phyllosilicate

  7. Characterization of terrestrial hydrothermal alteration products with Mars analog instrumentation: Implications for current and future rover investigations

    Science.gov (United States)

    Black, Sarah R.; Hynek, Brian M.

    2018-06-01

    Interpretation of Martian geology relies heavily on our understanding of terrestrial analog deposits and our ability to obtain comprehensive and accurate mineralogical compositions. Many previous studies of terrestrial hydrothermal deposits relied on limited datasets and/or did not use instruments analogous to those deployed on Mars. We analyzed 100 hydrothermally altered basalts from Costa Rica, Nicaragua, and Iceland with Mars analog Visible to Short Wave Infrared (VSWIR) spectroscopy, X-ray Diffraction (XRD), and Raman laser spectrometry. Alteration mineralogy consisted of amorphous and crystalline SiO2 (cristobalite, tridymite, quartz), Ca/Al/Fe/Mg-sulfates (gypsum, anhydrite, alunite, jarosite, hexahydrite, alunogen), Fe-, Ti-, and Mg-oxides/hydroxides (hematite, goethite, anatase/brookite, brucite), elemental sulfur, and phyllosilicates (montmorillonite, kaolinite). Results indicate VSWIR is best suited for identification of X-ray amorphous materials such as hydrated SiO2 and phyllosilicates, while XRD is best utilized for highly ordered crystalline materials such as sulfates, crystalline SiO2 polymorphs, elemental sulfur, and Mg-hydroxides identification. Surprisingly, XRD had the lowest identification rates for Fe-oxides/hydroxides (42% compared to 61% and 75% for VNIR and Raman, respectively), and nearly equal identification rates as VSWIR for kaolinite (76% for VSWIR, 71% for XRD). Identification of phyllosilicates in XRD, while possible, is not as effective as VSWIR without extensive sample preparation. Our observed identification rates may be attributed to the relative abundance of materials-Fe-oxides/hydroxides being present as surface coatings, the presence of large amounts of kaolinite in some samples, and an increased particle size for kaolinite relative to other clays. Elemental sulfur and Fe- and Ti-oxides/hydroxides were more readily identified with Raman. With NASA's current focus on habitability, hydrothermally altered areas-which we know to

  8. Uranium-contaminated soils: Ultramicrotomy and electron beam analysis

    International Nuclear Information System (INIS)

    Buck, E.C.; Dietz, N.L.; Bates, J.K.; Cunnane, J.C.

    1994-02-01

    Uranium-contaminated soils from the U.S. Department of Energy (DOE) Fernald Site, Ohio, have been examined by a combination of scanning electron microscopy with backscattered electron imaging (SEM/BSE) and analytical electron microscopy (AEM). The inhomogeneous distribution of particulate uranium phases in the soil required the development of a method for using ultramicrotomy to prepare transmission electron microscopy (TEM) thin sections of the SEM mounts. A water-miscible resin was selected that allowed comparison between SEM and TEM images, permitting representative sampling of the soil. Uranium was found in iron oxides, silicates (soddyite), phosphates (autunites), and fluorite (UO 2 ). No uranium was detected in association with phyllosilicates in the soil

  9. A relevante potencialidade dos centros básicos nitrogenados disponíveis em polímeros inorgânicos e biopol��meros na remoção catiônica The weighty potentiality of nitrogenated basic centers in inorganic polymers and biopolymers for cation removal

    Directory of Open Access Journals (Sweden)

    Claudio Airoldi

    2008-01-01

    Full Text Available This review reports the application of inorganic and organic polymeric materials for cation removal by using nitrogenated basic centers. The data demonstrate the importance of the desired groups when free or immobilized on natural or synthesized inorganic polymers through silanol groups. Thus, the most studied silica gel is followed by natural crysotile and talc polymers, and the synthesized mesopore silicas, talc-like, silicic acids, phosphates and phyllosilicates. The organic natural biopolymeric chitin and cellulose were chemically modified to improve the availability of the amine groups or the reactivity with desirable molecules to enlarge the content of basic centers. The cation removal takes place at the solid/liquid interface and some interactive effects have their thermodynamic data determined.

  10. Formation of organoclays by a one step synthesis

    Science.gov (United States)

    Jaber, Maguy; Miéhé-Brendlé, Jocelyne; Delmotte, Luc; Le Dred, Ronan

    2005-05-01

    Different lamellar hybrid inorganic-organic materials having as inorganic parent 2:1 (T.O.T.) phyllosilicates such as talc, saponite, pyrophyllite, beidellite and montmorillonite were prepared by a one step synthesis. The solids were characterized by X-ray diffraction, solid state 29Si, 27Al, and 19F nuclear magnetic resonance and transmission electron microscopy. XRD patterns show that solids with inorganic parents having octahedral sheet based on aluminium exhibit a lamellar structure similar to MCM-50, whereas those with magnesium have an organophyllosilicate structure. In the first case, the absence of hexacoordinated aluminium was confirmed by 27Al NMR and an ordered stacking of the layers is observed on TEM micrographs. In opposite, a disorder is observed on the TEM images of organophyllosilicates. The formation of the 2:1 structure was found to be controlled mainly by the insertion of silicic species in the interlamellar space of brucite like layers.

  11. Synthesis and characterization of rubbery epoxy/organoclay hectorite nanocomposites

    Directory of Open Access Journals (Sweden)

    2007-12-01

    Full Text Available The present research investigates the morphology, the mechanical, and the viscoelastic properties of rubbery epoxy/clay nanocomposites synthesized by in situ polymerisation of a prepolymer diglycidyl ether of bisphenol-A crosslinked with an aliphatic diamine based on a polyoxypropylene backbone. The inorganic phase was hectorite, exchanged with octadecylammonium ions in order to give organophilic properties to the phyllosilicate. An ultrasonicator was used to disperse the silicate clay layer into epoxy-amine matrix. The morphology of epoxy-hectorite nanocomposites examined by transmission electron microscopy (TEM showed that mixed delamination or intercalation or microdispersion could occur depending on type of organoclay. Moreover, the mechanical and viscoelastic properties were found to be improved with only the treated hectorite.

  12. Mineralogic Residence and Desorption Rates of Sorbed 90Sr in Contaminated Subsurface Sediments: Implications to Future Behavior and In-Ground Stability

    International Nuclear Information System (INIS)

    PIs: John M. Zachara; Jim P. McKinley; S. M. Heald; Chongxuan Liu; Peter C. Lichtner

    2006-01-01

    The project is investigating the adsorption/desorption process of 90Sr in coarse-textured pristine and contaminated Hanford sediment with the goal to define a generalized reaction-based model for use in reactive transport calculations. While it is known that sorbed 90Sr exists in an ion exchangeable state, the mass action relationships that control the solid-liquid distribution and the mineral phases responsible for adsorption have not been defined. Many coarse-textured Hanford sediment display significant sorptivity for 90Sr, but contain few if any fines that may harbor phyllosilicates with permanent negative charge and associated cation exchange capacity. Moreover, it is not known whether the adsorption-desorption process exhibits time dependence within context of transport, and if so, the causes for kinetic behavior

  13. Elemental Geochemistry of Sedimentary Rocks at Yellowknife Bay, Gale Crater, Mars

    Science.gov (United States)

    McLennan, S. M.; Anderson, R. B.; Bell, J. F.; Bridges, J. C.; Calef, F.; Campbell, J. L.; Clark, B. C.; Clegg, S.; Conrad, P.; Cousin, A.; Des Marais, D. J.; Dromart, G.; Dyar, M. D.; Edgar, L. A.; Ehlmann, B. L.; Fabre, C.; Forni, O.; Gasnault, O.; Gellert, R.; Gordon, S.; Grant, J. A.; Grotzinger, J. P.; Gupta, S.; Herkenhoff, K. E.; Hurowitz, J. A.; King, P. L.; Le Mouélic, S.; Leshin, L. A.; Léveillé, R.; Lewis, K. W.; Mangold, N.; Maurice, S.; Ming, D. W.; Morris, R. V.; Nachon, M.; Newsom, H. E.; Ollila, A. M.; Perrett, G. M.; Rice, M. S.; Schmidt, M. E.; Schwenzer, S. P.; Stack, K.; Stolper, E. M.; Sumner, D. Y.; Treiman, A. H.; VanBommel, S.; Vaniman, D. T.; Vasavada, A.; Wiens, R. C.; Yingst, R. A.; Kemppinen, Osku; Bridges, Nathan; Johnson, Jeffrey R.; Minitti, Michelle; Cremers, David; Farmer, Jack; Godber, Austin; Wadhwa, Meenakshi; Wellington, Danika; McEwan, Ian; Newman, Claire; Richardson, Mark; Charpentier, Antoine; Peret, Laurent; Blank, Jennifer; Weigle, Gerald; Li, Shuai; Milliken, Ralph; Robertson, Kevin; Sun, Vivian; Baker, Michael; Edwards, Christopher; Farley, Kenneth; Griffes, Jennifer; Miller, Hayden; Newcombe, Megan; Pilorget, Cedric; Siebach, Kirsten; Brunet, Claude; Hipkin, Victoria; Marchand, Geneviève; Sánchez, Pablo Sobrón; Favot, Laurent; Cody, George; Steele, Andrew; Flückiger, Lorenzo; Lees, David; Nefian, Ara; Martin, Mildred; Gailhanou, Marc; Westall, Frances; Israël, Guy; Agard, Christophe; Baroukh, Julien; Donny, Christophe; Gaboriaud, Alain; Guillemot, Philippe; Lafaille, Vivian; Lorigny, Eric; Paillet, Alexis; Pérez, René; Saccoccio, Muriel; Yana, Charles; Armiens-Aparicio, Carlos; Rodríguez, Javier Caride; Blázquez, Isaías Carrasco; Gómez, Felipe Gómez; Gómez-Elvira, Javier; Hettrich, Sebastian; Malvitte, Alain Lepinette; Jiménez, Mercedes Marín; Martínez-Frías, Jesús; Martín-Soler, Javier; Martín-Torres, F. Javier; Jurado, Antonio Molina; Mora-Sotomayor, Luis; Caro, Guillermo Muñoz; López, Sara Navarro; Peinado-González, Verónica; Pla-García, Jorge; Manfredi, José Antonio Rodriguez; Romeral-Planelló, Julio José; Fuentes, Sara Alejandra Sans; Martinez, Eduardo Sebastian; Redondo, Josefina Torres; Urqui-O'Callaghan, Roser; Mier, María-Paz Zorzano; Chipera, Steve; Lacour, Jean-Luc; Mauchien, Patrick; Sirven, Jean-Baptiste; Manning, Heidi; Fairén, Alberto; Hayes, Alexander; Joseph, Jonathan; Squyres, Steven; Sullivan, Robert; Thomas, Peter; Dupont, Audrey; Lundberg, Angela; Melikechi, Noureddine; Mezzacappa, Alissa; DeMarines, Julia; Grinspoon, David; Reitz, Günther; Prats, Benito; Atlaskin, Evgeny; Genzer, Maria; Harri, Ari-Matti; Haukka, Harri; Kahanpää, Henrik; Kauhanen, Janne; Kemppinen, Osku; Paton, Mark; Polkko, Jouni; Schmidt, Walter; Siili, Tero; Wray, James; Wilhelm, Mary Beth; Poitrasson, Franck; Patel, Kiran; Gorevan, Stephen; Indyk, Stephen; Paulsen, Gale; Bish, David; Schieber, Juergen; Gondet, Brigitte; Langevin, Yves; Geffroy, Claude; Baratoux, David; Berger, Gilles; Cros, Alain; d'Uston, Claude; Lasue, Jérémie; Lee, Qiu-Mei; Meslin, Pierre-Yves; Pallier, Etienne; Parot, Yann; Pinet, Patrick; Schröder, Susanne; Toplis, Mike; Lewin, Éric; Brunner, Will; Heydari, Ezat; Achilles, Cherie; Oehler, Dorothy; Sutter, Brad; Cabane, Michel; Coscia, David; Israël, Guy; Szopa, Cyril; Robert, François; Sautter, Violaine; Buch, Arnaud; Stalport, Fabien; Coll, Patrice; François, Pascaline; Raulin, François; Teinturier, Samuel; Cameron, James; DeLapp, Dorothea; Dingler, Robert; Jackson, Ryan Steele; Johnstone, Stephen; Lanza, Nina; Little, Cynthia; Nelson, Tony; Williams, Richard B.; Jones, Andrea; Kirkland, Laurel; Baker, Burt; Cantor, Bruce; Caplinger, Michael; Davis, Scott; Duston, Brian; Edgett, Kenneth; Fay, Donald; Hardgrove, Craig; Harker, David; Herrera, Paul; Jensen, Elsa; Kennedy, Megan R.; Krezoski, Gillian; Krysak, Daniel; Lipkaman, Leslie; Malin, Michael; McCartney, Elaina; McNair, Sean; Nixon, Brian; Posiolova, Liliya; Ravine, Michael; Salamon, Andrew; Saper, Lee; Stoiber, Kevin; Supulver, Kimberley; Van Beek, Jason; Van Beek, Tessa; Zimdar, Robert; French, Katherine Louise; Iagnemma, Karl; Miller, Kristen; Summons, Roger; Goesmann, Fred; Goetz, Walter; Hviid, Stubbe; Johnson, Micah; Lefavor, Matthew; Lyness, Eric; Breves, Elly; Fassett, Caleb; Blake, David F.; Bristow, Thomas; Edwards, Laurence; Haberle, Robert; Hoehler, Tori; Hollingsworth, Jeff; Kahre, Melinda; Keely, Leslie; McKay, Christopher; Wilhelm, Mary Beth; Bleacher, Lora; Brinckerhoff, William; Choi, David; Dworkin, Jason P.; Eigenbrode, Jennifer; Floyd, Melissa; Freissinet, Caroline; Garvin, James; Glavin, Daniel; Harpold, Daniel; Jones, Andrea; Mahaffy, Paul; Martin, David K.; McAdam, Amy; Pavlov, Alexander; Raaen, Eric; Smith, Michael D.; Stern, Jennifer; Tan, Florence; Trainer, Melissa; Meyer, Michael; Posner, Arik; Voytek, Mary; Anderson, Robert C.; Aubrey, Andrew; Beegle, Luther W.; Behar, Alberto; Blaney, Diana; Brinza, David; Christensen, Lance; Crisp, Joy A.; DeFlores, Lauren; Ehlmann, Bethany; Feldman, Jason; Feldman, Sabrina; Flesch, Gregory; Jun, Insoo; Keymeulen, Didier; Maki, Justin; Mischna, Michael; Morookian, John Michael; Parker, Timothy; Pavri, Betina; Schoppers, Marcel; Sengstacken, Aaron; Simmonds, John J.; Spanovich, Nicole; Juarez, Manuel de la Torre; Webster, Christopher R.; Yen, Albert; Archer, Paul Douglas; Cucinotta, Francis; Jones, John H.; Niles, Paul; Rampe, Elizabeth; Nolan, Thomas; Fisk, Martin; Radziemski, Leon; Barraclough, Bruce; Bender, Steve; Berman, Daniel; Dobrea, Eldar Noe; Tokar, Robert; Williams, Rebecca M. E.; Cleghorn, Timothy; Huntress, Wesley; Manhès, Gérard; Hudgins, Judy; Olson, Timothy; Stewart, Noel; Sarrazin, Philippe; Vicenzi, Edward; Wilson, Sharon A.; Bullock, Mark; Ehresmann, Bent; Hamilton, Victoria; Hassler, Donald; Peterson, Joseph; Rafkin, Scot; Zeitlin, Cary; Fedosov, Fedor; Golovin, Dmitry; Karpushkina, Natalya; Kozyrev, Alexander; Litvak, Maxim; Malakhov, Alexey; Mitrofanov, Igor; Mokrousov, Maxim; Nikiforov, Sergey; Prokhorov, Vasily; Sanin, Anton; Tretyakov, Vladislav; Varenikov, Alexey; Vostrukhin, Andrey; Kuzmin, Ruslan; Wolff, Michael; Botta, Oliver; Drake, Darrell; Bean, Keri; Lemmon, Mark; Lee, Ella Mae; Sucharski, Robert; Hernández, Miguel Ángel de Pablo; Ávalos, Juan José Blanco; Ramos, Miguel; Kim, Myung-Hee; Malespin, Charles; Plante, Ianik; Muller, Jan-Peter; Navarro-González, Rafael; Ewing, Ryan; Boynton, William; Downs, Robert; Fitzgibbon, Mike; Harshman, Karl; Morrison, Shaunna; Dietrich, William; Kortmann, Onno; Palucis, Marisa; Williams, Amy; Lugmair, Günter; Wilson, Michael A.; Rubin, David; Jakosky, Bruce; Balic-Zunic, Tonci; Frydenvang, Jens; Jensen, Jaqueline Kløvgaard; Kinch, Kjartan; Koefoed, Asmus; Madsen, Morten Bo; Stipp, Susan Louise Svane; Boyd, Nick; Pradler, Irina; Jacob, Samantha; Owen, Tobias; Rowland, Scott; Atlaskin, Evgeny; Savijärvi, Hannu; Boehm, Eckart; Böttcher, Stephan; Burmeister, Sönke; Guo, Jingnan; Köhler, Jan; García, César Martín; Mueller-Mellin, Reinhold; Wimmer-Schweingruber, Robert; McConnochie, Timothy; Benna, Mehdi; Franz, Heather; Bower, Hannah; Brunner, Anna; Blau, Hannah; Boucher, Thomas; Carmosino, Marco; Atreya, Sushil; Elliott, Harvey; Halleaux, Douglas; Rennó, Nilton; Wong, Michael; Pepin, Robert; Elliott, Beverley; Spray, John; Thompson, Lucy; Williams, Joshua; Vasconcelos, Paulo; Bentz, Jennifer; Nealson, Kenneth; Popa, Radu; Kah, Linda C.; Moersch, Jeffrey; Tate, Christopher; Day, Mackenzie; Kocurek, Gary; Hallet, Bernard; Sletten, Ronald; Francis, Raymond; McCullough, Emily; Cloutis, Ed; ten Kate, Inge Loes; Kuzmin, Ruslan; Arvidson, Raymond; Fraeman, Abigail; Scholes, Daniel; Slavney, Susan; Stein, Thomas; Ward, Jennifer; Berger, Jeffrey; Moores, John E.

    2014-01-01

    Sedimentary rocks examined by the Curiosity rover at Yellowknife Bay, Mars, were derived from sources that evolved from an approximately average martian crustal composition to one influenced by alkaline basalts. No evidence of chemical weathering is preserved, indicating arid, possibly cold, paleoclimates and rapid erosion and deposition. The absence of predicted geochemical variations indicates that magnetite and phyllosilicates formed by diagenesis under low-temperature, circumneutral pH, rock-dominated aqueous conditions. Analyses of diagenetic features (including concretions, raised ridges, and fractures) at high spatial resolution indicate that they are composed of iron- and halogen-rich components, magnesium-iron-chlorine-rich components, and hydrated calcium sulfates, respectively. Composition of a cross-cutting dike-like feature is consistent with sedimentary intrusion. The geochemistry of these sedimentary rocks provides further evidence for diverse depositional and diagenetic sedimentary environments during the early history of Mars.

  14. The growth of multi-walled carbon nanotubes on natural clay minerals (kaolinite, nontronite and sepiolite)

    International Nuclear Information System (INIS)

    Pastorková, K.; Jesenák, K.; Kadlečíková, M.; Breza, J.; Kolmačka, M.; Čaplovičová, M.; Lazišťan, F.; Michalka, M.

    2012-01-01

    The suitability of clay minerals - kaolinite, nontronite and sepiolite - is studied for synthesis of nanocomposites based on carbon nanotubes. Particles of iron were used as catalysts. Prior to synthesis, kaolinite and sepiolite were doped by the catalytically active metal, whereas in the case of nontronite the presence was used of this metal in the matrix of this mineral. Synthesis of CNTs was performed by hot filament chemical vapor deposition method. The produced nanocomposites were examined by transmission and scanning electron microscopies and energy dispersive X-ray spectroscopy. The experiment verified the potential of the three microcrystalline phyllosilicates for the growth of carbon nanotubes. Under the same technology conditions, the type of catalyst carrier affects the morphology and structure of the nanotube product markedly.

  15. Mineralogical characterization of selected shales in support of nuclear waste repository studies: Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.Y.; Hyder, L.K.; Alley, P.D.

    1987-12-01

    Because baseline characterization of shale mineralogy is critical to the interpretation of results from experiments on radionuclide retardation, groundwater-shale interactions, and physicochemical characteristics, a protocol for quantitative mineralogical analyses has been developed by integrating geochemical and instrumental techniques for the investigation of properties related to repository performance. Thermal analyses were used to estimate total organic matter and carbonate mineral contents. Scanning electron microscope backscattering and elemental mapping of polished sectors and particle-size distribution data were used to estimate the amounts of quartz plus feldspar and pyrite in the shales. X-ray diffraction, neutron activation, and size-distribution data were utilized to estimate phyllosilicate mineral contents. High-resolution transmission electron microscopy was used to identify clay mineral components.

  16. Deposition of talc - kerolite-smectite - smectite at seafloor hydrothermal vent fields: Evidence from mineralogical, geochemical and oxygen isotope studies

    Science.gov (United States)

    Dekov, V.M.; Cuadros, J.; Shanks, Wayne C.; Koski, R.A.

    2008-01-01

    Talc, kerolite-smectite, smectite, chlorite-smectite and chlorite samples from sediments, chimneys and massive sulfides from six seafloor hydrothermal areas have been analyzed for mineralogy, chemistry and oxygen isotopes. Samples are from both peridotite- and basalt-hosted hydrothermal systems, and basaltic systems include sediment-free and sediment-covered sites. Mg-phyllosilicates at seafloor hydrothermal sites have previously been described as talc, stevensite or saponite. In contrast, new data show tri-octahedral Mg-phyllosilicates ranging from pure talc and Fe-rich talc, through kerolite-rich kerolite-smectite to smectite-rich kerolite-smectite and tri-octahedral smectite. The most common occurrence is mixed-layer kerolite-smectite, which shows an almost complete interstratification series with 5 to 85% smectitic layers. The smectite interstratified with kerolite is mostly tri-octahedral. The degree of crystal perfection of the clay sequence decreases generally from talc to kerolite-smectite with lower crystalline perfection as the proportion of smectite layers in kerolite-smectite increases. Our studies do not support any dependence of the precipitated minerals on the type/subtype of hydrothermal system. Oxygen isotope geothermometry demonstrates that talc and kerolite-smectite precipitated in chimneys, massive sulfide mounds, at the sediment surface and in open cracks in the sediment near seafloor are high-temperature (> 250????C) phases that are most probably the result of focused fluid discharge. The other end-member of this tri-octahedral Mg-phyllosilicate sequence, smectite, is a moderate-temperature (200-250????C) phase forming deep within the sediment (??? 0.8??m). Chlorite and chlorite-smectite, which constitute the alteration sediment matrix around the hydrothermal mounds, are lower-temperature (150-200????C) phases produced by diffuse fluid discharge through the sediment around the hydrothermal conduits. In addition to temperature, other two

  17. Detection Limit of Smectite by Chemin IV Laboratory Instrument: Preliminary Implications for Chemin on the Mars Science Laboratory Mission

    Science.gov (United States)

    Archilles, Cherie; Ming, D. W.; Morris, R. V.; Blake, D. F.

    2011-01-01

    The CheMin instrument on the Mars Science Laboratory (MSL) is an miniature X-ray diffraction (XRD) and X-ray fluorescence (XRF) instrument capable of detecting the mineralogical and elemental compositions of rocks, outcrops and soils on the surface of Mars. CheMin uses a microfocus-source Co X-ray tube, a transmission sample cell, and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D XRD patterns and energy-dispersive X-ray histograms from powdered samples. CRISM and OMEGA have identified the presence of phyllosilicates at several locations on Mars including the four candidate MSL landing sites. The objective of this study was to conduct preliminary studies to determine the CheMin detection limit of smectite in a smectite/olivine mixed mineral system.

  18. Smectite Formation in Acid Sulfate Environments on Mars

    Science.gov (United States)

    Peretyazhko, T. S.; Niles, P. B.; Sutter, B.; Clark, J. V.; Morris, R. V.; Ming, D. W.

    2017-01-01

    Phyllosilicates of the smectite group detected in Noachian and early Hesperian terrains on Mars were hypothesized to form under aqueous conditions that were globally neutral to alkaline. These pH conditions and the presence of a CO2-rich atmosphere should have been favorable for the formation of large carbonate deposits. However, large-scale carbonate deposits have not been detected on Mars. We hypothesized that smectite deposits are consistent with perhaps widespread acidic aqueous conditions that prevented carbonate precipitation. The objective of our work was to investigate smectite formation under acid sulfate conditions in order to provide insight into the possible geochemical conditions required for smectite formation on Mars. Hydrothermal batch incubation experiments were performed with Mars-analogue, glass-rich, basalt simulant in the presence of sulfuric acid of variable concentration.

  19. Mineralogical and chemical study of Spanish common clays with regard to their use in pelotherapy; Estudio mineralogico y quomico de arcillas comunes espanolas para su empleo en peloterapia

    Energy Technology Data Exchange (ETDEWEB)

    Pozo Martin, E.; Martin Rubi, J. A.; Pozo Rodriguez, M.

    2011-07-01

    The mineralogical (whole sample and clay fraction) and chemical compositions of 5 representative samples of Spanish common clays have been studied to evaluate their use in pelotherapy. The mineralogy of the samples revealed clays with phyllosilicate contents of between 53% and 74% and minor quantities of quartz, calcite, dolomite, feldspars, gypsum, pyrite and hematite. Smectite was the predominant clay mineral, with the exception of one sample containing only illite. The results of analyses of the major chemical elements were consistent with the mineralogical composition. The samples contained low quantities (<130 ppm, with the exception of Ba) of potentially harmful elements; the CAR sample contained the highest quantities of Ba, V, Cr, Co, As, Sb, and Ni. Nevertheless, the concentrations of trace elements in the samples analysed showed lower levels of phytotoxicity than those permitted and were also lower than those found in peloids currently used in Spanish spas. (Author)

  20. Evaluation of the capacity of heavy metal adsorption in exfoliated vermiculite

    International Nuclear Information System (INIS)

    Lima, J.F.; Silva, P.S.; Hanken, R.B.L.; Raposo, C.M.O.

    2009-01-01

    Many groups from modern society have seen with attention the issues of pollutants, generally present in nature, those same that have caused irreversible damages to the environment. The Vermiculite, a phyllosilicate, with t-o-t structure, have high interlamelar charge, has been studied as cationic exchanger, whose application when exfoliated, are increased. This work has the objective of evaluate the absorption capacity of chromium (III), in different concentrations, in high, slim and medium concentrations of exfoliated vermiculites. The results obtained from the characterization by spectroscopy in infrared and by diffraction of x-ray from prepared solids showed important variations in the quantity of adsorbed metal in order the size of the concentrated particles. (author)

  1. Matrix mineralogy of the Lance CO3 carbonaceous chondrite - A transmission electron microscope study

    Science.gov (United States)

    Keller, Lindsay P.; Buseck, Peter R.

    1990-01-01

    Results are presented on electron microprobe analyses of three CO chondrites, all of which are falls: Lance, Kainsaz, and Warrenton. The TEM mineralogy results of Lance chondrite show that Fe-rich matrix olivines have been altered to Fe-bearing serpentine and Fe(3+) oxide; matrix metal was also altered to produce Fe(3+) oxides, leaving the residual metal enriched in Ni. Olivine grains in Lance's matrix contain channels along their 100-line and 001-line directions; the formation and convergence of such channels resulted in a grain-size reduction of the olivine. A study of Kainsaz and Warrenton showed that these meteorites do not contain phyllosilicates in their matrices, although both contain Fe(3+) oxide between olivine grains. It is suggested that, prior to its alteration, Lance probably resembled Kainsaz, an unaltered CO3 chondrite.

  2. Geological controls on soil parent material geochemistry along a northern Manitoba-North Dakota transect

    Science.gov (United States)

    Klassen, R.A.

    2009-01-01

    As a pilot study for mapping the geochemistry of North American soils, samples were collected along two continental transects extending east–west from Virginia to California, and north–south from northern Manitoba to the US–Mexican border and subjected to geochemical and mineralogical analyses. For the northern Manitoba–North Dakota segment of the north–south transect, X-ray diffraction analysis and bivariate relations indicate that geochemical properties of soil parent materials may be interpreted in terms of minerals derived from Shield and clastic sedimentary bedrock, and carbonate sedimentary bedrock terranes. The elements Cu, Zn, Ni, Cr and Ti occur primarily in silicate minerals decomposed by aqua regia, likely phyllosilicates, that preferentially concentrate in clay-sized fractions; Cr and Ti also occur in minerals decomposed only by stronger acid. Physical glacial processes affecting the distribution and concentration of carbonate minerals are significant controls on the variation of trace metal background concentrations.

  3. Geological controls on soil parent material geochemistry along a northern Manitoba-North Dakota transect

    International Nuclear Information System (INIS)

    Klassen, R.A.

    2009-01-01

    As a pilot study for mapping the geochemistry of North American soils, samples were collected along two continental transects extending east-west from Virginia to California, and north-south from northern Manitoba to the US-Mexican border and subjected to geochemical and mineralogical analyses. For the northern Manitoba-North Dakota segment of the north-south transect, X-ray diffraction analysis and bivariate relations indicate that geochemical properties of soil parent materials may be interpreted in terms of minerals derived from Shield and clastic sedimentary bedrock, and carbonate sedimentary bedrock terranes. The elements Cu, Zn, Ni, Cr and Ti occur primarily in silicate minerals decomposed by aqua regia, likely phyllosilicates, that preferentially concentrate in clay-sized fractions; Cr and Ti also occur in minerals decomposed only by stronger acid. Physical glacial processes affecting the distribution and concentration of carbonate minerals are significant controls on the variation of trace metal background concentrations.

  4. Mineralogical characterization of selected shales in support of nuclear waste repository studies: Progress report

    International Nuclear Information System (INIS)

    Lee, S.Y.; Hyder, L.K.; Alley, P.D.

    1987-12-01

    Because baseline characterization of shale mineralogy is critical to the interpretation of results from experiments on radionuclide retardation, groundwater-shale interactions, and physicochemical characteristics, a protocol for quantitative mineralogical analyses has been developed by integrating geochemical and instrumental techniques for the investigation of properties related to repository performance. Thermal analyses were used to estimate total organic matter and carbonate mineral contents. Scanning electron microscope backscattering and elemental mapping of polished sectors and particle-size distribution data were used to estimate the amounts of quartz plus feldspar and pyrite in the shales. X-ray diffraction, neutron activation, and size-distribution data were utilized to estimate phyllosilicate mineral contents. High-resolution transmission electron microscopy was used to identify clay mineral components

  5. From bulk soil to intracrystalline investigation of plant-mineral interaction

    Science.gov (United States)

    Lemarchand, D.; Voinot, A.; Chabaux, F.; Turpault, M.

    2011-12-01

    clear contribution of vegetation-recycled B to neoformed mineral phases, whereas B in minerals from the brown acidic soil rather indicates predominant mineral dissolution with little or even no B supply from the soil solution. If B isotopes thus proved their sensitivity to the soil forming conditions, a simple isotopic budget also demonstrates that the isotopic signature shown by the vegetation cannot result from fractionation during boron absorption. Analyses of B isotopes within intracrystalline phyllosilicate minerals further identify the interfoliar layers as the major source of B during plant nutrition. Additionally, weathering experiments placing phyllosilicates in contact with various alteration agents (protons, organic acid or siderophore) point to the role of the latters as likely responsible for the boron liberation from the phyllosilicate interfoliar layers. This scenario gives the phyllosilicate interfoliar layers a central function in the plant nutrition in context studied here of soils developed on granitic bedrocks. It also implies a very dynamic system in which plants and minerals can exchange matter over very short periods of time.

  6. Lunar and Planetary Science XXXV: Origin of Planetary Systems

    Science.gov (United States)

    2004-01-01

    The session titled Origin of Planetary Systems" included the following reports:Convective Cooling of Protoplanetary Disks and Rapid Giant Planet Formation; When Push Comes to Shove: Gap-opening, Disk Clearing and the In Situ Formation of Giant Planets; Late Injection of Radionuclides into Solar Nebula Analogs in Orion; Growth of Dust Particles and Accumulation of Centimeter-sized Objects in the Vicinity of a Pressure enhanced Region of a Solar Nebula; Fast, Repeatable Clumping of Solid Particles in Microgravity ; Chondrule Formation by Current Sheets in Protoplanetary Disks; Radial Migration of Phyllosilicates in the Solar Nebula; Accretion of the Outer Planets: Oligarchy or Monarchy?; Resonant Capture of Irregular Satellites by a Protoplanet ; On the Final Mass of Giant Planets ; Predicting the Atmospheric Composition of Extrasolar Giant Planets; Overturn of Unstably Stratified Fluids: Implications for the Early Evolution of Planetary Mantles; and The Evolution of an Impact-generated Partially-vaporized Circumplanetary Disk.

  7. Elemental geochemistry of sedimentary rocks at Yellowknife Bay, Gale crater, Mars.

    Science.gov (United States)

    McLennan, S M; Anderson, R B; Bell, J F; Bridges, J C; Calef, F; Campbell, J L; Clark, B C; Clegg, S; Conrad, P; Cousin, A; Des Marais, D J; Dromart, G; Dyar, M D; Edgar, L A; Ehlmann, B L; Fabre, C; Forni, O; Gasnault, O; Gellert, R; Gordon, S; Grant, J A; Grotzinger, J P; Gupta, S; Herkenhoff, K E; Hurowitz, J A; King, P L; Le Mouélic, S; Leshin, L A; Léveillé, R; Lewis, K W; Mangold, N; Maurice, S; Ming, D W; Morris, R V; Nachon, M; Newsom, H E; Ollila, A M; Perrett, G M; Rice, M S; Schmidt, M E; Schwenzer, S P; Stack, K; Stolper, E M; Sumner, D Y; Treiman, A H; VanBommel, S; Vaniman, D T; Vasavada, A; Wiens, R C; Yingst, R A

    2014-01-24

    Sedimentary rocks examined by the Curiosity rover at Yellowknife Bay, Mars, were derived from sources that evolved from an approximately average martian crustal composition to one influenced by alkaline basalts. No evidence of chemical weathering is preserved, indicating arid, possibly cold, paleoclimates and rapid erosion and deposition. The absence of predicted geochemical variations indicates that magnetite and phyllosilicates formed by diagenesis under low-temperature, circumneutral pH, rock-dominated aqueous conditions. Analyses of diagenetic features (including concretions, raised ridges, and fractures) at high spatial resolution indicate that they are composed of iron- and halogen-rich components, magnesium-iron-chlorine-rich components, and hydrated calcium sulfates, respectively. Composition of a cross-cutting dike-like feature is consistent with sedimentary intrusion. The geochemistry of these sedimentary rocks provides further evidence for diverse depositional and diagenetic sedimentary environments during the early history of Mars.

  8. Evaluation of the capacity of heavy metal adsorption in exfoliated vermiculite; Avaliacao da capacidade de adsorcao de metal pesado em vermiculitas esfoliadas

    Energy Technology Data Exchange (ETDEWEB)

    Lima, J.F.; Silva, P.S.; Hanken, R.B.L. [Universidade Federal de Campina Grande (UAEMa/UFCG), PB (Brazil). Unidade Academica de Engenharia de Materiais; Raposo, C.M.O., E-mail: raposo@dmg.ufcg.edu.b [Universidade Federal de Campina Grande (UAMG/UFCG), Bodocongo, PB (Brazil). Unidade Academica de Mineracao e Geologia

    2009-07-01

    Many groups from modern society have seen with attention the issues of pollutants, generally present in nature, those same that have caused irreversible damages to the environment. The Vermiculite, a phyllosilicate, with t-o-t structure, have high interlamelar charge, has been studied as cationic exchanger, whose application when exfoliated, are increased. This work has the objective of evaluate the absorption capacity of chromium (III), in different concentrations, in high, slim and medium concentrations of exfoliated vermiculites. The results obtained from the characterization by spectroscopy in infrared and by diffraction of x-ray from prepared solids showed important variations in the quantity of adsorbed metal in order the size of the concentrated particles. (author)

  9. Revealing the Formation of Copper Nanoparticles from a Homogeneous Solid Precursor by Electron Microscopy

    DEFF Research Database (Denmark)

    van den Berg, Roy; Elkjær, Christian Fink; Gommes, Cedric J.

    2016-01-01

    The understanding of processes leading to the formation of nanometer-sized particles is important for tailoring of their size, shape and location. The growth mechanisms and kinetics of nanoparticles from solid precursors are, however, often poorly described. Here we employ transmission electron...... microscopy (TEM) to examine the formation of copper nanoparticles on a silica support during the reduction by H2 of homogeneous copper phyllosilicate platelets, as a prototype precursor for a coprecipitated catalyst. Specifically, time-lapsed TEM image series acquired of the material during the reduction...... process provide a direct visualization of the growth dynamics of an ensemble of individual nanoparticles and enable a quantitative evaluation of the nucleation and growth of the nanoparticles. This quantitative information is compared with kinetic models and found to be best described by a nucleation...

  10. In situ detection of boron by ChemCam on Mars

    Science.gov (United States)

    Gasda, Patrick J.; Haldeman, Ethan B.; Wiens, Roger C.; Rapin, William; Bristow, Thomas F.; Bridges, John C.; Schwenzer, Susanne P.; Clark, Benton; Herkenhoff, Kenneth; Frydenvang, Jens; Lanza, Nina L.; Maurice, Sylvestre; Clegg, Samuel; Delapp, Dorothea M.; Sanford, Veronica L.; Bodine, Madeleine R.; McInroy, Rhonda

    2017-09-01

    We report the first in situ detection of boron on Mars. Boron has been detected in Gale crater at levels Curiosity rover ChemCam instrument in calcium-sulfate-filled fractures, which formed in a late-stage groundwater circulating mainly in phyllosilicate-rich bedrock interpreted as lacustrine in origin. We consider two main groundwater-driven hypotheses to explain the presence of boron in the veins: leaching of borates out of bedrock or the redistribution of borate by dissolution of borate-bearing evaporite deposits. Our results suggest that an evaporation mechanism is most likely, implying that Gale groundwaters were mildly alkaline. On Earth, boron may be a necessary component for the origin of life; on Mars, its presence suggests that subsurface groundwater conditions could have supported prebiotic chemical reactions if organics were also present and provides additional support for the past habitability of Gale crater.

  11. Optimization of the process of synthesis of hydrophobic clay; Otimizacao do processo de sintese de uma argila hidrofobica

    Energy Technology Data Exchange (ETDEWEB)

    Muniz, C.C.; Silva, S.M.L. da [Universidade Federal de Campina Grande (UAEMa/UFCG), PB (Brazil). Unidade Academica de Engenharia de Materiais; Raposo, C.M.O., E-mail: raposo@dmg.ufcg.edu.b [Universidade Federal de Campina Grande (UAMG/UFCG), PB (Brazil). Unidade Academica de Mineracao e Geologia

    2009-07-01

    Bentonite is a nature silicate pertaining subclass of phyllosilicates 2:1, being formed of accessories minerals, which montmorillonite there is in content more significant. The minerals and intrinsic impurities in the mineral predominant, such as, the procedure of organic modification, probably, influence so significant the obtainment of hydrophobic powders with crystallographic characteristics most appropriate to obtainment of materials nanostructured. The aim of the work was the optimization of synthesis process of hydrophobic clay promoted at the powder prepared a new structural profile. The original matter, bentonite, from Bentonit Uniao Nordeste- BUN/Paraiba, was previously purified and organophilized used an ammonium quaternary salt. The characterization of solids prepared was realized by infrared spectroscopy and x-ray diffraction indicating the obtainment of material with competitive profile when compared to the commercial one. (author)

  12. Control of clay minerals effect in flotation. A review

    Directory of Open Access Journals (Sweden)

    Taner Hasan Ali

    2016-01-01

    Full Text Available The increased exposure to low grade ores highlights the importance of understanding phyllosilicate gangue mineralogy which consists of common gangue minerals. To improve the flotation performance and ore quality the negative effect of the clay minerals on flotation should be identified. The presence of clay minerals leads to problems, such as changing the froth stability, which are related to swelling behaviour, increase in pulp viscosity, overconsumption of reagents, slime coating and mechanical entrainment. The clay content in the ore is changing from time to time and it is necessary to provide quick solutions to the issues caused by the new ore composition. The objective of this paper is to give an overview how to control the colloidal properties of clay minerals on flotation.

  13. Confidence Hills Mineralogy and Chemin Results from Base of Mt. Sharp, Pahrump Hills, Gale Crater, Mars

    Science.gov (United States)

    Cavanagh, P. D.; Bish, D. L.; Blake, D. F.; Vaniman, D. T.; Morris, R. V.; Ming, D. W.; Rampe, E. B.; Achilles, C. N.; Chipera, S. J.; Treiman, A. H.; hide

    2015-01-01

    The Mars Science Laboratory (MSL) rover Curiosity recently completed its fourth drill sampling of sediments on Mars. The Confidence Hills (CH) sample was drilled from a rock located in the Pahrump Hills region at the base of Mt. Sharp in Gale Crater. The CheMin X-ray diffractometer completed five nights of analysis on the sample, more than previously executed for a drill sample, and the data have been analyzed using Rietveld refinement and full-pattern fitting to determine quantitative mineralogy. Confidence Hills mineralogy has several important characteristics: 1) abundant hematite and lesser magnetite; 2) a 10 angstrom phyllosilicate; 3) multiple feldspars including plagioclase and alkali feldspar; 4) mafic silicates including forsterite, orthopyroxene, and two types of clinopyroxene (Ca-rich and Ca-poor), consistent with a basaltic source; and 5) minor contributions from sulfur-bearing species including jarosite.

  14. Chiral Biases in Solids by Effect of Shear Gradients: A Speculation on the Deterministic Origin of Biological Homochirality

    International Nuclear Information System (INIS)

    Arteaga, O.; Canillas, A.; Crusats, Joaquim; Hachemi, Zoubir; Jellison, Gerald Earle Jr.; Llorca, Jordi; Ribo, Josep M.

    2010-01-01

    We present an experimental approach to the study of the chirality of three CM2 meteorite solid samples by direct measurement of the optical activity (circular birefringence; CB). The measurements are based on transmission two modulator generalized ellipsometry in conjuction with microscope optics to map the CB of the samples. In spite of the complexity of such optical analysis, these first results indicate the presence of optically active areas in the meteorite solid matrix. In the case of the Murchison sample the statistics of the CB mapping shows a bimodal distribution with a bias to negative CB values. The composition of the active areas probably corresponds to serpentines and other poorly identified phyllosilicate phases. The results are compatible with the hypothesis that in a mineral-based scenario for the origin of life a CB sign bias in the chiral fractures originated by mechanical and flow shear gradients on clays could be later transferred to the reactions of the absorbed organic compounds.

  15. J6 Himalia: New Compositional Evidence and Interpretations for the Origin of Jupiter's Small Satellites

    Science.gov (United States)

    Vilas, Faith; Jarvis, K.; Larson, S.; Gaffey, M.

    1999-01-01

    New narrowband spectrophotometric data of J6 Himalia, some of which are spatially resolved, support its C-type classification. The new spectra confirm the presence of a weak absorption feature centered near 0.7 micron attributed to oxidized iron in phyllosilicates, products of aqueous alteration, which varies in depth on opposite sides of the satellite. Evaluation of older UBV photometry of J6 and J7 Elara compared to UBV photometry of C-class (and subclass) asteroids showing spectral evidence of the 0.7-microns absorption feature suggests that J6 Himalia is an F-class asteroid. We propose that the parent body of the prograde Jovian satellites originated as part of the Nysa asteroid family. Evolutionary models of the Jovian system are used to address the capture and dispersal of the irregular satellites.

  16. Chemical and Mineralogical Features of Smectite from the Morron de Mateo Bentonite Deposit (Cabo de Gata, Almeria) in Relation to the Parent Rocks and the Alteration Processes Occurred After the Bentonite Formation: Analogies and Implications for the Engineered Clayey Barrier of a Deep Geological Rad waste Repository; Naturaleza de las Esmectitas del Yacimiento de Morron de Mateo (Cabo de Gata, Almeria) en Relacion con la Roca Madre y con los Procesos Posteriores a la Bentonitizacion: Implicaciones Analogicas para la Barrera de Ingenieria de un Almacenamiento Geologico de Residuos Radiactivos

    Energy Technology Data Exchange (ETDEWEB)

    Pelayo, M; Labajo, M A; Garcia Romero, L; Perez del Villar, L

    2009-10-12

    The Morron de Mateo bentonite deposit is being studied as a natural analogue of the thermal and geochemical effects on the clayey barrier of a Deep Geological Rad waste Repository (DGRR) after its closure, in relation to the radioactive decay of the fission products and the container corrosion. This bentonite deposit and their host rocks were intruded by a rhyodacitic volcanic dome that induced a hydrothermal metasomatic process affecting the bioclastic calcarenite beds close to the dome. Bentonite from the NE sector of the deposit have been chemically and mineralogically characterized. Pyroclastic rocks (white tuffs), epyclastic rocks (mass flow) and andesitic breccia all of them hydrothermally altered, have been studied at the site. Samples are composed of feldspars, quartz and amphybols, as inherited minerals, and phyllosilicates, zeolites, crystoballite and calcite, as new formed minerals. White tuffs have the highest phyllosilicate contents, mainly dioctahedral smectite of montmorillonite type. Epyclastic rocks and andesitic breccia have a highest proportion of inherited minerals, the new formed phillosilicates being di octahedral smectite of beidellite type and an ordered interlayer chlorite/smectite mineral, of corrensite type. Smectite from the epyclastic rocks have higher Fe and Mg contents and chemical variability, as a consequence of nature of their parent rocks. The presence of corrensite in the epyclastic rocks suggests that in the Morron de Mateo area a propilitic alteration process occurred after bentonite formation, which transformed Fe-Mg-rich smectite into corrensite. This transformation was probably favoured by the sub volcanic intrusion, which also produced a temperature increase in the geological media and a supply of Fe-Mg-rich solutions, which also were the responsible for the metasomatic transformations observed in the calcarenite beds. (Author) 57 refs.

  17. Chemical and Mineralogical Features of Smectite from the Morron de Mateo Bentonite Deposit (Cabo de Gata, Almeria) in Relation to the Parent Rocks and the Alteration Processes Occurred After the Bentonite Formation: Analogies and Implications for the Engineered Clayey Barrier of a Deep Geological Rad waste Repository

    International Nuclear Information System (INIS)

    Pelayo, M.; Labajo, M. A.; Garcia Romero, L.; Perez del Villar, L.

    2009-01-01

    The Morron de Mateo bentonite deposit is being studied as a natural analogue of the thermal and geochemical effects on the clayey barrier of a Deep Geological Rad waste Repository (DGRR) after its closure, in relation to the radioactive decay of the fission products and the container corrosion. This bentonite deposit and their host rocks were intruded by a rhyodacitic volcanic dome that induced a hydrothermal metasomatic process affecting the bioclastic calcarenite beds close to the dome. Bentonite from the NE sector of the deposit have been chemically and mineralogically characterized. Pyroclastic rocks (white tuffs), epyclastic rocks (mass flow) and andesitic breccia all of them hydrothermally altered, have been studied at the site. Samples are composed of feldspars, quartz and amphybols, as inherited minerals, and phyllosilicates, zeolites, crystoballite and calcite, as new formed minerals. White tuffs have the highest phyllosilicate contents, mainly dioctahedral smectite of montmorillonite type. Epyclastic rocks and andesitic breccia have a highest proportion of inherited minerals, the new formed phillosilicates being di octahedral smectite of beidellite type and an ordered interlayer chlorite/smectite mineral, of corrensite type. Smectite from the epyclastic rocks have higher Fe and Mg contents and chemical variability, as a consequence of nature of their parent rocks. The presence of corrensite in the epyclastic rocks suggests that in the Morron de Mateo area a propilitic alteration process occurred after bentonite formation, which transformed Fe-Mg-rich smectite into corrensite. This transformation was probably favoured by the sub volcanic intrusion, which also produced a temperature increase in the geological media and a supply of Fe-Mg-rich solutions, which also were the responsible for the metasomatic transformations observed in the calcarenite beds. (Author) 57 refs

  18. Basalt Weathering in a Cold and Icy Climate: Three Sisters, Oregon as an Analog for Early Mars

    Science.gov (United States)

    Rampe, E. B.; Horgan, B.; Smith, R. J.; Scudder, N. A.; Rutledge, A. M.; Bamber, E.; Morris, R. V.

    2017-01-01

    There is abundant evidence for liquid water on early Mars, but the debate remains whether early Mars was warm and wet or cold and icy with punctuated periods of melting. To further investigate the hypothesis of a cold and icy early Mars, we collected rocks and sediments from the Collier and Diller glacial valleys in the Three Sisters volcanic complex in Oregon. We analyzed rocks and sediments with X-ray diffraction (XRD), scanning and transmission electron microscopies with energy dispersive spectroscopy (SEM, TEM, EDS), and visible, short-wave infrared (VSWIR) and thermal-IR (TIR) spectroscopies to characterize chemical weathering and sediment transport through the valleys. Here, we focus on the composition and mineralogy of the weathering products and how they compare to those identified on the martian surface. Phyllosilicates (smectite), zeolites, and poorly crystalline phases were discovered in pro- and supra-glacial sediments, whereas Si-rich regelation films were found on hand samples and boulders in the proglacial valleys. Most phyllosilicates and zeolites are likely detrital, originating from hydrothermally altered units on North Sister. TEM-EDS analyses of the flour samples demonstrate a variety of poorly crystalline (i.e., no long-range crystallographic order) phases: iron oxides, devitrified volcanic glass, and Fe-Si-Al phases. The CheMin XRD on the Curiosity rover in Gale crater has identified significant amounts of X-ray amorphous materials in all samples measured to date. The amorphous component is likely a combination of silicates, iron oxides, and sulfates. Although we have not yet observed amorphous sulfate in the samples from Three Sisters, the variety of poorly crystalline weathering products found at this site is consistent with the variable composition of the X-ray amorphous component identified by CheMin. We suggest that these amorphous phases on Mars could have formed in a similarly cold and icy environment.

  19. Impact of Oxidative Dissolution on Black Shale Fracturing: Implication for Shale Fracturing Treatment Design

    Science.gov (United States)

    You, L.; Chen, Q.; Kang, Y.; Cheng, Q.; Sheng, J.

    2017-12-01

    Black shales contain a large amount of environment-sensitive compositions, e.g., clay minerals, carbonate, siderite, pyrite, and organic matter. There have been numerous studies on the black shales compositional and pore structure changes caused by oxic environments. However, most of the studies did not focus on their ability to facilitate shale fracturing. To test the redox-sensitive aspects of shale fracturing and its potentially favorable effects on hydraulic fracturing in shale gas reservoirs, the induced microfractures of Longmaxi black shales exposed to deionized water, hydrochloric acid, and hydrogen peroxide at room-temperature for 240 hours were imaged by scanning electron microscopy (SEM) and CT-scanning in this paper. Mineral composition, acoustic emission, swelling, and zeta potential of the untreated and oxidative treatment shale samples were also recorded to decipher the coupled physical and chemical effects of oxidizing environments on shale fracturing processes. Results show that pervasive microfractures (Fig.1) with apertures ranging from tens of nanometers to tens of microns formed in response to oxidative dissolution by hydrogen peroxide, whereas no new microfracture was observed after the exposure to deionized water and hydrochloric acid. The trajectory of these oxidation-induced microfractures was controlled by the distribution of phyllosilicate framework and flaky or stringy organic matter in shale. The experiments reported in this paper indicate that black shales present the least resistance to crack initiation and subcritical slow propagation in hydrogen peroxide, a process we refer to as oxidation-sensitive fracturing, which are closely related to the expansive stress of clay minerals, dissolution of redox-sensitive compositions, destruction of phyllosilicate framework, and the much lower zeta potential of hydrogen peroxide solution-shale system. It could mean that the injection of fracturing water with strong oxidizing aqueous solution may

  20. Laboratory Astronomy Needs for the Study of Dust in Comets in the Next Decade

    Science.gov (United States)

    Lisse, Carey M.

    2009-05-01

    The Spitzer Space Telescope observed the mid-IR ( 5-40 µm) spectra of ejecta from the hypervelocity impact of the Deep Impact projectile with comet 9P/Tempel-1. Spectral modeling demonstrates that there are abundant minerals present in the ejecta including Ca/Fe/Mg-rich silicates, carbonates, phyllosilicates, water ice, amorphous carbon, and sulfides (Lisse et al. 2006). Other Infrared Space Observatory (ISO), Spitzer, and Akari observations provide evidence for large reservoirs of these dusty species not only in comets, but in related reservoirs: Centaurs, Kuiper Belt objects, and exo-solar Kuiper Belts. In the next 5 years, we can expect SOFIA, ASTRO-H and JWST measurements to build on these results in the mid-IR. Consistency with STARDUST sample return findings has bolstered confidence in these remote sensing results (Flynn et al. 2008). However, precise mineralogical identifications are hampered by the lack of detailed spectral measurements, particularly of transmission and of the associated derived absorption coefficient, for astrophysically relevant materials in the 3 - 40 µm range over which Spitzer, etc. sensitive. The upcoming Herschel Space Observatory mission will open up a new wavelength range, collecting mineralogically-characteristic far-IR emission spectra of comet dust populations in the range of 57 - 210 µm using its Photodetector Array Camera and Spectrometer (PACS), and out to 650 um using its Spectral and Photometric Imaging Receiver (SPIRE). Many astrophysically important minerals (e.g., pyroxenes, carbonates, phyllosilicates, water ice) have potentially distinctive, but poorly quantified, PACS-range emission features that are sensitive to chemical composition and crystal structure. Mineral identifications have often been based on a single strong mid-IR feature lack confidence [Molster & Waters 2003], which can be bolstered by measuring multiple complementary far-IR features. Full laboratory spectroscopic knowledge of candidate materials, as

  1. Nickel distribution and isotopic fractionation in a Brazilian lateritic regolith: Coupling Ni isotopes and Ni K-edge XANES

    Science.gov (United States)

    Ratié, G.; Garnier, J.; Calmels, D.; Vantelon, D.; Guimarães, E.; Monvoisin, G.; Nouet, J.; Ponzevera, E.; Quantin, C.

    2018-06-01

    Ultramafic (UM) rocks are known to be nickel (Ni) rich and to weather quickly, which makes them a good candidate to look at the Ni isotope systematics during weathering processes at the Earth's surface. The present study aims at identifying the Ni solid speciation and discussing the weathering processes that produce Ni isotope fractionation in two deep laterite profiles under tropical conditions (Barro Alto, Goiás State, Brazil). While phyllosilicates and to a lower extent goethite are the main Ni-bearing phases in the saprolitic part of the profile, iron (Fe) oxides dominate the Ni budget in the lateritic unit. Nickel isotopic composition (δ60Ni values) has been measured in each unit of the regolith, i.e., rock, saprock, saprolite and laterite (n = 52). δ60Ni varies widely within the two laterite profiles, from -0.10 ± 0.05‰ to 1.43 ± 0.05‰, showing that significant Ni isotope fractionation occurs during the weathering of UM rocks. Overall, our results show that during weathering, the solid phase is depleted in heavy Ni isotopes due to the preferential sorption and incorporation of light Ni isotopes into Fe oxides; the same mechanisms likely apply to the incorporation of Ni into phyllosilicates (type 2:1). However, an isotopically heavy Ni pool is observed in the solid phase at the bottom of the saprolitic unit. This feature can be explained by two hypotheses that are not mutually exclusive: (i) a depletion in light Ni isotopes during the first stage of weathering due to the preferential dissolution of light Ni-containing minerals, and (ii) the sorption or incorporation of isotopically heavy Ni carried by percolating waters (groundwater samples have δ60Ni of 2.20 and 2.27‰), that were enriched in heavy Ni isotopes due to successive weathering processes in the overlying soil and laterite units.

  2. Soils of slopes in the taiga zone of the Middle Ob reaches

    Science.gov (United States)

    Karavaeva, N. A.; Sokolova, T. A.

    2015-06-01

    The morphology, chemical properties, composition of phyllosilicates, as well as their transformation in loamy soils developing on slopes of ridges of the Vakh Upland in Western Siberia, are discussed. Data on two soil profiles-gleyic svetlozem of the middle slope and podzolized gleyzem of the footslope—are presented. Both soils have an acid reaction. The textural differentiation is weakly pronounced in the gleyic svetlozem and more pronounced in the podzolized gleyzem. The soils differ in their cryological conditions. The thawing depth in the svetlozem is about 60-70 cm, and the lower part of the profile to a depth of 3.2 m largely remains in the frozen state. Its complete thawing is only possible during the warm climatic cycles. This is a seasonally frozen soil with the long-lasting frozen state. It is characterized by the thick cryometamorphic (CRM) horizon. The gleyzem is a "normal" seasonally frozen soil with complete thawing of seasonal frost in summer. The CRM horizon is absent in its profile. The alteration of clay minerals in the soil profiles includes their partial dissolution, the formation of soil chlorites, and the transformation of illite into more labile structures. In the upper horizons of both soils, this transformation proceeds through the stage of mixed-layered illite-smectites. In the gleyzem, it reaches a more advanced stage of the formation of beidellite. The cryometamorphic horizons are specified by some amorphization of phyllosilicates and, probably, by the partial dissolution of their crystal lattices under the impact of frequent zero-temperature transitions and cryogenesis in the frozen state.

  3. Flash pyrolysis of adsorbed aromatic organic acids on carbonate minerals: Assessing the impact of mineralogy for the identification of organic compounds in extraterrestrial bodies

    Science.gov (United States)

    Zafar, R.

    2017-12-01

    The relationship between minerals and organics is an essential factor in comprehending the origin of life on extraterrestrial bodies. So far organic molecules have been detected on meteorites, comets, interstellar medium and interplanetary dust particles. While on Mars, organic molecules may also be present as indicated by the Sample Analysis at Mars (SAM) instrument suite on the Curiosity Rover in Martian sediments. Minerals including hydrated phyllosilicate, carbonate, and sulfate minerals have been confirmed in carbonaceous chondrites. The presence of phyllosilicate minerals on Mars has been indicated by in situ elemental analysis by the Viking Landers, remote sensing infrared observations and the presence of smectites in meteorites. Likewise, the presence of carbonate minerals on the surface of Mars has been indicated by both Phoenix Lander and Spirit Rover. Considering the fact that both mineral and organic matter are present on the surface of extraterrestrial bodies including Mars, a comprehensive work is required to understand the interaction of minerals with specific organic compounds. The adsorption of the organic molecule at water/mineral surface is a key process of concentrating organic molecules on the surface of minerals. Carboxylic acids are abundantly observed in extraterrestrial material such as meteorites and interstellar space. It is highly suspected that carboxylic acids are also present on Mars due to the average organic carbon infall rate of 108 kg/yr. Further aromatic organic acids have also been observed in carbonaceous chondrite meteorites. This work presents the adsorption of an aromatic carboxylic acid at the water/calcite interface and characterization of the products formed after adsorption via on-line pyrolysis. Adsorption and online pyrolysis results are used to gain insight into adsorbed aromatic organic acid-calcite interaction. Adsorption and online pyrolysis results are related to the interpretation of organic compounds identified

  4. Improvement of nitrogen utilization and soil properties by addition of a mineral soil conditioner: mechanism and performance.

    Science.gov (United States)

    Yan, Xiaodan; Shi, Lin; Cai, Rumeng

    2018-01-01

    A mineral soil conditioner (MSC) composed of activated potash feldspar, gypsum, and calcium carbonate and containing an amount of available mineral nutrients, is shown to be effective for plant growth and acidic soil amelioration. In this study, a field test was conducted over four rice seasons by examining treatment with control check (CK), MSC, biological active carbon, and lime to investigate the nitrogen-use efficiency and mechanism of soil characteristic variations due to the desilicification and allitization of soil as well as the unrestrained use of nitrogen (N) fertilizer in recent years. Influences of MSC on the xylem sap intensity and mean rice yields were evaluated, and the soil type was also analyzed using the FactSage 6.1 Reaction, phase diagram, and Equilib modules. The results of the field trial showed that MSC application increased the xylem sap intensity and nitrogen export intensity by 37.33-39.85% and 31.40-51.20%, respectively. A significant increase (5.63-15.48%) in mean grain yields was achieved with MSC application over that with biological active carbon and lime application. The effects of MSC had a tendency to increase with time in the field experiment results, and grain yields increased after the initial application. The new formation of clay minerals exhibits a significant influence on [Formula: see text] fixation, especially for 2:1 phyllosilicates with illite, owing to the interlayers of the clay minerals. Our preliminary results showed that kaolinite, the main 1:1 phyllosilicate clay mineral in ferralsol, transformed to illite at room temperature as a consequence of the presence of H 4 SiO 4 and available K + supplied by MSC. This indicated that improving the soil quality combined with reducing N losses from soils is an efficient way to control non-point source pollution from agriculture without the risk of decreased in grain yield.

  5. Nickel speciation in several serpentine (ultramafic) topsoils via bulk synchrotron-based techniques

    Energy Technology Data Exchange (ETDEWEB)

    Siebecker, Matthew G.; Chaney, Rufus L.; Sparks, Donald L.

    2017-07-01

    Serpentine soils have elevated concentrations of trace metals including nickel, cobalt, and chromium compared to non-serpentine soils. Identifying the nickel bearing minerals allows for prediction of potential mobility of nickel. Synchrotron-based techniques can identify the solid-phase chemical forms of nickel with minimal sample treatment. Element concentrations are known to vary among soil particle sizes in serpentine soils. Sonication is a useful method to physically disperse sand, silt and clay particles in soils. Synchrotron-based techniques and sonication were employed to identify nickel species in discrete particle size fractions in several serpentine (ultramafic) topsoils to better understand solid-phase nickel geochemistry. Nickel commonly resided in primary serpentine parent material such as layered-phyllosilicate and chain-inosilicate minerals and was associated with iron oxides. In the clay fractions, nickel was associated with iron oxides and primary serpentine minerals, such as lizardite. Linear combination fitting (LCF) was used to characterize nickel species. Total metal concentration did not correlate with nickel speciation and is not an indicator of the major nickel species in the soil. Differences in soil texture were related to different nickel speciation for several particle size fractionated samples. A discussion on LCF illustrates the importance of choosing standards based not only on statistical methods such as Target Transformation but also on sample mineralogy and particle size. Results from the F-test (Hamilton test), which is an underutilized tool in the literature for LCF in soils, highlight its usefulness to determine the appropriate number of standards to for LCF. EXAFS shell fitting illustrates that destructive interference commonly found for light and heavy elements in layered double hydroxides and in phyllosilicates also can occur in inosilicate minerals, causing similar structural features and leading to false positive results in

  6. Distribution of the Ammoniated Species on the Surface of Ceres

    Science.gov (United States)

    Ammannito, E.; De Sanctis, M. C.; Carrorro, F. G.; Ciarniello, M.; Combe, J. P.; De Angelis, S.; Ehlmann, B. L.; Frigeri, A.; Marchi, S.; McSween, H. Y., Jr.; Raponi, A.; Toplis, M. J.; Tosi, F.; Castillo, J. C.; Capaccioni, F.; Capria, M. T.; Fonte, S.; Giardino, M.; Jaumann, R.; Longobardo, A.; Joy, S. P.; Magni, G.; McCord, T. B.; McFadden, L. A.; Palomba, E.; Pieters, C. M.; Polanskey, C. A.; Prettyman, T. H.; Rayman, M.; Raymond, C. A.; Schenk, P.; Zambon, F.; Russell, C. T.

    2016-12-01

    The Dawn spacecraft has been acquiring data on dwarf planet Ceres since January 2015 (1). The VIR spectrometer (0.25-5.0 μm) acquired data at different altitudes providing information on the composition of the surface of Ceres at resolutions ranging from few kilometers to about one hundred meters (2). The average spectrum of Ceres is well represented by a mixture of dark minerals, Mg- phyllosilicates, ammoniated clays, and Mg carbonates (3). This result confirms previous studies based on ground based spectra (4, 5). Maps of the surface at about 1 km/px show that the components identified in the average spectrum are present all across the surface with variations in their relative abundance (6). Some localized areas however have peculiar spectral characteristics. One example is the spectrum of the bright regions within Occator crater that is most consistent with a large amount of Na-carbonates and possibly ammonium salts (7). The presence of ammoniated species poses a constraint on the pH and redox condition during the evolution of Ceres. Therefore, we have studied the distribution across the surface of such species to better understand the evolutionary pathway of Ceres. References : (1) Russell, C. T. et al. 2016, Science. (2) De Sanctis M.C. et al., The VIR Spectrometer, 2011, Space Science Reviews. (3) De Sanctis M.C. et al. Ammoniated phyllosilicates on dwarf planet Ceres reveal an outer solar system origin, Nature, 2015. (4) King T. et al. (1992) Science, 255, 1551-1553. (5) Rivkin A.S. et al. (2006) Icarus, 185, 563-567. (6) Ammannito E. et al., Spectral diversity of Ceres surface as measured by VIR, 2016, Science. (7) De Sanctis et al. (2016), Nature

  7. Investigating the response of biotite to impact metamorphism: Examples from the Steen River impact structure, Canada

    Science.gov (United States)

    Walton, E. L.; Sharp, T. G.; Hu, J.; Tschauner, O.

    2018-01-01

    Impact metamorphic effects from quartz and feldspar and to a lesser extent olivine and pyroxene have been studied in detail. Comparatively, studies documenting shock effects in other minerals, such as double chain inosilicates, phyllosilicates, carbonates, and sulfates, are lacking. In this study, we investigate impact metamorphism recorded in crystalline basement rocks from the Steen River impact structure (SRIS), a 25 km diameter complex crater in NW Alberta, Canada. An array of advanced analytical techniques was used to characterize the breakdown of biotite in two distinct settings: along the margins of localized regions of shock melting and within granitic target rocks entrained as clasts in a breccia. In response to elevated temperature gradients along shock vein margins, biotite transformed at high pressure to an almandine-Ca/Fe majorite-rich garnet with a density of 4.2 g cm-3. The shock-produced garnets are poikilitic, with oxide and silicate glass inclusions. Areas interstitial to garnets are vesiculated, in support of models for the formation of shock veins via oscillatory slip, with deformation continuing during pressure release. Biotite within granitic clasts entrained within the hot breccia matrix thermally decomposed at ambient pressure to produce a fine-grained mineral assemblage of orthopyroxene + sanidine + titanomagnetite. These minerals are aligned to the (001) cleavage plane of the original crystal. In this and previous work, the transformation of an inosilicate (pargasite) and a phyllosilicate (biotite) to form garnet, an easily identifiable, robust mineral, has been documented. We contend that in deeply eroded astroblemes, high-pressure minerals that form within or in the environs of shock veins may serve as one of the possibly few surviving indicators of impact metamorphism.

  8. A synthesis of Martian aqueous mineralogy after 1 Mars year of observations from the Mars Reconnaissance Orbiter

    Science.gov (United States)

    Murchie, S.L.; Mustard, J.F.; Ehlmann, B.L.; Milliken, R.E.; Bishop, J.L.; McKeown, N.K.; Noe Dobrea, E.Z.; Seelos, F.P.; Buczkowski, D.L.; Wiseman, S.M.; Arvidson, R. E.; Wray, J.J.; Swayze, G.; Clark, R.N.; Des Marais, D.J.; McEwen, A.S.; Bibring, J.-P.

    2009-01-01

    Martian aqueous mineral deposits have been examined and characterized using data acquired during Mars Reconnaissance Orbiter's (MRO) primary science phase, including Compact Reconnaissance Imaging Spectrometer for Mars hyperspectral images covering the 0.4-3.9 ??m wavelength range, coordinated with higher-spatial resolution HiRISE and Context Imager images. MRO's new high-resolution measurements, combined with earlier data from Thermal Emission Spectrometer; Thermal Emission Imaging System; and Observatoire pour la Min??ralogie, L'Eau, les Glaces et l'Activiti?? on Mars Express, indicate that aqueous minerals are both diverse and widespread on the Martian surface. The aqueous minerals occur in 9-10 classes of deposits characterized by distinct mineral assemblages, morphologies, and geologic settings. Phyllosilicates occur in several settings: in compositionally layered blankets hundreds of meters thick, superposed on eroded Noachian terrains; in lower layers of intracrater depositional fans; in layers with potential chlorides in sediments on intercrater plains; and as thousands of deep exposures in craters and escarpments. Carbonate-bearing rocks form a thin unit surrounding the Isidis basin. Hydrated silica occurs with hydrated sulfates in thin stratified deposits surrounding Valles Marineris. Hydrated sulfates also occur together with crystalline ferric minerals in thick, layered deposits in Terra Meridiani and in Valles Marineris and together with kaolinite in deposits that partially infill some highland craters. In this paper we describe each of the classes of deposits, review hypotheses for their origins, identify new questions posed by existing measurements, and consider their implications for ancient habitable environments. On the basis of current data, two to five classes of Noachian-aged deposits containing phyllosilicates and carbonates may have formed in aqueous environments with pH and water activities suitable for life. Copyright 2009 by the American

  9. Sedimentary evolution of the Mesozoic continental redbeds using geochemical and mineralogical tools: the case of Upper Triassic to Lowermost Jurassic Monte di Gioiosa mudrocks (Sicily, southern Italy)

    Science.gov (United States)

    Perri, Francesco; Critelli, Salvatore; Mongelli, Giovanni; Cullers, Robert L.

    2011-10-01

    The continental redbeds from the Internal Domains of the central-western Mediterranean Chains have an important role in the palaeogeographic and palaeotectonic reconstructions of the Alpine circum-Mediterranean orogen evolution since these redbeds mark the Triassic-Jurassic rift-valley stage of Tethyan rifting. The composition and the sedimentary evolution of the Middle Triassic to Lowermost Jurassic continental redbeds of the San Marco d'Alunzio Unit (Peloritani Mountains, Southern Italy), based on mineralogical and chemical analyses, suggests that the studied mudrock sediments share common features with continental redbeds that constitute the Internal Domains of the Alpine Mediterranean Chains. Phyllosilicates are the main components in the mudrocks. The 10 Å-minerals (illite and micas), the I-S mixed layers, and kaolinite are the most abundant phyllosilicates. The amount of illitic layers in I-S mixed layers coupled with the illite crystallinity values (IC) are typical of high degree of diagenesis, corresponding to a lithostatic/tectonic loading of about 4-5 km. The mineralogical assemblage coupled with the A-CN-K plot suggest post-depositional K-enrichments. Palaeoweathering proxies (PIA and CIW) record intense weathering at the source area. Further, the studied sediments are affected by reworking and recycling processes and, as consequence, it is likely these proxies monitor cumulative effect of weathering. The climate in the early Jurassic favoured recycling and weathering occurred under hot, episodically humid climate with a prolonged dry season. The source-area is the low-grade Paleozoic metasedimentary basement. Mafic supply is minor but not negligible as suggested by provenance proxies.

  10. Low-cost zinc-plated photoanode for fabric-type dye-sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Lingfeng; Bao, Yunna; Guo, Wanwan; Cheng, Li; Du, Jun; Liu, Renlong [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (China); Wang, Yundong [Department of Chemical Engineering, Tsinghua University, State Key Lab of Chemical Engineering, Beijing 100084 (China); Fan, Xing, E-mail: foxcqdx@cqu.edu.cn [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (China); Tao, Changyuan [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (China)

    2016-02-15

    Graphical abstract: - Highlights: • Fabric-type flexible solar cells have been assembled on Zn-plated wires and meshes. • Metal Zn can improve the carriers transfer over the metal/ZnO nanoarrays interface. • A current increase by ∼6 mA/cm{sup 2} was realized by plating Zn on various metal substrates. • All-solid fabric-type DSSC was also assembled on Zn-plated metal wires. - Abstract: Fabric-type flexible solar cells have been recently proposed as a very promising power source for wearable electronics. To increase the photocurrent of fabric-type flexible solar cells, low-cost zinc-plated wire and mesh photoanodes are assembled for the first time through a mild wet process. Given the protection of the compact protection layer, the DSSC device could benefit from the low work function of Zn and self-repairing behavior on the Zn/ZnO interface. An evident current increase by ∼6 mA/cm{sup 2} could be observed after coating a layer of metal Zn on various metal substrates, such as traditional stainless steel wire. Given the self-repairing behavior on Zn/ZnO interface, the Zn layer can help to improve the interfacial carrier transfer, leading to better photovoltaic performance, for both liquid-type and solid-type cells.

  11. Corrosion protective performance of amino trimethylene phosphonic acid-metal complex layers fabricated on the cold-rolled steel substrate via one-step assembly

    Science.gov (United States)

    Yan, Ru; He, Wei; Zhai, Tianhua; Ma, Houyi

    2018-06-01

    Seeing that amino trimethylene phosphonic acid (ATMP) possesses very strong complexation ability to metal ions and the phosphonic acid group has good affinity for the oxidized iron surface, herein a simple and rapid film-forming method (one-step assembly method) was developed to construct the ATMP-Zn complex conversion layers (ATMP-Zn layers for short) on the cold-rolled steel (CRS) substrate. Zinc ions were found to participate in the formation process of ATMP-based composite film, which made the Zn-containing ATMP film significantly different in appearance, thickness, microstructure and film-forming mechanisms from the Zn-free ATMP film. There was mainly iron (ш) phosphonate in the Zn-free ATMP film, whereas there were Zn2+-ATMP complex and a certain amount of ZnO in the ATMP-Zn composite film. In addition, electrochemical test results clearly indicate that corrosion resistance of ATMP-Zn composite film was greatly enhanced due to the presence of Zn component. Moreover, the corrosion resistance performance could be controlled by adjusting film-forming time, pH and ATMP concentration in the film-forming solutions. The present study provides a new method for the design and fabrication of high-quality environmentally-friendly conversion layers.

  12. Cycling behaviour of sponge-like nanostructured ZnO as thin-film Li-ion battery anodes

    International Nuclear Information System (INIS)

    Garino, Nadia; Lamberti, Andrea; Gazia, Rossana; Chiodoni, Angelica; Gerbaldi, Claudio

    2014-01-01

    Highlights: • Zn is thermally oxidized in ambient air to obtain sponge-like ZnO film. • Polycrystalline, transparent, porous thin film is obtained. • Film exhibits stabile specific capacity (∼300 mAh g −1 ) after prolonged cycling. • Sponge-like ZnO film shows promising prospects as Li-ion battery anode. - Abstract: Single phase wurtzitic porous ZnO thin films are obtained by a simple two-step method, involving the sputtering deposition of a sponge-like metallic Zn layer, followed by a moderately low temperature treatment for the complete zinc oxidation. Thanks to its 3D nanostructuration, the superimposition of small branches able to grow in length almost isotropically and forming a complex topography, sponge-like ZnO can combine the fast transport properties of one dimensional material and the high surface area usually provided by nanocrystalline electrodes. When galvanostatically tested in lithium cell, after the initial decay, it can provide an almost stable specific capacity higher than 50 μAh cm −2 after prolonged cycling at estimated 0.7 C, with very high Coulombic efficiency

  13. Effect of zinc addition on properties of cadmium sulfide layer and performance of Cu(In,Ga)Se{sub 2} solar cell

    Energy Technology Data Exchange (ETDEWEB)

    Bae, Dowon, E-mail: bae.dowon@yahoo.co.kr; Gho, Junghwan; Shin, Minjung; Kwon, Sehan

    2013-05-01

    Cd{sub (1−x)}Zn{sub x}S (CdS:Zn) thin films were grown on an indium tin oxide-coated glass substrate and Cu(In,Ga)Se{sub 2} (CIGS) surface by chemical bath deposition for solar cell applications, and their composition, and optical properties were studied to decide the optimum process conditions for buffer layer growth. The average conversion efficiency of CIGS solar panels (24-in.) with the CdS:Zn layer was 0.35% higher than that of conventional solar panels mainly because of the increased open-circuit voltage. This efficiency improvement was not due to modification of the optical properties of the buffer layer, but due to the change in the deposition rate during buffer layer growth. - Highlights: ► CdS:Zn buffer layers were fabricated for Cu(In,Ga)Se{sub 2} (CIGS) photovoltaic (PV) panels. ► Composition of buffer layers on indium–tin–oxide (ITO) and CIGS was investigated. ► Transmittance of CdS:Zn on ITO coated glass showed 5% higher than CdS. ► Efficiency of CdS:Zn solution adopted panels showed 0.47% higher than that with CdS. ► However, it was revealed that only Cd and S ions were found at the surface of CIGS.

  14. Cycling behaviour of sponge-like nanostructured ZnO as thin-film Li-ion battery anodes

    Energy Technology Data Exchange (ETDEWEB)

    Garino, Nadia, E-mail: nadia.garino@iit.it [Center for Space Human Robotics @Polito, Istituto Italiano di Tecnologia, Corso Trento, 21, 10129 Turin (Italy); Lamberti, Andrea; Gazia, Rossana; Chiodoni, Angelica [Center for Space Human Robotics @Polito, Istituto Italiano di Tecnologia, Corso Trento, 21, 10129 Turin (Italy); Gerbaldi, Claudio, E-mail: claudio.gerbaldi@polito.it [Center for Space Human Robotics @Polito, Istituto Italiano di Tecnologia, Corso Trento, 21, 10129 Turin (Italy); GAME Lab, Department of Applied Science and Technology – DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Turin (Italy)

    2014-12-05

    Highlights: • Zn is thermally oxidized in ambient air to obtain sponge-like ZnO film. • Polycrystalline, transparent, porous thin film is obtained. • Film exhibits stabile specific capacity (∼300 mAh g{sup −1}) after prolonged cycling. • Sponge-like ZnO film shows promising prospects as Li-ion battery anode. - Abstract: Single phase wurtzitic porous ZnO thin films are obtained by a simple two-step method, involving the sputtering deposition of a sponge-like metallic Zn layer, followed by a moderately low temperature treatment for the complete zinc oxidation. Thanks to its 3D nanostructuration, the superimposition of small branches able to grow in length almost isotropically and forming a complex topography, sponge-like ZnO can combine the fast transport properties of one dimensional material and the high surface area usually provided by nanocrystalline electrodes. When galvanostatically tested in lithium cell, after the initial decay, it can provide an almost stable specific capacity higher than 50 μAh cm{sup −2} after prolonged cycling at estimated 0.7 C, with very high Coulombic efficiency.

  15. Synthesis and controlled release properties of 2,4-dichlorophenoxy acetate–zinc layered hydroxide nanohybrid

    International Nuclear Information System (INIS)

    Bashi, Abbas M.; Hussein, Mohd Zobir; Zainal, Zulkarnain; Tichit, Didier

    2013-01-01

    Direct reaction of ZnO with 2,4-dichlorophenoxyacetic acid (24D) solutions of different concentrations allows obtaining new organic–inorganic nanohybrid materials formed by intercalation of 24D into interlayers of zinc layered hydroxide (ZLH). XRD patterns show a progressive evolution of the structure as 24D concentration increases. The nanohybrid obtained at higher 24D concentration (24D–ZLH(0.4)) reveals a well ordered layered structure with two different basal spacings at 25.2 Å and 24 Å. The FTIR spectrum showing the vibrations bands of the functional groups of 24D and of the ZLH confirms the intercalation. SEM images are in agreement with the structural evolution observed by XRD and reveal the ribbon morphology of the nanohybrids. The release studies of 24D showed a rapid release of 94% for the first 100 min governed by the pseudo-second order kinetic model. - Graphical abstract: The phenomenon indicates that the optical energy gap is enlarged with the increase of molar concentrations in 2,4-dichlorophenoxy acetate anion content into ZnO to create a ZLH–24D nanohybrid. - Highlights: • Nanohybrid was synthesized from 2,4-dichlorophenoxy acetate with-Zinc LHD, using wet chemistry. • Characterized using SEM, TEM, EDX, FTIR, XRD and TGA. • Ribbon-shaped 24D–Zn-layered hydroxide nanoparticles with (003) diffractions of 2.5 nm phase were synthesized

  16. Mechanism of ultraviolet photoconductivity in zinc oxide nanoneedles

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Sanjeev [School of Information and Communication Engineering, and SKKU Advanced Institute of Nanotechnology, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Kim, Gil-Ho [School of Information and Communication Engineering, and SKKU Advanced Institute of Nanotechnology, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Sreenivas, K [Department of Physics and Astrophysics, University of Delhi, Delhi-110007 (India); Tandon, R P [Department of Physics and Astrophysics, University of Delhi, Delhi-110007 (India)

    2007-11-28

    Ultraviolet photoconductivity in zinc oxide (ZnO) nanoneedles grown on the surface of a multilayer structure comprised of ZnO film (50 nm)/Zn layer (20 nm)/ZnO film (2 {mu}m) fabricated on a stainless steel substrate using an unbalanced magnetron sputtering technique is reported. It was observed that the multilayered structure with ZnO nanoneedles exhibited enhanced ultraviolet photoconductivity in comparison to the ZnO films that were without nanoneedles. The enhancement in the photoconductivity is attributed to the increase in the quantum yield of the photogenerated charge carriers due to the presence of nanoneedles. A successive slow photoresponse transient following after a fast rise is due to the establishment of equilibrium between the charge carriers in the conduction band and the trapping centers created due to the shallow defects in the ZnO film. The observed photoresponse is critically analyzed on the basis of trapping levels created by the oxygen species during the high pressure deposition of the ZnO multilayer. Results show the promise of ZnO nanostructures in ultraviolet detection applications. (fast track communication)

  17. Mechanism of ultraviolet photoconductivity in zinc oxide nanoneedles

    International Nuclear Information System (INIS)

    Kumar, Sanjeev; Kim, Gil-Ho; Sreenivas, K; Tandon, R P

    2007-01-01

    Ultraviolet photoconductivity in zinc oxide (ZnO) nanoneedles grown on the surface of a multilayer structure comprised of ZnO film (50 nm)/Zn layer (20 nm)/ZnO film (2 μm) fabricated on a stainless steel substrate using an unbalanced magnetron sputtering technique is reported. It was observed that the multilayered structure with ZnO nanoneedles exhibited enhanced ultraviolet photoconductivity in comparison to the ZnO films that were without nanoneedles. The enhancement in the photoconductivity is attributed to the increase in the quantum yield of the photogenerated charge carriers due to the presence of nanoneedles. A successive slow photoresponse transient following after a fast rise is due to the establishment of equilibrium between the charge carriers in the conduction band and the trapping centers created due to the shallow defects in the ZnO film. The observed photoresponse is critically analyzed on the basis of trapping levels created by the oxygen species during the high pressure deposition of the ZnO multilayer. Results show the promise of ZnO nanostructures in ultraviolet detection applications. (fast track communication)

  18. Zinc/manganese multilayer coatings for corrosion protection

    International Nuclear Information System (INIS)

    Muenz, R.; Wolf, G.K.; Guzman, L.; Adami, M.

    2004-01-01

    Zn alloys are able to surpass the performance of electrogalvanised or hot-dip Zn (at same thickness) for corrosion protection of car bodies. In particular, vacuum deposited Zn alloy layers have higher protection power on non-painted steel surfaces as compared with pure Zn layers. In the present work the Zn-Mn system was investigated: Zn/Mn alloys of different compositions as well as Zn/Mn multilayers of 5-6 μm total thickness were prepared on low alloy steel by ion beam assisted deposition (IBAD). The equipment contained two electron beam evaporators and a slit extraction ion source, delivering ions of 100-1500 eV energy. The corrosion behaviour of the samples was evaluated by standard salt spray tests (SST). The composition and microstructure of the coatings was studied by scanning electron microscopy (SEM) and EDX-depth profiling. The behaviour of the coating/substrate system is discussed in comparison with 'state of the art' Zn-coatings (EZ) produced by electrogalvanizing. Generally speaking, the performance of the optimised coatings is as good or better than the reference standard

  19. Factors affecting the performance of the Zn-Ce redox flow battery

    International Nuclear Information System (INIS)

    Nikiforidis, Georgios; Cartwright, Rory; Hodgson, David; Hall, David; Berlouis, Leonard

    2014-01-01

    The Hull Cell was used to investigate the impact of current density j on the morphology and uniformity of zinc electrodeposited from a 2.5 mol dm −3 Zn 2+ solution in 1.5 mol dm −3 methanesulfonic acid at 40 °C onto carbon-composite surfaces. The range of the applied deposition current density used was between 1 mA cm −2 and 100 mA cm −2 . Good, robust deposits were obtained when j ≥ 10 mA cm 2 whereas at j's lower than this, patchy films formed due to the competing hydrogen evolution reaction (HER) on the bare carbon-composite surface. An understanding of these effects and its application in the redox flow battery enabled both the coulombic and cell potential efficiencies to be maintained at relatively high values, 90% and 69% respectively, indicating a successful inhibition of the HER on the fully formed Zn layer. Flow velocity at the low Reynolds number in the cell (Re <200) had little impact on the electrochemical cell performance. Depletion of the cerium species became an issue for long charge times

  20. Low-cost zinc-plated photoanode for fabric-type dye-sensitized solar cells

    International Nuclear Information System (INIS)

    Kong, Lingfeng; Bao, Yunna; Guo, Wanwan; Cheng, Li; Du, Jun; Liu, Renlong; Wang, Yundong; Fan, Xing; Tao, Changyuan

    2016-01-01

    Graphical abstract: - Highlights: • Fabric-type flexible solar cells have been assembled on Zn-plated wires and meshes. • Metal Zn can improve the carriers transfer over the metal/ZnO nanoarrays interface. • A current increase by ∼6 mA/cm"2 was realized by plating Zn on various metal substrates. • All-solid fabric-type DSSC was also assembled on Zn-plated metal wires. - Abstract: Fabric-type flexible solar cells have been recently proposed as a very promising power source for wearable electronics. To increase the photocurrent of fabric-type flexible solar cells, low-cost zinc-plated wire and mesh photoanodes are assembled for the first time through a mild wet process. Given the protection of the compact protection layer, the DSSC device could benefit from the low work function of Zn and self-repairing behavior on the Zn/ZnO interface. An evident current increase by ∼6 mA/cm"2 could be observed after coating a layer of metal Zn on various metal substrates, such as traditional stainless steel wire. Given the self-repairing behavior on Zn/ZnO interface, the Zn layer can help to improve the interfacial carrier transfer, leading to better photovoltaic performance, for both liquid-type and solid-type cells.

  1. Effect of zinc addition on properties of cadmium sulfide layer and performance of Cu(In,Ga)Se2 solar cell

    International Nuclear Information System (INIS)

    Bae, Dowon; Gho, Junghwan; Shin, Minjung; Kwon, Sehan

    2013-01-01

    Cd (1−x) Zn x S (CdS:Zn) thin films were grown on an indium tin oxide-coated glass substrate and Cu(In,Ga)Se 2 (CIGS) surface by chemical bath deposition for solar cell applications, and their composition, and optical properties were studied to decide the optimum process conditions for buffer layer growth. The average conversion efficiency of CIGS solar panels (24-in.) with the CdS:Zn layer was 0.35% higher than that of conventional solar panels mainly because of the increased open-circuit voltage. This efficiency improvement was not due to modification of the optical properties of the buffer layer, but due to the change in the deposition rate during buffer layer growth. - Highlights: ► CdS:Zn buffer layers were fabricated for Cu(In,Ga)Se 2 (CIGS) photovoltaic (PV) panels. ► Composition of buffer layers on indium–tin–oxide (ITO) and CIGS was investigated. ► Transmittance of CdS:Zn on ITO coated glass showed 5% higher than CdS. ► Efficiency of CdS:Zn solution adopted panels showed 0.47% higher than that with CdS. ► However, it was revealed that only Cd and S ions were found at the surface of CIGS

  2. Mineralogy and the release of trace elements from slag from the Hegeler Zinc smelter, Illinois (USA)

    Science.gov (United States)

    Piatak, Nadine M.; Seal, Robert R.

    2010-01-01

    Slag from the former Hegeler Zn-smelting facility in Illinois (USA) is mainly composed of spinifex Ca-rich plagioclase, fine-grained dendritic or coarse-grained subhedral to anhedral clinopyroxenes, euhedral to subhedral spinels, spherical blebs of Fe sulfides, silicate glass, and less commonly fayalitic olivine. Mullite and quartz were also identified in one sample as representing remnants of the furnace lining. Secondary phases such as goethite, hematite and gypsum are significant in some samples and reflect surficial weathering of the dump piles or represent byproducts of roasting. A relatively rare Zn-rich material contains anhedral willemite, subhedral gahnite, massive zincite, hardystonite and a Zn sulfate (brianyoungite), among other phases, and likely represents the molten content of the smelting furnace before Zn extraction. The bulk major-element chemistry of most slag samples is dominated by SiO2, Al2O3, Fe2O3 and CaO. The bulk composition of the slag suggests a high viscosity of the melt and the mineralogy suggests a high silica content of the melt. Bulk slag trace-element chemistry shows that the dominant metal is Zn with >28.4 wt.% in the Zn-rich material and between 212 and 14,900 mg/kg in the other slags. The concentrations of other trace elements reach the following: 45 mg/kg As, 1170 mg/kg Ba, 191 mg/kg Cd, 242 mg/kg Co, 103 mg/kg Cr, 6360 mg/kg Cu, 107 mg/kg Ni, and 711 mg/kg Pb.Zinc, as the dominant metal in the slags, is likely the most environmentally significant metal in these samples; Cd, Cu, and Pb are also of concern and their concentrations exceed US Environmental Protection Agency preliminary remediation goals for residential soils. Spinel was found to be the dominant concentrator of Zn for samples containing significant Zn (>1 wt.%); the silicate glass also contained relatively high concentrations of Zn compared to other phases. Zinc partitioned into the silicates and oxides in these samples is generally more resistant to

  3. Metallic elements occurrences within metallic fragments in the municipal waste incineration bottom ash

    Science.gov (United States)

    Kowalski, Piotr; Kasina, Monika; Michalik, Marek

    2017-04-01

    Bottom ash (BA) from municipal solid waste incineration (MSWI) is composed of grainy ash material, residual components and metallic fragments (from few µm up to 3-5 cm). Its mineral and chemical composition is related to the composition of the waste stream in the incinerator operational area. Wide use of thermal techniques in management of solid waste makes important the studies on valuable components and their distribution within the material in terms of their further processing. By using various valorization or extraction techniques it is possible to extend the range of its possible further application. To investigate metallic elements distribution within metallic fragments of the MSWI BA material produced in municipal waste incineration plant in Poland were collected in 2015 and 2016. BA and its components were investigated using spectroscopic methods of chemical analysis: ICP-OES, ICP-MS, LECO and EDS (used for microanalysis during SEM observations). BA is a material rich in Si (22.5 wt%), Ca (13.4 wt%), Fe (4 wt%), Al (5.2 wt%) and Na (3.5 wt%), composed of equal part of amorphous (silicate glass dominated) and crystalline phase (rich in silicates, aluminosilicates, oxides of non- and metallic elements and sulphates). The content of metallic elements (Al, Fe, Mg, Ti, Mn, Cr, Ni, Sc, Mo, Cu, Pb, Zn, Sn) is 11.5 wt% with domination of Al (5.2 wt%) and Fe (4 wt%) and elevated values of Mg (1 wt%), Ti (0.54 wt%), Cu (0.26 wt%) and Zn (0.27 wt%) (Kowalski et al., 2016). They were mostly concentrated in the form of metallic fragments, mainly as metallic inclusions in the size of 1-20 µm and separated metallic grains in the size of 50-300 µm. Metallic fragments present in the BA are characterized by their composition heterogeneity and various oxygen content. Fragments are rarely composed of single metallic element and usually in their composition up to few main elements dominated over others. The most common were Fe-, Al- and Zn-rich fragments forming respectively

  4. Properties of Co-deposited indium tin oxide and zinc oxide films using a bipolar pulse power supply and a dual magnetron sputter source

    International Nuclear Information System (INIS)

    Hwang, Man-Soo; Seob Jeong, Heui; Kim, Won Mok; Seo, Yong Woon

    2003-01-01

    Multilayer coatings consisting of metal layers sandwiched between transparent conducting oxide layers are widely used for flat panel display electrodes and electromagnetic shield coatings for plasma displays, due to their high electrical conductivity and light transmittance. The electrical and optical properties of these multilayer films depend largely on the surface characteristics of the transparent conducting oxide thin films. A smoother surface on the transparent conducting oxide thin films makes it easier for the metal layer to form a continuous film, thus resulting in a higher conductivity and visible light transmittance. Indium tin oxide (ITO) and zinc oxide (ZnO) films were co-deposited using a dual magnetron sputter and a bipolar pulse power supply to decrease the surface roughness of the transparent conducting oxide films. The symmetric pulse mode of the power supply was used to simultaneously sputter an In 2 O 3 (90 wt %) : SnO 2 (10 wt %) target and a ZnO target. We varied the duty of the pulses to control the ratio of ITO : ZnO in the thin films. The electrical and optical properties of the films were studied, and special attention was paid to the surface roughness and the crystallinity of the films. By co-depositing ITO and ZnO at a pulse duty ratio of ITO:ZnO=45:45 using a dual magnetron sputter and a bipolar pulse power supply, we were able to obtain amorphous transparent conducting oxide films with a very smooth surface which had a Zn-rich buffer layer under a In-rich surface layer. All of the films exhibited typical electrical and optical properties of transparent conducting oxide films deposited at room temperature

  5. Improving precipitation hardening behavior of Mg−Zn based alloys with Ce−Ca microalloying additions

    Energy Technology Data Exchange (ETDEWEB)

    Langelier, B., E-mail: langelb@mcmaster.ca [Mechanical & Mechatronics Engineering, The University of Waterloo, N2L 3G1 (Canada); Canadian Centre for Electron Microscopy, McMaster University, L8S 4L8 (Canada); Korinek, A. [Canadian Centre for Electron Microscopy, McMaster University, L8S 4L8 (Canada); Donnadieu, P. [Univ. Grenoble Alpes, SIMAP, F-38000 Grenoble (France); CNRS, SIMAP, F-38000 Grenoble (France); Esmaeili, S. [Mechanical & Mechatronics Engineering, The University of Waterloo, N2L 3G1 (Canada)

    2016-10-15

    The precipitation hardening behavior of newly developed Mg−Zn−Ca−Ce alloys, with modified texture and improved ductility, is studied to delineate the microstructural characteristics that lead to effective hardening upon ageing treatments. Advanced electron microscopy and atom probe techniques are used to analyze the structural characteristics in relevance to the hardening potential. It has been found that the formation of a new basal precipitate phase, which evolves from a single atomic layer GP zone, and is finely distributed in both under-aged and peak-aged microstructures, has a significant impact in the improvement of the hardening response compared with the base Mg−Zn alloys. It has also been found that the β′{sub 1} rod precipitates, commonly formed during ageing treatments of Mg−Zn alloys, have their size and distribution significantly refined in the Ca−Ce containing alloys. The role of alloy chemistry in the formation of the fine basal plate GP zones and the refinement in β′{sub 1} precipitation and their relationships to the hardening behavior are discussed. It is proposed that Ca microalloying governs the formation of the GP zones and the enhancement of hardening, particularly in the under-aged conditions, but that this is aided by a beneficial effect from Ce. - Highlights: • Ce−Ca microalloying additions improve hardening in Mg−Zn, over Ce or Ca alone. • Improved hardening is due to refined β′{sub 1} rods, and fine basal plate precipitates. • Atom probe tomography identifies Ca in both β′{sub 1} and the fine basal plates. • The fine basal plates originate as ordered monolayer GP zones with 1:1 Zn:Ca (at.%). • With ageing GP zones become more Zn-rich and transform to the fine basal plates.

  6. Fluid inclusion gas chemistry in east Tennessee Mississippi Valley-type districts: Evidence for immiscibility and implications for depositional mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Jones, H.D.; Kesler, S.E. (Univ. of Michigan, Ann Arbor (United States))

    1992-01-01

    Analyses of fluid inclusion gases from Mississippi Valley-type districts in east Tennessee reveal the presence of several distinct aqueous solutions and vapors that were part of the mineralizing process. Inclusion contents were released by crushing 5 to 25 mg mineral samples and by decrepitating individual inclusions; all analyses were obtained by quadrupole mass spectrometry. Most analyzed inclusion fluids consist of H{sub 2}O with significant amounts of CH{sub 4} (0.3 to 2.9 mol%), CO{sub 2} (0.1 to 4.7 mol%), and smaller amounts of C{sub 2}H{sub 6}, C{sub 3}H{sub 8}, H{sub 2}S, SO{sub 2}, N{sub 2}, and Ar. Compositional similarities in the inclusion fluids from three districts imply that mineralization probably formed from fluids that permeated the entire region. Saturation pressures calculated for these fluid compositions range from 300 to 2,200 bars. Burial depths for the host unit have been estimated to be about 2 to 3 km during Devonian time, the age of mineralization indicated by recent isotopic ages. Exsolution of a vapor phase from the mineralizing brines should cause precipitation of carbonate and sulfide minerals, but reaction path modeling indicates that the resulting sparry dolomite:sphalerite ratios would be too high to form an ore-grade deposit. If the vapor phase was from a preexisting sour gas cap that was intercepted by a Zn-rich brine, large amounts of spalerite would precipitate in a fairly small region. Preliminary mass balance calculations suggest that a gas cap of dimensions similar to the individual districts in east Tennessee could have contained enough H{sub 2}S to account for the total amount of sphalerite precipitated.

  7. Stokes shift and fine structure splitting in composition-tunable Zn{sub x}Cd{sub 1−x}Se nanocrystals: Atomistic tight-binding theory

    Energy Technology Data Exchange (ETDEWEB)

    Sukkabot, Worasak, E-mail: w.sukkabot@gmail.com

    2017-02-01

    I report on the atomistic correlation of the structural properties and excitonic splitting of ternary alloy Zn{sub x}Cd{sub 1−x}Se wurtzite nanocrystals using the sp{sup 3}s* empirical tight-binding method with the description of the first nearest neighbouring interaction and bowing effect. Based on a successful model, the computations are presented under various Zn compositions (x) and diameters of alloy Zn{sub x}Cd{sub 1−x}Se nanocrystals with the experimentally synthesized compositions and sizes. With increasing Zn contents (x), the optical band gaps and electron-hole coulomb energies are improved, while ground electron-hole wave function overlaps, electron-hole exchange energies, stokes shift and fine structure splitting are reduced. A composition-tunable emission from blue to yellow wavelength is obviously demonstrated. The optical band gaps, ground electron-hole wave function overlaps, electron-hole interactions, stokes shift and fine structure splitting are progressively decreased with the increasing diameters. Alloy Zn{sub x}Cd{sub 1−x}Se nanocrystal with Zn rich and large diameter is the best candidate to optimistically be used as a source of entangled photon pairs. The agreement with the experimental data is remarkable. Finally, the present systematic study on the structural properties and excitonic splitting predominantly opens a new perspective to understand the size- and composition-dependent properties of Zn{sub x}Cd{sub 1−x}Se nanocrystals with a comprehensive strategy to design the optoelectronic devices.

  8. Geophysical exploration of historical mine dumps for the estimation of valuable residuals

    Science.gov (United States)

    Martin, Tina; Knieß, Rudolf; Noell, Ursula; Hupfer, Sarah; Kuhn, Kerstin; Günther, Thomas

    2015-04-01

    Within the project ROBEHA, funded by the German Federal Ministry of Education and Research (033R105) the economic potential of different abandoned dump sites for mine waste in the Harz Mountains was investigated. Two different mining dumps were geophysically and mineralogically analysed in order to characterize the mine dump structure and to estimate the volume of the potential recycling material. The geophysical methods comprised geoelectrics, radar, and spectral induced polarization (SIP). One about 100-year old mining dump containing residues from density separated Ag- and Sb-rich Pb (Zn)-gangue ores was investigated in detail. Like most small-scale mining waste disposal sites this investigated dump is very heterogeneously structured. Therefore, 27 geoelectrical profiles, more than 50 radar profiles, and several SIP profiles were measured and analysed. The results from the radar measurements, registered with the GSSI system and a shielded 200 MHz antenna, show the near surface boundary layer (down to 3-4 m beneath surface) of the waste residuals. These results can be used as pre-information for the inversion process of the geoelectrical data. The geoelectrical results reveal the mineral residues as layers with higher resistivities (> 300 Ohm*m) than the surrounding material. The SIP method found low phase signals (mine dump and other parameters we get a first estimate for the volume of the residues but the economical viability and the environmental impact of the reworking of the dump still needs to be evaluated in detail. The results of the second mine dump, an abandoned Cu and Zn-rich slag heap, show that the slag residues are characterized by higher resistivities and higher phases. A localization of the slag residues which are covered by organic material could be realized applying these geophysical methods.

  9. Hydrothermal processes in the Edmond deposits, slow- to intermediate-spreading Central Indian Ridge

    Science.gov (United States)

    Cao, Hong; Sun, Zhilei; Zhai, Shikui; Cao, Zhimin; Jiang, Xuejun; Huang, Wei; Wang, Libo; Zhang, Xilin; He, Yongjun

    2018-04-01

    The Edmond hydrothermal field, located on the Central Indian Ridge (CIR), has a distinct mineralization history owing to its unique magmatic, tectonic, and alteration processes. Here, we report the detailed mineralogical and geochemical characteristics of hydrothermal metal sulfides recovered from this area. Based on the mineralogical investigations, the Edmond hydrothermal deposits comprise of high-temperature Fe-rich massive sulfides, medium-temperature Zn-rich sulfide chimney and low-temperature Ca-rich sulfate mineral assemblages. According to these compositions, three distinctive mineralization stages have been identified: (1) low-temperature consisting largely of anhydrite and pyrite/marcasite; (2) medium-high temperature distinguished by the mineral assemblage of pyrite, sphalerite and chalcopyrite; and (3) low-temperature stage characterized by the mineral assemblage of colloidal pyrite/marcasite, barite, quartz, anglesite. Several lines of evidence suggest that the sulfides were influenced by pervasive low-temperature diffuse flows in this area. The hydrothermal deposits are relatively enriched in Fe (5.99-18.93 wt%), Zn (2.10-10.00 wt%) and Ca (0.02-19.15 wt%), but display low Cu (0.28-0.81 wt%). The mineralogical varieties and low metal content of sulfides in the Edmond hydrothermal field both indicate that extensive water circulation is prevalent below the Edmond hydrothermal field. With regard to trace elements, the contents of Pb, Ba, Sr, As, Au, Ag, and Cd are significantly higher than those in other sediment-starved mid-ocean ridges, which is indicative of contribution from felsic rock sources. Furthermore, the multiphase hydrothermal activity and the pervasive water circulation underneath are speculated to play important roles in element remobilization and enrichment. Our findings deepen our understanding about the complex mineralization process in slow- to intermediate-spreading ridges globally.

  10. Mixing of III-V compound semiconductor superlattices

    International Nuclear Information System (INIS)

    Mei, Ping.

    1989-01-01

    In this work, the methods as well as mechanisms of III-V compound superlattice mixing are discussed, with particular attention on the AlGaAs based superlattice system. Comparative studies of ion-induced mixing showed two distinct effects resulting from ion implantation followed by a thermal anneal; i.e. collisional mixing and impurity induced mixing. It was found that Ga and As ion induced mixing are mainly due to the collisional effect, where the extent of the mixing can be estimated theoretically, with the parameters of ion mass, incident energy and the implant dose. The impurity effect was dominant for Si, Ge, Be, Zn and Te. Quantitative studies of impurity induced mixing have been conducted on samples doped with Si or Te during the growth process. It was discovered that Si induced AlGaAs superlattice mixing yielded an activation energy of approximately 4 eV for the Al diffusion coefficient with a high power law dependence of the prefactor on the Si concentration. In the Te doped AlGaAs superlattice the Al diffusion coefficient exhibited an activation energy of ∼3.0 eV, with a prefactor approximately proportional to the Te concentration. These results are of importance in examining the current diffusion models. Zn and Si induced InP/InGaAs superlattice mixing are examined. It was found that Zn predominantly induces cation interdiffusion, while Si induces comparable cation and anion interdiffusion. In addition, widely dispersed Zn rich islands form with Zn residing in the InP layers in the form of Zn 3 P 2 . With unstrained starting material, the layer bandgap disparity increases due to mixing induced strain, while in the Si diffused sample the mixed region would be expected to exhibit bandgaps intermediate between those of the original layers. Semiconductor superlattice mixing shows technological potential for optoelectronic device fabrication

  11. The impact of rapid economic growth and globalization on zinc nutrition in South Korea.

    Science.gov (United States)

    Kwun, In-Sook; Do, Mi-Sook; Chung, Hae-Rang; Kim, Yang Ha; Beattie, John H

    2009-08-01

    Zn deficiency may be widespread in Asian countries such as South Korea. However, dietary habits have changed in response to rapid economic growth and globalization. Zn nutrition in South Koreans has therefore been assessed during a period (1969-1998) of unprecedented economic growth. Cross-sectional food consumption data from the Korean National Nutrition Survey Reports (KNNSR) of South Korea at four separate time points (1969, 1978, 1988 and 1998) were used to calculate Zn, Ca and phytate intakes using various food composition tables, databases and literature values. Nutrient values in local foods were cited from their analysed values. Average Zn intake was 5.8, 4.8 and 5.3 mg/d for 1969, 1978 and 1988 respectively, increasing to 7.3 mg/d in 1998 (73 % of the Korean Dietary Reference Intake). The phytate:Zn molar ratio decreased from 21 to 8 during the study period. Dietary Zn depletion due to marked decreases in cereal consumption, particularly barley which has a low Zn bioavailability, was counterbalanced by marked increases in the consumption of meat and fish, which are also Zn-rich foods. Reduced phytate consumption coincident with increased Zn intake suggests that Zn bioavailability also improved, particularly by 1998. Although total Zn intake was not greatly affected over the initial period of economic growth in South Korea (1969-1988), Zn contributions from different food sources changed markedly and both Zn intake and potential bioavailability were improved by 1998. The study may have implications for Zn nutrition in other Asian countries currently experiencing rapid economic growth.

  12. Microscopic evaluation of trace metals in cloud droplets in an acid precipitation region.

    Science.gov (United States)

    Li, Weijun; Wang, Yan; Collett, Jeffrey L; Chen, Jianmin; Zhang, Xiaoye; Wang, Zifa; Wang, Wenxing

    2013-05-07

    Mass concentrations of soluble trace metals and size, number, and mixing properties of nanometal particles in clouds determine their toxicity to ecosystems. Cloud water was found to be acidic, with a pH of 3.52, at Mt. Lu (elevation 1,165 m) in an acid precipitation region in South China. A combination of Inductively Coupled Plasma Mass Spectrometry (ICPMS) and Transmission Electron Microscopy (TEM) for the first time demonstrates that the soluble metal concentrations and solid metal particle number are surprisingly high in acid clouds at Mt. Lu, where daily concentrations of SO2, NO2, and PM10 are 18 μg m(-3), 7 μg m(-3), and 22 μg m(-3). The soluble metals in cloudwater with the highest concentrations were zinc (Zn, 200 μg L(-1)), iron (Fe, 88 μg L(-1)), and lead (Pb, 77 μg L(-1)). TEM reveals that 76% of cloud residues include metal particles that range from 50 nm to 1 μm diameter with a median diameter of 250 nm. Four major metal-associated particle types are Pb-rich (35%), fly ash (27%), Fe-rich (23%), and Zn-rich (15%). Elemental mapping shows that minor soluble metals are distributed within sulfates of cloud residues. Emissions of fine metal particles from large, nonferrous industries and coal-fired power plants with tall stacks were transported upward to this high elevation. Our results suggest that the abundant trace metals in clouds aggravate the impacts of acid clouds or associated precipitation on the ecosystem and human health.

  13. The Tianjin geothermal field (north-eastern China): Water chemistry and possible reservoir permeability reduction phenomena

    Energy Technology Data Exchange (ETDEWEB)

    Minissale, Angelo; Montegrossi, Giordano; Orlando, Andrea [Institute of Geosciences and Earth Resources, National Research Council of Italy (CNR), Via G. La Pira 4, 50121 Florence (Italy); Borrini, Daniele; Tassi, Franco [Department of Earth Sciences, University of Florence, Via G. La Pira 4, 50121 Florence (Italy); Vaselli, Orlando [Institute of Geosciences and Earth Resources, National Research Council of Italy (CNR), Via G. La Pira 4, 50121 Florence (Italy); Department of Earth Sciences, University of Florence, Via G. La Pira 4, 50121 Florence (Italy); Huertas, Antonio Delgado [Estacion Experimental de Zaidin (CSIC), Prof. Albareda 1, 18008 Granada (Spain); Yang, Jincheng; Cheng, Wanquing [Aode Renewable Energy Research Institute, 90 Weijin South Road, Nankai District, 300381 Tianjin (China); Tedesco, Dario [Department of Environmental Sciences, Second University of Naples, Via Vivaldi 43, Caserta 81100 (Italy); Institute of Environmental Geology and Geo Engineering (CNR), Piazzale A. Moro 5, Roma 00100 (Italy); Poreda, Robert [Department of Earth and Environmental Sciences, University of Rochester, 227 Hutchison Hall, Rochester, NY 14627 (United States)

    2008-08-15

    Injection of spent (cooled) thermal fluids began in the Tianjin geothermal district, north-eastern China, at the end of the 1990s. Well injectivities declined after 3-4 years because of self-sealing processes that reduced reservoir permeability. The study focuses on the factors that may have caused the observed decrease in permeability, using chemical and isotopic data on fluids (water and gas) and mineral phases collected from production and injection wells. The results of data processing and interpretation indicate that (1) it is very unlikely that calcite and silica precipitation is taking place in the reservoir; (2) the Fe- and Zn-rich mineral phases (e.g. sulfides, hydroxides and silicates) show positive saturation indexes; (3) SEM and XRD analyses of filtered material reveal that the latter mineral phases are common; (4) visual observation of casings and surface installations, and of corrosion products, suggests that a poor quality steel was used in their manufacture; (5) significant quantities of solids (e.g. quartz and feldspar crystals) are carried by the geothermal fluid; (6) seasonal changes in fluid composition lead to a reduction in casing corrosion during the summer. It was concluded that the decrease in injectivity in the Tianjin wells is caused only in part by the oxidation of casings, downhole pumps, and surface installations, triggered by free oxygen in the injected fluids; the utilization of better quality steels should drastically reduce this type of corrosion. Self-sealing of pores and fractures by reservoir formation solids and by the Fe-corrosion products suspended in the injected fluids seems to be a more important phenomenon, whose effect could be greatly reduced by installing filtering devices at all sites. (author)

  14. Germanium enrichment in supergene settings: evidence from the Cristal nonsulfide Zn prospect, Bongará district, northern Peru

    Science.gov (United States)

    Mondillo, Nicola; Arfè, Giuseppe; Herrington, Richard; Boni, Maria; Wilkinson, Clara; Mormone, Angela

    2018-02-01

    Supergene nonsulfide ores form from the weathering of sulfide mineralization. Given the geochemical affinity of Ge to Si4+ and Fe3+, weathering of Ge-bearing sulfides could potentially lead to Ge enrichments in silicate and Fe-oxy-hydroxide minerals, although bulk rock Ge concentrations in supergene nonsulfide deposits are rarely reported. Here, we present the results of an investigation into Ge concentrations and deportment in the Cristal supergene Zn nonsulfide prospect (Bongará, northern Peru), which formed from the weathering of a preexisting Mississippi Valley-type (MVT) sulfide deposit. Material examined in this study originates from drillcore recovered from oxidized Zn-rich bodies 15-20 m thick, containing 5-45 wt% Zn and Ge concentrations 100 ppm. Microanalysis and laser ablation-ICP-MS show that precursor sphalerite is rich in both Fe (mean Fe = 8.19 wt%) and Ge (mean Ge = 142 ppm). Using the mineral geothermometer GGIMFis—geothermometer for Ga, Ge, In, Mn, and Fe in sphalerite—proposed by Frenzel et al. (Ore Geol Rev 76:52-78, 2016), sphalerite trace element data from the Cristal prospect suggest a possible formation temperature ( T GGIMFis) of 225 ± 50 °C, anomalously high for a MVT deposit. Germanium concentrations measured in both goethite (mean values 100 to 229 ppm, max 511 ppm) and hemimorphite (mean values 39 to 137 ppm, max 258 ppm) are similar to concentrations measured in hypogene sphalerite. Additionally, the Ge concentrations recorded in bulk rock analyses of sphalerite-bearing and oxidized samples are also similar. A persistent warm-humid climate is interpreted for the region, resulting in the development of an oxidation zone favoring the formation of abundant Zn hydrosilicates and Fe hydroxides, both able to incorporate Ge in their crystal structure. In this scenario, Ge has been prevented from dispersion during the weathering of the Ge-bearing sulfide bodies and remains in the resultant nonsulfide ore.

  15. Composition controlled preparation of Cu–Zn–Sn precursor films for Cu{sub 2}ZnSnS{sub 4} solar cells using pulsed electrodeposition

    Energy Technology Data Exchange (ETDEWEB)

    Dang, Wenping; Ren, Xiaodong; Zi, Wei; Jia, Lujian [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, School of Materials Science and Engineering, Shaanxi Normal University, Xi' an 710062 (China); Liu, Shengzhong, E-mail: szliu@dicp.ac.cn [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, School of Materials Science and Engineering, Shaanxi Normal University, Xi' an 710062 (China); Dalian Institute of Chemical Physics, Dalian National Laboratory for Clean Energy, Chinese Academy of Sciences, Dalian, 116023 (China)

    2015-11-25

    A pulsed electrodeposition technique is developed to prepare Cu–Zn–Sn (CZT) precursor films for the Cu{sub 2}ZnSnS{sub 4} (CZTS) solar cells. The CZT precursor films are co-deposited on Mo-coated substrate using a cyanide-free electrolyte containing Zn (II) and Sn (II) salts. During the deposition, CuSO{sub 4} solution is supplied at controlled rate using a peristaltic pump to effectively regulate Cu{sup 2+} concentration. In addition, C{sub 6}H{sub 5}Na{sub 3}O{sub 7} is used as a coordination ligand to further balance activities of the Cu{sup 2+}, Sn{sup 2+} and Zn{sup 2+}. The CZTS films are then prepared using a sulfurization process to convert the electrodeposited CZT precursors at 580 °C in a sulphur atmosphere. The annealed thin films are characterized by X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FE-SEM), EDAX and X-ray photoelectron spectroscopy (XPS) techniques for their structural, morphological, compositional and chemical properties. It is found that the addition rate of Cu (II) has significant effects on the properties of the CZTS thin films. The CZTS film prepared using the optimized copper addition rate (0.15 ml/min) shows pure kesterite phase, Cu-poor and Zn-rich composition, compact morphology and good band gap ∼1.45 eV. Solar cells using the structure glass/Mo/CZTS/CdS/i-ZnO/ZnO:Al achieves a respectable external quantum efficiency and solar cell efficiency. - Highlights: • Developed a composition controlled pulsed electrodeposition for CZTS solar cells. • Electrochemistry and CZT composition regulated by measured Cu supply rate. • Complex chemistry used to regulate ion activities and electrodeposition. • Achieved a respectable CZTS solar cell quantum efficiency.

  16. Room temperature atomic layerlike deposition of ZnS on organic thin films: Role of substrate functional groups and precursors

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Zhiwei; Walker, Amy V., E-mail: amy.walker@utdallas.edu [Department of Materials Science and Engineering, University of Texas at Dallas, RL10, 800 W. Campbell Rd., Richardson, Texas 75080 (United States)

    2015-09-15

    The room temperature atomic layerlike deposition (ALLD) of ZnS on functionalized self-assembled monolayers (SAMs) was investigated, using diethyl zinc (DEZ) and in situ generated H{sub 2}S as reactants. Depositions on SAMs with three different terminal groups, –CH{sub 3,} –OH, and –COOH, were studied. It was found that the reaction of DEZ with the SAM terminal group is critical in determining the film growth rate. Little or no deposition is observed on –CH{sub 3} terminated SAMs because DEZ does not react with the methyl terminal group. ZnS does deposit on both –OH and –COOH terminated SAMs, but the grow rate on –COOH terminated SAMs is ∼10% lower per cycle than on –OH terminated SAMs. DEZ reacts with the hydroxyl group on –OH terminated SAMs, while on –COOH terminated SAMs it reacts with both the hydroxyl and carbonyl bonds of the terminal groups. The carbonyl reaction is found to lead to the formation of ketones rather than deposition of ZnS, lowering the growth rate on –COOH terminated SAMs. SIMS spectra show that both –OH and –COOH terminated SAMs are covered by the deposited ZnS layer after five ALLD cycles. In contrast to ZnO ALLD where the composition of the film differs for the first few layers on –COOH and –OH terminated SAMs, the deposited film composition is the same for both –COOH and –OH terminated SAMs. The deposited film is found to be Zn-rich, suggesting that the reaction of H{sub 2}S with the Zn-surface adduct may be incomplete.

  17. Experimental formation of cronstedtite from Cox argillite-iron interaction at decreasing temperature in the 90 deg. C-40 deg. C range

    International Nuclear Information System (INIS)

    Pignatelli, Isabella; Mosser-Ruck, Regine; Rozsypal, Christophe; Truche, Laurent; Randi, Aurelien; Bartier, Daniele; Cathelineau, Michel; Ghanbaja, Jaafar; Mouton, Ludovic; Michau, Nicolas

    2012-01-01

    Document available in extended abstract form only. Cronstedtite crystals experimentally formed during a cooling experiment (90 deg.C-40 deg. C) simulating the time-temperature evolution of the iron-clay system around the steel overpacks in nuclear waste disposal, were characterized by XRD, SEM and TEM study. Cronstedtite is a T-O phyllosilicate with general formula (Fe 2+ 3-x Fe 3+ x )(Si 2-x Fe 3+ x )O 5 (OH) 4 , with 0 2 ), Callovo-Oxfordian argillite (COx) of the Paris Basin (with a solution/COx mass ratio of 10) and metal iron (powder and plates, with an iron powder/COx mass ratio of 0.5). This system was put in Teflon-line autoclaves heated at (90±2) deg. C for 6 months; then the temperature was decreased every month by step of 10 deg. C until 40 deg. C. The XRD results on run products clearly show that the T-O phyllosilicates crystallize and replace the predominant clay in the starting argillite, e.g. illite-smectite mixed-layer clays when the experimental temperature decreases. The reflections at 7.1 Angstrom, 4.76 Angstrom, 3.55 Angstrom and 2.73 Angstrom indicate that the T-O phyllosilicate formed is cronstedtite, but this technique is not efficient to determine its polytype. The SEM analyses confirm the presence of cronstedtite and show the morphological evolution of crystals with the temperature. At 90 deg. C three morphologies are recognized: trigonal pyramids and cones with hexagonal or rounded cross-section (Fig. 1), these crystals coexist with hairy berthierine-like minerals, as described by [10] and [12] The three cronstedtite shapes are observed until 70 deg. C and at lower temperatures the pyramidal morphology is dominant. From the energy dispersive X-ray analyses, structural formula of cronstedtite were calculated. The Fe II / Fe III ratio was adjusted to fix the octahedron to 3 in the calculation of the structural formula. Slight differences in the chemical compositions of cronstedtites are noticed: the pyramidal crystals have more Fe 2+ in the

  18. Reactivity of micas and cap-rock in wet supercritical CO_2 with SO_2 and O_2 at CO_2 storage conditions

    International Nuclear Information System (INIS)

    Pearce, Julie K.; Dawson, Grant K.W.; Law, Alison C.K.; Biddle, Dean; Golding, Suzanne D.

    2016-01-01

    Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO_2, O_2, and NOx, may be present in CO_2 streams from coal combustion sources. SO_2 and O_2 have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO_2 fluid may also come into contact with the base of cap-rock after CO_2 injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation. The first observation of mineral dissolution and precipitation on phyllosilicates and CO_2 storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO_2 reactions with industrial impurities SO_2 and O_2 at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO_2 containing SO_2, or SO_2 and O_2, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO_2 dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO_2 containing SO_2 or in pure supercritical CO_2. In the presence of SO_2, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was

  19. Exploring Mars for Evidence of Habitable Environments and Life

    Science.gov (United States)

    DesMarais, David J.

    2014-01-01

    The climate of Mars has been more similar to that of Earth than has the climate of any other planet in our Solar System. But Mars still provides a valuable alternative example of how planetary processes and environments can affect the potential presence of life elsewhere. For example, although Mars also differentiated very early into a core, mantle and crust, it then evolved mostly if not completely without plate tectonics and has lost most of its early atmosphere. The Martian crust has been more stable than that of Earth, thus it has probably preserved a more complete record of its earliest history. Orbital observations determined that near-surface water was once pervasive. Orbiters have identified the following diverse aqueous sedimentary deposits: layered phyllosilicates, phyllosilicates in intracrater fans, plains sediments potentially harboring evaporitic minerals, deep phyllosilicates, carbonate-bearing deposits, intracrater clay-sulfate deposits, Meridiani-type layered deposits, valles-type layered deposits, hydrated silica-bearing deposits, and gypsum plains. These features, together with evidence of more vigorous past geologic activity, indicate that early climates were wetter and perhaps also somewhat warmer. The denser atmosphere that was required for liquid water to be stable on the surface also provided more substantial protection from radiation. Whereas ancient climates might have favored habitable environments at least in some localities, clearly much of the Martian surface for most of its history has been markedly less favorable for life. The combination of dry conditions, oxidizing surface environments and typically low rates of sedimentation are not conducive to the preservation of evidence of ancient environments and any biota. Thus a strategy is required whereby candidate sites are first identified and then characterized for their potential to preserve evidence of past habitable environments. Rovers are then sent to explore the most promising

  20. Sorption data bases for generic Swiss argillaceous rock systems

    International Nuclear Information System (INIS)

    Bradbury, M. H.; Baeyens, B.; Thoenen, T.

    2010-09-01

    In Switzerland the site selection procedure for both high level waste (HLW) and low and intermediate level waste (L/ILW) repositories is specified by the Swiss Federal Office of Energy in the Sectoral Plan for Deep Geological Repositories. In the forthcoming stage 2 of this plan, potential sites will be identified within regions previously selected based on the presence of suitable host rocks, namely Opalinus Clay, 'Brauner Dogger', Effingen Member and Helvetic Marl. Preliminary safety analyses are an integral part of this procedure, and require, amongst other information, the radionuclide sorption properties of the host rock. This report describes a methodology to develop a Generic Rock Sorption Data Base (GR-SDB) for argillaceous rocks. The method will be used to compile specific SDBs for the above mentioned host rocks. Arguments are presented that the main factor influencing sorption on argillaceous rocks is the phyllosilicate mineral content. These minerals are particularly effective at binding metals to their surfaces by cation exchange and surface complexation. Generally, the magnitude of sorption is directly correlated with the phyllosilicate content (2:1 type clays: illite/smectite/illitesmectite mixed layers), and this parameter best reflects the sorption potential of a given mineral assembly. Consequently, sorption measurements on illite were preferably used as source data for the GR-SDB. The second component influencing radionuclide sorption is the porewater chemistry. In the present report, generic water compositions were extracted from the analytical ranges of deep ground waters in various sedimentary formations in Switzerland. In order to cover the range of ionic strength (I) and pH values of Swiss ground waters in argillaceous rocks, five types of generic water compositions were defined, combining low, intermediate and high values of ionic strength and pH. The GR-SDB for in situ conditions was derived using conversion factors (CF). As the name

  1. Corrosion of metal iron in contact with anoxic clay at 90 °C: Characterization of the corrosion products after two years of interaction

    International Nuclear Information System (INIS)

    Schlegel, Michel L.; Bataillon, Christian; Brucker, Florence; Blanc, Cécile; Prêt, Dimitri; Foy, Eddy; Chorro, Matthieu

    2014-01-01

    Highlights: • Generalized, heterogeneous corrosion is observed. • The corrosion interface is made of several layers with distinct mineralogy. • Magnetite, chukanovite, Fe-phyllosilicate, ankerite are identified from metal to clay. • The estimated corrosion damage (15 μm in two years) supports surface passivation. • The corrosion products contain only half of oxidized Fe. - Abstract: Chemical and mineralogical properties of solids formed upon free corrosion of two iron probes (one massive iron rod, and one model overpack made by two pipes covering the ends of a glass rod) in saturated clay rock (Callovo-Oxfordian formation, East of Paris Basin, France) at 90 °C over two years were investigated by microscopic and spectroscopic techniques (X-ray tomography, scanning electron microscopy coupled with energy-dispersive X-ray analysis, Raman microspectroscopy, micro-X-ray diffraction, and micro-X-ray Absorption Fine Structure spectroscopy). The corrosion rate of the massive rod was monitored in situ by electrochemical impedance spectrometry, and found to decrease from about 90 μm/year during the first month of reaction, to less than 1 μm/year after two years. X-ray tomography revealed the presence of several fractures suggesting the presence of preferential flow and diffusion pathways along the iron samples. Microscopic observations revealed similar corrosion interfaces for both samples. Corrosion heterogeneously affected the interface, with damaged thickness from ∼0 to 80 μm. In extensively damaged areas, an inner discontinuous layer of magnetite in contact with metal, an intermediate chukanovite (Fe 2 CO 3 (OH) 2 ) layer (only when magnetite is present, and only for the overpack), and an outer layer of poorly ordered Fe phyllosilicate were observed. In areas with little damage, only the Fe-silicate solids are observed. The clay transformation layer is predominantly made of ankerite ((Fe,Ca,Mg)CO 3 ) forming a massive unit near the trace of the original

  2. Mineralogical characterization of tailing dams: incidence of abandoned mining works on soil pollution (Linares, Jaén)

    Science.gov (United States)

    de la Torre, M. J.; Hidalgo, C.; Rey, J.; Martínez, J.

    2012-04-01

    The metallogenic district of Linares-La Carolina (Jaén, Spain) consists of dyke mineralizations mainly of galena, accompanied by blende, chalcopyrite and barite. Associated to these abandoned mines, relatively extensive areas occupied by spoil heaps and tailing impoundments exist and constitute potential sources of soil pollution by metals and semimetals. In order to analyze the pollution potential of these mining wastes, we have carried out a mineralogical and geochemical study of seven tailing dams and surrounding soils in the area. The mineralogy of the samples was studied by x-ray diffraction (XRD) and scanning electron microscope (SEM). In addition, the total metal content of samples was determined by inductively coupled plasma mass spectrometry (ICP-MS) analysis. Samples were taken from the first 30 cm of the waste piles and soil deposits and white efflorescences were also obtained from the surface of the tailings. In all analyzed heaps, high to very high total contents in Pb (1220-22890 mg/kg), Zn (150-51280 mg/kg), Mn (2658-4160 mg/kg), Ba (1026-19610 mg/kg) and Fe (19400-138000 mg/kg) were observed. The concentrations for these same elements in the studied soils range from 527-9900 mg/kg for Pb, 27-1700 mg/kg for Zn, 506-2464 mg/kg for Mn, 2832-4306 for Ba and 8642-29753 mg/kg for Fe, and these figures indicate a contamination of the soils, according to the guidelines established by the Spanish law. The XRD and SEM results indicate that the tailings are primarily constituted by gangue of the exploited mineralization: quartz, calcite, ankerite, feldspars and phyllosilicates. They are inherited, primary mineral phases. Galena, also primary, appears in low proportion, as well as lepidocrocite, melanterite and cerussite, being these three last secondary minerals and indicating a certain remobilization of metal cations, especially lead and iron. On the other hand, quartz and phyllosilicates predominate in the soils, in which, in addition, is identified a

  3. Comparative Mineralogy of Comets and Exo-Systems Using the Deep Impact Results

    Science.gov (United States)

    Lisse, Carey M.

    2006-09-01

    We have used the infrared mineralogical model derived from the Spitzer IRS observations of the Deep Impact experiment to study the nature of the dust in the cometary systems 9P/Tempel 1 (Lisse et al. 2006), C/Hale-Bopp 1995 O1 (Crovisier et al. 1997), 73P/Schwassmann-Wachmann 3 (Sitko et al. 2007), and 29P/Schwassmann-Wachmann 1 (Stansberry et al. 2004), the YSO HD100546 (Malfait et al. 1998), and the debris disk found around the K0V star HD69830 (Beichman et al. 2005). The comets show common emission signatures due to silicates, carbonates, water ice, amorphous carbon, and sulfides. There are differences - unlike Tempel 1, no Fe-rich olivines or polycyclic aromatic hydrocarbons (PAHs) are found in Hale-Bopp, while HD100546 is lacking in carbonates and phyllosilicates but does demonstrate a huge PAH feature. The dust from SW1 and SW3 is much less crystalline, 30%, and does not show strong evidence for phyllosilicates. Located beyond the ice line, SW1 and Hale-Bopp emitted copious amounts of water ice, SW3 at 1.47 AU emitted only water gas. The material around HD100546 appears to be very fresh, rich in PAHs and amorphous silicates; that incorporated into Hale-Bopp, SW1, and SW3 to be middle aged; and that incorporated into Tempel 1 to be mature. Lacking in carbonaceous and ferrous materials but including small, icy, ephemeral grains, the composition of the HD 69830 dust resembles that of a disrupted P or D-type asteroid. The amount of mass responsible for the observed emission is the equivalent of a 6 km radius, 2500 kg m-3 sphere, while the effective temperature of the dust implies that the bulk of the observed material is at 0.5 AU from the central source, between the second and third Neptune-sized planets. The ephemeral nature of the dust implies that ongoing collisional fragmentation is occurring.

  4. Estudio arqueométrico y evaluación del deterioro de los materiales cerámicos de la fachada de la iglesia de Santa Maria del Carmine (Pavía, Italia

    Directory of Open Access Journals (Sweden)

    Setti, M.

    2012-03-01

    Full Text Available We performed an archaeometric study of the ceramic materials from the façade of the church of Santa Maria del Carmine in Pavia (Italy. We obtained useful information about the firing temperatures, the provenance of raw materials and the type of oven used. The ceramics used in the façade are mineralogically rich in quartz, feldspar and phyllosilicates, and newly formed calcium silicate phases were detected in some samples. Microtextural observations revealed the presence of incipient reaction rims, phyllosilicate sintering and partial vitrification of the matrix. Ceramics show high porosity (32 to 45% and pore sizes of between 0.4 and 1.3 µm. Our study of the different types of decay collected on the façade of the church (green and black patinas and efflorescences revealed the presence of gypsum, whewellite, thenardite and moolooite.

    Se ha llevado a cabo un estudio arqueométrico de los materiales cerámicos de la fachada de la iglesia de Santa Maria del Carmine en Pavía (Italia. Se han obtenido valiosas informaciones sobre las temperaturas de cocción, la procedencia de las materias primas arcillosas y el tipo de hornos utilizados. Mineralógicamente, las cerámicas utilizadas en la iglesia son ricas en cuarzo, feldespato y filosilicatos y en algunas muestras se han detectado silicatos de calcio de neoformación. Las observaciones microtexturales han revelado la presencia de incipientes bordes de reacción, la sinterización de los filosilicatos y la parcial vitrificación de la matriz. Las cerámicas poseen una porosidad elevada (del 32 al 45% y radio de poros comprendido entre 0,4 y 1,3 μm. El estudio de los diferentes tipos de deterioro muestreados en la fachada de la iglesia (pátinas verdes y negras y eflorescencias ha revelado la presencia de yeso, whewellita, thenardita e moolooita.

  5. Open Access Discovery of alunite in Cross crater, Terra Sirenum, Mars: Evidence for acidic, sulfurous waters

    Science.gov (United States)

    Ehlmann, Bethany L.; Swayze, Gregg A.; Milliken, Ralph E.; Mustard, John F.; Clark, Roger N.; Murchie, Scott L.; Breit, George N.; Wray, James J.; Gondet, Brigitte; Poulet, Francois; Carter, John; Calvin, Wendy M.; Benzel, William M.; Seelos, Kimberly D.

    2016-01-01

    Cross crater is a 65 km impact crater, located in the Noachian highlands of the Terra Sirenum region of Mars (30°S, 158°W), which hosts aluminum phyllosilicate deposits first detected by the Observatoire pour la Minéralogie, L’Eau, les Glaces et l’Activitié (OMEGA) imaging spectrometer on Mars Express. Using high-resolution data from the Mars Reconnaissance Orbiter, we examine Cross crater’s basin-filling sedimentary deposits. Visible/shortwave infrared (VSWIR) spectra from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) show absorptions diagnostic of alunite. Combining spectral data with high-resolution images, we map a large (10 km × 5 km) alunite-bearing deposit in southwest Cross crater, widespread kaolin-bearing sediments with variable amounts of alunite that are layered in <10 m scale beds, and silica- and/or montmorillonite-bearing deposits that occupy topographically lower, heavily fractured units. The secondary minerals are found at elevations ranging from 700 to 1550 m, forming a discontinuous ring along the crater wall beneath darker capping materials. The mineralogy inside Cross crater is different from that of the surrounding terrains and other martian basins, where Fe/Mg-phyllosilicates and Ca/Mg-sulfates are commonly found. Alunite in Cross crater indicates acidic, sulfurous waters at the time of its formation. Waters in Cross crater were likely supplied by regionally upwelling groundwaters as well as through an inlet valley from a small adjacent depression to the east, perhaps occasionally forming a lake or series of shallow playa lakes in the closed basin. Like nearby Columbus crater, Cross crater exhibits evidence for acid sulfate alteration, but the alteration in Cross is more extensive/complete. The large but localized occurrence of alunite suggests a localized, high-volume source of acidic waters or vapors, possibly supplied by sulfurous (H2S- and/or SO2-bearing) waters in contact with a magmatic source, upwelling

  6. Scaly fabrics and veins of the Mugi and Makimine mélanges in the Shimanto belt, SW Japan

    Science.gov (United States)

    Ramirez, G. E.; Fisher, D. M.; Yamaguchi, A.; Kimura, G.

    2016-12-01

    Two regionally extensive ancient subduction fault zones provide a microstructural record of the plate boundary deformation associated with underthrusting. These rocks exhibit many of the characteristics associated with exposed ancient subduction fault zones worldwide, including: (1) σ1 is near orthogonal to the deformation fabric (2) there are microstructurally pervasive quartz and calcite filled veins concentrated in coarser blocks and along extensional jogs on slip surfaces, (3) evidence for local diffusion of silica sourced from web-like arrays of slip surfaces (i.e., scaly fabrics), and (4) evidence for cycles of cracking and sealing that record cyclic variations in stress. We present new backscatter SEM observations of scaly fabrics from two ancient subduction-related shear zones from the Shimanto Belt in Japan that exemplify these characteristics and represent the full temperature range of the seismogenic zone: 1) the Mugi mélange (lower ( 130-150 °C) and upper ( 170-200 °C) sections) and 2) Makimine mélange (peak temperatures of 340 °C). The Mugi mélange is an underplated duplex consisting of two horses separated by an OOST. The upper section is bounded at the top by a pseudotachylite-bearing paleodécollement. The Makimine mélange was underplated at the downdip limit of the seismogenic zone. The scaly fabrics associated with these shear zones display significantly different microstructural characteristics. A slip surface from along the upper Mugi is characterized by broader ( 20-30 μm), zones of quartz-poor, anastomosing shear zones composed of fine-grained (0.5-2 μm in length) phyllosilicates. The Makimine mélange exhibits thinner (10-20 μm), anastomosing shear zones with coarser (1-4 μm in length) phyllosilicate grains that are more strongly oriented into parallelism with slip surfaces. Quartz veins are pervasively developed in more competent blocks and are oriented at near perpendicular angles to the slip surfaces. Microstructural analyses

  7. Terrestrial Analogs for Clay Minerals at Yellowknife Bay, Gale Crater, Mars

    Science.gov (United States)

    Treiman, Allan H; Morris, Richard V.; Bristow, Thomas; Ming, Douglas W.; Achillies, Cherie; Bish, David L.; Blake, David; Vaniman, David; Chipera, Steve

    2013-01-01

    Sediments of the Sheepbed unit, Gale Crater, were analyzed by the CheMin X-ray diffraction instrument on the Curiosity Rover. The sediments consist of typical basalt minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe oxide/hydroxides, Fesulfides, amorphous material, and a phyllosilicate. The phyllosilicate has a broad 001 peak at approx 1.0 nm, consistent with a poorly ordered smectite. However, in the absence of diagnostic tests possible on Earth, its identity is not clear. The position of the 06L diffraction band is generally used to distinguish dioctahedral from trioctahedral smectite, but it is beyond CheMin's range of 2 Theta. The measured position of the 02L diffraction band (approx 22.5deg 2 Theta by CheMin), implies that the smectite is trioctahedral. The exact position and shape of the 02L band is determined by the cations in the 'M' sites of the smectite; to constrain those cations, we sought analogs among terrestrial smectites, emphasizing those developed from basaltic precursors. A potential analog for the Sheepbed smectite is 'griffithite,' a variety of trioctahedral smectite in altered basalt of the Topanga formation, Griffith Park, Los Angeles. 'Griffithite' has an 02L diffraction band that is close in position and shape to that of the Sheepbed smectite, although 'griffithite' has a very sharp 001 peak, indicating a high degree of layer ordering not seen in the Sheepbed smectite. A typical chemical formula for 'griffithite,' determined by electron microprobe, is (Ca0.59 Na0.03) (Mg4.28 Fe1.83) (Si6.64 Al1.36) O20 (OH)4, normalized to Si+Al=8. This formula is consistent with a fully trioctahedral Fe-Mg smectite with Ca and Na as interlayer cations. In the Topanga basalt, four types of 'griffithite' are present: fine-grained, filling cracks and vesicles; coarse-grained, filling vesicles; coarse-grained, replacing olivine phenocrysts; and coarse-grained, replacing glassy mesostasis. The fine-grained 'griffithite' formed first, and

  8. Lipid peroxidation and cytotoxicity induced by respirable volcanic ash

    Energy Technology Data Exchange (ETDEWEB)

    Cervini-Silva, Javiera, E-mail: jcervini@correo.cua.uam.mx [Departamento de Procesos y Tecnología, Universidad Autónoma Metropolitana Unidad Cuajimalpa, México City (Mexico); Earth Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA (United States); Nieto-Camacho, Antonio [Laboratorio de Pruebas Biológicas, Instituto de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México City (Mexico); Gomez-Vidales, Virginia [Laboratorio de Resonancia Paramagnética Electrónica, Instituto de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México City (Mexico); Ramirez-Apan, María Teresa [Laboratorio de Pruebas Biológicas, Instituto de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México City (Mexico); Palacios, Eduardo; Montoya, Ascención [Dirección de Investigación y Posgrado, Instituto Mexicano del Petróleo (Mexico); Kaufhold, Stephan [BGR Bundesansaltfür Geowissenschaften und Rohstoffe, Stilleweg 2, D-30655 Hannover (Germany); and others

    2014-06-01

    Highlights: • Respirable volcanic ash induces oxidative degradation of lipids in cell membranes. • Respirable volcanic ash triggers cytotoxicity in murin monocyle/macrophage cells. • Oxidative stress is surface controlled but not restricted by surface- Fe{sup 3+}. • Surface Fe{sup 3+} acts as a stronger inductor in allophanes vs phyllosilicates or oxides. • Registered cell-viability values were as low as 68.5 ± 6.7%. - Abstract: This paper reports that the main component of respirable volcanic ash, allophane, induces lipid peroxidation (LP), the oxidative degradation of lipids in cell membranes, and cytotoxicity in murin monocyle/macrophage cells. Naturally-occurring allophane collected from New Zealand, Japan, and Ecuador was studied. The quantification of LP was conducted using the Thiobarbituric Acid Reactive Substances (TBARS) assay. The cytotoxic effect was determined by the 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide colorimetric assay. Electron-Paramagnetic Resonance (EPR) determinations of naturally-occurring allophane confirmed the incorporation in the structure and clustering of structural Fe{sup 3+}, and nucleation and growth of small-sized Fe (oxyhydr)oxide or gibbsite. LP induced by allophane varied with time, and solid concentration and composition, reaching 6.7 ± 0.2 nmol TBARS mg prot{sup −1}. LP was surface controlled but not restricted by structural or surface-bound Fe{sup 3+}, because redox processes induced by soluble components other than perferryl iron. The reactivity of Fe{sup 3+} soluble species stemming from surface-bound Fe{sup 3+} or small-sized Fe{sup 3+} refractory minerals in allophane surpassed that of structural Fe{sup 3+} located in tetrahedral or octahedral sites of phyllosilicates or bulk iron oxides. Desferrioxamine B mesylate salt (DFOB) or ethylenediaminetetraacetic acid (EDTA) inhibited LP. EDTA acted as a more effective inhibitor, explained by multiple electron transfer pathways. Registered cell

  9. Corrosion behaviors of Zn/Al-Mn alloy composite coatings deposited on magnesium alloy AZ31B (Mg-Al-Zn)

    International Nuclear Information System (INIS)

    Zhang Jifu; Zhang Wei; Yan Chuanwei; Du Keqin; Wang Fuhui

    2009-01-01

    After being pre-plated a zinc layer, an amorphous Al-Mn alloy coating was applied onto the surface of AZ31B magnesium alloy with a bath of molten salts. Then the corrosion performance of the coated magnesium alloy was examined in 3.5% NaCl solution by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the single Zn layer was active in the test solution with a high corrosion rate while the Al-Mn alloy coating could effectively protect AZ31B magnesium alloy from corrosion in the solution. The high corrosion resistance of Al-Mn alloy coating was ascribed to an intact and stable passive film formed on the coating. The performances of the passive film on Al-Mn alloy were further investigated by Mott-Schottky curve and X-ray photoelectron spectroscopy (XPS) analysis. It was confirmed that the passive film exhibited n-type semiconducting behavior in 3.5% NaCl solution with a carrier density two orders of magnitude less than that formed on pure aluminum electrode. The XPS analysis indicated that the passive film was mainly composed of AlO(OH) after immersion for long time and the content of Mn was negligible in the outer part of the passive film. Based on the EIS measurement, electronic structure and composition analysis of the passive film, a double-layer structure, with a compact inner oxide and a porous outer layer, of the film was proposed for understanding the corrosion process of passive film, with which the experimental observations might be satisfactorily interpreted.

  10. Electrochemistry of Zn(II)/Zn on Mg alloy from the N-butyl-N-methylpyrrolidinium dicyanamide ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Ming-Jay, E-mail: martinez730523@yahoo.com.tw [National Synchrotron Radiation Research Center, Hsinchu, Taiwan (China); Lin, Pei-Chiung [Department of Chemistry, National Cheng Kung University, Tainan, Taiwan (China); Chang, Jeng-Kuei, E-mail: jkchang@ncu.edu.tw [Institute of Materials Science and Engineering, National Central University, Taoyuan, Taiwan (China); Chen, Jin-Ming; Lu, Kueih-Tzu [National Synchrotron Radiation Research Center, Hsinchu, Taiwan (China)

    2011-07-01

    Highlights: > Electrodeposition of Zn was successfully demonstrnated in the water- and air-stable BMP-DCA ionic liquid. While ZnCl{sub 2} is insoluble in the BMP-TFSI ionic liquid, it dissolves easily in the BMP-DCA. > Amperometric titration experiments indicated that Zn(II) probably complexed as [Zn(DCA){sub 3}]- with DCA- anion. > Chronoamperometric experiments showed that the electrodeposition of Zn on GC and Mg alloy substrates involved 3D-instantaneous nucleation/growth process. > A lower deposition rate would bring out a more uniform and compact Zn coating layer (which is also thicker) and, consequently, this coating revealed a protection capability for the Mg substrate against corrosion. - Abstract: Electrochemical reaction of Zn(II)/Zn on glassy carbon electrode(GC) and Mg alloy substrates was investigated in the room-temperature ionic liquid, N-butyl-N-methyl-pyrrolidinium dicyanamide (BMP-DCA) containing ZnCl{sub 2} at 323 K. Amperometric titration experiments suggest that Zn(II) reacted with DCA anions forming [Zn(DCA){sub 3}]{sup -} complex anion, which also could be reduced to Zn metal via a single-step electron transfer process. By chronoamperometric measurements, the electrodeposition of Zn on GC and Mg alloy substrates involved three-dimensional instantaneous nucleation under diffusion control at 323 K. The Zn deposits are also systematically characterized by the techniques of powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The Zn layer deposited at a lower current density on Mg alloy substrates was more compact and uniform when compared to that deposited at a higher current density; consequently, this coating revealed a protection capability for the Mg substrate against corrosion.

  11. Development of Continuous Galvanization-compatible Martensitic Steel

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Y. F.; Song, T. J.; Kim, Han S.; De Cooman [Pohang Univ. of Science and Technology, Pohang (Korea, Republic of); Kwak, J. H. [POSCO Gwangyang Works, Gwangyang (Korea, Republic of)

    2012-01-15

    The development of martensitic grades which can be processed in continuous galvanizing lines requires the reduction of the oxides formed on the steel during the hot dip process. This reduction mechanism was investigated in detail by means of High Resolution Transmission Electron Microscopy (HR-TEM) of cross-sectional samples. Annealing of a martensitic steel in a 10% H{sub 2} + N{sub 2} atmosphere with the dew point of -35 .deg. C resulted in the formation of a thin c-xMno.SiO{sub 2} (x>1) oxide film and amorphous a-xMnO.SiO{sub 2} oxide particles on the surface. During the hot dip galvanizing in Zn-0.13%Al, the thin c-xMnO.SiO{sub 2} (x>1) oxide films was reduced by the Al. The a-xMnO.SiO{sub 2} (x<0.9) and a-SiO{sub 2} (x>1) oxide film was also reduced and the amorphous a-xMnO.SiO{sub 2} and a-SiO{sub 2} particles were embedded in the Fe{sub 2}Al{sub 5-x}Zn{sub x} inhibition layer formed at the steel/coating interface during hot dipping. The results clearly show that Al in the liquid Zn bath can reduce the crystalline c-xMn.SiO{sub 2} (x>1) oxides but not the amorphous a-xMnO.SiO{sub 2} (x<0.9) and a-SiO{sub 2} oxides. These oxides remain embedded in the Zn layer or in the inhibition layer, making it possible to apply a Zn or Zn-alloy coating on martensitic steel by hot dipping. The hot dipping process was also found to deteriorate the mechanical properties, independently of the Zn bath composition.

  12. Galvanizing and Galvannealing Behavior of CMnSiCr Dual-Phase Steels

    Science.gov (United States)

    Lin, Ko-Chun; Chu, Peng-Wei; Lin, Chao-Sung; Chen, Hon-Bor

    2013-06-01

    Alloying elements, such as Mn, Mo, Si, and Cr, are commonly used to enhance the strength of advanced high-strength steels. Those elements also play an important role in the hot-dip galvanizing (GI) and galvannealing (GA) process. In this study, two kinds of CMnSiCr dual-phase steels were galvanized and galvannealed using a hot-dip simulator to investigate the effect of the alloying elements on the microstructure of the GI and GA coatings. The results showed that the dual-phase steels had good galvanizability because no bare spots were observed and the Fe-Zn phases were readily formed at the interface. However, the alloying reaction during the GA process was significantly hindered. XPS analysis showed that external oxidation occurred under an extremely low dew point [213 K to 203 K (-60 °C to -70 °C)] atmosphere during the annealing prior to hot dipping. However, most of the oxides were reduced during the GI process. After the GI process, the Al was present as solid solutes in the Fe-Zn phase, suggesting that the Fe-Zn phase was formed from the transformation of the Fe-Al inhibition alloy. Meanwhile, the solubility of Si in the ζ phase was extremely low. With continued GA reaction, the ζ phase transformed into the δ phase, which contained approximately 1.0 at.pct Si. The Si also diffused into the Zn layer during the GA reaction. Hence, the ζ phase did not homogeneously nucleate at the steel substrate/Zn coating interface, but was found at the area away from the interface. Therefore, the Fe-Zn phases on the CMnSiCr dual-phase steels were relatively non-uniform compared to those on interstitial-free steel.

  13. Radiocesium retention in the aquatic, terrestrial and urban environment: a quantitative and unifying analysis

    International Nuclear Information System (INIS)

    Preter, P. de

    1990-01-01

    The frayed edges of 10 A phyllosilicates (micaceous minerals), responsible for the highly selective sorption of poorly hydrated alkali cations (Cs, Rb, K) in NH$/sb4$, are quantitatively characterized by masking the planar sites with silver-thiourea. Both the capacity of the frayed edge sites (FES) and the Cs-to-K selectivity coefficient of these sites can be measured. The loading dependence of the Cs-to-K selectivity coefficient in the FES of 4 micaceous minerals demonstrates a pronounced degree of heterogeneity. Only a small fraction of the FES ($<$10%) exhibits extremely high Cs preference. For studying complex mineralogical systems (soils, sediments, rocks and ceramics) a new parameter is introduced: the ''radiocesium interception potential'', defined as the product of FES capacity and the Cs-to-K (or NH$/sb4$) selectivity coefficient in the FES at ''zero'' Cs loading. This parameter is a powerful tool in describing and predicting the highly selective sorption processes in the FES. Under freshwater conditions the radiocesium distribution coefficient can be quantitatively predicted by considering a competition with K and NH$/sb4$ in the FES. In a marine environment Na, and to a lesser extent Ca and Mg, also have to be taken into account. Finally, evidences for a redistribution process are given: sorbed Cs ions diffuse to the interlayers of the clay particles. This phenomenon explains the increasing ''fixation'' of radiocesium with time

  14. Study of thermal, radiation and environmental effects on serpentine

    International Nuclear Information System (INIS)

    Raje, Naina; Kalekar, Bhupesh B.; Dubey, K.A.

    2016-01-01

    Physical and chemical properties of a material, such as particle size surface area, magnetic properties, water content, radiation and thermal stability, viscosity, porosity, are responsible for their specific applications. Serpentine is a greenish, layer structured phyllosilicate, known as magnesium hydroxy silicate. The availability of large number of hydroxyl group makes serpentine a potential candidate for nuclear shielding material. Hence present studies have been carried out to understand the stability of serpentine with the variation in thermal, radiation and environmental parameters. Serpentine samples were received from Reactor Projects Division, BARC. An accurately weighed sample was subjected to simultaneous TG - DTA - EGA measurements in air as well as inert atmosphere at the heating rate of 10 °C/min. The sample was heated from room temperature to 1000 °C with a gas flow rate of 100 mL/min in Netzsch thermal analyzer (Model STA409 PC LUXX) connected to Bruker FTIR system (Model - Tensor27) via a 1m long capillary. The sample was subjected to gamma radiation in the range of 10 - 100 kGy using 60 Co gamma source in gamma chamber and was subjected to TG measurements to understand the effect of radiation on the thermal stability of serpentine and the results are being discussed here

  15. FeO and H-2O and the homogeneous accretion of the earth

    Science.gov (United States)

    Lange, M. A.; Ahrens, T. J.

    1983-01-01

    Shock devolatilization recovery data for brunite (Mg(OH)2) shocked to 13 and 23 GPa are presented. These data combined with previous data for serpentine (Mg3Si2O5(OH)4) are used to constrain the minimum size terrestrial planet for which planetesimal infall will result in an impact generated water atmosphere. Assuming, in hydrous phyllosilicates, model calculations simulating the interaction of metallic iron with impact released free water on the surface of the accreting Earth were carried out. It is assumed that the reaction of water with iron in the presence of enstatite is the prime source of the terrestrial FeO component of silicates and oxides. Lower and upper bounds on the terrestrial FeO budget are based on mantle FeO content and possible incorporation of FeO in the outer core. We demonstrate that the iron water reaction would result in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed.

  16. FeO and H2O and the homogeneous accretion of the earth

    Science.gov (United States)

    Lange, M. A.; Ahrens, T. J.

    1984-01-01

    Shock devolatilization recovery data for brunite (Mg(OH)2) shocked to 13 and 23 GPa are presented. These data combined with previous data for serpentine (Mg3Si2O5(OH)4) are used to constrain the minimum size terrestrial planet for which planetesimal infall will result in an impact generated water atmosphere. Assuming, in hydrous phyllosilicates, model calculations simulating the interaction of metallic iron with impact released free water on the surface of the accreting earth were carried out. It is assumed that the reaction of water with iron in the presence of enstatite is the prime source of the terrestrial FeO component of silicates and oxides. Lower and upper bounds on the terrestrial FeO budget are based on mantle FeO content and possible incorporation of FeO in the outer core. We demonstrate that the iron water reaction would resuit in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed.

  17. Thallium occurrence and partitioning in soils and sediments affected by mining activities in Madrid province (Spain)

    International Nuclear Information System (INIS)

    Gomez-Gonzalez, M.A.; Garcia-Guinea, J.; Laborda, F.; Garrido, F.

    2015-01-01

    Thallium (Tl) and its compounds are toxic to biota even at low concentrations but little is known about Tl concentration and speciation in soils. An understanding of the source, mobility, and dispersion of Tl is necessary to evaluate the environmental impact of Tl pollution cases. In this paper, we examine the Tl source and dispersion in two areas affected by abandoned mine facilities whose residues remain dumped on-site affecting to soils and sediments of natural water courses near Madrid city (Spain). Total Tl contents and partitioning in soil solid phases as determined by means of a sequential extraction procedure were also examined in soils along the riverbeds of an ephemeral and a permanent streams collecting water runoff and drainage from the mines wastes. Lastly, electronic microscopy and cathodoluminescence probe are used as a suitable technique for Tl elemental detection on thallium-bearing phases. Tl was found mainly bound to quartz and alumino-phyllosilicates in both rocks and examined soils. Besides, Tl was also frequently found associated to organic particles and diatom frustules in all samples from both mine scenarios. These biogenic silicates may regulate the transfer of Tl into the soil-water system. - Highlights: • Abandoned mine residues are Tl sources in soils of Madrid catchment area. • Tl was associated to quartz and aluminosilicates in both rocks and soils. • Tl was frequently found associated to organic particles and diatom frustules. • Cathodoluminescence is a suitable technique for Tl detection on soils and rocks

  18. Compositional studies of primitive asteroids

    International Nuclear Information System (INIS)

    Vilas, F.

    1988-01-01

    The composition of primitive asteroids and their relationship to satellites in the solar system will be studied by analyzing existing narrowband charge coupled device (CCD) reflectance spectra, acquiring additional spectra of asteroids and small satellites in the 0.5 to 1.0 micrometer spectral range, and exploring possibilities for obtaining compositional information in the blue-UV spectral region. Comparison with laboratory spectra of terrestrial chlorites and serpentines (phyllosilicates) and the clay minerals found in carbonaceous chondrite meteorites will continue. During 1987, narrowband CCD reflectance spectra of 17 additional asteroids were acquired. These spectra and spectra of 34 other asteroids have been used primarily for two studies: weak absorption features similar to those due to Fe2(+) and Fe2(+) - Fe3(+) transitions in iron oxides f ound in terrestrial chlorites and serpentines and carbonaceous chondrites have been identified in some primitive asteroid spectra. There is a first indication that asteroids grouped by heliocentric distance show similar weak absorption features. Nonparametric statistics are being applied to test the hypothesis of discrete remnants of a gradation in composition of outer-belt asteroids

  19. Timescales and settings for alteration of chondritic meteorites

    Energy Technology Data Exchange (ETDEWEB)

    Krot, A N; Hutcheon, I D; Brearley, A J; Pravdivtseva, O V; Petaev, M I; Hohenberg, C M

    2005-11-16

    Most groups of chondritic meteorites experienced diverse styles of secondary alteration to various degrees that resulted in formation of hydrous and anhydrous minerals (e.g., phyllosilicates, magnetite, carbonates, ferrous olivine, hedenbergite, wollastonite, grossular, andradite, nepheline, sodalite, Fe,Ni-carbides, pentlandite, pyrrhotite, Ni-rich metal). Mineralogical, petrographic, and isotopic observations suggest that the alteration occurred in the presence of aqueous solutions under variable conditions (temperature, water/rock ratio, redox conditions, and fluid compositions) in an asteroidal setting, and, in many cases, was multistage. Although some alteration predated agglomeration of the final chondrite asteroidal bodies (i.e. was pre-accretionary), it seems highly unlikely that the alteration occurred in the solar nebula, nor in planetesimals of earlier generations. Short-lived isotope chronologies ({sup 26}Al-{sup 26}Mg, {sup 53}Mn-{sup 53}Cr, {sup 129}I-{sup 129}Xe) of the secondary minerals indicate that the alteration started within 1-2 Ma after formation of the Ca,Al-rich inclusions and lasted up to 15 Ma. These observations suggest that chondrite parent bodies must have accreted within the first 1-2 Ma after collapse of the protosolar molecular cloud and provide strong evidence for an early onset of aqueous activity on these bodies.

  20. The potassic sedimentary rocks in Gale Crater, Mars, as seen by ChemCam Onboard Curiosity

    Science.gov (United States)

    Le Deit, Laetitia; Mangold, Nicolas; Forni, Olivier; Cousin, Agnes; Lasue, Jeremie; Schröder, Susanne; Wiens, Roger C.; Sumner, Dawn Y.; Fabre, Cecile; Stack, Katherine M.; Anderson, Ryan; Blaney, Diana L.; Clegg, Samuel M.; Dromart, Gilles; Fisk, Martin; Gasnault, Olivier; Grotzinger, John P.; Gupta, Sanjeev; Lanza, Nina; Le Mouélic, Stephane; Maurice, Sylvestre; McLennan, Scott M.; Meslin, Pierre-Yves; Nachon, Marion; Newsom, Horton E.; Payre, Valerie; Rapin, William; Rice, Melissa; Sautter, Violaine; Treiman, Alan H.

    2016-01-01

    The Mars Science Laboratory rover Curiosity encountered potassium-rich clastic sedimentary rocks at two sites in Gale Crater, the waypoints Cooperstown and Kimberley. These rocks include several distinct meters thick sedimentary outcrops ranging from fine sandstone to conglomerate, interpreted to record an ancient fluvial or fluvio-deltaic depositional system. From ChemCam Laser-Induced Breakdown Spectroscopy (LIBS) chemical analyses, this suite of sedimentary rocks has an overall mean K2O abundance that is more than 5 times higher than that of the average Martian crust. The combined analysis of ChemCam data with stratigraphic and geographic locations reveals that the mean K2O abundance increases upward through the stratigraphic section. Chemical analyses across each unit can be represented as mixtures of several distinct chemical components, i.e., mineral phases, including K-bearing minerals, mafic silicates, Fe-oxides, and Fe-hydroxide/oxyhydroxides. Possible K-bearing minerals include alkali feldspar (including anorthoclase and sanidine) and K-bearing phyllosilicate such as illite. Mixtures of different source rocks, including a potassium-rich rock located on the rim and walls of Gale Crater, are the likely origin of observed chemical variations within each unit. Physical sorting may have also played a role in the enrichment in K in the Kimberley formation. The occurrence of these potassic sedimentary rocks provides additional evidence for the chemical diversity of the crust exposed at Gale Crater.

  1. Thallium occurrence and partitioning in soils and sediments affected by mining activities in Madrid province (Spain)

    Energy Technology Data Exchange (ETDEWEB)

    Gomez-Gonzalez, M.A.; Garcia-Guinea, J. [National Museum of Natural Sciences, CSIC, Jose Gutierrez Abascal 2, 28006 Madrid (Spain); Laborda, F. [Group of Analytical Spectroscopy and Sensors Group, Institute of Environmental Sciences, University of Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza (Spain); Garrido, F., E-mail: fernando.garrido@mncn.csic.es [National Museum of Natural Sciences, CSIC, Jose Gutierrez Abascal 2, 28006 Madrid (Spain)

    2015-12-01

    Thallium (Tl) and its compounds are toxic to biota even at low concentrations but little is known about Tl concentration and speciation in soils. An understanding of the source, mobility, and dispersion of Tl is necessary to evaluate the environmental impact of Tl pollution cases. In this paper, we examine the Tl source and dispersion in two areas affected by abandoned mine facilities whose residues remain dumped on-site affecting to soils and sediments of natural water courses near Madrid city (Spain). Total Tl contents and partitioning in soil solid phases as determined by means of a sequential extraction procedure were also examined in soils along the riverbeds of an ephemeral and a permanent streams collecting water runoff and drainage from the mines wastes. Lastly, electronic microscopy and cathodoluminescence probe are used as a suitable technique for Tl elemental detection on thallium-bearing phases. Tl was found mainly bound to quartz and alumino-phyllosilicates in both rocks and examined soils. Besides, Tl was also frequently found associated to organic particles and diatom frustules in all samples from both mine scenarios. These biogenic silicates may regulate the transfer of Tl into the soil-water system. - Highlights: • Abandoned mine residues are Tl sources in soils of Madrid catchment area. • Tl was associated to quartz and aluminosilicates in both rocks and soils. • Tl was frequently found associated to organic particles and diatom frustules. • Cathodoluminescence is a suitable technique for Tl detection on soils and rocks.

  2. Correlation of clayey gouge in a surface exposure of serpentinite in the San Andreas Fault with gouge from the San Andreas Fault Observatory at Depth (SAFOD)

    Science.gov (United States)

    Moore, Diane E.; Rymer, Michael J.

    2012-05-01

    Magnesium-rich clayey gouge similar to that comprising the two actively creeping strands of the San Andreas Fault in drill core from the San Andreas Fault Observatory at Depth (SAFOD) has been identified in a nearby outcrop of serpentinite within the fault zone at Nelson Creek. Each occurrence of the gouge consists of porphyroclasts of serpentinite and sedimentary rocks dispersed in a fine-grained, foliated matrix of Mg-rich smectitic clays. The clay minerals in all three gouges are interpreted to be the product of fluid-assisted, shear-enhanced reactions between quartzofeldspathic wall rocks and serpentinite that was tectonically entrained in the fault from a source in the Coast Range Ophiolite. We infer that the gouge at Nelson Creek connects to one or both of the gouge zones in the SAFOD core, and that similar gouge may occur at depths in between. The special significance of the outcrop is that it preserves the early stages of mineral reactions that are greatly advanced at depth, and it confirms the involvement of serpentinite and the Mg-rich phyllosilicate minerals that replace it in promoting creep along the central San Andreas Fault.

  3. Correlation of clayey gouge in a surface exposure of the San Andreas fault with gouge at depth from SAFOD: Implications for the role of serpentinite in fault mechanics

    Science.gov (United States)

    Moore, Diane E.; Rymer, Michael J.

    2012-01-01

    Magnesium-rich clayey gouge similar to that comprising the two actively creeping strands of the San Andreas Fault in drill core from the San Andreas Fault Observatory at Depth (SAFOD) has been identified in a nearby outcrop of serpentinite within the fault zone at Nelson Creek. Each occurrence of the gouge consists of porphyroclasts of serpentinite and sedimentary rocks dispersed in a fine-grained, foliated matrix of Mg-rich smectitic clays. The clay minerals in all three gouges are interpreted to be the product of fluid-assisted, shear-enhanced reactions between quartzofeldspathic wall rocks and serpentinite that was tectonically entrained in the fault from a source in the Coast Range Ophiolite. We infer that the gouge at Nelson Creek connects to one or both of the gouge zones in the SAFOD core, and that similar gouge may occur at depths in between. The special significance of the outcrop is that it preserves the early stages of mineral reactions that are greatly advanced at depth, and it confirms the involvement of serpentinite and the Mg-rich phyllosilicate minerals that replace it in promoting creep along the central San Andreas Fault.

  4. Evolution of Occator Crater on (1) Ceres

    Energy Technology Data Exchange (ETDEWEB)

    Nathues, A.; Platz, T.; Thangjam, G.; Hoffmann, M.; Corre, L. Le; Reddy, V.; Kallisch, J. [Max Planck Institute for Solar System Research, Justus-von-Liebig-Weg 3, 37077 Goettingen (Germany); Mengel, K. [IELF, TU Clausthal, Adolph-Roemer-Straße 2A, 38678 Clausthal-Zellerfeld (Germany); Cloutis, E. A. [University of Winnipeg, Winnipeg, MB R3B 2E (Canada); Crown, D. A., E-mail: nathues@mps.mpg.de, E-mail: platz@mps.mpg.de, E-mail: thangjam@mps.mpg.de, E-mail: hoffmann@mps.mpg.de, E-mail: kallisch@mps.mpg.de, E-mail: gkmengel@t-online.de, E-mail: e.cloutis@uwinnipeg.ca, E-mail: lecorre@psi.edu, E-mail: reddy@psi.edu, E-mail: crown@psi.edu [Planetary Science Institute, 1700 East Fort Lowell Rd, Suite 106, Tucson, AZ 85719-2395 (United States)

    2017-03-01

    The dwarf planet Ceres (diameter 939 km) is the largest object in the main asteroid belt. Recent investigations suggest that Ceres is a thermally evolved, volatile-rich body with potential geological activity, a body which was never completely molten but possibly differentiated into a rocky core, an ice-rich mantle, and which may contain remnant internal liquid water. Thermal alteration and exogenic material infall contribute to producing a (dark) carbonaceous chondritic-like surface containing ammoniated phyllosilicates. Here we report imaging and spectroscopic analyses of Occator crater derived from the Framing Camera and the Visible and Infrared Spectrometer onboard Dawn. We found that the central bright spot (Cerealia Facula) of Occator is ∼30 Myr younger than the crater itself. The central spot is located in a central pit which contains a dome that is spectrally homogenous, exhibiting absorption features that are consistent with carbonates. Multiple radial fractures across the dome indicate an extrusive formation process. Our results lead us to conclude that the floor region was subject to past endogenic activity. Dome and bright material in its vicinity formed likely due to a long-lasting, periodic, or episodic ascent of bright material from a subsurface reservoir rich in carbonates. Originally triggered by an impact event, gases, possibly dissolved from a subsurface water/brine layer, enabled material rich in carbonates to ascend through fractures and be deposited onto the surface.

  5. Analysis of clay smoking pipes from archeological sites in the region of the Guanabara Bay (Rio de Janeiro, Brazil) by FT-IR

    Science.gov (United States)

    Freitas, Renato P.; Ribeiro, Iohanna M.; Calza, Cristiane; Oliveira, Ana L.; Silva, Mariane L.; Felix, Valter S.; Ferreira, Douglas S.; Coelho, Felipe A.; Gaspar, Maria D.; Pimenta, André R.; Medeiros, Elanio A.; Lopes, Ricardo T.

    2016-06-01

    In this study, twenty samples of clay smoking pipes excavated in an 18 km2 area between the Macacu and Caceribu rivers, in the municipality of Itaboraí, Rio de Janeiro, Brazil were analyzed by FT-IR technique. The samples, excavated in different archeological sites of the region, are dated between the seventeenth and the nineteenth centuries and are part of the material culture left by Africans and African descendants that lived in the complex. FT-IR analyses and complementary SEM-EDS studies showed that the clay paste used in the manufacture of smoking pipes, mostly handcrafted, is composed of quartz, feldspar, phyllosilicates and iron oxides. Multivariate statistical tests (PCA) were applied to FT-IR data to assess the interactions between the archeological sites. The results indicated that one archeological site - Macacu IV - is greatly related to the other sites. The results obtained have helped archeologists and anthropologists in better understanding the manufacturing process employed in ancient ceramic artifacts produced during the period of colonial Brazil.

  6. Effects of pollution and bioleaching process on the mineral composition and texture of contaminated sediments of the Reconquista River, Argentina.

    Science.gov (United States)

    Tufo, Ana E; Porzionato, Natalia F; Curutchet, Gustavo

    2017-10-31

    In this work, we report on the structural and textural changes in fluvial sediments from Reconquista River´s basin, Argentina, due to processes of contamination with organic matter and remediation by bioleaching. The original uncontaminated matrix showed quartz and phyllosilicates as the main primary mineral constituents and phases of interstratified illite-montmorillonite as secondary minerals. It was found that in contaminated sediments, the presence of organic matter in high concentration causes changes in the specific surface area, particle size distribution, size and distribution of micro and meso, and the morphology of the particles with respect to the uncontaminated sediment. After the bioleaching process, there were even greater changes in these parameters at the level of secondary mineral formation and the appearance of nanoparticles, which were confirmed by SEM. Especially, we found the formation of cementing substances such as gypsum, promoting the formation of macroporous aggregates and the weathering of clay components. Our results indicate that the bioleaching not only decreases the content of metals but also favors the formation of a material with improved characteristics for potential future applications.

  7. Sorption behavior of bensulfuron-methyl on andisols and ultisols volcanic ash-derived soils: Contribution of humic fractions and mineral-organic complexes

    Energy Technology Data Exchange (ETDEWEB)

    Espinoza, Jeannette; Fuentes, Edwar [Department of Inorganic and Analytical Chemistry, Faculty of Chemical and Pharmaceutical Sciences, University of Chile, Olivos 1007, Casilla 233, Santiago (Chile); Baez, Maria E., E-mail: mbaez@ciq.uchile.c [Department of Inorganic and Analytical Chemistry, Faculty of Chemical and Pharmaceutical Sciences, University of Chile, Olivos 1007, Casilla 233, Santiago (Chile)

    2009-12-15

    Bensulfuron-methyl sorption was studied in Andisol and Ultisol soils in view of their characteristic physical and chemical properties, presenting acidic pH and variable charge. Humic and fulvic acids (HA and FA) and humin (HUM) contributions were established. Sorption was studied by using two synthetic sorbents, an aluminum-silicate with iron oxide coverage and the same sorbent coated with humic acid. Freundlich model described Bensulfuron-methyl behavior in all sorbents (R{sup 2} 0.969-0.998). K{sub f} for soils (8.3-20.7 mug{sup 1-1/n} mL{sup 1/n} g{sup -1}) were higher than those reported in the literature. Organic matter, halloysite or kaolinite, and specific surface area contributed to the global process. The highest K{sub f} for HA, FA and HUM were 539.5, 82.9, and 98.7 mug{sup 1-1/n} mL{sup 1/n} g{sup -1}. Model sorbents described the participation of variable charge materials with high adsorption capacity. The constant capacitance model was used to assess effects of Bensulfuron-methyl adsorption on the distribution of SOH, SOH{sub 2}{sup +} and SO{sup -} sites of sorbents. - Organic matter, phyllosilicates, variable charge minerals and organo-mineral complexes contribute to bensulfuron-methyl sorption on volcanic ash-derived soils.

  8. Anisotropic surface chemistry properties and adsorption behavior of silicate mineral crystals.

    Science.gov (United States)

    Xu, Longhua; Tian, Jia; Wu, Houqin; Fang, Shuai; Lu, Zhongyuan; Ma, Caifeng; Sun, Wei; Hu, Yuehua

    2018-03-07

    Anisotropic surface properties of minerals play an important role in a variety of fields. With a focus on the two most intensively investigated silicate minerals (i.e., phyllosilicate minerals and pegmatite aluminosilicate minerals), this review highlights the research on their anisotropic surface properties based on their crystal structures. Four surface features comprise the anisotropic surface chemistry of minerals: broken bonds, energy, wettability, and charge. Analysis of surface broken bond and energy anisotropy helps to explain the cleavage and growth properties of mineral crystals, and understanding surface wettability and charge anisotropy is critical to the analysis of minerals' solution behavior, such as their flotation performance and rheological properties. In a specific reaction, the anisotropic surface properties of minerals are reflected in the adsorption strengths of reagents on different mineral surfaces. Combined with the knowledge of mineral crushing and grinding, a thorough understanding of the anisotropic surface chemistry properties and the anisotropic adsorption behavior of minerals will lead to the development of effective relational models comprising their crystal structure, surface chemistry properties, and targeted reagent adsorption. Overall, such a comprehensive approach is expected to firmly establish the connection between selective cleavage of mineral crystals for desired surfaces and designing novel reagents selectively adsorbed on the mineral surfaces. As tools to characterize the anisotropic surface chemistry properties of minerals, DLVO theory, atomic force microscopy (AFM), and molecular dynamics (MD) simulations are also reviewed. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Mineralogy and origin of atmospheric particles in the industrial area of Huelva (SW Spain)

    Science.gov (United States)

    Bernabé, J. M.; Carretero, M. I.; Galán, E.

    The mineralogy of atmospheric particles at the confluence of the Tinto and Odiel rivers, south of Huelva (a highly industrialized city in the SW Spain), was characterized in view to identify source origins. In spite of the small amount of sample collected, mineralogical characterization was performed by X-ray diffraction, polarized light microscopy and scanning electron microscopy with EDS analysis system, using an adequate sample preparation methodology. Sedimentable (SP) and aerosols particles were sampled an one-week basis every two months for one year. Quartz, calcite and feldspars were found to be the major minerals in both fractions, and phyllosilicates, dolomite and gypsum were also identified in lower content. Minor mineral particles included barite, apatite, sphalerite and pyrite. SEM studies revealed the additional presence of chalcopyrite in both SP and aerosols, and of chalcocite-covellite, halite and sylvite in the latter. Siderite, hematite and ankerite were only detected in the SP fraction. The concentrations of the previous minerals increased in summer by effect of the limited rain and the resulting scarcity of atmosphere washing. Non-mineral particles detected by SEM in SP and aerosol fractions included spherical, biological and compositionally complex particles. The main source of mineral particles was found to be the soil suspension in addition to the metallurgical and fertilizer production industries in the area.

  10. Overview of the evolution of clay mineralogy in the Gulf of Mexico: implications for regional climate and drainage history of the Mississippi and Brazos-Trinity Rivers

    Science.gov (United States)

    Adatte, T.; John, C. M.; Flemings, P. B.; Behrmann, J.

    2005-12-01

    In this paper we present the overview and preliminary results of the analysis of clay minerals in two mini basins drilled during IODP Expedition 308. The goal of our project is to explore the vertical and temporal trends in clay mineralogy in the Ursa Basin and the Brazos-Trinity basin #4. The Brazos-Trinity basin was the sink for sands and clays carried by the Brazos and Trinity Rivers, while the Ursa basin was the sink for sediments carried by the Mississippi river. Reconstructing clay minerals (phyllosilicates turbidity current deposition (controlled mainly by sea-level changes and thus glacio-eustasy). Finally, a major focusing point of Expedition 308 was sediment physical properties in an overpressured basin. Because each clay mineral specie has a specific average grain sizes, physical properties and cation exchange capacity, the clay mineral composition of the sediment investigated here (dominated by clay-sized particles) may partly control how these sediments react to changes in pressure and temperature. Thus, clay mineral data could contribute to our understanding of the physical properties of the sediments in overpressured basins, and collaborations with geotechnical scientist are planned.

  11. {alpha}-Pinene conversion by modified-kaolinitic clay

    Energy Technology Data Exchange (ETDEWEB)

    Volzone, C. [CETMIC-Centro de Tecnologia de Recursos Minerales y Ceramica-(CONICET-CIC), C.C. 49, Cno. Centenario y 506 (1897) M.B. Gonnet, Prov., Buenos Aires (Argentina)]. E-mail: volzcris@netverk.com.ar; Masini, O. [INTEQUI (CONICET-UNSL), Facultad de Ingenieria y Ciencias Economico Sociales, 25 de Mayo 384, V. Mercedes, Prov., San Luis (Argentina); Comelli, N.A. [INTEQUI (CONICET-UNSL), Facultad de Ingenieria y Ciencias Economico Sociales, 25 de Mayo 384, V. Mercedes, Prov., San Luis (Argentina); Grzona, L.M. [INTEQUI (CONICET-UNSL), Facultad de Ingenieria y Ciencias Economico Sociales, 25 de Mayo 384, V. Mercedes, Prov., San Luis (Argentina); Ponzi, E.N. [CINDECA (CONICET-UNLP) calle 47 No. 257 (1900) La Plata, Prov., Buenos Aires (Argentina); Ponzi, M.I. [INTEQUI (CONICET-UNSL), Facultad de Ingenieria y Ciencias Economico Sociales, 25 de Mayo 384, V. Mercedes, Prov., San Luis (Argentina)

    2005-10-15

    The isomerization of {alpha}-pinene using natural kaolinitic clay before and after different treatments was studied in this work. The kaolinite is a clay material constituted by phyllosilicate 1:1 layer (one sheet of tetrahedral silicon and one sheet of octahedral alumina). The clay was treated at different times using 6.0 N solution of sulfuric acid previous heating to 500 or 700 K. The materials were characterized by X-ray diffraction, by chemical analyses and acidity measurements. The catalytic reactions were carried out at 373 K in a reactor batch with condenser and stirrer. Samples were taken at regular intervals, and reactants and products were quantitatively analyzed with a gas chromatograph after separation of the individual compounds. Conversions of alpha pinene between 67 and 94%, and selectivities in camphene and in limonene of 65 and 23%, respectively, were obtained with the clay treated at different conditions. The structural and textural changes of the clay by the treatments influenced on catalytic reactions.

  12. Effect of the radiation in the thermoluminescent properties of lava

    CERN Document Server

    Correcher, V; García, J

    2003-01-01

    Blue thermoluminescence (Tl) emission from different lavas of many places (Costa Rica, Canary Islands, Hawaii Islands, Iceland and Italy) corresponding to different eruptions has been studied to know its potential use in the field of dating and retrospective dosimetry. Due to the light emission is linked to the point defects of the crystalline lattice structure, X-ray diffraction analyses were performed to determine the components of this poly mineral material that mostly are cristobalite, plagioclase and phyllosilicates. Exposures to different doses (in a range of 1-25 Gy) were given to each sample to determine the evolution of the Tl signal with the irradiation under laboratory conditions. In all cases, a linear response could be observed and no saturation has been detected in this range of doses. Both natural (NTL) and induced (ITL) Tl signal exhibit a complex glow curve structure associated to a continuous trap distribution over 100 C that could be attributed to the formation-annihilation [Al0 sub 4 /alka...

  13. Stepwise effects of the BCR sequential chemical extraction procedure on dissolution and metal release from common ferromagnesian clay minerals: A combined solution chemistry and X-ray powder diffraction study

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, P.C. [Geology Department, Middlebury College, Middlebury, Vermont 05753 (United States)], E-mail: pryan@middlebury.edu; Hillier, S. [Macaulay Institute, Aberdeen, AB15 8QH UK (United Kingdom); Wall, A.J. [Department of Geosciences, Penn State University, University Park, Pennsylvania, 16802 (United States)

    2008-12-15

    Sequential extraction procedures (SEPs) are commonly used to determine speciation of trace metals in soils and sediments. However, the non-selectivity of reagents for targeted phases has remained a lingering concern. Furthermore, potentially reactive phases such as phyllosilicate clay minerals often contain trace metals in structural sites, and their reactivity has not been quantified. Accordingly, the objective of this study is to analyze the behavior of trace metal-bearing clay minerals exposed to the revised BCR 3-step plus aqua regia SEP. Mineral quantification based on stoichiometric analysis and quantitative powder X-ray diffraction (XRD) documents progressive dissolution of chlorite (CCa-2 ripidolite) and two varieties of smectite (SapCa-2 saponite and SWa-1 nontronite) during steps 1-3 of the BCR procedure. In total, 8 ({+-} 1) % of ripidolite, 19 ({+-} 1) % of saponite, and 19 ({+-} 3) % of nontronite (% mineral mass) dissolved during extractions assumed by many researchers to release trace metals from exchange sites, carbonates, hydroxides, sulfides and organic matter. For all three reference clays, release of Ni into solution is correlated with clay dissolution. Hydrolysis of relatively weak Mg-O bonds (362 kJ/mol) during all stages, reduction of Fe(III) during hydroxylamine hydrochloride extraction and oxidation of Fe(II) during hydrogen peroxide extraction are the main reasons for clay mineral dissolution. These findings underscore the need for precise mineral quantification when using SEPs to understand the origin/partitioning of trace metals with solid phases.

  14. The effect of intrinsic soil properties on soil quality assessments

    Directory of Open Access Journals (Sweden)

    Alessandro Samuel-Rosa

    2013-10-01

    Full Text Available The assessment of soil quality is based on indicators and indices derived from soil properties. However, intrinsic soil properties may interfere with other soil properties that vary under different land uses and are used to calculate the indices. The aim of this study was to assess the extent to which intrinsic soil properties (clay and iron oxide contents explain variable soil properties (sum of bases, potential acidity, organic carbon, total porosity, and bulk density under different land uses (native forest, no-tillage and conventional agriculture on small family farms in Southern Brazil. The results showed that the five properties evaluated can be included in soil quality assessments and are not influenced by the clay and iron oxide contents. It was concluded that for little weathered 1:1 and 2:1 phyllosilicate rich-soils, if the difference between the maximum and the minimum clay content under the different land uses is less than about 200 g kg-1 and the iron oxide content less than about 15 g kg-1, the physico-chemical soil properties in the surface layer are determined mostly by the land use.

  15. Organic and inorganic correlations for Northwest Africa 852 by synchrotron-based Fourier transform infrared microspectroscopy

    Science.gov (United States)

    Yesiltas, Mehmet; Peale, Robert E.; Unger, Miriam; Sedlmair, Julia; Hirschmugl, Carol J.

    2015-10-01

    Relationships between organic molecules and inorganic minerals are investigated in a single 34 μm diameter grain of the CR2 chondrite Northwest Africa 852 (NWA) 852 with submicron spatial resolution using synchrotron-based imaging micro-FTIR spectroscopy. Correlations based on absorption strength for the various constituents are determined using statistical correlation analysis. The silicate band is found to be correlated with the hydration band, and the latter is highly correlated with stretching modes of aliphatic hydrocarbons. Spatial distribution maps show that water+organic combination, silicate, OH, and C-H distributions overlap, suggesting a possible catalytic role of phyllosilicates in the formation of organics. In contrast, the carbonate band is anticorrelated with water+organic combination, however uncorrelated with any other spectral feature. The average ratio of asymmetric CH2 and CH3 band strengths (CH2/CH3 = 2.53) for NWA 852 is similar to the average ratio of interplanetary dust particles (~2.40) and Wild 2 cometary dust particles (2.50), but it significantly exceeds that of interstellar medium objects (~1.00) and several aqueously altered carbonaceous chondrites (~1.40). This suggests organics of similar length/branching, and perhaps similar formation regions, for NWA 852, Wild 2 dust particles, and interplanetary dust particles. The heterogeneous spatial distribution of ratio values indicates the presence of a mixture of aliphatic organic material with different length/branching, and thus a wide range of parent body processes, which occurred before the considered grain was formed.

  16. A simple and non-invasive method for nuclear transformation of intact-walled Chlamydomonas reinhardtii.

    Directory of Open Access Journals (Sweden)

    Sora Kim

    Full Text Available Genetic engineering in microalgae is gaining attraction but nuclear transformation methods available so far are either inefficient or require special equipment. In this study, we employ positively charged nanoparticles, 3-aminopropyl-functionalized magnesium phyllosilicate (aminoclay, approximate unit cell composition of [H2N(CH23]8Si8Mg6O12(OH4, for nuclear transformation into eukaryotic microalgae. TEM and EDX analysis of the process of transformation reveals that aminoclay coats negatively-charged DNA biomolecules and forms a self-assembled hybrid nanostructure. Subsequently, when this nanostructure is mixed with microalgal cells and plated onto selective agar plates with high friction force, cell wall is disrupted facilitating delivery of plasmid DNA into the cell and ultimately to the nucleus. This method is not only simple, inexpensive, and non-toxic to cells but also provides efficient transformation (5.03×10(2 transformants/µg DNA, second only to electroporation which needs advanced instrumentation. We present optimized parameters for efficient transformation including pre-treatment, friction force, concentration of foreign DNA/aminoclay, and plasticity of agar plates. It is also confirmed the successful integration and stable expression of foreign gene in Chlamydomonas reinhardtii through molecular methods.

  17. Iron Mineralogy and Speciation in Clay-Sized Fractions of Chinese Desert Sediments

    Science.gov (United States)

    Lu, Wanyi; Zhao, Wancang; Balsam, William; Lu, Huayu; Liu, Pan; Lu, Zunli; Ji, Junfeng

    2017-12-01

    Iron released from Asian desert dust may be an important source of bioavailable iron for the North Pacific Ocean and thereby may stimulate primary productivity. However, the Fe species of the fine dusts from this source region are poorly characterized. Here we investigate iron species and mineralogy in the clay-sized fractions (iron phases (ferrihydrite and lepidocrocite) and reducible iron oxides (dominated by goethite) are 0.81 wt % and 2.39 wt %, respectively, and Fe dissolved from phyllosilicates extracted by boiling HCl (dominated by chlorite) is 3.15 wt %. Dusts originating from deserts in northwestern China, particularly the Taklimakan desert, are relatively enriched in easily reducible Fe phases, probably due to abundant Fe contained in fresh weathering products resulting from the rapid erosion associated with active uplift of mountains to the west. Data about Fe speciation and mineralogy in Asian dust sources will be useful for improving the quantification of soluble Fe supplied to the oceans, especially in dust models.

  18. Nickel Solubility and Precipitation in Soils: A Thermodynamic Study

    International Nuclear Information System (INIS)

    Peltier, E.; Allada, R.; Navrotsky, A.; Sparks, D.

    2006-01-01

    The formation of mixed-metal-Al layered double hydroxide (LDH) phases similar to hydrotalcite has been identified as a significant mechanism for immobilization of trace metals in some environmental systems. These precipitate phases become increasingly stable as they age, and their formation may therefore be an important pathway for sequestration of toxic metals in contaminated soils. However, the lack of thermodynamic data for LDH phases makes it difficult to model their behavior in natural systems. In this work, enthalpies of formation for Ni LDH phases with nitrate and sulfate interlayers were determined and compared to recently published data on carbonate interlayer LDHs. Differences in the identity of the anion interlayer resulted in substantial changes in the enthalpies of formation of the LDH phases, in the order of increasing enthalpy carbonatephyllosilicates

  19. The Thermal Properties of CM Carbonaceous Chondrites

    Science.gov (United States)

    Britt, D. T.; Opeil, C.

    2017-12-01

    The physical properties of asteroid exploration targets are fundamental parameters for developing models, planning observations, mission operations, reducing operational risk, and interpreting mission results. Until we have returned samples, meteorites represent our "ground truth" for the geological material we expect to interact with, sample, and interpret on the surfaces of asteroids. The physical properties of the volatile-rich carbonaceous chondrites (CI, C2, CM, and CR groups) are of particular interest because of their high resource potential. We have measured the thermal conductivity, heat capacity and thermal expansion of five CM carbonaceous chondrites (Murchison, Murray, Cold Bokkeveld, NWA 7309, Jbilet Winselwan) at low temperatures (5-300 K) to mimic the conditions in the asteroid belt. The mineralogy of these meteorites are dominated by abundant hydrous phyllosilicates, but also contain anhydrous minerals such as olivine and pyroxene found in chondrules. The thermal expansion measurements for all these CMs indicate a substantial increase in meteorite volume as temperature decreases from 230 - 210 K followed by linear contraction below 210 K. Such transitions were unexpected and are not typical for anhydrous carbonaceous chondrites or ordinary chondrites. Our thermal diffusivity results compare well with previous estimates for similar meteorites, where conductivity was derived from diffusivity measurements and modeled heat capacities; our new values are of a higher precision and cover a wider range of temperatures.

  20. α-Pinene conversion by modified-kaolinitic clay

    International Nuclear Information System (INIS)

    Volzone, C.; Masini, O.; Comelli, N.A.; Grzona, L.M.; Ponzi, E.N.; Ponzi, M.I.

    2005-01-01

    The isomerization of α-pinene using natural kaolinitic clay before and after different treatments was studied in this work. The kaolinite is a clay material constituted by phyllosilicate 1:1 layer (one sheet of tetrahedral silicon and one sheet of octahedral alumina). The clay was treated at different times using 6.0 N solution of sulfuric acid previous heating to 500 or 700 K. The materials were characterized by X-ray diffraction, by chemical analyses and acidity measurements. The catalytic reactions were carried out at 373 K in a reactor batch with condenser and stirrer. Samples were taken at regular intervals, and reactants and products were quantitatively analyzed with a gas chromatograph after separation of the individual compounds. Conversions of alpha pinene between 67 and 94%, and selectivities in camphene and in limonene of 65 and 23%, respectively, were obtained with the clay treated at different conditions. The structural and textural changes of the clay by the treatments influenced on catalytic reactions

  1. Insight into the nature and formation of the organic matter observed on Ceres

    Science.gov (United States)

    Ammannito, E.; Vinogradoff, V.; De Sanctis, M. C.; De Angelis, S.; Ferrari, M.; Ciarniello, M.; Raponi, A.; Raymond, C. A.; Russell, C. T.

    2017-12-01

    Observed by the Dawn spacecraft since March 2015, Ceres is a fascinating world [1]. Its surface, covered by phyllosilicates, carbonates, ammoniated-bearing hydrated minerals, water ice, salts and opaque materials indicates a complex chemical environment [1,2,3]. VIR, the Visible and InfraRed mapping spectrometer onboard the Dawn mission, has revealed the presence of aliphatic carbons with the 3.3-3.5 µm bands, near the Ernutet crater [4]. The origin of this OM is likely related to an endogenous source [4] and new issues are raised: what is the origin formation and the true nature of the OM hidden behind these aliphatic signatures? We used the spectral imaging (SPIM) facility in use at the laboratory of IAPS-INAF (spare of the VIR instrument onboard Dawn) to measure organic materials in the range 0.2-5.1 µm. These materials, such as insoluble organic matter (IOM) of chondrites, synthetic polymers, asphaltite, as well as spectra from literature data have been compared to VIR data. The Ceres aliphatic bands might match with an aliphatic branched polymer structure, i.e. with a 1.3 Science, 353 (6303) 1008-1010. [2] De Sanctis et al., (2015) Nature 528, 241-244. [3] De Sanctis et al., (2016) Nature 536, 54- 57. [4] De Sanctis et al., (2017) Science, 355, 719-722. [5] Holm et al., (2015), Astrobiology, 15, 587-600.

  2. The geochemistry of the stable isotopes of silicon

    International Nuclear Information System (INIS)

    Douthitt, C.B.

    1982-01-01

    One hundred thirty two new measurements of the relative abundances of the stable isotopes of silicon in terrestrial materials are presented. The total variation of delta 30 Si found is 6.2 parts per thousand, centered on the mean of terrestrial mafic and ultramafic igneous rocks, delta 30 Si = -0.4 parts per thousand. Igneous rocks show limited variation; coexisting minerals exhibit small, systematic silicon isotopic fractionations that are roughly 1/3 the magnitude of concomitant oxygen isotopic fractionations at 1150 0 C. In both igneous minerals and rocks, delta 30 Si shows a positive correlation with silicon content, as does delta 18 O. Opal from both sponge spicules and sinters is light, with delta 30 Si = -2.3 and -1.4 parts per thousand respectively. Large delta 30 Si values of both positive and negative sign are reported for the first time from clay minerals, opaline phytoliths, and authigenic quartz. All highly fractionated samples were precipitated from solution at low temperatures; however, aqueous silicon is not measurably fractionated relative to quartz at equilibrium. A kinetic isotope fractionation of approximately 3.5 parts per thousand is postulated to occur during the low temperature precipitation of opal and, possibly, poorly ordered phyllosilicates, with the silicate phase being enriched in 28 Si. This fractionation, coupled with a Rayleigh precipitation model, is capable of explaining most non-magmatic delta 30 Si variations. (author)

  3. Determining the speciation of Zn in soils around the sediment ponds of chemical plants by XRD and XAFS spectroscopy and sequential extraction.

    Science.gov (United States)

    Minkina, Tatiana; Nevidomskaya, Dina; Bauer, Tatiana; Shuvaeva, Victoria; Soldatov, Alexander; Mandzhieva, Saglara; Zubavichus, Yan; Trigub, Alexander

    2018-09-01

    For a correct assessment of risk of polluted soil, it is crucial to establish the speciation and mobility of the contaminants. The aim of this study was to investigate the speciation and transformation of Zn in strongly technogenically transformed contaminated Spolic Technosols for a long time in territory of sludge collectors by combining analytical techniques and synchrotron techniques. Sequential fractionation of Zn compounds in studied soils revealed increasing metal mobility. Phyllosilicates and Fe and Mn hydroxides were the main stabilizers of Zn mobility. A high degree of transformation was identified for the composition of the mineral phase in Spolic Technosols by X-ray powder diffraction. Technogenic phases (Zn-containing authigenic minerals) were revealed in Spolic Technosols samples through the analysis of their Zn K-edge EXAFS and XANES spectra. In one of the samples Zn local environment was formed by predominantly oxygen atoms, and in the other one mixed ZnS and ZnO bonding was found. Zn speciation in the studied technogenically transformed soils was due to the composition of pollutants contaminating the floodplain landscapes for a long time, and, second, this is the combination of physicochemical properties controlling the buffer properties of investigated soils. X-ray spectroscopic and X-ray powder diffraction analyses combined with sequential extraction assays is an effective tool to check the affinity of the soil components for heavy metal cations. Copyright © 2018 Elsevier B.V. All rights reserved.

  4. Geochemistry of the stable isotopes of silicon

    Energy Technology Data Exchange (ETDEWEB)

    Douthitt, C B [California Inst. of Tech., Pasadena (USA). Div. of Geological and Planetary Sciences

    1982-08-01

    One hundred thirty two new measurements of the relative abundances of the stable isotopes of silicon in terrestrial materials are presented. The total variation of delta/sup 30/Si found is 6.2 parts per thousand, centered on the mean of terrestrial mafic and ultramafic igneous rocks, delta/sup 30/Si = -0.4 parts per thousand. Igneous rocks show limited variation; coexisting minerals exhibit small, systematic silicon isotopic fractionations that are roughly 1/3 the magnitude of concomitant oxygen isotopic fractionations at 1150/sup 0/C. In both igneous minerals and rocks, delta/sup 30/Si shows a positive correlation with silicon content, as does delta/sup 18/O. Opal from both sponge spicules and sinters is light, with delta/sup 30/Si = -2.3 and -1.4 parts per thousand respectively. Large delta/sup 30/Si values of both positive and negative sign are reported for the first time from clay minerals, opaline phytoliths, and authigenic quartz. All highly fractionated samples were precipitated from solution at low temperatures; however, aqueous silicon is not measurably fractionated relative to quartz at equilibrium. A kinetic isotope fractionation of approximately 3.5 parts per thousand is postulated to occur during the low temperature precipitation of opal and, possibly, poorly ordered phyllosilicates, with the silicate phase being enriched in /sup 28/Si. This fractionation, coupled with a Rayleigh precipitation model, is capable of explaining most non-magmatic delta/sup 30/Si variations.

  5. Smectite Formation from Basaltic Glass Under Acidic Conditions on Mars

    Science.gov (United States)

    Peretyazhko, T. S.; Sutter, B.; Morris, R. V.; Agresti, D. G.; Le, L.; Ming, D. W.

    2015-01-01

    Massive deposits of phyllosilicates of the smectite group, including Mg/Fe-smectite, have been identified in Mars's ancient Noachian terrain. The observed smectite is hypothesized to form through aqueous alteration of basaltic crust under neutral to alkaline pH conditions. These pH conditions and the presence of a CO2-rich atmosphere suggested for ancient Mars were favorable for the formation of large carbonate deposits. However, the detection of large-scale carbonate deposits is limited on Mars. We hypothesized that smectite deposits may have formed under acidic conditions that prevented carbonate precipitation. In this work we investigated formation of saponite at a pH of approximately 4 from Mars-analogue synthetic Adirondack basaltic glass of composition similar to Adirondack class rocks located at Gusev crater. Hydrothermal (200º Centigrade) 14 day experiments were performed with and without 10 millimoles Fe(II) or Mg under anoxic condition [hereafter denoted as anoxic_Fe, anoxic_Mg and anoxic (no addition of Fe(II) or Mg)] and under oxic condition [hereafter denoted as oxic (no addition of Fe(II) or Mg)]. Characterization and formation conditions of the synthesized saponite provided insight into the possible geochemical conditions required for saponite formation on Mars.

  6. Update on the Chemical Composition Of Crystalline, Smectite, and Amorphous Components for Rocknest Soil and John Klein and Cumberland Mudstone Drill Fines at Gale Crater, Mars

    Science.gov (United States)

    Morris, R. V.; Ming, D. W.; Gellert, R.; Vaniman, D. T.; Bish, D. L.; Blake, D. F.; Chipera, S. J.; Morrison, S. M.; Downs, R. T.; Rampe, E. B.; hide

    2015-01-01

    We have previously calculated the chemical compositions of the X-ray-diffraction (XRD) amorphous component of three solid samples (Rocknest (RN) soil, John Klein (JK) drill fines, and Cumberland (CB) drill fines) using major-element chemistry (APXS), volatile-element chemistry (SAM), and crystalline- phase mineralogy (CheMin) obtained by the Curiosity rover as a part of the ongoing Mars Science Laboratory mission in Gale Crater. According to CheMin analysis, the RN and the JK and CB samples are mineralogically distinct in that RN has no detectable clay minerals and both JK and CB have significant concentrations of high-Fe saponite. The chemical composition of the XRD amorphous component is the composition remaining after mathematical removal of the compositions of crystalline components, including phyllosilicates if present. Subsequent to, we have improved the unit cell parameters for Fe-forsterite, augite, and pigeonite, resulting in revised chemical compositions for the XRD-derived crystalline component (excluding clay minerals). We update here the calculated compositions of amorphous components using these revised mineral compositions.

  7. Nitrogen Concentrations and Isotopic Compositions of Seafloor-Altered Terrestrial Basaltic Glass: Implications for Astrobiology

    Science.gov (United States)

    Banerjee, N.R.; Izawa, M.R.M.; Kobayashi, K.; Lazzeri, K.; Ranieri, L.A.; Nakamura, E.

    2018-01-01

    Abstract Observed enrichments of N (and the δ15N of this N) in volcanic glasses altered on Earth's modern and ancient seafloor are relevant in considerations of modern global N subduction fluxes and ancient life on Earth, and similarly altered glasses on Mars and other extraterrestrial bodies could serve as valuable tracers of biogeochemical processes. Palagonitized glasses and whole-rock samples of volcanic rocks on the modern seafloor (ODP Site 1256D) contain 3–18 ppm N with δ15Nair values of up to +4.5‰. Variably altered glasses from Mesozoic ophiolites (Troodos, Cyprus; Stonyford volcanics, USA) contain 2–53 ppm N with δ15N of −6.3 to +7‰. All of the more altered glasses have N concentrations higher than those of fresh volcanic glass (for MORB, smectite, illite) in both the palagonitized cracks and the microtubules. These phyllosilicates (particularly illite), and possibly also zeolites, are the likely hosts for N in these glasses. Key Words: Nitrogen—Nitrogen isotope—Palagonite—Volcanic glass—Mars. Astrobiology 18, 330–342. PMID:29106312

  8. Characterization of bentonite, fibrous and kaolinite clays with regard to their use in pelotherapy; Caracterizacion de bentonitas, arcillas fibrosas y arcillas caoliniferas para su empleo en peloterapia

    Energy Technology Data Exchange (ETDEWEB)

    Pozo Martin, E.; Martin Rubi, J. A.; Pozo Rodriguez, M.

    2011-07-01

    We have characterized the mineralogical and chemical contents of several Spanish special clays (bentonite, fibrous clays and kaolin). Mineralogical analyses revealed that the samples were composed mainly of phyllosilicates (78 %-99 %) with a notable presence of dioctahedral and trioctahedral smectites in the bentonite, kaolinite in the kaolin and sepiolite or palygorskite in the fibrous clays. Illite was the common subordinate mineral in the bentonite, kaolin and palygorskite. Quartz, calcite, dolomite and feldspars were found as associate minerals with the occasional presence of zeolites and amphiboles. The chemical analysis was consistent with the mineralogy. With regard to trace elements (V, Cr, Ni, Co, Cu, Zn, As, Mo, Ba, Sb, Pb, U), the whole samples of the magnesium bentonite and sepiolite were found to have the lowest trace-element contents (<257,28 ppm ), whilst the aluminium bentonite, kaolin and particularly the palygorskite had higher contents than the other clays, with some elements occasionally exceeding the contents of previously studied common clays. Nevertheless, all the trace elements were found in lower quantities than the recommended toxicity levels and those quantities currently used in pelotherapy in Spanish spas. (Author)

  9. Bright soil units on Mars determined from ISM imaging spectrometer data

    Science.gov (United States)

    Murchie, Scott; Mustard, John

    1993-01-01

    The lithology of bright Martian soil provides evidence for chemical and physical processes that have modified the planet's surface. Data from the ISM imaging spectrometer, which observed much of the equatorial region at a spatial resolution of approximately 22 km, cover the NIR wavelength range critical to ascertaining the presence and abundance of Fe-containing phases, hydroxylated silicates, and H2O in the bright soil. ISM data previously have revealed spatial variations in depth of the 3.0-microns H2O absorption suggesting differences in water content, a weak absorption at 2.2 microns indicative of metal-OH in phyllosilicate, and variations in the 1-micron Fe absorption indicative of differences in Fe mineralogy. This paper summarizes first results of a systematic investigation of spectral heterogeneity in bright soils observed by ISM. At least seven 'units' with distinctive properties were discriminated. Comparison of their spatial distributions with Viking data shows that they generally correspond with previously recognized morphologic, color, and thermal features. These correspondences and the units' spectral attributes provide evidence for lithologic differences between the soils in different geologic settings.

  10. Thesis for being entitled to lead research work

    International Nuclear Information System (INIS)

    Muller, F.

    2004-11-01

    The study of the properties of clay minerals such as the di-octahedral phyllosilicates requires a multi-scale analysis of their features. The results that are presented here concern both the local scale (intern structure organisation of the sheet and the cation-sheet interaction) and the semi-local scale featuring the sheet piling up. Various investigation means have been used: X-ray and infra-red absorption, X-ray diffraction, small angle X-ray scattering, electron diffraction on selected spots and adequate simulation methods. The firs part is dedicated to order-disorder relationship in the organization of major octahedral cations (Al, Fe, Mg). The cation distribution is not due to random but is organized in domains that can be mono-cationic (Fe or Al) or mixed, in the latter case the trend is to promote the mixing of charges losses. The second part is devoted to the study of structure transformations induced by thermal and hydro-thermal treatments. Models for the cationic migration inside octahedral layers are proposed to explain structural changes. The composition and cationic distribution of octahedral layers play an important role in the process. In the case of smectite, treatments are responsible for the increase of disorder in the sheet distribution and for the decrease in hydration properties of some sheets

  11. Experimental seawater-basaltic glass interaction at 50°C: Study of early developed phases by electron microscopy and X-ray photoelectron spectrometry

    Science.gov (United States)

    Crovisier, J. L.; Thomassin, J. H.; Juteau, T.; Eberhart, J. P.; Touray, J. C.; Baillif, P.

    1983-03-01

    Experiments on seawater-basaltic glass interaction were made using a particulary high seawater-basaltic glass ratio (14.5 g/cm 2; weight ratio: 50). A layered alteration skin is observed at the glass surface, while the variations in the composition of the seawater are imperceptible. Three zones of different composition and structure are distinguished: 1) An external zone, the composition of which evolved to saponite. 2) A median zone of hydrotalcite-like hydroxycarbonate (Mg 6Al 2CO 3(OH) 164H 2O). 3) An internal zone, between glass and hydroxycarbonates, richer in Fe and in Mg and in which a 10 Å interval is observed (by dark field examination) compatible with a TOT type clay mineral. The composition of this zone indicates a mixing of poorly crystalline products. The principal chemical exchanges between glass and solution are the release of Ca in solution and the contribution of Mg and CO 2 from seawater to form hydroxycarbonates, which are considered precursors of phyllosilicates. Comparison with natural phenomena (palagonitization) is made.

  12. Mechanistic Processes Controlling Gas Sorption in Shale Reservoirs

    Science.gov (United States)

    Schaef, T.; Loring, J.; Ilton, E. S.; Davidson, C. L.; Owen, T.; Hoyt, D.; Glezakou, V. A.; McGrail, B. P.; Thompson, C.

    2014-12-01

    Utilization of CO2 to stimulate natural gas production in previously fractured shale-dominated reservoirs where CO2 remains in place for long-term storage may be an attractive new strategy for reducing the cost of managing anthropogenic CO2. A preliminary analysis of capacities and potential revenues in US shale plays suggests nearly 390 tcf in additional gas recovery may be possible via CO2 driven enhanced gas recovery. However, reservoir transmissivity properties, optimum gas recovery rates, and ultimate fate of CO2 vary among reservoirs, potentially increasing operational costs and environmental risks. In this paper, we identify key mechanisms controlling the sorption of CH4 and CO2 onto phyllosilicates and processes occurring in mixed gas systems that have the potential of impacting fluid transfer and CO2 storage in shale dominated formations. Through a unique set of in situ experimental techniques coupled with molecular-level simulations, we identify structural transformations occurring to clay minerals, optimal CO2/CH4 gas exchange conditions, and distinguish between adsorbed and intercalated gases in a mixed gas system. For example, based on in situ measurements with magic angle spinning NMR, intercalation of CO2 within the montmorillonite structure occurs in CH4/CO2 gas mixtures containing low concentrations (hydrocarbon recovery processes.

  13. Ab-Initio Modelling Of Surface Site Reactivity And Fluid Transport In Clay Minerals Case Study: Pyrophyllite

    International Nuclear Information System (INIS)

    Churakov, S.V.

    2005-01-01

    Pyrophyllite, Al 2 [Si 4 O 10 ](OH) 2 , is the simplest structural prototype for 2:1 dioctahedral phyllosilicate. Because the net electric charge in pyrophyllite is zero, it is the best candidate for investigating the non electrostatic contribution to sorption and transport phenomena in clays. Using ab-initio simulations, we have investigated the reactivity and structure of the water-solid interface on the basal plane and edge sites of pyrophyllite. The calculations predict slightly hydrophobic behaviour of the basal plane. For the high water coverage (100), (110) and (-110), lateral facets have a lower energy than for the (010), (130) and (-130) surfaces. Analysis of the surface reactivity reveals that the =Al-OH groups are most easily protonated on the (010), (130) and (-130) facets. The =Al-O-Si= sites will be protonated on the (100), (130), (110), (-110) and (-130) surfaces. The =Al-OH 2 complexes are more easily de-protonated than the =Si-OH and =Al-OH sites. A spontaneous, reversible exchange of the protons between the solution and the edge sites has been observed in ab-initio molecular dynamics simulations at 300 K. Such near-surface proton diffusion may result in a significant contribution to the diffusion coefficients measured in neutron scattering experiments. (author)

  14. Physical properties and chemical composition of Segamat Kaolin, Johor, Malaysia

    International Nuclear Information System (INIS)

    Umar Hamzah; Learn, K.K.; Sahibin Rahim

    2010-01-01

    Kaolin is a source of secondary mineral as a product of a weathering process of primary minerals. Its main component is fine grain kaolinite (< 2 μm) and it also contains other elements such as aluminium and iron phyllosilicate as the pigment. Aluminium rich kaolin is light in colour with high plasticity and is normally used in the ceramic, plastic, paint, paper, pesticide, pharmacology and cosmetic industries. The physical and chemical characteristics of kaolins are important for its potential application. In this study, about 25 kaolin samples were hand-augered from depths of 1-2 m at Buloh Kasap Segamat, Johor, Malaysia. Chemical analysis carried out included determination of oxides and types of minerals by X-ray diffraction and X-ray fluorescence. Shrinkage rate, rupture modulus and water absorption rate tests were carried out in the physical properties analysis. Plastic and liquid limits of the kaolin were also measured for plastic index. The Segamat kaolin was light in colour due to its high silicate composition. The highest mineral content in the kaolin was kaolinite and quartz occurred as impurities. The low shrinkage rate showed that the kaolin was dense with little voids, hence very suitable for use in the ceramic industry. This kaolin has low water absorption, plasticity and durable according to the rupture modulus test. (author)

  15. The Transformation of Coal-Mining Waste Minerals in the Pozzolanic Reactions of Cements

    Directory of Open Access Journals (Sweden)

    Rosario Giménez-García

    2016-06-01

    Full Text Available The cement industry has the potential to become a major consumer of recycled waste materials that are transformed and recycled in various forms as aggregates and pozzolanic materials. These recycled waste materials would otherwise have been dumped in landfill sites, leaving hazardous elements to break down and contaminate the environment. There are several approaches for the reuse of these waste products, especially in relation to clay minerals that can induce pozzolanic reactions of special interest in the cement industry. In the present paper, scientific aspects are discussed in relation to several inert coal-mining wastes and their recycling as alternative sources of future eco-efficient pozzolans, based on activated phyllosilicates. The presence of kaolinite in this waste indicates that thermal treatment at 600 °C for 2 h transformed these minerals into a highly reactive metakaolinite over the first seven days of the pozzolanic reaction. Moreover, high contents of metakaolinite, together with silica and alumina sheet structures, assisted the appearance of layered double hydroxides through metastable phases, forming stratlingite throughout the main phase of the pozzolanic reaction after 28 days (as recommended by the European Standard as the reaction proceeded.

  16. STXM-XANES Analysis of Organic Matter in Dark Clasts and Halite Crystals in Zag and Monahans Meteorites

    Science.gov (United States)

    Kebukawa, Y.; Zolensky, M. E.; Fries, M.; Nakato, A.; Kilcoyne, A. L. D.; Takeichi, Y.; Suga, H.; Miyamoto, C.; Rahman, Z.; Kobayashi, K.; hide

    2016-01-01

    Zag and Monahans meteorites (H5) contains xenolithic dark clasts and halite (NaCl) crystals [e.g., 1]. The proposed source of the H chondrites is asteroid 6 Hebe [2]. The modern orbits of 1 Ceres and 6 Hebe essentially cross, with aphelion/perihelion of Ceres and Hebe of 2.99/2.55 and 2.91/1.94 AU (Astronomical Units), respectively. Therefore, Ceres might be the source of the clasts and halite in Zag and Monahans meteorites. Recent results from NASA's Dawn mission shows that bright spots in Ceres's crater may be hydrated magnesium sulfate with some water ice, and an average global surface contains ammoniated phyllosilicates that is likely of outer Solar System origin. One dark clast and all halite crystals in Zag and Monahans meteorites contain carbon-rich particles. We report organic analyses of these carbon-rich particles using carbon, nitrogen, and oxygen X-ray absorption near edge structure (C-, N-, and O-XANES), in order to constrain the origin of the clast and halite crystals.

  17. Impact-generated Hydrothermal Activity at the Chicxulub Crater

    Science.gov (United States)

    Kring, D. A.; Zurcher, L.; Abramov, O.

    2007-05-01

    Borehole samples recovered from PEMEX exploration boreholes and an ICDP scientific borehole indicate the Chicxulub impact event generated hydrothermal alteration throughout a large volume of the Maya Block beneath the crater floor and extending across the bulk of the ~180 km diameter crater. The first indications of hydrothermal alteration were observed in the crater discovery samples from the Yucatan-6 borehole and manifest itself in the form of anhydrite and quartz veins. Continuous core from the Yaxcopoil-1 borehole reveal a more complex and temporally extensive alteration sequence: following a brief period at high temperatures, impact- melt-bearing polymict breccias and a thin, underlying unit of impact melt were subjected to metasomatism, producing alkali feldspar, sphene, apatite, and magnetite. As the system continued to cool, smectite-series phyllosilicates appeared. A saline solution was involved. Stable isotopes suggest the fluid was dominated by a basinal brine created mostly from existing groundwater of the Yucatan Peninsula, although contributions from down-welling water also occurred in some parts of the system. Numerical modeling of the hydrothermal system suggests circulation occurred for 1.5 to 2.3 Myr, depending on the permeability of the system. Our understanding of the hydrothermal system, however, is still crude. Additional core recovery projects, particularly into the central melt sheet, are needed to better evaluate the extent and duration of hydrothermal alteration.

  18. Microbial Analysis of Australian Dry Lake Cores; Analogs For Biogeochemical Processes

    Science.gov (United States)

    Nguyen, A. V.; Baldridge, A. M.; Thomson, B. J.

    2014-12-01

    Lake Gilmore in Western Australia is an acidic ephemeral lake that is analogous to Martian geochemical processes represented by interbedded phyllosilicates and sulfates. These areas demonstrate remnants of a global-scale change on Mars during the late Noachian era from a neutral to alkaline pH to relatively lower pH in the Hesperian era that continues to persist today. The geochemistry of these areas could possibly be caused by small-scale changes such as microbial metabolism. Two approaches were used to determine the presence of microbes in the Australian dry lake cores: DNA analysis and lipid analysis. Detecting DNA or lipids in the cores will provide evidence of living or deceased organisms since they provide distinct markers for life. Basic DNA analysis consists of extraction, amplification through PCR, plasmid cloning, and DNA sequencing. Once the sequence of unknown DNA is known, an online program, BLAST, will be used to identify the microbes for further analysis. The lipid analysis approach consists of phospholipid fatty acid analysis that is done by Microbial ID, which will provide direct identification any microbes from the presence of lipids. Identified microbes are then compared to mineralogy results from the x-ray diffraction of the core samples to determine if the types of metabolic reactions are consistent with the variation in composition in these analog deposits. If so, it provides intriguing implications for the presence of life in similar Martian deposits.

  19. Using presence of calcite cap rock in shales to predict occurrence of reservoirs composed of leached secondary porosity in the geopressured zone. Annual report, June 1, 1980-October 31, 1980

    Energy Technology Data Exchange (ETDEWEB)

    Kaiser, W.R.; Magara, K.; Milliken, K.L.; Richmann, D.L.

    1981-01-01

    The distribution of high-resistivity shale in the Frio Formation between hydropressured and geopressured strata has been mapped along the Texas Gulf Coast. Two high-resistivity intervals more than 1000 ft thick have been mapped, one in Brazoria and Galveston Counties and the other in Kenedy County. They coincide with Frio delta systems and may be related to extraordinary quantities of CO/sub 2/ produced by deltaic sediments rich in woody and herbaceous matter. Beyond being calcareous, the nature of the high-resistivity interval is enigmatic and its relationship to deep secondary porosity problematic. Most of the contained carbonate is microscopically and isotopically skeletal in origin, revealing no evidence of diagenetic modification. Minor rhombs of iron-bearing carbonate tens of microns in size were identified. Detrital feldspar compositions are being established to test subsequent changes in feldspar composition resulting from progressive burial and albitization. Hydrolysis reactions for authigenic minerals and reactions between key pairs of minerals have been written. Thermodynamic functions for complex phyllosilicates at temperatures up to 200/sup 0/C have been calculated. From thermodynamic calculations it was predicted that ferroan calcite would be the favored authigenic carbonate in shales.

  20. A field-practical assay for rapid detection of chlorophenols

    Energy Technology Data Exchange (ETDEWEB)

    Washburn, K.S.; Phillips, T.D. [Texas A and M Univ., College Station, TX (United States). Dept. of Veterinary Anatomy and Public Health

    1994-12-31

    Water-solvated chlorophenols (CPs) are environmental toxins associated with wood preservation and pesticide synthesis and usage. Their toxicity and association with dioxin-contaminated wastes are well-documented, as is their stability in most environmental settings. Several analytical procedures, mainly HPLC and GC/MS, are currently used to detect and quantify CPs, but these procedures are based on expensive equipment and technical expertise in a laboratory setting. The authors have developed an inexpensive, field-practical method for CPs, utilizing a small, packed glass minicolumn and derivatization of target CP molecules with dansyl chloride (5-dimethylaminonaphthalene-1sulfonyl chloride), or DsCl. A nonfluorescent borosilicate glass tube was used to house an array of inorganic sorbent materials, including preparative layers and a reactive neutral alumina interface separated by sand. DsCl is a substituted naphthalene with a conjugated X system that is responsible for its fluorescent complexation. Amines that reacted with DsCl were removed with a small amount of phyllosilicate clay to avoid interference. A neutral alumina/sand interface was used to strongly bind and immobilize the dansylated CPs. Activities greater than 3.0 for the alumina were avoided to prevent loss of selectivity, intensity and color of the fluorescence at the reactive interface. The results indicated that this assay was capable of rapidly screening potable water samples and detecting CP contamination at very low concentrations (i.e., 1.0 ppb of pentachlorophenol in drinking water).

  1. Preferred Orientation and Anisotropy of Clay minerals and Pores in Posidonia Shales

    Science.gov (United States)

    Kanitpanyacharoen, W.; Chen, K.; Wenk, H.

    2010-12-01

    Shales compose a large part of sedimentary basins and form the seal and source rocks for hydrocarbon reservoirs. They are also of great interest in context of repositories for nuclear waste and carbon sequestration. A comprehensive study of shale properties is thus crucial for seismic prospecting, particularly due to high elastic anisotropy that is contributed by the alignment of constituent clay minerals during compaction and diagenesis. In this study, we quantitatively analyze composition, crystal preferred orientation (or texture), and the 3D porosity structure in four Posidonia shales from Germany using high energy synchrotron x-rays. We can infer texture information from x-ray diffraction images relying on the Rietveld method, as well as determine the 3D porosity structure from tomography images. We observed that quartz and calcite are dominating phases while illite-smectite, illite-mica and kaolinite are the major clay minerals. The texture strength of clays range from 4.22 to 6.12 m.r.d. A comparison of shallow Posidonia shales with deep shales from the North Sea, Saudi Arabia, and the Gulf of Mexico documents that P-wave anisotropy increases with increasing phyllosilicate content (mainly illite-smectite and kaolinite) and increasing burial. Low absorption features in microtomography images indicate porosity (including kerogen and fractures), which is estimated at 1 vol% and observed to be anisotropic, mainly organized parallel to bedding with little connectivity of flat pores in direction perpendicular to the bedding plane.

  2. Rock magnetism and magnetic fabric of the Triassic rocks from the West Spitsbergen Fold-and-Thrust Belt and its foreland

    Science.gov (United States)

    Dudzisz, Katarzyna; Szaniawski, Rafał; Michalski, Krzysztof; Chadima, Martin

    2018-03-01

    Magnetic fabric and magnetomineralogy of the Early Triassic sedimentary rocks, collected along the length of the West Spitsbergen Fold-and-Thrust Belt (WSFTB) and from subhorizontal beds on its foreland, is presented with the aim to compare magnetic mineralogy of these areas, determine the carriers of magnetic fabric and identify tectonic deformation reflected in the magnetic fabric. Magnetic mineralogy varies and only in part depends on the lithology. The magnetic fabric at all sampling sites is controlled by paramagnetic minerals (phyllosilicates and Fe-carbonates). In the fold belt, it reflects the low degree of deformation in a compressional setting with magnetic lineation parallel to fold axis (NW-SE). This is consistent with pure orthogonal compression model of the WSFTB formation, but it also agrees with decoupling model. Inverse fabric, observed in few sites, is carried by Fe-rich carbonates. In the WSFTB foreland, magnetic lineation reflects the Triassic paleocurrent direction (NE-SW). The alternation between normal and inverse magnetic fabric within the stratigraphic profile could be related to sedimentary cycles.

  3. The stratigraphy and evolution of lower Mount Sharp from spectral, morphological, and thermophysical orbital data sets.

    Science.gov (United States)

    Fraeman, A A; Ehlmann, B L; Arvidson, R E; Edwards, C S; Grotzinger, J P; Milliken, R E; Quinn, D P; Rice, M S

    2016-09-01

    We have developed a refined geologic map and stratigraphy for lower Mount Sharp using coordinated analyses of new spectral, thermophysical, and morphologic orbital data products. The Mount Sharp group consists of seven relatively planar units delineated by differences in texture, mineralogy, and thermophysical properties. These units are (1-3) three spatially adjacent units in the Murray formation which contain a variety of secondary phases and are distinguishable by thermal inertia and albedo differences, (4) a phyllosilicate-bearing unit, (5) a hematite-capped ridge unit, (6) a unit associated with material having a strongly sloped spectral signature at visible near-infrared wavelengths, and (7) a layered sulfate unit. The Siccar Point group consists of the Stimson formation and two additional units that unconformably overlie the Mount Sharp group. All Siccar Point group units are distinguished by higher thermal inertia values and record a period of substantial deposition and exhumation that followed the deposition and exhumation of the Mount Sharp group. Several spatially extensive silica deposits associated with veins and fractures show that late-stage silica enrichment within lower Mount Sharp was pervasive. At least two laterally extensive hematitic deposits are present at different stratigraphic intervals, and both are geometrically conformable with lower Mount Sharp strata. The occurrence of hematite at multiple stratigraphic horizons suggests redox interfaces were widespread in space and/or in time, and future measurements by the Mars Science Laboratory Curiosity rover will provide further insights into the depositional settings of these and other mineral phases.

  4. The Case of the Lacking Carbonates and the Emergence of Early Life on Mars

    Directory of Open Access Journals (Sweden)

    Ricardo Amils

    2010-08-01

    Full Text Available The mineralogical characterization of Mars by different exploration missions, provides a new image of the earliest conditions that prevailed on the planet surface. The detection of extensive deposits of phyllosillicates has been considered to be as a result of the production of hydrated silicates through alteration and precipitation under neutral to sub-alkaline conditions. Although extensive deposits of carbonates should precipitate beneath a thick CO2-bearing atmosphere, only a few outcrops of Mg-rich carbonates have been detected on Mars. Paradoxically those carbonates occur in association with geological units exposed to acidic paleoenvironments. Given such geochemical conditions on Earth, the carbon cycle is intimately associated with life, then, we can assume that the presence or absence of microbial communities should have impacted the distribution of those carbonate compounds on Mars. In this paper, we suggest three potential geobiological scenarios to explain how the emergence of life on Mars would have impacted the carbon cycle and, hence, the formation of carbonates on a planetary scale.

  5. Thallium occurrence and partitioning in soils and sediments affected by mining activities in Madrid province (Spain).

    Science.gov (United States)

    Gomez-Gonzalez, M A; Garcia-Guinea, J; Laborda, F; Garrido, F

    2015-12-01

    Thallium (Tl) and its compounds are toxic to biota even at low concentrations but little is known about Tl concentration and speciation in soils. An understanding of the source, mobility, and dispersion of Tl is necessary to evaluate the environmental impact of Tl pollution cases. In this paper, we examine the Tl source and dispersion in two areas affected by abandoned mine facilities whose residues remain dumped on-site affecting to soils and sediments of natural water courses near Madrid city (Spain). Total Tl contents and partitioning in soil solid phases as determined by means of a sequential extraction procedure were also examined in soils along the riverbeds of an ephemeral and a permanent streams collecting water runoff and drainage from the mines wastes. Lastly, electronic microscopy and cathodoluminescence probe are used as a suitable technique for Tl elemental detection on thallium-bearing phases. Tl was found mainly bound to quartz and alumino-phyllosilicates in both rocks and examined soils. Besides, Tl was also frequently found associated to organic particles and diatom frustules in all samples from both mine scenarios. These biogenic silicates may regulate the transfer of Tl into the soil-water system. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Visible-near infrared point spectrometry of drill core samples from Río Tinto, Spain: results from the 2005 Mars Astrobiology Research and Technology Experiment (MARTE) drilling exercise.

    Science.gov (United States)

    Sutter, Brad; Brown, Adrian J; Stoker, Carol R

    2008-10-01

    Sampling of subsurface rock may be required to detect evidence of past biological activity on Mars. The Mars Astrobiology Research and Technology Experiment (MARTE) utilized the Río Tinto region, Spain, as a Mars analog site to test dry drilling technologies specific to Mars that retrieve subsurface rock for biological analysis. This work examines the usefulness of visible-near infrared (VNIR) (450-1000 nm) point spectrometry to characterize ferric iron minerals in core material retrieved during a simulated Mars drilling mission. VNIR spectrometry can indicate the presence of aqueously precipitated ferric iron minerals and, thus, determine whether biological analysis of retrieved rock is warranted. Core spectra obtained during the mission with T1 (893-897 nm) and T2 (644-652 nm) features indicate goethite-dominated samples, while relatively lower wavelength T1 (832-880 nm) features indicate hematite. Hematite/goethite molar ratios varied from 0 to 1.4, and within the 880-898 nm range, T1 features were used to estimate hematite/goethite molar ratios. Post-mission X-ray analysis detected phyllosilicates, which indicates that examining beyond the VNIR (e.g., shortwave infrared, 1000-2500 nm) will enhance the detection of other minerals formed by aqueous processes. Despite the limited spectral range of VNIR point spectrometry utilized in the MARTE Mars drilling simulation project, ferric iron minerals could be identified in retrieved core material, and their distribution served to direct core subsampling for biological analysis.

  7. Laser-induced breakdown spectroscopy analysis of minerals: Carbonates and silicates

    International Nuclear Information System (INIS)

    McMillan, Nancy J.; Harmon, Russell S.; De Lucia, Frank C.; Miziolek, Andrzej M.

    2007-01-01

    Laser-induced breakdown spectroscopy (LIBS) provides an alternative chemical analytical technique that obviates the issues of sample preparation and sample destruction common to most laboratory-based analytical methods. This contribution explores the capability of LIBS analysis to identify carbonate and silicate minerals rapidly and accurately. Fifty-two mineral samples (18 carbonates, 9 pyroxenes and pyroxenoids, 6 amphiboles, 8 phyllosilicates, and 11 feldspars) were analyzed by LIBS. Two composite broadband spectra (averages of 10 shots each) were calculated for each sample to produce two databases each containing the composite LIBS spectra for the same 52 mineral samples. By using correlation coefficients resulting from the regression of the intensities of pairs of LIBS spectra, all 52 minerals were correctly identified in the database. If the LIBS spectra of each sample were compared to a database containing the other 51 minerals, 65% were identified as a mineral of similar composition from the same mineral family. The remaining minerals were misidentified for two reasons: 1) the mineral had high concentrations of an element not present in the database; and 2) the mineral was identified as a mineral with similar elemental composition from a different family. For instance, the Ca-Mg carbonate dolomite was misidentified as the Ca-Mg silicate diopside. This pilot study suggests that LIBS has promise in mineral identification and in situ analysis of minerals that record geological processes

  8. Selection of the Mars Science Laboratory landing site

    Science.gov (United States)

    Golombek, M.; Grant, J.; Kipp, D.; Vasavada, A.; Kirk, Randolph L.; Fergason, Robin L.; Bellutta, P.; Calef, F.; Larsen, K.; Katayama, Y.; Huertas, A.; Beyer, R.; Chen, A.; Parker, T.; Pollard, B.; Lee, S.; Hoover, R.; Sladek, H.; Grotzinger, J.; Welch, R.; Dobrea, E. Noe; Michalski, J.; Watkins, M.

    2012-01-01

    The selection of Gale crater as the Mars Science Laboratory landing site took over five years, involved broad participation of the science community via five open workshops, and narrowed an initial >50 sites (25 by 20 km) to four finalists (Eberswalde, Gale, Holden and Mawrth) based on science and safety. Engineering constraints important to the selection included: (1) latitude (±30°) for thermal management of the rover and instruments, (2) elevation (surface that is safe for landing and roving and not dominated by fine-grained dust. Science criteria important for the selection include the ability to assess past habitable environments, which include diversity, context, and biosignature (including organics) preservation. Sites were evaluated in detail using targeted data from instruments on all active orbiters, and especially Mars Reconnaissance Orbiter. All of the final four sites have layered sedimentary rocks with spectral evidence for phyllosilicates that clearly address the science objectives of the mission. Sophisticated entry, descent and landing simulations that include detailed information on all of the engineering constraints indicate all of the final four sites are safe for landing. Evaluation of the traversabilty of the landing sites and target “go to” areas outside of the ellipse using slope and material properties information indicates that all are trafficable and “go to” sites can be accessed within the lifetime of the mission. In the final selection, Gale crater was favored over Eberswalde based on its greater diversity and potential habitability.

  9. DETECTION OF WATER AND/OR HYDROXYL ON ASTEROID (16) Psyche

    International Nuclear Information System (INIS)

    Takir, Driss; Reddy, Vishnu; Sanchez, Juan A.; Shepard, Michael K.; Emery, Joshua P.

    2017-01-01

    In order to search for evidence of hydration on M-type asteroid (16) Psyche, we observed this object in the 3 μ m spectral region using the long-wavelength cross-dispersed (LXD: 1.9–4.2 μ m) mode of the SpeX spectrograph/imager at the NASA Infrared Telescope Facility. Our observations show that Psyche exhibits a 3 μ m absorption feature, attributed to water or hydroxyl. The 3 μ m absorption feature is consistent with the hydration features found on the surfaces of water-rich asteroids, attributed to OH- and/or H 2 O-bearing phases (phyllosilicates). The detection of a 3 μ m hydration absorption band on Psyche suggests that this asteroid may not be a metallic core, or it could be a metallic core that has been impacted by carbonaceous material over the past 4.5 Gyr. Our results also indicate rotational spectral variations, which we suggest reflect heterogeneity in the metal/silicate ratio on the surface of Psyche.

  10. DETECTION OF WATER AND/OR HYDROXYL ON ASTEROID (16) Psyche

    Energy Technology Data Exchange (ETDEWEB)

    Takir, Driss [U.S. Geological Survey, Astrogeology Science Center, Flagstaff, AZ 86001 (United States); Reddy, Vishnu [Lunar and Planetary Laboratory, University of Arizona, Tucson, AZ 85721 (United States); Sanchez, Juan A. [Planetary Science Institute, 1700 E Fort Lowell Road, Suite 106, Tucson, AZ 85719 (United States); Shepard, Michael K. [Department of Geography and Geosciences, Bloomsburg University of Pennsylvania, 400 E. Second Street, Bloomsburg, PA 17815 (United States); Emery, Joshua P., E-mail: dtakir@usgs.gov [Earth and Planetary Science Department, Planetary Geosciences Institute, University of Tennessee, Knoxville, TN 37996 (United States)

    2017-01-01

    In order to search for evidence of hydration on M-type asteroid (16) Psyche, we observed this object in the 3 μ m spectral region using the long-wavelength cross-dispersed (LXD: 1.9–4.2 μ m) mode of the SpeX spectrograph/imager at the NASA Infrared Telescope Facility. Our observations show that Psyche exhibits a 3 μ m absorption feature, attributed to water or hydroxyl. The 3 μ m absorption feature is consistent with the hydration features found on the surfaces of water-rich asteroids, attributed to OH- and/or H{sub 2}O-bearing phases (phyllosilicates). The detection of a 3 μ m hydration absorption band on Psyche suggests that this asteroid may not be a metallic core, or it could be a metallic core that has been impacted by carbonaceous material over the past 4.5 Gyr. Our results also indicate rotational spectral variations, which we suggest reflect heterogeneity in the metal/silicate ratio on the surface of Psyche.

  11. Detection of Water and/or Hydroxyl on Asteroid (16) Psyche

    Science.gov (United States)

    Takir, Driss; Reddy, Vishnu; Sanchez, Juan A.; Shepard, Michael K.; Emery, Joshua P.

    2017-01-01

    In order to search for evidence of hydration on M-type asteroid (16) Psyche, we observed this object in the 3 μm spectral region using the long-wavelength cross-dispersed (LXD: 1.9-4.2 μm) mode of the SpeX spectrograph/imager at the NASA Infrared Telescope Facility. Our observations show that Psyche exhibits a 3 μm absorption feature, attributed to water or hydroxyl. The 3 μm absorption feature is consistent with the hydration features found on the surfaces of water-rich asteroids, attributed to OH- and/or H2O-bearing phases (phyllosilicates). The detection of a 3 μm hydration absorption band on Psyche suggests that this asteroid may not be a metallic core, or it could be a metallic core that has been impacted by carbonaceous material over the past 4.5 Gyr. Our results also indicate rotational spectral variations, which we suggest reflect heterogeneity in the metal/silicate ratio on the surface of Psyche.

  12. Potential use of gypsum and lime rich industrial by-products for induced reduction of Pb, Zn and Ni leachability in an acid soil

    International Nuclear Information System (INIS)

    Rodriguez-Jorda, M.P.; Garrido, F.; Garcia-Gonzalez, M.T.

    2010-01-01

    This study evaluates the potential use of four industrial by-products (phosphogypsum (PG), red gypsum (RG), sugar foam (SF), and ashes from biomass combustion (ACB)), applied at two rates in single and combined amendments to reduce the mobility and availability of Pb, Zn and Ni in a metal-spiked acid soil. Leaching experiments were done to estimate leachability indexes and assess their effectiveness. Most of the treatments significantly reduced the metal leachability although only a few were effective for all metals. Based on principal component and cluster analysis, sugar foam (SF) and a mixture of RG and ACB (RG+ACB), both applied at high rate, were selected as first choices to reduce mobility and availability of the three metals. Metal sorption mechanisms involved in the reduction of their leachability were identified using scanning electron microscopy. In the SF-treated samples, the metals were found associated to amorphous Al-hydroxy polymers deposited on phyllosilicates and organic matter particles. In the (RG+ACB)-treated samples, Pb, Zn, and traces of Ni were found associated to Fe/Ti oxide phases with a significant concentration of S, suggesting the formation of metal-sulfate ternary complexes.

  13. Push-out strength of modified Portland cements and resins.

    Science.gov (United States)

    Iacono, Francesco; Gandolfi, Maria Giovanna; Huffman, Bradford; Sword, Jeremy; Agee, Kelli; Siboni, Francesco; Tay, Franklin; Prati, Carlo; Pashley, David

    2010-02-01

    Modified calcium-silicate cements derived from white Portland cement (PC) were formulated to test their push-out strength from radicular dentin after immersion for 1 month. Slabs obtained from 42 single-rooted extracted teeth were prepared with 0.6 mm diameter holes, then enlarged with rotary instruments. After immersion in EDTA and NaOC1, the holes were filled with modified PCs or ProRoot MTA, Vitrebond and Clearfil SE. Different concentrations of phyllosilicate (montmorillonite-MMT) were added to experimental cements. ProRoot MTA was also included as reference material. Vitrebond and Clearfil SE were included as controls. Each group was tested after 1 month of immersion in water or PBS. A thin-slice push-out test on a universal testing machine served to test the push-out strength of materials. Results were statistically analyzed using the least squares means (LSM) method. The modified PCs had push-out strengths of 3-9.5 MPa after 1 month of immersion in water, while ProRoot MTA had 4.8 MPa. The push-out strength of PC fell after incubation in PBS for 1 month, while the push-out strength of ProRoot MTA increased. There were no significant changes in Clearfil SE Bond or Vitrebond after water or PBS storage.

  14. Adsorption of nucleotides onto Fe-Mg-Al rich swelling clays

    Science.gov (United States)

    Feuillie, Cécile; Daniel, Isabelle; Michot, Laurent J.; Pedreira-Segade, Ulysse

    2013-11-01

    Mineral surfaces may have played a role in the origin of the first biopolymers, by concentrating organic monomers from a dilute ocean. Swelling clays provide a high surface area for the concentration of prebiotic monomers, and have therefore been the subject of numerous investigations. In that context, montmorillonite, the most abundant swelling clay in modern environments, has been extensively studied with regard to adsorption and polymerization of nucleic acids. However, montmorillonite was probably rather marginal on the primitive ocean floor compared to iron-magnesium rich phyllosilicates such as nontronite that results from the hydrothermal alteration of a mafic or ultramafic oceanic crust. In the present paper, we study the adsorption of nucleotides on montmorillonite and nontronite, at various pH and ionic strength conditions plausible for Archean sea-water. A thorough characterization of the mineral surfaces shows that nucleotide adsorb mainly on the edge faces of the smectites by ligand exchange between the phosphate groups of the nucleotides and the -OH groups from the edge sites over a wide pH range (4-10). Nontronite is more reactive than montmorillonite. At low pH, additional ion exchange may play a role as the nucleotides become positively charged.

  15. The interior structure of Ceres as revealed by surface topography

    Science.gov (United States)

    Fu, Roger R.; Ermakov, Anton; Marchi, Simone; Castillo-Rogez, Julie C.; Raymond, Carol A.; Hager, Bradford; Zuber, Maria; King, Scott D.; Bland, Michael T.; De Sanctis, Maria Cristina; Preusker, Frank; Park, Ryan S.; Russell, Christopher T.

    2017-01-01

    Ceres, the largest body in the asteroid belt (940 km diameter), provides a unique opportunity to study the interior structure of a volatile-rich dwarf planet. Variations in a planetary body's subsurface rheology and density affect the rate of topographic relaxation. Preferential attenuation of long wavelength topography (≥150 km) on Ceres suggests that the viscosity of its crust decreases with increasing depth. We present finite element (FE) geodynamical simulations of Ceres to identify the internal structures and compositions that best reproduce its topography as observed by the NASA Dawn mission. We infer that Ceres has a mechanically strong crust with maximum effective viscosity ∼1025 Pa s. Combined with density constraints, this rheology suggests a crustal composition of carbonates or phyllosilicates, water ice, and at least 30 volume percent (vol.%) low-density, high-strength phases most consistent with salt and/or clathrate hydrates. The inference of these crustal materials supports the past existence of a global ocean, consistent with the observed surface composition. Meanwhile, we infer that the uppermost ≥60 km of the silicate-rich mantle is mechanically weak with viscosity <1021 Pa s, suggesting the presence of liquid pore fluids in this region and a low temperature history that avoided igneous differentiation due to late accretion or efficient heat loss through hydrothermal processes.

  16. Zn speciation in a soil contaminated by the deposition of a dredged sediment by synchrotron X-ray techniques

    International Nuclear Information System (INIS)

    Isaure, Marie-Pierre; Manceau, Alain; Laboudigue, Agnes; Tamura, Nobumichi; Marcus, Matthew A.

    2003-09-01

    The nature and proportion of Zn species present in an agricultural soil overlaid by a dredged contaminated sediment have been untangled by the novel combination of three non-invasive synchrotron-based x-ray techniques: x-ray microfluorescence (μSXRF), microdiffraction (μXRD), and absorption spectroscopy (EXAFS). One primary (franklinite) and two secondary (phyllomanganate and phyllosilicate) Zn-containing minerals were identified in the initial soil, and another primary (ZnS) and a new secondary (Fe-(oxyhydr)oxide) Zn species in the covered soil. The quantitative analysis of EXAFS spectra recorded on bulk samples indicated that ZnS and Zn-Fe (oxyhydr)oxides amounted to 71+-10 percent and 27+-10 percent, respectively, and the other Zn species to less than 10 percent. The two new Zn species found in the covered soil result from the gravitational migration of ZnS particles initially present in the sediment, and from their further oxidative dissolution and fixation of leached Zn on F e (oxyhydr) oxides

  17. Abiotic Protein Fragmentation by Manganese Oxide: Implications for a Mechanism to Supply Soil Biota with Oligopeptides.

    Science.gov (United States)

    Reardon, Patrick N; Chacon, Stephany S; Walter, Eric D; Bowden, Mark E; Washton, Nancy M; Kleber, Markus

    2016-04-05

    The ability of plants and microorganisms to take up organic nitrogen in the form of free amino acids and oligopeptides has received increasing attention over the last two decades, yet the mechanisms for the formation of such compounds in soil environments remain poorly understood. We used Nuclear Magnetic Resonance (NMR) and Electron Paramagnetic Resonance (EPR) spectroscopies to distinguish the reaction of a model protein with a pedogenic oxide (Birnessite, MnO2) from its response to a phyllosilicate (Kaolinite). Our data demonstrate that birnessite fragments the model protein while kaolinite does not, resulting in soluble peptides that would be available to soil biota and confirming the existence of an abiotic pathway for the formation of organic nitrogen compounds for direct uptake by plants and microorganisms. The absence of reduced Mn(II) in the solution suggests that birnessite acts as a catalyst rather than an oxidant in this reaction. NMR and EPR spectroscopies are shown to be valuable tools to observe these reactions and capture the extent of protein transformation together with the extent of mineral response.

  18. Surface mineral maps of Afghanistan derived from HyMap imaging spectrometer data, version 2

    Science.gov (United States)

    Kokaly, Raymond F.; King, Trude V.V.; Hoefen, Todd M.

    2013-01-01

    This report presents a new version of surface mineral maps derived from HyMap imaging spectrometer data collected over Afghanistan in the fall of 2007. This report also describes the processing steps applied to the imaging spectrometer data. The 218 individual flight lines composing the Afghanistan dataset, covering more than 438,000 square kilometers, were georeferenced to a mosaic of orthorectified Landsat images. The HyMap data were converted from radiance to reflectance using a radiative transfer program in combination with ground-calibration sites and a network of cross-cutting calibration flight lines. The U.S. Geological Survey Material Identification and Characterization Algorithm (MICA) was used to generate two thematic maps of surface minerals: a map of iron-bearing minerals and other materials, which have their primary absorption features at the shorter wavelengths of the reflected solar wavelength range, and a map of carbonates, phyllosilicates, sulfates, altered minerals, and other materials, which have their primary absorption features at the longer wavelengths of the reflected solar wavelength range. In contrast to the original version, version 2 of these maps is provided at full resolution of 23-meter pixel size. The thematic maps, MICA summary images, and the material fit and depth images are distributed in digital files linked to this report, in a format readable by remote sensing software and Geographic Information Systems (GIS). The digital files can be downloaded from http://pubs.usgs.gov/ds/787/downloads/.

  19. Magnetic properties of sheet silicates

    International Nuclear Information System (INIS)

    Ballet, O.; Coey, J.M.D.

    1982-01-01

    Susceptibility, magnetisation and Moessbauer measurements are reported for a representative selection of 2:1 layer phyllosilicates. Eight samples from the mica, vermiculite and smectite groups include examples diluted in iron which are paramagnetic at all temperatures, as well as iron-rich silicates which order magnetically below 10 K. Anisotropic susceptibility of crystals of muscovite, biotite and vermiculite is quantitatively explained with a model where the Fe 2+ ions lie in sites of effective trigonal symmetry, the trigonal axis lying normal to the sheets. The ferrous ground state is an orbital singlet. Ferric iron gives an isotropic contribution to the susceptibility. Fe 2+ -Fe 2+ exchange interactions are ferromagnetic with Gapprox. equal to2 K, whereas Fe 3+ -Fe 3+ coupling is antiferromagnetic in the purely ferric minerals. A positive paramagnetic Curie temperature for glauconite may be attributable to Fe 2+ → Fe 3+ charge transfer. Magnetic order was found to set in inhomogeneously for glauconite at 1-7 K. One biotite sample showed an antiferromagnetic transition at Tsub(N) = 7 K marked by a well-defined susceptibility maximum. Its magnetic structure, consisting of ferromagnetic sheets with moments in their planes coupled antiferromagnetically by other, weak interactions, resembles that found earlier for the 1:1 mineral greenalite. (orig.)

  20. Lessons Learned from Preparing OSIRIS-REx Spectral Analog Samples for Bennu

    Science.gov (United States)

    Schrader, D. L.; McCoy, T. J.; Cody, G. D.; King, A. J.; Schofield, P. F.; Russell, S. S.; Connolly, H. C., Jr.; Keller, L. P.; Donaldson Hanna, K.; Bowles, N.; hide

    2017-01-01

    NASA's OSIRIS-REx sample return mission launched on September 8th, 2016 to rendezvous with B-type asteroid (101955) Bennu in 2018. Type C and B asteroids have been linked to carbonaceous chondrites because of their similar visible - to - near infrared (VIS-NIR) spectral properties [e.g., 1,2]. The OSIRIS-REx Visible and Infrared Spectrometer (OVIRS) and the Thermal Emission Spectrometer (OTES) will make spectroscopic observations of Bennu during the encounter. Constraining the presence or absence of hydrous minerals (e.g., Ca-carbonate, phyllosilicates) and organic molecules will be key to characterizing Bennu [3] prior to sample site selection. The goal of this study was to develop a suite of analog and meteorite samples and obtain their spectral properties over the wavelength ranges of OVIRS (0.4- 4.3 micrometer) and OTES (5.0-50 micrometer). These spectral data were used to validate the mission science-data processing system. We discuss the reasoning behind the study and share lessons learned.

  1. Elemental imaging of organic matter and associated metals in ore deposits using micro PIXE and micro-EBS

    Energy Technology Data Exchange (ETDEWEB)

    Fuchs, S., E-mail: fuchs@geomin.eu [Department of Earth and Planetary Science, McGill University, 3450 University Street, Montreal H3A 0E8 (Canada); Przybylowicz, W.J., E-mail: przybylowicz@tlabs.ac.za [Materials Research Department, iThemba LABS, National Research Foundation, P.O. Box 722, Somerset West 7129 (South Africa); AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, Al. A. Mickiewicza 30, 30-059 Krakow (Poland); Williams-Jones, A.E., E-mail: anthony.williams-jones@mcgill.ca [Department of Earth and Planetary Science, McGill University, 3450 University Street, Montreal H3A 0E8 (Canada)

    2014-01-01

    Micro-PIXE and micro-EBS analyses were carried out on samples from the Au–U-bearing Carbon Leader Reef of the Witwatersrand in South Africa to investigate the role of organic matter in the formation of this deposit. Micro-PIXE and Micro-EBS shows a very complex metal distribution within the bitumen nodules and their interstitial spaces. The style of the gold distribution and its association with epigenetic minerals (REE phosphates, phyllosilicates) indicates that all observed gold migrated in aqueous solution and precipitated by reduction on the surfaces of the bitumen nodules. Uraninite occurrences are confined to the bitumen nodules, which supports the argument of a uraninite paleo-placer; however the pervasive distribution of uranium also supports the argument that uraninite is derived from organo-metallic complexes. This study shows that micro-PIXE is a powerful tool to characterize metals associated with hydrocarbons. However, the organic matrix, the complexity of the obtained spectra and the small size of the minerals have significant influence on the reliability of the quantitative data. Due to highly variable amounts of heavy metals (U, Au, Pb) the obtained micro-EBS results are of questionable quality.

  2. Seismic potential of weak, near-surface faults revealed at plate tectonic slip rates.

    Science.gov (United States)

    Ikari, Matt J; Kopf, Achim J

    2017-11-01

    The near-surface areas of major faults commonly contain weak, phyllosilicate minerals, which, based on laboratory friction measurements, are assumed to creep stably. However, it is now known that shallow faults can experience tens of meters of earthquake slip and also host slow and transient slip events. Laboratory experiments are generally performed at least two orders of magnitude faster than plate tectonic speeds, which are the natural driving conditions for major faults; the absence of experimental data for natural driving rates represents a critical knowledge gap. We use laboratory friction experiments on natural fault zone samples at driving rates of centimeters per year to demonstrate that there is abundant evidence of unstable slip behavior that was not previously predicted. Specifically, weak clay-rich fault samples generate slow slip events (SSEs) and have frictional properties favorable for earthquake rupture. Our work explains growing field observations of shallow SSE and surface-breaking earthquake slip, and predicts that such phenomena should be more widely expected.

  3. Matrix mineralogy of the Lance CO3 carbonaceous chondrite: A transmission electron microscope study

    International Nuclear Information System (INIS)

    Keller, L.P.; Buseck, P.R.

    1990-01-01

    The Lance CO3 carbonaceous chondrite (CC) is less altered than the CI and CM chondrites and so provides a view of the mineralogy and textures resulting from the earliest stages of aqueous alteration of CCs. Matrix olivine in Lance has been partly altered to fine-grained, Fe-bearing serpentine and poorly crystalline Fe 3+ oxide, a process that required both hydration and oxidation. Serpentine occurs as discrete packets separated from the olivine surfaces by the Fe 3+ oxide. The Fe released during the dissolution of olivine was partly incorporated into the serpentine; the remainder was oxidized to form Fe 3+ oxide. Matrix metal was also altered to produce Fe oxides, leaving the residual metal enriched in Ni. Olivine grains in Lance matrix contain channels along their [100] and [001] directions. The formation and convergence of such channels resulted in a grain-size reduction of the olivine. The alteration was pervasive but incomplete, suggesting a limited availability of fluid. A brief study of two other CO chondrites, Kainsaz and Warrenton, shows that these meteorites do not contain phyllosilicates in their matrices, although both contain Fe 3+ oxide between olivine grains. Prior to its alteration, Lance probably resembled Kainsaz, an unaltered CO3 chondrite. The alteration assemblage in Lance is only slightly different from that in Mokoia and essentially the same as that in C3 xenoliths from Murchison. Alteration products in Lance show greater similarities to CI than to CM chondrites

  4. Geochemical Triggers of Arsenic Mobilization during Managed Aquifer Recharge.

    Science.gov (United States)

    Fakhreddine, Sarah; Dittmar, Jessica; Phipps, Don; Dadakis, Jason; Fendorf, Scott

    2015-07-07

    Mobilization of arsenic and other trace metal contaminants during managed aquifer recharge (MAR) poses a challenge to maintaining local groundwater quality and to ensuring the viability of aquifer storage and recovery techniques. Arsenic release from sediments into solution has occurred during purified recycled water recharge of shallow aquifers within Orange County, CA. Accordingly, we examine the geochemical processes controlling As desorption and mobilization from shallow, aerated sediments underlying MAR infiltration basins. Further, we conducted a series of batch and column experiments to evaluate recharge water chemistries that minimize the propensity of As desorption from the aquifer sediments. Within the shallow Orange County Groundwater Basin sediments, the divalent cations Ca(2+) and Mg(2+) are critical for limiting arsenic desorption; they promote As (as arsenate) adsorption to the phyllosilicate clay minerals of the aquifer. While native groundwater contains adequate concentrations of dissolved Ca(2+) and Mg(2+), these cations are not present at sufficient concentrations during recharge of highly purified recycled water. Subsequently, the absence of dissolved Ca(2+) and Mg(2+) displaces As from the sediments into solution. Increasing the dosages of common water treatment amendments including quicklime (Ca(OH)2) and dolomitic lime (CaO·MgO) provides recharge water with higher concentrations of Ca(2+) and Mg(2+) ions and subsequently decreases the release of As during infiltration.

  5. Frictional stability-permeability relationships for fractures in shales

    Science.gov (United States)

    Fang, Yi; Elsworth, Derek; Wang, Chaoyi; Ishibashi, Takuya; Fitts, Jeffrey P.

    2017-03-01

    There is wide concern that fluid injection in the subsurface, such as for the stimulation of shale reservoirs or for geological CO2 sequestration (GCS), has the potential to induce seismicity that may change reservoir permeability due to fault slip. However, the impact of induced seismicity on fracture permeability evolution remains unclear due to the spectrum of modes of fault reactivation (e.g., stable versus unstable). As seismicity is controlled by the frictional response of fractures, we explore friction-stability-permeability relationships through the concurrent measurement of frictional and hydraulic properties of artificial fractures in Green River shale (GRS) and Opalinus shale (OPS). We observe that carbonate-rich GRS shows higher frictional strength but weak neutral frictional stability. The GRS fracture permeability declines during shearing while an increased sliding velocity reduces the rate of permeability decline. By comparison, the phyllosilicate-rich OPS has lower friction and strong stability while the fracture permeability is reduced due to the swelling behavior that dominates over the shearing induced permeability reduction. Hence, we conclude that the friction-stability-permeability relationship of a fracture is largely controlled by mineral composition and that shale mineral compositions with strong frictional stability may be particularly subject to permanent permeability reduction during fluid infiltration.

  6. Experimental reactivity with CO2 of clayey cap-rock and carbonate reservoir of the Paris basin

    International Nuclear Information System (INIS)

    Hubert, G.

    2009-01-01

    The constant increase in the quantity of carbon dioxide in the atmosphere is regarded as being the principal cause of the current global warming. The geological sequestration of CO 2 seems to be an ideal solution to reduce the increase of greenhouse gases (of which CO 2 ) in the atmosphere but only if the reservoir's cap-rock keep its integrity for several hundreds or thousands of years. Batch experimental simulations were conducted to observe the reactivity of a cap-rock made of clay and a carbonate reservoir with CO 2 at 80 C and 150 C for a pressure of 150 bar with an equilibrated water. The analytical protocol established allowed to compare the rocks before and after experimentations finding a very low reactivity, focusing on aluminium in phyllosilicates. Textural analysis shows that CO 2 does not affect the properties of adsorption and the specific surface. The study of carbonate reservoir by confocal microscopy has revealed phenomena of dissolution-precipitation which have no significant impact on chemistry and structure of the reservoir. The numerical simulations carried out on mineral reference as calcium montmorillonite or clinochlore show a significant reaction in the presence of CO 2 not achieved experimentally, probably due to lacunas in the thermodynamic databases or the kinetics of reactions. The simulations on Bure show no reaction on the major minerals confirming the results with batch experiments. (author)

  7. Magnetite as the indicator of ore genesis for the Huangshaping polymetallic deposit, southern Hunan Province, China

    Science.gov (United States)

    Ding, T.; Ma, D.; Lu, J.; Zhang, R.

    2017-12-01

    fluids might have undergone large scale circulation, the extraction from Zn-rich metamorphic basement and Mg, Al-rich strata probably have provided abundant Mg, Al, Zn in the hydrothermal fluids where Group-1 magnetites precipitated. As a conclusion, this study suggests that the compositions of magnetites can be the proxies of ore genesis.

  8. CZTS absorber layer for thin film solar cells from electrodeposited metallic stacked precursors (Zn/Cu-Sn)

    Energy Technology Data Exchange (ETDEWEB)

    Khalil, M.I., E-mail: mdibrahim.khalil@polimi.it [Dipartimento di Chimica, Materiali e Ing. Chimica “Giulio Natta”, Politecnico di Milano, Via Mancinelli 7, 20131 Milano (Italy); Atici, O. [Dipartimento di Chimica, Materiali e Ing. Chimica “Giulio Natta”, Politecnico di Milano, Via Mancinelli 7, 20131 Milano (Italy); Lucotti, A. [Dipartimento di Chimica, Materiali e Ing. Chimica “Giulio Natta”, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Binetti, S.; Le Donne, A. [Department of Materials Science and Solar Energy Research Centre (MIB-SOLAR), University of Milano- Bicocca, Via Cozzi 53, 20125 Milano (Italy); Magagnin, L., E-mail: luca.magagnin@polimi.it [Dipartimento di Chimica, Materiali e Ing. Chimica “Giulio Natta”, Politecnico di Milano, Via Mancinelli 7, 20131 Milano (Italy)

    2016-08-30

    Highlights: • CZTS absorber layer was fabricated by electrodeposition—annealing route from stacked bilayer precursor (Zn/Cu-Sn). • Different characterization techniques have ensured the well formed Kesterite CZTS along the film thickness also. • Two different excitation wavelengths of laser lines (514.5 and 785 nm) have been used for the Raman characterization of the films. • No significant Sn loss is observed in CZTS films after the sulfurization of the stacked bilayer precursors. • Photoluminescence spectroscopy reveals the PL peak of CZTS at 1.15 eV at low temperature (15 K). - Abstract: In the present work, Kesterite-Cu{sub 2}ZnSnS{sub 4} (CZTS) thin films were successfully synthesized from stacked bilayer precursor (Zn/Cu-Sn) through electrodeposition-annealing route. Adherent and homogeneous Cu-poor, Zn-rich stacked metal Cu-Zn-Sn precursors with different compositions were sequentially electrodeposited, in the order of Zn/Cu-Sn onto Mo foil substrates. Subsequently, stacked layers were soft annealed at 350 °C for 20 min in flowing N{sub 2} atmosphere in order to improve intermixing of the elements. Then, sulfurization was completed at 585 °C for 15 min in elemental sulfur environment in a quartz tube furnace with N{sub 2} atmosphere. Morphological, compositional and structural properties of the films were investigated using SEM, EDS and XRD methods. Raman spectroscopy with two different excitation lines (514.5 and 785 nm), has been carried out on the sulfurized films in order to fully characterize the CZTS phase. Higher excitation wavelength showed more secondary phases, but with low intensities. Glow discharge optical emission spectroscopy (GDOES) has also been performed on films showing well formed Kesterite CZTS along the film thickness as compositions of the elements do not change along the thickness. In order to investigate the electronic structure of the CZTS, Photoluminescence (PL) spectroscopy has been carried out on the films, whose

  9. On the origin of the marine zinc-silicon correlation

    Science.gov (United States)

    de Souza, Gregory F.; Khatiwala, Samar P.; Hain, Mathis P.; Little, Susan H.; Vance, Derek

    2018-06-01

    The close linear correlation between the distributions of dissolved zinc (Zn) and silicon (Si) in seawater has puzzled chemical oceanographers since its discovery almost forty years ago, due to the apparent lack of a mechanism for coupling these two nutrient elements. Recent research has shown that such a correlation can be produced in an ocean model without any explicit coupling between Zn and Si, via the export of Zn-rich biogenic particles in the Southern Ocean, consistent with the observation of elevated Zn quotas in Southern Ocean diatoms. Here, we investigate the physical and biological mechanisms by which Southern Ocean uptake and export control the large-scale marine Zn distribution, using suites of sensitivity simulations in an ocean general circulation model (OGCM) and a box-model ensemble. These simulations focus on the sensitivity of the Zn distribution to the stoichiometry of Zn uptake relative to phosphate (PO4), drawing directly on observations in culture. Our analysis reveals that OGCM model variants that produce a well-defined step between relatively constant, high Zn:PO4 uptake ratios in the Southern Ocean and low Zn:PO4 ratios at lower latitudes fare best in reproducing the marine Zn-Si correlation at both the global and the regional Southern Ocean scale, suggesting the presence of distinct Zn-biogeochemical regimes in the high- and low-latitude oceans that may relate to differences in physiology, ecology or (micro-)nutrient status. Furthermore, a study of the systematics of both the box model and the OGCM reveals that regional Southern Ocean Zn uptake exerts control over the global Zn distribution via its modulation of the biogeochemical characteristics of the surface Southern Ocean. Specifically, model variants with elevated Southern Ocean Zn:PO4 uptake ratios produce near-complete Zn depletion in the Si-poor surface Subantarctic Zone, where upper-ocean water masses with key roles in the global oceanic circulation are formed. By setting the

  10. Key Topics in Producing New Ultraviolet Led and Laser Devices Based on Transparent Semiconductor Zinc Oxide

    International Nuclear Information System (INIS)

    Tuezemen, S.

    2004-01-01

    Recently, it has been introduced that ZnO as II-VI semiconductor is promising various technological applications, especially for optoelectronic short wavelength light emitting devices due to its wide and direct band gap profile. The most important advantage of ZnO over the other currently used wide band gap semiconductors such as GaN is that its nearly 3 times higher exciton binding energy (60 meV), which permits efficient excitonic emission at room temperature and above. As-grown ZnO is normally n-type because of the Zn-rich defects such as zinc interstitials (Zn i ) oxygen vacancies (Vo), natively acting as shallow donors and main source of n-type conductivity in as-grown material. Therefore, making p-type ZnO has been more difficult due to unintentional compensation of possible acceptors by these residual donors. In order to develop electro luminescent and laser devices based on the ultraviolet (UV) exciton emission of ZnO, it will be important to fabricate good p-n junctions. Attempts to observe p-type conductivity in ours and our collaborators' laboratories in USA, either by co-doping with N or tuning O pressure have been first successful achievements, resulting in hole concentrations up to 10 1 9 cm - 3 in reactively sputtered thin layers of ZnO. Moreover, in order to produce ZnO based quantum well lasers similar to the previously introduced n-AlGaAs/GaAs/p-AlGaAs structures; we have attempted to grow Zn 1 -xSn x O thin films to enlarge the band gap energy. An increase up to 170 meV has been observed in Zn 1 -xSn x O thin films and this is enough barrier to be able to trap electron-hole pairs in quantum well structures. As a result, two important key issues; p-type conductivity and enhancement of the band gap energy in order to step forward towards the production of electro luminescent UV LEDs and quantum well lasers have been investigated and will be presented in this study

  11. Theoretical study of quaternary compounds as thin-film solar cell absorber

    International Nuclear Information System (INIS)

    Su, Huai Wei

    2010-01-01

    Zn+ZnCu] will not lead to a strong carrier separation, and thus will not contribute the same beneficial effect observed in ternary chalcopyrite compounds; (iv) We predict that to avoid the aforementioned issues in (ii) and (iii), it will be optimal to grow the sample under Cu-poor/Zn-rich conditions, so VCu and ZnCu become the dominant defects in the system. However, in this case, non-equilibrium growth techniques may be required to avoid the formation of secondary phases. All predictions will be compared with available experiments

  12. Crystallization kinetics of bioactive glasses in the ZnO-Na2O-CaO-SiO2 system.

    Science.gov (United States)

    Malavasi, Gianluca; Lusvardi, Gigliola; Pedone, Alfonso; Menziani, Maria Cristina; Dappiaggi, Monica; Gualtieri, Alessandro; Menabue, Ledi

    2007-08-30

    The crystallization kinetics of Na(2)O.CaO.2SiO(2) (x = 0) and 0.68ZnO.Na(2)O.CaO.2SiO(2) (x = 0.68, where x is the ZnO stoichiometric coefficient in the glass formula) bioactive glasses have been studied using both nonisothermal and isothermal methods. The results obtained from isothermal XRPD analyses have showed that the first glass crystallizes into the isochemical Na(2)CaSi(2)O(6) phase, whereas the Na(2)ZnSiO(4) crystalline phase is obtained from the Zn-rich glass, in addition to Na(2)CaSi(2)O(6). The activation energy (Ea) for the crystallization of the Na(2)O.CaO.2SiO(2) glass is 193 +/- 10 and 203 +/- 5 kJ/mol from the isothermal in situ XRPD and nonisothermal DSC experiments, respectively. The Avrami exponent n determined from the isothermal method is 1 at low temperature (530 degrees C), and its value increases linearly with temperature increase up to 2 at 607 degrees C. For the crystallization of Na(2)CaSi(2)O(6) from the Zn-containing glass, higher values of both the crystallization temperature (667 and 661 degrees C) and Ea (223 +/- 10 and 211 +/- 5 kJ/mol) have been found from the isothermal and nonisothermal methods, respectively. The Na(2)ZnSiO(4) crystalline phase crystallizes at lower temperature with respect to Na(2)CaSi(2)O(6), and the Ea value is 266 +/- 20 and 245 +/- 15 kJ/mol from the isothermal and nonisothermal methods, respectively. The results of this work show that the addition of Zn favors the crystallization from the glass at lower temperature with respect to the Zn-free glass. In fact, it causes an increase of Ea for the Na diffusion process, determined using MD simulations, and consequently an overall increase of Ea for the crystallization process of Na(2)CaSi(2)O(6). Our results show good agreement between the Ea and n values obtained with the two different methods and confirm the reliability of the nonisothermal method applied to kinetic crystallization of glassy systems. This study allows the determination of the temperature

  13. Effect of fuel zinc content on toxicological responses of particulate matter from pellet combustion in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Uski, O., E-mail: oskari.uski@uef.fi [University of Eastern Finland, Department of Environmental Science, P.O. Box 1627, FI-70211 Kuopio (Finland); National Institute for Health and Welfare, Department of Environmental Health, P.O. Box 95, FI-70701 Kuopio (Finland); Jalava, P.I., E-mail: pasi.jalava@uef.fi [University of Eastern Finland, Department of Environmental Science, P.O. Box 1627, FI-70211 Kuopio (Finland); Happo, M.S., E-mail: mikko.happo@uef.fi [University of Eastern Finland, Department of Environmental Science, P.O. Box 1627, FI-70211 Kuopio (Finland); Torvela, T., E-mail: tiina.torvela@uef.fi [University of Eastern Finland, Department of Environmental Science, P.O. Box 1627, FI-70211 Kuopio (Finland); Leskinen, J., E-mail: jani.leskinen@uef.fi [University of Eastern Finland, Department of Environmental Science, P.O. Box 1627, FI-70211 Kuopio (Finland); Mäki-Paakkanen, J., E-mail: jorma.maki-paakkanen@thl.fi [National Institute for Health and Welfare, Department of Environmental Health, P.O. Box 95, FI-70701 Kuopio (Finland); Tissari, J., E-mail: jarkko.tissari@uef.fi [University of Eastern Finland, Department of Environmental Science, P.O. Box 1627, FI-70211 Kuopio (Finland); Sippula, O., E-mail: olli.sippula@uef.fi [University of Eastern Finland, Department of Environmental Science, P.O. Box 1627, FI-70211 Kuopio (Finland); Lamberg, H., E-mail: heikki.lamberg@uef.fi [University of Eastern Finland, Department of Environmental Science, P.O. Box 1627, FI-70211 Kuopio (Finland); Jokiniemi, J., E-mail: jorma.jokiniemi@uef.fi [University of Eastern Finland, Department of Environmental Science, P.O. Box 1627, FI-70211 Kuopio (Finland); VTT Technical Research Centre of Finland, P.O. Box 1000, FI-02044 VTT, Espoo (Finland); and others

    2015-04-01

    pure pellet fuel with different concentrations. • Zinc enriches in PM{sub 1} emissions and enhances particulate toxicological responses. • Zn-rich samples caused cytotoxicity, ROS generation and cell cycle arrest in vitro.

  14. Mineralogy and environmental stability of slags from the Tsumeb smelter, Namibia

    International Nuclear Information System (INIS)

    Ettler, Vojtech; Johan, Zdenek; Kribek, Bohdan; Sebek, Ondrej; Mihaljevic, Martin

    2009-01-01

    Three types of smelting slags originating from historically different smelting technologies in the Tsumeb area (Namibia) were studied: (i) slags from processing of carbonate/oxide ore in a Cu-Pb smelter (1907-1948), (ii) slags from Cu and Pb smelting of sulphide ores (1963-1970) and (iii) granulated Cu smelting slags (1980-2000). Bulk chemical analyses of slags were combined with detailed mineralogical investigation using X-ray diffraction analysis (XRD), scanning electron microscopy (SEM/EDS) and electron microprobe (EPMA). The slags are significantly enriched in metals and metalloids: Pb (0.97-18.4 wt.%), Cu (0.49-12.2 wt.%), Zn (2.82-12.09 wt.%), Cd (12-6940 mg/kg), As (930-75,870 mg/kg) and Sb (67-2175 mg/kg). Slags from the oldest technology are composed of primary Ca- and Pb-bearing feldspars, spinels, complex Cu-Fe and Cu-Cr oxides, delafossite-mcconnellite phases and Ca-Pb arsenates. The presence of arsenates indicates that these slags underwent long-term alteration. More recent slags are composed of high-temperature phases: Ca-Fe alumosilicates (olivine, melilite), Pb- and Zn-rich glass, spinel oxides and small sulphide/metallic inclusions embedded in glass. XRD and SEM/EDS were used to study secondary alteration products developed on the surface of slags exposed for decades to weathering on the dumps. Highly soluble complex Cu-Pb-(Ca) arsenates (bayldonite, lammerite, olivenite, lavendulan) associated with litharge and hydrocerussite were detected. To determine the mineralogical and geochemical parameters governing the release of inorganic contaminants from slags, two standardized short-term batch leaching tests (European norm EN 12457 and USEPA TCLP), coupled with speciation-solubility modelling using PHREEQC-2 were performed. Arsenic in the leachate exceeded the EU regulatory limit for hazardous waste materials (2.5 mg/L). The toxicity limits defined by USEPA for the TCLP test were exceeded for Cd, Pb and As. The PHREEQC-2 calculation predicted that

  15. Effect of fuel zinc content on toxicological responses of particulate matter from pellet combustion in vitro

    International Nuclear Information System (INIS)

    Uski, O.; Jalava, P.I.; Happo, M.S.; Torvela, T.; Leskinen, J.; Mäki-Paakkanen, J.; Tissari, J.; Sippula, O.; Lamberg, H.; Jokiniemi, J.

    2015-01-01

    pellet fuel with different concentrations. • Zinc enriches in PM 1 emissions and enhances particulate toxicological responses. • Zn-rich samples caused cytotoxicity, ROS generation and cell cycle arrest in vitro

  16. Significância dos argilominerais em produtos cosméticos

    Directory of Open Access Journals (Sweden)

    Regina Gomes Daré

    2015-09-01

    Full Text Available Os argilominerais apresentam estrutura cristalina em camadas, fazendo parte do grupo de minerais denominados filossilicatos. Possuem composição química e propriedades físicas e físico-químicas singulares, como tamanho coloidal inferior a 2μm, elevada área superficial específica, capacidade de sorção e de troca iônica, sensação agradável quando aplicado na pele e características plásticas e tixotrópicas. Devido a isso, tais minerais são adequados a serem usados em produtos de uso tópico. De fato, suas propriedades já eram conhecidas e exploradas desde a pré-história com relatos de seu uso no tratamento de feridas e para a limpeza da pele. Este artigo de revisão enfatiza a importância desses minerais no uso em cosméticos, onde podem exercer diversas funções, como excipiente ou como componente ativo, sendo incluídos em inúmeros produtos, tais como emulsões para o cuidado da pele, máscaras faciais, protetores solares, produtos para limpeza da pele, xampus e produtos de maquiagem. O aumento verificado nos últimos anos no uso de produtos naturais, associado a uma maior conscientização da necessidade de preservação do meio ambiente, tem despertado crescente interesse pelos argilominerais. O Brasil, como detentor de uma das maiores reservas mundiais de argila é o terceiro país maior depositário de patentes nessa área. Considerando o amplo potencial de utilização dos argilominerais, pode-se afirmar que eles constituem grandes oportunidades para a pesquisa e o desenvolvimento de novos produtos cosméticos.Palavras-chave: Argilominerais. Filossilicatos. Produtos cosméticos. ABSTRACTSignificance of clay minerals in cosmetic productsThe clay minerals have layered crystal structure, they are part of the mineral group called phyllosilicates. They have chemical composition and physical and physicochemical properties different, such as colloidal size less than 2μm, high specific surface area, sorption and ion

  17. Occurrence of Fe-Mg-rich smectites and corrensite in the Morron de Mateo bentonite deposit (Cabo de Gata region, Spain): A natural analogue of the bentonite barrier in a radwaste repository

    Energy Technology Data Exchange (ETDEWEB)

    Pelayo, M., E-mail: m.pelayo@ciemat.es [Departamento de Medio Ambiente, CIEMAT, Avda. Complutense 22, 28040 Madrid (Spain); Garcia-Romero, E. [Departamento de Cristalografia y Mineralogia, Facultad C.C. Geologicas, UCM, 28040 Madrid (Spain); Labajo, M.A.; Perez del Villar, L. [Departamento de Medio Ambiente, CIEMAT, Avda. Complutense 22, 28040 Madrid (Spain)

    2011-07-15

    Highlights: > A hydrothermal process transformed Fe-Mg smectites into corrensite. > This transformation was favoured by the intrusion of the Morron de Mateo dome. > The intrusion caused a temperature increased and a supply of Fe-Mg rich solutions. > The system can be a good natural analogue of bentonite barrier in a radwaste disposal. > Experimental studies of stability of bentonite are in agreement with the results. - Abstract: The Morron de Mateo bentonite deposit is being studied as a natural analogue of the thermal and geochemical effects on a bentonite barrier in a deep geological repository of high level radioactive wastes. This bentonite deposit and its host rocks were intruded by a rhyodacitic volcanic dome that induced a hydrothermal metasomatic process affecting the biocalcarenite beds close to the dome. In this work, the mineralogical and chemical features of the clay minerals of the hydrothermally altered pyroclastic (white tuffs) and epiclastic rocks (mass flow), located in the NE sector of the Morron de Mateo deposit are described. White tuffs have a high content of phyllosilicates, mainly composed of dioctahedral smectites, while mass flow have a higher proportion of inherited minerals, the neoformed phyllosilicates are dioctahedral smectites and an interlayer chlorite/smectite mineral of corrensite type. The chemical composition of smectites reflects the different nature of the parent rocks, in such a way that smectites from white tuffs have a quite homogeneous chemical composition and their structural formulae correspond to montmorillonite type, while smectites from mass flow show more chemical variability, higher Fe and Mg contents and a mean structural formulae corresponding to Fe-Mg-rich beidellite and/or to an intermediate smectite member between beidellite and saponite. In addition, chemical composition and textural features of corrensite-like clay minerals in relation to Fe-Mg-rich smectites in the samples have also been studied, suggesting

  18. Clay raw materials from the Triassic Red Beds (Northern JaéUy Spain for making ceramic construction materials

    Directory of Open Access Journals (Sweden)

    Vázquez, M.

    2004-03-01

    Full Text Available The suitability of Triassic Red Beds from northern Jaén in the production of structural clay products has been evaluated. These materials have high phyllosilicate contents (36-69%, although some samples are enriched in quartz (<8-54% and feldspars (<5-2I%. Dolomite (<5-20% and calcite (< 7% are present. Illite is the main phyllosilicate (96-74%, kaolinite values are rather low (<17% and chlorite is present in low content (<14%. The studied samples have high silica (39.2-74.8% and alumina (6.9-18.3% content. K4ost of the samples have low CaO and MgO concentrations (<6%. <2 pm (64-36% and 2-20 pm (68-36% are the predominant grain size fraction of the studied samples. Low plasticity for extrusion process of the Triassic Red Beds is not appropriated for making bricks and roofing tiles by themselves. However, water absorption and linear shrinkage values are often suitable for manufacturing bricks. A small number of samples are appropriated for making roofing tiles, due to the its high firing shrinkage. Mixing of these materials with different proportions of complementary raw materials would allow to make porous bodies.

    En este trabajo se ha evaluado el uso de las Capas Rojas Triásicas de la Cobertera Tabular del Macizo Ibérico del norte de la provincia de Jaén para elaborar materiales cerámicos. Estos materiales tienen altos contenidos en filosilicatos (36-69%, aunque algunas muestras son ricas en cuarzo (hasta 54% y feldespatos (hasta 21%. Los carbonatos presentes en las muestras son dolomita (<5-20% y calcita (<7%. La illita es el principal filosilicato (96-74%, mientras que la caolinita y la clorita están presentes en bajos contenidos (< 17%. Las muestras estudiadas tienen altos contenidos en sílice (39,2-74,8% y alúmina (6,9-18,3%. La mayoría de estas arcillas tienen bajas concentraciones de CaO y MgO (<6%. Las fracciones granulométricas predominantes son la< 2 pm (64-36% y la situada entre 2 y 20 pm (68-36%. La baja plasticidad

  19. The 4D evolution of porosity during ongoing pressure-solution processes in NaCl using x-ray microtomography

    Science.gov (United States)

    Macente, Alice; Fusseis, Florian; Butler, Ian; Tudisco, Erika; Hall, Stephen; Andò, Edward

    2016-04-01

    DVC) to quantify the fields of displacements in each direction, as well as volumetric and maximum shear strain fields. Following the approach described above, we have been able to quantify and characterize in 4D the evolution of pressure-solution creep and porosity distribution in relation to different sample materials and increasing uniaxial load. The presence of phyllosilicates (biotite) and more competent materials (glass beads) allowed pressure-solution to develop in a much shorter time compared to pure halite sample. The same trend is observed in samples experiencing bigger uniaxial loads (6.6 MPa v 1.6 MPa). We also found that, in the presence of phyllosilicates (biotite), pore size distribution clearly reflects the localisation of pressure-solution processes, as for natural stylolites. In the presence of glass beads, pressure-solution has a greater effect on the pore orientations rather than pore sizes. Our results extend the current understanding of the effect of pressure-solution creep on the mechanical and hydraulic properties of rocks, with implications for natural rock-salt, salt-based repository systems (nuclear and chemical waste storage) and salt mining.

  20. Occurrence of Fe-Mg-rich smectites and corrensite in the Morron de Mateo bentonite deposit (Cabo de Gata region, Spain): A natural analogue of the bentonite barrier in a radwaste repository

    International Nuclear Information System (INIS)

    Pelayo, M.; Garcia-Romero, E.; Labajo, M.A.; Perez del Villar, L.

    2011-01-01

    Highlights: → A hydrothermal process transformed Fe-Mg smectites into corrensite. → This transformation was favoured by the intrusion of the Morron de Mateo dome. → The intrusion caused a temperature increased and a supply of Fe-Mg rich solutions. → The system can be a good natural analogue of bentonite barrier in a radwaste disposal. → Experimental studies of stability of bentonite are in agreement with the results. - Abstract: The Morron de Mateo bentonite deposit is being studied as a natural analogue of the thermal and geochemical effects on a bentonite barrier in a deep geological repository of high level radioactive wastes. This bentonite deposit and its host rocks were intruded by a rhyodacitic volcanic dome that induced a hydrothermal metasomatic process affecting the biocalcarenite beds close to the dome. In this work, the mineralogical and chemical features of the clay minerals of the hydrothermally altered pyroclastic (white tuffs) and epiclastic rocks (mass flow), located in the NE sector of the Morron de Mateo deposit are described. White tuffs have a high content of phyllosilicates, mainly composed of dioctahedral smectites, while mass flow have a higher proportion of inherited minerals, the neoformed phyllosilicates are dioctahedral smectites and an interlayer chlorite/smectite mineral of corrensite type. The chemical composition of smectites reflects the different nature of the parent rocks, in such a way that smectites from white tuffs have a quite homogeneous chemical composition and their structural formulae correspond to montmorillonite type, while smectites from mass flow show more chemical variability, higher Fe and Mg contents and a mean structural formulae corresponding to Fe-Mg-rich beidellite and/or to an intermediate smectite member between beidellite and saponite. In addition, chemical composition and textural features of corrensite-like clay minerals in relation to Fe-Mg-rich smectites in the samples have also been studied

  1. Mineralogy and microstructure of roofing slate: thermo-optical behaviour and fissility

    Directory of Open Access Journals (Sweden)

    García-Guinea, J.

    1998-09-01

    Full Text Available The mineralogy and microstructure, which affect the slaty cleavage, are linked with the strong preferred orientation of phyllosilicates and this enables the rock to be split into large, thin, flat sheets. Roofing slate samples with different commercial fissilities have been analyzed by radioluminescence (RL, thermoluminescence (3DTL, by X-ray diffraction (XRD, by scanning electron microscopy (SEM using the back-scattered mode (BSEI and by electron microprobe (EMP. They are made up of white micas, chlorite, quartz, detrital feldspars, ilmenite, pyrite, rutile apatite and tourmaline. Texturally, all consist of silt-sized clasts of detrital quartz, feldspars, chlorite-mica stacks, muscovite and ilmenite in a recrystalline, lepidoblastic matrix of white micas and chlorite with quartz lenses, all showing a very strong preferred orientation. The luminescence emission centers are a low broad blue band around the 400 nm spectra positions linked with alkali losses and formation of [AlO4]º defects; a peak at 473 nm interpreted as a the first thermal step (150-300ºC of a non-isothermal dehydroxylation of the slate phyllosilicates; and a 568 nm peak which agrees with Mn2+ point defects in aluminosilicate lattices. The studies on the slaty cleavage could be significant because Spain is the largest producer of roofing slate tiles in the world (87% of world production.

    La exfoliación de las pizarras depende fundamentalmente de su mineralogía y microestructura, especialmente de la fuerte orientación de los filosilicatos. Esta propiedad permite hendir o abrir las pizarras de techar en láminas muy grandes, delgadas y planas. Se han analizado varias pizarras de techar con diferentes calidades comerciales, correspondientes a diferentes grados de físibilidad, por radioluminiscencia (RL, termoluminiscencia espectral (TL3D, difracción de rayos X (DRX, microscopía electrónica de barrido (MEB utilizando el modo backscattered (BSEI

  2. Global map and spectroscopic analyses of Martian fluvial systems: paleoclimatic implications

    Science.gov (United States)

    Alemanno, Giulia; Orofino, Vincenzo; Mancarella, Francesca; Fonti, Sergio

    2017-04-01

    Currently environmental conditions on Mars do not allow the presence of liquid water on its surface for long periods of time. However, there are various evidences for past water flow at its surface. In fact, the ancient terrains of Mars are covered with fluvial and lacustrine features such as valley networks, longitudinal valleys and basin lakes. There are no doubts about the fact that the Martian valleys were originated by water flow. This led many researchers to think that probably, at the time of their formation, the conditions of atmospheric pressure and surface temperature were different from the present[1]. To infer the climate history of Mars from valley networks, a global approach is necessary. We produced a global map of Martian valleys. We manually mapped all the valleys (longer than 20 km) as vector-based polylines within the QGIS software, using THEMIS daytime IR (100 m/pixel), and where possible CTX images (up to 6 m/pixel), plus topographic MOLA data ( 500 m/pixel). Respect to the previous manual maps[1,2] data of higher image quality (new THEMIS mosaic) and topographic information allow us to identify new structures and more tributaries for a large number of systems. We also used the geologic map of Mars[3] in order to determine the valleys age distribution. Most valleys are too small for age determination from superposition of impact craters so we have assumed that a valley is as old as the terrain on which it has been carved[1]. Furthermore we are, currently, analyzing spectroscopic data from CRISM instrument (Compact Reconnaissance Imaging Spectrometer for Mars) onboard Mars Reconnaissance Orbiter, concerning the mapped valleys or associated basin lakes with the aim of assessing the mineralogy of these structures. Our attention is especially focused on the possible detection of any hydrated minerals (e.g. phyllosilicates, hydrated silica) or evaporites (e.g. carbonates, sulfates, chlorides). Phyllosilicates- bearing rocks are considered as an

  3. Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

    Science.gov (United States)

    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

  4. A divergent heritage for complex organics in Isheyevo lithic clasts

    Science.gov (United States)

    van Kooten, Elishevah M. M. E.; Nagashima, Kazuhide; Kasama, Takeshi; Wampfler, Susanne F.; Ramsey, Jon P.; Frimann, Søren; Balogh, Zoltan I.; Schiller, Martin; Wielandt, Daniel P.; Franchi, Ian A.; Jørgensen, Jes K.; Krot, Alexander N.; Bizzarro, Martin

    2017-05-01

    Primitive meteorites are samples of asteroidal bodies that contain a high proportion of chemically complex organic matter (COM) including prebiotic molecules such as amino acids, which are thought to have been delivered to Earth via impacts during the early history of the Solar System. Thus, understanding the origin of COM, including their formation pathway(s) and environment(s), is critical to elucidate the origin of life on Earth as well as assessing the potential habitability of exoplanetary systems. The Isheyevo CH/CBb carbonaceous chondrite contains chondritic lithic clasts with variable enrichments in 15N believed to be of outer Solar System origin. Using transmission electron microscopy (TEM-EELS) and in situ isotope analyses (SIMS and NanoSIMS), we report on the structure of the organic matter as well as the bulk H and N isotope composition of Isheyevo lithic clasts. These data are complemented by electron microprobe analyses of the clast mineral chemistry and bulk Mg and Cr isotopes obtained by inductively coupled plasma and thermal ionization mass spectrometry, respectively (MC-ICPMS and TIMS). Weakly hydrated (A) clasts largely consist of Mg-rich anhydrous silicates with local hydrated veins composed of phyllosilicates, magnetite and globular and diffuse organic matter. Extensively hydrated clasts (H) are thoroughly hydrated and contain Fe-sulfides, sometimes clustered with organic matter, as well as magnetite and carbonates embedded in a phyllosilicate matrix. The A-clasts are characterized by a more 15N-rich bulk nitrogen isotope composition (δ15N = 200-650‰) relative to H-clasts (δ15N = 50-180‰) and contain extremely 15N-rich domains with δ15N < 5000‰. The D/H ratios of the clasts are correlated with the degree of clast hydration and define two distinct populations, which we interpret as reflecting mixing between D-poor fluid(s) and distinct organic endmember components that are variably D-rich. High-resolution N isotope data of 15N

  5. Mineralogical and geochemical patterns of urban surface soils, the example of Pforzheim, Germany

    International Nuclear Information System (INIS)

    Norra, Stefan; Lanka-Panditha, Mahesh; Kramar, Utz; Stueben, Doris

    2006-01-01

    This study presents a combined geochemical and mineralogical survey of urban surface soils. Many studies on urban soils are restricted to purely chemical surveys in order to investigate soil pollution caused by anthropogenic activities such as traffic, heating, industrial processing, waste disposal and many more. In environmental studies, chemical elements are often distinguished as lithogenic and anthropogenic elements. As a novel contribution to those studies, the authors combined the analysis of a broad set of chemical elements with the analysis of the main mineralogical phases. The semi-quantification of mineralogical phases supported the assignment of groups of chemical elements to lithogenic or anthropogenic origin. Minerals are important sinks for toxic elements. Thus, knowledge about their distribution in soils is crucial for the assessment of the environmental hazards due to pollution of urban soils. In Pforzheim, surface soils (0-5 cm depth) from various land use types (forest, agriculture, urban green space, settlement areas of various site densities) overlying different geological units (clastic and chemical sediments) were investigated. Urban surface soils of Pforzheim reflect to a considerable degree the mineral and chemical composition of parent rocks. Irrespective of the parent rocks, elevated concentrations of heavy metals (Zn, Cu, Pb, Sn, Ag) were found in soils throughout the whole inner urban settlement area of Pforzheim indicating pollution. These pollutants will tend to accumulate in inner urban surface soils according to the available adsorption capacity, which is normally higher in soils overlying limestone than in soils overlying sandstone. However, inner urban surface soils overlying sandstone show elevated concentrations of carbonates, phyllo-silicates and Fe and elevated pH values compared with forest soils overlying sandstone. Thus, in comparison to forest soils overlying sandstones, inner urban soils overlying sandstone affected by

  6. Alkali trace elements in Gale crater, Mars, with ChemCam: Calibration update and geological implications

    International Nuclear Information System (INIS)

    Payre, Valerie; Fabre, Cecile; Cousin, Agnes; Sautter, Violaine; Wiens, Roger Craig

    2017-01-01

    The Chemistry Camera (ChemCam) instrument onboard Curiosity can detect minor and trace elements such as lithium, strontium, rubidium, and barium. Their abundances can provide some insights about Mars' magmatic history and sedimentary processes. We focus on developing new quantitative models for these elements by using a new laboratory database (more than 400 samples) that displays diverse compositions that are more relevant for Gale crater than the previous ChemCam database. These models are based on univariate calibration curves. For each element, the best model is selected depending on the results obtained by using the ChemCam calibration targets onboard Curiosity. New quantifications of Li, Sr, Rb, and Ba in Gale samples have been obtained for the first 1000 Martian days. Comparing these data in alkaline and magnesian rocks with the felsic and mafic clasts from the Martian meteorite NWA7533—from approximately the same geologic period—we observe a similar behavior: Sr, Rb, and Ba are more concentrated in soluble- and incompatible-element-rich mineral phases (Si, Al, and alkali-rich). Correlations between these trace elements and potassium in materials analyzed by ChemCam reveal a strong affinity with K-bearing phases such as feldspars, K-phyllosilicates, and potentially micas in igneous and sedimentary rocks. However, lithium is found in comparable abundances in alkali-rich and magnesium-rich Gale rocks. This very soluble element can be associated with both alkali and Mg-Fe phases such as pyroxene and feldspar. Here, these observations of Li, Sr, Rb, and Ba mineralogical associations highlight their substitution with potassium and their incompatibility in magmatic melts.

  7. Search for Extralunar Materials in Apollo Soil Samples

    Science.gov (United States)

    Lucey, P. G.; Honniball, C.; Crites, S.; Taylor, G. J.; Martel, L.

    2017-12-01

    It has long been proposed that the lunar surface is a pristine collector of material from across the solar system. The Moon is exposed to the same meteorite flux as the Earth, but because its surface is unaltered by processes such as plate tectonics, aqueous alteration, or recent volcanism, the Moon may have recorded a much longer meteoritic history than the chemically and physically active Earth. By studying lunar soils at the individual grain level, we have the potential to identify and study material from across the inner solar system. We have developed three hyperspectral imaging microscopes to search a large quantity of lunar soil grains for rare lunar, and extra-lunar minerals. We are using lunar-exotic mineralogy as a tracer to detect extralunar candidates. One hyperspectral microscope covers the 1-2.5 micron region for detection of water and hydroxyl overtones in alteration minerals such as phyllosilicates. The second instrument covers the 2.5 to 5 micron region to characterize the 3 micron water region, and for detection of organics and carbonates. The third covers the thermal infrared for detection of phosphates and zeolites as well as the major lunar silicates. We are examining 1 million grains of varying sizes from Apollo 11 ,12, 14 and 16 landing sites. Using the USGS spectral library and the Tetracorder mineral mapping algorithm, we are matching library mineral spectra with the grain spectra we acquire. To validate our ability to detect and match mineral spectra, we are conducting scans of relevent mineral seperates and mixtures at the individual grain level. Results of this mineral inventory will provide contraints on various models and estimates for material transfer between the terrestrial planets.

  8. Terahertz time-domain spectroscopy response of amines and amino acids intercalated smectites in far-infrared region

    Energy Technology Data Exchange (ETDEWEB)

    Janek, M., E-mail: marian.janek@fns.uniba.sk [Comenius University, Faculty of Natural Sciences, Department of Physical and Theoretical Chemistry, Mlynská dolina CH1, SK-84215 Bratislava (Slovakia); Zich, D. [Comenius University, Faculty of Natural Sciences, Department of Physical and Theoretical Chemistry, Mlynská dolina CH1, SK-84215 Bratislava (Slovakia); Naftaly, M., E-mail: mira.naftaly@npl.co.uk [National Physical Laboratory, Hampton Rd, Teddington, Middlesex TW11 0LW (United Kingdom)

    2014-06-01

    Layered clay minerals from the smectite group with different chemical composition and resulting layer charge (e.g. pyrophyllite, illite, hectorite and montmorillonite) were characterised for their dielectric properties in the far-infrared region using terahertz-time domain spectroscopy (THz-TDS). Samples with distinct cation exchange capacity such as hectorite and montmorillonite were modified using cation exchange reaction with alkylamines or amino acids. The presence of these species in 2D gallery was proved by X-ray diffraction and Fourier transform infrared spectroscopy. The frequency-dependent refractive index of these minerals was determined in the experimentally accessible range of 0.1–3.0 THz (3–100 cm{sup −1}) using THz-TDS. Pristine samples revealed their refractive indices to be 1.82–2.15 at about 1 THz while the modified montmorillonite samples had their refractive indices changed by organic molecules used for their modification to 1.70–2.35 for amines and 1.97–2.36 for amino acids. The presence of organic substances in 2D gallery of clays was detectable despite the relatively high absorption of smectites with magnitude of 100 cm{sup −1}. - Graphical abstract: Display Omitted - Highlights: • “Guest” molecules in “host” layered material were investigated. • Amines and amino-acids were selected as guest molecules. • Natural and synthetic host with smectite phyllosilicate structure were used. • Dielectric properties were investigated by terahertz time domain spectroscopy. • Resonance absorption peaks of guest were detected in far infrared region.

  9. Low strength of deep San Andreas fault gouge from SAFOD core.

    Science.gov (United States)

    Lockner, David A; Morrow, Carolyn; Moore, Diane; Hickman, Stephen

    2011-04-07

    The San Andreas fault accommodates 28-34 mm yr(-1) of right lateral motion of the Pacific crustal plate northwestward past the North American plate. In California, the fault is composed of two distinct locked segments that have produced great earthquakes in historical times, separated by a 150-km-long creeping zone. The San Andreas Fault Observatory at Depth (SAFOD) is a scientific borehole located northwest of Parkfield, California, near the southern end of the creeping zone. Core was recovered from across the actively deforming San Andreas fault at a vertical depth of 2.7 km (ref. 1). Here we report laboratory strength measurements of these fault core materials at in situ conditions, demonstrating that at this locality and this depth the San Andreas fault is profoundly weak (coefficient of friction, 0.15) owing to the presence of the smectite clay mineral saponite, which is one of the weakest phyllosilicates known. This Mg-rich clay is the low-temperature product of metasomatic reactions between the quartzofeldspathic wall rocks and serpentinite blocks in the fault. These findings provide strong evidence that deformation of the mechanically unusual creeping portions of the San Andreas fault system is controlled by the presence of weak minerals rather than by high fluid pressure or other proposed mechanisms. The combination of these measurements of fault core strength with borehole observations yields a self-consistent picture of the stress state of the San Andreas fault at the SAFOD site, in which the fault is intrinsically weak in an otherwise strong crust. ©2011 Macmillan Publishers Limited. All rights reserved

  10. Thermal and Infrared Studies of Garnierite from the Soroako Nickeliferous Laterite Deposit, Sulawesi, Indonesia

    Directory of Open Access Journals (Sweden)

    Sufriadin Sufriadin

    2014-06-01

    Full Text Available DOI: 10.17014/ijog.v7i2.137Mineralogical characterization of some garnierite samples from Soroako have been conducted using X-ray diffraction, thermal analysis, and infrared spectroscopy methods. XRD patterns reveal the samples mainly containing the mixture of kerolite (talc-like phase and serpentine with minor smectite, sepiolite, and silica. Thermal analyses of garnierite samples indicated by DTA curves are in good agreement with patterns that have been reported in literature. Three endothermic peaks normally occur in the ranges between 58º C and <800º C illustrating three steps of weight losses: adsorbed, bound, and hydroxyl/crystal water. One additional weight loss in low temperature region of sepiolite is corresponding to the lost of zeolitic water. Infrared spectra appeared in 3800 - 3200 cm-1 region generally exhibit broad absorption bands, indicating low crystallinities of studied samples and can be assigned to the presence of hydroxyl group bonded to octahedral coordination mainly Mg atom. The bands observed at 1660 cm-1, 1639 cm-1, 1637 cm-1, and 1633 cm-1 in all samples indicate water molecules. FTIR spectra displaying the strong bands at 1045 cm-1, 1038 cm-1, and 1036 cm-1 could be related to the presence of Si-O-Si bonds linking to tetrahedral coordination. The strong absorption bands appeared at 511 cm-1, 505 cm-1, 499 cm-1, and 496 cm-1 in respective samples are attributed to divalent cation bonds (e.g. Mg, Ni-O. Both TG/DTA and FTIR seem to be the powerful tool in diagnosing the crystal chemistry of garnierite which is mainly composed of phyllosilicate minerals.

  11. Mercury enrichment indicates volcanic triggering of the Valanginian environmental change

    Science.gov (United States)

    Charbonnier, Guillaume; Morales, Chloé; Duchamp-Alphonse, Stéphanie; Westermann, Stéphane; Adatte, Thierry; Föllmi, Karl

    2017-04-01

    The Valanginian stage (Early Cretaceous, ˜137-132 Ma) recorded an episode of pronounced palaeoenvironmental change, which is marked by a globally recorded positive δ13C excursion of 1.5 to 2‰ amplitude, also known as the "Weissert event or episode". Its onset near the early/late Valanginian boundary (B. campylotoxus-S. verrucosum ammonite Zones) coincides with a phase of warmer climate conditions associated with enhanced humidity, major changes in the evolution of marine plankton, and the drowning of tropical and subtropical marine shallow-water carbonate ecosystems. The globally recorded excursion indicates important transformations in the carbon cycle, which have tentatively been associated with Paraná-Etendeka large igneous province (LIP) volcanic activity. Incertainties in existing age models preclude, however, its positive identification as a trigger of Valanginian environmental change. Since very recently, mercury (Hg) chemostratigraphy offers the possibly to evaluate the role of LIP activity during major palaeoenvironmental perturbations. In this study we investigate the distribution of Hg contents in four Valanginian reference sections located in pelagic and hemipelagic environments in the Central Tethyan Realm (Lombardian Basin, Breggia section), the northern Tethyan margin (Vocontian Basin, Orpierre and Angles sections), and the narrow seaway connecting the Tethyan and Boreal Oceans (Polish Basin, Wawal core). All records show an enrichment in Hg concentrations at or near the onset of the Weissert Episode, with maximal values of 70.5 ppb at Angles, 59.5 ppb at Orpierre, 69.9 ppb at Wawal, and 17.0 ppb at Breggia. The persistence of the Hg anomaly in Hg/TOC and Hg/phyllosilicate ratios shows that organic-matter scavenging and/or adsorbtion onto clay minerals only played a limited role.We propose that volcanic outgassing was the primary source of the Hg enrichment and conclude that an important magmatic pulse triggered the Valanginian environmental

  12. Creep of Posidonia Shale at Elevated Pressure and Temperature

    Science.gov (United States)

    Rybacki, E.; Herrmann, J.; Wirth, R.; Dresen, G.

    2017-12-01

    The economic production of gas and oil from shales requires repeated hydraulic fracturing operations to stimulate these tight reservoir rocks. Besides simple depletion, the often observed decay of production rate with time may arise from creep-induced fracture closure. We examined experimentally the creep behavior of an immature carbonate-rich Posidonia shale, subjected to constant stress conditions at temperatures between 50 and 200 °C and confining pressures of 50-200 MPa, simulating elevated in situ depth conditions. Samples showed transient creep in the semibrittle regime with high deformation rates at high differential stress, high temperature and low confinement. Strain was mainly accommodated by deformation of the weak organic matter and phyllosilicates and by pore space reduction. The primary decelerating creep phase observed at relatively low stress can be described by an empirical power law relation between strain and time, where the fitted parameters vary with temperature, pressure and stress. Our results suggest that healing of hydraulic fractures at low stresses by creep-induced proppant embedment is unlikely within a creep period of several years. At higher differential stress, as may be expected in situ at contact areas due to stress concentrations, the shale showed secondary creep, followed by tertiary creep until failure. In this regime, microcrack propagation and coalescence may be assisted by stress corrosion. Secondary creep rates were also described by a power law, predicting faster fracture closure rates than for primary creep, likely contributing to production rate decline. Comparison of our data with published primary creep data on other shales suggests that the long-term creep behavior of shales can be correlated with their brittleness estimated from composition. Low creep strain is supported by a high fraction of strong minerals that can build up a load-bearing framework.

  13. Critical Assessment of Analytical Techniques in the Search for Biomarkers on Mars: A Mummified Microbial Mat from Antarctica as a Best-Case Scenario.

    Science.gov (United States)

    Blanco, Yolanda; Gallardo-Carreño, Ignacio; Ruiz-Bermejo, Marta; Puente-Sánchez, Fernando; Cavalcante-Silva, Erika; Quesada, Antonio; Prieto-Ballesteros, Olga; Parro, Víctor

    2017-10-01

    The search for biomarkers of present or past life is one of the major challenges for in situ planetary exploration. Multiple constraints limit the performance and sensitivity of remote in situ instrumentation. In addition, the structure, chemical, and mineralogical composition of the sample may complicate the analysis and interpretation of the results. The aim of this work is to highlight the main constraints, performance, and complementarity of several techniques that have already been implemented or are planned to be implemented on Mars for detection of organic and molecular biomarkers on a best-case sample scenario. We analyzed a 1000-year-old desiccated and mummified microbial mat from Antarctica by Raman and IR (infrared) spectroscopies (near- and mid-IR), thermogravimetry (TG), differential thermal analysis, mass spectrometry (MS), and immunological detection with a life detector chip. In spite of the high organic content (ca. 20% wt/wt) of the sample, the Raman spectra only showed the characteristic spectral peaks of the remaining beta-carotene biomarker and faint peaks of phyllosilicates over a strong fluorescence background. IR spectra complemented the mineralogical information from Raman spectra and showed the main molecular vibrations of the humic acid functional groups. The TG-MS system showed the release of several volatile compounds attributed to biopolymers. An antibody microarray for detecting cyanobacteria (CYANOCHIP) detected biomarkers from Chroococcales, Nostocales, and Oscillatoriales orders. The results highlight limitations of each technique and suggest the necessity of complementary approaches in the search for biomarkers because some analytical techniques might be impaired by sample composition, presentation, or processing. Key Words: Planetary exploration-Life detection-Microbial mat-Life detector chip-Thermogravimetry-Raman spectroscopy-NIR-DRIFTS. Astrobiology 17, 984-996.

  14. Zinc and cadmium mobility in a 5-year-old dredged sediment deposit: experiments and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Lions, J. [BRGM, Orleans (France). Water Div.; Centre National de Recherche sur les Sites et Sols Pollues, Douai (France); Lee, J. van der [Ecole des Mines de Paris, Fontainebleau (France). Geosciences - Reactive Hydrodynamics Group; Guerin, V.; Bataillard, P. [BRGM, Orleans (France). Environment and Process Div.; Centre National de Recherche sur les Sites et Sols Pollues, Douai (France); Laboudigue, A. [Ecole des Mines de Douai (France). Environmental and Civil Engineering; Centre National de Recherche sur les Sites et Sols Pollues, Douai (France)

    2007-08-15

    Background. Landfill deposits of contaminated, dredged sediments are subject to chemical alteration and especially to oxidation processes. Accordingly, sulphides are gradually oxidized leading to the formation of secondary phases and associated metals could become mobile and redistributed among the sediment components, such as carbonates, clay and freshly precipitated (hydr)oxides. Once mobilised, metals could represent a hazard for the environment and especially for drinking water supply facilities. Methods. In the present study, leaching experiments have been carried out on a dredged sediment to study metal mobilisation after 5 years of field aging. First, kinetic batch tests allowed one to evaluate the impact of solid-liquid contact time and to determine the kinetic parameters. Secondly, two types of dynamic experiments have been conducted: dynamic flush reactor and column leach test to evaluate the impact of solution renewing by excluding or not excluding the transport processes, respectively. In order to evaluate the impact of calcium on the metal mobilisation, the column leaching test is conducted with pure water and Ca(NO{sub 3}){sub 2} solution, at the beginning and at the end of the injection, respectively. Geochemical and reactive transport modelling of the experiments was performed using the geochemical code CHESS and the reactive transport model HYTEC. Results and Discussion. The studied sediment is complex with numerous reactive phases such as sulphides, (hydr)oxides, organic matter, phyllosilicates. All leaching tests highlight that zinc and cadmium are mobilised in significant concentrations and lead remains insoluble. A conceptual geochemical model of the sediment has been built to allow simulations of the whole experiments, based on a single, coherent phase description and parameter set. Simulations of the batch, flush and column experiments were performed taking into account the major reaction-controlling mechanisms including, among others, p

  15. Effects of Kapton Sample Cell Windows on the Detection Limit of Smectite: Implications for CheMin on the Mars Science Laboratory Mission

    Science.gov (United States)

    Achilles, C. N.; Ming, Douglas W.; Morris, R. V.; Blake, D. F.

    2012-01-01

    The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity is an X-ray diffraction (XRD) and X-ray fluorescence (XRF) instrument capable of providing the mineralogical and chemical compositions of rocks and soils on the surface of Mars. CheMin uses a microfocus X-ray tube with a Co target, transmission geometry, and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D XRD patterns and energy-dispersive X-ray histograms from powdered samples. CheMin has two different window materials used for sample cells -- Mylar and Kapton. Instrument details are provided elsewhere. Fe/Mg-smectite (e.g., nontronite) has been identified in Gale Crater, the MSL future landing site, by CRISM spectra. While large quantities of phyllosilicate minerals will be easily detected by CheMin, it is important to establish detection limits of such phases to understand capabilities and limitations of the instrument. A previous study indicated that the (001) peak of smectite at 15 Ang was detectable in a mixture of 1 wt.% smectite with olivine when Mylar is the window material for the sample cell. Complications arise when Kapton is the window material because Kapton itself also has a diffraction peak near 15 Ang (6.8 deg 2 Theta). This study presents results of mineral mixtures of smectite and olivine to determine smectite detection limits for Kapton sample cells. Because the intensity and position of the smectite (001) peak depends on the hydration state, we also analyzed mixtures with "hydrated" and "dehydrated"h smectite to examine the effects of hydration state on detection limits.

  16. Arsenic speciation in the dispersible colloidal fraction of soils from a mine-impacted creek

    International Nuclear Information System (INIS)

    Serrano, Susana; Gomez-Gonzalez, Miguel Angel; O’Day, Peggy A.; Laborda, Francisco; Bolea, Eduardo; Garrido, Fernando

    2015-01-01

    Highlights: • Nanoparticle scorodite may dissolve from mine wastes and release As down-gradient. • Large fractions of total As in soils may be associated with dispersible colloids. • Up to one third of total As in soils was associated with the colloid fraction. • AsFlFFF-ICP-MS and XAS provides information on the partitioning of contaminants in colloids. - Abstract: Arsenic and iron speciation in the dispersible colloid fraction (DCF; 10–1000 nm) from an As-rich mine waste pile, sediments of a streambed that collects runoff from waste pile, the streambed subsoil, and the sediments of a downstream pond were investigated by combining asymmetrical-flow field-flow fractionation (AsFlFFF)/inductively-coupled plasma–mass spectrometry (ICP–MS), transmission electron microscopy (TEM) and X-ray absorption (XAS) spectroscopy. Calcium, Fe and As (Fe/As molar ratio ∼ 1) were the main components of the DCF from waste pile. TEM/EDS and As and Fe XAS analysis revealed the presence of nanoparticle scorodite in this same DCF, as well as Fe nanoparticles in all samples downstream of the waste pile. Arsenic and Fe XAS showed As(V) adsorbed onto nanoparticulate ferrihydrite in the DCF of downstream samples. Micro-X-ray fluorescence indicated a strong correlation between Fe and As in phyllosilicate/Fe 3+ (oxi) hydroxide aggregates from the sediment pond. Fractionation analysis showed the mean particle size of the DCF from the streambed sample to be smaller than that of the streambed subsoil and sediment ponds samples. These results show that an important and variable fraction of As may be bound to dispersible colloids that can be released from contaminated soils and transported downstream in natural systems

  17. Wind-Eroded Crater Floors and Intercrater Plains, Terra Sabaea, Mars

    Science.gov (United States)

    Irwin, Rossman P.; Wray, James J.; Mest, Scott C.; Maxwell, Ted A.

    2018-02-01

    Ancient impact craters with wind-eroded layering on their floors provide a record of resurfacing materials and processes on early Mars. In a 54 km Noachian crater in Terra Sabaea (20.2°S, 42.6°E), eolian deflation of a friable, dark-toned layer up to tens of meters thick has exposed more resistant, underlying light-toned material. These layers differ significantly from strata of similar tone described in other regions of Mars. The light-toned material has no apparent internal stratification, and visible/near-infrared spectral analysis suggests that it is rich in feldspar. Its origin is ambiguous, as we cannot confidently reject igneous, pyroclastic, or clastic alternatives. The overlying dark-toned layer is probably a basaltic siltstone or sandstone that was emplaced mostly by wind, although its weak cementation and inverted fluvial paleochannels indicate some modification by water. Negative-relief channels are not found on the crater floor, and fluvial erosion is otherwise weakly expressed in the study area. Small impacts onto this crater's floor have exposed deeper friable materials that appear to contain goethite. Bedrock outcrops on the crater walls are phyllosilicate bearing. The intercrater plains contain remnants of a post-Noachian thin, widespread, likely eolian mantle with an indurated surface. Plains near Hellas-concentric escarpments to the north are more consistent with volcanic resurfacing. A 48 km crater nearby contains similar dark-over-light outcrops but no paleochannels. Our findings indicate that dark-over-light stratigraphy has diverse origins across Mars and that some dark-toned plains with mafic mineralogy are not of igneous origin.

  18. Effects of feeding bentonite clay upon ochratoxin A-induced immunosuppression in broiler chicks.

    Science.gov (United States)

    Khatoon, Aisha; Khan, Muhammad Zargham; Abidin, Zain Ul; Bhatti, Sheraz Ahmed

    2018-03-01

    A presence of mycotoxins in feed is one of the most alarming issues in the poultry feed industry. Ochratoxins, produced by several Aspergillus and Penicillium species, are important mycotoxin regarding the health status of poultry birds. Ochratoxins are further classified into to several subtypes (A, B, C, etc) depending on their chemical structures, but ochratoxin A (OTA) is considered the most important and toxic. Bentonite clay, belonging to phyllosilicates and formed from weathering of volcanic ashes, has adsorbent ability for several mycotoxins. The present study was designed to study the effects of bentonite clay upon OTA-induced immunosuppression in broiler chicks. For this, 480 day-old broiler chicks were procured from a local hatchery and then different combinations of OTA (0.15, 0.3, or 1.0 mg/kg) and bentonite clay (5, 10, and 20 g/kg) were incorporated into their feed. At 13, 30, and 42 days of age, parameters such as antibody responses to sheep red blood cells, in situ lymphoproliferative responses to mitogen (PHA-P), and in situ phagocytic activity (i.e., via carbon clearance) were determined respectively. The results indicated there was a significant reduction of total antibody and immunoglobulin titres, lymphoproliferative responses, and phagocytic potential in OTA-treated birds, suggesting clear immunosuppression by OTA in birds in a dose-dependent manner. These results were also significantly lower in all combination groups (OTA with bentonite clay), suggesting few to no effects of feeding bentonite clay upon OTA- induced alterations in different immune parameters.

  19. Critical Assessment of Analytical Techniques in the Search for Biomarkers on Mars: A Mummified Microbial Mat from Antarctica as a Best-Case Scenario

    Science.gov (United States)

    Blanco, Yolanda; Gallardo-Carreño, Ignacio; Ruiz-Bermejo, Marta; Puente-Sánchez, Fernando; Cavalcante-Silva, Erika; Quesada, Antonio; Prieto-Ballesteros, Olga; Parro, Víctor

    2017-10-01

    The search for biomarkers of present or past life is one of the major challenges for in situ planetary exploration. Multiple constraints limit the performance and sensitivity of remote in situ instrumentation. In addition, the structure, chemical, and mineralogical composition of the sample may complicate the analysis and interpretation of the results. The aim of this work is to highlight the main constraints, performance, and complementarity of several techniques that have already been implemented or are planned to be implemented on Mars for detection of organic and molecular biomarkers on a best-case sample scenario. We analyzed a 1000-year-old desiccated and mummified microbial mat from Antarctica by Raman and IR (infrared) spectroscopies (near- and mid-IR), thermogravimetry (TG), differential thermal analysis, mass spectrometry (MS), and immunological detection with a life detector chip. In spite of the high organic content (ca. 20% wt/wt) of the sample, the Raman spectra only showed the characteristic spectral peaks of the remaining beta-carotene biomarker and faint peaks of phyllosilicates over a strong fluorescence background. IR spectra complemented the mineralogical information from Raman spectra and showed the main molecular vibrations of the humic acid functional groups. The TG-MS system showed the release of several volatile compounds attributed to biopolymers. An antibody microarray for detecting cyanobacteria (CYANOCHIP) detected biomarkers from Chroococcales, Nostocales, and Oscillatoriales orders. The results highlight limitations of each technique and suggest the necessity of complementary approaches in the search for biomarkers because some analytical techniques might be impaired by sample composition, presentation, or processing.

  20. Water-soluble organo-building blocks of aminoclay as a soil-flushing agent for heavy metal contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Young-Chul [Department of Chemical and Biomolecular Engineering (BK21 program), KAIST, 335 Gwahak-ro, Yuseong-gu, Daejeon 305-701 (Korea, Republic of); Kim, Eun Jung [Advanced Biomass R and D Center, KAIST, 291 Daehakno, Yuseong-gu, Daejeon 305-701 (Korea, Republic of); Ko, Dong Ah [Department of Chemical and Biomolecular Engineering (BK21 program), KAIST, 335 Gwahak-ro, Yuseong-gu, Daejeon 305-701 (Korea, Republic of); Yang, Ji-Won, E-mail: jiwonyang@kaist.ac.kr [Department of Chemical and Biomolecular Engineering (BK21 program), KAIST, 335 Gwahak-ro, Yuseong-gu, Daejeon 305-701 (Korea, Republic of); Advanced Biomass R and D Center, KAIST, 291 Daehakno, Yuseong-gu, Daejeon 305-701 (Korea, Republic of)

    2011-11-30

    Highlights: Black-Right-Pointing-Pointer Aminoclays have synthesized using centered metals with aminopropyl silane. Black-Right-Pointing-Pointer Developed aminoclay has unique nano-sized and water-soluble properties. Black-Right-Pointing-Pointer Aminoclay showed high heavy metal capacity with metal ions and its less toxicity. Black-Right-Pointing-Pointer Aminoclay could be used to remediate heavy metals from soils an alternative soil-flushing agent. - Abstract: We demonstrated that water-soluble aminopropyl magnesium functionalized phyllosilicate could be used as a soil-flushing agent for heavy metal contaminated soils. Soil flushing has been an attractive means to remediate heavy metal contamination because it is less disruptive to the soil environment after the treatment was performed. However, development of efficient and non-toxic soil-flushing agents is still required. We have synthesized aminoclays with three different central metal ions such as magnesium, aluminum, and ferric ions and investigated applicability of aminoclays as soil flushing agents. Among them, magnesium (Mg)-centered aminoclay showed the smallest size distribution and superior water solubility, up to 100 mg/mL. Mg aminoclay exhibited cadmium and lead binding capacity of 26.50 and 91.31 mg/g of Mg clay, respectively, at near neutral pH, but it showed negligible binding affinity to metals in acidic conditions. For soil flushing with Mg clay at neutral pH showed cadmium and lead were efficiently extracted from soils by Mg clay, suggesting strong binding ability of Mg clay with cadmium and lead. As the organic matter and clay compositions increased in the soil, the removal efficiency by Mg clay decreased and the operation time increased.

  1. Biophysical evaluation of aminoclay as an effective protectant for protein stabilization during freeze-drying and storage

    Directory of Open Access Journals (Sweden)

    Song JG

    2016-12-01

    Full Text Available Jae Geun Song, Sang Hoon Lee, Hyo-Kyung Han College of Pharmacy, Dongguk University, Goyang, South Korea Abstract: This study aimed to evaluate aminoclay (3-aminopropyl-functionalized magnesium phyllosilicate as an effective protectant for the stabilization of protein formulation in freeze-drying. Bovine serum albumin (BSA, as a model protein, was freeze-dried with aminoclay at various concentrations, and the effects of aminoclay on the structural stability of proteins were compared with those of the conventional stabilizers. The structural characteristics of the protein were determined by size exclusion chromatography (SEC, circular dichroism (CD, and Fourier transform infrared (FTIR spectroscopy. Furthermore, physicochemical and morphological characteristics were examined by X-ray powder diffraction (XRPD, differential scanning calorimetry (DSC, and scanning electron microscopy (SEM. XRPD and DSC patterns indicated that the glass transition temperature (Tg of the amorphous formulation of aminoclay mixed with proteins was gradually elevated as the concentration of aminoclay increased. FTIR and CD spectral analysis suggested that the protein structure was well maintained with aminoclay during the freeze-drying process and 3 months of storage at 4°C and 40°C. Furthermore, aminoclay conferred the greatest protection against aggregation and retained the monomer content of BSA even at a high temperature. The morphological characteristics of lyophilized proteins were also well conserved during the storage with aminoclay. These results suggested that aminoclay may be useful as an alternative stabilizer for maintaining the structural stability of protein formulations. Keywords: aminoclay, cryoprotectant, lyoprotectant, freeze-drying, protein, stability

  2. Geochemical Characterization Of Cherts From The 3.46Ga Apex Basalt To Assess The Origins Of Possible Biosignatures

    Science.gov (United States)

    Bower, D. M.; Steele, A.; Ackerson, M. R.; Bullock, E. S.; Green, O. R.; Fries, M.; Conrad, P. G.

    2017-12-01

    Many terrestrial cherts contain compelling microtextures and mineral phases that are indicative of ancient life in hydrothermal systems on early Earth. In volcanically-derived hydrothermal deposits, cherts have undergone multiple alteration events often resulting in separate generations of quartz veins that are much younger than the host rocks. In some cases, multiple episodes of hydrothermal alteration obscure otherwise syngenetic biosignatures and likewise create false signatures in the form of secondary carbon emplacement or diagenetic phase changes. To better identify possible biosignatures in hydrothermal deposits and understand their origins, we used confocal micro Raman spectroscopy, electron probe microanalysis, and cathodoluminescence (CL) imaging to characterize the quartz fabrics, mineral phases, trace elements, and macromolecular carbon (MMC) in quartz veins from the 3.46 Ga Apex Basalt chert samples. MMC, anatase (TiO2), pyrite (Fe2S), jarosite-alunite (KFe3(SO4)2(OH)6 - Kal3(SO4)2(OH)6), chamosite-phyllosilicates, and Fe-oxides all occur in close association in multiple generations of quartz veins throughout the sample suite. Mineral phases xenotime (YPO4), scorodite (FeAsO4 . H2O), apatite (CaPO4), pentlandite ((Fe,Ni)9S8), barite (BaSO4), sphalerite ((Zn,Fe)S), dolomite ((CaMg(CO3)2) and halides occur in specific generations of quartz. Trace elements (Cr, Mn, Mo, Cu, Sc, Va, Sb, and Co) are heterogeneously distributed within individual samples and likely occur due to fluid scavenging of the host basalts. CL imaging of quartz demonstrates that the majority of silicate material in the Apex cherts underwent recrystallization. This could result in the alteration of MMC and associated mineral assemblages. The biogencity and true origins of morphological features and chemical signatures in the Apex cherts are hotly debated, yet discovering the causes and nature of these puzzling attributes will be key for determining the usefulness of interrogating

  3. Enhanced desorption of cesium from collapsed interlayer regions in vermiculite by hydrothermal treatment with divalent cations

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Xiangbiao, E-mail: yin.x.aa@m.titech.ac.jp [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1, Ookayama, Meguro-ku, Tokyo 152-8550 (Japan); Wang, Xinpeng [College of Resources and Metallurgy, Guangxi University, 100 Daxue East Road, Nanning 530004 (China); Wu, Hao; Ohnuki, Toshihiko; Takeshita, Kenji [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1, Ookayama, Meguro-ku, Tokyo 152-8550 (Japan)

    2017-03-15

    Highlights: • Desorption of Cs{sup +} fixed in collapsed interlayer region of vermiculite was studied. • Monovalent cations readily induced interlayer collapse inhibiting Cs{sup +} desorption. • Larger hydrous ionic radii of divalent cations greatly prevented Cs{sup +} desorption. • Effect of divalent cation on Cs{sup +} desorption changes depending on thermal treatment. • ∼100% removal of saturated Cs{sup +} was achieved by hydrothermal treatment at 250 °C. - Abstract: Adsorption of cesium (Cs) on phyllosilicates has been intensively investigated because natural soils have strong ability of immobilizing Cs within clay minerals resulting in difficulty of decontamination. The objectives of present study are to clarify how Cs fixation on vermiculite is influenced by structure change caused by Cs sorption at different loading levels and how Cs desorption is affected by various replacing cations induced at different treating temperature. As a result, more than 80% of Cs was readily desorbed from vermiculite with loading amount of 2% saturated Cs (5.49 × 10{sup −3} mmol g{sup −1}) after four cycles of treatment of 0.01 M Mg{sup 2+}/Ca{sup 2+} at room temperature, but less than 20% of Cs was desorbed from saturated vermiculite. These distinct desorption patterns were attributed to inhibition of Cs desorption by interlayer collapse of vermiculite, especially at high Cs loadings. In contrast, elevated temperature significantly facilitated divalent cations to efficiently desorb Cs from collapsed regions. After five cycles of treatment at 250 °C with 0.01 M Mg{sup 2+}, ∼100% removal of saturated Cs was achieved. X-ray diffraction analysis results suggested that Cs desorption was completed through enhanced diffusion of Mg{sup 2+} cations into collapsed interlayer space under hydrothermal condition resulting in subsequent interlayer decollapse and readily release of Cs{sup +}.

  4. A combined remote Raman and LIBS instrument for characterizing minerals with 532 nm laser excitation.

    Science.gov (United States)

    Sharma, Shiv K; Misra, Anupam K; Lucey, Paul G; Lentz, Rachel C F

    2009-08-01

    The authors have developed an integrated remote Raman and laser-induced breakdown spectroscopy (LIBS) system for measuring both the Raman and LIBS spectra of minerals with a single 532 nm laser line of 35 mJ/pulse and 20 Hz. The instrument has been used for analyzing both Raman and LIBS spectra of carbonates, sulfates, hydrous and anhydrous silicates, and iron oxide minerals in air. These experiments demonstrate that by focusing a frequency-doubled 532 nm Nd:YAG pulsed laser beam with a 10x beam expander to a 529-microm diameter spot on a mineral surface located at 9 m, it is possible to measure simultaneously both the remote Raman and LIBS spectra of calcite, gypsum and olivine by adjusting the laser power electronically. The spectra of calcite, gypsum, and olivine contain fingerprint Raman lines; however, it was not possible to measure the remote Raman spectra of magnetite and hematite at 9 m because of strong absorption of 532 nm laser radiation and low intensities of Raman lines from these minerals. The remote LIBS spectra of both magnetite and hematite contain common iron emission lines but show difference in the minor amount of Li present in these two minerals. Remote Raman and LIBS spectra of a number of carbonates, sulfates, feldspars and phyllosilicates at a distance of 9 m were measured with a 532-nm laser operating at 35 mJ/pulse and by changing photon flux density at the sample by varying the spot diameter from 10 mm for Raman to 530 microm for LIBS measurements. The complementary nature of these spectra is highlighted and discussed. The combined Raman and LIBS system can also be re-configured to perform micro-Raman and micro-LIBS analyses, which have applications in trace/residue analysis and analysis of very small samples in the nano-gram range.

  5. Thermal and Evolved Gas Analysis of Calcite Under Reduced Operating Pressures: Implications for the 2011 MSL Sample Analysis at Mars (SAM) Instrument

    Science.gov (United States)

    Lauer, H. V. Jr.; Ming, D. W.; Sutter, B.; Mahaffy, P. R.

    2010-01-01

    The Mars Science Laboratory (MSL) is scheduled for launch in 2011. The science objectives for MSL are to assess the past or present biological potential, to characterize the geology, and to investigate other planetary processes that influence habitability at the landing site. The Sample Analysis at Mars (SAM) is a key instrument on the MSL payload that will explore the potential habitability at the landing site [1]. In addition to searching for organic compounds, SAM will have the capability to characterized evolved gases as a function of increasing temperature and provide information on the mineralogy of volatile-bearing phases such as carbonates, sulfates, phyllosilicates, and Fe-oxyhydroxides. The operating conditions in SAM ovens will be maintained at 30 mb pressure with a He carrier gas flowing at 1 sccm. We have previously characterized the thermal and evolved gas behaviors of volatile-bearing species under reduced pressure conditions that simulated operating conditions of the Thermal and Evolved Gas Analyzer (TEGA) that was onboard the 2007 Mars Phoenix Scout Mission [e.g., 2-8]. TEGA ovens operated at 12 mb pressure with a N2 carrier gas flowing at 0.04 sccm. Another key difference between SAM and TEGA is that TEGA was able to perform differential scanning calorimetry whereas SAM only has a pyrolysis oven. The operating conditions for TEGA and SAM have several key parameter differences including operating pressure (12 vs 30 mb), carrier gas (N2 vs. He), and carrier gas flow rate (0.04 vs 1 sccm). The objectives of this study are to characterize the thermal and evolved gas analysis of calcite under SAM operating conditions and then compare it to calcite thermal and evolved gas analysis under TEGA operating conditions.

  6. Arsenic release and geochemical evolution of groundwater in an alluvial aquitard, West Bengal, India.

    Science.gov (United States)

    Desbarats, A. J.; Pal, T.; Mukherjee, P. K.; Beckie, R. D.

    2017-12-01

    According to the World Health Organization, contamination of groundwater by geogenic arsenic (As) represents the largest mass poisoning in history. At a field site in West Bengal, India, the source of As affecting a shallow aquifer was traced to silty sediments filling an abandoned river meander. Along with As-bearing phases, these sediments also contain 0.46 % organic carbon. The release of As within the channel fill is investigated using a geochemical mass balance model supported by detailed field observations of aqueous chemistry, sequential extraction analyses of sediment chemistry, and analyses of sediment mineralogy. The model explores the evolution of groundwater chemistry along a flow path extending from its recharge point in an abandoned channel pond, through the channel-fill sequence, to the underlying aquifer. Variations in groundwater composition within the host sediments are explained in terms of mineral weathering driven by organic carbon decay. The model yields reaction coefficients expressing amounts of minerals (and gases) reacting or precipitating along the flow path. Arsenic and phosphorus cycles appear closely linked as these species are hosted by goethite, Fe-rich chlorite, and vivianite. Arsenic is released through the rapid reductive dissolution of goethite and the slower weathering of chlorite. Concomitantly, some As is sequestered in precipitating vivianite. These competing processes reach equilibrium deeper in the channel-fill sequence as groundwater As concentrations stabilize. Using groundwater residence time in channel fill obtained from a numerical flow model and the calculated reaction coefficients, rates of organic carbon oxidation, goethite dissolution, and net As release are estimated at 1.15 mmol C L-1 a-1, 0.18 mmol L-1 a-1, and 4.57 10-4 mmol L-1 a-1, respectively. Fine-grained yet slightly permeable deposits such as channel-fill silts containing reactive organic carbon and As-bearing goethite and phyllosilicates are localized

  7. Paris vs. Murchison: Impact of hydrothermal alteration on organic matter in CM chondrites

    Science.gov (United States)

    Vinogradoff, V.; Le Guillou, C.; Bernard, S.; Binet, L.; Cartigny, P.; Brearley, A. J.; Remusat, L.

    2017-09-01

    Unravelling the origin of organic compounds that were accreted into asteroids requires better constraining the impact of asteroidal hydrothermal alteration on their isotopic signatures, molecular structures, and spatial distribution. Here, we conducted a multi-scale/multi-technique comparative study of the organic matter (OM) from two CM chondrites (that originate from the same parent body or from identical parent bodies that accreted the same mixture of precursors) and underwent a different degree of hydrothermal alteration: Paris (a weakly altered CM chondrite - CM 2.8) and Murchison (a more altered one - CM 2.5). The Paris insoluble organic matter (IOM) shows a higher aliphatic/aromatic carbon ratio, a higher radical abundance and a lower oxygen content than the Murchison IOM. Analysis of the OM in situ shows that two texturally distinct populations of organic compounds are present within the Paris matrix: sub-micrometric individual OM particles and diffuse OM finely distributed within phyllosilicates and amorphous silicates. These results indicate that hydrothermal alteration on the CM parent body induced aromatization and oxidation of the IOM, as well as a decrease in radical and nitrogen contents. Some of these observations were also reported by studies of variably altered fragment of Tagish Lake (C2), although the hydrothermal alteration of the OM in Tagish Lake was apparently much more severe. Finally, comparison with data available in the literature suggests that the parent bodies of other chondrite petrologic groups could have accreted a mixture of organic precursors different from that accreted by the parent body of CMs.

  8. Laboratory Study of Aliphatic Organic Spectral Signatures and Applications to Ceres and Primitive Asteroids

    Science.gov (United States)

    Kaplan, H. H.; Milliken, R.

    2017-12-01

    Aliphatic organics were recently discovered on the surface of Ceres with Dawn's Visible and InfraRed (VIR) mapping spectrometer, which has implications for prebiotic chemistry of Ceres and other asteroids. An absorption in the spectrum at 3.4 µm was used to identify and provide initial estimates of the amount of organic material. We have studied the 3.4 µm absorption in reflectance spectra of bulk rock and meteorite powders and isolated organic materials in the NASA RELAB facility at Brown University to determine how organic composition and abundance affects absorption strength. Reflectance spectra of insoluble organic matter (IOM) extracted from carbonaceous chondrites were measured from 0.35 - 25 µm. These IOM have known elemental (H, C, N, O) and isotopic compositions that were compared with spectral properties. Bulk meteorites were measured as chips and particulates over the same wavelength range. Despite overall low reflectance values (albedo IOM samples, specifically those with a H/C ratio greater than 0.4. The absorption strength (band depth) increases with increasing H/C ratio, which corroborates similar findings in our previous study of sedimentary rocks and isolated kerogens. The absorption strength in the bulk meteorites reflects both H/C of the IOM and the concentration of IOM in the inorganic (mineral) matrix. Overlapping absorptions from carbonates and phyllosilicates (OH/H2O) can also influence the aliphatic organic bands in bulk rocks and meteorites. This laboratory work provides a foundation that can be used to constrain the composition of Ceres' aliphatic organic matter using band depth as a proxy for H/C. Reflectance spectra collected for this work will also be used to model the Dawn VIR data and obtain abundance and H/C estimates assuming that the organic material on Ceres' surface is similar to carbonaceous chondrite IOM. These spectra and findings can aid interpretation of reflectance data from Ceres and other asteroid missions, such as

  9. Ion irradiation of the Murchison meteorite: Visible to mid-infrared spectroscopic results

    Science.gov (United States)

    Lantz, C.; Brunetto, R.; Barucci, M. A.; Dartois, E.; Duprat, J.; Engrand, C.; Godard, M.; Ledu, D.; Quirico, E.

    2015-05-01

    Aims: The goal of this study is to simulate space weathering processes on primitive bodies. We use ion implantation as a simulation of solar wind irradiation, which has been suggested by several authors to be the major component of space weathering on main belt asteroids. The laboratory analogs we irradiate and analyze are carbonaceous chondrites; we started the study with the Allende CV meteorite and in this companion paper we present results on the Murchison CM meteorite. Methods: We performed irradiations on pressed pellets of Murchison with 40 keV He+ and Ar+ ions using fluences up to 3 × 1016 ions/cm2. Reflectance spectra were acquired ex situ before and after irradiation in the visible to mid-infrared range (0.4-16 μm). A Raman analysis was also performed to investigate the modifications of the aromatic carbonaceous component. Results: Our results indicate that spectral variations after irradiation within the visible range are smaller than spectral variations due to sample grain size or viewing geometry of the Murchison meteorite. The aqueous alteration band profile near 3 μm changes after irradiation, as adsorbed water is removed, and phyllosilicates are affected. Raman spectroscopy highlights the insoluble organic matter (IOM) modification under irradiation. We observe a shift of the silicates band at 9.9 μm, probably due to a preferential loss of Mg (compared to Fe, the lighter Mg is more easily sputtered backward) and/or amorphization of Mg-rich materials. We compare our results to previous experiments on organic-rich materials (like asphaltite or carbonaceous chondrites), and on ordinary chondrites and olivine grains. We find that the reddening/darkening trend observed on silicate-rich surfaces is not valid for all carbonaceous chondrites, and that the spectral modifications after irradiation are a function of the initial albedo.

  10. Effects of Short-Term Thermal Alteration on Organic Matter in Experimentally-Heated Tagish Lake Observed by Raman Spectroscopy

    Science.gov (United States)

    Chan, Q. H. S.; Nakato, A.; Zolensky, M. E.; Nakamura, T.; Kebukawa, Y.; Maisano, J.; Colbert, M.; Martinez, J. E.

    2017-01-01

    Carbonaceous chondrites exhibit a wide range of aqueous and thermal alteration characteristics, while some are known to demonstrate mineralogical and petrologic evidence of having been thermally metamorphosed after aqueous alteration. This group of meteorites are commonly referred as thermally met-amorphosed carbonaceous chondrites (TMCCs), and their reflectance spectra show resemblances to that of C-type asteroids which typically have low albedos. This suggests that the surfaces of the C-type asteroids are also composed of both hydrous and dehydrated minerals, and thus TMCCs are among the best samples that can be studied in laboratory to reveal the true nature of the C-type asteroids. Although TMCCs are usually meteorites that were previously categorized as CI and CM chondrites, they are not strictly CI/CM because they exhibit isotopic and petrographic characteristics that significantly deviate from typical CI/CM. More appropriately, they are called CI-like and/or CM-like chondrites. Typical examples of TMCCs include the C2-ung/CM2TIV Belgica (B)-7904 and Yamato (Y) 86720. Thermal alteration is virtually complete in these meteorites and thus they are considered typical end-members of TMCCs exhibiting complete dehydration of matrix phyllosilicates. The estimated heating conditions are 10 to 103 days at 700 C to 1 to 100 hours at 890 C, i.e. short-term heating induced by impact and/or solar radiation. While the petrology and chemistry of TMCCs have only recently been extensively characterized, we have just begun to study in detail their organic contents. In order to understand how short-term heating affects the maturity of insoluble organic matter (IOM) in hydrous chondrites, we investigated experimentally-heated Tagish Lake meteorite using Raman spectroscopy, as the chemical and bulk oxygen isotopic compositions of the matrix of the carbonate (CO3)-poor lithology of the Tagish Lake (hereafter Tag) meteorite bears similarities to the TMCCs.

  11. Alkali trace elements in Gale crater, Mars, with ChemCam: Calibration update and geological implications

    Science.gov (United States)

    Payré, V.; Fabre, C.; Cousin, A.; Sautter, V.; Wiens, R. C.; Forni, O.; Gasnault, O.; Mangold, N.; Meslin, P.-Y.; Lasue, J.; Ollila, A.; Rapin, W.; Maurice, S.; Nachon, M.; Le Deit, L.; Lanza, N.; Clegg, S.

    2017-03-01

    The Chemistry Camera (ChemCam) instrument onboard Curiosity can detect minor and trace elements such as lithium, strontium, rubidium, and barium. Their abundances can provide some insights about Mars' magmatic history and sedimentary processes. We focus on developing new quantitative models for these elements by using a new laboratory database (more than 400 samples) that displays diverse compositions that are more relevant for Gale crater than the previous ChemCam database. These models are based on univariate calibration curves. For each element, the best model is selected depending on the results obtained by using the ChemCam calibration targets onboard Curiosity. New quantifications of Li, Sr, Rb, and Ba in Gale samples have been obtained for the first 1000 Martian days. Comparing these data in alkaline and magnesian rocks with the felsic and mafic clasts from the Martian meteorite NWA7533—from approximately the same geologic period—we observe a similar behavior: Sr, Rb, and Ba are more concentrated in soluble- and incompatible-element-rich mineral phases (Si, Al, and alkali-rich). Correlations between these trace elements and potassium in materials analyzed by ChemCam reveal a strong affinity with K-bearing phases such as feldspars, K-phyllosilicates, and potentially micas in igneous and sedimentary rocks. However, lithium is found in comparable abundances in alkali-rich and magnesium-rich Gale rocks. This very soluble element can be associated with both alkali and Mg-Fe phases such as pyroxene and feldspar. These observations of Li, Sr, Rb, and Ba mineralogical associations highlight their substitution with potassium and their incompatibility in magmatic melts.

  12. Polymer-layered silicate nano composite by UV-radiation curing: an original synthesis

    International Nuclear Information System (INIS)

    Keller, L.; Decker, C.; Zahouily, K.; Miehe-Brendle, J.; Le Meins, J.M.

    2004-01-01

    Full text.Because of the many hopes which they raise, the nano composite materials are the subject of an increasing number of scientific publications. Indeed, the intimate association of a polymer matrix and silicate nano-platelets leads to the formation of materials having mechanical and barriers properties improved (fire, gas, humidity...). A literature survey shows that these materials are generally produced by a thermal polymerization, which presents two major disadvantages: the use of organic solvents and a great consumption of energy. To overcome such limitations, photo initiated polymerization was chosen to synthesize nano composite materials. By this technology, called UV radiation curing, a solvent-free resin is transformed within seconds into a solid polymer upon exposure to UV-radiation at ambient temperature. The principal objective of this study was to develop photopolymerizable systems with clay particles having a layer structure (phyllosilicates). The clay mineral was made organophilic by treatment with an alkylammonium salt to allow the acrylate resin to penetrate into the expanded galleries. A morphological characterization of the materials obtained was carried out by X-rays diffraction and electronic microscopy transmission. The polymerization of the various resins under the UV exposure was followed in situ by using the real-time infrared spectroscopy (RT-FTIR) and attenuated total reflection (ATR). The results obtained show that the presence of the organo clay does not modify much the polymerization kinetics. The nano composite material thus obtained is transparent, insoluble in the organic solvents and presents improved mechanical properties, compared to the neat resin and the micro composite, for a load factor ranging between 2 and 5%wt. The addition of nanoparticles also makes it possible to reduce efficiently the brightness of coatings UV and finally confers to this material barriers properties higher than that of the photo crosslinked

  13. Polymer-layered silicate nanocomposites by UV-radiation curing: an original synthesis

    International Nuclear Information System (INIS)

    Keller, L.; Decker, C.; Zahouily, K.; Miehe-Brendle, J.; Le Meins, J.M.

    2004-01-01

    Full text.Because of the many hopes which they raise, the nanocomposite materials are the subject of an increasing number of scientific publications. Indeed, the intimate association of a polymer matrix and silicate nano-platelets leads to the formation of materials having mechanical and barriers properties improved (fire, gas, humidity,...). A literature survey shows that these materials are generally produced by a thermal polymerization, which presents two major disadvantages: the use of organic solvents and a great consumption of energy. To overcome such limitations, photoinitiated polymerization was chosen to synthesize nanocomposite materials. By this technology, called UV radiation curing, a solvent-free resin is transformed within seconds into a solid polymer upon exposure to UV-radiation at ambient temperature. The principal objective of this study was to develop photopolymerizable systems with clay particles having a layer structure (phyllosilicates). The clay mineral was made organophilic by treatment with an alkylammonium salt to allow the acrylate resin to penetrate into the expanded galleries. A morphological characterization of the materials obtained was carried out by X-rays diffraction and electronic microscopy transmission. The polymerization of the various resins under the UV exposure was followed in situ by using the real-time infrared spectroscopy (RT-FTIR) and attenuated total reflection (ATR). The results obtained show that the presence of the organoclay does not modify much the polymerization kinetics. The nanocomposite material thus obtained is transparent, insoluble int eh organic solvents and presents improved mechanical properties, compared to the neat resin and the microcomposite, for a load factor ranging between 2 and 5% wt. The addition of nanoparticles also makes it possible to reduce efficiently the brightness of coatings UV and finally confers to this material barriers properties higher than that of the photocrosslinked polymeric

  14. Transmission Electron Microscopy of Magnetite Plaquettes in Orgueil

    Science.gov (United States)

    Chan, Q. H. S.; Han, J.; Zolensky, M.

    2016-01-01

    Magnetite sometimes takes the form of a plaquette - barrel-shaped stack of magnetite disks - in carbonaceous chondrites (CC) that show evidence of aqueous alteration. The asymmetric nature of the plaquettes caused Pizzarello and Groy to propose magnetite plaquettes as a naturally asymmetric mineral that can indroduce symmetry-breaking in organic molecules. Our previous synchrotron X-ray computed microtomography (SXRCT) and electron backscatter diffraction (EBSD) analyses of the magnetite plaquettes in fifteen CCs indicate that magnetite plaquettes are composed of nearly parallel discs, and the crystallographic orientations of the discs change around a rotational axis normal to the discs surfaces. In order to further investigate the nanostructures of magnetite plaquettes, we made two focused ion beam (FIB) sections of nine magnetite plaquettes from a thin section of CI Orgueil for transmission electron microscope (TEM) analysis. The X-ray spectrum imaging shows that the magnetite discs are purely iron oxide Fe3O4 (42.9 at% Fe and 57.1 at% O), which suggest that the plaquettes are of aqueous origin as it is difficult to form pure magnetite as a nebular condensate. The selected area electron diffraction (SAED) patterns acquired across the plaquettes show that the magnetite discs are single crystals. SEM and EBSD analyses suggest that the planar surfaces of the magnetite discs belong to the {100} planes of the cubic inverse spinel structure, which are supported by our TEM observations. Kerridge et al. suggested that the epitaxial relationship between magnetite plaquette and carbonate determines the magnetite face. However, according to our TEM observation, the association of magnetite with porous networks of phyllosilicate indicates that the epitaxial relationship with carbonate is not essential to the formation of magnetite plaquettes. It was difficult to determine the preferred rotational orientation of the plaquettes due to the symmetry of the cubic structure

  15. Slip Zone versus Damage Zone Micromechanics, Arima-Takasuki Tectonic Line, Japan

    Science.gov (United States)

    White, J. C.; Lin, A.

    2017-12-01

    The Arima-Takasuki Tectonic Line (ATTL) of southern Honshu, Japan is defined by historically active faults and multiple splays producing M7 earthquakes. The damage zone of the ATTL comprises a broad zone of crushed, comminuted and pulverized granite/rhyolite1,2containing cm-scale slip zones and highly comminuted injection veins. In this presentation, prior work on the ATTL fault rocks is extending to include microstructural characterization by transmission electron microscopy (TEM) from recent trenching of the primary slip zone, as well as secondary slip zones. This is necessary to adequately characterize the extremely fine-grained material (typically less than 1mm) in both damage and core zones. Damage zone material exhibits generally random textures3 whereas slip zones are macroscopically foliated, and compositionally layered, notwithstanding a fairly homogeneous protolith. The latter reflects fluid-rock interaction during both coseismic and interseismic periods. The slip zones are microstructurally heterogeneous at all scales, comprising not only cataclasites and phyllosilicate (clay)-rich gouge zones, but Fe/Mn pellets or clasts that are contained within gouge. These structures appear to have rolled and would suggest rapid recrystallization and/or growth. A central question related to earthquake recurrence along existing faults is the nature of the gouge. In both near-surface exposures and ongoing drilling at depth, "plastic" or "viscous" gouge zones comprise ultra-fine-grained clay-siliciclastic particles that would not necessarily respond in a simple frictional manner. Depending on whether the plastic nature of these slip zones develops during or after slip, subsequent focusing of slip within them could be complicated. 1 Mitchell, T.A., Ben-Zion, Y., Shimamoto, T., 2011. Ear. Planet. Sci. Lett. 308, 284-297. 2 Lin, A., Yamashita, K, Tanaka, M. J., 2013. Struc. Geol. 48, 3-13. 3 White, J.C., Lin, A. 2016. Proc. AGU Fall Mtg., T42-02 San Francisco.

  16. Water-soluble organo-building blocks of aminoclay as a soil-flushing agent for heavy metal contaminated soil

    International Nuclear Information System (INIS)

    Lee, Young-Chul; Kim, Eun Jung; Ko, Dong Ah; Yang, Ji-Won

    2011-01-01

    Highlights: ► Aminoclays have synthesized using centered metals with aminopropyl silane. ► Developed aminoclay has unique nano-sized and water-soluble properties. ► Aminoclay showed high heavy metal capacity with metal ions and its less toxicity. ► Aminoclay could be used to remediate heavy metals from soils an alternative soil-flushing agent. - Abstract: We demonstrated that water-soluble aminopropyl magnesium functionalized phyllosilicate could be used as a soil-flushing agent for heavy metal contaminated soils. Soil flushing has been an attractive means to remediate heavy metal contamination because it is less disruptive to the soil environment after the treatment was performed. However, development of efficient and non-toxic soil-flushing agents is still required. We have synthesized aminoclays with three different central metal ions such as magnesium, aluminum, and ferric ions and investigated applicability of aminoclays as soil flushing agents. Among them, magnesium (Mg)-centered aminoclay showed the smallest size distribution and superior water solubility, up to 100 mg/mL. Mg aminoclay exhibited cadmium and lead binding capacity of 26.50 and 91.31 mg/g of Mg clay, respectively, at near neutral pH, but it showed negligible binding affinity to metals in acidic conditions. For soil flushing with Mg clay at neutral pH showed cadmium and lead were efficiently extracted from soils by Mg clay, suggesting strong binding ability of Mg clay with cadmium and lead. As the organic matter and clay compositions increased in the soil, the removal efficiency by Mg clay decreased and the operation time increased.

  17. Solid-Phase Fe Speciation along the Vertical Redox Gradients in Floodplains using XAS and Mössbauer Spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Chunmei [Department; Kukkadapu, Ravi K. [Environmental; Lazareva, Olesya [Department; Sparks, Donald L. [Department

    2017-06-30

    Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplain profiles, which exhibited a succession of oxic, anoxic and suboxic-oxic zones with increasing depth along the vertical profiles. The anoxic conditions at the intermediate horizon (55-80 cm) of the eastern floodplain resulted in extensive depletion of Fe(III)-oxides including both ferrihydrite and goethite, concurrent with a corresponding reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II). In addition, the anoxic conditions increased the crystallinity of Fe(III)-oxides in this reduced zone, relative to the oxic zones. In the most reduced intermediate sediments at 80-120cm of the western floodplain, the anoxic conditions drove the complete reductive dissolution of Fe(III) oxides, as well as the greatest reduction (48-55%) in PS-Fe(III). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.

  18. Terrestrial fate of coal-liquid constituents: behavior of alkyl anilines in soil

    Energy Technology Data Exchange (ETDEWEB)

    Felice, L.J.; Zachara, J.M.; Rogers, J.E.

    1982-07-01

    The low molecular weight aromatic amines (anilines) are important water soluble constituents of coal liquids. The impact of anilines released to the terrestrial environment will largely depend on their mobility and persistence. Studies were conducted to investigate those processes governing the mobility and persistence of the alkylanilines, namely, soil sorption and chemical/microbial degradation. Soil sorption measurements were conducted on aniline and several methyl substituted anilines on A and B horizons of a soil profile collected from Davies County, Kentucky. The magnitude of sorption was large in all horizons. Sorption in the B horizons was larger than in the A horizon for many of the anilines studied, indicating the importance of both the mineral matrix and organic carbon content of the soil in determining the magnitude of sorption. Results of these measurements indicate that movement of the anilines through the soil would be significantly attenuated by sorption reactions. Aniline sorption measurement in the A horizon after removal of the organic matter and in the B/sub 22/ horizon after removal of amorphous iron oxides and crystalline iron oxides indicate that organic matter largely controls aniline sorption in the A horizon, while crystalline iron oxides and phyllosilicates are important in the B horizons. The effects of pH on aniline sorption was also examined and shown to have significant effects on the magnitude of sorption in both A and B horizons. Soil degradation studies using /sup 14/C-3-methylaniline as a model for alkyl aniline degradation show that 3-methylaniline is readily metabolized by soil microorganisms during the 32-day period examined.

  19. Uranium(VI) sorption on iron oxides in Hanford Site sediment: Application of a surface complexation model

    International Nuclear Information System (INIS)

    Um, Wooyong; Serne, R. Jeffrey; Brown, Christopher F.; Rod, Kenton A.

    2008-01-01

    Sorption of U(VI) on Hanford fine sand (HFS) with varying Fe-oxide (especially ferrihydrite) contents showed that U(VI) sorption increased with the incremental addition of synthetic ferrihydrite into HFS, consistent with ferrihydrite being one of the most reactive U(VI) sorbents present in natural sediments. Surface complexation model (SCM) calculations for U(VI) sorption, using only U(VI) surface-reaction constants obtained from U(VI) sorption data on freshly synthesized ferrihydrite at different pHs, were similar to the measured U(VI) sorption results on pure synthetic ferrihydrite and on HFS with high contents of ferrihydrite (5 wt%) added. However, the SCM prediction using only U(VI) sorption reactions and constants for synthetic ferrihydrite overestimated U(VI) sorption on the natural HFS or HFS with addition of low amounts of added ferrihydrite (1 wt% added). Over-predicted U(VI) sorption was attributed to reduced reactivity of natural ferrihydrite present in Hanford Site sediments, compared to freshly prepared synthetic ferrihydrite. Even though the SCM general composite (GC) approach is considered to be a semi-quantitative estimation technique for contaminant sorption, which requires systematic experimental data on the sorbent-sorbate system being studied to obtain credible SCM parameters, the general composite SCM model was still found to be a useful technique for describing U(VI) sorption on natural sediments. Based on U(VI) batch sorption results, two simple U(VI) monodentate surface species, SO U O 2 HCO 3 and SO U O 2 OH on ferrihydrite and phyllosillicate in HFS, respectively, can be successfully used to describe U(VI) sorption onto Hanford Site sediment contacting varying geochemical solutions

  20. A microstructural study of fault rocks from the SAFOD: Implications for the deformation mechanisms and strength of the creeping segment of the San Andreas Fault

    Science.gov (United States)

    Hadizadeh, Jafar; Mittempergher, Silvia; Gratier, Jean-Pierre; Renard, Francois; Di Toro, Giulio; Richard, Julie; Babaie, Hassan A.

    2012-09-01

    The San Andreas Fault zone in central California accommodates tectonic strain by stable slip and microseismic activity. We study microstructural controls of strength and deformation in the fault using core samples provided by the San Andreas Fault Observatory at Depth (SAFOD) including gouge corresponding to presently active shearing intervals in the main borehole. The methods of study include high-resolution optical and electron microscopy, X-ray fluorescence mapping, X-ray powder diffraction, energy dispersive X-ray spectroscopy, white light interferometry, and image processing. The fault zone at the SAFOD site consists of a strongly deformed and foliated core zone that includes 2-3 m thick active shear zones, surrounded by less deformed rocks. Results suggest deformation and foliation of the core zone outside the active shear zones by alternating cataclasis and pressure solution mechanisms. The active shear zones, considered zones of large-scale shear localization, appear to be associated with an abundance of weak phases including smectite clays, serpentinite alteration products, and amorphous material. We suggest that deformation along the active shear zones is by a granular-type flow mechanism that involves frictional sliding of microlithons along phyllosilicate-rich Riedel shear surfaces as well as stress-driven diffusive mass transfer. The microstructural data may be interpreted to suggest that deformation in the active shear zones is strongly displacement-weakening. The fault creeps because the velocity strengthening weak gouge in the active shear zones is being sheared without strong restrengthening mechanisms such as cementation or fracture sealing. Possible mechanisms for the observed microseismicity in the creeping segment of the SAF include local high fluid pressure build-ups, hard asperity development by fracture-and-seal cycles, and stress build-up due to slip zone undulations.

  1. Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium.

    Science.gov (United States)

    Liu, D; Dong, H; Bishop, M E; Zhang, J; Wang, H; Xie, S; Wang, S; Huang, L; Eberl, D D

    2012-03-01

    Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate-reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu-2, mixed-layer illite-smectite RAr-1 and ISCz-1, and illite IMt-1) were exposed to D. vulgaris in a non-growth medium with and without anthraquinone-2,6-disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X-ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals. © 2011 Blackwell Publishing Ltd.

  2. Formation of Fe/mg Smectite Under Acidic Conditions from Synthetic Adirondack Basaltic Glass: an Analog to Fe/mg Smectite Formation on Mars

    Science.gov (United States)

    Sutter, B.; Peretyazhko, T.; Morris, R. V.; Ming, D. W.

    2014-01-01

    Smectite has been detected as layered material hundreds of meters thick, in intracrater depositional fans, in plains sediments, and deposits at depth on Mars. If early Mars hosted a dense CO2 atmosphere, then extensive carbonate should have formed in the neutral/alkaline conditions expected for smectite formation. However, large carbonate deposits on Mars have not been discovered. Instead of neutral to moderately alkaline conditions, early Mars may have experienced mildly acidic conditions that allowed for Fe/Mg smectite formation but prevented widespread carbonate formation. The objective of this work is to demonstrate that Fe(II)/Mg saponite and nontronite can form in mildly acidic solutions (e.g., pH 4). Synthetic basaltic glass (Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. Trioctahedral saponite was confirmed by the presence of a 4.58 to 4.63 Angstroms (02l) and 1.54Angstroms (060) peaks. Saponite concentration was highest, as indicated by XRD peak intensity, in the 10 mM Mg treatment followed by the 0 mM and then 10 mM Fe(II) treatments. This order of sapontite concentration suggests that Fe(II) additions may have a role in slowing the kinetics of saponite formation relative to the other treatments. Nontronite synthesis was attempted by exposing Adirondack basaltic glass to pH 4 oxic solutions (without N2 purge) at 200 C for 14 days. X-ray diffraction analysis indicated that mixtures of trioctahedral (saponite) and dioctahedral (nontronite) may have formed in these experiments based on the 02l and 060 peaks. Moessbauer analysis coupled with future experiments are planned to verify if nontronite can be formed under mildly acidic and oxic conditions. Results of this work demonstrate that acidic conditions could have occurred on an early Mars, which allowed for smectite formation but inhibited carbonate formation.

  3. Understanding the sorption mechanisms of aflatoxin B1 to kaolinite, illite, and smectite clays via a comparative computational study.

    Science.gov (United States)

    Kang, Fuxing; Ge, Yangyang; Hu, Xiaojie; Goikavi, Caspar; Waigi, Michael Gatheru; Gao, Yanzheng; Ling, Wanting

    2016-12-15

    In current adsorption studies of biotoxins to phyllosilicate clays, multiply weak bonding types regarding these adsorptions are not well known; the major attractive forces, especially for kaolinite and illite, are difficult to be identified as compared to smectite with exchangeable cations. Here, we discriminated the bonding types of aflatoxin B1 (AFB1) contaminant to these clays by combined batch experiment with model computation, expounded their bonding mechanisms which have been not quantitatively described by researchers. The observed adsorbent-to-solution distribution coefficients (K d ) of AFB1 presented in increasing order of 18.5-37.1, 141.6-158.3, and 354.6-484.7L/kg for kaolinite, illite, and smectite, respectively. Normalization of adsorbent-specific surface areas showed that adsorption affinity of AFB1 is mainly dependent on the outside surfaces of clay aggregates. The model computation and test of ionic effect further suggested that weakly electrostatic attractions ((Si/Al-OH) 2 ⋯(OC) 2 ) are responsible for AFB1-kaolinite adsorption (K d , 18.5-37.1L/kg); a moderate electron-donor-acceptor attraction ((CO) 2 ⋯K + ⋯(O-Al) 3 ) is related to AFB1-illite adsorption (K d , 141.6-158.3L/kg); a strong calcium-bridging linkage ((CO) 2 ⋯Ca 2+ ⋯(O-Si) 4 ) is involved in AFB1-smectite adsorption (K d , 354.6-484.7L/kg). Changes in Gibbs free energy (ΔG°) suggested that the computed result is reliable, providing a good reproduction of AFB1-clay interaction. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Insights into tetrabromobisphenol A adsorption onto soils: Effects of soil components and environmental factors.

    Science.gov (United States)

    Tong, Fei; Gu, Xueyuan; Gu, Cheng; Ji, Rong; Tan, Yinyue; Xie, Jinyu

    2015-12-01

    Concerns regarding tetrabromobisphenol A (TBBPA), the most widely utilized brominated flame retardant in the world, are growing because of the wide application and endocrine-disrupting potential of this compound. To properly assess its environmental impacts, it is important to understand the mobility and fate of TBBPA in soil environments. In this study, the effects of soil components, dissolved organic carbon (DOC) and heavy metal cations on TBBPA adsorption onto two Chinese soils (red soil and black soil) were investigated using batch sorption experiments. The desorption behavior of TBBPA when the two soils are irrigated with eutrophicated river water was also investigated. The results showed that pH greatly affects the adsorptive behavior of TBBPA in soils. Iron oxide minerals and phyllosilicate minerals are both active surfaces for TBBPA sorption, in addition to soil organic matter (SOM). DOC (50 mg OC L(-1)) exhibited a limited effect on TBBPA sorption only under neutral conditions. TBBPA sorption was only minimally affected by the heavy metals (Cu2+, Pb2+ and Cd2+) in the studied pH range. Eutrophicated river water significantly enhanced the desorption of TBBPA from red soil due to the change in soil solution pH. These findings indicate that mobility of TBBPA in soils is mainly associated with soil pH, organic matter and clay fractions: it will be retained by soils or sediments with high organic matter and clay fractions under acidic conditions but becomes mobile under alkaline conditions. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Arsenic speciation in the dispersible colloidal fraction of soils from a mine-impacted creek

    Energy Technology Data Exchange (ETDEWEB)

    Serrano, Susana [Institute of Agrochemistry and Food Technology, CSIC, Agustín Escardino 7, 46980 Paterna, Valencia (Spain); Gomez-Gonzalez, Miguel Angel [National Museum of Natural Sciences, CSIC, José Gutiérrez Abascal 2, 28006 Madrid (Spain); O’Day, Peggy A. [School of Natural Sciences,University of California, Merced, CA 95343 (United States); Laborda, Francisco; Bolea, Eduardo [Group of Analytical Spectroscopy and Sensors (GEAS), Institute of Environmental Sciences (IUCA), University of Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza (Spain); Garrido, Fernando, E-mail: fernando.garrido@mncn.csic.es [National Museum of Natural Sciences, CSIC, José Gutiérrez Abascal 2, 28006 Madrid (Spain)

    2015-04-09

    Highlights: • Nanoparticle scorodite may dissolve from mine wastes and release As down-gradient. • Large fractions of total As in soils may be associated with dispersible colloids. • Up to one third of total As in soils was associated with the colloid fraction. • AsFlFFF-ICP-MS and XAS provides information on the partitioning of contaminants in colloids. - Abstract: Arsenic and iron speciation in the dispersible colloid fraction (DCF; 10–1000 nm) from an As-rich mine waste pile, sediments of a streambed that collects runoff from waste pile, the streambed subsoil, and the sediments of a downstream pond were investigated by combining asymmetrical-flow field-flow fractionation (AsFlFFF)/inductively-coupled plasma–mass spectrometry (ICP–MS), transmission electron microscopy (TEM) and X-ray absorption (XAS) spectroscopy. Calcium, Fe and As (Fe/As molar ratio ∼ 1) were the main components of the DCF from waste pile. TEM/EDS and As and Fe XAS analysis revealed the presence of nanoparticle scorodite in this same DCF, as well as Fe nanoparticles in all samples downstream of the waste pile. Arsenic and Fe XAS showed As(V) adsorbed onto nanoparticulate ferrihydrite in the DCF of downstream samples. Micro-X-ray fluorescence indicated a strong correlation between Fe and As in phyllosilicate/Fe{sup 3+} (oxi) hydroxide aggregates from the sediment pond. Fractionation analysis showed the mean particle size of the DCF from the streambed sample to be smaller than that of the streambed subsoil and sediment ponds samples. These results show that an important and variable fraction of As may be bound to dispersible colloids that can be released from contaminated soils and transported downstream in natural systems.

  6. Chemical processes at the surface of various clays on acid-base titration

    International Nuclear Information System (INIS)

    Park, K. K.; Park, Y. S.; Jung, E. C.

    2010-01-01

    The chemical reaction of radionuclides at the interface between groundwater and geological mineral is an important process determining their retardation of transport through groundwater flow in a nuclear waste disposal. Clay minerals are major components of soil and argillaceous rock, and some of them are considered to be important base materials in the design of high-level nuclear waste repository due to their large swelling, low-permeability, large surface area, and strong and large sorption of radionuclides. Clay materials are phyllosilicates containing accessory minerals such as metal oxides, hydroxides, oxyhydroxides. Their structures are condensed 1:1 or 2:1 layers of tetrahedral SiO 3/2 OH and octahedral Al(OH) 6/2 sheets. An accurate knowledge about the properties of clay surface is required as a parameter for a long-term estimation of radionuclide retardation effects. Electric surface charge is a primary property determining ion exchange and surface complexation of radionuclides on its surface. The sources of electric surface charge are a permanent structural negative charge on a basal plane and a dissociable charge at an edge surface. Investigation of proton sorption is a prerequisite to the understanding of radionuclide sorption. The reactions on a permanently charged site and on an edge site are measured by an electrokinetic measurement and by potentiometric titration, respectively. However, side reactions such as complexation, proton/cation exchange, dissolution, hydrolysis, precipitation and re adsorption, and the reaction of secondary minerals hinder an experimental measurement of accurate acid-base properties. This presentation describes the pH change on dispersing various clays in water and adding acid, base or Eu(III) ion to these solutions, and the effect of Eu(III) ion on acid-base titration of clay solutions

  7. Chemical processes at the surface of various clays on acid-base titration

    Energy Technology Data Exchange (ETDEWEB)

    Park, K. K.; Park, Y. S.; Jung, E. C. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2010-10-15

    The chemical reaction of radionuclides at the interface between groundwater and geological mineral is an important process determining their retardation of transport through groundwater flow in a nuclear waste disposal. Clay minerals are major components of soil and argillaceous rock, and some of them are considered to be important base materials in the design of high-level nuclear waste repository due to their large swelling, low-permeability, large surface area, and strong and large sorption of radionuclides. Clay materials are phyllosilicates containing accessory minerals such as metal oxides, hydroxides, oxyhydroxides. Their structures are condensed 1:1 or 2:1 layers of tetrahedral SiO{sub 3/2}OH and octahedral Al(OH){sub 6/2} sheets. An accurate knowledge about the properties of clay surface is required as a parameter for a long-term estimation of radionuclide retardation effects. Electric surface charge is a primary property determining ion exchange and surface complexation of radionuclides on its surface. The sources of electric surface charge are a permanent structural negative charge on a basal plane and a dissociable charge at an edge surface. Investigation of proton sorption is a prerequisite to the understanding of radionuclide sorption. The reactions on a permanently charged site and on an edge site are measured by an electrokinetic measurement and by potentiometric titration, respectively. However, side reactions such as complexation, proton/cation exchange, dissolution, hydrolysis, precipitation and re adsorption, and the reaction of secondary minerals hinder an experimental measurement of accurate acid-base properties. This presentation describes the pH change on dispersing various clays in water and adding acid, base or Eu(III) ion to these solutions, and the effect of Eu(III) ion on acid-base titration of clay solutions

  8. Adsorption kinetics of maxilon yellow 4GL and maxilon red GRL dyes on kaolinite

    International Nuclear Information System (INIS)

    Dogan, Mehmet; Karaoglu, M. Hamdi; Alkan, Mahir

    2009-01-01

    Kaolinite, a low-costly material, is the most abundant phyllosilicate mineral in highly weathered soils. In this work, the adsorption kinetics of maxilon yellow 4GL (MY 4GL) and maxilon red GRL (MR GRL) dyes on kaolinite from aqueous solutions was investigated using the parameters such as contact time, stirring speed, initial dye concentration, initial pH, ionic strength, acid-activation, calcination and solution temperature. The equilibrium time was 150 min for both dyes. The results showed that alkaline pH was favorable for the adsorption of MY 4GL and MR GRL dyes and physisorption seemed to play a major role in the adsorption process. It was found that the rate of adsorption decreases with increasing temperature and the process is exothermic. The adsorption kinetics followed the pseudo-second-order equation for both dyes investigated in this work with the k 2 values lying in the region of 1.79 x 10 4 to 107.87 x 10 4 g/mol min for MY 4GL and 3.44 x 10 4 to 72.09 x 10 4 g/mol min for MR GRL. The diffusion coefficient values calculated for the dyes were in the range of 3.76 x 10 -9 to 62.50 x 10 -9 cm 2 /s for MY 4GL and 1.98 x 10 -9 to 44.00 x 10 -9 cm 2 /s for MR GRL, and are compatible with other studies reported in the literature. The thermodynamic activation parameters such as the enthalpy, entropy and free energy were determined. The obtained results confirmed the applicability of this clay as an efficient adsorbent for cationic dyes.

  9. Reproducing early Martian atmospheric carbon dioxide partial pressure by modeling the formation of Mg-Fe-Ca carbonate identified in the Comanche rock outcrops on Mars

    Science.gov (United States)

    Berk, Wolfgang; Fu, Yunjiao; Ilger, Jan-Michael

    2012-10-01

    The well defined composition of the Comanche rock's carbonate (Magnesite0.62Siderite0.25Calcite0.11Rhodochrosite0.02) and its host rock's composition, dominated by Mg-rich olivine, enable us to reproduce the atmospheric CO2partial pressure that may have triggered the formation of these carbonates. Hydrogeochemical one-dimensional transport modeling reveals that similar aqueous rock alteration conditions (including CO2partial pressure) may have led to the formation of Mg-Fe-Ca carbonate identified in the Comanche rock outcrops (Gusev Crater) and also in the ultramafic rocks exposed in the Nili Fossae region. Hydrogeochemical conditions enabling the formation of Mg-rich solid solution carbonate result from equilibrium species distributions involving (1) ultramafic rocks (ca. 32 wt% olivine; Fo0.72Fa0.28), (2) pure water, and (3) CO2partial pressures of ca. 0.5 to 2.0 bar at water-to-rock ratios of ca. 500 molH2O mol-1rock and ca. 5°C (278 K). Our modeled carbonate composition (Magnesite0.64Siderite0.28Calcite0.08) matches the measured composition of carbonates preserved in the Comanche rocks. Considerably different carbonate compositions are achieved at (1) higher temperature (85°C), (2) water-to-rock ratios considerably higher and lower than 500 mol mol-1 and (3) CO2partial pressures differing from 1.0 bar in the model set up. The Comanche rocks, hosting the carbonate, may have been subjected to long-lasting (>104 to 105 years) aqueous alteration processes triggered by atmospheric CO2partial pressures of ca. 1.0 bar at low temperature. Their outcrop may represent a fragment of the upper layers of an altered olivine-rich rock column, which is characterized by newly formed Mg-Fe-Ca solid solution carbonate, and phyllosilicate-rich alteration assemblages within deeper (unexposed) units.

  10. Infrared Spectrometer for ExoMars: A Mast-Mounted Instrument for the Rover

    Science.gov (United States)

    Korablev, Oleg I.; Dobrolensky, Yurii; Evdokimova, Nadezhda; Fedorova, Anna A.; Kuzmin, Ruslan O.; Mantsevich, Sergei N.; Cloutis, Edward A.; Carter, John; Poulet, Francois; Flahaut, Jessica; Griffiths, Andrew; Gunn, Matthew; Schmitz, Nicole; Martín-Torres, Javier; Zorzano, Maria-Paz; Rodionov, Daniil S.; Vago, Jorge L.; Stepanov, Alexander V.; Titov, Andrei Yu.; Vyazovetsky, Nikita A.; Trokhimovskiy, Alexander Yu.; Sapgir, Alexander G.; Kalinnikov, Yurii K.; Ivanov, Yurii S.; Shapkin, Alexei A.; Ivanov, Andrei Yu.

    2017-07-01

    ISEM (Infrared Spectrometer for ExoMars) is a pencil-beam infrared spectrometer that will measure reflect